Epoxy resin mixture, curable resin composition, and cured object therefrom

Abstract

This epoxy resin mixture is a product of reaction between an epihalohydrin and a phenolic-resin mixture comprising 50-95 mass% of a phenolic resin represented by formula (2) and 5-50 mass% of biphenol, the epoxy resin mixture having a content of an epoxidized product of biphenol of 5-35 area% with respect to the whole epoxy resin mixture in terms of areal percentage by GPC of the epoxy resin mixture. In formula (2), n is the average number of repetitions and is a real number satisfying 0<n≤10 and X is represented by any of formulae (a) to (g). In formulae (a) to (g), the R1 moieties, R2 moieties, symbols p, and symbols q are each independent, and R1 represents a hydrogen atom, a C1-C20 alkyl group, or an optionally substituted C6-C20 aromatic group, R2 represents a C1-C20 alkyl group or an optionally substituted C6-C20 aromatic group, p is an integer of 0-4, and q is an integer of 0-3; r is an average number of repetitions and is a real number satisfying 1<r<10; and * indicates a bonding site for the X.

Description

Epoxy resin mixture, curable resin composition and its cured product

[0001] The present invention relates to epoxy resin mixtures, epoxy resin compositions, and their cured products, and is suitable for electrical and electronic material applications where heat resistance is required.

[0002] Curable resin compositions containing epoxy resin are widely used in fields such as electrical and electronic components, structural materials, adhesives, and paints due to their workability and the excellent electrical properties, heat resistance, adhesiveness, and moisture resistance (water resistance) of their cured products.

[0003] Epoxy resins, when cured, generally become cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties, and are used in a wide range of fields such as adhesives, paints, laminates, molding materials, and casting materials. However, in recent years, with the development of the electrical and electronic fields, there has been a demand for further improvements in various properties, including higher purity of resin compositions, moisture resistance, adhesion, dielectric properties, lower viscosity for high-density filling of fillers (inorganic or organic fillers), and improved reactivity to shorten molding cycles. Furthermore, as structural materials, lightweight materials with excellent mechanical properties are required for applications such as aerospace materials and leisure and sports equipment. In particular, in the semiconductor encapsulation field and substrates (the substrate itself or its surrounding materials), the complexity has increased with the evolution of semiconductors, from thinning and stacking to systemization and three-dimensionality, requiring extremely high levels of heat resistance and high fluidity. Especially with the expansion into automotive applications, the demand for improved heat resistance in epoxy resins has become even more stringent. Furthermore, in order to reduce the overall coefficient of thermal expansion of the sealing material, it is necessary that the epoxy resin be able to be filled with a high amount of filler, meaning that the epoxy resin must have a low melt viscosity.

[0004] In applications such as semiconductor encapsulants, heat resistance and flame retardancy are required, so biphenyl novolac type epoxy resins are widely used. However, epoxy resins with high heat resistance, such as biphenyl novolac type epoxy resins, tend to have high softening points, making them difficult to use in encapsulant applications unless their viscosity is reduced.

[0005] Japanese Patent Publication No. 2002-338656 Japanese Patent No. 5252671 Japanese Patent No. 7594711

[0006] Patent Document 1 proposes a crystalline epoxy resin with an increased concentration of a difunctional compound as a means of reducing the melt viscosity of biphenyl novolac type epoxy resins. However, simply increasing the concentration of the difunctional compound may cause the epoxy resin to solidify. If an epoxy resin that is prone to solidification is used in a semiconductor encapsulant containing fillers, phenolic resin curing agents, and curing accelerators, the crystallinity in the semiconductor encapsulant composition cannot be maintained, leading to problems such as blocking and solidification of the semiconductor encapsulant composition when pressure and temperature are applied during transportation.

[0007] Patent Document 2 describes a biphenyl novolac type epoxy resin in which crystallinity is further enhanced by controlling the orientation. It also states that a highly crystalline biphenol epoxide may be used. However, because the biphenol epoxide is too crystalline, it precipitates during epoxidation synthesis, leading to the problem of an increased proportion of epoxy that does not undergo ring closure during the reaction. Therefore, epoxy resin mixtures simply made by mixing a biphenyl novolac type epoxy resin and a phenol epoxide result in a slower curing rate (longer gel time), which increases the cycle time during transfer molding and reduces production efficiency.

[0008] For these reasons, when an epoxy resin mixture is prepared by mixing a biphenyl novolac-type skeleton with a highly crystalline biphenol epoxidized compound, it is difficult to simultaneously satisfy low melt viscosity and low solidification without reducing the curing rate for semiconductor encapsulant applications.

[0009] Patent Document 3 describes an epoxy resin having a furfural skeleton with low melt viscosity. However, this epoxy resin has a low softening point and is tacky even at room temperature, so further improvements in handling properties during molding are required for encapsulant and CFRP applications.

[0010] However, even when epoxy resins with a furfural skeleton are mixed with epoxidized biphenols of high crystalline composition, it is difficult to simultaneously satisfy low melt viscosity and low solidification without reducing the curing rate for semiconductor encapsulant applications, due to the circumstances described above.

[0011] This invention has been made in view of the above circumstances, and aims to provide an epoxy resin mixture that simultaneously satisfies low melt viscosity and low solidification. Furthermore, it aims to provide a curable resin composition and its cured product that have a fast curing rate by using this epoxy resin mixture.

[0012] In other words, the present invention relates to an epoxy resin mixture which is a reaction product of a phenol resin mixture containing 50 to 95% by mass of a phenol resin represented by the following formula (2) and 5 to 50% by mass of biphenol and an epihalohydrin, wherein the content of the biphenol epoxidized product in the total amount of the epoxy resin mixture is 5 to 35 area percent in terms of the GPC area percentage of the epoxy resin mixture.

[0013] In equation (2), n is the average value of the number of repetitions, a real number such that 0 < n ≤ 10, and X is expressed by any of the following equations (a) to (g).

[0014] In equations (a) to (g), there are multiple R's. １ , R ２ p and q exist independently of each other, R １ R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may have substituents. ２ * represents an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, which may have substituents. p is an integer from 0 to 4, and q is an integer from 0 to 3. r is the average number of repeats, and is a real number between 1 and 10. * indicates the bond position of X.

[0015] According to the present invention, it is possible to provide an epoxy resin mixture that simultaneously satisfies low melt viscosity and low solidification. Furthermore, by using this epoxy resin mixture, it is possible to provide a curable resin composition with a fast curing rate and its cured product.

[0016] The GPC chart of the epoxy resin of Synthesis Example 1-1 is shown. The GPC chart of the phenolic resin of Synthesis Example 2-1 is shown. The GPC chart of the epoxy resin of Synthesis Example 3-1 is shown. The GPC chart of the epoxy resin mixture of Synthesis Example 4-1 is shown. The GPC chart of the epoxy resin of Synthesis Example 1-2 is shown. The GPC chart of the epoxy resin of Synthesis Example 3-2 is shown. The GPC chart of the epoxy resin mixture of Synthesis Example 4-2 is shown.

[0017] Hereinafter, embodiments according to the present invention (hereinafter also referred to as "the present embodiment") will be described in more detail.

[0018] The epoxy resin mixture of the present embodiment is obtained by reacting a phenolic resin represented by the following formula (2), a phenolic mixture containing biphenol, and epihalohydrin.

[0019] In formula (2), n is the average value of the number of repetitions, a real number of 0 < n ≤ 10, more preferably a real number of 0 < n ≤ 5, still more preferably 1 ≤ n ≤ 5, and particularly preferably 1 < n ≤ 3.

[0020] In the above formula (2), the value of n can be calculated from the number average molecular weight determined by measurement of gel permeation chromatography (GPC, detector: RI), or from the area ratio of each separated peak.

[0021] X is represented by any one of the following formulas (a) to (g).

[0022] In formulas (a), (d) to (g), a plurality of R １ , R ２ , p, and q exist independently of each other, and R １ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may have a substituent, and R ２ represents an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may have a substituent. The alkyl group in R １ and R ２ is preferably when the number of carbon atoms is 1 to 5, and more preferably when it is a methyl group. R １is preferably a hydrogen atom. p is an integer from 0 to 4, preferably from 0 to 2, and more preferably 0. q is an integer from 0 to 3, preferably from 0 to 2, and more preferably 0. r is the average value of the number of repetitions, a real number between 1 and 10, more preferably 1 and r < 7, and particularly preferably 1 and r < 5. * indicates the bond position of X.

[0023] In a phenol resin mixture, which is a mixture of phenol resin and biphenol represented by formula (2) above, if the biphenol component is too low, the crystallinity of the epoxy resin mixture after the reaction cannot be maintained, and the epoxy resin mixture may block and solidify. Blocking and solidification of the epoxy resin mixture can lead to the semiconductor encapsulant composition using it blocking and solidifying with each other when pressure and temperature are applied during transport. If the biphenol component is too high, the crystallinity of the epoxy resin mixture may be too high, raising the softening point and potentially worsening the handling properties during molding. Therefore, the mixing ratio of the phenol resin represented by formula (2) and biphenol (phenol resin represented by formula (2): biphenol) is preferably 50 to 95% by mass: 5 to 50% by mass, and more preferably 70 to 90% by mass: 10 to 30% by mass.

[0024] If the biphenol epoxidized content in the epoxy resin mixture is too low, crystallinity cannot be maintained, and the epoxy resin mixture may block and solidify. Blocking and solidification of the epoxy resin mixture can lead to the semiconductor encapsulant composition using it blocking and solidifying when pressure and temperature are applied during transport. If the biphenol epoxidized content is too high, the crystallinity will be too high, raising the softening point and potentially worsening handling during molding. Therefore, in the GPC area percentage of the epoxy resin mixture in this embodiment, the biphenol epoxidized content in the total amount of epoxy resin mixture is preferably 5 to 35 area%, and more preferably 10 to 25 area%.

[0025] The epoxy resin mixture of this embodiment preferably has a softening point of 50°C to 130°C, and more preferably 80°C to 110°C. Having a softening point within this range provides excellent handling properties.

[0026] The hydroxyl group equivalent of the phenol resin represented by formula (2) above is preferably 100 g / eq. to 240 g / eq., and more preferably 120 g / eq. to less than 200 g / eq. When the hydroxyl group equivalent of the phenol resin represented by formula (2) above is within the above range, the functional group density in the cured product increases, and the resulting cured product has excellent heat resistance and mechanical strength, which is therefore preferable.

[0027] The epihalohydrins mentioned above are readily available from the market. For example, epichlorohydrin, β-methylepichlorohydrin, and epibromohydrin can be used. The amount of epihalohydrin used is usually 2.0 to 10 moles, preferably 3.0 to 8.0 moles, and more preferably 3.5 to 6.0 moles, per mole of hydroxyl groups in the raw material phenol mixture.

[0028] In the reaction between the above-mentioned phenol resin mixture and epihalohydrin, an alkali metal hydroxide can be used as a catalyst to accelerate the epoxidation process. Examples of alkali metal hydroxides that can be used include sodium hydroxide and potassium hydroxide. A solid form may be used, or an aqueous solution thereof may be used. In this embodiment, the use of a solid form molded into flakes is particularly preferred in terms of solubility and handling. The amount of alkali metal hydroxide used is usually 0.90 to 1.5 moles per mole of hydroxyl groups in the raw material phenol mixture, preferably 0.95 to 1.25 moles, and more preferably 0.99 to 1.15 moles.

[0029] Furthermore, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride may be added as catalysts to accelerate the epoxidation reaction. The amount of quaternary ammonium salt used is 0.01 to 15 moles, preferably 0.2 to 5 moles, per mole of hydroxyl groups in the raw material phenol mixture.

[0030] The temperature of the epoxidation reaction is preferably 30 to 90 °C, more preferably 35 to 80 °C. The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and particularly preferably 1 to 3 hours. If the reaction time is short, the epoxidation reaction does not proceed completely, and if the reaction time is long, by-products are formed, which is not preferable.

[0031] After the reaction products of these epoxidation reactions are washed with water or without washing with water, epihalohydrin, solvent, etc. are removed under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the recovered epoxy resin is dissolved in a solvent, an aqueous solution of an alkali metal hydroxide is added and the reaction is carried out to ensure ring closure. Examples of the solvent include ketone compounds having 4 to 7 carbon atoms such as methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, and cyclohexanone. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the hydroxyl group of the raw material phenol mixture used for epoxidation. The reaction temperature is preferably 50 to 120 °C, and the reaction time is more preferably 0.5 to 2 hours.

[0032] After completion of the epoxidation reaction, the generated salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin mixture of this embodiment.

[0033] In one aspect of the present embodiment, if the content of the compound with n = 1 in the total amount of the phenolic resin represented by the formula (2) is too small, the crystallinity of the epoxy resin mixture after the reaction cannot be maintained, and the epoxy resin mixture may be blocked and solidified. The blocking and solidification of the epoxy resin mixture may lead to the risk that the semiconductor encapsulant compositions using it may be blocked and solidified when pressure and temperature are applied during transportation. If the content of the compound with n = 1 is too large, the crystallinity is too high and the softening point becomes high, which may deteriorate the handling property during molding. Therefore, in one aspect of the present embodiment, in the GPC area percentage of the phenolic resin represented by the above formula (2), the content of the compound with n = 1 in the total amount of the phenolic resin represented by the above formula (2) is preferably 40 to 100 area%, more preferably 60 to 90 area%, and particularly preferably 70 to 85 area%.

[0034] In one aspect of the present embodiment, in the phenolic resin mixture, the crystallinity of the epoxy resin mixture after the reaction changes depending on the component ratio between the compound represented by the following formula (3) and the compound represented by the following formula (4) among the compounds in which n in the formula (2) is represented by 1. Therefore, depending on the component ratio, the epoxy resin mixture may be blocked and solidified. The blocking and solidification of the epoxy resin mixture may lead to the risk that the semiconductor encapsulant compositions using it may be blocked and solidified when pressure and temperature are applied during transportation. In one aspect of the present embodiment, in the HPLC area percentage of the phenolic resin represented by the above formula (2), the value obtained by dividing the area of the compound represented by the following formula (3) by the area of the compound represented by the following formula (4) is preferably 1.15 or more and 1.30 or less, and more preferably 1.15 or more and 1.25 or less.

[0035] In the formulas (3) and (4), X is represented by any one of the above formulas (a) to (g).

[0036] In one embodiment of this embodiment, the epoxy resin mixture may include, in addition to the epoxidized phenol resin represented by formula (2) (the epoxidized phenol resin represented by formula (1) below) and the epoxidized biphenol, an epoxidized compound having the structures shown in formulas (6) and (7) below. If the amounts of the compound represented by formula (6) and the compound represented by formula (7) below are too large, the gel time may be prolonged. Therefore, in one embodiment of this embodiment, when the compound represented by n=1 in formula (1) below is taken as 100 area%, the total content of the compound represented by formula (6) and the compound represented by formula (7) below is preferably 0.1 to 25 area%, and more preferably 1 to 10 area%, in terms of the peak area percentage of the LC chart of the LC / MS measurement of the epoxy resin mixture.

[0037] On the other hand, in one embodiment of this embodiment, if the amount of the compound represented by formula (6) below is too large, the gel time may become longer, and the water absorption rate may also increase. For this reason, in one embodiment of the epoxy resin mixture of this embodiment, when the compound represented by n=1 in formula (1) below is taken as 100 area%, the content of the compound represented by formula (6) below is preferably 0.1 to 35 area%, more preferably 10 to 30 area%, and particularly preferably 20 to 30 area%, in terms of the peak area percentage of the LC chart measured by LC / MS.

[0038] In formulas (1), (6), and (7), X is represented by any of the above formulas (a) to (g). G represents a glycidyl group. In formula (1), n ​​is the average value of the number of repetitions, a real number between 0 < n ≤ 10, more preferably a real number between 0 < n ≤ 5, even more preferably 1 ≤ n ≤ 5, and particularly preferably 1 < n ≤ 3.

[0039] In one embodiment of this design, it is preferable that formulas (1) to (4), formula (6), and formula (7) are represented by the following formulas (1-1), (2-1), (3-1), (4-1), (6-1), and (7-1), respectively.

[0040] In equations (1-1) to (2-1), n ​​is the average number of repetitions and is a real number such that 0 < n ≤ 10. In equations (1-1), (6-1), and (7-1), G represents a glycidyl group.

[0041] In one embodiment, the epoxy resin mixture of this embodiment is obtained by reacting a phenol resin represented by the following formula (2-1), a phenol resin mixture containing biphenol, and an epihalohydrin.

[0042] In equation (2-1), n ​​is the average value of the number of repetitions, is a real number between 0 < n ≤ 10, more preferably a real number between 0 < n ≤ 5, even more preferably 1 ≤ n ≤ 5, and particularly preferably 1 < n ≤ 3.

[0043] In the above formula (2-1), the value of n can be calculated from the number-average molecular weight obtained by gel permeation chromatography (GPC, differential refractive index detector: RI), or from the area ratio of each of the separated peaks.

[0044] In a phenol resin mixture, which is a mixture of phenol resin and biphenol represented by formula (2-1), if the biphenol component is too low, the crystallinity of the epoxy resin mixture after reaction cannot be maintained, and the epoxy resin mixture may block and solidify. Blocking and solidification of the epoxy resin mixture can also lead to blocking and solidification of the semiconductor encapsulant composition when pressure and temperature are applied during transportation. If the biphenol component is too high, the crystallinity of the epoxy resin mixture after reaction becomes too high, raising the softening point, which may impair the handling properties of the semiconductor encapsulant composition during molding. Therefore, the mixing ratio of the phenol resin and biphenol represented by formula (2-1) (phenol resin represented by formula (2-1): biphenol) is preferably 50 to 95% by mass: 5 to 50% by mass, and more preferably 70 to 90% by mass: 10 to 30% by mass.

[0045] The hydroxyl group equivalent of the phenol resin represented by formula (2-1) above is preferably 180 g / eq. to 240 g / eq., and more preferably 180 g / eq. to less than 200 g / eq. When the hydroxyl group equivalent of the phenol resin represented by formula (2-1) above is within the above range, the functional group density in the cured product increases, and the resulting cured product has excellent heat resistance and mechanical strength, which is therefore preferable.

[0046] If the content of the compound with n=1 in the total amount of phenol resin represented by formula (2-1) is too low, the crystallinity of the epoxy resin mixture after the reaction cannot be maintained, and the epoxy resin mixture may block and solidify. Blocking and solidification of the epoxy resin mixture can lead to the semiconductor encapsulant composition using it blocking and solidifying with each other when pressure and temperature are applied during transport. If the content of the compound with n=1 is too high, the crystallinity of the epoxy resin mixture becomes too high, raising the softening point and potentially worsening the handling properties of the semiconductor encapsulant composition during molding. Therefore, in the GPC area percentage of the phenol resin represented by formula (2-1), the content of the compound with n=1 in the total amount of phenol resin represented by formula (2-1) is preferably 40 to 100 area%, more preferably 60 to 90 area%, and particularly preferably 70 to 85 area%.

[0047] Among the compounds represented by n = 1 in formula (2-1), the crystallinity of the epoxy resin mixture after the reaction changes depending on the component ratio of the compound represented by formula (3-1) and the compound represented by formula (4-1). Therefore, when semiconductor encapsulant compositions made using epoxy resin mixtures are subjected to pressure and temperature during transport, the semiconductor encapsulant compositions may block and solidify together. For this reason, in the HPLC area percentage of the phenolic resin represented by formula (2-1), the value obtained by dividing the area of ​​the compound represented by formula (3-1) by the area of ​​the compound represented by formula (4-1) is preferably 1.15 or more and 1.30 or less, and more preferably 1.15 or more and 1.25 or less.

[0048] The phenol resin represented by the above formula (2-1) can be obtained, for example, by reacting phenol with 4,4'-bis(chloromethyl)biphenyl or 4,4'-bis(hydroxymethyl)biphenyl under acidic conditions. When reacting phenol with 4,4'-bis(chloromethyl)biphenyl or 4,4'-bis(hydroxymethyl)biphenyl, the amount of phenol is preferably in the range of 1.5 to 20 moles, and particularly preferably 3 to 10 moles, per mole of 4,4'-bis(chloromethyl)biphenyl or 4,4'-bis(hydroxymethyl)biphenyl.

[0049] Examples of catalysts used in the reaction include hydrobromic acid, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, boron trifluoride, activated clay, ion exchange resins, and other acidic catalysts. These may be used individually or in combination of two or more. The amount of catalyst used is usually 0.1 to 50% by mass, preferably 1 to 30% by mass, relative to the phenol used. If too much catalyst is used, the viscosity of the reaction solution will be too high, making stirring difficult, and if too little is used, the reaction may proceed slowly.

[0050] If the biphenol epoxidized content in the epoxy resin mixture is too low, the crystallinity cannot be maintained, and the epoxy resin mixture may block and solidify. Furthermore, if the semiconductor encapsulant composition made using the epoxy resin mixture is subjected to pressure and temperature during transport, the semiconductor encapsulant compositions may block and solidify with each other. If the biphenol epoxidized content is too high, the crystallinity of the epoxy resin mixture becomes too high, raising the softening point, which may impair the handling properties of the semiconductor encapsulant composition during molding. Therefore, in the GPC area percentage of the epoxy resin mixture in this embodiment, the biphenol epoxidized content in the total amount of epoxy resin mixture is preferably 5 to 35 area%, and more preferably 10 to 25 area%.

[0051] In the epoxy resin mixture of this embodiment, if the amounts of the compound represented by formula (6-1) and the compound represented by formula (7-1) are too high, the gel time may be prolonged. Therefore, in the LC chart peak area percentage of the LC / MS measurement of the epoxy resin mixture of this embodiment, when the compound represented by n=1 in formula (1-1) is set to 100 area%, the total content of the compound represented by formula (6-1) and the compound represented by formula (7-1) is preferably 0.1 to 25 area%, and more preferably 1 to 10 area%.

[0052] In formulas (1-1), (6-1), and (7-1), G represents a glycidyl group.

[0053] In the above formula (1-1), n ​​is the average value of the number of repetitions, a real number between 0 < n ≤ 10, more preferably a real number between 0 < n ≤ 5, even more preferably 1 ≤ n ≤ 5, and particularly preferably 1 < n ≤ 3. The value of n can be calculated from the number-average molecular weight obtained by gel permeation chromatography (GPC, differential refractive index detector: RI) measurement, or from the area ratio of each separated peak.

[0054] In this embodiment, GPC (gel permeation chromatography), HPLC (high-performance liquid chromatography), and LC / MS (liquid chromatography-mass spectrometry) measurements are performed by the methods described below.

[0055] - Weigh approximately 4 mg of the LC / MS sample into a 6 mL vial and dissolve it in 1 mL of tetrahydrofuran (THF). Then, add an additional 2 mL of acetonitrile (ACN), filter through a 0.2 μm filter, and measure under the following conditions. Apparatus: Liquid chromatography system (Ultimate 3000), mass spectrometer (Q-Exactive), both manufactured by Thermo Fisher Science Column: CORTECS C18 (Waters, column size: particle diameter 2.7 μm, inner diameter 2.1 mm, column length 150 mm) Oven temperature: 40°C Mobile phase: Mobile phase A: 5 mM ammonium acetate (AcONH) ４Mobile phase B: ACN / THF (v / v = 2 / 1) Gradient conditions: The ratio of mobile phase B to the total volume of mobile phase A and mobile phase B was increased from 30% at the start to 95% over 15 minutes, and then maintained for 10 minutes (Total 25 minutes) Flow rate: 0.3 mL / min Sample injection volume: 1.0 μL LC detector: Photodiode array (PDA), wavelength range 190-800 nm MS detector: Fourier transform mass spectrometry (FT-MS), positive ion mode (Posi): m / z = 100-1500, negative ion mode (Nega): m / z = 100-1500 Ionization method: Electrospray ionization (ESI) Detection wavelength: 274 nm

[0056] - Dissolve approximately 10 mg of the HPLC analysis sample in 5 mL of acetonitrile. After filtering through a 0.2 μm filter, measure under the following conditions: HPLC instrument: Shimadzu Corporation Column: GL Science ODS-2 Oven temperature: 40°C Mobile phase: Mobile phase A: 5 mM AcONH ４ Mobile phase B: ACN Gradient conditions: The ratio of mobile phase B to the total volume of mobile phases A and B was increased from 70% at the start to 100% over 28 minutes, and then maintained for 40 minutes (Total 68 minutes). Flow rate: 1.0 mL / min Sample injection volume: 5.0 μL LC detector: Photodiode array (PDA), wavelength range 190–800 nm

[0057] - Dissolve approximately 10 mg of GPC analysis sample in 5 mL of THF. After filtering through a 0.2 μm filter, measure under the following conditions: GPC instrument: Shimadzu Corporation Guard column: KF-G 4A GPC columns: KF-601, KF-602, KF-602.5, KF-603 Flow rate: 0.5 mL / min Column temperature: 40°C Solvent used: THF (tetrahydrofuran) Detector: RI (differential refractive detector)

[0058] In one embodiment, the epoxy resin mixture of this embodiment is preferably represented by the following formulas (1-2), (2-2), and (6-2), respectively, of formula (1), (2), and (6).

[0059] In equations (1-2) and (2-2), n is the average value of the number of repetitions and is a real number such that 0 < n ≤ 10. In equations (1-2) and (6-2), G represents a glycidyl group.

[0060] The epoxy resin mixture of this embodiment can be obtained by the reaction of a phenol mixture containing a phenol resin represented by the following formula (2-2) and biphenol with an epihalohydrin.

[0061] In equation (2-2), n is the average value of the number of repetitions, is a real number between 0 < n ≤ 10, more preferably a real number between 0 < n ≤ 5, even more preferably 1 ≤ n ≤ 5, and particularly preferably 1 < n ≤ 3.

[0062] In the above formula (2-2), the value of n can be calculated from the number-average molecular weight obtained by gel permeation chromatography (GPC, detector: RI), or from the area ratio of each of the separated peaks.

[0063] If the biphenol component in the phenol resin mixture, which is a mixture of phenol resin and biphenol represented by formula (2-2), is too low, the crystallinity of the epoxy resin mixture after the reaction cannot be maintained, and the epoxy resin mixture may block and solidify. Blocking and solidification of the epoxy resin mixture can also occur in semiconductor encapsulant compositions using it when pressure and temperature are applied during transport. If the biphenol component is too high, the crystallinity of the epoxy resin mixture becomes too high, raising the softening point, which may worsen the handling properties of the semiconductor encapsulant composition during molding. Therefore, the mixing ratio of the phenol resin and biphenol represented by formula (2-2) (phenol resin represented by formula (2-2): biphenol) is preferably 50 to 95% by mass: 5 to 50% by mass, and more preferably 70 to 90% by mass: 10 to 30% by mass.

[0064] The epoxy resin mixture of this embodiment preferably has a softening point of 50°C to 130°C, and more preferably 80°C to 110°C. Having a softening point within this range provides excellent handling properties.

[0065] In one embodiment of this invention, a curable resin composition with low water absorption can be provided. In the epoxy resin mixture of this embodiment, if the amount of the compound represented by the following formula (6-2) is too large, the gel time may become longer. Also, the water absorption may increase. For this reason, in the LC / MS measurement of the epoxy resin mixture of this embodiment, when the compound represented by n=1 in the following formula (1-2) is taken as 100 area%, the total content of the compound represented by the following formula (6-2) is preferably 0.1 to 35 area%, more preferably 10 to 30 area%, and particularly preferably 20 to 30 area%.

[0066] In formulas (1-2) and (6-2), G represents a glycidyl group. In formula (1-2), n is the average value of the number of repetitions, a real number between 0 < n ≤ 10, more preferably a real number between 0 < n ≤ 5, even more preferably 1 ≤ n ≤ 5, and particularly preferably 1 < n ≤ 3.

[0067] In the above formula (1-2), the value of n can be calculated from the number-average molecular weight obtained by gel permeation chromatography (GPC, detector: RI), or from the area ratio of each of the separated peaks.

[0068] In this embodiment, GPC (gel permeation chromatography) and LC / MS (liquid chromatography-mass spectrometry) measurements are performed using the methods described above.

[0069] The method for producing the phenol resin represented by the above formula (2-2) is not limited, but for example, when a reaction (condensation) of furfural with phenols is carried out, the amount of phenols is preferably in the range of 1.5 to 20 moles, and particularly preferably 3 to 10 moles, per mole of furfural.

[0070] Examples of phenols include catechol, resorcinol, and hydroquinone as disubstituted phenols, and phenol, cresol, and xylenol as monosubstituted phenols. These may be used individually or in combination of two or more types.

[0071] Examples of solvents include methanol, ethanol, propanol, isopropanol, toluene, and xylene, but are not limited to these; they may be used alone or in combination of two or more. When a solvent is used, the amount used is preferably in the range of 5 to 500 parts by weight, more preferably 10 to 300 parts by weight, per 100 parts by weight of phenol.

[0072] In the condensation reaction between furfural and phenols, it is preferable to use a basic catalyst. Although condensation polymerization is possible with an acidic catalyst, reactions between furfural compounds also occur, resulting in a large amount of by-products. There is also a method using organometallic compounds, but it is disadvantageous in terms of cost. Specific examples of basic catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, and potassium-tert-butoxide; and alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide. However, the catalyst is not limited to these, and one or more catalysts may be used in combination. The amount of catalyst used is preferably 0.005 to 2.0 moles, more preferably 0.01 to 1.1 moles, per mole of phenol.

[0073] These condensation reactions in the presence of base catalysts are preferably carried out in the range of 40 to 180°C, and particularly preferably in the range of 80 to 165°C. The duration of the condensation reaction can preferably be selected in the range of 0.5 to 10 hours. The reactants thus obtained are neutralized to make the system neutral, or repeatedly washed with water in the presence of a solvent, then the water is separated and drained, and the solvent and unreacted substances are removed under reduced pressure to obtain the phenol resin represented by formula (2-2) above.

[0074] The hydroxyl group equivalent of the phenol resin represented by the above formula (2-2) is preferably 100 g / eq. to 200 g / eq., and more preferably 120 g / eq. to less than 160 g / eq. Having the hydroxyl group equivalent of the phenol resin within this range is preferable because it increases the functional group density in the cured product, resulting in superior heat resistance and mechanical strength of the resulting cured product.

[0075] The curable resin composition of this embodiment may contain, in addition to the epoxy resin mixture of this embodiment, the compounds listed below. Note that the compounds listed below do not include the epoxy resin mixture of this embodiment or the phenolic resin mixture.

[0076] [Curing Accelerator] The curable resin composition of this embodiment can also have its curability improved by adding a curing accelerator. Preferred curing accelerators are anionic curing accelerators that promote the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or by heating, or cationic curing accelerators that promote the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or by heating.

[0077] Examples of anionic curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred. Other examples include phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and quaternary ammonium salts such as hexadecyltrimethylammonium hydroxide, but are not limited to these. These may be used individually or in combination.

[0078] Examples of cationic curing accelerators include quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, and tetrabutylphosphonium salt (the counterions of the quaternary salts are halogens, organic acid ions, hydroxide ions, etc., with no particular preference, but organic acid ions and hydroxide ions are particularly preferred), tin octoate, zinc carboxylates (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate), and zinc phosphate esters (zinc octyl phosphate, zinc stearyl phosphate), but are not limited to these. Furthermore, these may be used individually or in combination of multiple types.

[0079] The amount of curing accelerator used is 0.01 to 5.0 parts by mass per 100 parts by mass of the curable resin composition, as needed.

[0080] [Inorganic Filler] The curable resin composition of this embodiment may contain an inorganic filler. Examples of inorganic fillers include, but are not limited to, powders such as fused silica, crystalline silica, porous silica, alumina, zircon, calcium silicate, calcium carbonate, quartz powder, silicon carbide, silicon nitride, boron nitride, zirconia, aluminum nitride, graphite, forsterite, steatite, spinel, mullite, titania, talc, clay, iron oxide, asbestos, and glass powder, or inorganic fillers made by shaping these into spheres or crushed forms. Furthermore, these may be used individually or in combination of multiple types.

[0081] When obtaining a curable resin composition for semiconductor encapsulation, the amount of inorganic filler used is preferably 80 to 92 parts by mass, and more preferably 83 to 90 parts by mass, per 100 parts by mass of the curable resin composition. Furthermore, when obtaining a curable resin composition for interlayer insulating layer forming materials, copper-clad laminates, prepregs, RCCs, and other substrate materials, the amount of the above-mentioned inorganic filler used is preferably 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of the curable resin composition.

[0082] [Polymerization Initiator] The curable resin composition of this embodiment can also have its curability improved by adding a polymerization initiator. A polymerization initiator is a compound capable of polymerizing olefin functional groups such as ethylenically unsaturated bonds, and examples include olefin metathesis polymerization initiators, anionic polymerization initiators, cationic polymerization initiators, and radical polymerization initiators. Among these, it is preferable to use a radical polymerization initiator that has curability and appropriate stability. A radical polymerization initiator is a compound that generates radicals by irradiation with ultraviolet light or visible light or by heating, and initiates a chain polymerization reaction. Examples of radical polymerization initiators that can be used include organic peroxides, azo compounds, and benzopinacols, and it is preferable to use organic peroxides because they have little effect on curing temperature control, outgassing suppression, and the electrical properties of decomposition products.

[0083] Examples of the above organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, diacyl peroxides such as benzoyl peroxide, dialkyl peroxides such as dicumyl peroxide and 1,3-bis-(t-butylperoxyisopropyl)benzene, peroxyketals such as t-butyl peroxybenzoate and 1,1-di-t-butylperoxycyclohexane, α-cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, and t-butyl peroxy Examples of alkyl peresters such as -oxy-2-ethylhexanoate, t-amyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy-3,5,5-trimethylhexanoate, and t-amyl peroxybenzoate; peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyisopropyl carbonate, and 1,6-bis(t-butyl peroxycarbonyloxy)hexane; t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxyoctoate, and lauroyl peroxide are examples, but are not limited to these. Furthermore, these may be used individually or in combination. Among the above organic peroxides, ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxycarbonates are preferred, with dialkyl peroxides being more preferred.

[0084] Examples of the above-mentioned azo compounds include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). Furthermore, these compounds may be used individually or in combination.

[0085] The amount of polymerization initiator added is preferably 0.01 to 5 parts by mass, and particularly preferably 0.01 to 3 parts by mass, per 100 parts by mass of the curable resin composition. If the amount of polymerization initiator used is less than 0.01 parts by mass, the molecular weight may not elongate sufficiently during the polymerization reaction, and if it is more than 5 parts by mass, dielectric properties such as dielectric constant and dielectric loss tangent may be impaired.

[0086] [Polymerization Inhibitor] The curable resin composition of this embodiment may contain a polymerization inhibitor. Including a polymerization inhibitor improves storage stability and allows control of the reaction initiation temperature. Controlling the reaction initiation temperature makes it easier to ensure fluidity, prevents impregnation into glass cloth and the like, and facilitates B-stage production such as prepreg formation. If the polymerization reaction proceeds too far during prepreg formation, problems such as difficulty in lamination during the lamination process are likely to occur.

[0087] The polymerization inhibitor may be added during the synthesis of the epoxy resin mixture of this embodiment, or after synthesis. The amount of polymerization inhibitor used is 0.008 to 1 part by mass, preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the epoxy resin mixture of this embodiment.

[0088] Examples of polymerization inhibitors include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based agents. Furthermore, polymerization inhibitors may be used individually or in combination of multiple types. Of these, phenol-based, hindered amine-based, nitroso-based, and nitroxyl radical-based agents are preferred in this embodiment.

[0089] Examples of the above phenolic polymerization inhibitors include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-c Monophenols such as resols, 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] N,N'-Hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl], 2,4,8,10-tetraoxaspiro[5,5]undecane, bis(3,5-di-t- Bisphenols such as calcium trimethyl-4-hydroxybenzylsulfonate ethyl, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tris-(3,Examples include, but are not limited to, high molecular weight phenols such as 5-di-t-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, and tocopherol.

[0090] Examples of sulfur-based polymerization inhibitors include, but are not limited to, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, and distearyl-3,3'-thiodipropionate.

[0091] Examples of the phosphorus polymerization inhibitors mentioned above include triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butyl-4-methylphenyl) phosphite, and bis[2- Examples include, but are not limited to, phosphites such as t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]hydrogen phosphite, oxaphosphaphenanthrene oxides such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0092] Examples of the nitroso polymerization inhibitors mentioned above include, but are not limited to, p-nitrosophenol, N-nitrosodiphenylamine, ammonium salts of N-nitrosophenylhydroxyamine, (cuperone), etc. Of these, ammonium salts of N-nitrosophenylhydroxyamine (cuperone) are preferred.

[0093] Examples of the above-mentioned nitroxyl radical polymerization inhibitors include, but are not limited to, di-tert-butylnitroxide, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl.

[0094] [Flame retardant] The curable resin composition of this embodiment may contain a flame retardant. Examples of flame retardants include halogen-based flame retardants, inorganic flame retardants (antimony compounds, metal hydroxides, nitrogen compounds, boron compounds, etc.), and phosphorus-based flame retardants, but phosphorus-based flame retardants are preferred from the viewpoint of achieving halogen-free flame retardancy.

[0095] The phosphorus-based flame retardants mentioned above may be reactive or additive types. Specific examples include phosphorus esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixyllenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixyllenyl phosphate, 1,3-phenylenebis(dixyllenyl phosphate), 1,4-phenylenebis(dixyllenyl phosphate), and 4,4'-biphenyl(dixyllenyl phosphate); phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the above phosphanes; and red phosphorus, but are not limited to these. Furthermore, these may be used individually or in combination of multiple types. Of the above example substances, phosphate esters, phosphans, or phosphorus-containing epoxy compounds are preferred, and 1,3-phenylenebis(dixyllenyl phosphate), 1,4-phenylenebis(dixyllenyl phosphate), 4,4'-biphenyl(dixyllenyl phosphate), or phosphorus-containing epoxy compounds are particularly preferred.

[0096] The flame retardant content is preferably in the range of 0.1 to 0.6 parts by mass per 100 parts by mass of the curable resin composition. If it is less than 0.1 parts by mass, the flame retardancy may be insufficient, and if it is more than 0.6 parts by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[0097] [Light stabilizer] The curable resin composition of this embodiment may also contain a light stabilizer. Suitable light stabilizers include hindered amine-based light stabilizers (HALS), etc. Examples of HALS include the reaction product of dibutylamine-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, the reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl Examples include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate bis(1,2,2,6,6-pentamethyl-4-piperidyl). Furthermore, these may be used individually or in combination of multiple types.

[0098] Examples of commercially available hindered amine-based light stabilizers include Adekastab (registered trademark) LA-40MP, Adekastab LA-40Si, Adekastab LA-402AF, Adekastab LA-87, Adekastab LA-82, Adekastab LA-81, Adekastab LA-77Y, Adekastab LA-77G, Adekastab LA-72, Adekastab LA-68, Adekastab LA-63P, Adekastab LA-57, and Adekastab LA-52 (all manufactured by ADE Co., Ltd.). Examples include, but are not limited to, KA-made Chimassorb® 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin® 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, and Tinuvin 791FB (all manufactured by BASF).

[0099] The amount of light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the curable resin composition. If the amount is less than 0.001 parts by mass, it may be insufficient to exhibit the light stabilization effect, and if it is more than 0.1 parts by mass, it may adversely affect the hygroscopicity and dielectric properties of the cured product.

[0100] [Binder Resin] The curable resin composition of this embodiment may also use a binder resin. Examples of binder resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenolic resins, epoxy-NBR resins, silicone resins, etc., but are not limited to these. Furthermore, these may be used individually or in combination of multiple types.

[0101] The amount of binder resin added is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass per 100 parts by mass of the curable resin composition, and more preferably 0.05 to 20 parts by mass as needed.

[0102] [Additives] The curable resin composition of this embodiment may also contain additives. Examples of additives include modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.

[0103] The amount of additive added is preferably 1,000 parts by mass or less, and more preferably 700 parts by mass or less, per 100 parts by mass of the curable resin composition.

[0104] The curable resin composition of this embodiment may further contain epoxy resins other than the epoxy resin mixture, active ester compounds, phenolic resins other than the phenolic resin mixture, polyphenylene ether compounds, amine resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, maleimide compounds, cyanate ester resins, polyimide resins, polybutadiene and its modified counterparts, polystyrene and its modified counterparts, polyethylene and its modified counterparts, benzoxazine compounds, etc., and these may be used individually or in combination of multiple types. Among these compounds, it is preferable to include polyphenylene ether compounds, compounds having ethylenically unsaturated bonds, cyanate ester resins, polybutadiene and its modified counterparts, polystyrene and its modified counterparts, in order to balance heat resistance, adhesion, and dielectric properties. By including these compounds, the brittleness of the cured product can be improved and adhesion to metal can be enhanced, and cracks in the package can be suppressed during reliability tests such as solder reflow and thermal cycling.

[0105] Unless otherwise specified, the amount of the above-mentioned compounds used is preferably 10 times or less by mass, more preferably 5 times or less by mass, and most preferably 3 times or less by mass, relative to the epoxy resin mixture of this embodiment. Furthermore, the preferred lower limit is 0.1 times or more by mass, more preferably 0.25 times or more by mass, and even more preferably 0.5 times or more by mass. Within this range, the effects of each added compound can be added while taking advantage of the low dielectric properties of the epoxy resin mixture of this embodiment. Examples of these components can be used as shown below.

[0106] [Epoxy resins other than the epoxy resin mixture] Preferred epoxy resins other than the epoxy resin mixture are given below, but are not limited to these. The epoxy resin may be liquid or solid, and may be used alone or in combination of multiple types.

[0107] Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure. Specific examples include "RE310S", "RE410S" (both manufactured by Nippon Kayaku Co., Ltd., bisphenol A type epoxy resin), "RE303S", "RE304S", "RE403S", "RE404S" (all manufactured by Nippon Kayaku Co., Ltd., bisphenol F type epoxy resin), "HP4032", "HP4032D", "HP4032SS" (all manufactured by DIC Corporation, naphthalene type epoxy resin), "828US", "jER(registered trademark)828EL", "825", "828EL" (all manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin), "jE807", "1750" (both manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin), and "jER152" (manufactured by Mitsubishi Chemical Corporation, phenol Examples include novolac-type epoxy resin, "630", "630LSD" (both manufactured by Mitsubishi Chemical Corporation, glycidylamine-type epoxy resin), "ZX1059" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin), "EX-721" (manufactured by Nagase ChemteX Corporation, glycidyl ester-type epoxy resin), "Celoxide (registered trademark) 2021P" (manufactured by Daicel Corporation, alicyclic epoxy resin with an ester skeleton), "PB-3600" (manufactured by Daicel Corporation, epoxy resin with a butadiene structure), "ZX1658", "ZX1658GS" (both manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., liquid 1,4-glycidylcyclohexane-type epoxy resin), etc. These may be used individually or in combination of two or more types.

[0108] Examples of solid epoxy resins include bixylenol-type epoxy resin, naphthalene-type epoxy resin, naphthalene-type tetrafunctional epoxy resin, cresol novolac-type epoxy resin, dicyclopentadiene-type epoxy resin, trisphenol-type epoxy resin, naphthol-type epoxy resin, biphenyl-type epoxy resin, naphthylene ether-type epoxy resin, anthracene-type epoxy resin, bisphenol A-type epoxy resin, bisphenol AF-type epoxy resin, and tetraphenylethane-type epoxy resin, with naphthol-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, and biphenyl-type epoxy resin being preferred.Specific examples include "HP4032H" (manufactured by DIC Corporation, naphthalene-type epoxy resin), "HP-4700", "HP-4710" (both manufactured by DIC Corporation, naphthalene-type tetrafunctional epoxy resin), "N-690" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "N-695" (manufactured by DIC Corporation, cresol novolac-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (both manufactured by DIC Corporation, dicyclopentadiene-type epoxy resin), "EXA-7311", "EXA-7311 -G3", "EXA-7311-G4", "EXA-7311-G4S", "HP-6000" (all manufactured by DIC Corporation, naphthylene ether type epoxy resin), "EPPN-502H" (manufactured by Nippon Kayaku Co., Ltd., trisphenol type epoxy resin), "NC-7000L", "NC-7300" (both manufactured by Nippon Kayaku Co., Ltd., naphthol-cresol novolac type epoxy resin), "NC-3000H", "NC-3000", "NC-3000L", "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd., biphenyl aralkyl type epoxy resin) ), "XD-1000-2L", "XD-1000-L", "XD-1000-H" (all manufactured by Nippon Kayaku Co., Ltd., dicyclopentadiene type epoxy resin), "ESN475V" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., naphthol type epoxy resin), "ESN485" (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., naphthol novolac type epoxy resin), "YX-4000H", "YX-4000", "YL6121" (all manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin), "YX-4000HK" (manufactured by Mitsubishi Chemical Corporation, bixylenol type epoxy resin) Examples include "YX-8800" (manufactured by Mitsubishi Chemical Corporation, anthracene-type epoxy resin), "PG-100", "CG-500" (manufactured by Osaka Gas Chemical Co., Ltd., fluorene-type epoxy resin), "YL-7760" (manufactured by Mitsubishi Chemical Corporation, bisphenol AF-type epoxy resin), "YL-7800" (manufactured by Mitsubishi Chemical Corporation, fluorene-type epoxy resin), "jER1010" (manufactured by Mitsubishi Chemical Corporation, solid bisphenol A-type epoxy resin), and "jER1031S" (manufactured by Mitsubishi Chemical Corporation, tetraphenylethane-type epoxy resin). These may be used individually or in combination of two or more types.

[0109] [Active Ester Compounds] Active ester compounds are compounds that contain at least one ester bond in their structure, and on both sides of the ester bond, aliphatic chains, aliphatic rings, or aromatic rings are bonded. Examples of active ester compounds include compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. They are obtained by a condensation reaction between at least one compound of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one compound of a hydroxy compound or a thiol compound. In particular, from the viewpoint of improving heat resistance, it is preferable that they be obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound, and phenol compounds or naphthol compounds are preferred as the hydroxy compound. Active ester compounds may be used alone or in combination of two or more.

[0110] Examples of the carboxylic acid compounds mentioned above include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0111] Examples of the above-mentioned acid chlorides include acetyl chloride, acrylate chloride, methacrylate chloride, malonyl chloride, succinate dichloride, diglycolyl chloride, glutarate dichloride, suberate dichloride, sebacate dichloride, adipic acid dichloride, dodecanediol dichloride, azera oil chloride, 2,5-franzicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.

[0112] Examples of the above-mentioned phenol compounds and naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and phenol resins described later. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by the condensation of two molecules of phenol with one molecule of dicyclopentadiene.

[0113] Preferred examples of active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, active ester compounds containing a benzoylated phenol novolac, the compound described in Example 2 of International Publication No. 2020 / 095829, and the compounds disclosed in International Publication No. 2020 / 059625. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The dicyclopentadiene-type diphenol structure represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0114] Commercially available active ester compounds include, for example, active ester compounds containing a dicyclopentadiene-type diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM", and "EXB-8150-65T" (manufactured by DIC Corporation), and active ester compounds containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation), and phenol no Examples of active ester compounds containing acetylated volac include "DC808" (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoylated phenol novolac include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), active ester curing agent which is an acetylated phenol novolac includes "DC808" (manufactured by Mitsubishi Chemical Corporation), and phosphorus atom-containing active ester curing agent includes "EXB-9050L-62M" manufactured by DIC Corporation.

[0115] Regarding the blending ratio of the active ester compound and epoxy resin, the ratio of the active ester equivalent (α) to the epoxy equivalent (β) (α / β) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If it falls outside the above range, there is a risk that excess epoxy groups or active ester groups will remain in the system, which may lead to deterioration of properties in high-temperature storage tests (e.g., 150°C, 1000 hours) or long-term reliability tests under high-temperature and high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).

[0116] [Phenol resins other than the phenol resin mixture] Phenolic resins other than the phenol resin mixture are compounds having two or more phenolic hydroxyl groups in their molecules, excluding phenol resins represented by formula (2) and biphenols. Examples of phenolic resins include, but are not limited to, reaction products of phenols and aldehydes, reaction products of phenols and diene compounds, reaction products of phenols and ketones, reaction products of phenols and substituted biphenyls, reaction products of phenols and substituted phenyls, reaction products of bisphenols and aldehydes. Furthermore, these may be used individually or in combination of multiple types. Specific examples of the above raw materials are given below, but are not limited to these. <Phenols> Phenol, alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc. <Aldehydes> Formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, etc. <Diene Compounds> Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. <Ketones> Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc. <Substitutive biphenyls> 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, etc. <Substitutive phenyls> 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, etc.

[0117] [Polyphenylene Ether Compounds] From the viewpoint of heat resistance and electrical properties, polyphenylene ether compounds are preferably polyphenylene ether compounds having ethylenically unsaturated bonds, and more preferably polyphenylene ether compounds having acrylic groups, methacrylic groups, or styrene structures. Commercially available products include SA-9000 (manufactured by SABIC, a polyphenylene ether compound having methacrylic groups) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd., a polyphenylene ether compound having a styrene structure). The number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5000, more preferably 2000 to 5000, and even more preferably 2000 to 4000. If the molecular weight is less than 500, the heat resistance of the cured product tends not to be sufficient. Also, if the molecular weight is greater than 5000, the melt viscosity becomes high, and sufficient fluidity cannot be obtained, which tends to lead to molding defects. Furthermore, reduced reactivity leads to a longer curing time, an increase in unreacted material not incorporated into the curing system, a decrease in the glass transition temperature of the cured product, and a tendency for the heat resistance of the cured product to decrease. If the number-average molecular weight of the polyphenylene ether compound is between 500 and 5000, it is possible to exhibit excellent heat resistance and moldability while maintaining excellent dielectric properties. Specifically, the number-average molecular weight can be measured using methods such as gel permeation chromatography.

[0118] The polyphenylene ether compound may be obtained by polymerization or by redistributing a high molecular weight polyphenylene ether compound with a number average molecular weight of about 10,000 to 30,000. Alternatively, these can be used as raw materials and reacted with compounds having ethylenically unsaturated bonds, such as methacrylate chloride, acrylate chloride, and chloromethylstyrene, to impart radical polymerizability. The polyphenylene ether compound obtained by redistribution is, for example, obtained by heating a high molecular weight polyphenylene ether compound in a solvent such as toluene in the presence of a phenolic compound and a radical initiator to redistribute it. Polyphenylene ether compounds obtained by this redistribution reaction are preferable because they have hydroxyl groups derived from phenolic compounds that contribute to curing at both ends of the molecular chain, thus maintaining even higher heat resistance, and because functional groups can be introduced to both ends of the molecular chain even after modification with a compound having ethylenically unsaturated bonds. Furthermore, polyphenylene ether compounds obtained by polymerization are preferable because they exhibit excellent fluidity.

[0119] The molecular weight of polyphenylene ether compounds can be adjusted by adjusting polymerization conditions, etc., in the case of polyphenylene ether compounds obtained by polymerization reactions. In the case of polyphenylene ether compounds obtained by redistribution reactions, the molecular weight of the resulting polyphenylene ether compound can be adjusted by adjusting the conditions of the redistribution reaction, etc. More specifically, this can be done by adjusting the amount of phenolic compound used in the redistribution reaction. That is, the higher the amount of phenolic compound used, the lower the molecular weight of the resulting polyphenylene ether compound. In this case, poly(2,6-dimethyl-1,4-phenylene ether) can be used as the high molecular weight polyphenylene ether compound that undergoes the redistribution reaction. Furthermore, the phenolic compound used in the above redistribution reaction is not particularly limited, but polyfunctional phenolic compounds having two or more phenolic hydroxyl groups in the molecule, such as bisphenol A, phenol novolac, and cresol novolac, are preferably used. These may be used individually or in combination of two or more.

[0120] The content of the polyphenylene ether compound is not particularly limited, but is preferably 5 to 1000 parts by mass, and more preferably 10 to 750 parts by mass, per 100 parts by mass of the curable resin composition. When the content of the polyphenylene ether compound is within the above range, it is preferable not only to obtain a cured product that is excellent in heat resistance and the like, but also in that the excellent dielectric properties of the polyphenylene ether compound are fully exhibited.

[0121] [Amine Resins] Amine resins are compounds having two or more amino groups in their molecule. Examples of amine resins include diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, naphthalenediamine, aniline novolac (reaction product of aniline and formalin), N-methylaniline novolac (reaction product of N-methylaniline and formalin), orthoethylaniline novolac (reaction product of orthoethylaniline and formalin), reaction product of 2-methylaniline and formalin, reaction product of 2,6-diisopropylaniline and formalin, reaction product of 2,6-diethylaniline and formalin, reaction product of 2-ethyl-6-ethylaniline and formalin, reaction product of 2,6-dimethylaniline and formalin, and those obtained by the reaction of aniline with xylylene chloride. Examples of aniline resins include, but are not limited to, aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) as described in Japanese Patent Publication No. 6429862, aniline and substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, aniline and diisopropenylbenzene, and dimer amines. Furthermore, these may be used individually or in combination.

[0122] [Compounds containing ethylenically unsaturated bonds] Compounds containing ethylenically unsaturated bonds are compounds that have one or more ethylenically unsaturated bonds in their molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not. Examples of compounds containing ethylenically unsaturated bonds include, but are not limited to, reaction products of the above-mentioned phenolic resin with halogenated compounds containing ethylenically unsaturated bonds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylate chloride, methacrylate chloride, etc.), reaction products of ethylenically unsaturated phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogenated compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuryl chloride, etc.), reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid, etc.), and acid-modified products thereof. Furthermore, these may be used individually or in combination of multiple types.

[0123] [Isocyanate resin] An isocyanate resin is a compound that has two or more isocyanate groups in its molecule. Examples of isocyanate resins include, but are not limited to, aromatic diisocyanates such as p-phenylenediisocyanate, m-phenylenediisocyanate, p-xylenediisocyanate, m-xylenediisocyanate, 2,4-tollylenediisocyanate, 2,6-tollylenediisocyanate, 4,4'-diphenylmethanediisocyanate, and naphthalenediisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylenediisocyanate, 4,4'-dicyclohexylmethanediisocyanate, hydrogenated xylenediisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more isocyanate monomers or isocyanate compounds obtained by trimerizing the above diisocyanate compounds; and polyisocyanates obtained by urethane reaction between the above isocyanate compounds and polyol compounds. Furthermore, these can be used individually or in combination.

[0124] [Polyamide Resins] Examples of polyamide resins include reaction products of one or more of diamines, diisocyanates, or oxazolines with dicarboxylic acids, reaction products of diamines and acid chlorides, and ring-opening polymers of lactam compounds. These may be used individually or in combination of multiple types. Specific examples of the above raw materials are given below, but the material is not limited to these.<Diamines> Ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine, pentadecanediamine, hexadecanediamine, heptadecanediamine, octadecanediamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-diaminopentane, 2-methyl 1,8-diaminooctane, dimer amine, cyclohexanediamine, bis-(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, xylylenediamine, norbornanediamine, isophoronediamine, bisaminomethyltricyclodecane, phenylenediamine, diethyltoluenediamine, naphthalenediamine, diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diethylphenyl)methane 4,4'-methylenebis-o-toluidine, 4,4'-methylenebis-o-ethylaniline, 4,4'-methylenebis-2-ethyl-6-methylaniline, 4,4'-methylenebis-2,6-diisopropylaniline, 4,4-ethylenedianiline, diaminodiphenylsulfone, diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4-bis(4-aminophenoxy)biphenyl, 2,2-bis[4-(4-amino [phenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, 9,9-bis(4-aminophenyl)fluorene, 2,7-diaminofluorene, aminobenzylamine, diaminobenzophenone, etc.<Diisocyanates> Benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, etc. <Dicarboxylic acids> Oxalic acid, malonic acid, succicic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanediic acid, dodecanediic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, francicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, etc. <Acid Chlorides> Acetyl chloride, acrylate chloride, methacrylate chloride, malonyl chloride, succinate dichloride, diglycolyl chloride, glutarate dichloride, suberate dichloride, sebacate dichloride, adipic acid dichloride, dodecane dioyl chloride, azera oil chloride, 2,5-franzicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesinate chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyl dicarbonyl chloride, 4,4'-azodibenzoyl dichloride, etc. <Lactams> ε-caprolactam, ω-undecane lactam, ω-laurolactam, etc.

[0125] [Polyimide Resin] Examples of polyimide resins include, but are not limited to, the reaction products of the above-mentioned diamine and the tetracarboxylic dianhydrides exemplified below. Furthermore, these may be used individually or in combination of multiple types. <Tetracarboxylic Dianhydrides> 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4 '-diphenylsulfontetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, methylene-4,4'-diphthalic acid dianhydride, 1,1-ethylidene-4,4'-diphthalic acid dianhydride, 2,2'-propyridene-4,4'-diphthalic acid dianhydride, 1,2-ethylene-4,4'-diphthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic acid dianhydride, 1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,5-pentamethylene-4,4'- Diphthalic acid dianhydride, 4,4'-oxydiphthalic acid dianhydride, thio-4,4'-diphthalic acid dianhydride, sulfonyl-4,4'-diphthalic acid dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,3-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4- [Dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, bis(3,4-dicarboxyphenoxy)dimethylsilane dianhydride, 1,3-bis(3,4-Dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, 2,3,6,7-anthracenetetracarboxylic acid dianhydride, 1,2,7,8-phenanthrenetetracarboxylic acid dianhydride, ethylenetetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 1, 2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride (Bonic acid) dianhydride, 1,1-ethylidene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propyridene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride Water compounds, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, ethylene glycol-bis-(3,4-dicarboxylic acid anhydride phenyl) ether, 4,4'-biphenylbis(trimellitic acid monoester anhydride), 9,9'-bis(3,4-dicarboxyphenyl)fluorene dianhydride, etc.

[0126] [Maleimide Compounds] The curable resin composition of this embodiment may contain maleimide compounds. Maleimide compounds are compounds having one or more maleimide groups in their molecule. Examples of maleimide compounds include 4,4'-diphenylmethanebismaleimide, polyphenylmethanemaleimide, m-phenylenebismaleimide, 2,2'-bis[4-(4-maleimoidphenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismaleimide, 1,3-bis(3-maleimoidphenoxy)benzene, 1,3-bis(4-maleimoidphenoxy) Phenoxybenzene, Zyloc-type maleimide compounds (anilix maleimide, manufactured by Mitsui Chemicals Fine Co., Ltd.), biphenylaralkyl-type maleimide compounds (solidified by solvent distillation under reduced pressure of a resin solution containing the maleimide compound (M2) described in Synthesis Example 4 of Japanese Patent Publication No. 2009-001783), bisaminocumylbenzene-type maleimide (maleimide compound described in International Publication No. 2020 / 054601), maleimide compounds having an indan structure described in Japanese Patent No. 6629692 or International Publication No. 2020 / 217679, MATERIAL STAGE Vol. 18, No. 12 2019 "Continued Epoxy Resin CAS Number Story - Curing Agent CAS Number Memo No. 31 Bismaleimide (1)" and MATERIAL STAGE Vol. 19, No. 2. Maleimide compounds, etc., as described in "Continued Story of Epoxy Resin CAS Numbers - Memorandum on CAS Numbers for Hardeners, Part 32: Bismaleimide (2)" (2019), are examples, but are not limited to these. Furthermore, these may be used individually or in combination of multiple types.

[0127] [Cyanate Ester Resins] Cyanate ester resins are cyanate ester compounds obtained by reacting phenol resins with cyanide halides. Specific examples include, but are not limited to, dicyanatebenzene, tricyanatebenzene, dicyanatenaphthalene, dicyanatebiphenyl, 2,2'-bis(4-cyanatephenyl)propane, bis(4-cyanatephenyl)methane, bis(3,5-dimethyl-4-cyanatephenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatephenyl)propane, 2,2'-bis(4-cyanatephenyl)ethane, 2,2'-bis(4-cyanatephenyl)hexafluoropropane, bis(4-cyanatephenyl)sulfone, bis(4-cyanatephenyl)thioether, phenol novolac cyanate, and phenol-dicyclopentadiene cocondensates in which the hydroxyl groups have been converted to cyanate groups. Furthermore, these may be used individually or in combination of multiple types. In addition, the cyanate ester compound whose synthesis method is described in Japanese Patent Publication No. 2005-264154 is particularly preferred as a cyanate ester compound because it has excellent low hygroscopicity, flame retardancy, and dielectric properties. The cyanate ester resin may also contain catalysts such as zinc naphthenate, cobalt naphthenate, copper naphthenate, lead naphthenate, zinc octoate, tin octoate, lead acetylacetonate, or dibutyltin maleate in order to trimerize the cyanate group and form a sym-triazine ring as needed.

[0128] It is preferable to use 0.0001 to 0.10 parts by mass, preferably 0.00015 to 0.0015 parts by mass, of the catalyst per 100 parts by mass of the cyanate ester resin and the curable resin composition.

[0129] [Polybutadiene and its modified products] Polybutadiene and its modified products are compounds that have polybutadiene or a structure derived from polybutadiene within their molecule. The structure derived from polybutadiene may have some or all of its unsaturated bonds converted to single bonds by hydrogenation. Examples of polybutadiene and its modified products include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, terminally (meth)acrylated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. Furthermore, these may be used individually or in combination. Of these, polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties. Examples of styrene-butadiene rubber (SBR) include RICON-100, RICON-181, RICON-184 (all manufactured by Clay Valley Corporation), and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.). Examples of polybutadiene include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.). The weight-average molecular weight of polybutadiene and styrene-butadiene rubber is preferably 500 to 10000, more preferably 750 to 7500, and even more preferably 1000 to 5000. Below the lower limit of the above range, the volatility is high, making it difficult to adjust the solid content during prepreg preparation, and above the upper limit of the above range, the compatibility with other curable resins deteriorates. In general, in the case of compounds containing heteroatoms such as oxygen and nitrogen, such as bismaleimide and polymaleimide, it is difficult to ensure compatibility with low-polarity compounds such as compounds mainly composed of hydrocarbons or compounds consisting only of hydrocarbons, due to their polarity.

[0130] [Polystyrene and its modified products] Polystyrene and its modified products are polystyrene or compounds that have a structure derived from polystyrene within their molecules. Examples of polystyrene and its modified products include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), and SEEPS (styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon 4003, Septon 4044, Septon 4055, Septon 4077, Septon 4099). All manufactured by Kuraray Co., Ltd.), SEBS (styrene-ethylene-butylene-styrene block copolymer: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Co., Ltd.), SEEPS-OH (compound having hydroxyl groups at the ends of styrene-ethylene / ethylene-propylene-styrene block copolymer: Septon HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: Septon 5125, Septon 5127, all manufactured by Kuraray Co., Ltd.), Hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: Hybrar 7125F, Hybrar 7311F Examples include, but are not limited to, polystyrene-isobutylene-styrene block copolymers (SIBS: SIBSTAR073T, SIBSTAR102T, SIBSTAR103T (all manufactured by Kaneka Corporation), Septon V9827 (manufactured by Kuraray Co., Ltd.)), etc. Furthermore, these may be used individually or in combination. Polystyrene and its modified products are preferable to have those without unsaturated bonds because they have higher heat resistance and are less susceptible to oxidative degradation.Furthermore, while there are no particular restrictions on the weight-average molecular weight of polystyrene and its modified products as long as it is 10,000 or more, if it is too high, the compatibility with polyphenylene ether compounds, as well as low molecular weight components with a weight-average molecular weight of about 50 to 1,000 and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferable that the weight-average molecular weight be around 10,000 to 300,000.

[0131] [Polyethylene and Modified Products thereof] Polyethylene and modified products thereof refer to polyethylene or compounds having a structure derived from polyethylene within their molecules. Examples of polyethylene and modified products thereof include, but are not limited to, ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene norbornene copolymers (Mitsui Chemicals, Ltd. EBT: K-8370EM, K-9330M, etc.), ethylene-propylene-vinyl norbornene copolymers (Mitsui Chemicals, Ltd. VNB-EPT: PX-006M, PX-008M, PX-009M, etc.), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers. From the viewpoint of improving heat resistance, it is preferable to use ethylene-propylene-ethylidene norbornene copolymers and ethylene-propylene-vinyl norbornene copolymers that contain a crosslinkable structure. Furthermore, these may be used individually or in combination of multiple types. While there are no particular restrictions on the weight-average molecular weight of polyethylene and its modified products as long as it is 10,000 or more, if it is too high, the compatibility with polyphenylene ether compounds, as well as low molecular weight components with a weight-average molecular weight of about 50 to 1,000 and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferable that the molecular weight be around 10,000 to 300,000.

[0132] [Benzoxazine Compounds] As benzoxazine compounds, any compound having two or more dihydrobenzoxazine rings in one molecule can be used, as long as it is generally known. Examples include bisphenol A type benzoxazine BA-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol F type benzoxazine BF-BXZ (manufactured by Konishi Chemical Co., Ltd.), bisphenol S type benzoxazine BS-BXZ (manufactured by Konishi Chemical Co., Ltd.), phenolphthalein type benzoxazine, etc., but are not particularly limited. These benzoxazine compounds can be used individually or in appropriate mixtures of two or more.

[0133] The curable resin composition of this embodiment is obtained by preparing the above components in predetermined proportions, pre-curing at 130 to 180°C for 30 to 500 seconds, and then post-curing at 150 to 200°C for 2 to 15 hours to allow the curing reaction to proceed sufficiently and obtain the cured product of this embodiment. Alternatively, the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, and then cured after removing the solvent.

[0134] The method for preparing the curable resin composition of this embodiment is not particularly limited, but may be done by simply uniformly mixing each component or by prepolymerization. For example, prepolymerization can be performed by heating a mixture containing the epoxy resin mixture of this embodiment in the presence or absence of a curing accelerator and polymerization initiator, and in the presence or absence of a solvent. Similarly, prepolymerization may be performed by adding compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and its modified products, polystyrene and its modified products, inorganic fillers, and other additives. Mixing or prepolymerization of each component can be performed using, for example, an extruder, kneader, or roll in the absence of a solvent, and a reaction vessel with a stirring device can be used in the presence of a solvent.

[0135] For uniform mixing, the resin composition is kneaded using equipment such as a kneader, roll, or planetary mixer at a temperature in the range of 50 to 100°C. After pulverization, the resulting resin composition can be molded into cylindrical tablets using a molding machine such as a tablet machine, or into granular powder or powdery molded bodies. Alternatively, these compositions can be melted on a surface support and molded into sheets with a thickness of 0.05 mm to 10 mm to produce curable resin composition molded bodies. The resulting molded bodies are non-sticky at 0 to 20°C and maintain their fluidity and curability with almost no decrease even after storage at -25 to 0°C for more than a week. The resulting molded bodies can be molded into cured products using a transfer molding machine or a compression molding machine.

[0136] The resulting curable resin composition can take various forms, such as resin sheets and prepregs, depending on the molding method. The prepreg form can be obtained, for example, by heating and melting the curable resin composition and / or resin sheet of this embodiment to reduce its viscosity and impregnating it into a fibrous substrate.

[0137] The curable resin composition of this embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone as needed to form a varnish-like composition (hereinafter also simply referred to as varnish), which can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to create a prepreg. In this case, the solvent used is in an amount that accounts for 10 to 70% by mass, preferably 15 to 70% by mass, of the mixture of the curable resin composition of this embodiment and the solvent.

[0138] Carbon fiber reinforced plastic (CFRP) can be obtained by cutting the above prepregs into the desired shape, laminating them, and then applying pressure to the laminate using methods such as press molding, autoclave molding, or sheet winding molding while heating and curing an epoxy resin composition. Furthermore, copper foil or organic film can also be laminated during the prepreg lamination process.

[0139] In addition to the methods described above, CFRP can also be obtained by known methods. For example, resin transfer molding (RTM) can be used, in which a preform (a pre-molded body before resin impregnation) is made by cutting, laminating, and shaping a carbon fiber substrate (usually carbon fiber fabric is used), the preform is placed in a mold and the mold is closed, resin is injected to impregnate and harden the preform, and then the mold is opened to remove the molded product. Furthermore, various RTM methods can be used, such as the VaRTM method, the SCRIMP (Seeman's Composite Resin Infusion Molding Process) method, and the CAPRI (Controlled Atmospheric Pressure Resin Infusion) method, which more appropriately controls the resin injection process, particularly the VaRTM method, by evacuating the resin supply tank described in Japanese Patent Publication No. 2005-527410 to a pressure lower than atmospheric pressure, using circulating compression, and controlling the net molding pressure. Furthermore, methods such as film stacking, which sandwiches the fiber substrate between resin sheets (films); attaching powdered resin to the reinforced fiber substrate to improve impregnation; molding methods using a fluidized bed or fluid slurry method in the process of mixing resin with the fiber substrate (Powder Impregnated Yarn); and methods of blending resin fibers into the fiber substrate can also be used.

[0140] Examples of carbon fibers include acrylic, pitch, and rayon-based carbon fibers, with acrylic-based carbon fibers being preferred due to their high tensile strength. While twisted, untwisted, and untwisted forms of carbon fibers can be used, untwisted or untwisted yarns are preferred because they offer a good balance between the moldability and strength characteristics of the fiber-reinforced composite material.

[0141] The cured product of the curable resin composition of this embodiment can be used for various applications other than those described above, such as adhesives, paints, coatings, molding materials (including sheets, films, CFRP, etc.), encapsulants for semiconductor devices, encapsulants for liquid crystal display devices, encapsulants for organic EL devices, printed circuit boards (BGA substrates, build-up substrates, etc.), electrical and electronic components, 3D printing, and as additives to other resins.

[0142] The adhesives mentioned above include those for civil engineering, construction, automotive, general office, and medical applications, as well as adhesives for electronic materials. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, underfills for BGA reinforcement, and adhesives for mounting such as anisotropic conductive films (ACF) and anisotropic conductive pastes (ACP), and are applicable to a wide range of uses.

[0143] When applying the curable resin composition of this embodiment to a semiconductor device encapsulant, the curable resin composition of this embodiment can be molded by placing a lead frame or semiconductor package substrate equipped with a semiconductor device into a mold, using a molten casting method, transfer molding method, injection molding method, compression molding method, etc., and then heating at 80 to 200°C for 2 to 10 hours to obtain a cured product. Examples of semiconductor devices manufactured using this encapsulant include potting, dipping, and transfer mold encapsulation for capacitors, transistors, diodes, light-emitting diodes, ICs, and LSIs; potting encapsulation for COB, COF, TAB, etc. of ICs and LSIs; underfill for flip chips; and encapsulation (including reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

[0144] When applying the curable resin composition of this embodiment to printed circuit board applications, a prepreg can be obtained by heating and melting it to reduce its viscosity and impregnating it with reinforcing fibers such as glass fibers and polyamide fibers. Specific examples include, but are not limited to, glass fibers such as E glass cloth, D glass cloth, S glass cloth, Q glass cloth, spherical glass cloth, NE glass cloth, and T glass cloth, and / or organic fibers. The shape of the base material is not particularly limited, but examples include woven fabrics, nonwoven fabrics, rovings, and chopped strand mats. As for the weaving method of the woven fabric, plain weave, twill weave, etc., are known, and these can be appropriately selected and used depending on the intended application and performance. In addition, glass woven fabrics that have been opened or surface-treated with a silane coupling agent are preferably used. The thickness of the base material is not particularly limited, but is preferably about 0.01 to 0.4 mm. Furthermore, a prepreg can be obtained by impregnating reinforcing fibers with the above varnish and heating and drying it, and a copper-clad laminate (CCL) can be made from this prepreg. A laminate using the curable resin composition of this embodiment can also be made by hot-press molding the obtained prepreg and CCL. The laminate is not particularly limited as long as it has one or more prepregs, and may have any other layers. In addition, a sheet-like adhesive can be obtained by applying the above varnish to a release film, removing the solvent under heating, and performing B-stage formation. This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates or as an adhesive sheet when mounting semiconductors. Furthermore, the curable resin composition of this embodiment can be suitably used for special substrate materials such as package substrates and HDI (high density interconnect).

[0145] The present invention will be described in more detail below with reference to synthesis examples and embodiments. The materials, processing content, processing procedures, etc., shown below can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the specific examples shown below. The various analytical methods used in the embodiments are described below.

[0146] The following conditions were used for various analytical methods: • Epoxy equivalent: Measured according to the method described in JIS K-7236, in units of g / eq. • Softening point: Measured according to the method compliant with ASTM D3104, in units of °C. • Viscosity: Measured using the ICI melt viscosity (125°C) cone plate method, in units of Pa·s. • Caking properties: Approximately 10 g of resin was placed in an 11 cm x 9 cm resealable bag, placed in an oven, and a 275 g weight was placed on top. The temperature was increased in 5°C increments. The temperature at which the resin solidified completely and crumbled when force was applied was measured. A higher temperature indicates lower caking properties, meaning the resin is less likely to solidify.

[0147] - Weigh approximately 4 mg of the LC / MS sample into a 6 mL vial and dissolve it in 1 mL of tetrahydrofuran (THF). Then, add an additional 2 mL of acetonitrile (ACN), filter through a 0.2 μm filter, and measure under the following conditions. Apparatus: Liquid chromatography system (Ultimate 3000), mass spectrometer (Q-Exactive), both manufactured by Thermo Fisher Science Column: CORTECS C18 (Waters, column size: particle diameter 2.7 μm, inner diameter 2.1 mm, column length 150 mm) Oven temperature: 40°C Mobile phase: Mobile phase A: 5 mM ammonium acetate (AcONH) ４Mobile phase B: ACN / THF (v / v = 2 / 1) Gradient conditions: The ratio of mobile phase B to the total volume of mobile phase A and mobile phase B was increased from 30% at the start to 95% over 15 minutes, and then maintained for 10 minutes (Total 25 minutes) Flow rate: 0.3 mL / min Sample injection volume: 1.0 μL LC detector: Photodiode array (PDA), wavelength range 190-800 nm MS detector: Fourier transform mass spectrometry (FT-MS), positive ion mode (Posi): m / z = 100-1500, negative ion mode (Nega): m / z = 100-1500 Ionization method: Electrospray ionization (ESI) Detection wavelength: 274 nm

[0148] - Dissolve approximately 10 mg of the HPLC analysis sample in 5 mL of acetonitrile. After filtering through a 0.2 μm filter, measure under the following conditions: HPLC instrument: Shimadzu Corporation Column: GL Science ODS-2 Oven temperature: 40°C Mobile phase: Mobile phase A: 5 mM AcONH ４ Mobile phase B: ACN Gradient conditions: The ratio of mobile phase B to the total volume of mobile phases A and B was increased from 70% at the start to 100% over 28 minutes, and then maintained for 40 minutes (Total 68 minutes). Flow rate: 1.0 mL / min Sample injection volume: 5.0 μL LC detector: Photodiode array (PDA), wavelength range 190–800 nm

[0149] - Dissolve approximately 10 mg of the GPC analysis sample in 5 mL of THF. After filtering through a 0.2 μm filter, measure under the following conditions: GPC instrument: Shimadzu Corporation Guard column: KF-G 4A GPC columns: KF-601, KF-602, KF-602.5, KF-603 Flow rate: 0.5 mL / min Column temperature: 40°C Solvent used: THF (tetrahydrofuran) Detector: RI (differential refractive detector)

[0150] [Synthesis Example 1-1] In a flask equipped with a stirrer, thermometer, and condenser, 47 parts by mass of biphenol, 185 parts by mass of epichlorohydrin (ECH), 93 parts by mass of dimethyl sulfoxide (DMSO, hereafter the same), and 2 parts by mass of water were charged into the reaction vessel. After heating, stirring, and dissolution, 21 parts by mass of flake sodium hydroxide were added in installments over 100 minutes while maintaining the temperature at 55°C. The reaction was then carried out further at 55°C for 90 minutes and at 70°C for 30 minutes. Then, excess ECH was removed from the oil layer under reduced pressure, and 150 parts by mass of methyl isobutyl ketone was added to the residue. The precipitated compound was recovered by suction filtration. The recovered precipitate was neutralized by stirring and washing with 200 parts by mass of 2% sodium dihydrogen phosphate aqueous solution. After suction filtration, the mixture was washed again with 200 parts by mass of water and stirred. After confirming that the filtrate had a pH of 7, the residual solvent was removed by distillation at 165°C to obtain 69 parts by mass of biphenol epoxy. The obtained epoxy resin was in a crystalline state and had an epoxy equivalent of 160 g / eq. The GPC results are shown in Figure 1.

[0151] [Synthesis Example 2-1] 955 parts by mass of phenol and 172 parts by mass of 47% hydrobromic acid were charged into a four-necked flask equipped with a stirrer, thermometer, and condenser. 125 parts by mass of 4,4'-bis(chloromethyl)-1,1'-biphenyl were added while stirring at 30°C, and the reaction was carried out at 30°C for 6 hours and then at 80°C for 2 hours. After the reaction was complete, the mixture was neutralized with a 25% aqueous sodium hydroxide solution, and then 2000 parts by mass of methyl isobutyl ketone were added and the mixture was washed with water repeatedly. Then, the unreacted phenol and methyl isobutyl ketone were removed from the oil layer under reduced pressure and heating to obtain 173 parts of phenol resin represented by formula (2). The softening point of the obtained phenol resin was 174°C, the hydroxyl group equivalent was 188 g / eq., and GPC analysis showed that the bifunctional component content was 78 area%. The GPC results are shown in Figure 2. Furthermore, HPLC analysis revealed that the value obtained by dividing the area of ​​the compound represented by formula (3) by the area of ​​the compound represented by formula (4) was 1.17.

[0152] [Synthesis Example 3-1] In a four-necked flask equipped with a stirrer, thermometer, and condenser, 376 parts by mass of phenol resin obtained in Synthesis Example 2-1, 1110 parts by mass of epichlorohydrin, and 222 parts by mass of dimethyl sulfoxide were charged and dissolved. The mixture was then heated to 50°C, and 82 parts by mass of flake sodium hydroxide (99% purity) were added over 90 minutes. The mixture was then further reacted at 50°C for 2 hours and at 75°C for 1 hour. The reaction mixture was then washed with water repeatedly until the aqueous wash solution became neutral. After that, excess epichlorohydrin was removed from the oil layer under reduced pressure and heated by distillation, and 976 parts by mass of methyl isobutyl ketone was added to the residue and dissolved. The methyl isobutyl ketone solution was then heated to 75°C, and 20 parts by mass of a 30% by mass aqueous sodium hydroxide solution was added. The mixture was reacted for 1 hour, and then the reaction mixture was washed with water repeatedly until the aqueous wash solution became neutral. Next, methyl isobutyl ketone was distilled off from the oil layer under reduced pressure at 180°C to obtain 464 parts by mass of epoxy resin. The obtained epoxy resin exhibited crystalline properties, with an epoxy equivalent of 258 g / eq., a softening point of 103°C, and a melt viscosity of 0.006 Pa·s at 125°C. The GPC results are shown in Figure 3.

[0153] [Synthesis Example 4-1] A flask equipped with a thermometer, dropping funnel, condenser, and stirrer was purged with nitrogen gas and charged with 230 parts by mass of phenol resin obtained in Synthesis Example 2-1, 47 parts by mass of biphenol, 994 parts by mass of epichlorohydrin, 226 parts by mass of dimethyl sulfoxide, and 6.3 parts by mass of water. The mixture was heated to 55°C under stirring and dissolved. Next, 72.5 parts by mass of flake sodium hydroxide were added in installments over 100 minutes, and the mixture was further reacted at 55°C for 100 minutes and then at 70°C for 30 minutes. After the reaction was complete, dimethyl sulfoxide and excess epichlorohydrin were removed by distillation using a rotary evaporator under reduced pressure, and 744 parts by mass of methyl isobutyl ketone were added to the residue and dissolved. 306 parts by mass of water were added to this methyl isobutyl ketone solution, and the by-product salt and dimethyl sulfoxide were washed with water, and the aqueous layer was separated and removed. Next, 23 parts by mass of a 30% by mass sodium hydroxide aqueous solution was added, and the mixture was reacted at 75°C for 1 hour. The mixture was then repeatedly washed with water until the washing solution became neutral. The aqueous layer was then separated and removed, and 360 parts by mass of the epoxy resin mixture of the present invention were obtained by distilling off methyl isobutyl ketone under reduced pressure using a rotary evaporator. The epoxy equivalent of the obtained epoxy resin mixture was 229 g / eq., the softening point was 102°C, and the melt viscosity at 125°C was 0.006 Pa·s. GPC analysis revealed that the content of biphenol epoxidized compounds was 25 area%. The GPC results are shown in Figure 4. LC / MS analysis also revealed that, when the compound represented by n=1 in formula (1) was considered as 100 area%, the total content of the compounds represented by formula (6) and formula (7) was 5.2 area%.

[0154] [Example 1-1, Comparative Examples 1-1, 2-1] The epoxy resin mixture obtained in Synthesis Example 4-1 was used as the epoxy resin mixture for Example 1-1. The epoxy resins obtained in Synthesis Example 1-1 and Synthesis Example 3-1 were mixed in the ratios shown in Table 1 to obtain the epoxy resin mixture for Comparative Example 1-1. The epoxy resin mixture obtained in Synthesis Example 3-1 was used as the epoxy resin mixture for Comparative Example 2-1. The properties of the epoxy resin mixtures for Example 1-1, Comparative Example 1-1, and Comparative Example 1-2 are shown in Table 1.

[0155] [Example 2-1, Comparative Example 3-1] The obtained epoxy resin and epoxy resin mixture were used as the main component, and phenol novolac resin (manufactured by Gun-ei Chemical Co., Ltd., softening point 83.6°C) was used as a curing agent, and TPP (manufactured by Hokko Chemical Industry Co., Ltd.: triphenylphosphine) was used as a curing accelerator. The mixture was then mixed in the mass ratio shown in Table 2, and cured under curing conditions of 160°C for 2 hours and 180°C for 6 hours to produce a cured product.

[0156] The physical properties were measured under the following conditions: <Gel Time Measurement Conditions> Gel time device: Madoka manufactured by Matsuo Sangyo Co., Ltd. Measurement conditions: The time required for curing was measured on a 175°C hot plate. A shorter gel time indicates a faster curing speed.

[0157] The results in Tables 1 and 2 show that the epoxy resin mixture obtained in Synthesis Example 4-1 exhibited similar epoxy equivalents, softening points, and viscosity to the epoxy resin mixtures of Comparative Examples 1-1 and 3-1, which were obtained by separately epoxidizing biphenol and phenol resin and then mixing them. However, it was confirmed to be a low-setting epoxy resin with an excellent curing speed.

[0158] [Synthesis Example 1-2] In a flask equipped with a stirrer, thermometer, and condenser, 47 parts by mass of biphenol, 185 parts by mass of epichlorohydrin (ECH), 93 parts by mass of dimethyl sulfoxide (DMSO, the same applies hereafter), and 2 parts by mass of water were charged into the reaction vessel. After heating, stirring, and dissolution, 21 parts by mass of flake sodium hydroxide were added in installments over 100 minutes while maintaining the temperature at 55°C. The reaction was then carried out further at 55°C for 90 minutes and at 70°C for 30 minutes. Then, excess ECH was removed from the oil layer under reduced pressure, and 150 parts by mass of methyl isobutyl ketone was added to the residue. The precipitated compound was recovered by suction filtration. The recovered precipitate was neutralized by stirring and washing with 200 parts by mass of 2% sodium dihydrogen phosphate aqueous solution. After suction filtration, the mixture was washed again with 200 parts by mass of water and stirred. After confirming that the filtrate had a pH of 7, the residual solvent was removed by distillation at 165°C to obtain 69 parts by mass of biphenol epoxy. The obtained epoxy resin was in a crystalline state and had an epoxy equivalent of 160 g / eq. The GPC results are shown in Figure 5.

[0159] [Synthesis Example 2-2] In a flask equipped with a stirrer, reflux condenser, and stirring device, 254 parts by mass of phenol, 63 parts by mass of water, and 27 parts by mass of sodium hydroxide were charged, stirred, dissolved, and heated to 110°C. 44 parts by mass of furfural were then added dropwise over 2 hours. The mixture was then reacted at 110°C for 3 hours, and then the temperature was raised to 145°C. During the heating process, the water distilled out was removed from the system. After reaching 145°C, the mixture was reacted for 4 hours. The mixture was then cooled to 80°C, 63 parts by mass of water was added, and neutralization was performed by adding 4 parts by mass of phosphoric acid and 63 parts by mass of 35% hydrochloric acid. After repeated washing with water, the unreacted phenol was removed by distillation under reduced pressure to obtain 109 parts by mass of phenol resin represented by formula (2). The hydroxyl group equivalent of the obtained phenol resin was 142 g / eq.

[0160] [Synthesis Example 3-2] In a four-necked flask equipped with a stirrer, thermometer, and condenser, 78 parts by mass of phenol resin obtained in Synthesis Example 2-2 were charged into a reaction vessel with 254 parts by mass of epichlorohydrin, 64 parts by mass of dimethyl sulfoxide, and 13 parts by mass of water. After heating, stirring, and dissolution, 23 parts by mass of flake sodium hydroxide were added in installments over 2 hours while maintaining the temperature at 45°C. The reaction was then carried out further at 45°C for 2 hours and at 70°C for 60 minutes. After repeated washing with water to remove by-product salts and dimethyl sulfoxide, excess epichlorohydrin was distilled off from the oil layer under reduced pressure, and 218 parts by mass of methyl isobutyl ketone were added to the residue and dissolved. This methyl isobutyl ketone solution was heated to 70°C, 7 parts by mass of 30% aqueous sodium hydroxide solution were added, and the mixture was reacted for 1 hour. After that, the reaction solution was washed with water repeatedly until the washing solution became neutral. Next, methyl isobutyl ketone was distilled off from the oil layer under reduced pressure to obtain 97 parts by weight of the epoxy resin represented by formula (1). The epoxy equivalent was 214 g / eq., the softening point was 49°C, the ICI melt viscosity was 0.04 Pa·s, and the average number of repeats n from the GPC was 2.1. The GPC chart of the epoxy resin is shown in Figure 6.

[0161] [Synthesis Example 4-2] A flask equipped with a thermometer, dropping funnel, condenser, and stirrer was purged with nitrogen gas and charged with 211 parts by mass of phenol resin obtained in Synthesis Example 2-2, 47 parts by mass of biphenol, 870 parts by mass of epichlorohydrin, 150 parts by mass of dimethyl sulfoxide, and 40 parts by mass of water. The mixture was heated to 55°C under stirring and dissolved. Next, 83 parts by mass of flake sodium hydroxide were added in installments over 100 minutes, and the mixture was further reacted at 55°C for 90 minutes and then at 70°C for 30 minutes. After the reaction was complete, dimethyl sulfoxide and excess epichlorohydrin were removed by distillation using a rotary evaporator under reduced pressure, and 742 parts of methyl isobutyl ketone were added to the residue and dissolved. 360 parts by mass of water were added to this methyl isobutyl ketone solution, and the by-product salt and dimethyl sulfoxide were washed with water, and the aqueous layer was separated and removed. Next, 74 parts by mass of methanol, 74 parts by mass of water, and 24 parts by mass of a 30% by weight sodium hydroxide aqueous solution were added, and the mixture was reacted at 75°C for 1 hour. The mixture was then washed with water repeatedly until the washing solution became neutral. The aqueous layer was then separated and removed, and methyl isobutyl ketone was distilled off using a rotary evaporator under reduced pressure to obtain 371 parts by mass of the epoxy resin mixture of the present invention. The epoxy equivalent of the obtained epoxy resin mixture was 201 g / eq., the softening point was 201°C, and the melt viscosity at 125°C was 0.009 Pa·s. GPC analysis revealed that the content of biphenol epoxidized compounds was 19 area%. The GPC results are shown in Figure 7. LC / MS analysis also revealed that when the compound represented by n=1 in formula (1) was considered as 100 area%, the total content of the compound represented by formula (3) was 28.1 area%.

[0162] [Examples 1-2, Comparative Examples 1-2, 2-2] The properties of the obtained epoxy resin and epoxy resin mixture are shown in Table 3.

[0163] Consolidation: × indicates that it solidified at room temperature.

[0164] [Example 2-2, Comparative Example 3-2] The epoxy resin obtained in Synthesis Examples 1-2 to 3-2 was used as the main component, and phenol novolac resin (manufactured by Gun-ei Chemical Co., Ltd., softening point 83.6°C) was used as the curing agent, and TPP (manufactured by Hokko Chemical Industry Co., Ltd.: triphenylphosphine) was used as the curing accelerator. The mixture was then mixed in the weight ratios shown in Table 2, and cured under curing conditions of 160°C for 2 hours and 180°C for 6 hours to produce a cured product.

[0165] The physical properties were measured under the following conditions: <Gel Time Measurement Conditions> Gel time apparatus: Madoka manufactured by Matsuo Sangyo Co., Ltd. Sample size: Time required for curing on a 175°C hot plate was measured.

[0166] <Water Absorption Measurement> Three films measuring 5 mm wide x 100 mm long x 0.25 mm thick were prepared by curing the resin composition described in Table 2. After immersion in 25°C water for 24 hours, the samples were removed and left in a 25°C environment for 24 hours, after which the weight increase rate was weighed. The measurement results are shown in Table 4.

[0167] The results in Tables 3 and 4 show that the epoxy resin mixture obtained in Synthesis Example 4-2 exhibited similar epoxy equivalents, softening points, and viscosity to the epoxy resin mixtures of Comparative Examples 1-2 and 3-2, which were obtained by separately epoxidizing biphenol and phenolic resin and then mixing them. However, it was confirmed to be a low-setting epoxy resin with excellent curing speed and low water absorption.

[0168] <Curing Test> [Reference Example 1] 20 parts of the epoxy resin mixture obtained in Synthesis Example 3-2, 0.5 parts of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 1 part of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., acid anhydride compound), KAYAHARD 0.5 parts of GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type phenol resin), 0.5 parts of Unifiner W-575 (manufactured by Unitika Corporation, activated ester resin), 0.5 parts of G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., carboxylic acid compound), 2.5 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 2.5 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 0.5 parts of Phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., maleimide compound), 0.5 parts of SYTESTER TA (manufactured by Mitsubishi Gas Chemical Company, bisphenol A type cyanate resin), OPE-2st 60 parts of 2200 (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3 parts of STR-2000 (a compound containing an ethylenically unsaturated bond manufactured by Nippon Kayaku Co., Ltd.), KAYARAD 1 part R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 0.5 parts acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., compound having an ethylenically unsaturated bond), 1 part polyimide compound obtained by the method described in WO2023 / 013224A1, 1 part TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, allyl compound), 1 part Septon 2104 (manufactured by Kuraray Co., Ltd., modified polystyrene), 0.5 parts P-d benzoxazine (manufactured by Shikoku Chemicals Co., Ltd., benzoxazine compound), 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., curing accelerator), 0.5 parts TPP: triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., curing accelerator), 0.1 parts Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator), Sun-Aid A cured product was obtained by mixing 0.1 parts of SI-B5 (manufactured by Sanshin Chemical Co., Ltd., curing accelerator), 1 part of DCP: dicumyl peroxide (manufactured by Kayaku Nurion Co., Ltd., polymerization initiator), 99.2 parts of toluene as a solvent, and 49.6 parts of tetrahydrofuran, and heating under a nitrogen atmosphere at 110°C for 10 minutes and then at 220°C for 1 hour.

[0169] [Reference Example 2] 50 parts of the epoxy resin mixture obtained in Synthesis Example 3-2, 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 5 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 1 part of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), and 1 part of Irgacure 290 (manufactured by BASF, polymerization initiator) were mixed and coated onto a PET film to a thickness of 100 μm. A PET film was also attached to the side not in contact with the film, and the mixture was heated under a high-pressure mercury lamp (365 nm) at a rate of 3000 mJ / cm². ２ By irradiating it with ultraviolet light, a cured product could be obtained.

[0170] [Reference Example 1-1] 20 parts of the epoxy resin mixture obtained in Synthesis Example 4-1, 0.5 parts of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 1 part of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., acid anhydride compound), KAYAHARD 0.5 parts of GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type phenol resin), 0.5 parts of Unifiner W-575 (manufactured by Unitika Corporation, activated ester resin), 0.5 parts of G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., carboxylic acid compound), 2.5 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 2.5 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 0.5 parts of Phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., maleimide compound), 0.5 parts of SYTESTER TA (manufactured by Mitsubishi Gas Chemical Company, bisphenol A type cyanate resin), OPE-2st 60 parts of 2200 (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3 parts of STR-2000 (a compound containing an ethylenically unsaturated bond manufactured by Nippon Kayaku Co., Ltd.), KAYARAD 1 part R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 0.5 parts acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., compound having an ethylenically unsaturated bond), 1 part polyimide compound obtained by the method described in WO2023 / 013224A1, 1 part TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, allyl compound), 1 part Septon 2104 (manufactured by Kuraray Co., Ltd., modified polystyrene), 0.5 parts P-d benzoxazine (manufactured by Shikoku Chemicals Co., Ltd., benzoxazine compound), 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., curing accelerator), 0.5 parts TPP: triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., curing accelerator), 0.1 parts Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator), Sun-Aid A cured product was obtained by mixing 0.1 parts of SI-B5 (manufactured by Sanshin Chemical Co., Ltd., curing accelerator), 1 part of DCP: dicumyl peroxide (manufactured by Kayaku Nurion Co., Ltd., polymerization initiator), 99.2 parts of toluene as a solvent, and 49.6 parts of tetrahydrofuran, and heating under a nitrogen atmosphere at 110°C for 10 minutes and then at 220°C for 1 hour.

[0171] [Reference Example 2-1] 50 parts of the epoxy resin mixture obtained in Synthesis Example 4-1, 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 5 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 1 part of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), and 1 part of Irgacure 290 (manufactured by BASF, polymerization initiator) were mixed and coated onto a PET film to a thickness of 100 μm. A PET film was also attached to the side not in contact with the film, and the mixture was heated under a high-pressure mercury lamp (365 nm) at a rate of 3000 mJ / cm². ２ By irradiating it with ultraviolet light, a cured product could be obtained.

[0172] [Reference Example 1-2] 20 parts of the epoxy resin mixture obtained in Synthesis Example 3-2, 0.5 parts of MDEA: 4,4'-methylenebis(2-ethyl-6-methylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., amine compound), 1 part of DICY: dicyandiamide (manufactured by Tokyo Chemical Industry Co., Ltd., amide compound), 0.5 parts of KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd., acid anhydride compound), KAYAHARD 0.5 parts of GPH-65 (manufactured by Nippon Kayaku Co., Ltd., biphenylaralkyl type phenol resin), 0.5 parts of Unifiner W-575 (manufactured by Unitika Corporation, activated ester resin), 0.5 parts of G4-142MHR (manufactured by Nippon Kayaku Co., Ltd., carboxylic acid compound), 2.5 parts of MIR-3000-70MT (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 2.5 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 0.5 parts of Phenylmaleimide (manufactured by Tokyo Chemical Industry Co., Ltd., maleimide compound), 0.5 parts of SYTESTER TA (manufactured by Mitsubishi Gas Chemical Company, bisphenol A type cyanate resin), OPE-2st 60 parts of 2200 (a polyphenylene ether compound manufactured by Mitsubishi Gas Chemical Co., Ltd.), 3 parts of STR-2000 (a compound containing an ethylenically unsaturated bond manufactured by Nippon Kayaku Co., Ltd.), KAYARAD 1 part R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 0.5 parts acenaphthylene (manufactured by Tokyo Chemical Industry Co., Ltd., compound having an ethylenically unsaturated bond), 1 part polyimide compound obtained by the method described in WO2023 / 013224A1, 1 part TAIC: triallyl isocyanurate (manufactured by Mitsubishi Chemical Corporation, allyl compound), 1 part Septon 2104 (manufactured by Kuraray Co., Ltd., modified polystyrene), 0.5 parts P-d benzoxazine (manufactured by Shikoku Chemicals Co., Ltd., benzoxazine compound), 2E4MZ: 2-ethyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., curing accelerator), 0.5 parts TPP: triphenylphosphine (manufactured by Hokko Chemical Co., Ltd., curing accelerator), 0.1 parts Octop Zn (manufactured by Hope Pharmaceutical Co., Ltd., curing accelerator), Sun-Aid A cured product was obtained by mixing 0.1 parts of SI-B5 (manufactured by Sanshin Chemical Co., Ltd., curing accelerator), 1 part of DCP: dicumyl peroxide (manufactured by Kayaku Nurion Co., Ltd., polymerization initiator), 99.2 parts of toluene as a solvent, and 49.6 parts of tetrahydrofuran, and heating under a nitrogen atmosphere at 110°C for 10 minutes and then at 220°C for 1 hour.

[0173] [Reference Example 2-2] 50 parts of the epoxy resin mixture obtained in Synthesis Example 3-2, 10 parts of MIZ-001 (manufactured by Nippon Kayaku Co., Ltd., maleimide compound), 5 parts of STR-2000 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 45 parts of KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd., compound having an ethylenically unsaturated bond), 1 part of Irgacure OXE-04 (manufactured by BASF, polymerization initiator), and 1 part of Irgacure 290 (manufactured by BASF, polymerization initiator) were mixed and coated onto a PET film to a thickness of 100 μm. A PET film was also attached to the side not in contact with the film, and the mixture was heated under a high-pressure mercury lamp (365 nm) at a rate of 3000 mJ / cm². ２ By irradiating it with ultraviolet light, a cured product could be obtained.

[0174] The epoxy resin mixture of the present invention is suitably used in electrical and electronic components such as semiconductor encapsulants, printed circuit boards, and build-up laminates.

[0175] [Note] As described above, this embodiment includes the following disclosures: [1] An epoxy resin mixture which is a reaction product of a phenol resin mixture containing 50 to 95% by mass of a phenol resin represented by the following formula (2) and 5 to 50% by mass of biphenol and an epihalohydrin, wherein the content of the biphenol epoxidized product in the total amount of the epoxy resin mixture is 5 to 35 area percent in terms of the GPC area percentage of the epoxy resin mixture.

[0176] (In equation (2), n is the average value of the number of repetitions, a real number such that 0 < n ≤ 10, and X is expressed by any of the following equations (a) to (g).)

[0177] (In equations (a) to (g), there are multiple R １ , R ２ p and q exist independently of each other, R １ R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may have substituents. ２* represents an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms, which may have substituents. p is an integer from 0 to 4, and q is an integer from 0 to 3. r is the average number of repeats, and is a real number between 1 and 10. * indicates the bond position of X. ) [2] The epoxy resin mixture according to [1], wherein, in the GPC area percentage of the phenol resin represented by formula (2), the content of the compound where n=1 in the total amount of the phenol resin represented by formula (2) is 60 to 90 area%, in the HPLC area percentage of the phenol resin represented by formula (2), the value obtained by dividing the area of ​​the compound represented by the following formula (3) by the area of ​​the compound represented by the following formula (4) is 1.15 or more and 1.30 or less, and in the peak area percentage of the LC chart of the LC / MS measurement of the epoxy resin mixture, when the compound represented by n=1 in the following formula (1) is taken as 100 area%, the total content of the compound represented by the following formula (6) and the compound represented by the following formula (7) is 0.1 to 25 area%,

[0178] (In formulas (1), (3), (4), (6), and (7), X is represented by any of the following formulas (a) to (g), n is the average value of the number of repetitions and is a real number such that 0 < n ≤ 10, and G represents a glycidyl group.) [3] The epoxy resin mixture according to [1] or [2], wherein formulas (1) to (4), (6), and (7) are represented by the following formulas (1-1), (2-1), (3-1), (4-1), (6-1), and (7-1), respectively.

[0179] (In formulas (1-1) to (4-1), (6-1), and (7-1), n ​​is the average value of the number of repetitions and is a real number such that 0 < n ≤ 10. G represents a glycidyl group.) [4] The epoxy resin mixture according to [1], wherein, in the peak area percentage of the LC chart measured by LC / MS, when the compound represented by n=1 in formula (1) below is taken as 100 area%, the content of the compound represented by formula (6) below is 0.1 to 35 area%.

[0180] (In formulas (1) and (6), X is represented by any of the above formulas (a) to (g), n is the average value of the number of repetitions and is a real number such that 0 < n ≤ 10, and G represents a glycidyl group.) [5] The epoxy resin mixture according to [1] or [4], wherein formula (1), formula (2), and formula (6) are represented by the following formulas (1-2), (2-2), and (6-2), respectively.

[0181] (In formulas (1-2), (2-2), and (6-2), n is the average value of the number of repetitions and is a real number such that 0 < n ≤ 10. G represents a glycidyl group.) [6] An epoxy resin mixture according to any one of [1] to [5], having a softening point of 50 to 130°C. [7] An epoxy resin mixture according to any one of [1] to [6], which is an epoxy resin mixture for semiconductor encapsulation. [8] A curable resin composition containing an epoxy resin mixture according to any one of [1] to [7]. [9] A curable resin composition according to any one of [1] to [8], further comprising a curing accelerator, a polymerization initiator, an epoxy resin other than the epoxy resin mixture, an active ester compound, a phenol resin other than the phenol resin mixture, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, a polybutadiene and a modified thereof, polystyrene and a modified thereof, polyethylene and a modified thereof, and a benzoxazine compound.

[10] A cured product obtained by curing the curable resin composition according to [8] or [9].

Claims

1. An epoxy resin mixture which is a reaction product of a phenol resin mixture containing 50 to 95% by mass of a phenol resin represented by the following formula (2) and 5 to 50% by mass of biphenol, wherein the content of the biphenol epoxidized product in the total amount of the epoxy resin mixture is 5 to 35 area % in terms of the GPC area percentage of the epoxy resin mixture: In equation (2), n is the average value of the number of repetitions, a real number such that 0 < n ≤ 10, and X is expressed by any of the following equations (a) to (g): In equations (a) to (g), there are multiple R １ , R ２ p and q exist independently of each other, R １ R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may have substituents. ２ represents an alkyl group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may have substituents; p is an integer from 0 to 4, q is an integer from 0 to 3, r is the average value of the number of repetitions and is a real number between 1 and 10; and * indicates the bond position of X.

2. In the GPC area percentage of the phenol resin represented by formula (2), the content of the compound where n=1 in the total amount of the phenol resin represented by formula (2) is 60 to 90 area%, in the HPLC area percentage of the phenol resin represented by formula (2), the value obtained by dividing the area of ​​the compound represented by formula (3) below by the area of ​​the compound represented by formula (4) below is 1.15 or more and 1.30 or less, and in the peak area percentage of the LC chart of the LC / MS measurement of the epoxy resin mixture, when the compound represented by n=1 in formula (1) below is taken as 100 area%, the total content of the compound represented by formula (6) below and the compound represented by formula (7) below is 0.1 to 25 area%, according to claim 1: In formulas (1), (3), (4), (6), and (7), X is represented by any of the above formulas (a) to (g), n is the average value of the number of repetitions and is a real number between 0 and 10, and G represents a glycidyl group.

3. The epoxy resin mixture according to claim 2, wherein formulas (1) to (4), (6), and (7) are represented by the following formulas (1-1), (2-1), (3-1), (4-1), (6-1), and (7-1), respectively: In equations (1-1) to (4-1), (6-1), and (7-1), n ​​is the average value of the number of repetitions, a real number between 0 and 10, and G represents a glycidyl group.

4. The epoxy resin mixture according to claim 1, wherein, in terms of the peak area percentage of the LC chart obtained by LC / MS measurement, when the compound represented by n=1 in the following formula (1) is taken as 100 area%, the content of the compound represented by the following formula (6) is 0.1 to 35 area%: In formulas (1) and (6), X is represented by any of the above formulas (a) to (g), n is the average value of the number of repetitions and is a real number between 0 and 10, and G represents a glycidyl group.

5. The epoxy resin mixture according to claim 4, wherein formula (1), formula (2), and formula (6) are represented by the following formulas (1-2), (2-2), and (6-2), respectively: In equations (1-2), (2-2), and (6-2), n is the average value of the number of repetitions, a real number between 0 and 10, and G represents a glycidyl group.

6. The epoxy resin mixture according to claim 1, wherein the softening point is 50 to 130°C.

7. The epoxy resin mixture according to claim 1, which is an epoxy resin mixture for semiconductor encapsulation.

8. A curable resin composition containing the epoxy resin mixture described in claim 1.

9. The curable resin composition according to claim 8, further comprising a curing accelerator, a polymerization initiator, an epoxy resin other than the epoxy resin mixture, an active ester compound, a phenol resin other than the phenol resin mixture, a polyphenylene ether compound, an amine resin, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, a polybutadiene and a modified thereof, polystyrene and a modified thereof, polyethylene and a modified thereof, and a benzoxazine compound.

10. A cured product obtained by curing the curable resin composition described in claim 8.

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