Multifunctional vinyl resins and methods for making the same

Abstract

This invention provides a resin material with low relative permittivity, low dielectric loss tangent, high thermal conductivity, and high heat resistance. A multifunctional vinyl resin is represented by the following general formula (1). Here, R... 1 R represents a hydrocarbon group with 1 to 8 carbon atoms independently. 2 Independently represents a hydrogen atom or a dicyclopentenyl group, with at least one being a dicyclopentenyl group. X independently represents a hydrogen atom or a vinyl-containing aromatic group represented by formula (1a) below, with at least one being a vinyl-containing aromatic group. n represents the number of repetitions, with an average value of 1 to 5. Ar represents an aromatic ring. -CH2-Ar-CH=CH2(1a).

Description

Technical Field

[0001] This invention relates to a multifunctional vinyl resin and a multifunctional vinyl resin composition, which are useful for printed circuit boards, sealing materials, casting materials, etc. of electronic devices and have both low dielectric loss tangent and high thermal conductivity, as well as the cured product thereof. Background Technology

[0002] With the increase in information and communication volume in recent years, there has been a surge in the development of high-frequency communication. To achieve superior electrical characteristics, particularly reducing transmission losses at high frequencies, there is a demand for electrical insulating materials with low relative permittivity, low dielectric loss tangent, and minimal change in dielectric properties after undergoing severe thermal processes. Furthermore, printed circuit boards or electronic components using these insulating materials are exposed to high-temperature reflow soldering during assembly, thus requiring materials with high heat resistance, i.e., high glass transition temperatures. In particular, recent environmental concerns have led to an increasing demand for electrical insulating materials with even higher heat resistance to facilitate the use of high-melting-point lead-free solders. To address these needs, curing resins using vinyl benzyl ether resins with various chemical structures have been proposed in the past.

[0003] Examples of such cured resins include bisphenol divinyl benzyl ether resins and phenolic varnish-type polyvinyl benzyl ether resins (Patent Document 1, Patent Document 2). However, these vinyl benzyl ether resins not only fail to achieve sufficient properties in terms of initial dielectric characteristics, but also cannot provide cured resins with minimal changes in dielectric properties relative to harsh thermal processes, and their heat resistance is not sufficiently high.

[0004] Several vinyl benzyl ether resins with specific structures have been proposed to improve these properties, and attempts have been made to suppress the change in dielectric loss tangent during severe thermal processes or to improve heat resistance. However, the improvement in properties is still insufficient, and further property improvements are desired. Therefore, as an installation material, it is not sufficient in terms of reliability and processability (Patent Documents 3, 4, and 5).

[0005] Furthermore, a multifunctional vinyl resin composition (Patent Document 6) is disclosed, characterized in that it contains a multifunctional vinyl resin obtained by vinyl benzyl etherification of at least one hydroxyl group selected from phenol aralkyl resin, naphthol aralkyl resin, biphenyl-type phenolic varnish resin, and biphenyl-type naphtholic varnish resin. However, the vinyl benzyl etherified multifunctional vinyl resin synthesized according to the manufacturing method disclosed therein has a high total halogen content and a large amount of residual vinyl aromatic halomethyl compounds. Therefore, its dielectric loss tangent and heat resistance after undergoing a severe thermal process cannot meet the requirements for an insulating material corresponding to high frequencies, and it is also prone to poor molding properties, making it a less than desirable multifunctional vinyl resin.

[0006] Furthermore, it is known to vinylbenzylate the phenolic hydroxyl groups of polyfunctional phenylene ether oligomers. These polyfunctional phenylene ether oligomers are obtained by reacting a polyphenol having 3 or more but fewer than 9 phenolic hydroxyl groups in the molecule, with an alkyl or alkylene group at the 2 and 6 positions of at least one of the phenolic hydroxyl groups, with a monohydric phenol compound (Patent Document 7). However, the vinylbenzyl ether resin obtained by this technique has the following disadvantages: high viscosity requires high molding processing temperature, and the dielectric loss tangent deteriorates significantly when exposed to high temperatures in an air atmosphere.

[0007] Thus, conventional vinyl benzyl ether resins cannot provide the heat-resistant cured products required for electrical insulation applications, especially for high-frequency electrical insulation applications, which have the ability to withstand lead-free soldering and meet the requirements of a low dielectric loss tangent after a harsh thermal history. In addition, they are also insufficient in terms of reliability and processability.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 63-68537

[0011] Patent Document 2: Japanese Patent Application Publication No. 64-65110

[0012] Patent Document 3: Japanese Patent Publication No. 1-503238

[0013] Patent Document 4: Japanese Patent Application Publication No. 9-31006

[0014] Patent Document 5: Japanese Patent Application Publication No. 2004-323730

[0015] Patent Document 6: Japanese Patent Application Publication No. 2003-306591

[0016] Patent Document 7: Japanese Patent Application Publication No. 2007-308685 Summary of the Invention

[0017] The objective of this invention is to provide an ethylene resin and a resin composition that provides a cured product with a low relative permittivity, a low dielectric loss tangent, and minimal change in dielectric properties after undergoing a severe thermal process, exhibiting high thermal conductivity and a high glass transition temperature. The aim is to provide a resin composition, cured product, or material containing the same that can be used as a dielectric material, insulating material, or heat-resistant material in the electrical and electronic industries, spacecraft and aircraft industries, and other fields.

[0018] The inventors conducted in-depth research on resin structure and functional groups, and found that a multifunctional vinyl resin obtained by aromatic vinylation of the phenolic hydroxyl groups of a multihydroxy resin with a dicyclopentenyl substituent obtained by the reaction of 2,6-disubstituted phenol with dicyclopentadiene can solve the above-mentioned problems, thus completing the present invention.

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

[0020]

[0021] -CH2-Ar-CH=CH2 (1a)

[0022] here,

[0023] R 1 Independently representing hydrocarbon groups with 1 to 8 carbon atoms,

[0024] R 2 It independently represents a hydrogen atom or a dicyclopentenyl group, with at least one of them being a dicyclopentenyl group.

[0025] X independently represents a hydrogen atom or a vinyl-containing aromatic group represented by formula (1a) above, and at least one of them is a vinyl-containing aromatic group.

[0026] n represents the number of repetitions, with an average value between 1 and 5.

[0027] Ar in formula (1a) represents an aromatic ring, preferably an aromatic ring selected from benzene ring, naphthalene ring and biphenyl ring. The aromatic ring Ar can be unsubstituted or have one or more substituents.

[0028] The present invention is a method for manufacturing a polyfunctional vinyl resin, characterized in that, in manufacturing the above-mentioned polyfunctional vinyl resin, dicyclopentadiene is reacted at a ratio of 0.28 to 2 moles relative to 1 mole of 2,6-disubstituted phenol represented by the following general formula (2) to obtain a polyhydroxy resin represented by the following general formula (3), and then the obtained polyhydroxy resin is reacted with an aromatic vinylizing agent represented by the following general formula (4).

[0029]

[0030] XR 3 (4)

[0031] here,

[0032] R 1 R 2 X and n have the same meaning as defined in the above general formula (1).

[0033] R 3 It represents halogens.

[0034] The present invention relates to a multifunctional vinyl resin composition containing a multifunctional vinyl resin and a free radical polymerization initiator as essential components, and a cured multifunctional vinyl resin product obtained by curing the composition thereof.

[0035] Furthermore, it is a prepreg consisting of a semi-cured product of a multifunctional vinyl resin composition and a fibrous substrate, a resin sheet having a semi-cured product of a multifunctional vinyl resin composition and a support film, and a laminate obtained by stacking and molding these prepregs and / or resin sheets.

[0036] The multifunctional vinyl resin and composition of the present invention, as well as the cured product formed by curing the composition, have low relative permittivity, low dielectric loss tangent, and high thermal conductivity. They are useful as electronic materials for high-speed communication devices, easily dissipating heat generated from electronic components and wiring, and as materials with low signal loss. In particular, they maintain excellent dielectric properties even after undergoing high-temperature thermal processes in air, and exhibit high reliability in electrical characteristics even under harsh operating conditions. Attached Figure Description

[0037] Figure 1 The GPC diagram shows the polyhydroxy resin obtained in Synthesis Example 1.

[0038] Figure 2 The image shows the IR spectrum of the polyhydroxy resin obtained in Synthesis Example 1.

[0039] Figure 3 The image shows the GPC diagram of the multifunctional vinyl resin obtained in Example 1. Detailed Implementation

[0040] The present invention will now be described in detail.

[0041] The multifunctional vinyl resin of the present invention is represented by the above general formula (1).

[0042] In general formula (1), R 1The hydrocarbon group having 1 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, or an allyl group. The alkyl group having 1 to 8 carbon atoms can be any of the following: linear, branched, or cyclic. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, methylbutyl, n-hexyl, dimethylbutyl, n-heptyl, methylhexyl, trimethylbutyl, n-octyl, dimethylpentyl, ethylpentyl, isooctyl, ethylhexyl, etc., as well as cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, methylcycloheptyl, etc., having 5 to 8 carbon atoms, but are not limited to these. Examples of aryl groups with 6 to 8 carbon atoms include phenyl, tolyl, xylyl, and ethylphenyl, but they are not limited to these. Examples of aralkyl groups with 7 to 8 carbon atoms include benzyl and α-methylbenzyl, but they are not limited to these. Among these substituents, methyl or phenyl is preferred from the viewpoint of ease of acquisition and reactivity when preparing a cured product, and methyl is particularly preferred.

[0043] The above R 2 It independently represents a hydrogen atom or a dicyclopentenyl group, with at least one of them being a dicyclopentenyl group.

[0044] The dicyclopentenyl group is a group derived from dicyclopentadiene, represented by formula (1b) or formula (1c) below.

[0045]

[0046] X independently represents a hydrogen atom or a vinyl-containing aromatic group represented by formula (1a) above, and at least one of them is a vinyl-containing aromatic group derived from an aromatic vinylizing agent used as a raw material. Ar in formula (1a) is an aromatic ring selected from benzene rings, naphthalene rings, and biphenyl rings.

[0047] The aromatic ring Ar can be unsubstituted or have one or more substituents. When substituents are present, one to four are preferred. The substituents are preferably alkyl or aryl groups having 1 to 10 carbon atoms, and more preferably alkyl or phenyl groups having 1 to 3 carbon atoms.

[0048] n is a repetition number, representing numbers greater than 1, and is used to represent numbers from 1 to 5 by their average value, preferably 1.1 to 4.0, more preferably 1.2 to 3.0, and even more preferably 1.3 to 2.0. The average value is the mean of numbers.

[0049] The preferred content, as measured by GPC, is 10% or less for n=0, 50-70% for n=1, and 20-40% for n=2 or more.

[0050] The number-average molecular weight (Mn) of the multifunctional vinyl resin of the present invention is preferably 400-3000, more preferably 500-1500. The vinyl equivalent (g / eq) is preferably 200-600, more preferably 220-550, further preferably 300-550, and particularly preferably 400-500. The total chlorine content is preferably 1500 ppm or less, more preferably 1300 ppm or less.

[0051] The multifunctional vinyl resin of the present invention can be suitably obtained by reacting the polyhydroxy resin represented by the above general formula (3) with the aromatic vinylizing agent represented by the above general formula (4).

[0052] For example, in a method for reacting dicyclopentadiene with 2,6-disubstituted phenol represented by general formula (2) at a specified ratio, the polyhydroxy resin represented by general formula (3) can be reacted by continuously adding dicyclopentadiene or by intermittently adding dicyclopentadiene in several stages (two or more batches). Regarding the ratio, the amount of dicyclopentadiene relative to 1 mole of 2,6-disubstituted phenol is 0.28 to 2 moles. Regarding the ratio when reacting by continuously adding dicyclopentadiene, the amount of dicyclopentadiene relative to 1 mole of 2,6-disubstituted phenol is 0.25 to 1 mole, preferably 0.28 to 1 mole, more preferably 0.3 to 0.5 moles. In the case of reacting by batches of dicyclopentadiene, the overall amount is preferably 0.8 to 2 moles, more preferably 0.9 to 1.7 moles. It should be noted that the preferred ratio of dicyclopentadiene used in each stage is 0.28 to 1 mole.

[0053] Examples of the aforementioned 2,6-disubstituted phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, 2,6-di(n-butyl)phenol, 2,6-di(tert-butyl)phenol, 2,6-dihexylphenol, 2,6-bicyclohexylphenol, and 2,6-diphenylphenol. From the viewpoint of ease of acquisition and reactivity when preparing a cured product, 2,6-diphenylphenol and 2,6-dimethylphenol are preferred, and 2,6-dimethylphenol is particularly preferred.

[0054] The catalyst used in the reaction of phenols with dicyclopentadiene is a Lewis acid, specifically a boron trifluoride compound such as boron trifluoride, boron trifluoride-phenol complex, or boron trifluoride-ether complex; metal chlorides such as aluminum chloride, tin chloride, zinc chloride, titanium tetrachloride, and ferric chloride; and organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid. Among these, boron trifluoride-ether complex is preferred for ease of operation. In the case of boron trifluoride-ether complex, the amount of catalyst used is 0.001 to 20 parts by mass relative to 100 parts by mass of dicyclopentadiene, preferably 0.5 to 10 parts by mass.

[0055] As a reaction method, it is preferable to load 2,6-disubstituted phenol and catalyst into the reactor and add dicyclopentadiene dropwise over 1 to 10 hours.

[0056] The reaction temperature is preferably 50–200°C, more preferably 100–180°C, and even more preferably 120–160°C. The reaction time is preferably 1–10 hours, more preferably 3–10 hours, and even more preferably 4–8 hours.

[0057] After the reaction is complete, alkalis such as sodium hydroxide, potassium hydroxide, and calcium hydroxide are added to deactivate the catalyst. Subsequently, solvents such as toluene, xylene, and other aromatic hydrocarbons, ketones such as methyl ethyl ketone and methyl isobutyl ketone are added for dissolution. After washing with water, the solvent is recovered under reduced pressure, thereby obtaining the target polyhydroxy resin. It should be noted that it is preferable to react as completely as possible with dicyclopentadiene, leaving a portion of the 2,6-disubstituted phenol unreacted, preferably less than 10%, and recovering it under reduced pressure.

[0058] It should be noted that during the reaction, solvents such as aromatic hydrocarbons like benzene, toluene, and xylene, halogenated hydrocarbons like chlorobenzene and dichlorobenzene, ethers like ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and ketones like methyl isobutyl ketone, cyclopentanone, and cyclohexanone can also be used as needed to adjust viscosity.

[0059] As a method to confirm the introduction of the dicyclopentenyl group into the above-mentioned polyhydroxy resin, mass spectrometry (MS) and Fourier transform infrared spectrophotometry (FT-IR) can be used.

[0060] When using mass spectrometry, electrospray ionization mass spectrometry (ESI-MS) or field desorption-emulation mass spectrometry (FD-MS) can be used. The introduction of dicyclopentenyl groups can be confirmed by performing mass spectrometry on samples obtained by separating components with different nucleus numbers using methods such as GPC.

[0061] When using FT-IR measurement, a sample dissolved in an organic solvent such as THF is coated onto a KRS-5 unit. FT-IR measurement of the unit with the sample film obtained after drying the organic solvent reveals that the peak of the CO stretching vibration from the phenol nucleus appears at 1210 cm⁻¹. －1 Nearby, only when dicyclopentenyl is introduced, at 3040 cm －1 A peak of CH stretching vibration from the olefinic region of the dicyclopentadiene skeleton appears nearby. When the baseline is defined as the line connecting the start and end points of the target peak, and the peak height is defined as the length from the peak apex to the baseline, the value is calculated based on 3040 cm⁻¹. －1 Nearby peak (A) 3040 ) and 1210cm －1 Nearby peak (A) 1210The ratio of (A) 3040 / A 1210 This allows for the quantification of the amount of dicyclopentenyl groups introduced. It has been confirmed that a higher ratio results in better physical properties. The optimal ratio (A) is chosen to meet the target physical properties. 3040 / A 1210 The value is 0.05 or more, more preferably 0.10 or more, and particularly preferably 0.10 to 0.30.

[0062] The hydroxyl equivalent of the multifunctional hydroxyl resin is preferably 150–500, more preferably 200–350. The weight-average molecular weight (Mw) is preferably 500–2000, more preferably 600–900, and the number-average molecular weight (Mn) is preferably 350–1200, more preferably 400–600. The softening point is preferably 70–120°C, more preferably 70–110°C.

[0063] The multifunctional vinyl resin of the present invention can be suitably obtained by reacting a polyhydroxy resin represented by general formula (3) obtained therefrom with an aromatic vinylizing agent represented by general formula (4).

[0064] As the aromatic vinylizing agent represented by general formula (4), halomethylstyrene is preferred. Specific examples of halomethylstyrene include chloromethylstyrene, bromomethylstyrene and its isomers, and halomethylstyrene with substituents. Regarding the substitution position of the halomethyl body, for example in the case of halomethylstyrene, the 4-position is preferred, and it is more preferably that the 4-position body accounts for 60% or more of the total mass.

[0065] 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.

[0066] Regarding the ratio of polyhydroxy resin to aromatic vinylizing agent, the reaction can be carried out in such a manner that the vinyl equivalent of the aromatic vinylizing agent is preferably 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents, relative to 1 equivalent of the hydroxyl equivalent of the polyhydroxy resin.

[0067] Solvents may include benzene, toluene, xylene, methyl isobutyl ketone, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, etc., but are not limited to these. Specific examples of metal hydroxides may include sodium hydroxide, potassium hydroxide, etc., but are not limited to these.

[0068] The reaction is carried out at a temperature below 100°C, preferably below 80°C. In cases where there are concerns about the self-polymerization of halogenated methylstyrene as an aromatic vinylizing agent, polymerization inhibitors such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitroketones, and oxygen can also be used.

[0069] 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, or by adjusting the addition rate and using an appropriate catalyst.

[0070] The multifunctional vinyl resin of the present invention can be cured alone, and is also preferably used as a multifunctional resin composition incorporating various additives. For example, a free radical polymerization initiator can be used to promote curing.

[0071] As a free radical polymerization initiator (also called a free radical polymerization catalyst), for example, the resin composition of the present invention is cured by means of heating or the like as described later. However, for the purpose of lowering the reaction temperature or promoting the crosslinking reaction of unsaturated groups, a free radical polymerization initiator may also be included. The amount of free radical polymerization initiator used for this purpose is preferably 0.01 to 12 parts by weight, more preferably 0.1 to 8 parts by weight, relative to 100 parts by weight of the multifunctional vinyl resin.

[0072] Representative examples of free radical polymerization initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-disperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, tert-butylcumyl peroxide, α,α'-bis(tert-butylperoxymisopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, cumyl peroxide, di-tert-butylperoxyisophthalate, tert-butylperoxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltriphenylsilyl peroxide, etc., but are not limited to these. Additionally, although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a free radical polymerization initiator (or polymerization catalyst). However, the catalysts and free radical polymerization initiators used in the curing of this resin composition are not limited to these examples.

[0073] The multifunctional vinyl resin composition of the present invention can be formulated with other vinyl resins or other thermally multifunctional vinyl resins. Examples include vinyl ester resins, polyvinyl benzyl resins, epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polycyanate resins, phenolic resins, and benzo[a]benzene resins. Azine resins, etc.

[0074] In addition, it can also be used with thermoplastic resins such as polystyrene resin, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, PPS resin, polycyclopentadiene resin, and polycyclic olefin resin; thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, and hydrogenated styrene-isoprene copolymer; and rubbers such as polybutadiene and polyisoprene.

[0075] In the multifunctional vinyl resin composition of the present invention, various known flame retardants can be used to improve the flame retardancy of the obtained cured product without compromising reliability. Examples of usable flame retardants include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organometallic salt-based flame retardants. From an environmental point of view, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants can be used alone, or two or more flame retardants from the same system can be used in combination. Furthermore, flame retardants from different systems can be used in combination.

[0076] The multifunctional vinyl resin composition of the present invention may also contain components other than those listed above for the purpose of further improving its functionality. Examples of such other components include fillers, UV inhibitors, antioxidants, coupling agents, plasticizers, fluxes, thixotropic agents, smoothers, colorants, pigments, dispersants, emulsifiers, low-elasticity agents, release agents, defoamers, and ion trapping agents.

[0077] Examples of filler materials include inorganic fillers such as fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, and carbon; fibrous fillers such as carbon fiber, glass fiber, alumina fiber, silica-alumina fiber, silicon carbide fiber, polyester fiber, polyamide fiber, cellulose fiber, aromatic polyamide fiber, and ceramic fiber; and microparticle rubber.

[0078] Other components may include organic pigments such as quinacridone, azo, and phthalocyanine pigments; inorganic pigments such as titanium dioxide, metallic foil pigments, and rust-preventing pigments; UV absorbers such as hindered amine, benzotriazole, and benzophenone pigments; antioxidants such as hindered phenol, phosphorus, sulfur, and hydrazide pigments; release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate; leveling agents; rheology control agents; pigment dispersants; anti-cratering agents; and defoamers. The preferred amount of these other components relative to the total solids content in the resin composition is in the range of 0.01 to 20% by mass.

[0079] The multifunctional vinyl resin composition of the present invention can be used to prepare resin varnishes by dissolving it in a solvent. Examples of solvents include methyl ethyl ketone, acetone, toluene, xylene, tetrahydrofuran, dioxolane, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, and γ-butyrolactone; the selection and appropriate amount used can be chosen according to the application. For example, in applications involving printed wiring boards, solvents with a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, toluene, xylene, and 1-methoxy-2-propanol, are preferred. Furthermore, it is preferable to use solvents with a non-volatile component content of 20-80% by mass. On the other hand, in applications involving build-up adhesive films, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, γ-butyrolactone, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred. Furthermore, it is preferable to use the non-volatile components in a proportion of 20-80% by mass. It should be noted that the laminate of the present invention is obtained by curing a resin varnish. Specifically, examples include printed wiring substrates, printed circuit boards, flexible printed wiring boards, and build-up wiring boards.

[0080] The cured product obtained by curing the multifunctional vinyl resin composition of the present invention can be used in the form of molded articles, laminates, castings, adhesives, coatings, and films. For example, the cured product of a semiconductor sealing material is a casting or a molded article. As a method to obtain a cured product for this purpose, the compound can be molded using a casting mold or a transfer molding machine, injection molding machine, etc., and then heated at 80 to 230°C for 0.5 to 10 hours to obtain a cured product. In addition, the cured product of a resin varnish is a laminate. As a method to obtain this cured product, the resin varnish can be impregnated in the above-mentioned fibrous filler, paper, or other substrate, heated and dried to obtain a prepreg, which can then be laminated individually or laminated with a metal foil such as copper foil and hot-pressed to obtain the product.

[0081] In addition, by combining it with inorganic high dielectric powders such as barium titanate or inorganic magnetic materials such as ferrite, it is useful as a material for electronic components, especially high-frequency electronic components.

[0082] Next, the prepreg and its cured product of the present invention will be described. To improve mechanical strength and increase dimensional stability, a base material is added to the prepreg of the present invention.

[0083] As such a substrate, two or more types of roving cloth, cloth, chopped strand mat, surface mat, etc., various glass cloth, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths can be used alone or in combination, or made of fully aromatic polyamide fiber, fully aromatic polyester fiber, polystyrene... Fabrics and papers made from liquid crystal fibers such as azole fibers, fabrics or non-woven fabrics made from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, and acrylic fibers, natural fiber fabrics such as cotton, linen, and felt, carbon fiber fabrics, kraft paper, cotton paper, and paper-glass blended fiber paper, etc.

[0084] In the prepreg, the proportion of the substrate is 5-90% by mass, preferably 10-80% by mass, and more preferably 20-70% by mass. If the substrate content is less than 5% by mass, there is a tendency for the dimensional stability and strength of the cured product to decrease. Conversely, if the substrate content is more than 90% by mass, there is a tendency for the dielectric properties of the cured product to decrease.

[0085] In the prepreg of the present invention, a coupling agent may be used as needed to improve the adhesion between the resin and the substrate interface. Common coupling agents such as silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and zirconium aluminate coupling agents can be used.

[0086] As a method for manufacturing the prepreg of the present invention, an example method is as follows: the multifunctional vinyl resin composition of the present invention and other components as needed are uniformly dissolved or dispersed in the above-mentioned aromatic, ketone, or other solvents or mixtures thereof, impregnated onto a substrate, and then dried. Impregnation is carried out by dipping, coating, or the like. Impregnation can also be repeated multiple times as needed. In addition, at this time, multiple solutions with different compositions and concentrations can be used for repeated impregnation to ultimately adjust to the desired resin composition and resin amount.

[0087] A cured product is obtained by curing the prepreg of the present invention using methods such as heating. The manufacturing method is not particularly limited; for example, multiple sheets of prepreg can be overlapped, and the layers can be bonded together under heat and pressure while simultaneously undergoing thermosetting to obtain a cured product (laminated board) of the desired thickness. Alternatively, a cured product that has been bonded and cured once can be combined with prepreg to obtain a multilayer laminate consisting of new layers. Lamination and curing are usually performed simultaneously using methods such as hot pressing, but they can also be performed separately. That is, the uncured or semi-cured prepreg obtained through prior lamination can be treated by heat treatment or other methods to cure it.

[0088] Molding and curing can be performed, for example, at temperatures of 80–300°C and pressures of 0.1–1000 kgf / cm². 2 Time: 1 minute to 10 hours, preferably Temperature: 150 to 250°C; Pressure: 1 to 500 kgf / cm² 2 Time: Within the range of 1 minute to 5 hours.

[0089] The laminate of the present invention is composed of a layer of prepreg of the present invention and a layer of metal foil. Examples of metal foils used herein include copper foil and aluminum foil. Its thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0090] As a method for manufacturing the laminate of the present invention, an example method can be given as follows: a prepreg obtained from the multifunctional vinyl resin composition of the present invention described above and a substrate is laminated with a metal foil according to the desired layer configuration; the layers are bonded together under heat and pressure, and thermosetting is performed simultaneously. In the laminate of the multifunctional vinyl resin composition of the present invention, the cured material is laminated with the metal foil with any layer configuration. The metal foil can be used as a surface layer or as an intermediate layer. In addition to the above, the lamination and curing can be repeated multiple times to achieve multilayering.

[0091] Adhesives can also be used for bonding to metal foil. Examples of adhesives include epoxy, acrylic, phenolic, and cyanoacrylate adhesives, but are not particularly limited to these. The above-described lamination and curing can be carried out under the same conditions as the manufacture of the cured product of the prepreg of the present invention.

[0092] Alternatively, the multifunctional vinyl resin composition of the present invention can also be molded into a film. Its thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0093] The method for manufacturing the film of the present invention is not particularly limited. For example, the following method can be used: the multifunctional vinyl resin composition and other components as needed are uniformly dissolved or dispersed in an aromatic solvent, ketone solvent, or a mixture thereof, coated onto a resin film such as a PET film, and then dried. The coating can be repeated multiple times as needed. In addition, multiple solutions with different compositions and concentrations can be used for repeated coating to ultimately adjust the desired resin composition and resin amount.

[0094] Furthermore, a resin-coated metal foil can be obtained from the multifunctional vinyl resin composition of the present invention and the metal foil. Examples of metal foils used herein include copper foil and aluminum foil. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0095] There are no particular limitations on the method for manufacturing resin-coated metal foil. For example, a method can be described as follows: a multifunctional vinyl resin composition and other required components are uniformly dissolved or dispersed in an aromatic, ketone, or other solvent or a mixture thereof, coated onto a metal foil, and then dried. The coating can be repeated multiple times as needed. In addition, multiple solutions with different compositions and concentrations can be used for repeated coating to ultimately adjust the desired resin composition and amount.

[0096] The electronic material substrate is formed using the laminate of the present invention. The aforementioned electronic material substrate is suitable for use in various electrical and electronic devices requiring reliability in environments demanding heat resistance, water resistance, or high-frequency signal transmission reliability, such as mobile phones, PHS devices, notebook computers, PDAs (portable information terminals), portable video phones, personal computers, supercomputers, servers, routers, LCD projectors, engineering workstations (EWS), pagers, word processors, televisions, viewfinder-type or monitor-type video recorders, electronic notebooks, electronic desktop calculators, car navigation devices, POS terminals, and devices with touch panels. In particular, due to the excellent dielectric properties, heat resistance stability, and dimensional stability and moldability corresponding to the formation of fine-patterned circuits of the cured material of the present invention, it is suitable for use as a circuit board for the aforementioned electrical and electronic devices. Specifically, examples include single-sided, double-sided, multilayer printed circuit boards, flexible boards, and additive boards. Preferred examples also include multilayer circuit boards using metal plating as the conductor layer.

[0097] Example

[0098] The present invention will be described in more detail through examples and comparative examples. Unless otherwise specified, parts refer to parts by mass and % refers to percentages by mass. It should be noted that the unit of equivalent is g / eq.

[0099] The test conditions for polyhydroxy resins, vinyl resins, and cured products are shown.

[0100] (1) Hydroxyl equivalent:

[0101] The determination was performed according to JIS K 0070 standard. Specifically, a potentiometric titration apparatus was used to determine the 1,4-dihydroxyethyl esters. Alkane was used as a solvent, and acetylation was carried out using 1.5 mol / L acetyl chloride. Excess acetyl chloride was decomposed with water, and titration was performed using 0.5 mol / L potassium hydroxide. It should be noted that, unless otherwise specified, the hydroxyl equivalent of polyhydroxy resins refers to the phenolic hydroxyl equivalent.

[0102] (2) Vinyl equivalent:

[0103] The determination was performed according to JIS K 0070 standard. Specifically, the sample was reacted with Wiegand's reagent (iodine monochloride solution), placed in the dark, and then excess iodine chloride was reduced to iodine. The iodine content was then titrated with sodium thiosulfate to calculate the iodine value. The iodine value was then converted to vinyl equivalents.

[0104] (3) Total chlorine:

[0105] Dissolve 1.0 g of the sample in 25 mL of butylcarbitol, add 25 mL of 1N-KOH propylene glycol solution, heat under reflux for 10 minutes, cool to room temperature, add 100 mL of 80% acetone-water solution, and perform potentiometric titration using 0.002N-AgNO3 aqueous solution to determine the sample.

[0106] (4) Molecular weight distribution (Mw, Mn):

[0107] The determination was performed using a GPC apparatus (Tosoh Corporation, HLC-8220GPC) and a tandem column (Tosoh Corporation, TSKGuardcolumn, TSKgelG2000HXL, TSKgelG3000HXL, TSKgelG4000HXL). The detector was set to a differential refractive index detector (RI), the solvent to tetrahydrofuran (THF), the flow rate to 1.0 mL / min, and the column temperature to 40 °C. A 50 μL sample was used, prepared by dissolving 0.1 g of the sample in 10 mL of THF and filtering it through a microfilter. Data processing was performed using Tosoh Corporation's GPC-8020model II version 6.00.

[0108] (5) Thermal conductivity:

[0109] The test was conducted in accordance with JISR 1611 standard.

[0110] (6) Relative permittivity and dielectric loss tangent:

[0111] The measurements were performed according to JIS C 2565 standard. Specifically, the sample was dried in an oven set at 105°C for 2 hours, cooled in a desiccator, and then measured using a cavity resonator method dielectric constant measuring device manufactured by AET Corporation. The measured frequency was expressed as a value of 1 GHz.

[0112] (7) Glass transition temperature (Tg):

[0113] The measurements were performed according to JIS C 6481 standard. Specifically, the tanδ peak value was expressed as the result of measurements taken using a dynamic viscoelasticity measuring device (manufactured by Hitachi High-Tech Science Company, EXSTAR DMS6100) at a heating rate of 5°C / min.

[0114] The abbreviations used in the examples and comparative examples are as follows.

[0115] [Polyhydroxy resin]

[0116] P1: The polyhydroxy resin obtained in Synthesis Example 1

[0117] P2: The polyhydroxy resin obtained in Synthesis Example 2

[0118] P3: The polyhydroxy resin obtained in Synthesis Example 3

[0119] P4: Biphenyl aralkyl type polyhydroxy resin (manufactured by Meiwa Kasei Corporation, MEH-7851, phenolic hydroxyl equivalent 223)

[0120] P5: Phenolic varnish resin (manufactured by Aica Kogyo Co., Ltd., BRG-555, phenolic hydroxyl equivalent 105).

[0121] [Vinyl compounds]

[0122] HV3: Vinyl compound (manufactured by Mitsubishi Gas Chemical Co., Ltd., OPE-2ST, Mn1187, vinyl equivalent 590)

[0123] PO: Organic peroxide (manufactured by Nippon Oil Co., Ltd., Perbutyl P)

[0124] AO: Antioxidant (manufactured by ADEKA Corporation, Adekastab AO-60)

[0125] Synthesis example 1

[0126] In a reaction apparatus consisting of a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and a detachable glass flask equipped with a cooling tube, 140 parts of 2,6-xylenol and 9.3 parts of 47% BF3 ether complex (0.1 molar ratio relative to the initially added dicyclopentadiene) were charged. The mixture was heated to 110°C with stirring. While maintaining the same temperature, 86.6 parts of dicyclopentadiene (0.57 molar ratio relative to 2,6-xylenol) were added dropwise over 1 hour. After reacting at 110°C for 3 hours, 68 parts of dicyclopentadiene (0.44 molar ratio relative to 2,6-xylenol) were added dropwise over 1 hour while maintaining the same temperature. The reaction was then carried out at 120°C for 2 hours. 14.6 parts of calcium hydroxide were added. 45 parts of a 10% oxalic acid aqueous solution were then added. Subsequently, after dehydration at 160°C, the unreacted raw material was evaporated and removed by heating to 200°C under reduced pressure (5 mmHg). 700 parts of MIBK were added to dissolve the product, followed by washing with 200 parts of warm water (80°C) to separate and remove the lower aqueous layer. Then, the MIBK was evaporated and removed by heating to 160°C under reduced pressure (5 mmHg), yielding 274 parts of a reddish-brown polyhydroxy resin (P1). This resin has a hydroxyl equivalent of 299, a softening point of 97°C, and an absorption ratio (A...). 3040 / A 1210 The value was 0.17. Mass spectra obtained using ESI-MS (negative) were confirmed to M=253, 375, 507, 629. The GPC of the obtained polyhydroxy resin (P1) is shown in [the figure]. Figure 1 FT-IR is shown Figure 2 The values ​​of Mw and Mn obtained using GPC are 690 and 510, respectively. Figure 1 The expression 'a' represents the n=1 body of equation (3) and the expression (3) without R. 2 The mixture of n=1 additive bodies, b represents the n=0 body of equation (3). Figure 2 c represents the peak of CH stretching vibration from the olefinic site of the dicyclopentadiene skeleton, and d represents the absorption caused by CO stretching vibration of the phenolic core.

[0127] Synthesis example 2

[0128] In the same reaction apparatus as in Synthesis Example 1, 140 parts of 2,6-xylenol and 9.3 parts of 47% BF3 ether complex (0.1 molar ratio relative to the initially added dicyclopentadiene) were charged, and the mixture was heated to 110°C with stirring. While maintaining the same temperature, 86.6 parts of dicyclopentadiene (0.57 molar ratio relative to 2,6-xylenol) were added dropwise over 1 hour. After reacting at 110°C for 3 hours, 90.6 parts of dicyclopentadiene (0.60 molar ratio relative to 2,6-xylenol) were added dropwise over 1 hour while maintaining the same temperature. The reaction was then carried out at 120°C for 2 hours. 14.6 parts of calcium hydroxide were added. Then, 45 parts of a 10% oxalic acid aqueous solution were added. Subsequently, the mixture was heated to 160°C for dehydration, and then heated to 200°C under reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials. 740 parts of MIBK were added to dissolve the product, followed by washing with 200 parts of warm water (80°C) to separate and remove the lower aqueous layer. Subsequently, the MIBK was evaporated at 160°C under reduced pressure (5 mmHg) to obtain 310 parts of a reddish-brown polyhydroxy resin (P2). This resin has a hydroxyl equivalent of 341, a softening point of 104°C, and an absorption ratio (A... 3040 / A 1210 The value was 0.27. Mass spectra obtained using ESI-MS (negative) were confirmed to M⁻ = 253, 375, 507, and 629. Mw and Mn obtained using GPC were 830 and 530, respectively.

[0129] Synthesis example 3

[0130] In the same reaction apparatus as in Synthesis Example 1, 970 parts of 2,6-xylenol and 14.5 parts of 47% BF3 ether complex were charged, and the mixture was heated to 70°C while stirring. While maintaining the same temperature, 300 parts of dicyclopentadiene (0.29 molar ratio relative to 2,6-xylenol) were added dropwise over 2 hours. The reaction was then carried out at 125–135°C for 6 hours, followed by the addition of 2.3 parts of calcium hydroxide. Then, 4.6 parts of a 10% oxalic acid aqueous solution were added. Subsequently, the mixture was heated to 160°C for dehydration, and then heated to 200°C under reduced pressure (5 mmHg) to evaporate and remove unreacted reactants. 1000 parts of MIBK were added to dissolve the product, followed by washing with 400 parts of warm water at 80°C to separate and remove the lower aqueous layer. Subsequently, MIBK was evaporated and removed by heating to 160℃ under reduced pressure of 5 mmHg, yielding 540 parts of a reddish-brown polyhydroxy resin (P3). The hydroxyl equivalent was 213, the softening point was 71℃, and the absorbance (A...)... 3040 / A 1210 The value was 0.11. Mass spectra obtained using ESI-MS (negative) were confirmed to M⁻ = 253, 375, 507, and 629. Mw obtained using GPC was 670, and Mn was 520.

[0131] Example 1

[0132] In the same apparatus as in Synthesis Example 1, 100 parts of polyhydroxy resin (P1), 230 parts of diethylene glycol dimethyl ether, and 51.1 parts of chloromethylstyrene were charged, and the mixture was heated to 70°C for dissolution. 39.5 parts of a 48% potassium hydroxide aqueous solution were added dropwise over 1 hour, and the reaction was continued at 75°C for 4 hours. Gas chromatography confirmed the absence of residual chloromethylstyrene, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 300 parts of toluene and washed with 100 parts of water until the pH of the aqueous layer reached 7. Subsequently, the solvent was removed by vacuum distillation, yielding 203 parts of a vinyl resin (V1) solution containing 65% non-volatile components in toluene. The vinyl equivalent was 417, and the total chlorine content was 1150 ppm.

[0133] Example 2

[0134] In the same apparatus as in Synthesis Example 1, 100.0 parts of polyhydroxy resin (P2), 230 parts of diethylene glycol dimethyl ether, and 44.7 parts of chloromethylstyrene were charged, and the mixture was heated to 70°C for dissolution. 34.6 parts of a 48% potassium hydroxide aqueous solution were added dropwise over 1 hour, and the reaction was continued at 75°C for 4 hours. Gas chromatography confirmed the absence of residual chloromethylstyrene, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 320 parts of toluene and washed with 100 parts of water until the pH of the aqueous layer reached 7. Subsequently, the solvent was removed by vacuum distillation, yielding 196 parts of a vinyl resin (V2) as a toluene solution with 65% non-volatile components. The vinyl equivalent was 462, and the total chlorine content was 1030 ppm.

[0135] Example 3

[0136] In the same apparatus as in Synthesis Example 1, 100 parts of polyhydroxy resin (P3), 230 parts of diethylene glycol dimethyl ether, and 71.7 parts of chloromethylstyrene were charged, and the mixture was heated to 70°C for dissolution. 55.4 parts of a 48% potassium hydroxide aqueous solution were added dropwise over 1 hour, and the reaction was continued at 75°C for 4 hours. Gas chromatography confirmed the absence of residual chloromethylstyrene, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 370 parts of toluene and washed with 100 parts of water until the pH of the aqueous layer reached 7. Subsequently, the solvent was removed by vacuum distillation, yielding 234 parts of a vinyl resin (V3) solution containing 65% non-volatile components in toluene. The vinyl equivalent was 334, and the total chlorine content was 1230 ppm.

[0137] Comparative Example 1

[0138] In the same apparatus as in Synthesis Example 1, 118.6 parts of polyhydroxy resin (P4), 277.1 parts of diethylene glycol dimethyl ether, and 81.2 parts of chloromethylstyrene were charged, and the mixture was heated to 70°C for dissolution. 62.8 parts of a 48% potassium hydroxide aqueous solution were added dropwise over 1 hour, and the reaction was continued at 75°C for 4 hours. Gas chromatography confirmed the absence of residual chloromethylstyrene, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 410 parts of toluene and washed with 100 parts of water until the pH of the aqueous layer reached 7. Subsequently, the solvent was removed by vacuum distillation to obtain 260 parts of a vinyl resin (HV1) solution containing 65% non-volatile components in toluene. The vinyl equivalent was 331, and the total chlorine content was 1680 ppm.

[0139] Comparative Example 2

[0140] In the same apparatus as in Synthesis Example 1, 95.0 parts of polyhydroxy resin (P5), 222 parts of diethylene glycol dimethyl ether, and 138.1 parts of chloromethylstyrene were charged, and the mixture was heated to 70°C for dissolution. 106.8 parts of a 48% potassium hydroxide aqueous solution were added dropwise over 1 hour, and the reaction was continued at 75°C for 4 hours. Gas chromatography confirmed the absence of residual chloromethylstyrene, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 500 parts of toluene and washed with 100 parts of water until the pH of the aqueous layer reached 7. Subsequently, the solvent was removed by vacuum distillation to obtain 302 parts of a vinyl resin (HV2) solution containing 65% non-volatile components in toluene. The vinyl equivalent was 235, and the total chlorine content was 1830 ppm.

[0141] Examples 4-7, Comparative Examples 3-5

[0142] The mixture was prepared according to the proportions shown in Table 1 and dissolved in a solvent to obtain a uniform varnish. The varnish was then coated onto a PET film and dried at 130°C for 5 minutes. The varnish was then peeled off from the PET film to obtain a resin composition. The resin composition was sandwiched between mirror panels and cured under reduced pressure at 130°C for 15 minutes and then at 210°C for 80 minutes at a pressure of 2 MPa to obtain a cured product. The relative permittivity, dielectric loss tangent, thermal conductivity, and Tg of the cured product are shown in Table 1.

[0143] [Table 1]

[0144]

[0145] In addition, the relative permittivity and dielectric loss tangent of the cured products of Examples 4-6 and Comparative Examples 3-4 were measured after being placed in an oven at 200°C in air atmosphere for 1 hour. The results and the rate of change of dielectric loss tangent before and after placement are shown in Table 2.

[0146] [Table 2]

[0147] Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Relative permittivity 2.75 2.73 2.77 2.86 2.90 Relative permittivity [after 200℃ × 1Hr] 2.78 2.76 2.81 2.90 2.94 Dielectric loss tangent 0.0024 0.0023 0.0028 0.0029 0.0051 Dielectric loss tangent [after 200℃ × 1Hr] 0.0031 0.0029 0.0036 0.0056 0.0079 Dielectric loss tangent change rate (%) 23 28 22 48 35

[0148] Compared to the comparative example, the multifunctional vinyl resin of the embodiment exhibits superior physical properties such as high glass transition temperature, high thermal conductivity, and consequently low relative permittivity and low dielectric loss tangent.

[0149] Industrial availability

[0150] The multifunctional vinyl resins and compositions of the present invention have excellent dielectric and thermal conductivity, and can be used for various applications such as lamination, molding, and bonding. They are particularly useful as electronic materials for high-speed communication equipment.

Claims

1. A multifunctional vinyl resin, characterized by, is a structure represented by the following general formula (1), the peak height of the peak near 3040 cm －1 from the C-H stretching vibration of the olefin portion of the dicyclopentadiene skeleton from the dicyclopentenyl group in FT-IR measurement 3040 is 0.10 or greater －1 from the C-O stretching vibration of the phenol nucleus in FT-IR measurement 1210 is 0.10 or greater 3040 is 0.10 or greater 1210 is 0.10 or greater ， Here, R 1 independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 independently represent a hydrogen atom or a dicyclopentenyl group, and at least 1 is a dicyclopentenyl group, X independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by the above formula (1a), and at least one is a vinyl group-containing aromatic group, and Ar represents an aromatic ring, n represents a repeating number, and has an average value of 1 to 5.

2. The multifunctional vinyl resin of claim 1, wherein, Ar of formula (1a) is an aromatic ring selected from a benzene ring, a naphthalene ring, and a biphenyl ring, and the aromatic ring Ar is unsubstituted or has one or more substituents.

3. A method for producing a polyfunctional vinyl resin, characterized by, is a method of producing the multifunctional vinyl resin according to claim 1, and dicyclopentadiene is reacted at a ratio of 0.28 to 2 times the moles with respect to 1 mole of 2,6-disubstituted phenol represented by the following general formula (2) to obtain a polyhydroxy resin represented by the following general formula (3), ， Here, R 1 , R 2 , n, X are the same as defined in the general formula (1), respectively, R 3 represents halogen.

4. A multifunctional vinyl resin composition comprising the multifunctional vinyl resin according to claim 1 and a free radical polymerization initiator as essential components.

5. A cured product obtained by curing the multifunctional vinyl resin according to claim 1 or the multifunctional vinyl resin composition according to claim 4.

6. A prepreg comprising the multifunctional vinyl resin composition according to claim 4 or a semi-cured product thereof, and a fibrous base material.

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

8. A laminate obtained by laminating and molding the prepreg according to claim 6 and / or the resin sheet according to claim 7.

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