Phenol composition, phenol resin, phenol resin composition, phenol resin molding material, and molded body

Abstract

Provided is a phenol composition containing phenols and xanthene, wherein the phenols have a weight average molecular weight (Mw) of 3000 or less as measured by <method 1>. <Method 1> The phenol composition is dissolved in THF, and filtered through a filter having a pore size of 0.2 μm, and the filtrate is taken as a THF-soluble fraction. Then, the THF-soluble fraction is subjected to GPC measurement under the following conditions to measure the weight average molecular weight (Mw) of the phenols. (Conditions) Eluent: THF, calibration curve: polystyrene equivalent, detector: differential refractometer, flow rate: 1 ml / min, temperature: 40°C

Description

Phenolic composition, phenolic resin, phenolic resin composition, phenolic resin molding material and molded article

[0001] The present invention relates to phenol compositions, phenol resins, phenol resin compositions, phenol resin molding materials, and molded articles.

[0002] Phenol compositions containing phenols are used, for example, as raw materials for resins such as phenolic resins, polycarbonate resins, epoxy resins, and aromatic polyester resins. Examples of technologies related to the chemical recycling of phenolic resins include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 describes a method for separating organic fillers by decomposing a phenolic resin cured product containing organic fillers in a solution containing phenols. According to this method, organic fillers can be easily separated from the phenolic resin cured product containing organic fillers.

[0004] Patent Document 2 describes a method for producing inorganic substances and phenolic compounds together from a composite material containing inorganic substances and thermosetting resin cured products, comprising the following steps 1 to 4: Step 1: Contacting a composite material containing inorganic substances and thermosetting resin cured products with a treatment solution containing a metal alkoxide and an organic solvent to obtain a decomposition solution A containing inorganic substances and phenolic compounds; Step 2: Solid-liquid separation of the decomposition solution A obtained in Step 1 into a dissolution solution C containing crude inorganic substances B and phenolic compounds; Step 3: Washing the crude inorganic substances B obtained in Step 2 to obtain inorganic substances; Step 4: Separating the phenolic compounds from the dissolution solution C obtained in Step 2. The document states that this method provides a chemical recycling method that does not cause corrosion damage to the decomposition tank and suppresses discoloration of the resulting inorganic substances and thermosetting resins.

[0005] Japanese Patent Publication No. 2005-054138 Japanese Patent Publication No. 2024-017469

[0006] The present invention provides a phenolic composition that can be obtained in which a phenolic resin composition with improved hardness can be obtained.

[0007] According to the present invention, the following phenolic compositions, phenolic resins, phenolic resin compositions, phenolic resin molding materials, and molded articles are provided.

[0008] [1] A phenol composition comprising phenols and xanthenes, wherein the weight-average molecular weight (Mw) of the phenols, as measured by the following Method 1, is 3000 or less. <Method 1> The phenol composition is dissolved in THF, filtered through a filter with a pore size of 0.2 μm, and the filtrate is used as the THF-soluble component. The THF-soluble component is then measured by GPC under the following conditions to determine the weight-average molecular weight (Mw) of the phenols. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C [2] The phenol composition according to [1], wherein the number-average molecular weight (Mn) of the phenols, as measured by the following Method 2, is 1000 or less. <Method 2> The phenol composition is dissolved in THF, filtered through a filter with a pore size of 0.2 μm, and the filtrate is used as the THF-soluble component. Next, the THF-soluble components are measured by GPC under the following conditions to determine the number-average molecular weight (Mn) of the phenols. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C [3] The phenol composition according to [1] or [2], wherein the phenols include a polynuclear phenol containing two or more aromatic rings, and when the content of the phenols is 100% by mass, the content of the polynuclear phenol containing two or more aromatic rings, as measured by the following <Method 3>, is 10% by mass or more. <Method 3> The phenol composition is dissolved in THF, filtered through a filter with a pore size of 0.2 μm, and the filtrate is used as the THF-soluble components. Next, the THF-soluble components are measured by GPC under the following conditions, and the content of the polynuclear phenol containing two or more aromatic rings in the phenols is determined from the ratio of the peak area derived from the polynuclear phenol containing two or more aromatic rings to the total peak area of ​​the measurement chart. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C [4] The phenol composition according to [3], wherein when the content of polynuclear phenol containing two or more aromatic rings is taken as 100% by mass, the content of dinuclear phenol containing two aromatic rings, as measured by <Method 3>, is 15% by mass or more.[5] The phenol composition according to [4], wherein the dinuclear phenol containing two aromatic rings is bisphenol F. [6] The phenol composition according to [5], wherein the ortho-ortho-bisphenol F ratio in the bisphenol F, as measured by Method 3, is 30.0% by mass or more. [7] The phenol composition according to any one of [1] to [6], wherein the phenols are one or more selected from the group consisting of cresol and xylenol. [8] The peak area X of the dinuclear phenol containing two aromatic rings, as measured by gas chromatography-mass spectrometry (GC-MS) according to Method 4 below. １ The peak area of ​​xanthene in relation to X ２ The ratio X (=X) ２ / X １A phenol composition according to any one of [1] to [7], wherein the ratio of the phenol composition to the phenol composition is 0.1 or greater. <Method 4> Using gas chromatography-mass spectrometry (GC-MS), 1 μL of a 10% by mass DMSO diluted solution of the phenol composition is analyzed according to the following (gas chromatography conditions), and the ratio X of the peak area of ​​the xanthene to the peak area of ​​the dinuclear phenol containing two aromatic rings is calculated. (Gas chromatograph conditions) Measuring instrument: Gas chromatograph mass spectrometer Column: Capillary column (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) GC inlet temperature: 300°C GC oven temperature: 40°C (hold for 5 minutes) → 10°C / min → 300°C (hold for 9 minutes) Injection method: Split method (split ratio: 50 / 1) Carrier gas flow rate: He (1 mL / min) MS ionization method: EI (electron shock) method Ionization voltage: 70 eV MS detection mass range: m / z = 25 to 800 MS temperature: Ion source: 230°C, interface: 300°C [9] The phenol composition according to any one of [1] to [8], wherein the phenols include phenol.

[10] The phenol composition according to [9], wherein when the content of the phenols is 100% by mass, the content of phenol is 20% by mass or more.

[11] A phenol resin comprising structural unit a derived from phenols contained in any of the phenol compositions described in [1] to

[10] .

[12] The phenol resin according to

[11] , which is a novolac-type phenol resin or a resol-type phenol resin.

[13] A phenol resin composition or phenol resin molding material comprising the phenol resin described in

[11] or

[12] .

[14] A molded article comprising a cured product of the phenol resin composition or phenol resin molding material described in

[13] .

[0009] According to the present invention, it is possible to provide a phenolic composition that can be obtained in which a phenolic resin composition with improved hardness is obtained.

[0010] The present invention will be described below based on embodiments. In these embodiments, unless otherwise specified, "A to B" indicating a numerical range represents A or greater and B or less.

[0011] <Phenol Composition> The phenol composition of this embodiment contains phenols and xanthenes, and the weight-average molecular weight (Mw) of the phenols, as measured by <Method 1> below, is 3000 or less. <Method 1> The phenol composition is dissolved in THF, filtered through a filter with a pore size of 0.2 μm, and the filtrate is used as the THF-soluble component. Next, the THF-soluble component is measured by GPC under the following conditions to determine the weight-average molecular weight (Mw) of the phenols. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C

[0012] According to the phenol composition of this embodiment, by setting the weight-average molecular weight (Mw) of the phenols to a predetermined value or less, the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition can be improved. The reason for this is not clear, but by setting the weight-average molecular weight (Mw) of the phenols to a predetermined value or less, that is, by reducing the molecular weight, a phenol resin composition with improved hardness can be obtained in the phenol resin produced using the phenol composition of this embodiment. When a phenol resin is produced using a phenol composition in which the weight-average molecular weight (Mw) exceeds a predetermined value, that is, a phenol composition containing phenols with high molecular weight, it is thought that the hardness of the resulting phenol resin composition containing the phenol resin will decrease compared to when a phenol composition in which the weight-average molecular weight (Mw) is below a predetermined value is used, for example, due to reasons such as polymerization and increased viscosity.

[0013] Note that "synthetic phenol" refers to synthesized phenol, not decomposition products of cured phenolic resin. Furthermore, "phenols" include phenols containing one aromatic ring (such as phenol), bisphenols containing two aromatic rings (such as bisphenol A, bisphenol F, and methyl adducts of bisphenol F), and phenols containing three or more aromatic rings. In this embodiment, bisphenol F means one or more selected from the group consisting of 2,2'-methylenediphenol, 2,4'-methylenediphenol, and 4,4'-methylenediphenol.

[0014] The phenol composition of this embodiment contains phenols, preferably one or more selected from the group consisting of phenols derived from decomposition products of phenol resin curing products and phenol, and more preferably one or more selected from the group consisting of phenols containing one aromatic ring (such as phenol), bisphenols containing two aromatic rings (such as bisphenol A and bisphenol F), and phenols containing three or more aromatic rings. When phenol resin curing products are decomposed, they are not easily decomposed down to phenols containing one aromatic ring, so the decomposition products of phenol resin curing products mainly consist of phenols containing two or more aromatic rings.

[0015] Furthermore, in this specification, phenols derived from the decomposition products of phenol resin cured products are referred to as regenerated phenols. The phenol composition of this embodiment preferably contains regenerated phenols.

[0016] The weight-average molecular weight (Mw) of the phenols measured by Method 1 above is 3000 or less, preferably 2500 or less, more preferably 2000 or less, even more preferably 1500 or less, and even more preferably 1000 or less, from the viewpoint of further improving the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition, and even more preferably 550 or less, even more preferably 530 or less, even more preferably 500 or less, even more preferably 450 or less, even more preferably 430 or less, even more preferably 420 or less, and even more preferably 410 or less. There is no lower limit to the weight-average molecular weight (Mw) of the phenols measured by Method 1 above, but it may be, for example, 94 or more, 100 or more, or 110 or more. Furthermore, the weight-average molecular weight (Mw) of phenols measured by the above-mentioned Method 1 is preferably 94 to 3000, more preferably 94 to 2500, even more preferably 94 to 2000, even more preferably 94 to 1500, and even more preferably 94 to 1000, and even more preferably 94 to 550, even more preferably 94 to 530, even more preferably 94 to 500, even more preferably 94 to 450, even more preferably 100 to 430, even more preferably 110 to 420, and even more preferably 110 to 410, from the viewpoint of obtaining a phenol resin composition having the same hardness as a phenol resin composition containing a phenol resin obtained using synthetic phenol.

[0017] Furthermore, the phenol composition of this embodiment contains xanthenes. The presence of xanthenes in the phenol composition is an indicator that the phenol composition contains regenerated phenols obtained by decomposing a cured phenol resin. Xanthenes are known to be produced when cured phenol resins are decomposed and are therefore detected in regenerated phenols. It is thought that xanthenes are produced in the process of decomposing the cured phenol resin, described later, when the hydroxyl groups of phenols are dehydrated by heating at, for example, 200°C or higher. It is also thought that the longer the heating time at 200°C or higher, the more xanthenes are produced.

[0018] Xanthenes are compounds represented by the following formula.

[0019]

[0020] The number-average molecular weight (Mn) of phenols measured by Method 2 below is preferably 1000 or less, more preferably 900 or less, even more preferably 800 or less, even more preferably 700 or less, even more preferably 600 or less, and even more preferably 550 or less, from the viewpoint of being able to further improve the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition. Even more preferably it is 300 or less, even more preferably 250 or less, even more preferably 200 or less, even more preferably 180 or less, even more preferably 160 or less, and even more preferably 150 or less, from the viewpoint of being able to obtain a phenol resin composition having the same hardness as a phenol resin composition containing the phenol resin obtained using synthetic phenol. There is no lower limit to the number-average molecular weight (Mn) of phenols measured by Method 2 below, but it may be, for example, 94 or more, or 100 or more. Furthermore, the number-average molecular weight (Mn) of phenols measured by the following <Method 2> is preferably 94 to 1000, more preferably 94 to 900, even more preferably 94 to 800, even more preferably 94 to 700, even more preferably 94 to 600, and even more preferably 94 to 550, from the viewpoint of being able to further improve the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition. Even more preferably, it is 94 to 300, even more preferably 94 to 250, even more preferably 94 to 200, even more preferably 100 to 180, even more preferably 100 to 160, and even more preferably 100 to 150.

[0021] <Method 2> The phenol composition is dissolved in THF, filtered through a 0.2 μm pore size filter, and the filtrate is used as the THF-soluble component. Next, the THF-soluble component is subjected to GPC measurement under the following conditions to determine the number-average molecular weight (Mn) of the phenols. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C

[0022] The phenol content in the phenol composition of this embodiment is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 85% by mass or more, and even more preferably 90% by mass or more, when the total amount of the phenol composition is considered as 100% by mass, and may also be less than 100% by mass and 95% by mass or less. By having a phenol content in the phenol composition that is above the above lower limit, the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition can be further improved. The phenol content in the phenol composition can be calculated by subtracting the water content and ash content from the total amount of the phenol composition.

[0023] In the phenol composition of this embodiment, the phenols preferably include polynuclear phenols containing two or more aromatic rings. In the phenol composition of this embodiment, when the content of phenols in the phenol composition is 100% by mass, the content of polynuclear phenols containing two or more aromatic rings, as measured by <Method 3> below, is preferably 10% by mass or more, more preferably 11% by mass or more, even more preferably 12% by mass or more, and even more preferably 13% by mass or more. There is no upper limit to the content of polynuclear phenols containing two or more aromatic rings, but for example it may be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 55% by mass or less. Furthermore, in the phenol composition of this embodiment, when the content of phenols in the phenol composition is 100% by mass, the content of polynuclear phenols containing two or more aromatic rings, as measured by <Method 3> below, is preferably 10% by mass or more and 90% by mass or less, more preferably 11% by mass or more and 80% by mass or less, even more preferably 12% by mass or more and 70% by mass or less, even more preferably 13% by mass or more and 60% by mass or less, and even more preferably 13% by mass or more and 55% by mass or less.

[0024] <Method 3> The phenol composition is dissolved in THF, filtered through a 0.2 μm pore size filter, and the filtrate is used as the THF-soluble component. Next, the THF-soluble component is measured by GPC under the following conditions, and the content of polynuclear phenols containing two or more aromatic rings in the phenols is determined from the ratio of the peak area derived from polynuclear phenols containing two or more aromatic rings to the total peak area of ​​the measurement chart. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C

[0025] In the phenol composition of this embodiment, when the content of polynuclear phenols containing two or more aromatic rings is set to 100% by mass, the content of dinuclear phenols containing two aromatic rings, as measured by Method 3 above, is preferably 15% by mass or more, more preferably 17% by mass or more, even more preferably 20% by mass or more, even more preferably 23% by mass or more, and even more preferably 25% by mass or more. There is no upper limit to the content of dinuclear phenols containing two aromatic rings, but it may be 90% by mass or less, 85% by mass or less, 80% by mass or less, or 75% by mass or less. Furthermore, in the phenol composition of this embodiment, when the content of polynuclear phenols containing two or more aromatic rings is set to 100% by mass, the content of dinuclear phenols containing two aromatic rings, as measured by Method 3 above, is preferably 15% by mass or more and 90% by mass or less, more preferably 17% by mass or more and 85% by mass or less, even more preferably 20% by mass or more and 80% by mass or less, even more preferably 23% by mass or more and 75% by mass or less, and even more preferably 25% by mass or more and 75% by mass or less. By having a content of dinuclear phenols containing two aromatic rings above the above lower limit, the phenol composition can be made even more molecularly low, and consequently the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition can be further improved.

[0026] In the phenol composition of this embodiment, the dinuclear phenol containing two aromatic rings preferably contains bisphenol F. By including bisphenol F in the dinuclear phenol containing two aromatic rings in the phenol composition, the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition can be further improved. In the phenol composition of this embodiment, when the content of phenols is 100% by mass, the content of bisphenol F is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, even more preferably 4% by mass or more, and even more preferably 5% by mass or more. In the phenol composition of this embodiment, there is no upper limit to the content of bisphenol F when the content of phenols is 100% by mass, but it may be 40% by mass or less, 30% by mass or less, 25% by mass or less, or 23% by mass or less. By having a bisphenol F content in the phenol composition that is above the above lower limit, the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition can be further improved. The bisphenol F content, when the phenol content is set to 100% by mass, can be measured by GPC according to Method 3 described above.

[0027] In the phenol composition of this embodiment, the ortho-ortho-bisphenol F ratio in bisphenol F measured by Method 3 above is preferably 30.0% by mass or more, more preferably 33.0% by mass or more, even more preferably 35.0% by mass or more, and even more preferably 37.0% by mass or more. There is no upper limit to the ortho-ortho-bisphenol F ratio in bisphenol F, but it may be, for example, 80.0% by mass or less, 70.0% by mass or less, or 65.0% by mass or less. Furthermore, the ortho-ortho-bisphenol F ratio in bisphenol F in the phenol composition is preferably 30.0% by mass or more and 80.0% by mass or less, more preferably 33.0% by mass or more and 80.0% by mass or less, even more preferably 35.0% by mass or more and 70.0% by mass or less, and even more preferably 37.0% by mass or more and 65.0% by mass or less. In a phenol composition, if the ortho-ortho-type bisphenol F ratio in bisphenol F is equal to or greater than the above lower limit, the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition can be further improved.

[0028] In the phenol composition of this embodiment, the phenols preferably include one or more selected from the group consisting of cresol and xylenol. Cresol and xylenol are known to be produced when phenol resin cured products are decomposed and are therefore detected in regenerated phenols. Thus, the inclusion of one or more selected from the group consisting of cresol and xylenol in the phenol composition is one indicator of the inclusion of regenerated phenols obtained by decomposing phenol resin cured products. Here, cresol includes one or more structural isomers selected from the group consisting of o-cresol, m-cresol, and p-cresol. Xylenol is a compound in which two methyl groups are added to phenol and includes one or more structural isomers selected from the group consisting of 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, and 3,5-dimethylphenol. The presence of cresol and xylenol in the phenol composition can be confirmed by gas chromatography-mass spectrometry (GC-MS) according to Method 4 described later.

[0029] In the phenol composition of this embodiment, the peak area X of a dinuclear phenol containing two aromatic rings is measured by gas chromatography-mass spectrometry (GC-MS) according to the method described in <Method 4> below. １ The peak area of ​​xanthene in relation to X ２ The ratio X (=X) ２ / X １ The ratio X of the peak area of ​​xanthene to the peak area of ​​dinuclear phenol containing two aromatic rings is preferably 0.1 to 10.0, more preferably 0.2 to 9.0, and even more preferably 0.3 to 8.0. It is preferable that the ratio X of the peak area of ​​xanthene to the peak area of ​​dinuclear phenol containing two aromatic rings is within the above range, as this makes it easier to understand that the phenol composition of this embodiment contains regenerated phenols obtained by decomposing a cured phenol resin.

[0030] <Method 4> Using gas chromatography-mass spectrometry (GC-MS), 1 μL of a 10% by mass DMSO dilution solution of the phenol composition is analyzed according to the following (gas chromatography conditions), and the ratio X of the peak area of xanthene to the peak area of the binuclear phenol containing two aromatic rings is calculated. (Gas chromatography conditions) Measuring instrument: Gas chromatography-mass spectrometer Column: Capillary column (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) GC injection port temperature: 300 °C GC oven temperature: 40 °C (held for 5 minutes) → 10 °C / min → 300 °C (held for 9 minutes) Injection method: Split method (split ratio: 50 / 1) Carrier gas flow rate: He (1 mL / min) MS ionization method: EI (electron impact) method Ionization voltage: 70 eV MS detection mass range: m / z = 25 - 800 MS temperature: Ion source: 230 °C, Interface: 300 °C Then, from each of the obtained peak areas, the ratio X is calculated according to the following formula. X = (peak area of xanthene X ２ ) / (peak area of binuclear phenol containing two aromatic rings X １ )

[0031] In the phenol composition of this embodiment, when the content of phenols in the phenol composition is set to 100% by mass, the content of regenerated phenols is preferably 10% by mass or more, more preferably 12% by mass or more, even more preferably 15% by mass or more, even more preferably 18% by mass or more, even more preferably 20% by mass or more, and even more preferably 25% by mass or more. There is no upper limit to the content of regenerated phenols, but for example it may be 90% by mass or less, or 70% by mass or less. Also, in the phenol composition of this embodiment, when the content of phenols in the phenol composition is set to 100% by mass, the content of regenerated phenols is preferably 10% by mass or more and 90% by mass or less, more preferably 12% by mass or more and 90% by mass or less, even more preferably 15% by mass or more and 90% by mass or less, even more preferably 18% by mass or more and 90% by mass or less, even more preferably 20% by mass or more and 70% by mass or less, and even more preferably 25% by mass or more and 70% by mass or less. The regenerated phenols are derived from decomposition products of phenol resin cured products and mainly consist of phenols containing two or more aromatic rings. Furthermore, recycled phenols do not contain phenol, which is added as a solvent when decomposing phenol resin cured products. Therefore, the recycling rate can be further improved by ensuring that the recycled phenol content is above the lower limit mentioned above. The recycled phenol content, when the phenol content in the phenol composition is taken as 100% by mass, can be calculated, for example, from the amount of raw materials used in the phenol composition. In this specification, the recycling rate refers to the proportion of recycled phenols among the phenols contained in the phenol composition.

[0032] In the phenol composition of this embodiment, the phenols preferably include phenol. In the phenol composition of this embodiment, when the content of phenols in the phenol composition is 100% by mass, the phenol content is preferably 20% by mass or more, more preferably 23% by mass or more, even more preferably 25% by mass or more, even more preferably 28% by mass or more, even more preferably 30% by mass or more, even more preferably 33% by mass or more, even more preferably 35% by mass or more, and even more preferably 40% by mass or more. In the phenol composition of this embodiment, when the content of phenols in the phenol composition is 100% by mass, there is no upper limit to the phenol content, but it may be 95% by mass or less, or 90% by mass or less. By having the phenol content in the phenols above the lower limit, the hardness of the phenol resin composition containing the phenol resin obtained using the phenol composition can be further improved. The phenol content when the content of phenols is 100% by mass can be measured by GPC according to Method 3 described above.

[0033] The phenol composition of this embodiment is preferably liquid at a temperature of 40°C. Being liquid facilitates transportation; for example, when using the phenol composition of this embodiment to produce phenol resin, it can be more easily transported from the equipment used to produce the phenol composition to the equipment used to produce the phenol resin, thereby improving work efficiency.

[0034] <Phenolic Resin> The phenolic resin of this embodiment contains structural unit a derived from phenols contained in the phenolic composition of this embodiment described above. The structural unit a derived from the phenolic composition of this embodiment preferably contains phenol and structural unit derived from polynuclear phenols containing two or more aromatic rings contained in the phenolic composition of this embodiment. In other words, the phenolic resin of this embodiment is obtained using the phenolic composition of this embodiment as a material. For this reason, the phenolic resin composition containing the phenolic resin of this embodiment has improved hardness.

[0035] The phenolic resin of the present embodiment can be a novolac-type phenolic resin or a resol-type phenolic resin.

[0036] <Phenolic resin composition> The phenolic resin composition of the present embodiment contains the phenolic resin of the present embodiment described above. Further, the phenolic resin composition of the present embodiment can contain other components other than the above-described components as long as the effects of the invention are not impaired. Examples of other components include thermosetting resins, thermoplastic resins, curing agents, inorganic fillers, organic fillers, inorganic fibers, organic fibers, mold release agents, pigments, flame retardants, adhesion improvers, coupling agents, elastomers, foaming agents, and the like. When the phenolic resin composition of the present embodiment contains these other components, it may contain only one kind or two or more kinds.

[0037] <Phenolic resin molding material> The phenolic resin molding material of the present embodiment contains the phenolic resin of the present embodiment described above. Further, the phenolic resin molding material of the present embodiment means a phenolic resin composition having a shape, composition, and properties suitable for molding processing. The phenolic resin molding material of the present embodiment is, for example, one filled with one or more materials selected from the group consisting of inorganic fillers, organic fillers, inorganic fibers, organic fibers, and flame retardants among the phenolic resin compositions of the present embodiment. When the content of the phenolic resin is 100 parts by mass, the content of one or more materials selected from the group consisting of inorganic fillers, organic fillers, inorganic fibers, organic fibers, and flame retardants in the phenolic resin molding material of the present embodiment is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, and still more preferably 90 parts by mass or more.

[0038] <Formed Body> The formed body of this embodiment includes a cured product of the phenolic resin composition or phenolic resin molding material of this embodiment described above. Further, when molding the phenolic resin composition or phenolic resin molding material of this embodiment, the molding method is not particularly limited as long as it is a method of curing the phenolic resin composition or phenolic resin molding material by heating or the like. For example, injection molding, transfer molding, compression molding, injection compression molding, etc. can be used. Examples of the uses of the formed body of this embodiment include automotive parts, electrical and electronic insulating parts, phenolic foams, abrasive products, refractory products, etc.

[0039] <Method for Producing Phenolic Composition> The method for producing the phenolic composition of this embodiment is, for example, a method of decomposing a cured phenolic resin to produce the phenolic composition of this embodiment. The method for producing the phenolic composition of this embodiment includes, for example, a decomposition step of heating and pressurizing a mixture containing a cured phenolic resin, phenol, and an alkali catalyst to decompose the cured phenolic resin and obtain a phenolic composition.

[0040] There is no particular limitation on the cured phenolic resin in the method for producing the phenolic composition. Examples include novolak-type phenolic resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin; resol-type phenolic resins such as unmodified resol phenolic resin and oil-modified resol phenolic resins modified with tung oil, linseed oil, walnut oil, etc.; and cured products thereof. Further, the cured phenolic resin in the method for producing the phenolic composition may be a composite material containing reinforcing fibers, fillers, additives, etc. Also, the cured phenolic resin in the method for producing the phenolic composition is not particularly limited as long as it is a cured product of the phenolic resin as described above, and products containing the above cured phenolic resin may be used. For example, molding materials and sealing materials containing a phenolic resin composition containing the above phenolic resin and an inorganic filler, or laminates produced by impregnating the above phenolic resin into an inorganic substrate or an organic substrate, and products containing the above cured phenolic resin such as a metal-clad laminate obtained by laminating a metal foil on this laminate.

[0041] In a method for producing a phenol composition, it is preferable that the cured phenol resin is pulverized before the decomposition step. The average particle size of the cured phenol resin after pulverization is preferably 1 mm or less, more preferably 100 μm or less, and even more preferably 50 μm or less. By keeping the average particle size of the cured phenol resin after pulverization below the above upper limit, the decomposition rate of the cured phenol resin can be further improved.

[0042] In the method for producing the phenol composition, phenol serves as a solvent for decomposing the cured phenol resin and remains in the phenol composition even after the decomposition of the cured phenol resin. Therefore, as described later, it also becomes a material for the phenol resin obtained by synthesizing the phenol composition of this embodiment. In the method for producing the phenol composition, the phenol content in the mixture is preferably 50 parts by mass or more and 1500 parts by mass or less, more preferably 100 parts by mass or more and 1200 parts by mass or less, even more preferably 100 parts by mass or more and 900 parts by mass or less, and even more preferably 100 parts by mass or more and 600 parts by mass or less, based on 100 parts by mass of the cured phenol resin. By having a phenol content in the mixture above the lower limit, the phenol composition can be made into a lower molecular weight composition. By having a phenol content in the mixture below the upper limit, the recycling rate of the phenol composition can be further improved.

[0043] In the method for producing the phenol composition, the alkali catalyst preferably includes one or more selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal phenolates, and alkaline earth metal phenolates, from the viewpoint of further improving the decompositionability of the cured phenol resin. The alkali metal hydroxide preferably includes one or more selected from the group consisting of potassium hydroxide and sodium hydroxide. The alkaline earth metal hydroxide preferably includes one or more selected from the group consisting of beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide, and more preferably includes calcium hydroxide. The alkali metal phenolates and alkaline earth metal phenolates preferably include one or more selected from the group consisting of sodium phenolate, potassium phenolate, and calcium phenolate. In the method for producing the phenol resin described later, when producing novolac resin, an acid catalyst is used in the synthesis of the novolac resin, so it is necessary to neutralize the alkali catalyst remaining in the phenol composition before synthesis. Therefore, from the viewpoint of promoting neutralization more smoothly, it is preferable to use a hydroxide of an alkaline earth metal with weaker alkalinity as the alkaline catalyst, and it is even more preferable to use calcium hydroxide.

[0044] In the method for producing a phenol composition, the content of the alkali catalyst in the mixture is preferably 0.1 parts by mass or more and 40 parts by mass or less, more preferably 0.2 parts by mass or more and 35 parts by mass or less, even more preferably 0.3 parts by mass or more and 30 parts by mass or less, and even more preferably 0.5 parts by mass or more and 25 parts by mass or less, when the total amount of the cured phenol resin is 100 parts by mass. By having an alkali catalyst content above the above lower limit, the decomposition rate of the cured phenol resin can be further improved, and the molecular weight of the resulting phenol composition can be further reduced.

[0045] Furthermore, in the method for producing the phenol composition, the above mixture may further contain water. By including water, the solubility of the alkaline catalyst in the mixture can be further improved when the alkaline catalyst contains an alkaline earth metal hydroxide. The water content in the mixture is preferably 0 to 150 parts by mass, more preferably 0 to 140 parts by mass, even more preferably 1 to 130 parts by mass, even more preferably 2 to 120 parts by mass, and even more preferably 3 to 110 parts by mass, based on 100 parts by mass of the phenol resin cured product.

[0046] In the method for producing a phenol composition, the content of the phenol resin cured product in the mixture is preferably 2 to 200 parts by mass, more preferably 5 to 150 parts by mass, even more preferably 8 to 100 parts by mass, even more preferably 8 to 80 parts by mass, and even more preferably 8 to 75 parts by mass, based on 100 parts by mass of phenol. By having a phenol resin cured product content above the lower limit, productivity can be further improved. By having a phenol resin cured product content below the upper limit, the decomposability of the phenol resin cured product can be further improved.

[0047] In the method for producing a phenol composition, the temperature and pressure used to heat and pressurize the mixture are preferably 200°C to 700°C and 0.5 MPa to 40.0 MPa, more preferably 213°C to 629°C and 0.6 MPa to 36.6 MPa, and even more preferably 255°C to 560°C and 1.0 MPa to 24.4 MPa, since the critical temperature of phenol is 421°C and the critical pressure is 6.1 MPa. By heating and pressurizing the mixture within the above range, the mixture containing phenol can be brought to a supercritical or subcritical state, thereby further improving the decomposition properties of the phenol resin cured product. That is, from the viewpoint of further improving the decomposition properties of the phenol resin cured product, it is preferable to carry out the decomposition step in this embodiment in a supercritical or subcritical state, and more preferably in a subcritical state. Furthermore, the pressure applied depends on the amount of water and phenol contained in the mixture. When the ratio of phenol content to water content in the mixture (P / W) is less than 10, the pressure is preferably 3.8 MPa or higher, and when P / W is 10 or higher, the pressure is preferably less than 3.8 MPa.

[0048] In the method for producing a phenol composition, the step of heating and pressurizing the mixture is preferably performed for 1 minute to 400 minutes, more preferably 2 minutes to 300 minutes, even more preferably 3 minutes to 200 minutes, and even more preferably 4 minutes to 100 minutes. Performing the heating and pressurizing step of the mixture for a time greater than or equal to the lower limit can further improve the decompositionability of the phenol resin cured product. Performing the heating and pressurizing step of the mixture for a time less than or equal to the upper limit can further improve productivity.

[0049] <Method for Producing Phenolic Resin> The method for producing phenolic resin according to this embodiment is, for example, a method for synthesizing phenolic resin using the phenolic composition of this embodiment. The method for producing phenolic resin according to this embodiment includes, for example, a step of heating a mixture containing the phenolic composition of this embodiment, formaldehyde, and a catalyst to synthesize phenolic resin. In addition, phenol may be added to the phenols in this step.

[0050] The method for producing the phenolic resin of this embodiment includes, for example, a method for synthesizing a resol-type phenolic resin and a method for synthesizing a novolac-type phenolic resin.

[0051] (Method for synthesizing resol-type phenolic resin) In a method for synthesizing resol-type phenolic resin, the catalyst preferably includes an alkaline catalyst. Examples of alkaline catalysts include alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, sodium carbonate, aqueous ammonia, tertiary amines such as triethylamine, and hexamethylenetetramine. Preferably, the catalyst includes one or more selected from the group consisting of alkali metal hydroxides and alkaline earth metal hydroxides, and more preferably, one or two selected from the group consisting of potassium hydroxide and sodium hydroxide.

[0052] In the method for synthesizing resol-type phenolic resin, for example, a mixture containing the phenolic composition of this embodiment, formaldehyde, and the above-mentioned alkaline catalyst can be heated to produce the resol-type phenolic resin. The heating can preferably be performed at a temperature of 50°C to 150°C, more preferably 60°C to 100°C. The heating time can preferably be 30 minutes to 500 minutes, more preferably 60 minutes to 250 minutes.

[0053] (Method for synthesizing novolac-type phenolic resin) In the method for synthesizing novolac-type phenolic resin, the catalyst preferably includes an acid catalyst. Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, phosphorous acid, oxalic acid, and p-toluenesulfonic acid; zinc acetate and lead naphthenate, which contain divalent metal ions when dissolved in phenol; and organic acids, preferably including oxalic acid. Furthermore, if high ortho novolac is desired, zinc acetate is preferably included. In addition, since an acid catalyst is used in the method for synthesizing novolac-type phenolic resin, it is preferable to neutralize the alkali catalyst used in the method for producing the phenolic composition (decomposition step of the cured phenolic resin) that remains in the phenolic composition before the step of synthesizing the phenolic resin. Neutralization can be carried out, for example, when using oxalic acid, until the pH of the phenolic composition is about 3 to 8, and after neutralization, it is preferable to remove the salt produced by filtration.

[0054] Furthermore, as a method for curing the novolac-type phenolic resin, it is preferable to incorporate a curing agent such as hexamethylenetetramine (hexamine) after the process of synthesizing the phenolic resin.

[0055] In the method for synthesizing novolac-type phenolic resin, for example, a mixture containing the phenolic composition of this embodiment, phenol, formaldehyde, the acid catalyst described above, and a curing agent can be heated and pressurized to synthesize a novolac-type phenolic resin. The heating can preferably be carried out at a temperature of 60°C to 120°C, more preferably 80°C to 100°C. The heating can preferably be carried out for 30 minutes to 500 minutes, more preferably 60 minutes to 300 minutes.

[0056] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and modifications, improvements, etc., that do not impair the effects of the present invention are included in the present invention.

[0057] 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.

[0058] The following phenolic resins and phenolic resin molding materials were cured and used as phenolic resin cured products for the production of the phenolic composition: ・Novolac-type phenolic resin molding material (containing glass filler (GF)): Sumitomo Bakelite Co., Ltd., product name: PM-9640 ・Novolac-type phenolic resin (13% hexamine, no GF): Sumitomo Bakelite Co., Ltd., product name: PR-51794 ・Novolac-type phenolic resin (7% hexamine, no GF): Sumitomo Bakelite Co., Ltd., product name: PR-217 ・Resol-type phenolic resin (no GF): Sumitomo Bakelite Co., Ltd., product name: PR-961A These phenolic resins and phenolic resin molding materials were cured by heating them in a dryer at 120°C for 2 hours, and then further cured by heating them at 200°C for 1 hour. After that, they were pulverized and sieved to obtain phenolic resin cured products with an average particle size of 50 μm.

[0059] <Example 1> (Production of phenol composition) 1000 parts by mass of phenol resin cured product obtained from novolac-type phenol resin molding material (containing GF), 107 parts by mass of calcium hydroxide, 693 parts by mass of water, and 2773 parts by mass of phenol were placed in an autoclave (internal volume: 6 L). The contents of the container were heated and pressurized while stirring at a rotation speed of 300 rpm, and maintained at a container temperature of 300°C and a container pressure of 6.1 MPa for 10 minutes. During the period of maintenance at a container temperature of 300°C and a container pressure of 6.1 MPa, the contents of the container were in a subcritical state. The ratio of the content of alkali catalyst M to the content of phenol resin cured product R (M / R) and the ratio of the content of phenol resin cured product R to the content of phenol P (R / P) are shown in Table 1. Next, 1000 parts by mass of the high-pressure reaction composition obtained in the above container and 1000 parts by mass of water were added to a 5 L three-necked flask equipped with a stirrer. Then, the temperature was maintained at 60°C and oxalic acid was further added to adjust the pH to 5. Next, 1000 parts by mass of methyl ethyl ketone (MEK) was further added to the three-necked flask to extract the phenol composition with MEK, and the MEK was removed by vacuum distillation to obtain a black liquid phenol composition.

[0060] (Weight-average molecular weight (Mw) and number-average molecular weight (Mn)) The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the phenols obtained in Example 1 were measured according to the following method. The results are shown in Table 1. <Method> The phenol composition was dissolved in THF at 25°C and 50 RH for 5 minutes by ultrasonic irradiation to a concentration of 0.3% by mass, filtered through a 0.2 μm pore size filter (Cytiva, product name: Whatman Puradisc 25, filter material: PTFE, membrane filter), and the filtrate was used as the THF-soluble matter. Next, the THF-soluble matter was measured by GPC under the following conditions to determine the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the phenols. The peak area was calculated as follows. In the elution curve, a straight line was drawn connecting the point where the rise from baseline began as the starting point and the point where the oligomer peak returned to baseline as the oligomer's endpoint. Similarly, a straight line was drawn connecting the point where the phenol peak began to rise from baseline as the starting point and the point where the elution peak returned to baseline as the phenol's endpoint. The sum of the areas enclosed by the two peak curves and the straight line was calculated. Measurement device: Product name HLC-8320 (manufactured by Tosoh Corporation) Column: Product name TSKgel G1000HXL, G2000HXL x 2, G3000HXL (manufactured by Tosoh Corporation) Eluent: THF Calibration curve: Polystyrene equivalent (Standard product: Product name TSKstandard POLYSTYRENE, manufactured by Tosoh Corporation, molecular weight range: 500 to 1,090,000, number of data points: 12) and phenol Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C

[0061] (Content of polynuclear phenols containing two or more aromatic rings, content of dinuclear phenols containing two aromatic rings, and content of phenol) The content of polynuclear phenols containing two or more aromatic rings and the content of dinuclear phenols containing two aromatic rings in the phenol composition obtained in Example 1 were measured according to the following method. The content of phenol in the phenol composition obtained in Example 1 was also measured. The results are shown in Table 1. Each content (mass%) is the value (mass%) when the content of phenols in the phenol composition is set to 100 mass%. <Method> The phenol composition was dissolved in THF at 25°C and 50 RH for 5 minutes by ultrasonic irradiation to a concentration of 0.3 mass%, filtered through a pore size 0.2 μm filter (Cytiva, product name: Whatman Puradisc 25, filter material: PTFE, membrane filter), and the filtrate was used as the THF soluble matter. Next, the THF-soluble components were measured by GPC under the following conditions, and the content of polynuclear phenols containing two or more aromatic rings in the phenol composition was calculated from the ratio of the peak area derived from polynuclear phenols containing two or more aromatic rings to the total peak area of ​​the measurement chart. Next, the content of dinuclear phenols containing two aromatic rings was calculated from the ratio of the peak area derived from dinuclear phenols containing two aromatic rings to the total peak area of ​​the measurement chart. Furthermore, the phenol content was calculated from the ratio of the peak area derived from phenol to the total peak area of ​​the measurement chart. The peak area was calculated as follows. In the elution curve, a straight line was drawn connecting the point where the oligomer started to rise from the baseline as the starting point, and the point where it returned to the baseline after the oligomer peak as the oligomer's endpoint. Of these, polynuclear phenols containing two or more aromatic rings and dinuclear phenols containing two aromatic rings were separated by drawing a vertical line at the minimum value before the dinuclear phenol, and the areas of the polynuclear phenols containing two or more aromatic rings and the dinuclear phenols containing two aromatic rings were calculated.Measuring device: Product name HLC-8320 (manufactured by Tosoh Corporation) Column: Product name DSKgel G1000HXL, G2000HXL x 2, G3000HXL (manufactured by Tosoh Corporation) Eluent: THF Calibration curve: Polystyrene equivalent (Standard product: Product name TSKstandard POLYSTYRENE, manufactured by Tosoh Corporation, molecular weight range: 500 to 1,090,000, number of data points: 12 points) and phenol Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C.

[0062] (Ortho-Ortho-Bisphenol F Ratio) The ortho-ortho-bisphenol F ratio in the phenol composition of Example 1 was measured by the following method. The results are shown in Table 1. <Method> The phenol composition was dissolved in THF at 25°C and 50 RH for 5 minutes by ultrasonic irradiation to a concentration of 0.3% by mass, filtered through a 0.2 μm pore size filter (Cytiva, product name: Whatman Puradisc 25, filter material: PTFE, membrane filter), and the filtrate was used as the THF-soluble component. Next, the THF-soluble component was measured by GPC under the following conditions, and the ortho-ortho-bisphenol F ratio (mass%) was calculated from the ratio of the peak area derived from ortho-ortho-bisphenol F to the peak area derived from bisphenol F. In the elution curve, the point where the rise from the baseline begins was used as the starting point, and the point where the oligomer returns to the baseline after the oligomer peak was used as the oligomer's endpoint, connected by a straight line. Of these, polynuclear phenols containing two or more aromatic rings and dinuclear phenols containing two aromatic rings were separated by drawing a vertical line based on the minimum value before the dinuclear phenol containing two aromatic rings, and the area of ​​the dinuclear phenol containing two aromatic rings was calculated. Furthermore, among the dinuclear phenols containing two aromatic rings, the peak with the slower elution time was designated as ortho-ortho-bisphenol F, and it was separated and calculated by drawing a vertical line at the minimum value between it and the other dinuclear phenols containing two aromatic rings. The peak area was calculated as follows: In the elution curve, the area of ​​the region enclosed by the above peak curve and the baseline was calculated. Measuring device: Product name HLC-8320 (manufactured by Tosoh Corporation) Column: Product name DSKgel G1000HXL, G2000HXL x 2, G3000HXL (manufactured by Tosoh Corporation) Eluent: THF Calibration curve: Polystyrene equivalent (Standard product: Product name TSKstandard POLYSTYRENE, manufactured by Tosoh Corporation, molecular weight range: 500 to 1,090,000, number of data points: 12 points) and phenol Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C

[0063] (Ratio of xanthene peak area X and presence or absence of cresol and xylenol) The peak area X of dinuclear phenol containing two aromatic rings in the phenol composition of Example 1 was determined by the following method. １ The peak area of ​​xanthene in relation to X ２ The ratio X was calculated. The presence or absence of one or more peaks selected from the group consisting of cresol and xylenol was also checked. The results are shown in Table 1. Note that if there was even one peak selected from the group consisting of cresol and xylenol, it was indicated as "Present". <Method> The phenol composition was dissolved in DMSO by shaking for 3 minutes under conditions of 25°C and 50 RH, and a 10 mass% DMSO diluted solution was prepared. 1 μL of this solution was introduced directly into the inlet of the GS / MS using an autosampler (product name: 7683B, manufactured by Agilent) and GC / MS measurement was performed to perform compositional analysis. Each detected peak was identified by its agreement with the retention time and mass spectrum of a separately measured standard. The peak area was calculated using the analysis software attached to the instrument (MassHunter Workstation Software, manufactured by Agilent). A straight line connecting the start and end points of each peak in the chromatogram was used as the baseline, and the area of ​​the region enclosed by the peak curve and the baseline was calculated. Measurement equipment GC: Agilent Technologies 6890N gas chromatograph MS: Agilent Technologies 5975B mass detector Column: Agilent Technologies HP-5MS (5% phenylpolydimethylsiloxane) (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Measurement conditions GC inlet temperature: 300°C GC oven temperature: 40°C (hold for 5 minutes) → 10°C / min → 300°C (hold for 9 minutes) Injection method: Split method (split ratio: 50 / 1) Carrier gas flow rate: He 1 mL / min (constant flow mode) MS ionization method: EI (electron ionization) method Ionization voltage: 70 eV MS detection mass range: m / z = 25 to 800 MS temperature: Ion source: 230°C, interface: 300°C Next, the ratio X was calculated from the obtained peak areas according to the following formula. X = (Xanthene peak area X) ２) / (peak area X of dinuclear phenol containing two aromatic rings) １ )

[0064] (Production of resol-type phenolic resin) 1000 parts by mass of the phenolic composition obtained in the above (production of phenolic composition), 862 parts by mass of 37% formalin (manufactured by Kanto Chemical Co., Ltd., product name: formaldehyde solution special grade), and 50 parts by mass of aqueous sodium hydroxide solution (manufactured by Kanto Chemical Co., Ltd., product name: 48% sodium hydroxide solution first grade) were charged into a reaction vessel and reacted at 80°C for 2 hours. Then, water was removed by vacuum distillation to obtain the phenolic resin.

[0065] (Hardness evaluation of cured products using resol-type phenolic resin) Using the obtained resol-type phenolic resin, a resin varnish was prepared by adjusting the phenolic resin content with acetone to 30% by mass. This varnish was impregnated into an aramid fiber substrate measuring 120 mm × 10 mm × 1 mm thick, and then dried and cured in an oven at 190°C for 30 minutes to obtain test specimens. The obtained test specimens were evaluated as follows. The results are shown in Table 1. Rockwell hardness (HRD): The hardness of the obtained test specimens was measured on the H scale according to the method in accordance with JIS Z 2245. A higher Rockwell hardness (HRD) value indicates a more hard test specimen.

[0066] <Examples 2-27, Comparative Examples 1-5> Except for the types of phenol resin cured products and alkali catalysts, the amounts of alkali catalyst, water, and phenol, and the temperature, pressure, and decomposition time during the production of the phenol composition, the production of the phenol composition and the phenol resin were carried out and evaluated in the same manner as in Example 1, as described in Table 1 or Table 2. The results are shown in Table 1 or 2.

[0067] <Reference Example 1> For comparison, the hardness of a phenol resin composition containing a phenol resin prepared using commercially available synthetic phenol was also evaluated. Specifically, 1000 parts by mass of commercially available synthetic phenol (manufactured by Kanto Chemical Co., Ltd., product name: Special Grade Phenol), 1294 parts by mass of 37% formalin (manufactured by Kanto Chemical Co., Ltd., product name: Special Grade Formaldehyde Solution), and 50 parts by mass of aqueous sodium hydroxide solution (manufactured by Kanto Chemical Co., Ltd., product name: 48% Sodium Hydroxide Solution Grade 1) were charged into a reaction vessel and reacted at 100°C for 2 hours. Then, water was removed by vacuum distillation to obtain a resol-type phenol resin. A cured product was prepared in the same manner as in Example 1, and its hardness was evaluated. The results are shown in Table 2.

[0068]

[0069]

[0070] Note that GF in Tables 1 and 2 refers to glass filler, M / R is the ratio of the alkali catalyst content M to the phenol resin curing content R, R / P is the ratio of the phenol resin curing content R to the phenol content P, and 100 × P ２ / P Ｘ is the content (mass%) of dinuclear phenols containing two aromatic rings, when the content of polynuclear phenols containing two or more aromatic rings in the phenol composition is taken as 100% by mass, and X represents the ratio X of the peak area of ​​xanthene to the peak area of ​​dinuclear phenols containing two aromatic rings.

[0071] This application claims priority based on Japanese Patent Application No. 2024-169351, filed on 27 September 2024, and incorporates all of its disclosures herein.

Claims

1. A phenol composition comprising phenols and xanthenes, wherein the weight-average molecular weight (Mw) of the phenols, as measured by the following Method 1, is 3000 or less. Method 1: The phenol composition is dissolved in THF, filtered through a 0.2 μm pore size filter, and the filtrate is used as the THF-soluble component. The THF-soluble component is then measured by GPC under the following conditions to determine the weight-average molecular weight (Mw) of the phenols. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C 2. The phenol composition according to claim 1, wherein the number average molecular weight (Mn) of the phenols, as measured by the following Method 2, is 1000 or less. Method 2 The phenol composition is dissolved in THF, filtered through a filter with a pore size of 0.2 μm, and the filtrate is used as the THF-soluble component. The THF-soluble component is then measured by GPC under the following conditions to determine the number average molecular weight (Mn) of the phenols. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C 3. The phenol composition according to claim 1 or 2, wherein the phenols include a polynuclear phenol containing two or more aromatic rings, and when the content of the phenols is 100% by mass, the content of the polynuclear phenol containing two or more aromatic rings, as measured by the following Method 3, is 10% by mass or more. <Method 3> The phenol composition is dissolved in THF and filtered through a filter with a pore size of 0.2 μm, and the filtrate is used as the THF-soluble component. The THF-soluble component is then measured by GPC under the following conditions, and the content of the polynuclear phenol containing two or more aromatic rings in the phenols is determined from the ratio of the peak area derived from the polynuclear phenol containing two or more aromatic rings to the total peak area of ​​the measurement chart. (Conditions) Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1 ml / min Temperature: 40°C 4. The phenol composition according to claim 3, wherein when the content of polynuclear phenols containing two or more aromatic rings is taken as 100% by mass, the content of dinuclear phenols containing two aromatic rings, as measured by Method 3, is 15% by mass or more.

5. The phenol composition according to claim 4, wherein the dinuclear phenol containing two aromatic rings contains bisphenol F.

6. The phenol composition according to claim 5, wherein the ortho-ortho-type bisphenol F ratio in the bisphenol F, as measured by Method 3, is 30.0% by mass or more.

7. The phenol composition according to any one of claims 1 to 6, wherein the phenols include one or more selected from the group consisting of cresol and xylenol.

8. The peak area X of dinuclear phenol containing two aromatic rings, measured by gas chromatography-mass spectrometry (GC-MS) according to Method 4 below. １ The peak area X of the xanthene in relation to the above. ２ The ratio X (=X) ２ / X １ The phenol composition according to any one of claims 1 to 7, wherein the ratio of the phenol composition to the phenol composition is 0.1 or greater. <Method 4> Using gas chromatography-mass spectrometry (GC-MS), 1 μL of a 10% by mass DMSO diluted solution of the phenol composition is analyzed according to the following (gas chromatography conditions), and the ratio X of the peak area of ​​the xanthene to the peak area of ​​the dinuclear phenol containing two aromatic rings is calculated. (Gas Chromatography Conditions) Measuring instrument: Gas chromatograph mass spectrometer Column: Capillary column (length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) GC inlet temperature: 300°C GC oven temperature: 40°C (hold for 5 minutes) → 10°C / min → 300°C (hold for 9 minutes) Injection method: Split method (split ratio: 50 / 1) Carrier gas flow rate: He (1 mL / min) MS ionization method: EI (electron ionization) method Ionization voltage: 70 eV MS detection mass range: m / z = 25 to 800 MS temperature: Ion source: 230°C, interface: 300°C 9. The phenol composition according to any one of claims 1 to 8, wherein the phenols include phenol.

10. The phenol composition according to claim 9, wherein when the content of the phenols is 100% by mass, the content of the phenol is 20% by mass or more.

11. A phenolic resin comprising structural unit a derived from phenols contained in any one of claims 1 to 10.

12. The phenolic resin according to claim 11, which is a novolac-type phenolic resin or a resol-type phenolic resin.

13. A phenolic resin composition or phenolic resin molding material comprising the phenolic resin according to claim 11 or 12.

14. A molded article comprising a cured product of the phenol resin composition or phenol resin molding material described in claim 13.

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