1,3-butylene glycol composition

Abstract

Provided is a 1,3-butylene glycol composition that has good elongation and moderate wetting and spreading properties. Solution: The following formula (1) TIFF0007797733000008.tif65170 (In the formula, R1 to R9 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) A 1,3-butylene glycol composition comprising a compound represented by the formula:

Description

[Technical Field]

[0001] The present disclosure relates to 1,3-butylene glycol compositions. [Background technology]

[0002] 1,3-Butylene glycol is a colorless, transparent, odorless liquid with properties such as low volatility, low toxicity, and high hygroscopicity, and has excellent chemical stability. Therefore, its uses are diverse, including as a raw material for various synthetic resins and surfactants, as well as cosmetics, moisture absorbents, high-boiling-point solvents, and antifreeze materials. In particular, 1,3-butylene glycol has recently attracted attention for its excellent properties as a moisturizing agent, and demand for it in the cosmetics industry is expanding (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 7-258129 Summary of the Invention [Problem to be solved by the invention]

[0004] 1,3-butylene glycol used in cosmetics is required to have good "spreadability" and moderate "wet-spreadability." Spreadability refers to the property of a substance spreading smoothly over the surface of the object to which it is applied. In cosmetics, how smoothly a substance spreads on skin or hair significantly affects the product's feel and finish. Wet-spreadability refers to the property of how naturally a substance spreads over a solid surface. In cosmetics, moderately suppressed wet-spreadability is effective in preventing dripping and running off. Therefore, the object of the present disclosure is to provide a 1,3-butylene glycol composition that has good "spreadability" and moderate "wet-spreadability." [Means for solving the problem]

[0005] As a result of intensive research to achieve the above object, the inventors of the present disclosure have found that by blending a specific compound with 1,3-butylene glycol, a 1,3-butylene glycol composition having good elongation and appropriate wetting and spreading properties can be obtained. The present disclosure has been completed based on these findings.

[0006] That is, in the present disclosure, the following formula (1) [ka] (In the formula, R1 to R8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R9 represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 6 carbon atoms. However, the hydrocarbon group represented by R9 may have one or more hydrogen atoms substituted with a hydroxyl group.) The present invention provides a 1,3-butylene glycol composition comprising a compound represented by the formula:

[0007] The content of the compound represented by the above formula (1) is preferably 10 ppm by mass or more and 2% by mass or less.

[0008] The 1,3-butylene glycol composition preferably contains 1,3-butylene glycol at a content of 98% by mass or more.

[0009] The 1,3-butylene glycol composition has an expansion degree (height / base area) of 0.6×10 -1 ~2.7×10 -1 It is preferable that:

[0010] The compound represented by the above formula (1) is represented by the following formula (2): [ka] It is preferable that the compound is a compound represented by the formula:

[0011] The present disclosure also provides a moisturizer comprising a 1,3-butylene glycol composition.

[0012] The present disclosure also provides a cosmetic composition comprising the 1,3-butylene glycol composition. [Effects of the Invention]

[0013] The 1,3-butylene glycol composition of the present disclosure has good spreadability and moderate wetting and spreading properties, and is therefore suitable for use in cosmetics and moisturizers. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a flowchart of a method for producing 1,3-butylene glycol according to the present disclosure. [Figure 2] 1 is an ion chromatogram chart of m / z 129 (retention time 0 to 30 minutes) of a 1,3-butylene glycol composition in Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0015] The 1,3-butylene glycol composition 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 present disclosure. The present disclosure is not limited by the embodiments, but is limited only by the scope of the claims.

[0016] [1,3-butylene glycol composition] The 1,3-butylene glycol composition of the present disclosure contains a compound represented by the following formula (1): That is, the composition contains a compound represented by the following formula (1) and 1,3-butylene glycol. [ka]

[0017] In the formula, R1 to R8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms (preferably 1 to 3). R9 represents a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 6 carbon atoms (preferably 1 to 3). However, the hydrocarbon group represented by R9 may have one or more hydrogen atoms substituted with hydroxyl groups.

[0018] In the compound represented by the above formula (1), R1 is preferably a methyl group or an ethyl group, R2 is preferably a hydrogen atom, R3 is preferably a methyl group or an ethyl group, and R 4~8 is preferably a hydrogen atom, and R9 is preferably a hydrogen atom, a hydroxyl group, or a hydroxymethyl group.

[0019] The 1,3-butylene glycol composition exhibits good elongation and moderate wetting and spreading properties due to the inclusion of the compound represented by formula (1). Although the reason for this is not clear, the following reasons are thought to be possible.

[0020] The extensibility and wet-spreadability of 1,3-butylene glycol are thought to be related to the presence of hydrogen bonds between 1,3-butylene glycol molecules. Specifically, by blending 1,3-butylene glycol with the compound represented by formula (1), the compound inhibits hydrogen bonds between 1,3-butylene glycol molecules, resulting in good extensibility and moderate wet-spreadability. Although the reason why the compound represented by formula (1) inhibits hydrogen bonds between 1,3-butylene glycol molecules and exhibits this effect is unclear, it is thought that the hydroxyl groups of the compound form hydrogen bonds with the hydroxyl groups of 1,3-butylene glycol, thereby suppressing the formation of hydrogen bonds between 1,3-butylene glycol molecules, and the oxygen atoms forming the tetrahydropyran skeleton of the compound form hydrogen bonds with 1,3-butylene glycol. As a result, the intermolecular forces (intermolecular interactions) between 1,3-butylene glycol molecules are weakened, reducing the density of the composition and thereby exhibiting good extensibility. Furthermore, it is believed that the surface tension of the composition is reduced due to the above results, and therefore, appropriate wetting and spreading properties are exhibited.

[0021] Examples of the compound represented by the above formula (1) include the following compounds represented by (2) to (13). [ka]

[0022] The compound represented by the formula (1) may contain stereoisomers. For example, the compound represented by the formula (2) may contain stereoisomers such as r-3-hydroxymethyl-cis-2,cis-6-dimethyltetrahydropyran and r-3-hydroxymethyl-trans-2,trans-6-dimethyltetrahydropyran.

[0023] The compound represented by formula (1) can be produced by a known, commonly used method. For example, the compound represented by formula (2) can be obtained by synthesizing cis-2,6-dimethyl-3-formyl-5,6-dihydro-2H-pyran by adding water to crotonaldehyde, followed by adding hydrogen using a reducing agent such as lithium aluminum hydride (LiAlH). Specifically, it can be obtained by the method described in "Conformational Analysis. XXIV. Effect of Dipolar and Eclipsing Forces on Intramolecular Hydrogen Bonding in 3-Hydroxymethyltetrahydropyran and 5-Hydroxymethyl-1,3-dioxane," Journal of the American Chemical Society, 94, 171 (1972).

[0024] Even a very small amount of the compound represented by formula (1) can impart good elongation and moderate wettability to the 1,3-butylene glycol composition. The content of the compound represented by formula (1) relative to the 1,3-butylene glycol composition (100% by mass) is not particularly limited as long as it exceeds 0 ppm by mass. For example, it is preferably 10 ppm by mass or more, more preferably 20 ppm by mass or more, even more preferably 40 ppm by mass or more, even more preferably 60 ppm by mass or more, even more preferably 80 ppm by mass or more, even more preferably 100 ppm by mass or more, even more preferably 150 ppm by mass or more, even more preferably 200 ppm by mass or more, even more preferably 300 ppm by mass or more, even more preferably 400 ppm by mass or more, and particularly preferably 500 ppm by mass or more. Furthermore, the content of the compound represented by formula (1) relative to the 1,3-butylene glycol composition (100% by mass) is, for example, 2% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.1% by mass or less, or 0.01% by mass or less.

[0025] The degree of expansion in the 1,3-butylene glycol composition of the present disclosure is not particularly limited, but may be, for example, 0.6 × 10 -1 It is preferable that the ratio is equal to or greater than 0.8×10 -1 or more, more preferably 1.0 × 10 -1 More preferably, 1.1 × 10 -1 More preferably, 1.2 × 10 -1 That's all. For example, 2.7 × 10 -1 It is preferably equal to or less than 2.65×10 -1 or less, more preferably 2.6 × 10 -1 The degree of spreadability is as follows. When the degree of spreadability is within the above range, the 1,3-butylene glycol composition tends to exhibit appropriate wetting and spreading properties. The degree of spreadability of the 1,3-butylene glycol composition can be measured and calculated by the method explained in the "Wetting and Spreading Test" in the Examples below.

[0026] Examples of 1,3-butylene glycol used in the 1,3-butylene glycol composition 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).

[0027] Among these, 1,3-butylene glycol 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 at high temperatures to form crotonaldehyde and the like. 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 high-purity 1,3-butylene glycol, liquid-phase reduction is preferred over gas-phase reduction.

[0028] 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, 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., acetals of 1,3-butylene glycol and acetaldol). In addition, other by-products include acetals of crotonaldehyde and 1,3-butylene glycol, acetals of acetaldehyde and 1,3-butylene glycol, and acetals of acetaldol, acetaldehyde, and the hydrogenated product of acetaldehyde trimer.

[0029] These by-products may have the properties of odor-causing substances. Here, odor-causing substances are defined to include not only substances that themselves currently emit an odor, but also substances that change over time to emit an odor.

[0030] A hydrogenation raw material containing an acetaldol may be used to produce 1,3-butylene glycol. The acetaldol may be any compound that can be reduced to 1,3-butylene glycol by hydrogenation, and examples thereof include acetaldol, its cyclized dimer, para-aldol, aldoxane, a type of cyclic trimer of acetaldehyde, and mixtures thereof. The hydrogenation raw material may or may not contain water.

[0031] 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 to produce 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."

[0032] 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.

[0033] The method for producing crude 1,3-butylene glycol will be described below. In this production 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, for example, relative to 100 parts by mass of the hydrogenation raw material. The amount of hydrogen used in the reduction reaction is not particularly limited, but is preferably 0.5 to 40 parts by mass, for example, relative to 100 parts by mass of the hydrogenation raw material. The pressure (total pressure) in the reaction system in the reduction reaction is not particularly limited, but is preferably 150 to 500 atm, for example. 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, for example. The hydrogen pressure (hydrogen partial pressure) in the reaction system is not particularly limited, but is preferably 100 to 500 atm, for example. The reaction temperature in the reduction reaction is not particularly limited, but is preferably 110 to 140°C, for example. The reaction time (residence time) in the reduction reaction is not particularly limited, but is preferably 30 to 300 minutes, for example.

[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 within the above ranges, the reaction rate (hydrogenation rate) of acetaldols to 1,3-butylene glycol is improved. 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 hydrogen reduction of the hydrogenation raw material is converted into purified 1,3-butylene glycol through, for example, a dehydration step, a desalting step, a high boiler removal distillation step, an alkali reaction step, a dealkalization step, and a distillation step.

[0037] FIG. 1 is a flow sheet of an apparatus showing an example of an embodiment for obtaining the 1,3-butylene glycol composition of the present disclosure. A is a dehydrating tower and is involved in the dehydration step. B is a demineralizing tower and is involved in the demineralizing step. C is a high boiler removal distillation tower and is involved in the high boiler removal distillation step. D is an alkali reactor and is involved in the alkali reaction step. E is a dealkalizing tower and is involved in the dealkalizing step. F is a product distillation tower and is involved in 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 the 1,3-butylene glycol composition of the present disclosure will be described using this flow sheet.

[0038] Crude 1,3-butylene glycol (corresponding to "X-1") obtained by hydrogen reduction of the hydrogenated feedstock is supplied to dehydration tower A. In dehydration tower A, water is distilled from the top of the tower by distillation, and a crude 1,3-butylene glycol stream containing 1,3-butylene glycol is obtained from the bottom of the tower. The crude 1,3-butylene glycol stream is supplied to demineralization tower B. In demineralization tower B, a crude 1,3-butylene glycol stream after desalting is obtained from the top of the tower by distillation, and salts, high boiling point substances, etc. are discharged from the bottom of the tower.

[0039] The desalted crude 1,3-butylene glycol stream is supplied to a high boiler removal distillation column C. In the high boiler removal distillation column C, high boilers (and 1,3-butylene glycol containing them) are discharged from the bottom of the column. Meanwhile, a crude 1,3-butylene glycol stream after the high boilers have been removed 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, for example, 10 to 50 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, for example, 50 to 90 parts per 100 parts of the charged liquid.

[0040] The crude 1,3-butylene glycol distilled in the high boiler removal distillation column C is supplied to an alkaline reactor (for example, a tubular flow reactor) D and treated with a base. In the alkaline reactor D or upstream thereof, a base is added in an amount of, for example, 0.05 to 10% by mass with respect to the crude 1,3-butylene glycol stream after the high boiler removal.

[0041] 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 composition, caustic soda and caustic potash are preferred. The base may be added as a solid as is, but is preferably added as 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.

[0042] The reaction temperature in the alkali reactor D is not particularly limited, but is preferably, for example, 90 to 140°C. If the reaction temperature is lower than 90°C, a long reaction residence time is required, which tends to increase the reactor capacity and be uneconomical. If the reaction temperature exceeds 140°C, the coloration of the finally obtained 1,3-butylene glycol composition tends to increase. The reaction residence time is, for example, 5 to 120 minutes.

[0043] 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), etc. 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, etc. discharged from the bottom of the column is preferably 5 to 40 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 60 to 95 parts per 100 parts of the charged liquid.

[0044] In the evaporator used in the dealkalizer E, evaporation is carried out at the top of the column under a reduced pressure of, for example, 100 torr or less. 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.

[0045] Examples of product distillation column F include perforated plate columns and bubble cap columns. However, a packed column with low pressure drop, 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 cause coloration, and therefore the distillation temperature must be low. 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 fluid, such as a gravity-flow thin-film evaporator or a forced-agitation thin-film evaporator.

[0046] 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. 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 at the top of the column. The reflux ratio is preferably, for example, 0.5 to 2.0.

[0047] 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 purified 1,3-butylene glycol is obtained from the bottom of product distillation column F (corresponding to "Y").

[0048] The content of 1,3-butylene glycol in the 1,3-butylene glycol composition (100% by mass) is not particularly limited, and may be, for example, 98% by mass or more, 98.5% by mass or more, 99% by mass or more, 99.3% by mass or more, 99.5% by mass or more, 99.6% by mass or more, 99.7% by mass or more, 99.8% by mass or more, 99.9% by mass or more, 99.95% by mass or more, or 99.99% by mass or more. Alternatively, it may be, for example, less than 100% by mass.

[0049] In the 1,3-butylene glycol composition of the present disclosure, the area ratio of the 1,3-butylene glycol peak in gas chromatography analysis 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. The gas chromatography analysis is performed using the method described in the Examples below. The "area ratio of the 1,3-butylene glycol peak" refers to the ratio of the area of ​​a specific peak to the sum of the areas of all peaks appearing in the chart. However, when an internal standard (e.g., diethylene glycol dimethyl ether) is used, the peak area derived from the internal standard is excluded from the calculation. Furthermore, "all peaks" refers to, for example, all peaks that appear when the analysis is continued until the relative retention time reaches 6.4, assuming that the relative retention time of the peak of diethylene glycol dimethyl ether as the internal standard is 1.0, and then stopped.

[0050] The 1,3-butylene glycol composition of the present disclosure can be produced, for example, by mixing the compound represented by the above formula (1) with 1,3-butylene glycol by a conventional method.

[0051] [Moisturizers and cosmetics] The moisturizing agent of the present disclosure contains the 1,3-butylene glycol composition. Therefore, it has excellent moisturizing properties, 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 composition, such as moisturizing agent components other than the 1,3-butylene glycol composition. The content of the 1,3-butylene glycol composition in the moisturizing agent of the present disclosure 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. The moisturizing agent may be composed solely of the 1,3-butylene glycol composition.

[0052] The cosmetic preparation of the present disclosure contains the moisturizing agent. The amount of the 1,3-butylene glycol composition in the cosmetic preparation of the present disclosure may be any amount that can exhibit moisturizing properties, depending on the type and form of the cosmetic. The amount of the 1,3-butylene glycol composition 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 composition, 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, UV absorbers, UV 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. [Example]

[0057] The present disclosure will be explained in more detail below with reference to examples.

[0058] The 1,3-butylene glycol compositions of Examples 1 to 5 and Comparative Example 1 were prepared by mixing 1,3-butylene glycol and the compound represented by formula (2) so that the content (ppm by mass) of the compound represented by formula (2) was as shown in Table 1.

[0059] The 1,3-butylene glycol used was product code B3770 from Tokyo Chemical Industry Co., Ltd. The compound represented by formula (2) was synthesized by the method described in "Conformational Analysis. XXIV. Effect of Dipolar and Eclipsing Forces on Intramolecular Hydrogen Bonding in 3-Hydroxymethyltetrahydropyran and 5-Hydroxymethyl-1,3-dioxane," Journal of the American Chemical Society, 94, 171 (1972), and is a mixture of r-3-hydroxymethyl-cis-2,cis-6-dimethyltetrahydropyran (CHEM1) and r-3-hydroxymethyl-trans-2,trans-6-dimethyltetrahydropyran (CHEM2).

[0060] Prior to the main experiments (i.e., Examples 1 to 5 and Comparative Example 1), a preliminary experiment was conducted to determine an appropriate blending ratio of 1,3-butylene glycol and the compound represented by formula (2). In the preliminary experiment, even when a small amount (approximately 0.1% by mass) of the compound represented by formula (2) was blended with 1,3-butylene glycol, good results were obtained in the elongation test and the wet spread test described below. Therefore, in Examples 1 to 5 and Comparative Example 1, 1,3-butylene glycol compositions containing only a very small amount of the compound represented by formula (2) were prepared to confirm whether similar effects could be obtained.

[0061] In order to accurately determine the content of the compound represented by formula (2) in the 1,3-butylene glycol compositions of the Examples and Comparative Examples, gas chromatography analysis was performed to measure the peak area of ​​the compound. Next, a calibration curve was created based on the peak areas of the compound at known concentrations measured separately. The peak areas obtained in the Examples and Comparative Examples were converted against the calibration curve to determine the content (concentration) of the compound. This is explained in detail below.

[0062] [Concentration analysis of the compound represented by formula (2)] The concentration (content) of the compound represented by formula (2) contained in the 1,3-butylene glycol composition was confirmed by gas chromatography analysis under the following conditions.

[0063] GC: Gas chromatography analysis conditions Analytical sample: 0.8 g of the 1,3-butylene glycol composition, 0.2 g of water, and 0.01 g of diethylene glycol dimethyl ether were mixed to prepare an analytical sample. Diethylene glycol dimethyl ether was used as an internal standard. Analyzer: Agilent 7890A / 5975C Analytical column: Agilent J&W GC column - HP-1MS (column with a stationary phase of dimethylpolysiloxane, film thickness 1.0 μm × length 30 m × inner diameter 0.25 mm, manufactured by Agilent Technologies, Inc.) Temperature increase conditions: Increase temperature from 80°C to 120°C at 5°C / min, then increase temperature to 160°C at 2°C / min and hold for 2 minutes. Further increase temperature to 230°C at 10°C / min and hold at 230°C for 18 minutes. Sample introduction and temperature: Split sample introduction method (1.0 μL), 250°C Initial pressure at injection port: 15.3 psi Control mode: Constant flow (average linear velocity: 24.7 cm / sec) Split ratio: 20 Carrier gas: Helium Column gas flow rate: 1 mL / min, helium Total flow: 24mL / min MS: Mass spectrometry conditions Ionization method: EI method Ionization voltage and current: 70 eV, 35 μA Ion source temperature: 230℃ Quadrupole temperature: 150℃ Interface temperature: 250℃ Measurement mode: Scan mode Scan mass range: m / z 29-550

[0064] When the relative retention time of the peak of the internal standard (diethylene glycol dimethyl ether) was set to 1.0, the relative retention time of the peak of 1,3-butylene glycol was 0.70 to 0.90 (extracted ion chromatogram m / z 72), the relative retention time of the peak of CHEM1 was 1.8 to 1.9 (extracted ion chromatogram m / z 129), and the relative retention time of the peak of CHEM2 was 1.9 to 2.0 (extracted ion chromatogram m / z 129). Figure 2 shows the m / z 129 ion chromatogram chart (retention time 0 to 30 minutes) for Example 3.

[0065] The area of ​​the compound represented by formula (2) was determined as the sum of the peak areas of CHEM1 and CHEM2 obtained. To calculate the concentration of the compound represented by formula (2) in the 1,3-butylene glycol composition, multiple standard solutions of known concentrations of the compound represented by formula (2) were prepared, and a calibration curve was created based on the peak areas of each. Using the created calibration curve, the concentration of the compound represented by formula (2) in the 1,3-butylene glycol composition was calculated from the area of ​​the compound represented by formula (2). The peak area at m / z 129 in the extracted ion chromatogram was used to calculate the concentration of the compound represented by formula (2).

[0066] [1,3-butylene glycol concentration analysis] The content (area ratio) of 1,3-butylene glycol contained in the 1,3-butylene glycol composition was confirmed by carrying out gas chromatography analysis (GC / FID) under the following conditions. As a result, the area ratio of 1,3-butylene glycol in Examples 1 to 5 and Comparative Example 1 was 99.9% or more. When the relative retention time of the peak of diethylene glycol dimethyl ether used as the internal standard was set to 1.0, all peaks that appeared when the analysis was continued until the relative retention time reached 6.4 and then stopped were summed, and the ratio of the peak area of ​​1,3-butylene glycol to that total was defined as the area ratio. (Gas chromatographic analysis conditions) Analytical column: Column with a stationary phase of dimethylpolysiloxane (film thickness 1.0 μm × length 30 m × inner diameter 0.25 mm) Temperature increase conditions: Increase temperature from 80°C to 120°C at 5°C / min, then increase temperature to 160°C at 2°C / min and hold for 2 minutes. Further increase temperature to 230°C at 10°C / min and hold at 230°C for 18 minutes. Sample introduction temperature: 250℃ Carrier gas: Helium Column gas flow rate: 1 mL / min Detector and detection temperature: Hydrogen flame ionization detector (FID), 280°C

[0067] [Elongation test] Four panelists conducted a spread test on the 1,3-butylene glycol compositions of the Examples and Comparative Examples. Each panelist took 0.5 g of each composition and gently rubbed it into their hands for one minute, after which they rated the spread on a five-point scale. Based on the average score, the results were classified into the following four categories. The results are shown in the "Spread Test" column of Table 1. Very good: 5.0 or less, 4.0 or more Good: Less than 4.0, 3.0 or more Poor: Less than 3.0, 2.0 or more Very poor: Less than 2.0, 1.0 or more

[0068] [Wetting and spreading test] Approximately 0.09 g of each of the 1,3-butylene glycol compositions of the Examples and Comparative Examples was dropped onto a 1 x 1 mm square test paper and allowed to stand for 30 seconds. The actual amounts dropped were 0.095 g for Comparative Example 1, 0.0902 g for Example 1, 0.0897 g for Example 2, 0.0762 g for Example 3, 0.0856 g for Example 4, and 0.0987 g for Example 5. The base area (cm) of the droplet of the 1,3-butylene glycol composition after standing was 2 ) was measured.

[0069] The weight (g) of the 1,3-butylene glycol composition was calculated based on the specific gravity (1.0053 g / cm 3 ) to calculate the volume, and then divide by the square of the base area to calculate the degree of expansion. That is, the degree of expansion was calculated using the following formula. The results are shown in the "Wet Spreading Test" column in Table 1. Expansion degree = ([weight (g) of 1,3-butylene glycol composition] / [specific gravity (g / cm 3 )]) / ([Base area (g / cm 2 )]^2)

[0070] [Table 1] [Explanation of symbols]

[0071] A: Dehydration tower B: Desalination tower C: High boiler removal distillation column D: Alkaline reactor E: Dealkalization tower F: Product distillation column 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 (drainage) X-3: Salt, high boiling point substances, and some 1,3-butylene glycol X-4: High boiling point substances and part of 1,3-butylene glycol X-5: Caustic soda, high boiling point substances, and some 1,3-butylene glycol X-6: Low boiling point substances and part of 1,3-butylene glycol Y: 1,3-butylene glycol

Claims

1. The following formulas (2) to (13) 【Chemistry 1】 and The content of the compound is 10 ppm by mass or more and 2% by mass or less, A 1,3-butylene glycol composition having a 1,3-butylene glycol content of 98% by mass or more.

2. The following formula (2) 【Chemistry 2】 The compound includes a compound represented by The content of the compound is 10 ppm by mass or more and 2% by mass or less, A 1,3-butylene glycol composition having a 1,3-butylene glycol content of 98% by mass or more.

3. Expansion degree (height / base area) is 0.6 x 10 －１ ~2.7 x 10 －１ 3. The 1,3-butylene glycol composition according to claim 1 or 2,

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

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

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