Polyfunctional vinyl compound, composition thereof, and cured product

Abstract

To provide: a compound excellent in solvent solubility and also excellent in heat resistance, thermal decomposition stability, thermal conductivity, low permittivity, low dielectric loss tangent, and flame retardancy; and a curable resin composition containing this compound.SOLUTION: Provided is a polyfunctional vinyl compound represented by the general formula (1) in the figure. In the formula (1), each of R1 to R6 independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, each X independently represents a biphenyl-containing structure, a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or a -(CH2)m- structure, m represents a number from 3 to 10, and n represents a number from 1 to 15.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Printed circuit boards, encapsulants, injection molded materials, etc. used in communication equipment are being actively studied for high-speed communication technologies to improve signal transmission speed due to the increasing communication speed and volume. For electronic materials in such applications, materials that can reduce dielectric loss are required, and in the case of printed circuit board applications, curable resins that enable multilayer formation are also required.

[0003] On the other hand, there is a lot of heat generated from electronic arithmetic components that process such a large amount of information, and problems such as a decrease in the processing speed of electronic arithmetic components occur due to heat accumulation. Therefore, in printed circuit boards, methods such as incorporating heat transfer members such as copper coins and copper inlays as a technique for appropriately cooling with a heat sink (Patent Document 1), and making the shape of the filler to be blended special (Patent Document 2) are known. However, such methods lead to an increase in weight and the size of the device, which is not preferable.

[0004] In addition, in the encapsulant composition, as a method for increasing the thermal conductivity, a method of removing heat from electronic arithmetic components by examining the type and amount of various fillers is taken. For example, attempts have been made to contain inorganic fillers such as crystalline silica, silicon nitride, aluminum nitride, and spherical alumina powder having a high thermal conductivity (Patent Documents 3 and 4). However, when the content rate of the inorganic filler is increased, the fluidity decreases along with an increase in viscosity during molding, and a problem occurs that the moldability is impaired. Therefore, there is a limit to simply increasing the content rate of the inorganic filler.

[0005] From the above background, methods for improving the thermal conductivity of the composition by increasing the thermal conductivity of the matrix resin itself have also been studied. For example, liquid crystalline epoxy resins having a rigid mesogenic group and epoxy resin compositions using the same have been proposed (Patent Documents 5 and 6). However, as the curing agent used in these epoxy resin compositions, aromatic diamine compounds are used. There are limitations in increasing the filling ratio of the inorganic filler, and there are also problems in terms of electrical insulation. In addition, when an aromatic diamine compound is used, although the liquid crystallinity of the cured product can be confirmed, the crystallinity of the cured product is low, and it is not sufficient in terms of high thermal conductivity, low thermal expansion, low moisture absorption, etc. Furthermore, in order to exhibit liquid crystallinity, it is necessary to apply a strong magnetic field to orient the molecules, and there are significant equipment constraints for wide industrial use. Also, in the blending system with the inorganic filler, the thermal conductivity of the inorganic filler is overwhelmingly larger than that of the matrix resin. Even if the thermal conductivity of the matrix resin itself is increased, there is a reality that it does not greatly contribute to the improvement of the thermal conductivity of the composite material, and a sufficient thermal conductivity improvement effect has not been obtained.

[0006] Patent Document 7 discloses a polyfunctional vinyl resin having a biphenyl skeleton as a polyfunctional vinyl resin that achieves both high thermal conductivity and low dielectric tangent. However, the solvent solubility of the polyfunctional vinyl resin and the polyhydric hydroxy resin as its raw material is not described, and no mention is made of the influence of impurities such as remaining polar groups on the thermal conductivity.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

[0008] An object of the present invention is to provide a vinyl composition useful for encapsulating electrical and electronic parts, circuit board materials, etc., which has excellent solvent solubility and gives a cured product excellent in heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, and to provide a cured product thereof. Another object is to provide a vinyl compound used in this vinyl composition. [Means for Solving the Problems]

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

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

[0011] X of the above polyfunctional vinyl compound preferably has the structure represented by formula (2).

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

Advantages of the Invention

[0013] The polyfunctional vinyl compound of the present invention has excellent solvent solubility and is suitable for vinyl resin compositions and their cured products used in applications such as lamination, molding, casting, and adhesion. And this cured product is also excellent in heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric tangent, and flame retardancy, so it is suitable for encapsulation of electrical and electronic components, circuit board materials, etc.

Brief Description of the Drawings

[0014]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0015] Hereinafter, the present invention will be described in detail.

[0016] The present invention is a polyfunctional vinyl compound represented by the following general formula (1).

Chemical formula

Chemical formula

[0017] R1 to R6 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. As the monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkyl group is preferable from the viewpoint of solvent solubility, and an aromatic group is preferable from the viewpoints of heat resistance and high thermal conductivity. An alkyl group having more than 6 carbon atoms makes it difficult to suppress molecular motion, and there is also concern about a decrease in compatibility. In addition, a bulky structure with a large steric hindrance has a concern about solvent solubility due to an increase in crystallinity. A more preferable structure is a hydrogen atom, a methyl group or a phenyl group. R1 to R6 may be a mixture of different structures.

[0018] In the polyfunctional vinyl compound of the present invention, the substitution position of vinyl benzyl ether is not particularly limited, but from the viewpoints of thermal conductivity and heat resistance, it is preferably in the para position with respect to the methine group connecting three aromatic rings. Particularly preferably, all three vinyl benzyl ethers are in the para position.

[0019] n is the number of repetitions and represents a number from 1 to 15. Preferably, it is a mixture of components having different n values. As the n value (average value), 1.0 to 5.0 is preferable, and more preferably 1.5 to 3.5. The polyfunctional vinyl resin of the present invention excludes the case of the n = 0 compound alone, but may be a mixture with the n = 0 compound. However, in terms of area% (GPC area%) measured by gel permeation chromatography, the n = 0 component is preferably 60% or less, and more preferably 50% or less.

[0020] X is independently a structure represented by formula (2), a benzonitrile structure, a sulfonyl structure, or -(CH2) m -. Regarding the alkyl structure represented by -(CH2)m-, m is the number of repetitions and represents a number from 3 to 10. More preferably, it is a number from 4 to 8. If it is less than 3, the flexibility is low and the effect of relaxing crystallinity tends to be low. If it is more than 10, the thermal conductivity and heat resistance of the cured product tend to decrease significantly. The vinyl resin of formula (1) of the present invention can be a mixture of structures where each X is different, as "independently", and it is possible to adjust 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.

[0021] As a preferred structure, specifically, a polyfunctional vinyl resin of the following formula (3) where X is a biphenyl-containing structure shown in formula (2) can be exemplified.

Chemical formula

[0022] For the polyfunctional vinyl compound of the present invention, the preferred range of vinyl equivalent is 150 to 450 g / eq, and the more preferred range is 200 to 350 g / eq. When it is smaller than this range, reaction control becomes difficult because it reacts rapidly, and when it is larger than this range, there is a concern that the reactivity decreases and it becomes difficult to obtain a uniform cured product. The number average molecular weight Mn is preferably 500 to 2,000, more preferably 700 to 1,500.

[0023] The polyfunctional vinyl compound of the present invention can be obtained by reacting a hydroxy compound with chloromethylstyrene. However, when the amount of unreacted hydroxyl groups remaining is less than 5000 g / eq, curing becomes insufficient, and the thermal conductivity and heat resistance decrease. Also, since the hydroxyl group is a polar group, there is a concern that its remaining inhibits the reduction of the dielectric constant and the dielectric loss tangent. The hydroxyl equivalent is preferably 5,000 g / eq or more, more preferably 10,000 g / eq or more. On the one hand, the chlorine component is derived from chloromethylstyrene as a raw material or from a halogen-based crosslinking agent. When the chlorine component remains as in the case of the hydroxyl group, there is a concern that it may inhibit the reduction of the dielectric constant and the dielectric loss tangent, and there is a concern that it may reduce the thermal conductivity and heat resistance due to the inhibition of the curing reaction by the polar group. The total chlorine content is preferably 5000 ppm or less, more preferably 3000 ppm or less, and still more preferably 1000 ppm or less.

[0024] The polyfunctional vinyl compound of the present invention can be obtained by reacting a polyfunctional hydroxy compound (resin) represented by formula (4) with an aromatic vinylating agent. R1 to R6, n, and X are the same as those in the vinyl compound of formula (1).

Chemical formula

[0025] The polyfunctional hydroxy compound of formula (4) preferably has a hydroxyl equivalent of 100 to 350 g / eq, more preferably 120 to 250 g / eq. The number average molecular weight Mn is preferably 500 to 1,500. The polyfunctional hydroxy compound (phenolic compound) represented by formula (4) is not limited in its production method as long as it has a predetermined structure, but can be preferably obtained by reacting a trifunctional trihydroxy compound with a dihalogen compound having an X group in the presence of a basic catalyst. In this case, examples of the trifunctional trihydroxy compound include 4,4’,4”-trihydroxytriphenylmethane, and 4,4’,4”-trihydroxytriphenylmethane may have one or more hydrocarbon groups such as a methyl group or a phenyl group as a substituent. Examples of the dihalogen compound having an X group include dihalogenonitrile compounds such as 2,4-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,6-dichlorobenzonitrile, 3,5-dichlorobenzonitrile, 2,4-dibromobenzonitrile, 2,5-dibromobenzonitrile, 2,6-dibromobenzonitrile, 3,5-dibromobenzonitrile, etc., dihalogenoalkyl compounds such as 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, etc., 4,4'-dibromodiphenyl sulfone, 4,4'-dichlorodiphenyl sulfone, 4,4'-bishydroxymethylbiphenyl, 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 4,4'-bis(methoxymethyl)biphenyl, 4,4'-bis(ethoxymethyl)biphenyl, p-xylene dichloride, and the like. As the crosslinked structure contributing to high thermal conductivity, a biphenyl structure is suitable, and 4,4'-bis(chloromethyl)biphenyl is particularly suitable as a crosslinking agent in terms of reactivity.

[0026] The trifunctional trihydroxy compound can be obtained by polycondensation of a phenol compound and an aromatic aldehyde. The reaction may use an acid catalyst, for example, acetic acid, oxalic acid, sulfuric acid, hydrochloric acid, phenolsulfonic acid, p-toluenesulfonic acid, zinc acetate, manganese acetate, etc. These acid catalysts can be used alone or in combination of two or more. Among these acid catalysts, sulfuric acid and p-toluenesulfonic acid are preferred in terms of excellent activity. The acid catalyst may be added before the reaction or during the reaction.

[0027] When polycondensing a phenol compound and an aromatic aldehyde to obtain a trifunctional trihydroxy compound, the reaction temperature is in the range of 20 to 140 °C, preferably in the range of 80 to 110 °C.

[0028] When polycondensing a phenolic compound and an aromatic aldehyde to obtain a trifunctional trihydroxy compound, the charging ratio of the phenolic compound / aromatic aldehyde is in the range of 1 / 0.1 to 1 / 0.5 in terms of molar ratio, because the phenolic compound after the reaction can be easily removed by reprecipitation or the like. More preferably, it is in the range of 1 / 0.3 to 1 / 0.5.

[0029] The polyfunctional vinyl compound (resin) of the present invention can be suitably obtained by reacting a polyfunctional hydroxy compound (resin) with an aromatic vinylating agent. For example, the vinyl compound of the present invention represented by the above formula (1) can be obtained by reacting the polyfunctional hydroxy compound represented by the above formula (4) with chloromethylstyrene. This reaction can be carried out in the same manner as a well-known vinylation reaction. The blending ratio is preferably 0.8 to 1.2 equivalents of an aromatic vinylating agent (for example, chloromethylstyrene) with respect to 1.0 equivalent of the hydroxyl group which is a functional group of the polyfunctional hydroxy compound. However, when the reactivity of the polyfunctional hydroxy compound is low, it is advisable to charge an excessive amount of the aromatic vinylating agent and remove it after the reaction.

[0030] As the aromatic vinylating agent, halomethylstyrene, particularly chloromethylstyrene, is preferred. Others include bromomethylstyrene and its isomers, those having substituents, etc. Regarding the substitution position of the halomethyl compound, for example, in the case of halomethylstyrene, the 4-position is preferred, and it is preferred that the 4-position isomer is 60% by weight or more of the whole.

[0031] The reaction between the polyfunctional hydroxy compound and the aromatic vinylating agent can be carried out without a solvent or in the presence of a solvent. The aromatic vinylating agent is added to the hydroxy compound, a metal hydroxide is added to carry out the reaction, and the produced metal salt can be removed by methods such as filtration or washing with water to enable the reaction. Solvents include, but are not limited to, methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc. From the perspective of reactivity, methyl ethyl ketone is preferred. Specific examples of metal hydroxides include, but are not limited to, sodium hydroxide, potassium hydroxide, etc.

[0032] The vinylation reaction is preferably carried out at a temperature of 90 °C or lower, more preferably 70 °C or lower. When the temperature is higher than this, self-polymerization of the vinyl benzyl ether group due to heat proceeds and reaction control becomes difficult. Polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitrosos, nitrone compounds, oxygen, etc. may be used to suppress self-polymerization.

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

[0034] The polyfunctional vinyl compound of the present invention can be cured alone, but it is also preferably used as a polyfunctional vinyl composition blended with various additives. In particular, for curing acceleration, radical polymerization initiators such as azo compounds and organic peroxides can be blended for curing.

[0035] The polyfunctional vinyl composition of the present invention has a polyfunctional vinyl compound and a radical polymerization initiator as essential components, but other vinyl compounds and other thermosetting resins can be blended, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, benzoxazine resins, etc.

[0036] To increase the thermal conductivity, for example, inorganic fillers such as glass cloth, carbon fiber, alumina, boron nitride, etc. may be blended.

[0037] For the purpose of imparting a higher thermal conductivity, the inorganic filler preferably has a higher thermal conductivity. Preferably, it is 20 W / m·K or more, more preferably 30 W / m·K or more, and still more preferably 50 W / m·K or more. And at least a part of the inorganic filler, preferably 50 wt% or more, preferably has a thermal conductivity of 20 W / m·K or more. And the average thermal conductivity of the entire inorganic filler preferably improves in the order of 20 W / m·K or more, 30 W / m·K or more, and 50 W / m·K or more.

[0038] Examples of such 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, magnesium oxide, etc.

[0039] For the improvement of adhesion and the improvement of the handling operation of the composition, various additives may be added, such as silane coupling agents, defoaming agents, internal release agents, flow regulators, etc.

[0040] The polyfunctional vinyl compound or polyfunctional vinyl composition of the present invention can also be dissolved in solvents such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., impregnated into substrates such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heat-dried to obtain a prepreg, and then heat-press formed to obtain a cured product.

[0041] Also, in some cases, it can be made into a laminate by coating on a sheet-like material such as copper foil, stainless steel foil, polyimide film, polyester film, etc., and a cured product can also be obtained by heat-press forming the resin sheet obtained by heat-drying.

Examples

[0042] 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 wt%. Also, the measurement methods were measured by the following methods respectively.

[0043] 1) OH equivalent (equivalent of hydroxyl group) Using a potentiometric titration apparatus, acetylated with 1.5 mol / L acetyl chloride using 1,4-dioxane as a solvent, decomposed the excess acetyl chloride with water, and titrated with 0.5 mol / L potassium hydroxide.

[0044] 2) Vinyl equivalent Reacted the sample with Wijs solution (iodine monochloride solution), left it in the dark, then reduced the excess iodine chloride to iodine, and titrated the iodine content with sodium thiosulfate to calculate the iodine value. The iodine value was converted to vinyl equivalent.

[0045] 3) Total chlorine After dissolving 1.0 g of the sample in 25 ml of butyl carbitol, added 25 ml of 1N-KOH propylene glycol solution, heated under reflux for 10 minutes, cooled to room temperature, further added 100 ml of 80% acetone water, and measured by potentiometric titration with 0.002N-AgNO3 aqueous solution.

[0046] 4) GPC measurement Used the one equipped with columns (4 TSKgel SuperMultipore HZ-N columns manufactured by Tosoh Corporation) in series on the main body (HLC-8220GPC manufactured by Tosoh Corporation), and set the column temperature to 40 °C. Also, used tetrahydrofuran (THF) as the eluent, set the flow rate to 0.35 mL / min, and used a differential refractive index detector as the detector. For the measurement sample, 50 μL of the sample obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering with a microfilter was used. For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.

[0047] 5) Solvent solubility (precipitation temperature) Weighed 2 g of the resin and 1 g of methyl ethyl ketone into a sample bottle, dissolved them by heating, then gradually lowered the temperature in a constant temperature bath, and measured the temperature in the bath at which the resin precipitated. The higher the precipitation temperature (°C), the poorer the solvent solubility.

[0048] 6) Glass transition temperature (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.

[0049] 7) 5% weight loss temperature (Td5), char yield Using a thermogravimetric / differential thermal analyzer (EXSTAR TG / DTA7300 manufactured by SII NanoTechnology), the 5% weight loss temperature (Td5) was measured 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.

[0050] 8) Thermal conductivity The thermal conductivity was measured by the transient hot wire method using an LFA447 type thermal conductivity meter manufactured by NETZSCH.

[0051] 9) Dielectric constant and dielectric tangent The measurement was carried out in accordance with JIS C 2138 standard. The measurement frequency was shown as a value of 1 GHz.

[0052] (Synthesis Example 1) In a 1000 ml four-necked flask, 140.3 g (0.48 mol) of 4,4’,4”-trihydroxytriphenylmethane (the following structural formula),

Chemical formula

Chemical formula

[0053] (Synthesis Example 2) The same operations as in Synthesis Example 1 were carried out except that the amount of 4,4’,4”-trihydroxytriphenylmethane used was 116.9 g (0.40 mol), and 142.5 g of hydroxy resin b was obtained. The hydroxyl equivalent of the obtained hydroxy resin b was 205 g / eq., Mn was 980, and the area percentage of n≥1 species in GPC was 80.0% (the area percentage of n = 0 species was 20.0%).

[0054] (Synthesis Example 3) Instead of 4,4’-bis(chloromethyl)biphenyl, 27.5 g (0.16 mol) of 2,6-dichlorobenzonitrile (the following structural formula)

Chemical formula

[0055] (Synthesis Example 4) Instead of 4,4’-bis(chloromethyl)biphenyl, 45.9 g (0.16 mol) of 4,4’-dichlorodiphenyl sulfone (the following structural formula)

Chemical formula

[0056] (Synthesis Example 5) Instead of 4,4'-bis(chloromethyl)biphenyl, 36.8 g (0.16 mol) of 1,4-dibromobutane (the following structural formula) [Chemical formula] The same procedure as in Synthesis Example 1 was carried out except that [used substance] was used, and 147.2 g of hydroxy resin e was obtained. The hydroxyl equivalent of the obtained hydroxy resin e was 159 g / eq., Mn was 560, and the proportion of the n≥1 species was 52.7% (the n = 0 species was 47.3%) in terms of GPC area%.

[0057] (Synthesis Example 6) Instead of 4,4'-bis(chloromethyl)biphenyl, 28.0 g (0.16 mol) of p-xylene dichloride (the following structural formula) [Chemical formula] The same procedure as in Synthesis Example 1 was carried out except that [used substance] was used, and 152.1 g of hydroxy resin f was obtained. The hydroxyl equivalent of the obtained hydroxy resin f was 177 g / eq., Mn was 960, and the proportion of the n≥1 species was 71.9% (the n = 0 species was 28.1%) in terms of GPC area%.

[0058] (Example 1) In a 1000 ml four-necked flask, 56.4 g (0.30 equivalent) of the hydroxy resin a obtained in Synthesis Example 1, 500 g of methyl ethyl ketone, and 54.9 g (0.36 equivalent) of 4-(chloromethyl)styrene (the following structural formula) [Chemical formula] Add, heat up to 60 °C, and dropwise add 20.2 g of potassium hydroxide dissolved in 60.6 g of methanol over 3 hours, and react for another 6 hours. After completion of the reaction, filter, distill off the solvent, reprecipitate with methanol, wash with a large amount of water, and obtain 63.8 g of a polyfunctional vinyl resin (vinyl resin A) by drying under reduced pressure. The vinyl equivalent of vinyl resin A was 231 g / eq., the hydroxyl equivalent was 12000 g / eq., the total chlorine was 550 ppm, Mn was 860, and the GPC area% of n≥1 species was 51.5% (n = 0 species was 48.5%).

[0059] (Example 2) The same operation as in Example 1 was carried out except that 61.5 g (0.30 equivalent) of hydroxy resin b obtained in Synthesis Example 2 was used instead of hydroxy resin a, and 71.2 g of a polyfunctional vinyl resin (vinyl resin B) was obtained. The vinyl equivalent of vinyl resin B was 242 g / eq., the hydroxyl equivalent was 14000 g / eq., the total chlorine was 500 ppm, Mn was 1370, and the GPC area% of n≥1 species was 71.9% (n = 0 species was 28.1%).

[0060] (Example 3) The same operation as in Example 1 was carried out except that 47.4 g (0.30 equivalent) of hydroxy resin c obtained in Synthesis Example 3 was used instead of hydroxy resin a, and 58.3 g of a polyfunctional vinyl resin (vinyl resin C) was obtained. The vinyl equivalent of vinyl resin C was 213 g / eq., the hydroxyl equivalent was 11000 g / eq., the total chlorine was 800 ppm, Mn was 930, and the GPC area% of n≥1 species was 54.0% (n = 0 species was 46.0%).

[0061] (Example 4) The same operation as in Example 1 was carried out except that 54.0 g (0.30 equivalent) of hydroxy resin d obtained in Synthesis Example 4 was used instead of hydroxy resin a, and 63.1 g of a polyfunctional vinyl resin (vinyl resin D) was obtained. The vinyl equivalent of vinyl resin D was 235 g / eq., the hydroxyl equivalent was 11000 g / eq., the total chlorine was 900 ppm, Mn was 930, and the GPC area% of n≥1 species was 60.0% (n = 0 species was 40.0%).

[0062] (Example 5) Instead of hydroxy resin a, 47.7 g (0.30 equivalent) of hydroxy resin e obtained in Synthesis Example 5 was used, and the same operations as in Example 1 were carried out to obtain 56.9 g of a polyfunctional vinyl resin (vinyl resin E). The vinyl equivalent of vinyl resin E was 200 g / eq., the hydroxyl equivalent was 16000 g / eq., the total chlorine was 900 ppm, Mn was 770, and the percentage of n≥1 species by GPC area was 44.4% (the percentage of n = 0 species was 55.6%).

[0063] (Example 6) Instead of hydroxy resin a, 47.7 g (0.30 equivalent) of hydroxy resin f obtained in Synthesis Example 6 was used, and the same operations as in Example 1 were carried out to obtain 56.9 g of a polyfunctional vinyl resin (vinyl resin F). The vinyl equivalent of vinyl resin F was 200 g / eq., the hydroxyl equivalent was 16000 g / eq., the total chlorine was 700 ppm, Mn was 710, and the percentage of n≥1 species by GPC area was 56.9% (the percentage of n = 0 species was 43.1%).

[0064] (Comparative Example 1) Instead of hydroxy resin a, 30.6 g (0.30 equivalent) of 1,1,1-tris(p-hydroxyphenyl)ethane (the following structural formula) [Chemical formula] was used, and the same operations as in Example 1 were carried out to obtain 58.9 g of a vinyl compound (vinyl compound G). The vinyl equivalent of vinyl compound G was 214 g / eq., the hydroxyl equivalent was 7000 g / eq., and the total chlorine was 1500 ppm.

[0065] (Comparative Example 2) In a 1000 ml four-necked flask, 40.8 g of 4,4'-bis(chloromethyl)biphenyl (the following structural formula), [Chemical formula] 75.5 g of 4,4'-biphenol (the following structural formula), [Chemical formula] 120 g of diethylene glycol dimethyl ether was charged, and the temperature was raised to 160 °C with stirring under a nitrogen stream and reacted for 10 hours. Subsequently, the temperature was adjusted to 70 °C, 280 g of diethylene glycol dimethyl ether and 129.5 g of chloromethylstyrene were added, and the reaction was carried out while dropping 100.0 g of 48% potassium hydroxide. It was confirmed by gas chromatography that there was no residual chloromethylstyrene, 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 a polyfunctional vinyl resin (vinyl resin H). The vinyl equivalent of the obtained vinyl resin H was 256 g / eq., the hydroxyl equivalent was 1500 g / eq., and the total chlorine was 1270 ppm.

[0066] (Comparative Example 3) In a 1000 ml four-necked flask, 50.0 g of dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane (the following structural formula): 36.2%, 2,4'-dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%), [Chemical formula] 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 reaction for another 6 hours. After completion of the reaction, filtration was carried out, the solvent was distilled off, reprecipitation was carried out with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 95.4 g of a vinyl compound (vinyl compound I). The vinyl equivalent of vinyl compound I was 217 g / eq., the hydroxyl equivalent was 17000 g / eq., and the total chlorine was 400 ppm.

[0067] Examples 7 to 12, Comparative Examples 4 to 7 As polyfunctional vinyl compounds, vinyl compounds A to I obtained in Examples 1 to 6 and Comparative Examples 1 to 3 and vinyl resin J (OPE-2ST: manufactured by Mitsubishi Gas Chemical Company, vinyl group equivalent: 590.0 g / eq, number average molecular weight 1187) were used. As a curing accelerator, Perbutyl P (manufactured by NOF Corporation), which is an organic peroxide, and as an antioxidant, Adeka Stab AO-60 (manufactured by ADEKA Corporation) were mixed at the blending ratios shown in Table 1 and dissolved in a solvent to obtain a uniform composition. This 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 mirror plates and cured under reduced pressure at 130°C for 15 minutes and at 210°C for 80 minutes while applying a pressure of 2 MPa. The properties of the obtained cured product are shown in Table 1.

[0068]

Table 1

[0069] Compared with the comparative examples, the polyfunctional vinyl compounds of the examples showed high thermal conductivity and excellent physical properties such as low dielectric constant and low dielectric tangent.

Industrial Applicability

[0070] The polyfunctional vinyl compound of the present invention is useful as a material for electronic parts and wiring in electronic materials for high-speed communication devices, which easily releases heat generated from the parts and has little signal loss.

Claims

Claim 1 A polyfunctional vinyl compound represented by the following general formula (1). 【Chemical Formula 1】 In formula (1), R1 to R6 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X independently represents a structure represented by formula (2), a benzonitrile structure, a diphenylsulfonyl structure, a xylylene structure, or -(CH ２ ) ｍ -, m represents a number from 3 to 10, and n represents a number from 1 to 15. [Chemical 2] Claim 2 The polyfunctional vinyl compound according to Claim 1, wherein X has the structure represented by the formula (2). Claim 3 A polyfunctional vinyl composition containing, as essential components, the polyfunctional vinyl compound according to Claim 1 and a radical polymerization initiator. Claim 4 A polyfunctional vinyl cured product obtained by curing the polyfunctional vinyl composition according to Claim 3.

Images