Polyfunctional vinyl compound, composition thereof, and cured product

Abstract

Provided is a vinyl compound which can be used in sealing of electrical / electronic components, circuit board materials, and the like, and which forms a cured product having excellent solvent solubility, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and excellent flame retardancy. A polyfunctional vinyl compound represented by general formula (1). In formula (1), R1 to R4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to vinyl compounds, and more specifically, to polyfunctional vinyl compounds having excellent solvent solubility and can be used in insulating materials for electrical and electronic components such as semiconductor seals, laminates, and heat dissipation substrates, compositions thereof, and cured resins thereof having excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy. Background Art

[0002] As for printed circuit boards, sealing materials, casting materials, etc. used in communication equipment, as the communication speed and the amount of communication increase, the signal transmission speed increases, and therefore high-speed communication technology is actively being studied. For electronic materials in such applications, materials that can reduce dielectric loss are required, and in printed circuit board applications, curable resins that can be multilayered are also required.

[0003] On the other hand, the electronic calculation parts that process a large amount of data generate a lot of heat, and due to heat accumulation, the processing speed of the electronic calculation parts is reduced. Therefore, as a technology for appropriately cooling the printed circuit board using a heat sink, various methods are known, such as introducing a heat transfer member such as a copper coin or a copper insert (Patent Document 1) and making the shape of the matching filler a special shape (Patent Document 2). However, such methods lead to an increase in weight and a large-scale device, which is not preferred.

[0004] In addition, as a method for improving thermal conductivity, a method for removing heat from electronic calculation components by studying the types and amounts of various fillers has been adopted for sealing material compositions. For example, attempts have been made to make them contain inorganic fillers such as crystalline silicon dioxide, silicon nitride, aluminum nitride, and spherical aluminum oxide powders with large thermal conductivity (Patent Documents 3 and 4). However, if the content of the inorganic filler is increased, as the viscosity during molding increases, the fluidity decreases, resulting in a problem of impaired moldability. Therefore, there is a limit to the method of simply increasing the content of the inorganic filler.

[0005] For the above background, the method of improving the thermal conductivity of the composition by the high thermal conductivity of the matrix resin itself has also been studied. For example, an epoxy resin with a rigid mesogen group having liquid crystal properties and an epoxy resin composition using the same (patent documents 5, 6) have been proposed. However, as the curing agent used in these epoxy resin compositions, an aromatic diamine compound is used, and there is a limit on the high filling rate of the inorganic filler, and there are also problems in terms of electrical insulation. In addition, when using an aromatic diamine compound, although the liquid crystal properties of the cured product can be confirmed, the crystallinity of the cured product is low, and it is insufficient in terms of high thermal conductivity, low thermal expansion, low hygroscopicity, etc. Further, in order to show liquid crystal properties, a strong magnetic field needs to be applied to orient the molecules, and in order to be widely used in industry, there are also large restrictions on the equipment. In addition, in the coordination system with the inorganic filler, compared with the thermal conductivity of the matrix resin, the thermal conductivity of the inorganic filler is overwhelmingly large, and even if the thermal conductivity of the matrix resin itself is improved, the reality is that there is no great contribution to the improvement of the thermal conductivity as a composite material, and sufficient thermal conductivity improvement effect cannot be obtained.

[0006] In Patent Document 7, a tetrafunctional or higher vinyl resin having a biphenyl skeleton is proposed as a multifunctional vinyl resin having both high thermal conductivity and low dielectric loss tangent, but there is no record of the solvent solubility of the multifunctional vinyl resin and the polyhydroxy resin serving as its raw material, and there is no mention of the effect of impurities such as residual polar groups on thermal conductivity.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2009-170493

[0010] Patent Document 2: International Publication No. 2013 / 100172

[0011] Patent Document 3: Japanese Patent Application Laid-Open No. 11-147936

[0012] Patent Document 4: Japanese Patent Application Publication No. 2002-309067

[0013] Patent Document 5: Japanese Patent Application Laid-Open No. 11-323162

[0014] Patent Document 6: Japanese Patent Application Laid-Open No. 9-118673

[0015] Patent Document 7: International Publication No. 2021-200414 Summary of the invention

[0016] The present invention aims to provide a vinyl composition and a cured product thereof which can be used for sealing of electric and electronic parts, circuit board materials, etc. and which can form a cured product having excellent solvent solubility, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and excellent flame retardancy. Another object is to provide a vinyl compound used in the vinyl composition.

[0017] The present inventors have conducted intensive studies and have found that a polyfunctional vinyl compound having a specific structure can solve the above-mentioned problems. They have also found that the cured product thereof exhibits effects in terms of heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy.

[0018] That is, the present invention is a polyfunctional vinyl compound represented by the following general formula (1).

[0019]

[0020] In formula (1), R1 to R4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

[0021] It is preferred that at least one of R1 to R4 in the polyfunctional vinyl compound is a methyl group or a phenyl group.

[0022] The present invention is also directed to a polyfunctional vinyl composition comprising the above-mentioned polyfunctional vinyl compound and a radical polymerization initiator as essential components, and a polyfunctional vinyl cured product obtained by curing the polyfunctional vinyl composition.

[0023] The multifunctional vinyl compound of the present invention is suitable for a vinyl resin composition and a cured product thereof which are excellent in solvent solubility and are used in lamination, molding, casting, bonding, etc. Moreover, the cured product is excellent in heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy, and is therefore suitable for sealing of electrical and electronic components, circuit substrate materials, and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the GPC chart of the multifunctional vinyl compound obtained in Example 1. DETAILED DESCRIPTION

[0025] The present invention is described in detail below.

[0026] The present invention is a polyfunctional vinyl compound represented by the following general formula (1).

[0027]

[0028] R1 to R4 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. From the viewpoint of solvent solubility, an alkyl group is preferred, and from the viewpoint of heat resistance and high thermal conductivity, an aromatic group is preferred. When the alkyl group has a carbon number greater than 6, it becomes difficult to inhibit molecular motion, and there is also a concern about reduced compatibility. In addition, a bulky structure with large steric hindrance has increased crystallinity, so solvent solubility is a concern. As a more preferred structure, a methyl group or a phenyl group is more preferred. It may be a mixture of different structures of R1 to R4.

[0029] In the polyfunctional vinyl compound of the present invention, the substitution position of the vinyl benzyl ether is not particularly limited, but is preferably para-positioned relative to the methine group connecting the three aromatic rings from the viewpoint of thermal conductivity and heat resistance. In particular, it is more preferred that all three vinyl benzyl ethers are para-positioned.

[0030] The number average molecular weight (Mn) of the polyfunctional vinyl compound of the present invention is preferably 2000 or less, more preferably 1500 or less. In addition, a multi-branched product represented by the following general formula (2) may be contained. n is a repeating number, which is 0 to 20. A mixture of components having different values ​​of n is preferred.

[0031] From the viewpoint of thermal conductivity, the content of n=0 form is preferably 50 wt % or more, more preferably 80 wt % or more.

[0032]

[0033] In formula (2), n=0 is a polyfunctional vinyl compound represented by formula (1). When the polyfunctional vinyl compound of the present invention is represented by formula (2), the average value (number average) of n is preferably in the range of 0.01 to 5.0, more preferably in the range of 0.01 to 2.0, and even more preferably in the range of 0.01 to 1.0.

[0034] Therefore, the polyfunctional vinyl compound of the present invention is also referred to as a polyfunctional vinyl resin.

[0035] The preferred range of the vinyl equivalent of the multifunctional vinyl compound of the present invention is 150 to 450 g / eq, and the more preferred range is 200 to 300 g / eq. When the vinyl equivalent is smaller than this range, the reaction is rapidly reacted, so that the reaction control becomes difficult, and when the vinyl equivalent is larger than this range, the reactivity decreases, and it is feared that it is difficult to obtain a uniform cured product.

[0036] The polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound with chloromethylstyrene, but when the unreacted and remaining hydroxyl group is less than 5000g / eq, curing becomes insufficient, and thermal conductivity and heat resistance are reduced. In addition, since the hydroxyl group is a polar group, it is feared that its remaining hinders the reduction of dielectric constant and dielectric loss tangent. The hydroxyl equivalent is preferably more than 5000g / eq, more preferably more than 10000g / eq.

[0037] On the other hand, the chlorine component is derived from chloromethylstyrene as a raw material. Similar to the hydroxyl group, if the chlorine component remains, there is a concern that the dielectric constant and dielectric loss tangent may be hindered from decreasing, and the curing reaction may be hindered by the polar group, so there is a concern that the thermal conductivity and heat resistance may be reduced. The total chlorine content is preferably 2000 ppm or less, and more preferably 1000 ppm or less.

[0038] The polyfunctional vinyl compound of the present invention can be obtained by reacting a trifunctional hydroxy compound represented by formula (3) with an aromatic vinylating agent. R1 to R4 are the same as those of the vinyl compound of formula (1).

[0039]

[0040] The hydroxyl equivalent of the trifunctional hydroxy compound of formula (3) is preferably 90 to 350 g / eq, more preferably 100 to 200 g / eq.

[0041] The trifunctional hydroxy compound of formula (3) can be produced by a common method, and can be obtained, for example, by polycondensing a monovalent phenol compound with an aromatic aldehyde.

[0042] Examples of the monovalent phenol compound include monoalkylphenols such as phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, p-octylphenol, p-tert-butylphenol, o-cyclohexylphenol, m-cyclohexylphenol, and p-cyclohexylphenol; dialkylphenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, 2,4-xylenol, and 2,6-xylenol; trialkylphenols such as 2,3,5-trimethylphenol and 2,3,6-trimethylphenol; and hydroxybiphenyls such as 2-phenylphenol, 4-phenylphenol, 3-benzyl-1,1'-biphenyl-2-phenol, 3-benzyl-1,1'-biphenyl-4-phenol, 3-phenylphenol, and 2,6-diphenylphenol. In terms of solvent solubility, reactivity, and supply properties, 2,5-xylenol, 2,6-xylenol, and 2-phenylphenol are particularly preferred. These phenol compounds may be used alone or in combination of two or more.

[0043] Examples of the aromatic aldehyde include hydroxybenzaldehydes such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, and 4-hydroxybenzaldehyde. From the viewpoint of heat resistance and thermal conductivity, 4-hydroxybenzaldehyde is preferred.

[0044] The polycondensation of phenolic compounds and aromatic aldehydes can use an acid catalyst, for example, acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, etc. can be listed. These acid catalysts can use only one, and two or more can be used in combination. In addition, among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferred from the aspect of excellent activity. It should be noted that the acid catalyst can be added before the reaction, and can also be added midway in the reaction.

[0045] The polycondensation of the phenol compound and the aromatic aldehyde can obtain a polycondensate in the presence of a solvent as required. Examples of the solvent include monohydric alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, trimethylene glycol, diethylene glycol, polyethylene glycol, and glycerol; glycol ethers such as 2-ethoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl methyl ether, and ethylene glycol monophenyl ether; cyclic ethers such as 1,3-dioxane, 1,4-dioxane, and tetrahydrofuran; glycol esters such as ethylene glycol acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, etc. These solvents may be used alone or in combination of two or more. Among these solvents, 2-ethoxyethanol is preferred because the obtained compound has excellent solubility.

[0046] The reaction temperature during the polycondensation of the phenol compound and the aromatic aldehyde is in the range of 20 to 140°C, preferably in the range of 80 to 110°C.

[0047] The feed ratio of the phenol compound / aromatic aldehyde is in the range of 1 / 0.1 to 1 / 0.5, more preferably 1 / 0.3 to 1 / 0.5 in terms of molar ratio, from the viewpoint of easily removing the phenol compound after the reaction by reprecipitation or the like.

[0048] The polyfunctional vinyl compound of the present invention can be suitably obtained by reacting a trifunctional hydroxy compound with an aromatic vinylating agent. For example, the vinyl compound of the present invention represented by the above formula (1) can be obtained by reacting a trifunctional hydroxy compound represented by the above formula (3) with chloromethylstyrene. The reaction can be carried out in the same manner as a known vinylation reaction.

[0049] In terms of the mixing ratio, the aromatic vinylating agent (e.g., chloromethylstyrene) is preferably used in an amount of 0.8 to 1.2 equivalents per 1.0 equivalent of the hydroxyl group as the functional group of the trifunctional hydroxy compound. However, when the reactivity of the trifunctional hydroxy compound is low, an excess amount of the aromatic vinylating agent may be added and removed after the reaction.

[0050] As the aromatic vinylating agent, halogenated methylstyrene is preferred, and chloromethylstyrene is particularly preferred. In addition, bromomethylstyrene and its isomers, halogenated methylstyrene having a substituent, etc. can be cited. As for the substitution position of the halogenated methyl form, for example, in the case of halogenated methylstyrene, the 4-position is preferred, and the 4-position form is preferably 60% by weight or more of the whole.

[0051] The reaction of the trifunctional hydroxy compound and the aromatic vinylating agent can be carried out in the absence of a solvent or in the presence of a solvent. The aromatic vinylating agent can be added to the hydroxy compound, a metal hydroxide can be added to carry out the reaction, and the generated metal salt can be removed by filtering, washing with water, etc., and then the reaction can be carried out.

[0052] As for the solvent, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone etc. can be listed, but it is not limited to these. From the viewpoint of reactivity, methyl ethyl ketone is preferred. As a specific example of metal hydroxide, sodium hydroxide, potassium hydroxide etc. can be listed, but it is not limited to these.

[0053] The vinylation reaction is preferably carried out at a temperature of 90° C. or less, more preferably 70° C. or less. At a temperature higher than this, thermal self-polymerization of the vinyl benzyl ether group proceeds, making it difficult to control the reaction. In order to suppress self-polymerization, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitroso groups, nitrone compounds, oxygen, etc. may be used.

[0054] The reaction endpoint can be determined by tracking the remaining amount of halogenated methylstyrene as the aromatic vinylating agent using various chromatography methods such as GPC, and the reaction rate can be adjusted by the type, amount, addition rate, solid content concentration, etc. of the metal hydroxide.

[0055] The polyfunctional vinyl compound of the present invention can be cured alone, but can also be preferably used as a polyfunctional vinyl composition blended with various additives.

[0056] In particular, in order to accelerate curing, a radical polymerization initiator such as an azo compound or an organic peroxide can be added to cause curing.

[0057] The multifunctional vinyl composition of the present invention contains a multifunctional vinyl compound and a radical polymerization initiator as essential components, and can be blended with other vinyl compounds and other thermosetting resins, for example, epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, benzoxazine resins, etc.

[0058] In order to improve the thermal conductivity, inorganic fillers such as glass cloth, carbon fiber, alumina, boron nitride, etc. may be added.

[0059] As for the inorganic filler material, in order to impart higher thermal conductivity, the higher the thermal conductivity, the more preferred. Preferably, it is 20 W / m·K or more, more preferably 30 W / m·K or more, and further preferably 50 W / m·K or more. Moreover, at least a portion of the inorganic filler material, preferably 50 wt% or more, has a thermal conductivity of 20 W / m·K or more. Moreover, the average thermal conductivity of the inorganic filler material as a whole is in the order of 20 W / m·K or more, 30 W / m·K or more, and 50 W / m·K or more, and the preference increases.

[0060] Examples of the inorganic filler 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, aluminum oxide, and magnesium oxide.

[0061] In order to improve the adhesive force and the handling of the composition, various additives may be added, for example, a silane coupling agent, a defoaming agent, an internal mold release agent, a flow regulator, etc. may be mentioned.

[0062] The multifunctional vinyl compound or multifunctional vinyl composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and the prepreg obtained by heating and drying is hot-pressed to obtain a cured product.

[0063] In addition, the resin may be coated on a sheet-like material such as copper foil, stainless foil, polyimide film, polyester film, etc. to form a laminate, or a cured product may be obtained by heat-pressing a heat-dried resin sheet.

[0064] Example

[0065] The following examples and comparative examples are given to specifically describe the present invention. However, the present invention is not limited to these examples. Unless otherwise specified, "part" means part by weight, and "%" means % by weight. In addition, with respect to the measuring method, the following methods are used to measure respectively.

[0066] 1) OH equivalent (hydroxyl equivalent)

[0067] A potentiometric titration apparatus was used, 1,4-dioxane was used as a solvent, acetylation was performed with 1.5 mol / L acetyl chloride, excess acetyl chloride was decomposed with water, and titration was performed with 0.5 mol / L potassium hydroxide.

[0068] 2) Vinyl equivalent

[0069] The sample is reacted with a Weiss solution (iodine monochloride solution) and left in a dark place, and then the excess iodine chloride is reduced to iodine, and the iodine is titrated with sodium thiosulfate to calculate the iodine value. The iodine value is converted into vinyl equivalent.

[0070] 3) Total chlorine

[0071] After dissolving 1.0 g of the sample in 25 ml of butyl carbitol, 25 ml of 1N-KOH propylene glycol solution was added, and the mixture was heated under reflux for 10 minutes, cooled to room temperature, and then 100 ml of 80% acetone water was added. The solution was measured by potentiometric titration using 0.002N-AgNO3 aqueous solution.

[0072] 4) GPC determination

[0073] An instrument with a column (TSKgel Super Multipore HZ-N 4, manufactured by Tosoh Corporation) in series was used in the main body (manufactured by Tosoh Corporation, HLC-8220GPC), and the column temperature was set to 40°C. In addition, tetrahydrofuran (THF) was used as the eluent, and the flow rate was set to 0.35 mL / min, and a differential refractive index detector was used as the detector. The sample was measured using 50 μL of the substance obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering with a microfilter. GPC-8020 Model II Version 6.00 manufactured by Tosoh Corporation was used for data processing.

[0074] 5) Solvent solubility (precipitation temperature)

[0075] Weigh 2g of resin and 1g of methyl ethyl ketone in a sample bottle, heat and dissolve, then slowly lower the temperature in a thermostatic bath, and measure the temperature in the bath where the resin precipitates. The higher the precipitation temperature (°C), the worse the solvent solubility.

[0076] 6) Glass transition temperature (Tg)

[0077] Tg was determined using a thermomechanical measuring apparatus (EXSTAR TMA / 7100 manufactured by SII Nanotechnology Co., Ltd.) at a temperature increase rate of 10° C. / min.

[0078] 7) 5% weight loss temperature (Td5), residual carbon rate

[0079] The 5% weight loss temperature (Td5) was measured using a thermogravimetric / differential thermal analyzer (EXSTAR TG / DTA7300 manufactured by SII Nanotechnology) under a nitrogen atmosphere and a heating rate of 10°C / min. The weight loss at 700°C was also measured and calculated as the residual carbon ratio.

[0080] 8) Thermal conductivity

[0081] The thermal conductivity was measured by a non-steady-state hot wire method using a LFA447 thermal conductivity meter manufactured by NETZSCH.

[0082] 9) Dielectric constant and dielectric loss tangent

[0083] The measurement was performed in accordance with JIS C 2138. The measurement frequency was expressed as a value of 1 GHz.

[0084] (Synthesis example 1)

[0085] In a 1000 mL four-necked flask, 73.6 g (0.60 mol) of 2,5-xylenol (structural formula shown below) and

[0086]

[0087] p-Hydroxybenzaldehyde (structural formula below) 24.4 g (0.20 mol),

[0088]

[0089] Dissolve in 200.0 g of 2-ethoxyethanol. Add 20.0 g of sulfuric acid while cooling in an ice bath, and heat at 100°C for 3 hours, stirring, and reacting. After the reaction, the obtained solution is reprecipitated with water, washed with water, filtered, and vacuum dried to obtain 65.0 g of trifunctional hydroxy compound a. In the trifunctional hydroxy compound a, R1 to R4 in formula (3) are all methyl groups, and the hydroxyl equivalent is 118 g / eg.

[0090] (Synthesis example 2)

[0091] The same operation as in Synthesis Example 1 was performed except that 36.8 g (0.30 mole) of 2,5-xylenol and 28.2 g (0.30 mole) of phenol were used instead of 73.6 g of 2,5-xylenol to obtain 60.8 g of trifunctional hydroxy compound b. The trifunctional hydroxy compound b is a mixture of compounds in which R1 to R4 in formula (3) are all hydrogen atoms or methyl groups, and the hydroxyl equivalent is 105 g / eg.

[0092] (Synthesis example 3)

[0093] Except that 102.0 g (0.60 mol) of 2-phenylphenol (structural formula shown below) was used instead of 73.6 g of 2,5-xylenol,

[0094]

[0095] The same operation as in Synthesis Example 1 was carried out to obtain 81.0 g of a trifunctional hydroxy compound c. In the trifunctional hydroxy compound c, R1 to R4 in the formula (3) were all phenyl groups, and the hydroxyl equivalent was 149 g / eg.

[0096] (Example 1)

[0097] In a 1000 ml four-necked flask, 59.0 g (0.17 mol) of the trifunctional hydroxy compound a obtained in Synthesis Example 1, 400 g of methyl ethyl ketone, and 91.6 g (0.60 mol) of chloromethylstyrene (the following structural formula) were added.

[0098]

[0099] The temperature was raised to 60°C, and 33.7 g of potassium hydroxide dissolved in 101 g of methanol was added dropwise over 3 hours, and the mixture was reacted for 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 102.4 g of a multifunctional vinyl compound (vinyl compound A). The vinyl equivalent of vinyl compound A was 225 g / eg., the hydroxyl equivalent was 12000 g / eg., and the total chlorine content was 600 ppm.

[0100] (Example 2)

[0101] The same operation as in Example 1 was performed except that 52.5 g (0.17 mol) of the trifunctional hydroxy compound b obtained in Synthesis Example 2 was used instead of the trifunctional hydroxy compound a to obtain 100.3 g of a multifunctional vinyl compound (vinyl compound B). The vinyl equivalent of the vinyl compound B was 212 g / eg., the hydroxyl equivalent was 14000 g / eg., and the total chlorine content was 500 ppm.

[0102] (Example 3)

[0103] The same operation as in Example 1 was carried out except that 74.5 g (0.17 mol) of the trifunctional hydroxy compound c obtained in Synthesis Example 3 was used instead of the trifunctional hydroxy compound a to obtain 121.2 g of a multifunctional vinyl compound (vinyl compound C). The vinyl equivalent of the vinyl compound C was 260 g / eg., the hydroxyl equivalent was 11000 g / eg., and the total chlorine content was 800 ppm.

[0104] (Comparative Example 1)

[0105] Except that 51.0 g of 1,1,1-tri(p-hydroxyphenyl)ethane (structural formula shown below) was used instead of the trifunctional hydroxy compound a,

[0106]

[0107] The same operation as in Example 1 was carried out to obtain 93.3 g of a polyfunctional vinyl compound (vinyl compound D). The vinyl compound D had a vinyl equivalent of 214 g / eg., a hydroxyl equivalent of 7000 g / eg., and a total chlorine content of 1500 ppm.

[0108] (Comparative Example 2)

[0109] In a 1000 ml four-necked flask, 40.8 g of 4,4'-bis(chloromethyl)biphenyl (structural formula shown below) was placed.

[0110]

[0111] 4,4'-biphenol (structural formula below) 75.5 g,

[0112]

[0113] 120 g of diethylene glycol dimethyl ether was heated to 160°C under a nitrogen stream while stirring, and the mixture was allowed to react for 10 hours. Next, the mixture was set to 70°C, 280 g of diethylene glycol dimethyl ether and 129.5 g of chloromethylstyrene were added, and 100.0 g of 48% potassium hydroxide was added dropwise while the reaction was carried out. The absence of residual chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, neutralized, and washed with water to obtain a multifunctional vinyl resin g (vinyl resin E). The vinyl equivalent of the obtained vinyl resin E was 256 g / eq., the hydroxyl equivalent was 1500 g / eq., and the total chlorine was 1270 ppm.

[0114] (Comparative Example 3)

[0115] In a 1000 ml four-necked flask, 50.0 g of dihydroxydiphenylmethane (an isomer mixture consisting of 36.2% of 4,4'-dihydroxydiphenylmethane (the following structural formula), 46.6% of 2,4'-dihydroxydiphenylmethane, and 17.2% of 2,2'-dihydroxydiphenylmethane) was added.

[0116]

[0117] 400 g of methyl ethyl ketone and 80.1 g of chloromethyl styrene were heated to 60°C, and 29.5 g of potassium hydroxide dissolved in 88 g of methanol was added dropwise over 3 hours, and the mixture was reacted for 6 hours. After the reaction was completed, the mixture was filtered, the solvent was distilled off, and reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 95.4 g of a multifunctional vinyl resin (vinyl resin F). The vinyl equivalent of vinyl resin F was 217 g / eg., the hydroxyl equivalent was 17000 g / eg., and the total chlorine content was 400 ppm.

[0118] Examples 4 to 6, Comparative Examples 4 to 7

[0119] As the multifunctional vinyl compound, the vinyl compounds A to F obtained in Examples 1 to 3 and Comparative Examples 1 to 3 and the vinyl resin G (OPE-2ST: manufactured by Mitsubishi Gas Chemical Co., Ltd., vinyl equivalent: 590.0 g / eq, number average molecular weight 1187) were used, and the organic peroxide Perbutyl P (manufactured by NOF Corporation) as a curing accelerator (radical polymerization initiator) and ADK STAB AO-60 (manufactured by ADEKA Corporation) as an antioxidant were mixed in the proportions shown in Table 1 and dissolved in a solvent to prepare a uniform composition. The composition was applied to a PET film and dried at 130°C for 5 minutes to obtain a resin composition. The composition taken out from the PET film was sandwiched between a mirror plate and cured at 130°C for 15 minutes under reduced pressure and at 210°C for 80 minutes while applying a pressure of 2 MPa. The properties of the obtained cured product are shown in Table 1.

[0120] [Table 1]

[0121]

[0122] The polyfunctional vinyl compounds of Examples have higher thermal conductivity than those of Comparative Examples, and exhibit excellent physical properties such as a low dielectric constant and a low dielectric loss tangent.

[0123] Industrial Applicability

[0124] The polyfunctional vinyl compound of the present invention can be used as a material that can easily dissipate heat from electronic parts and wiring, which are electronic materials for high-speed communication equipment, and has a small signal loss.

Claims

1. A polyfunctional vinyl compound represented by the following general formula (1), In formula (1), R1 to R4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.

2. The multifunctional vinyl compound according to claim 1, wherein At least one of R1 to R4 is a methyl group or a phenyl group.

3. A polyfunctional vinyl composition comprising the polyfunctional vinyl compound according to claim 1 or 2 and a radical polymerization initiator as essential components.

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

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