Polyfunctional vinyl resin, method for producing same, composition, and cured product

Abstract

Provided is a vinyl resin which can be used in sealing of electrical / electronic components, circuit board materials, and the like, and which forms a cured product having excellent solvent solubility, heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and excellent flame retardancy. The polyfunctional vinyl resin is represented by general formula (1), and is characterized in that the vinyl equivalent is 200-450 g / eq, the hydroxyl equivalent is not less than 5000 g / eq, and the total chlorine content is not more than 1000 ppm. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a multifunctional vinyl resin, and more specifically, to a multifunctional vinyl resin having excellent solvent solubility and can be used as insulating materials for electrical and electronic components such as semiconductor sealing, laminated boards, and heat dissipation substrates, a method for producing the same, a resin composition, and a cured resin obtained by curing the same, which has excellent heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy. Background Art

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

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

[0004] In addition, for the sealing material composition, as a method for improving thermal conductivity, a method for removing heat from the electronic calculation component by studying the type and amount of various fillers has been adopted, for example, it has been attempted to make it contain inorganic filling materials such as crystalline silicon dioxide, silicon nitride, aluminum nitride, spherical aluminum oxide powder with large thermal conductivity (Patent Documents 3, 4). However, if the content of the inorganic filling material is increased, as the viscosity during molding increases, the fluidity decreases, and the problem of impaired moldability occurs. Therefore, there is a limit to the method of simply increasing the content of the inorganic filling material.

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

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

[0007] Prior art literature

[0008] Patent Literature

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

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

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

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

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

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

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

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

[0017] The present inventors conducted intensive research and expected that a multifunctional vinyl resin having a specific structure could solve the above-mentioned problems. They also found that its cured product exhibited effects in terms of heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy.

[0018] That is, the present invention is a multifunctional vinyl resin represented by the following general formula (1), characterized in that the vinyl equivalent is 200 to 450 g / eq, the hydroxyl equivalent is 5000 g / eq or more, and the total chlorine content is 1000 ppm or less.

[0019]

[0020] In formula (1), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO- or a divalent hydrocarbon group having 1 to 6 carbon atoms, X is an aromatic ring selected from a benzene ring, a naphthalene ring and a biphenyl ring, and n represents a number from 0 to 20.

[0021] Preferred is a polyfunctional vinyl resin represented by the following general formula (2).

[0022]

[0023] In formula (2), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms, at least one of which is other than a single bond. p and q each independently represent a number of 0 to 20.

[0024] In addition, the present invention is a method for producing a polyfunctional vinyl resin, which is a method for producing the above-mentioned polyfunctional vinyl resin, characterized in that after reacting 4,4'-dihydroxybiphenyl represented by formula (3) with an aromatic cross-linking agent represented by formula (4), further reacting a difunctional phenol compound represented by formula (5) to obtain a polyhydroxy resin represented by general formula (6), and reacting the polyhydroxy resin with chloromethylstyrene.

[0025]

[0026] In formula (4), X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms.

[0027]

[0028] In the formula (5), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms.

[0029]

[0030] In formula (6), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms, at least one of which is other than a single bond. p and q each independently represent a number of 0 to 20.

[0031] The present invention is a polyhydroxy resin characterized by being represented by the following general formula (6) and having a hydroxyl equivalent of 100 to 350 g / eq.

[0032]

[0033] In formula (6), A, p and q have the same meanings as above.

[0034] Furthermore, the present invention relates to a polyfunctional vinyl resin composition containing the above-mentioned polyfunctional vinyl resin and a radical polymerization initiator as essential components, and to a polyfunctional vinyl resin cured product obtained by curing the polyfunctional vinyl resin composition.

[0035] The multifunctional vinyl resin of the present invention has excellent solvent solubility and is suitable for vinyl resin compositions and cured products thereof used in applications such as lamination, molding, casting, and bonding. Moreover, the cured product is also excellent in heat resistance, thermal decomposition stability, thermal conductivity, low dielectric constant, low dielectric loss tangent, and flame retardancy, and is therefore suitable for sealing of electrical and electronic components, circuit substrate materials, and the like. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the GPC chart of the multifunctional vinyl resin obtained in Example 1. DETAILED DESCRIPTION

[0037] The present invention is described in detail below.

[0038] The multifunctional vinyl resin of the present invention is a vinyl resin represented by the general formula (1), characterized in that the vinyl equivalent is 200 to 450 g / eq, the hydroxyl equivalent is 5000 g / eq or more, and the total chlorine content is 1000 ppm or less.

[0039]

[0040] n is a repetition number (number average), and represents a number from 0 to 20. The vinyl resin of the present invention is usually a mixture of components having different values ​​of the repetition number (n), and the average value (number average) of n is preferably in the range of 0.1 to 15, and more preferably in the range of 0.5 to 10. A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon group having 1 to 6 carbon atoms, and X is an aromatic ring selected from a benzene ring, a naphthalene ring, and a biphenyl ring. From the viewpoint of thermal conductivity, A is preferably a single bond, and X is preferably a biphenyl ring.

[0041] The vinyl equivalent of the multifunctional vinyl resin of the present invention is 200 to 450 g / eq. It is preferably 230 to 300 g / eq, and more preferably 240 to 280 g / eq. When it is smaller than this range, there is a concern that the solvent solubility may be reduced due to the increase in the content of n=0, and there is a concern that the heat resistance and thermal conductivity may be reduced due to the reduction in the restraining force of molecular motion after curing. On the other hand, when it is larger than this range, the reactivity is reduced, and there is a concern that it may be difficult to obtain a uniform cured product.

[0042] The multifunctional vinyl resin of the present invention has a hydroxyl equivalent of 5000 g / eq or more and a total chlorine content of 1000 ppm or less with respect to polar groups.

[0043] The multifunctional vinyl resin of the present invention can be obtained by reacting a polyvalent hydroxyl resin with chloromethylstyrene, but when the unreacted and remaining hydroxyl group is less than 5000 g / eq, curing becomes insufficient, and thermal conductivity and heat resistance are reduced. In addition, since the hydroxyl group is a polar group, its remaining hinders the reduction of the dielectric constant and the dielectric loss tangent. The hydroxyl equivalent is preferably 10000 g / eq or more, and more preferably 12000 g / eq or more.

[0044] On the other hand, as chlorine components, there are chlorine components from chloromethylstyrene and chlorine components from the crosslinking agent in the polyhydroxy resin. They are difficult to remove when the solvent solubility of the vinyl resin is low. When more than 1000ppm of chlorine components remain, the reduction of dielectric constant and dielectric loss tangent is hindered, and the curing reaction is hindered, thereby having a tendency to reduce thermal conductivity and heat resistance. The total chlorine content is preferably less than 700ppm, more preferably less than 500ppm.

[0045] The polyfunctional vinyl resin of the present invention is preferably a polyfunctional vinyl resin represented by the general formula (2).

[0046]

[0047] p and q are repetition numbers (number average), and represent numbers from 0 to 20. Preferably, it is a mixture of components having different values ​​for p and q. The ratio (molar ratio) of p / (p+q) is preferably 0.50 to 0.95, and more preferably 0.70 to 0.95. When it is less than 0.50, the effects of heat resistance and high thermal conductivity are small. When it is greater than 0.95, the crystallinity is enhanced and the solvent solubility is reduced. The average value of p is preferably 0.1 to 10, and more preferably 0.5 to 5. The average value of q is preferably 0.1 to 5, and more preferably 0.1 to 2.

[0048] A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms. The substitution positions of the two vinyl benzyl ether groups bonded to the biphenyl structure having A preferably include at least 2,2'. In the general formula (1), when A is a single bond, that is, when both ends are biphenyl rings, the substitution positions of the two vinyl benzyl ether groups bonded thereto are preferably 4,4' and 2,2', and the ratio of the biphenyl at both ends is preferably 40 to 90 mol% of the total at 2,2'. When A is other than a single bond, that is, when both ends of the vinyl resin are other than biphenyl rings, such as a diphenylmethane structure, the substitution positions of the two vinyl benzyl ether groups bonded thereto are preferably 30 to 100 mol% at 4,4'.

[0049] The polyfunctional vinyl resin represented by the above formula (2) can be produced by reacting a polyhydroxy resin represented by the formula (6) with chloromethylstyrene.

[0050]

[0051] In the polyhydroxy resin of formula (6), the ratio of A, p, q, and p / (p+q) is the same as that of the above-mentioned polyfunctional vinyl resin.

[0052] The hydroxyl equivalent of the polyhydroxy resin represented by formula (6) of the present invention is preferably 100 to 350 g / eq. These polyhydroxy groups are partially or completely vinylized to become the polyfunctional vinyl resin represented by formula (2) of the present invention.

[0053] The polyhydroxy resin can be produced by reacting 4,4'-dihydroxybiphenyl represented by formula (3) with an aromatic crosslinking agent having a biphenyl structure represented by formula (4) as shown in the following formula (7), and then reacting with a bifunctional phenol compound represented by formula (5).

[0054]

[0055] Here, X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms.

[0056]

[0057] Here, A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms.

[0058]

[0059] The molar ratio of the 4,4'-dihydroxybiphenyl represented by formula (3) and the bifunctional phenol compound represented by formula (5) as the synthetic raw materials is preferably 0.50 to 0.95, more preferably 0.70 to 0.95. When the ratio of 4,4'-dihydroxybiphenyl is less than this range, heat resistance and high thermal conductivity are insufficient, while when it is more, the crystallinity is strong, so that the solvent solubility is reduced.

[0060] Specific examples of the difunctional phenol compound of formula (5) include 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, dihydroxydiphenylmethanes, and 2,2-bis(4-hydroxyphenyl)propane. In particular, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, and dihydroxydiphenylmethanes are preferred from the viewpoint of solvent solubility. Dihydroxydiphenylmethanes may be a mixture of ortho, meta, and para positions. In terms of isomer ratio, 4,4'-dihydroxydiphenylmethane is preferably 40% or less. If the amount of 4,4'-dihydroxydiphenylmethane is high, the crystallinity is strong, and there is a concern that the solvent solubility is reduced.

[0061] In the aromatic crosslinking agent represented by the above formula (3), X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms. Specific examples of aromatic condensing agents include 4,4'-bishydroxymethylbiphenyl, 4,4'-bischloromethylbiphenyl, 4,4'-bisbromomethylbiphenyl, 4,4'-bismethoxymethylbiphenyl and 4,4'-bisethoxymethylbiphenyl. From the viewpoint of reactivity, 4,4'-bishydroxymethylbiphenyl or 4,4'-bischloromethylbiphenyl is preferred, and from the viewpoint of reducing ionic impurities, 4,4'-bishydroxymethylbiphenyl or 4,4'-bismethoxymethylbiphenyl is preferred.

[0062] In terms of the molar ratio when reacting phenols with aromatic condensing agents, generally, the aromatic condensing agent is in the range of 0.2 to 0.7 moles relative to 1 mole of phenols, and more preferably in the range of 0.4 to 0.7 moles. If it is less than 0.2 moles, the ratio of n=0 bodies of the obtained polyhydroxy resin increases, and there is a concern that the solubility such as crystallinity will be reduced. On the other hand, if it is more than 0.7 moles, the high molecular weight component increases, and stable production becomes difficult.

[0063] The reaction of phenols and aromatic condensing agent can be carried out in the absence of catalyst, or in the presence of acid catalysts such as mineral acid, organic acid. When using 4,4'-bischloromethylbiphenyl, can react in the absence of catalyst, but generally, in order to suppress the side reactions such as chloromethyl and hydroxyl reaction and generate ether bonds, it is advisable to carry out in the presence of an acidic catalyst. As this acidic catalyst, can suitably select from known mineral acid, organic acid, for example, can list Lewis acids such as mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, zinc chloride, aluminum chloride, iron chloride, boron trifluoride or solid acid etc.

[0064] Usually, the reaction is carried out at 100 to 250° C. for 1 to 20 hours. Preferably, the reaction is carried out at 100 to 180° C., more preferably 140 to 180° C. If the reaction temperature is low, the reactivity is poor and time is required, while if the reaction temperature is high, the resin may be decomposed.

[0065] During the reaction, as a solvent, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used, and among these, ethyl cellosolve, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and the like are particularly preferred. After the reaction is completed, the obtained polyhydroxy resin can be removed by vacuum distillation, water washing, or reprecipitation in a poor solvent, or it can be directly used as a raw material for vinylation reaction in a state where the solvent is left.

[0066] The multifunctional vinyl resin of the present invention can be suitably obtained by reacting a polyhydroxy resin with an aromatic vinylating agent. For example, the vinyl resin of the present invention represented by the above formula (2) can be obtained by reacting a polyhydroxy resin represented by the above formula (6) with chloromethylstyrene. The reaction can be carried out in the same manner as a known vinylation reaction.

[0067] As the aromatic vinylating agent, halogenated methylstyrene is preferred, and chloromethylstyrene is particularly preferred. In addition, bromomethylstyrene and its isomers, halogenated methylstyrene having a substituent, etc. can be cited. As for the substitution position of the halogenated methyl form, for example, in the case of halogenated methylstyrene, the 4-position is preferred, and the 4-position form is preferably 60% by weight or more of the total.

[0068] The reaction between the polyhydroxy resin and the aromatic vinylating agent can be carried out without a solvent or in the presence of a solvent. The aromatic vinylating agent can be added to the polyhydroxy resin, a metal hydroxide can be added to react, and the generated metal salt can be removed by filtering, washing with water, etc. to carry out the reaction.

[0069] The solvent may include methyl ethyl ketone, benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc., but are not limited to these. From the viewpoint of reactivity, methyl ethyl ketone is preferred. As specific examples of metal hydroxides, sodium hydroxide, potassium hydroxide, etc. may be included, but are not limited to these.

[0070] The vinylation reaction is carried out at a temperature of 90° C. or less, preferably 70° C. or less. At a temperature higher than this, thermal self-polymerization of the vinyl benzyl ether group proceeds, making it difficult to control the reaction. In order to suppress self-polymerization, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitroso groups, nitrone compounds, oxygen, etc. may be used.

[0071] The reaction endpoint can be determined by tracking the remaining amount of halogenated methylstyrene as the aromatic vinylating agent using various chromatography methods such as GPC, and the reaction rate can be adjusted by the type, amount, addition rate, solid content concentration, etc. of the metal hydroxide.

[0072] After the reaction is completed, the obtained polyfunctional vinyl resin is preferably purified by removing the solvent and the like by distillation under reduced pressure, washing with water, or reprecipitation in a poor solvent.

[0073] The multifunctional vinyl resin of the present invention can be cured alone, but can also be preferably used as a multifunctional resin composition blended with various additives.

[0074] For example, in order to accelerate curing, a radical polymerization initiator such as an azo compound or an organic peroxide may be added to cause curing.

[0075] The multifunctional vinyl resin of the present invention may be blended with other vinyl resins and other thermosetting resins, for example, epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polyphenylene ether resins, benzoxazine resins, and the like.

[0076] The multifunctional vinyl resin composition may contain a filler such as glass cloth, carbon fiber, alumina, or boron nitride in order to improve thermal conductivity.

[0077] As for the inorganic filler material, in order to impart higher thermal conductivity, the higher the thermal conductivity, the more preferred. Preferably, it is 20 W / m·K or more, more preferably 30 W / m·K or more, and further preferably 50 W / m·K or more. Moreover, at least a portion of the inorganic filler material, preferably 50 wt% or more, has a thermal conductivity of 20 W / m·K or more. Moreover, the average thermal conductivity of the inorganic filler material as a whole is in the order of 20 W / m·K or more, 30 W / m·K or more, and 50 W / m·K or more, and the preference increases.

[0078] Examples of the inorganic filler having such a thermal conductivity include inorganic powder fillers such as boron nitride, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide.

[0079] In order to improve the adhesive force and the handling of the composition, various additives may be added, for example, a silane coupling agent, a defoaming agent, an internal mold release agent, a flow regulator, etc. may be mentioned.

[0080] The multifunctional vinyl resin or multifunctional vinyl resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc., impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and the prepreg obtained by heating and drying is hot-pressed to obtain a cured product.

[0081] In addition, the resin may be coated on a sheet-like material such as copper foil, stainless foil, polyimide film, polyester film, etc. to form a laminate, or a cured product may be obtained by heat-pressing a heat-dried resin sheet.

[0082] Example

[0083] The following examples and comparative examples are given to specifically describe the present invention. However, the present invention is not limited to these examples. Unless otherwise specified, "part" means part by weight, and "%" means % by weight. In addition, with respect to the measuring method, the following methods are used to measure respectively.

[0084] 1) OH equivalent

[0085] A potentiometric titration apparatus was used, 1,4-dioxane was used as a solvent, acetylation was performed with 1.5 mol / L acetyl chloride, excess acetyl chloride was decomposed with water, and titration was performed with 0.5 mol / L potassium hydroxide.

[0086] 2) Vinyl equivalent

[0087] The sample is reacted with a Weiss solution (iodine monochloride solution) and left in a dark place, and then the excess iodine chloride is reduced to iodine, and the iodine is titrated with sodium thiosulfate to calculate the iodine value. The iodine value is converted into vinyl equivalent.

[0088] 3) Total chlorine

[0089] After dissolving 1.0 g of the sample in 25 ml of butyl carbitol, 25 ml of 1N-KOH propylene glycol solution was added, and the mixture was heated under reflux for 10 minutes, cooled to room temperature, and then 100 ml of 80% acetone water was added. The solution was measured by potentiometric titration using 0.002N-AgNO3 aqueous solution.

[0090] 4) GPC determination

[0091] An instrument with a column (TSKgel Super Multipore HZ-N 4, manufactured by Tosoh Corporation) in series was used in the main body (manufactured by Tosoh Corporation, HLC-8220GPC), and the column temperature was set to 40°C. In addition, tetrahydrofuran (THF) was used as the eluent, and the flow rate was set to 0.35 mL / min, and a differential refractive index detector was used as the detector. The sample was measured using 50 μL of the substance obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering with a microfilter. GPC-8020 Model II Version 6.00 manufactured by Tosoh Corporation was used for data processing.

[0092] 5) Solvent solubility (precipitation temperature)

[0093] 2 g of resin and 1 g of cyclohexanone were weighed in a sample bottle, heated to dissolve, and then the temperature was slowly lowered in a thermostatic bath to measure the temperature in the bath where the resin precipitated. The higher the precipitation temperature (°C), the worse the solvent solubility.

[0094] 6) Glass transition temperature (Tg)

[0095] Tg was determined using a thermomechanical measuring apparatus (EXSTAR TMA / 7100 manufactured by SII Nanotechnology Co., Ltd.) at a temperature increase rate of 10° C. / min.

[0096] 7) 5% weight loss temperature (Td5), residual carbon rate

[0097] The 5% weight loss temperature (Td5) was measured using a thermogravimetric / differential thermal analyzer (EXSTAR TG / DTA7300 manufactured by SII Nanotechnology) under a nitrogen atmosphere and a heating rate of 10°C / min. The weight loss at 700°C was also measured and calculated as the residual carbon ratio.

[0098] 8) Thermal conductivity

[0099] The thermal conductivity was measured by a non-steady-state hot wire method using a LFA447 thermal conductivity meter manufactured by NETZSCH.

[0100] 9) Dielectric constant and dielectric loss tangent

[0101] The measurement was performed in accordance with JIS C 2138. The measurement frequency was expressed as a value of 1 GHz.

[0102] Example 1

[0103] In a 1000 ml four-necked flask, 65.3 g (0.35 mol) of 4,4'-dihydroxybiphenyl (structural formula shown below) and

[0104]

[0105] 121.2 g of diethylene glycol dimethyl ether, 58.7 g (0.23 mol) of 4,4'-bis(chloromethyl)biphenyl (structural formula shown below),

[0106]

[0107] The temperature was raised to 170° C. under a nitrogen stream while stirring, and the reaction was allowed to proceed for 3 hours. 7.8 g (0.04 mol) of dihydroxydiphenylmethane (4,4′-dihydroxydiphenylmethane (the following structural formula): 36.2%, 2,4′-dihydroxydiphenylmethane: 46.6%, 2,2′-dihydroxydiphenylmethane: 17.2%) was further reacted.

[0108]

[0109] A polyhydroxy resin (hydroxyl equivalent weight 129 g / eg) was produced.

[0110] After the reaction was completed, 50.7 g of diethylene glycol dimethyl ether was recovered, 320 g of methyl ethyl ketone and 135.5 g of chloromethylstyrene (the following structural formula) were added,

[0111]

[0112] The temperature was raised to 60°C, and 49.8 g of potassium hydroxide dissolved in 150 g of methanol was dripped in over 3 hours, and the mixture was allowed to react for 6 hours. After the reaction was completed, the mixture was filtered, the solvent was distilled off, and reprecipitated with methanol. The mixture was washed with a large amount of water and dried under reduced pressure to obtain 141 g of a white solid vinyl resin (vinyl resin A). The vinyl equivalent of vinyl resin A was 275 g / eg., the hydroxyl equivalent was 15,000 g / eg., and the total chlorine was 300 ppm. The GPC diagram of the obtained multifunctional vinyl resin is shown in FIG. Figure 1 According to the feed ratio, the ratio (molar ratio) of p / (p+q) was 0.93, p was 4.2, and q was 0.3.

[0113] Example 2

[0114] Except that 7.3 g (0.04 mol) of 2,2'-dihydroxybiphenyl (structural formula shown below) was used instead of dihydroxydiphenylmethane,

[0115]

[0116] The reaction was carried out in the same manner as in Example 1 to obtain a polyvalent hydroxy resin (hydroxyl equivalent 116 g / eg) and further obtain 138 g of a multifunctional vinyl resin (vinyl resin B). The vinyl equivalent of vinyl resin B was 262 g / eg., the hydroxyl equivalent was 13000 g / eg., and the total chlorine content was 340 ppm. The ratio (molar ratio) of p / (p+q) was 0.93, p was 4.0, and q was 0.3.

[0117] Example 3

[0118] Except that 40.2 g (0.23 mol) of p-dichlorobenzyl was used instead of 4,4'-bischloromethylbiphenyl,

[0119]

[0120] The reaction was carried out in the same manner as in Example 1 to obtain a polyvalent hydroxy resin (hydroxyl equivalent 105 g / eg) and further obtain 129 g of a multifunctional vinyl resin (vinyl resin C). The vinyl equivalent of vinyl resin C was 252 g / eg., the hydroxyl equivalent was 13400 g / eg., and the total chlorine content was 320 ppm. The ratio (molar ratio) of p / (p+q) was 0.93, p was 3.7, and q was 0.3.

[0121] (Comparative Example 1)

[0122] In a 1000 ml four-necked flask, 40.8 g of 4,4'-bis(chloromethyl)biphenyl, 75.5 g of 4,4'-dihydroxybiphenyl, and 120 g of diethylene glycol dimethyl ether were placed, and the temperature was raised to 160°C under a nitrogen stream while stirring, and the mixture was reacted for 10 hours. Next, the temperature was set to 70°C, 280 g of diethylene glycol dimethyl ether and 129.5 g of chloromethylstyrene were added, and 100.0 g of 48% potassium hydroxide was added dropwise while the reaction was carried out. The absence of residual chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The obtained resin was dissolved in toluene, neutralized, and washed with water to obtain 172 g of a multifunctional vinyl resin (vinyl resin D). The vinyl equivalent of the obtained vinyl resin D was 256 g / eq., the hydroxyl equivalent was 1500 g / eq., and the total chlorine content was 1270 ppm.

[0123] (Comparative Example 2)

[0124] The same operation as in Comparative Example 1 was performed except that 63.0 g of phenol was used instead of 58.9 g of 4,4'-bis(chloromethyl)biphenyl and 4,4'-dihydroxybiphenyl, to obtain 160 g of a multifunctional vinyl resin (vinyl resin E). The vinyl equivalent of the obtained vinyl resin E was 331 g / eq., the hydroxyl equivalent was 2100 g / eq., and the total chlorine content was 1680 ppm.

[0125] (Comparative Example 3)

[0126] The same operation as in Example 1 was performed except that 320 g of diethylene glycol dimethyl ether was used instead of 320 g of methyl ethyl ketone and the reaction with chloromethyl styrene was carried out at 80° C. to obtain 135 g of a multifunctional vinyl resin (vinyl resin F). The vinyl equivalent of the vinyl resin F was 95 g / eg., the hydroxyl equivalent was 1000 g / eg., and the total chlorine content was 260 ppm. The ratio (molar ratio) of p / (p+q) was 0.90, and the mixture was in the range of p from 0 to 10 and q from 0 to 4.

[0127] (Comparative Example 4)

[0128] The same operation as in Example 1 was performed except that reprecipitation with methanol was not performed in the operation after the reaction in Example 1, thereby obtaining 150 g of a multifunctional vinyl resin (vinyl resin G). The vinyl equivalent of the vinyl resin G was 285 g / eg., the hydroxyl equivalent was 16000 g / eg., and the total chlorine content was 3000 ppm. The ratio (molar ratio) of p / (p+q) was 0.90, and the mixture was in the range of p from 0 to 8 and q from 0 to 2.

[0129] (Comparative Example 5)

[0130] In a 1000 ml four-necked flask, 50.0 g of dihydroxydiphenylmethane (4,4'-dihydroxydiphenylmethane: 36.2%, 2,4'-dihydroxydiphenylmethane: 46.6%, 2,2'-dihydroxydiphenylmethane: 17.2%), 400 g of methyl ethyl ketone, and 80.1 g of chloromethylstyrene were added, and the temperature was raised to 60°C. 29.5 g of potassium hydroxide dissolved in 88 g of methanol was added dropwise over 3 hours, and the mixture was reacted for 6 hours. After the reaction was completed, the mixture was filtered, the solvent was distilled off, and the mixture was reprecipitated with methanol, washed with a large amount of water, and dried under reduced pressure to obtain 95.4 g of a multifunctional vinyl resin (vinyl resin H). The vinyl equivalent of vinyl resin H was 217 g / eg., the hydroxyl equivalent was 17000 g / eg., and the total chlorine content was 400 ppm.

[0131] Examples 4 to 6, Comparative Examples 6 to 11

[0132] As the multifunctional vinyl resin, the vinyl resins A to H obtained in Examples 1 to 3 and Comparative Examples 1 to 5 and the vinyl resin I (OPE-2ST: manufactured by Mitsubishi Gas Chemical Co., Ltd., vinyl equivalent: 590.0 g / eq, number average molecular weight 1187) were used, and the organic peroxide Perbutyl P (manufactured by NOF Corporation) as a curing accelerator (radical polymerization initiator) and ADK STAB AO-60 (manufactured by ADEKA Corporation) as an antioxidant were mixed in the proportions shown in Table 1 and dissolved in a solvent to prepare a uniform composition. The composition was applied to a PET film and dried at 130°C for 5 minutes to obtain a resin composition. The composition taken out from the PET film was sandwiched between a mirror plate and cured at 130°C for 15 minutes under reduced pressure and at 210°C for 80 minutes while applying a pressure of 2 MPa. The properties of the obtained cured product are shown in Table 1.

[0133] [Table 1]

[0134]

[0135] The multifunctional vinyl resins of Examples have higher thermal conductivity than those of Comparative Examples, and exhibit excellent physical properties such as a low dielectric constant and a low dielectric loss tangent.

[0136] Industrial Applicability

[0137] The multifunctional vinyl resin of the present invention can be used as a material that can easily dissipate heat from electronic parts and wiring, which are electronic materials for high-speed communication equipment, and has a small signal loss.

Claims

1. A multifunctional vinyl resin, which is a multifunctional vinyl resin represented by the following general formula (1), characterized in that: The vinyl equivalent is 200 to 450 g / eq, the hydroxyl equivalent is 5000 g / eq or more, and the total chlorine content is 1000 ppm or less. In formula (1), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO- or a divalent hydrocarbon group having 1 to 6 carbon atoms, X is an aromatic ring selected from a benzene ring, a naphthalene ring and a biphenyl ring, and n represents a number from 0 to 20.

2. The multifunctional vinyl resin according to claim 1, which is represented by the following general formula (2): In formula (2), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO- or a divalent hydrocarbon having 1 to 6 carbon atoms, at least one of which is other than a single bond, and p and q each independently represent a number of 0 to 20.

3. A method for producing a multifunctional vinyl resin, which is a method for producing the multifunctional vinyl resin according to claim 2, characterized in that: After reacting 4,4'-dihydroxybiphenyl represented by formula (3) with an aromatic crosslinking agent represented by formula (4), further reacting with a difunctional phenol compound represented by formula (5) to obtain a polyhydroxy resin represented by general formula (6), and reacting the polyhydroxy resin with chloromethylstyrene, In formula (4), X represents a hydroxyl group, a halogen atom or an alkoxy group having 1 to 6 carbon atoms, In formula (5), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms, In formula (6), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms, at least one of which is other than a single bond, and p and q each independently represent a number of 0 to 20.

4. A polyhydroxy resin, characterized in that It is represented by the following general formula (6), and the hydroxyl equivalent is 100 to 350 g / eq. In formula (6), A represents a single bond, an oxygen atom, a sulfur atom, -SO2-, -CO-, or a divalent hydrocarbon having 1 to 6 carbon atoms, at least one of which is other than a single bond, and p and q each independently represent a number of 0 to 20.

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

6. A polyfunctional vinyl resin cured product obtained by curing the polyfunctional vinyl resin composition according to claim 5.

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