Phenol oligomer composition, bisphenol F composition, curing agent and epoxidized

Abstract

The present invention provides a phenol oligomer composition that can improve the curability of resin compositions. [Solution] A phenol oligomer composition comprising a dinuclear phenol containing two aromatic rings and a polynuclear phenol containing three or more aromatic rings, wherein the dinuclear phenol contains bisphenol F, the bisphenol F content in the phenol oligomer composition measured by a specific method is 35% by weight or more, and the ortho-ortho-bisphenol F content in the bisphenol F measured by a specific method is 15.0% by weight or more.

Description

[Technical Field]

[0001] This invention relates to phenol oligomer compositions, bisphenol F compositions, curing agents, and epoxidized products. [Background technology]

[0002] Bisphenol is used as a raw material for resins such as phenolic resins, polycarbonate resins, epoxy resins, and aromatic polyester resins.

[0003] Patent Document 1 discloses a method for producing a bisphenol compound represented by a specific general formula, comprising adding an organic solvent to at least one of a first mixture containing an acidic catalyst and a second mixture containing a phenol compound represented by a specific general formula and a ketone compound or aldehyde compound represented by a specific general formula, and then adding the second mixture to the first mixture to carry out a condensation reaction. Furthermore, Patent Document 1 describes "providing a method for producing bisphenol compounds that has a high reaction rate and selectivity and is efficient." [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-214248 [Overview of the project] [Problems that the invention aims to solve]

[0005] The present invention provides a phenol oligomer composition and a bisphenol F composition that can improve the curability of resin compositions. [Means for solving the problem]

[0006] The present invention is as follows. 1. A phenol oligomer composition comprising a dinuclear phenol containing two aromatic rings and a polynuclear phenol containing three or more aromatic rings, The aforementioned two nuclear phenols include bisphenol F, A phenol oligomer composition wherein the bisphenol F content in the phenol oligomer composition, as measured by the following <Method 1>, is 35% by weight or more, and the ortho-ortho-bisphenol F ratio in the bisphenol F, as measured by the following <Method 2>, is 15.0% by weight or more. <Method 1> The phenol oligomer 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 phenol oligomer 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℃ <Method 2> The phenol oligomer 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 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. 2. The phenol oligomer composition according to 1, wherein the bisphenol F content in the phenol oligomer composition measured by the above method 1 is 90% by weight or less. 3. The phenol oligomer composition according to 1. or 2., wherein the number average molecular weight (Mn) of the phenol oligomer composition measured by the following <Method 3> is 150 or more and 1000 or less. <Method 3> Dissolve the phenol oligomer 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 phenol oligomer composition. Eluent: THF Calibration curve: polystyrene conversion Detector: differential refractometer Flow rate: 1 ml / min Temperature: 40 °C 4. A bisphenol F composition containing bisphenol F, wherein the content of bisphenol F in the bisphenol F composition measured by the following <Method 4> is 70% by weight or more, and the ortho-ortho type bisphenol F ratio in the bisphenol F measured by the following <Method 5> is 15.0% by weight or more. <Method 4> 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 content of bisphenol F in the bisphenol F composition 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 conversion Detector: differential refractometer Flow rate: 1 ml / min Temperature: 40 °C <Method 5> The bisphenol F composition under the following conditions 1 Perform 1H-NMR measurement, 1 and obtain a 1H-NMR spectrum. Solvent: deuterated acetone Number of integrations: 32 times Next, the above-mentioned1 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 is used to calculate the ortho-ortho type bisphenol F ratio in the bisphenol F. 5. The bisphenol F composition according to 4., wherein the number average molecular weight (Mn) of the bisphenol F composition measured by the following <Method 6> is 130 or more and 1000 or less. <Method 6> The bisphenol F composition is dissolved in THF and filtered through a filter with a pore size of 1.0 μm, and the filtrate is used as the THF soluble content. Next, the THF soluble content is measured by GPC under the following conditions to calculate the number average molecular weight (Mn) of the bisphenol F composition. Eluent: THF Calibration curve: polystyrene conversion Detector: differential refractometer Flow rate: 1 ml / min Temperature: 40 °C 6. A curing agent containing the phenol oligomer composition according to any one of 1. to 3. 7. A curing agent containing the bisphenol F composition according to 4. or 5. 8. An epoxidized product of the phenol oligomer composition according to any one of 1. to 3. 9. An epoxidized product of the bisphenol F composition according to 4. or 5.

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a phenol oligomer composition and a bisphenol F composition that can improve the curability of the resin composition.

Embodiments for Carrying Out the Invention

[0008] 1. Phenol oligomer composition Hereinafter, the phenol oligomer composition of the present embodiment will be described.

[0009] The phenolic oligomer composition of this embodiment is a phenolic oligomer composition containing a binuclear phenol having two aromatic rings and a polynuclear phenol having three or more aromatic rings. The binuclear phenol of this embodiment contains bisphenol F, and the content of bisphenol F in the phenolic oligomer composition of this embodiment measured by the following <Method 1> is 35% by weight or more, and the content of ortho-ortho type bisphenol F in bisphenol F of this embodiment measured by the following <Method 2> is 15.0% by weight or more. <Method 1> Dissolve the phenolic oligomer composition of this embodiment in THF, filter it with a filter having 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 content of bisphenol F in the phenolic oligomer composition of this embodiment 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 conversion Detector: differential refractometer Flow rate: 1 ml / min Temperature: 40 °C <Method 2> Measure the phenolic oligomer composition of this embodiment under the following conditions 1 by 1H-NMR measurement, 1 and obtain a 1H-NMR spectrum. Solvent: deuterated acetone Number of integrations: 32 times Next, 1 calculate the ratio of ortho-ortho type bisphenol F in bisphenol F of this embodiment 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 1H-NMR spectrum.

[0010] 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.

[0011] Although the mechanism by which the phenol oligomer composition of this embodiment can improve the curability of the resin composition is not clear, it is presumed that by setting the content of bisphenol F in the phenol oligomer composition and the content of ortho-ortho-type bisphenol F in the bisphenol F to a certain range, the curing of the resin composition is promoted, thereby improving the curability of the resin composition.

[0012] The bisphenol F content in the phenol oligomer composition of this embodiment, as measured by Method 1 above, is preferably 38% by weight or more, more preferably 40% by weight or more, even more preferably 42% by weight or more, even more preferably 44% by weight or more, and even more preferably 46% by weight or more, from the viewpoint of further improving the curability of the resin composition.

[0013] The ortho-ortho-type bisphenol F ratio in the bisphenol F of this embodiment, measured by the above-described Method 2, is preferably 20.0% by weight or more and 99.0% by weight or less, 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 45.0% by weight or more and 85.0% by weight or less, even more preferably 50.0% by weight or more and 80.0% by weight or less, even more preferably 55.0% by weight or more and 75.0% by weight or less, and even more preferably 60.0% by weight or more and 70.0% by weight or less.

[0014] The bisphenol F content in the phenol oligomer composition of this embodiment, as measured by Method 1 above, is preferably 90% by weight or less, more preferably 80% by weight or less, even more preferably 70% by weight or less, even more preferably 60% by weight or less, even more preferably 50% by weight or less, and preferably 38% by weight or more and 90% by weight or less, more preferably 40% by weight or more and 80% by weight or less, even more preferably 42% by weight or more and 70% by weight or less, even more preferably 44% by weight or more and 60% by weight or less, and even more preferably 46% by weight or more and 50% by weight or less.

[0015] The number-average molecular weight (Mn) of the phenol oligomer composition of this embodiment, measured by the following Method 3, is preferably 150 to 1000, more preferably 160 to 800, even more preferably 170 to 600, even more preferably 180 to 400, even more preferably 190 to 300, and even more preferably 195 to 250, from the viewpoint of further improving the curability of the resin composition. <Method 3> The phenol oligomer 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 components are measured by GPC under the following conditions, and the number-average molecular weight (Mn) of the phenol oligomer composition of this embodiment is calculated. Eluent:THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃

[0016] The phenol oligomer 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 phenol oligomer composition of this embodiment with a resin such as a novolac-type phenol resin, a resol-type phenol resin, or 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.

[0017] The method for producing the phenol oligomer composition of this embodiment is not limited, but for example, it can be produced by a production method that 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.

[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 2.000, even more preferably 0.005 to 1.800, even more preferably 0.010 to 1.800, even more preferably 0.020 to 1.700, even more preferably 0.025 to 1.700, and even more preferably 0.030 to 1.600, from the viewpoint of further improving the ortho-ortho-bisphenol F ratio.

[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 when the cured phenol resin composition is decomposed, 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] 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, from the viewpoint of further improving the ortho-ortho-bisphenol F ratio.

[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 phenol oligomer 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] 2. Bisphenol F composition The bisphenol F composition of this embodiment will be described below.

[0030] The bisphenol F composition of this embodiment is a bisphenol F composition containing bisphenol F, wherein the bisphenol F content in the bisphenol F composition of this embodiment, as measured by <Method 4> below, is 70% by weight or more, and the ortho-ortho-bisphenol F ratio in the bisphenol F of this embodiment, as measured by <Method 5> below, is 15.0% by weight or more. <Method 4> 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℃ <Method 5> The bisphenol F composition of this embodiment 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, 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] Although the mechanism by which the bisphenol F composition of this embodiment can improve the curability of the resin composition is not clear, it is presumed that by setting the content of bisphenol F and the content of ortho-ortho-type bisphenol F in the bisphenol F composition to a certain range, the curing of the resin composition is promoted, thereby improving the curability of the resin composition.

[0032] The bisphenol F content in the bisphenol F composition of this embodiment, as measured by Method 4 above, is preferably 70% by weight or more and 99% by weight or less, more preferably 75% by weight or more and 98% by weight or less, even more preferably 77% by weight or more and 95% by weight or less, even more preferably 80% by weight or more and 92% by weight or less, even more preferably 82% by weight or more and 90% by weight or less, and even more preferably 84% by weight or more and 88% by weight or less, from the viewpoint of further improving the curability of the resin composition.

[0033] The ortho-ortho-type bisphenol F ratio in the bisphenol F of this embodiment, measured by Method 5 above, is preferably 20.0% by weight or more and 99.0% by weight or less, 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 45.0% by weight or more and 85.0% by weight or less, even more preferably 50.0% by weight or more and 80.0% by weight or less, even more preferably 53.0% 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.

[0034] The number-average molecular weight (Mn) of the bisphenol F composition of this embodiment, measured by the following Method 6, is preferably 130 to 1000, more preferably 131 to 800, even more preferably 132 to 600, even more preferably 133 to 400, even more preferably 134 to 300, even more preferably 135 to 200, and even more preferably 135 to 150, from the viewpoint of further improving the curability of the resin composition. <Method 6> 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℃

[0035] The uses of the bisphenol F composition of this embodiment are not particularly limited, and it 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 resins such as novolac-type phenol resins, resol-type phenol resins, and epoxy resins; curing agents such as hexamethylenetetramine; curing aids such as magnesium oxide and calcium hydroxide; and inorganic or organic fillers.

[0036] The method for producing the bisphenol F composition of this embodiment is not limited, but for example, it can be produced by a production method that includes step B of separating the bisphenol F composition from the phenol oligomer composition of this embodiment.

[0037] In step B of this embodiment, the method for separating the bisphenol F composition from the phenol oligomer 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.

[0038] 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.

[0039] 3. Hardener The curing agent of this embodiment will be described below.

[0040] The curing agent of this embodiment includes the phenol oligomer composition of this embodiment.

[0041] The curing agent of this embodiment comprises the bisphenol F composition of this embodiment.

[0042] The curing agent of this embodiment may contain components other than the phenol oligomer composition and / or the bisphenol F composition of this embodiment, and may also contain components known as curing agents, such as hexamethylenetetramine.

[0043] The curing agent 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 curing agent of this embodiment with a resin such as a novolac-type phenolic resin, a resol-type phenolic 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.

[0044] 4. Epoxy compounds The epoxidized compounds of this embodiment will be described below.

[0045] The epoxidized product of this embodiment is an epoxidized product of the phenol oligomer composition described above.

[0046] The epoxidized product of this embodiment is the epoxidized product of the bisphenol F composition described above.

[0047] The method for obtaining the epoxidized product of this embodiment is not particularly limited, and it can be obtained by epoxidizing the phenol oligomer composition and / or the bisphenol F composition of this embodiment by a known method.

[0048] The uses of the epoxidized product of this embodiment are not particularly limited, and it can be used, for example, as a raw material for resin compositions. For example, a resin composition can be obtained by mixing the epoxidized product of this embodiment with a resin such as a novolac-type phenolic resin, a resol-type phenolic 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.

[0049] 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]

[0050] 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.

[0051] <Example 1> The cured product of a phenolic resin 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 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 phenolic resin with adjusted particle size, 80g of calcium hydroxide (Kanto Chemical Co., Ltd., special grade), 130g of water, and 2470g of phenol (Kanto Chemical Co., Ltd., special grade) were placed in an autoclave (Toyo Koatsu Co., Ltd., internal volume: 6L). The contents were then heated and pressurized inside the container while stirring at 300 rpm, and maintained at an internal temperature of 300°C and internal pressure of 6 MPa for 10 minutes. Furthermore, while the internal temperature of the container was maintained at 300°C and the internal pressure at 6 MPa, the inside of the container was in a subcritical state. Next, the internal temperature of the container was set to 70°C and the internal pressure to atmospheric pressure. 230 parts by weight of oxalic acid (manufactured by Kanto Chemical, special grade) was added per 1000 parts by weight of the cured phenol resin, 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 a phenol oligomer composition. Next, 75 parts by weight of novolac-type phenolic resin, 25 parts by weight of the phenol oligomer composition obtained by the above method, and 15 parts by weight of hexamethylenetetramine were placed in a container and mixed under conditions of a rotation speed of 100 rpm and a temperature of 120°C to obtain a mixture. Next, a curing test was performed on the resulting mixture using a Curlastometer® (manufactured by JSR Trading, IID) set to a curing temperature of 150°C. The results are shown in Table 1.

[0052] <Example 2> The phenol oligomer composition obtained by the above method was subjected to vacuum steam distillation at 240°C to obtain a bisphenol F composition. Next, a curing test was performed in the same manner as in Example 1, except that 25 parts by weight of the bisphenol F composition obtained by the above method was used instead of 25 parts by weight of the phenol oligomer composition obtained by the above method. The results are shown in Table 1.

[0053] <Comparative Example 1> A curing test was performed in the same manner as in Example 1, except that 25 parts by weight of bisphenol F (Gun-ei Chemical Co., Ltd., Regitop BPF) was used instead of 25 parts by weight of the phenol oligomer composition obtained by the above method. The results are shown in Table 1.

[0054] The bisphenol F content in the phenol oligomer composition of Example 1, the bisphenol F composition of Example 2, and the bisphenol F of Comparative Example 1 (Gun-ei Chemical Co., Ltd., Regitop BPF) was measured using the method described below. The results are shown in Table 1. <Method> The phenol oligomer composition of Example 1, the bisphenol F composition of Example 2, or the bisphenol F of Comparative Example 1 (Regitop BPF, manufactured by Gun-ei Chemical Co., Ltd.) was dissolved in THF, filtered through a 1.0 μm pore size filter, and the filtrate was used as the THF-soluble component. Next, the obtained THF-soluble components were measured by GPC under the following conditions, and the bisphenol F content 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: Tosoh Corporation, HLC-8320GPC Eluent:THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃ Furthermore, the measurement chart for Example 1 obtained by the above method showed peaks derived from dinuclear phenols containing two aromatic rings and polynuclear phenols containing three or more aromatic rings. This indicates that the phenol oligomer composition of Example 1 contains dinuclear phenols containing two aromatic rings and polynuclear phenols containing three or more aromatic rings.

[0055] The ortho-ortho-bisphenol F ratio of bisphenol F in the phenol oligomer composition of Example 1, the bisphenol F composition of Example 2, and the bisphenol F of Comparative Example 1 (Gun-ei Chemical Co., Ltd., Regitop BPF) was measured using the method described below. The results are shown in Table 1. <Method> The phenol oligomer composition of Example 1, the bisphenol F composition of Example 2, or the bisphenol F of Comparative Example 1 (Regitop BPF, manufactured by Gun-ei Chemical Co., Ltd.) was subjected to the following conditions. 1 H-NMR measurement was performed, 1 1H-NMR spectra were obtained. NMR measurement device: JEOL, JMTC-400 Solvent: Deuterated acetone Total number of times: 32 Next, obtained 1 The ortho-ortho bisphenol F ratio in bisphenol F was calculated from the ratio of the area of ​​the peak at 3.925±0.100 ppm, which originates from ortho-ortho methylene bonds, to the area of ​​all peaks at 3.0–4.5 ppm, which originate from methylene bonds in the 1H-NMR spectrum.

[0056] The number-average molecular weight (Mn) of the phenol oligomer composition of Example 1, the bisphenol F composition of Example 2, and the bisphenol F (Regitop BPF, manufactured by Gun-ei Chemical Co., Ltd.) of Comparative Example 1 was measured using the method described below. The results are shown in Table 1. <Method 6> The bisphenol F composition was dissolved in THF, filtered through a 1.0 μm pore size filter, and the filtrate was used as the THF-soluble component. Next, the THF-soluble components were measured by GPC under the following conditions, and the number-average molecular weight (Mn) of the bisphenol F composition was calculated. Eluent:THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃

[0057] [Table 1]

[0058] In the example, the torque of the Curlastometer (registered trademark) increased more rapidly compared to the comparative example. This indicates that the phenol oligomer composition and bisphenol F composition of this embodiment can improve the curability of the resin composition.

Claims

1. A phenol oligomer composition comprising a dinuclear phenol containing two aromatic rings and a polynuclear phenol containing three or more aromatic rings, The aforementioned two-nuclear phenol contains bisphenol F, A phenol oligomer composition in which the bisphenol F content measured by the following <Method 1> is 35% by weight or more, and the ortho-ortho-bisphenol F ratio in the bisphenol F measured by the following <Method 2> is 15.0% by weight or more. <Method 1> The phenol oligomer 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 content is measured by GPC under the following conditions, and the bisphenol F content in the phenol oligomer 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℃ <Method 2> The phenol oligomer 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.

2. The phenol oligomer composition according to claim 1, wherein the bisphenol F content in the phenol oligomer composition measured by the above-mentioned Method 1 is 90% by weight or less.

3. The phenol oligomer composition according to claim 1 or 2, wherein the number average molecular weight (Mn) of the phenol oligomer composition measured by the following <Method 3> is 150 or more and 1000 or less. <Method 3> The phenol oligomer 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 phenol oligomer composition is calculated. Eluent: THF Calibration curve: Polystyrene equivalent Detector: Differential refractometer Flow rate: 1ml / min Temperature: 40℃

4. A bisphenol F composition containing bisphenol F, A bisphenol F composition in which the bisphenol F content measured by the following <Method 4> is 70% by weight or more, and the ortho-ortho-bisphenol F ratio in the bisphenol F measured by the following <Method 5> is 15.0% by weight or more. <Method 4> 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℃ <Method 5> 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.

5. The bisphenol F composition according to claim 4, wherein the number average molecular weight (Mn) of the bisphenol F composition measured by the method described in <Method 6> below is 130 or more and 1000 or less. <Method 6> 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℃

6. A curing agent comprising the phenol oligomer composition according to claim 1 or 2.

7. A curing agent comprising the bisphenol F composition according to claim 4 or 5.

8. An epoxidized phenol oligomer composition according to claim 1 or 2.

9. An epoxidized bisphenol F composition according to claim 4 or 5.

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