Polyether, base for cosmetics, and cosmetic

Abstract

The present application provides a polyether represented by the following formula (1) (the definitions of the symbols in the formula are described in the specification). The polyether of the present application is suitable for various uses such as a base material for cosmetics.

Description

Technical Field

[0001] This invention relates to polyethers, cosmetic bases, and cosmetics. Background Technology

[0002] Polyethers, which are produced by ring-opening addition polymerization of cyclic ethers such as ethylene oxide and propylene oxide, or by dehydration condensation of polyols, are used in various 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 skincare and cosmetics, glycerin and other polyols, as well as water-soluble polymers such as hyaluronic acid, are often added to enhance moisturizing effects. However, cosmetics obtained by adding large amounts of polyols and water-soluble polymers can sometimes feel sticky and have poor skin integration, leading to a deterioration in the user experience. Therefore, Patent Documents 1 and 2 disclose cosmetic compositions containing specific polyethers as cosmetics that offer both high moisturizing effects and a non-sticky, pleasant user experience.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2004-83541

[0007] Patent Document 2: Japanese Patent Application Publication No. 2020-105123 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] In the cosmetics industry, surfactants are sometimes used to stably add hydrophobic ingredients such as fragrances, preservatives, active ingredients, and oils. However, to improve the stickiness and reduce irritation, it is necessary to further reduce the amount of surfactant used. However, reducing the amount of surfactant used can sometimes reduce the transparency of cosmetics when using multiple oils with different polarities, such as hydrocarbon oils and greases. Furthermore, reducing the amount of surfactant can decrease low-temperature stability. For example, when cosmetics freeze at around -4°C, some components may precipitate out. Even after the cosmetics return to room temperature, sometimes the precipitates do not dissolve and remain.

[0010] Given this situation, there is a need to develop a cosmetic base that can achieve good transparency, good low-temperature stability, good moisturizing effect, and a non-sticky, pleasant user experience even with reduced surfactant usage.

[0011] The subject of this invention is to provide a polyether that is useful as a cosmetic base, which can produce cosmetics with good transparency, good low-temperature stability, good moisturizing effect and a non-sticky feel, even with reduced surfactant usage.

[0012] Methods for solving problems

[0013] In view of the above-mentioned situation, the inventors conducted in-depth research and discovered that polyethers with a specific structure can solve the aforementioned problems. Specifically, reducing the amount of surfactant used leads to unevenness, reduced transparency, or decreased low-temperature stability in cosmetics containing hydrophobic components. However, by using polyethers with a specific structure, even with reduced surfactant usage, the low-temperature stability of cosmetics containing hydrophobic components can be improved, while simultaneously achieving reduced stickiness and high moisturizing effects. Based on this insight, the present invention is described below.

[0014] [1] A polyether, represented by formula (1),

[0015]

Chemistry 1

[0016]

[0017] [In the formula, R] 1 R 2 and a R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

[0018] (R) 1 ~R 3 (Number of hydrogen atoms in R) / (R 1 ~R 3 The ratio of the number of hydrocarbon groups in the content is less than 20.

[0019] GL stands for glycerol residue.

[0020] CH2CH2O represents an ethylene glycol residue.

[0021] CH2CH2CH2O represents 1,3-propanediol residues.

[0022] C n H 2n O represents an alkane diol residue with 4 to 8 carbon atoms.

[0023] a, b, c, and d represent GL, CH2CH2O, CH2CH2CH2O, and C, respectively. n H 2n The average degree of polymerization of O,

[0024] a is a number between 0 and 30.

[0025] b is a number between 0 and 80.

[0026] a+b is a number between 1 and 80.

[0027] c is a number between 0 and 60.

[0028] d is a number between 0 and 60.

[0029] c+d are numbers from 1 to 70.

[0030] (a+b) / (c+d) is a number between 0.2 and 8.

[0031] n is a number between 4 and 8.

[0032] [2] A cosmetic base, which is composed of the polyether described in [1].

[0033] [3] A cosmetic product, wherein the cosmetic base described in [2] is contained in an amount of 0.1 to 30% by mass relative to the total cosmetic product.

[0034] The effects of the invention

[0035] According to the present invention, a polyether can be obtained, which can be used as a cosmetic base that can impart moisturizing effects, non-stickiness, and low-temperature stability to cosmetics.

[0036] Furthermore, cosmetics containing a specified amount of a cosmetic base made of the polyether of the present invention can achieve high moisturizing effects with a non-sticky feel, and can maintain good transparency and good low-temperature stability even with reduced amounts of surfactants used in cosmetics. Detailed Implementation

[0037] In this specification, the numerical range specified by “~” means the value including both ends (upper and lower limits) of “~”. For example, “2~5” means above 2 and below 5.

[0038] <Polyether>

[0039] The polyether of the present invention is represented by the following formula (1):

[0040]

Chemistry 2

[0041]

[0042] The polyether of the present invention can be used alone or in combination with two or more. The definitions of the symbols in formula (1) will be explained in turn below.

[0043] In equation (1), R 1 R 2 and a R3 Each group consists independently of a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. Polyethers with 21 or more hydrocarbon groups may reduce the moisturizing effect, transparency, or low-temperature stability in cosmetics.

[0044] Examples of hydrocarbon groups include alkyl, alkenyl, cycloalkyl, aryl, and aralkyl. Alkyl or alkenyl groups are preferred. Both alkyl and alkenyl groups can be either straight-chain or branched.

[0045] 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. The hydrocarbon group having 1 to 20 carbon atoms is most preferably methyl.

[0046] (R) 1 ~R 3 (Number of hydrogen atoms in R) / (R 1 ~R 3 The ratio of hydrogen atoms to hydrocarbon groups (hereinafter sometimes referred to as "hydrogen atoms / hydrocarbon groups") is preferably 20 or less, more preferably 15 or less, and more preferably 10 or less, from the viewpoint of inhibiting stickiness, transparency, and low-temperature stability in cosmetics. Alternatively, the hydrogen atom / hydrocarbon group ratio may be 0. Furthermore, in this specification, when R... 1 ~R 3 When the number of hydrocarbon groups is 0, the hydrogen atom / hydrocarbon group ratio is interpreted as ∞ (infinity).

[0047] As described in the Examples section below, the hydrogen atoms / hydrocarbon groups of the polyether (i.e., (R) 1 ~R 3 (Number of hydrogen atoms in R) / (R 1 ~R 3 The number of hydrocarbon groups in the polyether can be determined by acetylation of the polyether. 13 The signal integral values ​​of the carbonyl carbon derived from the acetyl group and the signal integral values ​​of the terminal CH3 derived from the hydrocarbon group obtained in C-NMR determination are calculated by the following formula:

[0048] Hydrogen atom / hydrocarbon group

[0049] =Signal integral value of the carbonyl carbon derived from the acetyl group / Signal integral value of the terminal CH3 derived from the hydrocarbon group.

[0050] 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. Additionally, 13 C-NMR measurements can be performed as described in the Examples section below.

[0051] As needed, combinations are possible. 13 C-NMR measurements and 1 Hydrogen atom / hydrocarbon group is calculated by measuring H-NMR, DEPT135, and two-dimensional NMR (HH COSY, HMQC, HMBC, NOESY, etc.).

[0052] In formula (1), GL represents a glycerol residue. Here, "glycerol residue" refers to the group represented by formula (2) or formula (3):

[0053]

Transformation 3

[0054]

[0055] (In the formula, * represents the relationship with R) 3 (The point of connection.)

[0056] In addition, the glycerol residue can be a group that has the structure represented by formula (2) or formula (3), or it can be a group formed by a compound different from glycerol. Hereinafter, the "group represented by formula (2)" and the "group represented by formula (3)" will sometimes be abbreviated as "group (2)" and "group (3)" respectively.

[0057] When GL (glycerol residue) is present in the polyether of the present invention, both group (2) and group (3) may be present. When GL (glycerol residue) is present in the polyether of the present invention, both group (2) and group (3) are preferably present.

[0058] In the presence of GL (glycerol residues) in the polyether of the present invention, the molar ratio of group (2) to group (3) is preferably 40 / 60 to 99 / 1 from the viewpoint of inhibiting stickiness, transparency, and low-temperature stability in cosmetics, more preferably 40 / 60 to 90 / 10, and even more preferably 50 / 50 to 80 / 20. The molar ratio of group (2) to group (3) can be determined by... 13 C-NMR measurements were performed. Specifically, the molar ratio of group (2) to group (3) can be calculated by comparing the integral value of the signal of the methylene carbon of group (2) (around 71 ppm) with the integral value of the signal of the methylene carbon of group (3) (around 79 ppm).

[0059] In formula (1), CH2CH2O is an ethylene glycol residue. Here, "ethylene glycol residue" means a group having a structure in which one hydroxyl group (HO-) is removed from ethylene glycol (HO-CH2CH2-OH), and a hydrogen atom (H) is removed from another hydroxyl group (-OH). In addition, ethylene glycol residue can be a group having the above structure, or it can be a group formed from a compound different from ethylene glycol (e.g., ethylene oxide).

[0060] In formula (1), CH2CH2CH2O is a 1,3-propanediol residue. Here, "1,3-propanediol residue" means a group having a structure in which one hydroxyl group (HO-) is removed from 1,3-propanediol (HO-), and a hydrogen atom (H) is removed from another hydroxyl group (-OH). In addition, as long as the 1,3-propanediol residue is a group having the aforementioned structure, it can also be a group formed from a compound different from 1,3-propanediol.

[0061] In equation (1), C n H 2n O represents an alkanediol residue with 4 to 8 carbon atoms. Here, "alkanediol residue with 4 to 8 carbon atoms" refers to alkanediols with 4 to 8 carbon atoms (HO-C...). n H 2n A group having a structure obtained by removing one hydroxyl group (HO-) from one hydroxyl group (-OH, n=4-8) and removing a hydrogen atom (H) from another hydroxyl group (-OH). The alkanediol can be either straight-chain or branched. Furthermore, any alkanediol residue with 4-8 carbon atoms that has the aforementioned structure can be a group formed from a compound different from an alkanediol with 4-8 carbon atoms. The terms "1,2-butanediol residue" and the like, used later, have the same meaning as "alkanediol residue with 4-8 carbon atoms."

[0062] Examples of alkane diol 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, neopentanediol 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.

[0063] C n H 2n O starts from the perspective of moisturizing effect, transparency and low temperature stability in cosmetics.

[0064] Preferably, the residues are alkane diols with 4 to 6 carbon atoms.

[0065] More preferably, it is 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.

[0066] Further preferred are 1,3-butanediol residues, 1,4-butanediol residues, or 1,6-hexanediol residues.

[0067] Particularly preferred are 1,3-butanediol residues or 1,6-hexanediol residues.

[0068] In polyethers containing alkane diol residues with 9 or more carbon atoms, the transparency or low-temperature stability in cosmetics may be reduced.

[0069] In equation (1), a, b, c, and d are GL, CH2CH2O, CH2CH2CH2O, and C, respectively. n H 2n The average degree of polymerization of O. Therefore, they can all be decimals.

[0070] From the viewpoint of inhibiting stickiness, transparency, and low-temperature stability in cosmetics, 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 does not exist. When b is 0, from the viewpoint of transparency and low-temperature stability in cosmetics, a is preferably a number from 2 to 10, and more preferably a number from 3 to 10.

[0071] From the viewpoint of moisturizing effect, transparency, and low-temperature stability in cosmetics, b is a number from 0 to 80, preferably from 0 to 50, and more preferably from 0 to 30. Here, "b is 0" means that CH2CH2O is not present. When a is 0, from the viewpoint of transparency and low-temperature stability in cosmetics, b is preferably a number from 4 to 50.

[0072] From the viewpoint of inhibiting stickiness, transparency and low-temperature stability in cosmetics, 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.

[0073] From the viewpoint of moisturizing effect, transparency, and low-temperature stability in cosmetics, c is a number from 0 to 60, preferably from 0 to 40, and more preferably from 0 to 30. Here, "c = 0" means that CH2CH2CH2O is not present. When d = 0, from the viewpoint of transparency and low-temperature stability in cosmetics, c is preferably a number from 2 to 30.

[0074] From the perspective of moisturizing effects in cosmetics, d is a number from 0 to 60, preferably from 0 to 40, and more preferably from 0 to 30. Here, "d = 0" means that C does not exist. n H 2n O. When c is 0, from the viewpoint of transparency and low-temperature stability in cosmetics, d is preferably a number between 2 and 30.

[0075] From the perspective of moisturizing effect in cosmetics, 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.

[0076] From the viewpoint of moisturizing effect, stickiness inhibition, transparency and low temperature stability in cosmetics, (a+b) / (c+d) is a number from 0.2 to 8, preferably from 0.25 to 5, and more preferably from 0.33 to 4. Furthermore, in this specification, when c+d is 0, (a+b) / (c+d) is interpreted as ∞ (infinity).

[0077] In equation (1), n ​​is C n H 2n The number of carbon atoms in O is between 4 and 8. From the viewpoint of transparency and low-temperature stability in cosmetics, n is preferably between 4 and 6, and more preferably 4 or 6.

[0078] The forward slash " / " in equation (1) indicates the relationship between GL, CH2CH2O, CH2CH2CH2O and C. n H 2n The order of O is not specified, meaning they exist in any order. Therefore, they can be bonded as follows: (i) GL, CH2CH2O, CH2CH2CH2O and C n H 2n O can bond randomly to each other, (ii) GL, CH2CH2O, CH2CH2CH2O and C n H 2n One or more of O can form blocks with the same groups forming each other, (iii) GL, CH2CH2O, CH2CH2CH2O and C n H 2n O can also be bonded in a manner that includes both (i) and (ii). For example, multiple CH2CH2O blocks form a block that is bonded to GL, CH2CH2CH2O and C. n H 2n O can bond randomly. When more than three CH2CH2O molecules are present in one molecule, it is preferable to form a (CH2CH2O)3 block.

[0079] From the viewpoint of inhibiting stickiness in cosmetics, the weight-average molecular weight (Mw) of the polyether of the present invention, calculated based on the chromatogram obtained by gel permeation chromatography (GPC), is preferably 300 to 10,000, more preferably 500 to 8,000.

[0080] The polyether of the present invention can be manufactured by known methods. For example, (i) a reaction intermediate can be manufactured by dehydration condensation reaction of a polyol at 80°C to 130°C and atmospheric pressure in the presence of an acid catalyst such as sulfuric acid, and (ii) the obtained reaction intermediate can then be etherified with a haloalkyl or haloalkenyl group at 80°C to 130°C in the presence of a catalyst such as potassium hydroxide, thereby manufacturing the polyether of the present invention.

[0081] The polyether of the present invention can be used as a base for cosmetics. Additionally, the polyether of the present invention can be used as a plasticizer, detergent, or humectant.

[0082] <Cosmetic bases and cosmetics>

[0083] This invention provides a cosmetic base made of the polyether of this invention. The cosmetic base of this invention can be used alone or in combination with two or more. Furthermore, this invention provides a cosmetic product containing the cosmetic base of this invention in an amount of 0.1 to 30% by weight relative to the total amount of the cosmetic product.

[0084] By using the cosmetic base of the present invention, cosmetics can be given a high moisturizing effect and a non-sticky feel, and the amount of surfactants contained in cosmetics can be relatively reduced.

[0085] The cosmetics of this invention are not particularly limited and can be any of the following: water-based cosmetics, water-in-oil or oil-in-water emulsion cosmetics, or oil-based cosmetics. Examples of cosmetics include skincare products such as toners, serums, lotions, creams, masks, and sunscreens; body cosmetics; makeup removers such as cleansing oils and waters; skin cleansing products such as shower gels, hand soaps, and facial cleansers; hair cosmetics such as shampoos, conditioners, hair liquids, hair oils, hair tonics, and hair growth agents; and makeup products such as foundations, liquid foundations, and BB creams.

[0086] From the viewpoint of inhibiting stickiness, the content of the cosmetic base of the present invention is 0.1 to 30% by mass relative to the total amount of the cosmetic of the present invention, preferably 0.5 to 15% by mass.

[0087] The cosmetic of the present invention preferably contains water (more preferably purified water). Furthermore, the cosmetic of the present invention may contain other ingredients different from the cosmetic base and water, as needed, without impairing the effects of the present invention. Other ingredients are not particularly limited as long as they are ingredients commonly used in cosmetics. Examples of other ingredients include: moisturizers, hydrocarbons, higher alcohols, higher fatty acids and their triglycerides, ester oils, animal and vegetable oils, organosilicones, vitamins, ultraviolet absorbers, water-soluble polymers, antioxidants, cationic surfactants, anionic surfactants, amphoteric surfactants, nonionic surfactants, metal ion capping agents, ethanol, thickeners, preservatives, pigments, colorants, fragrances, etc. Other ingredients may be used alone or in combination of two or more.

[0088] When the cosmetic of the present invention is a lotion, serum, or emulsion, and other ingredients are used, from the viewpoint of moisturizing effect, hydration, and user experience (e.g., refreshing feeling), the total amount of other ingredients, relative to the total amount of the lotion, serum, or emulsion of the present invention, is preferably 0.1 to 80% by mass, more preferably 0.5 to 40% by mass. Furthermore, water is the remaining portion of the lotion, serum, or emulsion of the present invention (i.e., the remaining portion of the lotion, serum, or emulsion of the present invention other than the base and other ingredients).

[0089] When the cosmetic of the present invention is a face cream, foundation, or sunscreen, and other ingredients are used, from the viewpoint of moisturizing effect and water evaporation inhibition effect, the total amount of other ingredients is preferably 5 to 99% by mass, more preferably 10 to 85% by mass, relative to the face cream, foundation, or sunscreen of the present invention as a whole. Furthermore, water is the remainder of the face cream, foundation, or sunscreen of the present invention (i.e., the remaining portion of the face cream, foundation, or sunscreen of the present invention other than the base and other ingredients).

[0090] When the cosmetic of the present invention is a shampoo or body wash and other ingredients are used, from the viewpoint of cleansing properties, 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 wash of the present invention. Additionally, water is the remainder of the shampoo or body wash of the present invention (i.e., the remaining portion of the shampoo or body wash other than the cosmetic base and other ingredients of the present invention).

[0091] In the case of a hair conditioner in the present invention, and when other ingredients are used, from the viewpoint of moisturizing effect and water evaporation inhibition effect, the total amount of other ingredients is preferably 10 to 90% by mass, more preferably 15 to 80% by mass, relative to the total amount of the hair conditioner of the present invention. In addition, water is the remainder of the hair conditioner of the present invention (i.e., the remaining portion of the hair conditioner other than the cosmetic base and other ingredients of the present invention).

[0092] When the cosmetic of the present invention is a cleansing oil and other ingredients are used, from the viewpoint of cleansing properties, the total amount of the other ingredients is preferably 40 to 99.5% by mass, more preferably 60 to 99% by mass, relative to the total amount of the cleansing oil of the present invention. In addition, water is the remainder of the cleansing oil of the present invention (i.e., the remaining portion of the cleansing oil of the present invention other than the cosmetic base and other ingredients).

[0093] When the cosmetic of the present invention is a makeup remover and other ingredients are used, from the viewpoint of cleansing properties, 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 amount of the makeup remover of the present invention. In addition, water is the remainder of the makeup remover of the present invention (i.e., the remaining portion of the makeup remover of the present invention other than the cosmetic base and other ingredients).

[0094] When the cosmetic of the present invention is a facial cleansing cream and other ingredients are used, from the viewpoint of cleansing properties, the total amount of the other ingredients, relative to the total amount of the facial cleansing cream of the present invention, is preferably 15 to 95% by mass, more preferably 30 to 85% by mass. In addition, water is the remainder of the facial cleansing cream of the present invention (i.e., the remaining portion of the facial cleansing cream of the present invention other than the cosmetic base and other ingredients).

[0095]

Example

[0096] The present invention will be described in detail below with examples and comparative examples. In addition, unless otherwise specified, "%" in the following ingredient amounts refers to "mass %".

[0097] (Manufacturing Example 1: Synthesis of Polyether 1 in Example)

[0098] In a four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and cooling tube, 540 g of triethylene glycol (manufactured by Kanto Chemical Co., Ltd.) as a polyol, 500 g of 1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.) as a polyol, and 13.8 g of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) as a catalyst were added. After nitrogen purging, 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 for 1 hour at a temperature of 90°C and a pressure below -0.097 MPa (gauge pressure) under nitrogen bubbling conditions. The mixture 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 the hydroxyl value determination method of JIS K-1557-1. The hydroxyl values ​​of polyethers other than this reaction intermediate were also calculated in the same manner.

[0099] Subsequently, in a high-pressure reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen inlet pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket, a reaction intermediate and 120g of potassium hydroxide were added. After nitrogen purging, 120g of chloromethane was introduced at 80℃~130℃ for 5 hours for etherification. The crude product was then removed from the high-pressure reactor, adsorbed with an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.), and then filtered to obtain polyether 1 of Example (hydroxyl value: 50 (mgKOH / g)).

[0100] (Manufacturing Example 2: Synthesis of Polyether 2 in Example)

[0101] In a four-necked flask equipped with a stirrer, nitrogen inlet tube, thermocouple, and cooling tube, 370 g of glycerol (manufactured by Kanto Chemical Co., Ltd.) as a polyol, 570 g of 1,3-propanediol (manufactured by Kanto Chemical Co., Ltd.), and 12.6 g of sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) as a catalyst were added. After nitrogen purging, 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 adsorption treatment was performed for 1 hour at a temperature of 90°C and a pressure below -0.097 MPa (gauge pressure) under nitrogen bubbling conditions. The mixture was then filtered to obtain the reaction intermediate (hydroxyl value: 320 (mg KOH / g)).

[0102] Subsequently, in a high-pressure reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen inlet pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket, a reaction intermediate and 67g of potassium hydroxide were added. After nitrogen purging, 51g of chloromethane was introduced at a temperature of 80°C–130°C, and an etherification reaction was carried out for 3 hours. The crude product was then removed from the high-pressure reactor, adsorbed with an adsorbent (manufactured by Kyowa Chemical Industry Co., Ltd.), and then filtered to obtain Example Polyether 2 (hydroxyl value: 265 (mgKOH / g)). The molar ratio of group (2) to group (3) of Example Polyether 2 was calculated according to the following method, and the result was 72 / 28.

[0103] (Calculation of the molar ratio of group (2) / group (3))

[0104] Example 2 polyether was decoupled using reverse gating. 13 C-NMR measurements were performed, and the molar ratio of group (2) to group (3) was calculated by comparing the integrated signal of the methylene carbon of group (2) (around 71 ppm) with that of the methylene carbon of group (3) (around 79 ppm). Further details... 13 The conditions for C-NMR determination are as follows.

[0105] • 13 C-NMR apparatus: JNM-ECA600 (JEOL-NMR)

[0106] • Solvent: D2O

[0107] • Sample concentration: 100 mg / 0.6 mL

[0108] • Temperature: 25℃

[0109] • Total number of times: 256

[0110] (Manufacturing Example 3: Synthesis of polyethers 3-12 of Examples and polyethers 1-9 of Comparative Examples)

[0111] Polyethers 3-12 of Examples and polyethers 1-9 of Comparative Examples were synthesized using the same method as in Manufacturing Examples 1 or 2. The polyols used in the dehydration condensation reaction and the haloalkyl or haloalkenyl groups used in the subsequent etherification reaction are shown in Tables 1 and 2.

[0112] (Manufacturing Example 4: Synthesis of Comparative Example Polyether 10)

[0113] In a high-pressure reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen inlet pipe, stirrer, 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 added. After nitrogen purging, 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 at a pressure below 0.5 MPa. After the addition was complete, the reaction was carried out at 115 °C for 1 hour, followed by vacuum treatment at 75–85 °C for 1 hour to obtain the reaction intermediate (hydroxyl value: 106 (mg KOH / g)).

[0114] Next, 110 g of potassium hydroxide was added to the autoclave, and after nitrogen purging, 50 g of chloromethane was introduced at a temperature of 80°C–130°C for 5 hours for etherification. The reaction composition was then removed from the autoclave and subjected to adsorption treatment with two adsorbents (Kyoward #700 and #1000), followed by filtration to obtain comparative example polyether 10 (hydroxyl value: 5.0 (mg KOH / g)). The weight-average molecular weight (hereinafter sometimes simply referred to as "Mw") of comparative example polyether 10, measured under the conditions described later, was 1050. Furthermore, comparative example polyether 10 differs 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 the linear 1,3-propanediol residues).

[0115] (Manufacturing Example 5: Synthesis of Comparative Example Polyether 11)

[0116] In a high-pressure reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen inlet pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket, 152 g of glycerol and 7.0 g of potassium hydroxide were added. After nitrogen purging, the temperature was raised to 120°C, and a mixture of 734.5 g of glycidyl ether and 1439.4 g of propylene oxide was added over 20 hours at a pressure below 0.5 MPa. After the addition was completed, the reaction mixture was allowed to react at 120°C for 2 hours. The reaction mixture was then removed from the high-pressure reactor, subjected to adsorption treatment for 1 hour, and then filtered to obtain comparative example polyether 11. The Mw of comparative example polyether 11, measured under the conditions described later, was 1430. Furthermore, comparative example polyether 11 differs from the polyether of the present invention in that it has repeating units derived from glycidyl ether and repeating units derived from propylene oxide (i.e., branched propylene oxide groups).

[0117] The obtained polyethers 1-12 of Examples and polyethers 1-9 of Comparative Examples were compared with R. 1 ~R 3 Hydrogen atom / hydrocarbon group (i.e., (R) 1 ~R 3 (Number of hydrogen atoms in R) / (R 1 ~R 3 The ratio of the number of hydrocarbon groups in the given information, a to d, a+b, c+d, n, and C. n H 2n The starting materials for O, (a+b) / (c+d), and Mw are shown in Tables 1 and 2. Additionally, the hydrogen atom / hydrocarbon group ratio and Mw are calculated as described below.

[0118] (Calculation of hydrogen atom / hydrocarbon group)

[0119] Hydrogen atom / hydrocarbon group (i.e., (R) 1 ~R 3 (Number of hydrogen atoms in R) / (R 1 ~R 3 The number of hydrocarbon groups in the polyether (based on the amount of hydrocarbon groups in the polyether) is determined by the amount of hydrocarbon groups in the polyether during acetylation. 13 The integrated values ​​of the signals from the carbonyl carbon derived from the acetyl group and the integrated values ​​of the signals from the terminal CH3 group obtained by C-NMR determination are calculated using the following formula:

[0120] 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 of the hydrocarbon group. The specific operation is as follows.

[0121] <acetylation>

[0122] Weigh 4.0 mL of pyridine and 1.0 mL of acetic anhydride into a flask, mix thoroughly by shaking, add 1 g of polyether, mix thoroughly by shaking, and heat for 1 hour. Then, add 1 mL of water and heat for 10 minutes, then remove the acetic anhydride to obtain the acetylated polyether.

[0123] < 13 C-NMR measurement>

[0124] Regarding the obtained acetylation 13 C-NMR measurements were performed, and the integrated signal values ​​for the carbonyl carbon originating from the acetyl group around 170 ppm and the integrated signal values ​​for the terminal CH3 originating from the hydrocarbon group around 10–15 ppm (around 60 ppm when the hydrocarbon group is methyl) were calculated. Using these values, the hydrogen atom / hydrocarbon group ratio (i.e., (R)) was calculated from the above formula. 1 ~R 3 (Number of hydrogen atoms in R) / (R 1 ~R 3 The number of hydrocarbon groups in the sample). Additionally, detailed... 13The conditions for C-NMR determination are as follows.

[0125] • 13 C-NMR apparatus: JNM-ECA600 (JEOL-NMR)

[0126] • Solvent: CDCl3

[0127] • Sample concentration: 40 mg / 0.6 mL

[0128] • Temperature: 25℃

[0129] • Total number of times: 4096

[0130] (Calculation of Mw)

[0131] Mw was calculated using gel permeation chromatography (GPC) under the following conditions. The GPC was continuously assembled with: a SHODEX (registered trademark) GPC101 GPC system as the system, a SHODEX RI-71s differential refractive index meter as the differential refractive index meter, a SHODEX KF-G guard column, and three SHODEX KF804L columns. The column temperature was 40°C, and tetrahydrofuran was injected as the developing solvent at a flow rate of 1 ml / min. 0.1 ml of a 0.1% tetrahydrofuran solution of the obtained example polyether or comparative example polyether was injected. The Mw was calculated using the BORWINGPC calculation program based on the chromatogram expressed as refractive index intensity and dissolution time.

[0132] Table 1

[0133]

[0134] Table 2

[0135]

[0136] (Evaluation of transparency of aqueous solutions or dispersions containing olive oil and squalane)

[0137] Add 2.0% of the polyether of the example or the comparative example, 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 oiling agents, and the balance of purified water to a beaker, and stir until homogeneous to prepare an aqueous solution or dispersion of the polyether of the example or the comparative example.

[0138] In a beaker, 3.0% PEG-40 hydrogenated castor oil and 3.0% polysorbate 80 as surfactants, 0.3% olive oil and 0.1% squalane as oiling agents, and the remainder purified water were added and stirred until homogeneous to prepare the dispersion of Reference Example 1.

[0139] 5.0% PEG-40 hydrogenated castor oil and 5.0% polysorbate 80 as surfactants, 0.3% olive oil and 0.1% squalane as oiling agents, and the remainder purified water were added to a beaker and stirred until homogeneous to prepare the dispersion of Reference Example 2.

[0140] 50 mL of the prepared 25°C aqueous solution or dispersion was filled into a 110 mL glass container (Maruemu screw-top tube No. 8 110 mL). The readability of text (font: MS Gothic, font size: 28 pt) placed at a distance of 5 cm from the glass container was assessed, and the transparency was evaluated according to the following criteria. The results are shown in Table 3.

[0141] <Evaluation Criteria>

[0142] ◎: The aqueous solution is transparent and the text is clearly legible.

[0143] ○: The aqueous solution is translucent, but the text is legible.

[0144] ×: The dispersion is turbid and the text is unreadable, or the dispersion has separated.

[0145] Table 3

[0146]

[0147] (Manufacturing Example 6: Manufacture of cosmetics 1-15 of Examples, cosmetics 1-11 of Comparative Examples, and cosmetics 1 and 2 of Reference Examples)

[0148] Using the amounts shown in Table 4 or Table 5, the polyethers of the examples or comparative examples, PEG-40 hydrogenated castor oil, common ingredients, and purified water were mixed and stirred to manufacture cosmetics of Examples 1-15, comparative examples 1-11, and reference examples 1 and 2. The composition of the common ingredients is shown in Table 6. Furthermore, "BG" in Table 6 is a cosmetic designation as defined by the Japan Cosmetic Industries Association, representing 1,3-butanediol.

[0149] (Review: No stickiness)

[0150] Ten men and women (aged 25–50) served as judges. Each judge applied 1.0 g of the cosmetic product obtained in Manufacturing Example 6 to the inner forearm of their right wrist, and the stickiness was scored according to the following criteria. The total scores of the ten judges were calculated, and the absence of stickiness was evaluated according to the following criteria. The results are shown in Tables 4 and 5.

[0151] <Scoring Criteria>

[0152] 3 points: Not sticky at all

[0153] 2 points: Slightly sticky

[0154] 1 point: Feels sticky

[0155] <Evaluation Criteria>

[0156] ◎: Total score of 25 or above

[0157] ○: Total score between 20 and 24 points

[0158] △: Total score below 19 points

[0159] (Evaluation of moisturizing effect)

[0160] Ten men and women (aged 25–50) served as judges. In a constant temperature and humidity chamber set at 20°C and 50% relative humidity, 1.0 g of each cosmetic product obtained in Manufacturing Example 6 was applied to the inner forearm of each judge's right wrist. The stratum corneum moisture content was measured using a skin surface stratum corneum moisture meter (SKICON-200EX, manufactured by IBS) before application and one hour after application. The relative value of the stratum corneum moisture content with the initial value set to 1 was calculated, and scores were awarded according to the following criteria. The total scores of the 10 judges were calculated, and the moisturizing effect was evaluated according to the following criteria. The results are shown in Tables 4 and 5.

[0161] <Scoring Criteria>

[0162] 3 points: Relative value of 3 or above

[0163] 2 points: Relative value of 2 or higher, less than 3

[0164] 1 point: Relative value less than 2

[0165] <Evaluation Criteria>

[0166] ◎: Total score of 25 or above

[0167] ○: Total score between 20 and 24 points

[0168] △: Total score below 19 points

[0169] (Evaluation of transparency)

[0170] Each cosmetic product, with a volume of 50 mL, obtained in Manufacturing Example 6 was filled into a 110 mL glass container (Maruemu manufactured screw-top tube No. 8 110 mL). The readability of the text (font: MS Gothic, font size: 28 pt) placed at a distance of 5 cm from the glass container was assessed, and the transparency was evaluated according to the following criteria. The results are shown in Tables 4 and 5.

[0171] <Evaluation Criteria>

[0172] ◎: The cosmetics are transparent and the text is clearly legible.

[0173] 〇: The cosmetic is semi-transparent, but the text is legible.

[0174] ×: The cosmetic is cloudy and the text is unreadable, or the cosmetic has separated.

[0175] (Evaluation of low-temperature stability)

[0176] The 30 mL samples of each cosmetic obtained in Manufacturing Example 6 were filled into 50 mL glass containers and stored in a light-proof -4°C constant temperature bath for 3 months. After being restored to room temperature, the low-temperature stability was evaluated according to the following criteria. The results are shown in Tables 4 and 5.

[0177] <Evaluation Criteria>

[0178] 〇: Makeup should remain transparent

[0179] ×: Extracts or separations were produced in the cosmetics.

[0180] Table 4

[0181]

[0182] Table 5

[0183]

[0184] Table 6

[0185]

[0186] As can be seen from the table above, the polyethers in Examples 1 to 12, which correspond to the polyethers of the present invention, are excellent in any of the above evaluations. In contrast, the table above shows that none of the above evaluations are sufficient for the comparative examples polyethers 1 to 11.

[0187] In R 1 ~R 3 In Comparative Example Polyether 1, where the hydrogen atom ratio is ∞, the dispersion containing olive oil and squalane exhibits insufficient transparency. Furthermore, Comparative Example Cosmetic 1, containing Comparative Example Polyether 1, lacks sufficient non-stickiness, transparency, and low-temperature stability.

[0188] In Comparative Example Polyether 2, where a+b is greater than 80, the dispersion containing olive oil and squalane lacks sufficient transparency. Furthermore, in Comparative Example Cosmetics 2 containing Comparative Example Polyether 2, there is insufficient non-stickiness, transparency, and low-temperature stability.

[0189] In comparative example polyether 3, where (a+b) / (c+d) is less than 0.2, the dispersion containing olive oil and squalane exhibits insufficient transparency. Furthermore, in comparative example cosmetic 3 containing comparative example polyether 3, there is insufficient non-stickiness, insufficient moisturizing effect, insufficient transparency, and insufficient low-temperature stability.

[0190] In Comparative Example Polyether 4, where (a+b) / (c+d) is greater than 8, the dispersion containing olive oil and squalane exhibits insufficient transparency. Furthermore, in Comparative Example Cosmetics 4 containing Comparative Example Polyether 4, there is insufficient non-stickiness, insufficient moisturizing effect, insufficient transparency, and insufficient low-temperature stability.

[0191] In comparative example polyether 5 where a+b is less than 1, the dispersion containing olive oil and squalane lacks sufficient transparency. In comparative example cosmetic 5 containing comparative example polyether 5, there is insufficient non-stickiness, insufficient moisturizing effect, insufficient transparency, and insufficient low-temperature stability.

[0192] In Comparative Example Polyether 6, where the hydrogen atom / hydrocarbon group ratio is greater than 20, d is greater than 60, and c+d is greater than 70, the dispersion containing olive oil and squalane exhibits insufficient transparency. Furthermore, in Comparative Example Cosmetics 6 containing Comparative Example Polyether 6, there is insufficient non-stickiness, insufficient moisturizing effect, insufficient transparency, and insufficient low-temperature stability.

[0193] In Comparative Example Polyether 7, where c and d are both 0 and (a+b) / (c+d) is ∞, the dispersion containing olive oil and squalane has insufficient transparency. Furthermore, in Comparative Example Cosmetics 7 containing Comparative Example Polyether 7, there is insufficient non-stickiness, insufficient moisturizing effect, insufficient transparency, and insufficient low-temperature stability.

[0194] In R 1 ~R 3 In comparative example polyether 8, where the hydrocarbon group has more than 20 carbon atoms, the dispersion containing olive oil and squalane exhibits insufficient transparency. Furthermore, in comparative example cosmetic 8 containing comparative example polyether 8, moisturizing effect, transparency, and low-temperature stability are insufficient.

[0195] In comparative example polyether 9 where n is greater than 8, the dispersion containing olive oil and squalane has insufficient transparency. Furthermore, in comparative example cosmetic 9 containing comparative example polyether 9, moisturizing effect, transparency, and low-temperature stability are insufficient.

[0196] In 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, the dispersion containing olive oil and squalane has insufficient transparency. Furthermore, in comparative example cosmetic 10 containing comparative example polyether 10, transparency and low-temperature stability are insufficient.

[0197] In comparative example polyether 11, which is a copolymer of glycidyl ether and propylene oxide and has a different structure from the polyether of the present invention, the dispersion containing olive oil and squalane has insufficient transparency. Furthermore, in comparative example cosmetic 11 containing comparative example polyether 11, transparency and low-temperature stability are insufficient.

[0198] (Prescription example)

[0199] Examples of formulations of cosmetics (lotions, serums, lotions, oil-in-water creams, water-in-oil creams, shampoos, conditioners, cleansing oils, cleansing waters, pump-type foaming cleansers, shower gels, facial cleansing creams, foundations, and sunscreens) containing the polyethers of the present invention are shown in Tables 7 to 20 below. The ingredient amounts shown in Tables 7 to 20 are values ​​based on the cosmetic as a whole. Furthermore, the names of the ingredients listed in Tables 7 to 20 below are appropriately used cosmetic designations as prescribed by the Japan Cosmetic Industries Association. The present invention is not limited to the formulation examples below.

[0200] Table 7

[0201]

[0202] Table 8-1

[0203]

[0204] Table 8-2

[0205]

[0206] Table 9-1

[0207]

[0208] Table 9-2

[0209]

[0210] Table 10-1

[0211]

[0212] Table 10-2

[0213]

[0214] Table 11

[0215]

[0216] Table 11-2

[0217]

[0218] Table 12

[0219]

[0220] Table 13

[0221]

[0222] Table 14

[0223]

[0224] Table 15

[0225]

[0226] Table 16

[0227]

[0228] Table 17

[0229]

[0230] Table 18

[0231]

[0232] Table 19

[0233]

[0234] Table 20

[0235]

[0236] Industrial availability

[0237] The polyether of this invention is suitable for various applications, such as cosmetic bases.

[0238] This application is based on Japanese Patent Application No. 2024-057119 filed in Japan, the contents of which are fully incorporated in this application specification. Claims (as amended under Article 19 of the Treaty) 1. A polyether, which is represented by formula (1),

Chemistry 1

Chemistry 2

Claims

1. A polyether, which is represented by formula (1), 【Chemistry 1】 ， In the formula, R 1 R 2 and a R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. (R) 1 ~R 3 (Number of hydrogen atoms in R) / (R 1 ~R 3 The ratio of the number of hydrocarbon groups in the content to that in the content is less than 20. GL stands for glycerol residue. CH2CH2O represents an ethylene glycol residue. CH2CH2CH2O represents 1,3-propanediol residues. C n H 2n O represents an alkane diol residue with 4 to 8 carbon atoms. a, b, c, and d represent GL, CH2CH2O, CH2CH2CH2O, and C, respectively. n H 2n 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 are numbers from 1 to 70. (a+b) / (c+d) is a number between 0.2 and 8. n is a number between 4 and 8.

2. A cosmetic base, comprising the polyether of claim 1.

3. A cosmetic product, wherein, The cosmetic base of claim 2 is contained in an amount of 0.1 to 30% by mass relative to the total cosmetic product.

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