1,3-butylene glycol product

Abstract

Provided is a 1,3-butylene glycol product unlikely to generate apple odor and pungent odor even when blended in a cosmetic composition.　The 1,3-butylene glycol product has an area ratio represented by the following formula of from 54 to 130.　Area ratio=peak X area / area obtained by subtracting peak area of diethylene glycol dimethyl ether from total peak area×106. Peak X area: area of a peak having a peak top in the retention time 6.2-6.32 range in gas chromatographic analysis under specific conditions when the retention time of diethylene glycol dimethyl ether, the internal standard, is taken to be 1.0.

Description

1,3-butylene glycol products

[0001] This disclosure relates to 1,3-butylene glycol products. This application claims priority from Japanese Patent Application No. 2024-114227, filed on July 17, 2024, the contents of which are incorporated herein by reference.

[0002] 1,3-Butylene glycol is a colorless, transparent, odorless liquid that has properties such as low volatility, low toxicity, and high hygroscopicity, and has excellent chemical stability. For this reason, 1,3-butylene glycol has a wide range of uses, including as a raw material for various synthetic resins and surfactants, as well as in cosmetics, moisture absorbents, high-boiling point solvents, and antifreeze materials. In particular, in recent years, 1,3-butylene glycol has attracted attention for its excellent properties as a moisturizing agent, and demand for it in the cosmetics industry is expanding.

[0003] 1,3-butylene glycol obtained by conventional manufacturing methods sometimes has an odor due to the influence of by-products. Furthermore, even if the product is clear immediately after production, it may become discolored over time, which poses a problem during long-term storage.

[0004] For example, cosmetics are exposed to air when they are used or stored after use. Furthermore, when cosmetics are manufactured, they are generally carried out in an air atmosphere, and may also be heated for sterilization or other purposes. When 1,3-butylene glycol obtained by conventional methods is used in cosmetics, discoloration may progress due to the presence of air or the effects of heat. To solve these problems, there has been a need to remove by-products from crude 1,3-butylene glycol and to highly purify the 1,3-butylene glycol.

[0005] As a method for obtaining high-purity 1,3-butylene glycol, a method has been proposed in which caustic soda is added to crude 1,3-butylene glycol obtained by hydrogen reduction of acetaldols and the mixture is distilled. Other methods have also been proposed, such as adding an alkali metal base to crude 1,3-butylene glycol from which high-boiling components have been removed, subjecting the mixture to heat treatment, distilling the 1,3-butylene glycol, separating the alkali metal compounds and high-boiling components as residue, and then distilling off the low-boiling components from the 1,3-butylene glycol fraction (Patent Documents 1 to 9). In this way, various methods for producing 1,3-butylene glycol have been proposed in order to obtain high-purity 1,3-butylene glycol.

[0006] Japanese Patent Application Laid-Open No. 7-258129 International Publication No. 00 / 07969 Japanese Patent Application Laid-Open No. 2001-213822 Japanese Patent Application Laid-Open No. 2001-213824 Japanese Patent Application Laid-Open No. 2001-213825 Japanese Patent Application Laid-Open No. 2001-213828 Japanese Patent Application Laid-Open No. 6804601 Japanese Patent Application Laid-Open No. 6804602 Japanese Patent Application Laid-Open No. 6979473

[0007] However, the 1,3-butylene glycol products obtained by the methods described in Patent Documents 1 to 9 also have the problem of generating an odor (particularly an apple odor) over time when blended into a cosmetic composition. Although the reason for this is not clear, it is thought that the generation of the odor is due to the reaction of specific by-products contained in the 1,3-butylene glycol product with components contained in the cosmetic composition (e.g., citric acid, etc.) to form odor-causing components.

[0008] Furthermore, the inventors of the present disclosure have discovered a 1,3-butylene glycol product that can solve the above-mentioned problems by improving the manufacturing method of the 1,3-butylene glycol product. However, the inventors of the present disclosure have discovered that the resulting 1,3-butylene glycol product also has the problem of generating an odor (irritating odor) different from the apple odor when blended into a cosmetic composition. This irritating odor is not generated by the 1,3-butylene glycol products described in Patent Documents 1 to 9, and is therefore believed to be an odor derived from the cosmetic composition itself. Furthermore, it is believed that a specific by-product contained in the 1,3-butylene glycol product has a masking effect on the irritating odor derived from the cosmetic composition, and that the inclusion of this by-product in a specific amount suppresses the irritating odor. Thus, until now, no 1,3-butylene glycol product has been discovered that suppresses the generation of both the apple odor and the irritating odor when blended into a cosmetic composition.

[0009] Therefore, an object of the present disclosure is to provide a 1,3-butylene glycol product that is less likely to produce an apple odor or an irritating odor even when incorporated into a cosmetic composition.

[0010] As a result of intensive research to achieve the above object, the inventors of the present disclosure have found that by improving the method for producing crude 1,3-butylene glycol, it is possible to obtain a 1,3-butylene glycol product that is less likely to emit odors (apple odor and irritating odor) when incorporated into a cosmetic composition. The invention of the present disclosure was completed based on these findings.

[0011] That is, the present disclosure provides a 1,3-butylene glycol product having an area ratio of 54 to 130, as shown in the following formula: Area ratio = Peak X area / Area obtained by subtracting the peak area of ​​diethylene glycol dimethyl ether from the total peak area × 10 ６Peak X area: In gas chromatography analysis under the following conditions, the area of ​​the peak having a peak top in the relative retention time range of 6.2 to 6.32, when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard substance, is set to 1.0. [Gas chromatography analysis conditions] Injected sample: a mixture of 1 g of an 80 mass % aqueous solution of 1,3-butylene glycol product and 0.01 g of diethylene glycol dimethyl ether Injection amount: 1 μL Analytical column: a column whose stationary phase is polyethylene glycol (film thickness 0.25 μm × length 30 m × inner diameter 0.25 mm) Heating conditions: after holding at 100° C. for 20 minutes, heat from 100° C. to 150° C. at 2° C. / min, and hold for 5 minutes. Sample introduction and temperature: Split sample introduction, 250°C Split gas flow rate and carrier gas: 71.1 mL / min, helium Column gas flow rate and carrier gas: 0.91 mL / min, helium Detector and temperature: Flame ionization detector (FID), 250°C

[0012] The 1,3-butylene glycol in the 1,3-butylene glycol product is preferably a reduced form of at least one compound selected from the group consisting of acetaldol, paraaldol, and aldoxane.

[0013] The present disclosure also provides a moisturizer containing the above 1,3-butylene glycol product.

[0014] The present disclosure also provides a cosmetic composition containing the 1,3-butylene glycol product.

[0015] The 1,3-butylene glycol product of the present disclosure is less likely to produce an apple odor or an irritating odor when incorporated into a cosmetic composition, and is therefore suitable for use in cosmetics, moisturizers, and the like.

[0016] 1 is a flowchart of a manufacturing method for a 1,3-butylene glycol product of the present disclosure. 2 is a chromatogram chart of GC / FID measurement for the 1,3-butylene glycol product of Example 1. 3 is a chromatogram chart of GC / FID measurement for the 1,3-butylene glycol product of Comparative Example 2.

[0017] The 1,3-butylene glycol products of the present disclosure will be described below, but the configurations and combinations thereof in each embodiment are merely examples, and additions, omissions, substitutions, and other modifications of the configurations are possible as appropriate within the scope of the gist of the present disclosure. The present disclosure is not limited by the embodiments.

[0018] The 1,3-butylene glycol product of the present disclosure has an area ratio of 54 or more and 130 or less, as shown in the following formula: Area ratio = Peak X area / Area obtained by subtracting the peak area of ​​diethylene glycol dimethyl ether from the total peak area × 10 ６ Peak X area: In gas chromatography analysis under the following conditions, the area of ​​a peak (referred to as "Peak X") having a peak top in the range of relative retention time 6.2 to 6.32 when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard, is set to 1.0.

[0019] [Gas Chromatography Analysis Conditions] Injected sample: A mixture of 1 g of an 80% by mass aqueous solution of 1,3-butylene glycol product and 0.01 g of diethylene glycol dimethyl ether. Injection volume: 1 μL. Analytical column: A column with a polyethylene glycol stationary phase (film thickness 0.25 μm x length 30 m x inner diameter 0.25 mm). Heating conditions: After holding at 100°C for 20 minutes, heat from 100°C to 150°C at 2°C / min and hold for 5 minutes. Sample introduction and temperature: Split sample introduction method, 250°C. Split gas flow rate and carrier gas: 71.1 mL / min, helium. Column gas flow rate and carrier gas: 0.91 mL / min, helium. Detector and temperature: Flame ionization detector (FID), 250°C.

[0020] The area ratio is not particularly limited as long as it is 54 or more and 130 or less, and is, for example, 125 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, or 30 or less. Furthermore, the area ratio is, for example, 55 or more, or 56 or more. It can be said that the area ratio correlates with the content of impurities corresponding to Peak X contained in the 1,3-butylene glycol product. In other words, it can be said that when the area ratio is large, the content of impurities corresponding to Peak X increases, and when the area ratio is small, the content of impurities corresponding to Peak X decreases. When the area ratio is within the above range, the generation of apple odor and irritating odor tends to be further suppressed when the 1,3-butylene glycol product is blended into a cosmetic composition.

[0021] In the 1,3-butylene glycol product of the present disclosure, when the relative retention time of the peak of the internal standard substance, diethylene glycol dimethyl ether, in gas chromatography analysis under the above conditions is taken as 1.0, 1,3-butylene glycol has a peak top in the range of relative retention times of 5.15 to 5.84. The area ratio of the above peak is, for example, preferably 99.5% or more, more preferably 99.7% or more, even more preferably 99.8% or more, and particularly preferably 99.9% or more.

[0022] The above-mentioned "area ratio" refers to the ratio of the area of ​​a specific peak to the area obtained by subtracting the peak area of ​​diethylene glycol dimethyl ether from the sum of the areas of all peaks appearing in the chart (total peak area). Furthermore, "all peaks" refers to all of the peaks that appear when, for example, the relative retention time of the 1,3-butylene glycol peak is set to 1.0 and the analysis is continued until the relative retention time reaches 8.6 and then stopped. Therefore, "the area obtained by subtracting the peak area of ​​diethylene glycol dimethyl ether from the total peak area" can be rephrased as the sum of the areas of all peaks, excluding the peak corresponding to diethylene glycol dimethyl ether, that appear when, for example, the relative retention time of the 1,3-butylene glycol peak is set to 1.0 and the analysis is continued until the relative retention time reaches 8.6 and then stopped.

[0023] Examples of 1,3-butylene glycol in the 1,3-butylene glycol product of the present disclosure include (1) reduced products of acetaldols, (2) hydrolysates of 1,3-butylene oxide, (3) selective hydrogenolysis products of erythritol, (4) selective water addition products to butadiene, (5) hydrogenated products of n-butanal-3-one, (6) hydrogenated products of 1-butanol-3-one, (7) hydrogenated products of 3-hydroxy-1-butanoic acid, (8) hydrogenated products of β-butyrolactone, and (9) hydrogenated products of diketene. Note that the 1,3-butylene glycol of the present disclosure may be one or a mixture of two or more of the above (1) to (9).

[0024] The 1,3-butylene glycol in the 1,3-butylene glycol product of the present disclosure is preferably (1) a reduced product of acetaldols. Furthermore, from the viewpoint of the yield of 1,3-butylene glycol, the reduced product of acetaldols is preferably a liquid-phase reduced product of acetaldols. This is because acetaldols have a high boiling point, are thermally unstable, and readily undergo dehydration reactions to form crotonaldehyde and the like at high temperatures. Furthermore, the dehydration reaction and reduction reaction (hydrogenation reaction) at high temperatures have a faster reaction rate than the reduction reaction (hydrogenation reaction). That is, when acetaldols are reduced in the gas phase, the reaction system must be heated to a high temperature. However, subjecting acetaldols to a high temperature causes a dehydration reaction to form crotonaldehyde and the like, and the subsequent reduction reaction produces by-products such as butanol. This results in a relatively low yield of the target 1,3-butylene glycol. Therefore, in order to obtain a high-purity 1,3-butylene glycol product, liquid-phase reduction is preferred over gas-phase reduction. Here, 1,3-butylene glycol as a reduced product of acetaldols can be rephrased as 1,3-butylene glycol obtained by a method of reducing acetaldols with hydrogen. Similarly, 1,3-butylene glycol as a liquid-phase reduced product of acetaldols can be rephrased as 1,3-butylene glycol obtained by a method of reducing acetaldols with hydrogen in a liquid phase. Furthermore, 1,3-butylene glycol as a hydrolyzate of 1,3-butylene oxide can be rephrased as 1,3-butylene glycol obtained by hydrolyzing 1,3-butylene oxide.

[0025] Generally, when 1,3-butylene glycol is produced, by-products are generated during the production process. For example, when 1,3-butylene glycol is produced by hydrogen reduction of acetaldols, by-products include low-boiling substances (low-boiling compounds) having unsaturated bonds, such as acetaldehyde, butylaldehyde, crotonaldehyde, acetone, and methyl vinyl ketone, as well as condensates thereof and condensates of 1,3-butylene glycol with the above-mentioned low-boiling substances (e.g., acetal compounds of 1,3-butylene glycol and acetaldol). In addition, by-products include acetal compounds of crotonaldehyde and 1,3-butylene glycol, acetal compounds of acetaldehyde and 1,3-butylene glycol, and acetal compounds of acetaldol or acetaldehyde with a hydrogenated acetaldehyde trimer.

[0026] These by-products may have the properties of odor-causing substances. Here, odor-causing substances are defined as including not only substances that themselves currently emit an odor, but also substances that change over time to emit an odor (e.g., apple odor).

[0027] The production of 1,3-butylene glycol uses a hydrogenation raw material containing an acetaldol. The acetaldol is not particularly limited as long as it is a compound that becomes 1,3-butylene glycol by hydrogen reduction, and examples thereof include acetaldol, its cyclized dimer, para-aldol, aldoxane, a type of cyclic trimer of acetaldehyde, and mixtures thereof.

[0028] The method for producing acetaldols (e.g., acetaldol and para-aldol) is not particularly limited. For example, acetaldols may be obtained by an aldol condensation reaction of acetaldehyde in the presence of a basic catalyst, or by thermal decomposition of aldoxane. The reaction crude liquid containing acetaldols obtained by the above reaction may be neutralized with an acid and used for producing 1,3-butylene glycol. Such a reaction crude liquid may contain, in addition to acetaldols, low-boiling substances such as acetaldehyde and crotonaldehyde, high-boiling substances such as aldehyde dimers and aldehyde trimers, water, salts, etc. In this specification, compounds having a boiling point lower than that of 1,3-butylene glycol may be referred to as "low-boiling substances," and compounds having a boiling point higher than that of 1,3-butylene glycol may be referred to as "high-boiling substances."

[0029] The reaction crude liquid may be subjected to pretreatment such as dealcoholization distillation, dehydration distillation, desalting, and removal of impurities, as necessary, to remove by-products such as unreacted acetaldehyde and crotonaldehyde. Pretreatment methods include distillation, adsorption, ion exchange, conversion to high-boiling substances by heating, decomposition, and the like. Various distillation methods can be used, such as reduced pressure, normal pressure, increased pressure, azeotropy, extraction, and reaction.

[0030] The hydrogenated raw material may or may not contain water, but preferably does. That is, in the 1,3-butylene glycol product of the present disclosure, 1,3-butylene glycol is preferably obtained by hydrogenating a hydrogenated raw material containing water and acetaldols. In other words, the 1,3-butylene glycol is a hydrogen reduction product of a hydrogenated raw material containing water and acetaldols.

[0031] The content of acetaldols in the hydrogenation raw material is not particularly limited, but is, for example, preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. When the content of acetaldols is within the above range, the amount of by-products contained in crude 1,3-butylene glycol tends to be reduced.

[0032] The water content in the hydrogenated raw material is not particularly limited, but is, for example, preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 40% by mass or more, even more preferably more than 50% by mass, and particularly preferably 55% by mass or more. Furthermore, for example, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. When the water content is within the above range, the generation of odors (apple odor and irritating odor) tends to be reduced when a 1,3-butylene glycol product is blended into a cosmetic composition. When the water content in the hydrogenated raw material exceeds 50% by mass, this tendency is intensified, and the generation of odors (particularly apple odor) is significantly reduced. Generally speaking, the production efficiency of 1,3-butylene glycol decreases as the water content in the hydrogenated raw material increases, so it is common to prevent the water content from becoming too high (for example, to be at least 50% by mass or less). For this reason, there has traditionally been no thought of increasing the water content in the hydrogenated raw material. The invention of the present disclosure solves a previously unknown problem of making it difficult for odors (apple odor and irritating odor) to be generated even when blended in a cosmetic composition by increasing the water content to a certain extent, appropriately adjusting the purification method for crude 1,3-butylene glycol, and a combination of these.

[0033] The method for producing crude 1,3-butylene glycol is described below. In this method, crude 1,3-butylene glycol is obtained by reducing a hydrogenation raw material containing acetaldols in the presence of a hydrogenation catalyst.

[0034] Examples of hydrogenation catalysts include Raney nickel. The hydrogenation catalyst can be used in a suspended or packed state, but is preferably used in a suspended state. The amount of hydrogenation catalyst used is not particularly limited, but is preferably 1 to 30 parts by mass, more preferably 4 to 25 parts by mass, even more preferably 8 to 20 parts by mass, and particularly preferably 12 to 18 parts by mass, per 100 parts by mass of the hydrogenation feedstock. The amount of hydrogen used in the reduction reaction is not particularly limited, but is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 4 to 20 parts by mass, and particularly preferably 8 to 12 parts by mass, per 100 parts by mass of the hydrogenation feedstock. The pressure (total pressure) in the reaction system during the reduction reaction is not particularly limited, but is preferably 150 to 500 atm, more preferably 180 to 450 atm, even more preferably 200 to 400 atm, and particularly preferably 250 to 350 atm. The ratio of the hydrogen pressure (hydrogen partial pressure) to the total pressure in the reaction system is not particularly limited, but is preferably 80% or more (80 to 100%) of the total pressure, more preferably 85 to 99.9%, even more preferably 90 to 99.5%, and particularly preferably 95 to 99%. The hydrogen pressure (hydrogen partial pressure) in the reaction system is not particularly limited, but is preferably 100 to 500 atm, more preferably 150 to 450 atm, even more preferably 150 to 400 atm, and particularly preferably 200 to 350 atm. The reaction temperature in the reduction reaction is not particularly limited, but is preferably 110 to 140°C, and more preferably 120 to 140°C. The reaction time (residence time) in the reduction reaction is not particularly limited, but is preferably 30 to 300 minutes, more preferably 80 to 280 minutes, and even more preferably 120 to 250 minutes.

[0035] When the amount of hydrogenation catalyst used in the reduction reaction, the amount of hydrogen, the hydrogen pressure in the reduction reaction, the reaction temperature, and the reaction time (residence time) are all within the above ranges, the reaction rate (hydrogenation rate) of acetaldols to 1,3-butylene glycol is improved. As a result, for example, the acetalization reaction between 1,3-butylene glycol and acetaldol is reduced, and a high-purity 1,3-butylene glycol product tends to be obtained. This tendency is particularly strongly influenced by the hydrogen pressure in the reduction reaction. That is, when the hydrogen pressure in the reduction reaction is within the above ranges, the reaction rate (reduction rate) of acetaldols to 1,3-butylene glycol is significantly improved, and as a result, the amount of acetalized 1,3-butylene glycol and acetaldol is reduced, resulting in a high-purity 1,3-butylene glycol product. This reaction can be carried out in any of a batch system, a semi-batch system, and a continuous system.

[0036] The crude 1,3-butylene glycol obtained by hydrogenation of the hydrogenated raw material can be subjected to, for example, a dehydration step, a desalting step, a high-boiling point distillation step, an alkali reaction step, a dealkalization step, and a distillation step to obtain a 1,3-butylene glycol product. Among these steps, depending on the conditions for hydrogenation of the hydrogenated raw material, the high-boiling point distillation step, and the dealkalization step, in particular, the generation of odors (apple odor and irritating odor) when the 1,3-butylene glycol product is incorporated into a cosmetic composition tends to be reduced.

[0037] The content of high boiling point substances in the crude 1,3-butylene glycol is not particularly limited, but is, for example, preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. Alternatively, it is, for example, 0.1% by mass or more, 1% by mass or more, or 2% by mass or more. When the content of high boiling point substances in the crude 1,3-butylene glycol is within the above range, the amount of by-products (particularly odor-causing substances) contained in the final 1,3-butylene glycol product tends to be reduced.

[0038] The content of high boiling point substances in the crude 1,3-butylene glycol after the high boiling point substance removal distillation step is 0.5% by mass or less, preferably 0.3% by mass or less, and more preferably 0.1% by mass or less. By using crude 1,3-butylene glycol with a low content of high boiling point substances, even when heat treated with a base in the alkali reaction step, there is no or very little production of low boiling point substances due to the decomposition reaction of the high boiling point substances. As a result, an extremely high-quality 1,3-butylene glycol product with few odor-causing substances tends to be obtained.

[0039] FIG. 1 is a flow sheet of an apparatus showing an example of an embodiment for obtaining a 1,3-butylene glycol product of the present disclosure. A is a dehydrating tower and is related to the dehydration step. B is a demineralizing tower and is related to the demineralizing step. C is a high boiler removal distillation tower and is related to the high boiler removal distillation step. D is an alkali reactor and is related to the alkali reaction step. E is a dealkalizing tower and is related to the dealkalizing step. F is a product distillation tower and is related to the distillation step. A-1, B-1, C-1, E-1, and F-1 are condensers. A-2, C-2, and F-2 are reboilers. Below, an example of an embodiment for obtaining a 1,3-butylene glycol product of the present disclosure will be described using this flow sheet.

[0040] Crude 1,3-butylene glycol (corresponding to "X-1") obtained by hydrogen reduction of the hydrogenation feedstock is supplied to dehydration column A. In dehydration column A, water is distilled from the top of the column by distillation, and a crude 1,3-butylene glycol stream containing 1,3-butylene glycol is obtained from the bottom of the column. The crude 1,3-butylene glycol stream is supplied to demineralization column B. In demineralization column B, a crude 1,3-butylene glycol stream after desalting is obtained from the top of the column by distillation, and salts, high boiling point substances, etc. are discharged from the bottom of the column.

[0041] The desalted crude 1,3-butylene glycol stream is supplied to high boiler removal distillation column C. In high boiler removal distillation column C, high boilers (and 1,3-butylene glycol containing high boilers) are discharged from the bottom of the column. Meanwhile, a crude 1,3-butylene glycol stream after high boiler removal is obtained from the top of the column. The amount of 1,3-butylene glycol containing high boilers discharged from the bottom of the column is preferably 10 to 50 parts, more preferably 20 to 45 parts, even more preferably 23 to 40 parts, even more preferably 25 to 35 parts, and particularly preferably 25 to 30 parts, per 100 parts of the charged liquid. Meanwhile, the amount of crude 1,3-butylene glycol obtained from the top of the column is preferably 50 to 90 parts, more preferably 55 to 85 parts, even more preferably 60 to 80 parts, and particularly preferably 65 to 75 parts, per 100 parts of the charged liquid. By ensuring that the amount of 1,3-butylene glycol containing high boiling points discharged from the bottom of the column and the amount of crude 1,3-butylene glycol obtained from the top of the column are within the above ranges, the generation of apple odor and irritating odor tends to be further reduced when the finally obtained 1,3-butylene glycol product is blended into a cosmetic composition. Although the reason for this is not clear, it is thought that this is because substances derived from the above odors are contained in large amounts as high boiling points in the crude 1,3-butylene glycol, and are discharged in large amounts from the bottom of the column in this step (high boiling point removal distillation step).

[0042] The crude 1,3-butylene glycol distilled in the high boiler removal distillation column C is supplied to an alkali reactor (e.g., a flow-type tubular reactor) D and treated with a base. In the alkali reactor D or upstream thereof, a base is added in an amount of 0.05 to 10 mass %, preferably 0.1 to 1.0 mass %, based on the crude 1,3-butylene glycol stream after high boiler removal. If the amount of base added exceeds 10 mass %, the base tends to precipitate in the distillation column, piping, etc., and cause blockage. In addition, a decomposition reaction of high boiling point compounds may occur, which tends to result in the generation of by-products. If the amount is less than 0.05 mass %, the effect of decomposing by-products is small, and neither is preferable.

[0043] The base added to the alkali reactor D or upstream thereof is not particularly limited, but is preferably, for example, an alkali metal compound. Examples of alkali metal compounds include caustic soda, caustic potash, sodium (bicarbonate), and potassium (bicarbonate). From the viewpoint of reducing by-products contained in the final 1,3-butylene glycol product, caustic soda and caustic potash are preferred. The base may be added as is in solid form, but is preferably added in the form of an aqueous solution for operational reasons and to promote contact with the target liquid. The above-mentioned bases may be used alone or in combination of two or more.

[0044] The reaction temperature in the alkaline reactor D is not particularly limited, but is preferably, for example, 90 to 140°C, more preferably 110 to 130°C. If the reaction temperature is less than 90°C, a long reaction residence time is required, which tends to increase the reactor capacity and become uneconomical. If the reaction temperature exceeds 140°C, the coloration of the finally obtained 1,3-butylene glycol product tends to increase. The reaction residence time is, for example, preferably 5 to 120 minutes, more preferably 10 to 30 minutes. If the reaction residence time is less than 5 minutes, the reaction will be insufficient, resulting in a deterioration in the quality of the finally obtained 1,3-butylene glycol product. If the reaction residence time exceeds 120 minutes, a large reactor will be required, which increases the equipment cost and is therefore disadvantageous from the economic standpoint.

[0045] After leaving the alkali reactor D, the crude reaction liquid stream is supplied to a dealkalizer (thin film evaporator) E, where the base, high boilers (and 1,3-butylene glycol containing these), and the like are removed from the bottom of the column by evaporation. Meanwhile, a crude 1,3-butylene glycol stream after debasing is obtained from the top of the dealkalizer E. The evaporator used in the dealkalizer E is suitably a gravity-flow thin film evaporator or a forced stirring thin film evaporator with a short residence time, in order to suppress the thermal history of the process fluid. The amount of 1,3-butylene glycol containing the base and the like discharged from the bottom of the column is preferably 5 to 40 parts, more preferably 10 to 30 parts, even more preferably 13 to 25 parts, and particularly preferably 15 to 20 parts, per 100 parts of the charged liquid. On the other hand, the amount of crude 1,3-butylene glycol obtained from the top of the column is preferably 60 to 95 parts, more preferably 70 to 90 parts, even more preferably 75 to 87 parts, and particularly preferably 80 to 85 parts, per 100 parts of the charged liquid. When the amount of 1,3-butylene glycol containing high boiling point substances discharged from the bottom of the column and the amount of crude 1,3-butylene glycol obtained from the top of the column are within the above ranges, the generation of apple odor and irritating odor tends to be further reduced when the final 1,3-butylene glycol product is blended into a cosmetic composition. While the reason for this is unclear, it is thought that this is because substances derived from the above odors are contained in large amounts as high boiling point substances in the crude 1,3-butylene glycol, and are discharged in large amounts from the bottom of the column in this step (dealkalization step).

[0046] When the amount charged to distillation column C is taken as 100, the total amount discharged from distillation column C and dealkalization column E (discharged to outside the system) is not particularly limited, but is, for example, preferably 20 to 60, more preferably 24 to 55, even more preferably 28 to 50, and particularly preferably 32 to 45.

[0047] In the evaporator used in the dealkalization column E, evaporation is carried out at a reduced pressure of, for example, 100 torr or less, preferably 5 to 20 torr, at the top of the column. The temperature of the evaporator is preferably, for example, 90 to 120° C. The crude 1,3-butylene glycol stream containing low boiling point substances distilled from the top of the column is supplied to the product distillation column F.

[0048] Examples of product distillation column F include a perforated plate column and a bubble cap column. However, a packed column with low pressure loss, such as Sulzer Packing or Melapak (both trade names of Sumitomo Heavy Industries, Ltd.), is more preferred. This is because 1,3-butylene glycol undergoes thermal decomposition at high temperatures (e.g., 150°C or higher) to produce low-boiling substances that are coloring components, and therefore the distillation temperature is lowered. Furthermore, a long thermal history (residence time) of 1,3-butylene glycol also has a similar effect. Therefore, the reboiler used is preferably one with a short residence time for the process-side fluid, such as a gravity-flow thin-film evaporator or a forced-agitation thin-film evaporator.

[0049] When the concentration of low boilers in the feed liquid is 5% by mass or less, the product distillation column F preferably has a theoretical plate number of, for example, 10 to 20 plates. The feed liquid is preferably supplied to a position 20 to 70% of the height of the column from the top of the column. The distillation in the product distillation column F is preferably carried out under a pressure of, for example, 100 torr or less, more preferably 5 to 20 torr. The reflux ratio is preferably, for example, 0.5 to 2.0.

[0050] In FIG. 1 , the feed to product distillation column F is a liquid obtained by condensing the overhead vapor of dealkalization column E in condenser E-1, but the overhead vapor from dealkalization column E may also be fed directly to product distillation column F. In product distillation column F, impurities such as low boiling point substances are distilled from the top of the column, and 1,3-butylene glycol as a product is obtained from the bottom of product distillation column F (corresponding to "Y").

[0051] [Moisturizing Agent and Cosmetic] The moisturizing agent of the present disclosure contains the 1,3-butylene glycol product described above. As a result, it has excellent moisturizing performance, is free from coloration and odor, is resistant to coloration over time, and is also resistant to an increase in acid concentration over time even when containing water. The moisturizing agent of the present disclosure may contain components other than the 1,3-butylene glycol product described above, for example, moisturizing agent components other than the 1,3-butylene glycol product described above. In the moisturizing agent of the present disclosure, the content of the 1,3-butylene glycol product described above is, for example, 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, and may be composed solely of the 1,3-butylene glycol product described above.

[0052] The cosmetic preparation of the present disclosure contains the moisturizing agent described above. The blend amount of the 1,3-butylene glycol product in the cosmetic preparation of the present disclosure may be any amount that can exhibit moisturizing performance, depending on the type and form of the cosmetic. The blend amount of the 1,3-butylene glycol product in the cosmetic preparation of the present disclosure is, for example, 0.01 to 40% by mass, preferably 0.1 to 30% by mass, more preferably 0.2 to 20% by mass, even more preferably 0.5 to 15% by mass, and particularly preferably 1 to 10% by mass.

[0053] In addition to the 1,3-butylene glycol product, the cosmetic composition of the present disclosure may contain, for example, other moisturizing agents; oils such as vegetable oils, hydrocarbon oils, higher fatty acids, higher alcohols, and silicones; surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants; preservatives, sequestering agents, thickeners, powders, ultraviolet absorbers, ultraviolet blockers, fragrances, pH adjusters; medicinal ingredients and physiologically active ingredients such as vitamins, skin activators, blood circulation promoters, whitening agents, antibacterial agents, and anti-inflammatory agents.

[0054] The cosmetic compositions of the present disclosure may be skin cosmetics such as lotions, emulsions, creams, gels, packs, and masks, or hair cosmetics such as shampoos, rinses, and hair growth agents. They may also be sunscreen cosmetics and makeup cosmetics. They may also be pharmaceuticals or quasi-drugs containing medical ingredients.

[0055] The cosmetic composition of the present disclosure can be produced by a method known per se.

[0056] Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Each configuration and combination thereof in each embodiment is an example, and addition, omission, substitution, and other modifications of configurations are possible as appropriate within the scope of the spirit of this disclosure. Furthermore, each invention according to this disclosure is not limited by the embodiments or the following examples.

[0057] The present disclosure will be described in more detail below with reference to examples. In the examples, "parts" means "parts by mass" unless otherwise specified.

[0058] Example 1 A method for producing 1,3-butylene glycol will be described with reference to Figure 1. 100 parts of an acetaldol solution containing 55% by mass of water as a raw material (a mixed solution of 45 parts of acetaldol and 55 parts of water) were charged with 10 parts of hydrogen into a liquid-phase hydrogen reduction reactor, and 15 parts of Raney nickel were added as a catalyst. The reactor was maintained at 135°C and 300 atm to carry out liquid-phase hydrogen reduction. After separating the catalyst from the liquid after the reaction, the liquid was neutralized with caustic soda and the alcohol was removed to obtain crude 1,3-butylene glycol (1).

[0059] Crude 1,3-butylene glycol (1) (corresponding to "X-1" in FIG. 1) was charged into a dehydrating column A. In the dehydrating column A, water was extracted from the top of the column relative to 100 parts of the charged liquid, 15 parts of fresh water was added as reflux water, the pressure was set to 50 torr, and crude 1,3-butylene glycol (2) having a water content of 0.5% by mass or less was obtained from the bottom of the column. The water extracted from the top of the column was discharged (corresponding to "X-2" in FIG. 1).

[0060] Next, crude 1,3-butylene glycol (2) was charged into demineralizing tower B. In demineralizing tower B, salts, high boiling point substances, and a portion of 1,3-butylene glycol were discharged as evaporation residue from the bottom of the tower (corresponding to "X-3" in FIG. 1). The amount of the evaporation residue discharged was 5 parts per 100 parts of the charged liquid. Meanwhile, crude 1,3-butylene glycol (3) containing 1,3-butylene glycol, low boiling point substances, and a portion of the high boiling point substances was obtained from the top of the tower.

[0061] Next, the crude 1,3-butylene glycol (3) was charged into a high boiler removal distillation column C. In the high boiler removal distillation column C, high boilers and a portion of the 1,3-butylene glycol were discharged from the bottom of the column (corresponding to "X-4" in FIG. 1). The amount discharged was 20 parts per 100 parts of the charged liquid. Meanwhile, 80 parts of crude 1,3-butylene glycol (4) containing low boilers was obtained from the top of the column. Next, the crude 1,3-butylene glycol (4) was charged into an alkali reactor D. At this time, a 10% by mass aqueous solution of caustic soda was added so that the concentration of caustic soda relative to the charged liquid was 0.2% by mass. The reaction temperature in the alkali reactor D was maintained at 120°C, and the reaction was carried out for a residence time of 20 minutes.

[0062] Next, the crude reaction liquid discharged from the alkali reactor D was charged into a dealkalizer E. In the dealkalizer E, caustic soda, high boiling point substances, and a portion of 1,3-butylene glycol were discharged from the bottom of the column (corresponding to "X-5" in FIG. 1). The amount of discharge was 10 parts per 100 parts of the charged liquid. Meanwhile, 90 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point substances was obtained from the top of the column.

[0063] When the amount charged to distillation column C was taken as 100, the total amount of discharged materials from distillation column C and dealkalization column E (discharged materials to outside the system) was 28.

[0064] Next, the crude 1,3-butylene glycol (5) was charged into product distillation column F. In product distillation column F, 10 parts of low boiling point materials and a portion of 1,3-butylene glycol were distilled from the top of the column relative to 100 parts of the charged liquid (corresponding to "X-6" in FIG. 1), and 90 parts of 1,3-butylene glycol product was obtained from the bottom of the column (corresponding to "Y" in FIG. 1).

[0065] The obtained 1,3-butylene glycol product was subjected to GC / FID analysis under the conditions described below, and the area ratio represented by the formula described below was 125. The odor test 1 score was 2, and the odor test 2 score was 1.

[0066] Example 2 A 1,3-butylene glycol product was obtained in the same manner as in Example 1, except that in distillation column C, the discharge amount was 25 parts relative to 100 parts of the charged liquid amount, and crude 1,3-butylene glycol (4) containing low boiling point substances obtained from the top of the column was 75 parts, and further, in dealkalization column E, the discharge amount was 17 parts relative to 100 parts of the charged liquid amount, and crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point substances obtained from the top of the column was 83 parts. When the amount charged to distillation column C was 100, the total amount discharged from distillation column C and dealkalization column E (discharged to outside the system) was 37.75.

[0067] The obtained 1,3-butylene glycol product was subjected to GC / FID analysis under the conditions described below, and the area ratio represented by the formula described below was 95. The odor test 1 score was 1, and the odor test 2 score was 1.

[0068] Example 3 When crude 1,3-butylene glycol (1) was obtained, 100 parts of an acetaldol solution containing 60% by mass of water (a mixed solution of 40 parts of acetaldol and 60 parts of water) was used as a raw material, and in distillation column C, the discharge amount was 25 parts relative to 100 parts of the charged liquid amount, and 75 parts of crude 1,3-butylene glycol (4) containing low boiling point substances obtained from the top of the column was obtained, and further, in dealkalization column E, the discharge amount was 17 parts relative to 100 parts of the charged liquid amount, and 83 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point substances obtained from the top of the column was obtained. Except for this, a 1,3-butylene glycol product was obtained in the same manner as in Example 1. When the amount charged to distillation column C was 100, the total amount discharged from distillation column C and dealkalization column E (discharged outside the system) was 37.75.

[0069] The obtained 1,3-butylene glycol product was subjected to GC / FID analysis under the conditions described below, and the area ratio represented by the formula described below was 81. The odor test 1 score was 1, and the odor test 2 score was 1.

[0070] Example 4 When crude 1,3-butylene glycol (1) was obtained, 100 parts of an acetaldol solution containing 60% by mass of water (a mixed solution of 40 parts of acetaldol and 60 parts of water) was used as a raw material, and in distillation column C, the discharge amount was 30 parts relative to 100 parts of the charged liquid amount, and 70 parts of crude 1,3-butylene glycol (4) containing low boiling point substances obtained from the top of the column was obtained. Furthermore, in dealkalization column E, the discharge amount was 20 parts relative to 100 parts of the charged liquid amount, and 80 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point substances obtained from the top of the column was obtained. Except for this, a 1,3-butylene glycol product was obtained in the same manner as in Example 1. When the amount charged to distillation column C was 100, the total amount discharged from distillation column C and dealkalization column E (discharged outside the system) was 44.

[0071] The obtained 1,3-butylene glycol product was subjected to GC / FID analysis under the conditions described below, and the area ratio represented by the formula described below was 57. The odor test 1 score was 1, and the odor test 2 score was 1.

[0072] Comparative Example 1 When obtaining crude 1,3-butylene glycol (1), 100 parts of an acetaldol solution containing 65% by mass of water (a mixed solution of 35 parts of acetaldol and 65 parts of water) was used as a raw material, and in distillation column C, the discharge amount was 32 parts relative to 100 parts of the charged liquid amount, and crude 1,3-butylene glycol (4) containing low boiling point materials obtained from the top of the column was 68 parts. Further, in dealkalization column E, the discharge amount was 23 parts relative to 100 parts of the charged liquid amount, and crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point materials obtained from the top of the column was 77 parts. Except for this, a 1,3-butylene glycol product was obtained in the same manner as in Example 1. When the amount charged to distillation column C was 100, the total amount discharged from distillation column C and dealkalization column E (discharged outside the system) was 47.64.

[0073] The obtained 1,3-butylene glycol product was subjected to GC / FID analysis under the conditions described below, and the area ratio represented by the formula described below was 51. The odor test 1 score was 1, and the odor test 2 score was 2.

[0074] Comparative Example 2 100 parts of an acetaldol solution containing 30% by mass of water as a raw material (a mixed solution of 30 parts of acetaldol and 70 parts of water) were charged with 10 parts of hydrogen in a liquid-phase hydrogen reduction reactor, and 15 parts of Raney nickel were added as a catalyst. Liquid-phase hydrogen reduction was carried out by maintaining the reactor at 135° C. and 300 atm. After separating the catalyst from the liquid after the reaction, the liquid was neutralized with caustic soda and the alcohol was removed to obtain crude 1,3-butylene glycol (1).

[0075] Crude 1,3-butylene glycol (1) (corresponding to "X-1" in FIG. 1) was charged into a dehydrating column A. In the dehydrating column A, water was extracted from the top of the column relative to 100 parts of the charged liquid, 15 parts of fresh water was added as reflux water, the pressure was set to 50 torr, and crude 1,3-butylene glycol (2) having a water content of 0.5% by mass or less was obtained from the bottom of the column. The water extracted from the top of the column was discharged (corresponding to "X-2" in FIG. 1).

[0076] Next, crude 1,3-butylene glycol (2) was charged into demineralizing tower B. In demineralizing tower B, salts, high boiling point substances, and a portion of 1,3-butylene glycol were discharged as evaporation residue from the bottom of the tower (corresponding to "X-3" in FIG. 1). The amount of the evaporation residue discharged was 5 parts per 100 parts of the charged liquid. Meanwhile, crude 1,3-butylene glycol (3) containing 1,3-butylene glycol, low boiling point substances, and a portion of the high boiling point substances was obtained from the top of the tower.

[0077] Next, the crude 1,3-butylene glycol (3) was charged into a high boiler removal distillation column C. In the high boiler removal distillation column C, high boilers and a portion of the 1,3-butylene glycol were discharged from the bottom of the column (corresponding to "X-4" in FIG. 1). The amount discharged was 20 parts per 100 parts of the charged liquid. Meanwhile, 80 parts of crude 1,3-butylene glycol (4) containing low boilers was obtained from the top of the column. Next, the crude 1,3-butylene glycol (4) was charged into an alkali reactor D. At this time, a 10% by mass aqueous solution of caustic soda was added so that the concentration of caustic soda relative to the charged liquid was 0.2% by mass. The reaction temperature in the alkali reactor D was maintained at 120°C, and the reaction was carried out for a residence time of 20 minutes.

[0078] Next, the crude reaction liquid discharged from the alkali reactor D was charged into a dealkalizer E. In the dealkalizer E, caustic soda, high boiling point substances, and a portion of 1,3-butylene glycol were discharged from the bottom of the column (corresponding to "X-5" in FIG. 1). The amount of discharge was 10 parts per 100 parts of the charged liquid. Meanwhile, 90 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point substances was obtained from the top of the column.

[0079] When the amount charged to distillation column C was taken as 100, the total amount of discharged materials from distillation column C and dealkalization column E (discharged materials to outside the system) was 28.

[0080] Next, the crude 1,3-butylene glycol (5) was charged into product distillation column F. In product distillation column F, 10 parts of low boiling point materials and a portion of 1,3-butylene glycol were distilled from the top of the column relative to 100 parts of the charged liquid (corresponding to "X-6" in FIG. 1), and 90 parts of 1,3-butylene glycol product was obtained from the bottom of the column (corresponding to "Y" in FIG. 1).

[0081] The obtained 1,3-butylene glycol product was subjected to GC / FID analysis under the conditions described below, and the area ratio represented by the formula described below was 132. The odor test 1 score was 3, and the odor test 2 score was 1.

[0082] Comparative Example 3 Assume that a 1,3-butylene glycol product was obtained in the same manner as in Comparative Example 2, except that 100 parts of an acetaldol solution containing 20% ​​by mass of water (a mixed solution of 80 parts of acetaldol and 20 parts of water) was used as the raw material to obtain crude 1,3-butylene glycol (1), and then GC / MS analysis was performed. The area ratio represented by the formula described below in the 1,3-butylene glycol product exceeds 132. Furthermore, since the area ratio represented by the formula described below exceeds 132, the score in odor test 1 is 3, and the score in odor test 2 is 1. This can be explained from the results of Example 1 and Comparative Example 2, in that the area ratio represented by the formula described below increases as the water content in the raw material decreases, and also in that the odor (apple odor) becomes stronger as the area ratio represented by the formula described below increases.

[0083] [Method for calculating area ratio] Area ratio = Peak X area / Area obtained by subtracting the peak area of ​​diethylene glycol dimethyl ether from the total peak area × 10 ６ Peak X area: In gas chromatography analysis under the following conditions, the area of ​​the peak having a peak top in the range of relative retention time 6.2 to 6.32 when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard, is set to 1.0.

[0084] [GC / FID Measurement Conditions] GC / FID measurements of the 1,3-butylene glycol products in the Examples and Comparative Examples were carried out under the following conditions: The analyzer used was a Shimadzu GC2010 (manufactured by Shimadzu Corporation).

[0085] GC: Gas Chromatography Analysis Conditions Analysis sample: A mixture was prepared by mixing 1 g of an 80% by mass 1,3-butylene glycol product aqueous solution with 0.01 g of diethylene glycol dimethyl ether. Injection volume: 1 μL Analysis column: TC-WAX (a column with a polyethylene glycol stationary phase, film thickness 0.25 μm x length 30 m x inner diameter 0.25 mm, manufactured by GL Sciences Inc.) Heating conditions: After holding at 100°C for 20 minutes, the temperature was raised from 100°C to 150°C at a rate of 2°C / min and held for 5 minutes. Sample introduction method: Split sample introduction method Sample introduction temperature: 250°C Split gas flow rate and carrier gas: 71.1 mL / min, helium Column gas flow rate and carrier gas: 0.91 mL / min, helium Detector and temperature: Flame ionization detector (FID), 250°C

[0086] [Identification of 1,3-butylene glycol] The peak appearing at a relative retention time of 5.15 to 5.84 was identified as 1,3-butylene glycol by performing GC / FID measurement using the same compound under the same conditions as above, and finding that the retention times matched. The analytical sample was a mixture of 1 g of the above compound and 0.01 g of an internal standard (diethylene glycol dimethyl ether).

[0087] [Odor Test 1] Odor Test 1 was conducted as a sensory evaluation in which four evaluators smelled the target samples in a room at 25° C. Specifically, (1) each of the 1,3-butylene glycol products of Examples 1 to 4 and Comparative Examples 1 and 2 was mixed with an aqueous solution containing citric acid, trisodium citrate, sodium EDTA, and phenoxyethanol so that the 1,3-butylene glycol product concentration was 20% by mass, the citric acid concentration was 0.01% by mass, the trisodium citrate concentration was 0.04% by mass, the sodium EDTA concentration was 0.25% by mass, and the phenoxyethanol concentration was 0.7% by mass. The mixture (100 ml) was then allowed to stand at 50° C. for four weeks, and the resulting mixture was placed in a wide-mouth reagent bottle (internal volume: 100 ml), sealed, and allowed to stand at room temperature for approximately 120 minutes. (2) The stopper of the wide-mouthed reagent bottle was then opened, and the bottle was transferred to a 300 ml wide-mouthed beaker, and 100 ml of pure water was added to make a total of 200 ml. The wide-mouthed beaker was stirred by shaking it by hand, and the odor was quickly smelled. (3) Each evaluator smelled the odor of each sample according to the procedures (1) and (2) above, and assigned a score based on the following evaluation, with the average score being the "odor (apple odor) test score." [Odor (apple odor) intensity] 1: No apple odor detected 2: Slight apple odor detected 3: Apple odor detected

[0088] [Odor Test 2] In Odor Test 2, similar to Odor Test 1, points were assigned based on the following evaluation, and the average value was designated as the "Odor (irritating odor) test score." [Odor (irritating odor) intensity] 1: No irritating odor detected 2: Slightly irritating odor detected

[0089] The apple odor intensity of Examples 1 to 4 and Comparative Example 1 was 1 or 2, the apple odor intensity of Comparative Example 2 was 3, and the irritating odor intensity of Examples 1 to 4 and Comparative Example 2 was 1, and the irritating odor intensity of Comparative Example 1 was 2. This confirms that, while neither apple odor nor irritating odor is detected from the 1,3-butylene glycol products of the presently disclosed invention (Examples 1 to 4), the 1,3-butylene glycol product of Comparative Example 1 has a irritating odor but no apple odor, and furthermore, the 1,3-butylene glycol product of Comparative Example 2 has an apple odor but no irritating odor.

[0090] From the above results, it became clear that even when the 1,3-butylene glycol products according to Examples 1 to 4 were blended into cosmetic compositions, they were less likely to produce apple odor and irritating odor. Furthermore, a comparison of Comparative Example 2 with Examples 1 to 4 and Comparative Example 1 revealed that the apple odor can be reduced by devising a manufacturing method for the 1,3-butylene glycol product, particularly by increasing the water content in the hydrogenated raw material to a certain extent or by increasing the amount of discharge in the high boiler removal distillation step and the dealkalization step. On the other hand, it became clear that excessive application of these conditions would result in a product, like the 1,3-butylene glycol product of Comparative Example 1, that, when blended into a cosmetic composition, would produce an odor (irritating odor) different from apple odor.

[0091] This irritating odor is thought to be an odor derived from the cosmetic composition itself. In Examples 1 to 4, a specific by-product contained in the obtained 1,3-butylene glycol product has a masking effect on the irritating odor derived from the cosmetic composition, and it is thought that the inclusion of a certain amount of this by-product suppresses the irritating odor. On the other hand, in Comparative Example 1, the amount of the above-mentioned by-product in the obtained 1,3-butylene glycol product was small, and the masking effect on the irritating odor was insufficient, which is thought to have resulted in the generation of the irritating odor.

[0092] In summary, the configuration of the present disclosure and its variations are described below. [1] A 1,3-butylene glycol product having an area ratio of 54 to 130 as shown in the following formula: Area ratio = Peak X area / Area obtained by subtracting the peak area of ​​diethylene glycol dimethyl ether from the total peak area × 10 ６Peak X area: In gas chromatography analysis under the following conditions, the area of ​​the peak having a peak top in the relative retention time range of 6.2 to 6.32, when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard substance, is set to 1.0. [Gas chromatography analysis conditions] Injected sample: a mixture of 1 g of an 80 mass % aqueous solution of 1,3-butylene glycol product and 0.01 g of diethylene glycol dimethyl ether Injection amount: 1 μL Analytical column: a column whose stationary phase is polyethylene glycol (film thickness 0.25 μm × length 30 m × inner diameter 0.25 mm) Heating conditions: after holding at 100° C. for 20 minutes, heat from 100° C. to 150° C. at 2° C. / min, and hold for 5 minutes. Sample introduction and temperature: split sample introduction method, 250°C Split gas flow rate and carrier gas: 71.1 mL / min, helium Column gas flow rate and carrier gas: 0.91 mL / min, helium Detector and temperature: flame ionization detector (FID), 250°C [2] The 1,3-butylene glycol product according to [1], wherein the area ratio is 125 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, or 30 or less. [3] The 1,3-butylene glycol product according to [1] or [2], wherein the area ratio is 55 or more, or 56 or more. [4] The 1,3-butylene glycol product according to at least one selected from [1] to [3], wherein the area ratio of the 1,3-butylene glycol peak in gas chromatography analysis under the above conditions is 99.5% or more, 99.7% or more, 99.8% or more, or 99.9% or more. [5] The 1,3-butylene glycol product according to at least one selected from [1] to [4], wherein the 1,3-butylene glycol in the 1,3-butylene glycol product is (1) a reduced product of an acetaldol, (2) a hydrolyzate of 1,3-butylene oxide, (3) a selective hydrogenolysis product of erythritol, (4) a selective water adduct of butadiene, (5) a hydrogenated product of n-butanal-3-one, (6) a hydrogenated product of 1-butanol-3-one, (7) a hydrogenated product of 3-hydroxy-1-butanoic acid, (8) a hydrogenated product of β-butyrolactone, or (9) a hydrogenated product of diketene.[6] A 1,3-butylene glycol product according to at least one selected from [1] to [5], wherein the 1,3-butylene glycol in the 1,3-butylene glycol product is a reduced form of acetaldols. [7] A 1,3-butylene glycol product according to at least one selected from [1] to [6], wherein the 1,3-butylene glycol in the 1,3-butylene glycol product is a reduced form of at least one compound selected from the group consisting of acetaldols, para-aldols, and aldoxanes. [8] A 1,3-butylene glycol product according to at least one selected from [1] to [7], wherein the 1,3-butylene glycol in the 1,3-butylene glycol product is obtained by hydrogenating a hydrogenated feedstock containing acetaldols. [9] The 1,3-butylene glycol product according to [8], wherein the content of acetaldols in the hydrogenated feedstock is 80% by mass or less, 60% by mass or less, or 50% by mass or less.

[10] The 1,3-butylene glycol product according to [8] or [9], wherein the hydrogenated raw material contains water.

[11] The 1,3-butylene glycol product according to at least one selected from [8] to

[10] , wherein the water content in the hydrogenated raw material is 10% by mass or more, 25% by mass or more, 40% by mass or more, more than 50% by mass, or 55% by mass or more.

[12] The 1,3-butylene glycol product according to

[11] , wherein the water content in the hydrogenated raw material is 80% by mass or less, 70% by mass or less, or 60% by mass or less.

[13] A moisturizer comprising the 1,3-butylene glycol product according to at least one selected from [1] to

[12] .

[14] A cosmetic composition comprising the 1,3-butylene glycol product according to at least one selected from [1] to

[12] .

[0093] A: Dehydration tower B: Demineralization tower C: High boiling point removal distillation tower D: Alkali reactor E: Dealkalization tower F: Product distillation tower A-1, B-1, C-1, E-1, F-1: Condenser A-2, C-2, F-2: Reboiler X-1: Crude 1,3-butylene glycol X-2: Water (wastewater) X-3: Salt, high boiling point materials, and part of the 1,3-butylene glycol X-4: High boiling point materials and part of the 1,3-butylene glycol X-5: Caustic soda, high boiling point materials, and part of the 1,3-butylene glycol X-6: Low boiling point materials and part of the 1,3-butylene glycol Y: 1,3-butylene glycol product

Claims

1. A 1,3-butylene glycol product whose area ratio, as shown in the following formula, is 54 or more and 130 or less. Area ratio = Peak X area / total peak area minus diethylene glycol dimethyl ether peak area × 10 ６ Peak X area: In gas chromatography analysis under the following conditions, the area of ​​the peak having a peak top in the relative retention time range of 6.2 to 6.32, when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard substance, is set to 1.

0. [Gas chromatography analysis conditions] Injected sample: a mixture of 1 g of an 80 mass % aqueous solution of 1,3-butylene glycol product and 0.01 g of diethylene glycol dimethyl ether Injection amount: 1 μL Analytical column: a column whose stationary phase is polyethylene glycol (film thickness 0.25 μm × length 30 m × inner diameter 0.25 mm) Heating conditions: after holding at 100° C. for 20 minutes, heat from 100° C. to 150° C. at 2° C. / min, and hold for 5 minutes. Sample introduction and temperature: Split sample introduction method, 250°C Split gas flow rate and carrier gas: 71.1 mL / min, helium Column gas flow rate and carrier gas: 0.91 mL / min, helium Detector and temperature: Flame ionization detector (FID), 250°C 2. The 1,3-butylene glycol product according to claim 1, wherein the 1,3-butylene glycol in the 1,3-butylene glycol product is a reduced form of at least one compound selected from the group consisting of acetaldol, paraaldol, and aldoxane.

3. A moisturizer comprising the 1,3-butylene glycol product according to claim 1 or 2.

4. A cosmetic composition comprising the 1,3-butylene glycol product according to claim 1 or 2.

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