Phenol composition and polymer

Abstract

To provide a phenol composition with enhanced balance between environmental compatibility and the color tone of the resulting polymer.SOLUTION: A phenol composition includes at least a phenol (A) having an actually measured bioavailability of 80% to 100% inclusive, where the actually measured bioavailability is measured in accordance with ASTM D6866-20 and indicates the content ratio of radioactive carbon 14C derived from biomass resources with respect to the concentration of radioactive carbon in circulating carbon in the 1950s. The phenol composition exhibits an absorbance of 0.001 to 0.70 inclusive at a wavelength of 425 nm when dissolved in pure water at a concentration of 90 mass%.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to phenolic compositions and polymers. [Background technology]

[0002] In light of the problems of global warming and the depletion of fossil fuel resources, the production of chemical products using renewable biomass resources as raw materials has attracted attention as a new industry aimed at realizing a low-carbon society. One example of such a chemical product 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. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2017-119765 A Summary of the Invention [Problem to be solved by the invention]

[0005] According to the studies of the present inventors, it has become clear that there is room for improvement in the biomass-derived phenol composition in terms of the color tone of a polymer synthesized using the phenol composition.

[0006] The present invention has been made in view of the above circumstances, and provides a phenolic composition having improved environmental compatibility and improved balance of the color tone of the resulting polymer. [Means for solving the problem]

[0007] 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 present invention.

[0008] [1] Radiocarbon from biomass resources determined based on the concentration of radiocarbon in circulating carbon in the 1950s, measured according to ASTM D6866-20 14 It contains at least phenol (A) with a measured bio-based content rate of 80% or more and 100% or less, which indicates the proportion of C, A phenol composition having 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 %. [2] In the phenol composition described in [1] above, A phenol composition having a content of the phenol (A) of 95% by mass or more and 100% by mass or less. [3] In the phenol composition according to the above [1] or [2], A phenol composition, in which the measured bio-content rate of the phenol (A) is 95% or more and 100% or less. [4] In the phenol composition according to any one of the above [1] to [3], A phenol composition having an absorbance of 0.62 or less. [5] In the phenol composition according to any one of the above [1] to [4], The above phenol (A) is Transformant HBA-2 (Accession No.: NITE BP-01838) and A phenol composition comprising at least a structure derived from a benzene ring of a product of one or more transformants selected from transformant HBA-47 (accession number: NITE BP-01849). [6] In the phenol composition according to any one of the above [1] to [5], The above phenol (A) is Transformant PHE7 (Accession No.: NITE BP-976), Transformant PHE18 (Accession No.: NITE BP-995), Transformant PHE21 (Accession No.: NITE BP-996) and A phenolic composition comprising at least a product of one or more transformants selected from transformant PHE31 (accession number: NITE BP-999). [7] A polymer comprising at least a structural unit derived from the phenol (A) in the phenol composition according to any one of the above [1] to [6]. [8] The polymer according to the above [7], which is a phenolic resin. Effect of the Invention

[0009] According to the present invention, a phenolic composition having improved environmental compatibility and a good balance of the color tone of the resulting polymer can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present invention will be described in detail. In the description of this embodiment, "pure water" refers to water having a conductivity of 1 MΩ·cm or more.

[0011] [Phenol composition] The phenol 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 based on ASTM D6866-20. 14 It contains at least phenol (A) with 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.

[0012] In such a phenol composition, the measured bio-content ratio indicates the amount of plant-derived carbon contained in the phenol (A), and the larger this value, the more the phenol composition is composed of naturally derived raw materials. Therefore, the larger the measured bio-content ratio, the better the environmental compatibility from the viewpoint of carbon neutrality. In addition, when the absorbance is 0.001 or more and 0.70 or less, a phenol composition can be obtained in which the color tone of the polymer obtained by using the phenol composition is more favorable, even when raw materials derived from plants are used.

[0013] Such a phenolic composition can be produced by the production method described below, in particular 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.

[0014] In the phenol composition of the present 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 based on ASTM D6866-20. 14 The measured bio-based content rate, 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. If the measured bio-based content rate is within the above range, environmental compatibility will be better from the perspective of carbon neutrality.

[0015] At this time, the radioactive carbon in the total carbon atoms of phenol (A) in the phenol composition 14 The actual biobased ratio, which indicates the proportion of C, is calculated based on the biobased concentration test standard ASTM D6866-20 established by the American Society for Testing and Materials (ASTM). 14 The C content was measured, and the results were compared with the radioactive carbon in the circulating carbon as of 1950. 14The concentration of C is calculated from the concentration of C. In addition, this test standard specifies several analytical methods, among which analytical method B (AMS method) is preferably used. For analytical method B, an analytical device such as an accelerator mass spectrometer Pelletron AMS manufactured by NEC Corporation is used.

[0016] In the phenol composition of this embodiment, when dissolved in pure water to a concentration of 90 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. By having the absorbance at a wavelength of 425 nm be equal to or less than the upper limit, the color tone of the polymer obtained by using the phenol composition of this embodiment becomes more suitable. In addition, the lower limit of the absorbance at a wavelength of 425 nm is not particularly limited, but is, for example, 0.001 or more, and from the viewpoint of production efficiency, is preferably 0.005 or more, more preferably 0.01 or more, 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.

[0017] In the phenol composition of this 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. By having the content of the phenol (A) within the above numerical range, environmental compatibility is improved from the viewpoint of carbon neutrality, and the color tone of the polymer obtained by using the phenol composition of this embodiment becomes more suitable. When the content of the phenol (A) is 100% by mass, the content of the other components described below is 0.000% by mass, including the case where the content of the other components is below the detection limit and cannot be detected by quantitative analysis.

[0018] In the phenol composition of this embodiment, the phenol (A) preferably contains at least a structure derived from a benzene ring of one or more transformant products selected from transformant HBA-2 (accession number: NITE BP-01838) and transformant HBA-47 (accession number: NITE BP-01849). By containing at least the above product in the phenol (A), environmental compatibility is improved from the viewpoint of carbon neutrality, and the color tone of the polymer obtained by using the phenol composition of this embodiment becomes more suitable.

[0019] In the phenol composition of this embodiment, the phenol (A) preferably contains at least one or more transformant products 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). By containing at least the above product in the phenol (A), environmental compatibility is improved from the viewpoint of carbon neutrality, and the color tone of the polymer obtained using the phenol composition of this embodiment becomes more suitable.

[0020] In the phenol composition of this embodiment, the phenol (A) contains at least a structure derived from a benzene ring of the product of one or more transformants selected from transformant HBA-2 and transformant HBA-47, or the phenol (A) contains at least the product of one or more transformants selected from transformant PHE7, transformant PHE18, transformant PHE21 and transformant PHE31, and it is presumed that this is because the presence of extremely small amounts of components that may have an adverse effect on the color tone is kept relatively low. Here, the amount of extremely small components derived from the transformant is extremely large, and the content of the extremely small components is below the detection limit and cannot be analyzed. Therefore, in the phenol composition of this embodiment, in the embodiment in which phenol (A) contains at least a structure derived from a benzene ring of one or more transformant products selected from transformant HBA-2 and transformant HBA-47, or in the embodiment in which phenol (A) contains at least a product of one or more transformants selected from transformant PHE7, transformant PHE18, transformant PHE21, and transformant PHE31, it is impossible to directly specify the characteristic portion of this embodiment by the structure or properties of the product, and it is almost impractical, and it is considered that so-called "impossible / impractical circumstances" exist.

[0021] (Other Ingredients) The phenol composition of the present embodiment may contain components other than those described above, so long as the balance between environmental compatibility and the color tone of the resulting polymer is not adversely affected. The other components include one or more compounds selected from the group consisting of the following compounds: Monosaccharides such as fructose, mannose, arabinose, xylose, galactose, etc.; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, cellobiose, xylobiose, etc.; saccharides such as dextrin or soluble starch, 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. 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. Examples of such salts include monopotassium phosphate, dipotassium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, and calcium carbonate. Solvent such as pure water.

[0022] In the phenol composition of the present 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 color tone of the polymer obtained by using the phenol composition of the present embodiment becomes more suitable. 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 the case where the content of the other components is below the lower detection limit and cannot be detected by quantitative analysis. In addition, in the case where the phenol composition of the present embodiment contains a plurality of the other components described above, the total content of the other components described above may be equal to or less than the upper limit value and equal to or more than the lower limit value.

[0023] Methods for quantifying the content of such phenol (A) and other components include, for example, 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.

[0024] [Method of producing phenol composition] Next, a method for producing the phenol composition of the present embodiment will be described.

[0025] The method for producing the phenol composition of the present embodiment preferably includes the following steps (A) to (D). (A) A step of reacting a first transformant with at least one raw material compound selected from the group consisting of sugars, compounds which the transformant can metabolize to produce chorismic acid, or chorismic acid and salts thereof, in a reaction intermediate solution containing the raw material compound, to produce a precursor. (B) A step of producing a phenolic composition from the precursor by the second transformant to obtain a reaction solution containing the phenolic composition. (C) A step of removing the transformants from the reaction solution. (D) A process for separating and concentrating the phenolic composition in the reaction solution.

[0026] [(A) reacting a first transformant with at least one raw material compound selected from the group consisting of saccharides, compounds which the transformant can metabolize to produce chorismic acid, or chorismic acid and salts thereof in a reaction intermediate solution to produce a precursor] The method for producing the phenol composition of this embodiment first involves (A) reacting a first transformant with at least one raw material compound selected from the group consisting of sugars, compounds that the transformant can metabolize to produce chorismic acid, or chorismic acid and salts thereof, in a reaction intermediate solution to produce a precursor. Each compound used in this step and the reaction conditions are described in detail below.

[0027] (First transformant) In the method for producing a phenolic composition of the present embodiment, any transformant can be used as the first transformant as long as it can generate a precursor from sugars through metabolism. Examples of the precursor include 4-hydroxybenzoic acid. Examples of such transformants include the coryneform bacteria transformant HBA-2 (Accession Number: NITE BP-01838) described in Japanese Patent No. 6327653 and the coryneform bacteria transformant HBA-47 (Accession Number: NITE BP-01849) described in Japanese Patent No. 6327654.

[0028] Prior to the reaction, it is preferable to culture the first transformant 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.

[0029] (Culture medium) The medium used for aerobic cultivation of the first transformant prior to the reaction may be a natural medium or a synthetic medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients. As carbon sources, 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 can also be used. The carbon source may be used alone or in combination of two or more. The concentration of the carbon source in the medium may vary depending on the compound used, but may be, for example, 0.1 w / v% to 20 w / v%.

[0030] As the nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, and potassium nitrate can be used. In addition, 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 source can be used alone or in combination of two or more. The concentration of the nitrogen source in the medium varies depending on the nitrogen compound used, but may be, for example, 0.1 w / v% to 10 w / v%. Examples of inorganic salts include potassium dihydrogen phosphate, potassium dihydrogen phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, etc. The inorganic salts can be used alone or in combination of two or more. The concentration of the inorganic salts in the medium varies depending on the inorganic salts used, but may be, for example, 0.01 w / v% to 1 w / v%.

[0031] Examples of the nutritional substances include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, hydrolyzed skim soybeans with hydrochloric acid, extracts of animals, plants or microbial cells, and decomposition products thereof, etc. The concentration of the nutritional substance in the medium varies depending on the nutritional substance used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as necessary, such as biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the medium is preferably 6 or more and 8 or less.

[0032] 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)], BT medium [Omumasaba, CA et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8:91-103 (2004)], etc. In these media, the sugar concentration may be set within the above range.

[0033] (Raw material compound) The raw material compound is preferably a compound that can be incorporated into cells of the first transformant, and more preferably one that is easily utilized industrially, such as one that is abundant in plants. Among the above raw material compounds, the saccharides are preferably saccharides capable of producing glucose by the metabolism of the first transformant, and more preferably glucose. Such saccharides include oligosaccharides and polysaccharides having glucose units. The above oligosaccharides and polysaccharides include monosaccharides such as fructose, mannose, arabinose, xylose, and galactose; disaccharides such as cellobiose, sucrose, lactose, maltose, trehalose, cellobiose, and xylobiose; and polysaccharides such as dextrin or soluble starch. In addition, the use of glucose is preferable from the viewpoint of improving the production efficiency of the precursor and improving the production efficiency of the phenol composition of the present embodiment. Among the above-mentioned raw material compounds, examples of compounds that can be metabolized by the first transformant to produce chorismic acid include quinic acid and shikimic acid. Furthermore, for example, raw materials derived from plants can be used as raw materials containing these raw material compounds. Examples of raw materials derived from plants include molasses, inedible agricultural waste such as straw (rice straw, barley straw, wheat straw, rye straw, oat straw, etc.), bagasse, corn stover, etc., energy crops such as switchgrass, napier grass, and miscanthus, wood chips, waste paper, etc., which are saccharified with saccharifying enzymes and the like to produce saccharified liquids containing multiple sugars such as glucose. Among these, glucose, chorismic acid, quinic acid, and shikimic acid are preferred as raw material compounds, and it is preferable to use raw materials of plant origin as raw materials containing these.

[0034] (Reaction intermediate liquid) As the reaction intermediate liquid, a natural reaction liquid or a synthetic reaction liquid containing a carbon source, a nitrogen source, inorganic salts, etc. can be used. The carbon source may be the above-described raw material compound or molasses or saccharified liquid containing the raw material compound. In addition to sugars, other carbon sources that may be used include 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. The carbon source can be used alone or in combination of two or more. The concentration of the raw material compound in the reaction intermediate is preferably 1 w / v% or more and 20 w / v% or less, more preferably 2 w / v% or more and 10 w / v% or less, and even more preferably 2 w / v% or more and 5 w / v% or less. The concentration of the total carbon source including the raw material compounds may be 2 w / v % or more and 5 w / v % or less.

[0035] As the nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, and potassium nitrate can be used. 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 source can be used alone or in combination of two or more. 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 dihydrogen phosphate, potassium dihydrogen phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, etc. The inorganic salts can be used alone or in combination of two or more. The concentration of the inorganic salts 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%.

[0036] Examples of the nutritional substances include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, hydrolyzate of skim soybeans with hydrochloric acid, extracts of animals, plants or microbial cells, and decomposition products thereof, etc. The concentration of the nutritional substance in the reaction intermediate solution varies depending on the nutritional substance used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as necessary, such as biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the reaction intermediate is preferably 6 or more and 8 or less.

[0037] Specific preferred reaction intermediate solutions include the above-mentioned A medium and BT medium, etc. In these reaction intermediate solutions, the sugar concentration may be set within the above range.

[0038] (Reaction conditions) From the viewpoint of the production efficiency of the phenol 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 production efficiency of the phenol 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 any of a batch system, a fed-batch system, and a continuous system, among which the batch system is preferred from the viewpoint of production efficiency of the phenol composition. The reaction may be carried out under aerobic conditions or reducing conditions. The productivity of the first transformant itself for the phenol composition is higher under aerobic conditions. However, since the first transformant grows under aerobic conditions, the raw material compound is consumed for the growth, and the production efficiency of the phenol composition is accordingly reduced. Therefore, it is preferable to carry out the reaction under aerobic conditions in which the first transformant does not grow. In this specification, "not growing" includes substantially no growth or almost no growth. For example, the growth of the first transformant can be avoided or suppressed by using a reaction solution that is deficient or limited in one or more of compounds essential for the growth of microorganisms, such as vitamins such as biotin and thiamine, and nitrogen sources.

[0039] In addition, under reducing conditions, the first transformant does not substantially grow, and therefore the raw material compound is not consumed for growth, improving the production efficiency of the precursor, and as a result, improving the production efficiency of the phenol composition. The reduction conditions are determined by the redox potential of the reaction intermediate solution, which is preferably from -500 mV to -200 mV, more preferably from -500 mV to -150 mV. The reduction state of the reaction intermediate can be easily estimated using a resazurin indicator (when in a reduced state, it decolorizes from blue to colorless), but can be measured more accurately using an oxidation-reduction potentiometer (for example, ORP Electrodes, manufactured by BROADLEY JAMES).

[0040] The reaction intermediate under reducing conditions can be prepared by any known method without any restrictions. For example, an aqueous solution for the reaction intermediate can be used instead of distilled water as the liquid medium for the reaction intermediate, and the aqueous solution for the reaction intermediate can be prepared by referring to, for example, a method for preparing a culture medium for obligate anaerobic microorganisms such as sulfate-reducing microorganisms (Pfennig, N. et al., (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, MP et al., p926-940, Berlin, Springer Verlag.) or "Agricultural Chemistry Experiment Book, Vol. 3, Kyoto University Faculty of Agriculture, Agricultural Chemistry Class, 26th edition, 1990, Sangyo Tosho Publishing Co., Ltd.", and the like. The aqueous solution under the desired reducing conditions can be obtained. Specifically, an aqueous solution for a reaction intermediate under reducing conditions can be obtained by removing dissolved gases by heating or reducing the pressure of distilled water, etc. In this case, the aqueous solution for a reaction intermediate under reducing conditions can be prepared by treating the distilled water, etc. 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 or more and 60 minutes or less, and more preferably 5 minutes or more and 40 minutes or less, with the dissolved gases, particularly dissolved oxygen, being removed.

[0041] Furthermore, an appropriate reducing agent (eg, thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide, etc.) can be added to prepare an aqueous solution for the reaction intermediate under reducing conditions. An appropriate combination of these methods is also an effective method for preparing an aqueous solution for the reaction intermediate under reducing conditions.

[0042] When the reaction is carried out under reducing conditions, it is preferable to maintain the reaction intermediate solution under reducing conditions during the reaction. In order to maintain the reducing conditions during the reaction, it is desirable to prevent the inclusion of oxygen from outside the reaction system as much as possible. Specifically, the reaction system may be sealed with an inert gas such as nitrogen gas or carbon dioxide gas. As a method for more effectively preventing oxygen inclusion, in order to efficiently function the metabolic function in the first transformant of this embodiment during the reaction, it may be necessary to add a pH maintenance adjustment solution to the reaction system or various nutrient dissolving solutions appropriately. In such cases, it is effective to remove oxygen from the added solution in advance.

[0043] [(A)' Step of Removing the First Transformant from the Precursor] Furthermore, in the method for producing a phenolic composition of this embodiment, from the viewpoint of the yield of the phenolic composition, after the step of reacting (A) a first transformant with at least one raw material compound selected from the group consisting of sugars, compounds which the transformant can metabolize 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 a phenolic composition from the precursor using the second transformant described below (B) to obtain a reaction solution containing the phenolic composition, a step of removing the first transformant from the precursor (A)' may be included. In the step (A)' of removing the first transformant from the precursor, a method for recovering the reaction solution exemplified in the step (C) of removing the transformant in the reaction solution described below can be used. By applying the method for recovering the reaction solution to the precursor, the first transformant can be removed from the precursor and the precursor can be recovered.

[0044] [(B) Producing a phenol composition from a precursor by the second transformant and obtaining a reaction solution containing the phenol composition] Next, (B) a step of producing a phenol composition from the 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, the phenol composition can be produced from the precursor, and a reaction liquid containing the phenol composition can be obtained. Each compound used in this step and the reaction conditions are described in detail below.

[0045] (Second transformant) In the method for producing a phenolic composition of the present 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 the precursor include 4-hydroxybenzoic acid. Examples of such transformants include the coryneform bacteria transformant PHE7 (accession number: NITE BP-976) described in Japanese Patent No. 5932649, the coryneform bacteria transformant PHE18 (accession number: NITE BP-995) described in Japanese Patent No. 5996434, the coryneform bacteria transformant PHE21 (accession number: NITE BP-996) described in Japanese Patent No. 5932660, and the coryneform bacteria transformant PHE31 (accession number: NITE BP-999) described in Japanese Patent No. 5887277.

[0046] Prior to the reaction, it is preferable to culture the second transformant 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] (Culture medium) The medium used for aerobic cultivation of the second transformant prior to the reaction may be a natural medium or a synthetic medium containing a carbon source, a nitrogen source, inorganic salts, and other nutrients. As carbon sources, 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 can also be used. The carbon source may be used alone or in combination of two or more. The concentration of the carbon source in the medium may vary depending on the compound used, but may be, for example, 0.1 w / v% to 20 w / v%.

[0048] As the nitrogen source, inorganic or organic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium acetate, urea, aqueous ammonia, sodium nitrate, and potassium nitrate can be used. In addition, 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 source can be used alone or in combination of two or more. The concentration of the nitrogen source in the medium varies depending on the nitrogen compound used, but may be, for example, 0.1 w / v% to 10 w / v%. Examples of inorganic salts include potassium dihydrogen phosphate, potassium dihydrogen phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, ferrous nitrate, manganese sulfate, zinc sulfate, cobalt sulfate, calcium carbonate, etc. The inorganic salts can be used alone or in combination of two or more. The concentration of inorganic salts 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 the nutritional substances include meat extract, peptone, polypeptone, yeast extract, dry yeast, corn steep liquor, skim milk powder, hydrolyzed skim soybeans with hydrochloric acid, extracts of animals, plants or microbial cells, and decomposition products thereof, etc. The concentration of the nutritional substance in the medium varies depending on the nutritional substance used, but may be, for example, 0.1 w / v% to 10 w / v%. Furthermore, vitamins can be added as necessary, such as biotin, thiamine (vitamin B1), pyridoxine (vitamin B6), pantothenic acid, inositol, and nicotinic acid. The pH of the medium is preferably 6 or more and 8 or less.

[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)], BT medium [Omumasaba, CA et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8:91-103 (2004)], etc. In these media, the sugar concentration may be set within the above range.

[0051] (Reaction solution) As the reaction liquid, in addition to the reaction intermediate liquid used in the above step (A), a buffer solution, an inorganic salt medium, etc. can also be used. In the reaction liquid, the precursor may be a salt such as a sodium salt or a potassium salt; an ester with an alcohol having 1 to 4 carbon atoms, etc. Among them, a salt is preferable, and a sodium salt is more preferable. The precursor may be used alone or in combination of two or more kinds. The concentration of the precursor in the reaction solution is preferably 1 w / v% or more and 20 w / v% or less, more preferably 2 w / v% or more and 10 w / v% or less, and even more preferably 2 w / v% or more and 5 w / v% or less. By having the precursor concentration within the above numerical range, the production efficiency of the phenol composition is further improved.

[0052] Examples of the buffer solution include a phosphate buffer, a Tris buffer, a carbonate buffer, etc. The concentration of the buffer solution is preferably 10 mM or more and 150 mM or less from the viewpoint of the production efficiency of the phenol composition.

[0053] Examples of inorganic salt media include media containing one or more of inorganic salts such as potassium dihydrogen phosphate, potassium dihydrogen 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 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, CA et al., Corynebacterium glutamicum glyceraldehyde-3-phosphate dehydrogenase isoforms with opposite, ATP-dependent regulation. J. Mol. Microbiol. Biotechnol. 8:91-103 (2004)]. The concentration of inorganic salts in the medium varies depending on the inorganic salt used, but is usually set to 0.01 w / v% or more and 1 w / v% or less.

[0054] 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 (e.g., Able Co., Ltd., Model: DT-1023).

[0055] (Reaction conditions) From the viewpoint of the production efficiency of the phenol composition, 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 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 phenol 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 any of a batch system, a fed-batch system, and a continuous system, among which the batch system is preferred from the viewpoint of production efficiency of the phenol composition.

[0056] 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 efficiency of production of the phenol composition. In this specification, "does not grow" includes substantially no growth or almost no growth. The reduction conditions are determined by the redox potential of the reaction solution. From the viewpoint of the production efficiency of the phenol composition, the redox potential of the reaction intermediate solution is preferably from -500 mV to -200 mV, and more preferably from -500 mV to -150 mV. The reduction state of the reaction solution can be easily estimated using a resazurin indicator (in a reduced state, the indicator discolors from blue to colorless), but can be measured more accurately using an oxidation-reduction potentiometer (for example, ORP Electrodes, manufactured by BROADLEY JAMES).

[0057] The reaction solution under reducing conditions can be prepared by any known method without any restrictions. For example, an aqueous solution for the reaction solution can be used instead of distilled water as the liquid medium for the reaction solution, and the aqueous solution for the reaction solution can be prepared by referring to, for example, a culture medium preparation method for obligate anaerobic microorganisms such as sulfate-reducing microorganisms (Pfennig, N. et al., (1981): The dissimilatory sulfate-reducing bacteria, In The Prokaryotes, A Handbook on Habitats Isolation and Identification of Bacteria, Ed. by Starr, MP et al., p926-940, Berlin, Springer Verlag.) or "Agricultural Chemistry Experiment Book, Vol. 3, Kyoto University Faculty of Agriculture, Agricultural Chemistry Class, 26th edition, 1990, Sangyo Tosho Publishing Co., Ltd.", and the like. The aqueous solution under the desired reducing conditions can be obtained. Specifically, an aqueous solution for a reaction solution under reducing conditions can be obtained by removing dissolved gases by heating or reducing the pressure of distilled water, etc. In this case, the aqueous solution for a reaction solution under reducing conditions can be prepared by treating the distilled water, etc. under reduced pressure of preferably 10 mmHg or less, more preferably 5 mmHg or less, and even more preferably 3 mmHg or less, preferably for 1 minute or more and 60 minutes or less, and more preferably for 5 minutes or more and 40 minutes or less, with the dissolved gases, particularly dissolved oxygen, being removed.

[0058] Furthermore, an appropriate reducing agent (eg, thioglycolic acid, ascorbic acid, cysteine ​​hydrochloride, mercaptoacetic acid, thiolacetic acid, glutathione, sodium sulfide, etc.) can be added to prepare an aqueous solution for the reaction under reducing conditions. An appropriate combination of these methods is also an effective method for adjusting an aqueous solution for a reaction liquid under reducing conditions.

[0059] 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 the reducing conditions during the reaction, it is desirable to prevent the inclusion of oxygen from outside the reaction system as much as possible. Specifically, the reaction system may be sealed with an inert gas such as nitrogen gas or carbon dioxide gas. As a method for more effectively preventing oxygen inclusion, in order to efficiently function the metabolic function in the second transformant of this embodiment during the reaction, it may be necessary to add a pH maintenance adjustment solution to the reaction system or various nutrient dissolving solutions appropriately. In such cases, it is effective to remove oxygen from the added solution in advance.

[0060] (C) Step of Removing Transformants from the Reaction Solution Then, (C) a step of removing the transformant from the reaction solution is carried out. By culturing as described above, phenol is produced in the reaction solution, but the transformant remains in the reaction solution. By removing the transformant, the reaction solution containing the phenol composition can be recovered.

[0061] The reaction solution can be recovered by separating the transformant from the reaction solution. In this case, the step of removing the first transformant from the (A)' precursor described above may be carried out, and the first transformant and the second transformant may be separated separately from the reaction solution, or the first transformant and the second transformant may be simultaneously separated from the reaction solution without carrying out the step of removing the first transformant from the (A)' precursor. A known method can be used to separate the transformant. Examples of known methods include collection of the supernatant by leaving the transformant to stand, membrane filtration, centrifugation, etc. These methods can be used alone or in combination of two or more.

[0062] The membrane filtration can be carried out under general filtration conditions. From the viewpoint of improving the production efficiency of the phenol composition, the membrane pore size is preferably 0.01 μm or more, more preferably 0.03 μm or more, more preferably 0.05 μm or more, more preferably 0.07 μm or more, more preferably 0.10 μm or more, more preferably 0.15 μm or more, and 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 more preferably 1 μm or less. In addition, the membrane pore size can be measured by general measurement methods such as mercury porosimetry, bubble point test, and bacterial filtration method, 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 polymer membrane, ceramic membrane, and stainless steel membrane.

[0063] As the centrifuge used for the centrifugation, a general machine 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 phenol composition, the lower limit of the temperature during centrifugation is preferably 0°C or more, more preferably 1°C or more, and even more preferably 3°C or more. From the same viewpoint, the upper limit of the temperature during centrifugation is preferably 70°C or less, more preferably 50°C or less, even more preferably 30°C or less, even more preferably 10°C or less, and even more preferably 5°C or less.

[0064] The relative centrifugal force and time can be appropriately set, but the lower limit of the relative centrifugal force is preferably 3000 g or more, more preferably 5000 g or more, even more preferably 7000 g or more, even more preferably 10000 g or more, and even more preferably 15000 g or more from the viewpoint of improving the polymerizability of the phenol composition. The upper limit of the relative centrifugal force is preferably 50000 g or less, more preferably 25000 g or less, and even more preferably 20000 g or less from the viewpoint of improving the production efficiency of the phenol 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 by using the phenol composition. Also, 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 phenol composition.

[0065] [(D) Step of separating and concentrating the phenol composition in the reaction solution] Finally, a step (D) of separating and concentrating the phenol composition in the reaction solution is carried out. In this embodiment, the phenol composition in the reaction solution can be recovered as described above, but in order to increase the phenol concentration in the phenol composition and further improve the color tone of the obtained polymer, the phenol composition is separated and concentrated from the reaction solution by a known method. Examples of such known methods include a distillation method, a pervaporation method, a membrane permeation method, and an organic solvent extraction method. These methods can be carried out by appropriately combining one or more of them.

[0066] 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, and the like.

[0067] The pervaporation method is a method of obtaining a gaseous phenol composition by permeating the pervaporation membrane using a pervaporation membrane. The pervaporation membrane has a function of preferentially permeating phenol over water. Therefore, the phenol composition in the reaction solution moves from the supply side space to the permeation side space through the pervaporation membrane preferentially over water. As a result, the phenol composition obtained in the permeation side space has a higher phenol concentration than the reaction solution. In this way, by using the pervaporation method, a gaseous phenol composition can be obtained from the reaction solution, and the phenol concentration in the obtained phenol composition can be made higher than that of the reaction solution.

[0068] The shape of the pervaporation membrane is not particularly limited, and for example, a dense membrane such as a bag-type, flat membrane type, hollow fiber type, tubular type, or spiral type can be used.

[0069] The average thickness of the pervaporation membrane is not particularly limited, but is preferably about 10 to 500 μm, and more preferably about 20 to 400 μm. By setting the average thickness of the pervaporation membrane within the above range, the supply 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.

[0070] The material of the pervaporation membrane is not particularly limited, but examples thereof 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 can improve the mechanical properties of the pervaporation membrane while improving the phenol separation performance.

[0071] [Application] The phenol composition of the present embodiment can be used in the same applications as those of phenol compositions synthesized by conventional petrochemical processes using fossil resources as raw materials. That is, applications of the phenol composition of the present embodiment include a precursor of bisphenol A, a raw material for polymers, industrial chemicals, and fibers. Among these, it is preferable to use it for polymer applications. That is, a polymer using the phenol composition of the present embodiment is a polymer containing at least a structural unit derived from the phenol (A) in the phenol composition of the present embodiment.

[0072] The polymer of the present embodiment may be any polymer that requires phenol for synthesis, and is preferably a phenolic resin, since the phenolic composition of the present embodiment provides an improved balance of environmental compatibility and color tone of the resulting polymer.

[0073] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention. EXAMPLES

[0074] 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.

[0075] <Examples and Comparative Examples> Example 1 A test tube was prepared by dissolving 10 ml of A liquid medium (2 g of (NH2)2CO, 7 g of (NH4)2SO4, 0.5 g of KH2PO4, 0.5 g of K2HPO4, 0.5 g of MgSO4·7H2O, 1 ml of 0.06% (w / v) FeSO4·7H2O + 0.042% (w / v) MnSO4·2H2O, 1 ml of 0.02% (w / v) biotin solution, 2 ml of 0.01% (w / v) thiamin solution, 2 g of yeast extract, 7 g of vitamin assay casamino acid, and 40 g of glucose in 1 L of distilled water) containing 50 μg / ml of kanamycin, and further containing 2% by mass of calcium carbonate. A loopful of HBA-47 (BP-01849) was inoculated into the test solution and aerobically cultured at 33° C. for 24 hours at 200 rpm. The test solution was then vacuum filtered using a membrane filter with a pore size of 0.22 μm (Merck Millipore, Steritop 0.22 μm×33 mm) to separate HBA-47 from the test solution. Thereafter, the coryneform bacteria transformant PHE21 (Accession Number: NITE BP-996) prepared by the method described in Example 1 and paragraph

[0135] of Japanese Patent No. 5932660 was added to the above 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 while 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 with 2.5 N ammonia water using a pH controller (manufactured by Able Co., Ltd., model: DT-1023) so that the pH did not fall below 7.0. The reaction solution was centrifuged (4°C, 15000 g, 10 minutes) to obtain a solution containing a phenol composition synthesized from glucose 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 a DDR-type zeolite membrane by pervaporation (60°C, 50 Torr). This concentrated liquid was left to stand at room temperature to separate into two phases, a phenol phase and an aqueous phase, of which the phenol phase was collected (phenol concentration: 72% by mass). This phenol phase was further concentrated to a concentration of 99% by mass by removing water using an evaporator (60°C / 20 hPa). Furthermore, the remaining water was evaporated using an evaporator (150°C / 20 hPa) to obtain a phenol composition.

[0076] Example 2 A phenol composition was obtained in the same manner as in Example 1, except that the conditions for pervaporation using the DDR-type zeolite membrane were 85° C. and 250 Torr.

[0077] Example 3 The product of Example 1 was stored in a transparent glass bottle at room temperature under air for half a year to obtain a phenol composition.

[0078] Comparative Example 1 A phenol composition was obtained in the same manner as in Example 1, except that the residual water was not evaporated using an evaporator (150°C·20 hPa).

[0079] Comparative Example 2 A commercially available phenol product (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was prepared.

[0080] Comparative Example 3 A waste liquid containing phenol (phenol concentration: 6.2% by mass) was prepared when a phenolic resin was synthesized by the method described later in (Production of phenolic resin) using the phenolic product of Comparative Example 2. 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 dehydration using a pervaporation (60°C, 50 Torr) using a DDR-type zeolite membrane. The concentrated liquid was left to stand at room temperature, separated into a phenol phase and an aqueous phase, and the phenol phase was collected (phenol concentration: 72% by mass). Furthermore, water was further removed using an evaporator (60°C·20 hPa), and the solution was concentrated to a phenol concentration of 99% by mass to obtain a phenol composition.

[0081] (Phenol resin production) Phenolic resins were prepared using the phenolic compositions prepared in each of the Examples and Comparative Examples. In a reactor equipped with a stirrer, a reflux condenser, and a thermometer, 100 parts by mass of the phenol composition obtained in each Example and Comparative Example, 2 parts by mass of oxalic acid dihydrate, and 82 parts by mass of 37% aqueous formalin solution were reacted at 100°C for 3 hours. The temperature was then increased to 180°C in 90 minutes at a vacuum of 40 torr to distill off water, and the unreacted phenol composition was distilled off while blowing in water vapor at 180°C for 30 minutes, and the distilled off water and phenol composition were used as waste liquid. A phenolic resin was obtained using the phenolic composition of each Example and Comparative Example.

[0082] (Physical property evaluation) The physical properties of the phenol compositions obtained in each of the Examples and Comparative Examples were evaluated by the following methods.

[0083] (Phenol concentration analysis) The amount of phenol in the phenol composition of each Example and Comparative Example was determined by gas chromatography based on JIS K2437. The phenol composition of each Example and Comparative Example was dissolved in pure water to a concentration of 90% by mass to prepare an analysis sample. This analysis sample was analyzed by gas chromatography using a blank prepared by dissolving a phenol composition (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in pure water at a concentration of 90% by mass. The analytical conditions for gas chromatography are shown below in <Analysis Conditions>. The results are shown in Table 1. <Analysis conditions> ·GC device: GC-2030 (manufactured by Shimadzu Corporation) Carrier gas: N2 Detector: Flame ionization (FID) detector, FID temperature: 300℃ Column: SH-RXi-1HT, inner diameter 0.25, length 30 m, film thickness 0.25 μm (Shimadzu GLC Corporation) Vaporizer temperature: 210℃ Column flow rate: 0.64mL / min Column heating conditions: Hold at 50℃ for 5 min, heat to 300℃ at 20℃ / min, hold at 300℃ for 10 min

[0084] (Actual bio-based rate) The phenol (A) in the phenol composition of each Example and Comparative Example was subjected to radioactive carbon concentration test based on the biobased concentration test standard ASTM D6866-20 defined 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 in 1950 were then compared. 14 From the concentration of C, the radioactive carbon in the circulating carbon of phenol (A) in the phenol compositions of each Example and Comparative Example in 1950 was 14 Radioactive carbon in the total carbon atoms when the C concentration is taken as 100% 14The C concentration was calculated as the actual bio-based rate and evaluated as an index of environmental compatibility. The calculation results are shown in Table 1.

[0085] (absorbance) The phenol composition of each Example and Comparative Example was dissolved in pure water so that the phenol concentration was 90% by mass to prepare a measurement sample. The measurement sample was measured for absorbance at a wavelength of 425 nm using a UV-visible spectrophotometer (Shimadzu Corporation, UV-2400PC) with pure water as a blank. The results are shown in Table 1.

[0086] (color tone) According to the above (Production of phenolic resin), the phenolic resin prepared using the phenolic composition of each Example and Comparative Example was heated at 130°C for 10 minutes to prepare a molten sample. The color of the molten sample was then quantified based on the iodine color number measured in accordance with DIN6162, 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 but less than 9 C (yellow-brown): iodine color number is 9 or more but less than 44 D (dark brown): Iodine color number 44 or more

[0087] [Table 1]

[0088] 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 the environmental compatibility and the color tone of the obtained phenol resin was improved.

[0089] 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, deposit number: NITE BP-976).

[0090] 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) (date of domestic deposit: October 21, 2010; date of international deposit under the Budapest Treaty: September 28, 2011; deposit number: NITE BP-995).

[0091] 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, deposit number: NITE BP-996).

[0092] 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, deposit number: NITE BP-999).

[0093] Corynebacterium glutamicum HBA-2 was deposited at the Patent Microorganisms Depositary of the 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, deposit number: NITE BP-01838).

[0094] Corynebacterium glutamicum HBA-47 was deposited at the National Institute of Technology and Evaluation, Patent Microorganisms Depositary, 2-5-8 Kazusa Kamatari, Kisarazu, Chiba, Japan (postal code 292-0818) (date of international deposit under the Budapest Treaty: April 25, 2014, deposit number: NITE BP-01849). These strains have been deposited internationally under the terms of the Budapest Treaty and are publicly available under the conditions set forth in 37 CFR 1.808.

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 The present invention comprises at least phenol (A) having a measured bio-based content rate of 80% or more and 100% or less, which indicates the proportion of phenol (C); A phenol composition having 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 %.

2. The phenolic composition of claim 1, A phenol composition, wherein the content of the phenol (A) is 95% by mass or more and 100% by mass or less.

3. The phenolic composition according to claim 1 or 2, A phenol composition, wherein the measured bio-content rate of the phenol (A) is 95% or more and 100% or less.

4. The phenolic composition according to claim 1 or 2, A phenol composition, wherein the absorbance is 0.62 or less.

5. The phenolic composition according to claim 1 or 2, The phenol (A) is Transformant HBA-2 (Accession No.: NITE BP-01838) and A phenol composition comprising at least a structure derived from a benzene ring of a product of one or more transformants selected from transformant HBA-47 (accession number: NITE BP-01849).

6. The phenolic composition according to claim 1 or 2, The phenol (A) is Transformant PHE7 (Accession No.: NITE BP-976), Transformant PHE18 (Accession No.: NITE BP-995), Transformant PHE21 (Accession No.: NITE BP-996) and A phenol composition comprising at least one product of one or more transformants selected from transformant PHE31 (accession number: NITE BP-999).

7. A polymer comprising at least a structural unit derived from the phenol (A) in the phenol composition according to claim 1 or 2.

8. The polymer of claim 7 which is a phenolic resin.

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