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

Abstract

The present invention aims to provide a compound having excellent solvent solubility and excellent heat resistance, thermal decomposition stability, thermal conductivity, and flame retardancy, and a curable resin composition containing the compound. A multifunctional vinyl resin represented by the following general formula (1A) or an epoxy resin represented by the following general formula (1B) is provided. In formula (1), R 1 ~R 6 each independently represents 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 of 3 to 10, and n represents a number of 1 to 15. (1A) (1B) (2).

Description

Technical Field

[0001] This invention relates to multifunctional vinyl resins, polyhydroxy resins, and epoxy resins. More specifically, it relates to multifunctional resins useful in insulating materials for electrical and electronic components such as semiconductor seals, laminates, and heat dissipation substrates, compositions thereof, and cured resin products that exhibit excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy. Background Technology

[0002] With the increasing speed and volume of communication, high-speed communication technologies are being actively researched to improve signal transmission speed, particularly for printed circuit boards, sealing materials, and molding materials used in communication equipment. Electronic materials for such applications require materials that can reduce dielectric loss. Furthermore, in printed circuit board applications, curable resins capable of multilayering are needed.

[0003] On the other hand, electronic processing units that handle such large amounts of data generate significant heat, leading to reduced processing speed due to heat accumulation. Therefore, in printed circuit boards, various designs are known as methods for appropriate cooling using heat sinks or similar heat transfer components (Patent Document 1), and designs that use specially shaped fillers (Patent Document 2). However, such methods result in increased weight or larger device size, and are therefore not preferred.

[0004] In sealing material compositions, methods to improve thermal conductivity include removing heat from electronic components by studying the types and amounts of various fillers. For example, attempts have been made to include 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 leads to increased viscosity and decreased flowability during molding, resulting in impaired moldability. Therefore, there are limitations to simply increasing the content of inorganic fillers.

[0005] Based on the above background, methods to improve the thermal conductivity of compositions by increasing the thermal conductivity of the matrix resin itself have also been studied. For example, liquid crystallizable epoxy resins with rigid mesocrystalline groups and epoxy resin compositions using these resins have been proposed (Patent Documents 5 and 6). However, the use of aromatic diamine compounds as curing agents in these epoxy resin compositions has limitations in terms of increasing the filling rate of inorganic fillers and also presents problems in terms of electrical insulation. While the liquid crystallization of the cured product can be confirmed when using aromatic diamine compounds, the crystallinity of the cured product is low, resulting in insufficient performance in terms of high thermal conductivity, low thermal expansion, and low hygroscopicity. Furthermore, to exhibit liquid crystallization, a strong magnetic field is required to orient the molecules, which poses significant limitations in terms of equipment for widespread industrial application. Furthermore, in systems with inorganic fillers, the thermal conductivity of the inorganic filler is overwhelmingly higher than that of the matrix resin. Even if the thermal conductivity of the matrix resin itself is increased, the contribution to improving the thermal conductivity of the composite material is not significant, and a sufficient improvement in thermal conductivity cannot be achieved.

[0006] In Patent Document 7, a multifunctional vinyl resin with four or more functions having a biphenyl skeleton was disclosed as a multifunctional vinyl resin that balances high thermal conductivity and low dielectric loss tangent. However, the solvent solubility of the multifunctional vinyl resin and the polyhydroxy resin used as its raw material was not described, and the influence of residual polar groups and other impurities on thermal conductivity was not mentioned at all.

[0007] Patent Document 8 proposes reducing crystallinity by removing the crystalline components of epoxy resins with a biphenyl-biphenyl aralkyl structure, but this results in insufficient solvent solubility, posing a problem in practicality. When other epoxy resins are mixed to improve moldability and solvent solubility, the resin's melting point decreases, making it easier to mix uniformly. However, it is difficult to maintain the physical properties of the cured product, namely heat resistance, thermal decomposition stability, mechanical strength, and thermal conductivity. Patent Document 9 proposes a resin composition obtained by combining biphenyl aralkyl type epoxy resins with bisphenol methane type epoxy resins, etc., but due to its strong crystallinity, it is difficult to melt-mix, and the solvent solubility is also insufficient for practical applications in laminates.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 2009-170493

[0011] Patent Document 2: International Publication No. 2013 / 100172

[0012] Patent Document 3: Japanese Patent Application Publication No. 11-147936

[0013] Patent Document 4: Japanese Patent Application Publication No. 2002-309067

[0014] Patent Document 5: Japanese Patent Application Publication No. 11-323162

[0015] Patent Document 6: Japanese Patent Application Publication No. 9-118673

[0016] Patent Document 7: International Publication No. 2021-200414

[0017] Patent Document 8: Japanese Patent Application Publication No. 2017-95524

[0018] Patent Document 9: Japanese Patent Application Publication No. 2015-160893 Summary of the Invention

[0019] The object of this invention is to provide a vinyl composition useful in sealing and circuit board materials for electrical and electronic components, which has excellent solvent solubility and can form a cured product with excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy, as well as to provide the cured product thereof. Another object is to provide a vinyl compound used in this vinyl composition.

[0020] The present invention aims to provide an epoxy resin composition useful in sealing and circuit board materials for electrical and electronic components, which exhibits good melt-mixing properties below 100°C, excellent solvent solubility, and the ability to form a cured product with excellent heat resistance, thermal decomposition stability, thermal conductivity, and flame retardancy, as well as to provide the cured product thereof. Other objectives include providing an epoxy resin for use in this epoxy resin composition and a polyhydroxy resin suitable as an intermediate for this epoxy resin.

[0021] The inventors conducted in-depth research and found that, as the first invention, a multifunctional vinyl compound with a specific structure can be expected to solve the above-mentioned problems, and its cured product exhibits good performance in terms of heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy.

[0022] That is, the first invention is a multifunctional vinyl resin, represented by the following general formula (1A).

[0023] (1A)

[0024] In equation (1A), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2A), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m-, m represents a number from 3 to 10, and n represents a number from 1 to 15.

[0025] (2A)

[0026] X of the above-mentioned multifunctional vinyl resin is preferably the structure shown in formula (2A).

[0027] The first invention is a multifunctional vinyl composition containing a multifunctional vinyl resin and a free radical polymerization initiator as essential components, and a multifunctional vinyl cured product formed by curing the multifunctional vinyl resin composition.

[0028] The inventors conducted in-depth research and found that, as a second invention, epoxy resins with specific structures can be expected to solve the above-mentioned problems, and their cured products exhibit effects in terms of heat resistance, thermal decomposition stability, thermal conductivity, and flame retardancy.

[0029] That is, the second invention is an epoxy resin, represented by the following general formula (1B).

[0030] (1B)

[0031] In equation (1B), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2B), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m -, m represents a number from 3 to 10, and n represents a number from 1 to 15.

[0032] (2B)

[0033] X of the above-mentioned epoxy resin is preferably the structure shown in formula (2B).

[0034] Furthermore, the second invention is a polyhydroxy resin, represented by the following general formula (3B).

[0035] (3B)

[0036] In equation (3B), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2B), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m -, m represents a number from 3 to 10, and n represents a number from 1 to 15.

[0037] X of the above-mentioned polyhydroxy resin is preferably the structure shown in formula (2B).

[0038] The second invention is an epoxy resin composition, characterized in that it contains the aforementioned epoxy resin or polyhydroxy resin curing agent as an essential component. Furthermore, the second invention is a cured resin product, characterized in that it is formed by curing the resin composition.

[0039] The multifunctional vinyl resin of the first invention has excellent solvent solubility, making it suitable for vinyl resin compositions and their cured products used in applications such as lamination, molding, injection molding, and bonding. Furthermore, the cured product also exhibits excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy, making it suitable for sealing electrical and electronic components, circuit board materials, and the like.

[0040] The polyhydroxy resin and epoxy resin of the second invention exhibit good melt mixing properties below 100°C and excellent solvent solubility, making them suitable for epoxy resin compositions and their cured products used in applications such as lamination, molding, injection molding, and bonding. Furthermore, the cured products also possess excellent heat resistance, thermal decomposition stability, and thermal conductivity, making them suitable for sealing electrical and electronic components, circuit board materials, and the like. Attached Figure Description

[0041] Figure 1 This is a GPC diagram of the compound of the multifunctional vinyl resin obtained in Example 1A of the first invention.

[0042] Figure 2 This is a GPC diagram of the hydroxyl resin obtained in Example 1B of the second invention.

[0043] Figure 3 This is a GPC diagram of the epoxy resin obtained in Example 7B of the second invention. Detailed Implementation

[0044] First, the multifunctional vinyl resin of the first invention will be described in detail.

[0045] The first invention is a multifunctional vinyl resin represented by the following general formula (1A).

[0046] (1A)

[0047] In equation (1A), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2A), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m -, m represents a number from 3 to 10, and n represents a number from 1 to 15.

[0048] (2A)

[0049] R 1 ~R 6 Each group is independently a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. From the viewpoint of solvent solubility, alkyl groups are preferred as hydrocarbon groups with 1 to 6 monovalent carbon atoms; from the viewpoint of heat resistance and high thermal conductivity, aromatic groups are preferred. Alkyl groups with more than 6 carbon atoms are less likely to inhibit molecular motion, and there are concerns about reduced compatibility. Furthermore, structures with large steric hindrance and large volume are problematic due to increased crystallinity, raising concerns about solvent solubility. More preferred structures are hydrogen atoms, methyl groups, or phenyl groups. 1 ~R 6 It can be a mixture of different structures.

[0050] In the multifunctional vinyl resin of the present invention, the substitution position of the vinyl benzyl ether is not particularly limited, but from the viewpoint of thermal conductivity and heat resistance, it is preferable that the vinyl benzyl ether is in the para position relative to the methylene group connecting the three aromatic rings. In particular, it is more preferable that all three vinyl benzyl ethers are in the para position.

[0051] n is a repetition number, representing a number from 1 to 15. A mixture of components with different n values ​​is preferred. The average value of n is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

[0052] The multifunctional vinyl resin of the present invention may be a mixture of n=0 compounds, except for the n=0 compound alone. Preferably, the n=0 compound comprises 60% or less, more preferably 50% or less, based on the area % (GPC area %) determined by gel permeation chromatography.

[0053] X independently represents the structure shown in formula (2A), the benzonitrile structure, the sulfonyl structure, or -(CH2). m —. For — (CH2) m - indicates an alkyl structure, and m is the repeating number, representing 3 to 10. More preferably, it is 4 to 8. If it is less than 3, there is a tendency for low flexibility and poor crystallinity mitigation effect. If it is greater than 10, there is a tendency for a significant decrease in the thermal conductivity and heat resistance of the cured product.

[0054] The vinyl resin of formula (1A) of the present invention, as shown "independently", can be a mixture of different structures for each X, and its thermal conductivity, moldability, and solvent solubility can be adjusted. When X has the structure shown in formula (2A), there is a tendency for the thermal conductivity of the cured product to increase.

[0055] As a preferred structure, specifically, X can be exemplified as a multifunctional vinyl resin of the following formula (3A) containing a biphenyl structure as shown in formula (2A).

[0056] (3A)

[0057] In equation (3A), R 1 ~R 6 R in equation (1) above 1 ~R 6 They have the same meaning.

[0058] The preferred range for the vinyl equivalent of the multifunctional vinyl resin of the present invention is 150–450 g / eq, and a more preferred range is 200–350 g / eq. Below this range, the reaction becomes difficult to control due to its rapid pace; above this range, reactivity decreases, raising concerns about obtaining a uniform cured product.

[0059] The number-average molecular weight Mn is preferably 500 to 2000, more preferably 700 to 1500.

[0060] The multifunctional vinyl resin of the present invention can be obtained by reacting a hydroxyl compound with chloromethylstyrene. However, if the amount of unreacted hydroxyl groups remaining is less than 5000 g / eq, curing is insufficient, resulting in decreased thermal conductivity and heat resistance. Furthermore, since hydroxyl groups are polar groups, there is concern that their residue may hinder the reduction of dielectric constant and dielectric loss tangent. The hydroxyl equivalent is preferably 5000 g / eq or more, more preferably 10000 g / eq or more.

[0061] On the other hand, the chlorine component, whether derived from chloromethylstyrene as a raw material or obtained through a halogen-based crosslinking agent, may hinder the reduction of dielectric constant and dielectric loss tangent if chlorine remains in the same manner as the hydroxyl group. Furthermore, it may impede the curing reaction due to the formation of polar groups, leading to concerns about reduced thermal conductivity and heat resistance. The total chlorine content is preferably 5000 ppm or less, more preferably 3000 ppm or less, and even more preferably 1000 ppm or less.

[0062] The multifunctional vinyl resin of the present invention can be obtained by reacting a multifunctional hydroxyl compound (resin) represented by formula (4B) with an aromatic vinylizing agent. 1 ~R 6 , n, X are the same as the vinyl compounds of formula (1A).

[0063] (4A)

[0064] The polyfunctional hydroxyl compound (resin) of formula (4A) can use the same substance as the polyfunctional hydroxyl compound (resin) of formula (3B) described later.

[0065] The polyfunctional vinyl resin of the present invention can be suitably obtained by reacting a polyfunctional hydroxyl compound (resin) with an aromatic vinylizing agent. For example, the vinyl compound of the present invention represented by formula (1A) can be obtained by reacting the polyfunctional hydroxyl compound represented by formula (4A) above with chloromethylstyrene. This reaction can be carried out in the same manner as known vinylization reactions.

[0066] The preferred ratio is 1.0 equivalent of the functional group (hydroxyl group) of the polyfunctional hydroxyl resin, using an aromatic vinylizing agent (e.g., chloromethylstyrene) in an amount of 0.8 to 1.2 equivalents. However, if the polyfunctional hydroxyl compound has low reactivity, an excess of aromatic vinylizing agent can be added and removed after the reaction.

[0067] Halomethylstyrene, particularly chloromethylstyrene, is preferred as an aromatic vinylizing agent. Other examples include bromomethylstyrene and its isomers, and substances with substituents. Regarding the substitution position of the halomethyl group, in the case of halomethylstyrene, the 4-position is preferred, and preferably the 4-position group constitutes 60% or more of the total.

[0068] The reaction of polyfunctional hydroxyl compounds with aromatic vinylating agents can be carried out in the absence of solvent or in the presence of solvent. An aromatic vinylating agent can be added to the hydroxyl compound, followed by the addition of a metal hydroxide to initiate the reaction. The resulting metal salt can then be removed by methods such as filtration or washing with water.

[0069] Solvents include, but are not limited to, methyl ethyl ketone (MEK), benzene, toluene, xylene, methyl isobutyl ketone (MEK), diethylene glycol dimethyl ether (DEME), cyclopentanone, and cyclohexanone. From a reactivity point of view, MEK is preferred. Specific examples of metal hydroxides include, but are not limited to, sodium hydroxide and potassium hydroxide.

[0070] The vinylation reaction is preferably carried out at a temperature below 90°C, more preferably below 70°C. Above this temperature, vinyl benzyl ether undergoes self-polymerization due to heat, making the reaction difficult to control. To inhibit self-polymerization, polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitroketone compounds, and oxygen can be used.

[0071] The reaction endpoint can be determined by tracking the residual amount of halomethylstyrene, which is an aromatic vinylizing agent, using various chromatograms such as GPC. The reaction rate can be adjusted by the type and amount of metal hydroxide, the addition rate, and the concentration of solid components.

[0072] The multifunctional vinyl resin of the present invention can be cured even on its own, but it is preferred to use it in the form of a multifunctional vinyl composition incorporating various additives.

[0073] In particular, to promote curing, it can be cured in conjunction with free radical polymerization initiators such as azo compounds and organic peroxides.

[0074] Next, the epoxy resin of the second invention will be described in detail.

[0075] The second invention is an epoxy resin represented by the following general formula (1B).

[0076] (1B)

[0077] In equation (1B), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2B), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m -, m represents a number from 3 to 10, and n represents a number from 1 to 15.

[0078] (2B)

[0079] R 1 ~R 6 Each group is independently a hydrogen atom or a hydrocarbon group having 1 to 6 monovalent carbon atoms. From the viewpoint of solvent solubility, alkyl groups are preferred as hydrocarbon groups having 1 to 6 monovalent carbon atoms; from the viewpoint of heat resistance and high thermal conductivity, aromatic groups are preferred. Alkyl groups with more than 6 carbon atoms are less likely to inhibit molecular motion, and there are concerns about reduced compatibility. Furthermore, structures with large steric hindrance and large volume are problematic due to increased crystallinity, raising concerns about solvent solubility. As a more preferred structure, hydrogen atoms, methyl groups, or phenyl groups are even more preferred. 1 ~R 6 It can be a mixture of different structures.

[0080] n is a repetition number, representing a number from 1 to 15. A mixture of components with different n values ​​is preferred. The average value of n is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

[0081] The epoxy resin of the present invention may be a mixture of n=0 compounds, except for the n=0 compound alone. Preferably, the n=0 compound comprises 50% or less, based on the area % (GPC area %) determined by gel permeation chromatography.

[0082] X independently represents the structure shown in formula (2B), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m —. For — (CH2) m- represents an alkyl structure, m is the number of repetitions, representing 3 to 10. More preferably, it is 4 to 8. If it is less than 3, there is a tendency for low flexibility and low crystallinity mitigation effect. If it is greater than 10, there is a tendency for a significant decrease in the thermal conductivity and heat resistance of the cured product. The epoxy resin of formula (1B) of the present invention can be a mixture of different structures of each X, as "independently", and the thermal conductivity, moldability, and solvent solubility can be adjusted to be high. When X is the structure shown in formula (2B), there is a tendency for an increase in the thermal conductivity of the cured product.

[0083] As a preferred structure, specifically, X can be exemplified as an epoxy resin of the following formula (4B) containing a biphenyl structure as shown in formula (2B).

[0084] (4B)

[0085] In equation (4B), R 1 ~R 6 R in equation (1) above 1 ~R 6 They have the same meaning.

[0086] The preferred range for the epoxy equivalent of the epoxy resin of the present invention is 150 to 450 g / eq, and a more preferred range is 200 to 350 g / eq. Below this range, the reaction becomes difficult to control due to its rapid pace; above this range, reactivity decreases, raising concerns about obtaining a uniform cured product.

[0087] The number-average molecular weight Mn is preferably 500–2000, more preferably 500–1000. The softening point is preferably 60–100℃, more preferably 70–90℃.

[0088] The epoxy resin of the present invention can be obtained by reacting a polyhydroxy compound (resin) represented by formula (3B) with epichlorohydrin. 1 ~R 6 The epoxy resins n and X are the same as those in formula (1).

[0089] (3B)

[0090] The hydroxyl equivalent of the polyfunctional hydroxyl compound of formula (3B) is preferably 100-350 g / eq, more preferably 120-250 g / eq. The number average molecular weight Mn is preferably 500-1500.

[0091] The polyfunctional hydroxyl compound (phenolic compound) represented by formula (3B) is not limited in its preparation method as long as it has a specified structure. It can be appropriately obtained by reacting a trifunctional trihydroxyl compound with a dihalogenated compound having an X group in the presence of a basic catalyst.

[0092] At this point, a trifunctional trihydroxy compound, for example, 4,4',4”-trihydroxytriphenylmethane, can have one or more methyl or phenyl hydrocarbon groups as substituents.

[0093] Examples of dihalogenated compounds with an X group include dihalogenated 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; dihalogenated alkyl compounds such as 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, and 1,6-dibromohexane; and dihalogenated alkyl compounds such as 4,4'-dibromodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfone, 4,4'-dihydroxymethylbiphenyl, 4,4'-dichloromethylbiphenyl, 4,4'-dibromomethylbiphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-diethoxymethylbiphenyl, and p-xylylenedichloro. As a crosslinking structure that contributes to high thermal conductivity, a biphenyl structure is preferred. From a reactivity perspective, 4,4'-dichloromethylbiphenyl is particularly preferred as a crosslinking agent.

[0094] Regarding the molar ratio of phenols to aromatic condensing agents during the reaction, generally, the ratio of aromatic condensing agent to phenols is in the range of 0.2 to 0.7 moles, more preferably 0.4 to 0.7 moles. If it is less than 0.2 moles, the proportion of the n=0 polyhydroxy resin increases, raising concerns about reduced solubility, such as crystallinity. On the other hand, if it is more than 0.7 moles, the high molecular weight component increases, making stable manufacturing difficult.

[0095] The reaction of phenols with aromatic condensing agents can be carried out in the absence of a catalyst or in the presence of an acid catalyst such as an inorganic acid or organic acid. When using 4,4'-dichloromethylbiphenyl, the reaction can also be carried out without a catalyst, but generally, to suppress side reactions such as the formation of ether bonds due to the reaction between the chloromethyl group and the hydroxyl group, it is carried out in the presence of an acid catalyst. This acid catalyst can be appropriately selected from well-known inorganic and organic acids, such as inorganic acids like hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids like formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; or solid acids.

[0096] Typically, the reaction is carried out at 100–250°C for 1–20 hours. Preferably, it is carried out at 100–180°C, and more preferably at 140–180°C. If the reaction temperature is too low, the reactivity will be insufficient and time will be required; if the reaction temperature is too high, there is a risk of resin decomposition.

[0097] During the reaction, solvents such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, or aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene, can be used. Among these, ethyl cellosolve, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether are particularly preferred. After the reaction, the solvent in the obtained polyhydroxy resin can be removed by methods such as vacuum distillation, washing with water, or reprecipitation in a lean solvent. However, it can also be used directly as a raw material for the epoxidation reaction with residual solvent.

[0098] The polyhydroxy resin obtained in this way 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 curing agents such as hexamethylenetetramine, it can also be used as a phenolic resin molding material.

[0099] Trifunctional trihydroxy compounds can be obtained by the condensation polymerization of phenolic compounds with aromatic aldehydes. This reaction can be carried out using acid catalysts, such as acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, and manganese acetate. These acid catalysts can be used alone or in combination. Among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferred for their superior activity. It should be noted that the acid catalyst can be added before or during the reaction.

[0100] In order to obtain trifunctional trihydroxy compounds, the reaction temperature for the condensation polymerization of phenolic compounds with aromatic aldehydes is in the range of 20 to 140°C, preferably in the range of 80 to 110°C.

[0101] In order to obtain a trifunctional trihydroxy compound, the feed ratio of phenol compound to aromatic aldehyde during the condensation of phenol compound and aromatic aldehyde is in the range of 1 / 0.1 to 1 / 0.5 in molar ratio, more preferably in the range of 1 / 0.3 to 1 / 0.5, so as to make it easy to remove the phenol compound after the reaction by means of reprecipitation.

[0102] The method for producing the epoxy resin of the present invention by reacting the polyhydroxy resin represented by formula (3) above with epichlorohydrin will be described. This reaction can be carried out in the same manner as the well-known epoxidation reaction.

[0103] For example, the following method can be used: dissolving the above-mentioned polyhydroxy resin in excess epichlorohydrin, and reacting it for 1 to 10 hours in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide at a temperature of 50 to 150°C, preferably 60 to 120°C. The amount of epichlorohydrin used is 0.8 to 2 moles, preferably 0.9 to 1.2 moles, relative to 1 mole of hydroxyl groups in the polyhydroxy resin. After the reaction is complete, the excess epichlorohydrin is distilled off, and the residue is dissolved in solvents such as toluene and methyl isobutyl ketone, filtered, and washed with water to remove inorganic salts. Then, the solvent is distilled off, thereby obtaining the target epoxy resin represented by the above general formula (1). A quaternary ammonium salt or other catalyst can be used during the epoxidation reaction.

[0104] From the viewpoint of improving the reliability of the applied electronic components, the lower the purity, especially the amount of hydrolyzable chlorine, of the epoxy resin of the present invention, the better. While not particularly limited, it is preferably 1000 ppm or less, more preferably 500 ppm or less. It should be noted that the term "hydrolyzable chlorine" in the present invention refers to a value measured by the following method: that is, a value obtained by dissolving 0.5 g of the sample in 30 ml of... After adding 10 ml of 1N-KOH, boil and reflux for 30 minutes, cool to room temperature, then add 100 ml of 80% acetone water, and obtain the value by potentiometric titration with 0.002N-AgNO3 aqueous solution.

[0105] The multifunctional vinyl composition of the first invention uses a multifunctional vinyl compound and a free radical polymerization initiator as essential components, but may be combined with other vinyl compounds or other thermosetting resins, such as epoxy resins, oxetine resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzo[a]benzene resins. Azine resins, etc.

[0106] To improve thermal conductivity, inorganic filler materials such as glass cloth, carbon fiber, alumina, and boron nitride can be used.

[0107] For the purpose of imparting higher thermal conductivity, the higher the thermal conductivity of the inorganic filler material, the more preferred. Preferably, it is 20 W / m·K or higher, more preferably 30 W / m·K or higher, and even more preferably 50 W / m·K or higher. Furthermore, at least a portion, preferably 50 wt% or more, of the inorganic filler material needs to have a thermal conductivity of 20 W / m·K or higher. Moreover, the average thermal conductivity of the inorganic filler material as a whole is preferred in the order of 20 W / m·K or higher, 30 W / m·K or higher, and 50 W / m·K or higher.

[0108] Examples of inorganic filler materials with such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide.

[0109] To improve adhesion and the handling of the composition, various additives can be added, such as silane coupling agents, defoamers, internal release agents, and flow regulators.

[0110] The multifunctional vinyl compounds or multifunctional vinyl compositions of the present invention can also be dissolved in solvents such as toluene, xylene, acetone, methyl ethyl ketone, and methyl isobutyl ketone, impregnated in substrates such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, and heated and dried to obtain a prepreg, and then the prepreg is hot-pressed to obtain a cured product, etc.

[0111] Depending on the circumstances, a laminate can be formed by coating it onto sheet materials such as copper foil, stainless steel foil, polyimide film, or polyester film, or a cured product can be obtained by hot pressing the resin sheet obtained by heating and drying.

[0112] The epoxy resin composition of the second invention comprises an epoxy resin and a curing agent, wherein the epoxy resin component comprises the epoxy resin of the above general formula (1).

[0113] In the epoxy resin composition of the second invention, in addition to the epoxy resin of general formula (1) used as an essential component, other common epoxy resins having two or more epoxy groups in the molecule may also be used. Examples include bisphenol A, bisphenol F, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, fluorenebisphenol, 4,4'-biphenol, 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,2'-biphenol, resorcinol, and catechol. tert-butylcatechol, tert-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-dihydroxynaphthalene, and the above dihydroxynaphthalenes Allylated or polyallylated naphthyl compounds, allylated bisphenol A, allylated bisphenol F, allylated phenolic varnish and other diphenols, or phenolic varnish, bisphenol A varnish, o-cresol varnish, m-cresol varnish, p-cresol varnish, xylenol varnish, poly(p-hydroxystyrene), tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane These epoxy resins include fluoroglycinol, pyrogallol, tert-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, phenolic aralkyl resins, naphthol aralkyl resins, dicyclopentadiene resins, and other ternary or higher-order phenols, or glycidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A. One or more of these epoxy resins can be used, or a mixture of two or more.

[0114] The epoxy resin composition of the present invention preferably contains at least 50 wt% of the epoxy resin of the above-described general formula (1). More preferably, it contains at least 70 wt% of all epoxy resin, and more preferably at least 80 wt%. If the proportion used is less than this range, the moldability of the epoxy resin composition deteriorates, and the improvement effect on heat resistance, thermal conductivity, etc., when the cured product is formed is small.

[0115] As the curing agent used in the epoxy resin composition of the present invention, all substances commonly known as curing agents for epoxy resins can be used, including dicyandiamide, acid anhydrides, polyphenols, aromatic and aliphatic amines, etc. Among these, polyphenols are preferred as curing agents in fields requiring high electrical insulation, such as semiconductor sealing materials.

[0116] It is suitable to use the polyhydroxy resin represented by the general formula (3) of the present invention as a curing agent. When using the polyhydroxy resin of the present invention as a curing agent for epoxy resin, it is preferable to use a polyhydroxy resin containing 50 wt% or more of the polyhydroxy resin of formula (3) as a curing agent.

[0117] The following are specific examples of curing agents.

[0118] As polyphenols, examples include diphenols such as bisphenol A, bisphenol F, bisphenol S, fluorenebisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthol, or tertiary or higher phenols represented by tri-(4-hydroxyphenyl)methane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, phenolic varnish, o-cresol varnish, naphthol varnish, and polyvinylphenol. Furthermore, there are polyphenolic compounds synthesized from diphenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorenebisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcinol, and naphthol with condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, and terephthalic acid dimethyl glycol.

[0119] Examples of anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, dodecenylsuccinic anhydride, nadic anhydride, trimellitic anhydride, etc.

[0120] As amine-based curing agents, there are aromatic amines such as 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl sulfone, m-phenylenediamine, and p-xylylene diamine, as well as aliphatic amines such as ethylenediamine, hexamethylenediamine, triethylenetriamine, and triethylenetetramine.

[0121] In epoxy resin compositions, one or more of these curing agents may be mixed together.

[0122] The preferred ratio of epoxy resin to curing agent is 0.8 to 1.5 in equivalent proportions of epoxy groups to functional groups in the curing agent. If the ratio is outside this range, unreacted epoxy groups or functional groups in the curing agent will remain after curing, reducing the reliability of the sealing function, and is therefore not preferred.

[0123] In the epoxy resin composition of the present invention, oligomers or polymers such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, and phenoxy resin may be appropriately incorporated as other modifiers. The amount added is generally in the range of 1 to 30 parts by weight relative to 100 parts by weight of the total resin components.

[0124] The epoxy resin composition of the present invention may be formulated with inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, flow improvers, and other additives. Examples of inorganic fillers include spherical or fragmented fused silica, crystalline silica powder, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, hydrated alumina, etc., and when used in semiconductor sealing materials, the preferred amount is 70% by weight or more, more preferably 80% by weight or more.

[0125] To improve thermal conductivity, inorganic filler materials such as glass cloth, carbon fiber, alumina, and boron nitride can be used.

[0126] For the purpose of imparting higher thermal conductivity, the higher the thermal conductivity of the inorganic filler material, the more preferred it is. Preferably, it is 20 W / m·K or higher, more preferably 30 W / m·K or higher, and even more preferably 50 W / m·K or higher. Furthermore, at least a portion, preferably 50 wt% or more, of the inorganic filler material has a thermal conductivity of 20 W / m·K or higher. Moreover, the average thermal conductivity of the inorganic filler material as a whole is preferred in the order of 20 W / m·K or higher, 30 W / m·K or higher, and 50 W / m·K or higher.

[0127] Examples of inorganic filler materials with such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide.

[0128] As pigments, there are organic or inorganic extender pigments, flake pigments, etc. As thixotropic agents, examples include silicon-based, castor oil-based, aliphatic amide waxes, oxidized polyethylene waxes, and organobentonite-based agents.

[0129] Curing accelerators may be used in the epoxy resin compositions of the present invention as needed. Examples include amines, imidazoles, organophosphorus compounds, Lewis acids, etc., specifically tertiary amines such as 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecanylimidazole, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, tetraphenylphosphine, etc. Tetraphenylborate, tetraphenyl ·Ethyltriphenylborate, tetrabutyl Tetra-substituted tetrabutylborate and other tetrasubstituted... Tetraphenylborates, such as tetrasubstituted borates, 2-ethyl-4-methylimidazolium tetraphenylborate, and N-methylmorpholine tetraphenylborate, are among the tetraphenylborates added. The amount added is typically in the range of 0.01 to 5 parts by weight relative to 100 parts by weight of the total resin composition.

[0130] Depending on the requirements, the epoxy resin composition of the present invention may use release agents such as carnauba wax and OP wax, silane coupling agents such as γ-epoxypropoxypropyltrimethoxysilane, colorants such as carbon black, flame retardants such as antimony trioxide, low-stress agents such as silicone oil, and lubricants such as calcium stearate.

[0131] The epoxy resin composition of the present invention can be prepared by impregnating fibrous materials such as glass cloth, aromatic polyamide nonwoven fabric, liquid crystal polymer, and polyester nonwoven fabric after being made into a varnish state in which organic solvents are dissolved, and then removing the solvent to prepare a prepreg. Alternatively, depending on the circumstances, it can be laminated by coating it onto sheet materials such as copper foil, stainless steel foil, polyimide film, and polyester film to form a laminate.

[0132] If the epoxy resin composition of the present invention is heated and cured, the cured resin product of the present invention can be prepared. This cured product can be obtained by molding the epoxy resin composition using methods such as injection molding, compression molding, or transfer molding. The temperature at this time is typically in the range of 120–220°C.

[0133] Example

[0134] The present invention will now be specifically described with reference to examples and comparative examples. However, the present invention is not limited thereto. Unless otherwise specified, "parts" refers to parts by weight, and "%" refers to percentage by weight. Furthermore, the determination methods are performed using the following methods respectively.

[0135] 1) OH equivalent (hydroxyl equivalent)

[0136] Using a potentiometric titration apparatus, with 1,4- Using alkane as a solvent, acetylation was carried out with 1.5 mol / L acetyl chloride. Excess acetyl chloride was decomposed with water and titrated with 0.5 mol / L potassium hydroxide.

[0137] 2) Vinyl equivalent

[0138] React the sample with Widmanstätten solution (iodine monochloride solution), place it in the dark, then reduce excess iodine chloride to iodine, titrate the iodine content with sodium thiosulfate, and calculate the iodine value. Convert the iodine value to vinyl equivalents.

[0139] 3) Epoxy equivalent

[0140] A potentiometric titration apparatus was used, with methyl ethyl ketone as the solvent, and tetraethylammonium bromide acetic acid solution was added. The determination was performed using a 0.1 mol / L perchloric acid-acetic acid solution.

[0141] 4) Total chlorine

[0142] The sample was dissolved in 25 ml of butylcarbitol, followed by the addition of 25 ml of 1N-KOH propylene glycol solution. The mixture was heated under reflux for 10 minutes, cooled to room temperature, and then 100 ml of 80% acetone aqueous solution was added. The sample was then determined by potentiometric titration using 0.002N-AgNO3 aqueous solution.

[0143] 5) Softening point

[0144] According to JIS-K-2207, the determination was performed using the ring and ball method.

[0145] 6) GPC measurement

[0146] The apparatus used consisted of four columns (Tosoh Corporation, TSKgel SuperMultipore HZ-N) connected in series on a substrate (Tosoh Corporation, HLC-8220GPC), with the column temperature set at 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. For sample analysis, 50 μL of a solution containing 0.1 g of the sample dissolved in 10 mL of THF and filtered through a microfilter was used. Data processing was performed using Tosoh Corporation GPC-8020 Model II version 6.00.

[0147] 7) Solvent solubility (precipitation temperature)

[0148] Weigh 2g of resin and 1g of methyl ethyl ketone into a sample vial, heat to dissolve, and then gradually lower the temperature in a constant temperature bath. Measure the temperature at which the resin precipitates within the bath. The higher the precipitation temperature (°C), the worse the solvent solubility.

[0149] 8) Glass transition point (Tg)

[0150] Tg was determined using a thermomechanical measuring apparatus (SII NanoTechnology Co., Ltd. EXSTAR TMA / 7100) at a heating rate of 10°C / min.

[0151] 9) 5% weight reduction temperature (Td5), residual carbon content

[0152] The 5% weight loss temperature (Td5) was determined using a thermogravimetric / differential calorimetry (SII NanoTechnology EXSTAR TG / DTA7300) apparatus under a nitrogen atmosphere and a heating rate of 10 °C / min. The weight loss at 700 °C was measured and calculated as the residual carbon percentage.

[0153] 10) Thermal conductivity

[0154] Thermal conductivity was measured using a NETZSCH LFA447 thermal conductivity meter via the unsteady-state hot-wire method.

[0155] 11) Dielectric constant and dielectric loss tangent

[0156] The measurements were performed according to JIS C 2138 standard. The measured frequency is expressed as a value of 1 GHz.

[0157] Examples of synthesis and embodiments of the first invention will be described. (Synthesis Example 1A)

[0158] 140.3 g (0.48 mol) of 4,4',4''-trihydroxytriphenylmethane (structural formula below) was added to a 1000 ml four-necked flask.

[0159]

[0160] 420 g of N-methyl-2-pyrrolidone and 39.8 g of potassium carbonate were mixed and heated to 120 °C under a nitrogen atmosphere with stirring. Then, 40.2 g (0.16 mol) of 4,4'-bis(chloromethyl)biphenyl (structural formula below) was added.

[0161]

[0162] The temperature was raised to 145℃ and the reaction was allowed to proceed for 6 hours. After neutralization with 34.6 g of acetic acid, N-methyl-2-pyrrolidone was removed by distillation under reduced pressure. 350 mL of methyl isobutyl ketone was added to the reaction solution to dissolve the product, and the resulting salt was removed by washing with water. Then, methyl isobutyl ketone was removed by distillation under reduced pressure to obtain 163.8 g of hydroxyl resin a. The hydroxyl equivalent of the obtained hydroxyl resin a was 188 g / eq., Mn was 700, and the GPC area percentage (n≥1) was 74.0% (n=0) for the fraction with n≥1 and 26.0% for the fraction with n=0.

[0163] (Synthesis Example 2A)

[0164] The amount of 4,4',4''-trihydroxytriphenylmethane used was 116.9 g (0.40 mol), and otherwise the same procedure as in Synthesis Example 1 was performed to obtain 142.5 g of hydroxyl resin b. The hydroxyl equivalent of the obtained hydroxyl resin b was 205 g / eq., Mn was 980, and the GPC area % was 80.0% for n≥1 (20.0% for n=0).

[0165] (Synthesis Example 3A)

[0166] 27.5 g (0.16 mol) of 2,6-dichlorobenzonitrile (structural formula below) was used.

[0167]

[0168] Instead of 4,4'-bis(chloromethyl)biphenyl, the same procedure as in Synthesis Example 1 was performed to obtain 149.3 g of hydroxyl resin c. The hydroxyl equivalent of the obtained hydroxyl resin c was 158 g / eq., Mn was 580, and the GPC area % was 60.7% for n≥1 (39.3% for n=0).

[0169] (Synthetic Example 4A)

[0170] 45.9 g (0.16 mol) of 4,4'-dichlorodiphenyl sulfone (structural formula below) was used.

[0171]

[0172] Instead of 4,4'-bis(chloromethyl)biphenyl, the same procedure as in Synthesis Example 1A was performed to obtain 170.2 g of hydroxyl resin d. The hydroxyl equivalent of the obtained hydroxyl resin d was 180 g / eq., Mn was 720, and the GPC area % was 67.5% for n≥1 (32.5% for n=0).

[0173] (Synthetic Example 5A)

[0174] 36.8 g (0.16 mol) of 1,4-dibromobutane (structural formula below) was used.

[0175]

[0176] Instead of 4,4'-bis(chloromethyl)biphenyl, the same procedure as in Synthesis Example 1A was performed to obtain 147.2 g of hydroxyl resin e. The hydroxyl equivalent of the obtained hydroxyl resin e was 159 g / eq., Mn was 560, and the GPC area % was 52.7% for n≥1 (47.3% for n=0).

[0177] (Synthesis Example 6A)

[0178] 28.0 g (0.16 mol) of p-diphenylmethyl dichloro (structural formula below) was used.

[0179]

[0180] Instead of 4,4'-bis(chloromethyl)biphenyl, the same procedure as in Synthesis Example 1A was performed to obtain 152.1 g of hydroxyl resin f. The hydroxyl equivalent of the obtained hydroxyl resin f was 177 g / eq., Mn was 960, and the GPC area % was 71.9% for n≥1 (28.1% for n=0).

[0181] (Example 1A)

[0182] Add 56.4 g (0.30 equivalents) of hydroxyl resin a obtained in Synthesis Example 1A, 500 g of methyl ethyl ketone, and 54.9 g (0.36 equivalents) of 4-(chloromethyl)styrene (the following structural formula) to a 1000 ml four-necked flask.

[0183]

[0184] The temperature was raised to 60℃, and 20.2g of potassium hydroxide dissolved in 60.6g of methanol was added dropwise over 3 hours, with the reaction proceeding for another 6 hours. After the reaction was complete, the mixture was filtered, the solvent was removed by distillation, the precipitate was re-precipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 63.8g of multifunctional vinyl resin (vinyl resin A). Vinyl resin A had a vinyl equivalent of 231g / eq., a hydroxyl equivalent of 12000g / eq., a total chlorine content of 550ppm, a Mn content of 860, and a GPC area percentage of 51.5% for n≥1 (48.5% for n=0). The GPC of the obtained vinyl resin A is illustrated in the figure below. Figure 1 .

[0185] (Example 2A)

[0186] Using 61.5 g (0.30 equivalent) of hydroxyl resin b obtained in Synthesis Example 2A instead of hydroxyl resin a, the same procedures as in Example 1A were performed to obtain 71.2 g of multifunctional vinyl resin (vinyl resin B). Vinyl resin B had a vinyl equivalent of 242 g / eq., a hydroxyl equivalent of 14000 g / eq., a total chlorine content of 500 ppm, a Mn content of 1370, and a GPC area % of 71.9% for n≥1 (28.1% for n=0).

[0187] (Example 3A)

[0188] Using 47.4 g (0.30 equivalent) of hydroxyl resin c obtained in Synthesis Example 3A instead of hydroxyl resin a, the same procedures as in Example 1A were performed to obtain 58.3 g of multifunctional vinyl resin (vinyl resin C). Vinyl resin C had a vinyl equivalent of 213 g / eq., a hydroxyl equivalent of 11000 g / eq., a total chlorine content of 800 ppm, a Mn content of 930, and a GPC area % of 54.0% for n≥1 (46.0% for n=0).

[0189] (Example 4A)

[0190] Using 54.0 g (0.30 equivalent) of hydroxyl resin d obtained in Synthesis Example 4A instead of hydroxyl resin a, the same procedures as in Example 1A were performed to obtain 63.1 g of multifunctional vinyl resin (vinyl resin D). Vinyl resin D had a vinyl equivalent of 235 g / eq., a hydroxyl equivalent of 11000 g / eq., a total chlorine content of 900 ppm, a Mn content of 930, and a GPC area % of 60.0% for n≥1 (40.0% for n=0).

[0191] (Example 5A)

[0192] Using 47.7 g (0.30 equivalent) of hydroxyl resin e obtained in Synthesis Example 5A instead of hydroxyl resin a, the same procedures as in Example 1 were performed to obtain 56.9 g of multifunctional vinyl resin (vinyl resin E). Vinyl resin E had a vinyl equivalent of 200 g / eq., a hydroxyl equivalent of 16000 g / eq., a total chlorine content of 900 ppm, a Mn content of 770, and a GPC area % of 44.4% for n≥1 (55.6% for n=0).

[0193] (Example 6A)

[0194] Using 47.7 g (0.30 equivalent) of hydroxyl resin f obtained in Synthesis Example 6A instead of hydroxyl resin a, the same procedures as in Example 1 were performed to obtain 56.9 g of multifunctional vinyl resin (vinyl resin F). Vinyl resin F had a vinyl equivalent of 200 g / eq., a hydroxyl equivalent of 16000 g / eq., a total chlorine content of 700 ppm, a Mn content of 710, and a GPC area % of 56.9% for n≥1 (43.1% for n=0).

[0195] (Comparative Example 1A)

[0196] 30.6 g (0.30 equivalent) of 1,1,1-tris(p-hydroxyphenyl)ethane (structural formula below) was used.

[0197]

[0198] Replacing hydroxyl resin a, the same procedure as in Example 1A was performed to obtain 58.9 g of vinyl compound (vinyl compound G). Vinyl compound G had a vinyl equivalent of 214 g / eq., a hydroxyl equivalent of 7000 g / eq., and a total chlorine content of 1500 ppm.

[0199] (Comparative Example 2A)

[0200] 40.8 g of 4,4'-bis(chloromethyl)biphenyl (structural formula below) was added to a 1000 ml four-necked flask.

[0201]

[0202] 4,4'-Biphenyl (structural formula below) 75.5g

[0203]

[0204] 120 g of diethylene glycol dimethyl ether was heated to 160 °C and reacted for 10 hours under a nitrogen atmosphere with stirring. Then, the temperature was lowered 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 while the reaction proceeded. After gas chromatography confirmed the absence of residual chloromethylstyrene, the solvent was recovered under reduced pressure. The resulting resin was dissolved in toluene for neutralization and washed with water to obtain 172 g of a multifunctional vinyl resin (vinyl resin H). The vinyl resin H had a vinyl equivalent of 256 g / eq., a hydroxyl equivalent of 1500 g / eq., and a total chlorine content of 1270 ppm.

[0205] (Comparative Example 3A)

[0206] Add 50.0 g of dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane (structural formula below): 36.2%, 2,4'-dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%) to a 1000 ml four-necked flask.

[0207]

[0208] 400g of methyl ethyl ketone and 80.1g of chloromethylstyrene were mixed and heated to 60°C. 29.5g of potassium hydroxide dissolved in 88g of methanol was added dropwise over 3 hours, and the reaction was continued for another 6 hours. After the reaction was complete, the mixture was filtered, the solvent was removed by distillation, the precipitate was re-precipitated with methanol, washed with copious amounts of water, and dried under reduced pressure to obtain 95.4g of vinyl compound (vinyl compound I). Vinyl compound I has a vinyl equivalent of 217g / eq., a hydroxyl equivalent of 17000g / eq., and a total chlorine content of 400ppm.

[0209] Examples 7A-12A, Comparative Examples 4A-7A

[0210] As a 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 Co., Ltd., vinyl equivalent: 590.0 g / eq, number average molecular weight 1187) were used as curing accelerators. Perbutyl P (manufactured by Nippon Oil Co., Ltd.) was used as an organic peroxide, and Adeka Stab AO-60 (manufactured by ADEKA Co., Ltd.) was used as an antioxidant. The mixtures were prepared according to the proportions shown in Table 1A and dissolved in a solvent to form a homogeneous composition. This composition was coated onto a PET film and dried at 130°C for 5 minutes to obtain a resin composition. The composition removed from the PET film was clamped on a mirror panel and cured under reduced pressure while applying a pressure of 2 MPa at 130°C for 15 minutes and at 210°C for 80 minutes. The properties of the obtained cured products are shown in Table 1A.

[0211] [Table 1A]

[0212]

[0213] The multifunctional vinyl resin of the first embodiment of the invention exhibits superior physical properties compared to the comparative example, including high thermal conductivity, low dielectric constant, and low dielectric loss tangent.

[0214] Next, an embodiment of the second invention will be described. (Embodiment 1B)

[0215] 140.3 g (0.48 mol) of 4,4',4''-trihydroxytriphenylmethane (structural formula below) was added to a 1000 ml four-necked flask.

[0216]

[0217] 420 g of N-methyl-2-pyrrolidone and 39.8 g of potassium carbonate were mixed and heated to 120 °C under a nitrogen atmosphere with stirring. Then, 40.2 g (0.16 mol) of 4,4'-bis(chloromethyl)biphenyl (structural formula below) was added.

[0218]

[0219] The temperature was raised to 145℃ and the reaction was allowed to proceed for 6 hours. After neutralization with 34.6 g of acetic acid, N-methyl-2-pyrrolidone was removed by distillation under reduced pressure. 350 mL of methyl isobutyl ketone was added to the reaction solution to dissolve the product, and the resulting salt was removed by washing with water. Then, methyl isobutyl ketone was removed by distillation under reduced pressure to obtain 163.8 g of hydroxyl resin a. The hydroxyl equivalent of the obtained hydroxyl resin a was 188 g / eq., Mn was 700, and the GPC area % was 74.0% for n≥1 (26.0% for n=0). The GPC of the obtained hydroxyl resin a is illustrated in the figure. Figure 2 .

[0220] (Example 2B)

[0221] The amount of 4,4',4''-trihydroxytriphenylmethane used was 116.9 g (0.40 mol), and otherwise the same operation as in Example 1B was performed to obtain 142.5 g of hydroxyl resin b. The obtained hydroxyl resin b had a hydroxyl equivalent of 205 g / eq., Mn of 980, and GPC area % of 80.0% for n≥1 (20.0% for n=0).

[0222] (Example 3B)

[0223] 27.5 g (0.16 mol) of 2,6-dichlorobenzonitrile (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl.

[0224]

[0225] In addition, the same operation as in Example 1B was performed to obtain 149.3 g of hydroxyl resin c. The hydroxyl equivalent of the obtained hydroxyl resin c was 158 g / eq., Mn was 580, and the GPC area % was 60.7% for n≥1 (39.3% for n=0).

[0226] (Example 4B)

[0227] 45.9 g (0.16 mol) of 4,4'-dichlorodiphenyl sulfone (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl.

[0228]

[0229] In addition, the same operation as in Example 1B was performed to obtain 170.2 g of hydroxyl resin d. The hydroxyl equivalent of the obtained hydroxyl resin d was 180 g / eq., Mn was 720, and the GPC area % was 67.5% for n≥1 (32.5% for n=0).

[0230] (Example 5B)

[0231] 36.8 g (0.16 mol) of 1,4-dibromobutane (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl.

[0232]

[0233] In addition, the same operation as in Example 1B was performed to obtain 147.2 g of hydroxyl resin e. The hydroxyl equivalent of the obtained hydroxyl resin e was 159 g / eq., Mn was 560, and the GPC area % was 52.7% for n≥1 (47.3% for n=0).

[0234] (Example 6B)

[0235] 28.0 g (0.16 mol) of p-xylenedichloro (structural formula below) was used instead of 4,4'-bis(chloromethyl)biphenyl.

[0236]

[0237] In addition, the same operation as in Example 1B was performed to obtain 152.1 g of hydroxyl resin f. The hydroxyl equivalent of the obtained hydroxyl resin f was 177 g / eq., Mn was 960, and the GPC area % was 71.9% for n≥1 (28.1% for n=0).

[0238] (Example 7B)

[0239] Add 94.0 g (0.50 equivalent) of hydroxyl resin a obtained in Example 1B and 460 g of epichlorohydrin (structural formula below) to a 1000 ml four-necked flask.

[0240]

[0241] 50.0 g of a 48% sodium hydroxide aqueous solution was added dropwise over 4 hours at 62°C under reduced pressure (approximately 130 Torr). During this period, the generated water was removed from the system by azeotropic reaction with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the addition was complete, the reaction continued for another hour. Then, epichlorohydrin was removed by distillation, methyl isobutyl ketone was added, and the salt was removed by washing with water. The mixture was then filtered, washed with water, and then distilled under reduced pressure to remove methyl isobutyl ketone, yielding 103.2 g of epoxy resin (epoxy resin A). Epoxy resin A had an epoxy equivalent of 243, a softening point of 72°C, a hydrolyzable chlorine content of 50 ppm, a Mn content of 740, and a content of 75.2% for n≥1 (24.8% for n=0) as determined by GPC. The GPC diagram of the obtained epoxy resin A is shown below. Figure 3 As shown.

[0242] (Example 8B)

[0243] Using 102.5 g (0.50 equivalent) of hydroxyl resin b obtained in Example 2B instead of hydroxyl resin a, the same procedures as in Example 7 were performed to obtain 109.6 g of epoxy resin (epoxy resin B). Epoxy resin B has an epoxy equivalent of 261 g / eq, a softening point of 79°C, a hydrolytic chlorine content of 57 ppm, a Mn content of 980, and a GPC area percentage of 81.1% for n≥1 (18.9% for n=0).

[0244] (Example 9B)

[0245] Using 79.0 g (0.50 equivalent) of hydroxyl resin c obtained in Example 3B instead of hydroxyl resin a, the same procedures as in Example 7B were performed to obtain 88.6 g of epoxy resin (epoxy resin C). Epoxy resin C has an epoxy equivalent of 213 g / eq, a softening point of 78°C, a hydrolytic chlorine content of 60 ppm, a Mn content of 570, and a GPC area percentage of 65.1% for n≥1 (34.9% for n=0).

[0246] (Example 10B)

[0247] Using 90.0 g (0.50 equivalent) of hydroxyl resin d obtained in Example 4B instead of hydroxyl resin a, the same procedures as in Example 7B were performed to obtain 102.2 g of epoxy resin (epoxy resin D). Epoxy resin D has an epoxy equivalent of 238 g / eq, a softening point of 84°C, a hydrolytic chlorine content of 70 ppm, a Mn content of 650, and a GPC area percentage of 72.1% for n≥1 (27.9% for n=0).

[0248] (Example 11B)

[0249] Using 79.5 g (0.50 equivalent) of hydroxyl resin e obtained in Example 5B instead of hydroxyl resin a, the same procedures as in Example 7B were performed to obtain 84.9 g of epoxy resin (epoxy resin E). Epoxy resin E has an epoxy equivalent of 215 g / eq, a softening point of 84°C, a hydrolytic chlorine content of 85 ppm, a Mn content of 580, and a GPC area percentage of 59.8% for n≥1 (40.2% for n=0).

[0250] (Example 12B)

[0251] Using 88.5 g (0.30 equivalent) of hydroxyl resin f obtained in Example 6B instead of hydroxyl resin a, the same procedures as in Example 7B were performed to obtain 102.6 g of epoxy resin (epoxy resin F). Epoxy resin F has an epoxy equivalent of 233 g / eq., a softening point of 70°C, a hydrolytic chlorine content of 50 ppm, a Mn content of 970, and a GPC area % of 74.0% for n≥1 (26.0% for n=0).

[0252] (Refer to Example 1B)

[0253] 48.7 g (0.50 equivalent) of 4,4',4”-trihydroxytriphenylmethane (the above structural formula) was used instead of hydroxyl resin a, and the same procedure as in Example 7 was performed to obtain 72.4 g of epoxy resin (epoxy resin G). Epoxy resin G has an epoxy equivalent of 155 g / eq, a softening point of 50°C, a hydrolytic chlorine content of 40 ppm, a Mn content of 410, and a GPC area % of 2.0% for n≥1 (98.0% for n=0).

[0254] (Refer to Example 2B)

[0255] In a 1000 ml four-necked flask, 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'-dichloromethylbiphenyl were added. Under a nitrogen stream, the mixture was stirred and heated to 170 °C and reacted for 10 hours to generate a polyhydroxy resin. After the reaction was complete, 50.7 g of diethylene glycol dimethyl ether was recovered, and 470 g of epichlorohydrin was added. Then, under reduced pressure (approximately 130 Torr), 68.7 g of a 48% sodium hydroxide aqueous solution was added dropwise over 4 hours at 62 °C. During this process, the generated water was removed from the system through azeotropic reaction with the epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the addition was complete, the reaction was continued for another hour. Then, epichlorohydrin was removed by distillation, methyl isobutyl ketone was added, and the salt was removed by washing with water. The mixture was then filtered, washed with water, and then methyl isobutyl ketone was removed by vacuum distillation to obtain 130g of epoxy resin (epoxy resin H). Epoxy resin H has an epoxy equivalent of 196, a softening point of 97℃, a hydrolyzable chlorine content of 65ppm, a Mn content of 450, and, as determined by GPC, a content of n≥1 of 72.0% (n=0 of 28.0%).

[0256] Examples 13B-19B and Comparative Examples 1B-3B

[0257] As epoxy resin components, epoxy resins A to F obtained in Examples 7B to 12B, epoxy resins G to H obtained in Reference Examples 1B to 2B, and epoxy resin I: o-cresol phenolic varnish type epoxy resin (YDCN-700-3 manufactured by JITCO Chemical Materials, epoxy equivalent 200) were used as curing agents. Polyhydroxy resin a and phenolic varnish resin g (hydroxyl equivalent 105) obtained in Example 1 were used as curing accelerators. Triphenylphosphine was used, and epoxy resin compositions were obtained according to the formulations shown in Table 1B. The values ​​in the table represent parts by weight in the formulation.

[0258] The epoxy resin composition was molded at 175°C and cured for 5 hours to obtain cured test pieces, which were then used for various physical property tests. The results are also shown in Table 1B.

[0259] [Table 1B]

[0260]

[0261] Compared with the comparative example, the epoxy resin and the polyhydroxy resin of the curing agent in the second embodiment of the invention exhibit excellent physical properties such as superior solvent solubility, high thermal conductivity, and high heat resistance.

[0262] Industrial availability

[0263] The multifunctional vinyl resin of the first invention is useful as an electronic material for high-speed communication equipment, as it can easily dissipate heat from electronic components and wiring, and is also useful as a material with low signal loss.

[0264] The polyhydroxy resin and epoxy resin of the second invention have excellent solvent solubility, high heat resistance and good thermal conductivity, and are therefore suitable for power devices and automotive applications.

Claims

1. A multifunctional vinyl resin, represented by the following general formula (1A), 　（1A）， In equation (1A), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2A), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m -, m represents a number from 3 to 10, and n represents a number from 1 to 15. （2A）。 2. The multifunctional vinyl resin according to claim 1, wherein, X represents the structure shown in equation (2A).

3. A multifunctional vinyl composition comprising the multifunctional vinyl resin of claim 1 and a free radical polymerization initiator as essential components.

4. A multifunctional vinyl curable, which is formed by curing the multifunctional vinyl composition of claim 3.

5. An epoxy resin, represented by the following general formula (1B), （1B）， In equation (1B), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2B), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m -, m represents a number from 3 to 10, and n represents a number from 1 to 15. （2B）。 6. The epoxy resin according to claim 5, wherein, X represents the structure shown in equation (2B).

7. A polyhydroxy resin, represented by the following general formula (3B), （3B）， In equation (3B), R 1 ~R 6 Each of the following groups independently represents a hydrogen atom or a hydrocarbon group with 1 to 6 monovalent carbon atoms. X independently represents the structure shown in formula (2B), the benzonitrile structure, the diphenylsulfonyl structure, the xyleneyl structure, or -(CH2). m -, m represents a number from 3 to 10, and n represents a number from 1 to 15.

8. The polyhydroxy resin according to claim 7, wherein, X represents the structure shown in equation (2B).

9. An epoxy resin composition, characterized in that, In an epoxy resin composition consisting of an epoxy resin and a curing agent, the epoxy resin of claim 5 is included as an essential component as part or all of the epoxy resin.

10. A resin composition, characterized in that, It contains the polyhydroxy resin of claim 7 as an essential component.

11. A resin cured product, characterized in that, It is formed by curing the resin composition according to claim 9.

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