Method for producing bisphenol F composition

Abstract

The present invention provides a method for producing a bisphenol F composition in which the ortho-ortho-type bisphenol F ratio of bisphenol F in the bisphenol F composition is improved. [Solution] A method for producing a bisphenol F composition, comprising step A, which involves decomposing a cured phenol resin composition by heat-treating the cured phenol resin composition in a solution containing water, phenols, and one or more metal hydroxides selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.

Description

[Technical Field]

[0001] This invention relates to a method for producing a bisphenol F composition.

[0002] Research is underway regarding the recycling of cured phenolic resins.

[0003] Patent Document 1 discloses a method for separating organic fillers by decomposing a phenolic resin cured product containing organic fillers in a solution containing phenols. Furthermore, Patent Document 1 states that "according to the present invention, organic fillers can be easily separated from a phenolic resin cured product containing organic fillers." [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2005-054138 [Overview of the project] [Problems that the invention aims to solve]

[0005] Regarding the recycling of cured phenolic resin compositions, when producing a bisphenol F composition by decomposing the cured phenolic resin composition, there was room for improvement in increasing the ortho-ortho-type bisphenol F ratio of bisphenol F in the bisphenol F composition.

[0006] The present invention provides a method for producing a bisphenol F composition in which the ortho-ortho-type bisphenol F ratio of bisphenol F in the bisphenol F composition is improved. [Means for solving the problem]

[0007] The present invention is as follows. 1. A method for producing a bisphenol F composition, comprising step A, of decomposing a cured phenol resin composition by heat-treating the cured phenol resin composition in a solution containing water, phenols, and one or more metal hydroxides selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. 2. A method for producing the bisphenol F composition according to 1, wherein the metal hydroxide includes an alkaline earth metal hydroxide. 3. A method for producing a bisphenol F composition according to 1. or 2., wherein the M / R value, which is the ratio of the weight M of the metal hydroxide to the weight R of the cured phenol resin composition, is 0.001 or more and 2.000 or less. 4. A method for producing a bisphenol F composition according to any one of 1 to 3, wherein the value of R / (W+P), which is the ratio of the weight R of the cured product of the phenol resin composition to the total amount of the weight W of the water and the weight P of the phenols, is 0.010 or more and 1.000 or less. 5. A method for producing a bisphenol F composition according to any one of 1 to 4, wherein the heating temperature in step A is 200°C or more and 350°C or less. 6. A method for producing a bisphenol F composition according to any one of 1 to 5, wherein the pressure inside the reaction vessel in step A is 1 MPa or more and 20 MPa or less. 7. A method for producing a bisphenol F composition according to any one of 1 to 6, wherein the heat treatment time in step A is 5 minutes or more and 10 hours or less. 8. A method for producing a bisphenol F composition according to any one of 1 to 7, wherein step A is carried out in a subcritical state. 9. A method for producing a bisphenol F composition according to any one of 1 to 8, wherein the alkali metal hydroxide comprises one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide. 10. A method for producing a bisphenol F composition according to any one of 1 to 9, wherein the alkaline earth metal hydroxide comprises one or more selected from the group consisting of beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. 11. A method for producing the bisphenol F composition according to any one of 1 to 10, wherein the phenols include one or more selected from the group consisting of mononuclear phenols and dinuclear phenols. 12. A method for producing the bisphenol F composition according to 11, wherein the mononuclear phenols include phenol. 13. A method for producing a bisphenol F composition according to any one of 1 to 12, wherein the average particle size of the cured product of the phenol resin composition is 10 μm or more and 10 mm or less. 14. A method for producing a bisphenol F composition according to any one of 1 to 13, wherein the bisphenol F content in the bisphenol F composition, as measured by <Method 1> below, is 15% by weight or more. <Method 1> The bisphenol F composition is dissolved in THF, filtered through a 1.0 μm pore size filter, and the filtrate is used as the THF-soluble portion. Next, the THF-soluble content is measured by GPC under the following conditions, and the bisphenol F content in the bisphenol F composition is calculated from the ratio of the peak area derived from bisphenol F to the total peak area of ​​the measurement chart. Eluent:THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃ 15. A method for producing a bisphenol F composition according to any one of 1 to 14, wherein the ortho-ortho-type bisphenol F ratio in the bisphenol F measured by <Method 2> below is 15.0% by weight or more. <Method 2> The bisphenol F composition is prepared under the following conditions 1 H-NMR measurement was performed, 1 Obtain the 1H-NMR spectrum. Solvent: Heavy acetone Number of integration times: 32 times Next, the 1 From the ratio of the area of the peak at 3.925 ± 0.100 ppm derived from the ortho-ortho type methylene bond to the area of all peaks at 3.0 to 4.5 ppm derived from the methylene bond in the H-NMR spectrum, the ortho-ortho type bisphenol F ratio in the bisphenol F is calculated. 16. The method for producing a bisphenol F composition according to any one of 1. to 15., wherein the number average molecular weight (Mn) of the bisphenol F composition measured by the following <Method 3> is 130 or more and 1000 or less. <Method 3> Dissolve the bisphenol F composition in THF, filter it through a filter with a pore size of 1.0 μm, and use the filtrate as the THF-soluble component. Next, measure the THF-soluble component by GPC under the following conditions, and calculate the number average molecular weight (Mn) of the bisphenol F composition. [[ID=1⑥]]Eluent: THF Calibration curve: Polystyrene conversion Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40 °C 17. The method for producing a bisphenol F composition according to any one of 1. to 16., further comprising step B of separating the bisphenol F composition from the decomposition product of the cured product of the phenol resin composition.

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a method for producing a bisphenol F composition in which the ortho-ortho type bisphenol F ratio of bisphenol F in the bisphenol F composition is improved.

Embodiments for Carrying Out the Invention

[0009] Hereinafter, the method for producing the bisphenol F composition of the present embodiment will be described.

[0010] The manufacturing method of the bisphenol F composition of the present embodiment includes a step A of decomposing a cured product of a phenolic resin composition by heat-treating the cured product of the phenolic resin composition in a solution containing water, phenols, and a metal hydroxide selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.

[0011] In the present embodiment, bisphenol F means one or more selected from the group consisting of 2,2'-methylenediphenol, 2,4'-methylenediphenol, and 4,4'-methylenediphenol.

[0012] The manufacturing method of the bisphenol F composition of the present embodiment can improve the ortho-ortho type bisphenol F ratio of bisphenol F in the bisphenol F composition. Here, if the ortho-ortho type bisphenol F ratio of bisphenol F in the bisphenol F composition can be improved, for example, it is preferable because the curability of the resin composition containing the bisphenol F composition can be improved.

[0013] Although the mechanism by which the ortho-ortho type bisphenol F ratio of bisphenol F in the bisphenol F composition can be improved by the manufacturing method of the bisphenol F composition of the present embodiment is not clear, in a solution containing water, phenols, and a metal hydroxide selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, the components interact with each other, resulting in conditions suitable for the production of ortho-ortho type bisphenol F. It is presumed that this enables the improvement of the ortho-ortho type bisphenol F ratio. <​​​​​​The cured product of the phenolic resin composition of this embodiment includes, for example, a molded article containing an inorganic filler such as silica fine particles or glass fibers, or an organic filler such as wood powder; a laminate containing an inorganic substrate such as glass woven fabric or glass nonwoven fabric, or an organic substrate such as paper or cloth; a metal-clad laminate obtained by laminating a metal foil such as copper foil onto a laminate, and a printed circuit board obtained by processing a metal-clad laminate.

[0016] The cured product of the phenolic resin composition of this embodiment contains a phenolic resin. The cured product of the phenolic resin composition of this embodiment may also contain resins other than phenolic resin, for example, one or more selected from the group consisting of epoxy resin, melamine resin, and urea resin.

[0017] The metal hydroxide in this embodiment preferably includes an alkaline earth metal hydroxide, from the viewpoint of further improving the ortho-ortho-type bisphenol F ratio.

[0018] The M / R value, which is the ratio of the weight M of the metal hydroxide in this embodiment to the weight R of the cured phenol resin composition in this embodiment, is preferably 0.001 to 2.000, more preferably 0.002 to 1.000, even more preferably 0.005 to 0.500, even more preferably 0.010 to 0.200, even more preferably 0.020 to 0.150, even more preferably 0.025 to 0.120, even more preferably 0.030 to 0.100, even more preferably 0.050 to 0.090, and even more preferably 0.060 to 0.090, from the viewpoint of further improving the ortho-ortho-bisphenol F ratio and the bisphenol F content in the bisphenol composition.

[0019] The value of R / (W+P), which is the ratio of the weight R of the cured phenol resin composition of this embodiment to the total amount of the weight W of water and the weight P of phenols of this embodiment, is preferably 0.010 to 1.000, more preferably 0.100 to 0.900, even more preferably 0.150 to 0.800, even more preferably 0.170 to 0.700, and even more preferably 0.190 to 0.600, from the viewpoint of further improving the ortho-ortho-bisphenol F ratio.

[0020] The heating temperature in step A of this embodiment is preferably 200°C or higher, more preferably 220°C or higher, even more preferably 240°C or higher, even more preferably 250°C or higher, and even more preferably 260°C or higher, from the viewpoint of accelerating the decomposition rate of the cured phenol resin composition and further improving the ortho-ortho-bisphenol F ratio, and preferably 350°C or lower, more preferably 330°C, from the viewpoint of suppressing side reactions during the decomposition of the cured phenol resin composition and further improving the ortho-ortho-bisphenol F ratio. More preferably, the temperature is 320°C or lower, even more preferably 310°C or lower, and even more preferably 300°C or lower. Furthermore, from the viewpoint of improving the balance between the decomposition rate of the cured phenol resin composition and the suppression of side reactions during the decomposition of the cured phenol resin composition, and from the viewpoint of further improving the ortho-ortho-type bisphenol F ratio, the temperature is preferably 200°C to 350°C, more preferably 220°C to 330°C, even more preferably 240°C to 320°C, even more preferably 250°C to 310°C, and even more preferably 260°C to 300°C.

[0021] The pressure inside the reaction vessel in step A of this embodiment is preferably 1 MPa or more, more preferably 3 MPa or more, even more preferably 4 MPa or more, even more preferably 5 MPa or more, and even more preferably 6 MPa or more, from the viewpoint of being able to speed up the decomposition rate of the cured phenol resin composition and to further improve the ortho-ortho-bisphenol F ratio. Furthermore, from the viewpoint of being able to suppress side reactions when the cured phenol resin composition is decomposed and to further improve the ortho-ortho-bisphenol F ratio, it is preferably 20 MPa or less, more preferably 16 MPa or less, even more preferably 12 MPa or less, even more preferably 10 MPa or less, and even more preferably 8 MPa or less. Furthermore, from the viewpoint of being able to improve the balance between the decomposition rate of the cured phenol resin composition and the suppression of side reactions when the cured phenol resin composition is decomposed and to further improve the ortho-ortho-bisphenol F ratio, it is preferably 1 MPa or more and 20 MPa or less, more preferably 3 MPa or more and 16 MPa or less, even more preferably 4 MPa or more and 12 MPa or less, even more preferably 5 MPa or more and 10 MPa or less, and even more preferably 6 MPa or more and 8 MPa or less.

[0022] The heat treatment time in step A of this embodiment is preferably 5 minutes or more, more preferably 7 minutes or more, and even more preferably 10 minutes or more, from the viewpoint of increasing the decomposition rate of the cured phenol resin composition and further improving the ortho-ortho-bisphenol F ratio. Furthermore, from the viewpoint of suppressing side reactions when the cured phenol resin composition decomposes and further improving the ortho-ortho-bisphenol F ratio, it is preferably 10 hours or less, more preferably 8 hours or less, and even more preferably 6 hours or less. Furthermore, from the viewpoint of improving the balance between the decomposition rate of the cured phenol resin composition and the suppression of side reactions when the cured phenol resin composition decomposes and further improving the ortho-ortho-bisphenol F ratio, it is preferably 5 minutes to 10 hours, more preferably 7 minutes to 8 hours, and even more preferably 10 minutes to 6 hours.

[0023] From the viewpoint of further improving the ortho-ortho-type bisphenol F ratio, it is preferable to carry out step A of this embodiment in a subcritical state.

[0024] From the viewpoint of further improving the ortho-ortho-bisphenol F ratio, the alkali metal hydroxide of this embodiment preferably comprises one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide, and more preferably comprises sodium hydroxide.

[0025] The alkaline earth metal hydroxide of this embodiment preferably comprises one or more selected from the group consisting of beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, and more preferably comprises calcium hydroxide, from the viewpoint of further improving the ortho-ortho-bisphenol F ratio.

[0026] From the viewpoint of further improving the ortho-ortho-bisphenol F ratio, the phenols of this embodiment preferably include one or more selected from the group consisting of mononuclear phenols and dinuclear phenols, and more preferably include phenol. Examples of mononuclear phenols include phenol, cresol, xylenol, resorcinol, and alkyl-substituted phenols, while examples of dinuclear phenols include 1-naphthol and 2-naphthol.

[0027] The method for producing the bisphenol F composition of this embodiment includes step A, in which the cured phenol resin composition is decomposed by heat treatment in a solution containing water, phenols, and one or more metal hydroxides selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. However, the solution may also contain components other than metal hydroxides, such as water, phenols, and one or more metal hydroxides selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides. For example, it may contain monomer alcohols such as methanol and ethanol, glycols such as ethylene glycol and propylene glycol, ketones, ethers, esters, organic acids, acid anhydrides, etc., which are commonly used as solvents in chemical reactions.

[0028] The average particle size of the cured phenol resin composition of this embodiment is not particularly limited, and can be pulverized to an appropriate size considering the cost required for pulverization and the decomposition rate. However, from the viewpoint of reducing the cost required for pulverization, it is preferably 10 μm or more, more preferably 20 μm or more, even more preferably 25 μm or more, even more preferably 30 μm or more, even more preferably 35 μm or more, and even more preferably 40 μm or more. Furthermore, from the viewpoint of increasing the decomposition rate of the cured phenol resin composition and further improving the ortho-ortho-type bisphenol F ratio, it is preferably 10 mm or less, more preferably 5 mm or less. More preferably, the particle size is 1 mm or less, even more preferably 500 μm or less, even more preferably 300 μm or less, and even more preferably 200 μm or less. Furthermore, from the viewpoint of improving the balance between the cost required for grinding and the decomposition rate of the cured product of the phenolic resin composition, and from the viewpoint of further improving the ortho-ortho-type bisphenol F ratio, the particle size is preferably 10 μm or more and 10 mm or less, more preferably 20 μm or more and 5 mm or less, even more preferably 25 μm or more and 1 mm or less, even more preferably 30 μm or more and 500 μm or less, even more preferably 35 μm or more and 300 μm or less, and even more preferably 40 μm or more and 200 μm or less.

[0029] The bisphenol F content in the bisphenol F composition of this embodiment, as measured by <Method 1> below, is preferably 15% by weight or more and 99% by weight or less, more preferably 20% by weight or more and 98% by weight or less, even more preferably 25% by weight or more and 95% by weight or less, even more preferably 30% by weight or more and 92% by weight or less, even more preferably 35% by weight or more and 90% by weight or less, even more preferably 40% by weight or more and 88% by weight or less, even more preferably 45% by weight or more and 85% by weight or less, and even more preferably 50% by weight or more and 80% by weight or less, from the viewpoint of improving the curability of the resin composition when bisphenol F is applied to the resin composition. <Method 1> The bisphenol F composition of this embodiment is dissolved in THF, filtered through a 1.0 μm pore size filter, and the filtrate is used as the THF-soluble portion. Next, the THF-soluble content is measured by GPC under the following conditions, and the bisphenol F content in the bisphenol F composition of this embodiment is calculated from the ratio of the peak area derived from bisphenol F to the total peak area of ​​the measurement chart. Eluent:THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃

[0030] The ortho-ortho-type bisphenol F ratio in the bisphenol F of this embodiment, measured by <Method 2> below, is preferably 15.0% by weight or more and 99.0% by weight or less, more preferably 20.0% by weight or more and 99.0% by weight or less, even more preferably 25.0% by weight or more and 95.0% by weight or less, even more preferably 35.0% by weight or more and 90.0% by weight or less, even more preferably 40.0% by weight or more and 85.0% by weight or less, even more preferably 45.0% by weight or more and 80.0% by weight or less, even more preferably 50.0% by weight or more and 75.0% by weight or less, and even more preferably 55.0% by weight or more and 70.0% by weight or less. <Method 2> The bisphenol F composition of this embodiment is prepared under the following conditions 1H-NMR measurement was performed, 1 Obtain the 1H-NMR spectrum. Solvent: Deuterated acetone Total number of times: 32 Next, 1 The ortho-ortho bisphenol F ratio in this embodiment is calculated from the ratio of the area of ​​the 3.925 ± 0.100 ppm peak, which originates from ortho-ortho methylene bonds, to the area of ​​all peaks in the 3.0–4.5 ppm region of the H-NMR spectrum, which originates from methylene bonds.

[0031] The number-average molecular weight (Mn) of the bisphenol F composition of this embodiment, as measured by Method 3 below, is preferably 130 or more and 1000 or less, more preferably 131 or more and 800 or less, even more preferably 132 or more and 600 or less, even more preferably 133 or more and 400 or less, even more preferably 134 or more and 300 or less, even more preferably 135 or more and 200 or less, and even more preferably 135 or more and 150 or less. <Method 3> The bisphenol F composition of this embodiment is dissolved in THF, filtered through a 1.0 μm pore size filter, and the filtrate is used as the THF-soluble portion. Next, the THF-soluble content is measured by GPC under the following conditions, and the number-average molecular weight (Mn) of the bisphenol F composition of this embodiment is calculated. Eluent:THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃

[0032] The method for producing the bisphenol F composition of this embodiment preferably further includes step B, which involves separating the bisphenol F composition from the decomposition products of the cured phenol resin composition of this embodiment.

[0033] In step B of this embodiment, the method for separating the bisphenol F composition from the decomposition products of the cured phenol resin composition of this embodiment is not particularly limited, and separation can be performed by distillation such as steam distillation, flash distillation, or vacuum distillation; solid-liquid separation such as cyclone, filtration, or gravity sedimentation; or solvent extraction.

[0034] Step B of this embodiment preferably includes steam distillation, from the viewpoint of further improving the ortho-ortho-type bisphenol F ratio. The temperature of steam distillation is not particularly limited, but from the viewpoint of promoting distillation, it is preferably 150°C or higher, more preferably 170°C or higher, even more preferably 190°C or higher, and even more preferably 200°C or higher. Furthermore, from the viewpoint of suppressing polymerization and side reactions, it is preferably 350°C or lower, more preferably 300°C or lower, even more preferably 280°C or lower, even more preferably 260°C or lower, even more preferably 250°C or lower, and even more preferably 240°C or lower.

[0035] The bisphenol F composition obtained by the method for producing the bisphenol F composition of this embodiment is not particularly limited in its use and can be used, for example, as a raw material for resin compositions. For example, a resin composition can be obtained by mixing the bisphenol F composition of this embodiment with a resin such as a novolac-type phenol resin, a resol-type phenol resin, and an epoxy resin; a curing agent such as hexamethylenetetramine; a curing aid such as magnesium oxide or calcium hydroxide; or an inorganic or organic filler.

[0036] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention. [Examples]

[0037] This embodiment will be described in detail below with reference to examples and other relevant information. However, this embodiment is not limited in any way to the descriptions of these examples.

[0038] <Examples 1-9> The cured product of a phenolic resin composition containing glass filler (manufactured by Sumitomo Bakelite Co., Ltd., product name: PM-9640) was pulverized, sieved, and the particle size was adjusted to 200 μm or less. The cured product of the phenolic resin composition containing glass filler was obtained by heating the phenolic resin containing glass filler at 120°C for 2 hours, followed by heating at 200°C for 1 hour. Next, 1000g of cured phenol resin composition with adjusted particle size, the amounts of calcium hydroxide (manufactured by Kanto Chemical, special grade), water, and phenol (manufactured by Kanto Chemical, special grade) listed in Table 1 were placed in an autoclave (manufactured by Toyo Koatsu, internal volume: 6L). The contents were then heated and pressurized inside the container while stirring at 300 rpm, and maintained at the container temperature and pressure of 6 MPa listed in Table 1 for the time listed in Table 1. In all of Examples 1 to 9, the container remained in a subcritical state while being held under the conditions of the container temperature and container pressure of 6 MPa as described in Table 1. Next, the internal temperature of the container was set to 70°C and the internal pressure to atmospheric pressure. 250 parts by weight of oxalic acid (manufactured by Kanto Chemical, special grade) was added to 1000 parts by weight of the cured phenol resin composition, and the pH inside the container was adjusted to 6.5. Subsequently, the reaction solution was filtered to remove the glass filler, and phenol was removed by vacuum steam distillation at 150°C to obtain the bisphenol F composition.

[0039] <Example 10> A bisphenol F composition was obtained using the same method as in Examples 1 to 9, except that the amount of sodium hydroxide (manufactured by Kanto Chemical Co., Ltd., special grade) listed in Table 1 was used instead of the amount of calcium hydroxide listed in Table 1.

[0040] The bisphenol F content in the bisphenol F composition was measured using the method described below. The results are shown in Table 1. <Method> The bisphenol F composition obtained by the above method was dissolved in THF and filtered through a filter with a pore size of 1.0 μm, and the filtrate was used as the THF-soluble component. Next, the obtained THF-soluble component was measured by GPC under the following conditions, and the content of bisphenol F in the bisphenol F composition was calculated from the ratio of the peak area derived from bisphenol F to the total peak area of the measurement chart. GPC measuring device: manufactured by Tosoh Corporation, HLC-8320GPC Eluent: THF Calibration curve: polystyrene conversion Detector: differential refractometer Flow rate: 1 ml / min Temperature: 40 °C

[0041] The ortho-ortho type bisphenol F ratio in the bisphenol F composition was measured by the following <method>. The results are shown in Table 1. <Method> The bisphenol F composition obtained by the above method was 1 measured by 1H-NMR under the following conditions, 1 and a 1H-NMR spectrum was obtained. NMR measuring device: manufactured by JEOL Ltd., JMTC-400 Solvent: deuterated acetone Number of integrations: 32 times Next, from the ratio of the peak area at 3.925 ± 0.100 ppm derived from the ortho-ortho type methylene bond to the area of all peaks in the region of 3.0 to 4.5 ppm derived from the methylene bond in the obtained 1 1H-NMR spectrum, the ortho-ortho type bisphenol F ratio in bisphenol F was calculated.

[0042]

Table 1

Claims

1. A method for producing a bisphenol F composition, comprising step A, of decomposing a cured phenol resin composition by heat-treating the cured phenol resin composition in a solution containing water, phenols, and one or more metal hydroxides selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides.

2. The method for producing the bisphenol F composition according to claim 1, wherein the metal hydroxide includes an alkaline earth metal hydroxide.

3. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the value of M / R, which is the ratio of the weight M of the metal hydroxide to the weight R of the cured product of the phenol resin composition, is 0.001 or more and 2.000 or less.

4. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the value of R / (W+P), which is the ratio of the weight R of the cured product of the phenol resin composition to the total amount of the weight W of the water and the weight P of the phenols, is 0.010 or more and 1.000 or less.

5. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the heating temperature in step A is 200°C or higher and 350°C or lower.

6. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the pressure inside the reaction vessel in step A is 1 MPa or more and 20 MPa or less.

7. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the heat treatment time in step A is 5 minutes or more and 10 hours or less.

8. A method for producing a bisphenol F composition according to claim 1 or 2, wherein step A is carried out in a subcritical state.

9. The method for producing the bisphenol F composition according to claim 1 or 2, wherein the alkali metal hydroxide comprises one or more selected from the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide.

10. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the alkaline earth metal hydroxide comprises one or more selected from the group consisting of beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.

11. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the phenols include one or more selected from the group consisting of mononuclear phenols and dinuclear phenols.

12. A method for producing the bisphenol F composition according to claim 11, wherein the mononuclear phenols include phenol.

13. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the average particle size of the cured product of the phenol resin composition is 10 μm or more and 10 mm or less.

14. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the bisphenol F content in the bisphenol F composition, as measured by the following <Method 1>, is 15% by weight or more. <Method 1> The bisphenol F composition is dissolved in THF, filtered through a filter with a pore size of 1.0 μm, and the filtrate is used as the THF-soluble component. Next, the THF-soluble portion is measured by GPC under the following conditions, and the bisphenol F content in the bisphenol F composition is calculated from the ratio of the peak area derived from bisphenol F to the total peak area of ​​the measurement chart. Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃

15. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the ortho-ortho-type bisphenol F ratio in the bisphenol F measured by the following <Method 2> is 15.0% by weight or more. <Method 2> The bisphenol F composition is prepared under the following conditions １ H-NMR measurement was performed. １ Obtain the 1H-NMR spectrum. Solvent: Deuterated acetone Total number of times: 32 Next, the above １ The ortho-ortho bisphenol F ratio in the bisphenol F is calculated from the ratio of the area of ​​the 3.925 ± 0.100 ppm peak, which originates from ortho-ortho type methylene bonds, to the area of ​​all peaks in the 3.0–4.5 ppm region of the H-NMR spectrum, which originates from methylene bonds.

16. A method for producing a bisphenol F composition according to claim 1 or 2, wherein the number average molecular weight (Mn) of the bisphenol F composition, as measured by the following <Method 3>, is 130 or more and 1000 or less. <Method 3> The bisphenol F composition is dissolved in THF, filtered through a filter with a pore size of 1.0 μm, and the filtrate is used as the THF-soluble component. Next, the THF-soluble components are measured by GPC under the following conditions, and the number-average molecular weight (Mn) of the bisphenol F composition is calculated. Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃

17. A method for producing a bisphenol F composition according to claim 1 or 2, further comprising step B of separating the bisphenol F composition from the decomposition products of the cured phenol resin composition.

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