Aromatic compound composition and polymer

Abstract

The present invention provides an aromatic compound composition containing at least an aromatic compound (A) having a measured bio-based content of 80% to 100% (inclusive), the measured bio-based content indicating the proportion of radioactive carbon 14C derived from a biomass resource, the measured bio-based content being determined on the basis of the concentration of radioactive carbon in circulating carbon at 1950 as measured in accordance with ASTM D6866-20, the aromatic compound (A) is phenol (A) or 4-hydroxybenzoic acid (A), and when the aromatic compound (A) is phenol (A), the aromatic compound composition is dissolved in pure water so that the concentration of the aromatic compound composition is 90 mass%, the absorbance at a wavelength of 425 nm is 0.001-0.70, and when the aromatic compound (A) is phenol (A), the absorbance at a wavelength of 425 nm is 0.001-0.70. When the aromatic compound (A) is 4-hydroxybenzoic acid (A), the aromatic compound composition has an absorbance of 0.015 or less at a wavelength of 425 nm when the aromatic compound composition is dissolved in ethanol at a concentration of 20 g / L, or when the total amount of the aromatic compound composition is 100 mass%, the absorbance is 0.015 or less at a wavelength of 425 nm. The content of shikimic acid in the aromatic compound composition is 0.012 mass% or less.

Description

TECHNICAL FIELD

[0001] The present application relates to an aromatic compound composition and a polymer. BACKGROUND

[0002] In the context of global warming and depletion of fossil resources, the production of chemicals using renewable biomass resources as raw materials is attracting attention as a new industry for achieving a low-carbon society. As such chemicals, for example, phenol derived from biomass can be cited.

[0003] As a technology related to phenol derived from biomass, for example, described in Patent Literature 1. In Patent Literature 1, a phenol-formaldehyde resin is described, characterized by having a structure derived from a specific plant-derived phenol, a structure derived from another phenol, a structure derived from an aldehyde, and a structure derived from a sugar.

[0004] Further, 4-hydroxybenzoic acid (4-HBA) is a useful chemical substance, and can be used as a raw material for a polymer of a liquid crystal, or as a raw material for the synthesis of parahydroxybenzoic acid esters as preservatives, and the like.

[0005] At present, 4-hydroxybenzoic acid is produced by a chemical method using crude oil as a raw material. The preparation method of chemical 4-hydroxybenzoic acid includes, for example, a method of reacting phenol, potassium hydroxide, and carbon dioxide under high pressure conditions.

[0006] However, in this method, the phenol as a raw material not only depends on fossil raw materials, but also requires a strong base or carbon dioxide, high temperature and high pressure conditions during the reaction, and harmful waste liquid and waste gas and the like generated during the manufacturing process, which causes a huge burden on the environment.

[0007] In view of this background, therefore, there is an urgent need to establish an energy-saving and harmful waste liquid-reducing technology for producing 4-hydroxybenzoic acid by an environmentally compatible biological method using renewable resources as raw materials.

[0008] For example, in Non-Patent Literatures 1 and 2, and Patent Literatures 2 and 3, it is clarified that 4-HBA is synthesized from shikimic acid, which is an intermediate of the shikimic acid pathway related to the synthesis of aromatic amino acids and the like, by shikimate-pyruvate lyase encoded by ubiC, using Escherichia coli.

[0009] Prior Art Documents

[0010] Patent Literature

[0011] Non-Patent Literature 1: J. Bacteriol., 174, 5309-5316 (1992).

[0012] Non-Patent Literature 2: Microbiology, 140, 897-904 (1994).

[0013] Patent Literature 1: Japanese Patent Application Laid-Open No. 2017-119765

[0014] Patent Literature 2: U.S. Patent No. 6030819

[0015] Patent Literature 3: U.S. Patent No. 6114157 SUMMARY

[0016] Technical Problem to be Solved by the Invention

[0017] According to the present inventors' studies, it has been clarified that a biomass-derived aromatic compound composition has room for improvement from the viewpoint of improving the balance between environmental adaptability and color tone or polymerizability.

[0018] The present invention was made in view of the above circumstances, and aims to provide an aromatic compound composition that improves the balance between environmental adaptability and color tone or polymerizability.

[0019] Further, according to the present inventors' studies, it has been clarified that a biomass-derived phenol composition has room for improvement from the viewpoint of the color tone of a polymer synthesized using the phenol composition.

[0020] The first embodiment of the present invention was made in view of the above circumstances, and provides a phenol composition that improves the balance between environmental adaptability and the color tone of an obtained polymer.

[0021] Further, according to the present inventors' studies, it has been clarified that, in a case where the biomass-derived 4-hydroxybenzoic acid as described above is used for polymerization of a resin as a downstream product, polymerizability has room for improvement.

[0022] The second embodiment of the present invention was made in view of the above circumstances, and provides a 4-hydroxybenzoic acid composition and a polymer that improve the balance between environmental adaptability and polymerizability.

[0023] Further, according to the present inventors' studies, it has been clarified that the biomass-derived 4-hydroxybenzoic acid as described above has room for improvement from the viewpoint of color tone.

[0024] The third embodiment of the present invention was made in view of the above circumstances, and provides a 4-hydroxybenzoic acid composition that improves the balance between environmental adaptability and color tone.

[0025] Means for Solving the Technical Problem

[0026] According to the present application, there is provided an aromatic compound composition comprising at least radiocarbon derived from a biomass resource as represented by a concentration of radiocarbon in recycled carbon in the 1950s, measured according to ASTM D6866-20 14 An aromatic compound (A) having a measured bio-based content of 80% or more and 100% or less of the proportion of C, wherein the aromatic compound (A) is a phenol (A) or 4-hydroxybenzoic acid (A), in the case where the aromatic compound (A) is the phenol (A), an absorbance at a wavelength of 425 nm is 0.001 or more and 0.70 or less when the aromatic compound composition is dissolved in pure water so as to have a concentration of 90% by mass, in the case where the aromatic compound (A) is the 4-hydroxybenzoic acid (A), an absorbance at a wavelength of 425 nm is 0.015 or less when the aromatic compound composition is dissolved in ethanol at a concentration of 20 g / L, or a content of shikimic acid in the aromatic compound composition is 0.012% by mass or less when the total amount of the aromatic compound composition is taken as 100% by mass.

[0027] Furthermore, the present inventors have conducted intensive research in order to achieve the above-described object. As a result, it has been found that by setting the absorbance of light having a wavelength of 425 nm within a specific range, it is possible to improve the balance between environmental adaptability and the color tone of the obtained polymer, thereby completing the first embodiment of the present application.

[0028] [1a] A phenol composition comprising at least radiocarbon derived from a biomass resource as represented by a concentration of radiocarbon in recycled carbon in the 1950s, measured according to ASTM D6866-20 14 A phenol (A) having a measured bio-based content of 80% or more and 100% or less of the proportion of C, and an absorbance at a wavelength of 425 nm is 0.001 or more and 0.70 or less when dissolved in pure water so as to have a concentration of 90% by mass.

[0029] [2a] The phenol composition according to the above-mentioned [1a], wherein the content of the phenol (A) is 95% by mass or more and 100% by mass or less.

[0030] [3a] The phenol composition according to the above-mentioned [1a] or [2a], wherein the measured bio-based content of the phenol (A) is 95% or more and 100% or less.

[0031] [4a] The phenol composition according to any one of the above-mentioned [1a] to [3a], wherein the absorbance is 0.62 or less.

[0032] [5a] The phenol composition according to any one of the above [1a] to [4a], wherein the above phenol (A) contains at least a structure derived from a benzene ring of a product derived from one or two or more transformants selected from the group consisting of transformant HBA-2 (Deposit No. NITE BP-01838) and transformant HBA-47 (Deposit No. NITE BP-01849).

[0033] [6a] The phenol composition according to any one of the above [1a] to [5a], wherein the above phenol (A) contains at least a product derived from one or two or more transformants selected from the group consisting of transformant PHE7 (Deposit No. NITE BP-976), transformant PHE18 (Deposit No. NITE BP-995), transformant PHE21 (Deposit No. NITE BP-996), and transformant PHE31 (Deposit No. NITE BP-999).

[0034] [7a] A polymer, wherein the polymer contains at least a structural unit derived from the phenol (A) in the phenol composition according to any one of the above [1a] to [6a].

[0035] [8a] The polymer according to the above [7a], wherein the polymer is a phenol-formaldehyde resin.

[0036] And, the present inventors have repeatedly conducted intensive research in order to achieve the above-described problem. As a result, it was found that by setting the shikimic acid contained in the 4-hydroxybenzoic acid composition to be the prescribed concentration or less, the balance between environmental adaptability and polymerizability was improved, thereby completing the second embodiment of the present invention.

[0037] [1b] A 4-hydroxybenzoic acid composition, wherein it contains at least a measured bio-based content of 80% or more and 100% or less of the proportion of radioactive carbon in the 1950s' circulating carbon as measured according to ASTM D6866-20, and the content of shikimic acid is 0.012% by mass or less when the total amount of the 4-hydroxybenzoic acid composition is taken as 100% by mass. 14 C of 80% or more and 100% or less, and the content of shikimic acid is 0.012% by mass or less when the total amount of the 4-hydroxybenzoic acid composition is taken as 100% by mass.

[0038] [2b] The 4-hydroxybenzoic acid composition according to the above [1b], wherein the content of the above 4-hydroxybenzoic acid (A) is 95% by mass or more and 100% by mass or less when the total amount of the 4-hydroxybenzoic acid composition is taken as 100% by mass.

[0039] [3b] The 4-hydroxybenzoic acid composition according to any one of the above [1b] or [2b], wherein the measured biobased content of the above 4-hydroxybenzoic acid (A) is 95% or more and 100% or less.

[0040] [4b] The 4-hydroxybenzoic acid composition according to any one of the above [1b] to [3b], wherein the content of the shikimic acid is 0.008 mass% or less when calculated from the total amount of the above 4-hydroxybenzoic acid composition as 100 mass%.

[0041] [5b] The 4-hydroxybenzoic acid composition according to any one of the above [1b] to [4b], wherein the 4-hydroxybenzoic acid (A) comprises at least a product of one or two transformants selected from transformant HBA-2 (Deposit No. NITE BP-01838) and transformant HBA-47 (Deposit No. NITE BP-01849).

[0042] [6b] A polymer, wherein the polymer comprises at least a structure derived from the above 4-hydroxybenzoic acid (A) of the 4-hydroxybenzoic acid composition according to any one of the above [1b] to [5b].

[0043] [7b] The polymer according to the above [6b], which is a liquid crystal polymer.

[0044] Further, the present inventors have repeatedly conducted intensive studies in order to achieve the above-described object. As a result, it has been found that by setting the absorbance of light having a wavelength of 425 nm within a specific range, it is possible to improve the balance between the environmental adaptability and the color tone of the 4-hydroxybenzoic acid composition, thereby completing the third embodiment of the present application.

[0045] [1c] A 4-hydroxybenzoic acid composition, wherein it comprises at least a measured biobased content of 80% or more and 100% or less of the proportion of C, which is calculated from the concentration of radioactive carbon in the circulating carbon in the 1950s, measured according to ASTM D6866-20, representing radioactive carbon derived from a biomass resource 14 4-hydroxybenzoic acid (A) having a measured biobased content of 80% or more and 100% or less of the proportion of C, and the absorbance at a wavelength of 425 nm when the 4-hydroxybenzoic acid composition is dissolved in ethanol at a concentration of 20 g / L is 0.015 or less.

[0046] [2c] The 4-hydroxybenzoic acid composition according to the above [1c], wherein the content of the above 4-hydroxybenzoic acid (A) is 95 mass% or more and 100 mass% or less when calculated from the total amount of the above 4-hydroxybenzoic acid composition as 100 mass%.

[0047] [3c] The 4-hydroxybenzoic acid composition according to any one of the above [lc] or [2c], wherein the measured biobased content of the above 4-hydroxybenzoic acid (A) is 95% or more and 100% or less.

[0048] [4c] The 4-hydroxybenzoic acid composition according to any one of the above [lc] to [3c], wherein the absorbance is 0.010 or less.

[0049] [5c] The 4-hydroxybenzoic acid composition according to any one of the above [lc] to [4c], wherein the absorbance is 0.001 or more.

[0050] [6c] The 4-hydroxybenzoic acid composition according to any one of the above [lc] to [5c], wherein the 4-hydroxybenzoic acid (A) comprises at least a product of one or two transformants selected from transformant HBA-2 (Deposit No. NITE BP-01838) and transformant HBA-47 (Deposit No. NITE BP-01849).

[0051] Effects of the Invention

[0052] According to the present application, it is possible to provide an aromatic compound composition which improves the balance between environmental adaptability and color tone or polymerizability.

[0053] Also, according to the first embodiment of the present application, it is possible to provide a phenol composition which improves the balance between environmental adaptability and color tone of the obtained polymer.

[0054] Also, according to the second embodiment of the present application, it is possible to provide a 4-hydroxybenzoic acid composition and a polymer which improve the balance between environmental adaptability and polymerizability.

[0055] Also, according to the third embodiment of the present application, it is possible to provide a 4-hydroxybenzoic acid composition which improves the balance between environmental adaptability and color tone. DETAILED DESCRIPTION

[0056] Hereinafter, the embodiments of the present application will be described in detail.

[0057] In the description of the present embodiment, "pure water" refers to water having a conductivity of 1 MΩ-cm or more.

[0058] The term "liquid crystalline polymer" in the present specification generally refers to a polymer which can have a rod-like structure and which can exhibit liquid crystalline properties (e.g., thermotropic nematic state) in its molten state.

[0059] The aromatic compound composition of the present embodiment contains at least radiocarbon derived from a biomass resource, which is calculated based on the concentration of radiocarbon in recycled carbon in the 1950s, measured according to ASTM D6866-20 14 An aromatic compound (A) having a measured biobased content of a proportion of C of 80% or more and 100% or less, wherein the aromatic compound (A) is a phenol (A) or a 4-hydroxybenzoic acid (A), and in the case where the aromatic compound (A) is the phenol (A), an absorbance at a wavelength of 425 nm when the aromatic compound composition is dissolved in pure water so as to have a concentration of 90% by mass is 0.001 or more and 0.70 or less, in the case where the aromatic compound (A) is the 4-hydroxybenzoic acid (A), an absorbance at a wavelength of 425 nm when the aromatic compound composition is dissolved in ethanol at a concentration of 20 g / L is 0.015 or less, or a content of shikimic acid in the aromatic compound composition is 0.012% by mass or less when the total amount of the aromatic compound composition is taken as 100% by mass.

[0060] Hereinafter, a more specific mode of the present embodiment will be shown as a first embodiment to a third embodiment.

[0061] <First Embodiment>

[0062] [Phenol Composition]

[0063] The phenol composition of the first embodiment contains at least radiocarbon derived from a biomass resource, which is calculated based on the concentration of radiocarbon in recycled carbon in the 1950s, measured according to ASTM D6866-20 14 The phenol (A) having a measured biobased content of a proportion of C of 80% or more and 100% or less, and an absorbance at a wavelength of 425 nm when the aromatic compound composition is dissolved in pure water so as to have a concentration of 90% by mass is 0.001 or more and 0.70 or less.

[0064] In such a phenol composition, the measured biobased content indicates the amount of carbon derived from plants included in the phenol (A), and the larger this value, the higher the proportion of the phenol composition composed of natural raw materials. Therefore, the larger the measured biobased content, the better the environmental suitability from the viewpoint of carbon neutralization. Also, when the above absorbance is 0.001 or more and 0.70 or less, even in the case of using a raw material derived from plants, a phenol composition that is more suitable in terms of the color tone of a polymer obtained using the phenol composition can be obtained.

[0065] Such a phenol composition can be produced by the production method described later, and in particular, by (i) a step of producing a precursor from a plant-derived raw material compound using the first transformant, (ii) a step of producing a phenol composition from the precursor described above using the second transformant, and (iii) a step of separating and concentrating the produced phenol composition.

[0066] In the phenol composition of the first embodiment, the concentration of radioactive carbon in the total carbon atoms of phenol (A) in the phenol composition, which is measured based on the concentration of radioactive carbon in the circulating carbon in the 1950s according to ASTM D6866-20, is 0.0001% or more and less than 0.001%. 14 The above measured biobased content of the proportion of C is 80% or more and 100% or less, preferably 85% or more and 100% or less, more preferably 90% or more and 100% or less, further preferably 95% or more and 100% or less. Since the above measured biobased content is within the above numerical range, environmental suitability becomes better from the viewpoint of carbon neutrality.

[0067] At this time, the concentration of radioactive carbon in the total carbon atoms of phenol (A) in the phenol composition, which is measured based on the concentration of radioactive carbon in the circulating carbon in the 1950s according to ASTM D6866-20, is 0.0001% or more and less than 0.001%. 14 The measured biobased content of the proportion of C is measured by ASTM D6866-20, which is a biobased concentration test standard established by the American Society for Testing Materials (ASTM), for radioactive carbon in a sample. 14 The content of C, and based on the measurement result thereof and the concentration of radioactive carbon in the circulating carbon in 1950 14 In addition, in this test standard, a plurality of analysis methods are shown, and among them, analysis method B (AMS (accelerator mass spectrometry) method) is preferably used. In analysis method B, for example, an analysis device such as Pelletron AMS manufactured by National Electrostatics Corp. is used.

[0068] In the phenol composition of the first embodiment, the upper limit value of the absorbance at a wavelength of 425 nm when dissolved in pure water so as to become a concentration of 90% by mass is 0.70 or less, preferably 0.65 or less, more preferably 0.62 or less, more preferably 0.60 or less, further preferably 0.50 or less, further preferably 0.40 or less, further preferably 0.25 or less, further preferably 0.20 or less, further preferably 0.15 or less, further preferably 0.10 or less. Since the absorbance at a wavelength of 425 nm is the above upper limit value or less, the color tone of a polymer obtained using the phenol composition of the first embodiment is more suitable.

[0069] Further, the lower limit of the absorbance at a wavelength of 425 nm is not particularly limited, but is, for example, 0.001 or more, and from the viewpoint of production efficiency, is preferably 0.005 or more, more preferably 0.01 or more, further preferably 0.02 or more, further preferably 0.03 or more, further preferably 0.05 or more, further preferably 0.07 or more.

[0070] In the phenol composition of the first embodiment, the content of the above-described phenol (A) is preferably 95% by mass or more and 100% by mass or less, more preferably 96% by mass or more and 100% by mass or less, further preferably 97% by mass or more and 100% by mass or less, further preferably 98% by mass or more and 100% by mass or less, further preferably 99% by mass or more and 100% by mass or less, based on 100% by mass of the total amount of the phenol composition. Since the content of the above-described phenol (A) is within the above-described numerical range, from the viewpoint of carbon neutrality, environmental suitability becomes better, and furthermore, the hue of the polymer obtained using the phenol composition of the first embodiment is more suitable.

[0071] Further, when the content of the above-described phenol (A) is 100% by mass, the content of the other components described later is 0.000% by mass. At this time, the content of the other components is below the detection limit, and also includes a case where quantitative detection is not possible.

[0072] In the phenol composition of the first embodiment, the above-described phenol (A) preferably contains at least a structure of a benzene ring derived from a product derived from one or two or more transformants selected from transformant HBA-2 (deposition number: NITE BP-01838) and transformant HBA-47 (deposition number: NITE BP-01849). Since the above-described phenol (A) contains at least the above-described product, from the viewpoint of carbon neutrality, environmental suitability becomes better, and furthermore, the hue of the polymer obtained using the phenol composition of the first embodiment is more suitable.

[0073] In the phenol composition of the first embodiment, the above-described phenol (A) preferably contains at least a product of one or two or more transformants selected from transformant PHE7 (deposition number: NITE BP-976), transformant PHE18 (deposition number: NITE BP-995), transformant PHE21 (deposition number: NITE BP-996), and transformant PHE31 (deposition number: NITE BP-999). Since the above-described phenol (A) contains at least the above-described product, from the viewpoint of carbon neutrality, environmental suitability becomes better, and furthermore, the hue of the polymer obtained using the phenol composition of the first embodiment is more suitable.

[0074] In the phenol composition of the first embodiment, since the phenol (A) contains at least a structure of a benzene ring derived from a product of one or two or more transformants selected from among transformant HBA-2 and transformant HBA-47, or the phenol (A) contains at least a product of one or two or more transformants selected from among transformant PHE7, transformant PHE18, transformant PHE21, and transformant PHE31, it can be presumed that the reason why the hue of the obtained polymer is more suitable is that the presence of a trace amount of components that can adversely affect the hue is relatively low.

[0075] Among them, there are a large number of trace components derived from transformants, and the content of the above-mentioned trace components is less than the detection limit, and analysis cannot be performed. Therefore, in the phenol composition of the first embodiment, in the manner in which the phenol (A) contains at least a structure of a benzene ring derived from a product of one or two or more transformants selected from among transformant HBA-2 and transformant HBA-47, or contains at least a product of one or two or more transformants selected from among transformant PHE7, transformant PHE18, transformant PHE21, and transformant PHE31, it is not possible to directly determine the characteristic part of the present manner by the structure or the property of the object, and it can be said that it is almost unrealistic, and it can be considered that there is a so-called "impossible, unrealistic situation".

[0076] (Other components)

[0077] In the phenol composition of the first embodiment, other components other than the above-mentioned components can be contained as long as the balance of environmental suitability and the hue of the obtained polymer is not lowered.

[0078] As the other components, one or two or more selected from the group consisting of the following compounds can be mentioned.

[0079] Monosaccharides such as glucose, fructose, mannose, arabinose, xylose, galactose, disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, xylobiose, polysaccharides such as dextrin or soluble starch, and the like.

[0080] Sugar alcohols such as mannitol, sorbitol, xylitol, glycerol, organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, gluconic acid, alcohols such as ethanol, propanol, hydrocarbons such as n-alkanes, and the like.

[0081] Inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, nitrogen-containing organic compounds such as urea, aqueous ammonia, sodium nitrate, potassium nitrate, corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acids, and the like.

[0082] Monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like.

[0083] A solvent such as pure water.

[0084] In the phenol composition of the first embodiment, the content of the above other component is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less, and further preferably 1% by mass or less. Since the content of the above other component is the above upper limit value or less, the color tone of the polymer obtained by using the phenol composition of the first embodiment is more suitable.

[0085] Further, the lower limit value of the content of the above other component is not particularly limited, but is, for example, 0.000% by mass or more. At this time, 0.000% by mass means that the content of the above other component is below the lower limit of detection, and also includes a case where it cannot be detected quantitatively.

[0086] In addition, in the phenol composition of the first embodiment, in the case where a plurality of the above other components are contained, the content of the above other components in total is the above upper limit value or less and the above lower limit value or more.

[0087] As a method for quantifying the content of such a phenol (A) and other components, for example, high-performance liquid chromatography using a high-performance liquid chromatograph (manufactured by Hitachi High-Tech Science Corporation, Chromaster (registered trademark)) equipped with a UV detector, ion chromatography, gas chromatography mass spectrometry (GC / MS), inductively coupled plasma mass spectrometry (ICP-MS), and the like can be given.

[0088] [Method for producing phenol composition]

[0089] Next, a method for producing the phenol composition of the first embodiment will be described.

[0090] As the method for producing the phenol composition of the first embodiment, a process (A) to (D) including the following is preferable.

[0091] (A) A process of generating a precursor by allowing a reaction intermediate liquid containing the 1st transformant and at least one raw material compound selected from the group consisting of a saccharide, a compound capable of generating chorismate through metabolism of the above transformant, or chorismate and a salt thereof to react.

[0092] (B) A process of generating a phenol composition from the precursor by the 2nd transformant, thereby obtaining a reaction liquid containing the phenol composition.

[0093] (C) a step of removing the transformant from the reaction solution.

[0094] (D) a step of separating and concentrating the phenol composition in the reaction solution.

[0095] [(A) a step of generating a precursor by allowing a reaction intermediate solution containing a first transformant and at least one raw material compound selected from the group consisting of a saccharide, a compound from which the above transformant can generate chorismic acid through metabolism, or chorismic acid and a salt thereof to react]

[0096] As the method for producing the phenol composition of the first embodiment, first, the following step (A) is performed: (A) a step of generating a precursor by allowing a reaction intermediate solution containing a first transformant and at least one raw material compound selected from the group consisting of a saccharide, a compound from which the above transformant can generate chorismic acid through metabolism, or chorismic acid and a salt thereof to react.

[0097] Each of the compounds and the reaction conditions used in the present step will be described in detail below.

[0098] (First transformant)

[0099] In the method for producing the phenol composition of the first embodiment, as the first transformant, any transformant can be used as long as it is a transformant that can generate a precursor from a saccharide through metabolism. Examples of the precursor at this time include 4-hydroxybenzoic acid and the like. As such a transformant, for example, the coryneform bacterial transformant HBA-2 (deposition number: NITE BP-01838) described in Japanese Patent No. 6327653 or the coryneform bacterial transformant HBA-47 (deposition number: NITE BP-01849) described in Japanese Patent No. 6327654, and the like can be given.

[0100] Before the reaction, the first transformant is preferably cultured under aerobic conditions. As the culture temperature and the culture time, there are no particular limitations as long as the transformant can be cultured and the transformant in an amount of at least the desired amount can be obtained. As the culture temperature, for example, it is 25°C or higher and 38°C or lower. As the culture time, for example, it is 12 hours or longer and 48 hours or shorter.

[0101] (Culture medium for culture)

[0102] The culture medium for aerobic culture of the first transformant before the reaction can use a natural culture medium or a synthetic culture medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients.

[0103] As a carbon source, a saccharide (e.g., monosaccharides such as glucose, fructose, mannose, xylose, arabinose, galactose; disaccharides such as sucrose, maltose, lactose, cellobiose, xylobiose, trehalose; polysaccharides such as starch; molasses; and the like), a sugar alcohol such as mannitol, sorbitol, xylitol, glycerol; an organic acid such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, gluconic acid; an alcohol such as ethanol, propanol; a hydrocarbon such as n-alkane; and the like can also be used.

[0104] The carbon source can be used alone or in combination of two or more. The concentration of the carbon source in the medium varies depending on the compound used, but can be set to 0.1 w / v% or more and 20 w / v% or less, for example.

[0105] As a nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, and the like can be used. In addition, nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acids, and the like can also be used. The nitrogen source can be used alone or in combination of two or more. The concentration of the nitrogen source in the medium varies depending on the nitrogen compound used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0106] As an inorganic salt, monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like can be used. The inorganic salt can be used alone or in combination of two or more. The concentration of the inorganic salt in the medium varies depending on the inorganic salt used, but can be set to 0.01 w / v% or more and 1 w / v% or less, for example.

[0107] As a nutrient, meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloride, extracts or decomposed products of animal, plant, or microbial cells, and the like can be used. The concentration of the nutrient in the medium varies depending on the nutrient used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0108] In addition, vitamins can also be added as needed. As vitamins, biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, nicotinic acid, and the like can be used.

[0109] The pH of the medium is preferably 6 or more and 8 or less.

[0110] As a specific preferred medium, A medium [Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004): Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004)], BT medium [Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004): Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004)], and the like can be given. In these media, the sugar concentration can be set within the above range.

[0111] (raw material compound)

[0112] The raw material compound is preferably a compound that can be taken into the cell by the first transformant, and more preferably a compound that is abundant in plants and the like, and is industrially easily available.

[0113] Among the above raw material compounds, as a saccharide, a saccharide that can be produced by the metabolism of the first transformant to glucose is preferable, and glucose is more preferable. Such saccharides include monosaccharides such as fructose, mannose, arabinose, xylose, galactose, and the like; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, xylobiose, and the like; polysaccharides such as dextrin or soluble starch, and the like. Furthermore, it is preferable from the viewpoint that the production efficiency of the precursor can be improved by using glucose, and thus the production efficiency of the phenol composition of the first embodiment can be improved.

[0114] Furthermore, among the above raw material compounds, as a compound that can be produced by the metabolism of the first transformant to shikimic acid, quinic acid, shikimic acid, and the like can be given.

[0115] Also, for example, as a raw material containing these raw material compounds, a plant-derived raw material can be used. As the plant-derived raw material, for example, molasses, or straw (rice straw, barley straw, wheat straw, rye straw, oat straw, and the like), bagasse, corn stover, and the like, non-edible crop waste, or energy crops such as switchgrass, napiergrass, and miscanthus, or sawdust, waste paper, and the like, saccharified liquid containing plural kinds of sugars such as glucose obtained by saccharification with saccharifying enzymes and the like can be used.

[0116] Among these, as the raw material compound, glucose, shikimic acid, quinic acid, and oroboric acid are preferable, and as the raw material containing these, a plant-derived raw material is preferably used.

[0117] (Reaction intermediate liquid)

[0118] As the reaction intermediate liquid, a natural reaction liquid or a synthetic reaction liquid containing a carbon source, a nitrogen source, and inorganic salts and the like can be used.

[0119] As the carbon source, the raw material compound described above or molasses or saccharified liquid containing the raw material compound and the like can be used. Also, as the carbon source, in addition to sugars, sugar alcohols such as mannitol, sorbitol, xylitol, and glycerol; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and carbon hydrides such as n-alkanes can be used.

[0120] The carbon source can be used alone or in combination of two or more.

[0121] The concentration of the raw material compound in the reaction intermediate liquid is preferably 1 w / v% or more and 20 w / v% or less, more preferably 2 w / v% or more and 10 w / v% or less, and further preferably 2 w / v% or more and 5 w / v% or less.

[0122] Also, the concentration of the total carbon source containing the raw material compound can be set to 2 w / v% or more and 5 w / v% or less.

[0123] As the nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, and the like can be used. Also, nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acids, and the like can be used. The nitrogen source can be used alone or in combination of two or more. The concentration of the nitrogen source in the reaction intermediate liquid varies depending on the nitrogen compound used, but for example, it can be set to 0.1 w / v% or more and 10 w / v% or less.

[0124] As the inorganic salts, monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like can be given. The inorganic salts can be used singly or in combination of two or more. The concentration of the inorganic salts in the reaction intermediate liquid varies depending on the inorganic salt used, but can be set to 0.01 w / v% or more and 1 w / v% or less, for example.

[0125] As the nutrients, meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloric acid hydrolysate, extract or decomposition product of animal, plant or microbial cells, and the like can be given. The concentration of the nutrients in the reaction intermediate liquid varies depending on the nutrient used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0126] Further, vitamins can be added as needed. As the vitamins, biotin, thiamine (vitamin Bl), pyridoxine (vitamin B6), pantothenic acid, inositol, nicotinic acid, and the like can be given.

[0127] The pH of the reaction intermediate liquid is preferably 6 or more and 8 or less.

[0128] As the specific preferred reaction intermediate liquid, the aforementioned A medium and BT medium, and the like can be given. In these reaction intermediate liquids, the sugar concentration can be set to be used within the above range.

[0129] (Reaction conditions)

[0130] The reaction temperature, i.e., the survival temperature of the first transformant, is preferably 20°C or more, more preferably 23°C or more, and further preferably 25°C or more from the viewpoint of the production efficiency of the phenol composition. Also, the above survival temperature is preferably 50°C or less, more preferably 48°C or less, and further preferably 47°C or less from the same viewpoint.

[0131] The reaction time is preferably 7 days or less, more preferably 5 days or less, and further preferably 3 days or less from the viewpoint of the production efficiency of the phenol composition. Also, the above reaction time is not particularly limited as long as the reaction proceeds sufficiently, but is, for example, 1 day or more.

[0132] The cultivation can be any of batch, fed-batch, and continuous. Among them, the batch is preferred from the viewpoint of the production efficiency of the phenol composition.

[0133] The reaction can be performed under aerobic conditions or under reducing conditions. The production capacity of the phenol composition by the first transformant itself is higher under aerobic conditions. However, under aerobic conditions, the first transformant proliferates, and thus the raw material compound is consumed for the proliferation, and accordingly the production efficiency of the phenol composition decreases.

[0134] Therefore, it is preferable to carry out the reaction under aerobic conditions and conditions in which the first transformant does not proliferate. In the present specification, "does not proliferate" includes does not substantially proliferate or hardly proliferate. For example, proliferation of the first transformant can be avoided or inhibited by using a reaction solution that lacks or limits one or more compounds necessary for proliferation of the microorganism, i.e., vitamins such as biotin, thiamine, and the like, nitrogen sources, and the like.

[0135] Also, under reducing conditions, since the first transformant does not substantially proliferate, the raw material compound is not consumed for proliferation, and accordingly the production efficiency of the precursor is improved, as a result, the production efficiency of the phenol composition becomes high.

[0136] The reducing conditions are determined by the oxidation-reduction potential of the reaction intermediate solution. The oxidation-reduction potential of the reaction intermediate solution is preferably -500 mV or more and -200 mV or less, more preferably -500 mV or more and -150 mV or less.

[0137] The reducing state of the reaction intermediate solution can be simply estimated using a resazurin indicator (fading from blue to colorless if in a reducing state), but can be accurately measured using an oxidation-reduction potential difference meter (for example, ORP Electrodes manufactured by Broadley-James Corporation).

[0138] The method of preparing the reaction medium under reducing conditions can be carried out without limitation using a known method. For example, as the liquid medium of the reaction medium, a reaction medium aqueous solution can be used instead of distilled water or the like, and with respect to the method of preparing the reaction medium aqueous solution, for example, reference can be made to the method of preparing a culture solution for an obligate anaerobic microorganism such as a sulfur-reducing microorganism (Pfennig, N. et al., (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, M. P. et al., p 926-940, Berlin, Springer Verlag.: Pfenning, N. et al. (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, M. P. et al., p 926-940, Berlin, Springer Verlag.) or "Agricultural Chemistry Experiment Book, Vol. 3, edited by the Department of Agricultural Chemistry, Kyoto University, 26th printing in 1990, published by Sangyo Tosho Publishing Co., Ltd." or the like, and a desired aqueous solution under reducing conditions can be obtained.

[0139] Specifically, by subjecting distilled water or the like to a heating treatment or a reduced pressure treatment to remove dissolved gas, an aqueous solution for a reaction medium under reducing conditions can be prepared. In this case, it is preferable to remove dissolved gas, particularly dissolved oxygen, by subjecting distilled water or the like to a treatment under reduced pressure of 10 mmHg or less, more preferably 5 mmHg or less, and further preferably 3 mmHg or less, and preferably for 1 minute or more and 60 minutes or less, and more preferably for 5 minutes or more and 40 minutes or less, to thereby prepare an aqueous solution for a reaction medium under reducing conditions.

[0140] Further, the aqueous solution for a reaction medium under reducing conditions can also be adjusted by adding an appropriate reducing agent (for example, thio glycolic acid, ascorbic acid, cysteine hydrochloride, mercapto acetic acid, thiol acetic acid, glutathione, sodium sulfide, or the like).

[0141] It is also effective to appropriately combine these methods as a method of preparing an aqueous solution for a reaction medium under reducing conditions.

[0142] In the case where it is reacted under reducing conditions, it is preferable that the reaction medium during the reaction is also maintained under reducing conditions. In order to maintain reducing conditions during the reaction, it is ideal to prevent as much as possible the mixing of oxygen from the outside of the reaction system, and as specific examples, there can be mentioned a method in which the reaction system is closed with a non-active gas such as nitrogen gas or carbonic acid gas. As a method for more effectively preventing the mixing of oxygen, in order for the metabolic function within the first conversion body of the first embodiment to function effectively during the reaction, it is sometimes necessary to add a pH adjustment liquid for maintaining the pH of the reaction system or to appropriately add various nutrient solutions, but in this case, it is effective to remove oxygen in advance from the added solution.

[0143] [ (A) 'Removing the first conversion body from the precursor]

[0144] Also, in the production method of the phenol composition of the first embodiment, from the viewpoint of the yield of the phenol composition, (A) the step of generating a precursor by reacting in a reaction medium containing the first conversion body and at least one raw material compound selected from the group consisting of a saccharide, a compound from which the conversion body can generate chorismic acid through metabolism, or chorismic acid and a salt thereof, and (B) the step of generating a phenol composition from the precursor by the second conversion body, thereby obtaining a reaction liquid containing the phenol composition, which will be described later, can include (A) 'the step of removing the first conversion body from the precursor.

[0145] (A) 'In the step of removing the first conversion body from the precursor, the recovery method of the reaction liquid exemplified in the step of removing the conversion body from the reaction liquid described later (C) can be used. By applying the recovery method of the reaction liquid to the precursor, the first conversion body can be removed from the precursor, and thus the precursor can be recovered.

[0146] [ (B) The step of generating a phenol composition from a precursor by a second conversion body, thereby obtaining a reaction liquid containing the phenol composition]

[0147] Next, the following step is performed: (B) generating a phenol composition from a precursor by a second conversion body, thereby obtaining a reaction liquid containing the phenol composition. By culturing by the method described above, the precursor is generated in a reaction medium. By adding the second conversion body to this reaction medium, a phenol composition can be generated from the precursor, and a reaction liquid containing the phenol composition can be obtained.

[0148] Each of the compounds and reaction conditions used in this step will be described in detail below.

[0149] (Second conversion body)

[0150] In the production method of the phenol composition of the first embodiment, as the second transformant, any transformant can be used as long as it is a transformant that can produce a phenol composition from a precursor. Examples of the precursor at this time include 4-hydroxybenzoic acid and the like. As such a transformant, for example, the coryneform bacterial transformant PHE7 (deposition number: NITE BP-976) described in Japanese Patent No. 5932649, the coryneform bacterial transformant PHE18 (deposition number: NITE BP-995) described in Japanese Patent No. 5996434, the coryneform bacterial transformant PHE21 (deposition number: NITE BP-996) described in Japanese Patent No. 5932660, or the coryneform bacterial transformant PHE31 (deposition number: NITE BP-999) described in Japanese Patent No. 5887277, and the like can be given.

[0151] Before the reaction, the second transformant is preferably cultured under aerobic conditions. As the culture temperature and the culture time, as long as the transformant can be cultured and the transformant in an amount of at least the desired amount can be obtained, there are no particular limitations. As the culture temperature, for example, it is 25°C or higher and 38°C or lower. As the culture time, for example, it is 12 hours or longer and 48 hours or shorter.

[0152] (Culture medium for culture)

[0153] As the culture medium for aerobic culture of the second transformant before the reaction, a natural culture medium or a synthetic culture medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients, and the like can be used.

[0154] As the carbon source, a saccharide (such as a monosaccharide such as glucose, fructose, mannose, xylose, arabinose, galactose; a disaccharide such as sucrose, maltose, lactose, cellobiose, xylobiose, trehalose; a polysaccharide such as starch; molasses; and the like), a sugar alcohol such as mannitol, sorbitol, xylitol, glycerol; an organic acid such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, gluconic acid; an alcohol such as ethanol, propanol; a hydrocarbon such as a normal alkane; and the like can also be used.

[0155] The carbon source can be used alone or in combination with two or more. The concentration of the carbon source in the culture medium varies depending on the compound used, but for example, it can be set to 0.1 w / v% or more and 20 w / v% or less.

[0156] As the nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, and the like can be used. Also, nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acids, and the like can be used. The nitrogen source can be used alone or in combination of two or more. The concentration of the nitrogen source in the medium varies depending on the nitrogen compound used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0157] As the inorganic salt, monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like can be mentioned. The inorganic salt can be used alone or in combination of two or more. The concentration of the inorganic salt in the medium varies depending on the inorganic salt used, but can be set to 0.01 w / v% or more and 1 w / v% or less, for example.

[0158] As the nutrient substance, meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloride, extract or decomposition product of animal, plant, or microbial cells, and the like can be mentioned. The concentration of the nutrient substance in the medium varies depending on the nutrient substance used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0159] Also, vitamins can be added as needed. As the vitamins, biotin, thiamine (vitamin Bl), pyridoxine (vitamin B6), pantothenic acid, inositol, nicotinic acid, and the like can be mentioned.

[0160] The pH of the medium is preferably 6 or more and 8 or less.

[0161] As a specific preferred medium, A medium [Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004): Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004)], BT medium [Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004): Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004)], and the like can be cited. In these media, the saccharide concentration can be set within the above range.

[0162] (reaction solution)

[0163] As the reaction solution, in addition to the reaction intermediate solution used in the above procedure (A), a buffer solution, an inorganic salt medium, and the like can be used.

[0164] In the reaction solution, the precursor can be a salt such as a sodium salt, a potassium salt, an ester with an alcohol having a carbon number of 1 to 4, and the like. Among these, a salt is preferred, and a sodium salt is more preferred. The precursor can be used alone or in combination with two or more kinds.

[0165] The concentration of the precursor in the reaction solution is preferably 1 w / v% or more and 20 w / v% or less, more preferably 2 w / v% or more and 10 w / v% or less, and further preferably 2 w / v% or more and 5 w / v% or less. Since the precursor concentration is within the above numerical range, the production efficiency of the phenol composition is further improved.

[0166] As the buffer solution, a phosphoric acid buffer, a tris buffer, a carbonic acid buffer, and the like can be given. The concentration of the buffer solution is preferably 10 mM or more and 150 mM or less from the viewpoint of the production efficiency of the phenol composition.

[0167] As the inorganic salt medium, a medium containing one or two or more kinds of inorganic salts such as monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like can be given. Among them, a medium containing magnesium sulfate is preferred. As the inorganic salt medium, specifically, A medium [Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004): Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004)], a BT medium [Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004): Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004)], and the like can be given. The concentration of the inorganic salt in the medium varies depending on the inorganic salt used, but can be generally set to 0.01 w / v% or more and 1 w / v% or less.

[0168] The pH of the reaction solution is preferably 6 or more and 8 or less. During the reaction, an aqueous ammonia solution, an aqueous sodium hydroxide solution, or the like is preferably used, and the pH of the reaction solution is controlled to be close to the vicinity of neutral by a pH controller (for example, manufactured by ABLE INC., model number: DT-1023) while the reaction is performed, and in particular, controlled to 7.

[0169] (Reaction conditions)

[0170] The reaction temperature, i.e., the survival temperature of the second transformant, is preferably 20°C or higher, more preferably 23°C or higher, and further preferably 25°C or higher, from the viewpoint of the production efficiency of the phenol composition. Also, the above survival temperature is preferably 50°C or lower, more preferably 48°C or lower, and further preferably 47°C or lower, from the same viewpoint.

[0171] The reaction time is preferably 7 days or less, more preferably 5 days or less, and further preferably 3 days or less, from the viewpoint of the production efficiency of the phenol composition. Also, the above reaction time is not particularly limited as long as the reaction proceeds sufficiently, but is, for example, 1 day or more.

[0172] The cultivation can be any of batch, fed-batch, and continuous. Among them, the batch is preferred from the viewpoint of the production efficiency of the phenol composition.

[0173] The reaction can be performed under aerobic conditions, but is preferably performed under reducing conditions. Under the reducing conditions, the second transformant does not proliferate, and thus the production efficiency of the phenol composition is increased. In the present specification, "does not proliferate" includes substantially does not proliferate or almost does not proliferate.

[0174] The reducing conditions are determined by the oxidation-reduction potential of the reaction solution. The oxidation-reduction potential of the reaction solution is preferably -500 mV or higher and -200 mV or higher, and more preferably -500 mV or higher and -150 mV or lower, from the viewpoint of the production efficiency of the phenol composition.

[0175] The reducing state of the reaction solution can be simply estimated using resazurin indicator (which fades from blue to colorless in the reducing state), but can be accurately measured using an oxidation-reduction potential difference meter (for example, ORP Electrodes manufactured by Broadley-James Corporation).

[0176] The method of preparing the reaction solution under reducing conditions can use known methods without limitation. For example, as the liquid medium of the reaction solution, a reaction solution aqueous solution can be used instead of distilled water or the like, and with respect to the method of preparing the reaction solution aqueous solution, for example, reference can be made to the method of preparing a culture solution for absolute anaerobic microorganisms such as sulfur-reducing microorganisms (Pfennig, N. et al., (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, M. P. et al., p 926-940, Berlin, Springer Verlag.: Pfenning, N. et al. (1981): Dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, M. P. et al., p 926-940, Berlin, Springer Verlag.) or "Agricultural Chemistry Experiment Book, Vol. 3, edited by the Department of Agricultural Chemistry, Kyoto University, 26th printing in 1990, published by Sangyo Tosho Publishing Co., Ltd." or the like, and a reaction solution aqueous solution under desired reducing conditions can be obtained.

[0177] Specifically, by removing dissolved gas by heat treatment or reduced pressure treatment of distilled water or the like, a reaction solution aqueous solution under reducing conditions can be prepared. In this case, by treating distilled water or the like under reduced pressure of 10 mmHg or less, more preferably 5 mmHg or less, further preferably 3 mmHg or less, and preferably for 1 minute or more and 60 minutes or less, more preferably for 5 minutes or more and 40 minutes or less, dissolved gas, particularly dissolved oxygen, can be removed, and a reaction solution aqueous solution under reducing conditions can be prepared.

[0178] Also, a reaction solution aqueous solution under reducing conditions can be prepared by adding an appropriate reducing agent (for example, thioglycolic acid, ascorbic acid, cysteine hydrochloride, mercaptoacetic acid, mercaptoethanol, glutathione, sodium sulfide, or the like).

[0179] It is also effective to appropriately combine these methods as a method of preparing a reaction solution aqueous solution under reducing conditions.

[0180] In the case where the reaction is carried out under reducing conditions, it is preferable that the reaction liquid is also maintained under reducing conditions during the reaction. In order to maintain the reducing conditions during the reaction, it is ideal that oxygen is prevented from being mixed into the reaction system as much as possible, and as a specific example, a method in which the reaction system is closed with a non-active gas such as nitrogen gas or carbonic acid gas can be given. As a method for more effectively preventing oxygen from being mixed in, in order for the metabolic function in the second transformant of the first embodiment to effectively function during the reaction, it is sometimes necessary to add a pH adjustment liquid for maintaining the pH of the reaction system or to appropriately add various nutrient solutions, but in this case, it is effective to previously remove oxygen from the added solution.

[0181] [ (C) Step of removing the transformant from the reaction liquid]

[0182] Then, the step of removing the transformant from the reaction liquid is carried out. As described above, phenol is generated in the reaction liquid by the cultivation, but the transformant remains in the reaction liquid. By removing the transformant, the reaction liquid containing the phenol composition can be recovered.

[0183] As a method for recovering the reaction liquid, a method for separating the reaction liquid from the transformant can be given. At this time, the aforementioned (A) 'Step of removing the first transformant from the precursor' can be carried out, and the first transformant and the second transformant can be separated from the reaction liquid, respectively, or the first transformant and the second transformant can be simultaneously separated from the reaction liquid without carrying out (A) 'Step of removing the first transformant from the precursor'.

[0184] As a method for separating the transformant, a publicly known separation method can be used. As a publicly known separation method, for example, a method for collecting the supernatant by standing, membrane filtration, centrifugal separation, or the like can be given. These methods can be used alone or two or more of them can be appropriately combined.

[0185] As a treatment condition for the membrane filtration, a general filtration condition can be used. From the viewpoint of improving the production efficiency of the phenol composition, the membrane pore diameter is preferably 0.01 μm or more, more preferably 0.03 μm or more, further preferably 0.05 μm or more, further preferably 0.07 μm or more, further preferably 0.10 μm or more, further preferably 0.15 μm or more, further preferably 0.20 μm or more. Also from the same viewpoint, it is preferably 3 μm or less, more preferably 2 μm or less, further preferably 1 μm or less. As a method for measuring the membrane pore diameter, a general measuring method using a mercury intrusion method, a bubble point test, a bacterial filtration method, or the like can be given, but it is preferable to use a value obtained by a bubble point test. As a material for the membrane used in the membrane filtration, for example, a high molecular membrane, a ceramic membrane, a stainless steel membrane, or the like can be given.

[0186] As a centrifugal separator for centrifugal separation, a general apparatus such as a separation plate type, a cylindrical type, a decanter type, and the like can be used. The lower limit value of the temperature at the time of centrifugal separation is preferably 0°C or higher, more preferably 1°C or higher, and further preferably 3°C or higher from the viewpoint of improving the production efficiency of the phenol composition. Also, the upper limit value of the temperature at the time of centrifugal separation is preferably 70°C or lower, more preferably 50°C or lower, further preferably 30°C or lower, further preferably 10°C or lower, and further preferably 5°C or lower from the same viewpoint.

[0187] Also, the relative centrifugal force and the time can be appropriately set, but the lower limit value of the relative centrifugal force is preferably 3000 g or higher, more preferably 5000 g or higher, further preferably 7000 g or higher, further preferably 10000 g or higher, and further preferably 15000 g or higher from the viewpoint of improving the polymerizability of the phenol composition. Also, the upper limit value of the relative centrifugal force is preferably 50000 g or lower, more preferably 25000 g or lower, and further preferably 20000 g or lower from the viewpoint of improving the production efficiency of the phenol composition.

[0188] Also, the lower limit value of the time is preferably 0.2 minutes or higher, more preferably 0.5 minutes or higher, further preferably 1 minute or higher, and further preferably 5 minutes or higher from the viewpoint of improving the color tone of the polymer obtained using the phenol composition. Also, the upper limit value of the time is preferably 75 minutes or lower, more preferably 60 minutes or lower, further preferably 30 minutes or lower, further preferably 15 minutes or lower, and further preferably 10 minutes or lower from the viewpoint of improving the production efficiency of the phenol composition.

[0189] [ (D) Step of separating / concentrating the phenol composition in the reaction liquid]

[0190] Finally, the step of separating / concentrating the phenol composition in the reaction liquid is performed. In the first embodiment, the phenol composition in the reaction liquid can be recovered by the above-described method, but in order to improve the phenol concentration in the phenol composition and further improve the color tone of the obtained polymer, the phenol composition is separated / concentrated from the reaction liquid by a publicly known method. As such a publicly known method, a distillation method, a pervaporation method, a permeation membrane method, an organic solvent extraction method, and the like can be given. These methods can be used alone or two or more of them can be appropriately combined.

[0191] As the distillation method, any one of publicly known distillation methods can be used. As the publicly known distillation method, there is no particular limitation, but a normal pressure distillation method using a distillation column, a reduced pressure distillation method using an evaporator, a steam distillation method, a thin film distillation method, and the like can be used.

[0192] The permeation gasification method is a method in which a permeation gasification membrane is used, and a gasified phenol composition is obtained by permeating the phenol composition through the permeation gasification membrane. The permeation gasification membrane has a function of allowing the phenol composition to permeate more preferentially than water. Therefore, the phenol composition in the reaction solution moves to the permeation side space from the supply side space more preferentially than water by permeating the permeation gasification membrane. As a result, the phenol composition obtained in the permeation side space becomes a composition having a higher phenol concentration than the reaction solution. Thus, by using the permeation gasification method, a gasified phenol composition can be obtained from the reaction solution, and the phenol concentration in the obtained phenol composition can be made higher than the reaction solution.

[0193] The shape of the permeation gasification membrane is not particularly limited, and for example, a dense membrane such as a bag type, a flat membrane type, a hollow fiber type, a tubular type, a spiral type, or the like can be used.

[0194] The average thickness of the permeation gasification membrane is not particularly limited, but is preferably about 10 to 500 μm, and more preferably about 20 to 400 μm. By setting the average thickness of the permeation gasification membrane within the above range, the supply side space and the permeation side space can be reliably separated, and a gasified phenol composition can be more reliably obtained from the reaction solution.

[0195] The material of the permeation gasification membrane is not particularly limited, but for example, an inorganic membrane such as a DDR type zeolite membrane, or a high molecular membrane such as a polyimide, a polyamide, a polysulfone, a polyethersulfone, a polyamide-imide, or a composite membrane thereof can be used. Among these, an inorganic membrane is preferred, and a DDR type zeolite membrane is more preferred. Thereby, the separation performance of the phenol can be improved while the mechanical properties of the permeation gasification membrane are improved.

[0196] [Use]

[0197] The phenol composition in the first embodiment can be used for the same use as a phenol composition synthesized by a conventional petrochemical process using fossil resources as a raw material. That is, as the use of the phenol composition in the first embodiment, a precursor of bisphenol A, a raw material of a polymer, an industrial chemical, a fiber, or the like can be given.

[0198] Among these, use for a polymer is preferred. That is, the polymer obtained using the phenol composition in the first embodiment is a polymer containing at least a structural unit derived from the phenol (A) in the phenol composition in the first embodiment.

[0199] As the polymer of the first embodiment, any polymer can be used as long as the polymer requires phenol in the synthesis. The phenol composition of the first embodiment improves the balance between the environmental adaptability and the color tone of the obtained polymer, and therefore the polymer of the first embodiment is preferably a phenol resin.

[0200] <Second Embodiment>

[0201] [4-hydroxybenzoic acid composition]

[0202] The 4-hydroxybenzoic acid composition of the second embodiment contains at least radioactive carbon derived from a biomass resource, which is calculated based on the concentration of radioactive carbon in the carbon circulating in the 1950s, measured according to ASTM D6866-20 14 The 4-hydroxybenzoic acid (A) has a measured biobased content of 80% or more and 100% or less of the proportion of C, and the content of shikimic acid is 0.012% by mass or less, based on the total amount of the above 4-hydroxybenzoic acid composition being 100% by mass.

[0203] In such a 4-hydroxybenzoic acid composition, the measured biobased content represents the amount of plant-derived carbon contained in the 4-hydroxybenzoic acid (A), and the greater this value, the higher the proportion of the 4-hydroxybenzoic acid composition composed of natural raw materials. Therefore, the greater the measured biobased content, the better the environmental adaptability from the viewpoint of carbon neutrality. Also, when the content of shikimic acid is 0.012% by mass or less, a 4-hydroxybenzoic acid composition having more suitable polymerizability can be obtained.

[0204] Such a 4-hydroxybenzoic acid composition can be produced by the production method described below, particularly by steps (i) using a raw material derived from a specific plant as a raw compound, (ii) removing impurities by adding an adsorbent material to the reaction solution, and (iii) washing with pure water at the time of recovery.

[0205] In the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition of the second embodiment, radioactive carbon derived from a biomass resource, which is calculated based on the concentration of radioactive carbon in the carbon circulating in the 1950s, measured according to ASTM D6866-20 14 The above measured biobased content of the proportion of C is 80% or more and 100% or less, preferably 85% or more and 100% or less, more preferably 90% or more and 100% or less, and further preferably 95% or more and 100% or less. Since the above measured biobased content is within the above numerical range, the environmental adaptability becomes better from the viewpoint of carbon neutrality.

[0206] At this time, radioactive carbon in the total carbon atoms of the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition 14 The measured biobased content of the proportion of C is measured according to the biobased content test standard ASTM D6866-20 established by the American Society for Testing Materials (ASTM) for radioactive carbon in the sample 14 The content of C, and based on the measurement result thereof and the radioactive carbon in the carbon circulating in the year 1950 14The concentration of C is calculated from the concentration of B. In addition, in this test standard, a plurality of analysis methods are shown, and among them, analysis method B (AMS method) is preferably used. In analysis method B, for example, an analysis device such as Pelletron AMS manufactured by National Electrostatics Corp. is used.

[0207] In the 4-hydroxybenzoic acid composition of the second embodiment, the upper limit value of the content of shikimic acid is 0.012 mass% or less, preferably 0.008 mass% or less, more preferably 0.006 mass% or less, further preferably 0.003 mass% or less, further preferably 0.001 mass% or less, when the total amount of the 4-hydroxybenzoic acid composition is 100 mass%. Since the content of shikimic acid is the above upper limit value or less, the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment is more suitable.

[0208] Also, the lower limit value of the content of shikimic acid is not particularly limited, but is, for example, 0.000 mass% or more. At this time, 0.000 mass% means that the content of shikimic acid is below the detection lower limit, and also includes a case where it cannot be detected quantitatively.

[0209] In the 4-hydroxybenzoic acid composition of the second embodiment, the content of the above 4-hydroxybenzoic acid (A) is preferably 95 mass% or more and 100 mass% or less, more preferably 96 mass% or more and 100 mass% or less, further preferably 97 mass% or more and 100 mass% or less, further preferably 98 mass% or more and 100 mass% or less, further preferably 99 mass% or more and 100 mass% or less, when the total amount of the 4-hydroxybenzoic acid composition is 100 mass%. Since the content of the above 4-hydroxybenzoic acid (A) is in the above numerical range, from the viewpoint of carbon neutralization, the environmental adaptability becomes better, and in addition, the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment is more suitable.

[0210] In addition, when the content of the above 4-hydroxybenzoic acid (A) is 100 mass%, the content of the above shikimic acid and the content of other components described later are 0.000 mass%. At this time, the content of shikimic acid and other components is below the detection lower limit, and also includes a case where it cannot be detected quantitatively.

[0211] In the 4-hydroxybenzoic acid composition of the second embodiment, the above 4-hydroxybenzoic acid (A) preferably contains at least a product of one or two of the transformants selected from the group consisting of transformant HBA-2 (deposition number: NITE BP-01838) and transformant HBA-47 (deposition number: NITE BP-01849). Since the above 4-hydroxybenzoic acid (A) contains at least the above product, the environmental adaptability becomes better from the viewpoint of carbon neutralization, and furthermore, the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment is more suitable.

[0212] In the 4-hydroxybenzoic acid composition of the second embodiment, since the 4-hydroxybenzoic acid (A) contains at least a product of one or more of the transformants selected from the group consisting of transformant HBA-2 and transformant HBA-47, it is presumed that the reason for the more suitable polymerizability is that the presence of a trace amount of components that can adversely affect the polymerizability is relatively low.

[0213] Among them, the number of trace components derived from the transformants is extremely large, and the content of the above trace components is less than the detection limit, and analysis cannot be performed. Therefore, in the 4-hydroxybenzoic acid composition of the second embodiment, the manner in which the 4-hydroxybenzoic acid (A) contains at least a product of one or more of the transformants selected from the group consisting of transformant HBA-2 and transformant HBA-47 is directly determined by the structure or characteristics of the object, and it can be said that it is almost unrealistic, and therefore it can be considered that there is a so-called "impossible, unrealistic situation".

[0214] (Other components)

[0215] In the 4-hydroxybenzoic acid composition of the second embodiment, other components other than the above components can be contained as long as the balance between the environmental adaptability and the polymerizability is not lowered.

[0216] As the other components, one or more selected from the group consisting of the following compounds can be mentioned.

[0217] Monosaccharides such as glucose, fructose, mannose, arabinose, xylose, galactose, disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, xylobiose, polysaccharides such as dextrin or soluble starch, and the like.

[0218] Sugar alcohols such as mannitol, sorbitol, xylitol, glycerol, organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, gluconic acid, alcohols such as ethanol, propanol, and the like, and hydrocarbons such as n-alkanes.

[0219] Inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, nitrogen-containing organic compounds such as urea, aqueous ammonia, sodium nitrate, potassium nitrate, corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acids, and the like.

[0220] Monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like.

[0221] In the 4-hydroxybenzoic acid composition of the second embodiment, the content of the above-described other component is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less, and further preferably 1% by mass or less. Since the content of the above-described other component is the above-described upper limit value or less, the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment is more suitable.

[0222] Also, the lower limit value of the content of the above-described other component is not particularly limited, but is, for example, 0.000% by mass or more. At this time, 0.000% by mass means that the content of the above-described other component is below the lower limit of detection, and also includes cases where quantitative detection is not possible.

[0223] In addition, in the 4-hydroxybenzoic acid composition of the second embodiment, in the case where a plurality of the above-described other components are contained, the total content of the above-described other components may be the above-described upper limit value or less and the above-described lower limit value or more.

[0224] As a method for quantifying the content of such shikimic acid, 4-hydroxybenzoic acid (A), and other components, for example, high-performance liquid chromatography using a high-performance liquid chromatograph (manufactured by Hitachi High-Tech Science Corporation, Chromaster (registered trademark)) equipped with a UV detector, ion chromatography, gas chromatography mass spectrometry (GC / MS), inductively coupled plasma mass spectrometry (ICP-MS), and the like can be given.

[0225] The method for producing the 4-hydroxybenzoic acid composition of the second embodiment will be described later.

[0226] <Third Embodiment>

[0227] [4-Hydroxybenzoic Acid Composition]

[0228] The 4-hydroxybenzoic acid composition of the third embodiment contains at least radiocarbon derived from a biomass resource, which is represented by the concentration of radiocarbon in recycled carbon in the 1950s, as measured according to ASTM D6866-20 144-hydroxybenzoic acid (A) having a measured biobased content of C in a proportion of 80% or more and 100% or less, and having an absorbance of 0.015 or less at a wavelength of 425 nm when dissolved in ethanol at a concentration of 20 g / L.

[0229] In such a 4-hydroxybenzoic acid composition, the measured biobased content indicates the amount of plant-derived carbon contained in the 4-hydroxybenzoic acid (A), and the greater this value, the higher the proportion of the 4-hydroxybenzoic acid composition composed of natural raw materials. Therefore, the greater the measured biobased content, the better the environmental suitability from the viewpoint of carbon neutrality. Also, when the above absorbance is 0.015 or less, a 4-hydroxybenzoic acid composition having a more suitable color tone can be obtained even in the case of using a plant-derived raw material.

[0230] Such a 4-hydroxybenzoic acid composition can be produced by the production method described below, particularly by steps of (i) using a plant-derived raw material as a raw compound, (ii) removing impurities by adding an adsorbent material to the reaction solution, and (iii) washing with pure water at the time of recovery.

[0231] In the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition of the third embodiment, the radiocarbon derived from biomass resources 14 The above measured biobased content of C in a proportion of 80% or more and 100% or less, preferably 85% or more and 100% or less, more preferably 90% or more and 100% or less, and further preferably 95% or more and 100% or less. Since the above measured biobased content is within the above numerical range, the environmental suitability becomes better from the viewpoint of carbon neutrality.

[0232] At this time, the radiocarbon in the total carbon atoms of the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition is 14 The measured biobased content of C in a proportion is measured for radiocarbon in a sample according to the biobased concentration test standard ASTM D6866-20 established by the American Society for Testing Materials (ASTM). 14 The content of C, and the radiocarbon in the 1950s circulating carbon is calculated from the measurement result thereof and the radiocarbon 14 The concentration of C. In this test standard, a plurality of analysis methods are shown, and the analysis method B (AMS method) is preferably used. In the analysis method B, for example, an analysis device such as an accelerator mass spectrometry device Pelletron AMS manufactured by National Electrostatics Corp. is used.

[0233] In the 4-hydroxybenzoic acid composition of the third embodiment, the upper limit value of the absorbance at a wavelength of 425 nm when dissolved in ethanol at a concentration of 20 g / L is 0.015 or less, preferably 0.013 or less, more preferably 0.010 or less, and further preferably 0.006 or less. Since the absorbance at a wavelength of 425 nm is the above upper limit value or less, the color tone of the 4-hydroxybenzoic acid composition of the third embodiment is more suitable.

[0234] Also, the lower limit value of the absorbance at a wavelength of 425 nm when dissolved in ethanol at a concentration of 20 g / L is not particularly limited, but is, for example, 0.000 or more, and from the viewpoints of environmental suitability and production efficiency, is preferably 0.001 or more, and can be 0.003 or more. At this time, the absorbance of 0.000 means that the absorbance at a wavelength of 425 nm is below the detection lower limit, and also includes cases where quantitative detection is not possible.

[0235] In the 4-hydroxybenzoic acid composition of the third embodiment, the content of the above 4-hydroxybenzoic acid (A) is preferably 95 mass% or more and 100 mass% or less, more preferably 96 mass% or more and 100 mass% or less, further preferably 97 mass% or more and 100 mass% or less, further preferably 98 mass% or more and 100 mass% or less, and further preferably 99 mass% or more and 100 mass% or less, based on the total amount of the 4-hydroxybenzoic acid composition as 100 mass%. Since the content of the above 4-hydroxybenzoic acid (A) is within the above numerical range, from the viewpoint of carbon neutrality, environmental suitability becomes even better, and in addition, the color tone of the 4-hydroxybenzoic acid composition of the third embodiment is more suitable.

[0236] In addition, when the content of the above 4-hydroxybenzoic acid (A) is 100 mass%, the content of the other components described later is 0.000 mass%. At this time, the content of the other components is below the detection lower limit, and also includes cases where quantitative detection is not possible.

[0237] In the 4-hydroxybenzoic acid composition of the third embodiment, the above 4-hydroxybenzoic acid (A) preferably contains at least a product selected from one or two of transformant HBA-2 (deposition number: NITE BP-01838) and transformant HBA-47 (deposition number: NITE BP-01849). Since the above 4-hydroxybenzoic acid (A) contains at least the above product, from the viewpoint of carbon neutrality, environmental suitability becomes even better, and in addition, the color tone of the 4-hydroxybenzoic acid composition of the third embodiment is more suitable.

[0238] In the 4-hydroxybenzoic acid composition of the third embodiment, since the 4-hydroxybenzoic acid (A) contains at least a product of one or two or more selected from among the transformant HBA-2 and the transformant HBA-47, it is presumed that the reason why the color tone is more suitable is that the presence of a trace amount of components that can adversely affect the color tone is relatively suppressed.

[0239] Among them, the trace amount of components derived from the transformants are numerous, and the content of the above-mentioned trace amount of components is less than the detection limit, and analysis cannot be performed. Therefore, in the 4-hydroxybenzoic acid composition of the third embodiment, the way in which the 4-hydroxybenzoic acid (A) contains at least a product of one or two or more selected from among the transformant HBA-2 and the transformant HBA-47 is directly determined by the structure or characteristics of the object, and it is almost impossible to say that it is practical, and it can be said that there is a so-called "impossible, impractical situation".

[0240] (Other components)

[0241] In the 4-hydroxybenzoic acid composition of the third embodiment, other components other than the above-mentioned components can be contained as long as the balance between environmental adaptability and color tone is not lowered.

[0242] As the other components, one or two or more selected from the group consisting of the following compounds can be mentioned.

[0243] Monosaccharides such as glucose, fructose, mannose, arabinose, xylose, galactose, disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, xylobiose, polysaccharides such as dextrin or soluble starch, and the like.

[0244] Sugar alcohols such as mannitol, sorbitol, xylitol, glycerol, organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, gluconic acid, alcohols such as ethanol, propanol, carbon hydrides such as n-alkanes, and the like.

[0245] Inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, nitrogen-containing organic compounds such as urea, aqueous ammonia, sodium nitrate, potassium nitrate, corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acids, and the like.

[0246] Monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like.

[0247] In the 4-hydroxybenzoic acid composition of the third embodiment, the content of the other aforementioned component is preferably 5% by mass or less, more preferably 4% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less, further preferably 1% by mass or less. Since the content of the other aforementioned component is the above upper limit value or less, the hue of the 4-hydroxybenzoic acid composition of the third embodiment is more suitable.

[0248] Also, the lower limit value of the content of the other aforementioned component is not particularly limited, but is, for example, 0.000% by mass or more. At this time, 0.000% by mass means that the content of the other aforementioned component is below the lower limit of detection, and also includes cases where quantitative detection is not possible.

[0249] In addition, in the 4-hydroxybenzoic acid composition of the third embodiment, in the case where a plurality of the other aforementioned components are contained, the total content of the other aforementioned components is the above upper limit value or less and the above lower limit value or more.

[0250] As a method for quantifying the content of such 4-hydroxybenzoic acid (A) and the other components, for example, high-performance liquid chromatography using a high-performance liquid chromatograph (manufactured by Hitachi High-Tech Science Corporation, Chromaster (registered trademark)) equipped with a UV detector, ion chromatography, gas chromatography mass spectrometry (GC / MS), inductively coupled plasma mass spectrometry (ICP-MS), or the like can be given.

[0251] [Method for producing 4-hydroxybenzoic acid composition]

[0252] Next, the method for producing the 4-hydroxybenzoic acid composition of the second embodiment and the third embodiment will be described.

[0253] As the method for producing the 4-hydroxybenzoic acid composition of the second embodiment and the third embodiment, a process (A) to (C) including the following is preferable.

[0254] (A) A process of allowing a reaction solution containing a transformant and at least one raw material compound selected from the group consisting of a saccharide, a compound that can be metabolized by the transformant to produce chorismic acid, or chorismic acid and a salt thereof to react.

[0255] (B) A process of removing impurities from the reaction solution.

[0256] (C) A process of recovering the 4-hydroxybenzoic acid composition from the reaction solution.

[0257] [(A) a step of allowing the transformant to react in a reaction solution containing the transformant and at least one raw material compound selected from the group consisting of a saccharide, a compound from which the transformant can produce chorismic acid through metabolism, or chorismic acid and a salt thereof]

[0258] As the production method of the 4-hydroxybenzoic acid composition of the second and third embodiments, first, the following step (A) is performed: (A) a step of allowing the transformant to react in a reaction solution containing the transformant and at least one raw material compound selected from the group consisting of a saccharide, a compound from which the transformant can produce chorismic acid through metabolism, or chorismic acid and a salt thereof.

[0259] Each compound and reaction condition used in the present step will be described in detail below.

[0260] (Transformant)

[0261] In the production method of the 4-hydroxybenzoic acid composition of the second and third embodiments, as the transformant, any transformant can be used as long as it is a transformant that can produce 4-hydroxybenzoic acid from a saccharide through metabolism. As such a transformant, for example, the coryneform bacterial transformant HBA-2 (deposition number: NITE BP-01838) described in Japanese Patent No. 6327653 or the coryneform bacterial transformant HBA-47 (deposition number: NITE BP-01849) described in Japanese Patent No. 6327654, or the like can be given.

[0262] Before the reaction, the transformant is preferably cultured under aerobic conditions. As the culture temperature and the culture time, there is no particular limitation as long as the transformant can be cultured and the transformant in an amount of at least the desired amount can be obtained. As the culture temperature, for example, it is 25°C or higher and 38°C or lower. As the culture time, for example, it is 12 hours or longer and 48 hours or shorter.

[0263] (Culture medium for culture)

[0264] The culture medium used for aerobic culture of the transformant before the reaction can use a natural culture medium or a synthetic culture medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients, and the like.

[0265] As the carbon source, a saccharide (such as a monosaccharide such as glucose, fructose, mannose, xylose, arabinose, galactose; a disaccharide such as sucrose, maltose, lactose, cellobiose, xylobiose, trehalose; a polysaccharide such as starch; molasses; and the like), a sugar alcohol such as mannitol, sorbitol, xylitol, glycerol; an organic acid such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, gluconic acid; an alcohol such as ethanol, propanol; a hydrocarbon such as a normal alkane; and the like can also be used.

[0266] The carbon source can be used singly or in combination of two or more. The concentration of the carbon source in the medium varies depending on the compound used, but can be set to 0.1 w / v% or more and 20 w / v% or less, for example.

[0267] As the nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, and the like can be used. Also, nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acid, and the like can be used. The nitrogen source can be used singly or in combination of two or more. The concentration of the nitrogen source in the medium varies depending on the nitrogen compound used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0268] As the inorganic salt, monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like can be mentioned. The inorganic salt can be used singly or in combination of two or more. The concentration of the inorganic salt in the medium varies depending on the inorganic salt used, but can be set to 0.01 w / v% or more and 1 w / v% or less, for example.

[0269] As the nutrient substance, meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloride, extract or decomposition product of animal, plant, or microbial cells, and the like can be mentioned. The concentration of the nutrient substance in the medium varies depending on the nutrient substance used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0270] Also, vitamins can be added as needed. As the vitamins, biotin, thiamine (vitamin Bl), pyridoxine (vitamin B6), pantothenic acid, inositol, nicotinic acid, and the like can be mentioned.

[0271] The pH of the medium is preferably 6 or more and 8 or less.

[0272] As a specific preferred medium, A medium [Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004): Inui, M. et al., Metabolic analysis of Corynebacterium glutamicum during lactate and succinate productions under oxygen deprivation conditions. J. Mol. Microbiol. Biotechnol. 7: 182-196 (2004)], BT medium [Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004): Omumasaba, C. A. et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8: 91-103 (2004)], and the like can be given. In these media, the concentration of a saccharide can be set within the above range.

[0273] (Starting compound)

[0274] The starting compound is preferably a compound that is taken into a cell by a transformant, and more preferably a compound that is abundant in plants and the like, and is industrially easily available.

[0275] Among the above starting compounds, as a saccharide, a saccharide that is capable of being metabolized by a transformant to produce glucose is preferable, and glucose is more preferable. Such a saccharide includes an oligosaccharide having a glucose unit and a polysaccharide. As the above oligosaccharide and the above polysaccharide, monosaccharides such as fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, and xylobiose; polysaccharides such as dextrin or soluble starch; and the like can be given. Furthermore, it is preferable from the viewpoint that the production efficiency of the 4-hydroxybenzoic acid composition of the second embodiment and the third embodiment can be improved by using glucose.

[0276] Furthermore, among the above starting compounds, as a compound that is capable of being metabolized by a transformant to produce shikimic acid, quinic acid, shikimic acid, and the like can be given.

[0277] Also, for example, as a raw material containing these raw material compounds, a plant-derived raw material can be used. As the plant-derived raw material, for example, molasses, or straw (rice straw, barley straw, wheat straw, rye straw, oat straw, and the like), sugar cane residue, corn stover, and the like, non-edible crop waste, or energy crops such as switchgrass, napiergrass, and miscanthus, or sawdust, waste paper, and the like, which are saccharified with saccharifying enzymes and the like to obtain a saccharified liquid containing a plurality of sugars such as glucose can be used.

[0278] Among these, as the raw material compound, glucose, shikimic acid, quinic acid, and oroboric acid are preferable, and as a raw material containing these, a plant-derived raw material is preferably used.

[0279] (Reduction solution)

[0280] As the reduction solution, a natural reduction solution or a synthetic reduction solution containing a carbon source, a nitrogen source, and inorganic salts, and the like can be used.

[0281] As the carbon source, the raw material compound described above or molasses or a saccharified liquid containing the raw material compound, and the like can be used. Also, as the carbon source, in addition to sugars, sugar alcohols such as mannitol, sorbitol, xylitol, and glycerol; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and carbon hydrides such as n-alkanes can be used.

[0282] The carbon source can be used alone or in combination with two or more.

[0283] The concentration of the raw material compound in the reduction solution is preferably 1 w / v% or more and 20 w / v% or less, more preferably 2 w / v% or more and 10 w / v% or less, and further preferably 2 w / v% or more and 5 w / v% or less.

[0284] Also, the concentration of the total carbon source containing the raw material compound can be set to 2 w / v% or more and 5 w / v% or less.

[0285] As the nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, and the like can be used. Also, nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, amino acids, and the like can be used. The nitrogen source can be used alone or in combination with two or more. The concentration of the nitrogen source in the reduction solution varies depending on the nitrogen compound used, but for example, it can be set to 0.1 w / v% or more and 10 w / v% or less.

[0286] As the inorganic salts, monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, and the like can be given. The inorganic salts can be used singly or in combination of two or more. The concentration of the inorganic salts in the reaction solution varies depending on the inorganic salts used, but can be set to 0.01 w / v% or more and 1 w / v% or less, for example.

[0287] As the nutrients, meat extract, peptone, polypeptone, yeast extract, dried yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloric acid hydrolysate, extract or decomposition product of a microorganism, and the like can be given. The concentration of the nutrients in the culture medium varies depending on the nutrients used, but can be set to 0.1 w / v% or more and 10 w / v% or less, for example.

[0288] Further, vitamins can be added as needed. As the vitamins, biotin, thiamine (vitamin Bl), pyridoxine (vitamin B6), pantothenic acid, inositol, nicotinic acid, and the like can be given.

[0289] The pH of the reaction solution is preferably 6 or more and 8 or less.

[0290] As the specific preferred reaction solution, the aforementioned A medium and BT medium, and the like can be given. In these reaction solutions, the sugar concentration can be set to be used within the above range.

[0291] (Reaction conditions)

[0292] The reaction temperature, i.e., the survival temperature of the transformant, is preferably 20°C or more, more preferably 23°C or more, and further preferably 25°C or more, from the viewpoint of the production efficiency of the 4-hydroxybenzoic acid composition. Also, the above survival temperature is preferably 50°C or less, more preferably 48°C or less, and further preferably 47°C or less, from the same viewpoint.

[0293] The reaction time is preferably 7 days or less, more preferably 5 days or less, and further preferably 3 days or less, from the viewpoint of the production efficiency of the 4-hydroxybenzoic acid composition. Also, the above reaction time is not particularly limited as long as the reaction proceeds sufficiently, but is, for example, 1 day or more.

[0294] The culture can be any one of batch, fed-batch, and continuous. Among them, the batch is preferred from the viewpoint of the production efficiency of the 4-hydroxybenzoic acid composition.

[0295] The reaction can be carried out under aerobic conditions or under reducing conditions. The production ability of the 4-hydroxybenzoic acid composition from the transformant is higher under aerobic conditions. However, under aerobic conditions, since the transformant proliferates, the raw material compound is consumed for proliferation, and accordingly the production efficiency of the 4-hydroxybenzoic acid composition decreases.

[0296] Therefore, it is preferable to carry out the reaction under conditions under which the transformant does not proliferate and the oxygen is supplied. In the present specification, "does not proliferate" includes does not substantially proliferate or hardly proliferate. For example, by using a reaction solution which lacks or limits one or more compounds necessary for the proliferation of the microorganism, i.e., vitamins such as biotin, thiamine, nitrogen sources, etc., the proliferation of the transformant can be avoided or inhibited.

[0297] Also, under reducing conditions, since the transformant does not substantially proliferate, the raw material compound is not consumed for proliferation, and accordingly the production efficiency of the 4-hydroxybenzoic acid composition becomes high.

[0298] The reducing conditions are determined by the oxidation-reduction potential of the reaction solution. The oxidation-reduction potential of the reaction solution is preferably -500 mV or more and -200 mV or less, and more preferably -500 mV or more and -150 mV or less.

[0299] The reducing state of the reaction solution can be simply estimated using resazurin indicator (if in the reducing state, the blue color fades to colorless), but can be accurately measured using an oxidation-reduction potential difference meter (for example, ORP Electrodes manufactured by Broadley-James Corporation).

[0300] The method of preparing the reaction solution under reducing conditions can use known methods without limitation. For example, as the liquid medium of the reaction solution, a reaction solution aqueous solution can be used instead of distilled water or the like, and with respect to the method of preparing the reaction solution aqueous solution, for example, reference can be made to the method of preparing a culture solution for absolute anaerobic microorganisms such as sulfur-reducing microorganisms (Pfennig, N. et al., (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, M. P. et al., p 926-940, Berlin, Springer Verlag.: Pfenning, N. et al. (1981): Dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, M. P. et al., p 926-940, Berlin, Springer Verlag.) or "Agricultural Chemistry Experiment Book, Vol. 3, edited by the Department of Agricultural Chemistry, Kyoto University, 26th printing in 1990, published by Sangyo Tosho Publishing Co., Ltd." or the like, and a reaction solution aqueous solution under desired reducing conditions can be obtained.

[0301] Specifically, by removing dissolved gas by heat treatment or reduced pressure treatment of distilled water or the like, a reaction solution aqueous solution under reducing conditions can be prepared. In this case, by treating distilled water or the like under reduced pressure of 10 mmHg or less, more preferably 5 mmHg or less, further preferably 3 mmHg or less, and preferably for 1 minute or more and 60 minutes or less, more preferably for 5 minutes or more and 40 minutes or less, dissolved gas, particularly dissolved oxygen, can be removed, and a reaction solution aqueous solution under reducing conditions can be prepared.

[0302] Also, a reaction solution aqueous solution under reducing conditions can be prepared by adding an appropriate reducing agent (e.g., thio glycolic acid, ascorbic acid, cysteine hydrochloride, mercapto acetic acid, thiol acetic acid, glutathione, sodium sulfide, or the like).

[0303] It is also effective to appropriately combine these methods as a method of preparing a reaction solution aqueous solution under reducing conditions.

[0304] In the case where the reaction is carried out under reducing conditions, it is preferable that the reaction liquid is also maintained under reducing conditions during the reaction. In order to maintain the reducing conditions during the reaction, it is ideal that oxygen is prevented from being mixed into the reaction system as much as possible, and as a specific example, a method in which the reaction system is closed with a non-active gas such as nitrogen or carbonic acid gas can be given. As a method for more effectively preventing oxygen from being mixed in, in order for the metabolic function within the transformant of the second embodiment and the third embodiment to function effectively during the reaction, it is sometimes necessary to add a solution for adjusting the pH of the reaction system or to appropriately add various nutrient solutions, but in such a case, it is effective to remove oxygen from the added solution in advance.

[0305] [Process for removing impurities from the reaction liquid]

[0306] Next, the process for removing impurities from the reaction liquid (B) is carried out. By the cultivation by the above-described method, a 4-hydroxybenzoic acid composition is produced in the reaction liquid. By recovering the reaction liquid, the 4-hydroxybenzoic acid composition can be recovered, but the reaction liquid contains components such as the transformant, unreacted raw material compounds, by-products of the transformant, and components contained in the reaction liquid itself, which affect the polymerizability and color tone of the 4-hydroxybenzoic acid composition. Therefore, by removing these components from the reaction liquid, the polymerizability and color tone of the 4-hydroxybenzoic acid composition can be further improved.

[0307] As the components that affect the polymerizability and color tone of such a 4-hydroxybenzoic acid composition, various intermediate metabolites produced by the transformant, or substances contained in the aforementioned "other components", "culture medium", and the like, or specific elements, and the like can be given.

[0308] As the aforementioned intermediate metabolites, for example, shikimic acid, dehydroshikimic acid, quinic acid, protocatechuic acid, amino acids, and the like can be given, but are not limited to these. Also, as the aforementioned specific elements, for example, nitrogen, phosphorus, potassium, magnesium, sodium, iron, manganese, zinc, cobalt, and the like can be given, but are not limited to these.

[0309] As the method for removing the impurities of the reaction liquid at the time of preparing the 4-hydroxybenzoic acid composition of the second embodiment and the third embodiment, both separation of the transformant and adsorption of chemical components are carried out. By carrying out both, the impurities can be further removed from the 4-hydroxybenzoic acid composition, and as a result, the polymerizability and color tone of the 4-hydroxybenzoic acid composition can be further improved.

[0310] First, the separation method of the transformant will be described.

[0311] As the separation method of the transformant, a publicly known separation method can be used, but for example, methods such as recovery of the supernatant by standing, membrane filtration, centrifugal separation, and the like can be given. One of these methods or two or more of these methods can be used in combination as appropriate.

[0312] As the treatment conditions for membrane filtration, treatment can be performed using usual filtration conditions. From the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition, the membrane pore diameter is preferably 0.01 μm or more, more preferably 0.03 μm or more, further preferably 0.05 μm or more, further preferably 0.07 μm or more, further preferably 0.10 μm or more, further preferably 0.15 μm or more, further preferably 0.20 μm or more. Also, from the same viewpoint, it is preferably 3 μm or less, more preferably 2 μm or less, further preferably 1 μm or less. As the measurement method of the membrane pore diameter, usual measurement methods such as the mercury intrusion method, the bubble point test, and the bacterial filtration method can be given, but it is preferable to use the value obtained by the bubble point test. As the material of the membrane used in the membrane filtration, for example, a high molecular membrane, a ceramic membrane, a stainless steel membrane, and the like can be given.

[0313] As the centrifugal separator used for centrifugal separation, usual devices such as a separation plate type, a cylindrical type, a decanter type, and the like can be used. The lower limit value of the temperature at the time of centrifugal separation is preferably 5°C or more, more preferably 10°C or more, further preferably 20°C or more, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition. Also, the upper limit value of the temperature at the time of centrifugal separation is preferably 70°C or less, more preferably 60°C or less, further preferably 40°C or less, from the same viewpoint.

[0314] Also, the relative centrifugal force and the time at the time of centrifugal separation can be appropriately set, but the lower limit value of the relative centrifugal force is preferably 3000 g or more, more preferably 5000 g or more, further preferably 7000 g or more, further preferably 10000 g or more, further preferably 15000 g or more, from the viewpoint of improving the polymerizability and the color tone of the 4-hydroxybenzoic acid composition. Also, the upper limit value of the relative centrifugal force is preferably 50000 g or less, more preferably 25000 g or less, further preferably 20000 g or less, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition.

[0315] Similarly, the lower limit value of the time is preferably 0.2 minutes or more, more preferably 0.5 minutes or more, further preferably 1 minute or more, from the viewpoint of improving the polymerizability and the color tone of the 4-hydroxybenzoic acid composition. Also, the upper limit value of the time is preferably 75 minutes or less, more preferably 60 minutes or less, further preferably 30 minutes or less, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition.

[0316] Next, the adsorption method of the chemical component will be described.

[0317] As the adsorption method of the chemical component, for example, an adsorbent material which does not have activity to 4-hydroxybenzoic acid can be added to the reaction solution after the conversion body is removed by the above method.

[0318] As the adsorbent material, there is no particular limitation as long as it does not have activity to 4-hydroxybenzoic acid and can adsorb the unreacted raw material compound and the components contained in the reaction solution itself. As such an adsorbent material, for example, inorganic adsorbent materials such as natural adsorbent materials (natural zeolite, agilite, acid clay, etc.) or synthetic adsorbent materials (synthetic zeolite, molecular sieve, bacterial adsorption polymer, hydroxyapatite, phosphorite, titanium silicate, silica gel, silica alumina gel, porous glass, etc.); activated carbon such as powdered activated carbon, granular activated carbon, fibrous activated carbon, blocky activated carbon, extrusion-molded activated carbon, molded activated carbon, synthetic granular activated carbon, synthetic fibrous activated carbon; and organic adsorbent materials such as molecular adsorption resin, ion exchange resin, ion exchange fiber, chelate resin, chelate fiber, etc. can be mentioned.

[0319] Among these, from the viewpoint of environmental adaptability, it is preferable to use activated carbon.

[0320] In the second embodiment, as the amount of the added adsorbent material, from the viewpoint of further improving the color tone of the 4-hydroxybenzoic acid composition, it is preferable to be 0.1 g or more, more preferably 0.2 g or more, further preferably 0.3 g or more, further preferably 0.4 g or more, with respect to 100 g of the reaction solution.

[0321] Also, in the second embodiment, the upper limit value of the amount of the added adsorbent material is not particularly limited, but from the viewpoint of the work efficiency of the process of recovering the 4-hydroxybenzoic acid composition from the reaction solution described later (C), it is preferable to be 5.0 g or less, more preferably 4.0 g or less, further preferably 3.0 g or less, further preferably 2.0 g or less, further preferably 1.0 g or less, further preferably 0.5 g or less, with respect to 100 g of the reaction solution.

[0322] In the third embodiment, as the amount of the added adsorbent material, from the viewpoint of further improving the color tone of the 4-hydroxybenzoic acid composition, it is preferable to be 0.3 g or more, more preferably 0.5 g or more, further preferably 0.8 g or more, further preferably 1.0 g or more, further preferably 1.5 g or more, further preferably 1.8 g or more, further preferably 2.0 g or more, with respect to 100 g of the reaction solution.

[0323] Further, in the third embodiment, the upper limit of the amount of the added adsorbing material is not particularly limited, but from the viewpoint of the work efficiency of the process (C) to be described later for recovering the 4-hydroxybenzoic acid composition from the reaction liquid, it is preferably 5.0 g or less, more preferably 4.0 g or less, further preferably 3.0 g or less, further preferably 2.5 g or less, further preferably 2.1 g or less, relative to 100 g of the reaction liquid.

[0324] [Process (C) to recover the 4-hydroxybenzoic acid composition from the reaction liquid]

[0325] Then, the process (C) to recover the 4-hydroxybenzoic acid composition from the reaction liquid is performed. As described above, by removing the impurities, the reaction liquid containing the 4-hydroxybenzoic acid composition with relatively high purity can be prepared, and further the 4-hydroxybenzoic acid composition can be separated from the reaction liquid by a publicly known method. As such a publicly known method, there can be mentioned a crystallization method, a membrane separation method, an organic solvent extraction method, various adsorption methods (use of ion exchange resin, synthetic adsorbing material, etc.), and the like.

[0326] Further, after recovering the 4-hydroxybenzoic acid composition, a process for washing the 4-hydroxybenzoic acid composition or a process for purifying the 4-hydroxybenzoic acid composition can be provided as necessary.

[0327] As the process for washing the 4-hydroxybenzoic acid composition, a publicly known washing method can be used. As the publicly known washing method, there can be mentioned, for example, an ultrasonic washing, an agitation washing, a flow washing, an immersion washing, and the like. Among these, the agitation washing is preferred.

[0328] As the washing solvent, a washing solvent which does not dissolve the 4-hydroxybenzoic acid composition but dissolves only the impurities is preferred. As such a washing solvent, for example, pure water is preferred. Among these, the pure water refers to water having a conductivity of 1 MΩ-cm or more. The water satisfying the above conductivity is of high purity, and contains very little impurities such as chlorine or salts.

[0329] The amount of the washing solvent in the process for washing the 4-hydroxybenzoic acid composition is preferably 7 times or more, more preferably 8 times or more, further preferably 9 times or more, further preferably 10 times or more, relative to the mass of the obtained 4-hydroxybenzoic acid composition, from the viewpoint of further improving the polymerizability and the color tone of the 4-hydroxybenzoic acid composition.

[0330] Further, the amount of the washing solvent is preferably 50 times or less, more preferably 25 times or less, further preferably 15 times or less, further preferably 12 times or less, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition.

[0331] The number of times of washing in the process of washing the 4-hydroxybenzoic acid composition is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more from the viewpoint of further improving the polymerizability and the color tone of the 4-hydroxybenzoic acid composition.

[0332] Further, the number of times of washing is preferably 10 or less, more preferably 7 or less, further preferably 5 or less, and further preferably 4 or less from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition.

[0333] [USES]

[0334] The 4-hydroxybenzoic acid composition in the second embodiment and the third embodiment can be used for the same use as the 4-hydroxybenzoic acid composition synthesized by the conventional petrochemical process using fossil resources as a raw material. That is, as the use of the 4-hydroxybenzoic acid composition in the second embodiment and the third embodiment, a polymer raw material such as a polyester, a polyester resin, a polyester fiber, a liquid crystal polyester, a liquid crystal polyester resin, a liquid crystal polyester fiber, a raw material for the synthesis of a paraben as an antiseptic, a dye, a pigment, an adhesive resin, a plasticizer, and the like can be exemplified.

[0335] Among these, use for a polymer is preferable. That is, the polymer obtained using the 4-hydroxybenzoic acid composition in the second embodiment and the third embodiment is a polymer containing at least a structure derived from the 4-hydroxybenzoic acid (A) of the 4-hydroxybenzoic acid composition in the second embodiment or the 4-hydroxybenzoic acid (A) of the 4-hydroxybenzoic acid composition in the third embodiment.

[0336] As described above, the 4-hydroxybenzoic acid composition in the second embodiment and the third embodiment improves the balance between the environmental adaptability and the polymerizability or the balance between the environmental adaptability and the color tone. Therefore, it can be preferably used for a biomass plastic polymer (bio-based polymer) that highly balances the environmental adaptability and the polymerizability or the environmental adaptability and the color tone.

[0337] As examples of products made of the polymer obtained using the 4-hydroxybenzoic acid composition in the second embodiment and the third embodiment, various power supply lines, electrical equipment, various components, building materials, furniture, fishing lines and the like, fishing nets, ropes, liquid crystal polymers, and the like can be exemplified.

[0338] As the polymer of the second embodiment and the third embodiment, a liquid crystal polymer is preferable. The structure of the 4-hydroxybenzoic acid (A) included in the polymer of the second embodiment and the 4-hydroxybenzoic acid (A) included in the polymer of the third embodiment has a molecular chain in which the molecule is elongated and flat and the rigidity along the long chain of the molecule is high (this rigid molecular chain is referred to as "mesogen skeleton" for example). Also, as described above, the 4-hydroxybenzoic acid composition in the second embodiment and the third embodiment improves the balance between the environmental adaptability and the polymerizability or the balance between the environmental adaptability and the color tone. That is, the polymer of the second embodiment and the third embodiment can be preferably used as a liquid crystal polymer which improves the balance between the environmental adaptability, the thermal conductivity and the mechanical strength because the balance between the environmental adaptability and the polymerizability or the balance between the environmental adaptability and the color tone of the 4-hydroxybenzoic acid composition is improved.

[0339] Among them, as the liquid crystal polymer, as long as the properties of the downstream product obtained using the liquid crystal polymer are not significantly impaired within a range, additives such as a reinforcing agent can be contained in addition to the polymer of the second embodiment and the third embodiment, depending on the desired properties.

[0340] Among them, as the additives, for example, fibrous reinforcing agents such as glass fibers, silica alumina fibers, alumina fibers, carbon fibers, acicular reinforcing agents such as aluminum borate whiskers, potassium titanate whiskers, inorganic fillers such as glass beads, talc, mica, graphite, wollastonite, dolomite, mold release improvers such as fluororesins, metal soaps, coloring agents such as dyes, pigments, antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, surfactants, and the like can be given. Two or more of these additives can be used at the same time.

[0341] Also, an additive having an external lubricant effect of higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, fluorocarbon surfactants, and the like can be used. Also, a small amount of a thermoplastic resin other than the polymer of the second embodiment and the third embodiment (for example, polyamides, crystalline polyesters, polyphenylene sulfide, polyether ketone, polycarbonate, polyphenylene ether and its modified products, polysulfone, polyether sulfone, polyether imide, and the like) or a thermosetting resin (for example, phenol resins, epoxy resins, and the like) can be contained. In the case where such a thermoplastic resin or a thermosetting resin other than the polymer of the second embodiment and the third embodiment is used, in the second embodiment and the third embodiment, the kind and the amount of addition thereof need to be selected so as not to impair the liquid crystallinity or the moldability of the polymer itself.

[0342] In the product made of the polymer obtained using the 4-hydroxybenzoic acid composition of the second and third embodiments, the proportion of the 4-hydroxybenzoic acid composition of the second and third embodiments to the total amount of 4-hydroxybenzoic acid used in the raw material of the prescribed product (product) can be prescribed for each manufacturer.

[0343] By measuring the measured biobased content of the product emitted, discarded, etc. in accordance with the proportion of the 4-hydroxybenzoic acid composition of the second and third embodiments prescribed for each manufacturer, the manufacturer who should bear the obligation of recycling the product can be determined. Also, at a certain manufacturer, the proportion of the 4-hydroxybenzoic acid composition of the second and third embodiments to the total amount of 4-hydroxybenzoic acid can be prescribed for each production lot of the product of the manufacturer, and thus the production lot can be tracked. In the past traceability imparting method (e.g., mixing of pigments, etc.), there was a possibility that the strength of various products would be reduced, but according to the 4-hydroxybenzoic acid composition of the second and third embodiments, the desired polymerizability and color tone can be obtained, and thus the strength of various products can be ensured while the manufacturer is determined.

[0344] The above describes the embodiments of the present application, but these are merely examples of the present application, and various structures other than the above can also be employed. Also, the present application is not limited to the above-described embodiments, and modifications, etc. within the scope of achieving the object of the present application are included in the present application.

[0345] Specifically, in the second and third embodiments, 4-hydroxybenzoic acid is cited as an example of the chemical substance produced using biomass resources as a raw material, but the technical idea of the present application also includes phenol, etc., and can be applied to various substances produced using biomass resources as a raw material.

[0346] Also, in the second embodiment, the embodiment in which the concentration of shikimic acid contained in 4-hydroxybenzoic acid is prescribed is cited as an example, but the present application in which the content of various intermediate metabolites produced by the transformant, the aforementioned "other components", "culture medium", etc., and specific elements, etc. are prescribed is also included in the scope of the technical idea of the present application.

[0347] In addition, as the aforementioned intermediate metabolite, for example, shikimic acid, dehydroshikimic acid, quinic acid, protocatechuic acid, amino acid, etc. can be cited, but are not limited to these. Also, as the aforementioned specific element, for example, nitrogen, phosphorus, potassium, magnesium, sodium, iron, manganese, zinc, cobalt, etc. can be cited, but are not limited to these.

[0348] Example

[0349] The embodiments of the present application are described in detail according to the examples and comparative examples. Note that the present application is not limited to the examples. Among them, the examples and comparative examples related to the first embodiment of the present application are Examples 1a to 3a and Comparative Examples 1a to 3a, the examples and comparative examples related to the second embodiment of the present application are Examples 1b to 3b and Comparative Examples 1b to 3b, and the examples and comparative examples related to the third embodiment of the present application are Examples 1c to 3c and Comparative Examples 1c to 3c.

[0350] Examples, Comparative Examples

[0351] (Example 1a)

[0352] In 10 ml of a liquid culture medium A containing kanamycin 50 μg / ml [a solution obtained by dissolving (NH2)2CO 2 g, (NH4)2SO4 7 g, KH2PO4 0.5 g, K2HPO4 0.5 g, MgSO4·7H2O 0.5 g, 0.06% (w / v) FeSO4·7H2O + 0.042% (w / v) MnSO4·2H2O 1 ml, 0.02% (w / v) biotin solution 1 ml, 0.01% (w / v) thiamin solution 2 ml, yeast extract 2 g, vitamin assay casamino acid 7 g, glucose 40 g in distilled water 1 L], calcium carbonate was further added at a ratio of 2 mass%, and a test tube was inoculated with coryneform bacterium transformant HBA-47 (deposition number: NITE BP-01849) described in Japanese Patent No. 6327654 with a platinum ear, and aerobic shaking culture was performed at 33°C for 24 hours at 200 rpm. Then, the above HBA-47 was isolated from the above test solution by vacuum filtration using a membrane filter (manufactured by Merck Millipore company, Steritop 0.22 μm x 33 mm) with a pore size of 0.22 μm, and a test solution was obtained.

[0353] After that, the coryneform bacterium transformant PHE21 (depository number: NITE BP-996) prepared by the method described in Example 1a and

[0135] paragraph of Japanese Patent No. 5932660 was added to the above test solution so that the final cell concentration became 10%, thereby preparing a cell suspension. The cell suspension was put in a culture medium bottle with a capacity of 100 ml, and 4-hydroxybenzoic acid sodium was added as a substrate under reducing conditions (oxidation-reduction potential; -450 mV) so that the concentration became 250 mM, and it was allowed to react in a water bath kept at 33°C while stirring. At this time, the reaction solution was allowed to react while controlling the pH of the reaction solution to be 7.0 or more using 2.5 N ammonia and a pH controller (manufactured by ABLE INC., model number: DT-1023). By centrifuging the reaction solution (4°C, 15000 g, 10 minutes), a solution containing a phenol composition synthesized from glucose as a supernatant was obtained (phenol concentration: 0.8 mass%).

[0354] After concentrating the solution to a phenol concentration of 4.3 mass% by continuous distillation, it was concentrated to a phenol concentration of 22 mass% by dehydration using osmotic gasification with a DDR-type zeolite membrane (60°C, 50 Torr). The concentrated solution was left to stand at room temperature, and it was separated into a phenol phase and an aqueous phase, and the phenol phase was recovered (phenol concentration: 72 mass%). The phenol phase was further dehydrated using an evaporator (60°C / 20 hPa) and concentrated to a concentration of 99 mass%. Furthermore, a phenol composition was obtained by evaporating the residual moisture using an evaporator (150°C / 20 hPa).

[0355] (Example 2a)

[0356] A phenol composition was obtained by the same method as described in Example 1a, except that the conditions for osmotic gasification using a DDR-type zeolite membrane were set to 85°C, 250 Torr.

[0357] (Example 3a)

[0358] The substance of Example 1a was stored in a transparent glass bottle at room temperature under air for half a year, thereby obtaining a phenol composition.

[0359] (Comparative Example 1a)

[0360] A phenol composition was obtained by the same method as described in Example 1a, except that the residual moisture was not evaporated using an evaporator (150°C / 20 hPa).

[0361] (Comparative Example 2a)

[0362] A commercially available phenol product (manufactured by FUJIFILM Wako Pure Chemical Corporation) was prepared.

[0363] (Comparative Example 3a)

[0364] A waste liquid containing phenol (phenol concentration: 6.2 mass%) generated when a phenol product of Comparative Example 2a was prepared and a phenol formaldehyde resin was synthesized by the method described below (Preparation of phenol formaldehyde resin) was prepared. After the solution was concentrated to a phenol concentration of 7.0 mass% by continuous distillation, it was concentrated to a phenol concentration of 29 mass% by pervaporation (60°C, 50 Torr) dehydration using a DDR-type zeolite membrane. The concentrated liquid was left to stand at room temperature, and separated into a phenol phase and an aqueous phase, and the phenol phase (phenol concentration: 72 mass%) was recovered. Subsequently, water was further removed using an evaporator (60°C / 20 hPa), and concentrated to a phenol concentration of 99 mass%, thereby obtaining a phenol composition.

[0365] (Preparation of phenol formaldehyde resin)

[0366] Using the phenol compositions prepared in Examples 1a to 3a and Comparative Examples 1a to 3a, phenol formaldehyde resins were prepared.

[0367] In a reactor equipped with a stirring device, a reflux condenser, and a thermometer, 100 parts by mass of the phenol composition obtained in Examples 1a to 3a and Comparative Examples 1a to 3a, 2 parts by mass of oxalic acid dihydrate, and 82 parts by mass of a 37% formaldehyde aqueous solution were reacted at 100°C for 3 hours. Subsequently, the temperature was increased to 180°C over 90 minutes under a vacuum of 40 Torr, and water was distilled off, and unreacted phenol composition was distilled off while passing steam for 30 minutes at 180°C, and the distilled water and phenol composition were recovered as a waste liquid. Phenol formaldehyde resins were obtained using the phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a.

[0368] (Evaluation of physical properties)

[0369] The physical properties of the phenol compositions obtained in Examples 1a to 3a and Comparative Examples 1a to 3a were evaluated by the following methods.

[0370] (Analysis of phenol concentration)

[0371] The quantification of phenol in the phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a was performed by gas chromatography based on JIS K2437.

[0372] The phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a were dissolved in pure water so as to become a concentration of 90 mass%, thereby preparing analysis samples. The analysis samples were analyzed by gas chromatography with a solution obtained by dissolving a phenol composition (manufactured by FUJIFILM Wako Pure Chemical Corporation) in pure water at a concentration of 90 mass% as a blank.

[0373] The analysis conditions of the gas chromatography are shown in the following Analysis Conditions . The results are shown in Table 1.

[0374] Analysis Conditions

[0375] GC device: GC-2030 (manufactured by SHIMADZU CORPORATION).

[0376] Carrier gas: N2.

[0377] Detector: hydrogen flame ionization (FID) detector; FID temperature: 300°C.

[0378] Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 µm (manufactured by Shimadzu GLC Ltd.).

[0379] Vaporization chamber temperature: 210°C.

[0380] Column flow rate: 0.64 mL / minute.

[0381] Column temperature rising conditions: 5 minutes at 50°C, temperature rise at 20°C / minute to 300°C, 10 minutes at 300°C.

[0382] (Measured Bio-based Content)

[0383] Regarding the phenol (A) in the phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a, the content of radioactive carbon 14 C in the total carbon atoms was measured in accordance with the bio-based concentration test standard ASTM D6866-20 established by the American Society for Testing Materials (ASTM). 14 C in the total carbon atoms was measured in accordance with the bio-based concentration test standard ASTM D6866-20 established by the American Society for Testing Materials (ASTM). 14 C in the total carbon atoms was measured in accordance with the bio-based concentration test standard ASTM D6866-20 established by the American Society for Testing Materials (ASTM). 14The concentration of C was evaluated as the measured bio-based content and as an index of environmental adaptability. The calculation results are shown in Table 1.

[0384] (Absorbance)

[0385] The phenol compositions of Examples la to 3a and Comparative Examples la to 3a were dissolved in pure water so that the phenol concentration became 90 mass%, thereby preparing measurement samples. With respect to the measurement samples, using a UV-visible spectrophotometer (manufactured by SHIMADZU CORPORATION, UV-2400PC), the absorbance of the measurement samples at a wavelength of 425 nm when pure water was used as a blank was measured. The results are shown in Table 1.

[0386] (Tone)

[0387] The phenol resins prepared using the phenol compositions of Examples la to 3a and Comparative Examples la to 3a were heated at 130°C for 10 minutes in accordance with the above-described (Preparation of phenol resin), thereby preparing molten samples. Thereafter, the color of the molten samples was quantified in accordance with the iodine value measured in accordance with DIN 6162, and was evaluated in accordance with the following criteria. The evaluation results are shown in Table 1.

[0388] A (light yellow): iodine value of 1 or more and less than 6.

[0389] B (yellow): iodine value of 6 or more and less than 9.

[0390] C (yellowish brown): iodine value of 9 or more and less than 44.

[0391] D (dark brown): iodine value of 44 or more.

[0392] [Table 1]

[0393] As shown in Table 1, since the absorbance of the phenol composition was 0.001 or more and 0.70 or less, the balance between environmental adaptability and the tone of the obtained phenol resin was improved.

[0394] (Example 1b)

[0395] In 10 ml of a liquid culture medium A containing kanamycin 50 μg / ml [a solution obtained by dissolving (NH2)2CO 2 g, (NH4)2SO4 7 g, KH2PO4 0.5 g, K2HPO4 0.5 g, MgSO4·7H2O 0.5 g, 0.06% (w / v) FeSO4·7H2O + 0.042% (w / v) MnSO4·2H2O 1 ml, 0.02% (w / v) biotin solution 1 ml, 0.01% (w / v) thiamin solution 2 ml, yeast extract 2 g, vitamin assay casamino acid 7 g, glucose 40 g in distilled water 1 L], further, calcium carbonate was added at a ratio of 2 mass% in a test tube, and a coryneform bacterium transformant HBA-47 (deposition number: NITE BP-01849) described in Japanese Patent No. 6327654 was inoculated with a platinum ear, and aerobic shaking culture was performed at 33°C for 24 hours at 200 rpm. Thus, a test solution containing 4-hydroxybenzoic acid synthesized from glucose (4-hydroxybenzoic acid concentration: 7.3 mass%) was obtained.

[0396] From the above test solution, the above HBA-47 was separated by vacuum filtration using a membrane filter (manufactured by Merck Millipore company, Steritop 0.22 μm x 33 mm) having a pore size of 0.22 μm. Then, to the above test solution, powdered activated carbon was added, and activated carbon treatment was performed. In addition, for every 100 g of test solution, 0.4 g of powdered activated carbon was used. Next, by adding sulfuric acid 25% to the test solution in which activated carbon treatment was performed, the pH was lowered from 8 to 3, and a crystallization operation for precipitating solutes was performed. Next, the precipitated solutes were separated by filtration, and a solid precipitate was recovered. Next, the obtained precipitate was washed with 10 times the amount of pure water with respect to the mass of the above precipitate, and using a stirrer, stirring was performed at 200 rpm for 3 times, and then dried, and thus a solid 4-hydroxybenzoic acid composition was obtained.

[0397] (Example 2b)

[0398] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example 1b, except that the number of times the obtained precipitate was washed with 10 times the amount of pure water with respect to the mass of the above precipitate was changed to 2 times.

[0399] (Example 3b)

[0400] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example Ib, except that the number of times of stirring washing of the obtained precipitate with 10 times the amount of pure water relative to the mass of the precipitate was changed to one time.

[0401] (Comparative Example 2b)

[0402] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example Ib, except that the method of washing of the obtained precipitate was changed to stirring washing with 5 times the amount of pure water for one time.

[0403] (Comparative Example 2b)

[0404] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example Ib, except that the method of washing of the obtained precipitate was changed as follows.

[0405] The obtained precipitate was dissolved in 10 times the amount of methanol, and insolubles were removed by filtration. Thereafter, under the condition of 40°C, the pressure was gradually reduced to 100 hPa or less, and methanol was evaporated until the liquid component of methanol disappeared, whereby a solid 4-hydroxybenzoic acid composition was obtained.

[0406] (Comparative Example 3b)

[0407] A commercially available 4-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code: H0207) was prepared.

[0408] (Physical property evaluation)

[0409] Each physical property of the 4-hydroxybenzoic acid composition obtained in Examples Ib to 3b and Comparative Examples Ib to 3b was evaluated by the following method.

[0410] (Concentration analysis)

[0411] The quantification of the 4-hydroxybenzoic acid and shikimic acid concentrations in the 4-hydroxybenzoic acid compositions of Examples Ib to 3b and Comparative Examples Ib to 3b was performed by high-performance liquid chromatography using a high-performance liquid chromatograph equipped with a UV detector (manufactured by Hitachi High-Tech Science Corporation, Chromaster (registered trademark)), under the following <analysis conditions>. The results are shown in Table 2.

[0412] <Analysis Conditions>

[0413] String: COSMOSIL 5C18-AR-II ( (4.6mm × 250mm), manufactured by NACALAITESQUE, INC.

[0414] Mobile phase: water / methanol / perchloric acid = 4 / 1 / 0.0075 (volume ratio / volume ratio / volume ratio) isocratic elution.

[0415] Flow rate: 1 mL / min.

[0416] Column temperature: 40℃.

[0417] Detection method: Photodiode array (PDA) detector (210nm).

[0418] (Measured bio-based content)

[0419] Regarding the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1b-3b and Comparative Examples 1b-3b, the radioactive carbon in the total carbon atoms was measured according to the bio-based concentration test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). 14 The C content. Then, based on its measurement results and the radioactive carbon in the circulating carbon at the 1950 point in time. 14 The concentration of C was calculated using radioactive carbon in the circulating carbon at the 1950 time point of 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1b-3b and Comparative Examples 1b-3b. 14 When calculating the total radioactive carbon in carbon atoms with a C concentration of 100%, 14 The concentration of C was used as the measured bio-based content and evaluated as an indicator of environmental adaptability. The calculation results are shown in Table 2.

[0420] (aggregation)

[0421] In a 1L polymerization kettle equipped with a distillation device, a stirrer, and a nitrogen inlet tube, 4-hydroxybenzoic acid composition 241.7g (4-hydroxybenzoic acid content: 1.75 mol) of Examples 1b to 3b and Comparative Examples 1b to 3b, diphenylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd., product code: B0464) 93.1g (0.5 mol), terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code: T0166) 83.0g (0.5 mol), and acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., product code: A2036) 326.4g (3.2 mol) were charged. After acetoxylation reaction was performed at 150°C for 3 hours, the temperature was raised to 240°C and held for 6 hours, and then further raised to 300°C, and polymerization was continued until the content solidified. The polymer (prepolymer) taken out was ground to a fine powder, and then subjected to solid-phase polymerization at 300°C in nitrogen, and the polycondensation reaction was completed at the point at which a prescribed stirring torque was reached, thereby obtaining a liquid crystal polymer.

[0422] The obtained liquid crystal polymer was subjected to injection molding under the conditions of resin temperature 340°C, mold temperature 150°C, and injection pressure 110 MPa, thereby producing a bending test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. Using the produced bending test piece, measurement of the bending strength was performed in accordance with ASTM D790.

[0423] The polymerizability was evaluated in accordance with the obtained bending strength. The results are shown in Table 2.

[0424] A: The bending strength was 100 MPa or more.

[0425] B: The bending strength was more than 90 MPa and less than 100 MPa.

[0426] C: The bending strength was less than 90 MPa.

[0427] [Table 2]

[0428] As shown in Table 2, by setting the shikimic acid contained in the 4-hydroxybenzoic acid composition to be prescribed concentration or less, the balance between the environmental suitability and the polymerizability was improved.

[0429] (Example 1c)

[0430] In 10 ml of a liquid culture medium A containing kanamycin 50 μg / ml [a solution obtained by dissolving (NH2)2CO 2 g, (NH4)2SO4 7 g, KH2PO4 0.5 g, K2HPO4 0.5 g, MgSO4·7H2O 0.5 g, 0.06% (w / v) FeSO4·7H2O + 0.042% (w / v) MnSO4·2H2O 1 ml, 0.02% (w / v) biotin solution 1 ml, 0.01% (w / v) thiamin solution 2 ml, yeast extract 2 g, vitamin assay casamino acid 7 g, glucose 40 g in distilled water 1 L], further, calcium carbonate was added at a ratio of 2 mass% in a test tube, and a coryneform bacterium transformant HBA-47 (deposited number: NITE BP-01849) described in Japanese Patent No. 6327654 was inoculated with a platinum ear, and aerobic shaking culture was performed at 33°C for 24 hours at 200 rpm. Thus, a test solution containing 4-hydroxybenzoic acid synthesized from glucose (4-hydroxybenzoic acid concentration: 7.3 mass%) was obtained.

[0431] From the above test solution, the above HBA-47 was separated by vacuum filtration using a membrane filter (manufactured by Merck Millipore company, Steritop 0.22 μm x 33 mm) having a pore size of 0.22 μm. Then, to the above test solution, powdered activated carbon was added, and activated carbon treatment was performed. In addition, with respect to 100 g of the test solution, 2.0 g of powdered activated carbon was used. Next, by adding sulfuric acid 25% to the test solution in which the activated carbon treatment was performed, the pH was lowered from 8 to 3, and a crystallization operation for precipitating solutes was performed. Next, the precipitated solutes were separated by filtration, and a solid precipitate was recovered. Next, the obtained precipitate was washed three times with 10 times the amount of pure water with respect to the mass of the above precipitate, using a stirrer at 200 rpm, and then dried, and thus a solid 4-hydroxybenzoic acid composition was obtained.

[0432] (Example 2c)

[0433] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example 1c, except that the amount of powdered activated carbon added to the test solution was changed to 1.0 g.

[0434] (Example 3c)

[0435] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example lc, except that the amount of powder activated carbon added to the test solution was changed to 0.4 g.

[0436] (Comparative Example lc)

[0437] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example lc, except that the amount of powder activated carbon added to the test solution was changed to 0.2 g.

[0438] (Comparative Example 2c)

[0439] A solid 4-hydroxybenzoic acid composition was obtained by the same method as described in Example lc, except that the amount of powder activated carbon added to the test solution was changed to 0.4 g, and further, except that the number of times of stirring and washing the obtained precipitate with pure water in an amount 10 times the mass of the above precipitate was changed to 2 times.

[0440] (Comparative Example 3c)

[0441] A commercially available 4-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code: H0207) was prepared.

[0442] (Physical property evaluation)

[0443] Each physical property of the 4-hydroxybenzoic acid composition obtained in Examples lc to 3c and Comparative Examples lc to 3c was evaluated by the following method.

[0444] (Concentration analysis)

[0445] The quantification of 4-hydroxybenzoic acid in the 4-hydroxybenzoic acid compositions of Examples lc to 3c and Comparative Examples lc to 3c was performed by high performance liquid chromatography using a high performance liquid chromatograph (manufactured by Hitachi High-Tech Science Corporation, Chromaster (registered trademark)) equipped with the above UV detector under the following <analysis conditions>. The results are shown in Table 3.

[0446] <Analysis conditions>

[0447] Column: COSMOSIL 5C18-AR-II (4.6 mm x 250 mm), manufactured by NACALAITESQUE, INC.

[0448] ​Mobile phase: water / methanol / perchloric acid = 4 / 1 / 0.0075 (volume ratio / volume ratio / volume ratio) isocratic elution.

[0449] Flow rate: 1 mL / min.

[0450] Column temperature: 40℃.

[0451] Detection method: Photodiode array (PDA) detector (210nm).

[0452] (Measured bio-based content)

[0453] Regarding the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1c-3c and Comparative Examples 1c-3c, the radioactive carbon in the total carbon atoms was measured according to the bio-based concentration test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). 14 The C content. Then, based on its measurement results and the radioactive carbon in the circulating carbon at the 1950 point in time. 14 The concentration of C was calculated using radioactive carbon in the circulating carbon at the 1950 time point of 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1c-3c and Comparative Examples 1c-3c. 14 When calculating the total radioactive carbon in carbon atoms with a C concentration of 100%, 14 The concentration of C was used as the measured bio-based content and evaluated as an indicator of environmental adaptability. The calculation results are shown in Table 3.

[0454] (Absorbance)

[0455] The 4-hydroxybenzoic acid compositions of Examples 1c-3c and Comparative Examples 1c-3c were dissolved in ethanol to a concentration of 20 g / L to prepare a measurement sample. The absorbance of this measurement sample at a wavelength of 425 nm was measured using a UV-Vis spectrophotometer (Shimadzu Corporation, UV-2400PC) with pure water as a blank. The results are shown in Table 3.

[0456] (tone)

[0457] A 1-L reactor equipped with a stirrer and a nitrogen inlet tube was charged with the 4-hydroxybenzoic acid composition of Examples 1c to 3c and Comparative Examples 1c to 3c, 241.7 g (4-hydroxybenzoic acid content: 1.75 mol). After 1 L of nitrogen was introduced into the reactor, the temperature was raised to 240°C, and the heating was performed under a nitrogen atmosphere for 6 hours. After the heating, the 4-hydroxybenzoic acid composition in the reactor was dissolved in ethanol to give a concentration of 20 mass%, the color of the dissolved solution was quantified based on the iodine value measured according to DIN 6162, and the evaluation was performed according to the following criteria. The evaluation results are shown in Table 3.

[0458] A: iodine value is 1 or more and less than 10.

[0459] B: iodine value is more than 10 and less than 20.

[0460] C: iodine value is more than 20.

[0461] [Table 3]

[0462] As shown in Table 3, by setting the absorbance of the 4-hydroxybenzoic acid composition to 0.015 or less, the balance between the environmental suitability and the color tone was improved.

[0463] Corynebacterium glutamicum PHE7 has been deposited with the Patent Microorganism Deposit of National Institute of Technology and Evaluation, 2-5-8, Kamitsuma Kayashiki, Kimitsu-shi, Chiba-ken, Japan (postal code 292-0818) (date of deposit in Japan: August 31, 2010, date of deposit under the Budapest Treaty: August 12, 2011, accession number: NITE BP-976).

[0464] Corynebacterium glutamicum PHE18 has been deposited with the Patent Microorganism Deposit of National Institute of Technology and Evaluation, 2-5-8, Kamitsuma Kayashiki, Kimitsu-shi, Chiba-ken, Japan (postal code 292-0818) (date of deposit in Japan: October 21, 2010, date of deposit under the Budapest Treaty: September 28, 2011, accession number: NITE BP-995).

[0465] Corynebacterium glutamicum PHE21 has been deposited with the Patent Microorganism Deposit Center of the National Institute of Technology and Evaluation, 2-5-8, Kamitsuma Kayashiki, Katori-shi, Chiba-ken, Japan (postal code 292-0818) (date of deposit in Japan: October 21, 2010, date of international deposit under the Budapest Treaty: September 28, 2011, accession number: NITE BP-996).

[0466] Corynebacterium glutamicum PHE31 has been deposited with the Patent Microorganism Deposit Center of the National Institute of Technology and Evaluation, 2-5-8, Kamitsuma Kayashiki, Katori-shi, Chiba-ken, Japan (postal code 292-0818) (date of deposit in Japan: November 2, 2010, date of international deposit under the Budapest Treaty: September 28, 2011, accession number: NITE BP-999).

[0467] Corynebacterium glutamicum HBA-2 has been deposited with the Patent Microorganism Deposit Center of the National Institute of Technology and Evaluation, 2-5-8, Kamitsuma Kayashiki, Katori-shi, Chiba-ken, Japan (postal code 292-0818) (date of deposit in Japan: March 27, 2014, date of international deposit under the Budapest Treaty: February 23, 2015, accession number: NITE BP-01838).

[0468] Corynebacterium glutamicum HBA-47 has been deposited with the Patent Microorganism Deposit Center of the National Institute of Technology and Evaluation, 2-5-8, Kamitsuma Kayashiki, Katori-shi, Chiba-ken, Japan (postal code 292-0818) (date of international deposit under the Budapest Treaty: April 25, 2014, accession number: NITE BP-01849).

[0469] These strains have been internationally deposited under the Budapest Treaty and are available to the public under the conditions specified in 37 C.F.R. § 1.808.

[0470] This application claims priority to Japanese Application No. 2023-096317, Japanese Application No. 2023-096338, and Japanese Application No. 2023-096350, filed on June 12, 2023, and incorporates the entire disclosures thereof by reference.

[0471]

Claims

1. An aromatic compound composition comprising at least radiocarbon derived from biomass resources, calculated based on the concentration of radiocarbon in 1950s recycled carbon as measured according to ASTM D6866-20. 14 Aromatic compounds (A) with a measured bio-based content of C of 80% or more and 100% or less, of which, The aromatic compound (A) is phenol (A) or 4-hydroxybenzoic acid (A). When the aromatic compound (A) is phenol (A), the absorbance at a wavelength of 425 nm is 0.001 or more and 0.70 or less when the aromatic compound composition is dissolved in pure water to achieve a concentration of 90% by mass. When the aromatic compound (A) is the 4-hydroxybenzoic acid (A), the absorbance of the aromatic compound composition dissolved in ethanol at a concentration of 20 g / L is 0.015 or less at a wavelength of 425 nm, or the content of shikimic acid in the aromatic compound composition is 0.012% by mass or less when the total amount of the aromatic compound composition is 100% by mass.

2. The aromatic compound composition according to claim 1, wherein, The aromatic compound (A) is phenol (A).

3. The aromatic compound composition according to claim 2, wherein, The content of phenol (A) is 95% by mass or more and 100% by mass or less.

4. The aromatic compound composition according to claim 2 or 3, wherein, The measured bio-based content of the phenol (A) is above 95% and below 100%.

5. The aromatic compound composition according to any one of claims 2 to 4, wherein, The absorbance is below 0.

62.

6. The aromatic compound composition according to any one of claims 2 to 5, wherein, The phenol (A) comprises at least a benzene ring structure derived from one or more of the products selected from transformants HBA-2 and HBA-47. The accession number for transformant HBA-2 is NITE BP-01838, and the accession number for transformant HBA-47 is NITE BP-01849.

7. The aromatic compound composition according to any one of claims 2 to 6, wherein, The phenol (A) comprises at least one or more products selected from transformants PHE7, PHE18, PHE21, and PHE31. The accession number for PHE7 is NITE BP-976, for PHE18 it is NITE BP-995, for PHE21 it is NITE BP-996, and for PHE31 it is NITE BP-999.

8. A polymer, wherein, The polymer contains at least one structural unit of phenol (A) derived from the aromatic compound composition of any one of claims 2 to 7.

9. The polymer according to claim 8, wherein, The polymer is a phenolic resin.

10. The aromatic compound composition according to claim 1, wherein, The aromatic compound (A) is 4-hydroxybenzoic acid (A). When the total amount of the aromatic compound composition is 100% by mass, the content of shikimic acid in the aromatic compound composition is less than 0.012% by mass.

11. The aromatic compound composition according to claim 10, wherein, When the total amount of the aromatic compound composition is 100% by mass, the content of shikimic acid is less than 0.008% by mass.

12. The aromatic compound composition according to claim 1, wherein, The aromatic compound (A) is 4-hydroxybenzoic acid (A). When the aromatic compound composition is dissolved in ethanol at a concentration of 20 g / L, the absorbance at a wavelength of 425 nm is less than 0.

015.

13. The aromatic compound composition according to claim 12, wherein, The absorbance is below 0.

010.

14. The aromatic compound composition according to claim 12 or 13, wherein, The absorbance is greater than or equal to 0.

001.

15. The aromatic compound composition according to any one of claims 10 to 14, wherein, When the total amount of the aromatic compound composition is 100% by mass, the content of 4-hydroxybenzoic acid (A) is 95% by mass or more and 100% by mass or less.

16. The aromatic compound composition according to any one of claims 10 to 15, wherein, The measured bio-based content of the 4-hydroxybenzoic acid (A) is above 95% and below 100%.

17. The aromatic compound composition according to any one of claims 10 to 16, wherein, The 4-hydroxybenzoic acid (A) comprises at least one or two products selected from transformants HBA-2 and HBA-47. The accession number for transformant HBA-2 is NITE BP-01838, and the accession number for transformant HBA-47 is NITE BP-01849.

18. A polymer, wherein, The polymer contains at least the structure of the 4-hydroxybenzoic acid (A) derived from the aromatic compound composition of any one of claims 10 to 17.

19. The polymer according to claim 18, wherein, The polymer is a liquid crystal polymer.

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