Multifunctional vinyl resins and methods for making the same

Abstract

Provided is a resin material that exhibits high thermal conductivity while being low in dielectric constant and low in dielectric loss tangent, and that is also high in heat resistance. Provided is a multifunctional vinyl resin obtained by aromatic vinylization of the phenolic hydroxyl groups of a phenolic aralkyl resin having a biphenyl structure in the skeleton and having two or more phenolic hydroxyl groups, and a resin composition. The multifunctional vinyl resin has good dielectric properties and high thermal conductivity, and is suitable for use in electronic materials and composite materials.

Description

Technical Field

[0001] This invention relates to multifunctional vinyl resins and multifunctional vinyl resin compositions, as well as cured products thereof, which are useful in printed circuit boards, packaging materials, casting materials, etc. of electronic devices and possess both low dielectric loss tangent and high thermal conductivity. Background Technology

[0002] With the increasing speed and volume of communication, research into high-speed communication technology is booming to improve signal transmission speed, particularly for printed circuit boards, packaging materials, and casting materials used in communication equipment. Electronic materials used in such applications require materials that can reduce dielectric loss, and in printed circuit board applications, multilayer curable resins are also required.

[0003] On the other hand, electronic computing components that process large amounts of information generate a lot of heat, leading to problems such as reduced processing speed due to heat accumulation. Therefore, various methods are known for cooling the printed circuit board using heat sinks or similar means, including mounting heat-conducting components such as copper coins or copper inserts (Patent Document 1) or using special shapes for the filling material (Patent Document 2). However, these methods result in increased weight and larger machines, and are therefore not preferred.

[0004] In addition, as a method to improve thermal conductivity in encapsulation material compositions, a method is adopted to remove heat from electronic computing components by studying the types and amounts of various fillers. Increasing the amount of filler increases thermal conductivity, but this leads to an increase in the viscosity of the composition and a decrease in workability such as flowability, resulting in workability problems.

[0005] Even when the filler is formulated to its limit, the thermal conductivity of the composition is limited because the resin itself, which acts as the binder layer, has low thermal conductivity and is not heat-conducting.

[0006] Methods for improving thermal conductivity, such as using epoxy resin as the adhesive layer and incorporating liquid crystal structures, have been disclosed (Non-Patent Document 1). For example, aralkyl-type epoxy resins with a biphenyl backbone are known (Patent Documents 1, 2, 3). While these epoxy resins exhibit high thermal conductivity, their dielectric constant and dielectric loss tangent are not yet sufficient due to the secondary hydroxyl groups generated during curing.

[0007] Under such circumstances, a resin material with low dielectric constant, low dielectric loss tangent, and high thermal conductivity is required.

[0008] Existing technical documents

[0009] Patent documents

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

[0011] Patent Document 2: WO2013 / 100172

[0012] Patent Document 3: Japanese Patent Application Publication No. 5-117350

[0013] Patent Document 4: Japanese Patent Application Publication No. 8-143648

[0014] Patent Document 5: Japanese Patent Application Publication No. 8-239454

[0015] Non-patent literature

[0016] Non-Patent Literature 1: Miyuki Harada, "General Theory of Functionalization of Epoxy Network Polymers Based on Liquid Crystal Proto-Frames", Network Polymers, Vol. 36, No. 4, 2015. Summary of the Invention

[0017] The objective of this invention is to provide a resin material that exhibits high thermal conductivity while having a low dielectric constant and a low dielectric loss tangent.

[0018] The inventors conducted in-depth research on resin structure and functional groups, and found that by using the phenolic hydroxyl groups of a polyhydroxy resin with a biphenyl structure in the skeleton and more than four functional phenolic hydroxyl groups, the above-mentioned problems can be solved, thus completing the present invention.

[0019] That is, the present invention relates to a multifunctional vinyl resin, characterized by being represented by the following general formula (1).

[0020]

[0021] Here,

[0022] X independently represents the divalent aralkyl group shown in formula (2) below.

[0023] Y independently represents a divalent or higher aromatic group as shown in formula (3) below.

[0024] Among them, Ar in equation (2) 1 Or Ar of equation (3) 2 At least one of them is a biphenyl ring.

[0025] Z independently represents a hydrogen atom or a vinyl-containing aromatic group as shown in formula (4) below, and one or more of them are vinyl-containing aromatic groups.

[0026] n represents the number of repetitions, which is an integer from 0 to 15.

[0027] m independently represents the substitution number, which is an integer greater than 2.

[0028] -CH2-Ar 1 -CH2- (2)

[0029] -Ar 2 - (3)

[0030] -CH2-Ar 3 -CH=CH2 (4)

[0031] Here,

[0032] Ar 1 Ar 2 Ar 3 Each of them independently represents an aromatic ring.

[0033] The present invention relates to a method for manufacturing a polyfunctional vinyl resin, characterized in that the method for manufacturing the above-mentioned polyfunctional vinyl resin involves reacting a polyfunctional phenolic compound represented by the following general formula (5) with an aromatic crosslinking agent represented by the following general formula (6) to obtain a polyhydroxy resin represented by the following general formula (7), and then reacting the obtained polyhydroxy resin with an aromatic vinylizing agent represented by the following general formula (8).

[0034]

[0035] R 1 -XR 1 (6)

[0036]

[0037] ZR 2 (8)

[0038] Here,

[0039] X, Y, n, and m are the same as those defined in the general formula (1) above.

[0040] Z is defined in the same way as in the general formula (4) above.

[0041] R 1 Independently represent halogen groups, hydroxyl groups, or alkoxy groups.

[0042] R 2 It represents a halogen group.

[0043] The present invention relates to a multifunctional vinyl resin containing a multifunctional vinyl resin and, if necessary, a multifunctional vinyl resin composition containing a free radical initiator, and a multifunctional vinyl resin cured product obtained by curing the latter.

[0044] Furthermore, the present invention relates to a prepreg composed of a semi-cured product of a multifunctional vinyl resin composition and a fibrous substrate, a resin sheet having a support film, and a laminate obtained by stacking and molding these prepregs or resin sheets.

[0045] The multifunctional vinyl resin and composition of the present invention, as well as the cured product formed by curing the composition, have low dielectric constant and dielectric loss tangent, and high thermal conductivity, making them suitable as electronic materials for high-speed communication. Attached Figure Description

[0046] Figure 1 The GPC represents the molecular weight distribution of the polyhydroxy resin obtained in Synthesis Example 3 and the vinyl resin C of Example 3 obtained using it. Detailed Implementation

[0047] The multifunctional vinyl resin of the present invention is represented by the above general formula (1).

[0048] In general formula (1), X independently represents the divalent aralkyl group shown in formula (2) above, which is a group of the aromatic crosslinking agent derived from the raw material. Ar in formula (2) 1 It is an aromatic ring selected from benzene ring, naphthalene ring and biphenyl ring.

[0049] Y independently represents a divalent or higher aromatic group as shown in formula (3) above, which is a group derived from a polyphenolic compound of the raw material. It becomes a divalent or 2+m valent aromatic group. Formula (3) Ar 2 It is an aromatic ring selected from benzene ring, naphthalene ring, biphenyl ring and bisphenol type ring structure.

[0050] Among them, Ar in equation (2) 1 Or Ar of equation (3) 2 At least one of them must be a biphenyl ring.

[0051] Z independently represents a hydrogen atom, or a vinyl-containing aromatic group as shown in formula (4) above, and one or more of them are vinyl-containing aromatic groups, which are groups of an aromatic vinylizing agent derived from the raw material. Ar in formula (4) 3 It is an aromatic ring selected from benzene ring, naphthalene ring and biphenyl ring.

[0052] These aromatic rings Ar 1 Ar 2 Ar 3 It may be unsubstituted or have one or more substituents independently. When substituents are present, it is preferred to have 1 to 4 substituents, preferably alkyl or aryl groups having 1 to 10 carbon atoms, and more preferably alkyl or phenyl groups having 1 to 3 carbon atoms.

[0053] n represents the number of repetitions, an integer from 0 to 15. The average value is 0 to 5.

[0054] m independently represents the substitution number, which is an integer of 2 or more. Preferably, it is 2 to 9, and more preferably 2 or 3.

[0055] The number-average molecular weight (Mn) of the multifunctional vinyl resin of the present invention is preferably 500-3000, more preferably 600-1500, and the vinyl equivalent is 200-500 g / eq, more preferably 220-350 g / eq.

[0056] The polyfunctional vinyl resin of the present invention can be obtained by reacting the polyfunctional phenolic compound represented by the above general formula (5) with the aromatic crosslinking agent represented by the above general formula (6) to obtain the polyhydroxy resin represented by the above general formula (7), and then reacting the obtained polyhydroxy resin with the aromatic vinylizing agent represented by the above general formula (8).

[0057] The polyhydroxy resin represented by general formula (7) can be obtained, for example, by reacting a difunctional or higher polyphenol compound with an aromatic crosslinking agent such as a dihalomethylbiphenyl or a dimethoxymethylbiphenyl, but is not limited to this method.

[0058] Specific examples of aromatic crosslinking agents represented by general formula (6) include 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, dichloroxylene, xylene-1,4'-ethylene glycol, xylene-1,4'-dialkoxy and its isomers, and aromatic crosslinking agents with substituents. For two R... 1 The substitution position on X, the Ar of X 1 When it is a benzene ring, it is preferred that the Ar of X is at the 1,4- or 1,3-position. 1 When it is a naphthalene ring, the 1,5-position or 1,6-position of X is preferred. 1 When the ring is biphenyl, the 4,4' position is preferred. In the aromatic crosslinking agent used, the substituted components at these positions are preferably 50 mol% or more.

[0059] Examples of polyfunctional phenolic compounds represented by general formula (5) include mononuclear compounds, polycyclic aromatic compounds, and various bisphenol compounds. The following structures are specific examples.

[0060]

[0061] As compounds representing various bisphenol-type structures using the general formula at the end of the above description, examples of structures containing a single bond as the linking group A are given below. Preferably, the single bond or an alkylene group having 1 to 3 carbon atoms is preferred. It should be noted that substituents R may be present. 3 When it has substituents, it is preferred to have 1 to 4 substituents, preferably alkyl with 1 to 3 carbon atoms or aryl with 6 to 10 carbon atoms.

[0062]

[0063] Polyfunctional phenolic compounds with more than two functionalities can be those with the structure represented by general formula (5), and more preferably include hydroquinone, 1,4-naphthol, 1,6-naphthol, 2,6-naphthol, 4,4'-bisphenol, 3,3'-diphenylbisphenol, etc. Regarding the substitution position of the difunctional hydroxyl group on Y, the Ar of Y... 2 When it is a benzene ring, it is preferably at the 1,4-position or the 1,3-position, where Y is Ar 2 When it is a naphthalene ring, it is preferably at the 1,5-position or the 1,6-position, with Ar of Y. 2 When the ring is biphenyl, the 4,4' position is preferred. In the difunctional or higher phenolic compounds used, the substituted components at these positions are preferably 50 mol% or more.

[0064] The reaction between a difunctional or higher polyfunctional phenolic compound and an aromatic crosslinking agent is in the range of 0.1 to 0.9 moles, preferably 0.15 to 0.85 moles, relative to 1 mole of the difunctional or higher phenolic compound.

[0065] The reaction of polyfunctional phenolic compounds with difunctional or higher functions with aromatic crosslinking agents can be synthesized by known methods, preferably through a condensation reaction in the presence of an acid catalyst, while removing byproducts such as hydrochloric acid, alcohol, or water. Specific examples of acid catalysts are preferably Lewis acids such as hydrochloric acid, sulfuric acid, oxalic acid, p-toluenesulfonic acid or organic acids, boron trifluoride, anhydrous aluminum chloride, and zinc chloride, with p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid being particularly preferred.

[0066] The multifunctional vinyl resin of the present invention can be suitably obtained by reacting a polyhydroxy resin represented by general formula (7) obtained therefrom with an aromatic vinylizing agent represented by general formula (8).

[0067] As an aromatic vinylizing agent represented by general formula (8), halomethylstyrene is preferred. Specific examples of halomethylstyrene include chloromethylstyrene, bromomethylstyrene and its isomers, and halomethylstyrene with substituents. For the substitution position of the halomethyl body, for example, when it is halomethylstyrene, the 4-position is preferred, and the 4-position body is preferably 50 mol% or more of the total.

[0068] The reaction between polyhydroxy resins and halomethylstyrene, an aromatic vinylizing agent, can be carried out in the absence of solvent or in the presence of solvent. Halomethylstyrene can be added to the polyhydroxy resin, followed by the addition of metal hydroxide to initiate the reaction. The resulting metal salt can then be removed by methods such as filtration or washing with water.

[0069] Examples of solvents include benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, and cyclohexanone, but these are not limited to. Specific examples of metal hydroxides include sodium hydroxide and potassium hydroxide, but these are not limited to.

[0070] The reaction can be set to a temperature below 100°C, preferably below 80°C. If there are concerns about the self-polymerization of halomethylstyrene as an aromatic vinyl ester, polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitrosamines, nitro compounds, and oxygen can be used.

[0071] The reaction endpoint can be determined by tracking the residual amount of halomethylstyrene as an aromatic vinylizing agent using various chromatograms. As a method to adjust the reaction rate, it can be adjusted by changing the type and amount of metal hydroxide, the addition rate, and the use of appropriate catalysts.

[0072] The multifunctional vinyl resin of the present invention can be cured alone, but is also preferably used as a multifunctional resin composition incorporating various additives.

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

[0074] The multifunctional vinyl resin of the present invention can be combined with other vinyl resins and other thermosetting resins, such as epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, and benzo[a]benzene resins. Azamine resin, etc.

[0075] As a multifunctional vinyl resin composition, fillers such as glass cloth, carbon fiber, alumina, and boron nitride can be added to improve thermal conductivity.

[0076] For inorganic filler materials used as fillers, higher thermal conductivity is preferred in order to impart higher thermal conductivity. Preferably, it is 20 W / m·K or higher, more preferably 30 W / m·K or higher, and even more preferably 50 W / m·K or higher. Furthermore, at least a portion, preferably 50 wt% or more, of the inorganic filler material has a thermal conductivity of 20 W / m·K or higher. Moreover, the average thermal conductivity of the inorganic filler material as a whole preferably increases in the order of 20 W / m·K or higher, 30 W / m·K or higher, and 50 W / m·K or higher.

[0077] Examples of inorganic filler materials with such thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide.

[0078] To improve adhesion and enhance the processing of the composition, various additives can be added, such as silane coupling agents, defoamers, internal release agents, and flow regulators.

[0079] Alternatively, the multifunctional vinyl resin or multifunctional vinyl resin composition of the present invention can be dissolved in solvents such as toluene, xylene, acetone, methyl ethyl ketone, and methyl isobutyl ketone, and impregnated in fibrous substrates such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper. After heating and drying, the resulting prepreg can be hot-pressed to obtain a cured product. In this case, the multifunctional vinyl resin or multifunctional vinyl resin composition can be a semi-cured product. Furthermore, a cured product (laminate) of the desired thickness can be produced by stacking multiple sheets of such prepreg and molding them. When obtaining the laminate, a single-cured product can be combined with the prepreg and molded.

[0080] Similarly, a multifunctional vinyl resin or a multifunctional vinyl resin composition, or a resin layer as a semi-cured product thereof, can be coated onto a substrate (support film) such as a PET film, subjected to heating and drying, and the resulting resin sheet can be hot-pressed to obtain a cured product. Alternatively, as described above, a cured product (laminate) of the desired thickness can be produced by stacking multiple such resin sheets and molding them. When obtaining the laminate, a single-cured product can be combined with the resin sheets and molded together.

[0081] Example

[0082] The present invention will be described in more detail through examples and comparative examples. Unless otherwise specified, parts are parts by weight.

[0083] The test conditions for polyhydroxy resins, vinyl resins, and cured products are shown.

[0084] (1) Hydroxyl equivalent

[0085] Using a potentiometric titrator, the solvent is 1,4-didioxanone. Alkane was acetylated with 1.5 mol / L acetyl chloride, and excess acetyl chloride was decomposed with water and titrated with 0.5 mol / L potassium hydroxide.

[0086] (2) Vinyl equivalent

[0087] The sample is reacted with Wiegand's reagent (iodine monochloride solution) and placed in the dark. Then, excess iodine chloride is reduced to iodine, and the iodine content is titrated with sodium thiosulfate to calculate the iodine value. The iodine value is then converted to vinyl equivalents.

[0088] (3) Total chlorine

[0089] The sample can be determined by dissolving 1.0 g of the sample in 25 ml of butylcarbidol, adding 25 ml of 1N-KOH propylene glycol solution, heating under reflux for 10 minutes, cooling to room temperature, adding 100 ml of 80% acetone water, and then performing potentiometric titration with 0.002N-AgNO3 aqueous solution.

[0090] (4) Molecular weight distribution of resin

[0091] The determination was performed using a GPC apparatus (manufactured by TOSOH, HLC-8220GPC). The columns used included one TSK guard column (manufactured by TOSOH), one TSKgel 2000H XL column (manufactured by TOSOH), one TSKgel 3000H XL column (manufactured by TOSOH), and one TSKgel 4000H XL column (manufactured by TOSOH). The detector was RI, and the solvent was tetrahydrofuran. The determination was performed at a flow rate of 1.0 mL / min and a column temperature of 40 °C.

[0092] (5) Thermal conductivity

[0093] Determined based on JIS R 1611 standard.

[0094] (6) Dielectric constant and dielectric loss tangent

[0095] Measurements were taken based on JIS C 2138 standard. The measured frequency is expressed as a value of 1 GHz.

[0096] Polyhydroxy resin A: Product name BRG-555, manufactured by Aica Kogyo Co., Ltd.

[0097] (Synthesis example 1)

[0098] 186.1 g of 4,4'-bis(chloromethyl)biphenyl, 272.1 g of hydroquinone, and 458.2 g of diethylene glycol dimethyl ether were added to a 1000 ml four-necked flask. The mixture was heated to 160 °C under a nitrogen atmosphere with stirring and reacted for 10 hours. Then, 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 solution was added dropwise to a large volume of pure water, and the resin was recovered by reprecipitation, yielding 110 g of a pale yellow resin. The obtained polyhydroxy resin had a hydroxyl equivalent of 110.9 g / eq and a total chlorine content of 460 ppm.

[0099] (Synthesis example 2)

[0100] In the same apparatus as in Synthesis Example 1, 127.9 g of 4,4'-bis(chloromethyl)biphenyl, 272.1 g of 1,6-naphthol, and 400.0 g of diethylene glycol dimethyl ether were added, and the same procedures were performed otherwise. The resulting polyhydroxy resin had a hydroxyl equivalent of 106.8 g / eq and a total chlorine content of 490 ppm.

[0101] (Synthesis example 3)

[0102] In the same apparatus as in Synthesis Example 1, 140.3 g of 4,4'-bis(chloromethyl)biphenyl, 260.0 g of 4,4'-bisphenol, and 400.0 g of diethylene glycol dimethyl ether were added, and the same procedures were performed otherwise. The resulting polyhydroxy resin had a hydroxyl equivalent of 128.7 g / eq and a total chlorine content of 300 ppm.

[0103] (Synthesis Example 4)

[0104] In the same apparatus as in Synthesis Example 1, instead of 4,4'-bis(chloromethyl)biphenyl, 87.5 g of p-dichloroxylene, 186 g of 4,4'-dihydroxybiphenyl, 273 g of diethylene glycol dimethyl ether as solvent, and 1.37 g of p-toluenesulfonic acid as acid catalyst were added. Otherwise, the same procedures were performed. The resulting polyhydroxy resin had a hydroxyl equivalent of 120.0 g / eq and a total chlorine content of 420 ppm.

[0105] (Synthesis Example 5)

[0106] In the same apparatus as in Synthesis Example 1, 87.7 g of 4,4'-bis(chloromethyl)biphenyl, 94.0 g of phenol, and 181.7 g of diethylene glycol dimethyl ether were added, and the same procedures were performed otherwise. The resulting polyhydroxy resin had a hydroxyl equivalent of 78.8 g / eq and a total chlorine content of 360 ppm.

[0107] (Synthesis Example 6)

[0108] In the same apparatus as in Synthesis Example 1, 87.5 g of p-dichloroxylene, 94 g of phenol, and 182 g of diethylene glycol dimethyl ether were added instead of 4,4'-bis(chloromethyl)biphenyl, and the same procedures were performed otherwise. The resulting polyhydroxy resin had a hydroxyl equivalent of 73.0 g / eq and a total chlorine content of 550 ppm.

[0109] Example 1

[0110] In the same apparatus as in Synthesis Example 1, 85.0 g of the polyhydroxy resin obtained in Synthesis Example 1, 198.3 g of diethylene glycol dimethyl ether, and 117.1 g of chloromethylstyrene were added, and the mixture was heated to 70°C to dissolve them. 87.9 g of a 48% potassium hydroxide aqueous solution was added dropwise to initiate the reaction. Gas chromatography confirmed the absence of residual chloromethylstyrene, and the solvent was recovered under reduced pressure. The resulting 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.

[0111] Example 2

[0112] Instead of the polyhydroxy resin of Synthesis Example 1, Synthesis Example 2 used 96.2 g of polyhydroxy resin, 224.4 g of diethylene glycol dimethyl ether, 149.4 g of chloromethylstyrene, and 112.4 g of 48% potassium hydroxide aqueous solution. Otherwise, the same procedures as in Example 1 were performed to obtain vinyl resin B. The vinyl resin B obtained had a vinyl equivalent of 223.5 g / eq and a total chlorine content of 1670 ppm.

[0113] Example 3

[0114] Instead of the polyhydroxy resin of Synthesis Example 1, the polyhydroxy resin of Synthesis Example 3 was 104.8 g, and the following were also used: 231.0 g of diethylene glycol dimethyl ether, 129.5 g of chloromethylstyrene, and 100.0 g of 48% potassium hydroxide aqueous solution. Otherwise, the same procedures as in Example 1 were performed to obtain vinyl resin C. The vinyl resin C obtained had a vinyl equivalent of 255.6 g / eq and a total chlorine content of 1270 ppm.

[0115] Example 4

[0116] Instead of the polyhydroxy resin of Synthesis Example 1, the polyhydroxy resin of Synthesis Example 4 was 118.6 g, and the following were also used: 277.1 g of diethylene glycol dimethyl ether, 89.81 g of chloromethylstyrene, and 86.4 g of 48% potassium hydroxide aqueous solution. Otherwise, the same procedures as in Example 1 were performed to obtain vinyl resin D. The vinyl resin D obtained had a vinyl equivalent of 236.8 g / eq and a total chlorine content of 1300 ppm.

[0117] Comparative Example 1

[0118] Instead of the polyhydroxy resin of Synthesis Example 1, the polyhydroxy resin of Synthesis Example 5 was 118.6 g, and the following were also used: 277.1 g of diethylene glycol dimethyl ether, 89.81 g of chloromethylstyrene, and 86.4 g of 48% potassium hydroxide aqueous solution. Otherwise, the same procedures as in Example 1 were performed to obtain vinyl resin E. The vinyl equivalent of the obtained vinyl resin E was 330.5 g / eq, and the total chlorine content was 1680 ppm.

[0119] Comparative Example 2

[0120] Instead of the polyhydroxy resin used in Synthesis Example 1, 95.0 g of polyhydroxy resin A was used, along with 221.8 g of diethylene glycol dimethyl ether, 145.0 g of chloromethylstyrene, and 121.8 g of 48% potassium hydroxide aqueous solution. Otherwise, the same procedures as in Example 1 were performed to obtain vinyl resin F. The vinyl equivalent of the obtained vinyl resin F was 235.7 g / eq, and the total chlorine content was 1830 ppm.

[0121] Comparative Example 3

[0122] Instead of the polyhydroxy resin of Synthesis Example 1, the polyhydroxy resin of Synthesis Example 6 was 118.6 g, and the following were also used: 277.1 g of diethylene glycol dimethyl ether, 89.81 g of chloromethylstyrene, and 86.4 g of 48% potassium hydroxide aqueous solution. Otherwise, the same procedures as in Example 1 were performed to obtain vinyl resin G. The vinyl equivalent of the obtained vinyl resin G was 192.7 g / eq, and the total chlorine content was 1970 ppm.

[0123] Examples 5-9, Comparative Examples 4-7

[0124] The properties of each resin composition obtained by mixing the obtained vinyl resins A to G with the resins shown below, initiators (organic peroxides), and antioxidants in the proportions shown in Table 1, and the cured products formed by curing them are shown.

[0125] Vinyl resin H: OPE-2ST, manufactured by Mitsubishi Gas Chemical Co., Ltd. (number average molecular weight 1187, vinyl equivalent: 590.0 g / eq)

[0126] Organic peroxide: PERBUTYL P manufactured by Nippon Oil Co., Ltd.

[0127] Antioxidant: ADK STAB AO-60, manufactured by ADK STAB Co., Ltd.

[0128] In Examples 5-9 and Comparative Examples 4-7, homogeneous compositions were prepared by mixing and dissolving in solvents according to the proportions shown in Table 1. This composition was coated onto 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 clamped onto a mirror panel and cured under reduced pressure at 130°C for 15 minutes at 2 MPa and then at 210°C for 80 minutes at 2 MPa.

[0129] The values ​​of dielectric constant, dielectric loss tangent, and thermal conductivity of the cured material are shown in Table 1.

[0130]

[0131] Compared with the comparative example, the multifunctional vinyl resins of the embodiments exhibit superior physical properties such as high thermal conductivity, low dielectric constant, and low dielectric loss tangent.

[0132] Industrial availability

[0133] The multifunctional vinyl resin of the present invention is useful as a material that can easily dissipate heat from electronic components and wiring, thus minimizing signal loss, when used as an electronic material in high-speed communication devices.

Claims

1. A vinyl resin, characterized in that, It is represented by the following general formula (1), Here, X independently represents the divalent arylene alkyl group shown in formula (2) below. Y independently represents Ar 2 The aromatic group represented by a trivalent or higher valence group, Where 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-containing aromatic group as shown in formula (4) below, wherein one or more are vinyl-containing aromatic groups. n represents the number of repetitions, which is an integer from 0 to 15. m independently represents the substitution number, which is an integer greater than 2. Here, Ar 1 Ar 2 Ar 3 Each of the aromatic rings represents an independent aromatic ring, Ar in formula (2). 1 Ar is an aromatic ring selected from benzene ring, naphthalene ring, and biphenyl ring. 2 Ar is an aromatic ring selected from benzene rings, naphthalene rings, biphenyl rings, and bisphenol type ring structures, and is the Ar of formula (4). 3 These aromatic rings are selected from benzene rings, naphthalene rings, and biphenyl rings. 1 Ar 2 Ar 3 It can be unsubstituted or can have more than one substituent independently.

2. A method for manufacturing a vinyl resin, characterized in that, The method for manufacturing the vinyl resin according to claim 1 involves reacting a polyfunctional phenolic compound represented by general formula (5) with an aromatic crosslinking agent represented by general formula (6) to obtain a polyhydroxy resin represented by general formula (7), and then reacting the obtained polyhydroxy resin with an aromatic vinylizing agent represented by general formula (8). Here, X, n, and m are the same as those defined in the general formula (1). In the general formula (5), Y independently represents the expression of Ar. 2 The aromatic group represented by a divalent or higher valence, In the general formula (7), Y independently represents the expression of Ar. 2 The aromatic group represented by a trivalent or higher valence group, However, regarding X, the Ar of equation (2) 1 Or Ar in Y of the general formula (7) 2 At least one of them is a biphenyl ring. Z is defined in the general formula (4). R 1 Independently representing halogen, hydroxyl, or alkoxy. R 2 Indicates halogen, Wherein, the Ar 2 Ar is an aromatic ring selected from benzene rings, naphthalene rings, biphenyl rings, and bisphenol type ring structures. 2 It can be unsubstituted or may have more than one substituent.

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

4. A vinyl resin cured product, which is formed by curing the vinyl resin of claim 1 or the vinyl resin composition of claim 3.

5. A prepreg comprising the vinyl resin of claim 1, or the vinyl resin composition of claim 3, or a semi-cured thereof, and a fibrous substrate.

6. A resin sheet comprising a resin layer and a support film of the vinyl resin of claim 1, or the vinyl resin composition of claim 3, or a semi-cured thereof.

7. A laminated board, which is obtained by laminating and molding the prepreg as described in claim 5.

8. A laminated board, which is obtained by laminating and molding the resin sheets as described in claim 6.

Images