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

Abstract

Provided is a resin material which has high solvent solubility, while exhibiting a low dielectric constant, a low dielectric loss tangent, and high heat resistance. A polyfunctional vinyl resin represented by general formula (1). In the formula, R1 represents a hydrocarbon group having 1-8 carbon atoms, R2 represents a hydrogen atom and a dicyclopentenyl group, and at least one of R2 represents a dicyclopentenyl group. X represents a hydrogen atom, and at least one of the vinyl group-containing groups represented by formula (1a) is a vinyl group-containing group. And R3 represents a hydrogen atom or an alkyl group or alkenyl group having 1-8 carbon atoms. And n represents a number of repetitions, the average value of which is 1-5. # imgabs0 #-CO-CR3 = CH2 (1a), and a method for producing the same.

Description

Technical Field

[0001] The present invention relates to a multifunctional vinyl resin and a multifunctional vinyl resin composition having both low dielectric loss tangent and high heat resistance, and a cured product thereof, which can be used for printed circuit boards, sealing materials, casting materials, etc. of electronic devices. Background Art

[0002] With the increase of information communication volume in recent years, information communication in high frequency band is prevalent. In order to have more excellent electrical properties, especially to reduce the transmission loss in high frequency band, it is necessary to have an electrical insulating material with low dielectric constant and low dielectric loss tangent. Furthermore, printed substrates or electronic components using these electrical insulating materials are exposed to high temperature reflow soldering during installation, so it is desirable to have a material with high heat resistance, that is, a material showing a high glass transition temperature. Especially recently, due to environmental problems, a lead-free solder with a high melting point is used, so the demand for electrical insulating materials with higher heat resistance is rising. For these requirements, it has been proposed to use a curing resin of a vinyl resin with various chemical structures.

[0003] As such a curing resin, for example, a curing resin such as a divinyl benzyl ether resin of bisphenol or a polyvinyl benzyl ether resin of a phenol novolac type has been proposed (Patent Documents 1 and 2). However, these vinyl benzyl ether resins not only fail to obtain sufficient dielectric properties, but also have insufficient heat resistance.

[0004] As vinyl benzyl ether resins having improved properties, several vinyl benzyl ether resins having specific structures have been proposed, and attempts have been made to improve heat resistance (Patent Documents 3, 4, and 5). However, the improvement in properties is not sufficient, and further improvement in properties is desired.

[0005] A multifunctional vinyl resin composition is disclosed, characterized in that it contains a multifunctional vinyl resin obtained by vinylbenzyl etherifying at least one hydroxyl group selected from phenol aralkyl resin, naphthol aralkyl resin, biphenyl phenol novolac resin and biphenyl naphthol novolac resin (Patent Document 6). However, the vinylbenzyl etherified multifunctional vinyl resin synthesized according to the disclosed manufacturing method has a large total halogen content and a large amount of residual vinyl aromatic halomethyl compounds, so the dielectric loss tangent and heat resistance are not satisfactory as an insulating material corresponding to high frequencies. In terms of moldability, it is also prone to poor molding and is not a desired material.

[0006] It is known that the phenolic hydroxyl groups of a polyfunctional phenyl ether oligomer obtained by reacting a polyphenol having 3 or more and less than 9 phenolic hydroxyl groups in the molecule and having an alkyl group or an alkylene group at the 2- and 6-positions of at least one of the phenolic hydroxyl groups with a monophenol compound are vinylbenzylated (Patent Document 7). However, the vinylbenzyl ether resin obtained by this technology has the disadvantages of high viscosity, high molding processing temperature, and greatly deteriorating dielectric loss tangent when exposed to high temperature in an air atmosphere.

[0007] A technique related to methacryloyl-terminated PPE in which the phenolic hydroxyl groups of polyfunctional phenyl ether (PPE) oligomers are terminated with methacryloyl groups has also been widely proposed. In order to improve the convenience during the manufacture of prepreg materials, the molecular weight of PPE is reduced, or the solubility in solvents is improved by using PPE with a branched structure (Patent Documents 8 and 9). However, since the molecular weight of PPE is reduced, it is found that the dielectric properties and heat resistance are reduced. In addition, the solvent solubility improvement effect caused by the introduction of the branched structure is also limited, and further improvement is needed.

[0008] Therefore, existing vinyl resins do not form heat-resistant cured products having a low dielectric loss tangent that can withstand the harsh thermal experience of lead-free solder processing, which is required for use as electrical insulating materials, especially electrical insulating materials for high frequencies. In addition, they are also insufficient in terms of reliability and processability.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 63-68537

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 64-65110

[0013] Patent Document 3: Japanese Patent Publication No. 1-503238

[0014] Patent Document 4: Japanese Patent Application Laid-Open No. 9-31006

[0015] Patent Document 5: Japanese Patent Application Publication No. 2004-323730

[0016] Patent Document 6: Japanese Patent Application Publication No. 2003-306591

[0017] Patent Document 7: Japanese Patent Application Publication No. 2007-308685

[0018] Patent Document 8: Japanese Patent Application No. 2003-515642

[0019] Patent Document 9: Japanese Patent Application Publication No. 2021-109944 Summary of the invention

[0020] The present invention aims to provide a vinyl resin and a resin composition which have high solvent solubility, a low dielectric constant, a low dielectric loss tangent and form a cured product having a high glass transition temperature. The purpose is to provide a resin composition, a cured product or a material containing the same which can be used as a dielectric material, an insulating material or a heat-resistant material in the fields of the electrical and electronic industries and the aerospace and aircraft industries.

[0021] The present inventors have conducted intensive studies to solve the problems and have found that the above-mentioned problems can be solved by using a polyfunctional vinyl resin represented by the following general formula (1), thereby completing the present invention.

[0022] That is, the present invention is a polyfunctional vinyl resin represented by the following general formula (1).

[0023] [Chemistry 1]

[0024]

[0025] -CO-CR 3 =CH2 (1a)

[0026] in,

[0027] R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms,

[0028] R2 independently represents a hydrogen atom or a dicyclopentenyl group, and at least one of them is a dicyclopentenyl group.

[0029] X independently represents a hydrogen atom or a vinyl group represented by the above formula (1a), at least one of which is a vinyl group,

[0030] R3 is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms.

[0031] n represents the number of repetitions, and its average value is a number from 1 to 5.

[0032] The present invention is a method for producing a multifunctional vinyl resin, which is a method for producing the above-mentioned multifunctional vinyl resin, characterized in that dicyclopentadiene is reacted at a molar ratio of 0.23 to 2 times with respect to a 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 one or more acid anhydrides or acid halides represented by the following general formula (4).

[0033] [Chemistry 2]

[0034]

[0035] [Chemistry 3]

[0036]

[0037] [Chemistry 4]

[0038]

[0039] in,

[0040] R1, R2, and n are each the same as those defined in the above general formula (1),

[0041] R3 has the same definition as in the above formula (1a),

[0042] R4 represents halogen.

[0043] The present invention provides a polyfunctional vinyl resin composition containing a polyfunctional vinyl resin and a radical polymerization initiator as essential components, and a polyfunctional vinyl resin cured product obtained by curing the polyfunctional vinyl resin composition.

[0044] Furthermore, the present invention is a laminated plate formed by laminating a semi-cured product of a multifunctional vinyl resin composition, a prepreg of a fibrous base material, a resin sheet including a support film, and these prepregs and / or resin sheets.

[0045] The multifunctional vinyl resin and resin composition of the present invention have good solvent solubility, and the cured product obtained by curing the resin composition has low dielectric constant and dielectric loss tangent and high heat resistance, and is suitable as an electronic material for high-speed communication. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 The GPC chart of the multifunctional vinyl resin obtained in Example 1 is shown.

[0047] Figure 2 The IR chart of the multifunctional vinyl resin obtained in Example 1 is shown. DETAILED DESCRIPTION

[0048] The present invention is described in detail below.

[0049] The polyfunctional vinyl resin of the present invention is represented by the following general formula (1).

[0050] [Chemistry 5]

[0051]

[0052] In the general formula (1), R1 represents a hydrocarbon group having 1 to 8 carbon atoms, 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 may be any of linear, branched, and cyclic groups, and examples thereof include hydrocarbon groups such as 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, and ethylhexyl, and cycloalkyl groups having 5 to 8 carbon atoms such as cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, and methylcycloheptyl, but are not limited thereto. As the aryl group having 6 to 8 carbon atoms, phenyl, tolyl, xylyl, ethylphenyl, etc. can be listed, but not limited to these. As the aralkyl group having 7 to 8 carbon atoms, benzyl, α-methylbenzyl, etc. can be listed, but not limited to these. Among these substituents, from the viewpoint of ease of acquisition and reactivity when made into a cured product, methyl or phenyl is preferred, and methyl is particularly preferred.

[0053] The above R2 independently represents a hydrogen atom or a dicyclopentenyl group, and at least one of them is a dicyclopentenyl group. The dicyclopentenyl group is a group derived from dicyclopentadiene and is represented by the following formula (1b) or formula (1c).

[0054] [Chemistry 6]

[0055]

[0056] In the general formula (1), X independently represents a hydrogen atom or a vinyl group represented by the following formula (1a), and at least one of the vinyl groups is a group derived from an acid anhydride or an acid halide of the raw material.

[0057] [Chemistry 7]

[0058] -CO-CR 3 =CH2 (1a)

[0059] R3 is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms.

[0060] In the general formula (1), n ​​is a repetition number, which is 1 or more, and its average value is a number of 1 to 5, preferably 1.1 to 4.0, more preferably 1.2 to 3.0, and further preferably 1.3 to 2.0. The average value is a number average.

[0061] The average molecular weight of the multifunctional vinyl resin of the present invention is preferably 500 to 5000, more preferably 600 to 2000, and the number average molecular weight (Mn) is preferably 300 to 3000, more preferably 400 to 1500, and further preferably 450 to 1000. The upper limit of the vinyl equivalent (g / eq,) is preferably 600, more preferably 550, further preferably 500, and particularly preferably 450, and the lower limit is preferably 200, more preferably 220, further preferably 250, and particularly preferably 300. On the other hand, the hydroxyl equivalent (g / eq,) is preferably 10000 or more, more preferably 15000 or more, and particularly preferably in the range of 20000 to 30000.

[0062] As for the molecular weight distribution, the n=0 body content is preferably 5 to 20 area %, preferably 7 to 15 area %, the n=1 body content is preferably 40 to 80 area %, preferably 50 to 70 area %, and the content of n=2 or more bodies is 15 to 40 area %, preferably 20 to 30 area %.

[0063] The polyfunctional vinyl resin of the present invention can be preferably obtained by reacting a polyhydroxy resin represented by the following general formula (3) with an acid anhydride represented by the following general formula (4a) or an acid halide represented by the following general formula (4b).

[0064] [Chemistry 8]

[0065]

[0066] [Chemistry 9]

[0067]

[0068] R1, R2 and n have the same meanings as those defined in the above general formula (1).

[0069] R3 is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups. Examples of the alkenyl group include vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, and octenyl groups. From the perspective of ease of acquisition and reactivity when a cured product is prepared, R3 is preferably a hydrogen atom or a methyl group.

[0070] R4 represents a halogen atom, preferably a chlorine atom or a bromine atom.

[0071] The polyhydric hydroxy resin represented by the general formula (3) can be obtained, for example, by reacting 2,6-disubstituted phenols represented by the following general formula (2) with dicyclopentadiene in the presence of a Lewis acid such as a boron trifluoride / ether catalyst.

[0072] [Chemistry 10]

[0073]

[0074] R1 has the same meaning as in the above general formula (1).

[0075] Examples of the 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-dicyclohexylphenol, 2,6-diphenylphenol, 2,6-di(tolyl)phenol, 2,6-dibenzylphenol, 2,6-bis(α-methylbenzyl)phenol, 2-ethyl-6-methylphenol, 2-allyl-6-methylphenol, and 2-tolyl-6-phenylphenol. From the viewpoint of availability and reactivity when a cured product is obtained, 2,6-diphenylphenol and 2,6-dimethylphenol are preferred, and 2,6-dimethylphenol is particularly preferred.

[0076] The catalyst used in the above reaction is a Lewis acid, specifically, boron trifluoride, boron trifluoride / phenol complex, boron trifluoride / ether complex, aluminum chloride, tin chloride, zinc chloride, ferric chloride, etc. Among them, boron trifluoride / ether complex is preferred from the perspective of ease of handling. The amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 15 parts by mass, relative to 100 parts by mass of dicyclopentadiene in the case of boron trifluoride / ether complex.

[0077] As a reaction method for introducing the above-mentioned dicyclopentenyl group into 2,6-disubstituted phenols, dicyclopentadiene is reacted at a predetermined ratio with respect to 2,6-disubstituted phenols. Dicyclopentadiene may be continuously added to react, or may be intermittently added in several stages (two or more stages of sequential addition). The ratio is 0.23 to 2 times the mole of dicyclopentadiene with respect to 1 mole of 2,6-disubstituted phenols.

[0078] In terms of the ratio when dicyclopentadiene is continuously added and reacted, the ratio of dicyclopentadiene is 0.25 to 1 times the mole, preferably 0.28 to 1 times the mole, and more preferably 0.3 to 0.5 times the mole relative to 1 mole of 2,6-disubstituted phenols. In the case where dicyclopentadiene is added successively in stages and reacted, it is preferably 0.23 to 2 times the mole as a whole, and more preferably 0.23 to 1.7 times the mole. It should be noted that the ratio of dicyclopentadiene used in each stage is preferably 0.1 to 1 times the mole. In addition, unreacted 2,6-disubstituted phenols can be recovered midway in the reaction. Preferably, in order to introduce dicyclopentadiene as the main chain and then introduce the dicyclopentadienyl group as the side chain R2, it is added successively in two or more stages.

[0079] This reaction includes not only isomers having different substitution positions but also a structure in which a dicyclopentadiene structure and a hydroxyl group of phenol are bonded.

[0080] As a method for confirming that a dicyclopentenyl group has been introduced into the polyhydroxy resin represented by the above general formula (3), mass spectrometry (MS) and Fourier transform infrared spectrophotometry (FT-IR) can be used.

[0081] When mass spectrometry is used, electrospray mass spectrometry (ESI-MS), field desorption ionization (FD-MS), etc. can be used. Introduction of a dicyclopentenyl group can be confirmed by performing mass spectrometry on a sample obtained by separating components having different numbers of nuclei using GPC or the like.

[0082] When the FT-IR measurement method is used, a sample dissolved in an organic solvent such as tetrahydrofuran (THF) is applied to a KRS-5 element (cell), and the element with the sample film obtained by drying the organic solvent is measured by FT-IR. The peak derived from the CO stretching vibration of the phenol nucleus is at 1210 cm -1 Only when a dicyclopentenyl group is introduced, the peak of CH stretching vibration from the olefin part of the dicyclopentadiene skeleton is at 3040 cm -1 The dicyclopentadiene introduced into the main chain was not detected because the olefin part disappeared, and only the olefin introduced as the dicyclopentenyl group of the side chain R2 could be measured. The line formed by connecting the starting point and the end point of the target peak in a straight line was used as the baseline, and the length from the peak apex to the baseline was used as the peak height. 3040cm -1 Nearby peaks (A 3040 ) and 1210cm -1 Nearby peaks (A 1210 ) ratio (A 3040 / A 1210 ), the amount of dicyclopentenyl introduced can be quantified. The larger the ratio, the better the physical property value can be confirmed, and the preferred ratio (A) for satisfying the target physical property is 3040 / A 1210 ) is 0.05 or more, more preferably 0.10 or more, and particularly preferably 0.10 to 0.30.

[0083] The hydroxyl equivalent (g / eq.) of the multifunctional hydroxy resin is preferably 150 to 500, more preferably 200 to 350. In terms of average molecular weight, the weight average molecular weight (Mw) is preferably 400 to 2000, more preferably 500 to 2000, and the number average molecular weight (Mn) is preferably 350 to 1000, more preferably 400 to 800. The softening point is preferably 70 to 150°C, more preferably 80 to 120°C.

[0084] As a reaction method, 2,6-disubstituted phenol and a catalyst are charged into a reactor, and dicyclopentadiene is added dropwise over 1 to 10 hours.

[0085] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and further preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and further preferably 4 to 8 hours.

[0086] After the reaction is completed, a base such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. Then, a solvent such as aromatic hydrocarbons such as toluene and xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone is added to dissolve the phenol resin, and after washing with water, the solvent is recovered under reduced pressure to obtain the target phenol resin. It is preferred that all of the dicyclopentadiene is reacted as much as possible, and a portion of the 2,6-disubstituted phenol is left unreacted, preferably less than 10%, and the unreacted phenol is recovered under reduced pressure.

[0087] During the reaction, solvents such as aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and ketones such as methyl isobutyl ketone, cyclopentanone and cyclohexanone may be used as needed for viscosity adjustment.

[0088] The polyfunctional vinyl resin of the present invention can be preferably obtained by reacting the thus obtained polyhydroxy resin with an acid anhydride or an acid halide.

[0089] Examples of the acid anhydride include acrylic anhydride and methacrylic anhydride, and methacrylic anhydride is preferred. Examples of the acid halide include acryloyl chloride, methacryloyl chloride, and methacryloyl bromide, and methacryloyl chloride and methacryloyl bromide are preferred.

[0090] The reaction of the polyhydroxy resin with an acid anhydride or an acid halide may be carried out by reacting the polyhydroxy resin in a solvent in the presence of a basic compound. In this case, the polyhydroxy resin, the basic compound and the solvent may be placed in a reactor, dissolved, and then an acid anhydride or an acid halide may be added to react.

[0091] The polyhydroxy resin and the acid anhydride or acid halide may be used in a ratio such that the acid anhydride or acid halide is preferably reacted in an amount of 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents, per 1 equivalent of the phenolic hydroxyl group of the polyhydroxy resin.

[0092] The solvent used in the manufacture of the multifunctional vinyl resin of the present invention is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone, alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol, ethers such as tetrahydrofuran, dioxane, and diethylene glycol dimethyl ether, and aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. One or more of these solvents can be used. In addition, water can also be mixed with the above solvents and used.

[0093] The amount of the solvent used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, and particularly preferably 25 to 200% by mass relative to the total mass of the polyhydroxy resin. In particular, since aprotic polar solvents are not suitable for purification such as washing with water, and have a high boiling point and are difficult to remove, the amount used is not preferably greater than 300% by mass relative to the total mass of the polyhydroxy resin.

[0094] As the basic compound used in the preparation of the multifunctional vinyl resin of the present invention, organic basic compounds, alkali metal hydroxides, carbonates, etc. are preferred. Specific examples include triethylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate. Preferably, sodium hydroxide, potassium hydroxide, triethylamine, and dimethylaminopyridine are used.

[0095] The amount of the basic compound used is usually 1.0 to 2.5 mol, preferably 1.0 to 1.8 mol, and more preferably 1.0 to 1.5 mol, based on 1 mol of the phenolic hydroxyl groups of the polyhydroxy resin.

[0096] The reaction temperature for producing the polyfunctional vinyl resin of the present invention is usually 15 to 90° C., preferably 35 to 80° C. In order to obtain a polyfunctional vinyl resin with higher purity, it is preferred to increase the reaction temperature in two or more stages, for example, it is particularly preferred to increase the reaction temperature in the first stage to 15 to 50° C. and in the second stage to 45 to 80° C.

[0097] The reaction time for producing the multifunctional vinyl resin of the present invention is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. When the reaction time is 0.5 hours or more, the reaction proceeds sufficiently, and when the reaction time is 10 hours or less, the amount of by-products generated can be suppressed to a low level.

[0098] When there is a concern about self-polymerization of the acid anhydride or the acid halide, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitrone compounds, phenols, oxygen, etc. can be used.

[0099] After the reaction is completed, the by-product salts and impurities can be removed by distilling off the solvent under heating and reduced pressure or directly dissolving it in a ketone solvent having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.), benzene, toluene, xylene and other aromatic hydrocarbon solvents without distilling off, and adding water, methanol and other lower alcohols or their mixed solvents with low solubility in the target product for washing.

[0100] The production of the polyfunctional vinyl resin of the present invention is usually carried out while blowing an inert gas such as nitrogen into the system (in the air or in the liquid). By blowing an inert gas into the system while reacting, it is possible to prevent the obtained product from being colored.

[0101] The amount of the inert gas blown in per unit time varies depending on the volume of the reactor used in the reaction, and is preferably adjusted so that the volume of the reactor can be replaced in 0.5 to 20 hours.

[0102] The polyfunctional vinyl resin of the present invention can be cured alone, or can be preferably used as a polyfunctional resin composition blended with various additives. For example, a radical polymerization initiator can be blended to accelerate curing.

[0103] As a free radical polymerization initiator (also referred to as a free radical polymerization catalyst), for example, a crosslinking reaction is induced by heating or the like as described later to cure the resin composition of the present invention. In order to reduce the reaction temperature at this time or to promote the crosslinking reaction of the unsaturated group, a free radical polymerization initiator may also be contained and used. The amount of the free radical polymerization initiator used for this purpose is preferably 0.01 to 12 parts by mass, more preferably 0.1 to 8 parts by mass relative to 100 parts by mass of the multifunctional vinyl resin. The free radical polymerization initiator is a free radical polymerization catalyst, so the free radical polymerization initiator is used as a representative below.

[0104] Representative examples of the radical polymerization initiator include peroxides such as benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, tert-butylcumyl peroxide, α,α′-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl 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, bis(trimethylsilyl)peroxide, and trimethylsilyltriphenylsilyl peroxide, but are not limited thereto. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator (or polymerization catalyst). However, the catalyst and radical polymerization initiator used for curing the resin composition are not limited to these examples.

[0105] The multifunctional vinyl resin of the present invention may be mixed with other vinyl resins or other thermal multifunctional vinyl resins, for example, vinyl ester resins, polyvinyl benzyl resins, polyallyl resins, epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polycyanate resins, phenolic resins, benzoxazine resins, etc.

[0106] It can also be combined with thermoplastic resins such as polystyrene resin, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin, thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, and rubbers such as polybutadiene and polyisoprene.

[0107] As the vinyl resin that can be matched, there is no particular limitation on the type of the vinyl compound having one or more polymerizable unsaturated hydrocarbon groups in the molecule. That is, the vinyl compound can be any compound that can react with the multifunctional vinyl resin of the present invention to form a crosslinked and cured compound. More preferably, the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferably, the compound has two or more carbon-carbon unsaturated double bonds in the molecule.

[0108] The average number of carbon-carbon unsaturated double bonds per molecule of the vinyl compound as a curable resin (the number of vinyl groups (including substituted vinyl groups). It is also referred to as the number of terminal double bonds) varies depending on the Mw of the vinyl compound, and is preferably 1 to 20, and more preferably 2 to 18. If the number of terminal double bonds is too small, it tends to be difficult to obtain sufficient heat resistance as a cured product. In addition, if the number of terminal double bonds is too large, the reactivity is excessively increased, and unfavorable situations such as reduced storage stability of the composition or reduced fluidity of the composition may occur.

[0109] As vinyl compounds, for example, triallyl isocyanurate (TAIC) and other triallyl isocyanurate compounds, (meth) acryloyl, styrene-modified modified polyphenylene ether (PPE), multifunctional (meth) acrylate compounds with more than 2 (meth) acryloyl groups in the molecule, vinyl compounds (multifunctional vinyl compounds) with more than 2 vinyl groups in the molecule such as polybutadiene, and vinyl benzyl compounds such as styrene and divinylbenzene, etc. can be listed. Among them, preferably there are more than 2 carbon-carbon double bonds in the molecule, specifically, TAIC, multifunctional (meth) acrylate compounds, modified PPE resins, multifunctional vinyl compounds and divinylbenzene compounds, etc. can be listed. If these are used, it is believed that curing reaction is adopted, crosslinking is more suitably formed, and the heat resistance of the cured product of the resin combination can be further improved. In addition, these can be used alone, and more than 2 kinds can also be used in combination. In addition, compounds with 1 carbon-carbon unsaturated double bond in the molecule can be used in combination. Examples of the compound having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).

[0110] In the multifunctional vinyl resin composition of the present invention, in order to improve the flame retardancy of the cured product obtained, various known flame retardants can be used within the scope of not reducing reliability. As the flame retardant that can be used, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. can be listed. From the viewpoint of the environment, halogen-free flame retardants are preferably used, and phosphorus flame retardants are particularly preferred. These flame retardants can be used alone, and two or more flame retardants of the same system can also be used in combination. In addition, flame retardants of different systems can be used in combination.

[0111] In order to further improve the functionality, the multifunctional vinyl resin composition of the present invention may contain components other than the components listed above (sometimes referred to as "other components" in the present invention). Such other components include fillers, ultraviolet light inhibitors, antioxidants, coupling agents, plasticizers, fluxes, thixotropy-imparting agents, smoothing agents, colorants, pigments, dispersants, emulsifiers, low-elasticity agents, release agents, defoaming agents, ion trapping agents, and the like.

[0112] Examples of fillers include 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 inorganic fillers such as carbon; fibrous fillers such as carbon fibers, glass fibers, alumina fibers, silica alumina fibers, silicon carbide fibers, polyester fibers, polyamide fibers, cellulose fibers, aramid fibers, and ceramic fibers; and fine-particle rubber.

[0113] As other components, there can be mentioned organic pigments such as quinacridone, azo, and phthalocyanine, inorganic pigments such as titanium oxide, metallic foil pigments, and rust-proof pigments, ultraviolet absorbers such as hindered amine, benzotriazole, and benzophenone, antioxidants such as hindered phenol, phosphorus, sulfur, and hydrazide, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, leveling agents, rheology control agents, pigment dispersants, shrinkage inhibitors, defoaming agents, etc. The amount of these other components is preferably in the range of 0.01 to 20% by mass relative to the total solid content in the resin composition.

[0114] The multifunctional vinyl resin composition of the present invention can be made into a resin varnish by dissolving in a solvent. As a solvent, 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, γ-butyrolactone, etc. can be listed, and its selection and appropriate usage amount can be appropriately selected according to the purpose. For example, in the use of printed wiring boards, preferably methyl ethyl ketone, acetone, toluene, xylene, 1-methoxy-2-propanol and other solvents with a boiling point of less than 160°C are used, and it is preferably used in a ratio of 20 to 80% by mass of non-volatile components. On the other hand, in the application of adhesive film for increasing the layer, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, acetate cellosolve, propylene glycol monomethyl ether acetate, carbitol acetate, ester compounds such as γ-butyrolactone, cellosolve, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and in addition, it is preferably used in a ratio of 20 to 80% by mass of non-volatile components. It should be noted that for the laminated board of the present invention, the resin varnish is cured to obtain it. Specifically, printed wiring substrates, printed circuit boards, flexible printed wiring boards, increasing layer wiring boards, etc. can be listed.

[0115] The cured product obtained by curing the multifunctional vinyl resin composition of the present invention can be used as a molded product, a laminated product, a casting, an adhesive, a coating, or a film. For example, the cured product of the semiconductor sealing material is a casting or a molded product. As a method for obtaining the cured product for this purpose, the compound can be molded using a casting or transfer molding machine, an 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 the resin varnish is a laminated product. As a method for obtaining the cured product, the resin varnish can be impregnated with the above-mentioned fibrous filler, a substrate such as paper, heated and dried to obtain a prepreg material, which is laminated alone or laminated with a metal foil such as copper foil, and hot-pressed to obtain. In addition, the uncured sheet or partially cured sheet of the multifunctional vinyl resin composition of the present invention can be suitable for use as a build-up film, a bonding sheet, a cover sheet, a bump sheet for a flip-chip bonding machine, an insulating layer for a substrate, and an adhesive layer.

[0116] By adding inorganic high dielectric powder such as barium titanate or inorganic magnetic material such as ferrite, it can be used as a material for electronic components, especially a material for high-frequency electronic components.

[0117] Next, the prepreg material of the present invention and its cured product are described. In order to improve the mechanical strength and increase the dimensional stability, a base material is added to the prepreg material of the present invention.

[0118] As such a substrate, various glass cloths such as untwisted gauze, cloth, chopped strand mat, and surface mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloths, woven or non-woven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers, woven or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, and acrylonitrile fibers, natural fiber cloths such as cotton cloth, linen, and felt, carbon fiber cloth, natural cellulose cloths such as kraft paper, cotton paper, and paper-glass mixed fiber paper, and the like, and paper and the like are used individually or in combination of two or more thereof.

[0119] The proportion of the substrate in the prepreg material can be 5 to 90% by mass, preferably 10 to 80% by mass, and more preferably 20 to 70% by mass. If the substrate is less than 5% by mass, the dimensional stability and strength of the cured product tend to decrease. In addition, if the substrate is more than 90% by mass, the dielectric properties of the cured product tend to decrease.

[0120] In the prepreg material of the present invention, a coupling agent can be used as needed to improve the adhesion at the interface between the resin and the substrate. As the coupling agent, a general coupling agent such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconium aluminate coupling agent, etc. can be used.

[0121] As a method for manufacturing the prepreg material of the present invention, for example, the following method can be cited: the multifunctional vinyl resin composition of the present invention and other components as needed are uniformly dissolved or dispersed in the above-mentioned aromatic solvent, ketone solvent, etc., or a mixed solvent thereof, and then impregnated into a substrate, and then dried. The impregnation is performed by dipping (impregnation), coating, etc. As for the impregnation, it can be repeated multiple times as needed. In addition, at this time, it is also possible to use multiple solutions with different compositions and concentrations for repeated impregnation, and finally adjust to the desired resin composition and resin amount.

[0122] By curing the prepreg of the present invention by methods such as heating, a cured product is obtained. There is no particular limitation on its manufacturing method. For example, multiple prepregs can be overlapped, and each layer is bonded under heating and pressure while being thermally cured to obtain a cured product (laminated plate) of the desired thickness. In addition, it is also possible to combine the cured product once bonded and cured with the prepreg to obtain a multilayer laminate of a new layer structure. Stacking molding and curing are usually carried out simultaneously by hot pressing, and both can also be carried out separately. That is, by using heat treatment or another method to process the uncured or semi-cured prepreg obtained by pre-stack molding, it can be cured.

[0123] The molding and curing can be performed at a temperature of 80 to 300°C and a pressure of 0.1 to 1000 kgf / cm 2, time: 1 minute to 10 hours, more preferably, at a temperature of 150 to 250°C and a pressure of 1 to 500 kgf / cm 2 , Time: range from 1 minute to 5 hours.

[0124] The laminate of the present invention is a laminate composed of a layer of the prepreg material of the present invention and a layer of a metal foil. Examples of the metal foil used herein include copper foil and aluminum foil. The thickness thereof is not particularly limited, but is in the range of 3 to 200 μm, more preferably in the range of 3 to 105 μm.

[0125] As a method for manufacturing the laminate of the present invention, for example, the following method can be cited: the prepreg material obtained from the multifunctional vinyl resin composition of the present invention and the substrate described above and the metal foil are stacked in a layer structure consistent with the purpose, and the layers are bonded together under heating and pressure and thermally cured. In the laminate of the multifunctional vinyl resin composition of the present invention, the cured product and the metal foil are stacked in an arbitrary layer structure. The metal foil can be used as a surface layer or as an intermediate layer. In addition to the above, it is also possible to repeat stacking and curing multiple times to make it multilayered.

[0126] In the bonding with the metal foil, an adhesive can also be used. As the adhesive, epoxy, acrylic, phenolic, cyanoacrylate, etc. can be listed, but it is not particularly limited to these. The above-mentioned stacking molding and curing can be carried out under the same conditions as the production of the cured product of the prepreg material of the present invention.

[0127] The polyfunctional vinyl resin composition of the present invention can also be formed into a film. The thickness thereof is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0128] The method for producing the film of the present invention is not particularly limited, and examples thereof include a method in which the multifunctional vinyl resin composition and other components used as required are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof, and then applied to a resin film such as a PET film and dried. The coating may be repeated multiple times as required, and in this case, multiple solutions with different compositions and concentrations may be repeatedly coated to ultimately adjust to the desired resin composition and resin amount.

[0129] When the resin sheet of the present invention is used as a bonding sheet, for example, two substrates can be bonded with a resin sheet. Each of the two substrates is, for example, a laminate or a printed wiring board. Specifically, for example, by heating after the multifunctional vinyl resin composition is formed into a sheet by a coating method on a supporting film, a resin sheet is made by drying or semi-curing it. The resin sheet is overlapped on the substrate (the first substrate), the supporting film is peeled off from the resin sheet, and another substrate (the second substrate) is overlapped. That is, the first substrate, the resin sheet (the multifunctional vinyl resin composition) and the second substrate are stacked in sequence. Then, by heat curing, the first substrate and the second substrate are bonded via the cured product of the multifunctional vinyl resin composition.

[0130] The multifunctional vinyl resin composition and metal foil of the present invention can be used to obtain a metal foil with resin. Examples of the metal foil used herein include copper foil and aluminum foil. The thickness thereof is not particularly limited, but is in the range of 3 to 200 μm, more preferably in the range of 5 to 105 μm.

[0131] There is no particular limitation on the method for producing the metal foil with resin, and examples thereof include a method in which the multifunctional vinyl resin composition and other components used as required are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof, applied to the metal foil, and then dried. The application may be repeated multiple times as required, and in this case, multiple solutions with different compositions and concentrations may be repeatedly applied to finally adjust the desired resin composition and resin amount.

[0132] The substrate for electronic materials is formed using the laminate of the present invention. The substrate for electronic materials can be suitable for use as a mobile phone, PHS, notebook personal computer, PDA (portable information terminal), portable video phone, personal computer, supercomputer, server, router, liquid crystal projector, engineering workstation (EWS), pager, word processor, TV, video recorder of viewfinder type or monitor direct view type, electronic notepad, electronic desktop computer, car navigation device, POS terminal, various electrical and electronic equipment such as the device including touch panel, which require reliability in an environment requiring heat resistance and water resistance, and transmission reliability of high-frequency signals. In particular, due to the heat resistance stability of the excellent dielectric properties of the cured product of the present invention and the dimensional stability and formability corresponding to the circuit formation of the fine pattern, it can be suitable for use as a circuit substrate for the above-mentioned electrical and electronic equipment. Specifically, single-sided, double-sided, multi-layer printed substrates, flexible substrates, and build-up substrates can be listed. A multi-layer circuit substrate using a metal plating layer as the above-mentioned conductor layer is also included as a preferred example.

[0133] Example

[0134] The present invention is specifically described by way of examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" represent parts by mass, "%" represents mass %, and "ppm" represents mass ppm. In addition, the following methods are used for determination.

[0135] The test conditions of polyhydric hydroxy resin, polyvinyl resin and cured product are shown.

[0136] (1) Hydroxyl equivalent:

[0137] The measurement is carried out in accordance with JIS K0070, and the unit is expressed as "g / eq." It should be noted that, unless otherwise specified, the hydroxyl equivalent of the polyhydroxy resin means a phenolic hydroxyl equivalent.

[0138] (2) Softening point:

[0139] The softening point was measured by the ring and ball method according to JIS K7234. Specifically, an automatic softening point device (manufactured by Meitech Co., Ltd., ASP-MG4) was used.

[0140] (3) Vinyl equivalent:

[0141] The iodine value is determined according to JIS K0070. Specifically, the sample is reacted with Wijs solution (iodine monochloride solution) and placed in a dark place. Then, the excess iodine chloride is reduced to iodine, and the iodine component is titrated with sodium thiosulfate to calculate the iodine value. The iodine value is converted into vinyl equivalent.

[0142] (4) Solvent solubility:

[0143] The resin was placed in various solvents (acetone (AC), methyl ethyl ketone (MEK), toluene (TL), methyl cellosolve (MC), and propylene glycol monomethyl ether acetate (PMA)) so that the solid content concentration (resin / (resin+solvent)×100), that is, the non-volatile content was 60% and 70%, and after being fully stirred at room temperature, it was visually confirmed whether the resin was completely dissolved. In the case of turbidity or insoluble components, it was recorded as ×, and in the case of no insoluble components, it was recorded as 0.

[0144] (5) Relative dielectric constant and dielectric loss tangent:

[0145] Measured according to IPC-TM-650 2.5.5.9. Specifically, the relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were obtained and evaluated by a volumetric method using a material analyzer (manufactured by AGILENT Technologies).

[0146] (6) Glass transition temperature (Tg):

[0147] The viscosity was measured according to JIS C6481. Specifically, it was expressed by the tan δ peak top when measured using a dynamic viscoelasticity measuring apparatus (manufactured by Hitachi High-Technologies Corporation, EXSTAR DMS6100) under the condition of a temperature increase of 5°C / min.

[0148] (7) GPC (gel permeation chromatography) determination:

[0149] A device having a column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) in series with a main body (manufactured by Tosoh Corporation, HLC-8220GPC) was used, and the column temperature was set to 40 ° C. In addition, tetrahydrofuran (THF) was used as an eluent, and the flow rate was set to 1 mL / min, and a differential refractive index detector was used as the detector. The sample was measured using 50 μL of a substance obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering with a microfilter. Mw and Mn were calculated by converting the calibration line obtained using standard polystyrene (manufactured by Tosoh Corporation, PStQuick Kit-H). It should be noted that data processing uses GPC-8020 Model II Version 6.00 manufactured by Tosoh Corporation.

[0150] (8)IR:

[0151] A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, SpectrumOne FT-IR Spectrometer 1760X) was used. A sample dissolved in toluene was applied to the ATR using diamond ATR, and after drying, the wave number of 650 to 4000 cm was measured. -1 The absorbance.

[0152] The abbreviations used in Examples and Comparative Examples are as follows.

[0153] [Aromatic hydroxy compounds]

[0154] P1: Aromatic hydroxy compound obtained in Synthesis Example 1

[0155] P2: Aromatic hydroxy compound obtained in Synthesis Example 2

[0156] P3: Aromatic hydroxy compound obtained in Synthesis Example 3

[0157] [Multifunctional vinyl resins, vinyl compounds]

[0158] V1: Multifunctional vinyl resin obtained in Example 1

[0159] V2: Multifunctional vinyl resin obtained in Example 2

[0160] V3: Multifunctional vinyl resin obtained in Example 3

[0161] V4: Multifunctional vinyl resin obtained in Example 4

[0162] VH1: Multifunctional vinyl resin (Mitsubishi Gas Chemical Co., Ltd., terminal vinyl benzyl ether-modified PPE resin, OPE-2ST, Mn1187)

[0163] VH2: Multifunctional vinyl resin (manufactured by SABIC Japan, terminal methacryloyl-modified PPE resin, SA9000, Mw1600)

[0164] VH3: Vinyl compound (manufactured by Tokyo Chemical Industry Co., Ltd., triallyl isocyanurate)

[0165] PO: Organic peroxide (manufactured by NOF Corporation, Perbutyl P)

[0166] DO: Organic peroxide (Percumyl D, manufactured by NOF Corporation)

[0167] AO: Antioxidant (manufactured by ADEKA Corporation, ADK STAB AO-60)

[0168] Synthesis example 1

[0169] In a reaction apparatus including a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a condenser, 500 parts of 2,6-xylenol (structural formula shown below) and

[0170] [Chemistry 11]

[0171]

[0172] 7.3 parts of 47% BF3 ether complex (0.1 times the mole of dicyclopentadiene initially added) were heated to 100° C. with stirring. While maintaining this temperature, 67.6 parts of dicyclopentadiene (structural formula below) (0.12 times the mole of 2,6-xylenol) were added dropwise over 1 hour.

[0173] [Chemistry 12]

[0174]

[0175] Then, the reaction was carried out at a temperature of 115 to 125°C for 4 hours. Then, the reaction was carried out at a reduced pressure of 5 mmHg to 200°C, the unreacted raw materials were evaporated and removed, and 46.7 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product. After 3.3 parts of 47% BF3 ether complex was added, the reaction was heated to 100°C, and 74.7 parts of dicyclopentadiene were added dropwise over 1 hour while maintaining the temperature. Then, the reaction was carried out at 115 to 125°C for 4 hours. 5 parts of calcium hydroxide were added. Then, 9 parts of a 10% aqueous oxalic acid solution were added. 350 parts of MIBK were added to dissolve the product, 120 parts of warm water at 80°C were added, the product was washed with water, and the lower water layer was separated and removed. The product was heated to 120°C, refluxed for dehydration, filtered, and heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK to obtain 259 parts of a reddish brown polyhydroxy resin (P1).

[0176] The obtained polyhydroxy resin (P1) has a hydroxyl equivalent of 323, a softening point of 97°C, and an absorption ratio (A 3040 / A 1210 ) was 0.27. Mw obtained by GPC was 740, Mn was 490, n=0 body content was 6.6 area%, n=1 body content was 70.1 area%, and n=2 body content or more was 23.3 area%. The mass spectrum obtained by ESI-MS (negative) was measured, and M-=375, 507, 629, 639, 761 were confirmed.

[0177] Synthesis example 2

[0178] In the same reaction apparatus as in Synthesis Example 1, 500 parts of 2,6-xylenol and 7.3 parts of 47% BF3 ether complex were charged, and heated to 100°C while stirring. While maintaining this temperature, 67.6 parts of dicyclopentadiene (0.12 times the mole relative to 2,6-xylenol) were dripped in for 1 hour. The reaction was then carried out at a temperature of 115-125°C for 4 hours. Then, the reaction was heated to 200°C under a reduced pressure of 5 mmHg, the unreacted raw materials were evaporated and removed, and 46.7 parts of MIBK were added to dissolve the product. After 3.3 parts of 47% BF3 ether complex were charged, the reaction was heated to 100°C, and while maintaining this temperature, 56.0 parts of dicyclopentadiene were dripped in for 1 hour. The reaction was then carried out at 115-125°C for 4 hours. 5 parts of calcium hydroxide were added. Furthermore, 9 parts of a 10% aqueous solution of oxalic acid were added. 320 parts of MIBK were added to dissolve the product, 110 parts of warm water at 80°C were added, washed with water, and the lower water layer was separated and removed. The mixture was heated to 120°C, refluxed for dehydration, filtered, and heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, thereby obtaining 240 parts of a reddish brown polyhydroxy resin (P2).

[0179] The obtained polyhydroxy resin (P2) has a hydroxyl equivalent of 276, a softening point of 94°C, and an absorption ratio (A 3040 / A 1210 ) was 0.17. Mw obtained by GPC was 670, Mn was 490, n=0 body content was 6.6 area%, n=1 body content was 70.3 area%, and n=2 body content or more was 23.1 area%. The mass spectrum obtained by ESI-MS (negative) was measured, and M-=375, 507, 629, 639, 761 were confirmed.

[0180] Synthesis example 3

[0181] In the same reaction apparatus as in Synthesis Example 1, 500 parts of 2,6-xylenol and 7.3 parts of 47% BF3 ether complex (0.1 times the mole of dicyclopentadiene initially added) were charged, and heated to 100°C while stirring. While maintaining this temperature, 67.6 parts of dicyclopentadiene (0.12 times the mole of 2,6-xylenol) were added dropwise over 1 hour. The reaction was then carried out at a temperature of 115-125°C for 4 hours. Then, the reaction was heated to 200°C under a reduced pressure of 5 mmHg, the unreacted raw materials were evaporated and removed, and 46.7 parts of MIBK were added to dissolve the product. After charging 3.3 parts of 47% BF3 ether complex, the reaction was heated to 100°C, and while maintaining this temperature, 28.0 parts of dicyclopentadiene were added dropwise over 1 hour. The reaction was then carried out at 115-125°C for 4 hours, and 5 parts of calcium hydroxide were added. Furthermore, 9 parts of a 10% aqueous solution of oxalic acid were added. 280 parts of MIBK were added to dissolve the product, 100 parts of warm water at 80°C were added, washed with water, and the lower water layer was separated and removed. The mixture was heated to 120°C, refluxed for dehydration, filtered, and heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, thereby obtaining 213 parts of a reddish brown polyhydroxy resin (P3).

[0182] The obtained polyhydroxy resin (P3) has a hydroxyl equivalent of 234, a softening point of 86°C, and an absorption ratio (A 3040 / A 1210 ) was 0.11. Mw obtained by GPC was 560, Mn was 470, n=0 body content was 6.2 area%, n=1 body content was 74.0 area%, and n=2 body content or more was 19.8 area%. The mass spectrum obtained by ESI-MS (negative) was measured, and M-=375, 507, 629, 639, 761 were confirmed.

[0183] Example 1

[0184] Into the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (P1) obtained in Synthesis Example 1, 37.8 parts of dimethylaminopyridine and 150 parts of toluene were placed, and the mixture was heated to 60°C to dissolve. After cooling to 20°C, 71.6 parts of methacrylic anhydride (structural formula below) (1.5 equivalents relative to the hydroxyl group equivalent of P1) was added dropwise over 30 minutes.

[0185] [Chemistry 13]

[0186]

[0187] The reaction was further carried out at 80°C for 3 hours. The obtained resin was dissolved in 340 parts of toluene and washed with 210 parts of methanol water having a methanol concentration of 30% by weight. Then, the solvent was distilled off under reduced pressure to obtain 190 parts of a toluene solution of a polyfunctional vinyl resin (V1) having a nonvolatile content of 60%.

[0188] The obtained multifunctional vinyl resin (V1) had a hydroxyl equivalent of 23400 and a vinyl equivalent of 420. It was a multifunctional vinyl resin represented by formula (1), R1 was a methyl group, i was 2, Mw obtained by GPC was 870, Mn was 510, the n=0 isomer content was 9.8 area%, the n=1 isomer content was 64.6 area%, and the content of n=2 or more isomers was 25.6 area%.

[0189] The GPC of the multifunctional vinyl resin (V1) is shown in Figure 1 , the IR diagram is shown in Figure 2 .

[0190] Example 2

[0191] In the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (P2) obtained in Synthesis Example 2, 44.3 parts of dimethylaminopyridine and 150 parts of toluene were charged, and the temperature was raised to 60°C to dissolve them. After cooling to 20°C, 83.8 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl equivalent of P2) were dripped over 30 minutes, and then reacted at 80°C for 3 hours. The obtained resin was dissolved in 380 parts of toluene and washed with 230 parts of methanol water with a methanol concentration of 30% by weight. Then, the solvent was distilled off under reduced pressure to obtain 220 parts of a polyfunctional vinyl resin (V2) in a toluene solution with a non-volatile component of 60%.

[0192] The obtained multifunctional vinyl resin (V2) had a hydroxyl equivalent of 22,000 and a vinyl equivalent of 370. It was a multifunctional vinyl resin represented by formula (1), R1 was methyl, i was 2, Mw obtained by GPC was 790, Mn was 510, the n=0 isomer content was 9.8 area%, the n=1 isomer content was 64.8 area%, and the content of n=2 or more isomers was 25.4 area%.

[0193] Example 3

[0194] In the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (P3) obtained in Synthesis Example 3, 52.2 parts of dimethylaminopyridine and 150 parts of toluene were placed, and the temperature was raised to 60°C to dissolve them. After cooling to 20°C, 98.8 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl equivalent of P3) were dripped over 30 minutes, and then reacted at 80°C for 3 hours. The obtained resin was dissolved in 440 parts of toluene and washed with 250 parts of methanol water with a methanol concentration of 30% by weight. Then, the solvent was distilled off under reduced pressure to obtain 260 parts of a polyfunctional vinyl resin (V3) in a toluene solution with a non-volatile component of 60%.

[0195] The obtained multifunctional vinyl resin (V3) had a hydroxyl equivalent of 20,000 and a vinyl equivalent of 330. It was a multifunctional vinyl resin represented by formula (1), R1 was methyl, i was 2, Mw obtained by GPC was 660, Mn was 490, the n=0 isomer content was 9.2 area%, the n=1 isomer content was 69.0 area%, and the content of n=2 or more isomers was 21.8 area%.

[0196] Example 4

[0197] Into the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (P1) obtained in Synthesis Example 1, 37.8 parts of dimethylaminopyridine and 150 parts of toluene were placed, and the mixture was heated to 60°C to dissolve. After cooling to 20°C, 38.8 parts of methacryloyl chloride (structural formula below) (1.2 equivalents relative to the hydroxyl group equivalent of P1) was added dropwise over 30 minutes.

[0198] [Chemistry 14]

[0199]

[0200] The reaction was further carried out at 80°C for 3 hours. The obtained resin was dissolved in 340 parts of toluene and washed with 210 parts of methanol water having a methanol concentration of 30% by weight. Then, the solvent was distilled off under reduced pressure to obtain 190 parts of a toluene solution of a polyfunctional vinyl resin (V4) having a nonvolatile content of 60%.

[0201] The obtained multifunctional vinyl resin (V4) had a hydroxyl equivalent of 25,000 and a vinyl equivalent of 425. It was a multifunctional vinyl resin represented by formula (1), R1 was methyl, i was 2, Mw obtained by GPC was 880, Mn was 520, the n=0 isomer content was 9.8 area%, the n=1 isomer content was 63.6 area%, and the content of n=2 or more isomers was 26.6 area%.

[0202] Table 1 shows the results of solvent solubility of the polyfunctional vinyl resins (V1 to V4) obtained in Examples 1 to 4 and the comparative example (VH2).

[0203] [Table 1]

[0204]

[0205] Examples 5 to 13, Comparative Examples 1 to 2

[0206] Mix in the proportions (parts) shown in Tables 2 and 3, dissolve in toluene, and obtain a uniform vinyl resin composition varnish with a non-volatile component of 50%. Apply the obtained vinyl resin composition varnish to a PET film, dry at 130°C for 5 minutes, and peel off from the PET film to obtain a resin composition. The resin composition is sandwiched between a mirror plate, cured at 130°C for 30 minutes under reduced pressure and cured at 220°C for 100 minutes while applying a pressure of 2MPa to obtain a cured product. The relative dielectric constant, dielectric loss tangent and Tg of the obtained cured product are shown in Tables 2 and 3.

[0207] [Table 2]

[0208]

[0209] [Table 3]

[0210]

[0211] The multifunctional vinyl resins of Examples exhibited excellent physical properties such as good solvent solubility, low dielectric constant, and low dielectric loss tangent, as compared with Comparative Examples.

[0212] Industrial Applicability

[0213] The multifunctional vinyl resin of the present invention can be used for printed circuit boards, sealing materials, casting materials, etc. of electronic devices, and can be used as an electronic material for high-speed communication devices and as a material with low signal loss in electronic parts.

Claims

1. A multifunctional vinyl resin represented by the following general formula (1): [Chemistry 1] -CO-CR 3 =CH2 (1a) in, R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms, R2 independently represents a hydrogen atom or a dicyclopentenyl group, at least one of which is a dicyclopentenyl group, X independently represents a hydrogen atom, or a vinyl-containing group represented by the above formula (1a), at least one of which is a vinyl-containing group, R3 is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms, and n represents the number of repetitions, the average value of which is a number from 1 to 5.

2. A method for producing a multifunctional vinyl resin, which is a method for producing the multifunctional vinyl resin according to claim 1, characterized in that: A 2,6-disubstituted phenol represented by the following general formula (2) is reacted with dicyclopentadiene at a molar ratio of 0.23 to 2 to obtain a polyhydroxy resin represented by the following general formula (3), and the obtained polyhydroxy resin is reacted with one or more of an acid anhydride represented by the following general formula (4a) or an acid halide represented by the following general formula (4b), [Chemistry 2] [Chemistry 3] [Chemistry 4] wherein R1, R2, and n are each the same as those defined in the above general formula (1), R3 is the same as that defined in the above formula (1a), and R4 represents a halogen.

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

4. A cured product obtained by curing the multifunctional vinyl resin according to claim 1 or the multifunctional vinyl resin composition according to claim 3.

5. A prepreg comprising the multifunctional vinyl resin composition according to claim 3 or a semi-cured product thereof, and a fibrous substrate. 6 . A resin sheet comprising a resin layer of the multifunctional vinyl resin composition according to claim 3 or a semi-cured product thereof, and a supporting film.

7. A laminated board formed by laminating the prepreg material according to claim 5 and / or the resin sheet according to claim 6.

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