1, 3-butanediol product

Abstract

Provided is a high-purity 1, 3-butanediol product which is colorless and odorless, is not susceptible to discoloration over time, and is not susceptible to an increase in acid concentration over time even in a water-containing state. Provided is a 1, 3-butanediol product in which, when the relative retention time of the peak of 1, 3-butanediol is 1.0, the area ratio of peaks appearing within the range of 1.6-1.8 of the relative retention time is 2000 ppm or less in a gas chromatography analysis under specific conditions.

Description

[0001] This application is a divisional application of an application with a filing date of September 3, 2020, application number 202080062393.2, and invention name “1,3-Butanediol Products”. Technical Field

[0002] The present disclosure relates to a 1,3-butanediol product. This application claims priority to Japanese Patent Application Nos. 2019-162351 and 2019-162352 filed in Japan on September 5, 2019, and Japanese Patent Application No. 2020-001084 filed in Japan on January 7, 2020, and the contents thereof are incorporated herein by reference. Background Art

[0003] 1,3-Butanediol is a colorless, transparent, odorless liquid with low volatility, low toxicity, high hygroscopicity, and excellent chemical stability. Therefore, the uses of 1,3-Butanediol include raw materials for various synthetic resins and surfactants, as well as cosmetics, hygroscopic agents, high-boiling point solvents, and raw materials for antifreeze. In recent years, 1,3-Butanediol has attracted much attention for its excellent properties as a moisturizer, which has expanded its demand in the cosmetics industry.

[0004] 1,3-Butanediol obtained by conventional production methods may have an odor due to the influence of by-products. In addition, even if the product is transparent immediately after production, it may be colored over time, which becomes a problem during long-term storage.

[0005] When using cosmetics and storing them after use, the cosmetics are exposed to air. In addition, when manufacturing cosmetics, the work is usually carried out in an air atmosphere, and sometimes heating is used for the purpose of sterilization. When 1,3-butanediol obtained by the existing method is used in cosmetics, coloring may occur due to the presence of air and the influence of heating.

[0006] In addition, 1,3-butanediol obtained by the conventional production method has a problem that the acid concentration (acidity) increases when it is in a water-containing state for a long time. The reason for the increase in acid concentration is not clear, but it is believed to be related to by-products contained in crude 1,3-butanediol.

[0007] Cosmetics usually contain water, and it takes a long time from the time of manufacture to the time of actual use by ordinary consumers. In addition, for cosmetics, the liquid properties are strictly adjusted from the perspective of storage stability. When 1,3-butylene glycol obtained by the existing method is used in cosmetics, the liquid balance of the cosmetics is lost due to the increase in acid concentration, and it is likely to lose the effect that should be exerted. In addition, due to the increase in acid concentration, the user's skin may become rough, etc. In addition, even cosmetics that do not contain water may sometimes increase their acid concentration due to moisture absorption during use and storage.

[0008] In order to solve such a problem, it is required to remove by-products from crude 1,3-butanediol and purify 1,3-butanediol.

[0009] As a method for obtaining high-purity 1,3-butanediol, a method has been proposed in which caustic soda is added to crude 1,3-butanediol obtained by hydrogen reduction of butanol aldehydes and distilled. In addition, a method has been proposed in which an alkali metal base is added to crude 1,3-butanediol from which high-boiling substances have been removed and heat-treated, 1,3-butanediol is distilled off, and the alkali metal compound and high-boiling substances are separated as a residue, and then low-boiling substances are removed by distillation from the 1,3-butanediol fraction (Patent Documents 1 to 6). In this way, various methods for purifying 1,3-butanediol have been proposed in order to obtain high-purity 1,3-butanediol.

[0010] Prior art literature

[0011] Patent Literature

[0012] Patent Document 1: Japanese Patent Application Laid-Open No. 7-258129

[0013] Patent Document 2: International Publication No. 00 / 07969

[0014] Patent Document 3: Japanese Patent Application Publication No. 2001-213822

[0015] Patent Document 4: Japanese Patent Application Publication No. 2001-213824

[0016] Patent Document 5: Japanese Patent Application Publication No. 2001-213825

[0017] Patent Document 6: Japanese Patent Application Publication No. 2001-213828 Summary of the invention

[0018] Problem that the invention aims to solve

[0019] However, the 1,3-butanediol products obtained by these purification methods still have the following problems: they contain by-products and have odors. In addition, there is the problem that coloration occurs over time. In addition, there is the problem that the acid concentration increases over time if water is contained.

[0020] Therefore, an object of the present disclosure is to provide a high-purity 1,3-butanediol product which is colorless and odorless, is unlikely to be colored over time, and is unlikely to have an acid concentration increase over time even in a water-containing state.

[0021] Technical Solution

[0022] The inventors of the present disclosure have repeatedly conducted research to achieve the above-mentioned purpose, and as a result, they have found that one of the reasons for the increase in the acid concentration of the 1,3-butanediol product obtained by the existing production method is that the byproducts contained in the 1,3-butanediol product are hydrolyzed in the presence of water to produce organic acids (such as acetic acid). It is also found that by improving the production method of crude 1,3-butanediol, a colorless and odorless 1,3-butanediol product that is not easily colored by time and is not easily increased in acid concentration by time even in a water-containing state can be obtained. The present disclosure is completed based on these findings.

[0023] That is, in the present disclosure, a 1,3-butanediol product is provided, which, in a gas chromatography analysis under the following conditions,

[0024] When the relative retention time of the peak of 1,3-butanediol is defined as 1.0, the area ratio of the peak appearing in the range of relative retention times of 1.6 to 1.8 is 2000 ppm or less.

[0025] (Conditions for gas chromatography analysis)

[0026] Analytical column: a column with dimethylpolysiloxane as the stationary phase (film thickness 1.0 μm×length 30 m×inner diameter 0.25 mm).

[0027] Heating conditions: After heating from 80°C to 120°C at 5°C / min, heating to 160°C at 2°C / min and maintaining for 2 minutes, heating to 230°C at 10°C / min and maintaining at 230°C for 18 minutes.

[0028] Sample introduction temperature: 250°C.

[0029] Carrier gas: Helium.

[0030] Column gas flow rate: 1 mL / min.

[0031] Detector and detection temperature: hydrogen flame ionization detector (FID), 280°C.

[0032] In the above-mentioned 1,3-butanediol product, it is preferred that the area ratio of the peak appearing in the range of relative retention time 2.3 to 2.4 is 1000 ppm or less.

[0033] In the 1,3-butanediol product, it is preferred that the area ratio of the peak appearing in the range of relative retention time 1.35 to 1.45 is 100 ppm or less.

[0034] The 1,3-butanediol product preferably has an APHA of 60 or less after being kept at 180° C. for 3 hours in an air atmosphere.

[0035] In the 1,3-butanediol product, it is preferred that the acid concentration (calculated as acetic acid) of a 90 wt % aqueous solution after being kept at 100° C. for one week be 0.002 wt % or less.

[0036] Preferably, the 1,3-butanediol in the 1,3-butanediol product is a reduced form of at least one compound selected from the group consisting of butanol, paraldol and aldoxane.

[0037] Furthermore, in the present disclosure, a moisturizer comprising a 1,3-butylene glycol preparation is also provided.

[0038] In addition, the present disclosure also provides a cosmetic comprising the moisturizing agent.

[0039] Effects of the Invention

[0040] The 1,3-butanediol product of the present disclosure is colorless and odorless, is unlikely to be colored over time, and is unlikely to have an increase in acid concentration over time even in a water-containing state, and is therefore preferably used in cosmetics, moisturizers, and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a flow chart of a method for producing a 1,3-butanediol product (purification method) related to the present disclosure.

[0042] Figure 2 This is a spectrum of the 1,3-butanediol product in Example 1 analyzed by gas chromatography.

[0043] Figure 3 This is a spectrum of the 1,3-butanediol product in Comparative Example 1 analyzed by gas chromatography. DETAILED DESCRIPTION

[0044] [1,3-Butanediol products]

[0045] The first embodiment of the 1,3-butanediol product disclosed herein is characterized in that, in the gas chromatography analysis under the following conditions, when the relative retention time of the peak of 1,3-butanediol is set to 1.0, the area ratio of the peak appearing in the range of relative retention time 1.6 to 1.8 is 2000 ppm or less. The second embodiment of the 1,3-butanediol product disclosed herein is characterized in that, in the gas chromatography analysis under the following conditions, when the relative retention time of the peak of 1,3-butanediol is set to 1.0, the area ratio of the peak appearing in the range of relative retention time 2.3 to 2.4 is 1000 ppm or less, and the area ratio of the peak appearing in the range of relative retention time 1.35 to 1.45 is 100 ppm or less. In combination with the first embodiment and the second embodiment of the 1,3-butanediol product disclosed herein, there is a case referred to as "the 1,3-butanediol product disclosed herein" hereinafter.

[0046] (Conditions for gas chromatography analysis)

[0047] Analytical column: a column with dimethylpolysiloxane as the stationary phase (film thickness 1.0 μm×length 30 m×inner diameter 0.25 mm).

[0048] Heating conditions: After heating from 80°C to 120°C at 5°C / min, heating to 160°C at 2°C / min and maintaining for 2 minutes, heating to 230°C at 10°C / min and maintaining at 230°C for 18 minutes.

[0049] Sample introduction temperature: 250°C.

[0050] Carrier gas: Helium.

[0051] Column gas flow rate: 1 mL / min.

[0052] Detector and detection temperature: hydrogen flame ionization detector (FID), 280°C.

[0053] It should be noted that in the present disclosure, the "area ratio" of a peak refers to the ratio of the area of ​​a specific peak that appears in the spectrum to the sum of the areas of all peaks. In addition, all peaks refer to, for example, all peaks that appear when the relative retention time of the peak of 1,3-butanediol is set to 1.0 and the analysis is continued until the relative retention time reaches 7.8 and then stopped. When the area ratio of the above peak is within the above range, there is a tendency to reduce the generation of odor and reduce coloration caused by time.

[0054] In the 1,3-butanediol product disclosed herein, when the relative retention time of the peak of 1,3-butanediol in the gas chromatography analysis under the above conditions is set to 1.0, the area ratio of the peak appearing in the range of relative retention time 1.6 to 1.8 is, for example, preferably 2000 ppm or less, more preferably 1000 ppm or less, further preferably 600 ppm or less, further preferably 400 ppm or less, and particularly preferably 200 ppm or less. When the area ratio of the above peak is within the above range, there is a tendency to reduce the generation of odor and reduce coloration caused by time. The lower limit of the above area ratio may be, for example, 10 ppm, 20 ppm, 50 ppm, or 100 ppm.

[0055] In the gas chromatography analysis under the above conditions, the component corresponding to the peak that appears in the range of relative retention time 1.6 to 1.8 when the relative retention time of the peak of 1,3-butanediol is set to 1.0 has not yet been fully clarified, but its main component is believed to be the hydride of the trimer of the raw material (acetaldehyde). That is, for the 1,3-butanediol product disclosed in the present invention, it is preferred that the content of by-products such as the hydride is small.

[0056] In the 1,3-butanediol product of the present disclosure, when the relative retention time of the peak of 1,3-butanediol in the gas chromatography analysis under the above conditions is set to 1.0, the area ratio of the peak appearing in the range of relative retention times of 2.3 to 2.4 is, for example, preferably 1000 ppm or less, more preferably 500 ppm or less, further preferably 250 ppm or less, further preferably 200 ppm or less, further preferably 150 ppm or less, further preferably 100 ppm or less, particularly preferably 50 ppm or less, and most preferably 20 ppm or less.

[0057] In the gas chromatography analysis under the above conditions, as a component corresponding to the peak that appears in the range of relative retention time 2.3 to 2.4 when the relative retention time of the peak of 1,3-butanediol is set to 1.0, for example, acetals of 1,3-butanediol and butanol aldehyde can be listed. The acetal is a by-product having a higher boiling point than 1,3-butanediol. That is, for the 1,3-butanediol product disclosed in the present invention, it is preferred that the content of the acetal as a by-product is small.

[0058] In the 1,3-butanediol product of the present disclosure, when the relative retention time of the peak of 1,3-butanediol in the gas chromatography analysis under the above conditions is set to 1.0, the area ratio of the peak appearing in the range of relative retention time 1.35 to 1.45 is, for example, preferably 100 ppm or less, more preferably 50 ppm or less, further preferably 20 ppm or less, and particularly preferably 10 ppm or less. When the area ratio of the peak is within the above range, there is a tendency that the generation of odor is reduced and the increase in acid concentration due to time in the water-containing state is reduced.

[0059] As a component corresponding to the peak that appears in the range of relative retention time 1.35 to 1.45 when the relative retention time of the peak of 1,3-butanediol is set to 1.0, for example, esters of acetic acid and 1,3-butanediol can be cited. That is, for the 1,3-butanediol product of the present disclosure, it is preferred that the content of the ester as a by-product is small.

[0060] In the 1,3-butanediol product of the present disclosure, the area ratio of the peak of 1,3-butanediol in the gas chromatography analysis under the above conditions is, for example, preferably 99.5% or more, more preferably 99.7% or more, further preferably 99.8% or more, and particularly preferably 99.9% or more. When the area ratio of the peak is within the above range, there is a tendency that the generation of odor is reduced, the coloration caused by time is reduced, and the increase in acid concentration caused by time in the water-containing state is reduced.

[0061] The 1,3-butanediol product disclosed herein has a Hazen color (APHA) after being kept at 180°C for 3 hours in an air atmosphere, but is not particularly limited, and is, for example, preferably 60 or less, more preferably 40 or less, and further preferably 30 or less. In addition, the APHA after being kept at 100°C for 75 days in an air atmosphere is not particularly limited, but is preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. The lower limit of any of the above APHAs may be, for example, 1, 3, 5, or 10.

[0062] The APHA of the 1,3-butanediol product disclosed herein (APHA of the 1,3-butanediol product not stored at high temperature) is not particularly limited, but is, for example, preferably 20 or less, more preferably 10 or less, and even more preferably 5 or less. The lower limit of the APHA may be 1 or 2.

[0063] The APHA ratio of the APHA after holding at 180°C for 3 hours to the APHA before holding [(APHA after holding at 180°C for 3 hours) / (APHA before holding)] of the 1,3-butanediol product of the present disclosure is not particularly limited, but is preferably 15 or less, more preferably 12 or less. The above ratio only needs to be 1 or more, and may be 2 or more, or 5 or more.

[0064] Regarding the APHA of the 1,3-butanediol product of the present disclosure, the ratio of the APHA after being kept at 100°C for 75 days to the APHA before being kept [(APHA after being kept at 100°C for 75 days) / (APHA before being kept)] is not particularly limited, but is preferably 10 or less, and more preferably 7 or less. In addition, the above ratio only needs to be 1 or more, and may be 2 or more.

[0065] In the 1,3-butanediol product disclosed herein, the acid concentration (converted into acetic acid) of a 90 wt % aqueous solution after being kept at 100° C. for 1 week is not particularly limited, but, for example, is preferably 0.002 wt % or less, more preferably 0.0015 wt % or less, further preferably 0.001 wt % or less, and particularly preferably 0.0005 wt % or less. The lower limit of the above acid concentration may be, for example, 0.00005 wt % or 0.0001 wt %. It should be noted that the 90 wt % aqueous solution refers to an aqueous solution prepared by mixing a 1,3-butanediol product with water (e.g., pure water) and adjusting the 1,3-butanediol product to 90 wt %. In addition, in the 1,3-butanediol product disclosed herein (before being kept at 100° C. for 1 week), the acid concentration (converted into acetic acid) of the 90 wt % aqueous solution is preferably within the above range.

[0066] Regarding the acid concentration (in terms of acetic acid) of a 90 wt% aqueous solution of the 1,3-butanediol product of the present invention, the ratio of the acid concentration after being kept at 100°C for one week to the acid concentration before being kept [(acid concentration after being kept at 100°C for one week) / (acid concentration before being kept)×100(%)] is not particularly limited, but is preferably 200% or less, more preferably 150% or less, and even more preferably 120% or less.

[0067] For example, the 1,3-butanediol in the 1,3-butanediol product of the present disclosure includes: (1) a reduced form of butanol aldehydes; (2) a hydrolyzate of 1,3-butylene oxide; (3) a selective hydrogenation cracking product of erythritol; (4) a selective water addition product of butadiene; (5) a hydride of n-butyraldehyde-3-one; (6) a hydride of 1-butanol-3-one; (7) a hydride of 3-hydroxy-1-butyric acid; (8) a hydride of β-butyrolactone; and (9) a hydride of diketene. It should be noted that the 1,3-butanediol of the present disclosure may be one or a mixture of two or more of the above (1) to (9).

[0068] The 1,3-butanediol in the 1,3-butanediol product disclosed herein is preferably a reduced form of (1) butanol aldehydes. In addition, as a reduced form of butanol aldehydes, from the viewpoint of the yield of 1,3-butanediol, it is preferably a liquid phase reduced form of butanol aldehydes. The reason is that butanol aldehydes have a high boiling point, and butanol aldehydes are thermally unstable, and are easily dehydrated at high temperatures to become crotonaldehyde, etc., and, in the dehydration reaction and reduction reaction (hydrogenation reaction) at high temperatures, the reaction rate of the former is fast. That is, in the case of gas phase reduction of butanol aldehydes, it is necessary to set the reaction system to a high temperature, but if a high temperature is applied to butanol aldehydes, a dehydration reaction occurs to produce crotonaldehyde, etc., and by-products such as butanol are produced by the subsequent reduction reaction. Therefore, the yield of the target 1,3-butanediol is relatively reduced. Therefore, in order to obtain a high-purity 1,3-butanediol product, liquid phase reduction is more preferably performed than gas phase reduction. Here, 1,3-butanediol as a reduced product of butanol aldehydes can be referred to as 1,3-butanediol obtained by a method of hydrogen reduction of butanol aldehydes. Similarly, 1,3-butanediol as a liquid phase reduced product of butanol aldehydes can be referred to as 1,3-butanediol obtained by a method of hydrogen reduction of butanol aldehydes in a liquid phase. In addition, 1,3-butanediol as a hydrolyzate of 1,3-butylene oxide can be referred to as 1,3-butanediol obtained by hydrolyzing 1,3-butylene oxide.

[0069] Generally, when 1,3-butanediol is produced, byproducts are generated during its production process. For example, when 1,3-butanediol is produced by hydrogen reduction of butanol aldehydes, low-boiling substances (low-boiling compounds) having unsaturated bonds such as acetaldehyde, butyraldehyde, crotonaldehyde, acetone, and methyl vinyl ketone, their condensates (e.g., trimers of acetaldehyde), hydrides of the condensates, condensates of 1,3-butanediol and the above-mentioned low-boiling substances (e.g., acetals of 1,3-butanediol and butanol aldehydes), etc. are produced as byproducts.

[0070] In addition, the following substances are produced as by-products: acetal of crotonaldehyde and 1,3-butanediol, acetal of acetaldehyde and 1,3-butanediol, acetal of butanolaldehyde or acetaldehyde and a hydrogenated product of a trimer of acetaldehyde, and the like.

[0071] In addition, other substances are also produced as by-products: acetic acid contained as an impurity in the butanol aldehydes as a raw material, and a condensate of acetic acid and 1,3-butanediol (ester of acetic acid and 1,3-butanediol) used for neutralization of caustic soda used in the production of butanol aldehydes.

[0072] Furthermore, these by-products have properties of being substances that cause coloration, substances that cause odor, and substances that cause acidity.

[0073] As for the above-mentioned acetal body, it is uncertain whether it is a substance that causes coloration, a substance that causes odor, or a substance that causes acidity. It is also believed that it has all the properties, but it is believed that it strongly has the properties of a substance that causes odor. Specifically, although the possibility that the above-mentioned acetal body itself is a substance that causes odor is low, it may produce a substance that causes odor due to changes over time and heating. In addition, the above-mentioned acetal body produces butanol aldehyde due to hydrolysis, but this is a substance that causes odor and also has an oxidation (coloration) promoting effect, so it can also be said to be a substance that causes coloration. Here, the substance that causes coloration is defined as: not only includes substances that currently have hue themselves, but also includes the following substances: substances that change over time to have hue. The substance that causes odor is defined as: not only includes substances that currently emit odor themselves, but also includes the following substances: substances that change over time to emit odor. The substance that causes acidity is defined as: a substance whose acid concentration increases over time when it contains water.

[0074] It is not clear whether the ester is a substance that causes coloration, a substance that causes odor, or a substance that causes acidity, and it is believed that it has all the properties, but it is believed that it strongly has both properties of a substance that causes odor and a substance that causes acidity. This is because when the ester is hydrolyzed by water, acetic acid is generated.

[0075] It should be noted that, in the case of producing 1,3-butanediol, the by-products in the production process thereof are believed to include, in addition to the above-mentioned acetal and ester, various by-products corresponding to substances causing coloration, substances causing odor, or substances causing acidity. For example, it is believed that the above-mentioned hydrogenated product of the trimer of acetaldehyde may correspond to any of the substances causing coloration, substances causing odor, and substances causing acidity.

[0076] Therefore, the following 1,3-butanediol product is characterized in that it is colorless and odorless, is not easily colored by time, and is not easily increased in acid concentration by time even in a water-containing state, and in which the hydrogenated product of the trimer of acetaldehyde, which is considered to be a component corresponding to the peak appearing in the range of relative retention time 1.6 to 1.8 when the relative retention time of the peak of 1,3-butanediol is set to 1.0, is reduced to a certain extent (for example, the area ratio of the peak is 2000 ppm or less). In addition, the following 1,3-butanediol product also has the same characteristics, wherein the acetal body, which is considered to be one of the components of the peak appearing in the range of relative retention time 2.3 to 2.4 when the relative retention time of the peak of 1,3-butanediol is set to 1.0, and the ester body, which is considered to be one of the components of the peak appearing in the range of relative retention time 1.35 to 1.45, is reduced to a certain extent (for example, the area ratio of the former peak is 1000 ppm or less, and the area ratio of the latter peak is 100 ppm or less). Furthermore, the 1,3-butanediol product in which the hydrogenated product of the trimer of acetaldehyde, the acetal form, and the ester form are all reduced strongly has the above-mentioned characteristics.

[0077] Even if existing purification methods such as distillation are used, these by-products are difficult to completely remove. It is believed that the reason is that in the purification step of crude 1,3-butanediol, crude 1,3-butanediol is subjected to high temperature conditions and alkaline treatment, thereby generating new by-products. For such reasons, as described above, the 1,3-butanediol products of Patent Documents 1 to 6 contain a large amount of by-products, and thus have an odor, coloration caused by time, and an increase in acid concentration caused by time in a water-containing state. Therefore, in order to obtain a high-purity 1,3-butanediol product, it is not sufficient to only improve the method for purifying crude 1,3-butanediol, and it is also necessary to improve the method for producing crude 1,3-butanediol itself.

[0078] In the production of 1,3-butanediol, a hydrogenation raw material containing butanol aldehydes is used. The butanol aldehydes are not particularly limited as long as they are compounds that are reduced to 1,3-butanediol by hydrogen, and examples thereof include butanol aldehyde, dimer m-hydroxybutyraldehyde as a cyclic dimer thereof, 2,6-dimethyl-1,3-dioxane-4-ol as a cyclic trimer of acetaldehyde, and mixtures thereof.

[0079] The production method of butanol aldehydes (such as butanol aldehyde and dimerized meta-hydroxybutyraldehyde) is not particularly limited. For example, it can be obtained by the aldol condensation reaction of acetaldehyde in the presence of an alkaline catalyst, or by the thermal decomposition of 2,6-dimethyl-1,3-dioxane-4-ol. The crude reaction liquid containing butanol aldehydes obtained by the above reaction is neutralized with an acid and used to produce 1,3-butanediol. In addition to butanol aldehydes, such a crude reaction liquid may also contain acetaldehyde, crotonaldehyde, other aldehyde components, low boiling point substances, high boiling point substances such as aldehyde dimers or trimers, water, salts, etc. It should be noted that in this specification, compounds with a lower boiling point than 1,3-butanediol are sometimes referred to as "low boiling point substances", and compounds with a higher boiling point than 1,3-butanediol are sometimes referred to as "high boiling point substances".

[0080] The above-mentioned reaction crude liquid can be used to remove the substances of by-products such as unreacted acetaldehyde and crotonaldehyde by pre-treatment such as dealcoholization distillation, dehydration distillation, desalination, and impurity removal as needed. As the method of pre-treatment, distillation, adsorption, ion exchange, heating high boiling point physicochemical, decomposition, etc. can be listed. Distillation can use various distillation methods such as reduced pressure, normal pressure, pressurization, azeotropic, extraction, reaction, etc.

[0081] The content of butanol aldehydes in the hydrogenation raw material is not particularly limited, and is, for example, preferably 50% by weight or more (e.g., 50 to 99% by weight), more preferably 60% by weight or more (e.g., 60 to 98% by weight), further preferably 65 to 98% by weight, particularly preferably 80 to 95% by weight, and most preferably 85 to 95% by weight. When the content of butanol aldehydes is within the above range, there is a tendency for impurities contained in crude 1,3-butanediol to decrease.

[0082] The hydrogenation raw material may contain water or not contain water, but from the viewpoint of the purity of the 1,3-butanediol product, it is preferably contained water. The content of water in the hydrogenation raw material is not particularly limited, for example, preferably 2% by weight or more, more preferably 5% by weight or more, further preferably 10% by weight or more, and particularly preferably 15% by weight or more. It should be noted that its upper limit value may be, for example, 50% by weight, 40% by weight, or 35% by weight.

[0083] When the water content is within the above range, the various by-products contained in the obtained crude 1,3-butanediol are reduced, and the by-products include: acetals of 1,3-butanediol and butanol aldehyde, and esters of acetic acid and 1,3-butanediol, so there is a tendency for the purity of the finally obtained 1,3-butanediol product to be higher. This is because the acetals are hydrolyzed to 1,3-butanediol by the inclusion of a certain amount of water in the hydrogenation raw material, and butanol aldehyde produced together is reduced to 1,3-butanediol. In addition, this is because the esters are hydrolyzed to 1,3-butanediol by the inclusion of a certain amount of water in the hydrogenation raw material.

[0084] Hereinafter, a method for producing crude 1,3-butanediol will be described. This production method is characterized in that crude 1,3-butanediol is obtained by reducing a hydrogenation raw material containing butanol aldehydes in the presence of a hydrogenation catalyst.

[0085] As a hydrogenation catalyst, for example, Raney nickel and the like can be cited. The hydrogenation catalyst can be used in a suspended or filled state, but it is preferably used in a suspended state. The amount of the hydrogenation catalyst used is not particularly limited, but relative to 100 parts by weight of the hydrogenation raw material, for example, it is preferably 1 to 30 parts by weight, more preferably 4 to 25 parts by weight, further preferably 8 to 20 parts by weight, and particularly preferably 12 to 18 parts by weight. The amount of hydrogen used for the reduction reaction is not particularly limited, but relative to 100 parts by weight of the hydrogenation raw material, for example, it is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, further preferably 4 to 20 parts by weight, and particularly preferably 8 to 12 parts by weight. The pressure (total pressure) in the reaction system during the reduction reaction is not particularly limited, for example, it is preferably 150 to 500 atm, more preferably 180 to 450 atm, further preferably 200 to 400 atm, and particularly preferably 250 to 350 atm. The ratio of the hydrogen pressure to the total pressure (partial pressure of hydrogen) in the reaction system is not particularly limited, but, for example, is preferably 80% or more (80 to 100%) of the total pressure, more preferably 85% to 99.9%, further preferably 90% to 99.5%, and particularly preferably 95% to 99%. The hydrogen pressure (partial pressure of hydrogen) in the reaction system is not particularly limited, but, for example, is preferably 100 to 500 atm, more preferably 150 to 450 atm, further preferably 150 to 400 atm, and particularly preferably 200 to 350 atm. The reaction temperature in the reduction reaction is not particularly limited, but, for example, 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, for example, is preferably 30 to 300 minutes, more preferably 80 to 280 minutes, and further preferably 120 to 250 minutes.

[0086] By the amount of the 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) being within the above range, the reaction rate (hydrogenation rate) from butanol aldehydes to 1,3-butanediol is increased. Therefore, for example, there is a tendency that the acetalization reaction of 1,3-butanediol and butanol aldehyde is weakened, and a high-purity 1,3-butanediol product of the present disclosure is obtained. This tendency is particularly strongly affected by the hydrogen pressure in the reduction reaction. That is, by the hydrogen pressure in the reduction reaction being within the above range, the reaction rate (reduction rate) from butanol aldehydes to 1,3-butanediol is significantly increased, and as a result, the acetal body of 1,3-butanediol and butanol aldehyde is reduced, and a high-purity 1,3-butanediol product is obtained. In addition, by being within the above range, the hydrogenation of the carboxylic acid part of the ester body is rapidly carried out to become an alcohol. As a result, the ester body of acetic acid and 1,3-butanediol is reduced, and a high-purity 1,3-butanediol product of the present disclosure is obtained. The present reaction can be carried out in a batch mode, a semi-batch mode or a continuous mode.

[0087] The crude 1,3-butanediol obtained by hydrogen reduction of the hydrogenation raw material can be obtained as a 1,3-butanediol product by, for example, undergoing a dehydration step, a desalting step, a high boiling point removal distillation step, an alkali reaction step, a dealkalization step, and a distillation step.

[0088] The content of the high boiling point substances in the crude 1,3-butanediol is not particularly limited, but is, for example, preferably 0.1 to 20% by weight, more preferably 1 to 15% by weight, and still more preferably 2 to 10% by weight. When the content of the high boiling point substances in the crude 1,3-butanediol is within the above range, there is a tendency that the amount of by-products contained in the finally obtained 1,3-butanediol product is reduced.

[0089] The content of high boiling point substances in the crude 1,3-butanediol after the high boiling point substance removal distillation step is 1.0 wt% or less, preferably 0.5 wt% or less. By using crude 1,3-butanediol with a low content of high boiling point substances, even if the crude 1,3-butanediol is heated with an alkali in the alkali reaction step, there is no generation of low boiling point substances due to the decomposition reaction of the high boiling point substances, or the generation of low boiling point substances is very small. As a result, a high-quality 1,3-butanediol product is obtained that is free of odor, is less likely to be colored over time, and is less likely to increase in acid concentration over time in a water-containing state.

[0090] Figure 1This is a flow chart of an apparatus for obtaining an example of an implementation method of the 1,3-butanediol product disclosed herein. A is a dehydration tower, which is related to the dehydration process. B is a desalination tower, which is related to the desalination process. C is a high-boiling-point distillation tower, which is related to the high-boiling-point distillation process. D is an alkali reactor, which is related to the alkali reaction process. E is a dealkalization tower, which is related to the dealkalization process. F is a product distillation tower, which is related to the distillation process. A-1, B-1, C-1, E-1, and F-1 are condensers. A-2, C-2, and F-2 are reboilers. Below, this flow chart is used to illustrate an example of an implementation method for obtaining the 1,3-butanediol product disclosed herein.

[0091] The crude 1,3-butanediol (corresponding to "X-1") obtained by hydrogen reduction of the hydrogenation raw material is supplied to the dehydration tower A. Water is distilled off from the top of the tower by distillation in the dehydration tower A, and a crude 1,3-butanediol stream containing 1,3-butanediol is obtained from the bottom of the tower. The above crude 1,3-butanediol stream is supplied to the demineralization tower B. In the demineralization tower B, a desalted crude 1,3-butanediol stream 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.

[0092] The crude 1,3-butanediol stream after desalting is supplied to the high-boiling-point substance removal distillation column C. In the high-boiling-point substance removal distillation column C, high-boiling-point substances are discharged from the bottom of the column. On the other hand, a crude 1,3-butanediol stream after high-boiling-point substance removal is obtained from the top of the column. The crude 1,3-butanediol distilled by the high-boiling-point substance removal distillation column C is supplied to an alkali reactor (for example, a flow-through tubular reactor) D for alkali treatment. In the alkali reactor D or its upstream, 0.05 to 10% by weight, preferably 0.1 to 1.0% by weight, of the crude 1,3-butanediol stream after high-boiling-point substance removal is added. If the amount of alkali added exceeds 10% by weight, there is a tendency for alkali to precipitate in the distillation column, piping, etc., which may cause clogging. In addition, sometimes a decomposition reaction of high-boiling-point compounds also occurs, and there is a tendency to produce by-products. In the case of less than 0.05% by weight, the effect of decomposing by-products is small, so it is not preferred.

[0093] The alkali added in the alkali reactor D or its upstream is not particularly limited, but is preferably an alkali metal compound, for example. As the alkali metal compound, for example, caustic soda, caustic potash, sodium carbonate (bicarbonate), potassium carbonate (bicarbonate) can be listed, but from the viewpoint of reducing the by-products contained in the final 1,3-butanediol product, caustic soda and caustic potash are preferred. The alkali can be directly added to the solid substance, but for operation and to promote contact with the object liquid, it is preferably added in an aqueous solution. It should be noted that the above-mentioned alkali can be used alone or in combination of two or more.

[0094] The reaction temperature in the alkaline reactor D is not particularly limited, but is preferably 90°C to 140°C, more preferably 110°C to 130°C, for example. When the reaction temperature is less than 90°C, a long reaction residence time is required, so the reactor capacity becomes large and uneconomical. If the reaction temperature exceeds 140°C, the coloring of the final 1,3-butanediol product increases. The reaction residence time is preferably 5 minutes to 120 minutes, and more preferably 10 to 30 minutes. When the reaction residence time is less than 5 minutes, the reaction becomes insufficient and the quality of the final 1,3-butanediol product deteriorates. If the reaction residence time exceeds 120 minutes, a large reactor is required and the equipment cost becomes high, so it is disadvantageous from an economic point of view.

[0095] After leaving the alkali reactor D, the reaction crude liquid stream is supplied to the dealkalization tower (thin film evaporator) E, and the alkali and the like are removed from the bottom of the tower by evaporation. On the other hand, a dealkalized crude 1,3-butanediol stream is obtained from the top of the dealkalization tower E. For the purpose of suppressing the thermal process of the process fluid, the evaporator used in the dealkalization tower E is preferably a natural falling film evaporator with a short residence time or a forced stirring type thin film evaporator.

[0096] In the evaporator used in the dealkalization column E, evaporation is performed under 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, for example, preferably 90° C. to 120° C. The crude 1,3-butanediol stream containing low boiling point substances distilled from the top of the column is supplied to the product distillation column F.

[0097] The product distillation tower F may be, for example, a porous plate tower, a bubble cap tower, etc., but a packed tower with low pressure loss filled with Sulzer Packings, Mellapak (both are trade names of Sumitomo Heavy Industries, Ltd.) or the like is more preferred. The reason is that 1,3-butanediol is thermally decomposed at high temperatures (e.g., above 150°C) to produce low-boiling substances, thereby lowering the distillation temperature. In addition, the same influence is also exerted when the thermal history (residence time) of 1,3-butanediol is long. Therefore, the reboiler used is preferably one with a shorter residence time of the process side fluid, for example, a thin film evaporator such as a natural falling film evaporator and a forced stirring thin film evaporator is preferred.

[0098] When the concentration of low boiling point substances in the feed liquid is 5 wt% or less, the theoretical number of stages of the product distillation tower F is preferably 10 to 20, for example. The feed liquid is preferably supplied to a position of 20 to 70% of the tower height from the top. In the distillation in the product distillation tower F, the pressure at the top of the tower is preferably, for example, 100 torr or less, more preferably 5 to 20 torr. The reflux ratio is preferably, for example, 0.5 to 2.0.

[0099] exist Figure 1In the charging to the product distillation tower F, the liquid after condensing the vapor from the top of the dealkalization tower E by the condenser E-1 may be fed, or the vapor from the top of the dealkalization tower E may be directly fed to the product distillation tower F. In the product distillation tower F, impurities such as low boiling point substances are distilled off from the top of the tower, and 1,3-butanediol as a product is obtained from the bottom of the product distillation tower F (equivalent to "Y").

[0100] [Moisturizers and cosmetics]

[0101] The moisturizing agent disclosed in the present invention includes the above-mentioned 1,3-butanediol product. Therefore, it has excellent moisturizing performance, no coloring, no odor, and is not prone to coloring caused by time, and even in a water-containing state, it is not easy to cause an increase in acid concentration caused by time. The moisturizing agent disclosed in the present invention may also include ingredients other than the above-mentioned 1,3-butanediol product, for example, moisturizing agent ingredients other than the above-mentioned 1,3-butanediol product. In the moisturizing agent disclosed in the present invention, the content of the above-mentioned 1,3-butanediol product is, for example, 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, further preferably 80% by weight or more, and particularly preferably 90% by weight or more, and may also be composed only of the above-mentioned 1,3-butanediol product.

[0102] The cosmetic disclosed herein contains the above-mentioned moisturizing agent. Depending on the type and form of the cosmetic, the amount of the above-mentioned 1,3-butanediol product in the cosmetic disclosed herein can be an amount that can exert moisturizing performance. The amount of the above-mentioned 1,3-butanediol product in the cosmetic disclosed herein is, for example, 0.01 to 40% by weight, preferably 0.1 to 30% by weight, more preferably 0.2 to 20% by weight, further preferably 0.5 to 15% by weight, and particularly preferably 1 to 10% by weight.

[0103] In addition to the above-mentioned 1,3-butylene glycol products, the cosmetics disclosed in the present invention may also include, for example: other moisturizers; 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, chelating agents, thickeners, powders, ultraviolet absorbers, ultraviolet shielding agents, fragrances, and pH adjusters; vitamins, skin activators, blood circulation promoters, whitening agents, antibacterial agents, anti-inflammatory agents, and other medicinal ingredients, physiologically active ingredients, etc.

[0104] The cosmetics disclosed in the present invention can be made into skin cosmetics such as lotions, emulsions, creams, gels, facial masks (packs), facial masks, and hair cosmetics such as shampoos, conditioners, and hair growth agents. In addition, they can also be made into sunscreen cosmetics and color cosmetics. In addition, they can also be made into pharmaceuticals and quasi-drugs containing medical ingredients.

[0105] The cosmetic disclosed in the present invention can be produced by a method known per se.

[0106] Example

[0107] Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples. It should be noted that "parts" used in the examples refer to "parts by weight" unless otherwise specified.

[0108] [Example 1]

[0109] use Figure 1 The method for producing 1,3-butanediol will be described.

[0110] 100 parts of a butanol aldehyde solution containing 30% by weight of water as a raw material (a mixed solution of 70 parts of butanol aldehyde and 30 parts of water) were charged into a reactor for liquid phase hydrogen reduction, 15 parts of Raney nickel as a catalyst were added, and the reactor was maintained at 135° C. and 300 atm to perform liquid phase hydrogen reduction. After the catalyst was separated from the liquid after the reaction, it was neutralized with caustic soda to remove alcohols and obtain crude 1,3-butanediol (1).

[0111] The crude 1,3-butanediol (1) (equivalent to Figure 1 "X-1" in the above) was loaded into the dehydration tower A. With respect to 100 parts of the liquid loaded into the dehydration tower A, water was extracted from the top of the tower, 15 parts of fresh water was added as reflux water, the pressure was set to 50 torr, and crude 1,3-butanediol (2) with a water content of less than 0.5% by weight was obtained from the bottom of the tower. It should be noted that the water extracted from the top of the tower was discharged (equivalent to Figure 1 2 in the figure).

[0112] Next, the crude 1,3-butanediol (2) is fed into a demineralization tower B. In the demineralization tower B, salts, high boiling point substances, and a portion of 1,3-butanediol are discharged from the bottom of the tower as an evaporation residue (equivalent to Figure 1 The discharge amount of the evaporation residue was 5 parts with respect to 100 parts of the loading liquid. On the other hand, crude 1,3-butanediol (3) containing 1,3-butanediol, low boiling point substances, and a part of high boiling point substances was obtained from the top of the column.

[0113] Next, the crude 1,3-butanediol (3) is fed to a high boiling point removal distillation column C. In the high boiling point removal distillation column C, high boiling points and a portion of 1,3-butanediol (equivalent to Figure 1"X-4" in the column). The discharge amount was 20 parts relative to 100 parts of the loading liquid. On the other hand, 80 parts of crude 1,3-butanediol (4) containing low boiling point substances were obtained from the top of the column. Next, the crude 1,3-butanediol (4) was charged into the alkali reactor D. At this time, a 10 wt% caustic soda aqueous solution was added in such a manner that the concentration of caustic soda relative to the loading liquid became 0.2 wt%. The reaction temperature in the alkali reactor D was maintained at 120°C, and the reaction was carried out with a residence time of 20 minutes.

[0114] Next, the crude reaction liquid discharged from the alkali reactor D is fed into the dealkalization tower E. In the dealkalization tower E, caustic soda, high boiling point substances, and a portion of 1,3-butanediol (relative to Figure 1 The discharge amount was 10 parts with respect to 100 parts of the loading liquid. On the other hand, 90 parts of crude 1,3-butanediol (5) containing 1,3-butanediol and low boiling point substances were obtained from the top of the column.

[0115] Next, the crude 1,3-butanediol (5) was charged to the product distillation column F. In the product distillation column F, 10 parts (equivalent to 100 parts) of low boiling point substances and a portion of 1,3-butanediol were distilled from the top of the column. Figure 1 From the bottom of the tower, 90 parts of 1,3-butanediol product (equivalent to Figure 1 in the text box).

[0116] The above-mentioned 1,3-butanediol product was analyzed by gas chromatography under the conditions described below. As a result, the peak in the range of relative retention time 2.3 to 2.4 was below the detection limit (below 10 ppm). In addition, the peak in the range of relative retention time 1.35 to 1.45 was also below the detection limit (below 10 ppm). In addition, the area ratio of the peak appearing in the range of relative retention time 1.6 to 1.8 was 130 ppm. Time-dependent coloring test 1 was performed, and the result was that the APHA after being kept at 180°C for 3 hours in an air atmosphere was 21. In addition, time-dependent coloring test 2 was performed, and the result was that the APHA after being kept at 100°C for 75 days in an air atmosphere was 10. It should be noted that the APHA before these tests was 2. When the moisture addition heating test was performed, it was found that the acid concentration was 0.0005% by weight, which was unchanged from the acid concentration of 0.0005% by weight before heating. In addition, the score of the odor test was 1.

[0117] [Comparative Example 1]

[0118] For 13-butanediol (product number: 13BGO) manufactured by Daicel Co., Ltd., gas chromatography analysis was performed under the conditions described below. As a result, the area ratio of the peak appearing in the range of relative retention time of 2.3 to 2.4 was 1137ppm. In addition, the area ratio of the peak appearing in the range of relative retention time of 1.35 to 1.45 was 135ppm. In addition, the area ratio of the peak appearing in the range of relative retention time of 1.6 to 1.8 was 1010ppm. The moisture addition heating test described below was performed, and as a result, it was found that the acid concentration was 0.0024% by weight, which was a significant increase compared to the acid concentration of 0.0005% by weight before heating. Time-dependent coloring test 1 was performed, and the result was that the APHA after being kept at 180°C for 3 hours in an air atmosphere was 80. In addition, time-dependent coloring test 2 was performed, and the result was that the APHA after being kept at 100°C for 75 days in an air atmosphere was 46. It should be noted that the APHA before these tests was 4. Furthermore, the score of the odor test was 2.

[0119] [Gas chromatography analysis]

[0120] The gas chromatography analysis of the target 1,3-butanediol product was carried out under the following conditions. The gas chromatography analysis spectrum of 1,3-butanediol in Example 1 is shown in FIG. Figure 2 In addition, the gas chromatography spectrum of 1,3-butanediol in Comparative Example 1 is shown in Figure 3 .

[0121] (Conditions for gas chromatography analysis)

[0122] Analytical equipment: Shimadzu GC2010.

[0123] Analytical column: Agilent J&W GC column-DB-1 (column with dimethylpolysiloxane as the stationary phase, film thickness 1.0 μm×length 30 m×inner diameter 0.25 mm, manufactured by Agilent Technologies, Inc.).

[0124] Heating conditions: After heating from 80°C to 120°C at 5°C / min, heating to 160°C at 2°C / min and maintaining for 2 minutes, heating to 230°C at 10°C / min and maintaining at 230°C for 18 minutes.

[0125] Sample introduction and temperature: split sample introduction method, 250°C.

[0126] Gas flow rate of slit and carrier gas: 23 mL / min, helium.

[0127] Column gas flow and carrier gas: 1 mL / min, helium.

[0128] Detector and temperature: flame ionization detector (FID), 280°C.

[0129] Injection sample: 0.2 μL of 80 wt% 1,3-butanediol product aqueous solution.

[0130] [Coloration test 1 over time]

[0131] The 1,3-butanediol product was placed in a wide-mouth bottle, sealed, and kept in a thermostatic chamber set at 180° C. for 3 hours. The Hazen color (APHA) of the 1,3-butanediol product after keeping was measured using a colorimeter (“ZE6000” manufactured by Nippon Denshoku Industries Co., Ltd.) using a quartz cell with an optical path length of 10 mm.

[0132] [Coloration test 2 over time]

[0133] The 1,3-butanediol product was sealed in a wide-mouth bottle and kept for 75 days in a thermostatic chamber set at 100° C. The Hazen color (APHA) of the 1,3-butanediol product after storage was measured using a colorimeter (“ZE6000” manufactured by Nippon Denshoku Industries Co., Ltd.) using a quartz cell with an optical path length of 10 mm.

[0134] [Water addition heating test (acid concentration analysis)]

[0135] The target 1,3-butanediol product was adjusted to a 90 wt% aqueous solution, and the sample was kept at 100°C for one week, and the acid concentration analysis was performed by the following method. It should be noted that the acid concentration analysis before the storage was performed in the same manner except that the 1,3-butanediol product before the storage at 100°C for one week was used as the target.

[0136] (Acid concentration analysis)

[0137] The measurement was performed by potentiometric titration using a potentiometric automatic titrator (AT-510 manufactured by Kyoto Electronics Co., Ltd.). 50 g of the sample was diluted with 50 g of distilled water, and a 0.01 N sodium hydroxide aqueous solution was titrated from a burette while stirring until the automatic endpoint was reached. Next, the acid concentration in terms of acetic acid was calculated based on the following formula.

[0138] Acid concentration (weight %) = titration amount (ml) × F × A × (100 / sample amount (g)).

[0139] F: 1.0 (factor of 0.01N sodium hydroxide aqueous solution).

[0140] A: 0.0006 (the number of grams of acetic acid equivalent to 1 ml of sodium hydroxide aqueous solution).

[0141] [Odor test]

[0142] The 1,3-butanediol product (100 ml) to be the subject was placed in a wide-mouth reagent bottle (content volume: 100 ml), tightly stoppered and left to stand at room temperature for about 120 minutes, then the stopper was opened and transferred to a 300 ml wide-mouth beaker, to which 100 ml of pure water was added to make a total of 200 ml, and the wide-mouth beaker was shaken by hand to stir, and the odor was quickly smelled and points were given according to the following evaluation.

[0143] 1: No smell is detected.

[0144] 2: Slightly smelly.

[0145] Modifications of the invention disclosed herein will be described below.

[0146] [1] A 1,3-butanediol product.

[0147] [2] The 1,3-butanediol product according to [1], wherein, in a gas chromatography analysis under the following conditions,

[0148] When the relative retention time of the peak of 1,3-butanediol is set to 1.0, the area ratio of the peak appearing in the range of relative retention times of 1.6 to 1.8 is 2000 ppm or less, 1000 ppm or less, 600 ppm or less, 400 ppm or less, or 200 ppm or less, or the lower limit of the area ratio of the peak is 10 ppm, 20 ppm, 50 ppm, or 100 ppm.

[0149] (Conditions for gas chromatography analysis)

[0150] Analytical column: a column with dimethylpolysiloxane as the stationary phase (film thickness 1.0 μm×length 30 m×inner diameter 0.25 mm).

[0151] Heating conditions: After heating from 80°C to 120°C at 5°C / min, heating to 160°C at 2°C / min and maintaining for 2 minutes, heating to 230°C at 10°C / min and maintaining at 230°C for 18 minutes.

[0152] Sample introduction temperature: 250°C.

[0153] Carrier gas: Helium.

[0154] Column gas flow rate: 1 mL / min.

[0155] Detector and detection temperature: hydrogen flame ionization detector (FID), 280°C.

[0156] [3] The 1,3-butanediol product according to [1] or [2], wherein

[0157] When the relative retention time of the peak of 1,3-butanediol is set to 1.0, the area ratio of the peak appearing in the range of relative retention times of 2.3 to 2.4 is 1000 ppm or less, 500 ppm or less, 250 ppm or less, 200 ppm or less, 150 ppm or less, 100 ppm or less, 50 ppm or less, or 20 ppm or less.

[0158] (Conditions for gas chromatography analysis)

[0159] Analytical column: a column with dimethylpolysiloxane as the stationary phase (film thickness 1.0 μm×length 30 m×inner diameter 0.25 mm).

[0160] Heating conditions: After heating from 80°C to 120°C at 5°C / min, heating to 160°C at 2°C / min and maintaining for 2 minutes, heating to 230°C at 10°C / min and maintaining at 230°C for 18 minutes.

[0161] Sample introduction temperature: 250°C.

[0162] Carrier gas: Helium.

[0163] Column gas flow rate: 1 mL / min.

[0164] Detector and detection temperature: hydrogen flame ionization detector (FID), 280°C.

[0165] [4] The 1,3-butanediol product according to any one of [1] to [3], wherein

[0166] When the relative retention time of the peak of 1,3-butanediol is defined as 1.0, the area ratio of the peak appearing in the range of relative retention times of 1.35 to 1.45 is 100 ppm or less, 50 ppm or less, 20 ppm or less, or 10 ppm or less.

[0167] (Conditions for gas chromatography analysis)

[0168] Analytical column: a column with dimethylpolysiloxane as the stationary phase (film thickness 1.0 μm×length 30 m×inner diameter 0.25 mm).

[0169] Heating conditions: After heating from 80°C to 120°C at 5°C / min, heating to 160°C at 2°C / min and maintaining for 2 minutes, heating to 230°C at 10°C / min and maintaining at 230°C for 18 minutes.

[0170] Sample introduction temperature: 250°C.

[0171] Carrier gas: Helium.

[0172] Column gas flow rate: 1 mL / min.

[0173] Detector and detection temperature: hydrogen flame ionization detector (FID), 280°C.

[0174] [5] The 1,3-butanediol product according to [2], wherein the component corresponding to the peak appearing in the range of 1.6 to 1.8 contains a hydrogenated product of a trimer of the raw material (acetaldehyde).

[0175] [6] The 1,3-butanediol product according to [3], wherein the component corresponding to the peak appearing in the range of 2.3 to 2.4 contains an acetal of 1,3-butanediol and butanol aldehyde.

[0176] [7] The 1,3-butanediol product according to [4], wherein the component corresponding to the peak in the range of 1.35 to 1.45 contains an ester of acetic acid and 1,3-butanediol.

[0177] [8] The 1,3-butanediol product according to any one of [1] to [7], wherein the area ratio of the peak of 1,3-butanediol in the 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.

[0178] [9] The 1,3-butanediol product according to any one of [1] to [8], wherein the APHA after being kept at 180°C in an air atmosphere for 3 hours is 60 or less, 40 or less, or 30 or less, and the lower limit is 1, 3, 5, or 10.

[0179]

[10] The 1,3-butanediol product according to any one of [1] to [9], wherein the APHA after being kept at 100°C in an air atmosphere for 75 days is 40 or less, 30 or less, 20 or less, or 15 or less, with the lower limit being 1, 3, 5, or 10.

[0180]

[11] The 1,3-butanediol product according to any one of [1] to

[10] , wherein APHA is 20 or less, 10 or less, or 5 or less, with a lower limit of 1 or 2.

[0181]

[12] The 1,3-butanediol product according to any one of [1] to

[11] , wherein the ratio of APHA after being kept at 180°C for 3 hours to APHA before being kept [(APHA after being kept at 180°C for 3 hours) / (APHA before being kept)] is 15 or less, or 12 or less, and 1 or more, 2 or more, or 5 or more.

[0182]

[13] The 1,3-butanediol product according to any one of [1] to

[12] , wherein the ratio of APHA after being kept at 100°C for 75 days to APHA before being kept [(APHA after being kept at 100°C for 75 days) / (APHA before being kept)] is 10 or less, or 7 or less, and 1 or more, or 2 or more.

[0183]

[14] The 1,3-butanediol product according to any one of [1] to

[13] , wherein the acid concentration (calculated as acetic acid) of a 90 wt % aqueous solution after being kept at 100° C. for one week is 0.002 wt % or less, 0.0015 wt % or less, 0.001 wt % or less, or 0.0005 wt % or less, and the lower limit of the acid concentration is 0.00005 wt % or 0.0001 wt %.

[0184]

[15] The 1,3-butanediol product according to any one of [1] to

[14] , wherein the ratio of the acid concentration (calculated as acetic acid) of a 90 wt % aqueous solution after being kept at 100° C. for one week to the acid concentration before being kept [(acid concentration after being kept at 100° C. for one week) / (acid concentration before being kept)×100(%)] is 200% or less, 150% or less, or 120% or less.

[0185]

[16] The 1,3-butanediol product according to any one of [1] to

[15] , which is a reduced form of butanol aldehydes.

[0186]

[17] The 1,3-butanediol product according to any one of [1] to

[16] , wherein the 1,3-butanediol in the 1,3-butanediol product is a reduced product of at least one compound selected from the group consisting of butanolaldehyde, dimer-m-hydroxybutyraldehyde, and 2,6-dimethyl-1,3-dioxane-4-ol.

[0187]

[18] A moisturizing agent comprising the 1,3-butanediol product according to any one of [1] to

[17] .

[0188]

[19] A cosmetic comprising the moisturizing agent described in

[18] .

[0189] Description of Reference Numerals

[0190] A: Dehydration tower

[0191] B: Desalination tower

[0192] C: Distillation tower for removing high boiling point substances

[0193] D: Alkali Reactor

[0194] E: Dealkalization Tower

[0195] F: Product distillation tower

[0196] A-1, B-1, C-1, E-1, F-1: Condenser

[0197] A-2, C-2, F-2: Reboiler

[0198] X-1: Crude 1,3-butanediol

[0199] X-2: Water (drainage)

[0200] X-3: Salt, high boiling point substances and part of 1,3-butanediol

[0201] X-4: high boiling point substances and part of 1,3-butanediol

[0202] X-5: caustic soda, high boiling point substances and part of 1,3-butanediol

[0203] X-6: Low boiling point substances and part of 1,3-butanediol

[0204] Y: 1,3-Butanediol products

[0205] Industrial Applicability

[0206] The 1,3-butanediol product of the present disclosure is colorless and odorless, is unlikely to be colored over time, and is unlikely to have an increase in acid concentration over time even in a water-containing state, and is therefore preferably used in cosmetics, moisturizers, and the like.

Claims

1. A 1,3-butanediol product, which, in a gas chromatography analysis under the following conditions, When the relative retention time of the peak of 1,3-butanediol is set to 1.0, the area ratio of the peak appearing in the range of relative retention times of 1.6 to 1.8 is 2000 ppm or less. Gas chromatography analysis conditions: Analytical column: The stationary phase is dimethylpolysiloxane column, film thickness 1.0μm×length 30m×inner diameter 0.25mm, Heating conditions: After heating from 80°C to 120°C at 5°C / min, heating to 160°C at 2°C / min and maintaining for 2 minutes, further heating to 230°C at 10°C / min and maintaining 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.

2. The 1,3-butanediol product according to claim 1, wherein Furthermore, the area ratio of the peak appearing in the range of relative retention time 2.3 to 2.4 was 1000 ppm or less.

3. The 1,3-butanediol product according to claim 1, wherein Furthermore, the area ratio of the peak appearing in the range of relative retention time 1.35 to 1.45 was 100 ppm or less.

4. The 1,3-butanediol product according to claim 2, wherein Furthermore, the area ratio of the peak appearing in the range of relative retention time 1.35 to 1.45 was 100 ppm or less.

5. The 1,3-butanediol product according to any one of claims 1 to 4, wherein The APHA after being kept at 180°C for 3 hours in an air atmosphere was 60 or less.

6. The 1,3-butanediol product according to any one of claims 1 to 5, wherein The acid concentration of a 90 wt % aqueous solution after being kept at 100° C. for one week is 0.002 wt % or less in terms of acetic acid.

7. The 1,3-butanediol product according to any one of claims 1 to 6, wherein The 1,3-butanediol in the 1,3-butanediol product is a reduced form of at least one compound selected from the group consisting of butanolaldehyde, dimer-m-hydroxybutyraldehyde, and 2,6-dimethyl-1,3-dioxane-4-ol. 8 . A moisturizer comprising the 1,3-butanediol product according to claim 1 .

9. A cosmetic comprising the moisturizing agent according to claim 8.

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