JP7848587B2 - Cosmetic compositions and cosmetics - Google Patents

Description

This invention relates to cosmetic compositions and cosmetics containing alkylene oxide adducts.

Alkylene oxide adducts are used as raw materials for cosmetics. Hair cosmetics containing high molecular weight alkylene oxide adducts, which have an asymmetrical molecular weight distribution pattern biased towards the high molecular weight side, are known to be effective in preventing stickiness and stiffness, and providing excellent slipperiness when rinsing hair. (See Patent Document 1)

However, the hair cosmetic containing the alkylene oxide adduct described in Patent Document 1 had the problem of leaving the hair sticky after drying.

Japanese Patent Publication No. 2018-28066

The present invention aims to provide a cosmetic composition that can be used in hair cosmetics and the like, exhibiting excellent slipperiness when removing water from hair after rinsing and excellent effectiveness in reducing stickiness of hair after drying.

The inventors of this invention arrived at this present invention after diligently studying to solve these problems.
In other words, the present invention relates to a cosmetic composition containing an alkylene oxide adduct (A) that satisfies the following (1) to (6 ), and a cosmetic composition containing an alkylene oxide adduct (A) that satisfies the following (1) to (6 ).
(1) The alkylene oxide adduct (A) is an alkylene oxide adduct of a compound having 1 to 6 hydroxyl groups.
(2) The alkylene oxide adduct (A) contains an oxypropylene unit as an oxyalkylene unit.
(3) The total weight percentage of oxyalkylene units in alkylene oxide adduct (A) is 10% by weight or more, based on the weight of alkylene oxide adduct (A).
(4) The alkylene oxide adduct (A) has an oxypropylene chain consisting of three or more oxypropylene units in a row.
(5) The proportion of isotactic triplets in the oxypropylene chain of alkylene oxide adduct (A) is 26% or more of the total number of isotactic triplets, heterotactic triplets and syndiotactic triplets :
(6) The compound having 1 to 6 hydroxyl groups is one or more selected from the group consisting of 1 to 6-valent alcohols and hydroxyl group-modified polymer compounds with Mn 1000 to 5000 .

The cosmetic composition of the present invention, when incorporated into hair cosmetics, provides excellent slipperiness when removing water from hair after rinsing and superior reduction of stickiness after drying.

The present invention will be described in detail below.
The first cosmetic composition of the present invention is a cosmetic composition containing an alkylene oxide adduct (A) that satisfies the following conditions (1) to (6 ).
(1) The alkylene oxide adduct (A) is an alkylene oxide adduct of a compound having 1 to 6 hydroxyl groups:
(2) The alkylene oxide adduct (A) contains an oxypropylene unit as an oxyalkylene unit:
(3) The total weight percentage of oxyalkylene units in alkylene oxide adduct (A) is 10% by weight or more, based on the weight of the alkylene oxide adduct:
(4) The alkylene oxide adduct (A) has an oxypropylene chain consisting of three or more oxypropylene units in a row:
(5) The proportion of isotactic triplets in the oxypropylene chain of alkylene oxide adduct (A) is 26% or more of the total number of isotactic triplets, heterotactic triplets and syndiotactic triplets :
(6) The compound having 1 to 6 hydroxyl groups is one or more selected from the group consisting of 1 to 6-valent alcohols and hydroxyl group-modified polymer compounds with Mn 1000 to 5000 .

<Alkylene oxide adduct (A)>
The alkylene oxide adduct (A) contained in the cosmetic composition of the present invention is an alkylene oxide adduct of a compound having 1 to 6 hydroxyl groups, and is a 1 to 6-valent alcohol having residues obtained by removing hydroxyl groups from a compound having 1 to 6 hydroxyl groups and an oxyalkylene unit.

<Compounds containing 1 to 6 hydroxyl groups>
Compounds having 1 to 6 hydroxyl groups include 1 to 6-valent alcohols without ether groups, 1 to 6-valent alcohols with ether groups, hydroxyl-modified polymer compounds with a number-average molecular weight (hereinafter referred to as Mn) of 1000 to 5000, and monovalent or divalent phenols.

As monohydric alcohols without an ether group, monohydric aliphatic alcohols having 1 to 20 carbon atoms are preferred, including methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, oleyl alcohol, linolyl alcohol, 1-nonadecanol, 1-eicosanol, and allyl alcohol.

As divalent alcohols that do not have an ether group, divalent aliphatic alcohols having 2 to 8 carbon atoms are preferred, including ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butylene glycol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, and 1,4-bis(hydroxymethyl)cyclohexane.

As trivalent alcohols that do not have an ether group, trivalent aliphatic alcohols having 3 to 5 carbon atoms are preferred, such as glycerin and trimethylolpropane.

As tetravalent alcohols without an ether group, tetravalent aliphatic alcohols with 4 to 14 carbon atoms are preferred, such as erythritol and pentaerythritol.

As pentavalent alcohols that do not have an ether group, pentavalent aliphatic alcohols with 5 or 6 carbon atoms are preferred, such as xylitol.

Preferred hexavalent alcohols without an ether group are hexavalent aliphatic alcohols with 6 to 10 carbon atoms, such as sorbitol, inositol, and mannitol.

Examples of 1-6 valent alcohols having an ether group include diethylene glycol, sorbitan, glucose, diglycerin, n-octyl-β-D-glucoside, n-decyl-β-D-glucoside, n-dodecyl-β-D-glucoside, dipentaerythritol, and compounds obtained by adding a C2-C4 alkylene oxide to the aforementioned alcohols or water ( _H2O ) that do not have an ether group. Polyalkylene glycol is preferred, and polypropylene glycol is even more preferred. As for polypropylene glycol, polypropylene glycol with a number average molecular weight of 130 to 1000 is preferred.

Hydroxyl-modified polymer compounds are compounds obtained by reacting a polymer compound with another compound so that it has hydroxyl groups in its structure. Preferred hydroxyl-modified polymer compounds with Mn 1000 to 5000 include hydroxyl-modified polyolefins. Hydroxyl-modified polyolefins may be double-ended hydroxyl polyolefins in which hydroxyl groups are introduced at both ends of the polyolefin chain, single-ended hydroxyl polyolefins in which hydroxyl groups are introduced at only one end of the polyolefin chain, or internal hydroxyl polyolefins in which hydroxyl groups are introduced in places other than the ends of the polyolefin chain. Among these, double-ended hydroxyl polyolefins are preferred.
Examples of polyolefins with hydroxyl groups at both ends include polybutadiene with hydroxyl groups at both ends, hydrogenated polybutadiene with hydroxyl groups at both ends, and polyfarnesene with hydroxyl groups at both ends.

Polybutadiene with hydroxyl groups at both ends can be obtained from the market as NISSO-PB G-1000 [Mn1400 (manufactured by Nippon Soda Co., Ltd.), NISSO-PB is a registered trademark of Nippon Soda Co., Ltd.], NISSO-PB G-2000 [Mn1900 (manufactured by Nippon Soda Co., Ltd.)], and NISSO-PB G-3000 [Mn3000 (manufactured by Nippon Soda Co., Ltd.)], etc.
Hydrogenated polybutadienes with hydrogenated hydrogenation at both ends can be obtained from the market as NISSO-PB GI-1000 [Mn1500 (manufactured by Nippon Soda Co., Ltd.)], NISSO-PB GI-2000 [Mn2000 (manufactured by Nippon Soda Co., Ltd.)], and NISSO-PB GI-3000 [Mn3100 (manufactured by Nippon Soda Co., Ltd.)], etc.

Polyfarnesenes with hydroxyl groups at both ends can be obtained from the market as KRASOL F-3000 [Mn3000 (manufactured by Cray Valley), KRASOL is a registered trademark of Total Petrochemicals Refining USA Inc.], etc.

Preferred monovalent or divalent phenols include those having 6 to 15 carbon atoms, such as phenol, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, and bisphenol S.

The manganese (Mn) content of hydroxyl-modified polymer compounds with Mn values ranging from 1000 to 5000 is measured by GPC (gel permeation chromatography) under the following conditions.
• Equipment: "WATERS ALLIANCE 2695" [Manufactured by WATERS Corporation]
- Column: "GUARDCOLUMN SUPER H-L" (1 unit), "TSKGEL SUPERH2000, TSKGEL SUPERH3000, TSKGEL SUPERH4000 (all manufactured by Tosoh Corporation) connected together"
• Sample solution: 0.25% by weight tetrahydrofuran solution • Solution injection volume: 10 mL
・Flow rate: 0.6mL/min ・Measurement temperature: 40℃
• Detection device: Refractive index detector • Reference material: Standard polyethylene glycol

Compounds having 1 to 6 hydroxyl groups may be used individually or in combination of two or more.
Of these compounds having 1 to 6 hydroxyl groups, from the viewpoint of the stickiness of the hair after drying, preferred are alcohols with 1 to 6 hydrides and hydroxyl-modified polymer compounds with Mn 1000 to 5000, and more preferably methanol, ethanol, isopropanol, butanol, glycerin, pentaerythritol, sorbitol, hydrogenated polybutadiene with hydroxyl groups at both ends, and polyfarnesene with hydroxyl groups at both ends.

<Oxyalkylene units present in alkylene oxide adduct (A)>
The alkylene oxide adduct (A) contains an oxypropylene unit as an oxyalkylene unit.
In the present invention, the oxypropylene unit is a structure obtained by using 1,2-propylene oxide as the alkylene oxide, opening the three-membered ring of 1,2-propylene oxide, and adding it to the aforementioned compound having 1 to 6 hydroxyl groups. Depending on the manner in which the three-membered ring is cleaved, it can become an oxy-1-methylethylene unit or an oxy-2-methylethylene unit.
In the present invention, the oxypyrropylene unit may be either an oxy-1-methylethylene unit or an oxy-2-methylethylene unit, or both, and if both are present, there is no limit to their ratio.
If the compound having 1 to 6 hydroxyl groups that constitutes the alkylene oxide adduct (A) has an oxypropylene unit, the oxypropylene unit that the compound having 1 to 6 hydroxyl groups had is included in the oxyalkylene unit of the alkylene oxide adduct (A) in the present invention.

The alkylene oxide adduct (A) may also contain oxyethylene units, oxybutylene units, or both as oxyalkylene units.
The oxyethylene unit is a structure obtained by using ethylene oxide as the alkylene oxide and adding it to the aforementioned compound having 1 to 6 hydroxyl groups.
The oxybutylene unit is a structure obtained by adding 1,2-butylene oxide and/or tetrahydrofuran as the alkylene oxide to the aforementioned compound having 1 to 6 hydroxyl groups. When 1,2-butylene oxide is used, the result is either an oxy-1-ethylethylene unit or an oxy-2-ethylethylene unit depending on the manner of cleavage of the three-membered ring, and when tetrahydrofuran is used, the result is an oxy-1,4-butylene unit.
If the alkylene oxide adduct (A) contains oxybutylene units, the oxybutylene units may be at least one selected from the group consisting of oxy-1-ethylethylene units, oxy-2-ethylethylene units, and oxy-1,4-butylene units, and there is no restriction on the ratio if there are two or more.

Examples of alkylene oxide adducts (A) include alkylene oxide adducts in which the oxyalkylene group consists of oxypropylene units (A1), alkylene oxide adducts in which the oxyalkylene group consists of oxypropylene units and oxyethylene units (A2), alkylene oxide adducts in which the oxyalkylene group consists of oxypropylene units and oxybutylene units (A3), and alkylene oxide adducts in which the oxyalkylene group consists of oxypropylene units, oxyethylene units, and oxybutylene units (A4). Preferred are alkylene oxide adducts in which the oxyalkylene group consists of oxypropylene units (A1) and alkylene oxide adducts in which the oxyalkylene group consists of oxypropylene units and oxyethylene units (A2), with alkylene oxide adducts in which the oxyalkylene group consists of oxypropylene units (A1) being even more preferred.

The alkylene oxide adduct (A) contained in the cosmetic composition of the present invention preferably contains 3 to 500 moles of oxyalkylene units per molecule, and more preferably 5 to 200 moles, from the viewpoint of the stickiness of the hair after drying.
The number of moles of oxyalkylene groups in alkylene oxide adduct (A) can be calculated from the amount of oxyalkylene used during the production of alkylene oxide adduct (A), and can also be analyzed from ^¹H -NMR and ^¹³C -NMR of alkylene oxide adduct (A).

When alkylene oxide adduct (A) is alkylene oxide adduct (A2), the weight ratio of oxypropylene units to the total weight of oxypropylene units and oxyethylene units is preferably 40 to 90% by weight, and more preferably 50 to 80% by weight, from the viewpoint of slipperiness when removing water from hair during rinsing.

When alkylene oxide adduct (A) is alkylene oxide adduct (A3), the weight ratio of oxypropylene units to the total weight of oxypropylene units and oxybutylene units is preferably 50 to 90% by weight, and more preferably 60 to 90% by weight, from the viewpoint of the stickiness of the hair after drying.

When alkylene oxide adduct (A) is alkylene oxide adduct (A4), the weight ratio of oxypropylene units to the total weight of oxypropylene units, oxyethylene units, and oxybutylene units is preferably 5 to 90% by weight, more preferably 30 to 90% by weight, from the viewpoint of slipperiness when draining water from hair after rinsing. Furthermore, the weight ratio of ethylene oxide units to the total weight of oxypropylene units, oxyethylene units, and oxybutylene units is preferably 5 to 60% by weight, more preferably 5 to 50% by weight, from the viewpoint of slipperiness when draining water from hair after rinsing.

The total weight percentage of oxyalkylene units in alkylene oxide adduct (A) is 10% by weight or more, preferably 50% by weight or more, and more preferably 60% by weight or more, based on the weight of alkylene oxide adduct (A), from the viewpoint of slipperiness when draining water from hair after rinsing.

The weight percentage of oxypropylene units in the alkylene oxide adduct (A) is preferably 50% by weight or more, and more preferably 60% by weight or more, based on the weight of oxyalkylene units in the alkylene oxide adduct (A), from the viewpoint of slipperiness when removing water from hair after rinsing.

The alkylene oxide adduct (A) contained in the cosmetic composition of the present invention has an oxyalkylene chain containing an oxypropylene chain consisting of three or more oxypropylene units in a row.
Structures consisting of three consecutive oxypropylene units (also called triplets) are classified into three types based on the arrangement of methyl groups in the oxypropylene units: isotactic triplets, heterotactic triplets, and syndiotactic triplets.
The isotactic triplets, heterotactic triplets, and syndiotactic triplets mentioned above are defined as follows:
In a structure consisting of two consecutive oxypropylene units, a dipgane with the same stereoconfiguration is defined as a mesostructure (hereinafter abbreviated as "M2 ligament"), while a dipgane with different stereoconfigurations is defined as a racemostructure (hereinafter abbreviated as "R2 ligament"). Furthermore, among triplets of oxypropylene units, a triplet containing two M2 ligaments is defined as an isotactic triplet, a triplet containing two R2 ligaments is defined as a syndiotactic triplet, and a triplet containing one M2 ligament and one R2 ligament is defined as a heterotactic triplet.
Furthermore, the regularity of the stereochemistry of the oxypropylene chain in alkylene oxide adduct (A) (also called tacticity or stereoregularity) is one of the structural factors that determine the higher-order structure of alkylene oxide adduct (A), such as its crystal structure and degree of crystallinity, and that influences its physical properties.

The proportion of isotactic triplets in the oxypropylene chain of the alkylene oxide adduct (A) contained in the cosmetic composition of the present invention is 26% or more of the total number of isotactic triplets, heterotactic triplets, and syndiotactic triplets, from the viewpoint of slipperiness when draining water from hair after rinsing.
Using a calcined product of a composite oxide of Al and Mg (B1) and/or a calcined product of hydrotalcite (B2) containing Al and Mg, as described later, the proportion of isotactic triplets in the oxypropylene chain of the alkylene oxide adduct (A) can be increased to 26% or more by the production method described later, in which an alkylene oxide is added to a compound having 1 to 6 hydroxyl groups.

The proportions of isotactic triplets, heterotactic triplets, and syndiotactic triplets in an oxypropylene chain are determined by ^13C -NMR measurements using the Distortionless Enhancement by Polarization Transfer method (hereinafter abbreviated as DEPT method), and the integral value of the ^13C -NMR signal originating from the carbon atoms of the methine groups contained in the oxypropylene unit is obtained.
In ^13C -NMR measurements using the DEPT method, the flip angle (θ) dependence of the signal intensity differs depending on the number of hydrogen atoms bonded to the carbon atoms of the compound being measured.
In ^13C -NMR measurements using the DEPT 90° method (a DEPT method that irradiates with pulses that give θ = 90°), the peaks of the methyl group carbon atom (bonded to 3 hydrogen atoms), the methylene group carbon atom (bonded to 2 hydrogen atoms), and the quaternary carbon (bonded to no hydrogen atoms) in the compound being measured can be eliminated or significantly attenuated. Therefore, it becomes possible to detect the peak of the methine group carbon atom (bonded to 1 hydrogen atom) in the compound being measured with high sensitivity.
As a result, it becomes possible to accurately distinguish the differences in the ^13C -NMR signals of methine carbons caused by the tacticity (stereoregularity) of the oxypropylene chain, and the proportion of isotactic triplets, heterotactic triplets, and syndiotactic triplets in the oxypropylene chain of the ^alkylene oxide adduct (A) of the present invention can be calculated from the integral value of the 13C-NMR signals.

The details of the ^13C -NMR measurement using the DEPT90° method and the method for calculating the proportion of isotactic triplets, heterotactic triplets, and syndiotactic triplets in the oxypropylene chain of alkylene oxide adduct (A) are described below.

< ¹³ . Preparation of 13C-NMR Samples>
Approximately 40 mg of the sample to be measured is weighed into a 5 mm diameter NMR sample tube, and approximately 0.7 mL of deuterated solvent is added to dissolve it. Suitable deuterated solvents include deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, and deuterated dimethylformamide; a solvent capable of dissolving the sample should be selected as appropriate.

< ^13C -NMR measurement>
^13C -NMR measurements will be performed using the DEPT90° method under the following conditions.
• Equipment: BRUKER AVANCE III HD400 [Frequency: 100MHz, manufactured by BRUKER OPTICS Co., Ltd.]
Sample temperature: 25°C
Total number of times: 256

<Calculation of the ratio of the number of triplets>
The proportions of isotactic triplets, heterotactic triplets, and syndiotactic triplets in the oxypropylene chain of alkylene oxide adduct (A) are calculated using the following formulas (1) to (3).
• Percentage of isotactic triplets (%) = (d/g) × 100 (Calculation formula (1))
• Percentage of heterotactic triplets (%) = (e/g) × 100 (Calculation formula (2))
• Percentage of syndiotactic triples (%) = (f/g) × 100 (Calculation formula (3))

In formula (1), d is the integral value of the ^13C -NMR signal originating from the carbon atom of the methine group present in the oxypropylene unit at the center of the isotactic triplicate. The ^13C -NMR signal of d is detected in the range of chemical shift between 75.4 ppm and less than 75.6 ppm.
In calculation formula (2), e is the integral value of the ^13C -NMR signal originating from the carbon atom of the methine group present in the oxypropylene unit at the center of the heterotactic triplets. The ^13C -NMR signal of e is detected in the range of a chemical shift between 75.2 ppm and less than 75.4 ppm.
In calculation formula (3), f is the integral value of the ^13C -NMR signal originating from the carbon atom of the methine group present in the oxypropylene unit at the center of the syndiotactic triplet. The ^13C -NMR signal of f is detected in the range of chemical shift between 75.0 ppm and less than 75.2 ppm.
In formulas (1) to (3), g is the sum of the integral values of the 13C-NMR signals originating from the carbon atoms of the ^methine groups of the oxypropylene units at the center of each of the isotactic triplets, heterotactic triplets, and syndiotactic triplets of the oxypropylene chain.

The molecular weight distribution (Mw/Mn) of the alkylene oxide adduct (A) contained in the cosmetic composition of the present invention is preferably 1.05 to 1.4, from the viewpoint of slipperiness when removing water from hair after rinsing. Mw represents the weight-average molecular weight.
Using a calcined product of a composite oxide of Al and Mg (B1) and/or a calcined product of hydrotalcite (B2) containing Al and Mg, as described later, an alkylene oxide can be added to a compound having 1 to 6 hydroxyl groups by the production method described later, thereby achieving a molecular weight distribution (Mw/Mn) of 1.05 to 1.4.

The Mw and Mn values of alkylene oxide adduct (A) shall be those measured by GPC (gel permeation chromatography) under the following conditions.
• Equipment: "WATERS ALLIANCE 2695" [Manufactured by WATERS Corporation]
- Column: "GUARDCOLUMN SUPER H-L" (1 unit), "TSKGEL SUPERH2000, TSKGEL SUPERH3000, TSKGEL SUPERH4000 (all manufactured by Tosoh Corporation) connected together"
• Sample solution: 0.25% by weight tetrahydrofuran solution • Solution injection volume: 10 mL
・Flow rate: 0.6mL/min ・Measurement temperature: 40℃
• Detection device: Refractive index detector • Reference material: Standard polyethylene glycol

<Method for producing alkylene oxide adduct (A)>
The alkylene oxide adduct (A) contained in the cosmetic composition of the present invention can be obtained by reacting a compound having 1 to 6 hydroxyl groups with 1,2-propylene oxide at a temperature of 50 to 200°C in the presence of a calcined product of a composite oxide of Al and Mg (B1) and/or a calcined product of hydrotalcite (B2) having Al and Mg. Furthermore, if it contains oxyethylene units and/or oxybutylene units, it can be obtained by carrying out an addition reaction of ethylene oxide, 1,2-butylene oxide and/or tetrahydrofuran under similar conditions before or after the reaction of 1,2-propylene oxide.
In a reaction to add 1,2-propylene oxide and, if necessary, ethylene oxide, 1,2-butylene oxide, and/or tetrahydrofuran to a compound having 1 to 6 hydroxyl groups, the calcined product of a composite oxide of Al and Mg (B1) and the calcined product of hydrotalcite containing Al and Mg (B2) function as catalysts for the addition reaction.
In the following, the calcined product of the Al-Mg composite oxide (B1) and/or the calcined product of hydrotalcite (B2) containing Al and Mg may be referred to as calcined product (B').

A method for producing alkylene oxide adduct (A) comprises the step of adding 1,2-propylene oxide dropwise to a mixture containing a calcined product of a composite oxide of Al and Mg (B1) and/or a calcined product of hydrotalcite (B2) having Al and Mg, and a compound having 1 to 6 hydroxyl groups, and being heated at 50 to 200°C.
The addition reaction of 1,2-propylene oxide can be carried out by adding 1,2-propylene oxide dropwise to a mixture containing the aforementioned calcined product (B') and a compound having 1 to 6 hydroxyl groups, and at a temperature of 70 to 160°C.
Furthermore, if the alkylene oxide adduct (A) further contains oxyethylene units and/or oxybutylene units, the addition reactions of ethylene oxide, 1,2-butylene oxide, and/or tetrahydrofuran can be carried out under the same conditions as the addition reaction of 1,2-propylene oxide.

The Al-Mg composite oxide (B1) is not particularly limited as long as it is an oxide containing Al and Mg, but preferred Al-Mg composite oxides include compounds represented by the following general formulas (1) or (2).
[aMgO・Al ₂ O ₃・bH ₂ O] (1)
[Mg _X Al _Y O _Z ] (2)

In general formula (1), a and b are independent positive numbers.
In general formula (2), X, Y, and Z are independent positive numbers.

From the viewpoint of reactivity, in general formula (2), the ratio of X to Y (X/Y) is preferably 0.1 or more and less than 0.9.

Examples of composite oxides of Al and Mg (B1) include 2.5MgO・_Al₂O₃・_nH₂O ( _where n is a positive number) and _{Mg₀.7Al₀.3O₁.15 ,} which can be obtained from the market as _Kyoward 300 [manufactured by Kyowa Chemical Industry Co., Ltd., Kyoward is a registered trademark of Kyowa Chemical Industry Co., Ltd.] and KW-2000 [manufactured by Kyowa Chemical Industry Co., Ltd.], respectively.

A calcined product of the Al-Mg composite oxide (B1) can be obtained by heating the Al-Mg composite oxide (B1) in an air atmosphere (preferably under a nitrogen atmosphere) at a temperature of 100 to 1500°C (preferably 600 to 900°C) for 1 to 48 hours, or by other methods.

The hydrotalcite (B2) having Al and Mg is not particularly limited as long as it is a hydrotalcite having Al and Mg, but preferred hydrotalcites having Al and Mg include the compound represented by the following general formula (3).
[Mg _1-C Al _C (OH) ₂ ] ^C+ [CO _3C/2・DH ₂ O] ^C- (3)

In general formula (3), C is a number satisfying 0 < C ≤ 0.33, and D is a number satisfying 0 < D ≤ 1.0.

Examples of hydrotalcite (B2) containing Al and Mg include _Mg₆Al₂ (OH _{) ₁₆CO₃} · _{4H₂O ,} which can be obtained from the market as Kyoward 500 [manufactured by Kyowa Chemical Industry Co., Ltd.].
Furthermore, known minerals described in West German Patent Publication No. 1592126 and European Patent Publication No. 0207811, etc., can also be used as hydrotalcite (B2) containing Al and Mg.

A calcined hydrotalcite (B2) containing Al and Mg can be obtained by heating the aforementioned hydrotalcite (B2) in an air atmosphere (preferably under a nitrogen atmosphere) at a temperature of 100 to 1500°C (preferably 600 to 900°C) for 1 to 48 hours, or by other methods.

The calcined product of the composite oxide of Al and Mg (B1) and the calcined product of hydrotalcite containing Al and Mg (B2) may be used individually or in combination of two or more types.
Of these, from the viewpoint of reactivity, the preferred is a calcined product of a composite oxide of Al and Mg _{( B1} ), and even more preferred are the calcined products of 2.5MgO・_Al₂O₃・_nH₂O (where n is a positive number) and the calcined _products of _{Mg₀.7Al₀.3O₁.15} .

The amount of calcined product (B') used in the reaction to add 1,2-propylene oxide and, if necessary, ethylene oxide, 1,2-butylene oxide, and/or tetrahydrofuran to the compound having 1 to 6 hydroxyl groups is not particularly limited. However, from the viewpoint of the rate of the alkylene oxide addition reaction and the filtration efficiency of the calcined product (B'), it is preferably 0.0001 to 10% by weight, and more preferably 0.001 to 1.0% by weight, relative to the total weight of the compound having 1 to 6 hydroxyl groups and all the alkylene oxides used in the reaction.

Furthermore, from the viewpoint of facilitating the stirring of the reaction system in which 1,2-propylene oxide and, if necessary, ethylene oxide, 1,2-butylene oxide, and/or tetrahydrofuran are added to the compound having 1 to 6 hydroxyl groups, a solvent may be added to the mixture of the calcined product (B') and the compound having 1 to 6 hydroxyl groups.
Examples of solvents include toluene, xylene, benzene, dimethyl sulfoxide, diglyme, triglyceride, 1,4-dioxane, cyclohexane, hexane, diethyl ether, dimethylformamide, carbon tetrachloride, N-methylpyrrolidone, 1,2-dimethoxyethane, 1,2-dichloroethane, chloroform, and dialkyl polypropylene glycol.
The solvent may be used individually or in combination of two or more types.
Of these, toluene and xylene are preferred from the viewpoint of miscibility with the aforementioned compounds having 1 to 6 hydroxyl groups, boiling point, and ease of distillation removal.
The alkylene oxide adduct (A) obtained by this manufacturing method may be used in cosmetic compositions after removing the solvent by distillation, or it may be used in cosmetic compositions without removing the solvent by distillation.
From the viewpoint of reaction rate and other factors, the solvent content is preferably 0 to 99% by weight, and more preferably 0 to 90% by weight, relative to the total weight of the compound having 1 to 6 hydroxyl groups, the calcined product (B'), and all the alkylene oxides used in the reaction.

A method for producing alkylene oxide adduct (A) may include a step of adding 1,2-propylene oxide dropwise to a mixture containing calcined product (B') and the compound having 1 to 6 hydroxyl groups, at a temperature of 50 to 200°C. However, from the viewpoint of catalytic activity of calcined product (B'), it is preferable to mix calcined product (B') and the compound having 1 to 6 hydroxyl groups in a reaction vessel (such as a stainless steel autoclave with a stirring device and temperature control function) before reacting the compound having 1 to 6 hydroxyl groups with the alkylene oxide, and to perform a dehydration treatment at atmospheric pressure (preferably under reduced pressure, and more preferably under reduced pressure while bubbling nitrogen into the compound having 1 to 6 hydroxyl groups), setting the temperature in the reaction vessel to 80 to 300°C, preferably 80 to 110°C, for 1 to 4 hours.
In the following, 1,2-propylene oxide, ethylene oxide, 1,2-butylene oxide, and tetrahydrofuran may be abbreviated as PO, EO, BO, and THF, respectively.

Among the alkylene oxide adducts (A), alkylene oxide adduct (A1), which has only oxypropylene units as oxyalkylene groups, can be obtained by dehydrating a mixture of the calcined product (B') and the aforementioned compound having 1 to 6 hydroxyl groups using the method described above, and then carrying out the addition reaction of PO. The temperature in the reaction vessel for the addition reaction is 50 to 200°C.

Among the alkylene oxide adducts (A), alkylene oxide adduct (A2), which has oxypropylene units and oxyethylene units as oxyalkylene groups, can be obtained by dehydrating a mixture of the calcined product (B') and the aforementioned compound having 1 to 6 hydroxyl groups using the method described above, and then carrying out the addition reaction of PO and the addition reaction of EO in any order. The temperature in the reaction vessel for both addition reactions is 50 to 200°C.

Among the alkylene oxide adducts (A), alkylene oxide adduct (A3), which has oxypropylene units and oxybutylene units as oxyalkylene groups, can be obtained by dehydrating a mixture of the calcined product (B') and the aforementioned compound having 1 to 6 hydroxyl groups using the method described above, and then carrying out addition reactions of PO, BO, and/or THF, in any order. The temperature in the reaction vessel for each addition reaction is 50 to 200°C.

Among the alkylene oxide adducts (A), alkylene oxide adduct (A4) having oxyalkylene units of oxypropylene, oxyethylene, and oxybutylene units as oxyalkylene groups can be obtained by dehydrating a mixture of the calcined product (B') and the aforementioned compound having 1 to 6 hydroxyl groups using the method described above, and then carrying out addition reactions of PO, EO, BO, and/or THF, in any order. The temperature in the reaction vessel for each addition reaction is 50 to 200°C.

In the method for producing alkylene oxide adduct (A), the addition reactions of PO, EO, BO, and THF can be carried out by dropwise adding PO, EO, BO, and THF to a mixture of a calcined product (B') and the aforementioned compound having 1 to 6 hydroxyl groups. It is preferable to adjust the amount of PO, EO, BO, and THF added during the dropwise addition step so that the pressure in the reaction vessel is between 1.3 and 701 kPa.

In the method for producing alkylene oxide adduct (A), the temperature in the reaction vessel when PO, EO, BO, and THF are added dropwise is 50 to 200°C, preferably 80 to 180°C, from the viewpoint of the hydroxyl value and tacticity (stereoregularity) of alkylene oxide adduct (A).
When PO, EO, BO, and THF are added dropwise to react with the aforementioned compound having 1 to 6 hydroxyl groups, if the temperature in the reaction vessel is lower than 50°C, it is impractical in terms of the manufacturing process from the standpoint of the reaction rate of the alkylene oxide addition reaction. Conversely, if the temperature in the reaction vessel exceeds 200°C, there is a problem in that the byproducts of the alkylene oxide addition reaction increase.

The method for producing alkylene oxide adduct (A) preferably includes a maturation step in which, after the completion of the step of dropwise adding predetermined amounts of PO, EO, BO, and THF, the temperature in the reaction vessel is maintained at 50 to 200°C until the pressure in the reaction vessel reaches equilibrium.

The method for producing alkylene oxide adduct (A) preferably includes a step of dropping PO, EO, BO, and THF as described above, and a filtration step of removing calcined material (B') from the alkylene oxide adduct (A) obtained through a maturation step if necessary.
In this case, if necessary, a diatomaceous earth-based filter aid (such as Radiolite #700 manufactured by Showa Chemical Industry Co., Ltd.; Radiolite is a registered trademark of Showa Chemical Industry Co., Ltd.) can be used as a filter aid to shorten the time required for the filtration operation.
The filtration process can be carried out by known filtration operations described in Japanese Patent Publication No. 2011-213864, etc.

Furthermore, if a solvent was used in the production of the alkylene oxide adduct (A), it is preferable to have a step to remove the solvent from the alkylene oxide adduct (A). As a method for removing the solvent, known methods such as vacuum distillation of the solvent using an evaporator can be used.

<Compositions and cosmetics for cosmetic use>
The first invention of this application is a cosmetic composition containing the alkylene oxide adduct (A).
The cosmetic composition, which is the first invention of this application (hereinafter referred to as the cosmetic composition of the present invention), can be used as a cosmetic raw material or a cosmetic.
Furthermore, a cosmetic composition containing alkylene oxide adduct (A) is the second invention of this application, and the same alkylene oxide adduct (A) as in the cosmetic composition can be used, and the preferred alkylene oxide adduct when used in a cosmetic composition is the same as in the cosmetic composition.

The cosmetic composition of the present invention, which contains alkylene oxide adduct (A), is preferably used as a raw material for hair care cosmetics such as shampoo, conditioner, hair treatment, leave-in treatment, hair spray, hair wax, hair mousse, and hair dye, or as a hair care cosmetic.
Alkylene oxide adduct (A) can be incorporated into hair care cosmetics such as shampoos, conditioners, hair treatments, leave-in treatments, hair sprays, hair waxes, hair mousses, and hair dyes to impart to these cosmetics the effect of making hair slippery when removing water and reducing stickiness after drying.

The cosmetic composition of the first invention of this application is not limited to containing alkylene oxide adduct (A), and the content of alkylene oxide adduct (A) in the cosmetic composition can be adjusted according to the intended use of the cosmetic composition. However, when used as a raw material for cosmetics, from the viewpoint of handling, stability, and transportation costs, the amount of alkylene oxide adduct (A) in the cosmetic composition is preferably 50 to 100% by weight, and more preferably 100% by weight, based on the total weight of the cosmetic composition.

Furthermore, in the cosmetic composition containing alkylene oxide adduct (A), which is the second invention of this application, from the viewpoint of slipperiness when draining water from hair after rinsing, it is preferable that the cosmetic composition contains 0.001 to 10% by weight of the alkylene oxide adduct (A) based on the total weight of the cosmetic composition, more preferably 0.5 to 5% by weight, and particularly preferably 1 to 5% by weight.

Other components that may be included in the cosmetic composition of the present invention besides the alkylene oxide adduct (A) include oils, silicone compounds, alcohols, gelling agents, anionic surfactants, nonionic surfactants [compounds other than the alkylene oxide adduct (A)], amphoteric surfactants, cationic surfactants, inorganic pigments, polymer compounds, chelating agents, pH adjusters, cooling agents, whitening agents, moisturizers, UV absorbers, conditioning agents, fragrances, and colorants, as well as other known cosmetic raw material components used in cosmetics.

Examples of oils and fats include oils and fats (almond oil, olive oil, soybean oil, hydrogenated oil, camellia oil, rapeseed oil, castor oil, coconut oil, beef tallow, and lard, etc.), waxes (lanolin, beeswax, jojoba oil, and candelilla wax, etc.), higher fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid (DHA), isostearic acid, and 12-hydroxystearic acid, etc.), and hydrocarbons (ceresin, paraffin, mineral oil, petrolatum, squalane, and liquid paraffin, etc.).

Examples of silicone compounds include methylphenylpolysiloxane, methylpolysiloxane, octamethylcyclotetrasiloxane, dimethylsiloxane/methyl(polyoxyethylene)siloxane copolymer, decamethylcyclopentanesiloxane, dimethylsiloxanemethyl(polyoxyethylene/polyoxypropylene)siloxane copolymer, methylhydrogenpolysiloxane, dodecamethylcyclohexanesiloxane, methylpolycyclosiloxane, dimethylsiloxane/methylstearyloxysiloxane copolymer, methylpolysiloxane emulsion, octamethyltrisiloxane, cyclic silicone resins, highly polymerized methylpolysiloxane, tetradecamethylhexanesiloxane, and trimethylsiloxysilicate.

Examples of alcohols include monohydric alcohols (methanol, ethanol, isopropyl alcohol, n-butyl alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyldodecanol, octyldodecanol, cetearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, polyoxyethylene cholesteryl ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (cerakyl alcohol), and medusa seed oil, etc.), dihydric to hexahydric polyhydric alcohols (ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,2-pentanediol, hexylene glycol, glycerin, diglycerin, and sorbitol, etc.), and cholesterol.

Examples of gelling agents include guar gum, starch, carboxymethylcellulose, acetylmethylcellulose, polyvinyl alcohol, sodium polyacrylate, disteardimonium hectorite, sucrose palmitate, dextrin stearate, monobenzylidene sorbitol, and N-lauroyl-L-glutamic acid.

Anionic surfactants include hydrocarbon ether carboxylic acids with 8 to 24 carbon atoms or their salts [e.g., sodium (poly)oxyethylene lauryl ether acetate and disodium (poly)oxyethylene lauryl sulfosuccinate], hydrocarbon sulfate ester salts with 8 to 24 carbon atoms [e.g., sodium lauryl sulfate, sodium (poly)oxyethylene lauryl sulfate, triethanolamine (poly)oxyethylene lauryl sulfate and sodium (poly)oxyethylene coconut oil fatty acid monoethanolamide sulfate], and hydrocarbon sulfonates with 8 to 24 carbon atoms [e.g., sodium dodecylbenzenesulfonate] Examples include [e.g., sodium lauryl phosphate, etc.], hydrocarbon phosphate ester salts with 8 to 24 carbon atoms [e.g., sodium lauryl phosphate and (poly)oxyethylene lauryl ether sodium phosphate], fatty acid salts [e.g., sodium laurate and triethanolamine laurate], and acylated amino acid salts [e.g., sodium methyl taurate, sodium sarcosinate, triethanolamine sarcosinate, triethanolamine acyl-L-glutamate, triethanolamine acyl-L-glutamate, sodium lauroyl methyl-β-alanine, etc.].

Other known nonionic surfactants used as cosmetic raw material components besides alkylene oxide adduct (A) include: aliphatic alcohol (8-24 carbon atoms) alkylene oxide (2-8 carbon atoms) adducts, (poly)oxyalkylene (2-8 carbon atoms) higher fatty acid (8-24 carbon atoms) esters [polyethylene glycol monostearate and polyethylene glycol distearate, etc.], polyhydric (2-10 or more valencies) alcohol fatty acid (8-24 carbon atoms) esters [glyceryl monostearate, ethylene glycol monostearate and sorbitan monolaurate, etc.], and (poly)oxyalkylene (2-8 carbon atoms) polyhydric (2-10 or more valencies) alcohol higher fatty acid (8-24 carbon atoms) esters [polyoxyethylene sorbitan monolaurate and methyl polyoxyethylene dioleate]. Examples include compounds such as gluglucoside, fatty acid alkanolamides [1:1 type coconut oil fatty acid diethanolamide and 1:1 type lauric acid diethanolamide, etc.], (poly)oxyalkylene (C2-C8) alkyl (C1-C22) phenyl ethers, (poly)oxyalkylene (C2-C8) alkyl (C8-C24) amino ethers, and alkyl (C8-C24) dialkyl (C1-C6) amine oxides [lauryldimethylamine oxide, etc.], which do not contain triplets consisting of oxypropylene units in the oxyalkylene chain, or compounds in which the proportion of isotactic triplets in the oxypropylene chain contained in the oxyalkylene chain is less than 26% of the total number of isotactic triplets, heterotactic triplets, and syndiotactic triplets.

Examples of amphoteric surfactants include betaine-type amphoteric surfactants [such as coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl hydroxysulfobetaine, and lauroylamide ethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate] and amino acid-type amphoteric surfactants [such as β-laurylaminopropionate sodium].

Examples of cationic surfactants include tetraalkyl (1-18 carbon atoms) ammonium salts [behentrimonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, etc.] and alkyl (1-4 carbon atoms) sulfate higher fatty acid aminoalkyl (2-4 carbon atoms) trialkyl (1-4 carbon atoms) ammonium salts [ethyl sulfate lanolin fatty acid aminopropylethyldimethylammonium, etc.].

Examples of inorganic pigments include mica, talc, calcium carbonate, red iron oxide, yellow iron oxide, black iron oxide, carbon black, and titanium dioxide.

Examples of polymeric compounds include natural polymers (guar gum, locust bean gum, carrageenan, galactan, gum arabic, starch, xanthan gum, gelatin, and collagen, etc.), semi-synthetic polymers (methylcellulose, ethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, cationized cellulose, soluble starch, and propylene glycol alginate, etc.), and synthetic polymers (polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, sodium polyacrylate, polyacrylic acid ester copolymer, amphoteric methacrylic acid ester copolymer, cationized polyurethane polymer, highly polymerized polyethylene glycol, and polyoxyethylene polyoxypropylene block polymer, etc.).

Examples of chelating agents include ethylenediaminetetraacetic acid, polyphosphate, pyrophosphate, gluconic acid, ascorbic acid, and their salts.

Examples of pH adjusters include potassium carbonate, sodium bicarbonate, ammonium bicarbonate, lactic acid, succinic acid, and citric acid.

Examples of cooling agents include L-menthol and camphor.

Examples of skin whitening agents include arbutin, kojic acid, glutathione, hydroquinone, hydroquinone derivatives, resorcinol, resorcinol derivatives, and glabrane.

Examples of humectants include glycerin, polyethylene glycol, sorbitol, sodium lactate, sodium pyrrolidone carboxylate, sodium hyaluronate, and chondroitin sulfate.

Examples of UV absorbers include benzophenone derivatives, para-aminobenzoic acid derivatives, methoxycinnamic acid derivatives, salicylic acid derivatives, and urocanic acid derivatives.

Examples of conditioning agents include cationized cellulose with Mw 500 to 500 million, cationized guar gum, silicones, polyethylene glycol, sodium polyacrylate, hydroxyethylcellulose, protein derivatives, ceramides, pseudo-ceramides, fatty acids with 16 to 40 carbon atoms, and panthenol.

Examples of fragrances include d-limonene, β-caryophyllene, cis-3-hexenol, linalool, farnesol, β-phenylethyl alcohol, 2,6-nonadienal, citral, α-hexyl cinnamic aldehyde, β-ionone, l-carbone, cyclopentadecanone, linalyl acetate, benzyl benzoate, γ-undecalactone, eugenol, rose oxide, indole, phenylacetaldehyde dimethyl acetal, aurantiol, cinnamic aldehyde, methyl ionone, musk, anise essential oil, cinnamon essential oil, and jasmine essential oil.

Examples of colorants include Blue No. 1, Blue No. 2, Green No. 3, and Red No. 1; all colorants permitted for use in cosmetics are permitted.

The types and amounts of known cosmetic raw materials that can be used in the cosmetic composition of the present invention as needed can be adjusted according to the intended use of the cosmetic composition. However, when used as cosmetic raw materials, the preferred amounts of known cosmetic raw materials that can be used as needed are as follows.
Oils, silicone compounds, alcohols, anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, inorganic pigments, polymer compounds, and humectants are preferably present in amounts of 50% by weight or less, and more preferably 10% by weight or less, based on the total weight of the cosmetic composition containing alkylene oxide adduct (A).
The gelling agent, chelating agent, whitening agent, and conditioning agent are preferably present in amounts of 50% by weight or less, and more preferably 10% by weight or less, based on the total weight of the cosmetic composition containing alkylene oxide adduct (A).
pH adjusters, cooling agents, UV absorbers, fragrances, and colorants are preferably present in amounts of 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the cosmetic composition containing alkylene oxide adduct (A).

The cosmetic composition containing alkylene oxide adduct (A) may further contain water. The amount of water contained in the cosmetic composition is appropriately selected depending on the intended use of the cosmetic composition. However, when used as a cosmetic raw material, the amount of water is preferably 0 to 50% by weight, and more preferably 0.01 to 20% by weight, based on the total weight of the cosmetic composition containing alkylene oxide adduct (A).

Furthermore, in the cosmetic composition which is the second invention of this application, the preferred content of known cosmetic raw material components used as needed is as follows:
The oils, silicone compounds, alcohols, anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, inorganic pigments, polymer compounds, and humectants are preferably present in amounts of 50% by weight or less, and more preferably 40% by weight or less, based on the total weight of the cosmetic composition containing alkylene oxide adduct (A).
The gelling agent, chelating agent, whitening agent, and conditioning agent are preferably present in amounts of 30% by weight or less, and more preferably 20% by weight or less, based on the total weight of the cosmetic composition containing alkylene oxide adduct (A).
pH adjusters, cooling agents, UV absorbers, fragrances, and colorants are preferably present in amounts of 30% by weight or less, and more preferably 20% by weight or less, based on the total weight of the cosmetic composition containing alkylene oxide adduct (A).

In the cosmetic composition of the second invention of this application, the water content is appropriately selected depending on the type of cosmetic composition containing alkylene oxide adduct (A). Based on the total weight of the cosmetic composition containing alkylene oxide adduct (A), the water content is preferably 10 to 98% by weight, and more preferably 20 to 95% by weight.

Cosmetic compositions and cosmetics containing alkylene oxide adduct (A) can be prepared by uniformly mixing alkylene oxide adduct (A), known cosmetic raw material components used as needed, and water using a homodisperser or the like.
The order of mixing is not particularly limited, but when water is used, it is preferable to add the alkylene oxide adduct (A) and any known cosmetic raw material components to the water, as this makes the alkylene oxide adduct (A) more easily soluble.
The preferred temperature for mixing is 25°C to 80°C, from the viewpoint of the solubility of alkylene oxide adduct (A) in water.
Suitable stirring blades for mixing include paddle-type or spiral-type stirring blades.

The cosmetic composition and cosmetic containing the alkylene oxide adduct (A) of the present invention are solid, liquid, or paste-like at 25°C, and are preferably liquid in terms of ease of handling.

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. Hereinafter, parts refer to parts by weight, and % refers to weight percent.

<Manufacturing Example 1>
(Synthesis of calcined product (B'-1))
"Kyoword 300" [Chemical formula: 2.5MgO・_Al₂O₃・_nH₂O ( _n is a positive number), manufactured by Kyowa Chemical Industry Co., Ltd.] was heat-treated in an electric furnace at 900°C under a nitrogen atmosphere for 3 hours to prepare the calcined product (B'-1).

<Manufacturing Example 2>
(Synthesis of the complex metal cyanide catalyst (X'-1))
To a 2.0 ml aqueous solution containing 2.1 g of zinc chloride, a 15 ml aqueous solution containing 0.84 g of potassium hexacyanocobaltate _K3Co (CN) ₆ was added dropwise over 15 minutes at 40°C while stirring. After the addition was complete, 16 ml of water and 16 g of tert-butyl alcohol were added, and the temperature was raised to 70°C and stirred for 1 hour. After cooling to room temperature, filtration (first filtration) was performed to obtain a solid. To this solid, 14 ml of water and 8.0 g of tert-butyl alcohol were added, and after stirring for 30 minutes, filtration (second filtration) was performed to obtain a solid.
Furthermore, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid again, and after stirring for 30 minutes, a filtration procedure (third filtration) was performed. The resulting solid was dried at 40°C under reduced pressure for 3 hours to obtain 0.7 g of the complex metal cyanide catalyst (X'-1).

<Example 1>
(Cosmetic composition containing polypropylene glycol (A-1))
In a stainless steel autoclave equipped with a stirring device and temperature control function, 600 parts (1 mole) of Mn600 polypropylene glycol [product name: Newpol PP-600, manufactured by Sanyo Chemical Industries, Ltd., Newpol is a registered trademark of Sanyo Chemical Industries, Ltd.] and 10 parts of the calcined product (B'-1) obtained in Production Example 1 were mixed, and dehydration was carried out under reduced pressure (1.3 kPa) at 100°C for 1 hour. Next, the temperature in the reaction vessel was raised to 175°C, and 400 parts (6.9 moles) of PO were added dropwise over 10 hours. After the addition of PO, the mixture was aged at 175°C in the reaction vessel for 10 hours to obtain crude polypropylene glycol (E-1). Next, after cooling the temperature in the reaction vessel to 90°C, the crude polypropylene glycol (E-1) was filtered using a suction funnel filled in layers with 10 parts of the filtration aid Radiolite #700 (manufactured by Showa Chemical Industry Co., Ltd.) to obtain a cosmetic composition containing polypropylene glycol (A-1).
Table 1 shows the stereoregularity (ratio of isotactic triplets, heterotactic triplets, and syndiotactic triplets), molecular weight distribution (Mw/Mn), and total weight percentage of oxyalkylene units based on polypropylene glycol (A-1) calculated from the weight of the raw materials, as measured by the method described above.

<Example 2>
(Cosmetic composition containing polypropylene glycol (A-2))
A cosmetic composition containing polypropylene glycol (A-2) was obtained in the same manner as in Example 1, except that 400 parts (6.9 mol parts) of PO were changed to 1400 parts (24.1 mol parts) of PO. For the obtained polypropylene glycol (A-2), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on polypropylene glycol (A-2), are shown in Table 1, in the same manner as in Example 1.

<Example 3>
(Cosmetic composition containing polypropylene glycol (A-3))
A cosmetic composition containing polypropylene glycol (A-3) was obtained in the same manner as in Example 1, except that 400 parts (6.9 mol parts) of PO were changed to 2400 parts (41.3 mol parts) of PO. For the obtained polypropylene glycol (A-3), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight ratio of oxyalkylene units based on polypropylene glycol (A-3), are shown in Table 1, in the same manner as in Example 1.

<Example 4>
(Cosmetic composition containing polypropylene glycol (A-4))
A cosmetic composition containing polypropylene glycol (A-4) was obtained in the same manner as in Example 1, except that 600 parts (1 mole) of Mn600 polypropylene glycol was replaced with 1,000 parts (1 mole) of Mn1000 polypropylene glycol [product name: Newpol PP-1000, manufactured by Sanyo Chemical Industries, Ltd.], and 400 parts (6.9 moles) of PO was replaced with 3,000 parts (51.7 moles) of PO. For the obtained polypropylene glycol (A-4), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on polypropylene glycol (A-4), were shown in Table 1, in the same manner as in Example 1.

<Example 5>
(Cosmetic composition containing polypropylene glycol (A-5))
A cosmetic composition containing a butanol propylene oxide adduct (A-5) was obtained in the same manner as in Example 1, except that 600 parts (1 mole) of Mn600 polypropylene glycol was replaced with 1234 parts (1 mole) of n-butanol propylene oxide adduct 20 moles [product name: Newpol LB-285, manufactured by Sanyo Chemical Industries, Ltd.], and 400 parts (6.9 moles) of PO was replaced with 762 parts (13.2 moles) of PO. For the obtained butanol propylene oxide adduct (A-5), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on the butanol propylene oxide adduct (A-5), were shown in Table 1 in the same manner as in Example 1.

<Example 6>
(Cosmetic composition containing polypropylene glycol (A-6))
A cosmetic composition containing a butanol propylene oxide adduct (A-6) was obtained in the same manner as in Example 1, except that 600 parts (1 mole) of Mn600 polypropylene glycol was replaced with 1234 parts (1 mole) of n-butanol propylene oxide adduct 20 moles [product name: Newpol LB-285, manufactured by Sanyo Chemical Industries, Ltd.], and 400 parts (6.9 moles) of PO was replaced with 1762 parts (30.4 moles) of PO. For the obtained butanol propylene oxide adduct (A-6), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on the butanol propylene oxide adduct (A-6), are shown in Table 1, in the same manner as in Example 1.

<Example 7>
(Cosmetic composition containing polypropylene glycol (A-7))
A cosmetic composition containing a butanol propylene oxide adduct (A-7) was obtained in the same manner as in Example 1, except that 600 parts (1 mole) of Mn600 polypropylene glycol was replaced with 1234 parts (1 mole) of n-butanol propylene oxide adduct 20 moles [product name: Newpol LB-285, manufactured by Sanyo Chemical Industries, Ltd.], and 400 parts (6.9 moles) of PO was replaced with 2762 parts (47.7 moles) of PO. For the obtained butanol propylene oxide adduct (A-7), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on the butanol propylene oxide adduct (A-7), are shown in Table 1, in the same manner as in Example 1.

<Example 8>
(Cosmetic composition containing polypropylene glycol (A-8))
A cosmetic composition containing glycerin propylene oxide adduct (A-8) was obtained in the same manner as in Example 1, except that 600 parts (1 mole) of polypropylene glycol with Mn 600 was replaced with 3,000 parts (1 mole) of glycerin propylene oxide adduct with Mn 3000 [product name: Newport GP-3000, manufactured by Sanyo Chemical Industries, Ltd.], and 400 parts (6.9 moles) of PO was replaced with 2,762 parts (48.3 moles) of PO. For the obtained glycerin propylene oxide adduct (A-8), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on glycerin propylene oxide adduct (A-8), were shown in Table 1 in the same manner as in Example 1.

<Example 9>
(Cosmetic composition containing polypropylene glycol (A-9))
In a stainless steel autoclave equipped with a stirring device and temperature control function, 5 parts (0.036 mol) of pentaerythritol, 3 parts of the calcined product (B'-1) obtained in Production Example 1, and 40 parts of N,N-dimethylformamide (hereinafter abbreviated as DMF) were mixed, and dehydration and desolvation were carried out under reduced pressure (1.3 kPa) at 100°C for 1 hour. Next, after cooling the temperature in the reaction vessel to 90°C, 30 parts of DMF dehydrated with a molecular sieve were added, and 32 parts (0.55 mol) of PO were added dropwise over 10 hours, followed by aging at 90°C for 5 hours to obtain a cosmetic composition containing a crude pentaerythritol propylene oxide adduct (E-9). Next, the crude pentaerythritol propylene oxide adduct (E-9) was filtered using a suction funnel filled in layers with 5 parts of the filtration aid Radiolite #700 (manufactured by Showa Chemical Industry Co., Ltd.) to obtain a cosmetic composition containing pentaerythritol propylene oxide adduct (A-9). For the obtained pentaerythritol propylene oxide adduct (A-9), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on pentaerythritol propylene oxide adduct (A-9), are shown in Table 1, as in Example 1.

<Example 10>
(Cosmetic composition containing polypropylene glycol (A-10))
In a stainless steel autoclave equipped with a stirring device and temperature control function, 5 parts (0.027 mol) of sorbitol, 3 parts of the calcined product (B'-1) obtained in Production Example 1, and 40 parts of DMF were mixed, and dehydration and desolvation were carried out under reduced pressure (1.3 kPa) at 100°C for 1 hour. Next, after cooling the temperature in the reaction vessel to 90°C, 30 parts of DMF dehydrated with a molecular sieve were added, and 35 parts (0.6 mol) of PO were added dropwise over 10 hours, followed by aging at 90°C for 5 hours to obtain crude sorbitol propylene oxide adduct (E-10). Next, the crude sorbitol propylene oxide adduct (E-10) was filtered using a suction funnel filled in layers with 5 parts of the filtration aid Radiolite #700 (manufactured by Showa Chemical Industry Co., Ltd.). Then, desolvation was carried out under reduced pressure (1.3 kPa) at 100°C to obtain a cosmetic composition containing sorbitol propylene oxide adduct (A-10). For the obtained sorbitol propylene oxide adduct (A-10), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on sorbitol propylene oxide adduct (A-10), are shown in Table 1, as in Example 1.

<Example 11>
(Cosmetic composition containing polypropylene glycol (A-11))
A cosmetic composition containing a propylene oxide adduct of a hydroxylated polybutadiene (A-11) was obtained in the same manner as in Example 1, except that 600 parts (1 mole) of Mn600 polypropylene glycol was replaced with 1500 parts (1 mole) of Mn1500 hydroxylated polybutadiene at both ends [product name: NISSO-PB GI-1000, manufactured by Nippon Soda Co., Ltd.], and 400 parts (6.9 moles) of PO was replaced with 1000 parts (17.2 moles) of PO. For the obtained hydroxylated polybutadiene propylene oxide adduct (A-11), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on the hydroxylated polybutadiene propylene oxide adduct (A-11), were shown in Table 1 in the same manner as in Example 1.

<Example 12>
(Cosmetic composition containing polypropylene glycol (A-12))
A cosmetic composition containing a propylene oxide adduct of a polyfarnesene with hydroxyl groups at both ends (A-12) was obtained in the same manner as in Example 1, except that 600 parts (1 mole) of polypropylene glycol with Mn600 was replaced with 3,000 parts (1 mole) of polyfarnesene with hydroxyl groups at both ends (product name: KRASOL F-3000, manufactured by Cray Valley), and 400 parts (6.9 moles) of PO was replaced with 1,000 parts (17.2 moles) of PO. For the obtained propylene oxide adduct of a polyfarnesene with hydroxyl groups at both ends (A-12), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on the propylene oxide adduct of a polyfarnesene with hydroxyl groups at both ends (A-12), were shown in Table 1 in the same manner as in Example 1.

<Comparative Example 1>
(A cosmetic composition containing a propylene oxide adduct (A'-4) of n-butanol)
In a stainless steel autoclave equipped with a stirring device and temperature control function, 74 parts (1 mole) of n-butanol and 0.2 parts of the complex metal cyanide catalyst (X'-1) obtained in Production Example 2 were mixed and the mixture was purged with nitrogen. Next, the temperature in the reaction vessel was raised to 110°C, and 36 parts (52 moles) of PO were added to the liquid over 20 hours under conditions of 0.6 MPa or less. After that, the reaction vessel was aged at 110°C for 10 hours to obtain the crude n-butanol propylene oxide adduct (E'-4). After aging, the temperature in the reaction vessel was cooled to 80°C, and unreacted PO was removed by reducing the pressure (1.3 kPa) for 1 hour. Then, the mixture was filtered to obtain a cosmetic composition containing the n-butanol propylene oxide adduct (A'-4). For the obtained n-butanol propylene oxide adduct (A'-4), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on the n-butanol propylene oxide adduct (A'-4), are shown in Table 1, similar to Example 1.

<Comparative Example 2>
(A cosmetic composition containing a propylene oxide adduct (A'-5) of n-butanol)
A cosmetic composition containing n-butanol propylene oxide adduct (A'-5) was obtained in the same manner as in Comparative Example 1, except that 16 parts (52 mol parts) of PO30 were changed to 22 parts (90 mol parts) of PO5. For the obtained n-butanol propylene oxide adduct (A'-5), the stereoregularity and molecular weight distribution (Mw/Mn), as well as the total weight percentage of oxyalkylene units based on n-butanol propylene oxide adduct (A'-5), are shown in Table 1, in the same manner as in Example 1.

<Comparative Example 3>
(A cosmetic composition containing a propylene oxide adduct (A'-6) of n-butanol)
A cosmetic composition containing a propylene oxide adduct (A'-6) of a hydroxylated polybutadiene with both ends hydroxylated (Hydrogenated Poly

Table 1 shows the stereoregularity (ratio of isotactic triplets, heterotactic triplets, and syndiotactic triplets), molecular weight distribution (Mw/Mn), and total percentage of oxyalkylene units based on the alkylene oxide adducts for the following materials: the alkylene oxide adducts contained in cosmetic compositions containing alkylene oxide adducts (A-1) to (A-12) obtained in Examples 1 to 12, the alkylene oxide adducts contained in cosmetic compositions containing alkylene oxide adducts (A'-4) to (A'-6) obtained in Comparative Examples 1 to 3, and the alkylene oxide adducts (A'-1) to (A'-3) obtained from the market.
The alkylene oxide adducts (A'-1) to (A'-3) obtained from the market were as follows:
(A'-1): Polypropylene glycol with Mn1000 [Product name: Newpol PP-1000, manufactured by Sanyo Chemical Industries, Ltd.]
(A'-2): Polypropylene glycol with Mn2000 [Product name: Newpol PP-2000, manufactured by Sanyo Chemical Industries, Ltd.]
(A'-3): Polypropylene glycol with Mn3000 [Product name: Newpol PP-3000, manufactured by Sanyo Chemical Industries, Ltd.]

(Examples 13-24, Comparative Examples 4-9)
The hair treatments described in the following instructions for manufacturing a hair treatment were used to prepare the cosmetic hair treatments of the present invention in Examples 13 to 24 and the comparative hair treatments in Comparative Examples 4 to 9.
A panel of 10 female experts aged 30-50 evaluated each hair treatment based on the following: "slipperiness of hair during rinsing,""slipperiness when removing water after rinsing,""smoothness of hair after drying," and "lack of stickiness of hair after drying." The results are shown in Tables 2 and 3.
In Tables 2 and 3, cetearyl alcohol was represented by Conol 1668 (manufactured by Shin-Nippon Rika Co., Ltd., Conol is a registered trademark of Shin-Nippon Rika Co., Ltd.), and behentrimonium chloride was represented by VARISOFT BT 85 Pellets (Evonik Operations GmbH, VARISOFT is a registered trademark of Evonik Goldschmidt Corporation).

(Method of manufacturing hair treatment)
[1] The parts by weight of cetearyl alcohol and behentrimonium chloride listed in Tables 2 and 3 were heated to 80°C and homogeneously mixed.
[2]: The parts by weight of water listed in Tables 2 and 3 were heated to 80°C, and the entire amount of 80°C water was mixed and stirred with the mixture prepared in [1] above to prepare an emulsion. The emulsion was then cooled to below 30°C while being stirred.
[3]: To the emulsion prepared in [2] above, one of the alkylene oxide adducts (A-1) to (A-12) and (A'-1) to (A'-6) in parts by weight as listed in Tables 2 and 3 was added and stirred until homogeneous to obtain a hair treatment.

(Hair treatment evaluation)
After thoroughly wetting the hair with 40°C water, 1g of a 10% by weight aqueous solution of polyoxyethylene lauryl ether sodium sulfate (EO 2 molar adduct) was used for washing, and then the hair was rinsed thoroughly with 40°C water. Next, 1g of the prepared hair treatment was applied evenly to each panelist's hair, and after thoroughly distributing it throughout the hair, the "slipperiness of the hair during rinsing" was evaluated while rinsing with 40°C warm water for 30 seconds.
Next, after rinsing the hair treatment, participants were asked to wring out the water from their hair, and the "slipperiness of the hair when wringing out water after rinsing" was evaluated.
Furthermore, the hair was dried with a hairdryer, and the "smoothness of the hair after drying" and "lack of stickiness after drying" were evaluated.
Each evaluation is rated on a 5-point scale from 1 to 5 points, with higher scores indicating better results.

Tables 2 and 3 show the total scores from a panel of 10 expert females aged 30-50 for each evaluation item. A higher total score indicates better performance in "hair slipperiness during rinsing," "slipperiness when removing water from hair after rinsing," "smoothness of hair after drying," and "lack of stickiness of hair after drying."

As shown in Examples 13-24 of Table 2, the hair treatment of the present invention, containing alkylene oxide adducts (A-1) to (A-12), was superior to the hair treatments of Comparative Examples 4-9 of Table 3 in terms of "hair slipperiness during rinsing," "slipperiness when removing water from hair," "smoothness of hair after drying," and "lack of stickiness of hair after drying."

The hair treatments of Comparative Examples 4 to 6 contained alkylene oxide adducts in which the proportion of isotactic triplets was less than 26% and the molecular weight distribution (Mw/Mn) was less than 1.05. Compared to the hair treatments of Examples 1 to 12, which are the cosmetic composition of the present invention, they had poorer "slipperiness when removing water from the hair after rinsing".
The hair treatments of Comparative Examples 7 and 8 contained alkylene oxide adducts with an isotactic triplicate ratio of less than 26%. Compared to the hair treatments of Examples 1 to 12, which are cosmetics of the present invention, they exhibited poor "slipperiness when draining water from hair after rinsing" and poor "lack of stickiness in hair after drying with a hairdryer."
The hair treatment of Comparative Example 9 had a total weight percentage of oxyalkylene units in the alkylene oxide adduct it contained that was 10% or less based on the weight of the alkylene oxide adduct. Compared to the hair treatments of Examples 1 to 12, which are cosmetics of the present invention, it had poor "slipperiness when draining water from the hair after rinsing" and also poor "lack of stickiness in the hair after drying."

The alkylene oxide adduct (A) obtained by the manufacturing method of the present invention, when incorporated into hair cosmetics, provides hair cosmetics with excellent slipperiness during rinsing, slipperiness when draining water from hair after rinsing, smoothness of hair after drying, and reduced stickiness of hair after drying. Therefore, it is suitable as a cosmetic composition and cosmetic.

Claims (3)

A cosmetic composition containing an alkylene oxide adduct (A) that satisfies the following conditions (1) to (6 ):
(1) The alkylene oxide adduct (A) is an alkylene oxide adduct of a compound having 1 to 6 hydroxyl groups:
(2) The alkylene oxide adduct (A) contains an oxypropylene unit as an oxyalkylene unit:
(3) The total weight percentage of oxyalkylene units in alkylene oxide adduct (A) is 10% by weight or more, based on the weight of alkylene oxide adduct (A):
(4) The alkylene oxide adduct (A) has an oxypropylene chain consisting of three or more oxypropylene units in a row:
(5) The proportion of isotactic triplets in the oxypropylene chain of alkylene oxide adduct (A) is 26% or more of the total number of isotactic triplets, heterotactic triplets and syndiotactic triplets :
(6) The compound having 1 to 6 hydroxyl groups is one or more selected from the group consisting of 1 to 6-valent alcohols and hydroxyl-modified polymer compounds with Mn 1000 to 5000 . The cosmetic composition according to claim 1, wherein the molecular weight distribution (Mw/Mn) of the alkylene oxide adduct (A) is 1.05 to 1.4. Cosmetics containing alkylene oxide adduct (A) that satisfy the following conditions (1) to (6 ):
(1) The alkylene oxide adduct (A) is an alkylene oxide adduct of a compound having 1 to 6 hydroxyl groups:
(2) The alkylene oxide adduct (A) contains an oxypropylene unit as an oxyalkylene unit:
(3) The total weight percentage of oxyalkylene units having alkylene oxide adduct (A) is 10% by weight or more, based on the weight of alkylene oxide adduct (A):
(4) The alkylene oxide adduct (A) has an oxypropylene chain consisting of three or more oxypropylene units in a row:
(5) The proportion of isotactic triplets in the oxypropylene chain of alkylene oxide adduct (A) is 26% or more of the total number of isotactic triplets, heterotactic triplets and syndiotactic triplets :
(6) The compound having 1 to 6 hydroxyl groups is one or more selected from the group consisting of 1 to 6-valent alcohols and hydroxyl group-modified polymer compounds with Mn 1000 to 5000 .