WO2026018557A1 - Produit de 1,3-butylène glycol - Google Patents

Produit de 1,3-butylène glycol

Info

Publication number
WO2026018557A1
WO2026018557A1 PCT/JP2025/018561 JP2025018561W WO2026018557A1 WO 2026018557 A1 WO2026018557 A1 WO 2026018557A1 JP 2025018561 W JP2025018561 W JP 2025018561W WO 2026018557 A1 WO2026018557 A1 WO 2026018557A1
Authority
WO
WIPO (PCT)
Prior art keywords
butylene glycol
peak
product
parts
area
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/018561
Other languages
English (en)
Japanese (ja)
Inventor
泰照 梶川
碧 梅原
瞳 景行
裕太 坂本
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daicel Corp
Original Assignee
Daicel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daicel Corp filed Critical Daicel Corp
Publication of WO2026018557A1 publication Critical patent/WO2026018557A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34—Alcohols
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols

Definitions

  • 1,3-butylene glycol is a colorless, transparent, odorless liquid with properties such as low volatility, low toxicity, and high moisture absorption, and has excellent chemical stability. For this reason, 1,3-butylene glycol has a wide range of uses, including as a raw material for various synthetic resins and surfactants, as well as cosmetics, moisture absorbents, high-boiling point solvents, and antifreeze materials. In recent years, 1,3-butylene glycol has particularly attracted attention for its excellent properties as a moisturizer, and demand in the cosmetics industry is expanding.
  • 1,3-butylene glycol obtained using conventional manufacturing methods can have an odor due to by-products. Furthermore, even if the product is clear immediately after production, it can become discolored over time, posing problems when stored for long periods of time.
  • the 1,3-butylene glycol products obtained using the methods described in Patent Documents 1 to 9 also have the problem of generating an odor (particularly an apple odor) over time when incorporated into cosmetic compositions. While the reason for this is unclear, it is thought that the odor is generated when specific by-products contained in 1,3-butylene glycol products react with components contained in the cosmetic composition (such as citric acid) to become odorous components.
  • the inventors of the present disclosure discovered a 1,3-butylene glycol product that can solve the above problems.
  • the inventors of the present disclosure discovered that the resulting 1,3-butylene glycol product also has the problem of generating an odor (an irritating odor) different from the apple odor when blended into a cosmetic composition.
  • This irritating odor is not generated by the 1,3-butylene glycol products described in Patent Documents 1 to 9, and is therefore thought to be an odor derived from the cosmetic composition itself.
  • a specific by-product contained in the 1,3-butylene glycol product has a masking effect on the irritating odor derived from the cosmetic composition, and that the irritating odor is suppressed by including a specific amount of this by-product.
  • the object of this disclosure is to provide a 1,3-butylene glycol product that is less likely to produce an apple odor or irritating odor even when incorporated into a cosmetic composition.
  • the inventors of the present disclosure discovered that by improving the method for producing crude 1,3-butylene glycol, it is possible to obtain a 1,3-butylene glycol product that is less likely to produce odors (apple odor and irritating odor) when incorporated into cosmetic compositions.
  • the invention of the present disclosure was completed based on these findings.
  • the present disclosure provides a 1,3-butylene glycol product having an area ratio represented by the following formula of 54 or more and 130 or less.
  • Area ratio Peak X area / total peak area minus diethylene glycol dimethyl ether peak area ⁇ 10 6
  • Peak X area In gas chromatography analysis under the following conditions, the area of a peak having a peak top in the range of relative retention time 6.2 to 6.32 when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard, is set to 1.0 [Gas chromatography analysis conditions]
  • Injection sample a mixture of 1 g of an 80% by mass aqueous solution of 1,3-butylene glycol product and 0.01 g of diethylene glycol dimethyl ether
  • Injection amount 1 ⁇ L
  • Analytical column a column with a stationary phase of polyethylene glycol (film thickness 0.25 ⁇ m ⁇ length 30 m ⁇ inner diameter 0.25 mm)
  • Temperature increase conditions After maintaining at 100°C for 20 minutes, the
  • the 1,3-butylene glycol in the above-mentioned 1,3-butylene glycol product is preferably a reduced form of at least one compound selected from the group consisting of acetaldol, paraaldol, and aldoxane.
  • the present disclosure also provides a moisturizer containing the above-mentioned 1,3-butylene glycol product.
  • the present disclosure also provides a cosmetic composition containing the above-mentioned 1,3-butylene glycol product.
  • 1,3-butylene glycol products disclosed herein are less likely to produce apple or irritating odors when incorporated into cosmetic compositions, making them suitable for use in cosmetics, moisturizers, and other applications.
  • 1 is a flowchart of a manufacturing process for the 1,3-butylene glycol product of the present disclosure.
  • 1 is a chromatogram chart of GC/FID measurement of the 1,3-butylene glycol product of Example 1.
  • 1 is a chromatogram chart of GC/FID measurement for the 1,3-butylene glycol product of Comparative Example 2.
  • the 1,3-butylene glycol product of the present disclosure has an area ratio represented by the following formula of 54 or more and 130 or less.
  • Area ratio Peak X area / total peak area minus diethylene glycol dimethyl ether peak area ⁇ 10 6
  • Peak X area In gas chromatography analysis under the following conditions, the area of a peak (referred to as "Peak X") having a peak top in the range of relative retention time 6.2 to 6.32 when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard, is set to 1.0.
  • Injection sample a mixture of 1 g of an 80% by mass aqueous solution of 1,3-butylene glycol product and 0.01 g of diethylene glycol dimethyl ether
  • Injection amount 1 ⁇ L
  • Analytical column a column with a stationary phase of polyethylene glycol (film thickness 0.25 ⁇ m ⁇ length 30 m ⁇ inner diameter 0.25 mm)
  • Temperature increase conditions After maintaining at 100°C for 20 minutes, the temperature was increased from 100°C to 150°C at a rate of 2°C/min and maintained for 5 minutes.
  • the area ratio is not particularly limited as long as it is 54 or more and 130 or less, but is, for example, 125 or less, 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, or 30 or less.
  • the area ratio is, for example, 55 or more, or 56 or more. It can be said that the area ratio is correlated with the content of impurities corresponding to Peak X contained in the 1,3-butylene glycol product. In other words, when the area ratio is large, the content of impurities corresponding to Peak X increases, and when the area ratio is small, the content of impurities corresponding to Peak X decreases. By keeping the area ratio within the above range, the generation of apple odor and irritating odor tends to be further suppressed when the 1,3-butylene glycol product is incorporated into a cosmetic composition.
  • 1,3-butylene glycol product when the relative retention time of the peak of the internal standard substance, diethylene glycol dimethyl ether, in gas chromatography analysis under the above conditions is taken to be 1.0, 1,3-butylene glycol has a peak top in the relative retention time range of 5.15 to 5.84.
  • the area ratio of the above peak is, for example, preferably 99.5% or more, more preferably 99.7% or more, even more preferably 99.8% or more, and particularly preferably 99.9% or more.
  • area ratio refers to the ratio of the area of a specific peak to the area obtained by subtracting the diethylene glycol dimethyl ether peak area from the sum of the areas of all peaks appearing in the chart (total peak area).
  • all peaks refers to all of the peaks that appear when, for example, the relative retention time of the 1,3-butylene glycol peak is set to 1.0 and the analysis is continued until the relative retention time reaches 8.6 and then stopped.
  • the area obtained by subtracting the diethylene glycol dimethyl ether peak area from the total peak area can be rephrased as the sum of the areas of all peaks, excluding the peak corresponding to diethylene glycol dimethyl ether, that appear when, for example, the relative retention time of the 1,3-butylene glycol peak is set to 1.0 and the analysis is continued until the relative retention time reaches 8.6 and then stopped.
  • the 1,3-butylene glycol in the 1,3-butylene glycol product of the present disclosure may be, for example, (1) a reduced product of acetaldols, (2) a hydrolyzate of 1,3-butylene oxide, (3) a selective hydrogenolysis product of erythritol, (4) a selective water adduct of butadiene, (5) a hydrogenated product of n-butanal-3-one, (6) a hydrogenated product of 1-butanol-3-one, (7) a hydrogenated product of 3-hydroxy-1-butanoic acid, (8) a hydrogenated product of ⁇ -butyrolactone, and (9) a hydrogenated product of diketene.
  • 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).
  • the 1,3-butylene glycol in the 1,3-butylene glycol product of the present disclosure is preferably (1) a reduced form of acetaldols.
  • the reduced form of acetaldols is preferably a liquid-phase reduced form of acetaldols. This is because acetaldols have a high boiling point, are thermally unstable, and readily undergo dehydration reactions to form crotonaldehyde and the like at high temperatures. Furthermore, the dehydration reaction and reduction reaction (hydrogenation reaction) at high temperatures have a faster reaction rate than the reduction reaction (hydrogenation reaction).
  • 1,3-butylene glycol as a reduced form of acetaldols can be rephrased as 1,3-butylene glycol obtained by a method of hydrogenating acetaldols.
  • 1,3-butylene glycol when 1,3-butylene glycol is produced, by-products are generated during the manufacturing process.
  • by-products include low-boiling substances (low-boiling compounds) with unsaturated bonds such as acetaldehyde, butylaldehyde, crotonaldehyde, acetone, and methyl vinyl ketone, as well as condensations of these substances and condensations of 1,3-butylene glycol with the above-mentioned low-boiling substances (for example, acetals of 1,3-butylene glycol and acetaldol).
  • low-boiling substances low-boiling compounds
  • unsaturated bonds such as acetaldehyde, butylaldehyde, crotonaldehyde, acetone, and methyl vinyl ketone
  • acetals of crotonaldehyde and 1,3-butylene glycol 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 acetaldehyde trimer.
  • odor-causing substances are defined to include not only substances that currently emit an odor themselves, but also substances that change over time to emit an odor (e.g., apple odor).
  • 1,3-butylene glycol uses hydrogenated raw materials containing acetaldols.
  • acetaldols There are no particular restrictions on acetaldols, as long as they are compounds that can be reduced to 1,3-butylene glycol by hydrogenation. Examples include acetaldol, its cyclized dimer, para-aldol, aldoxane, a type of cyclic trimer of acetaldehyde, and mixtures of these.
  • the method for producing acetaldols is not particularly limited, but may include those obtained by, for example, the aldol condensation reaction of acetaldehyde in the presence of a basic catalyst, or by the 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.
  • reaction crude liquids may contain low-boiling substances such as acetaldehyde and crotonaldehyde, high-boiling substances such as aldehyde dimers and aldehyde trimers, water, salts, etc.
  • low-boiling substances compounds with a boiling point lower than that of 1,3-butylene glycol
  • high-boiling substances compounds with a boiling point higher than that of 1,3-butylene glycol
  • the above-mentioned reaction crude liquid may be subjected to pretreatment such as dealcoholization distillation, dehydration distillation, desalting, and removal of impurities to remove by-products such as unreacted acetaldehyde and crotonaldehyde before use.
  • Pretreatment methods include distillation, adsorption, ion exchange, heating to produce high-boiling substances, and decomposition.
  • Various distillation methods can be used, including reduced pressure, atmospheric pressure, increased pressure, azeotropy, extraction, and reaction.
  • the hydrogenated raw material may or may not contain water, but it is preferable that it does. That is, in the 1,3-butylene glycol product disclosed herein, the 1,3-butylene glycol is preferably obtained by hydrogenating a hydrogenated raw material containing water and acetaldols. In other words, the above-mentioned 1,3-butylene glycol is a hydrogen reduction product of a hydrogenated raw material containing water and acetaldols.
  • the content of acetaldols in the hydrogenation raw material is not particularly limited, but is preferably 80% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less. By keeping the content of acetaldols within the above range, the amount of by-products contained in crude 1,3-butylene glycol tends to be reduced.
  • the water content in the hydrogenated raw material is not particularly limited, but is, for example, preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 40% by mass or more, even more preferably more than 50% by mass, and particularly preferably 55% by mass or more. Also, for example, it is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.
  • the generation of odors (apple odor and irritating odor) tends to be reduced when a 1,3-butylene glycol product is blended into a cosmetic composition.
  • the invention of the present disclosure solves the previously unknown problem of reducing odors (apple odor and irritating odor) even when blended in a cosmetic composition by increasing the water content to a certain extent, appropriately adjusting the purification method for crude 1,3-butylene glycol, or a combination of these.
  • the following describes a method for producing crude 1,3-butylene glycol.
  • This production method involves reducing a hydrogenation feedstock containing acetaldols in the presence of a hydrogenation catalyst to obtain crude 1,3-butylene glycol.
  • Examples of hydrogenation catalysts include Raney nickel.
  • the hydrogenation catalyst can be used in a suspended or packed state, but is preferably used in a suspended state.
  • the amount of hydrogenation catalyst used is not particularly limited, but is preferably 1 to 30 parts by mass, more preferably 4 to 25 parts by mass, even more preferably 8 to 20 parts by mass, and particularly preferably 12 to 18 parts by mass, per 100 parts by mass of the hydrogenation feedstock.
  • the amount of hydrogen used in the reduction reaction is not particularly limited, but is preferably 0.5 to 40 parts by mass, more preferably 1 to 30 parts by mass, even more preferably 4 to 20 parts by mass, and particularly preferably 8 to 12 parts by mass, per 100 parts by mass of the hydrogenation feedstock.
  • the pressure (total pressure) within the reaction system during the reduction reaction is not particularly limited, but is preferably 150 to 500 atm, more preferably 180 to 450 atm, even more preferably 200 to 400 atm, and particularly preferably 250 to 350 atm.
  • the ratio of the hydrogen pressure (hydrogen partial pressure) to the total pressure in the reaction system is not particularly limited, but is preferably 80% or more (80 to 100%) of the total pressure, more preferably 85 to 99.9%, even more preferably 90 to 99.5%, and particularly preferably 95 to 99%.
  • the hydrogen pressure (hydrogen partial pressure) in the reaction system is not particularly limited, but is preferably 100 to 500 atm, more preferably 150 to 450 atm, even more preferably 150 to 400 atm, and particularly preferably 200 to 350 atm.
  • the reaction temperature in the reduction reaction is not particularly limited, but is preferably 110 to 140°C, for example, and more preferably 120 to 140°C.
  • the reaction time (residence time) in the reduction reaction is not particularly limited, but is preferably 30 to 300 minutes, more preferably 80 to 280 minutes, and even more preferably 120 to 250 minutes, for example.
  • the reaction rate (hydrogenation rate) of acetal aldols to 1,3-butylene glycol is improved.
  • the acetalization reaction between 1,3-butylene glycol and acetaldol is reduced, tending to produce a high-purity 1,3-butylene glycol product. This tendency is particularly strongly influenced by the hydrogen pressure during the reduction reaction.
  • reaction rate (reduction rate) of acetal aldols to 1,3-butylene glycol is significantly improved, resulting in a reduction in the amount of acetalized 1,3-butylene glycol and acetaldol, and a high-purity 1,3-butylene glycol product.
  • This reaction can be carried out batchwise, semi-batchwise, or continuously.
  • the crude 1,3-butylene glycol obtained by hydrogen reduction of the hydrogenated raw material can be obtained as a 1,3-butylene glycol product by, for example, undergoing a dehydration process, a desalting process, a high-boiling point distillation process, an alkali reaction process, a dealkalization process, and a distillation process.
  • the conditions for hydrogen reduction of the hydrogenated raw material, the high-boiling point distillation process, and the dealkalization process tend to reduce the generation of odors (apple odor and irritating odor) when the 1,3-butylene glycol product is incorporated into a cosmetic composition.
  • the content of high boiling point substances in the crude 1,3-butylene glycol is not particularly limited, but is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less. It is also, for example, 0.1% by mass or more, 1% by mass or more, or 2% by mass or more.
  • the content of high boiling point substances in the crude 1,3-butylene glycol after the high boiling point substance removal distillation process is 0.5% by mass or less, preferably 0.3% by mass or less, and more preferably 0.1% by mass or less.
  • Figure 1 is a flow sheet of an apparatus showing an example of an embodiment for obtaining a 1,3-butylene glycol product according to the present disclosure.
  • A is a dehydrating tower and is related to the dehydration process.
  • B is a demineralizing tower and is related to the demineralizing process.
  • C is a high-boiling point removal distillation tower and is related to the high-boiling point removal distillation process.
  • D is an alkali reactor and is related to the alkali reaction process.
  • E is a dealkalizing tower and is related to the dealkalizing process.
  • F is a product distillation tower and 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.
  • the crude 1,3-butylene glycol (corresponding to "X-1") obtained by hydrogen reduction of the hydrogenation feedstock is supplied to dehydration tower A.
  • 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.
  • demineralization tower B a desalted crude 1,3-butylene glycol 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.
  • the desalted crude 1,3-butylene glycol stream is supplied to high-boiler removal distillation column C.
  • high boilers and 1,3-butylene glycol containing high boilers
  • a crude 1,3-butylene glycol stream after high boiler removal is obtained from the top of the column.
  • the amount of 1,3-butylene glycol containing high boilers discharged from the bottom of the column is preferably 10 to 50 parts, more preferably 20 to 45 parts, even more preferably 23 to 40 parts, even more preferably 25 to 35 parts, and particularly preferably 25 to 30 parts, per 100 parts of the charged liquid.
  • the amount of crude 1,3-butylene glycol obtained from the top of the column is preferably 50 to 90 parts, more preferably 55 to 85 parts, even more preferably 60 to 80 parts, and particularly preferably 65 to 75 parts, per 100 parts of the charged liquid.
  • the crude 1,3-butylene glycol distilled in the high-boiling point removal distillation column C is supplied to an alkaline reactor (e.g., a tubular flow reactor) D and treated with a base.
  • a base is added in an amount of 0.05 to 10 mass %, preferably 0.1 to 1.0 mass %, based on the crude 1,3-butylene glycol stream after high-boiling point removal. If the amount of base added exceeds 10 mass %, the base tends to precipitate in the distillation column, piping, etc., and cause blockages. Furthermore, decomposition reactions of high-boiling point compounds may occur, which may result in the generation of by-products. If the amount is less than 0.05 mass %, the effect of decomposing by-products is small, and neither is preferred.
  • the base added to alkaline reactor D or upstream thereof is not particularly limited, but is preferably an alkali metal compound.
  • alkali metal compounds include caustic soda, caustic potash, sodium (bicarbonate), and potassium (bicarbonate). From the perspective of reducing by-products contained in the final 1,3-butylene glycol product, caustic soda and caustic potash are preferred.
  • the base may be added as a solid, but it is preferable to add it as an aqueous solution for operational reasons and to promote contact with the target liquid.
  • the above bases may be used alone or in combination of two or more.
  • the reaction temperature in alkaline reactor D is not particularly limited, but is preferably 90 to 140°C, and more preferably 110 to 130°C. If the reaction temperature is below 90°C, a long reaction residence time is required, which increases the reactor capacity and tends to be uneconomical. If the reaction temperature exceeds 140°C, the color of the final 1,3-butylene glycol product tends to increase.
  • the reaction residence time is preferably 5 to 120 minutes, and more preferably 10 to 30 minutes. If the reaction residence time is less than 5 minutes, the reaction will be insufficient, resulting in a deterioration in the quality of the final 1,3-butylene glycol product. If the reaction residence time exceeds 120 minutes, a large reactor will be required, which increases equipment costs and is therefore disadvantageous from an economic standpoint.
  • the crude reaction liquid stream is supplied to a dealkalizer (thin film evaporator) E, where base, high boilers (and 1,3-butylene glycol containing these), etc. are removed from the bottom of the tower 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 base, etc.
  • 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, more preferably 70 to 90 parts, even more preferably 75 to 87 parts, and particularly preferably 80 to 85 parts.
  • the total amount discharged from distillation column C and dealkalization column E (discharged to outside the system) is not particularly limited, but is preferably, for example, 20 to 60, more preferably 24 to 55, even more preferably 28 to 50, and particularly preferably 32 to 45.
  • evaporation is carried out at a reduced pressure of, for example, 100 torr or less, preferably 5 to 20 torr, at the top of the tower.
  • the temperature of the evaporator is preferably, for example, 90 to 120°C.
  • the crude 1,3-butylene glycol stream containing low-boiling substances distilled from the top of the tower is supplied to product distillation tower F.
  • Product distillation column F can be, for example, a perforated plate column or a bubble cap column.
  • a packed column with low pressure loss such as Sulzer Packing or Melapak (both trade names of Sumitomo Heavy Industries, Ltd.) is more preferable.
  • Sulzer Packing or Melapak both trade names of Sumitomo Heavy Industries, Ltd.
  • the reboiler used should preferably be 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.
  • the product distillation column F 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 count of, for example, 10 to 20 plates.
  • the feed liquid is preferably supplied to a position 20 to 70% of the height of the column from the top of the column.
  • the pressure at the top of the column 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.
  • 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 can also be fed directly to product distillation column F.
  • product distillation column F impurities such as low boiling points are distilled from the top of the column, and the product 1,3-butylene glycol is obtained from the bottom of product distillation column F (corresponding to "Y").
  • the moisturizing agent of the present disclosure contains the 1,3-butylene glycol product described above. Therefore, the moisturizing agent has excellent moisturizing performance, is free from coloration and odor, is resistant to coloration over time, and is also resistant to an increase in acid concentration over time, even when containing water.
  • the moisturizing agent of the present disclosure may contain components other than the 1,3-butylene glycol product described above, for example, moisturizing agent components other than the 1,3-butylene glycol product described above.
  • the moisturizing agent of the present disclosure may contain, 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, of the 1,3-butylene glycol product described above.
  • the moisturizing agent may be composed solely of the 1,3-butylene glycol product described above.
  • the cosmetic preparation of the present disclosure contains the moisturizing agent described above.
  • the amount of the 1,3-butylene glycol product blended 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 preparation.
  • the amount of the 1,3-butylene glycol product blended 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.
  • the cosmetic composition of the present disclosure may contain, 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, sequestering agents, thickeners, powders, UV absorbers, UV blockers, fragrances, pH adjusters; medicinal and physiologically active ingredients such as vitamins, skin activators, blood circulation promoters, whitening agents, antibacterial agents, and anti-inflammatory agents.
  • the cosmetics disclosed herein can be skin cosmetics such as lotions, emulsions, creams, gels, packs, and masks, or hair cosmetics such as shampoos, rinses, and hair growth agents. They can also be sunscreen cosmetics and makeup cosmetics. They can also be pharmaceuticals or quasi-drugs containing medical ingredients.
  • the cosmetics disclosed herein can be produced by methods known per se.
  • Example 1 The method for producing 1,3-butylene glycol will be described with reference to FIG.
  • a liquid-phase hydrogen reduction reactor was charged with 100 parts of an acetaldol solution containing 55% by mass of water as a raw material (a mixed solution of 45 parts of acetaldol and 55 parts of water) and 10 parts of hydrogen, and 15 parts of Raney nickel was added as a catalyst.
  • the reactor was maintained at 135°C and 300 atm to carry out liquid-phase hydrogen reduction. After separating the catalyst from the liquid after the reaction, the liquid was neutralized with caustic soda and the alcohol was removed to obtain crude 1,3-butylene glycol (1).
  • Crude 1,3-butylene glycol (1) (corresponding to "X-1" in Figure 1) was charged into dehydrating tower A.
  • dehydrating tower A water was extracted from the top of the tower per 100 parts of the charged liquid, 15 parts of fresh water was added as reflux water, and the pressure was set to 50 torr.
  • Crude 1,3-butylene glycol (2) with a water content of 0.5% by mass or less was obtained from the bottom of the tower. The water extracted from the top of the tower was discharged (corresponding to "X-2" in Figure 1).
  • crude 1,3-butylene glycol (2) was charged into demineralizer B.
  • demineralizer B salts, high boiling point materials, and a portion of the 1,3-butylene glycol were discharged as evaporation residue from the bottom of the tower (corresponding to "X-3" in Figure 1).
  • the amount of evaporation residue discharged was 5 parts per 100 parts of the charged liquid.
  • crude 1,3-butylene glycol (3) containing 1,3-butylene glycol, low boiling point materials, and a portion of the high boiling point materials was obtained from the top of the tower.
  • crude 1,3-butylene glycol (3) was charged into high boiler removal distillation column C.
  • high boilers and a portion of the 1,3-butylene glycol were discharged from the bottom of the column (corresponding to "X-4" in Figure 1).
  • the discharge amount was 20 parts per 100 parts of the charged liquid.
  • 80 parts of crude 1,3-butylene glycol (4) containing low boilers was obtained from the top of the column.
  • crude 1,3-butylene glycol (4) was charged into alkaline reactor D. At this time, a 10% by mass aqueous solution of caustic soda was added so that the caustic soda concentration relative to the charged liquid was 0.2% by mass.
  • the reaction temperature in alkaline reactor D was maintained at 120°C, and the reaction was carried out for a residence time of 20 minutes.
  • dealkalization tower E caustic soda, high boiling point substances, and a portion of 1,3-butylene glycol were discharged from the bottom of the tower (corresponding to "X-5" in Figure 1). The amount discharged was 10 parts per 100 parts of the charged liquid. Meanwhile, 90 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point substances was obtained from the top of the tower.
  • the resulting 1,3-butylene glycol product was subjected to GC/FID analysis under the conditions described below, and the area ratio, as shown in the formula below, was 125.
  • the odor test 1 score was 2, and the odor test 2 score was 1.
  • Example 2 In distillation column C, the discharge amount was 25 parts per 100 parts of the charged liquid amount, and 75 parts of crude 1,3-butylene glycol (4) containing low boiling point materials obtained from the top of the column was obtained, and further, in dealkalization column E, the discharge amount was 17 parts per 100 parts of the charged liquid amount, and 83 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point materials obtained from the top of the column was obtained. Except for this, a 1,3-butylene glycol product was obtained in the same manner as in Example 1. When the amount charged to distillation column C was 100, the total amount discharged from distillation column C and dealkalization column E (discharged outside the system) was 37.75.
  • the resulting 1,3-butylene glycol product was subjected to GC/FID analysis under the conditions described below, and the area ratio, as expressed by the formula described below, was 95.
  • the odor test 1 score was 1, and the odor test 2 score was 1.
  • Example 3 When obtaining crude 1,3-butylene glycol (1), 100 parts of an acetaldol solution containing 60% by mass of water (a mixed solution of 40 parts of acetaldol and 60 parts of water) was used as a raw material, and in the distillation column C, the discharge amount was 25 parts relative to 100 parts of the charged liquid amount, and 75 parts of crude 1,3-butylene glycol (4) containing low boiling point materials obtained from the top of the column, and further, in the dealkalization column E, the discharge amount was 17 parts relative to 100 parts of the charged liquid amount, and 83 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point materials obtained from the top of the column.
  • the resulting 1,3-butylene glycol product was subjected to GC/FID analysis under the conditions described below, and the area ratio, as expressed by the formula described below, was 81.
  • the odor test 1 score was 1, and the odor test 2 score was 1.
  • Example 4 When obtaining crude 1,3-butylene glycol (1), 100 parts of an acetaldol solution containing 60% by mass of water (a mixed solution of 40 parts of acetaldol and 60 parts of water) was used as a raw material, and in distillation column C, the discharge amount was 30 parts relative to 100 parts of the charged liquid amount, and 70 parts of crude 1,3-butylene glycol (4) containing low boiling point materials obtained from the top of the column was obtained. Further, in dealkalization column E, the discharge amount was 20 parts relative to 100 parts of the charged liquid amount, and 80 parts of crude 1,3-butylene glycol (5) containing 1,3-butylene glycol and low boiling point materials obtained from the top of the column was obtained.
  • the resulting 1,3-butylene glycol product was subjected to GC/FID analysis under the conditions described below, and the area ratio, as expressed by the formula described below, was 57.
  • the odor test 1 score was 1, and the odor test 2 score was 1.
  • the resulting 1,3-butylene glycol product was subjected to GC/FID analysis under the conditions described below, and the area ratio, as expressed by the formula described below, was 51.
  • the odor test 1 score was 1, and the odor test 2 score was 2.
  • Crude 1,3-butylene glycol (1) (corresponding to "X-1" in Figure 1) was charged into dehydrating tower A.
  • dehydrating tower A water was extracted from the top of the tower per 100 parts of the charged liquid, 15 parts of fresh water was added as reflux water, and the pressure was set to 50 torr.
  • Crude 1,3-butylene glycol (2) with a water content of 0.5% by mass or less was obtained from the bottom of the tower. The water extracted from the top of the tower was discharged (corresponding to "X-2" in Figure 1).
  • crude 1,3-butylene glycol (2) was charged into demineralizer B.
  • demineralizer B salts, high boiling point materials, and a portion of the 1,3-butylene glycol were discharged as evaporation residue from the bottom of the tower (corresponding to "X-3" in Figure 1).
  • the amount of evaporation residue discharged was 5 parts per 100 parts of the charged liquid.
  • crude 1,3-butylene glycol (3) containing 1,3-butylene glycol, low boiling point materials, and a portion of the high boiling point materials was obtained from the top of the tower.
  • crude 1,3-butylene glycol (3) was charged into high boiler removal distillation column C.
  • high boilers and a portion of the 1,3-butylene glycol were discharged from the bottom of the column (corresponding to "X-4" in Figure 1).
  • the discharge amount was 20 parts per 100 parts of the charged liquid.
  • 80 parts of crude 1,3-butylene glycol (4) containing low boilers was obtained from the top of the column.
  • crude 1,3-butylene glycol (4) was charged into alkaline reactor D. At this time, a 10% by mass aqueous solution of caustic soda was added so that the caustic soda concentration relative to the charged liquid was 0.2% by mass.
  • the reaction temperature in alkaline reactor D was maintained at 120°C, and the reaction was carried out for a residence time of 20 minutes.
  • Area ratio Peak X area / total peak area minus diethylene glycol dimethyl ether peak area ⁇ 10 6 Peak X area: In gas chromatography analysis under the following conditions, the area of the peak having a peak top in the range of relative retention time 6.2 to 6.32 when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard, is set to 1.0.
  • GC/FID measurement conditions GC/FID measurements of the 1,3-butylene glycol products in the examples and comparative examples were carried out under the following conditions:
  • the analyzer used was a Shimadzu GC2010 (manufactured by Shimadzu Corporation).
  • GC Conditions for gas chromatography analysis Analysis sample: A mixture was prepared by mixing 1 g of an 80% by mass aqueous solution of 1,3-butylene glycol product with 0.01 g of diethylene glycol dimethyl ether. Injection volume: 1 ⁇ L Analytical column: TC-WAX (column with a stationary phase of polyethylene glycol, film thickness 0.25 ⁇ m ⁇ length 30 m ⁇ inner diameter 0.25 mm, manufactured by GL Sciences Inc.) Temperature increase conditions: After maintaining at 100°C for 20 minutes, the temperature was increased from 100°C to 150°C at a rate of 2°C/min and maintained for 5 minutes.
  • Sample introduction method Split sample introduction method Sample introduction temperature: 250°C Split gas flow rate and carrier gas: 71.1 mL/min, helium Column gas flow rate and carrier gas: 0.91 mL/min, helium Detector and temperature: flame ionization detector (FID), 250°C
  • Odor Test 1 was conducted as a sensory evaluation in which four evaluators smelled the target samples in a room at 25° C. Specifically, (1) each of the 1,3-butylene glycol products of Examples 1 to 4 and Comparative Examples 1 and 2 was mixed with an aqueous solution containing citric acid, trisodium citrate, sodium EDTA, and phenoxyethanol so that the 1,3-butylene glycol product concentration was 20% by mass, the citric acid concentration was 0.01% by mass, the trisodium citrate concentration was 0.04% by mass, the sodium EDTA concentration was 0.25% by mass, and the phenoxyethanol concentration was 0.7% by mass. The mixture (100 ml) was then allowed to stand at 50° C.
  • the apple odor intensity of Examples 1 to 4 and Comparative Example 1 was 1 or 2
  • the apple odor intensity of Comparative Example 2 was 3, and the irritating odor intensity of Examples 1 to 4 and Comparative Example 2 was 1, while the irritating odor intensity of Comparative Example 1 was 2.
  • the 1,3-butylene glycol product of Comparative Example 1 has a irritating odor but no apple odor
  • the 1,3-butylene glycol product of Comparative Example 2 has an apple odor but no irritating odor.
  • This irritating odor is thought to be an odor derived from the cosmetic composition itself.
  • a specific by-product contained in the resulting 1,3-butylene glycol product has a masking effect on the irritating odor derived from the cosmetic composition, and it is thought that the inclusion of a certain amount of this by-product suppresses the irritating odor.
  • Comparative Example 1 the amount of the above-mentioned by-product in the resulting 1,3-butylene glycol product was small, and the masking effect on the irritating odor was insufficient, resulting in the generation of the irritating odor.
  • Area ratio Peak X area / total peak area minus diethylene glycol dimethyl ether peak area ⁇ 10 6
  • Peak X area In gas chromatography analysis under the following conditions, the area of a peak having a peak top in the range of relative retention time 6.2 to 6.32 when the relative retention time of the peak of diethylene glycol dimethyl ether, an internal standard, is set to 1.0
  • Injection sample a mixture of 1 g of an 80% by mass aqueous solution of 1,3-butylene glycol product and 0.01 g of diethylene glycol dimethyl ether
  • Injection amount 1 ⁇ L
  • Analytical column a column with a stationary phase of polyethylene glycol (film thickness 0.25 ⁇ m ⁇ length 30 m ⁇ inner diameter 0.25 mm)
  • Temperature increase conditions After maintaining at 100
  • the 1,3-butylene glycol product according to at least one selected from [1] to [3], wherein the area ratio of the 1,3-butylene glycol peak in gas chromatography analysis under the above conditions is 99.5% or more, 99.7% or more, 99.8% or more, or 99.9% or more.
  • the 1,3-butylene glycol product according to at least one selected from [1] to [4], wherein the 1,3-butylene glycol in the 1,3-butylene glycol product is (1) a reduced product of an acetaldol, (2) a hydrolyzate of 1,3-butylene oxide, (3) a selective hydrogenolysis product of erythritol, (4) a selective water adduct of butadiene, (5) a hydrogenated product of n-butanal-3-one, (6) a hydrogenated product of 1-butanol-3-one, (7) a hydrogenated product of 3-hydroxy-1-butanoic acid, (8) a hydrogenated product of ⁇ -butyrolactone, or (9) a hydrogenated product of diketene.
  • the 1,3-butylene glycol in the 1,3-butylene glycol product is (1) a reduced product of an acetaldol, (2) a hydrolyzate of 1,3-butylene oxide, (3) a selective hydrogeno
  • the 1,3-butylene glycol product according to [8] or [9] wherein the hydrogenated raw material contains water.
  • a moisturizer comprising at least one 1,3-butylene glycol product selected from [1] to [12].
  • a cosmetic composition comprising at least one 1,3-butylene glycol product selected from [1] to [12].

Landscapes

  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Emergency Medicine (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un produit de 1,3-butylène glycol peu susceptible de générer une odeur de pomme et une odeur âcre même lorsqu'il est mélangé dans une composition cosmétique.　Le produit de 1,3-butylène glycol a un rapport de surface de 54 à 130, représenté par la formule suivante.　Rapport de surface = surface du pic X/surface obtenue par soustraction de la surface du pic de l'éther diméthylique de diéthylène glycol de la surface totale des pics × 106. Surface du pic X : surface d'un pic ayant un sommet de pic dans la plage de temps de rétention de 6,2 à 6,32 dans une analyse chromatographique en phase gazeuse dans des conditions spécifiques lorsque le temps de rétention de l'éther diméthylique de diéthylène glycol, l'étalon interne, est considéré comme étant de 1,0.
PCT/JP2025/018561 2024-07-17 2025-05-22 Produit de 1,3-butylène glycol Pending WO2026018557A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024114227 2024-07-17
JP2024-114227 2024-07-17

Publications (1)

Publication Number Publication Date
WO2026018557A1 true WO2026018557A1 (fr) 2026-01-22

Family

ID=98437073

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/018561 Pending WO2026018557A1 (fr) 2024-07-17 2025-05-22 Produit de 1,3-butylène glycol

Country Status (1)

Country Link
WO (1) WO2026018557A1 (fr)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258129A (ja) * 1994-03-17 1995-10-09 Daicel Chem Ind Ltd １，３−ブチレングリコ−ルの精製方法
WO2000007969A1 (fr) * 1998-08-07 2000-02-17 Daicel Chemical Industries, Ltd. 1,3-butylene-glycol tres pur et son procede de production
JP2000086557A (ja) * 1998-09-04 2000-03-28 Degussa Huels Ag 反応混合物中のアセタ―ル又はケタ―ル含量の還元法
JP2001213825A (ja) * 2000-02-04 2001-08-07 Daicel Chem Ind Ltd 高純度１，３−ブチレングリコール
JP2001213822A (ja) * 2000-02-04 2001-08-07 Daicel Chem Ind Ltd １，３−ブチレングリコールの製造方法
JP2001213824A (ja) * 2000-02-04 2001-08-07 Daicel Chem Ind Ltd 精製１，３−ブチレングリコールの製造方法
WO2001056963A1 (fr) * 2000-02-04 2001-08-09 Daicel Chemical Industries, Ltd. 1,3-butylene glycol tres pur, procede de production associe, et procede de production des sous-produits butanol et acetate de butyle
JP2001288131A (ja) * 2000-02-04 2001-10-16 Daicel Chem Ind Ltd 精製１，３−ブチレングリコールの製造方法
JP2004323406A (ja) * 2003-04-23 2004-11-18 Sanko Bussan Kk 保湿剤および植物抽出物の使用方法ならびに外用剤
JP2021038189A (ja) * 2019-09-05 2021-03-11 株式会社ダイセル １，３−ブチレングリコール製品
JP2021038190A (ja) * 2019-09-05 2021-03-11 株式会社ダイセル １，３−ブチレングリコール製品
WO2021132370A1 (fr) * 2019-12-28 2021-07-01 株式会社ダイセル Produit de 1,3-butylène glycol

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258129A (ja) * 1994-03-17 1995-10-09 Daicel Chem Ind Ltd １，３−ブチレングリコ−ルの精製方法
WO2000007969A1 (fr) * 1998-08-07 2000-02-17 Daicel Chemical Industries, Ltd. 1,3-butylene-glycol tres pur et son procede de production
JP2000086557A (ja) * 1998-09-04 2000-03-28 Degussa Huels Ag 反応混合物中のアセタ―ル又はケタ―ル含量の還元法
JP2001213825A (ja) * 2000-02-04 2001-08-07 Daicel Chem Ind Ltd 高純度１，３−ブチレングリコール
JP2001213822A (ja) * 2000-02-04 2001-08-07 Daicel Chem Ind Ltd １，３−ブチレングリコールの製造方法
JP2001213824A (ja) * 2000-02-04 2001-08-07 Daicel Chem Ind Ltd 精製１，３−ブチレングリコールの製造方法
WO2001056963A1 (fr) * 2000-02-04 2001-08-09 Daicel Chemical Industries, Ltd. 1,3-butylene glycol tres pur, procede de production associe, et procede de production des sous-produits butanol et acetate de butyle
JP2001288131A (ja) * 2000-02-04 2001-10-16 Daicel Chem Ind Ltd 精製１，３−ブチレングリコールの製造方法
JP2004323406A (ja) * 2003-04-23 2004-11-18 Sanko Bussan Kk 保湿剤および植物抽出物の使用方法ならびに外用剤
JP2021038189A (ja) * 2019-09-05 2021-03-11 株式会社ダイセル １，３−ブチレングリコール製品
JP2021038190A (ja) * 2019-09-05 2021-03-11 株式会社ダイセル １，３−ブチレングリコール製品
WO2021132370A1 (fr) * 2019-12-28 2021-07-01 株式会社ダイセル Produit de 1,3-butylène glycol

Similar Documents

Publication Publication Date Title
JP2025148555A (ja) １，３－ブチレングリコール製品、及び１，３－ブチレングリコールの製造方法
JP6979544B2 (ja) １，３−ブチレングリコール製品
KR102682257B1 (ko) 1,3-부틸렌 글리콜 제품
WO2026018557A1 (fr) Produit de 1,3-butylène glycol
WO2026018556A1 (fr) Produit de 1,3-butylène glycol
WO2026018555A1 (fr) Produit de 1,3-butylène glycol
JP7797733B1 (ja) １，３－ブチレングリコール組成物
JP2026067935A (ja) １，３－ブチレングリコール製品
US20260042724A1 (en) 1,3-butylene glycol product

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25840658

Country of ref document: EP

Kind code of ref document: A1