Polyfunctional vinyl compound and composition and cured product from same

Abstract

The purpose of the present invention is to provide: a compound that not only has excellent solvent solubility but also has excellent heat resistance, thermal decomposition stability, thermal conductivity, and flame retardance and a superiorly low dielectric constant and low dielectric loss tangent; and a curable resin composition that contains the compound.　The present invention provides a polyfunctional vinyl compound that is represented by general formula (1). In formula (1), the X's are each independently a structure represented by formula (2), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH2)m-, m is a number from 3 to 10, inclusive, and n is a number from 0 to 15, inclusive.

Description

Polyfunctional vinyl compounds, their compositions, and cured products

[0001] The present invention relates to vinyl compounds, and more specifically to polyfunctional vinyl compounds with excellent solvent solubility useful as insulating materials for electrical and electronic components such as semiconductor encapsulants, laminates, and heat dissipation substrates, compositions thereof, and cured resin products obtained by curing them, which have excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy.

[0002] Printed circuit boards, encapsulants, and casting materials used in communication equipment are being actively researched to improve signal transmission speed in line with the increasing communication speed and volume. Electronic materials for such applications require materials that can reduce dielectric loss, and for printed circuit board applications, there is also a demand for curable resins that allow for multilayer construction.

[0003] On the other hand, electronic computing components that process such large amounts of data generate a lot of heat, and heat accumulation can cause malfunctions such as a decrease in the processing speed of the electronic computing components. Therefore, various techniques are known for cooling printed circuit boards appropriately using heat sinks, such as incorporating heat transfer materials such as copper coins and copper inlays (Patent Document 1), or making the shape of the filler material special (Patent Document 2). However, these methods are undesirable because they lead to increased weight and larger equipment.

[0004] Furthermore, in encapsulant compositions, methods have been employed to remove heat from electronic computing components by examining the types and amounts of various fillers to increase thermal conductivity. 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 an increase in viscosity during molding and a decrease in fluidity, resulting in impaired moldability. Therefore, simply increasing the content of inorganic fillers has its limitations.

[0005] Given the above background, methods for improving the thermal conductivity of a composition by increasing the thermal conductivity of the matrix resin itself have also been investigated. For example, liquid crystalline epoxy resins having rigid mesogenic groups and epoxy resin compositions using the same have been proposed (Patent Documents 5 and 6). However, aromatic diamine compounds are used as curing agents in these epoxy resin compositions, which limits the ability to increase the filling density of the inorganic filler and also presents problems in terms of electrical insulation. Furthermore, when aromatic diamine compounds are used, although the liquid crystalline properties of the cured product can be confirmed, the degree of crystallinity of the cured product is low, and it is not sufficient in terms of high thermal conductivity, low thermal expansion, and low hygroscopicity. Moreover, in order to exhibit liquid crystalline properties, it is necessary to apply a strong magnetic field to orient the molecules, which presents significant equipment constraints for widespread industrial use. In addition, in compounding systems with inorganic fillers, the thermal conductivity of the inorganic filler is overwhelmingly greater than that of the matrix resin, and even if the thermal conductivity of the matrix resin itself is increased, it does not contribute significantly to improving the thermal conductivity of the composite material, and a sufficient improvement in thermal conductivity has not been obtained.

[0006] Patent Document 7 discloses a polyfunctional vinyl resin having a biphenyl skeleton with four or more functions as a polyfunctional vinyl resin that achieves both high thermal conductivity and low dielectric loss tangent. However, it does not describe the solvent solubility of the polyfunctional vinyl resin or the polyvalent hydroxy resin used as its raw material, and does not mention at all the effect of residual polar groups and other impurities on the thermal conductivity.

[0007] JP 2009-170493, WO 2013 / 100172, JP 11-147936, JP 2002-309067, JP 11-323162, JP 9-118673, WO 2021-200414

[0008] The object of the present invention is to provide a polyfunctional vinyl composition useful for sealing electrical and electronic components, circuit board materials, etc., which yields a cured product with excellent solvent solubility, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy, and to provide a cured product thereof. Another object is to provide a polyfunctional vinyl compound used in this polyfunctional vinyl composition.

[0009] The inventors have conducted diligent research and found that a polyfunctional vinyl compound having a specific structure is expected to solve the above problems, and that its cured product exhibits effects on heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy.

[0010] In other words, the present invention is a polyfunctional vinyl compound represented by the following general formula (1). In formula (1), X is independently the structure shown in formula (2), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH ２ ) ｍ The negative sign indicates a value between 3 and 10, and n indicates a value between 0 and 15.

[0011] The polyfunctional vinyl compound X is preferably structured as shown in formula (2).

[0012] Furthermore, the present invention relates to a polyfunctional vinyl composition containing the above-mentioned polyfunctional vinyl compound and a radical polymerization initiator as essential components, and a polyfunctional vinyl cured product obtained by curing this polyfunctional vinyl composition.

[0013] The polyfunctional vinyl compound of the present invention exhibits excellent solvent solubility and is suitable for polyfunctional vinyl compositions and their cured products used in applications such as lamination, molding, casting, and bonding. Furthermore, the cured product 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.

[0014] This is the GPC chart for the hydroxy resin a obtained in Synthesis Example 1. This is the GPC chart for the polyfunctional vinyl resin A obtained in Example 1. This is the GPC chart for the polyfunctional vinyl compound F obtained in Example 6.

[0015] The present invention will be described in detail below. In this specification, polyfunctional vinyl compounds may be referred to as "polyfunctional vinyl resins," or simply as "vinyl compounds" or "vinyl resins."

[0016] The present invention relates to a polyfunctional vinyl compound represented by the following general formula (1). In formula (1), X is independently the structure shown in formula (2), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH ２ ) ｍ The negative sign indicates a value between 3 and 10, and n indicates a value between 0 and 15.

[0017] In the polyfunctional vinyl compound of the present invention, the substitution position of vinylbenzyl ether is not particularly limited.

[0018] n is the number of repetitions and represents a number from 0 to 15. Preferably, it is a mixture of components with different n values. The n value (average value) is at least 0.5 or higher, preferably 1.0 to 5.0, and more preferably 1.5 to 3.5. The polyfunctional vinyl resin of the present invention may be a compound with n=0 alone, or a mixture with a compound with n=0. In the case of a mixture, from the viewpoint of high thermal conductivity, the area % (GPC area %) measured by gel permeation chromatography should preferably be 60% or less for the n=0 component, and more preferably 50% or less.

[0019] X is independently the structure shown in formula (2), a benzonitrile structure, a sulfonyl structure, or -(CH ２ ) ｍ — indicates. These structures are not limited, but are derived from compounds having an X group, such as the dihalogen compounds having an X group described later. For example, they correspond to the remaining structure after two halogens are removed from the dihalogen compounds having an X group described later. —(CH ２ ) ｍ In the alkyl structure represented by -, m is the repeating number, and is a number from 3 to 10. More preferably, it is a number from 4 to 8. If it is less than 3, flexibility tends to be low and the crystallinity relaxation effect tends to be low. If it is greater than 10, the thermal conductivity and heat resistance of the cured product tend to decrease significantly. As indicated by "independently", the vinyl resin of formula (1) of the present invention can be a mixture in which each X has a different structure, and it is possible to adjust the high thermal conductivity, moldability and solvent solubility. When X has the structure shown in formula (2), the thermal conductivity of the cured product tends to improve.

[0020] A preferred structure is specifically a polyfunctional vinyl resin of the following formula (3), where X is the biphenyl-containing structure shown in formula (2). In formula (3), n is the same as n in formula (1).

[0021] The polyfunctional vinyl compound of the present invention has a preferred vinyl equivalent range of 100 to 450 g / eq., and a more preferred range of 150 to 300 g / eq. If the vinyl equivalent is smaller than this range, there is a concern that the reaction will be too rapid and difficult to control, and if it is larger than this range, there is a concern that the reactivity will decrease and it will be difficult to obtain a uniform cured product. The number average molecular weight Mn is preferably 200 to 2,000, more preferably 400 to 1,500.

[0022] The polyfunctional vinyl compounds of the present invention can be suitably obtained by reacting a hydroxy compound with an aromatic vinylizing agent such as chloromethylstyrene, as described later. However, if the amount of unreacted hydroxyl groups remaining is less than 5,000 g / eq., curing will be insufficient, resulting in reduced thermal conductivity and heat resistance. Furthermore, since hydroxyl groups are polar groups, their presence may hinder the reduction of dielectric constant and dielectric loss tangent. The hydroxyl group equivalent is preferably 5,000 g / eq. or more, more preferably 10,000 g / eq. or more. On the other hand, the chlorine component may be derived from the raw material chloromethylstyrene or from a halogen-based crosslinking agent. Similar to hydroxyl groups, if the chlorine component remains, there is a concern that it may hinder the reduction of dielectric constant and dielectric loss tangent, and that the inhibition of the curing reaction by polar groups may reduce thermal conductivity and heat resistance. The polyfunctional vinyl compounds of the present invention have a total chlorine content of preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and even more preferably 1,000 ppm or less.

[0023] The polyfunctional vinyl compound of the present invention is not limited as long as the structure represented by formula (1) can be obtained, but preferably it can be obtained by reacting a polyfunctional hydroxy compound (resin) represented by formula (4) with an aromatic vinylizing agent. In formula (4), X and n are the same as X and n in formula (1).

[0024] The polyfunctional hydroxy compound of formula (4) preferably has a hydroxyl group equivalent of 25 to 350 g / eq., more preferably 35 to 150 g / eq. The number average molecular weight Mn is preferably 100 to 1,500, more preferably 150 to 1,000. The polyfunctional hydroxy compound (phenolic compound) represented by formula (4) is not limited in terms of its manufacturing method as long as it has a predetermined structure, but it can be suitably obtained by reacting a polyvalent hydroxy compound with a dihalogen compound having an X group in the presence of a basic catalyst.

[0025] Here, the polyhydric hydroxy compounds that give the polyfunctional hydroxy compound (phenolic compound) represented by formula (4) are not limited, but examples include trihydroxybenzenes such as 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene, and 1,3,5-trihydroxybenzene.

[0026] Examples of dihalogen compounds having 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; diphenyl sulfone compounds such as 4,4'-dibromodiphenylsulfone and 4,4'-dichlorodiphenylsulfone; biphenyl compounds such as 4,4'-bishydroxymethylbiphenyl, 4,4'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4,4'-bismethoxymethylbiphenyl, and 4,4'-bisethoxymethylbiphenyl; and p-xylene chloride. A biphenyl structure is suitable as a crosslinking structure that contributes to high thermal conductivity, and it is preferable to use a biphenyl compound that gives a biphenyl structure. Among these, 4,4'-bischloromethylbiphenyl is particularly suitable as a crosslinking agent from the viewpoint of reactivity.

[0027] The polyfunctional vinyl compound (resin) of the present invention can be suitably obtained by reacting the aforementioned polyfunctional hydroxy compound (resin) with an aromatic vinylizing agent. For example, the vinyl compound of the present invention represented by formula (1) can be obtained by reacting the polyfunctional hydroxy compound represented by formula (4) with chloromethylstyrene. This reaction can be carried out in the same manner as well-known vinylization reactions. The mixing ratio is preferably 0.8 to 1.2 equivalents of the aromatic vinylizing agent (e.g., chloromethylstyrene) per 1.0 equivalent of the hydroxyl group, which is the functional group of the polyfunctional hydroxy compound. However, if the reactivity of the polyfunctional hydroxy compound is low, an excess amount of aromatic vinylizing agent may be added and removed after the reaction.

[0028] As aromatic vinylizing agents, halomethylstyrene, particularly chloromethylstyrene, is preferred. Other examples include bromomethylstyrene and its isomers. Regarding the substitution position of the halomethyl compound, for example, in the case of halomethylstyrene, the 4-position is preferred, and it is preferable that the 4-position constitutes 60% by weight or more of the total.

[0029] The reaction between a polyfunctional hydroxy compound and an aromatic vinylizing agent can be carried out without a solvent or in the presence of a solvent. The reaction can be carried out by adding the aromatic vinylizing agent to the polyfunctional hydroxy compound, adding a metal hydroxide, and removing the resulting metal salt by filtration or washing with water. Suitable solvents include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, and cyclohexanone. Methyl ethyl ketone is preferred from the viewpoint of reactivity. Specific examples of metal hydroxides include, but are not limited to, sodium hydroxide and potassium hydroxide.

[0030] The vinylization reaction preferably takes place at a temperature of 90°C or lower, more preferably 70°C or lower. At temperatures higher than this, thermal self-polymerization of the vinylbenzyl ether group proceeds, making reaction control difficult. Polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso and nitrone compounds, and oxygen may be used to suppress self-polymerization.

[0031] The reaction endpoint can be determined by tracking the remaining amount of halomethylstyrene as an aromatic vinyling agent using various chromatograms such as GPC, and the reaction rate can be adjusted by the type and amount of metal hydroxide, the rate of addition, the solid content concentration, etc.

[0032] The polyfunctional vinyl compound of the present invention can be cured on its own, but it is also suitable for use as a polyfunctional vinyl composition containing various additives. In particular, it can be cured by adding radical polymerization initiators such as azo compounds and organic peroxides to accelerate curing.

[0033] The polyfunctional vinyl composition of the present invention comprises a polyfunctional vinyl compound and a radical polymerization initiator as essential components, but other vinyl compounds and other thermosetting resins can be added, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoxazine resins.

[0034] To increase thermal conductivity, the polyfunctional vinyl composition may contain inorganic fillers such as glass cloth, carbon fiber, alumina, or boron nitride.

[0035] For the purpose of providing a higher thermal conductivity, the inorganic filler should preferably have a high thermal conductivity. Preferably, it should be 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, it is desirable that at least a portion of the inorganic filler, preferably 50 wt% or more, has a thermal conductivity of 20 W / m·K or higher. Then, the preference for the average thermal conductivity of the inorganic filler as a whole increases in the order of 20 W / m·K or higher, 30 W / m·K or higher, and 50 W / m·K or higher.

[0036] Examples of inorganic fillers with such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, alumina, and magnesium oxide.

[0037] For the purpose of improving the adhesion and the handling work of the composition, various additives may be added to the polyfunctional vinyl composition. Examples thereof include silane coupling agents, defoaming agents, internal mold release agents, flow regulators, and the like.

[0038] The polyfunctional vinyl cured product of the present invention is obtained by curing the aforementioned polyfunctional vinyl compound or polyfunctional vinyl composition. The method for forming the cured product is not limited. For example, the polyfunctional vinyl compound or polyfunctional vinyl composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., and impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heat-dried to obtain a prepreg, which can be hot-pressed and molded to obtain a cured product.

[0039] Further, in some cases, it can be made into a laminate by coating on a sheet-like material such as a copper foil, stainless steel foil, polyimide film, polyester film, etc., and a cured product can also be obtained by hot-pressing and molding the resin sheet obtained by heat-drying.

[0040] Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited thereto. Unless otherwise specified, "parts" represents parts by weight, and "%" represents % by weight. Also, the measurement methods were measured by the following methods respectively.

[0041] 1) OH equivalent (hydroxyl equivalent) Using a potentiometric titrator, 1,4-dioxane was used as a solvent, acetylated with 1.5 mol / L acetyl chloride, the excess acetyl chloride was decomposed with water, and titrated with 0.5 mol / L potassium hydroxide.

[0042] 2) Vinyl equivalent The sample was reacted with Wijs solution (iodine monochloride solution), left in the dark, and then the excess iodine chloride was reduced to iodine, and the iodine content was titrated with sodium thiosulfate to calculate the iodine value. The iodine value was converted to vinyl equivalent.

[0043] 3) After dissolving 1.0 g of the total chlorine 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 measurement was carried out by potentiometric titration with 0.002N-AgNO ３ aqueous solution.

[0044] 4) A GPC measurement main body (manufactured by Tosoh Corporation, HLC-8220GPC) equipped with four columns (manufactured by Tosoh Corporation, TSKgel SuperMultiporeHZ-N) in series was used, and the column temperature was set to 40 °C. Tetrahydrofuran (THF) was used as the eluent, the flow rate was 0.35 mL / min, and a differential refractive index detector was used as the detector. For the measurement sample, 50 μL of a solution obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering it through a microfilter was used. For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.

[0045] 5) Solvent solubility (precipitation temperature) 2 g of the resin composition and 1 g of methyl ethyl ketone were weighed into a sample bottle, heated and dissolved, and then the temperature was gradually decreased in a thermostatic bath, and the temperature in the bath at which the resin precipitated was measured. The higher the precipitation temperature (°C), the poorer the solvent solubility.

[0046] 6) Glass transition point (Tg) The Tg was determined by a thermomechanical measuring device (EXSTAR TMA / 7100 manufactured by SII NanoTechnology Inc.) under the condition of a heating rate of 10 °C / min.

[0047] 7) 5% weight loss temperature (Td5), char yield The 5% weight loss temperature (Td5) was measured using a thermogravimetry / differential thermal analyzer (EXSTAR TG / DTA7300 manufactured by SII NanoTechnology Inc.) under a nitrogen atmosphere at a heating rate of 10 °C / min. Also, the weight loss at 700 °C was measured and calculated as the char yield. [[ID= (15)]] [[ID= (16)]]

[0048] [[ID= (17)]] 8) Thermal conductivity The thermal conductivity was measured by the transient hot wire method using an LFA447 type thermal conductivity meter manufactured by NETZSCH. [[ID= (18)]] [[ID=(19)]]

[0049] [[ID=(20)]] 9) Dielectric constant and dielectric tangent Measured according to JIS C 2138 standard. The measurement frequency was shown as a value of [1] GHz.

[0050] (Synthesis Example 1) In a 1000 ml four-necked flask, 100.9 g (0.80 mol) of pyrogallol (1,2,3-trihydroxybenzene, see structural formula below) 350 g of N-methyl-2-pyrrolidone and 41.5 g (0.3 mol) of potassium carbonate were charged and heated to 120°C under a nitrogen atmosphere while stirring. Then, 50.2 g (0.2 mol) of 4,4'-bis(chloromethyl)biphenyl (structural formula below) was added. The reaction was carried out at 145°C for 6 hours. After neutralizing the reaction solution with 34.0 g of acetic acid, N-methyl-2-pyrrolidone was removed by distillation under reduced pressure. After dissolving the product with 350 mL of methyl isobutyl ketone, the resulting salt was removed by washing with water. Subsequently, methyl isobutyl ketone was removed by vacuum distillation to obtain 129.7 g of hydroxy resin a represented by formula (4). The hydroxyl group equivalent of the obtained hydroxy resin a was 105 g / eq., the number average molecular weight was 290, and the GPC area % for n≧1 was 69.3% (for n=0 was 30.7%). The GPC chart of the obtained hydroxy resin a is shown in Figure 1.

[0051] (Synthesis Example 2) 35.0 g (0.20 mol) of p-xylylene chloride (structural formula below) instead of 4,4'-bis(chloromethyl)biphenyl. Except for the use of [specific compound], the same procedure as in Synthesis Example 1 was followed to obtain 111.6 g of hydroxy resin b. The hydroxyl group equivalent of the obtained hydroxy resin b was 82 g / eq., the number-average molecular weight was 270, and the GPC area percentage was 61.1% for n≧1 (38.9% for n=0).

[0052] (Synthesis Example 3) 34.4 g (0.20 mol) of 2,6-dichlorobenzonitrile (structural formula below) instead of 4,4'-bis(chloromethyl)biphenyl. Except for the use of [specific compound], the same procedure as in Synthesis Example 1 was followed to obtain 107.4 g of hydroxy resin c. The hydroxyl group equivalent of the obtained hydroxy resin c was 80 g / eq., the number-average molecular weight was 260, and the GPC area percentage was 60.9% for n≧1 (39.1% for n=0).

[0053] (Synthesis Example 4) 57.4 g (0.20 mol) of 4,4'-dichlorodiphenylsulfone (structural formula below) instead of 4,4'-bis(chloromethyl)biphenyl. Except for the use of [specific compound], the same procedure as in Synthesis Example 1 was followed to obtain 129.3 g of hydroxy resin d. The hydroxyl group equivalent of the obtained hydroxy resin d was 127 g / eq., the number-average molecular weight was 370, and the GPC area percentage was 64.5% for n≧1 (35.5% for n=0).

[0054] (Synthesis Example 5) 43.2 g (0.20 mol) of 1,4-dibromobutane (structural formula below) instead of 4,4'-bis(chloromethyl)biphenyl. Except for the use of [specific compound], the same procedure as in Synthesis Example 1 was followed to obtain 98.3 g of hydroxy resin e. The hydroxyl group equivalent of the obtained hydroxy resin e was 51 g / eq., the number-average molecular weight was 210, and the GPC area percentage was 65.7% for n≧1 (34.3% for n=0).

[0055] (Example 1) 52.5 g (0.50 equivalent) of hydroxy resin a obtained in Synthesis Example 1, 420 g of methyl ethyl ketone, and 91.6 g (0.60 equivalent) of 4-(chloromethyl)styrene (structural formula below) were placed in a 1000 ml four-necked flask. The mixture was then heated to 60°C, and 33.7 g of potassium hydroxide dissolved in 101.0 g of methanol was added dropwise over 3 hours, followed by a further reaction for 6 hours. After the reaction was complete, the mixture was filtered, the solvent was removed by distillation, reprecipitation was performed with methanol, and the mixture was washed with a large amount of water. 82.9 g of polyfunctional vinyl resin was obtained by vacuum drying (vinyl resin A). The vinyl equivalent of vinyl resin A was 220 g / eq., the hydroxyl group equivalent was 12000 g / eq., the total chlorine content was 650 ppm, the number-average molecular weight was 720, and the GPC area percentage for n≧1 was 71.4% (n=0 was 28.6%). The GPC chart of the obtained vinyl resin A is shown in Figure 2.

[0056] (Example 2) The same procedure as in Example 1 was followed, except that 41.0 g (0.50 equivalents) of hydroxy resin b obtained in Synthesis Example 2 was used instead of hydroxy resin a, to obtain 76.2 g of polyfunctional vinyl resin (vinyl resin B). The vinyl equivalent of vinyl resin B was 200 g / eq., the hydroxyl group equivalent was 14000 g / eq., the total chlorine was 500 ppm, the number average molecular weight was 500, and the GPC area % for n≧1 was 64.1% (for n=0 was 35.9%).

[0057] (Example 3) The same procedure as in Example 1 was carried out, except that 40.0 g (0.50 equivalents) of hydroxy resin c obtained in Synthesis Example 3 was used instead of hydroxy resin a, to obtain 71.5 g of polyfunctional vinyl resin (vinyl resin C). The vinyl equivalent of vinyl resin C was 195 g / eq., the hydroxyl group equivalent was 11000 g / eq., the total chlorine was 800 ppm, the number average molecular weight was 490, and the GPC area % for n≧1 was 63.9% (n=0 was 36.1%).

[0058] (Example 4) The same procedure as in Example 1 was followed, except that 63.5 g (0.50 equivalents) of hydroxy resin d obtained in Synthesis Example 4 was used instead of hydroxy resin a, to obtain 87.5 g of polyfunctional vinyl resin (vinyl resin D). The vinyl equivalent of vinyl resin D was 250 g / eq., the hydroxyl group equivalent was 11000 g / eq., the total chlorine was 700 ppm, the number average molecular weight was 920, and the GPC area % for n≧1 was 67.0% (n=0 was 33.0%).

[0059] (Example 5) The same procedure as in Example 1 was carried out, except that 25.5 g (0.50 equivalents) of hydroxy resin e obtained in Synthesis Example 5 was used instead of hydroxy resin a, to obtain 58.5 g of polyfunctional vinyl resin (vinyl resin E). The vinyl equivalent of vinyl resin E was 167 g / eq., the hydroxyl group equivalent was 13000 g / eq., the total chlorine was 700 ppm, the number average molecular weight was 470, and the GPC area % for n≧1 was 68.9% (n=0 was 31.1%).

[0060] (Example 6) The same procedure as in Example 1 was carried out, except that 21.0 g (0.50 equivalents) of pyrogallol was used instead of hydroxy resin a, to obtain 56.9 g of a polyfunctional vinyl compound (vinyl compound F). The vinyl equivalent of vinyl compound F was 160 g / eq., the hydroxyl group equivalent was 16000 g / eq., the total chlorine was 700 ppm, the number average molecular weight was 450, and the GPC area % for n≧1 was 2.6% (for n=0 was 97.4%). The GPC chart of the obtained vinyl compound F is shown in Figure 3.

[0061] (Comparative Example 1) Instead of hydroxy resin a, 51.0 g (0.50 equivalent) of 1,1,1-tris(p-hydroxyphenyl)ethane (structural formula below) was used. Except for the use of [specific ingredient], the same procedure as in Example 1 was followed to obtain 97.8 g of vinyl compound (vinyl compound G). The vinyl equivalent of vinyl compound G was 214 g / eq., the hydroxyl group equivalent was 7000 g / eq., and the total chlorine content was 1500 ppm.

[0062] (Comparative Example 2) 40.8 g of 4,4'-bis(chloromethyl)biphenyl (structural formula below) was placed in a 1000 ml four-necked flask. 4,4'-biphenol (structural formula below) 75.5 g, 120 g of diethylene glycol dimethyl ether was charged and reacted under a nitrogen stream, stirring until the temperature rose to 160°C for 10 hours. Subsequently, the temperature was reduced to 70°C, 280 g of diethylene glycol dimethyl ether and 129.5 g of chloromethylstyrene were added, and the reaction was carried out dropwise while adding 100.0 g of 48% potassium hydroxide. Gas chromatography was used to confirm that no residual chloromethylstyrene remained, and the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, neutralized, and washed with water to obtain 172 g of polyfunctional vinyl resin (vinyl resin H). The vinyl equivalent of the obtained vinyl resin H was 256 g / eq., the hydroxyl group equivalent was 1500 g / eq., and the total chlorine content was 1270 ppm.

[0063] (Comparative Example 3) 50.0 g of dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane (structural formula below): 36.2%, 2,4'-dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%) was placed in a 1000 ml four-necked flask. 400 g of methyl ethyl ketone and 80.1 g of chloromethylstyrene were added, the temperature was raised to 60°C, and 29.5 g of potassium hydroxide dissolved in 88 g of methanol was added dropwise over 3 hours, followed by a further reaction for 6 hours. After the reaction was complete, the mixture was filtered, the solvent was removed by distillation, reprecipitation was performed with methanol, and the mixture was washed with a large amount of water. 95.4 g of vinyl compound I was obtained by vacuum drying (Vinyl Compound I). The vinyl equivalent of Vinyl Compound I was 217 g / eq., the hydroxyl group equivalent was 17000 g / eq., and the total chlorine content was 400 ppm.

[0064] Examples 7-12, Comparative Examples 4-7: As polyfunctional vinyl compounds, vinyl resins or vinyl compounds A-I obtained in Examples 1-6 and Comparative Examples 1-3, and vinyl resin J (OPE-2ST: manufactured by Mitsubishi Gas Chemical Company, Inc., vinyl group equivalent: 590.0 g / eq., number average molecular weight 1187) were used. Perbutyl P (manufactured by NOF Corporation), an organic peroxide, was used as a curing accelerator, and ADEKA stab AO-60 (manufactured by ADEKA Corporation) was used as an antioxidant. These were mixed in the proportions shown in Table 1 and dissolved in a solvent to obtain a homogeneous composition. This composition was applied to a PET film and dried at 130°C for 5 minutes to obtain a resin composition. The composition removed from the PET film was sandwiched between mirror plates and cured under reduced pressure at 130°C for 15 minutes and at 210°C for 80 minutes under a pressure of 2 MPa. The properties of the obtained cured product are shown in Table 1.

[0065] The polyfunctional vinyl compound in the example exhibited superior physical properties compared to the comparative example, including high thermal conductivity, low dielectric constant, and low dielectric loss tangent.

[0066]

[0067] The polyfunctional vinyl compound of the present invention is useful as an electronic material for high-speed communication equipment because it easily dissipates heat from electronic components and wiring and has low signal loss.

Claims

1. A polyfunctional vinyl compound represented by the following general formula (1). In formula (1), X is independently the structure shown in formula (2), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH ２ ) ｍ The negative sign indicates a value between 3 and 10, and n indicates a value between 0 and 15.

2. The polyfunctional vinyl compound according to claim 1, wherein X has the structure shown in formula (2).

3. A polyfunctional vinyl composition containing the polyfunctional vinyl compound described in claim 1 and a radical polymerization initiator as essential components.

4. A polyfunctional vinyl cured product obtained by curing the polyfunctional vinyl composition described in claim 3.

Images