Aromatic compound composition and polymer

Abstract

Provided is an aromatic compound composition containing at least an aromatic compound (A) having an actually measured biobased content of 80% to 100% inclusive, wherein the actually measured biobased content is measured in accordance with ASTM D6866-20 and indicates the content ratio of radioactive carbon 14C derived from a biomass resource with respect to the concentration of radioactive carbon in circulating carbon in the 1950s. In the aromatic compound composition, the aromatic compound (A) is phenol (A) or 4-hydroxybenzoic acid (A). When the aromatic compound (A) is the phenol (A), the absorbance of a solution, the solution being prepared by dissolving the aromatic compound composition in pure water at a concentration of 90% by mass, at a wavelength of 425 nm is 0.001 to 0.70 inclusive. When the aromatic compound (A) is the 4-hydroxybenzoic acid (A), the absorbance of a solution, the solution being prepared by dissolving the aromatic compound composition in ethanol at a concentration of 20 g / L, at a wavelength of 425 nm is 0.015 or less, or the content of shikimic acid in the aromatic compound composition is 0.012% by mass or less with respect to 100% by mass, i.e., the whole mass, of the aromatic compound composition.

Description

Aromatic Compound Compositions and Polymers

[0001] The present invention relates to aromatic compound compositions and polymers.

[0002] Against the backdrop of global warming and the depletion of fossil fuel resources, the production of chemicals from renewable biomass resources is attracting attention as a new industry aimed at realizing a low-carbon society. One example of such chemicals is biomass-derived phenol.

[0003] A technology relating to biomass-derived phenols is described, for example, in Patent Document 1. Patent Document 1 describes a phenolic resin characterized by having a structure derived from specific plant-derived phenols, a structure derived from other phenols, a structure derived from aldehydes, and a structure derived from carbohydrates.

[0004] 4-hydroxybenzoic acid (4-HBA) is also a useful chemical substance that is used as a raw material for liquid crystal polymers and as a synthetic raw material for the preservative paraben. Currently, 4-hydroxybenzoic acid is produced chemically using crude oil as a raw material. One method for chemically producing 4-hydroxybenzoic acid is to react phenol, potassium hydroxide, and carbon dioxide under high-pressure conditions.

[0005] However, these methods not only rely on fossil fuels for the raw material phenol, but also require strong alkali, carbon dioxide, and high-temperature and high-pressure conditions during the reaction process, and generate hazardous waste liquids and exhaust gases during the production process, placing a significant burden on the environment. In light of this background, there is a strong demand for the establishment of an environmentally friendly bio-based production technology for 4-hydroxybenzoic acid that uses renewable resources as raw materials, saves energy, and reduces hazardous waste liquids.

[0006] For example, Non-Patent Documents 1 and 2 and Patent Documents 2 and 3 have revealed using Escherichia coli that 4-HBA is synthesized from chorismate, an intermediate in the shikimate pathway involved in the synthesis of aromatic amino acids, by chorismate-pyruvate lyase encoded by ubiC.

[0007] J. Bacteriol., 174, 5309-5316 (1992) Microbiology, 140, 897-904 (1994) JP 2017-119765 A U.S. Patent No. 6,030,819 U.S. Patent No. 6,114,157

[0008] According to the investigations of the present inventors, it has become clear that there is room for improvement in the biomass-derived aromatic compound composition from the viewpoint of improving the balance between environmental compatibility and color tone or polymerizability.

[0009] The present invention has been made in view of the above circumstances, and provides an aromatic compound composition having an improved balance between environmental compatibility and color tone or polymerizability.

[0010] Furthermore, the inventors' investigations have revealed that there is room for improvement in the biomass-derived phenolic composition in terms of the color tone of the polymer synthesized using the phenolic composition.

[0011] The first embodiment of the present invention has been made in view of the above circumstances, and provides a phenolic composition having improved environmental compatibility and a good balance of color tone of the resulting polymer.

[0012] Furthermore, according to the investigations of the present inventors, it has become clear that when the above-mentioned biomass-derived 4-hydroxybenzoic acid is used in the polymerization of a resin, which is a downstream product, there is room for improvement in polymerization properties.

[0013] The second embodiment of the present invention has been made in view of the above circumstances, and provides a 4-hydroxybenzoic acid composition and polymer with an improved balance between environmental compatibility and polymerizability.

[0014] Furthermore, according to the investigations of the present inventors, it has become clear that there is room for improvement in terms of color tone of the above-mentioned biomass-derived 4-hydroxybenzoic acid.

[0015] The third embodiment of the present invention has been made in view of the above circumstances, and provides a 4-hydroxybenzoic acid composition having an improved balance between environmental compatibility and color tone.

[0016] According to the present invention, the radiocarbon concentration derived from biomass resources is determined based on the radiocarbon concentration in circulating carbon in the 1950s, as measured in accordance with ASTM D6866-20. １４ and an aromatic compound composition containing at least an aromatic compound (A) having a measured bio-based content indicating the proportion of biomass C of 80% or more and 100% or less, wherein 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 has an absorbance of 0.001 or more and 0.70 or less at a wavelength of 425 nm when dissolved in pure water to a concentration of 90% by mass, and 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 dissolved in ethanol to a concentration of 20 g / L, or the content of shikimic acid in the aromatic compound composition is 0.012% by mass or less when the entire aromatic compound composition is taken as 100% by mass.

[0017] Furthermore, the present inventors have conducted extensive research to achieve the above object, and as a result have 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 compatibility and the color tone of the resulting polymer, thereby completing the first embodiment of the present invention.

[0018] [1a] Radiocarbon derived from biomass resources, determined based on the concentration of radiocarbon in circulating carbon in the 1950s, measured according to ASTM D6866-20. １４A phenol composition comprising at least phenol (A) having a measured bio-content rate, which indicates the proportion of phenol (A) in the phenolic composition, of 80% to 100% and having an absorbance of 0.001 to 0.70 at a wavelength of 425 nm when dissolved in pure water to a concentration of 90% by mass. [2a] The phenol composition according to [1a] above, wherein the content of phenol (A) is 95% to 100% by mass. [3a] The phenol composition according to [1a] or [2a] above, wherein the measured bio-content rate of phenol (A) is 95% to 100%. [4a] The phenol composition according to any of [1a] to [3a] above, wherein the absorbance is 0.62 or less. [5a] The phenol composition according to any one of [1a] to [4a] above, wherein the phenol (A) contains at least a structure derived from a benzene ring of a product of one or more transformants selected from transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849). [6a] The phenol composition according to any one of [1a] to [5a] above, wherein the phenol (A) at least comprises a product of one or more transformants selected from transformant PHE7 (accession number: NITE BP-976), transformant PHE18 (accession number: NITE BP-995), transformant PHE21 (accession number: NITE BP-996), and transformant PHE31 (accession number: NITE BP-999). [7a] A polymer comprising at least a structural unit derived from the phenol (A) in the phenol composition according to any one of [1a] to [6a] above. [8a] The polymer according to [7a] above, which is a phenolic resin.

[0019] Furthermore, the present inventors have conducted extensive research to achieve the above object, and as a result have found that the balance between environmental compatibility and polymerizability can be improved by adjusting the concentration of shikimic acid contained in a 4-hydroxybenzoic acid composition to a predetermined level or less, thereby completing a second embodiment of the present invention.

[0020] [1b] Radiocarbon derived from biomass resources, determined based on the concentration of radiocarbon in circulating carbon in the 1950s, measured according to ASTM D6866-20. １４ A 4-hydroxybenzoic acid composition comprising at least 4-hydroxybenzoic acid (A) having a measured biocontent rate, which indicates the proportion of C, of ​​80% to 100%, and having a shikimic acid content of 0.012% by mass or less, when the total 4-hydroxybenzoic acid composition is taken as 100% by mass. [2b] The 4-hydroxybenzoic acid composition according to [1b] above, wherein the content of the 4-hydroxybenzoic acid (A) is 95% to 100% by mass, when the total 4-hydroxybenzoic acid composition is taken as 100% by mass. [3b] The 4-hydroxybenzoic acid composition according to [1b] or [2b] above, wherein the measured biocontent rate of the 4-hydroxybenzoic acid (A) is 95% to 100%. [4b] The 4-hydroxybenzoic acid composition according to any one of [1b] to [3b] above, wherein the content of shikimic acid is 0.008% by mass or less, when the total mass of the 4-hydroxybenzoic acid composition is taken as 100% by mass. [5b] The 4-hydroxybenzoic acid composition according to any one of [1b] to [4b] above, wherein the 4-hydroxybenzoic acid (A) contains at least a product of one or two transformants selected from transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849). [6b] A polymer comprising at least the structure of the 4-hydroxybenzoic acid (A) derived from the 4-hydroxybenzoic acid composition according to any one of [1b] to [5b] above. [7b] The polymer according to [6b] above, which is a liquid crystal polymer.

[0021] Furthermore, the present inventors have conducted extensive research to achieve the above object, and as a result have found that the balance between environmental compatibility and color tone of a 4-hydroxybenzoic acid composition can be improved by adjusting the absorbance of light having a wavelength of 425 nm to a specific range, thereby completing a third embodiment of the present invention.

[0022] [1c] Radiocarbon derived from biomass resources, determined based on the concentration of radiocarbon in circulating carbon in the 1950s, measured according to ASTM D6866-20. １４ A 4-hydroxybenzoic acid composition comprising at least 4-hydroxybenzoic acid (A) having a measured bio-based content, which indicates the proportion of C, of ​​80% to 100%, 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. [2c] The 4-hydroxybenzoic acid composition according to [1c] above, wherein the content of the 4-hydroxybenzoic acid (A) is 95% to 100% by mass, when the total amount of the 4-hydroxybenzoic acid composition is taken as 100% by mass. [3c] The 4-hydroxybenzoic acid composition according to [1c] or [2c] above, wherein the measured bio-based content of the 4-hydroxybenzoic acid (A) is 95% to 100% by mass. [4c] The 4-hydroxybenzoic acid composition according to any one of [1c] to [3c] above, wherein the absorbance is 0.010 or less. [5c] The 4-hydroxybenzoic acid composition according to any one of [1c] to [4c] above, wherein the absorbance is 0.001 or more. [6c] The 4-hydroxybenzoic acid composition according to any one of [1c] to [5c] above, wherein the 4-hydroxybenzoic acid (A) contains at least a product of one or two transformants selected from transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849).

[0023] According to the present invention, it is possible to provide an aromatic compound composition that has an improved balance between environmental compatibility and color tone or polymerizability.

[0024] Furthermore, according to the first embodiment of the present invention, a phenolic composition can be provided that has improved environmental compatibility and a good balance of color tones of the resulting polymer.

[0025] Furthermore, according to the second embodiment of the present invention, it is possible to provide a 4-hydroxybenzoic acid composition and a polymer that have an improved balance between environmental compatibility and polymerizability.

[0026] Furthermore, according to the third embodiment of the present invention, a 4-hydroxybenzoic acid composition having an improved balance between environmental compatibility and color tone can be provided.

[0027] Hereinafter, embodiments of the present invention will be described in detail. In the description of the present embodiments, "pure water" refers to water having a conductivity of 1 MΩ cm or more. The term "liquid crystal polymer" as used herein generally refers to a polymer that can have a rod-like structure that enables it to exhibit liquid crystalline behavior (e.g., a thermotropic nematic state) in its molten state.

[0028] The aromatic compound composition of the present embodiment has a radioactive carbon content derived from biomass resources, which is determined based on the radioactive carbon concentration in circulating carbon in the 1950s, as measured in accordance with ASTM D6866-20. １４An aromatic compound composition comprising at least an aromatic compound (A) having a measured bio-based content, which indicates the proportion of biomass, biomass, and tertiary esters (C), of 80% to 100%, wherein 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, when dissolved in pure water to a concentration of 90% by mass, exhibits an absorbance of 0.001 to 0.70 at a wavelength of 425 nm; when the aromatic compound (A) is 4-hydroxybenzoic acid (A), the aromatic compound composition, when dissolved in ethanol to a concentration of 20 g / L, exhibits an absorbance of 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 entire aromatic compound composition is taken as 100% by mass. More specific aspects of this embodiment are shown below as a first to third embodiments.

[0029] First Embodiment [Phenol Composition] The phenol composition of the first embodiment contains a radiocarbon content derived from a biomass resource, which is determined based on the radiocarbon concentration in circulating carbon in the 1950s, measured in accordance with ASTM D6866-20. １４ The phenol (A) contains at least phenol (A) having a measured bio-content rate indicating the proportion of C of 80% or more and 100% or less, and when dissolved in pure water to a concentration of 90% by mass, the absorbance at a wavelength of 425 nm is 0.001 or more and 0.70 or less.

[0030] In such a phenolic composition, the measured bio-based content indicates the amount of plant-derived carbon contained in the phenol (A), and the higher this value, the more the phenolic composition is composed of naturally derived raw materials. Therefore, the higher the measured bio-based content, the better the environmental compatibility from the perspective of carbon neutrality. Furthermore, when the absorbance is 0.001 or more and 0.70 or less, a phenolic composition can be obtained in which the color tone of the polymer obtained using the phenolic composition is more favorable, even when plant-derived raw materials are used.

[0031] Such a phenolic composition can be produced by the production method described below, particularly by (i) producing a precursor from a plant-derived raw material compound using a first transformant, (ii) producing a phenolic composition from the precursor using a second transformant, and (iii) separating and concentrating the produced phenolic composition.

[0032] In the phenol composition of the first embodiment, radiocarbon derived from biomass resources is determined based on the concentration of radiocarbon in circulating carbon in the 1950s, as measured based on ASTM D6866-20. １４ The measured bio-based content, which indicates 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 even more preferably 95% or more and 100% or less. When the measured bio-based content falls within the above range, environmental compatibility is improved from the viewpoint of carbon neutrality.

[0033] At this time, the radioactive carbon in the total carbon atoms of the phenol (A) in the phenol composition １４ The actual biobased content, which indicates the proportion of radioactive carbon in the sample, is calculated based on the biobased content test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). １４ The C content was measured, and the measurement results and radioactive carbon in the circulating carbon as of 1950 were compared. １４ The concentration of C is calculated from the concentration of C. Although this test standard specifies several analytical methods, analytical method B (AMS method) is preferably used. For analytical method B, an analytical device such as the accelerator mass spectrometer Pelletron AMS manufactured by NEC Corporation is used.

[0034] In the phenol composition of the first embodiment, when dissolved in pure water to a concentration of 90% by mass, the upper limit of the absorbance at a wavelength of 425 nm is 0.70 or less, preferably 0.65 or less, more preferably 0.62 or less, more preferably 0.60 or less, even more preferably 0.50 or less, even more preferably 0.40 or less, even more preferably 0.25 or less, even more preferably 0.20 or less, even more preferably 0.15 or less, and even more preferably 0.10 or less. Having an absorbance at a wavelength of 425 nm that is equal to or less than the upper limit makes the color tone of the polymer obtained using the phenol composition of the first embodiment more favorable. The lower limit of the absorbance at a wavelength of 425 nm is not particularly limited, but is, for example, 0.001 or more. From the viewpoint of production efficiency, it is preferably 0.005 or more, more preferably 0.01 or more, even more preferably 0.02 or more, even more preferably 0.03 or more, even more preferably 0.05 or more, and even more preferably 0.07 or more.

[0035] In the phenol composition of the first embodiment, the content of the 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, even more preferably 97% by mass or more and 100% by mass or less, even more preferably 98% by mass or more and 100% by mass or less, and even more preferably 99% by mass or more and 100% by mass or less, when the entire phenol composition is taken as 100% by mass. When the content of the phenol (A) is within the above numerical range, environmental compatibility is improved from the viewpoint of carbon neutrality, and the color tone of the polymer obtained using the phenol composition of the first embodiment is more suitable. Note that when the content of the phenol (A) is 100% by mass, the content of the other components described below is 0.000% by mass. In this case, the content of the other components may be below the lower detection limit and may not be detected by quantitative analysis.

[0036] In the phenol composition of the first embodiment, the phenol (A) preferably contains at least a structure derived from a benzene ring of a product of one or more transformants selected from transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849). When the phenol (A) contains at least the product, environmental compatibility is improved from the viewpoint of carbon neutrality, and the color tone of the polymer obtained using the phenol composition of the first embodiment is more favorable.

[0037] In the phenol composition of the first embodiment, the phenol (A) preferably contains at least a product of one or more transformants selected from transformant PHE7 (accession number: NITE BP-976), transformant PHE18 (accession number: NITE BP-995), transformant PHE21 (accession number: NITE BP-996), and transformant PHE31 (accession number: NITE BP-999). When the phenol (A) contains at least the above product, environmental compatibility is improved from the viewpoint of carbon neutrality, and the color tone of the polymer obtained using the phenol composition of the first embodiment becomes more favorable.

[0038] In the phenol composition of the first embodiment, when phenol (A) contains at least a structure derived from a benzene ring of a product of one or more transformants selected from transformant HBA-2 and transformant HBA-47, or when phenol (A) contains at least a product of one or more transformants selected from transformant PHE7, transformant PHE18, transformant PHE21, and transformant PHE31, the color tone of the resulting polymer is presumably more favorable because the presence of trace amounts of components that may adversely affect the color tone is kept relatively low. Here, the trace amounts of components derived from the transformants are extremely numerous, and the contents of these trace amounts of components are below the detection limit and cannot be analyzed. Therefore, in the phenol composition of the first embodiment, in an aspect in which phenol (A) at least includes a structure derived from a benzene ring of a product of one or more transformants selected from transformant HBA-2 and transformant HBA-47, or an aspect in which phenol (A) at least includes a product of one or more transformants selected from transformant PHE7, transformant PHE18, transformant PHE21, and transformant PHE31, it is impossible to directly identify the characteristic part of this aspect by the structure or properties of the substance, and it can be said to be almost impractical, and it is considered that so-called "impossible / impractical circumstances" exist.

[0039] (Other Components) The phenolic composition of the first embodiment may contain other components in addition to the above-mentioned components, as long as the balance between environmental compatibility and the color tone of the resulting polymer is not impaired. Examples of other components include one or more selected from the group consisting of the following compounds: monosaccharides such as glucose, fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, and xylobiose; and polysaccharides such as dextrin and soluble starch. Sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. Inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and nitrogen-containing organic compounds such as amino acids, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Solvents such as pure water.

[0040] In the phenol composition of the first embodiment, the content of the other components is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less. When the content of the other components is equal to or less than the upper limit, the color tone of the polymer obtained using the phenol composition of the first embodiment becomes more favorable. The lower limit of the content of the other components is not particularly limited, but is, for example, 0.000% by mass or more. In this case, 0.000% by mass includes cases where the content of the other components is below the lower detection limit and cannot be detected by quantification. When the phenol composition of the first embodiment contains multiple other components, the total content of the other components may be equal to or less than the upper limit and equal to or greater than the lower limit.

[0041] Examples of methods for quantifying the contents of such phenol (A) and other components include 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)), ion chromatography, gas chromatography mass spectrometry (GC / MS), inductively coupled plasma mass spectrometry (ICP-MS), and the like.

[0042] [Method for Producing Phenol Composition] Next, a method for producing the phenol composition of the first embodiment will be described.

[0043] The method for producing a phenolic composition according to the first embodiment preferably includes the following steps (A) to (D): (A) reacting a first transformant with at least one raw material compound selected from the group consisting of sugars, compounds that can be metabolized by the transformant to produce chorismic acid, or chorismic acid and salts thereof, in a reaction intermediate solution containing the first transformant to produce a precursor; (B) producing a phenolic composition from the precursor using a second transformant to obtain a reaction solution containing the phenolic composition; (C) removing the transformant from the reaction solution; and (D) separating and concentrating the phenolic composition from the reaction solution.

[0044] [(A) A step of reacting a first transformant with at least one raw material compound selected from the group consisting of sugars and compounds that can be metabolized by the transformant to produce chorismic acid, or chorismic acid and salts thereof, to produce a precursor] The method for producing a phenolic composition of the first embodiment first involves (A) a step of reacting a first transformant with at least one raw material compound selected from the group consisting of sugars and compounds that can be metabolized by the transformant to produce chorismic acid, or chorismic acid and salts thereof, to produce a precursor, in a reaction intermediate solution containing the sugars and at least one raw material compound selected from the group consisting of compounds that can be metabolized by the transformant to produce chorismic acid, or chorismic acid and salts thereof. The compounds used in this step and the reaction conditions are described in detail below.

[0045] (First Transformant) In the method for producing a phenolic composition according to the first embodiment, any transformant can be used as the first transformant as long as it is capable of producing a precursor from a sugar through metabolism. Examples of such precursors include 4-hydroxybenzoic acid. Examples of such transformants include the coryneform bacterium transformant HBA-2 (accession number: NITE BP-01838) described in Japanese Patent No. 6327653 and the coryneform bacterium transformant HBA-47 (accession number: NITE BP-01849) described in Japanese Patent No. 6327654.

[0046] Prior to the reaction, the first transformant is preferably cultured under aerobic conditions. The culture temperature and culture time are not particularly limited as long as the transformant can be cultured and a required amount or more of the transformant can be obtained. The culture temperature is, for example, 25°C or higher and 38°C or lower. The culture time is, for example, 12 hours or higher and 48 hours or lower.

[0047] (Cultivation Medium) The medium used for aerobic cultivation of the first transformant prior to the reaction can be a natural or synthetic medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients. Carbon sources include sugars (monosaccharides such as glucose, fructose, mannose, xylose, arabinose, and galactose; disaccharides such as sucrose, maltose, lactose, cellobiose, xylobiose, and trehalose; polysaccharides such as starch; molasses, etc.), sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. Carbon sources 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 may be, for example, 0.1 w / v % to 20 w / v %.

[0048] Examples of nitrogen sources that can be used include inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate. Nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. Nitrogen sources 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 may be, for example, 0.1 w / v% to 10 w / v%. Examples of inorganic salts include potassium diphosphate, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Inorganic salts 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 may be, for example, 0.01 w / v% to 1 w / v%.

[0049] Examples of nutrients include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloric acid hydrolysate, extracts of animals, plants, or microbial cells, and their decomposition products. The concentration of the nutrients in the medium varies depending on the nutrients used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the medium is preferably 6 to 8.

[0050] Specific preferred media include 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)] and 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)]. These media may be used with the sugar concentration within the above range.

[0051] (Raw Material Compound) The raw material compound is preferably a compound that can be incorporated into the cells of the first transformant, and more preferably a compound that is easily industrially usable, such as one that is abundant in plants. Among the raw material compounds, sugars are preferably sugars that can produce glucose through metabolism by the first transformant, and glucose is more preferred. Such sugars include oligosaccharides and polysaccharides having glucose units. Examples of the oligosaccharides and polysaccharides include monosaccharides such as fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, and xylobiose; and polysaccharides such as dextrin or soluble starch. Furthermore, the use of glucose is preferred from the viewpoint of improving the efficiency of precursor production and improving the production efficiency of the phenolic composition of the first embodiment. Among the raw material compounds, compounds that can produce chorismic acid through metabolism by the first transformant include quinic acid and shikimic acid. Furthermore, for example, plant-derived raw materials can be used as raw materials containing these raw material compounds. Examples of plant-derived raw materials that can be used include molasses, straw (rice straw, barley straw, wheat straw, rye straw, oat straw, etc.), bagasse, corn stover, and other inedible agricultural waste, energy crops (switchgrass, napier grass, miscanthus, etc.), wood chips, waste paper, etc., which are saccharified solutions containing multiple sugars such as glucose, obtained by saccharifying enzymes, etc. Among these, glucose, chorismic acid, quinic acid, and shikimic acid are preferred as raw material compounds, and plant-derived raw materials containing these compounds are preferably used.

[0052] (Reaction Intermediate Liquid) The reaction intermediate liquid can be a natural or synthetic reaction liquid containing a carbon source, a nitrogen source, inorganic salts, etc. The carbon source can be the raw material compounds described above, or molasses or a saccharified solution containing them. In addition to sugars, other carbon sources can also be used: sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. A single carbon source can be used alone, or two or more can be mixed. The concentration of the raw material compounds in the reaction intermediate liquid is preferably 1 w / v% to 20 w / v%, more preferably 2 w / v% to 10 w / v%, and even more preferably 2 w / v% to 5 w / v%. The concentration of the total carbon source, including the raw material compounds, can be 2 w / v% to 5 w / v%.

[0053] Examples of nitrogen sources that can be used include inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate. Nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. The nitrogen sources can be used alone or in combination. The concentration of the nitrogen source in the reaction intermediate solution varies depending on the nitrogen compound used, but may be, for example, 0.1 w / v% to 10 w / v%. Examples of inorganic salts include potassium diphosphate, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. The inorganic salts can be used alone or in combination. The concentration of the inorganic salt in the reaction intermediate solution varies depending on the inorganic salt used, but may be, for example, 0.01 w / v% to 1 w / v%.

[0054] Examples of nutrients include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloric acid hydrolysate, extracts of animals, plants, or microbial cells, and their decomposition products. The concentration of the nutrients in the reaction intermediate solution varies depending on the nutrients used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the reaction intermediate solution is preferably 6 to 8.

[0055] Specific preferred reaction intermediate solutions include the above-mentioned A medium and BT medium, etc. These reaction intermediate solutions may be used with the sugar concentration in the above range.

[0056] (Reaction Conditions) From the viewpoint of the production efficiency of the phenolic composition, the reaction temperature, i.e., the survival temperature of the first transformant, is preferably 20°C or higher, more preferably 23°C or higher, and even more preferably 25°C or higher. From the same viewpoint, the survival temperature is preferably 50°C or lower, more preferably 48°C or lower, and even more preferably 47°C or lower. From the viewpoint of the production efficiency of the phenolic composition, the reaction time is preferably 7 days or less, more preferably 5 days or less, and even more preferably 3 days or less. The reaction time is not particularly limited as long as the reaction proceeds sufficiently, but is, for example, 1 day or more. The culture may be performed in a batch, fed-batch, or continuous manner. Among these, the batch method is preferred from the viewpoint of the production efficiency of the phenolic composition. The reaction may be performed under aerobic conditions or under reducing conditions. The phenolic composition production capacity of the first transformant itself is higher under aerobic conditions. However, under aerobic conditions, the first transformant grows, and the raw material compounds are consumed for growth, thereby reducing the production efficiency of the phenolic composition. Therefore, it is preferable to carry out the reaction under aerobic conditions under which the first transformant does not grow. As used herein, "not growing" includes substantially no growth or almost no growth. For example, growth of the first transformant can be avoided or suppressed by using a reaction solution that is deficient or limited in one or more compounds essential for microbial growth, such as vitamins (e.g., biotin and thiamine) and nitrogen sources.

[0057] Furthermore, under reducing conditions, the first transformant does not substantially grow, and therefore the raw material compound is not consumed for growth, thereby improving the precursor production efficiency and, as a result, increasing the production efficiency of the phenol composition. The reducing conditions are determined by the redox potential of the reaction intermediate. The redox potential of the reaction intermediate is preferably −500 mV or more and −200 mV or less, and more preferably −500 mV or more and −150 mV or less. The reduction state of the reaction intermediate can be easily estimated using a resazurin indicator (which discolors from blue to colorless in the reduced state), but can also be measured more accurately using an oxidation-reduction potentiometer (e.g., ORP Electrodes, manufactured by Broadley James).

[0058] The reaction intermediate solution under reducing conditions can be prepared by any known method without any limitation. For example, an aqueous solution for the reaction intermediate may be used instead of distilled water as the liquid medium for the reaction intermediate. The method for preparing the aqueous solution for the reaction intermediate may be, for example, a method for preparing a culture medium for strictly anaerobic microorganisms such as sulfate-reducing microorganisms (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., pp. 926-940, Berlin, Springer Verlag) or "Agricultural Chemistry Experiment Book, Vol. 3, Faculty of Agriculture, Kyoto University." References such as "Agricultural Chemistry Classroom, 26th Edition, 1990, Sangyo Tosho Publishing Co., Ltd." can be used to obtain an aqueous solution under the desired reducing conditions. Specifically, an aqueous solution for a reaction intermediate solution under reducing conditions can be obtained by heating or reducing the pressure of distilled water or the like to remove dissolved gases. In this case, the aqueous solution for a reaction intermediate solution under reducing conditions can be prepared by treating the distilled water or the like under a reduced pressure of preferably 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 3 mmHg or less, for preferably 1 minute to 60 minutes, more preferably 5 minutes to 40 minutes, thereby removing dissolved gases, particularly dissolved oxygen.

[0059] Alternatively, an aqueous solution for the reaction intermediate under reducing conditions can be prepared by adding a suitable reducing agent (e.g., thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide, etc.) Appropriate combinations of these methods are also effective methods for preparing an aqueous solution for the reaction intermediate under reducing conditions.

[0060] When the reaction is carried out under reducing conditions, it is preferable to maintain the reaction intermediate solution under reducing conditions even during the reaction. In order to maintain reducing conditions during the reaction, it is desirable to prevent oxygen contamination from outside the reaction system as much as possible. Specifically, a method of sealing the reaction system with an inert gas such as nitrogen gas or carbon dioxide gas can be mentioned. As a method for more effectively preventing oxygen contamination, in order to efficiently function the metabolic function within the first transformant of the first embodiment during the reaction, it may be necessary to add a pH maintenance adjusting solution to the reaction system or various nutrient solutions as appropriate. In such cases, it is effective to remove oxygen from the added solution in advance.

[0061] [Step of Removing the First Transformant from the (A)' Precursor] Furthermore, in the first embodiment of the method for producing a phenolic composition, from the viewpoint of the yield of the phenolic composition, the method may further include a step of removing the first transformant from the (A)' precursor after the step of reacting the first transformant with at least one raw material compound selected from the group consisting of sugars, compounds that can be metabolized by the transformant to produce chorismic acid, or chorismic acid and salts thereof in a reaction intermediate solution containing the first transformant to produce a precursor, and before the step of producing the phenolic composition from the precursor using the second transformant, as described below, to obtain a reaction solution containing the phenolic composition. In the step of removing the first transformant from the (A)' precursor, a reaction solution recovery method exemplified in the step of removing the transformant from the reaction solution, as described below, can be used. By applying the reaction solution recovery method to the precursor, the first transformant can be removed from the precursor, and the precursor can be recovered.

[0062] [(B) Step of Producing a Phenol Composition from a Precursor by the Second Transformant and Obtaining a Reaction Liquid Containing the Phenol Composition] Next, (B) step of producing a phenol composition from a precursor by the second transformant and obtaining a reaction liquid containing the phenol composition is carried out. By culturing as described above, a precursor is produced in the reaction intermediate liquid. By adding the second transformant to this reaction intermediate liquid, a phenol composition can be produced from the precursor, and a reaction liquid containing the phenol composition can be obtained. The compounds used in this step and the reaction conditions are described in detail below.

[0063] (Second Transformant) In the method for producing a phenolic composition according to the first embodiment, any transformant can be used as the second transformant as long as it is capable of producing a phenolic composition from a precursor. Examples of such precursors include 4-hydroxybenzoic acid and the like. Examples of such transformants include the coryneform bacterial transformant PHE7 (accession number: NITE BP-976) described in Japanese Patent No. 5,932,649, the coryneform bacterial transformant PHE18 (accession number: NITE BP-995) described in Japanese Patent No. 5,932,660, the coryneform bacterial transformant PHE21 (accession number: NITE BP-996), and the coryneform bacterial transformant PHE31 (accession number: NITE BP-999) described in Japanese Patent No. 5,887,277.

[0064] Prior to the reaction, the second transformant is preferably cultured under aerobic conditions. The culture temperature and culture time are not particularly limited as long as the transformant can be cultured and a required amount or more of the transformant can be obtained. The culture temperature is, for example, 25°C or higher and 38°C or lower. The culture time is, for example, 12 hours or higher and 48 hours or lower.

[0065] (Cultivation Medium) The medium used for aerobic cultivation of the second transformant prior to the reaction can be a natural or synthetic medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients. Carbon sources include sugars (monosaccharides such as glucose, fructose, mannose, xylose, arabinose, and galactose; disaccharides such as sucrose, maltose, lactose, cellobiose, xylobiose, and trehalose; polysaccharides such as starch; molasses, etc.), sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. Carbon sources 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 may be, for example, between 0.1% and 20% (w / v).

[0066] Examples of nitrogen sources that can be used include inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate. Nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. Nitrogen sources 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 may be, for example, 0.1 w / v% to 10 w / v%. Examples of inorganic salts include potassium diphosphate, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Inorganic salts 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 may be, for example, 0.01 w / v% to 1 w / v%.

[0067] Examples of nutrients include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloric acid hydrolysate, extracts of animals, plants, or microbial cells, and their decomposition products. The concentration of the nutrients in the medium varies depending on the nutrients used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the medium is preferably 6 to 8.

[0068] Specific preferred media include 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)] and 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)]. These media may be used with the sugar concentration within the above range.

[0069] (Reaction Solution) In addition to the reaction intermediate solution used in step (A) above, a buffer solution, an inorganic salt medium, or the like can be used as the reaction solution. In the reaction solution, the precursor may be a salt such as a sodium salt or a potassium salt; or an ester with an alcohol having 1 to 4 carbon atoms. Among these, a salt is preferred, and a sodium salt is more preferred. The precursor may be used alone or in combination of two or more. The concentration of the precursor in the reaction solution is preferably 1 w / v% to 20 w / v%, more preferably 2 w / v% to 10 w / v%, and even more preferably 2 w / v% to 5 w / v%. By having the precursor concentration within the above numerical range, the production efficiency of the phenol composition is further improved.

[0070] Examples of the buffer solution include phosphate buffer, Tris buffer, carbonate buffer, etc. The concentration of the buffer solution is preferably 10 mM or more and 150 mM or less from the viewpoint of production efficiency of the phenol composition.

[0071] Examples of inorganic salt media include media containing one or more inorganic salts such as monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Among these, a medium containing magnesium sulfate is preferred. Specific examples of inorganic salt media include medium A [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)], etc. The concentration of inorganic salts in the medium varies depending on the inorganic salt used, but is usually 0.01 w / v % or more and 1 w / v % or less.

[0072] The pH of the reaction solution is preferably 6 or more and 8 or less. During the reaction, it is preferable to control the pH of the reaction solution to near neutral, particularly 7, using an aqueous ammonia solution, an aqueous sodium hydroxide solution, or the like with a pH controller (for example, Model: DT-1023, manufactured by Able Co., Ltd.).

[0073] (Reaction Conditions) 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 even more preferably 25°C or higher, from the viewpoint of production efficiency of the phenolic composition. From the same viewpoint, the survival temperature is preferably 50°C or lower, more preferably 48°C or lower, and even more preferably 47°C or lower. From the viewpoint of production efficiency of the phenolic composition, the reaction time is preferably 7 days or shorter, more preferably 5 days or shorter, and even more preferably 3 days or shorter. The reaction time is not particularly limited as long as the reaction proceeds sufficiently, but is, for example, 1 day or longer. The culture may be performed in a batch, fed-batch, or continuous manner. Among these, the batch method is preferred from the viewpoint of production efficiency of the phenolic composition.

[0074] The reaction may be carried out under aerobic conditions, but is preferably carried out under reducing conditions. Under reducing conditions, the second transformant does not grow, thereby increasing the production efficiency of the phenolic composition. As used herein, "not growing" includes substantially no growth or almost no growth. The reducing conditions are defined by the redox potential of the reaction solution. From the viewpoint of the production efficiency of the phenolic composition, the redox potential of the reaction intermediate solution is preferably -500 mV or more to -200 mV or more, and more preferably -500 mV or more to -150 mV or less. The reduced state of the reaction solution can be easily estimated using a resazurin indicator (which decolorizes from blue to colorless in the reduced state), but can be more accurately measured using an oxidation-reduction potentiometer (e.g., ORP Electrodes, manufactured by Broadley James).

[0075] The reaction mixture under reducing conditions can be prepared by any known method without any limitation. For example, an aqueous solution for the reaction solution may be used as the liquid medium for the reaction solution instead of distilled water, and the method for preparing the aqueous solution for the reaction solution may be, for example, a method for preparing a culture solution for strictly anaerobic microorganisms such as sulfate-reducing microorganisms (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., pp. 926-940, Berlin, Springer Verlag) or "Agricultural Chemistry Experiment Book, Vol. 3, Faculty of Agriculture, Kyoto University." References such as "Agricultural Chemistry Classroom, 26th Edition, 1990, Sangyo Tosho Publishing Co., Ltd." can be used to obtain an aqueous solution under the desired reducing conditions. Specifically, an aqueous solution for a reaction solution under reducing conditions can be obtained by heating or reducing the pressure of distilled water or the like to remove dissolved gases. In this case, by treating distilled water or the like under reduced pressure of preferably 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 3 mmHg or less, for preferably 1 minute to 60 minutes, more preferably 5 minutes to 40 minutes, the dissolved gases, particularly dissolved oxygen, can be removed to prepare an aqueous solution for a reaction solution under reducing conditions.

[0076] Alternatively, an aqueous solution for the reaction under reducing conditions can be prepared by adding a suitable reducing agent (e.g., thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide, etc.) A suitable combination of these methods is also an effective method for preparing an aqueous solution for the reaction under reducing conditions.

[0077] When the reaction is carried out under reducing conditions, it is preferable to maintain the reaction solution under reducing conditions during the reaction. In order to maintain reducing conditions during the reaction, it is desirable to prevent oxygen contamination from outside the reaction system as much as possible. Specifically, a method of sealing the reaction system with an inert gas such as nitrogen gas or carbon dioxide gas can be mentioned. As a method for more effectively preventing oxygen contamination, in order to efficiently function the metabolic function within the second transformant of the first embodiment during the reaction, it may be necessary to add a pH maintenance adjusting solution to the reaction system or various nutrient solutions as appropriate. In such cases, it is effective to remove oxygen from the added solution in advance.

[0078] [(C) Step of Removing Transformants from the Reaction Solution] Then, (C) step of removing transformants from the reaction solution is carried out. By culturing as described above, phenol is produced in the reaction solution, but the transformants remain in the reaction solution. By removing the transformants, the reaction solution containing the phenol composition can be recovered.

[0079] Examples of methods for recovering the reaction solution include separating the reaction solution from the transformant. In this case, the step of removing the first transformant from the (A)' precursor described above may be performed, and the first transformant and the second transformant may be separated separately from the reaction solution, or the step of removing the first transformant from the (A)' precursor may be omitted, and the first transformant and the second transformant may be simultaneously separated from the reaction solution. Known separation methods can be used to separate the transformant. Examples of known separation methods include collection of the supernatant by leaving the mixture to stand, membrane filtration, and centrifugation. These methods can be performed singly or in combination of two or more types as appropriate.

[0080] As the treatment conditions for membrane filtration, treatment can be performed under general filtration conditions.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, even more preferably 0.05 μm or more, even more preferably 0.07 μm or more, even more preferably 0.10 μm or more, even more preferably 0.15 μm or more, and even more preferably 0.20 μm or more.From the same viewpoint, it is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.In addition, as the method for measuring the membrane pore diameter, general measurement methods using mercury porosimetry, bubble point test, bacterial filtration method, etc. can be mentioned, but it is preferable to use the value obtained by bubble point test.As the material of the membrane used in membrane filtration, for example, polymer membrane, ceramic membrane, stainless steel membrane, etc. can be mentioned.

[0081] As the centrifuge used for centrifugation, general machines such as a separator plate type, a cylindrical type, a decanter type, etc. can be used. From the viewpoint of improving the production efficiency of the phenol composition, the lower limit of the temperature during centrifugation is preferably 0°C or higher, more preferably 1°C or higher, and even more preferably 3°C or higher. From the same viewpoint, the upper limit of the temperature during centrifugation is preferably 70°C or lower, more preferably 50°C or lower, even more preferably 30°C or lower, even more preferably 10°C or lower, and even more preferably 5°C or lower.

[0082] The relative centrifugal force and time can be set appropriately. The lower limit of the relative centrifugal force is preferably 3,000 g or more, more preferably 5,000 g or more, even more preferably 7,000 g or more, even more preferably 10,000 g or more, and even more preferably 15,000 g or more, from the viewpoint of improving the polymerizability of the phenolic composition. The upper limit of the relative centrifugal force is preferably 50,000 g or less, more preferably 25,000 g or less, and even more preferably 20,000 g or less, from the viewpoint of improving the production efficiency of the phenolic composition. Similarly, the lower limit of the time is preferably 0.2 minutes or more, more preferably 0.5 minutes or more, even more preferably 1 minute or more, and even more preferably 5 minutes or more, from the viewpoint of improving the color tone of the polymer obtained using the phenolic composition. The upper limit of the time is preferably 75 minutes or less, more preferably 60 minutes or less, even more preferably 30 minutes or less, even more preferably 15 minutes or less, and even more preferably 10 minutes or less, from the viewpoint of improving the production efficiency of the phenolic composition.

[0083] [(D) Step of Separating and Concentrating the Phenol Composition in the Reaction Solution] Finally, (D) step of separating and concentrating the phenol composition in the reaction solution is carried out. In the first embodiment, the phenol composition can be recovered from the reaction solution as described above. However, in order to increase the phenol concentration in the phenol composition and further improve the color tone of the resulting polymer, the phenol composition is separated and concentrated from the reaction solution by a known method. Examples of such known methods include distillation, pervaporation, membrane permeation, and organic solvent extraction. These methods can be carried out singly or in combination of two or more.

[0084] As the distillation method, any known distillation method can be used, including, but not limited to, atmospheric distillation using a distillation column, reduced pressure distillation using an evaporator, steam distillation, thin film distillation, etc.

[0085] Pervaporation is a method of obtaining a gaseous phenol composition by permeating a pervaporation membrane. The pervaporation membrane has the function of preferentially permeating phenol over water. Therefore, the phenol composition in the reaction solution permeates the pervaporation membrane from the feed space to the permeation space preferentially over water. As a result, the phenol composition obtained in the permeation space has a higher phenol concentration than the reaction solution. In this way, by using pervaporation, it is possible to obtain a gaseous phenol composition from the reaction solution and to increase the phenol concentration in the obtained phenol composition compared to the reaction solution.

[0086] The shape of the pervaporation membrane is not particularly limited, and for example, a dense membrane such as a bag-type, flat membrane, hollow fiber, tubular, or spiral type can be used.

[0087] The average thickness of the pervaporation membrane is not particularly limited, but is preferably about 10 to 500 μm, more preferably about 20 to 400 μm. By setting the average thickness of the pervaporation membrane within this range, the feed side space and the permeation side space can be reliably separated, and the phenol composition in a vaporized state can be more reliably obtained from the reaction solution.

[0088] The material of the pervaporation membrane is not particularly limited, but examples include inorganic membranes such as DDR-type zeolite membranes, polymer membranes such as polyimide, polyamide, polysulfone, polyethersulfone, and polyamideimide, and composite membranes thereof. Among these, inorganic membranes are preferred, and DDR-type zeolite membranes are more preferred. This allows for improved phenol separation performance while also improving the mechanical properties of the pervaporation membrane.

[0089] [Uses] The phenol composition of the first embodiment can be used in the same applications as phenol compositions synthesized by conventional petrochemical processes using fossil resources as raw materials. That is, uses of the phenol composition of the first embodiment include a precursor of bisphenol A, a raw material for polymers, industrial chemicals, fibers, etc. Among these, use in polymer applications is preferred. That is, a polymer using the phenol composition of the first embodiment is a polymer containing at least a structural unit derived from the phenol (A) in the phenol composition of the first embodiment.

[0090] The polymer of the first embodiment may be any polymer that requires phenol for synthesis, and is preferably a phenolic resin, since the phenolic composition of the first embodiment has improved environmental compatibility and a better balance of color tones for the resulting polymer.

[0091] Second Embodiment [4-Hydroxybenzoic Acid Composition] The 4-hydroxybenzoic acid composition of the second embodiment contains a radioactive carbon concentration derived from a biomass resource, which is determined based on the radioactive carbon concentration in circulating carbon in the 1950s, measured in accordance with ASTM D6866-20. １４ The 4-hydroxybenzoic acid composition contains at least 4-hydroxybenzoic acid (A) having a measured bio-content rate, which indicates the proportion of C, of ​​80% to 100%, and the shikimic acid content is 0.012% by mass or less when the entire 4-hydroxybenzoic acid composition is taken as 100% by mass.

[0092] In such a 4-hydroxybenzoic acid composition, the measured biomass content indicates the amount of plant-derived carbon contained in the 4-hydroxybenzoic acid (A), and the higher this value, the more the 4-hydroxybenzoic acid composition is composed of naturally derived raw materials. Therefore, the higher the measured biomass content, the better the environmental compatibility from the perspective of carbon neutrality. Furthermore, when the shikimic acid content is 0.012% by mass or less, a 4-hydroxybenzoic acid composition with more favorable polymerizability can be obtained.

[0093] Such a 4-hydroxybenzoic acid composition can be produced by the production method described below, particularly by (i) using raw materials derived from specific plants as raw material compounds, (ii) removing impurities by adding an adsorbent to the reaction solution, and (iii) washing with pure water during recovery.

[0094] In the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition of the second embodiment, the radioactive carbon derived from biomass resources is determined based on the concentration of radioactive carbon in circulating carbon in the 1950s, as measured in accordance with ASTM D6866-20. １４ The measured bio-based content, which indicates 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 even more preferably 95% or more and 100% or less. When the measured bio-based content falls within the above range, environmental compatibility is improved from the viewpoint of carbon neutrality.

[0095] At this time, the radioactive carbon in the total carbon atoms of 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition １４ The actual biobased content, which indicates the proportion of radioactive carbon in the sample, is calculated based on the biobased content test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). １４ The C content was measured, and the measurement results and radioactive carbon in the circulating carbon as of 1950 were compared. １４ The concentration of C is calculated from the concentration of C. Although this test standard specifies several analytical methods, analytical method B (AMS method) is preferably used. For analytical method B, an analytical device such as the accelerator mass spectrometer Pelletron AMS manufactured by NEC Corporation is used.

[0096] In the 4-hydroxybenzoic acid composition of the second embodiment, the upper limit of the shikimic acid content is 0.012% by mass or less, preferably 0.008% by mass or less, more preferably 0.006% by mass or less, even more preferably 0.003% by mass or less, and even more preferably 0.001% by mass or less, when the entire 4-hydroxybenzoic acid composition is taken as 100% by mass. By having the shikimic acid content be equal to or less than the upper limit, the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment becomes more favorable. Furthermore, the lower limit of the shikimic acid content is not particularly limited, but is, for example, 0.000% by mass or more. In this case, 0.000% by mass includes cases where the shikimic acid content is below the lower detection limit and cannot be detected by quantification.

[0097] In the 4-hydroxybenzoic acid composition of the second embodiment, the content of the 4-hydroxybenzoic acid (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, even more preferably 97% by mass or more and 100% by mass or less, even more preferably 98% by mass or more and 100% by mass or less, and even more preferably 99% by mass or more and 100% by mass or less, when the entire 4-hydroxybenzoic acid composition is taken as 100% by mass. Having the content of the 4-hydroxybenzoic acid (A) within the above numerical range not only improves environmental compatibility from the standpoint of carbon neutrality, but also makes the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment more favorable. Note that when the content of the 4-hydroxybenzoic acid (A) is 100% by mass, the content of the shikimic acid described above and the contents of the other components described below are 0.000% by mass. This also includes cases where the contents of shikimic acid and other components are below the lower detection limit and cannot be detected by quantification.

[0098] In the 4-hydroxybenzoic acid composition of the second embodiment, the 4-hydroxybenzoic acid (A) preferably contains at least a product of one or two transformants selected from transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849). When the 4-hydroxybenzoic acid (A) contains at least the product, environmental compatibility is improved from the viewpoint of carbon neutrality, and the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment is more favorable.

[0099] In the 4-hydroxybenzoic acid composition of the second embodiment, the polymerizability is more favorable when the 4-hydroxybenzoic acid (A) contains at least the product of one or more transformants selected from the transformant HBA-2 and the transformant HBA-47. This is presumably because the presence of trace amounts of components that may adversely affect the polymerizability is relatively low. Here, the trace amounts of components derived from the transformant are extremely numerous, and the contents of these trace amounts of components are below the detection limit and therefore cannot be analyzed. Therefore, in the 4-hydroxybenzoic acid composition of the second embodiment, the aspect in which the 4-hydroxybenzoic acid (A) contains at least the product of one or more transformants selected from the transformant HBA-2 and the transformant HBA-47 is considered to be almost impractical because it is impossible to directly identify the characteristic features of this aspect based on the structure or properties of the product, and is therefore considered to be "impossible or impractical circumstances."

[0100] (Other Components) The 4-hydroxybenzoic acid composition of the second embodiment may contain other components in addition to the components described above, as long as the balance between environmental compatibility and polymerizability is not impaired. Examples of other components include one or more selected from the group consisting of the following compounds: monosaccharides such as glucose, fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, and xylobiose; and polysaccharides such as dextrin and soluble starch. Sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. Inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, and amino acids, as well as nitrogen-containing organic compounds such as potassium diphosphate, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate.

[0101] In the 4-hydroxybenzoic acid composition of the second embodiment, the content of the other components is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less. By having the content of the other components be equal to or less than the upper limit, the polymerizability of the 4-hydroxybenzoic acid composition of the second embodiment becomes more favorable. The lower limit of the content of the other components is not particularly limited, but is, for example, 0.000% by mass or more. In this case, 0.000% by mass includes cases where the content of the other components is below the lower limit of detection and cannot be detected by quantitative analysis. When the 4-hydroxybenzoic acid composition of the second embodiment contains multiple other components, the total content of the other components may be equal to or less than the upper limit and equal to or greater than the lower limit.

[0102] Examples of methods for quantifying the contents of shikimic acid, 4-hydroxybenzoic acid (A), and other components include 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)), ion chromatography, gas chromatography mass spectrometry (GC / MS), inductively coupled plasma mass spectrometry (ICP-MS), and the like.

[0103] The method for producing the 4-hydroxybenzoic acid composition of the second embodiment will be described later.

[0104] Third Embodiment [4-Hydroxybenzoic Acid Composition] The 4-hydroxybenzoic acid composition of the third embodiment contains a radiocarbon concentration derived from a biomass resource, which is determined based on the radiocarbon concentration in circulating carbon in the 1950s measured in accordance with ASTM D6866-20. １４ The wastewater contains at least 4-hydroxybenzoic acid (A) having a measured bio-content rate, which indicates the proportion of C, of ​​80% or more and 100% or less, and when dissolved in ethanol at a concentration of 20 g / L, the absorbance at a wavelength of 425 nm is 0.015 or less.

[0105] In such a 4-hydroxybenzoic acid composition, the measured bio-based content indicates the amount of plant-derived carbon contained in the 4-hydroxybenzoic acid (A), and the higher this value, the more the 4-hydroxybenzoic acid composition is composed of naturally derived raw materials. Therefore, the higher the measured bio-based content, the better the environmental compatibility from the perspective of carbon neutrality. Furthermore, when the absorbance is 0.015 or less, a 4-hydroxybenzoic acid composition with a more favorable color tone can be obtained even when using plant-derived raw materials.

[0106] Such a 4-hydroxybenzoic acid composition can be produced by the production method described below, particularly by (i) using raw materials derived from specific plants as raw material compounds, (ii) removing impurities by adding an adsorbent to the reaction solution, and (iii) washing with pure water during recovery.

[0107] In the 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition of the third embodiment, the radioactive carbon derived from biomass resources is determined based on the concentration of radioactive carbon in circulating carbon in the 1950s, as measured in accordance with ASTM D6866-20. １４ The measured bio-based content, which indicates 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 even more preferably 95% or more and 100% or less. When the measured bio-based content falls within the above range, environmental compatibility is improved from the viewpoint of carbon neutrality.

[0108] At this time, the radioactive carbon in the total carbon atoms of 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid composition １４ The actual biobased content, which indicates the proportion of radioactive carbon in the sample, is calculated based on the biobased content test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). １４ The C content was measured, and the measurement results and radioactive carbon in the circulating carbon as of 1950 were compared. １４ The concentration of C is calculated from the concentration of C. Although this test standard specifies several analytical methods, analytical method B (AMS method) is preferably used. For analytical method B, an analytical device such as the accelerator mass spectrometer Pelletron AMS manufactured by NEC Corporation is used.

[0109] In the 4-hydroxybenzoic acid composition of the third embodiment, when dissolved in ethanol at a concentration of 20 g / L, the upper limit of the absorbance at a wavelength of 425 nm is 0.015 or less, preferably 0.013 or less, more preferably 0.010 or less, and even more preferably 0.006 or less. Having an absorbance at a wavelength of 425 nm that is equal to or less than the upper limit makes the color tone of the 4-hydroxybenzoic acid composition of the third embodiment more favorable. Furthermore, the lower limit 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. From the viewpoints of environmental compatibility and production efficiency, it is preferably 0.001 or more, and may be 0.003 or more. In this case, an absorbance of 0.000 includes cases where the absorbance at a wavelength of 425 nm is below the lower detection limit and cannot be detected by quantification.

[0110] In the 4-hydroxybenzoic acid composition of the third embodiment, the content of the 4-hydroxybenzoic acid (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, even more preferably 97% by mass or more and 100% by mass or less, even more preferably 98% by mass or more and 100% by mass or less, and even more preferably 99% by mass or more and 100% by mass or less, when the entire 4-hydroxybenzoic acid composition is taken as 100% by mass. Having the content of the 4-hydroxybenzoic acid (A) within the above numerical range not only improves environmental compatibility from the standpoint of carbon neutrality, but also makes the color tone of the 4-hydroxybenzoic acid composition of the third embodiment more suitable. Note that when the content of the 4-hydroxybenzoic acid (A) is 100% by mass, the contents of the other components described below are 0.000% by mass. This also includes cases where the contents of the other components are below the lower detection limit and cannot be detected by quantification.

[0111] In the 4-hydroxybenzoic acid composition of the third embodiment, the 4-hydroxybenzoic acid (A) preferably contains at least a product of one or two transformants selected from transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849). When the 4-hydroxybenzoic acid (A) contains at least the product, environmental compatibility is improved from the viewpoint of carbon neutrality, and the color tone of the 4-hydroxybenzoic acid composition of the third embodiment becomes more favorable.

[0112] In the 4-hydroxybenzoic acid composition of the third embodiment, the 4-hydroxybenzoic acid (A) containing at least the product of one or more transformants selected from transformant HBA-2 and transformant HBA-47 provides a more favorable color tone. This is presumably because the presence of trace amounts of components that may adversely affect the color tone is relatively low. Here, the trace amounts of components derived from the transformants are extremely numerous, and the contents of these trace amounts are below the detection limit and therefore cannot be analyzed. Therefore, in the 4-hydroxybenzoic acid composition of the third embodiment, the 4-hydroxybenzoic acid (A) containing at least the product of one or more transformants selected from transformant HBA-2 and transformant HBA-47 is considered to be "impossible or impractical" because it is impossible to directly identify the characteristic features of this embodiment based on the structure or properties of the product.

[0113] (Other Components) The 4-hydroxybenzoic acid composition of the third embodiment may contain other components in addition to the components described above, as long as the balance between environmental compatibility and color tone is not impaired. Examples of other components include one or more selected from the group consisting of the following compounds: monosaccharides such as glucose, fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, and xylobiose; and polysaccharides such as dextrin and soluble starch. Sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. Inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, potassium nitrate, corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysate, and amino acids, as well as nitrogen-containing organic compounds such as potassium diphosphate, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate.

[0114] In the 4-hydroxybenzoic acid composition of the third embodiment, the content of the other components is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less. When the content of the other components is equal to or less than the upper limit, the color tone of the 4-hydroxybenzoic acid composition of the third embodiment becomes more favorable. The lower limit of the content of the other components is not particularly limited, but is, for example, 0.000% by mass or more. In this case, 0.000% by mass includes cases where the content of the other components is below the lower limit of detection and cannot be detected by quantitative analysis. When the 4-hydroxybenzoic acid composition of the third embodiment contains multiple other components, the total content of the other components may be equal to or less than the upper limit and equal to or greater than the lower limit.

[0115] Examples of methods for quantifying the contents of 4-hydroxybenzoic acid (A) and other components include 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)), ion chromatography, gas chromatography mass spectrometry (GC / MS), inductively coupled plasma mass spectrometry (ICP-MS), and the like.

[0116] [Method for Producing 4-Hydroxybenzoic Acid Composition] Next, the method for producing the 4-hydroxybenzoic acid composition of the second and third embodiments will be described.

[0117] The method for producing a 4-hydroxybenzoic acid composition according to the second and third embodiments preferably comprises the following steps (A) to (C): (A) reacting a transformant with at least one raw material compound selected from the group consisting of saccharides, compounds that can be metabolized by the transformant to produce chorismic acid, or chorismic acid and salts thereof in a reaction solution containing the transformant; (B) removing impurities from the reaction solution; and (C) recovering the 4-hydroxybenzoic acid composition from the reaction solution.

[0118] [(A) Step of Reacting a Transformant with Sugars and at Least One Starting Compound Selected from the Group Consisting of Compounds Metabolized by the Transformant to Produce Chorismic Acid, or Chorismic Acid and Salts Thereof] The method for producing a 4-hydroxybenzoic acid composition of the second and third embodiments first involves a step of reacting a Transformant with Sugars and at Least One Starting Compound Selected from the Group Consisting of Compounds Metabolized by the Transformant to Produce Chorismic Acid, or Chorismic Acid and Salts Thereof in a reaction solution containing the Sugars. The compounds used in this step and the reaction conditions are described in detail below.

[0119] (Transformant) In the methods for producing a 4-hydroxybenzoic acid composition according to the second and third embodiments, any transformant can be used as long as it is capable of producing 4-hydroxybenzoic acid from sugars through metabolism. Examples of such transformants include the coryneform bacterium transformant HBA-2 (accession number: NITE BP-01838) described in Japanese Patent No. 6327653 and the coryneform bacterium transformant HBA-47 (accession number: NITE BP-01849) described in Japanese Patent No. 6327654.

[0120] Prior to the reaction, the transformant is preferably cultured under aerobic conditions. The culture temperature and culture time are not particularly limited as long as the transformant can be cultured and a required amount or more of the transformant can be obtained. The culture temperature is, for example, 25°C or higher and 38°C or lower. The culture time is, for example, 12 hours or higher and 48 hours or lower.

[0121] (Culture Medium) The medium used for aerobic cultivation of the transformant prior to the reaction can be a natural or synthetic medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients. Carbon sources include sugars (monosaccharides such as glucose, fructose, mannose, xylose, arabinose, and galactose; disaccharides such as sucrose, maltose, lactose, cellobiose, xylobiose, and trehalose; polysaccharides such as starch; molasses, etc.), sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. Carbon sources 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 may be, for example, between 0.1% and 20% (w / v).

[0122] Examples of nitrogen sources that can be used include inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate. Nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. Nitrogen sources 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 may be, for example, 0.1 w / v% to 10 w / v%. Examples of inorganic salts include potassium diphosphate, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Inorganic salts 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 may be, for example, 0.01 w / v% to 1 w / v%.

[0123] Examples of nutrients include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloric acid hydrolysate, extracts of animals, plants, or microbial cells, and their decomposition products. The concentration of the nutrients in the medium varies depending on the nutrients used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the medium is preferably 6 to 8.

[0124] Specific preferred media include 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)] and 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)]. These media may be used with the sugar concentration within the above range.

[0125] (Raw Material Compound) The raw material compound is preferably a compound that can be incorporated into cells by the transformant, and more preferably one that is easily utilized industrially, such as one that is abundant in plants. Among the raw material compounds, sugars are preferably those that can produce glucose through the metabolism of the transformant, with glucose being more preferred. Such sugars include oligosaccharides and polysaccharides having glucose units. Examples of the oligosaccharides and polysaccharides include monosaccharides such as fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, and xylobiose; and polysaccharides such as dextrin or soluble starch. Furthermore, the use of glucose is preferred from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid compositions of the second and third embodiments. Furthermore, among the raw material compounds, compounds that can produce chorismic acid through metabolism by the transformant include quinic acid and shikimic acid. Furthermore, for example, plant-derived raw materials can be used as raw materials containing these raw material compounds. Examples of plant-derived raw materials that can be used include molasses, straw (rice straw, barley straw, wheat straw, rye straw, oat straw, etc.), bagasse, corn stover, and other inedible agricultural waste, energy crops (switchgrass, napier grass, miscanthus, etc.), wood chips, waste paper, etc., which are saccharified solutions containing multiple sugars such as glucose, obtained by saccharifying enzymes, etc. Among these, glucose, chorismic acid, quinic acid, and shikimic acid are preferred as raw material compounds, and plant-derived raw materials containing these compounds are preferably used.

[0126] (Reaction Solution) The reaction solution can be a natural or synthetic reaction solution containing a carbon source, a nitrogen source, inorganic salts, etc. The carbon source can be the raw material compounds described above, or molasses or a saccharified solution containing them. In addition to sugars, other carbon sources can also be used: sugar alcohols such as mannitol, sorbitol, xylitol, and glycerin; organic acids such as acetic acid, citric acid, lactic acid, fumaric acid, maleic acid, and gluconic acid; alcohols such as ethanol and propanol; and hydrocarbons such as normal paraffin. A single carbon source can be used alone, or two or more can be mixed. The concentration of the raw material compounds in the reaction solution is preferably 1% w / v to 20% w / v, more preferably 2% w / v to 10% w / v, and even more preferably 2% w / v to 5% w / v. The concentration of the total carbon source, including the raw material compounds, can be 2% w / v to 5% w / v.

[0127] Examples of nitrogen sources that can be used include inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, as well as urea, aqueous ammonia, sodium nitrate, and potassium nitrate. Nitrogen-containing organic compounds such as corn steep liquor, meat extract, peptone, NZ-amine, protein hydrolysates, and amino acids can also be used. The nitrogen sources can be used alone or in combination. The concentration of the nitrogen source in the reaction solution varies depending on the nitrogen compound used, but may be, for example, 0.1 w / v% to 10 w / v%. Examples of inorganic salts include potassium diphosphate, potassium diphosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. The inorganic salts can be used alone or in combination. The concentration of the inorganic salt in the reaction solution varies depending on the inorganic salt used, but may be, for example, 0.01 w / v% to 1 w / v%.

[0128] Examples of nutrients include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, defatted soybean hydrochloric acid hydrolysate, extracts of animals, plants, or microbial cells, and their decomposition products. The concentration of the nutrients in the medium varies depending on the nutrients used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as needed. Examples of vitamins include biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the reaction solution is preferably 6 to 8.

[0129] Specific preferred reaction solutions include the above-mentioned A medium and BT medium, etc. These reaction solutions may be used with the sugar concentration in the above range.

[0130] (Reaction Conditions) From the viewpoint of production efficiency of the 4-hydroxybenzoic acid composition, the reaction temperature, i.e., the survival temperature of the transformant, is preferably 20°C or higher, more preferably 23°C or higher, and even more preferably 25°C or higher. From the same viewpoint, the survival temperature is preferably 50°C or lower, more preferably 48°C or lower, and even more preferably 47°C or lower. From the viewpoint of production efficiency of the 4-hydroxybenzoic acid composition, the reaction time is preferably 7 days or less, more preferably 5 days or less, and even more preferably 3 days or less. The reaction time is not particularly limited as long as the reaction proceeds sufficiently, but is, for example, 1 day or more. The culture may be batch-type, fed-batch-type, or continuous-type. Among these, from the viewpoint of production efficiency of the 4-hydroxybenzoic acid composition, the batch-type is preferred. The reaction may be carried out under aerobic conditions or reducing conditions. The productivity of the 4-hydroxybenzoic acid composition of the transformant itself is higher under aerobic conditions. However, under aerobic conditions, the transformant grows, consuming the raw material compounds for growth and correspondingly reducing the production efficiency of the 4-hydroxybenzoic acid composition. Therefore, it is preferable to carry out the reaction under aerobic conditions in which the transformant does not grow. As used herein, "no growth" includes substantially no growth or almost no growth. For example, the growth of the transformant can be avoided or suppressed by using a reaction solution that is deficient or limited in one or more compounds essential for microbial growth, such as vitamins (e.g., biotin and thiamine) and nitrogen sources.

[0131] Furthermore, under reducing conditions, the transformant does not substantially grow, and therefore the raw material compounds are not consumed for growth, resulting in higher production efficiency of the 4-hydroxybenzoic acid composition. 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. The reduction state of the reaction solution can be easily estimated using a resazurin indicator (which decolorizes from blue to colorless in the reduced state), but can be more accurately measured using an oxidation-reduction potentiometer (e.g., ORP Electrodes, manufactured by Broadley James).

[0132] The reaction mixture under reducing conditions can be prepared by any known method without any limitation. For example, an aqueous solution for the reaction solution may be used as the liquid medium for the reaction solution instead of distilled water, and the method for preparing the aqueous solution for the reaction solution may be, for example, a method for preparing a culture solution for strictly anaerobic microorganisms such as sulfate-reducing microorganisms (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., pp. 926-940, Berlin, Springer Verlag) or "Agricultural Chemistry Experiment Book, Vol. 3, Faculty of Agriculture, Kyoto University." References such as "Agricultural Chemistry Classroom, 26th Edition, 1990, Sangyo Tosho Publishing Co., Ltd." can be used to obtain an aqueous solution under the desired reducing conditions. Specifically, an aqueous solution for a reaction solution under reducing conditions can be obtained by heating or reducing the pressure of distilled water or the like to remove dissolved gases. In this case, by treating distilled water or the like under reduced pressure of preferably 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 3 mmHg or less, for preferably 1 minute to 60 minutes, more preferably 5 minutes to 40 minutes, the dissolved gases, particularly dissolved oxygen, can be removed to prepare an aqueous solution for a reaction solution under reducing conditions.

[0133] Alternatively, an aqueous solution for the reaction under reducing conditions can be prepared by adding a suitable reducing agent (e.g., thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide, etc.) A suitable combination of these methods is also an effective method for preparing an aqueous solution for the reaction under reducing conditions.

[0134] When the reaction is carried out under reducing conditions, it is preferable to maintain the reaction solution under reducing conditions during the reaction. In order to maintain reducing conditions during the reaction, it is desirable to prevent oxygen contamination from outside the reaction system as much as possible. Specifically, a method of sealing the reaction system with an inert gas such as nitrogen gas or carbon dioxide gas can be mentioned. As a method for more effectively preventing oxygen contamination, in order to efficiently function the metabolic functions within the transformants of the second and third embodiments during the reaction, it may be necessary to add a pH maintenance adjusting solution to the reaction system or various nutrient solutions as appropriate. In such cases, it is effective to remove oxygen from the added solution in advance.

[0135] (B) Step of Removing Impurities from the Reaction Solution Next, (B) step of removing impurities from the reaction solution is carried out. By culturing as described above, a 4-hydroxybenzoic acid composition is produced in the reaction solution. The 4-hydroxybenzoic acid composition can be recovered by recovering the reaction solution. However, the reaction solution contains components that affect the polymerizability and color of the 4-hydroxybenzoic acid composition, such as the transformant, unreacted raw material compounds, by-products of the transformant, and components contained in the reaction solution itself. Therefore, removing these components from the reaction solution can further improve the polymerizability and color of the 4-hydroxybenzoic acid composition. Examples of components that affect the polymerizability and color of the 4-hydroxybenzoic acid composition include various intermediate metabolic substances produced by the transformant, substances contained in the aforementioned "other components" and "culture medium," and specific elements. Examples of the intermediate metabolic substances include, but are not limited to, shikimic acid, dehydroshikimic acid, quinic acid, protocatechuic acid, and amino acids. Furthermore, examples of the specific elements include, but are not limited to, nitrogen, phosphorus, potassium, magnesium, sodium, iron, manganese, zinc, and cobalt.

[0136] In the second and third embodiments, impurities can be removed from the reaction solution when preparing the 4-hydroxybenzoic acid composition by both isolating the transformant and adsorbing the chemical components. By performing both of these steps, impurities can be more effectively removed from the 4-hydroxybenzoic acid composition, resulting in improved polymerizability and color tone of the 4-hydroxybenzoic acid composition.

[0137] First, a method for isolating a transformant will be described. A known method can be used to isolate a transformant, such as collection of a supernatant after standing, membrane filtration, or centrifugation. These methods can be used alone or in combination of two or more.

[0138] As the treatment conditions for membrane filtration, treatment can be performed under general filtration conditions. From the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition, the membrane pore size is preferably 0.01 μm or more, more preferably 0.03 μm or more, even more preferably 0.05 μm or more, even more preferably 0.07 μm or more, even more preferably 0.10 μm or more, even more preferably 0.15 μm or more, and even more preferably 0.20 μm or more. From the same viewpoint, it is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. Note that, as a method for measuring the membrane pore size, general measurement methods using mercury porosimetry, bubble point test, bacterial filtration method, etc. can be mentioned, but it is preferable to use the value obtained by the bubble point test. Examples of the material of the membrane used in membrane filtration include a polymer membrane, a ceramic membrane, a stainless steel membrane, etc.

[0139] As the centrifuge used for centrifugation, general machines such as a separation plate type, a cylindrical type, a decanter type, etc. can be used. From the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition, the lower limit of the temperature during centrifugation is preferably 5°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher. From the same viewpoint, the upper limit of the temperature during centrifugation is preferably 70°C or lower, more preferably 60°C or lower, and even more preferably 40°C or lower.

[0140] The relative centrifugal force and time during centrifugation can be set as appropriate, but the lower limit of the relative centrifugal force is preferably 3,000 g or more, more preferably 5,000 g or more, even more preferably 7,000 g or more, even more preferably 10,000 g or more, and even more preferably 15,000 g or more, from the viewpoint of improving the polymerizability and color tone of the 4-hydroxybenzoic acid composition. The upper limit of the relative centrifugal force is preferably 50,000 g or less, more preferably 25,000 g or less, and even more preferably 20,000 g or less, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition. Similarly, the lower limit of the time is preferably 0.2 minutes or more, more preferably 0.5 minutes or more, and even more preferably 1 minute or more, from the viewpoint of improving the polymerizability and color tone of the 4-hydroxybenzoic acid composition. The upper limit of the time is preferably 75 minutes or less, more preferably 60 minutes or less, and even more preferably 30 minutes or less, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition.

[0141] Next, a method for adsorbing chemical components will be described. For example, an adsorption method for chemical components can be performed by adding an adsorbent that is inactive toward 4-hydroxybenzoic acid to the reaction solution after the transformant has been removed by the above-described method. The adsorbent is not particularly limited as long as it is inactive toward 4-hydroxybenzoic acid and can adsorb the unreacted raw material compounds and the components contained in the reaction solution itself. Examples of such adsorbents include inorganic adsorbents such as natural adsorbents (natural zeolite, silver zeolite, acid clay, etc.) and synthetic adsorbents (synthetic zeolite, molecular sieve, bacteria-adsorbing polymer, hydroxyapatite, phosphate rock, titanium silicate, silica gel, silica-alumina gel, porous glass, etc.); activated carbon such as powdered activated carbon, granular activated carbon, fibrous activated carbon, block-shaped activated carbon, extruded activated carbon, molded activated carbon, synthetic granular activated carbon, and synthetic fibrous activated carbon; and organic adsorbents such as molecular adsorption resins, ion-exchange resins, ion-exchange fibers, chelating resins, and chelating fibers. Among these, activated carbon is preferably used from the viewpoint of environmental compatibility.

[0142] In the second embodiment, the amount of adsorbent added is preferably 0.1 g or more, more preferably 0.2 g or more, even more preferably 0.3 g or more, and even more preferably 0.4 g or more, relative to 100 g of the reaction solution, from the viewpoint of further improving the color tone of the 4-hydroxybenzoic acid composition. Furthermore, in the second embodiment, the upper limit of the amount of adsorbent added is not particularly limited, but from the viewpoint of the operational efficiency of the step (C) of recovering the 4-hydroxybenzoic acid composition from the reaction solution, which will be described later, it is preferably 5.0 g or less, more preferably 4.0 g or less, even more preferably 3.0 g or less, even more preferably 2.0 g or less, even more preferably 1.0 g or less, and even more preferably 0.5 g or less, relative to 100 g of the reaction solution.

[0143] In the third embodiment, the amount of adsorbent added is, from the viewpoint of further improving the color tone of the 4-hydroxybenzoic acid composition, preferably 0.3 g or more, more preferably 0.5 g or more, even more preferably 0.8 g or more, even more preferably 1.0 g or more, even more preferably 1.5 g or more, even more preferably 1.8 g or more, and even more preferably 2.0 g or more, relative to 100 g of the reaction solution. Furthermore, in the third embodiment, the upper limit of the amount of adsorbent added is not particularly limited, but from the viewpoint of the operational efficiency of the step (C) of recovering the 4-hydroxybenzoic acid composition from the reaction solution described below, it is preferably 5.0 g or less, more preferably 4.0 g or less, even more preferably 3.0 g or less, even more preferably 2.5 g or less, and even more preferably 2.1 g or less, relative to 100 g of the reaction solution.

[0144] [(C) Step of Recovering the 4-hydroxybenzoic acid Composition from the Reaction Solution] Then, (C) step of recovering the 4-hydroxybenzoic acid composition from the reaction solution is carried out. By removing impurities as described above, a reaction solution containing a 4-hydroxybenzoic acid composition with a relatively high purity can be obtained. Furthermore, the 4-hydroxybenzoic acid composition can also be separated from the reaction solution by a known method. Such known methods include crystallization, membrane separation, organic solvent extraction, and various adsorption methods (using ion exchange resins, synthetic adsorbents, etc.).

[0145] After the 4-hydroxybenzoic acid composition is recovered, a step of washing or purifying the 4-hydroxybenzoic acid composition may be provided, if necessary.

[0146] A known washing method can be used in the step of washing the 4-hydroxybenzoic acid composition. Examples of known washing methods include ultrasonic washing, stirring washing, flow washing, and immersion washing. Among these, stirring washing is preferred. A washing solvent that does not dissolve the 4-hydroxybenzoic acid composition but dissolves only impurities is preferred. A preferred example of such a washing solvent is pure water. Here, pure water refers to water with a conductivity of 1 MΩ cm or more. Water that satisfies the above conductivity is highly pure and contains very little impurities such as chlorine and salts.

[0147] The amount of the washing solvent in the step of washing the 4-hydroxybenzoic acid composition is preferably 7 times or more, more preferably 8 times or more, even more preferably 9 times or more, and even more 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 color tone of the 4-hydroxybenzoic acid composition. Furthermore, the amount of the washing solvent is preferably 50 times or less, more preferably 25 times or less, even more preferably 15 times or less, and even more preferably 12 times or less, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition.

[0148] The number of washings in the step of washing the 4-hydroxybenzoic acid composition is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, from the viewpoint of further improving the polymerizability and color tone of the 4-hydroxybenzoic acid composition. Moreover, the number of washings is preferably 10 or less, more preferably 7 or less, even more preferably 5 or less, and even more preferably 4 or less, from the viewpoint of improving the production efficiency of the 4-hydroxybenzoic acid composition.

[0149] [Uses] The 4-hydroxybenzoic acid compositions of the second and third embodiments can be used in the same applications as 4-hydroxybenzoic acid compositions synthesized by conventional petrochemical processes using fossil resources as raw materials. That is, uses of the 4-hydroxybenzoic acid compositions of the second and third embodiments include polymer raw materials such as polyesters, polyester resins, polyester fibers, liquid crystal polyesters, liquid crystal polyester resins, and liquid crystal polyester fibers; raw materials for synthesizing parabens, which are preservatives; dyes, pigments, adhesive resins, and plasticizers. Among these, use in polymer applications is preferred. That is, the polymers produced using the 4-hydroxybenzoic acid compositions of the second and third embodiments are polymers containing at least the structure of 4-hydroxybenzoic acid (A) derived from the 4-hydroxybenzoic acid composition of the second embodiment or the structure of 4-hydroxybenzoic acid (A) derived from the 4-hydroxybenzoic acid composition of the third embodiment.

[0150] The 4-hydroxybenzoic acid compositions of the second and third embodiments have an improved balance between environmental compatibility and polymerizability or between environmental compatibility and color tone, as described above, and are therefore suitable for use as polymers for biomass plastics (bio-based polymers) that achieve a high degree of compatibility between environmental compatibility and polymerizability or between environmental compatibility and color tone.

[0151] Examples of products using the polymers using the 4-hydroxybenzoic acid compositions in the second and third embodiments include various power cords, electrical devices, various parts, building materials, furniture, fishing tackle such as fishing lines, fishing nets, ropes, liquid crystal polymers, etc.

[0152] The polymers of the second and third embodiments are preferably liquid crystal polymers. The structure of the 4-hydroxybenzoic acid (A) contained in the polymer of the second embodiment and the 4-hydroxybenzoic acid (A) contained in the polymer of the third embodiment has a molecular shape that is elongated and flat, and has a molecular chain with high rigidity along the long chain of the molecule (this high rigidity molecular chain is referred to as a "mesogenic skeleton," for example). The 4-hydroxybenzoic acid compositions of the second and third embodiments have an improved balance between environmental compatibility and polymerizability or a balance between environmental compatibility and color tone, as described above. In other words, the polymers of the second and third embodiments can be suitably used as liquid crystal polymers with an improved balance of environmental compatibility, thermal conductivity, and mechanical strength, which is due to the improved balance between environmental compatibility and polymerizability or the improved balance between environmental compatibility and color tone of the 4-hydroxybenzoic acid composition.

[0153] In addition to the polymers of the second and third embodiments, the liquid crystal polymer may contain additives such as reinforcing agents depending on the required properties, as long as the additives do not significantly impair the properties of downstream products obtained using the liquid crystal polymer. Examples of additives include fibrous reinforcing agents such as glass fiber, silica-alumina fiber, alumina fiber, and carbon fiber; acicular reinforcing agents such as aluminum borate whiskers and potassium titanate whiskers; inorganic fillers such as glass beads, talc, mica, graphite, wollastonite, and dolomite; release modifiers such as fluororesins and metal soaps; colorants such as dyes and pigments; antioxidants; heat stabilizers; UV absorbers; antistatic agents; surfactants; and the like. Two or more of these additives may be used in combination.

[0154] It is also possible to use additives having an external lubricant effect, such as higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, and fluorocarbon surfactants. Furthermore, small amounts of thermoplastic resins other than the polymers of the second and third embodiments (e.g., polyamides, crystalline polyesters, polyphenylene sulfides, polyether ketones, polycarbonates, polyphenylene ethers and their modifications, polysulfones, polyether sulfones, polyether imides, etc.) and thermosetting resins (e.g., phenolic resins, epoxy resins, etc.) may be added. When using such thermoplastic resins or thermosetting resins other than the polymers of the second and third embodiments, it is necessary to select the type and amount added so as not to impair the liquid crystallinity or moldability of the polymers of the second and third embodiments themselves.

[0155] In products using polymers that use the 4-hydroxybenzoic acid compositions of the second and third embodiments, the ratio of the 4-hydroxybenzoic acid compositions of the second and third embodiments to the total 4-hydroxybenzoic acid used as a raw material for a given processed product (product) may be specified for each manufacturer. By specifying the ratio of the 4-hydroxybenzoic acid compositions of the second and third embodiments for each manufacturer, the actual bio-based content of discharged or discarded products can be measured, making it possible to identify manufacturers that are required to recover such products. Furthermore, a manufacturer may specify the ratio of the 4-hydroxybenzoic acid compositions of the second and third embodiments to the total 4-hydroxybenzoic acid for each production lot of its own products, thereby enabling production lots to be traced. While conventional means of providing traceability (e.g., mixing pigments, etc.) may reduce the strength of various products, the 4-hydroxybenzoic acid compositions of the second and third embodiments can achieve desired polymerizability and color, thereby ensuring the strength of various products and making it possible to identify manufacturers.

[0156] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0157] Specifically, in the second and third embodiments, 4-hydroxybenzoic acid is given as an example of a chemical substance produced from a biomass resource as a raw material, but the technical concept of the present disclosure is applicable to various substances produced from a biomass resource as a raw material, including phenol and the like.

[0158] Furthermore, in the second embodiment, an embodiment in which the concentration of shikimic acid contained in 4-hydroxybenzoic acid is specified is given as an example. However, inventions that specify the contents of various intermediate metabolic substances produced by the transformant, substances contained in the aforementioned "other components," "culture medium," etc., and specific elements are also included within the scope of the technical concept of the present disclosure. Examples of the intermediate metabolic substances include, but are not limited to, shikimic acid, dehydroshikimic acid, quinic acid, protocatechuic acid, amino acids, etc. Examples of the specific elements include, but are not limited to, nitrogen, phosphorus, potassium, magnesium, sodium, iron, manganese, zinc, cobalt, etc.

[0159] The embodiments of the present invention will be described in detail based on Examples and Comparative Examples. It should be noted that the present invention is not limited to the Examples. Examples and Comparative Examples related to the first embodiment of the present invention are Examples 1a to 3a and Comparative Examples 1a to 3a, Examples and Comparative Examples related to the second embodiment of the present invention are Examples 1b to 3b and Comparative Examples 1b to 3b, and Examples and Comparative Examples related to the third embodiment of the present invention are Examples 1c to 3c and Comparative Examples 1c to 3c.

[0160] <Examples and Comparative Examples> (Example 1a) Liquid medium A containing 50 μg / ml of kanamycin [(NH ２ ) ２ CO 2g, (NH ４ ) ２ SO ４ 7g, KH ２ P.O.４ ..__.. ２ .. ４ ..|..、|.. ４ ･HH ２ __________________________________________ ４ ･HH ２ ___________________) ４ ・.| ２0 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 dissolved in 1 L of distilled water], and further 2 mass% calcium carbonate was added to a test tube. A platinum loop of the coryneform bacteria transformant HBA-47 (accession number: NITE BP-01849) described in Japanese Patent No. 6327654 was inoculated and cultured aerobically with shaking at 33 ° C. for 24 hours at 200 rpm. Next, HBA-47 was separated from the test solution by vacuum filtration using a 0.22 μm pore size membrane filter (Merck Millipore, Steritop 0.22 μm × 33 mm) to obtain a test solution. Thereafter, the coryneform bacterium transformant PHE21 (accession number: NITE BP-996) prepared by the method described in Example 1a and paragraph

[0135] of Japanese Patent No. 5,932,660 was added to the test solution to a final cell concentration of 10%, to obtain a cell suspension. This cell suspension was placed in a 100 ml medium bottle, and sodium-4-hydroxybenzoate was added as a substrate to a concentration of 250 mM under reducing conditions (oxidation-reduction potential: -450 mV), and the reaction was carried out with stirring in a water bath maintained at 33 ° C. At this time, the reaction was carried out while controlling the pH of the reaction solution using 2.5N aqueous ammonia with a pH controller (manufactured by Able Co., Ltd., model: DT-1023) so that the pH did not fall below 7.0. By centrifuging this reaction solution (4 ° C, 15,000 g, 10 minutes), a solution containing a phenol composition synthesized from glucose was obtained as a supernatant (phenol concentration: 0.8% by mass). This solution was concentrated to a phenol concentration of 4.3% by mass by continuous distillation, and then concentrated to a phenol concentration of 22% by mass by dehydration using pervaporation (60 ° C, 50 Torr) using a DDR-type zeolite membrane. This concentrated solution was allowed to stand at room temperature and separated into two phases: a phenol phase and an aqueous phase, of which the phenol phase was recovered (phenol concentration: 72% by mass). This phenol phase was further removed using an evaporator (60 ° C / 20 hPa) and concentrated to a concentration of 99% by mass.Furthermore, residual water was evaporated using an evaporator (150°C / 20 hPa) to obtain a phenol composition.

[0161] Example 2a A phenol composition was obtained in the same manner as in Example 1a, except that the pervaporation conditions using a DDR-type zeolite membrane were 85° C. and 250 Torr.

[0162] Example 3a The product of Example 1a was stored in a transparent glass bottle at room temperature in the air for six months to obtain a phenol composition.

[0163] Comparative Example 1a A phenol composition was obtained in the same manner as in Example 1a, except that the residual water was not evaporated using an evaporator (150° C., 20 hPa).

[0164] Comparative Example 2a A commercially available phenol product (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0165] (Comparative Example 3a) A phenol-containing waste liquid (phenol concentration: 6.2% by mass) was prepared using the phenol product of Comparative Example 2a, generated when synthesizing a phenolic resin using the method described below (Production of Phenolic Resin). The solution was concentrated to a phenol concentration of 7.0% by mass by continuous distillation, and then concentrated to a phenol concentration of 29% by mass by dehydration using a DDR-type zeolite membrane via pervaporation (60°C, 50 Torr). The concentrated liquid was allowed to stand at room temperature, separated into a phenol phase and an aqueous phase, and the phenol phase was recovered (phenol concentration: 72% by mass). Further, water was removed using an evaporator (60°C, 20 hPa), and the solution was concentrated to a phenol concentration of 99% by mass, thereby obtaining a phenol composition.

[0166] (Production of Phenolic Resin) Phenolic resins were produced using the phenolic compositions produced in Examples 1a to 3a and Comparative Examples 1a to 3a. In a reactor equipped with a stirrer, reflux condenser, and thermometer, 100 parts by mass of the phenolic 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% aqueous formalin solution were reacted at 100°C for 3 hours. The mixture was then heated to 180°C under a vacuum of 40 torr over 90 minutes to distill off water, and unreacted phenolic composition was distilled off while blowing in water vapor at 180°C for 30 minutes. The distilled off water and phenolic composition were treated as waste liquid. Phenolic resins were obtained using the phenolic compositions of Examples 1a to 3a and Comparative Examples 1a to 3a.

[0167] (Evaluation of Physical Properties) 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.

[0168] (Phenol Concentration Analysis) The phenol content in the phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a was determined by gas chromatography according to JIS K2437. The phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a were dissolved in pure water to a concentration of 90% by mass to prepare analytical samples. These analytical samples were analyzed by gas chromatography using a phenol composition (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) dissolved in pure water at a concentration of 90% by mass as a blank. The analytical conditions for gas chromatography are shown in the <Analysis Conditions> below. The results are shown in Table 1. <Analysis Conditions> GC Apparatus: GC-2030 (manufactured by Shimadzu Corporation) Carrier Gas: N ２ Detector: Hydrogen flame ionization (FID) detector, FID temperature: 300°C Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Corporation) Vaporization chamber temperature: 210°C Column flow rate: 0.64 mL / min Column heating conditions: 50°C 5 min hold, heat to 300°C at 20°C / min, hold at 300°C 10 min

[0169] (Measured Bio-based Ratio) For the phenol (A) in the phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a, the radioactive carbon content of the total carbon atoms was measured based on the bio-based content test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). １４ The C content was measured. The measurement results and the radioactive carbon in the circulating carbon as of 1950 were compared. １４ From the concentration of C, the radioactive carbon in the circulating carbon of phenol (A) in the phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a as of 1950 was １４ Radioactive carbon in all carbon atoms when the concentration of C is 100% １４ The concentration of C was calculated as the actual bio-based rate and evaluated as an index of environmental compatibility. The calculation results are shown in Table 1.

[0170] (Absorbance) Measurement samples were prepared by dissolving the phenol compositions of Examples 1a to 3a and Comparative Examples 1a to 3a in pure water to a phenol concentration of 90% by mass. The absorbance of each measurement sample at a wavelength of 425 nm was measured using a UV-visible spectrophotometer (Shimadzu Corporation, UV-2400PC) with pure water as a blank. The results are shown in Table 1.

[0171] (Color Tone) According to the above-mentioned (Production of Phenolic Resin), the phenolic resins prepared using the phenolic compositions of Examples 1a to 3a and Comparative Examples 1a to 3a were heated at 130°C for 10 minutes to prepare molten samples. The color of the molten sample was then quantified based on the iodine color number measured in accordance with DIN 6162 and evaluated according to the following criteria. The evaluation results are shown in Table 1. A (Light Yellow): Iodine color number is 1 or more and less than 6 B (Yellow): Iodine color number is 6 or more and less than 9 C (Yellowish Brown): Iodine color number is 9 or more and less than 44 D (Dark Brown): Iodine color number is 44 or more

[0172]

[0173] As shown in Table 1, when the absorbance of the phenol composition was 0.001 or more and 0.70 or less, the balance between environmental compatibility and the color tone of the obtained phenolic resin was improved.

[0174] (Example 1b) Liquid medium A containing 50 μg / ml kanamycin [(NH ２ ) ２ CO 2g, (NH ４ ) ２ SO ４ 7g, KH ２ P.O. ４ 0.5g, K ２ HPO ４ 0.5g MgSO ４ ・7H ２ O 0.5g, 0.06% (w / v) FeSO ４ ・7H ２ O + 0.042% (w / v) MnSO ４ ・2H ２ 0 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 dissolved in 1 L of distilled water], and further 2 mass% calcium carbonate was added to a test tube. A platinum loop of the coryneform bacteria transformant HBA-47 (accession number: NITE BP-01849) described in Japanese Patent No. 6327654 was inoculated and cultured aerobically with shaking at 33 ° C. for 24 hours at 200 rpm. This resulted in a test solution containing 4-hydroxybenzoic acid synthesized from glucose (4-hydroxybenzoic acid concentration: 7.3% by mass). The test solution was subjected to vacuum filtration using a membrane filter with a pore size of 0.22 μm (Merck Millipore, Steritop 0.22 μm x 33 mm), thereby separating the HBA-47 from the test solution. Next, powdered activated carbon was added to the test solution, and the activated carbon treatment was performed. 0.4 g of powdered activated carbon was used per 100 g of test solution. Next, 25% sulfuric acid was added to the activated carbon-treated test solution to lower the pH from 8 to 3, thereby performing a crystallization operation to precipitate the solute. Next, the precipitated solute was separated by filtration, and the solid precipitate was recovered. Next, the obtained precipitate was washed three times with pure water in an amount 10 times the mass of the precipitate, stirring at 200 rpm using a stirrer, and then dried to obtain a solid 4-hydroxybenzoic acid composition.

[0175] Example 2b A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1b, except that the number of times the obtained precipitate was washed with pure water in an amount 10 times the mass of the precipitate was changed to two times.

[0176] (Example 3b) A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1b, except that the number of times the obtained precipitate was stirred and washed with pure water in an amount 10 times the mass of the precipitate was changed to one time.

[0177] Comparative Example 1b A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1b, except that the washing method for the obtained precipitate was changed to washing once with a five-fold amount of pure water while stirring.

[0178] (Comparative Example 2b) A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1b, except that the washing method for the obtained precipitate was changed as follows. The obtained precipitate was dissolved in 10 times the amount of methanol, and the insoluble matter was removed by filtration. Thereafter, the pressure was gradually reduced to 100 hPa or less at 40°C, and the methanol was evaporated until the liquid component of the methanol disappeared, thereby obtaining a solid 4-hydroxybenzoic acid composition.

[0179] Comparative Example 3b Commercially available 4-hydroxybenzoic acid (Tokyo Chemical Industry Co., Ltd., product code: H0207) was prepared.

[0180] (Evaluation of Physical Properties) The physical properties of the 4-hydroxybenzoic acid compositions obtained in Examples 1b to 3b and Comparative Examples 1b to 3b were evaluated by the following methods.

[0181] (Concentration Analysis) The concentrations of 4-hydroxybenzoic acid and shikimic acid in the 4-hydroxybenzoic acid compositions of Examples 1b to 3b and Comparative Examples 1b to 3b were quantified by high performance liquid chromatography using a high performance liquid chromatograph equipped with a UV detector (Chromaster (registered trademark), manufactured by Hitachi High-Tech Science Corporation) under the following analytical conditions. The results are shown in Table 2. <Analysis Conditions> Column: COSMOSIL 5C18-AR-II (φ4.6 mm × 250 mm) manufactured by Nacalai Tesque, Inc. Mobile phase: water / methanol / perchloric acid = 4 / 1 / 0.0075 (vol / vol / vol) isocratic elution Flow rate: 1 mL / mmin Column temperature: 40°C Detection method: photodiode array (PDA) detector (210 nm)

[0182] (Measured Bio-based Ratio) For 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1b to 3b and Comparative Examples 1b to 3b, the radioactive carbon content of the total carbon atoms was measured based on the bio-based concentration test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). １４ The C content was measured. The measurement results and the radioactive carbon in the circulating carbon as of 1950 were compared. １４ From the concentration of C, the radioactive carbon in the circulating carbon of 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1b to 3b and Comparative Examples 1b to 3b was calculated. １４ Radioactive carbon in all carbon atoms when the concentration of C is 100% １４ The concentration of C was calculated as the actual bio-based rate and evaluated as an index of environmental compatibility. The calculation results are shown in Table 2.

[0183] (Polymerization) A 1 L polymerization vessel equipped with a distillation apparatus, a stirrer, and a nitrogen inlet tube was charged with 241.7 g (4-hydroxybenzoic acid content: 1.75 mol) of the 4-hydroxybenzoic acid composition of Examples 1b to 3b and Comparative Examples 1b to 3b, 93.1 g (0.5 mol) of biphenol (manufactured by Tokyo Chemical Industry Co., Ltd., product code: B0464), 83.0 g (0.5 mol) of terephthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd., product code: T0166), and 326.4 g (3.2 mol) of acetic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., product code: A2036). After an acetoxylation reaction at 150°C for 3 hours, the temperature was increased to 240°C and then to 300°C for 6 hours, and polymerization was continued until the contents solidified. The extracted polymer (prepolymer) was finely pulverized and then solid-phase polymerized in nitrogen at 300°C. Polycondensation was completed when a predetermined stirring torque was reached, yielding a liquid crystal polymer. The obtained liquid crystal polymer was injection molded under conditions of a resin temperature of 340°C, a mold temperature of 150°C, and an injection pressure of 110 MPa to prepare a bending test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm. The bending strength of the prepared bending test piece was measured in accordance with ASTM D790. The polymerizability was evaluated based on the obtained bending strength as follows. The results are shown in Table 2. A: Bending strength of 100 MPa or more B: Bending strength of 90 MPa or more but less than 100 MPa C: Bending strength of less than 90 MPa

[0184]

[0185] As shown in Table 2, by adjusting the concentration of shikimic acid contained in the 4-hydroxybenzoic acid composition to a predetermined level or less, the balance between environmental compatibility and polymerizability was improved.

[0186] (Example 1c) Liquid medium A containing 50 μg / ml kanamycin [(NH ２ ) ２ CO 2g, (NH ４ ) ２ SO ４ 7g, KH ２ P.O. ４ 0.5g, K ２ HPO ４ 0.5g MgSO ４ ・7H ２ O 0.5g, 0.06% (w / v) FeSO ４・7H ２ O + 0.042% (w / v) MnSO ４ ・2H ２ 0 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 dissolved in 1 L of distilled water], and further 2 mass% calcium carbonate was added to a test tube. A platinum loop of the coryneform bacteria transformant HBA-47 (accession number: NITE BP-01849) described in Japanese Patent No. 6327654 was inoculated and cultured aerobically with shaking at 33 ° C. for 24 hours at 200 rpm. This resulted in a test solution containing 4-hydroxybenzoic acid synthesized from glucose (4-hydroxybenzoic acid concentration: 7.3% by mass). The test solution was subjected to vacuum filtration using a membrane filter with a pore size of 0.22 μm (Merck Millipore, Steritop 0.22 μm x 33 mm), thereby separating the HBA-47 from the test solution. Next, powdered activated carbon was added to the test solution, and the activated carbon treatment was performed. 2.0 g of powdered activated carbon was used per 100 g of test solution. Next, 25% sulfuric acid was added to the activated carbon-treated test solution to lower the pH from 8 to 3, thereby performing a crystallization operation to precipitate the solute. Next, the precipitated solute was separated by filtration, and the solid precipitate was recovered. Next, the obtained precipitate was washed three times with pure water in an amount 10 times the mass of the precipitate, stirring at 200 rpm using a stirrer, and then dried to obtain a solid 4-hydroxybenzoic acid composition.

[0187] Example 2c A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1c, except that the amount of powdered activated carbon added to the test solution was changed to 1.0 g.

[0188] Example 3c A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1c, except that the amount of powdered activated carbon added to the test solution was changed to 0.4 g.

[0189] Comparative Example 1c A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1c, except that the amount of powdered activated carbon added to the test liquid was changed to 0.2 g.

[0190] Comparative Example 2c A solid 4-hydroxybenzoic acid composition was obtained in the same manner as in Example 1c, except that the amount of powdered activated carbon added to the test solution was changed to 0.4 g and the number of times the obtained precipitate was stirred and washed with pure water in an amount 10 times the mass of the precipitate was changed to two times.

[0191] Comparative Example 3c Commercially available 4-hydroxybenzoic acid (Tokyo Chemical Industry Co., Ltd., product code: H0207) was prepared.

[0192] (Evaluation of Physical Properties) The physical properties of the 4-hydroxybenzoic acid compositions obtained in Examples 1c to 3c and Comparative Examples 1c to 3c were evaluated by the following methods.

[0193] (Concentration Analysis) The quantification of 4-hydroxybenzoic acid in the 4-hydroxybenzoic acid compositions of Examples 1c to 3c and Comparative Examples 1c to 3c was carried out by high performance liquid chromatography under the following analytical conditions using a high performance liquid chromatograph equipped with the UV detector (Chromaster (registered trademark), manufactured by Hitachi High-Tech Science Corporation). The results are shown in Table 3. <Analysis Conditions> Column: COSMOSIL 5C18-AR-II (φ4.6 mm × 250 mm) manufactured by Nacalai Tesque, Inc. Mobile phase: water / methanol / perchloric acid = 4 / 1 / 0.0075 (vol / vol / vol) isocratic elution Flow rate: 1 mL / mmin Column temperature: 40°C Detection method: photodiode array (PDA) detector (210 nm)

[0194] (Measured Bio-based Ratio) The 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1c to 3c and Comparative Examples 1c to 3c was measured for radioactive carbon in total carbon atoms based on the bio-based concentration test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). １４ The C content was measured. The measurement results and the radioactive carbon in the circulating carbon as of 1950 were compared. １４From the concentration of C, the radioactive carbon in the circulating carbon of 4-hydroxybenzoic acid (A) in the 4-hydroxybenzoic acid compositions of Examples 1c to 3c and Comparative Examples 1c to 3c as of 1950 was １４ Radioactive carbon in all carbon atoms when the concentration of C is 100% １４ The concentration of C was calculated as the actual bio-based rate and evaluated as an index of environmental compatibility. The calculation results are shown in Table 3.

[0195] (Absorbance) Each of the 4-hydroxybenzoic acid compositions of Examples 1c to 3c and Comparative Examples 1c to 3c was 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-visible spectrophotometer (Shimadzu Corporation, UV-2400PC) with pure water as a blank. The results are shown in Table 3.

[0196] (Color Tone) 241.7 g (4-hydroxybenzoic acid content: 1.75 mol) of the 4-hydroxybenzoic acid compositions of Examples 1c to 3c and Comparative Examples 1c to 3c was charged into a 1 L reactor equipped with a stirrer and a nitrogen inlet tube. 1 L of nitrogen was introduced into this reactor, and then the temperature was raised to 240°C and heated under a nitrogen atmosphere for 6 hours. After heating, the 4-hydroxybenzoic acid composition in the reactor was dissolved in ethanol to a concentration of 20 mass%, and the color of the solution was quantified based on the iodine color number measured in accordance with DIN 6162 and evaluated according to the following criteria. The evaluation results are shown in Table 3. A: Iodine color number is 1 or more and 10 or less B: Iodine color number is more than 10 and 20 or less C: Iodine color number is more than 20

[0197]

[0198] As shown in Table 3, by reducing the absorbance of the 4-hydroxybenzoic acid composition to 0.015 or less, the balance between environmental compatibility and color tone was improved.

[0199] Corynebacterium glutamicum PHE7 was deposited at the Patent Microorganisms Depositary, National Institute of Technology and Evaluation, 2-5-8 Kazusa Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (domestic deposit date: August 31, 2010, international deposit date under the Budapest Treaty: August 12, 2011, accession number: NITE BP-976).

[0200] Corynebacterium glutamicum PHE18 was deposited at the Patent Microorganisms Depositary, National Institute of Technology and Evaluation, 2-5-8 Kazusa Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (domestic deposit date: October 21, 2010, international deposit date under the Budapest Treaty: September 28, 2011, accession number: NITE BP-995).

[0201] Corynebacterium glutamicum PHE21 was deposited at the Patent Microorganisms Depositary, National Institute of Technology and Evaluation, 2-5-8 Kazusa Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (domestic deposit date: October 21, 2010, international deposit date under the Budapest Treaty: September 28, 2011, accession number: NITE BP-996).

[0202] Corynebacterium glutamicum PHE31 was deposited at the Patent Microorganisms Depositary, National Institute of Technology and Evaluation, 2-5-8 Kazusa Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (domestic deposit date: November 2, 2010, international deposit date under the Budapest Treaty: September 28, 2011, accession number: NITE BP-999).

[0203] Corynebacterium glutamicum HBA-2 was deposited at the Patent Microorganisms Depositary, National Institute of Technology and Evaluation, 2-5-8 Kazusa Kamatari, Kisarazu City, Chiba Prefecture, Japan (postal code 292-0818) (domestic deposit date: March 27, 2014, international deposit date under the Budapest Treaty: February 23, 2015, accession number: NITE BP-01838).

[0204] Corynebacterium glutamicum HBA-47 was deposited with the Patent Microorganisms Depositary, National Institute of Technology and Evaluation, 2-5-8 Kazusa Kamatari, Kisarazu City, Chiba Prefecture, Japan (Postal Code: 292-0818) (Date of international deposit under the Budapest Treaty: April 25, 2014, Accession Number: NITE BP-01849). These strains have been internationally deposited under the Budapest Treaty and are publicly available under the conditions set forth in 37 CFR 1.808.

[0205] This application claims priority based on Japanese Patent Application Nos. 2023-096317, 2023-096338, and 2023-096350, filed on June 12, 2023, the disclosures of which are incorporated herein in their entireties.

[0206] [Rule 26 amendment 04.07.2024]

Claims

1. Radiocarbon derived from biomass resources, determined based on the concentration of radiocarbon in circulating carbon in the 1950s, measured according to ASTM D6866-20. １４ an aromatic compound composition comprising at least an aromatic compound (A) having a measured bio-based content rate, which indicates a ratio of C, of ​​80% or more and 100% or less, wherein the aromatic compound (A) is phenol (A) or 4-hydroxybenzoic acid (A); when the aromatic compound (A) is phenol (A), the aromatic compound composition has an absorbance of 0.001 or more and 0.70 or less at a wavelength of 425 nm when dissolved in pure water to a concentration of 90 mass%, and 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 dissolved in ethanol to a concentration of 20 g / L, or the content of shikimic acid in the aromatic compound composition is 0.012 mass% or less when the entire aromatic compound composition is taken as 100 mass%.

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

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

5. The aromatic compound composition according to any one of claims 2 to 4, wherein the absorbance is 0.62 or less.

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

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

8. A polymer comprising at least a structural unit derived from the phenol (A) in the aromatic compound composition according to any one of claims 2 to 7.

9. The polymer of claim 8 which is a phenolic resin.

10. The aromatic compound composition according to claim 1, wherein the aromatic compound (A) is 4-hydroxybenzoic acid (A), and the content of shikimic acid in the aromatic compound composition is 0.012 mass% or less when the entire aromatic compound composition is taken as 100 mass%.

11. The aromatic compound composition according to claim 10, wherein the content of the shikimic acid is 0.008% by mass or less when the entire aromatic compound composition is taken as 100% by mass.

12. The aromatic compound composition according to claim 1, wherein the aromatic compound (A) is 4-hydroxybenzoic acid (A), and the aromatic compound composition has an absorbance of 0.015 or less at a wavelength of 425 nm when dissolved in ethanol at a concentration of 20 g / L.

13. The aromatic compound composition according to claim 12, wherein the absorbance is 0.010 or less.

14. The aromatic compound composition according to claim 12 or 13, wherein the absorbance is 0.001 or more.

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

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

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

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

19. The polymer of claim 18 which is a liquid crystal polymer.

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