Vinyl resin and method for producing the same

Abstract

Provided is a resin material which has a low permittivity and a low dielectric dissipation factor and nevertheless exhibits high thermal conductivity and high heat resistance.　The present invention relates to: a polyfunctional vinyl resin obtained from a phenol-aralkyl resin having biphenyl structures in the skeleton and having two or more phenolic hydroxyl groups as functional groups, by converting the phenolic hydroxyl groups into aromatic vinyl; and a resin composition. This polyfunctional vinyl resin has satisfactory dielectric properties and a high thermal conductivity and is suited for use as electronic materials and composite materials.

Description

[Technical Field]

[0001] This invention provides a material that combines low dielectric loss tangent and high thermal conductivity, which is useful for printed circuit boards, encapsulants, and casting materials for electronic devices. vinyl resin and vinyl This relates to resin compositions and their cured products. [Background technology]

[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 sealing material 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. While increasing the amount of filler can increase thermal conductivity, it leads to an increase in the viscosity of the composition, resulting in decreased workability such as flowability, and thus causing problems with workability.

[0005] Even when the filler was incorporated to its maximum extent, the thermal conductivity of the resin itself, which forms the binder layer, was low, so heat was not transferred effectively, limiting the thermal conductivity of the composition.

[0006] Epoxy resins are used as binder layers, and methods for improving thermal conductivity, such as introducing mesogenic structures, have been disclosed (Non-Patent Document 1). For example, aralkyl epoxy resins having a biphenyl skeleton are also known (Patent Documents 1, 2, and 3). When these epoxy resins are used, although the thermal conductivity is high, the dielectric constant and dielectric loss tangent properties are still insufficient due to the secondary hydroxyl groups generated during curing.

[0007] In this situation, there is a need for resin materials with low dielectric constant, low dielectric loss tangent, and high thermal conductivity. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2009-170493 [Patent Document 2] WO2013 / 100172 issue [Patent Document 3] Japanese Patent Application Publication No. 5-117350 [Patent Document 4] Japanese Patent Application Publication No. 8-143648 [Patent Document 5] Japanese Patent Application Publication No. 8-239454 [Non-patent literature]

[0009] [Non-Patent Document 1] "Review Article: Functionalization of Epoxy Network Polymers by Mesogenic Skeletons" by Miyuki Harada, Network Polymers Vol. 36 No. 4, 2015. [Overview of the project] [Problems that the invention aims to solve]

[0010] The object of the present invention is to provide a resin material that exhibits high thermal conductivity while having a low dielectric constant and a low dielectric loss tangent. [Means for solving the problem]

[0011] As a result of earnestly studying while paying attention to the resin structure and the functional group, the inventor of the present invention has found that the above problems can be solved by a vinyl resin in which the phenolic hydroxyl groups of a polyhydric hydroxy resin having a biphenyl structure in the skeleton and having four or more phenolic hydroxyl groups are aromatically vinylated, and has completed the present invention. That is, the present invention is a vinyl resin characterized by being represented by the following general formula (1). [Chemical formula] Here, n represents the number of repetitions and is an integer between 0 and 15. m is an integer greater than or equal to 2, independently representing the number of permutations. X independently represents a divalent aralkylene group represented by the following formula (2), Within the unit defined by the number of repetitions n mentioned above Y independently represents an aromatic group consisting of the aromatic ring Ar [[ID=二十二]] 2 consisting of (2+m) value represents. Y, located outside the unit enclosed by the aforementioned number of repetitions n, independently comprises the aromatic ring Ar 2 This represents an aromatic group consisting of (1+m) valence. However, at least one of Ar in formula (2) 1 or the above Ar 2 is a biphenyl ring. Z independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by the following formula (4), and one or more are vinyl group-containing aromatic groups. [Chemical formula] Here, Ar 1 and Ar 3 each independently represent an aromatic ring.

[0012] The present invention is a method for producing the above vinyl resin, which comprises reacting a polyfunctional phenol compound represented by the following general formula (5) with an aromatic crosslinking agent represented by the following general formula (6) to obtain a polyhydric hydroxy resin represented by the following general formula (7), and then reacting the obtained polyhydric hydroxy resin with an aromatic vinylating agent represented by the following general formula (8). [Chemical formula] [Chemical formula] [Chemical formula] <00D0130> Here, X, n, and m are synonymous with the definitions in the general formula (1) above, respectively. The above general formula (5) Y is independently Aromatic ring Ar 2 m-value consisting of represents an aromatic group of In the above general formula (7), the Y present within the unit enclosed by the number of repetitions n is independently the aromatic ring Ar 2 This shows an aromatic group consisting of (2+m) valence. In the above general formula (7), Y located outside the unit enclosed by the number of repetitions n is independently the aromatic ring Ar 2 This represents an aromatic group consisting of (1+m) valence. However, Ar in the formula (2) for X 1 or The aforementioned Ar 2 at least one of which is a biphenyl ring. Z is synonymous with the definition in the general formula (4) above. R 1 independently represents a halogen group, a hydroxy group, or an alkoxy group. R 2 represents a halogen group.

[0013] The present invention is vinyl a resin composition containing a resin and, if necessary, a radical initiator, vinyl and a resin cured product obtained by curing the same. vinyl That is. Furthermore vinyl a prepreg composed of a semi-cured product of the resin composition and a fibrous substrate, a resin sheet provided with a support film, and a laminate formed by laminating and molding these prepregs or resin sheets. [Advantages of the Invention]

[0014] In the present invention vinylThe resin and composition, and further the cured product obtained by curing the composition, have low dielectric constant and dielectric loss tangent while exhibiting high thermal conductivity, making them suitable as electronic materials for high-speed communications. [Brief explanation of the drawing]

[0015] [Figure 1] The molecular weight distribution (GPC) of the polyvalent hydroxy resin obtained in Synthesis Example 3 and the vinyl resin C of Example 3 obtained using it is shown. [Modes for carrying out the invention]

[0016] This invention vinyl The resin is represented by the above general formula (1). In general formula (1), X is independently a divalent aralkyl group represented by formula (2) above. Ren This group is derived from the aromatic crosslinking agent in the raw material. The Ar group in formula (2) 1 However, it is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring. Y independently represents a divalent or greater aromatic group represented by formula (3) above, and is a group derived from the polyvalent phenol compound of the starting material. It becomes a divalent or 2+m valent aromatic group. Ar in formula (3) 2 However, it is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, and a bisphenol-type ring structure. However, Ar in equation (2) 1 Or Ar in equation (3) 2 At least one of them must be a biphenyl ring. Z independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by formula (4) above, and one or more of them are vinyl group-containing aromatic groups, which are groups derived from the aromatic vinylizing agent of the raw material. 3 However, it is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring. These aromatic rings Ar 1 Ar 2 Ar 3Each component may be unsubstituted or independently have one or more substituents. If substituents are present, there are preferably 1 to 4 substituents, and the substituents are preferably C1 to C10 alkyl or aryl groups, more preferably C1 to C3 alkyl or phenyl groups. n represents the number of repetitions and is an integer between 0 and 15. The average value is between 0 and 5. m independently represents the number of substitutions and is an integer of 2 or more. Preferably it is 2 to 9, more preferably 2 or 3.

[0017] This invention vinyl The resin preferably has a number-average molecular weight (Mn) of 500 to 3000, more preferably 600 to 1500, and a vinyl equivalent of 200 to 500 g / eq, more preferably 220 to 350 g / eq.

[0018] This invention vinyl The resin can be suitably obtained by reacting a polyfunctional phenol compound represented by the general formula (5) with an aromatic crosslinking agent represented by the general formula (6) to obtain a polyvalent hydroxy resin represented by the general formula (7), and then reacting the obtained polyvalent hydroxy resin with an aromatic vinylizing agent represented by the general formula (8).

[0019] Polyvalent hydroxy resins represented by general formula (7) can be obtained, for example, by the reaction of a bifunctional or more polyvalent phenol compound with an aromatic crosslinking agent such as bishalomethylbiphenyl or bismethoxymethylbiphenyl, but are not limited to this method.

[0020] Specific examples of aromatic crosslinking agents represented by general formula (6) include 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, xylylene chloride, xylylene glycol, xylylene dialkoxy and their isomers, and those with substituents. Two R to X 1 Regarding the substitution position, X's Ar 1 If the ring is a benzene ring, the 1,4- or 1,3-position is preferred, and the Ar of X 1If the ring is a naphthalene ring, the 1,5- or 1,6-position is preferred, and the Ar of X 1 When the ring is a biphenyl ring, the 4,4'-position is preferred. It is preferable that the substituted products at these positions constitute 50 mol% or more of the aromatic crosslinking agent used.

[0021] Polyfunctional phenol compounds with two or more functions represented by general formula (5) include mononuclear compounds, polycyclic aromatic compounds, and various bisphenol compounds, and the following structures are examples of this. [ka]

[0022] As examples of various bisphenol-type compounds represented by the general formula at the end of the above, the following structural examples include A as a linking group, which includes a single bond. Among these, a single bond or an alkylene group having 1 to 3 carbon atoms is preferred. Note that substituent R 3 It may have substituents, and if it does, there are preferably 1 to 4 substituents, and the substituents are preferably C1 to C3 alkyl groups or C6 to C10 aryl groups. [ka]

[0023] The polyfunctional phenolic compounds with two or more functions can have any structure represented by general formula (5), and more preferably include hydroquinone, 1,4-naphthalenediol, 1,6-naphthalenediol, 2,6-naphthalenediol, 4,4'-biphenol, and 3,3'-diphenylbiphenol. Regarding the substitution position of the bifunctional hydroxyl group on Y, the Ar of Y 2 If the ring is a benzene ring, the 1,4- or 1,3-position is preferred, and the Ar of Y 2 If the ring is a naphthalene ring, the 1,5- or 1,6-position is preferred, and the Ar of Y 2 If the ring is a biphenyl ring, the 4,4'-position is preferred. In the bifunctional or more functional phenol compound used, it is preferable that the substituted products at these positions make up 50 mol% or more.

[0024] The reaction between a bifunctional or polyfunctional phenol compound and an aromatic crosslinking agent occurs in a range of 0.1 to 0.9 moles, preferably 0.15 to 0.85 moles, per mole of the bifunctional or polyfunctional phenol compound.

[0025] The reaction between a bifunctional or polyfunctional phenol compound and an aromatic crosslinking agent can be synthesized by known methods, specifically, by carrying out a condensation reaction in the presence of an acid catalyst while removing the by-products of hydrochloric acid, alcohol, or water. Specific examples of acid catalysts include hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid, or organic acids, Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride, with p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid being particularly preferred.

[0026] This invention vinyl The resin can be suitably obtained by reacting the polyvalent hydroxy resin represented by general formula (7) obtained in this way with an aromatic vinylizing agent represented by general formula (8).

[0027] As an aromatic vinylizing agent represented by general formula (8), halomethylstyrene is preferred. Specific examples of halomethylstyrene include chloromethylstyrene, bromomethylstyrene and their isomers, and substituted compounds. 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 compound accounts for 50 mol% or more of the total.

[0028] The reaction between polyvalent hydroxy resins and halomethylstyrene as 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 halomethylstyrene to the polyvalent hydroxy resin, adding metal hydroxide, and removing the resulting metal salt by methods such as filtration or washing with water. Examples of solvents include, but are not limited to, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, and cyclohexanone. Specific examples of metal hydroxides include, but are not limited to, sodium hydroxide and potassium hydroxide.

[0029] The reaction should be carried out at a temperature of 100°C or lower, preferably 80°C or lower. If there is concern about the self-polymerization of halomethylstyrene as an aromatic vinyling agent, polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso, nitrone compounds, and oxygen may be used.

[0030] The reaction endpoint can be determined by tracking the remaining amount of halomethylstyrene as an aromatic vinylizing agent using various chromatograms. The reaction rate can be adjusted by changing the type and amount of metal hydroxide, adjusting the addition rate, or using an appropriate catalyst.

[0031] This invention vinyl While the resin can be cured on its own, it is also preferable to use it as a polyfunctional resin composition containing various additives. For example, curing can be accelerated by incorporating radical initiators such as azo compounds and organic peroxides.

[0032] This invention vinyl The resin can be compounded with other vinyl resins or other thermosetting resins, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzoxazine resins.

[0033] vinyl The resin composition may contain fillers such as glass cloth, carbon fiber, alumina, or boron nitride to increase thermal conductivity.

[0034] Inorganic fillers used as fillers are preferred to have higher thermal conductivity in order to provide a higher thermal conductivity. Preferably, they are 20 W / m·K or higher, more preferably 30 W / m·K or higher, and even more preferably 50 W / m·K or higher. At least a portion of the inorganic filler, preferably 50 wt% or more, has a thermal conductivity of 20 W / m·K or higher. The 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.

[0035] 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.

[0036] Various additives may be added to improve adhesive strength and ease of handling the composition, such as silane coupling agents, defoaming agents, internal mold release agents, and flow regulators.

[0037] Furthermore, this invention vinyl resin or vinyl The resin composition can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, or methyl isobutyl ketone, and impregnated into a fibrous substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper. The resulting prepreg is then heat-dried, and the resulting prepreg is hot-press-molded to obtain a cured product. vinyl resin or vinyl The resin composition may be a semi-cured product. Alternatively, a cured product (laminated body) of a desired thickness can be obtained by laminating multiple such prepregs. To obtain the laminate, a previously cured product and a prepreg may be combined and molded together.

[0038] Similarly, vinyl resin or vinylA resin composition or a resin layer which is a semi-cured product thereof can be applied to a substrate (support film) such as a PET film, and a resin sheet obtained by heat drying or the like can be hot-pressed to obtain a cured product. Similarly, multiple such resin sheets can be laminated and molded to obtain a cured product (laminated body) of a desired thickness, and when obtaining a laminate, a cured product that has been cured once and a resin sheet can be combined and molded. [Examples]

[0039] The present invention will be described in more detail by examples and comparative examples, but unless otherwise specified, parts refer to parts by weight.

[0040] The test conditions for polyvalent hydroxy resins, vinyl resins, and cured products are shown.

[0041] (1) Hydroxyl group equivalent Using a potentiometric titrator, 1,4-dioxane was used as the solvent, and acetylation was performed with 1.5 mol / L acetyl chloride. The excess acetyl chloride was decomposed with water, and the titration was performed using 0.5 mol / L potassium hydroxide.

[0042] (2) Vinyl equivalent The sample was reacted with Wies' solution (iodine monochloride solution), left in the dark, and then the excess iodine chloride was reduced to iodine. The iodine value was calculated by titrating the iodine content with sodium thiosulfate. The iodine value was converted to vinyl equivalents.

[0043] (3) Total chlorine 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. After cooling to room temperature, 100 ml of 80% acetone water was added, and the sample was measured by potentiometric titration with 0.002 N-AgNO3 aqueous solution.

[0044] (4) Molecular weight distribution of resin A GPC measuring device (Tosoh, HLC-8220GPC) was used, with one TSK Guardclumn (Tosoh), one TSKgel 2000H XL (Tosoh), one TSKgel 3000H XL (Tosoh), and one TSKgel 4000H XL (Tosoh) column. The detector was an RI, the solvent was tetrahydrofuran, the flow rate was 1.0 mL / min, and the column temperature was 40°C.

[0045] (5) Thermal conductivity Measurements were taken in accordance with the JIS R 1611 standard.

[0046] (6) Dielectric constant and dielectric loss tangent Measurements were taken in accordance with the JIS C 2138 standard. The measurement frequency is shown as 1 GHz.

[0047] Polyvalent hydroxy resin A: Product name BRG-555, manufactured by Aica Kogyo Co., Ltd.

[0048] (Synthesis Example 1) In a 1000 ml four-necked flask, 186.1 g of 4,4'-bis(chloromethyl)biphenyl, 272.1 g of hydroquinone, and 458.2 g of diethylene glycol dimethyl ether were charged and reacted under a nitrogen stream, stirring over 10 hours at a temperature of 160°C. Subsequently, 3 g of 48% potassium hydroxide solution was added and the reaction was carried out at 130°C for 3 hours. After the reaction, the mixture was recovered by reprecipitation after being added dropwise to a large amount of pure water, yielding 110 g of pale yellow resin. The hydroxyl group equivalent of the obtained polyvalent hydroxy resin was 110.9 g / eq, and the total chlorine content was 460 ppm.

[0049] (Synthesis Example 2) The same procedure as in Synthesis Example 1 was followed, except that 127.9 g of 4,4'-bis(chloromethyl)biphenyl, 272.1 g of 1,6-naphthalenediol, and 400.0 g of diethylene glycol dimethyl ether were charged into the same apparatus. The resulting polyvalent hydroxyl resin had a hydroxyl group equivalent of 106.8 g / eq and a total chlorine content of 490 ppm.

[0050] (Synthesis Example 3) The same procedure as in Synthesis Example 1 was followed, except that 140.3 g of 4,4'-bis(chloromethyl)biphenyl, 260.0 g of 4,4'-biphenol, and 400.0 g of diethylene glycol dimethyl ether were charged into the same apparatus. The hydroxyl group equivalent of the obtained polyvalent hydroxy resin was 128.7 g / eq, and the total chlorine content was 300 ppm.

[0051] (Synthesis Example 4) The same procedure as in Synthesis Example 1 was followed, except that 87.5 g of p-xylylenedichloride, 186 g of 4,4'-dihydroxybiphenyl, 273 g of diethylene glycol dimethyl ether as a solvent, and 1.37 g of p-toluenesulfonic acid as an acid catalyst were charged into the same apparatus. The resulting polyvalent hydroxy resin had a hydroxyl group equivalent of 120.0 g / eq and a total chlorine content of 420 ppm.

[0052] (Synthesis Example 5) The same procedure as in Synthesis Example 1 was followed, except that 87.7 g of 4,4'-bis(chloromethyl)biphenyl, 94.0 g of phenol, and 181.7 g of diethylene glycol dimethyl ether were charged into the same apparatus. The obtained polyvalent hydroxy resin had a hydroxyl group equivalent of 78.8 g / eq and a total chlorine content of 360 ppm.

[0053] (Synthesis Example 6) The same procedure as in Synthesis Example 1 was followed, except that 87.5 g of p-xylylenedichloride, 94 g of phenol, and 182 g of diethylene glycol dimethyl ether were charged in place of 4,4'-bis(chloromethyl)biphenyl in the same apparatus. The resulting polyvalent hydroxy resin had a hydroxyl group equivalent of 73.0 g / eq and a total chlorine content of 550 ppm.

[0054] Example 1 In an apparatus similar to that used in Synthesis Example 1, 85.0 g of the polyvalent hydroxy resin obtained in Synthesis Example 1, 198.3 g of diethylene glycol dimethyl ether, and 117.1 g of chloromethylstyrene were charged and heated to 70°C to dissolve. The reaction was carried out while adding 87.9 g of 48% potassium hydroxide aqueous solution dropwise. After confirming the absence of residual chloromethylstyrene by gas chromatography, the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, neutralized, and washed with water to obtain vinyl resin A. The vinyl equivalent of the obtained vinyl resin A was 247.2 g / eq, and the total chlorine content was 1530 ppm.

[0055] Example 2 Vinyl resin B was obtained by following the same procedure as in Example 1, except that 96.2 g of the polyvalent hydroxy resin from Synthesis Example 2 was used instead of the polyvalent hydroxy resin from Synthesis Example 1, along with 224.4 g of diethylene glycol dimethyl ether, 149.4 g of chloromethylstyrene, and 112.4 g of a 48% potassium hydroxide aqueous solution. The vinyl equivalent of the obtained vinyl resin B was 223.5 g / eq, and the total chlorine content was 1670 ppm.

[0056] Example 3 Vinyl resin C was obtained by following the same procedure as in Example 1, except that 104.8 g of the polyvalent hydroxy resin from Synthesis Example 3 was used instead of the polyvalent hydroxy resin from Synthesis Example 1, along with 231.0 g of diethylene glycol dimethyl ether, 129.5 g of chloromethylstyrene, and 100.0 g of a 48% potassium hydroxide aqueous solution. The vinyl equivalent of the obtained vinyl resin C was 255.6 g / eq, and the total chlorine content was 1270 ppm.

[0057] Example 4 Vinyl resin D was obtained by following the same procedure as in Example 1, except that 118.6 g of the polyvalent hydroxy resin from Synthesis Example 4 was used instead of the polyvalent hydroxy resin from Synthesis Example 1, 277.1 g of diethylene glycol dimethyl ether, 89.81 g of chloromethylstyrene, and 86.4 g of a 48% potassium hydroxide aqueous solution. The vinyl equivalent of the obtained vinyl resin D was 236.8 g / eq, and the total chlorine content was 1300 ppm.

[0058] Comparative Example 1 Vinyl resin E was obtained by following the same procedure as in Example 1, except that 118.6 g of the polyvalent hydroxy resin from Synthesis Example 5 was used instead of the polyvalent hydroxy resin from Synthesis Example 1, 277.1 g of diethylene glycol dimethyl ether, 89.81 g of chloromethylstyrene, and 86.4 g of a 48% potassium hydroxide aqueous solution. The vinyl equivalent of the obtained vinyl resin E was 330.5 g / eq, and the total chlorine content was 1680 ppm.

[0059] Comparative Example 2 Vinyl resin F was obtained by following the same procedure as in Example 1, except that 95.0 g of polyvalent hydroxy resin A, 221.8 g of diethylene glycol dimethyl ether, 145.0 g of chloromethylstyrene, and 121.8 g of 48% potassium hydroxide aqueous solution were used instead of the polyvalent hydroxy resin in Synthesis Example 1. The vinyl equivalent of the obtained vinyl resin F was 235.7 g / eq, and the total chlorine content was 1830 ppm.

[0060] Comparative Example 3 Vinyl resin G was obtained by following the same procedure as in Example 1, except that 118.6 g of the polyvalent hydroxy resin from Synthesis Example 6 was used instead of the polyvalent hydroxy resin from Synthesis Example 1, 277.1 g of diethylene glycol dimethyl ether, 89.81 g of chloromethylstyrene, and 86.4 g of 48% potassium hydroxide aqueous solution. The vinyl equivalent of the obtained vinyl resin G was 192.7 g / eq, and the total chlorine content was 1970 ppm.

[0061] Examples 5-9, Comparative Examples 4-7 The properties of each resin composition obtained by mixing the obtained vinyl resins A to G and the resins, initiators (organic peroxides), and antioxidants shown below in the proportions shown in Table 1, as well as the properties of the cured products obtained by curing them, are shown below.

[0062] Vinyl resin H:OPE-2ST, manufactured by Mitsubishi Gas Chemical Company, Inc. (Number average molecular weight: 1187, vinyl group equivalent: 590.0 g / eq) Organic peroxide: Perbutyl P, manufactured by NOF Corporation. Antioxidant: ADEKA Stab AO-60, manufactured by ADEKA Corporation.

[0063] Examples 5-9 and Comparative Examples 4-7 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 resin 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.

[0064] Table 1 shows the dielectric constant, dielectric loss tangent, and thermal conductivity values ​​of the cured material.

[0065] [Table 1]

[0066] Examples vinyl Compared to the comparative example, the resin exhibited superior physical properties, including high thermal conductivity, low dielectric constant, and low dielectric loss tangent. [Industrial applicability]

[0067] This invention vinyl Resin is useful as an electronic material in high-speed communication equipment because it easily dissipates heat from electronic components and wiring, resulting in low signal loss.

Claims

1. A vinyl resin characterized by being represented by the following general formula (1). 【Chemistry 1】 Here, n represents the number of repetitions and is an integer between 0 and 15. m is an integer greater than or equal to 2, independently representing the number of permutations. X independently represents a divalent aralkylene group represented by the following formula (2): Within the unit defined by the number of repetitions n, Y independently comprises the aromatic ring Ar ２ This represents an aromatic group consisting of (2+m) valence. Y located outside the unit enclosed by the aforementioned number of repetitions n independently represents an aromatic group with a (1+m) valency consisting of the aromatic ring Ar2. However, Ar in equation (2) １ or the Ar ２ At least one of them is a biphenyl ring. Z independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by the following formula (4), and one or more of them are vinyl group-containing aromatic groups. 【Chemistry 2】 Here, Ar １ Ar ３ Each of these independently represents an aromatic ring.

2. Ar in formula (2) １ is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring, and said Ar ２ is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, a biphenyl ring, and a bisphenol-type ring structure, and Ar in formula (4) ３ is an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring, and these aromatic rings Ar １ , Ar ２ , Ar ３ are unsubstituted or each independently may have, as one or more substituents, an alkyl group or an aryl group having 1 to 10 carbon atoms. The vinyl resin according to claim 1

3. A method for producing a vinyl resin according to claim 1, characterized in that a polyfunctional phenol compound represented by the following general formula (5) is reacted with an aromatic crosslinking agent represented by the following general formula (6) to obtain a polyvalent hydroxy resin represented by the following general formula (7), and then the obtained polyvalent hydroxy resin is reacted with an aromatic vinylizing agent represented by the following general formula (8). 【Transformation 3】 【Chemistry 4】 【Transformation 5】 Here, X, n, and m are the same as their definitions in the general formula (1) above. In the above general formula (5), Y independently represents an m-valent aromatic group consisting of an aromatic ring Ar2. In the above general formula (7), Y within the unit enclosed by the number of repetitions n independently represents an aromatic group with a (2+m) valency consisting of an aromatic ring Ar2. In the above general formula (7), Y located outside the unit enclosed by the number of repetitions n independently represents an aromatic group with a (1+m) valency consisting of an aromatic ring Ar2. However, Ar in equation (2) above for X １ or the Ar ２ At least one of them is a biphenyl ring. Z is equivalent to the definition in the general formula (4) above. R １ These independently represent a halogen, a hydroxyl group, or an alkoxy group. R ２ This indicates a halogen.

4. A vinyl resin composition containing the vinyl resin described in claim 1 and a radical polymerization initiator as essential components.

5. A cured vinyl resin product obtained by curing the vinyl resin described in claim 1, or the vinyl resin composition described in claim 4.

6. A prepreg comprising a vinyl resin according to claim 1, or a vinyl resin composition according to claim 4, or a semi-cured product thereof, and a fibrous substrate.

7. A resin sheet comprising a resin layer of the vinyl resin described in claim 1, or the vinyl resin composition described in claim 4, or a semi-cured product thereof, and a support film.

8. A laminated board formed by laminating the prepreg described in claim 6.

9. A laminated board formed by laminating the resin sheets described in claim 7.

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