Method for producing additive for cosmetics

Abstract

Provided is a method for producing, using a biomass raw material, an additive for cosmetics having performance equivalent to or superior to that of a conventional, fossil-fuel-derived additive for cosmetics. A method for producing an additive for cosmetics according to the present invention involves producing an additive for cosmetics that contains an acrylic polymer derived from a bio-raw material, said method comprising a step (i) for obtaining acetone from bioethanol, a step (ii) for obtaining isopropanol from the acetone, a step (iii) for obtaining propylene from the isopropanol, a step (iv) for obtaining acrylic acid from the propylene, and a step (v) for polymerizing a monomer containing acrylic acid and / or a salt thereof to obtain an acrylic polymer. The acrylic acid introduced in step (v) contains the acrylic acid obtained in step (iv).

Description

Manufacturing method of cosmetic additives

[0001] The present invention relates to a method for producing a cosmetic additive, and more particularly to a method for producing a cosmetic additive using renewable bio-based raw materials that exhibits performance equivalent to or superior to that of cosmetic additives derived from fossil raw materials.

[0002] Cosmetics, such as skin cosmetics and hair cosmetics, may contain thickeners, such as polymers and surfactants, as cosmetic additives to retain active ingredients and improve usability. Acrylic polymers containing (meth)acrylic acid as a structural unit may be used as the thickener, as they have a high thickening effect, gel with a small amount, and provide a fresh, excellent usability (see, for example, Patent Documents 1 and 2). A method for producing such acrylic polymers is disclosed, for example, in Patent Document 3.

[0003] In recent years, from the viewpoint of carbon neutrality, cosmetic additives derived from raw materials (e.g., biomass raw materials) that are not derived from fossil fuels have been in demand. As a method for producing acrylic acid derived from biomass raw materials, which is a raw material for acrylic polymers, for example, Patent Documents 4 and 5 disclose a method for producing acrylic acid or acrolein by using isopropanol obtained by fermentation as a raw material, vaporizing it by heating, and then partially oxidizing it in the presence of oxygen using a partial oxidation catalyst.

[0004] International Publication No. 2017 / 170961 International Publication No. 2009 / 084469 JP-A-1-217017 JP-A-2015-160806 JP-A-2015-160807

[0005] However, conventional cosmetic additives derived from biomass raw materials have been inferior in performance when used in cosmetics, i.e., thickening effect, feel when used, and transparency, compared to cosmetic additives derived from fossil raw materials.

[0006] Therefore, an object of the present invention is to provide a method for producing a cosmetic additive using biomass raw materials that has performance equivalent to or superior to that of conventional cosmetic additives derived from fossil raw materials.

[0007] In order to solve the above problems, the present inventors have focused for the first time on ethanol as a starting material for the monomer that constitutes the main chain of a cosmetic additive, and have investigated a method for producing a cosmetic additive derived from biomaterials, in which a cosmetic additive is obtained from ethanol, which has conventionally been used mainly as a fuel, instead of using natural polymers, which have a poor feel when used, as a cosmetic additive.

[0008] That is, the present inventors have conceived a production method that can reduce the production cost of acrylic acid using bioethanol, which is produced in large quantities, as a starting material.

[0009] The present invention has also found that by using bioacrylic acid obtained from bioethanol through a specific process (bioethanol → bioacetone → bioisopropanol → biopropylene → bioacrylic acid) as a monomer, this bioacrylic acid, which is produced at low production costs through a specific process derived from bioethanol, does not cause problems related to usability or impurities (e.g., coloration or odor), and is equally or even more suitable as a raw material acrylic acid for cosmetic additives than conventional acrylic acid derived from fossil raw materials. Furthermore, the present invention has found that by using acrylic acid derived from biomaterials with a water content of a specific amount or less as a raw material, cosmetic additives with an excellent usability can be obtained. Based on these findings, the present invention has been completed to solve the above problems.

[0010] That is, the present invention provides a method for producing a cosmetic additive containing an acrylic polymer derived from a biomaterial, comprising the following steps (i) to (v), wherein the acrylic acid added in step (v) contains the acrylic acid obtained in step (iv): step (i) of obtaining acetone from bioethanol; step (ii) of obtaining isopropanol from the acetone; step (iii) of obtaining propylene from the isopropanol; step (iv) of obtaining acrylic acid from the propylene; and step (v) of obtaining an acrylic polymer by polymerizing a monomer containing acrylic acid and / or a salt thereof.

[0011] The above-mentioned production method preferably further comprises the following step (vi): a step (vi) of drying the acrylic polymer.

[0012] The total content of ethanol and acetaldehyde in the acetone is preferably 20,000 ppm or less.

[0013] The ethanol content in the isopropanol is preferably 20,000 ppm or less.

[0014] The raw material for obtaining the isopropanol preferably contains the hydrogen obtained in the step (i).

[0015] It is preferable to reuse at least a part of the water generated in the steps up to obtaining the acrylic acid in at least one of the steps using water.

[0016] In the above production method, the bioethanol is preferably obtained by fermentation of one or more genetically modified or non-genetically modified plant materials selected from the group consisting of sugar cane, corn, and sugar beet.

[0017] The water content in the acrylic acid and / or salt thereof added in the step (v) is preferably 4000 ppm or less.

[0018] In the step (v), in addition to the acrylic acid and / or its salt obtained in the step (iv), another acrylic acid (salt) may be used in combination in the monomer, and the acrylic acid and / or its salt obtained in the step (iv) may account for 1 mol % or more of the total amount of acrylic acid (salt) subjected to the step (v).

[0019] The cosmetic additive is preferably a thickener.

[0020] The present invention also provides a method for producing a cosmetic comprising the cosmetic additive obtained by the above-mentioned production method.

[0021] The present invention also provides a method for producing a cosmetic additive containing an acrylic polymer, comprising a step (v) of polymerizing acrylic acid and / or a salt thereof, wherein the acrylic acid and / or a salt thereof is derived from a biomaterial and has a water content of 4000 ppm or less.

[0022] In the above production method, the polymerization is preferably carried out by precipitation polymerization.

[0023] In the above production method, it is preferable to use a hydrophobic organic solvent in the polymerization.

[0024] According to the method for producing a cosmetic additive of the present invention, a cosmetic additive having performance (e.g., feel when used, transparency, etc.) equivalent to or superior to that of conventional cosmetic additives derived from fossil raw materials can be obtained using renewable biomass raw materials. ２ Therefore, by producing a cosmetic additive using bioethanol as a raw material, it is possible to aim for a carbon-neutral, high-performance cosmetic additive. Furthermore, the cosmetic additive obtained by the cosmetic additive production method of the present invention can be obtained inexpensively with the same or even reduced impurity content as cosmetic additives derived from fossil raw materials.

[0025] 1 is a flow sheet showing steps (1) to (8) in a method for producing acrylic acid according to one embodiment of the present invention. FIG. 2 is a flow sheet showing steps (9) to (11) in a method for producing acrylic acid according to one embodiment of the present invention.

[0026] [Explanation of Terms] (Biomass Raw Materials) In this specification, biomass raw materials (sometimes referred to as "biomass raw materials") refer to raw materials derived from living organisms. The biomass raw materials may be animal-derived biomaterials (e.g., wool, etc.), but renewable plant raw materials are preferably used. Specifically, biomaterials whose starting materials are plant components containing natural polymers such as sugars, starch, and cellulose are preferably used.

[0027] In this specification, bioethanol, bioacetone, bioisopropanol, biopropylene, and bioacrylic acid refer to ethanol, acetone, isopropanol (also known as 2-propanol and isopropyl alcohol), propylene, and acrylic acid, which are produced using biomaterials as raw materials or upstream raw materials of the raw materials, and the carbon isotopes １４ Except for the amount of C, there is no difference in chemical structure from known ethanol, acetone, isopropanol, propylene, and acrylic acid.

[0028] Hereinafter, to emphasize that ethanol, acetone, isopropanol, propylene, and acrylic acid are obtained from bio-based raw materials, they may be referred to as bioethanol, bioacetone, bioisopropanol, biopropylene, and bioacrylic acid, respectively.

[0029] In this specification, a cosmetic additive derived from a biomaterial means that the acrylic polymer contained as the cosmetic additive contains a monomer derived from a biomaterial as a monomer constituting the main chain.

[0030] (Other) In this specification, mass and weight are treated as synonyms. Furthermore, the range "X to Y" means "X or more and Y or less." Furthermore, the "X" in the range "X to Y" can be the basis for the legitimacy of an amendment to "X or more" or "X or less." Furthermore, the "Y" in the range "X to Y" can be the basis for the legitimacy of an amendment to "Y or more" or "Y or less." Furthermore, unless otherwise noted, "%" and "ppm" mean "% by mass" and "ppm by mass." Furthermore, "~acid (salt)" means "~acid and / or its salt," and "(meth)acrylic" means "acrylic and / or methacrylic." Furthermore, measurements of physical properties, etc., are performed at room temperature (20-25°C) and a relative humidity of 40-50% RH, unless otherwise noted.

[0031] [Method for producing a cosmetic additive] The method for producing a cosmetic additive of the present invention (sometimes referred to as the "production method of the present invention") is, in a first aspect, a method for producing a cosmetic additive containing an acrylic polymer derived from a biomaterial. The production method of the present invention comprises at least the following steps (i) to (v). The acrylic acid input in step (v) includes the acrylic acid obtained in step (iv). Step (i) for obtaining acetone from bioethanol; Step (ii) for obtaining isopropanol from the acetone; Step (iii) for obtaining propylene from the isopropanol; Step (iv) for obtaining acrylic acid from the propylene; Step (v) for polymerizing a monomer containing acrylic acid and / or a salt thereof to obtain an acrylic polymer.

[0032] (Bioethanol) The present invention is the first to focus on bioethanol as a raw material for cosmetic additives, and its greatest feature is that cosmetic additives are obtained from bioethanol, which has conventionally been used mainly as fuel.

[0033] Global bioethanol production is expected to exceed 113 billion liters (approximately 89 million tons) in 2022. Bioethanol accounts for approximately 3% of the approximately 4.6 trillion liters of petroleum production, making it a cheap and readily available bio-based raw material. Bioethanol is primarily used as fuel (approximately 85% is used for automobiles and other purposes), as well as industrial applications such as solvents and food-related applications such as beverages and disinfectants. While bioethanol is sometimes used to produce chemical products such as ethyl esters, this invention is characterized by its use as a starting material for cosmetic additives, a use of bioethanol that is primarily used as fuel.

[0034] Bioethanol can be obtained from glucose, sucrose, or the like by known fermentation methods, for example, by using molasses (blackstrap molasses) obtained after separating refined sugar as the fermentation raw material, according to the following reaction formula: ６ H １２ O ６ →2CH ３ CH ２ OH + 2CO ２

[0035] In the first step, one molecule of glucose is broken down into two molecules of pyruvic acid by multiple enzymes in the glycolytic pathway. From the second step onwards, the reactions specific to alcoholic fermentation take place. One molecule of carbon dioxide is removed from one molecule of pyruvic acid to produce acetaldehyde. Afterwards, acetaldehyde is quickly reduced to ethanol by the electrons of reduced NADH.

[0036] In the present invention, ethanol obtained from a biological raw material can be used, but preferably ethanol obtained from a plant raw material is used, and more preferably bioethanol obtained by fermenting one or more plant materials selected from the group consisting of sugar cane, corn, and sugar beet. Sugar cane, corn, and sugar beet may be further crushed or juiced before fermentation.

[0037] The plant raw material may be a genetically modified plant (typically genetically modified corn) or a non-genetically modified plant. However, the production method of the present invention uses the route of bioethanol, acetone, isopropanol, propylene, and acrylic acid, and is therefore not subject to genetic modification restrictions, unlike when bioethanol is directly used or eaten, and a wide range of genetically modified plant raw materials can be used, which is preferable.

[0038] Bioethanol is determined by radiocarbon dating. １４ C / １２ Traceable ethanol can also be obtained. In addition, acetone, isopropanol, propylene, and acrylic acid, which are sequentially obtained from bioethanol in this invention, can also be measured by radiocarbon dating. １４ C / １２ C or records of acquisition and production routes can confirm that the compound is derived from a biological source.

[0039] <Method for Producing Acrylic Acid> Bioacrylic acid can be produced by the above steps (i) to (iv). The method for producing acrylic acid (bioacrylic acid) including the above steps (i) to (iv) may be referred to as the "method for producing acrylic acid of the present invention."

[0040] Step (i) is a step of obtaining acetone (bioacetone) from bioethanol, and preferably includes an acetone synthesis step (1) in which bioethanol is reacted with water (a) to obtain a mixed gas (A) containing acetone, water vapor, carbon dioxide, and hydrogen, an acetone separation step (2) in which an acetone-containing aqueous solution and a mixed gas (B) containing carbon dioxide and hydrogen are separated from the mixed gas (A), and an acetone distillation step (3) in which the acetone-containing aqueous solution is distilled to separate acetone and water (c). The method for producing acrylic acid of the present invention may also include a hydrogen separation step (4) in which hydrogen is separated from the mixed gas (B).

[0041] Step (ii) is a step of obtaining isopropanol (bioisopropanol) from the acetone (bioacetone), and preferably includes a step of reacting the acetone obtained in the acetone distillation step (3) with hydrogen to obtain a mixed gas containing isopropanol, and more preferably includes an isopropanol synthesis step (5) in which the acetone is reacted with the hydrogen obtained in the hydrogen separation step (4) to obtain a mixed gas (C) containing isopropanol. That is, according to one embodiment of the present invention, the raw material for obtaining the isopropanol contains the hydrogen obtained in step (i). Step (ii) also preferably includes an isopropanol separation step (6) in which isopropanol is separated from the mixed gas (C).

[0042] Step (iii) is a step of obtaining propylene (biopropylene) from the isopropanol (bioisopropanol), and preferably includes a propylene synthesis step (7) in which the isopropanol obtained in the isopropanol separation step (6) is dehydrated to obtain a mixed gas (D) containing propylene and water, and a propylene separation step (8) in which propylene and water (d) are separated from the mixed gas (D).

[0043] Step (iv) is a step of obtaining acrylic acid (bioacrylic acid) from the propylene (biopropylene), and preferably includes an acrylic acid synthesis step (9) in which the propylene obtained in the propylene separation step (8) is subjected to an oxidation reaction to obtain a mixed gas (E) containing acrylic acid, an acrylic acid absorption step (10) in which the mixed gas (E) is brought into contact with a collection liquid to obtain an acrylic acid-containing solution, and an acrylic acid purification step (11) in which the acrylic acid-containing solution is purified to obtain acrylic acid. More preferably, the acrylic acid absorption step (10) is a step in which the mixed gas (E) is brought into contact with water (e) to obtain an acrylic acid-containing aqueous solution.

[0044] First, with reference to the drawings, the overall flow of steps (1) to (11), which are preferred embodiments of steps (i) to (iv) for obtaining bioacrylic acid, will be described. Note that identical elements in the drawings are designated by the same reference numerals, and redundant explanations will be omitted. Furthermore, the dimensional proportions in the drawings are exaggerated for the sake of simplicity and may differ from the actual proportions. For the sake of simplicity, only one device and each step are depicted in Figures 1 and 2, but multiple devices may be connected in series or parallel. Furthermore, the reaction and purification in each step may be continuous or batchwise, with continuous being preferred.

[0045] 1 and 2 are flow sheets showing steps (1) to (8) and steps (9) to (11), respectively, in one embodiment of the method for producing acrylic acid of the present invention. As shown in FIGS. 1 and 2, an acetone synthesis reactor 1 in which step (1) is performed, an acetone separation column 2 in which step (2) is performed, an acetone distillation column 3 in which step (3) is performed, a hydrogen separation unit 4 in which step (4) is performed, an isopropanol synthesis reactor 5 in which step (5) is performed, an isopropanol separation unit 6 in which step (6) is performed, a propylene synthesis reactor 7 in which step (7) is performed, a propylene separation unit 8 in which step (8) is performed, an acrylic acid synthesis reactor 9 in which step (9) is performed, an acrylic acid absorption column 10 in which step (10) is performed, an acrylic acid distillation column 11A in which step (11A) is performed, and an acrylic acid crystallization unit 11B in which step (11B) is performed are connected by piping. Here, the piping 90 shown in FIG. 1 and the piping 90 shown in FIG. 2 are the same piping, and therefore the propylene separation unit 8 and the acrylic acid synthesis reactor 9 are connected to each other. As a result, the acetone synthesis reactor 1 to the acrylic acid crystallizer 11B are connected in series, and as a result, steps (1) to (11) can be carried out in a continuous flow.

[0046] Although it is a preferred embodiment of the present invention to connect the steps (1) to (11) with piping to form a continuous flow, as will be described later, one or more of the steps may be performed at different locations, and instead of connecting the steps with piping, the raw materials may be transported by other means (for example, railroad, ship, truck, etc.). In this case, the piping for the raw materials in Figures 1 and 2 can be interpreted as other means of transportation.

[0047] As shown in FIG. 1, raw materials ethanol and water (a) are supplied to an acetone synthesis reactor 1 through a pipe 12. In the acetone synthesis reactor 1, an acetone synthesis reaction "2CH ３ CH ２ OH+H ２ O → CH ３ C(=O)CH ３ +CO ２ +4H ２ " produces a mixed gas (A) containing acetone, water vapor, carbon dioxide and hydrogen as products.

[0048] The mixed gas (A) obtained in the acetone synthesis reactor 1 is supplied to the acetone separation column 2 via a pipe 20. In the acetone separation column 2, an acetone-containing aqueous solution and a mixed gas (B) containing carbon dioxide and hydrogen are separated from the mixed gas (A). If necessary, water (b) may be supplied to the acetone separation column 2 via a pipe 21, and the mixed gas (A) may be brought into contact with the water (b) to form an acetone-containing aqueous solution.

[0049] The acetone-containing aqueous solution obtained in the acetone separation column 2 is supplied to the acetone distillation column 3 via a pipe 30. In the acetone distillation column 3, the acetone-containing aqueous solution is distilled to separate acetone and water (c). The water (c) can be supplied (reused) via a pipe 31 to at least one selected from the acetone synthesis reactor 1, the acetone separation column 2, and the acrylic acid absorption column 10. Here, reuse means that the water is reused in a process other than the process in which the water is generated. Before being reused, the water may be subjected to other treatments, such as removing impurities, or may not be subjected to other treatments. In addition, reuse also refers to the case where water generated in a process subsequent to the process in which the reused water is used is reused in a further process.

[0050] The mixed gas (B) obtained in the acetone separation column 2 is supplied to the hydrogen separation device 4 via a pipe 40. In the hydrogen separation device 4, hydrogen is separated from the mixed gas (B).

[0051] Acetone obtained in the acetone distillation column 3 can be supplied to the isopropanol synthesis reactor 5 via a pipe 50, and hydrogen obtained in the hydrogen separation unit 4 can be supplied to the isopropanol synthesis reactor 5 via a pipe 41. Furthermore, unreacted hydrogen that can be obtained in the isopropanol separation unit 6 described below can be supplied to the isopropanol synthesis reactor 5 via a pipe 61. Furthermore, the hydrogen supplied to the isopropanol synthesis reactor 5 may be fresh, and the hydrogen may be supplied to the isopropanol synthesis reactor 5 via a pipe (not shown) separate from the pipe 41.

[0052] In the isopropanol synthesis reactor 5, the isopropanol synthesis reaction “CH ３ C(=O)CH ３ +H ２ →CH ３CH(OH)CH ３ " produces a mixed gas (C) containing the product isopropanol (also called 2-propanol or isopropyl alcohol) and unreacted hydrogen.

[0053] The mixed gas (C) obtained in the isopropanol synthesis reactor 5 is supplied to the isopropanol separation device 6 via a pipe 60. In the isopropanol separation device 6, isopropanol is separated from the mixed gas (C). In addition, in the isopropanol separation device 6, unreacted hydrogen can be separated from the mixed gas (C).

[0054] The isopropanol obtained in the isopropanol separation device 6 is supplied to the propylene synthesis reactor 7 via a pipe 70. In the propylene synthesis reactor 7, the isopropanol undergoes a dehydration reaction "CH ３ CH(OH)CH ３ →CH ２ =CHCH ３ +H ２ O” produces a mixed gas (D) containing the product propylene and water.

[0055] The mixed gas (D) obtained in the propylene synthesis reactor 7 is supplied to the propylene separation unit 8 via a pipe 80. In the propylene separation unit 8, propylene and water (d) are separated from the mixed gas (D). The water (d) can be recycled via a pipe 81 to at least one selected from the acetone synthesis reactor 1, the acetone separation column 2, and the acrylic acid absorption column 10.

[0056] As shown in FIG. 2, propylene obtained in the propylene separation device 8 is supplied to the acrylic acid synthesis reactor 9 via a pipe 90. Oxygen is also supplied to the acrylic acid synthesis reactor 9 via a pipe 91. In the acrylic acid synthesis reactor 9, the acrylic acid synthesis reaction "CH ２ =CHCH ３ +1.5O ２ →CH ２ =CHCOOH+H ２ O" produces a mixed gas (E) containing the product acrylic acid.

[0057] The mixed gas (E) obtained in the acrylic acid synthesis reactor 9 is supplied to the acrylic acid absorption tower 10 via a pipe 100. Furthermore, water can be supplied to the acrylic acid absorption tower 10 via a pipe 101 as a liquid for capturing acrylic acid from the mixed gas (E). In the acrylic acid absorption tower 10, the mixed gas (E) is brought into contact with a collecting liquid (preferably water (e)) to obtain an acrylic acid-containing solution (preferably an acrylic acid-containing aqueous solution). The mixed gas (F) that has not been absorbed (dissolved) in water is discharged via a pipe 102. If necessary, the mixed gas (F) is cooled and separated into a condensate and gas components. The condensate may be returned to the acrylic acid absorption tower 10. The gas components may be returned to the acrylic acid synthesis reactor 9. The liquid (collecting liquid) for capturing acrylic acid from the mixed gas (E) is typically water, but other liquids may also be used. In such a case, the term "acrylic acid-containing aqueous solution" should be read as "acrylic acid-containing solution." That is, the following description of "acrylic acid-containing aqueous solution" is not to be construed as meaning that the liquid for absorbing acrylic acid (absorbing liquid) is limited to water, but rather as meaning that the absorbing liquid may be composed of a liquid other than water or a mixture of a liquid other than water and water.

[0058] The aqueous solution containing acrylic acid obtained in the acrylic acid absorption tower 10 is supplied to an acrylic acid purification apparatus via a pipe 110. In an embodiment shown in FIG. 2, an acrylic acid distillation tower 11A and an acrylic acid crystallizer 11B are arranged in this order as an example of an acrylic acid purification apparatus. The acrylic acid purification apparatus may consist only of the acrylic acid distillation tower 11A. When the acrylic acid purification apparatus consists only of the acrylic acid distillation tower 11A, the aqueous solution containing acrylic acid obtained in the acrylic acid absorption tower 10 is supplied to the acrylic acid distillation tower 11A via a pipe 110, and the acrylic acid crystallizer 11B and the pipes 113, 114, and 120 are not included in the acrylic acid production system.

[0059] The acrylic acid purification apparatus may consist only of the acrylic acid crystallizer 11B. In this case, the acrylic acid-containing aqueous solution obtained in the acrylic acid absorption tower 10 is supplied to the acrylic acid crystallizer 11B through the pipe 114. When the acrylic acid purification apparatus consists only of the acrylic acid crystallizer 11B, the acrylic acid production system does not include the acrylic acid distillation tower 11A and the pipes 110, 111, and 112.

[0060] In the acrylic acid distillation column 11A, the acrylic acid-containing aqueous solution is distilled to separate roughly purified acrylic acid and water (f). The water (f) can be recycled via a pipe 112 to at least one selected from the acetone synthesis reactor 1, the acetone separation column 2, and the acrylic acid absorption column 10. The roughly purified acrylic acid is supplied to an acrylic acid crystallizer 11B via a pipe 111.

[0061] In the acrylic acid crystallizer 11B, the partially purified acrylic acid is separated into purified acrylic acid by crystallization and a mother liquor. The mother liquor may be returned to the acrylic acid distillation column 11A or the acrylic acid absorption column 10. As described above, acrylic acid is produced from the raw material ethanol through steps (1) to (11). Next, each of steps (1) to (11) will be described.

[0062] (Acetone Synthesis Step (1)) In the acetone synthesis step (1) (also referred to as "step (1)"), ethanol and water (a) are reacted to obtain a mixed gas (A) containing acetone, water vapor, carbon dioxide, and hydrogen.

[0063] The raw material ethanol includes bioethanol derived from biomass raw materials (biomass ethanol) from the perspective of carbon neutrality.

[0064] The content of bioethanol relative to 100% by mass of raw material ethanol is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more. Whether the ethanol is bioethanol or derived from a fossil fuel can be confirmed by radiocarbon dating.

[0065] The bioethanol content can be measured as follows: 1. The ethanol used in the raw gas is burned and all of it is converted into carbon dioxide. 2. The carbon dioxide is separated and purified using a vacuum line. 3. The carbon dioxide produced from the ethanol is completely reduced with hydrogen using iron as a catalyst to produce graphite. 4. １４ Using a C-AMS measurement device (for example, manufactured by NEC Corporation), １４ C concentration and １３ Ratio to C concentration ( １４ C / １３ 5. The same method as above 1 to 4 was used to measure oxalic acid (hereinafter also referred to as the standard sample) from the same year that the raw material ethanol was produced, provided by the National Institute of Standards (NIST). １４ C concentration and １３ Ratio to C concentration ( １４ C / １３ C) is measured. 6. Graphite derived from raw material ethanol １４ C / １３ The value of C is １４ C / １３ The value divided by the value of C is multiplied by 100 to obtain the bioethanol content.

[0066] The water (a) is not particularly limited, and tap water, industrial water, pure water (RO water, ion-exchanged water, distilled water), etc. can be used. These waters may be groundwater, river water, or treated versions of these. The water obtained in the method for producing acrylic acid according to this embodiment (at least one selected from the group consisting of water (c) in step (3), water (d) in step (8), and water (f) in step (11a)) may be reused as water (a).

[0067] Acetone synthesis reaction "2CH ３ CH ２ OH+H ２ O → CH ３ C(=O)CH ３ +CO ２ +4H ２The catalyst used in " is not particularly limited, but preferably contains at least one metal (Me) selected from the group consisting of magnesium, calcium, manganese, copper, and zinc, iron, and zirconium. The state of these metal elements (metal (Me), iron, and zirconium) is not particularly limited, and for example, a metal oxide containing the above metal element, a metal oxide supported on a carrier, a carrier containing the above metal element, or a metal element supported on a carrier can be used as the catalyst.

[0068] The metal oxide may be a composite metal oxide. Examples of the crystal structure of the composite metal oxide include spinel, perovskite, magnetoplumbite, and garnet types, and among these, the spinel type is preferred. The composite metal oxide may be a metal oxide having a general formula: MeO.nFe ２ O ３ (Me represents at least one metal selected from the group consisting of magnesium, calcium, manganese, and zinc, and n represents an integer of 1 to 6), and specifically, iron composite oxides (also called ferrites) represented by the formula: MgFe ２ O ４ , ZnFe ２ O ４ Examples include:

[0069] The carrier may be activated carbon or silica (SiO ２ ), alumina (Al ２ O ３ ), zeolite, silica-calcia, zirconia (ZrO ２ ), ceria (CeO ２ ), magnesia (MgO), etc. Among these, activated carbon, silica-calcia, zirconia, ceria, and magnesia are more preferred, and zirconia is particularly preferred. The shape of the carrier is not particularly limited, and examples include spherical, pellet, and honeycomb shapes. The BET specific surface area of ​​the carrier is 20 to 200 m ２ / g, and more preferably 40 to 200m ２ The use of a carrier having a large specific surface area is preferred because it makes it easier for the catalyst components to be supported in a dispersed state, thereby increasing the catalytic activity.

[0070] The state of zirconium element contained in the catalyst is not particularly limited, and may be contained as a compound containing zirconium alone as a metal, as an element of a composite metal oxide containing other metal elements, or as a carrier. Examples of compounds containing zirconium alone as a metal include zirconium oxide (ZrO ２ Examples of composite metal oxides containing other metal elements include composite metal oxides of zirconium and Sn, Pb, Zn, Cu, Fe, Mn, In, etc. Among these, zirconium oxide (ZrO ２ ); a composite metal oxide of zirconium, Zn, and Fe is preferred, and from the viewpoint of catalytic performance, zirconium oxide (ZrO ２ ) is more preferable.

[0071] The amount of metal (Me) in the catalyst is preferably 0.4 to 0.7 mol, more preferably 0.4 to 0.6 mol, and even more preferably 0.45 to 0.55 mol per mol of iron. When the amount of metal (Me) is within the above range, good catalytic activity can be obtained. The amount of zirconium in the catalyst is preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.5 mol, and may be 0.1 to 0.4 mol per mol of iron. When the amount of zirconium is within the above range, the durability of the catalyst can be improved.

[0072] The total content of the metal (Me), iron, and zirconium in the catalyst is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, based on 100% by mass of the catalyst. The acetone synthesis reaction can be carried out in either a batch or continuous manner, but from the viewpoint of productivity, a continuous manner is preferred. The acetone synthesis reaction is preferably carried out as a gas phase reaction. Reaction formats for the gas phase reaction include fixed bed, moving bed, and fluidized bed, but the simpler fixed bed format is preferred.

[0073] In the case of a fixed-bed reactor, ethanol gas and water vapor may be mixed and then supplied to the acetone synthesis reactor to contact the catalyst, or ethanol gas and water vapor may be supplied separately to the acetone synthesis reactor to contact the catalyst. Ethanol gas and water vapor can be obtained by heating ethanol and water, respectively, in a vaporizer. In addition to ethanol gas and water vapor, an inert gas such as nitrogen or helium may also be supplied to the acetone synthesis reactor.

[0074] The concentration of ethanol gas is preferably 3 to 66 mol %, more preferably 5 to 50 mol %, relative to 100 mol % of the total amount of gas supplied to the acetone synthesis reactor. The molar ratio of water vapor to ethanol gas (water vapor / ethanol gas) is preferably 0.5 to 10, more preferably 1 to 5.

[0075] The reaction pressure in the acetone synthesis reaction may be reduced pressure, normal pressure, or increased pressure, but is preferably 0.07 to 2 MPa, and more preferably 0.1 to 1 MPa. The reaction temperature in the acetone synthesis reaction is preferably 250 to 600°C, more preferably 300 to 550°C, and even more preferably 330 to 500°C. The space velocity in the acetone synthesis reaction is preferably 300 to 10,000 (1 / h), more preferably 400 to 8,000 (1 / h), and even more preferably 500 to 6,000 (1 / h).

[0076] (Acetone Separation Step (2)) In the acetone separation step (2) (also referred to as "step (2)"), an acetone-containing aqueous solution and a mixed gas (B) containing carbon dioxide and hydrogen are separated from the mixed gas (A) obtained in the above step (1). As a result, water vapor and acetone gas are condensed, and the acetone aqueous solution and the mixed gas (B) are separated (gas-liquid separation). In this case, it is preferable to bring the liquid component obtained by condensation into contact with the gas component by stirring or the like, because this dissolves the acetone gas remaining in the gas component in water, thereby improving the recovery rate of acetone.

[0077] Water (b) may be supplied to the acetone separation device as needed, separate from the water vapor in the mixed gas (A). Supplying water (b) can improve the acetone absorption efficiency in the acetone separation device. Water (b), together with condensed water from the water vapor, serves as a solvent for the acetone-containing aqueous solution. The water (b) is not particularly limited, and tap water, industrial water, pure water (RO water, ion-exchanged water, distilled water), etc. may be used. Water obtained in the method for producing acrylic acid according to this embodiment (at least one selected from the group consisting of water (c) in step (3), water (d) in step (8), and water (f) in step (11a)) may be reused as water (b).

[0078] The pressure in the separation operation is preferably 0.1 to 2 MPa, more preferably 0.2 to 1 MPa. The temperature in the separation operation is preferably 0 to 90°C, more preferably 0 to 50°C, and even more preferably 5 to 40°C.

[0079] (Acetone Distillation Step (3)) In the acetone distillation step (3) (also referred to as "step (3)"), the acetone-containing aqueous solution obtained in the above step (2) is distilled to separate acetone and water (c). The distillation can be carried out by a known method. Examples of the distillation method include thin film distillation and rectification. The distillation can be carried out in either a batch system or a continuous system, but from the viewpoint of productivity, a continuous system is preferred.

[0080] The distillation is carried out once or multiple times until the desired acetone purity is obtained. The purity of the acetone obtained in step (3) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, from the viewpoint of improving the isopropanol yield in the isopropanol synthesis step (5) described below and the isopropanol purity in the isopropanol separation step (6). When the acetone obtained above is used in the next step (ii), it is preferable that the aldehydes, alcohols, and ketones (excluding acetone) in the acetone have been reduced. In particular, ethanol and acetaldehyde are preferably reduced because they may become acetic acid after passing through steps (ii) to (iv). The total content of ethanol and acetaldehyde in acetone is preferably 20,000 ppm or less, more preferably 10,000 ppm or less, and even more preferably 5,000 ppm or less.

[0081] The water (c) can be reused as the water used in the method for producing acrylic acid of the present embodiment (at least one selected from the group consisting of the water (a) in the step (1), the water (b) in the step (2), and the water (e) in the step (10)).

[0082] (Hydrogen Separation Step (4)) In the hydrogen separation step (4) (also referred to as "step (4)"), hydrogen is separated from the mixed gas (B) containing carbon dioxide and hydrogen obtained in the above step (2). The method used for separation (hydrogen purification) is not particularly limited, and known methods such as physical absorption, chemical absorption, membrane separation, cryogenic separation, and compression liquefaction can be appropriately used.

[0083] Physical absorption is a method of separating and recovering carbon dioxide from a mixed gas by physical actions such as adsorption (e.g., adsorption onto an adsorbent such as activated carbon) or dissolution (e.g., dissolution into an organic solvent) without chemical reaction. A preferred example of physical adsorption is pressure swing adsorption (PSA). Chemical absorption is a method in which carbon dioxide is reacted (absorbed) with a basic substance such as an amine or alkali, converted into a form such as bicarbonate, and then separated and recovered from a mixed gas. Carbon dioxide can be recovered by heating or reducing the pressure of the absorption liquid after absorbing carbon dioxide. Membrane separation is a method of separating and recovering hydrogen or carbon dioxide from a mixed gas by selectively allowing hydrogen or carbon dioxide to permeate through a separation membrane. Examples of separation membranes include polymer membranes, dendrimer membranes, amine-containing membranes, and inorganic membranes such as zeolite membranes. The separation membrane may contain metal atoms. Examples of metal atoms include Pd.

[0084] The purity of the hydrogen obtained in the step (4) is preferably 90 mol % or more, more preferably 95 mol % or more, and even more preferably 98 mol % or more, from the viewpoint of improving the catalytic activity of the catalyst in the isopropanol synthesis step (5) described below.

[0085] (Isopropanol synthesis step (5)) In the isopropanol synthesis step (5) (also referred to as "step (5)"), the acetone obtained in the step (3) above is reacted with hydrogen (preferably the hydrogen obtained in the step (4) above) to obtain a mixed gas (C) containing isopropanol.

[0086] Isopropanol synthesis reaction (acetone hydrogenation reaction) "CH ３ C(=O)CH ３ +H ２ →CH ３ CH(OH)CH ３The catalyst used in " is not particularly limited, and examples thereof include Raney catalysts. Other catalysts include, for example, solid catalysts containing metal elements such as Ba, Co, Cr, Cu, Fe, Mn, Ni, Pd, Pt, Zn, Zr, Ru, and Rh. Among these, solid catalysts containing at least one metal element selected from the group consisting of Pt, Ru, Ni, Fe, and Co are preferred, and it is more preferred to use at least one solid catalyst selected from the group consisting of Ru catalysts, Ni—Pt catalysts, Ru—Pt catalysts, and Ni—Ru catalysts. By using a solid catalyst containing such a metal element, the activity inhibitory effect of carbon dioxide in the isopropanol synthesis reaction is suppressed, and acetone hydrogenation can proceed efficiently.

[0087] The catalyst may be in the form of a metal element, an alloy, an oxide, or the like. The catalyst may also be in the form of a mixture of metal elements, a mixture of metal elements and metal oxides, a mixture of metal oxides, or a mixed metal oxide. The catalyst may also be in the form of a metal element that is bonded to activated carbon, silica (SiO ２ ), alumina (Al ２ O ３ ), titania (TiO ２ ), zirconia (ZrO ２ ), ceria (CeO ２ The catalyst may be supported on a carrier such as silica (SiO ２ ), zirconia (ZrO ２ The above catalysts may be used singly or in combination of two or more.

[0088] The isopropanol synthesis reaction can be carried out in either a batch or continuous system, but a continuous system is preferred from the viewpoint of productivity. The isopropanol synthesis reaction is preferably carried out as a gas-phase reaction. Examples of reaction formats for gas-phase reactions include fixed beds, moving beds, and fluidized beds, but the simpler fixed bed system is preferred. In the fixed bed system, acetone gas and hydrogen may be mixed and then supplied to the isopropanol synthesis reactor to be contacted with the catalyst, or acetone gas and hydrogen may be supplied separately to the isopropanol synthesis reactor to be contacted with the catalyst. Note that acetone gas can be obtained by heating acetone in a vaporizer. In addition to acetone and hydrogen, an inert gas such as nitrogen or helium may be supplied to the isopropanol synthesis reactor.

[0089] The molar ratio of hydrogen to acetone gas (hydrogen / acetone gas) supplied to the isopropanol synthesis reactor is preferably 1 to 10, more preferably 1 to 5. The reaction pressure in the isopropanol synthesis reaction may be reduced pressure, normal pressure, or increased pressure, but is preferably 0.1 to 2 MPa, more preferably 0.1 to 1 MPa. The reaction temperature in the isopropanol synthesis reaction is preferably 20 to 200°C, more preferably 25 to 150°C. A lower reaction temperature is advantageous in terms of equilibrium, but tends to make hydrogenation less likely to proceed. On the other hand, a higher reaction temperature tends to prevent an increase in the acetone hydrogenation conversion rate due to equilibrium constraints, and in addition, hydrogenolysis of acetone and isopropyl alcohol occurs simultaneously, resulting in a decrease in yield. The space velocity in the acetone synthesis reaction is preferably 200 to 50,000 (1 / h), more preferably 1,000 to 20,000 (1 / h), and even more preferably 2,000 to 10,000 (1 / h).

[0090] (Isopropanol Separation Step (6)) In the acetone separation step (6) (also referred to as "step (6)"), isopropanol is separated from the mixed gas (C) obtained in the step (5) above. The mixed gas (C) may contain hydrogen used in the step (5) above in addition to isopropanol. More specifically, in the step (6), the mixed gas (C) is supplied to an isopropanol separation apparatus, and the mixed gas (C) is cooled in the apparatus. This condenses the isopropanol, and isopropanol (liquid) is separated from gas components such as hydrogen (gas-liquid separation). The hydrogen contained in the gas components may be reused in the isopropanol synthesis step (5) above.

[0091] The pressure in the separation operation is preferably 0.1 to 2 MPa, more preferably 0.2 to 1 MPa. The temperature in the separation operation is preferably 0 to 50°C, more preferably 5 to 40°C. The isopropanol obtained by separation (gas-liquid separation) may be supplied directly to the next step (7), or, if necessary, may be further purified by distillation before being supplied to the next step (7). The purity of the isopropanol obtained in step (6) is preferably 85% by mass or more, more preferably 90% by mass or more, and even more preferably 93% by mass or more, from the viewpoint of improving the propylene yield in the propylene synthesis step (7) described below and the propylene purity in the propylene separation step (8). Ethanol in the isopropanol obtained above is preferably reduced because it may turn into acetic acid through steps (iii) to (iv). The ethanol content in isopropanol is preferably 20,000 ppm or less, more preferably 10,000 ppm or less, and even more preferably 5,000 ppm or less.

[0092] (Propylene Synthesis Step (7)) In the propylene synthesis step (7) (also referred to as "step (7)"), the isopropanol obtained in the step (6) is subjected to a dehydration reaction to obtain a mixed gas (D) containing propylene and water.

[0093] Propylene synthesis reaction (isopropanol dehydration reaction) "CH ３ CH(OH)CH ３ →CH ２ =CHCH３ +H ２ Examples of catalysts used in "O" include alumina catalysts, silica-alumina catalysts, magnesia catalysts, zeolite catalysts, activated clay, etc., and titanium oxide (TiO ２ ), tungsten oxide, zirconium oxide (ZrO ２ ) or the like. Among these, alumina catalysts are preferred, γ-alumina catalysts are more preferred, and specifically, catalysts in which tungsten oxide is supported on γ-alumina are even more preferred. The shape of the catalyst is not particularly limited, and examples thereof include tablet, ring, spherical, cylindrical extruded, trilobe extruded, and granular. Among these, spherical, tablet, and extruded types are preferred because they have high catalytic strength and can be uniformly packed into a reaction tube.

[0094] The catalyst may be any of the above-mentioned catalysts that have been subjected to an acid treatment and / or a calcination treatment, as necessary. The acid treatment is carried out by immersing the catalyst (e.g., a γ-alumina catalyst) in an acid to adjust the acid strength of the catalyst. Examples of acids used in the acid treatment include aqueous solutions of hydrochloric acid, nitric acid, boric acid, etc., and carboxylic acids such as acetic acid, formic acid, and oxalic acid. When the catalyst is a γ-alumina catalyst, a catalyst having an average pore diameter of 30 to 150 Å, with a standard deviation of 10 to 40 Å, as determined by statistical calculation based on the relationship between pore diameter and pore volume, is preferably used.

[0095] The propylene synthesis reaction can be carried out in either a batch system or a continuous system, but from the viewpoint of productivity, a continuous system is preferred. The propylene synthesis reaction is preferably carried out as a gas phase reaction. Examples of the gas phase reaction include a fixed bed, a moving bed, and a fluidized bed, but the simpler fixed bed system is preferred.

[0096] In the case of a gas-phase reaction, isopropanol can be heated in a vaporizer and supplied as isopropanol gas to the propylene synthesis reaction. In addition to isopropanol gas, an inert gas (e.g., nitrogen, helium, argon) may be supplied to the propylene synthesis reactor.

[0097] The reaction temperature in the propylene synthesis reaction is preferably 150 to 500° C., more preferably 180 to 400° C. The reaction pressure in the propylene synthesis reaction may be any of reduced pressure, normal pressure, and increased pressure, but is preferably a pressure at which a gas phase reaction can be maintained.

[0098] (Propylene Separation Step (8)) In the propylene separation step (8) (also referred to as "step (8)"), propylene and water (d) are separated from the mixed gas (D) obtained in the above step (8). More specifically, the mixed gas (D) is supplied to a propylene separation apparatus, and water is condensed by pressurization and cooling. This allows separation into a gas phase mainly consisting of propylene and an aqueous phase mainly consisting of water (d). The water (d) can be reused as water (at least one selected from the group consisting of water (a) in step (1), water (b) in step (2), and water (e) in step (10)) used in the method for producing acrylic acid according to this embodiment.

[0099] The pressure when the pressurized state is established is preferably 0.5 to 5 MPaG from the viewpoint of separation and purification costs. Furthermore, the reaction product (gaseous) can be easily liquefied by simply cooling it to 20 to 50°C. The propylene obtained by separation (gas-liquid separation) may be supplied directly to the next step (9), or, if necessary, may be further purified by distillation and then supplied to the next step (9). The purity of the propylene obtained in step (8) is preferably 90% by mass or more, more preferably 93% by mass or more, and even more preferably 95% by mass or more, from the viewpoint of improving the yield of acrylic acid in the acrylic acid synthesis step (9) described below and the purity of acrylic acid in the acrylic acid separation step (11).

[0100] (Acrylic Acid Synthesis Step (9)) In the acrylic acid synthesis step (9) (also referred to as "step (9)"), the propylene obtained in the step (8) is subjected to an oxidation reaction to obtain a mixed gas (E) containing acrylic acid. ２ =CHCH ３ +1.5O ２ →CH ２ =CHCOOH+H ２For "O", known methods (for example, the methods described in Japanese Patent Nos. 3,948,837 and 3,938,646) can be appropriately adopted.

[0101] In the acrylic acid synthesis reaction, propylene is oxidized by contacting it with a molecular oxygen-containing gas such as oxygen or air in the presence of a known catalyst. Usually, the oxidation reaction is carried out in two stages. The catalyst used in the first stage reaction is one that can produce acrolein through the gas phase oxidation of propylene gas, and the catalyst used in the second stage reaction is not particularly limited as long as it can produce acrylic acid through the gas phase oxidation of acrolein gas.

[0102] The catalyst used in the first-stage reaction may be a solid catalyst containing at least one element selected from the group consisting of Fe, Co, Ni, Mo, Bi, Al, and Si, and preferably contains at least one element selected from the group consisting of Fe, Mo, and Bi, and more preferably contains a composite oxide containing Fe, Mo, and Bi.

[0103] The catalyst used in the second-stage reaction may be a solid catalyst containing at least one element selected from the group consisting of V, Mo, Cu, W, Sb, Al, and Si. Preferably, the solid catalyst contains at least one element selected from the group consisting of Mo, V, and W, and more preferably contains Mo or V.

[0104] The acrylic acid synthesis reaction can be carried out either batchwise or continuously, but from the viewpoint of productivity, the continuous method is preferred. The reaction temperature in the acrylic acid synthesis reaction is usually in the range of 200 to 400°C.

[0105] (Acrylic Acid Absorption Step (10)) In the acrylic acid absorption step (10) (also referred to as "step (10)"), the mixed gas (E) obtained in the above step (9) is contacted with an absorbent (typically water (e)) for collecting acrylic acid from the mixed gas (E) to obtain an aqueous solution containing acrylic acid. The mixed gas (E) may contain acrylic acid, the molecular oxygen-containing gas used in the above step (9), unreacted components (propylene, acrolein), and by-products (e.g., acetone, acetic acid, furfural, formaldehyde, etc.). As described above, the liquid for collecting acrylic acid from the mixed gas (E) is typically water, but other liquids can also be used. In that case, the aqueous solution containing acrylic acid should be read as an acrylic acid-containing solution. As a collecting liquid for acrylic acid in the mixed gas (E), at least one of water and an organic solvent is used. As the organic solvent, an organic solvent such as methyl isobutyl ketone, diisopropyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, n-propyl acetate, n-butyl acetate, diphenyl ether, and diphenyl ether is used. Preferably, water or diphenyl ether, more preferably water, is used as the collecting liquid.

[0106] The water (e) used as the absorption liquid for absorbing acrylic acid is not particularly limited, and tap water, industrial water, pure water (RO water, ion-exchanged water, distilled water), etc. can be used. These waters may be groundwater, river water, or treated versions of these. The water obtained in the method for producing acrylic acid according to this embodiment (at least one selected from the group consisting of water (c) in step (3), water (d) in step (8), and water (f) in step (11a)) may be reused as water (e).

[0107] The method for contacting the mixed gas (E) with water (e) is not particularly limited, and any known contact method can be appropriately adopted. Specific examples of the contact method include cross-current contact using a bubble cap tray, a uniflat tray, a perforated plate tray, a jet tray, a bubble tray, or a Venturi tray; and countercurrent contact using a turbogrid tray, a dual flow tray, a ripple tray, a Kittel tray, or a gauze-type, sheet-type, or grit-type structured packing or a random packing.

[0108] (Acrylic purification step (11)) In the acrylic purification step (11) (also referred to as "step (11)"), the acrylic acid-containing aqueous solution obtained in the above step (10) is purified to obtain acrylic acid. The aqueous acrylic acid solution may contain acrylic acid, acetic acid, water, and other impurities (maleic acid, propionic acid, furfural, formaldehyde, etc.).

[0109] The method for purifying acrylic acid is not particularly limited, and known techniques such as distillation and crystallization can be appropriately adopted. The purification may involve only distillation (acrylic acid distillation step (11A)), only crystallization (acrylic acid crystallization step (11B)), or a combination of distillation (acrylic acid distillation step (11A)) and crystallization (acrylic acid crystallization step (11B)). In the embodiment shown in FIG. 2, the acrylic acid distillation step (11A) and the acrylic acid crystallization step (11B) are combined in this order. Furthermore, distillation may be performed only once, or multiple times in combination. Furthermore, crystallization may be performed only once, or multiple times in combination. Furthermore, distillation and crystallization may be performed continuously or batchwise.

[0110] When distillation is included as a purification method, water (f) is separated from the aqueous acrylic acid solution by distillation. Azeotropic distillation using an azeotropic solvent is preferred. Examples of azeotropic solvents used include heptane, toluene, ethyl methacrylate, methyl isobutyl ketone, n-propyl acrylate, methyl acetate, and n-butyl acetate, with toluene being preferred, methyl isobutyl ketone, methyl acetate, and n-butyl acetate being more preferred, and toluene being more preferred. When multiple azeotropic solvents are used, they may be a mixture thereof. Water (f) can be reused as water (at least one selected from the group consisting of water (a) in step (1), water (b) in step (2), and water (e) in step (10)) used in the method for producing acrylic acid according to this embodiment.

[0111] In the method for producing acrylic acid according to this embodiment, it is preferable to reuse the water obtained by the method as the water used in the method. That is, it is preferable to reuse at least one selected from the group consisting of water (c) and water (d) as at least one selected from the group consisting of water (a) and water (e). When the mixed gas (A) is contacted with water (b) (water (b) is supplied) in the acetone separation step (2), it is preferable to reuse at least one selected from the group consisting of water (c) and water (d) as at least one selected from the group consisting of water (a), water (b), and water (e). When the acrylic acid purification step (11) includes an acrylic acid distillation step (11A), it is preferable to reuse at least one selected from the group consisting of water (c), water (d), and water (f) as at least one selected from the group consisting of water (a), water (b), and water (e). The reuse described above not only reduces the cost of water procurement, but also reduces the total amount of wastewater discharged from the production process, thereby reducing the environmental burden and the cost of wastewater treatment, thereby providing an acrylic acid production method that is excellent in both environmental and economic terms. In the present specification, "reusing water (X) as water (Y)" encompasses both "a form in which water (Y) is only water (X)" and "a form in which water (Y) is composed of water (X) and water other than water (X) (for example, tap water, industrial water, pure water)." "Reusing water (X) as water (Y)" preferably means "a form in which water (Y) is only water (X)." In the present specification, water (a) to water (f) are each H ２ Impurities other than O may be contained in an amount of 25% by mass or less (preferably 20% by mass or less, more preferably 18% by mass or less).

[0112] Water (c) is preferably reused as water (a) and / or water (b), and more preferably reused as water (a). This reduces the amount of wastewater, and when unreacted ethanol remains in water (c) from the acetone synthesis step (1), the unreacted ethanol can be reused again for acetone synthesis without being discarded, thereby improving the yield of acetone synthesis from raw material ethanol. It is preferable that the content of methyl propyl ketone in water (c) is 5000 ppm or less and the content of methyl isobutyl ketone is 500 ppm or less; more preferably, the content of methyl propyl ketone in water (c) is 3000 ppm or less and the content of methyl isobutyl ketone is 200 ppm or less. When the contents of methyl propyl ketone and methyl isobutyl ketone are within the above ranges, the water can be suitably reused as water (a) and / or water (b).

[0113] Water (d) is preferably reused as at least one selected from the group consisting of water (a), water (b), and water (e), more preferably reused as water (a) and / or water (b), and even more preferably reused as water (a). This reduces the amount of wastewater and enables the reuse of acetone, which is a small amount of by-product during the isopropanol dehydration reaction, without being discarded together with the wastewater. The isopropanol content in water (d) is preferably 10,000 ppm or less, more preferably 5,000 ppm or less. When the isopropanol content is within the above range, the water can be suitably reused as at least one selected from the group consisting of water (a), water (b), and water (e).

[0114] It is preferable to reuse water (f) as water (e). This reduces the amount of wastewater and enables recovery of acrylic acid remaining in water (f), thereby improving the production efficiency of acrylic acid. When the water (f) is reused as water (e), the impurities contained in the water (f) preferably include components used in the distillation step 11(A), and it is preferable that the amount of these components is not more than a predetermined amount. For example, when the distillation step is azeotropic distillation using an azeotropic solvent, the content of the azeotropic solvent component in the water (f) is preferably 1000 ppm or less, more preferably 500 ppm or less. When the content of the azeotropic solvent component is within the above range, the water can be suitably reused as water (e).

[0115] According to one embodiment of the present invention, it is preferable to reuse at least a portion of the water generated in the process leading up to the production of acrylic acid in at least one of the processes using water. As described above, in order to reuse water, it is important to appropriately determine the process to which the water is to be reused depending on the type and content of impurities contained in the water. By appropriately determining the process to which the water is to be reused, it is possible to prevent problems such as a decrease in the yield of the target product and an increase in the load in the purification process. As a result, production costs are further reduced, which is preferable.

[0116] In the method for producing acrylic acid according to this embodiment, steps (1) to (11) are preferably carried out in a continuous flow. This eliminates the need for ancillary equipment such as an intermediate tank, allowing for a simpler production facility, thereby shortening production time and reducing facility costs. Furthermore, wastewater generated in the process can be utilized in other steps within the process, thereby reducing the overall amount of wastewater produced in the process, resulting in reduced wastewater treatment costs.

[0117] According to another aspect of the present invention, there is provided a system for producing acrylic acid, which comprises an acetone reactor, an acetone separation column, an acetone distillation column, a hydrogen separation unit, an isopropanol synthesis reactor, an isopropanol separation unit, a propylene synthesis reactor, a propylene separation unit, an acrylic acid synthesis reactor, an acrylic acid absorption column, and an acrylic acid distillation column and / or an acrylic crystallizer.

[0118] (Impurities in bioacrylic acid) In step (iv), the propionic acid content in the acrylic acid obtained by propylene oxidation and purification is preferably 500 ppm or less, more preferably 400 ppm or less, and even more preferably 300 ppm or less, and the acetic acid content is preferably 1500 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less. The low propionic acid (and more preferably acetic acid) content in the acrylic acid reduces the odor (acid odor) of the resulting cosmetic additive. Furthermore, the yield of the cosmetic additive (the ratio of the acrylic acid used to the cosmetic additive obtained) is improved.

[0119] Of the six impurities in the acrylic acid, namely protoanemonin, allyl acrylate, allyl alcohol, aldehydes (particularly furfural), maleic acid, and benzoic acid, preferably one or more, more preferably two or more, even more preferably three or more, even more preferably four or more, particularly preferably five or more, and particularly preferably all six impurities are each 0 to 20 ppm (by mass, the same applies hereinafter). More preferably, each is 0 to 10 ppm, even more preferably 0 to 5 ppm, even more preferably 0 to 3 ppm, particularly preferably 0 to 1 ppm, and most preferably N.D. (below the detection limit). Among these impurities, aldehydes may increase in acrylic acid derived from biomaterials, so it is preferable to control them to reduce their content. Control methods include using an aldehyde treatment agent or performing crystallization. The total amount of protoanemonin, allyl acrylate, allyl alcohol, aldehyde, maleic acid, and benzoic acid (based on the mass of acrylic acid) is preferably 100 ppm or less, more preferably 0 to 20 ppm, even more preferably 0 to 10 ppm, and particularly preferably 0 to 5 ppm.

[0120] Moisture in acrylic acid promotes the formation of acrylic acid dimers, and the increase in acrylic acid dimers increases the amount of residual monomers in the cosmetic additive. In particular, when precipitation polymerization is used as a polymerization method for acrylic acid, the cosmetic additive and the cosmetic using the same are likely to achieve excellent thickening properties and a pleasant feeling when used. However, a high water content in acrylic acid affects the precipitation behavior of the precipitation polymerization, making it more likely to produce lumps, which can leave particles when the cosmetic additive is dissolved in water, affecting the pleasant feeling when used. Therefore, the water content of the acrylic acid obtained in step (iv) is preferably 2% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass or less (5000 ppm or less), and particularly preferably 0.45% by mass or less (4500 ppm or less), and may be 0.4% by mass or less (4000 ppm or less), 0.3% by mass or less (3000 ppm or less), or 0.25% by mass or less (2500 ppm or less). For the same reason, the amount of acrylic acid dimer in the acrylic acid (salt) to be supplied to the step (v) described later is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 200 ppm or less. The amount of acrylic acid dimer in the acrylic acid (salt) to be supplied to the step (v) described later is, for example, 1 ppm or more.

[0121] It is desirable that these impurities in the acrylic acid (salt) be N.D. However, it is difficult to completely remove them even by steps (i) to (iv). Therefore, a certain amount of the acrylic acid contained may be used in step (v), and impurities in the acrylic acid (salt) (for example, acetic acid and propionic acid in the acrylic acid (salt)) may be removed in step (v) and / or step (vi) by heating in the production process of the cosmetic additive.

[0122] <Method for Producing Acrylic Polymer> In a first aspect of the production method of the present invention, an acrylic polymer can be produced via the following step (v) using bioacrylic acid obtained by the above steps (i) to (iv). In a second aspect of the production method of the present invention, an acrylic polymer can be produced via the following step (v) using acrylic acid and / or a salt thereof derived from a biomaterial having a water content of 4000 ppm or less. The production method of the present invention (first and second aspects) preferably includes the following step (vi), and when the polymerization method is suspension polymerization or precipitation polymerization, it is preferable to include step (vi) after the filtration step: step (v) of polymerizing a monomer containing acrylic acid and / or a salt thereof to obtain an acrylic polymer; and step (vi) of drying the acrylic polymer.

[0123] (Acrylic Acid (Salt) and Monomer) In the first aspect, the acrylic acid and / or its salt obtained in step (iv) is essentially used as a monomer for the acrylic polymer. In the second aspect, acrylic acid and / or its salt derived from a biomaterial having a water content of 4000 ppm or less is essentially used. The acrylic polymer is a crosslinked polymer obtained by crosslinking a monomer composition containing acrylic acid (salt) as a main component, as needed. The acrylic polymer may contain a graft component. As described below, the acrylic polymer may be a homopolymer of acrylic acid (salt) (polyacrylic acid (salt)) or a copolymer of acrylic acid (salt) and another monomer.

[0124] From the viewpoint of polymerizability, it is preferably a copolymer of acrylic acid and other monomers, and more preferably a homopolymer of acrylic acid (polyacrylic acid). Specifically, the content of acrylic acid (salt) in 100% by mass of the monomers constituting the acrylic polymer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 99% by mass or more, or may be 100% by mass.

[0125] The content of acrylic acid in 100% by mass of acrylic acid (salt) used as a monomer constituting the acrylic polymer is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass.

[0126] The acrylic acid (salt) to be polymerized may be only the acrylic acid and / or its salt obtained in the above step (iv), or may be used in combination with other acrylic acid (salt). Examples of the acrylic acid (salt) to be used in combination include acrylic acid (salt) derived from fossil raw materials and other bioacrylic acid (salt) obtained from sources other than bioethanol. The combination ratio can be determined appropriately, but when the acrylic acid and / or its salt obtained in the above step (iv) is used in combination with other acrylic acid (salt), from the viewpoints of performance, sustainability, and renewability, the higher the use ratio of the acrylic acid and / or its salt obtained in the above step (iv), the more preferable it is. The acrylic acid and / or its salt obtained in the step (iv) is preferably 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, and 70 mol% or more, in this order, relative to the total amount (100 mass%) of the acrylic acid (salt) to be subjected to the step (v). The upper limit may be less than 100 mol%, 95 mol% or less, or 90 mol% or less, depending on the production capacity of the acrylic acid obtained in the above step (iv), etc. Examples of a method for using the acrylic acid and / or its salt obtained in the above step (iv) in combination with other acrylic acid (salt) include mixing the acrylic acid and / or its salt obtained in the above step (iv) with other acrylic acid (acrylic acid derived from a fossil raw material) and / or its salt.

[0127] Furthermore, the acrylic acid obtained in the above step (iv) is preferably used in step (v) shortly after purification in order to prevent an increase in residual monomers in the cosmetic additive. The time between step (iv) and step (v), particularly including transportation and storage, is preferably within 10 days, more preferably within 5 days, even more preferably within 2 days, and particularly preferably within 1 day.

[0128] The water content of the acrylic acid (salt) added in step (v) is preferably 0.5% by mass or less (5000 ppm or less), more preferably 0.45% by mass or less (4500 ppm or less), even more preferably 0.4% by mass or less (4000 ppm or less), particularly preferably 0.3% by mass or less (3000 ppm or less), and may be 0.25% by mass or less (2500 ppm or less). When precipitation polymerization is used as a method for polymerizing acrylic acid (salt), excellent thickening properties and usability are likely to be obtained in cosmetic additives and cosmetics using the same, but if the water content in the acrylic acid (salt) is high, it affects the precipitation behavior of the precipitate in the precipitation polymerization, making it easy to produce lumps, and when the cosmetic additive is dissolved in water, particles tend to remain, affecting the usability.

[0129] A polymerization inhibitor may be added to the acrylic acid (salt) used in step (v). The amount of the polymerization inhibitor added is, for example, 1 to 300 ppm, preferably 10 to 200 ppm, and more preferably 20 to 80 ppm. As the polymerization inhibitor, p-methoxyphenol is preferred.

[0130] The monomer composition for obtaining the acrylic polymer may essentially consist of only acrylic acid (salt) as a monomer, or may contain other monomers copolymerizable with acrylic acid (salt). Examples of such other monomers include, but are not limited to, methacrylic acid, maleic acid, itaconic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid, (meth)acrylamide, and salts thereof. These monomers may be used alone or in a suitable mixture of two or more. Among these, itaconic acid is preferred when used in combination with other monomers because it can be obtained by fermentation and contributes to the use of bio-based raw materials.

[0131] From the viewpoint of the performance of the cosmetic additive, the proportion of acrylic acid (salt) in the monomer composition is preferably 50 to 100 mol %, more preferably 70 to 100 mol %, and even more preferably 90 to 100 mol %, relative to the total amount of monomers (100 mass %). The proportion of the other monomers in the monomer composition is, for example, 0 to 50 mol %, and preferably 5 to 45 mol %.

[0132] When the crosslinking polymerization is carried out, a crosslinking agent is used. The crosslinking agent may be added before or after the polymerization of the monomer composition. Examples of the crosslinking agent include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol di(meth)acrylate. Examples of the crosslinking agent include compounds having two or more ethylenically unsaturated groups in one molecule, such as tol triallyl ether neoallyl, N,N'-methylenebis(meth)acrylamide, triallyl isocyanurate, trimethylolpropane di(meth)allyl ether, triallylamine, tetraallyloxyethane, and glycerol propoxy triacrylate, and preferred are compounds having two ethylenically unsaturated groups in one molecule, such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. Either one type of crosslinking agent or two or more types may be used.

[0133] The polymerization method for the monomer composition is not particularly limited, and any known or commonly used method can be used. Examples of the polymerization method include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among these, precipitation polymerization is preferred from the viewpoint of achieving superior thickening properties of the cosmetic additive and superior usability of the cosmetic.

[0134] A solvent may be used in the polymerization of the monomer composition. A hydrophobic organic solvent may be used as the solvent used in the polymerization of the monomer composition. Examples of the hydrophobic organic solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, aliphatic alcohols, aliphatic ketones, and aliphatic esters.

[0135] Examples of aliphatic hydrocarbons include those having 5 or more carbon atoms, specifically n-pentane, n-hexane, n-heptane, etc. Examples of alicyclic hydrocarbons include those having 5 or more carbon atoms, specifically cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, etc. Examples of aromatic hydrocarbons include benzene, toluene, xylene, etc. Examples of aliphatic alcohols include those having 4 or more carbon atoms, preferably 4 to 6 carbon atoms, specifically n-butyl alcohol, n-amyl alcohol, etc. Examples of aliphatic ketones include those having 4 or more carbon atoms, preferably 4 to 6 carbon atoms, specifically methyl ethyl ketone, etc. Examples of aliphatic esters include those having 4 or more carbon atoms, preferably 4 to 6 carbon atoms, specifically ethyl acetate, etc.

[0136] The solvents such as hydrophobic organic solvents may be used alone or in combination of two or more. For example, the hydrophobic organic solvents listed above may be used alone or in combination of two or more.

[0137] As the solvent used in the polymerization of the monomer composition, in terms of controlling the precipitation of the polymer, it is preferable to use at least one selected from the group consisting of aliphatic hydrocarbons and alicyclic hydrocarbons in combination with at least one selected from the group consisting of aliphatic ketones and aliphatic esters, and it is more preferable to use an alicyclic hydrocarbon in combination with an aliphatic ester.

[0138] The mass ratio of the aliphatic hydrocarbons and alicyclic hydrocarbons to the aliphatic ketones and aliphatic esters (total mass of aliphatic hydrocarbons and alicyclic hydrocarbons / total mass of aliphatic ketones and aliphatic esters) used as the solvent for polymerizing the monomer composition is preferably 100 / 0 to 50 / 50, and more preferably 90 / 10 to 70 / 30.

[0139] The mass ratio of the alicyclic hydrocarbon to the aliphatic ester (mass of the alicyclic hydrocarbon / mass of the aliphatic ester) in the solvent used for polymerizing the monomer composition is preferably 100 / 0 to 50 / 50, more preferably 90 / 10 to 70 / 30.

[0140] A polymerization initiator can be used for polymerizing the monomer composition. A radical polymerization initiator is preferably used as the polymerization initiator. A thermal polymerization initiator is preferred as the radical polymerization initiator, and examples thereof include peroxide-based polymerization initiators and azo compound-based polymerization initiators. Examples of peroxide-based polymerization initiators include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, and diisopropylbenzene hydroperoxide. Examples of azo compound polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,3-dimethylbutyronitrile), 2,2'-azobis-(2-methylbutyronitrile), 2,2'-azobis(2,3,3-trimethylbutyronitrile), 2,2'-azobis(2-isopropylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoylazo)isobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and dimethyl-2,2'-azobisisobutyrate. One or more of the above polymerization initiators may be used.

[0141] In the polymerization of the monomer composition, the monomer and polymerization initiator are preferably supplied separately and continuously and mixed (e.g., dropwise) from the viewpoint of heat generation control. Furthermore, by appropriately selecting the supply time, not only can high viscosity be obtained but also filtration time can be shortened. From the viewpoint of heat generation control, the supply time when supplied at a uniform rate is, for example, when the monomer is supplied over 60 to 350 minutes and the polymerization initiator is supplied over 80 to 400 minutes, preferably when the monomer is supplied over 90 to 300 minutes and the polymerization initiator is supplied over 100 to 350 minutes. Furthermore, from the viewpoint of thickening effect and filtration time, for example, when the monomer is supplied over 45 to 300 minutes and the polymerization initiator is supplied over 60 to 350 minutes, preferably when the monomer is supplied over 45 to 250 minutes and the polymerization initiator is supplied over 60 to 300 minutes, and more preferably when the monomer is supplied over 45 to 200 minutes and the polymerization initiator is supplied over 60 to 250 minutes. In either case, it is preferable to supply the polymerization initiator for a longer time than the monomer.

[0142] By carrying out step (vi) of drying the acrylic polymer, the cosmetic additive can be obtained as a powder. Furthermore, at the same time, impurities remaining in the obtained acrylic polymer (monomers such as acrylic acid (salt), and those exemplified and explained as impurities that may be contained in bioacrylic acid) can be removed. The drying can be carried out under normal pressure or under reduced pressure. The drying temperature is, for example, 60 to 120°C, preferably 80 to 110°C. A drying temperature of 120°C or less can prevent deterioration of the acrylic polymer, and can prevent a decrease in viscosity and a deterioration in feel. A drying temperature of 60°C or higher can improve productivity in the drying process and can sufficiently remove the solvent.

[0143] From the viewpoint of productivity when precipitation polymerization is performed, the neutralization rate of the acid groups of the acrylic polymer is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less. Neutralization may be performed on the monomer (monomer composition containing acrylic acid (salt)), on the acrylic polymer after polymerization, or on both. Examples of neutralization salts include alkali metal salts of (poly)acrylic acid, such as sodium, potassium, and lithium, ammonium salts, and amine salts.

[0144] In the step (v) or the step (vi), acrylic acid (boiling point: 141°C) may volatilize during polymerization or drying. The volatilized acrylic acid may be discarded, but this is not recommended from an environmental standpoint and may also result in CO ２ From the viewpoint of reduction and carbon neutrality, the volatilized acrylic acid is preferably collected and recycled. Acrylic acid can be collected by known means such as absorption with water or alkaline water or cooling. As a method for recycling acrylic acid, the collected bioacrylic acid or its aqueous solution (e.g., alkaline aqueous solution) can be reused in the polymerization of step (v).

[0145] Furthermore, just as the acrylic acid (salt) used in step (v) may be used in combination with other bioacrylic acids derived from fossil raw materials or from sources other than bioethanol, as long as at least a portion of the monomers constituting the main chain of the acrylic polymer in the cosmetic additive contain a monomer derived from bioethanol, a portion of the acetone in step (ii), the isopropanol in step (iii), and the propylene in step (iv) may contain acetone, isopropanol, or propylene derived from fossil raw materials or from biosources other than bioethanol, respectively. For example, in the event of a poor harvest of crops used as raw materials for bioethanol, or when treating surplus or by-products of compounds derived from fossil raw materials generated in the production of other compounds, acetone, isopropanol, or propylene derived from fossil raw materials or from biosources other than bioethanol can be used in combination. Furthermore, depending on the type of plant used as the raw material, or whether the raw material is fossil or non-fossil, the carbon isotope ratio may vary. １３C amount and １４ By utilizing the different C amounts, multiple raw materials can be used in various ratios to produce various carbon isotopes. １３ C amount and １４ It becomes possible to produce a cosmetic additive having the amount C. １３ C amount and １４ Measurement of the C amount makes it possible to achieve traceability (identifiability) of the cosmetic additive after production. When at least one selected from the group consisting of acetone, isopropanol, propylene, and acrylic acid derived from fossil raw materials or bio-based raw materials other than bioethanol is used in combination, the proportion of bioethanol-derived acrylic acid (salt) among the monomers constituting the main chain of the final cosmetic additive is preferably 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 30 mol% or more, 40 mol% or more, 50 mol% or more, 60 mol% or more, and 70 mol% or more, in this order.

[0146] The acrylic polymer (cosmetic additive) obtained in the above step (v) or (vi) may be subjected to a classification step to make the particle size uniform.

[0147] In the production method of the present invention, the steps (i) to (vi) may be connected and carried out continuously, or may be carried out individually. Furthermore, the individual purification of acetone, isopropanol, propylene, or acrylic acid described in the steps (i) to (iv) may be omitted. Furthermore, the steps (i) to (vi) may be carried out by the same producer, or some or all of them may be carried out by different producers. For example, the tasks may be shared as follows:

[0148] Company A: (i) a process for obtaining acetone from bioethanol; Company B: (ii) a process for obtaining isopropanol from bioacetone; Company C: (iii) a process for obtaining propylene from bioisopropanol; Company D: (iv) a process for obtaining acrylic acid from biopropylene; Company E: (v) a process for obtaining an acrylic polymer by polymerizing a monomer containing bioacrylic acid; Company F: (vi) a process for drying the acrylic polymer.

[0149] The steps (i) to (vi) may be carried out at the same location or at different locations. The term "same location" refers to a location within an industrial site that allows for connection by pipeline. If the steps are carried out at different locations, transportation methods other than pipelines, such as long-distance transportation by tanker, truck, rail, etc., may be used.

[0150] From the viewpoint of the performance of the cosmetic additive, it is preferable that step (v) and step (vi) are carried out at the same location, and it is also preferable that steps (i) to (vi) are carried out at a maximum of four locations, further at a maximum of three locations, or even at a maximum of two locations, and it is particularly preferable that all steps are carried out at a single location.

[0151] Furthermore, since step (iv) is an exothermic reaction accompanied by oxidation, by carrying out steps (iv), (v), and (vi) at the same location, the heat generated in step (iv) can be used for heating such as polymerization in step (v) and drying in step (vi), thereby reducing CO ２ This can reduce CO emissions, resulting in an environmentally friendly method for producing cosmetic additives. For example, heat can be supplied to steps (v) and (vi) as high-pressure steam through a pipeline. Furthermore, since the dehydration in step (iii) and the oxidation in step (iv) are both gas-phase reactions, and the isopropanol dehydration reaction in step (iii) also produces a high yield of biopropylene, it is possible to omit the purification of biopropylene in step (iii) and perform steps (iii) and (iv) continuously. ２ From the viewpoint of cost reduction, it is preferable to carry out step (iii) and step (iv), and further step (iii) to step (vi) continuously at the same location.

[0152] On the other hand, since acetone has a reduced weight compared to the consumed ethanol and is therefore easy to transport, and since isopropanol is easy to handle and transport, step (i) and / or step (ii) may be carried out at a location separate from steps (iii) to (vi).

[0153] The ethanol (boiling point 78°C), acetone (boiling point 56°C), isopropanol (boiling point 82°C), propylene (boiling point -47°C), and acrylic acid (boiling point 141°C) used or produced in the above steps (i) to (v) are handled as liquids or gases, and of these, propylene may be cooled and liquefied before being handled, or may be handled as a gas. The process may involve transporting the liquid or gas (e.g., pipeline transport) and storing (e.g., storage in a tank having a liquid cooling or circulation mechanism) as appropriate between steps. When propylene is liquefied and transported, when the liquefied propylene is used in step (iv), a cooling medium may be produced by recovering latent heat from the propylene, and this may be used for cooling in steps after step (iv). Furthermore, for example, when suspension polymerization or precipitation polymerization is performed in step (v), the polyacrylic acid obtained in step (v) from liquid acrylic acid is in the form of a slurry, and therefore, transport and storage methods suitable for the slurry state are selected between step (v) and step (vi).

[0154] Furthermore, although the transportation between adjacent steps among the steps (i) to (vi) depends on the location of each step and the manufacturing company, in order to solve the above problem, the transportation of the biomaterial between at least one of the steps (i) to (vi) is carried out by long-distance transportation of 10 km or more by tanker, truck, or rail, and other transportation is also used in combination between at least one other step. This configuration enables the production of a more optimal cosmetic additive.

[0155] In order to solve the above problems, the transportation of the bio-based raw material between at least one of the steps (i) to (vi) is carried out through a pipeline connecting the steps, and optionally between the other steps, the transportation is carried out by a means other than a pipeline. This configuration enables the production of more optimal cosmetic additives.

[0156] Furthermore, from the viewpoint of reducing residual monomers in the cosmetic additive, as described above in step (v), it is preferable that step (iv) and step (v) are carried out within a certain time period (particularly including transportation and storage), that is, within 10 days, further within 5 days, within 2 days, or within 1 day.

[0157] Some or all of the steps (i) to (vi) may be carried out at multiple locations, by multiple manufacturing companies, or by methods under different conditions within the scope of the present invention. Note that, within the scope of the present invention, methods under different conditions correspond to, for example, a case where raw materials that differ in whether they have been purified are used together in the next step, or a case where raw materials obtained using different catalysts are used together in the next step.

[0158] [Cosmetic additive] The cosmetic additive obtained by the production method of the present invention (sometimes referred to as the "cosmetic additive of the present invention") contains at least an acrylic polymer obtained via step (v). The cosmetic additive has, for example, the following properties.

[0159] ( １４ The ratio of bio-based raw materials to the amount of acrylic polymer obtained is １４ C (radiocarbon) / １２ It can be identified by C (carbon). Conventional cosmetic additives based on acrylic acid (salt) obtained from fossil raw materials (especially petroleum, and more specifically propylene) １４ C / １２ C is 1.0 x 10 －１４ On the other hand, the acrylic polymer in the cosmetic additive of the present invention is １４ C / １２ C is preferably 1.0 × 10 －１４ or more, more preferably 1.0 × 10 －１３ More preferably, 5.0 × 10 －１３ More preferably, 1.0 × 10 －１２ If nearly 100% by mass of the raw material is non-fossil, the upper limit is 1.25 × 10 －１２ is. １４ C / １２ C can be measured by isotope mass spectrometry, etc., and is shown, for example, in U.S. Patent Nos. 3,885,155, 4,427,884, 5,438,194, and 5,661,299. Specific measurement procedures are as follows: 1. The cosmetic additive is burned and converted into carbon dioxide. 2. The carbon dioxide is separated and purified using a vacuum line. 3. The carbon dioxide produced from the cosmetic additive is reduced with hydrogen using iron as a catalyst to produce graphite. 4. １４Using a C-AMS measuring device, the graphite derived from cosmetic additives １４ C concentration and １２ C concentration ratio ( １４ C / １２ C) is measured.

[0160] １４ C (radioactive carbon) can be adjusted by the ratio of bio-based raw materials (especially bioethanol) used.

[0161] ( １３ C content) Carbon stable isotope ratio (δ １３ The carbon stable isotope ratio (δ C) can be adjusted appropriately within the range of 0 to -40% (per mille). １３ C) can be adjusted depending on the type of plant material, and δ １３ C≦-20%. C3 plants (wheat, potato, rice, etc.) and δ １３ C≧-20%. This can be adjusted appropriately by adjusting the raw material of C4 plants (such as corn). For measurement methods, see WO 2011 / 136237 and WO 2011 / 136238.

[0162] (Residual Monomer) The cosmetic additive of the present invention has the advantage that the residual monomer is low because the bioacrylic acid is obtained with high purity. From the viewpoint of safety, the residual monomer is controlled to, as an example of a means for achieving the above-mentioned polymerization, typically 500 ppm or less, preferably less than 500 ppm, more preferably 0 to 450 ppm, even more preferably 0 to 400 ppm, even more preferably 0 to 300 ppm, and particularly preferably 0 to 200 ppm. The residual monomer can be appropriately controlled by the polymerization initiator used during polymerization and the subsequent drying conditions, etc.

[0163] ​(Amount of impurities other than residual monomers) The cosmetic additive of the present invention has a purity of acrylic acid obtained by the method for producing acrylic acid of the present invention that is equal to or higher than that of conventional fossil raw materials, so there is no increase in the amount of impurities. Furthermore, there are no problems with coloration or odor. Typical impurities in cosmetic additives other than residual monomers include acetic acid and propionic acid, and the total content thereof is preferably 1000 ppm or less, more preferably 800 ppm or less, even more preferably 600 ppm or less, even more preferably 500 ppm or less, even more preferably 400 ppm or less, and particularly 300 ppm or less.

[0164] The total content of acetic acid, propionic acid, and residual monomers (particularly acrylic acid), which are responsible for the acidic odor of cosmetic additives, is preferably 1500 ppm or less, more preferably 1200 ppm or less, and even more preferably 1000 ppm or less.

[0165] (Viscosity Measurement) The viscosity of an aqueous solution prepared so that the concentration of the cosmetic additive is 0.5% by mass and the pH is 7.3 to 7.8 with a 50% by mass aqueous sodium hydroxide solution is preferably 40,000 to 100,000 mPa s, more preferably 45,000 to 90,000 mPa s, and even more preferably 50,000 to 80,000 mPa s. The viscosity is measured using a Brookfield viscometer at 25°C and a rotation speed of 4 rpm.

[0166] (Coloring) The YI (Yellow Index) is preferably 20 or less, more preferably 15 or less, and may be 10 or less.

[0167] (Transparency) It is preferable that the cosmetic additive does not cause turbidity. Transparent cosmetic products and products with various visual effects have been developed, and as long as the cosmetic additive does not cause turbidity, the visual effect can be freely selected.

[0168] (Feel of use of cosmetics) Cosmetic additives that have a fresh feel when used are preferred. The feel of the cosmetic when used and the texture when applied to the skin are important characteristics of cosmetics. There are a variety of options, such as a fresh and light feel or a moist and heavy feel. Among these, there are few cosmetic additives that can provide a fresh and light feel, and there is a high demand in the market. A sticky feel is an undesirable feel that many people find uncomfortable.

[0169] According to the production method of the present invention, a cosmetic additive having performance equivalent to or superior to that of conventional cosmetic additives derived from fossil raw materials can be obtained using biomass raw materials. Furthermore, since the production method of the present invention uses inexpensive bioethanol as the biomass raw material, production can be performed inexpensively with good productivity. Furthermore, according to the production method of the present invention, the cosmetic additive is produced using acrylic acid (salt) with few impurities, so the cosmetic additive of the present invention has few impurities.

[0170] The cosmetic additive of the present invention can be used as a known or conventional cosmetic additive. Examples of the additive include thickeners, gelling agents, texture improvers, moisturizers, film-forming agents, UV absorbers, antibacterial agents, emulsifiers, surfactants, dispersants, etc. The additives may be used alone or in combination of two or more.

[0171] [Cosmetics] Cosmetics can be produced using the cosmetic additive of the present invention. The cosmetic contains at least the cosmetic additive of the present invention. The cosmetic may contain other ingredients in addition to the cosmetic additive of the present invention.

[0172] Examples of the other components include solvents (e.g., water, organic solvents, etc.), oils, lower alcohols, polyhydric alcohols, thickeners, moisturizers, surfactants (anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants), fatty acid alkanolamides, antioxidants, antioxidant aids, powder components (e.g., organic powders, pigments, colorants, etc.), natural water-soluble polymers, semi-synthetic water-soluble polymers, synthetic water-soluble polymers, chelating agents, sugars and derivatives thereof, amino acids and derivatives thereof, organic amines, polymer emulsions, pH adjusters (acids, alkalis, etc.), vitamins, preservatives / antibacterial agents, anti-inflammatory agents, various extracts, activators, blood circulation promoters, antiseborrheic agents, anti-inflammatory agents, fragrances, etc. One or more of the above other components may be used.

[0173] The above-mentioned cosmetics include known or commonly used cosmetics, such as skin cosmetics, hair cosmetics, and bath cosmetics. Here, topical preparations are applied to the skin, nails, hair, etc. of the human body, and can be used to treat various diseases by incorporating active pharmaceutical ingredients, for example. Cosmetics are also applied to the skin, nails, hair, etc. of the human body, but are used for cosmetic purposes. Even when used as "topical preparations," they may actually be used in the same manner and dosage as cosmetics. Therefore, in this specification, the term "cosmetics" also includes such topical preparations. Examples of such topical preparations include antiperspirants, skin cleansers, topical skin preparations, hair cleansers, and topical hair preparations. Pharmaceutical uses of these topical preparations include hair growth agents, hair restorers, analgesics, disinfectants, anti-inflammatory agents, cooling agents, and skin anti-aging agents.

[0174] The skin cosmetics can be used on any part of the body, including the scalp, face (including lips, eyebrows, and cheeks), fingers, nails, and the entire body. Specific examples include skin cleansing products such as cleansing gel, cleansing cream, cleansing foam, facial cleanser, eye makeup remover, facial cleanser, liquid soap (body soap), hand soap, gel soap, shaving cream, nail polish remover, and anti-acne cosmetics; skin care products such as skin cream, scalp treatment, skin milk, milk lotion, emulsion, facial pack, body powder, essence, shaving lotion, and massage lotion; makeup products such as foundation, liquid foundation, oil-based foundation, makeup base, face powder, blusher, lip balm, rouge paste, lip gloss, eye cream, mascara, eyebrow pencil, and eyelash cosmetics; antiperspirants such as deodorants; UV protection products such as sunscreens and suntanning agents (sun tanning agents); and deodorant products.

[0175] Examples of the hair cosmetics include eyelash cosmetics, hair cleansers such as shampoos and rinse-in shampoos, hair styling products such as hair wax, hair curl retainers, setting agents, hair creams, hair sprays and hair liquids, hair coloring products such as hair dyes, hair color sprays, hair color rinses and hair color sticks, hair care products such as hair tonics, hair treatment essences and hair packs, and hair rinses or hair conditioning products such as oil rinses, cream rinses, treatment rinses, hair conditioners and hair treatments. Examples of the bath cosmetics include foam baths.

[0176] The form of the cosmetic preparation is not particularly limited, and may be any of a solution, emulsion, cream, solid, semi-solid, paste, gel, powder, multi-layered, mousse, water-in-oil type, or oil-in-water type emulsion composition (emulsion composition). The cosmetic preparation of the present invention can be formulated by known methods in the form of, for example, a solution, suspension, emulsion, cream, ointment, gel, liniment, lotion, aerosol, powder, spray, sheet preparation in which a sheet such as a nonwoven fabric is impregnated with the cosmetic preparation of the present invention, or stick preparation.

[0177] The content of the cosmetic additive of the present invention in the cosmetic is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, relative to the total amount (100% by mass) of the cosmetic, and is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less.

[0178] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0179] [Production Example 1] (Production of Acrylic Acid Derived from Bioethanol) "Specific Alcohol Traceable 95 Grade 1" manufactured by Japan Alcohol Sales Co., Ltd. was used as bioethanol.

[0180] In step (i), acetone was synthesized by reacting bioethanol / water vapor / nitrogen gas (molar ratio: 2 / 8 / 1) at 400°C in the presence of a composite metal oxide catalyst (molar ratio: Fe / Zn / Zr: 1 / 0.5 / 0.5). The acetone was purified to obtain acetone with a purity of 95% by mass or more. The impurities contained ethanol and acetaldehyde at a total of 4000 ppm, with the majority of the remainder being water.

[0181] Next, in step (ii), isopropanol was synthesized by reacting a gas of hydrogen / acetone having a purity of 95% or higher (molar ratio) of 2.7 / 1 in the presence of a catalyst in which 5% by mass of nickel and 5% by mass of ruthenium were supported on spherical silica (particle size 1.7 to 4 mm) at 0.5 MPa and 100°C, thereby obtaining isopropanol with a purity of 98% by mass. The ethanol content in the isopropanol was 2,200 ppm, and the majority of the remaining impurities were water and acetone.

[0182] Furthermore, in step (iii), the above gas of isopropanol with a purity of 98 mass% and consisting of isopropanol / oxygen / nitrogen=6.8 / 12.5 / 80.7 vol% was reacted at 325°C in the presence of a catalyst in which 10 mass% tungsten oxide was supported on spherical γ-alumina having a particle size of 2 to 4 mm, to obtain propylene.

[0183] Next, in step (iv), the propylene was oxidized at 325°C in the presence of a bismuth molybdenum catalyst (acrolein production catalyst) with a particle size of 5 to 7 mm to obtain acrolein, and the acrolein was then reacted at 275°C in the presence of a molybdenum vanadium catalyst with a particle size of 5 to 7 mm to obtain acrylic acid. This was purified to obtain acrylic acid (bioacrylic acid) with a purity of 99% by mass or more. The water content of the bioacrylic acid was 2,300 ppm.

[0184] [Production Example 2] (Production of Acrylic Acid A Derived from Fossil Raw Materials) Acrylic acid A was produced by catalytic gas phase oxidation in the same manner as in step (iv) except that propylene derived from fossil raw materials was used instead of biopropylene, as a conventional method, instead of the method of obtaining biopropylene from bioethanol in steps (i) to (iii) of Production Example 1. The water content in the acrylic acid A was 1,100 ppm.

[0185] [Production Example 3] (Production of Acrylic Acid B Derived from Fossil Raw Materials) Instead of the method of obtaining biopropylene from bioethanol in steps (i) to (iii) of Production Example 1 above, propylene derived from fossil raw materials was used, and the conditions of step (11) in the method for producing acrylic acid were changed to produce acrylic acid B. The water content in acrylic acid B was 5000 ppm.

[0186] Example 1 (Production of a cosmetic additive from bioacrylic acid) A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 43.4 g of ethyl acetate and 173.6 g of cyclohexane, and the mixture was heated to 70°C under stirring. Next, a monomer solution containing 33.0 g of the bioacrylic acid obtained in Production Example 1, 0.44 g of pentaerythritol triallyl ether neoallyl (trade name "Neoallyl P-30M", manufactured by Osaka Soda Co., Ltd.), and 0.95 g of potassium carbonate, and an initiator solution containing 0.08 g of di(2-ethylhexyl)peroxydicarbonate (trade name "Perloyl OPP", manufactured by NOF Corporation) as an initiator, 10.0 g of ethyl acetate, and 40.0 g of cyclohexane were each added dropwise from separate dropping nozzles to a polymerization reaction system maintained at a constant temperature of 70°C under stirring. The monomer solution and the initiator solution were simultaneously added, and the monomer solution was added over 180 minutes, and the initiator solution over 210 minutes. After the entire addition was completed, the reaction solution was maintained at 70°C for an additional 150 minutes to mature and complete the polymerization (precipitation polymerization). The reaction solution was then filtered to recover the polymer precipitate, which was then dried under reduced pressure at 90°C for 3 hours and at 105°C for 5 hours, yielding the cosmetic additive 1 of Example 1.

[0187] Example 2 (Production of a cosmetic additive using both bioethanol-derived acrylic acid and fossil raw material-derived acrylic acid) Polymerization was carried out under the same conditions as in Example 1, except that a mixture of 16.5 g of fossil raw material-derived acrylic acid A obtained in Production Example 2 and 16.5 g of bioacrylic acid obtained in Production Example 1 was used instead of 33.0 g of bioacrylic acid obtained in Production Example 1. After completion of the polymerization, drying was carried out under the same conditions as in Example 1, and cosmetic additive 2 of Example 2 was obtained.

[0188] Comparative Example 1 (Production of a cosmetic additive using acrylic acid derived from fossil raw materials) Polymerization was carried out under the same conditions as in Example 1, except that acrylic acid A derived from fossil raw materials obtained in Production Example 2 was used instead of the bioacrylic acid obtained in Production Example 1. After completion of the polymerization, drying was carried out under the same conditions as in Example 1, and a cosmetic additive 3 of Comparative Example 1 was obtained.

[0189] Comparative Example 2 (Production of a cosmetic additive using acrylic acid derived from fossil raw materials) Polymerization was carried out under the same conditions as in Example 1, except that 33.0 g of acrylic acid B derived from fossil raw materials obtained in Production Example 3 was used instead of 33.0 g of bioacrylic acid obtained in Production Example 1. The water content in the total acrylic acid was 5000 ppm. The formation of coarse particles was confirmed during polymerization. Furthermore, after polymerization, stickiness to the filter paper increased, requiring significantly longer filtration times. Drying was carried out under the same conditions as in Example 1, and cosmetic additive 4 of Comparative Example 2 was obtained.

[0190] Comparative Example 3 A natural thickener xanthan gum (Echo Gum T, manufactured by CP Kelco U.S., Inc.) was used to prepare cosmetic additive 5 of Comparative Example 3.

[0191] [Moisturizing Gel] The cosmetic additives prepared in the Examples and Comparative Examples were mixed with the various components shown in Table 1 to prepare moisturizing gels adjusted to a pH of 5.8 to 6.0. In addition to the cosmetic additives, the moisturizing gels also contained 1,3-butylene glycol (manufactured by Daicel Corporation), glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), EDTA-2Na (manufactured by Chubu Cherest Co., Ltd.), potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), sodium hyaluronate (manufactured by Kewpie Corporation), and phenoxyethanol (manufactured by Yokkaichi Synthetic Co., Ltd.). Note that the cosmetic additive of Comparative Example 3 had significantly low thickening properties, so the amount added was increased to prepare the moisturizing gel. Note that the units of addition amounts shown in Table 1 are "% by mass."

[0192]

[0193] <Evaluation> The cosmetic additives obtained in the examples and comparative examples, and the moisturizing gels obtained using the cosmetic additives were evaluated as follows. The results are shown in Table 2.

[0194] (1) Viscosity Measurement A measurement aqueous solution was prepared so that the concentration of the cosmetic additive was 0.5% by mass and the pH was adjusted to 7.3 to 7.8 using a 50% by mass aqueous sodium hydroxide solution. The viscosity was measured using a B-type viscometer (product name "TVB-10", manufactured by Toki Sangyo Co., Ltd., rotor No. M4) at 25°C and a rotation speed of 4 rpm.

[0195] (2) Transparency The aqueous solutions and moisturizing gels for which the viscosity measurements were carried out were filled into UV quartz glass cells (optical path length 10 mm, optical path width 10 mm, fluorescent completely transparent, volume 3.5 ml), and visual transparency evaluation was carried out. The evaluation criteria were A (clear, no turbidity), B (slight turbidity), C (turbidity), and D (significant turbidity overall).

[0196] (3) Texture—Freshness upon application—The moisturizing gel was applied to the upper arm, and a sensory evaluation was conducted on the freshness of the application. The evaluation criteria were A (very fresh), B (fresh), C (not very fresh), and D (not fresh at all).

[0197] (4) Texture—Non-stickiness upon application—The moisturizing gel was applied to the upper arm, and a sensory evaluation was conducted to assess the non-stickiness from the time the gel was first applied to the skin until immediately after it had been applied. The evaluation criteria were A (no stickiness), B (almost no stickiness), C (slight stickiness), and D (stickiness).

[0198]

[0199] As shown in Table 2, the moisturizing gels using the cosmetic additives of the Examples obtained by the production method of the present invention using bioethanol, a biomass raw material, were evaluated as having better feel (usage sensation) and transparency than moisturizing gels using cosmetic additives derived from fossil raw materials.

[0200] The cosmetic additives of the examples obtained by the manufacturing method of the present invention using bioethanol, a biomass raw material, can be used in various cosmetics in addition to the moisturizing gel described above. Formulation examples are shown below as reference cosmetics, but cosmetics using the cosmetic additives of the present invention are not limited to these. The pH of each reference cosmetic was measured at 25°C using a glass electrode pH meter (model name: LAQUA F-72, manufactured by Horiba, Ltd.), and the viscosity was measured using a TVB-10 viscometer (manufactured by Toki Sangyo Co., Ltd.) with a rotor No. 4 and a rotation speed of 12 rpm for 1 minute.

[0201] [Reference Cosmetic 1] A cosmetic serum was prepared by mixing the cosmetic additive 1 prepared in Example 1 with the various components shown in Table 3. Other components used included 1,3-butylene glycol: 1,3-butylene glycol (UK) (manufactured by Daicel Corporation), glycerin: concentrated cosmetic glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), xanthan gum: Eco Gum T (manufactured by CP Kelco U.S., Inc.), (acrylates / alkyl acrylate (C10-30)) crosspolymer: Carbopol ETD2020 (manufactured by Lubrizol Corporation), sodium hydroxide: sodium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), phospholipids and others: LiNPOSOME-V-MC (manufactured by Lilac Pharma Co., Ltd.), and phenoxyethanol: Phenoxyethanol-S (manufactured by Yokkaichi Synthetic Co., Ltd.).

[0202]

[0203] [Reference Cosmetic 2] Cosmetic additive 1 prepared in Example 1 was mixed with the various ingredients shown in Table 4 to prepare a gel. Other ingredients included 1,3-butylene glycol: 1,3-butylene glycol (UK) (manufactured by Daicel Corporation), glycerin: concentrated glycerin for cosmetics (manufactured by Miyoshi Oil & Fats Co., Ltd.), xanthan gum: Eco Gum T (manufactured by CP Kelco U.S., Inc.), (hydroxyethyl acrylate / sodium acryloyldimethyl taurate) copolymer: SEPINOV EMT10 (manufactured by SEPPIC), squalane: olive squalane (manufactured by Kokyu Alcohol Kogyo Co., Ltd.), and meadowfoam oil: CROPURE. MEADOWFOAM (manufactured by Croda), dimethicone: KF-96A-10CS (manufactured by Shin-Etsu Chemical Co., Ltd.), sodium hydroxide: sodium hydroxide (Fujifilm Wako Pure Chemical Industries, Ltd.), niacinamide: nicotinamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and phenoxyethanol: phenoxyethanol-S (manufactured by Yokkaichi Chemical Co., Ltd.) were used.

[0204]

[0205] [Reference Cosmetic 3] Cosmetic additive 1 prepared in Example 1 was mixed with the various ingredients shown in Table 5 to prepare a disinfecting gel. Other ingredients used included glycerin: concentrated cosmetic glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), ethanol: 99.5% ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), TEA: triethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), sodium hyaluronate: Hyaluronic Acid HA-LQ (manufactured by Kewpie Corporation), 1,3-butylene glycol: 1,3-butylene glycol (UK) (manufactured by Daicel Corporation), and phenoxyethanol: Phenoxyethanol-S (manufactured by Yokkaichi Chemical Co., Ltd.).

[0206]

[0207] [Reference Cosmetic 4] A styling gel was prepared by mixing the cosmetic additive 1 prepared in Example 1 with the various ingredients shown in Table 6. Other ingredients used included: glycerin: concentrated cosmetic glycerin (manufactured by Miyoshi Oil & Fats Co., Ltd.), ethanol: 99.5% ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), EDTA-2Na: Chelest 2B-SD (manufactured by Chubu Chelest Co., Ltd.), PVP: CV-8896 (manufactured by Nippon Shokubai Co., Ltd.), AMP: 2-amino-2-methyl-1-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), PEG-40 hydrogenated castor oil: NIKKOL HC-40 (manufactured by Nikko Chemicals Co., Ltd.), and fragrance: CITRUS GREEN BC181504 (manufactured by Toyotama Fragrance Co., Ltd.).

[0208]

[0209] [Reference Cosmetic 5] Cosmetic additive 1 prepared in Example 1 was mixed with the various ingredients shown in Table 7 to prepare a sunscreen gel. Other ingredients included EDTA-2Na: Chelest 2B-SD (manufactured by Chubu Chelest Co., Ltd.), (sodium acrylate / sodium acryloyldimethyltaurate) copolymer: SIMULGEL EG QD (manufactured by SEPPIC), diethylaminohydroxybenzoylhexyl benzoate: Uvinul A Plur Granular (manufactured by BASF), bisethylhexyloxyphenol methoxyphenyl triazine: Parsol Shield (manufactured by DSM), ethylhexyl triazone: Uvinul T150 (manufactured by BASF), homosalate: Parsol HMS (manufactured by DSM), and ethylhexyl salicylate: Parsol. EHS (manufactured by DSM), diisopropyl sebacate: FineNeo-iPSE (manufactured by Nippon Fine Chemical Co., Ltd.), dimethicone: KF-96A-6CS (manufactured by Shin-Etsu Chemical Co., Ltd.), (Acrylates / C10-30 alkyl acrylate crosspolymer: Carbopol ETD2020 (manufactured by Lubrizol Corporation), xanthan gum: Echo Gum T (manufactured by CP Kelco U.S., Inc.), potassium hydroxide: potassium hydroxide (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), sodium hyaluronate: Hyaluronsan HA-LQ (manufactured by Kewpie Corporation), titanium oxide, others: DIS-AB-10W (manufactured by Sakai Chemical Industry Co., Ltd.), 1,3-butylene glycol: 1,3-butylene glycol (UK) (manufactured by Daicel Corporation), silica: Godball G-6C (manufactured by Suzuki Oil & Fat Industries Co., Ltd.), ethanol: 99.5% ethanol (manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.), and phenoxyethanol: Phenoxyethanol-S (manufactured by Yokkaichi Chemical Co., Ltd.) were used.

[0210]

[0211] Variations of the present invention are described below. [Appendix 1] A method for producing a cosmetic additive containing an acrylic polymer derived from biomaterials, comprising the following steps (i) to (v), wherein the acrylic acid added in step (v) includes the acrylic acid obtained in step (iv): step (i) of obtaining acetone from bioethanol; step (ii) of obtaining isopropanol from the acetone; step (iii) of obtaining propylene from the isopropanol; step (iv) of obtaining acrylic acid from the propylene; and step (v) of polymerizing a monomer containing acrylic acid and / or a salt thereof to obtain an acrylic polymer. [Appendix 2] The production method according to Appendix 1, further comprising the following step (vi): step (vi) of drying the acrylic polymer. [Appendix 3] The production method according to Appendix 1 or 2, wherein the total content of ethanol and acetaldehyde in the acetone is 20,000 ppm or less. [Appendix 4] The production method according to any one of Appendices 1 to 3, wherein the ethanol content in the isopropanol is 20,000 ppm or less. [Appendix 5] The production method according to any one of Appendices 1 to 4, wherein the raw material for obtaining isopropanol includes the hydrogen obtained in the step (i). [Appendix 6] The production method according to any one of Appendices 1 to 5, wherein at least a portion of the water generated in the steps up to obtaining acrylic acid is reused in at least one step using water. [Appendix 7] The production method according to any one of Appendices 1 to 6, wherein the bioethanol is obtained by fermenting one or more genetically modified or non-genetically modified plant materials selected from the group consisting of sugar cane, corn, and sugar beet. [Appendix 8] The production method according to any one of Appendices 1 to 7, wherein the water content in the acrylic acid and / or a salt thereof input in the step (v) is 4000 ppm or less. [Appendix 9] The manufacturing method according to any one of Appendices 1 to 8, wherein in the step (v), in addition to the acrylic acid and / or its salt obtained in the step (iv), another acrylic acid (salt) is used in combination in the monomer, and the acrylic acid and / or its salt obtained in the step (iv) accounts for 1 mol % or more of the total amount of acrylic acid (salt) used in the step (v). [Appendix 10] The manufacturing method according to any one of Appendices 1 to 9, wherein the cosmetic additive is a thickener.[Appendix 11] A method for producing a cosmetic comprising a cosmetic additive obtained by the production method according to any one of Appendices 1 to 10. [Appendix 12] A method for producing a cosmetic additive comprising an acrylic polymer, comprising a step (v) of polymerizing acrylic acid and / or a salt thereof, wherein the acrylic acid and / or a salt thereof is acrylic acid derived from a biomaterial having a water content of 4000 ppm or less. [Appendix 13] A method for producing a cosmetic additive according to Appendices 12, wherein the polymerization is precipitation polymerization. [Appendix 14] A method for producing a cosmetic additive according to Appendices 12 or 13, wherein a hydrophobic organic solvent is used for the polymerization.

Claims

1. A method for producing a cosmetic additive containing an acrylic polymer derived from biomaterials, comprising the following steps (i) to (v), wherein the acrylic acid added in step (v) contains the acrylic acid obtained in step (iv): step (i) of obtaining acetone from bioethanol; step (ii) of obtaining isopropanol from the acetone; step (iii) of obtaining propylene from the isopropanol; step (iv) of obtaining acrylic acid from the propylene; and step (v) of obtaining an acrylic polymer by polymerizing a monomer containing acrylic acid and / or a salt thereof.

2. The method according to claim 1, further comprising the following step (vi): step (vi) of drying the acrylic polymer.

3. The method according to claim 1 or 2, wherein the total content of ethanol and acetaldehyde in the acetone is 20,000 ppm or less.

4. The method according to claim 1 or 2, wherein the ethanol content in the isopropanol is 20,000 ppm or less.

5. The method according to claim 1 or 2, wherein the raw material for obtaining isopropanol contains the hydrogen obtained in step (i).

6. The method according to claim 1 or 2, wherein at least a portion of the water generated in the steps up to obtaining acrylic acid is reused in at least one of the steps using water.

7. The method of claim 1 or 2, wherein the bioethanol is obtained by fermentation of one or more genetically modified or non-genetically modified plant materials selected from the group consisting of sugarcane, corn, and sugar beet.

8. The method according to claim 1 or 2, wherein the water content in the acrylic acid and / or salt thereof added in step (v) is 4000 ppm or less.

9. The production method according to claim 1 or 2, wherein in step (v), in addition to the acrylic acid and / or its salt obtained in step (iv), another acrylic acid (salt) is used in combination in the monomer, and the acrylic acid and / or its salt obtained in step (iv) accounts for 1 mol % or more of the total amount of acrylic acid (salt) subjected to step (v).

10. The manufacturing method according to claim 1 or 2, wherein the cosmetic additive is a thickener.

11. A method for producing a cosmetic comprising a cosmetic additive obtained by the method of claim 1 or 2.

12. A method for producing a cosmetic additive containing an acrylic polymer, comprising step (v) of polymerizing acrylic acid and / or a salt thereof, wherein the acrylic acid and / or a salt thereof is derived from a biomaterial and has a water content of 4000 ppm or less.

13. The method for producing a cosmetic additive according to claim 12, wherein the polymerization is carried out by precipitation polymerization.

14. The method for producing a cosmetic additive according to claim 12 or 13, wherein a hydrophobic organic solvent is used in the polymerization.