Polyfunctional vinyl resin, polyvalent hydroxy resin, epoxy resin, composition thereof, and cured product

Abstract

The purpose of the present invention is to provide: a compound excellent in solvent solubility and excellent in heat resistance, thermal decomposition stability, thermal conductivity, and flame retardancy; and a curable resin composition containing this compound. Provided is a polyfunctional vinyl resin represented by general formula (1A) below or an epoxy resin represented by general formula (1B) below. In formula (1), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X independently represents a structure represented by formula (2), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m -, m represents a number from 3-10, and n represents a number from 1-15.

Description

Polyfunctional vinyl resins, polyhydroxy resins, epoxy resins, compositions thereof, and cured products

[0001] The present invention relates to a polyfunctional vinyl resin, a polyhydroxy resin, and an epoxy resin, and more particularly to a polyfunctional resin useful as an insulating material for electric and electronic components such as semiconductor encapsulation, laminates, and heat dissipation substrates, a composition thereof, and a cured resin obtained by curing the resin or compositions thereof, which has excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric dissipation factor, and flame retardancy.

[0002] As communication speeds and volumes increase, research into high-speed communication technologies is actively underway to improve signal transmission speeds for printed circuit boards, encapsulants, and casting materials used in communication devices. Electronic materials for such applications require materials that can reduce dielectric loss, and for printed circuit board applications, curable resins that can be multilayered are also required.

[0003] On the other hand, electronic computing components that process such large amounts of data generate a lot of heat, and heat accumulation can cause problems such as a decrease in the processing speed of the electronic computing components, so various methods have been known to appropriately cool printed circuit boards using heat sinks or the like, such as incorporating heat transfer members such as copper coins and copper inlays (Patent Document 1), or using fillers with special shapes (Patent Document 2).However, these methods are undesirable because they lead to increased weight and larger equipment.

[0004] In encapsulant compositions, methods for increasing thermal conductivity have been adopted to remove heat from electronic computing components by examining the type and amount of various fillers. For example, attempts have been made to incorporate inorganic fillers with high thermal conductivity, such as crystalline silica, silicon nitride, aluminum nitride, and spherical alumina powder (Patent Documents 3 and 4). However, increasing the content of inorganic fillers increases viscosity during molding, reducing fluidity and impairing moldability. Therefore, there are limitations to simply increasing the content of inorganic fillers.

[0005] Given the above background, methods for improving the thermal conductivity of compositions by increasing the thermal conductivity of the matrix resin itself have also been investigated. For example, liquid crystalline epoxy resins with rigid mesogenic groups and epoxy resin compositions using such resins have been proposed (Patent Documents 5 and 6). However, these epoxy resin compositions use aromatic diamine compounds as curing agents, which limit the high inorganic filler loading and also pose problems with electrical insulation. When aromatic diamine compounds are used, although liquid crystallinity can be confirmed in the cured product, the degree of crystallinity of the cured product is low, and the cured product is insufficient in terms of high thermal conductivity, low thermal expansion, low moisture absorption, etc. Furthermore, to achieve liquid crystallinity, a strong magnetic field is required to orient the molecules, which poses significant equipment limitations for widespread industrial use. Furthermore, in systems containing inorganic fillers, the thermal conductivity of the inorganic filler is overwhelmingly greater than that of the matrix resin. Therefore, increasing the thermal conductivity of the matrix resin itself does not significantly contribute to improving the thermal conductivity of the composite material, and sufficient thermal conductivity improvement has not been achieved.

[0006] Patent Document 7 discloses a tetrafunctional or higher vinyl resin having a biphenyl skeleton as a multifunctional vinyl resin that combines high thermal conductivity and low dielectric loss tangent. However, the solvent solubility of the multifunctional vinyl resin and its raw material, the polyhydroxy resin, is not described, and the influence of impurities such as residual polar groups on thermal conductivity is not mentioned at all. Patent Document 8 proposes reducing crystallinity by removing crystalline components from an epoxy resin having a biphenol-biphenyl aralkyl structure, but the solvent solubility is insufficient, making it difficult to use. When mixing another epoxy resin to improve moldability and solvent solubility, the melting point of the resin is lowered, making it easier to mix uniformly, but it becomes difficult to maintain the physical properties of the cured product, such as heat resistance, thermal decomposition stability, mechanical strength, and thermal conductivity. Patent Document 9 proposes a resin composition using a biphenol aralkyl epoxy resin and a bisphenol methane epoxy resin in combination. However, due to the strong crystallinity, melt-kneading is difficult, and the solvent solubility is insufficient for practical use in laminates.

[0007] Japanese Patent Application Laid-Open No. 2009-170493 International Publication No. 2013 / 100172 Japanese Patent Application Laid-Open No. 11-147936 Japanese Patent Application Laid-Open No. 2002-309067 Japanese Patent Application Laid-Open No. 11-323162 Japanese Patent Application Laid-Open No. 9-118673 International Publication No. 2021-200414 Japanese Patent Application Laid-Open No. 2017-95524 Japanese Patent Application Laid-Open No. 2015-160893

[0008] An object of the present invention is to provide a vinyl composition that has excellent solvent solubility and gives a cured product that is excellent in heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric dissipation factor, and flame retardancy, and is useful for sealing electric and electronic components, as a circuit board material, etc., and to provide a cured product thereof. Another object is to provide a vinyl compound that can be used in this vinyl composition. An object of the present invention is to provide an epoxy resin composition that has good melt-kneadability at 100°C or less, has excellent solvent solubility, and gives a cured product that is excellent in heat resistance, thermal decomposition stability, thermal conductivity, and flame retardancy, and is useful for sealing electric and electronic components, as a circuit board material, etc., and to provide a cured product thereof. Another object is to provide an epoxy resin that can be used in this epoxy resin composition and a polyhydric hydroxy resin that is suitable as an intermediate for this epoxy resin.

[0009] The present inventors have conducted extensive research and have found, as a first invention, that a polyfunctional vinyl compound having a specific structure is expected to solve the above-mentioned problems, and that a cured product thereof exhibits effects in terms of heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric dissipation factor, and flame retardancy.

[0010] That is, a first invention is a polyfunctional vinyl resin represented by the following general formula (1A). In formula (1A), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a structure represented by formula (2A), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, where m is a number from 3 to 10 and n is a number from 1 to 15. X of the polyfunctional vinyl resin is preferably a structure represented by formula (2A).

[0011] The first invention is a polyfunctional vinyl composition containing a polyfunctional vinyl resin and a radical polymerization initiator as essential components, and a polyfunctional vinyl cured product obtained by curing this polyfunctional vinyl resin composition.

[0012] The present inventors have conducted extensive research and have found, as a second invention, that an epoxy resin having a specific structure is expected to solve the above-mentioned problems, and that a cured product thereof exhibits effects in terms of heat resistance, thermal decomposition stability, thermal conductivity, and flame retardancy.

[0013] That is, the second invention is an epoxy resin represented by the following general formula (1B): In formula (1B), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a structure represented by formula (2B), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, where m is a number from 3 to 10 and n is a number from 1 to 15. X of the epoxy resin preferably has a structure represented by formula (2B).

[0014] A second aspect of the present invention is a polyhydroxy resin represented by the following general formula (3B): In formula (3B), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a structure shown in formula (2B), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, where m represents a number from 3 to 10 and n represents a number from 1 to 15. X of the polyvalent hydroxy resin is preferably a structure shown in formula (2B).

[0015] The second invention is an epoxy resin composition comprising the above-mentioned epoxy resin or polyhydroxy resin curing agent as an essential component, and a cured resin product obtained by curing the cured resin.

[0016] The multifunctional vinyl resin of the first invention has excellent solvent solubility and is suitable for vinyl resin compositions and cured products thereof used in applications such as lamination, molding, casting, and adhesion. The cured products also have excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric dissipation factor, and flame retardancy, making them suitable for sealing electrical and electronic components, circuit board materials, and the like. The polyhydroxy resin and epoxy resin of the second invention have good melt-kneadability at temperatures below 100°C and excellent solvent solubility, making them suitable for epoxy resin compositions and cured products thereof used in applications such as lamination, molding, casting, and adhesion. The cured products also have excellent heat resistance, thermal decomposition stability, and thermal conductivity, making them suitable for sealing electrical and electronic components, circuit board materials, and the like.

[0017] 1A is a GPC chart of a polyfunctional vinyl resin compound obtained in Example 1A of the first invention; 1B is a GPC chart of a hydroxy resin obtained in Example 1B of the second invention; and 7B is a GPC chart of an epoxy resin obtained in Example 7B of the second invention.

[0018] First, the polyfunctional vinyl resin of the first invention will be described in detail. The first invention is a polyfunctional vinyl resin represented by the following general formula (1A). In formula (1A), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a structure represented by formula (2A), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, where m is a number from 3 to 10 and n is a number from 1 to 15.

[0019] R1 to R6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. As the monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkyl group is preferred from the viewpoint of solvent solubility, and an aromatic group is preferred from the viewpoint of heat resistance and high thermal conductivity. With an alkyl group having more than 6 carbon atoms, it becomes difficult to suppress molecular motion, and there is a concern that compatibility may decrease. Furthermore, a bulky structure with significant steric hindrance increases crystallinity, which may result in concerns about solvent solubility. More preferred structures are a hydrogen atom, a methyl group, or a phenyl group. R1 to R6 may be a mixture of different structures.

[0020] In the polyfunctional vinyl resin of the present invention, the substitution positions of the vinylbenzyl ethers are not particularly limited, but from the viewpoints of thermal conductivity and heat resistance, they are preferably para-positions relative to the methine groups connecting the three aromatic rings. In particular, it is more preferable that all three vinylbenzyl ethers are para-positions.

[0021] n is the number of repetitions and represents a number from 1 to 15. Preferably, the mixture is made of components with different n values. The n value (average value) is preferably 1.0 to 5.0, more preferably 1.5 to 3.5. The polyfunctional vinyl resin of the present invention excludes compounds where n=0 alone, but may also be a mixture with a compound where n=0. However, the area % measured by gel permeation chromatography (GPC area %) where n=0 is preferably 60% or less, more preferably 50% or less.

[0022] X independently represents a structure shown in formula (2A), a benzonitrile structure, a sulfonyl structure, or -(CH2)m-. In the alkyl structure represented by -(CH2)m-, m is the repeating number and represents a number of 3 to 10. More preferably, it is a number of 4 to 8. If it is less than 3, flexibility tends to be low and the crystallinity relaxation effect tends to be low. If it is greater than 10, the thermal conductivity and heat resistance of the cured product tend to be significantly reduced. As stated "independently," the vinyl resin of formula (1A) of the present invention can be a mixture of Xs with different structures, making it possible to adjust high thermal conductivity, moldability, and solvent solubility. When X is a structure shown in formula (2A), the thermal conductivity of the cured product tends to be improved.

[0023] A specific example of a preferred structure is a polyfunctional vinyl resin of the following formula (3A) in which X is a biphenyl-containing structure represented by formula (2A). In formula (3A), R1 to R6 have the same meanings as R1 to R6 in formula (1) above.

[0024] The polyfunctional vinyl resin of the present invention preferably has a vinyl equivalent weight in the range of 150 to 450 g / eq, more preferably 200 to 350 g / eq. If the vinyl equivalent weight is less than this range, the reaction will proceed too rapidly, making it difficult to control the reaction. If the vinyl equivalent weight is greater than this range, the reactivity will decrease, making it difficult to obtain a uniform cured product. The number average molecular weight Mn is preferably 500 to 2,000, more preferably 700 to 1.50.

[0025] The multifunctional vinyl resin of the present invention can be obtained by reacting a hydroxy compound with chloromethylstyrene. If the amount of unreacted hydroxyl groups remaining is less than 5,000 g / eq, curing will be insufficient, resulting in reduced thermal conductivity and heat resistance. Furthermore, since hydroxyl groups are polar groups, their remaining presence may hinder the reduction of the dielectric constant and dielectric loss tangent. The hydroxyl group equivalent is preferably 5,000 g / eq or more, more preferably 10,000 g / eq or more. Meanwhile, the chlorine component is derived from the raw material chloromethylstyrene or a halogen-based crosslinking agent. If chlorine components remain, as with hydroxyl groups, there is a concern that they may hinder the reduction of the dielectric constant and dielectric loss tangent, and that the curing reaction may be inhibited by the polar groups, resulting in reduced thermal conductivity and heat resistance. The total chlorine content is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and even more preferably 1,000 ppm or less.

[0026] The polyfunctional vinyl resin of the present invention can be obtained by reacting a polyfunctional hydroxy compound (resin) represented by formula (4B) with an aromatic vinylating agent, where R1 to R6, n, and X are the same as those of the vinyl compound of formula (1A).

[0027] The polyfunctional hydroxy compound (resin) of formula (4A) may be the same as the polyfunctional hydroxy compound (resin) of formula (3B) described below.

[0028] The polyfunctional vinyl resin of the present invention can be suitably obtained by reacting a polyfunctional hydroxy compound (resin) with an aromatic vinylating agent. For example, the vinyl compound of the present invention represented by the above formula (1A) can be obtained by reacting a polyfunctional hydroxy compound represented by the above formula (4A) with chloromethylstyrene. This reaction can be carried out in the same manner as in well-known vinylation reactions.

[0029] The blending ratio is preferably 0.8 to 1.2 equivalents of aromatic vinylating agent (e.g., chloromethylstyrene) per 1.0 equivalent of hydroxyl groups, which are functional groups of the polyfunctional hydroxy resin. However, if the reactivity of the polyfunctional hydroxy compound is low, it is advisable to charge an excess amount of aromatic vinylating agent and remove it after the reaction.

[0030] As the aromatic vinylating agent, halomethylstyrene, particularly chloromethylstyrene, is preferred. Other examples include bromomethylstyrene and its isomers, and those having a substituent. Regarding the substitution position of the halomethyl compound, for example, in the case of halomethylstyrene, the 4-position is preferred, and it is preferred that the 4-position compound accounts for 60% by weight or more of the total.

[0031] The reaction between a polyfunctional hydroxy compound and an aromatic vinylating agent can be carried out in the absence of a solvent or in the presence of a solvent. The reaction can be carried out by adding the aromatic vinylating agent to the hydroxy compound, adding a metal hydroxide, and then removing the resulting metal salt by filtration, washing with water, or other methods. Examples of solvents include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, and cyclohexanone. From the viewpoint of reactivity, methyl ethyl ketone is preferred. Specific examples of metal hydroxides include, but are not limited to, sodium hydroxide and potassium hydroxide.

[0032] The vinylation reaction is preferably carried out at a temperature of 90° C. or less, more preferably 70° C. or less. At temperatures higher than this temperature, self-polymerization of the vinylbenzyl ether group due to heat proceeds, making it difficult to control the reaction. To suppress self-polymerization, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitrone compounds, or oxygen may be used.

[0033] The end point of the reaction can be determined by tracking the remaining amount of halomethylstyrene as an aromatic vinylating agent using various chromatograms such as GPC, and the reaction rate can be adjusted by the type and amount of metal hydroxide, the addition rate, the solids concentration, etc.

[0034] The polyfunctional vinyl resin of the present invention can be cured by itself, but it is also suitable to use it as a polyfunctional vinyl composition containing various additives. In particular, it can be cured by adding a radical polymerization initiator such as an azo compound or an organic peroxide to accelerate curing.

[0035] Next, the epoxy resin of the second invention will be described in detail. The second invention is an epoxy resin represented by the following general formula (1B). In formula (1B), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a structure represented by formula (2B), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, where m is a number from 3 to 10 and n is a number from 1 to 15.

[0036] R1 to R6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. As the monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkyl group is preferred from the viewpoint of solvent solubility, and an aromatic group is preferred from the viewpoint of heat resistance and high thermal conductivity. With an alkyl group having more than 6 carbon atoms, it becomes difficult to suppress molecular motion, and there is a concern that compatibility may decrease. Furthermore, a bulky structure with significant steric hindrance increases crystallinity, which may result in concerns about solvent solubility. A hydrogen atom, a methyl group, or a phenyl group is more preferred. R1 to R6 may be a mixture of different structures.

[0037] n is the number of repetitions and represents a number from 1 to 15. Preferably, the epoxy resin is a mixture of components with different n values. The n value (average value) is preferably 1.0 to 5.0, more preferably 1.5 to 3.5. The epoxy resin of the present invention excludes compounds where n=0 alone, but may be a mixture with a compound where n=0. However, the area % measured by gel permeation chromatography (GPC area %) where n=0 is preferably 50% or less.

[0038] X independently represents a structure shown in formula (2B), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-. In the alkyl structure represented by -(CH2)m-, m is the repeating number and is a number from 3 to 10. More preferably, it is a number from 4 to 8. If it is less than 3, flexibility tends to be low and the crystallinity relaxation effect tends to be low. If it is more than 10, the thermal conductivity and heat resistance of the cured product tend to be significantly reduced. As stated "independently," the epoxy resin of formula (1B) of the present invention can be a mixture of Xs with different structures, making it possible to adjust high thermal conductivity, moldability, and solvent solubility. When X is a structure shown in formula (2B), the thermal conductivity of the cured product tends to be improved.

[0039] A specific example of a preferred structure is an epoxy resin of the following formula (4B) in which X is a biphenyl-containing structure represented by formula (2B). In formula (4B), R1 to R6 have the same meanings as R1 to R6 in formula (1) above.

[0040] The epoxy resin of the present invention preferably has an epoxy equivalent weight in the range of 150 to 450 g / eq, more preferably 200 to 350 g / eq. If the epoxy equivalent weight is less than this range, the reaction will proceed too rapidly, making it difficult to control the reaction. If the epoxy equivalent weight is greater than this range, the reactivity will decrease, making it difficult to obtain a uniform cured product. The number average molecular weight Mn is preferably 500 to 2,000, more preferably 500 to 1,000. The softening point is preferably 60 to 100°C, more preferably 70 to 90°C.

[0041] The epoxy resin of the present invention can be obtained by reacting a polyhydric hydroxy compound (resin) represented by formula (3B) with epichlorohydrin. R1 to R6, n, and X are the same as those in the epoxy resin of formula (1).

[0042] The polyfunctional hydroxy compound of formula (3B) preferably has a hydroxyl group equivalent of 100 to 350 g / eq, more preferably 120 to 250 g / eq. The number average molecular weight Mn is preferably 500 to 1,500. The polyfunctional hydroxy compound (phenolic compound) of formula (3B) may be produced by any method as long as it has a predetermined structure, but can be suitably obtained by reacting a trifunctional trihydroxy compound with a dihalogen compound having an X group in the presence of a basic catalyst. In this case, an example of the trifunctional trihydroxy compound is 4,4',4"-trihydroxytriphenylmethane, which may have one or more hydrocarbon groups such as methyl groups or phenyl groups as substituents. Examples of dihalogen compounds having an X group include dihalogen nitrile compounds such as 2,4-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,6-dichlorobenzonitrile, 3,5-dichlorobenzonitrile, 2,4-dibromobenzonitrile, 2,5-dibromobenzonitrile, 2,6-dibromobenzonitrile, and 3,5-dibromobenzonitrile; dihalogen alkyl compounds such as 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, and 1,6-dibromohexane; 4,4'-dibromodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfone, 4,4'-bishydroxymethylbiphenyl, 4,4'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4,4'-bismethoxymethylbiphenyl, 4,4'-bisethoxymethylbiphenyl, and p-xylene dichloride. As a crosslinked structure that contributes to high thermal conductivity, a biphenyl structure is suitable, and 4,4'-bischloromethylbiphenyl is particularly suitable as a crosslinking agent in terms of reactivity.

[0043] The molar ratio when reacting a phenol with an aromatic condensing agent is generally in the range of 0.2 to 0.7 moles of aromatic condensing agent per mole of phenol, and more preferably in the range of 0.4 to 0.7 moles. If the ratio is less than 0.2 moles, the proportion of n=0 in the resulting polyhydroxy resin will be high, raising concerns about reduced solubility, such as crystallinity. On the other hand, if the ratio is more than 0.7 moles, the amount of high-molecular-weight components will increase, making stable production difficult.

[0044] The reaction between a phenol and an aromatic condensing agent can be carried out without a catalyst or in the presence of an acid catalyst such as an inorganic acid or an organic acid. When 4,4'-bischloromethylbiphenyl is used, the reaction can be carried out without a catalyst; however, it is generally preferable to carry out the reaction in the presence of an acid catalyst to suppress side reactions such as the reaction of a chloromethyl group with a hydroxyl group to form an ether bond. The acid catalyst can be appropriately selected from well-known inorganic and organic acids, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethansulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids.

[0045] This reaction is usually carried out at 100 to 250° C. for 1 to 20 hours, preferably at 100 to 180° C., and more preferably at 140 to 180° C. If the reaction temperature is low, the reactivity is poor and the reaction takes a long time, whereas if the reaction temperature is high, there is a risk of decomposition of the resin.

[0046] As a solvent for the reaction, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, etc., or aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc. are preferably used, and among these, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme, etc. After completion of the reaction, the solvent may be removed from the resulting polyhydric hydroxy resin by methods such as distillation under reduced pressure, washing with water, or reprecipitation in a poor solvent, or the solvent may remain and be used as a raw material for the epoxidation reaction.

[0047] The polyhydroxy resin thus obtained can be used not only as a raw material for epoxy resins but also as an epoxy resin curing agent. Furthermore, by combining it with a curing agent such as hexamine, it can also be used as a molding material for phenolic resins.

[0048] Trifunctional trihydroxy compounds can be obtained by polycondensation of a phenol compound and an aromatic aldehyde, and the reaction may be carried out using an acid catalyst, such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, paratoluenesulfonic acid, zinc acetate, or manganese acetate. These acid catalysts may be used alone or in combination of two or more. Among these acid catalysts, sulfuric acid and paratoluenesulfonic acid are preferred because of their excellent activity. The acid catalyst may be added before or during the reaction.

[0049] The reaction temperature during polycondensation of a phenol compound with an aromatic aldehyde to obtain a trifunctional trihydroxy compound is in the range of 20 to 140°C, preferably 80 to 110°C.

[0050] The charging ratio of the phenol compound / aromatic aldehyde when polycondensing the phenol compound with the aromatic aldehyde to obtain a trifunctional trihydroxy compound is in the range of 1 / 0.1 to 1 / 0.5 in terms of molar ratio, more preferably 1 / 0.3 to 1 / 0.5, since the phenol compound after the reaction can be easily removed by reprecipitation or the like.

[0051] The method for producing the epoxy resin of the present invention by reacting the polyhydric hydroxy resin represented by the above formula (3) with epichlorohydrin will now be described. This reaction can be carried out in the same manner as the well-known epoxidation reaction.

[0052] For example, the polyhydric hydroxy resin may be dissolved in excess epichlorohydrin and then reacted for 1 to 10 hours at 50 to 150°C, preferably 60 to 120°C, in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The amount of epichlorohydrin used is 0.8 to 2 moles, preferably 0.9 to 1.2 moles, per mole of hydroxyl groups in the polyhydric hydroxy resin. After the reaction is complete, the excess epichlorohydrin is distilled off, and the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain the desired epoxy resin represented by general formula (1). A catalyst such as a quaternary ammonium salt may be used in the epoxidation reaction.

[0053] The purity of the epoxy resin of the present invention, particularly the amount of hydrolyzable chlorine, should be low from the viewpoint of improving the reliability of the electronic components to which it is applied. While not particularly limited, the content is preferably 1000 ppm or less, and more preferably 500 ppm or less. The hydrolyzable chlorine content in this invention refers to a value measured by the following method. Specifically, 0.5 g of a sample was dissolved in 30 ml of dioxane, 10 ml of 1N KOH was added, and the mixture was boiled under reflux for 30 minutes, cooled to room temperature, and 100 ml of 80% acetone water was added. The value was obtained by electrolytic titration with a 0.002 N AgNO3 aqueous solution.

[0054] The polyfunctional vinyl composition of the first invention contains a polyfunctional vinyl compound and a radical polymerization initiator as essential components, but can also contain other vinyl compounds and other thermosetting resins, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoxazine resins.

[0055] In order to increase the thermal conductivity, inorganic fillers such as glass cloth, carbon fiber, alumina, and boron nitride may be added.

[0056] For the purpose of imparting higher thermal conductivity, inorganic fillers with higher thermal conductivity are preferred. It is preferably 20 W / m·K or higher, more preferably 30 W / m·K or higher, and even more preferably 50 W / m·K or higher. At least a portion of the inorganic filler, preferably 50 wt% or more, should have a thermal conductivity of 20 W / m·K or higher. The average thermal conductivity of the inorganic filler as a whole increases in order of 20 W / m·K or higher, 30 W / m·K or higher, and 50 W / m·K or higher.

[0057] Examples of inorganic fillers having such a thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide.

[0058] Various additives may be added to improve adhesive strength and ease of handling of the composition, such as silane coupling agents, antifoaming agents, internal mold release agents, and flow control agents.

[0059] The polyfunctional vinyl compound or polyfunctional vinyl composition of the present invention can also be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone, impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to obtain a prepreg, which can then be hot-press molded to obtain a cured product.

[0060] In some cases, the composition can be applied to a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film to form a laminate, and the resin sheet obtained by heating and drying can be hot-press molded to obtain a cured product.

[0061] The epoxy resin composition of the second invention contains an epoxy resin and a curing agent, and contains the epoxy resin of the above general formula (1) as the epoxy resin component.

[0062] In addition to the epoxy resin of general formula (1) used as an essential component, the epoxy resin composition of the second invention may contain other ordinary epoxy resins having two or more epoxy groups in the molecule, such as bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, fluorene bisphenol, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2'-biphenol, resorcinol, catechol, and t-butyl catechol. t-butylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxy Naphthalene, allylated or polyallylated products of the above dihydroxynaphthalene, dihydric phenols such as allylated bisphenol A, allylated bisphenol F, and allylated phenol novolac, or phenol novolac, bisphenol A novolac, o-cresol novolac, m-cresol novolac, p-cresol novolac, xylenol novolac, poly-p-hydroxystyrene, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(2-hydroxyphenyl)-2-propanol ... Examples of suitable epoxy resins include glycidyl ethers derived from trivalent or higher phenols such as (4-hydroxyphenyl)ethane, fluoroglycinol, pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenol aralkyl resins, naphthol aralkyl resins, and dicyclopentadiene-based resins, or halogenated bisphenols such as tetrabromobisphenol A. These epoxy resins can be used alone or in combination of two or more.

[0063] The epoxy resin composition of the present invention preferably contains the epoxy resin of general formula (1) as the epoxy resin in an amount of 50 wt % or more of the epoxy resin component. More preferably, it is 70 wt % or more, and even more preferably 80 wt % or more of the total epoxy resin. If the proportion used is less than this, the moldability of the epoxy resin composition deteriorates, and the effect of improving the heat resistance, thermal conductivity, etc. of the cured product is small.

[0064] The curing agent used in the epoxy resin composition of the present invention can be any of those generally known as curing agents for epoxy resins, including dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines, etc. Among these, polyhydric phenols are preferably used as curing agents in fields requiring high electrical insulation, such as semiconductor encapsulation materials. The polyhydric hydroxy resin of the present invention represented by general formula (3) is suitable as a curing agent. When the polyhydric hydroxy resin of the present invention is used as a curing agent for epoxy resins, it is desirable to contain 50 wt % or more of the polyhydric hydroxy resin of formula (3) as the curing agent. Specific examples of curing agents are shown below.

[0065] Examples of polyhydric phenols include dihydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcinol, and naphthalenediol, and trihydric or higher phenols such as tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenol novolac, o-cresol novolac, naphthol novolac, and polyvinylphenol. Further examples include polyhydric phenolic compounds synthesized from dihydric phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthalenediol, and condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and p-xylylene glycol.

[0066] Examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhimic anhydride, dodecynylsuccinic anhydride, nadic anhydride, and trimellitic anhydride.

[0067] Examples of amine curing agents include aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, and aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

[0068] The epoxy resin composition may contain one or more of these curing agents in combination.

[0069] The compounding ratio of the epoxy resin to the curing agent is preferably in the range of 0.8 to 1.5 in terms of the equivalent ratio of the epoxy group to the functional group in the curing agent. If the ratio is outside this range, unreacted epoxy groups or functional groups in the curing agent will remain even after curing, which is undesirable because it reduces the reliability of the sealing function.

[0070] The epoxy resin composition of the present invention may contain oligomers or polymeric compounds such as polyesters, polyamides, polyimides, polyethers, polyurethanes, petroleum resins, indene resins, indene-coumarone resins, and phenoxy resins as other modifiers, etc. The amount added is usually in the range of 1 to 30 parts by weight per 100 parts by weight of the total resin components.

[0071] The epoxy resin composition of the present invention may contain additives such as inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, flow improvers, etc. Examples of inorganic fillers include silica powders such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, etc. When used as a semiconductor encapsulant, the amount of inorganic fillers to be added is preferably 70% by weight or more, more preferably 80% by weight or more.

[0072] In order to increase the thermal conductivity, inorganic fillers such as glass cloth, carbon fiber, alumina, and boron nitride may be added.

[0073] For the purpose of imparting higher thermal conductivity, inorganic fillers with higher thermal conductivity are preferred. It is preferably 20 W / m K or higher, more preferably 30 W / m K or higher, and even more preferably 50 W / m K or higher. At least a portion of the inorganic filler, preferably 50 wt % or more, has a thermal conductivity of 20 W / m K or higher. The average thermal conductivity of the inorganic filler as a whole increases in order of preference from 20 W / m K or higher, to 30 W / m K or higher, and to 50 W / m K or higher.

[0074] Examples of inorganic fillers having such a thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide.

[0075] Examples of pigments include organic or inorganic extender pigments, scaly pigments, etc. Examples of thixotropic agents include silicone-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based agents.

[0076] The epoxy resin composition of the present invention may contain a curing accelerator as needed. Examples of the compound include amines, imidazoles, organic phosphines, Lewis acids, and the like. Specific examples include tertiary amines such as 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate; and tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate. The amount added is usually in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total resin components.

[0077] If necessary, the epoxy resin composition of the present invention may contain a release agent such as carnauba wax or OP wax, a coupling agent such as γ-glycidoxypropyltrimethoxysilane, a colorant such as carbon black, a flame retardant such as antimony trioxide, a stress reducer such as silicone oil, a lubricant such as calcium stearate, or the like.

[0078] The epoxy resin composition of the present invention can be dissolved in an organic solvent to form a varnish, which can then be impregnated into a fibrous material such as glass cloth, aramid nonwoven fabric, or polyester nonwoven fabric made of liquid crystal polymer or the like, followed by removing the solvent to form a prepreg. In some cases, the composition can also be applied to a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film to form a laminate.

[0079] The epoxy resin composition of the present invention can be heat-cured to form the cured resin product of the present invention. This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, or transfer molding. The temperature at which this is done is usually in the range of 120 to 220°C.

[0080] The present invention will be specifically explained below with reference to examples and comparative examples. However, the present invention is not limited to these. Unless otherwise specified, "parts" means parts by weight, and "%" means % by weight. Measurement methods were as follows.

[0081] 1) OH equivalent (hydroxyl group equivalent) Using a potentiometric titrator, acetylation was carried out with 1.5 mol / L acetyl chloride in 1,4-dioxane as a solvent, and the excess acetyl chloride was decomposed with water, followed by titration with 0.5 mol / L potassium hydroxide.

[0082] 2) Vinyl equivalent: The sample was reacted with Wiess's solution (iodine monochloride solution) and left in the dark. After that, excess iodine chloride was reduced to iodine, and the iodine content was titrated with sodium thiosulfate to calculate the iodine value. The iodine value was converted to vinyl equivalent.

[0083] 3) Epoxy Equivalent: Using a potentiometric titrator, methyl ethyl ketone was used as a solvent, and a tetraethylammonium bromide acetate solution was added, followed by measurement using a 0.1 mol / L perchloric acid-acetic acid solution in the potentiometric titrator.

[0084] 4) Total chlorine: 1.0 g of sample was dissolved in 25 ml of butyl carbitol, and then 25 ml of 1N KOH propylene glycol solution was added and the mixture was heated under reflux for 10 minutes. After that, the mixture was cooled to room temperature, and 100 ml of 80% acetone water was added. The total chlorine was measured by potentiometric titration with a 0.002 N AgNO3 aqueous solution.

[0085] 5) Softening point: Measured by the ring and ball method in accordance with JIS-K-2207.

[0086] 6) GPC Measurement A main body (Tosoh Corporation, HLC-8220GPC) equipped with four columns (Tosoh Corporation, TSKgel SuperMultipore HZ-N) in series was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 0.35 mL / min, and a differential refractive index detector was used as the detector. 0.1 g of sample was dissolved in 10 mL of THF and filtered through a microfilter, and 50 μL of the solution was used as the measurement sample. Data processing was performed using Tosoh Corporation's GPC-8020 Model II Version 6.00.

[0087] 7) Solvent solubility (precipitation temperature) 2 g of resin and 1 g of methyl ethyl ketone were weighed into a sample bottle, heated to dissolve, and then the temperature was gradually lowered in a thermostatic chamber, and the temperature in the chamber at which the resin precipitated was measured. The higher the precipitation temperature (°C), the poorer the solvent solubility.

[0088] 8) Glass Transition Point (Tg) Tg was determined using a thermomechanical measuring device (EXSTAR TMA / 7100 manufactured by SII Nanotechnology Inc.) at a temperature rise rate of 10°C / min.

[0089] 9) 5% Weight Loss Temperature (Td5), Carbon Residual Ratio The 5% weight loss temperature (Td5) was measured under a nitrogen atmosphere at a heating rate of 10°C / min using a thermogravimetric / differential thermal analyzer (EXSTAR TG / DTA7300 manufactured by SII Nano Technology). The weight loss at 700°C was measured and calculated as the carbon residual ratio.

[0090] 10) Thermal Conductivity The thermal conductivity was measured by the transient hot wire method using a thermal conductivity meter LFA447 manufactured by NETZSCH.

[0091] 11) Dielectric constant and dielectric loss tangent: Measured in accordance with JIS C 2138. The measurement frequency was 1 GHz.

[0092] Synthesis examples and working examples of the first invention will be described. (Synthesis Example 1A) In a 1000 ml four-neck flask, 140.3 g (0.48 mol) of 4,4',4"-trihydroxytriphenylmethane (structural formula below), 420 g of N-methyl-2-pyrrolidone and 39.8 g of potassium carbonate were charged, and the mixture was heated to 120° C. under a nitrogen stream while stirring. Then, 40.2 g (0.16 mol) of 4,4′-bis(chloromethyl)biphenyl (structural formula below) was added, The temperature was raised to 145°C and the reaction was carried out for 6 hours. 34.6 g of acetic acid was added to the reaction solution to neutralize it, and then N-methyl-2-pyrrolidone was distilled off under reduced pressure. 350 mL of methyl isobutyl ketone was added to the reaction solution to dissolve the product, and the salt formed was removed by washing with water. The methyl isobutyl ketone was then removed by distillation under reduced pressure to obtain 163.8 g of hydroxy resin a. The hydroxyl group equivalent of the resulting hydroxy resin a was 188 g / eq., Mn was 700, and the GPC area % was 74.0% for n≧1 (26.0% for n=0).

[0093] Synthesis Example 2A The same procedure as in Synthesis Example 1 was carried out, except that the amount of 4,4',4"-trihydroxytriphenylmethane used was 116.9 g (0.40 mol), to obtain 142.5 g of hydroxy resin b. The hydroxyl group equivalent of the obtained hydroxy resin b was 205 g / eq., Mn was 980, and the GPC area % ratio of n≧1 was 80.0% (n=0 was 20.0%).

[0094] (Synthesis Example 3A) 27.5 g (0.16 mol) of 2,6-dichlorobenzonitrile (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl. The same procedure as in Synthesis Example 1 was carried out, except that 149.3 g of hydroxy resin c was obtained. The hydroxyl group equivalent of the resulting hydroxy resin c was 158 g / eq., Mn was 580, and the GPC area % of n≧1 was 60.7% (n=0 was 39.3%).

[0095] (Synthesis Example 4A) 45.9 g (0.16 mol) of 4,4'-dichlorodiphenyl sulfone (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl. The same procedure as in Synthesis Example 1A was carried out, except that 170.2 g of hydroxy resin d was obtained. The hydroxyl group equivalent of the resulting hydroxy resin d was 180 g / eq., Mn was 720, and the GPC area % of n≧1 was 67.5% (n=0 was 32.5%).

[0096] (Synthesis Example 5A) 36.8 g (0.16 mol) of 1,4-dibromobutane (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl. The same procedure as in Synthesis Example 1A was carried out, except that 147.2 g of hydroxy resin e was obtained. The hydroxyl group equivalent of the resulting hydroxy resin e was 159 g / eq., Mn was 560, and the GPC area % of n≧1 was 52.7% (n=0 was 47.3%).

[0097] (Synthesis Example 6A) 28.0 g (0.16 mol) of p-xylene dichloride (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl. The same procedure as in Synthesis Example 1A was carried out, except that 152.1 g of hydroxy resin f was obtained. The hydroxyl group equivalent of the resulting hydroxy resin f was 177 g / eq., Mn was 960, and the GPC area % of n≧1 was 71.9% (n=0 was 28.1%).

[0098] Example 1A Into a 1000 ml four-neck flask, 56.4 g (0.30 equivalents) of the hydroxy resin a obtained in Synthesis Example 1A, 500 g of methyl ethyl ketone, and 54.9 g (0.36 equivalents) of 4-(chloromethyl)styrene (structural formula below) were added. The mixture was heated to 60°C, and 20.2 g of potassium hydroxide dissolved in 60.6 g of methanol was added dropwise over 3 hours, followed by a further reaction for 6 hours. After completion of the reaction, the mixture was filtered, the solvent was distilled off, and the mixture was reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 63.8 g of a multifunctional vinyl resin (vinyl resin A). The vinyl equivalent of vinyl resin A was 231 g / eq., the hydroxyl equivalent was 12,000 g / eq., the total chlorine was 550 ppm, the Mn was 860, and the GPC area % was 51.5% for n≧1 (48.5% for n=0). The GPC chart of the resulting vinyl resin A is shown in Figure 1.

[0099] Example 2A The same procedure as in Example 1A was carried out, except that 61.5 g (0.30 equivalents) of hydroxy resin b obtained in Synthesis Example 2A was used instead of hydroxy resin a, to obtain 71.2 g of a multifunctional vinyl resin (vinyl resin B). Vinyl resin B had a vinyl equivalent of 242 g / eq., a hydroxyl equivalent of 14,000 g / eq., a total chlorine content of 500 ppm, an Mn of 1,370, and a GPC area % of n≧1 units of 71.9% (n=0 units of 28.1%).

[0100] Example 3A The same procedure as in Example 1A was carried out, except that 47.4 g (0.30 equivalents) of hydroxy resin c obtained in Synthesis Example 3A was used instead of hydroxy resin a, to obtain 58.3 g of a multifunctional vinyl resin (vinyl resin C). Vinyl resin C had a vinyl equivalent of 213 g / eq., a hydroxyl equivalent of 11,000 g / eq., a total chlorine content of 800 ppm, an Mn of 930, and a GPC area percentage of n≧1 units of 54.0% (n=0 units of 46.0%).

[0101] Example 4A The same procedure as in Example 1A was carried out, except that 54.0 g (0.30 equivalents) of hydroxy resin d obtained in Synthesis Example 4A was used instead of hydroxy resin a, to obtain 63.1 g of a multifunctional vinyl resin (vinyl resin D). Vinyl resin D had a vinyl equivalent of 235 g / eq., a hydroxyl equivalent of 11,000 g / eq., a total chlorine content of 900 ppm, an Mn of 930, and a GPC area percentage of n≧1 isomers of 60.0% (n=0 isomers of 40.0%).

[0102] Example 5A The same procedure as in Example 1 was carried out, except that 47.7 g (0.30 equivalents) of hydroxy resin e obtained in Synthesis Example 5A was used instead of hydroxy resin a, to obtain 56.9 g of a multifunctional vinyl resin (vinyl resin E). Vinyl resin E had a vinyl equivalent of 200 g / eq., a hydroxyl equivalent of 16,000 g / eq., a total chlorine content of 900 ppm, an Mn of 770, and a GPC area percentage of n≧1 units of 44.4% (n=0 units of 55.6%).

[0103] Example 6A The same procedure as in Example 1 was carried out, except that 47.7 g (0.30 equivalents) of hydroxy resin f obtained in Synthesis Example 6A was used instead of hydroxy resin a, to obtain 56.9 g of a multifunctional vinyl resin (vinyl resin F). Vinyl resin F had a vinyl equivalent of 200 g / eq., a hydroxyl equivalent of 16,000 g / eq., a total chlorine content of 700 ppm, an Mn of 710, and a GPC area percentage of n≧1 units of 56.9% (n=0 units of 43.1%).

[0104] (Comparative Example 1A) 30.6 g (0.30 equivalents) of 1,1,1-tris(p-hydroxyphenyl)ethane (structural formula below) was used instead of hydroxy resin a. The same procedure as in Example 1A was carried out except that 58.9 g of a vinyl compound (vinyl compound G) was obtained. The vinyl equivalent of vinyl compound G was 214 g / eq., the hydroxyl equivalent was 7000 g / eq., and the total chlorine content was 1500 ppm.

[0105] (Comparative Example 2A) Into a 1000 ml four-neck flask, 40.8 g of 4,4'-bis(chloromethyl)biphenyl (structural formula below) 75.5 g of 4,4'-biphenol (structural formula below), 120 g of diethylene glycol dimethyl ether was charged, and the mixture was heated to 160 ° C. under a nitrogen stream while stirring and reacted for 10 hours. Subsequently, the temperature was raised to 70 ° C., and 280 g of diethylene glycol dimethyl ether and 129.5 g of chloromethylstyrene were added. 100.0 g of 48% potassium hydroxide was added dropwise to the mixture. Gas chromatography confirmed that there was no residual chloromethylstyrene, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in toluene, neutralized, and washed with water to obtain 172 g of a multifunctional vinyl resin (vinyl resin H). The vinyl equivalent of the resulting vinyl resin H was 256 g / eq., the hydroxyl equivalent was 1500 g / eq., and the total chlorine was 1270 ppm.

[0106] (Comparative Example 3A) Into a 1000 ml four-neck flask, 50.0 g of dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane (structural formula below): 36.2%, 2,4'-dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%), 400 g of methyl ethyl ketone and 80.1 g of chloromethylstyrene were added, and the mixture was heated to 60°C. 29.5 g of potassium hydroxide dissolved in 88 g of methanol was added dropwise over 3 hours, and the reaction was continued for another 6 hours. After the reaction was completed, the mixture was filtered, the solvent was distilled off, and the mixture was reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 95.4 g of a vinyl compound (vinyl compound I). The vinyl equivalent of vinyl compound I was 217 g / eq., the hydroxyl equivalent was 17,000 g / eq., and the total chlorine content was 400 ppm.

[0107] Examples 7A to 12A, Comparative Examples 4A to 7A As the multifunctional vinyl resin, vinyl compounds A to I obtained in Examples 1A to 6A and Comparative Examples 1A to 3A and vinyl resin J (OPE-2ST: manufactured by Mitsubishi Gas Chemical Company, Inc., vinyl group equivalent: 590.0 g / eq, number average molecular weight 1187) were used, and Perbutyl P (manufactured by NOF Corporation), an organic peroxide, was used as a curing accelerator, and Adeka Stab AO-60 (manufactured by ADEKA Corporation) was used as an antioxidant. The mixture was mixed in the proportions shown in Table 1A and dissolved in a solvent to form a homogeneous composition. This composition was applied to a PET film and dried at 130 ° C. for 5 minutes to obtain a resin composition. The composition removed from the PET film was sandwiched between mirror plates and cured under reduced pressure at 130 ° C. for 15 minutes and at 210 ° C. for 80 minutes while applying a pressure of 2 MPa. The properties of the resulting cured product are shown in Table 1A.

[0108]

[0109] The polyfunctional vinyl resins of the examples of the first invention exhibited excellent physical properties such as high thermal conductivity, low dielectric constant and low dielectric loss tangent, as compared with the comparative examples.

[0110] Next, an example of the second invention will be described. (Example 1B) Into a 1000 ml four-neck flask, 140.3 g (0.48 mol) of 4,4',4"-trihydroxytriphenylmethane (structural formula below), 420 g of N-methyl-2-pyrrolidone and 39.8 g of potassium carbonate were charged, and the mixture was heated to 120° C. under a nitrogen stream while stirring. Then, 40.2 g (0.16 mol) of 4,4′-bis(chloromethyl)biphenyl (structural formula below) was added, The temperature was raised to 145°C and the reaction was carried out for 6 hours. 34.6 g of acetic acid was added to the reaction solution to neutralize it, and then N-methyl-2-pyrrolidone was distilled off under reduced pressure. 350 mL of methyl isobutyl ketone was added to the reaction solution to dissolve the product, and the salt formed was removed by washing with water. The methyl isobutyl ketone was then removed by distillation under reduced pressure to obtain 163.8 g of hydroxy resin a. The hydroxyl group equivalent of the obtained hydroxy resin a was 188 g / eq., the Mn was 700, and the GPC area % of n≧1 was 74.0% (n=0 was 26.0%). The GPC chart of the obtained hydroxy resin a is shown in Figure 2.

[0111] Example 2B The same procedure as in Example 1B was carried out except that the amount of 4,4',4"-trihydroxytriphenylmethane used was 116.9 g (0.40 mol), to obtain 142.5 g of hydroxy resin b. The hydroxyl group equivalent of the obtained hydroxy resin b was 205 g / eq., Mn was 980, and the GPC area % of n≧1 was 80.0% (n=0 was 20.0%).

[0112] (Example 3B) 27.5 g (0.16 mol) of 2,6-dichlorobenzonitrile (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl. The same procedure as in Example 1B was carried out except that 149.3 g of hydroxy resin c was obtained. The hydroxyl equivalent of the resulting hydroxy resin c was 158 g / eq., Mn was 580, and the GPC area % of n≧1 was 60.7% (n=0 was 39.3%).

[0113] (Example 4B) 4,4'-dichlorodiphenyl sulfone (structural formula below) 45.9 g (0.16 mol) instead of 4,4'-bis(chloromethyl)biphenyl The same procedure as in Example 1B was carried out except that 170.2 g of hydroxy resin d was obtained. The hydroxyl equivalent of the obtained hydroxy resin d was 180 g / eq., Mn was 720, and the GPC area % of n≧1 was 67.5% (n=0 was 32.5%).

[0114] (Example 5B) 36.8 g (0.16 mol) of 1,4-dibromobutane (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl. The same procedure as in Example 1B was carried out except that 147.2 g of hydroxy resin e was obtained. The hydroxyl equivalent of the obtained hydroxy resin e was 159 g / eq., Mn was 560, and the GPC area % of n≧1 was 52.7% (n=0 was 47.3%).

[0115] (Example 6B) 28.0 g (0.16 mol) of p-xylene dichloride (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl. The same procedure as in Example 1B was carried out except that 152.1 g of hydroxy resin f was obtained. The hydroxyl equivalent of the obtained hydroxy resin f was 177 g / eq., Mn was 960, and the GPC area % of n≧1 was 71.9% (n=0 was 28.1%).

[0116] (Example 7B) In a 1000 ml four-neck flask, 94.0 g (0.50 equivalents) of the hydroxy resin a obtained in Example 1B and 460 g of epichlorohydrin (structural formula below) were added. To the mixture, 50.0 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours under reduced pressure (approximately 130 Torr) at 62°C. During this time, the water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the addition was completed, the reaction was continued for another hour. The epichlorohydrin was then distilled off, methyl isobutyl ketone was added, and the mixture was washed with water to remove salts, filtered, and washed with water. The methyl isobutyl ketone was then distilled off under reduced pressure to obtain 103.2 g of epoxy resin (epoxy resin A). This epoxy resin A had an epoxy equivalent of 243, a softening point of 72°C, a hydrolyzable chlorine content of 50 ppm, an Mn of 740, and a GPC measurement of 75.2% n≧1 (24.8% n=0). The GPC chart of the resulting epoxy resin A is shown in Figure 3.

[0117] Example 8B The same procedure as in Example 7 was carried out, except that 102.5 g (0.50 equivalents) of hydroxy resin b obtained in Example 2B was used instead of hydroxy resin a, to obtain 109.6 g of epoxy resin (epoxy resin B). Epoxy resin B had an epoxy equivalent of 261 g / eq., a softening point of 79°C, a hydrolyzable chlorine content of 57 ppm, an Mn of 980, and a GPC area % of n≧1 being 81.1% (n=0 being 18.9%).

[0118] Example 9B: The same procedure as in Example 7B was carried out, except that 79.0 g (0.50 equivalents) of hydroxy resin c obtained in Example 3B was used instead of hydroxy resin a, to obtain 88.6 g of epoxy resin (epoxy resin C). Epoxy resin C had an epoxy equivalent of 213 g / eq., a softening point of 78°C, a hydrolyzable chlorine content of 60 ppm, an Mn of 570, and a GPC area % of n≧1 being 65.1% (n=0 being 34.9%).

[0119] Example 10B: The same procedure as in Example 7B was repeated, except that 90.0 g (0.50 equivalents) of hydroxy resin d obtained in Example 4B was used instead of hydroxy resin a, to obtain 102.2 g of epoxy resin (epoxy resin D). Epoxy resin D had an epoxy equivalent of 238 g / eq., a softening point of 84°C, a hydrolyzable chlorine content of 70 ppm, an Mn of 650, and a GPC area percentage of n≧1 units of 72.1% (n=0 units of 27.9%).

[0120] Example 11B: The same procedure as in Example 7B was carried out, except that 79.5 g (0.50 equivalents) of hydroxy resin e obtained in Example 5B was used instead of hydroxy resin a, to obtain 84.9 g of epoxy resin (epoxy resin E). Epoxy resin E had an epoxy equivalent of 215 g / eq., a softening point of 84°C, a hydrolyzable chlorine content of 85 ppm, an Mn of 580, and a GPC area percentage of n≧1 resins of 59.8% (n=0 resins of 40.2%).

[0121] Example 12B: The same procedure as in Example 7B was repeated, except that 88.5 g (0.30 equivalents) of hydroxy resin f obtained in Example 6B was used instead of hydroxy resin a, to obtain 102.6 g of epoxy resin (epoxy resin F). Epoxy resin F had an epoxy equivalent of 233 g / eq., a softening point of 70°C, a hydrolyzable chlorine content of 50 ppm, an Mn of 970, and a GPC area % of n≧1 74.0% (n=0 26.0%).

[0122] Reference Example 1B The same procedure as in Example 7 was carried out, except that 48.7 g (0.50 equivalents) of 4,4',4"-trihydroxytriphenylmethane (structural formula shown above) was used instead of hydroxy resin a, to obtain 72.4 g of epoxy resin (epoxy resin G). Epoxy resin G had an epoxy equivalent of 155 g / eq., a softening point of 50°C, a hydrolyzable chlorine content of 40 ppm, an Mn of 410, and a GPC area % concentration of n≧1 resins of 2.0% (n=0 resins of 98.0%).

[0123] Reference Example 2B: A 1000 ml four-neck flask was charged with 55.1 g of 4,4'-dihydroxybiphenyl, 23.6 g of 2,2'-dihydroxybiphenyl, 121.2 g of diethylene glycol dimethyl ether, and 42.5 g of 4,4'-bischloromethylbiphenyl. The mixture was heated to 170°C under a nitrogen stream with stirring and reacted for 10 hours to produce a polyhydric hydroxy resin. After completion of the reaction, 50.7 g of diethylene glycol dimethyl ether was recovered, 470 g of epichlorohydrin was added, and 68.7 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours at 62°C under reduced pressure (approximately 130 Torr). During this time, the produced water was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After completion of the dropwise addition, the reaction was continued for another hour. Thereafter, epichlorohydrin was distilled off, methyl isobutyl ketone was added, and the resulting mixture was washed with water to remove salts, filtered, and washed with water. The methyl isobutyl ketone was then distilled off under reduced pressure to obtain 130 g of an epoxy resin (Epoxy Resin H). This epoxy resin H had an epoxy equivalent of 196, a softening point of 97°C, a hydrolyzable chlorine content of 65 ppm, an Mn of 450, and a content of n≧1 as measured by GPC of 72.0% (the content of n=0 components was 28.0%).

[0124] Examples 13B-19B, Comparative Examples 1B-3B: Epoxy resins A-F obtained in Examples 7B-12B, epoxy resins G-H obtained in Reference Examples 1B-2B, and epoxy resin I (o-cresol novolac epoxy resin (YDCN-700-3, manufactured by Nippon Steel Chemical & Material, epoxy equivalent: 200)) were used as the epoxy resin components. Polyhydric hydroxy resin A obtained in Example 1 and phenol novolac resin G (hydroxyl group equivalent: 105) were used as the curing agents, and triphenylphosphine was used as the curing accelerator. Epoxy resin compositions were obtained according to the formulation shown in Table 1B. The values ​​in the table indicate parts by weight of the formulation. These epoxy resin compositions were molded at 175°C and post-cured at 175°C for 5 hours to obtain cured specimens, which were then subjected to various physical property measurements. The results are also shown in Table 1B.

[0125]

[0126] The epoxy resins and polyhydroxy resin curing agents of the examples of the second invention exhibited excellent physical properties such as superior solvent solubility, high thermal conductivity and high heat resistance compared to the comparative examples.

[0127] The polyfunctional vinyl resin of the first invention is useful as an electronic material for high-speed communication devices, as it allows heat to escape easily from electronic components and wiring, resulting in little signal loss. The polyhydric hydroxyl resin and epoxy resin of the second invention have excellent solvent solubility, high heat resistance, and good thermal conductivity, making them suitable for power devices and automotive applications.

Claims

1. A polyfunctional vinyl resin represented by the following general formula (1A). In the formula (1A), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a structure represented by the formula (2A), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, where m represents a number from 3 to 10 and n represents a number from 1 to 15.

2. The polyfunctional vinyl resin according to claim 1, wherein X has the structure represented by formula (2A).

3. A polyfunctional vinyl composition containing, as essential components, the polyfunctional vinyl resin according to claim 1 and a radical polymerization initiator.

4. A polyfunctional vinyl cured product obtained by curing the polyfunctional vinyl composition according to claim 3.

5. An epoxy resin represented by the following general formula (1B). In the formula (1B), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X independently represents a structure represented by the formula (2B), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, m represents a number from 3 to 10, and n represents a number from 1 to 15.

6. The epoxy resin according to claim 5, wherein X has the structure represented by formula (2B).

7. A polyhydroxy resin represented by the following general formula (3B). In formula (3B), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, X independently represents a structure represented by formula (2B), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, m represents a number from 3 to 10, and n represents a number from 1 to 15.

8. The polyhydric hydroxy resin according to claim 7, wherein X has the structure represented by formula (2B).

9. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin according to claim 5 is included as an essential component in part or in whole of the epoxy resin.

10. A resin composition characterized by containing, as an essential component, the polyhydric hydroxy resin according to claim 7.

11. A resin cured product characterized by curing the resin composition according to claim 9.

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