Vinyl resin, production method for vinyl resin, vinyl resin composition, cured product, prepreg, resin sheet, and laminate

Abstract

Provided is a resin material that has a superiorly low melt viscosity and still has a low dielectric constant and a low dielectric loss tangent.　Provided are a vinyl resin represented by general formula (1) and a production method for the vinyl resin. The R1s independently represent a hydrogen atom or a C1–8 hydrocarbon group. The R2s independently represent a hydrogen atom or a dicyclopentenyl group that may include a C1–8 hydrocarbon group, at least one being a dicyclopentenyl group that may include a C1–8 hydrocarbon group. R3 and R4 independently represent a hydrogen atom or a C1–8 hydrocarbon group, and a and b are 0–2. The Xs independently represent a hydrogen atom or a vinyl group–containing group represented by formula (1a) or (1b), at least one being the vinyl group–containing group. R5 is a hydrogen atom or a C1–8 alkyl group or alkenyl group. Ar represents an aromatic ring. n represents the number of repeats, the average value being less than 1.

Description

Vinyl resin, method for producing vinyl resin, vinyl resin composition, cured product, prepreg, resin sheet, and laminate

[0001] The present invention relates to a vinyl resin having both a low dielectric tangent and high heat resistance, which is useful for printed circuit boards, sealing materials, casting materials, etc. of electronic devices, a method for producing the vinyl resin, a vinyl resin composition, a cured product thereof, etc.

[0002] With the recent increase in the volume of information and communication, high-frequency information and communication has become increasingly common, and electrical insulating materials with better electrical properties, particularly low dielectric constants and low dielectric loss tangents, are required to reduce transmission loss in high-frequency bands. To meet these requirements, cured resins using vinyl resins with various chemical structures have been proposed.

[0003] As a cured resin using such a vinyl resin, the applicant of the present application has demonstrated that a polyfunctional vinyl resin obtained by reacting 2,6-disubstituted phenol with dicyclopentadiene, in which the phenolic hydroxyl group of a polyhydric hydroxy resin having a dicyclopentadienyl group as a substituent, is vinylated, can produce a cured product with excellent low dielectric properties and a high glass transition temperature compared to vinyl resins that have been proposed in the past (Patent Documents 1, 2, and 3). However, the vinyl resins obtained by the techniques of these Patent Documents 1 to 3 have problems such as relatively high viscosity and limited flexibility in blending fillers, etc.

[0004] WO2024 / 018918 WO2021 / 241255 WO2023 / 032534

[0005] An object of the present invention is to provide a vinyl resin and a resin composition that have an excellent low melt viscosity and yet give a cured product with a low dielectric constant and a low dielectric loss tangent, and that can be used as a dielectric material, an insulating material, or a heat-resistant material in fields such as the electrical and electronic industries and the aerospace and aircraft industries, and that is particularly suitable as an electronic material for high-speed communications. Another object of the present invention is to provide a resin composition, a cured product, or a material containing the same that is suitable as an electronic material for high-speed communications.

[0006] As a result of extensive research into solving the problems, the present inventors have found that the above problems can be solved by using a vinyl resin represented by the following general formula (1), and have thus completed the present invention.

[0007] That is, the present invention is a vinyl resin represented by the following general formula (1). Here, R １ R independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. ２ R independently represent a hydrogen atom or a dicyclopentenyl group which may have a hydrocarbon group having 1 to 8 carbon atoms, and at least one of them is a dicyclopentenyl group which may have a hydrocarbon group having 1 to 8 carbon atoms. ３ , R ４ R independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and a and b are each an integer of 0 to 2. X independently represent a hydrogen atom or a vinyl group-containing group represented by the above formula (1a) or (1b), and at least one X is the vinyl group-containing group. ５ is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms. Ar is an aromatic ring. n is the number of repetitions, the average value of which is less than 1.

[0008] The present invention provides a method for producing the vinyl resin, comprising reacting a phenol represented by the following general formula (2) with dicyclopentadiene, which may have a hydrocarbon group having 1 to 8 carbon atoms, in the presence of a Lewis acid catalyst to obtain a hydroxy resin represented by the following general formula (3), and then reacting the obtained hydroxy resin with one or more acid anhydrides represented by the following general formula (4a) or acid halides represented by the following general formula (4b), or a halogenated methyl group-containing aromatic vinyl compound represented by the following general formula (5), wherein the Lewis acid catalyst is used in an amount of 0.1 to 8 parts by mass per 100 parts by mass of the cyclopentadiene, and the dicyclopentadiene is used in a molar ratio of 0.5 to 2 times the molar ratio of the phenol to the phenol.

[0009]

[0010]

[0011] Here, R １ , R ２ , R ３ , R ４ , R ５ , a, b, and n are each defined as in the general formula (1). ６ , R ７ indicates a halogen.

[0012] The present invention relates to a vinyl resin composition containing the above-mentioned vinyl resin and a radical polymerization initiator as essential components, and a cured product obtained by curing the above-mentioned vinyl resin or the above-mentioned vinyl resin composition.Furthermore, the present invention relates to a prepreg comprising the above-mentioned vinyl resin composition or a semi-cured product thereof and a fibrous substrate, a resin sheet comprising a resin layer of the above-mentioned vinyl resin composition or a semi-cured product thereof and a support film, and a laminate formed by laminating these prepregs and / or resin sheets.

[0013] The vinyl resin and vinyl resin composition of the present invention have an excellent low melt viscosity, and furthermore, a cured product obtained by curing the vinyl resin composition has a low dielectric constant and dielectric loss tangent. Therefore, the vinyl resin and vinyl resin composition of the present invention can be used as a dielectric material, an insulating material, or a heat-resistant material in fields such as the electric and electronic industries and the aerospace and aircraft industries, and are particularly suitable as electronic materials for high-speed communications.

[0014] 1 shows a GPC chart of the hydroxy resin obtained in Synthesis Example 1. 2 shows an IR chart of the hydroxy resin obtained in Synthesis Example 1. 3 shows a GPC chart of the vinyl resin obtained in Example 1. 4 shows an IR chart of the vinyl resin obtained in Example 1. 5 shows a GPC chart of the vinyl resin obtained in Example 7. 6 shows an IR chart of the vinyl resin obtained in Example 7.

[0015] The present invention will be described in detail below. The vinyl resin of the present invention is represented by the following general formula (1).

[0016] In general formula (1), R １are independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the 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 having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and examples thereof include hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-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. Examples of aryl groups having 6 to 8 carbon atoms include, but are not limited to, phenyl, tolyl, xylyl, and ethylphenyl. Examples of the aralkyl group having 7 to 8 carbon atoms include, but are not limited to, a benzyl group, an α-methylbenzyl group, etc. Among these substituents, a methyl group or a phenyl group is preferred, and a methyl group is particularly preferred, from the viewpoints of availability and reactivity when formed into a cured product.

[0017] The above R ２ are independently a dicyclopentenyl group which may have a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and at least one of them is a dicyclopentenyl group which may have a hydrocarbon group having 1 to 8 carbon atoms. The dicyclopentenyl group which may have a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms is a group derived from dicyclopentadiene which may have a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and is represented by the following formula (1c) or formula (1d):

[0018]

[0019] R in the above formulas (1), (1c) and (1d) ３ , R ４are independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and a and b are 0 to 2. Preferably, a and b are each 0, 1, or 2. When both a and b are zero, the substituent R ３ , R ４ Since it shows that R ３ and R ４ is a hydrogen atom. ３ , R ４ When either or both of the above are hydrocarbon groups having 1 to 8 carbon atoms, it is preferable that a+b≧1 or more is satisfied, and it is more preferable that a+b is 1 or 2. The hydrocarbon group having 1 to 8 carbon atoms is the same as above, but is preferably an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, and examples thereof include hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, methylbutyl, n-hexyl, dimethylbutyl, n-heptyl, methylhexyl, trimethylbutyl, n-octyl, dimethylpentyl, ethylpentyl, isooctyl, and ethylhexyl, as well as cycloalkyl groups having 5 to 8 carbon atoms such as cyclohexyl, cycloheptyl, cyclooctyl, methylcyclohexyl, dimethylcyclohexyl, ethylcyclohexyl, and methylcycloheptyl. Of these substituents, the methyl group is preferred from the standpoints of availability and reactivity when formed into a cured product.

[0020] In general formula (1), X independently represents a hydrogen atom or a vinyl group-containing group represented by the following formula (1a) or (1b), and at least one X is a vinyl group-containing group derived from a compound represented by the formula (4a), (4b), or (5) of the raw material described below.

[0021] R ５ is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms, and Ar is an aromatic ring. ５is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. From the viewpoints of availability and reactivity when forming a cured product, R ５ is preferably a hydrogen atom or a methyl group. The aromatic ring Ar in formula (1b) is preferably an aromatic ring selected from the group consisting of a benzene ring, a naphthalene ring, and a biphenyl ring, and may be unsubstituted or may have one or more substituents. When it has a substituent, the number of substituents is preferably 1 to 4, and the substituent is preferably an alkyl group or aryl group having 1 to 10 carbon atoms, more preferably an alkyl group or phenyl group having 1 to 3 carbon atoms.

[0022] In general formula (1), n ​​is the number of repeats and is a number of 0 or more, and its average value is a number smaller than 1. The average value is a number average. The average value of n is preferably 0.95 or less, more preferably 0.90 or less. On the other hand, although there is no lower limit to the average value of n, it is preferably 0.1 or more, more preferably 0.2 or more.

[0023] The average molecular weight of the vinyl resin of the present invention, as a weight average molecular weight (Mw), is preferably 200 to 1,000, more preferably 250 to 800, and the number average molecular weight (Mn) is preferably 200 to 800, more preferably 230 to 500. The vinyl equivalent (g / eq.) is preferably 200 to 800, more preferably 300 to 600. On the other hand, the hydroxyl group equivalent (g / eq.) is preferably 10,000 or more, more preferably 15,000 or more, and particularly preferably in the range of 15,000 to 50,000. With regard to molecular weight distribution, the content of n=0 isomers is preferably 40 to 90 area%, more preferably 50 to 85 area%. The content of n=1 isomers is preferably 10 to 40 area%, more preferably 14 to 30 area%. The content of n=2 or more isomers is preferably 0 to 40 area%, more preferably 0 to 35 area%.

[0024] The vinyl resin of the present invention can be suitably obtained by reacting a hydroxy resin represented by the following general formula (3) 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), or a halogenated methyl group-containing aromatic vinyl compound represented by the following general formula (5).

[0025] R １ , R ２ , R ３ , R ４ , R ５ , a, b, and n are defined as in the general formula (1). ６ , R ７ represents a halogen, preferably a chlorine atom or a bromine atom.

[0026] The hydroxy resin represented by the general formula (3) can be obtained, for example, by reacting a phenol represented by the following general formula (2) with a dicyclopentadiene in the presence of a Lewis acid such as a boron trifluoride ether catalyst. Here, the dicyclopentadiene is a dicyclopentadiene which may have a hydrocarbon group having 1 to 8 carbon atoms, and the hydrocarbon group having 1 to 8 carbon atoms is the above-mentioned R ３ , R ４ Specific examples of dicyclopentadienes include dicyclopentadiene and methylcyclopentadiene dimer, which will be described later in the Examples section.

[0027] R １ has the same definition as in the above general formula (1).

[0028] Examples of the phenols include phenol, cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, cyclohexylphenol, phenylphenol, tolylphenol, benzylphenol, α-methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(t-butyl)phenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, ditolylphenol, dibenzylphenol, bis(α-methylbenzyl)phenol, methylethylphenol, methylpropylphenol, methylisopropylphenol, methylbutylphenol, methyl-t-butylphenol, methylallylphenol, tolylphenylphenol, etc. From the viewpoints of availability and reactivity when formed into a cured product, phenol, cresol, phenylphenol, dimethylphenol, or diphenylphenol is preferred, and cresol and dimethylphenol are particularly preferred.

[0029] 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, iron chloride, etc., with boron trifluoride ether complex being preferred due to ease of handling. In the case of boron trifluoride ether complex, the amount of catalyst used is 0.1 to 8 parts by mass, preferably 0.5 to 5 parts by mass, more preferably 0.5 to 4 parts by mass, even more preferably 0.5 to 3 parts by mass, and even more preferably 0.5 to 2 parts by mass, per 100 parts by mass of dicyclopentadienes.

[0030] The reaction method for introducing the dicyclopentenyl group into the phenol is a method in which the phenol is reacted with a dicyclopentadiene at a predetermined ratio. The dicyclopentadiene may be added continuously or added in several stages (two or more divided successive additions) to react intermittently. The ratio is preferably 0.5 to 2 moles, more preferably 0.5 to 1 mole, and even more preferably 0.5 to 0.95 moles, of the dicyclopentadiene per mole of the phenol. This reaction may produce not only isomers with different substitution positions, but also structures in which the dicyclopentadiene structure and the phenolic hydroxyl group are bonded.

[0031] To confirm that the dicyclopentenyl group has been introduced into the hydroxy resin represented by the general formula (3), mass spectrometry (MS) and Fourier transform infrared spectroscopy (FT-IR) can be used.

[0032] When mass spectrometry is used, electrospray ionization mass spectrometry (ESI-MS), field desorption mass spectrometry (FD-MS), etc. can be used. By subjecting a sample obtained by separating components with different numbers of nuclei by GPC or the like to mass spectrometry, it is possible to confirm that the dicyclopentenyl group has been introduced.

[0033] When using the FT-IR measurement method, a sample dissolved in an organic solvent such as tetrahydrofuran (THF) is applied to a KRS-5 cell, and the organic solvent is dried to obtain a cell with a thin film of the sample. When the cell is measured by FT-IR, a peak due to the C-O stretching vibration of the phenol nucleus is observed at 1210 cm －１ Only when a dicyclopentenyl group is introduced does the peak due to the C-H stretching vibration of the olefin moiety of the dicyclopentadiene skeleton appear at 3040 cm －１ The dicyclopentadiene incorporated into the main chain is not detected because it has no olefin moiety, and the side chain R ２Only the olefin of the dicyclopentenyl group introduced as above can be measured. When the baseline is a linear connection between the start and end of the target peak, and the length from the peak apex to the baseline is the peak height, the peak height is 3040 cm －１ Nearby peaks (A ３０４０ ) and 1210 cm －１ Nearby peaks (A １２１０ ) ratio (A ３０４０ / A １２１０ The amount of dicyclopentenyl groups introduced can be quantified by the above ratio. It has been confirmed that the larger the ratio, the better the physical properties. ３０４０ / A １２１０ ) is preferably 0.05 or more, more preferably 0.10 or more, and particularly preferably 0.10 to 0.30.

[0034] The hydroxyl group equivalent (g / eq.) of the hydroxy resin is preferably 150 to 800, more preferably 200 to 500. The average molecular weight is preferably a weight average molecular weight (Mw) of 200 to 1,000, more preferably 250 to 800, and a number average molecular weight (Mn) of 200 to 800, more preferably 240 to 400.

[0035] A suitable reaction method is to charge a phenol and a catalyst into a reactor and then add a dicyclopentadiene dropwise over 1 to 10 hours.

[0036] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and even more preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and even more preferably 4 to 8 hours.

[0037] After the reaction is complete, an alkali such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. The resulting mixture is then dissolved in a solvent such as an aromatic hydrocarbon such as toluene or xylene, or a ketone such as methyl ethyl ketone or methyl isobutyl ketone. The resulting mixture is washed with water, and the solvent is recovered under reduced pressure to obtain the desired phenolic resin. It is preferable to react as much of the dicyclopentadienes as possible, leaving a portion of the phenols unreacted, preferably 10% or less, which is then recovered under reduced pressure.

[0038] During the reaction, if necessary for viscosity adjustment or the like, solvents such as aromatic hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, etc., ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc., and ketones such as methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. may be used.

[0039] The vinyl resin of the present invention can be suitably obtained by reacting the thus obtained hydroxy resin with an acid anhydride represented by the above general formula (4a) or an acid halide represented by the above general formula (4b), or a halogenated methyl group-containing aromatic vinyl compound represented by the above general formula (5).

[0040] Examples of acid anhydrides include acrylic anhydride and methacrylic anhydride, with methacrylic anhydride being preferred. Examples of acid halides include acrylic acid chloride, methacrylic acid chloride, methacrylic acid bromide, with methacrylic acid chloride and methacrylic acid bromide being preferred. Examples of halogenated methyl group-containing aromatic vinyl compounds include halomethylstyrenes. Specific examples of halomethylstyrenes include chloromethylstyrene, bromomethylstyrene, and their isomers, as well as those having a substituent. Regarding the substitution position of the halomethyl compound, for example, in the case of halomethylstyrene, the 3rd or 4th position is preferred, with the respective contents ranging from 1 / 99 to 99 / 1.

[0041] The reaction of a hydroxy resin with an acid anhydride or an acid halide may be carried out by reacting the hydroxy resin in a solvent in the presence of a basic compound. In this case, a preferred method is to charge the hydroxy resin, the basic compound, and the solvent into a reactor, dissolve the hydroxy resin, and then add the acid anhydride or the acid halide to carry out the reaction.

[0042] The ratio of the hydroxy resin to the acid anhydride or acid halide used is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents, of the acid anhydride or acid halide relative to 1 equivalent of the phenolic hydroxyl group of the hydroxy resin.

[0043] The solvent used in the reaction between the hydroxy resin and the acid anhydride or acid halide is not particularly limited, but examples include aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as chlorobenzene and dichlorobenzene; 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 ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, and diglyme; and aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. One or more of these solvents can be used. Water can also be mixed with the solvent. The amount of solvent used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, and particularly preferably 25 to 200% by mass, based on the total mass of the hydroxy resin. In particular, aprotic polar solvents are not useful for purification such as washing with water, and have high boiling points that make them difficult to remove, so it is not preferable for the amount of aprotic polar solvents used to exceed 300% by mass based on the total mass of the hydroxy resin.

[0044] The basic compound used in the reaction between the hydroxy resin and the acid anhydride or acid halide is preferably an organic basic compound, an alkali metal hydroxide, a carbonate, or the like. Specific examples include triethylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, with triethylamine, pyridine, dimethylaminopyridine, sodium hydroxide, and potassium hydroxide being preferred. The acid halide or acid anhydride generates an equimolar acidic substance upon reaction with the phenolic hydroxyl group, inhibiting the progress of the reaction, and can therefore be neutralized with a basic compound. The amount of the basic compound used is typically 1.0 to 2.5 mol, preferably 1.0 to 1.8 mol, and more preferably 1.0 to 1.5 mol, per mol of phenolic hydroxyl group on the hydroxy resin.

[0045] The reaction temperature of the hydroxy resin with the acid anhydride or acid halide is usually 15 to 150° C., preferably 35 to 120° C. In order to obtain a vinyl resin of higher purity, it is preferable to increase the reaction temperature in two or more stages. For example, it is particularly preferable to increase the reaction temperature to 15 to 50° C. in the first stage and 45 to 120° C. in the second stage.

[0046] The reaction time for producing the 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. A reaction time of 0.5 hours or more allows the reaction to proceed sufficiently, while a reaction time of 10 hours or less makes it possible to keep the amount of by-products produced low.

[0047] In the reaction between the hydroxy resin and the acid anhydride or acid halide, if there is a concern about self-polymerization of the acid anhydride or acid halide, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitrone compounds, phenols, or oxygen may be used.

[0048] After the reaction of the hydroxy resin with the acid anhydride or acid halide is complete, the solvent may be distilled off under heating and reduced pressure, or the residue may be dissolved directly in a ketone solvent having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, etc.), an aromatic hydrocarbon solvent such as benzene, toluene, or xylene, or an ether such as cyclopentyl methyl ether, and washed with water, a lower alcohol such as methanol, or a mixed solvent of these, which has low solubility for the target product, to remove by-produced salts and impurities.

[0049] While typical vinyl resins are unstable under heating conditions, the vinyl resin of the present invention is highly stable, allowing the solvent to be distilled off under heating conditions and volatile impurities to be removed. Therefore, the vinyl resin can be stored stably even after the solvent is removed. The heating conditions for distilling off the solvent and removing impurities from the vinyl resin as the reaction product obtained are preferably 100°C to 180°C, and more preferably 120°C to 160°C. At temperatures lower than this range, the resin viscosity increases, making it more likely that the acid generated from the acid anhydride or acid halide will remain. At temperatures higher than this range, the vinyl resin is more likely to gel. Furthermore, distilling off the solvent and removing volatile impurities are preferably carried out under reduced pressure.

[0050] The production of the vinyl resin of the present invention is usually carried out while blowing an inert gas such as nitrogen into the system (air or liquid). By carrying out the reaction while blowing an inert gas into the system, it is possible to prevent the resulting product from becoming discolored. The amount of inert gas blown in per unit time varies depending on the volume of the kettle (reactor) used in the reaction, and it is preferable to adjust the amount of inert gas blown in per unit time so that the volume of the kettle can be replaced in, for example, 0.5 to 20 hours.

[0051] On the other hand, the etherification method is an excellent method for reacting a hydroxy resin with a halogenated methyl group-containing aromatic vinyl compound. One example is a method in which a hydroxy resin represented by general formula (3) is reacted with a halogenated methyl group-containing aromatic vinyl compound represented by general formula (5) in a solvent in the presence of an alkali compound. The etherification reaction referred to here refers to a bimolecular nucleophilic substitution reaction between the phenolic hydroxyl group of the hydroxy resin and the halogenated methyl group of the halogenated methyl group-containing aromatic vinyl compound. In this case, a preferred method is to charge the hydroxy resin (3) and a solvent into a reactor, dissolve the hydroxy resin, and then add a solution of the halogenated methyl group-containing aromatic vinyl compound (5) and an alkali compound to carry out the reaction.

[0052] The hydroxy resin and the halogenated methyl group-containing aromatic vinyl compound are reacted in such a ratio that the amount of halogenated methyl groups in the halogenated methyl group-containing aromatic vinyl compound is preferably 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents, per equivalent of the phenolic hydroxyl group in the hydroxy resin.

[0053] The alkali compound used in the reaction of the hydroxy resin with the halogenated methyl group-containing aromatic vinyl compound is preferably an alkali metal hydroxide or carbonate, and specific examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, with sodium hydroxide and potassium hydroxide being preferred. Such alkali metal hydroxides may be used in the form of a solid or a solution.

[0054] The amount of the alkali compound used is usually 1.0 to 2.0 mol, preferably 1.0 to 1.8 mol, more preferably 1.0 to 1.5 mol, still more preferably 1.0 to 1.3 mol, and particularly preferably 1.0 to 1.1 mol, per mol of the phenolic hydroxyl group of the hydroxy resin.

[0055] The solvent used in the reaction between the hydroxy resin and the halogenated methyl group-containing aromatic vinyl compound is not particularly limited, but examples include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as tetrahydrofuran, dioxane, and diglyme; and aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. One or more of these solvents can be used. Water can also be mixed with the solvent. In addition to the water and solvent, a solvent (another organic solvent) such as toluene can be contained. The amount of the other organic solvent used is in the range of 0.5 to 400% by mass, preferably 100 to 300% by mass, and more preferably 150 to 250% by mass, of the amount of the solvent used.

[0056] The amount of the solvent used is preferably 20 to 500% by mass, more preferably 25 to 400% by mass, and particularly preferably 25 to 350% by mass, based on the total mass of the hydroxy resin. In particular, aprotic polar solvents are not useful for purification such as washing with water, and have high boiling points that make them difficult to remove, so it is not preferable for the amount used to exceed 500% by mass, based on the total mass of the hydroxy resin.

[0057] The reaction temperature between the hydroxy resin and the halogenated methyl group-containing aromatic vinyl compound is usually 30 to 90°C, preferably 35 to 80°C. To obtain a vinyl resin of higher purity, it is preferable to increase the reaction temperature in two or more stages; for example, it is particularly preferable to set the first stage at 15 to 50°C and the second stage at 45 to 70°C. The reaction time between the hydroxy resin and the halogenated methyl group-containing aromatic vinyl compound is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. A reaction time of 0.5 hours or more allows the reaction to proceed sufficiently, while a reaction time of 10 hours or less makes it possible to keep the amount of by-products produced low.

[0058] After the reaction between the hydroxy resin and the halogenated methyl group-containing aromatic vinyl compound is complete, the solvent is distilled off under heating and reduced pressure, or the residue is dissolved in a solvent such as a ketone solvent having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) or toluene without being distilled off, and washed with water at a temperature of 40 to 90°C, preferably 50 to 80°C, until the aqueous layer reaches a pH of 5 to 8, thereby removing by-product salts. During the water washing, alcohols such as methanol, ethanol, and propanol may be added.

[0059] The reaction between the hydroxy resin and the halogenated methyl group-containing aromatic vinyl compound is usually carried out while blowing an inert gas such as nitrogen into the system (air or liquid). By blowing an inert gas into the system, coloration of the resulting product can be prevented. The amount of inert gas blown in per unit time varies depending on the volume of the reactor used in the reaction. It is preferable to adjust the amount of inert gas blown in per unit time so that the volume of the reactor can be replaced in, for example, 0.5 to 20 hours.

[0060] When there is a concern about self-polymerization of the halogenated methyl group-containing aromatic vinyl compound, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitrone compounds, phenols, or oxygen may be used.

[0061] The end point of the reaction between the hydroxy resin and the halogenated methyl group-containing aromatic vinyl compound can be determined by tracing the remaining amount of the halogenated methyl group-containing aromatic vinyl compound on various chromatograms. The reaction rate can be adjusted by adjusting the type and amount of metal hydroxide, adjusting the addition rate, or using an appropriate catalyst.

[0062] The vinyl resin of the present invention can be cured alone, but it is also suitable to use it as a resin composition containing various additives, for example, a radical polymerization initiator to accelerate curing.

[0063] A radical polymerization initiator (also referred to as a radical polymerization catalyst) may be used, for example, to lower the reaction temperature or to promote the crosslinking reaction of unsaturated groups when the vinyl resin composition of the present invention is cured by a crosslinking reaction caused by heating or other means, as described below. The amount of radical polymerization initiator used for this purpose is preferably 0.01 to 12 parts by mass, and more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the vinyl resin. Since the radical polymerization initiator is a radical polymerization catalyst, it will be hereinafter referred to as the radical polymerization initiator.

[0064] 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(t-butylperoxy)hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, and trimethylsilyltriphenylsilyl peroxide, but are not limited to these. 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 present resin composition are not limited to these examples.

[0065] The vinyl resin of the present invention can be blended with other vinyl resins or other thermoplastic vinyl resins, such as vinyl ester resins, polyvinylbenzyl resins, polyallyl resins, epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polycyanate resins, phenolic resins, and benzoxazine resins.

[0066] It is also possible to compound thermoplastic resins such as polystyrene resin, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, PPS resin, polycyclopentadiene resin, and polycycloolefin resin; thermoplastic elastomers such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, and hydrogenated styrene-isoprene copolymer; and rubbers such as polybutadiene and polyisoprene.

[0067] When the other vinyl resin that can be blended is one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule, the type of vinyl compound is not particularly limited. That is, the vinyl compound may be any vinyl compound that can form crosslinks and harden by reacting with the vinyl resin of the present invention. More preferably, the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferably, a compound having two or more carbon-carbon unsaturated double bonds in the molecule.

[0068] The average number of carbon-carbon unsaturated double bonds (the number of vinyl groups (including substituted vinyl groups); also referred to as the number of terminal double bonds) per molecule of vinyl compounds as curable resins varies depending on the Mw of the vinyl compounds, but is, for example, 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 a cured product with sufficient heat resistance. On the other hand, if the number of terminal double bonds is too large, the reactivity becomes too high, and problems such as reduced storage stability and reduced fluidity of the composition may occur.

[0069] Examples of vinyl compounds include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), modified polyphenylene ethers (PPE) whose terminals are modified with (meth)acryloyl groups or styryl groups, polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in the molecule, vinyl compounds having two or more vinyl groups in the molecule (polyfunctional vinyl compounds) such as polybutadiene, and vinylbenzyl compounds such as styrene and divinylbenzene. Among these, compounds having two or more carbon-carbon double bonds in the molecule are preferred, and specific examples include TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, and divinylbenzene compounds. The use of these compounds is believed to more favorably form crosslinks through the curing reaction, thereby further enhancing the heat resistance of the cured resin composition. These compounds may be used alone or in combination of two or more. Compounds having one carbon-carbon unsaturated double bond in the molecule may also be used in combination. Examples of compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).

[0070] In order to improve the flame retardancy of the resulting cured product, various known flame retardants can be used in the vinyl resin composition of the present invention, as long as the reliability is not reduced. Usable flame retardants include, for example, halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. From an environmental perspective, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used alone, or two or more of the same type of flame retardants may be used in combination, or different types of flame retardants may be used in combination.

[0071] For the purpose of further improving its functionality, the vinyl resin composition of the present invention may contain components other than those listed above (sometimes referred to as "other components" in the present invention.) Examples of such other components include fillers, ultraviolet protection agents, antioxidants, coupling agents, plasticizers, fluxes, thixotropic agents, smoothing agents, colorants, pigments, dispersants, emulsifiers, elasticity reducing agents, release agents, antifoaming agents, and ion-trapping agents.

[0072] Examples of fillers 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, aramid fiber, and ceramic fiber; and fine particle rubber.

[0073] Specific examples of other components include organic pigments such as quinacridone, azo, and phthalocyanine pigments, inorganic pigments such as titanium oxide, metal foil pigments, and anti-rust pigments, ultraviolet absorbers such as hindered amine, benzotriazole, and benzophenone, antioxidants such as hindered phenol, phosphorus, sulfur, and hydrazide, release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, and additives such as leveling agents, rheology control agents, pigment dispersants, anti-cision agents, and defoamers. The amount of these other components added is preferably in the range of 0.01 to 20% by mass based on the total solids content of the resin composition.

[0074] The vinyl resin composition of the present invention can be made into a resin varnish 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 diglycol acetate, propylene glycol monomethyl ether acetate, and γ-butyrolactone. The solvent and the appropriate amount used can be selected appropriately depending on the application. For example, for printed wiring board applications, solvents with a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, toluene, xylene, and 1-methoxy-2-propanol, are preferred, and they are preferably used in a proportion that results in a nonvolatile content of 20 to 80% by mass. On the other hand, for build-up adhesive film applications, preferred solvents include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ester compounds such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and γ-butyrolactone; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and preferably used in a proportion that results in a nonvolatile content of 20 to 80% by mass. The laminate of the present invention can be obtained by curing a resin varnish. Specific examples include printed wiring boards, printed circuit boards, flexible printed wiring boards, and build-up wiring boards.

[0075] The cured product obtained by curing the vinyl resin composition of the present invention can be used as a molded product, laminate, cast product, adhesive, coating, or film. For example, a cured product of a semiconductor encapsulating material is a cast product or molded product. A method for obtaining a cured product for this application is to mold the compound using a cast molding machine, transfer molding machine, injection molding machine, or the like, and then heat the molded product at 80 to 230°C for 0.5 to 10 hours. Furthermore, a cured product of a resin varnish is a laminate. This cured product can be obtained by impregnating a substrate such as the above-mentioned fibrous filler or paper with the resin varnish and drying it by heating to obtain a prepreg, which can then be laminated alone or with a metal foil such as copper foil and hot-press molded. Furthermore, uncured or partially cured sheets of the vinyl resin composition of the present invention can be suitably used, for example, as build-up films, bonding sheets, coverlay sheets, bump sheets for flip-chip bonders, and insulating or adhesive layers for substrates.

[0076] Furthermore, by compounding inorganic high dielectric powder such as barium titanate or inorganic magnetic material such as ferrite, the composition is useful as a material for electronic parts, particularly as a material for high frequency electronic parts.

[0077] Next, the prepreg of the present invention and its cured product will be described. A base material is added to the prepreg of the present invention in order to increase the mechanical strength and dimensional stability.

[0078] As such a substrate, it is preferable to use a fibrous substrate. For example, various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat, asbestos cloth, metal fiber cloth, and other synthetic or natural inorganic fiber cloths, woven or nonwoven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fiber, wholly aromatic polyester fiber, and polybenzozal fiber, woven or nonwoven fabrics obtained from synthetic fibers such as polyvinyl alcohol fiber, polyester fiber, and acrylic fiber, natural fiber cloths such as cotton cloth, linen cloth, and felt, carbon fiber cloth, and natural cellulose-based cloths such as kraft paper, cotton paper, and paper-glass mixed fiber paper, and paper and the like, can be used alone or in combination of two or more kinds.

[0079] The proportion of the substrate in the prepreg is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass. If the substrate content is less than 5% by mass, the dimensional stability and strength of the cured product tend to decrease. Furthermore, if the substrate content is more than 90% by mass, the dielectric properties of the cured product tend to decrease. If necessary, a coupling agent can be used in the prepreg of the present invention to improve adhesion at the interface between the resin and the substrate. Typical coupling agents that can be used include silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and zircoaluminate coupling agents.

[0080] The prepreg of the present invention can be produced, for example, by uniformly dissolving or dispersing the vinyl resin composition of the present invention and, if necessary, other components in the above-mentioned aromatic or ketone solvent or a mixed solvent thereof, impregnating the substrate with the resulting solution, and then drying or semi-curing the solution. Impregnation can be performed by immersion (dipping), coating, or the like. Impregnation can be repeated multiple times as needed, and in this case, impregnation can be repeated using multiple solutions with different compositions and concentrations to adjust the final resin composition and resin amount to the desired level.

[0081] A cured product can be obtained by curing the prepreg of the present invention by heating or other methods. The manufacturing method is not particularly limited; for example, multiple prepregs can be stacked, and the layers can be bonded together under heat and pressure, while simultaneously thermally curing to obtain a cured product (laminate) of the desired thickness. It is also possible to combine a cured product that has been bonded and cured once with a prepreg to obtain a multilayer laminate with a new layer structure. Lamination molding and curing are usually performed simultaneously using a hot press or the like, but they can also be performed separately. That is, uncured or semi-cured prepregs obtained by prior laminate molding can be cured by heat treatment or another method.

[0082] Molding and curing are carried out, for example, at a temperature of 80 to 300°C and a pressure of 0.1 to 1,000 kgf / cm. ２ , time: in the range of 1 minute to 10 hours, more preferably, temperature: 150 to 250°C, pressure: 1 to 500 kgf / cm２ The time can be set within the range of 1 minute to 5 hours.

[0083] The laminate of the present invention may be composed of a layer of the prepreg of the present invention and a layer of metal foil. Examples of the metal foil used here include copper foil and aluminum foil. The thickness of the metal foil is not particularly limited, but is in the range of 3 to 200 μm, more preferably 3 to 105 μm.

[0084] One example of a method for producing such a laminate is to laminate a prepreg obtained from the vinyl resin composition of the present invention and a substrate with metal foil in a layer configuration appropriate for the purpose, and then bond the layers together under heat and pressure while simultaneously thermosetting the laminate. In the laminate, the cured product and metal foil are laminated in any layer configuration. The metal foil can be used as both a surface layer and an intermediate layer. In addition to the above, it is also possible to repeat the lamination and curing process multiple times to create a multilayer structure.

[0085] An adhesive can be used to bond the metal foil. Examples of adhesives include, but are not limited to, epoxy, acrylic, phenolic, and cyanoacrylate adhesives. The lamination molding and curing can be carried out under the same conditions as those for producing the cured product of the prepreg of the present invention.

[0086] The vinyl resin composition of the present invention can also be formed into a film to form a resin sheet. The thickness of the resin layer is not particularly limited, but is preferably in the range of 3 to 200 μm, more preferably 5 to 105 μm. The method for producing the resin sheet of the present invention is not particularly limited, and examples include a method in which the vinyl resin composition and, if necessary, other components are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof, and then coated on a support film such as a PET film, followed by drying or semi-curing to form a resin layer. The coating can be repeated multiple times as needed, and in this case, it is also possible to repeatedly coat multiple solutions with different compositions and concentrations to adjust the final resin composition and resin amount to the desired level.

[0087] Furthermore, when the resin sheet of the present invention is used as a bonding sheet, for example, two substrates can be bonded with the resin sheet. Each of the two substrates is, for example, a laminate or a printed wiring board. Specifically, for example, a vinyl resin composition is formed into a sheet on a support film by a coating method or the like, and then heated to dry or semi-cure, thereby producing a resin sheet. This resin sheet is then superimposed on a substrate (first substrate), the support film is peeled off from the resin sheet, and another substrate (second substrate) is superimposed. That is, the first substrate, the resin layer (a resin layer of the vinyl resin composition or its semi-cured product), and the second substrate are laminated in this order. Subsequently, the first substrate and the second substrate are bonded together via the cured vinyl resin composition by heating and curing.

[0088] Furthermore, a resin-coated metal foil can be obtained by combining the vinyl resin composition of the present invention with a metal foil. Examples of the metal foil used here include copper foil and aluminum foil. The thickness is not particularly limited, but is preferably in the range of 3 to 200 μm, more preferably 5 to 105 μm. The method for producing the resin-coated metal foil is not particularly limited, and examples include a method in which the vinyl resin composition and, if necessary, other components are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof, and then applied to the metal foil, followed by drying or semi-curing. The application can be repeated multiple times as needed, and in this case, it is also possible to repeatedly apply multiple solutions with different compositions and concentrations to adjust the final resin composition and resin amount to the desired level.

[0089] The electronic material substrate is formed using the laminate of the present invention. The electronic material substrate can be suitably used as a component for various electrical and electronic devices, such as mobile phones, PHSs, notebook computers, PDAs (personal digital assistants), mobile videophones, personal computers, supercomputers, servers, routers, liquid crystal projectors, engineering workstations (EWSs), pagers, word processors, televisions, viewfinder-type or direct-view monitor videotape recorders, electronic organizers, electronic desk calculators, car navigation systems, POS terminals, and devices equipped with touch panels, which require reliability in environments requiring heat resistance and water resistance, as well as reliable transmission of high-frequency signals. In particular, the cured product of the present invention is suitable for use as a circuit board for the above-mentioned electrical and electronic devices due to its excellent heat resistance stability of dielectric properties, dimensional stability, and moldability suitable for forming fine patterned circuits. Specific examples include single-sided, double-sided, and multilayer printed circuit boards, flexible boards, and build-up boards. Multilayer circuit boards using metal plating as the conductor layer are also preferred examples.

[0090] The present invention will be specifically explained using examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "parts" represents parts by mass, "%" represents mass %, and "ppm" represents mass ppm. In addition, the measurement methods were as follows.

[0091] The test conditions for hydroxy resin, vinyl resin and cured product are shown below.

[0092] (1) Hydroxyl group equivalent: Measured in accordance with JIS K0070, and expressed in units of g / eq. Unless otherwise specified, the hydroxyl group equivalent of a hydroxy resin means the phenolic hydroxyl group equivalent.

[0093] (2) Melt Viscosity: The melt viscosity at 150° C. was measured using an ICI viscosity measuring device (CV-1S, manufactured by Toa Kogyo Co., Ltd.).

[0094] (3) Viscosity at 25°C: The viscosity at 25°C was measured using an E-type viscosity measuring device (RE85H, manufactured by Toki Sangyo Co., Ltd.).

[0095] (4) Softening point: Measured in accordance with the ring and ball method of JIS K7234. Specifically, an automatic softening point analyzer (ASP-MG4, manufactured by Meitec Corporation) was used.

[0096] (5) Vinyl equivalent: Measured in accordance with JIS K0070. Specifically, a sample was reacted with Wiess's solution (iodine monochloride solution) and left in a dark place. Thereafter, excess iodine chloride was reduced to iodine, and the iodine content was titrated with sodium thiosulfate to calculate the iodine value. The iodine value was converted into a vinyl equivalent.

[0097] (6) Dielectric constant and dielectric loss tangent: Measured in accordance with IPC-TM-650 2.5.5.9. Specifically, the dielectric constant and dielectric loss tangent were determined at a frequency of 10 GHz by a capacitance method using a material analyzer (manufactured by AGILENT Technologies).

[0098] (7) GPC (gel permeation chromatography) measurement: A main body (Tosoh Corporation, HLC-8220GPC) equipped with columns (Tosoh Corporation, TSKgel G4000HXL, TSKgel G3000HXL, TSKgel G2000HXL) in series was used, and the column temperature was 40 ° C. The eluent was tetrahydrofuran (THF), the flow rate was 1 mL / min, and the detector was a differential refractive index detector. The measurement sample was 0.1 g of sample dissolved in 10 mL of THF and 50 μL of the sample filtered through a microfilter was used. Mw and Mn were calculated by conversion from the calibration curve obtained from standard polystyrene (Tosoh Corporation, PStQuick Kit-H). For data processing, Tosoh Corporation's GPC-8020 Model II version 6.00 was used.

[0099] (8) IR: Using a Fourier transform infrared spectrophotometer (Spectrum One FT-IR Spectrometer 1760X, manufactured by Perkin Elmer Precisly), a sample dissolved in toluene was applied to the ATR using a diamond ATR, dried, and then measured at a wave number of 650 to 4000 cm. －１ The absorbance was measured.

[0100] The abbreviations used in the examples and comparative examples are as follows.

[0101] [Hydroxy resin] P1: Hydroxy resin obtained in Synthesis Example 1 P2: Hydroxy resin obtained in Synthesis Example 2 P3: Hydroxy resin obtained in Synthesis Example 3 P4: Hydroxy resin obtained in Synthesis Example 4 P5: Hydroxy resin obtained in Synthesis Example 5 P6: Hydroxy resin obtained in Synthesis Example 6 P7: Hydroxy resin obtained in Reference Example 1 P8: Hydroxy resin obtained in Reference Example 2

[0102] [Vinyl resin] V1: vinyl resin obtained in Example 1 V2: vinyl resin obtained in Example 2 V3: vinyl resin obtained in Example 3 V4: vinyl resin obtained in Example 4 V5: vinyl resin obtained in Example 5 V6: vinyl resin obtained in Example 6 V7: vinyl resin obtained in Example 7 V8: vinyl resin obtained in Example 8 V9: vinyl resin obtained in Example 9 V10: vinyl resin obtained in Example 10 V11: vinyl resin obtained in Example 11 V12: vinyl resin obtained in Example 12 VH1: vinyl resin obtained in Comparative Example 1 VH2: vinyl resin obtained in Comparative Example 2 VH3: vinyl resin obtained in Comparative Example 3 VH4: vinyl resin obtained in Comparative Example 4 VH5: multifunctional vinyl resin (manufactured by Mitsubishi Gas Chemical Company, Inc., terminal vinylbenzyl ether modified PPE resin, OPE-2ST, Mn1187) VH6: Multifunctional vinyl resin (manufactured by SABIC Japan LLC, methacrylic-terminated PPE resin, SA9000, Mw1600)

[0103] PO: organic peroxide (manufactured by NOF Corporation, Perbutyl P) AO: antioxidant (manufactured by ADEKA Corporation, Adekastab AO-60)

[0104] Synthesis Example 1 Into a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser, 100 parts of 2,6-xylenol (structural formula below), 47% BF ３ 0.96 parts of ether complex (1.6 parts by mass per 100 parts by mass of dicyclopentadiene) was charged and heated to 100°C with stirring. While maintaining the temperature, 59.5 parts of dicyclopentadiene (structural formula below) (0.55 times the molar equivalent of 2,6-xylenol) was added. was added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 115-125°C. Thereafter, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials, and 1.5 parts of calcium hydroxide was added. 2.6 parts of a 10% aqueous oxalic acid solution were then added. 160 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product, and 50 parts of 80°C hot water was added for washing, and the lower aqueous layer was separated and removed. The mixture was heated to 120°C and refluxed for dehydration, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove the MIBK, yielding 118 parts of a reddish-brown hydroxy resin (P1).

[0105] The obtained hydroxy resin (P1) had a hydroxyl group equivalent of 255 and was a semi-solid resin at room temperature. １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, and GPC revealed that Mw was 330, Mn was 270, the content of n=0 isomer was 72.3 area%, the content of n=1 isomer was 20.2 area%, and the content of n=2 or more isomers was 7.5 area%, with the average value of n being 0.42. Mass spectrometry by ESI-MS (negative) confirmed M- values ​​of 253, 375, 507, 629, and 639. The viscosity at 150°C (Pa s) was 0.001. The GPC chart of hydroxy resin (P1) is shown in Figure 1, and the IR chart is shown in Figure 2.

[0106] Synthesis Example 2 Into a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser, 100 parts of 2,6-xylenol, 47% BF ３1.30 parts of an ether complex (1.6 parts by mass per 100 parts by mass of dicyclopentadiene) was charged and heated to 100°C with stirring. While maintaining the same temperature, 81.2 parts of dicyclopentadiene (0.75 times the molar ratio of 2,6-xylenol) was added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 115 to 125°C. The mixture was then heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 2.0 parts of calcium hydroxide was added. 3.5 parts of a 10% aqueous oxalic acid solution were then added. 180 parts of MIBK were added to dissolve the product, and 55 parts of 80°C warm water was added for washing, and the lower aqueous layer was separated and removed. The mixture was heated to 120°C and refluxed for dehydration, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 134 parts of a reddish-brown hydroxy resin (P2). The obtained hydroxy resin (P2) had a hydroxyl group equivalent of 278 and was a semi-solid resin at room temperature. １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, and the Mw measured by GPC was 285, Mn was 244, the content of n=0 isomer was 72.7 area%, the content of n=1 isomer was 21.1 area%, and the content of n=2 or more isomers was 6.2 area%, with the average value of n being 0.40. Mass spectrometry by ESI-MS (negative) confirmed M- values ​​of 253, 375, 507, 629, and 639. The viscosity at 150°C (Pa s) was 0.001.

[0107] Synthesis Example 3: 100 parts of 2,6-xylenol, 47% BF, and a mixture of 2,6-xylenol and 47% BF were added to a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser. ３1.66 parts of an ether complex (1.6 parts by mass relative to 100 parts by mass of dicyclopentadiene) was charged and heated to 100°C with stirring. While maintaining the same temperature, 102.8 parts of dicyclopentadiene (0.95 times the molar ratio of 2,6-xylenol) was added dropwise over 1 hour. The reaction was then continued for 4 hours at a temperature of 115 to 125°C. Thereafter, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 2.6 parts of calcium hydroxide was added. 4.4 parts of a 10% aqueous oxalic acid solution were then added. 200 parts of MIBK were added to dissolve the product, and the product was washed with 60 parts of 80°C warm water, after which the lower aqueous layer was separated and removed. The mixture was heated to 120°C and dehydrated under reflux, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 150 parts of a reddish-brown hydroxy resin (P3). The obtained hydroxy resin (P3) had a hydroxyl group equivalent of 327 and was a semi-solid resin at room temperature. １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, and the Mw measured by GPC was 271, Mn was 240, the content of n=0 isomer was 81.5 area%, the content of n=1 isomer was 15.1 area%, and the content of n=2 or more isomers was 3.4 area%, with the average value of n being 0.27. Mass spectrometry by ESI-MS (negative) confirmed M- values ​​of 253, 375, 507, 629, and 639. The viscosity at 150°C (Pa s) was 0.001.

[0108] Synthesis Example 4 Into a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser, 100 parts of 2,6-xylenol, 47% BF ３ 1.15 parts of ether complex (1.6 parts by mass per 100 parts by mass of methylcyclopentadiene dimer) was charged and heated to 100°C with stirring. While maintaining the temperature, 72.2 parts of methylcyclopentadiene dimer (structural formula below) (0.55 times the molar ratio of 2,6-xylenol) was added. was added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 115 to 125°C. Thereafter, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove unreacted raw materials, and 1.8 parts of calcium hydroxide was added. 3.1 parts of a 10% aqueous oxalic acid solution were then added. 170 parts of MIBK was added to dissolve the product, and 50 parts of 80°C warm water was added for washing, and the lower aqueous layer was separated and removed. The mixture was heated to 120°C and refluxed for dehydration, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove the MIBK, yielding 127 parts of a reddish-brown hydroxy resin (P4).

[0109] The obtained hydroxy resin (P4) had a hydroxyl group equivalent of 379 and was a semi-solid resin at room temperature. １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, and the Mw measured by GPC was 610, Mn was 360, the content of n=0 isomer was 52.3 area%, the content of n=1 isomer was 16.4 area%, and the content of n=2 or more isomers was 31.3 area%, with the average value of n being 0.88. Mass spectrometry by ESI-MS (negative) confirmed M- values ​​of 281, 404, 564, 686, and 724. The viscosity at 150°C (Pa s) was 0.02.

[0110] Synthesis Example 5: 100 parts of 2,6-xylenol, 47% BF, and a mixture of 2,6-xylenol and 47% BF were added to a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser. ３1.57 parts of an ether complex (1.6 parts by mass relative to 100 parts by mass of methylcyclopentadiene dimer) was charged and heated to 100°C with stirring. While maintaining the same temperature, 98.4 parts of methylcyclopentadiene dimer (structural formula shown above) (0.75 times the molar ratio relative to 2,6-xylenol) was added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 115 to 125°C. Thereafter, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 2.5 parts of calcium hydroxide was added. 4.2 parts of a 10% aqueous oxalic acid solution were then added. 200 parts of MIBK were added to dissolve the product, and the product was washed with 60 parts of 80°C warm water, after which the lower aqueous layer was separated and removed. The mixture was heated to 120°C and dehydrated under reflux, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 147 parts of a reddish-brown hydroxy resin (P5). The obtained hydroxy resin (P5) had a hydroxyl group equivalent of 410 and was a semi-solid resin at room temperature. １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, and the Mw measured by GPC was 530, Mn was 330, the content of n=0 isomer was 59.8 area%, the content of n=1 isomer was 18.3 area%, and the content of n=2 or more isomers was 21.9 area%, with the average value of n being 0.71. Mass spectrometry by ESI-MS (negative) confirmed M- values ​​of 281, 404, 564, 686, and 724. The viscosity at 150°C (Pa s) was 0.02.

[0111] Synthesis Example 6: Into a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser, 100 parts of 2,6-xylenol, 47% BF ３1.99 parts of an ether complex (1.6 parts by mass relative to 100 parts by mass of methylcyclopentadiene dimer) was charged and heated to 100°C with stirring. While maintaining the same temperature, 124.6 parts of methylcyclopentadiene dimer (structural formula shown above) (0.95 times the molar ratio relative to 2,6-xylenol) was added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 115 to 125°C. Thereafter, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 3.1 parts of calcium hydroxide was added. 5.3 parts of a 10% aqueous oxalic acid solution were then added. 230 parts of MIBK were added to dissolve the product, and the product was washed with 70 parts of 80°C warm water, after which the lower aqueous layer was separated and removed. The mixture was heated to 120°C and dehydrated under reflux, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 166 parts of a reddish-brown hydroxy resin (P6). The obtained hydroxy resin (P6) had a hydroxyl equivalent of 485 and was a semi-solid resin at room temperature. １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, and the Mw measured by GPC was 500, Mn was 320, the content of n=0 isomer was 63.3 area%, the content of n=1 isomer was 19.2 area%, and the content of n=2 or more isomers was 17.5 area%, with the average value of n being 0.63. Mass spectrometry by ESI-MS (negative) confirmed M- values ​​of 281, 404, 564, 686, and 724. The viscosity at 150°C (Pa s) was 0.01.

[0112] Reference Example 1 Into a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser, 100 parts of 2,6-xylenol, 47% BF ３1.44 parts of an ether complex (10.7 parts by mass per 100 parts by mass of dicyclopentadiene) was charged and heated to 100°C with stirring. While maintaining the same temperature, 13.5 parts of dicyclopentadiene (0.12 times the molar equivalent of 2,6-xylenol) was added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 115 to 125°C. The mixture was then heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 2.3 parts of calcium hydroxide was added. 3.8 parts of a 10% aqueous oxalic acid solution were then added. 110 parts of MIBK were added to dissolve the product, and 30 parts of 80°C hot water were added for washing, after which the lower aqueous layer was separated and removed. The mixture was heated to 120°C and refluxed for dehydration, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 33 parts of a reddish-brown hydroxy resin (P7). The obtained hydroxy resin (P7) had a hydroxyl equivalent of 195 and a softening point of 73° C. The hydroxy resin represented by formula (3), R １ is a methyl group, R ２ is a hydrogen atom, R ３ and R ４ is a hydrogen atom, and GPC revealed that Mw was 470, Mn was 440, the content of n=0 was 2.8 area%, the content of n=1 was 86.2 area%, and the content of n=2 or more was 11.0 area%, with the average value of n being 1.08. Mass spectrometry by ESI-MS (negative) confirmed M- = 375,629. The viscosity at 150°C (Pa s) was 0.09.

[0113] Reference Example 2 Into a reaction apparatus consisting of a separable glass flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a condenser, 100 parts of 2,6-xylenol, 47% BF ３1.45 parts of an ether complex (8.8 parts by mass relative to 100 parts by mass of methylcyclopentadiene dimer) was charged and heated to 100°C with stirring. While maintaining the same temperature, 16.4 parts of methylcyclopentadiene dimer (0.13 times the molar ratio relative to 2,6-xylenol) was added dropwise over 1 hour. The reaction was continued for another 4 hours at a temperature of 115 to 125°C. Thereafter, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to remove unreacted raw materials by evaporation, and 2.3 parts of calcium hydroxide was added. 3.9 parts of a 10% aqueous oxalic acid solution were then added. 120 parts of MIBK were added to dissolve the product, and the product was washed with 40 parts of 80°C warm water, after which the lower aqueous layer was separated and removed. The mixture was heated to 120°C and dehydrated under reflux, filtered, and then heated to 160°C under a reduced pressure of 5 mmHg to remove the MIBK by evaporation, yielding 36 parts of a reddish-brown hydroxy resin (P8). The obtained hydroxy resin (P8) had a hydroxyl equivalent of 231 and a softening point of 85°C. １ is a methyl group, R ２ is a hydrogen atom, R ３ and R ４ is a methyl group or a hydrogen atom, and the Mw measured by GPC was 620, Mn was 470, the content of n=0 isomer was 16.1 area%, the content of n=1 isomer was 54.2 area%, and the content of n=2 or more isomers was 29.7 area%, with the average value of n being 1.16. Mass spectrometry by ESI-MS (negative) confirmed M-=404, 686. The viscosity at 150°C (Pa s) was 0.1.

[0114] Example 1: 100 parts of hydroxy resin (P1), 48.0 parts of dimethylaminopyridine, and 150 parts of toluene were charged into an apparatus similar to that used in Synthesis Example 1, and the mixture was heated to 60°C to dissolve. After cooling to 20°C, 90.8 parts of methacrylic anhydride (structural formula below) (1.5 equivalents relative to the hydroxyl group equivalent of P1) was added. was added dropwise over 30 minutes, and the mixture was allowed to react at 80°C for a further 3 hours. The resulting resin was dissolved in 210 parts of toluene and washed with 180 parts of aqueous methanol having a methanol concentration of 30% by weight. The solvent was then distilled off under reduced pressure to obtain 120 parts of vinyl resin (V1) which was semi-solid at room temperature. The resulting vinyl resin (V1) had a hydroxyl equivalent of 25,500 and a vinyl equivalent of 320. １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, X is (1a), and R ５ was a methyl group, and the Mw measured by GPC was 350, the Mn was 270, the content of n=0 was 72.1 area%, the content of n=1 was 20.4 area%, and the content of n=2 or more was 7.5 area%, with the average value of n being 0.42. The GPC chart of vinyl resin (V1) is shown in FIG. 3, and the IR chart is shown in FIG. 4.

[0115] Example 2 100 parts of hydroxy resin (P2), 44.0 parts of dimethylaminopyridine, and 150 parts of toluene were charged into an apparatus similar to that of Synthesis Example 1, and the mixture was heated to 60°C to dissolve. After cooling to 20°C, 83.2 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl group equivalent of P2) was added dropwise over 30 minutes, and the mixture was further reacted at 80°C for 3 hours. The resulting resin was dissolved in 190 parts of toluene and washed with 170 parts of aqueous methanol having a methanol concentration of 30% by weight. The solvent was then distilled off under reduced pressure to obtain 118 parts of vinyl resin (V2) that was semi-solid at room temperature. The resulting vinyl resin (V2) had a hydroxyl group equivalent of 27,800 and a vinyl equivalent of 350. A vinyl resin represented by formula (1), R １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, X is (1a), and R ５ is a methyl group, Mw was 300, Mn was 250, the content of n=0 isomer was 72.5 area%, the content of n=1 isomer was 21.3 area%, the content of n=2 or more isomers was 6.2 area%, and the average value of n was 0.40.

[0116] Example 3: 100 parts of hydroxy resin (P3), 37.3 parts of dimethylaminopyridine, and 150 parts of toluene were charged into an apparatus similar to that of Synthesis Example 1, and the mixture was heated to 60°C to dissolve. After cooling to 20°C, 70.6 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl group equivalent of P3) was added dropwise over 30 minutes, and the mixture was further reacted at 80°C for 3 hours. The resulting resin was dissolved in 160 parts of toluene and washed with 160 parts of aqueous methanol having a methanol concentration of 30% by weight. The solvent was then distilled off under reduced pressure to obtain 115 parts of vinyl resin (V3) that was semi-solid at room temperature. The resulting vinyl resin (V3) had a hydroxyl group equivalent of 32,700 and a vinyl equivalent of 395. A vinyl resin represented by formula (1), R １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, X is (1a), and R ５ is a methyl group, Mw was 290, Mn was 240, the content of n=0 isomer was 81.1 area%, the content of n=1 isomer was 15.3 area%, the content of n=2 or more isomers was 3.6 area%, and the average value of n was 0.27.

[0117] Example 4: In a similar apparatus to that of Synthesis Example 1, 100 parts of hydroxy resin (P4), 32.3 parts of dimethylaminopyridine, and 150 parts of toluene were charged, and the mixture was heated to 60°C and dissolved. After cooling to 20°C, 61.0 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl group equivalent of P4) was added dropwise over 30 minutes, and the mixture was further reacted at 80°C for 3 hours. The resulting resin was dissolved in 140 parts of toluene and washed with 150 parts of aqueous methanol having a methanol concentration of 30% by weight. The solvent was then distilled off under reduced pressure to obtain 112 parts of vinyl resin (V4) that was semi-solid at room temperature. The resulting vinyl resin (V4) had a hydroxyl group equivalent of 37,800 and a vinyl equivalent of 450. A vinyl resin represented by formula (1), R １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, X is (1a), and R ５is a methyl group, Mw was 650, Mn was 370, the content of n=0 isomer was 52.8 area%, the content of n=1 isomer was 16.9 area%, the content of n=2 or more isomers was 30.3 area%, and the average value of n was 0.88.

[0118] Example 5: 100 parts of hydroxy resin (P5), 29.8 parts of dimethylaminopyridine, and 150 parts of toluene were charged into an apparatus similar to that of Synthesis Example 1, and the mixture was heated to 60°C to dissolve. After cooling to 20°C, 56.4 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl group equivalent of P5) was added dropwise over 30 minutes, and the mixture was further reacted at 80°C for 3 hours. The resulting resin was dissolved in 130 parts of toluene and washed with 140 parts of aqueous methanol having a methanol concentration of 30% by weight. The solvent was then distilled off under reduced pressure to obtain 111 parts of vinyl resin (V5) that was semi-solid at room temperature. The resulting vinyl resin (V5) had a hydroxyl group equivalent of 41,000 and a vinyl equivalent of 480. A vinyl resin represented by formula (1), R １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, X is (1a), and R ５ is a methyl group, Mw was 560, Mn was 330, the content of n=0 isomer was 60.1 area%, the content of n=1 isomer was 18.8 area%, the content of n=2 or more isomers was 21.1 area%, and the average value of n was 0.71.

[0119] Example 6: 100 parts of hydroxy resin (P6), 25.2 parts of dimethylaminopyridine, and 150 parts of toluene were charged into an apparatus similar to that used in Synthesis Example 1, and the mixture was heated to 60°C to dissolve. After cooling to 20°C, 47.7 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl group equivalent of P5) were added dropwise over 30 minutes, and the mixture was further reacted at 80°C for 3 hours. The resulting resin was dissolved in 110 parts of toluene and washed with 130 parts of aqueous methanol containing 30% by weight of methanol. The solvent was then distilled off under reduced pressure to obtain 108 parts of vinyl resin (V6) that was semi-solid at room temperature. The resulting vinyl resin (V6) had a hydroxyl group equivalent of 48,500 and a vinyl equivalent of 530. A vinyl resin represented by formula (1), R １ is a methyl group, R ２ is a group (1c) or (1d), R３ and R ４ is a methyl group or a hydrogen atom, X is (1a), and R ５ is a methyl group, Mw was 530, Mn was 330, the content of n=0 isomer was 63.8 area%, the content of n=1 isomer was 19.5 area%, the content of n=2 or more isomers was 16.7 area%, and the average value of n was 0.63.

[0120] Comparative Example 1 In a similar apparatus to that of Synthesis Example 1, 100 parts of hydroxy resin (P7), 62.7 parts of dimethylaminopyridine, and 150 parts of toluene were charged and heated to 60°C to dissolve. After cooling to 20°C, 118.6 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl group equivalent of P7) were added dropwise over 30 minutes, and the reaction was continued at 80°C for 3 hours. The resulting resin was dissolved in 270 parts of toluene and washed with 210 parts of aqueous methanol having a methanol concentration of 30% by weight. The solvent was then distilled off under reduced pressure to obtain 128 parts of vinyl resin (VH1). The resulting vinyl resin (VH1) had a hydroxyl group equivalent of 19,500, a vinyl equivalent of 260, and a softening point of 88°C. A vinyl resin represented by formula (1), R １ is a methyl group, R ２ is a hydrogen atom, R ３ and R ４ is a hydrogen atom, X is (1a), and R ５ is a methyl group, Mw was 500, Mn was 450, the content of n=0 isomer was 3.0 area%, the content of n=1 isomer was 86.8 area%, the content of n=2 or more isomers was 10.2 area%, and the average value of n was 1.08.

[0121] Comparative Example 2 100 parts of hydroxy resin (P8), 52.9 parts of dimethylaminopyridine, and 150 parts of toluene were charged into an apparatus similar to that of Synthesis Example 1, and the mixture was heated to 60°C and dissolved. After cooling to 20°C, 100.0 parts of methacrylic anhydride (1.5 equivalents relative to the hydroxyl group equivalent of P8) was added dropwise over 30 minutes, and the mixture was further reacted at 80°C for 3 hours. The resulting resin was dissolved in 230 parts of toluene and washed with 190 parts of aqueous methanol with a methanol concentration of 30% by weight. The solvent was then distilled off under reduced pressure to obtain 123 parts of a vinyl resin (VH2) that was semi-solid at room temperature. The resulting vinyl resin (VH2) had a hydroxyl group equivalent of 23,100, a vinyl equivalent of 300, and a softening point of 98°C. A vinyl resin represented by formula (1), R １ is a methyl group, R ２ is a hydrogen atom, R ３ and R ４ is a methyl group or a hydrogen atom, X is (1a), and R ５ is a methyl group, Mw was 660, Mn was 480, the content of n=0 isomer was 16.5 area%, the content of n=1 isomer was 55.0 area%, the content of n=2 or more isomers was 28.5 area%, and the average value of n was 1.16.

[0122] Example 7 100 parts of hydroxy resin (P1), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged into an apparatus similar to that used in Synthesis Example 1, and the mixture was heated to 60°C to dissolve. 28.2 parts of 86% potassium hydroxide was added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, chloromethylstyrene (AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula below) was added. 67 parts (1.13 equivalents relative to the hydroxyl group equivalent of P1) was added dropwise over 1 hour, and the reaction was further carried out at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The obtained resin was dissolved in 260 parts of toluene and washed with 230 parts of water until the pH of the aqueous layer reached 7. Thereafter, the solvent was distilled off under reduced pressure to obtain 117 parts of vinyl resin (V7) having a viscosity of 21 Pa s at 25°C. The obtained vinyl resin (V7) had a hydroxyl group equivalent of 17,000, a vinyl equivalent of 370, and a total chlorine content of 850 ppm. A vinyl resin represented by formula (1), wherein R １ is a methyl group, R２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, X is (1b) and Ar is a benzene ring. GPC revealed that Mw was 380, Mn was 300, the content of n=0 isomer was 73.3 area%, the content of n=1 isomer was 19.5 area%, the content of n=2 or more isomers was 7.2 area%, and the average value of n was 0.42. The GPC chart of vinyl resin (V7) is shown in FIG. 5, and the IR chart is shown in FIG. 6.

[0123] Example 8: In a similar apparatus to that used in Synthesis Example 1, 100 parts of hydroxy resin (P2), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged and heated to 60°C for dissolution. 25.8 parts of 86% potassium hydroxide were added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, 62 parts of chloromethylstyrene (AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula shown above) (1.13 equivalents relative to the hydroxyl group equivalent of P2) were added dropwise over 1 hour, and the mixture was further reacted at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 240 parts of toluene and washed with 220 parts of water until the pH of the aqueous layer reached 7. The solvent was then distilled off under reduced pressure to obtain 114 parts of vinyl resin (V8) having a viscosity of 15 Pa s at 25°C. The obtained vinyl resin (V8) had a hydroxyl equivalent of 18,500, a vinyl equivalent of 395, and a total chlorine content of 820 ppm. １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, X is (1b) and Ar is a benzene ring. As measured by GPC, Mw was 320, Mn was 280, the content of n=0 isomer was 73.7 area%, the content of n=1 isomer was 20.5 area%, the content of n=2 or more isomers was 5.8 area%, and the average value of n was 0.40.

[0124] Example 9: In a similar apparatus to that used in Synthesis Example 1, 100 parts of hydroxy resin (P3), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged and heated to 60°C for dissolution. 21.9 parts of 86% potassium hydroxide were added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, 52 parts of chloromethylstyrene (manufactured by AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula above) (1.13 equivalents relative to the hydroxyl group equivalent of P3) were added dropwise over 1 hour, and the mixture was further reacted at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 210 parts of toluene and washed with 210 parts of water until the pH of the aqueous layer reached 7. The solvent was then distilled off under reduced pressure to obtain 109 parts of vinyl resin (V9) having a viscosity of 10 Pa s at 25°C. The obtained vinyl resin (V9) had a hydroxyl equivalent of 22,800, a vinyl equivalent of 445, and a total chlorine content of 750 ppm. １ is a methyl group, R ２ is a dicyclopentenyl group, R ３ and R ４ is a hydrogen atom, X is (1b) and Ar is a benzene ring. As measured by GPC, Mw was 310, Mn was 270, the content of n=0 isomer was 82.5 area%, the content of n=1 isomer was 14.2 area%, the content of n=2 or more isomers was 3.3 area%, and the average value of n was 0.27.

[0125] Example 10: Into an apparatus similar to that of Synthesis Example 1, 100 parts of hydroxy resin (P4), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged, and the mixture was heated to 60°C and dissolved. 18.9 parts of 86% potassium hydroxide was added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, 45 parts of chloromethylstyrene (manufactured by AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula above) (1.13 equivalents relative to the hydroxyl group equivalent of P4) was added dropwise over 1 hour, and the mixture was further reacted at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 180 parts of toluene and washed with 200 parts of water until the pH of the aqueous layer reached 7. The solvent was then distilled off under reduced pressure, yielding 105 parts of a vinyl resin (V10) that was semi-solid at room temperature. The obtained vinyl resin (V10) had a hydroxyl equivalent of 25,300, a vinyl equivalent of 495, and a total chlorine content of 820 ppm. １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, X is (1b) and Ar is a benzene ring. As measured by GPC, Mw was 690, Mn was 410, the content of n=0 isomer was 53.3 area%, the content of n=1 isomer was 16.3 area%, and the content of n=2 or more isomers was 30.4 area%, and the average value of n was 0.88.

[0126] Example 11: Into an apparatus similar to that of Synthesis Example 1, 100 parts of hydroxy resin (P5), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged, and the mixture was heated to 60°C and dissolved. 17.5 parts of 86% potassium hydroxide was added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, 42 parts of chloromethylstyrene (AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula above) (1.13 equivalents relative to the hydroxyl group equivalent of P5) was added dropwise over 1 hour, and the mixture was further reacted at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 170 parts of toluene and washed with 190 parts of water until the pH of the aqueous layer reached 7. The solvent was then distilled off under reduced pressure, yielding 103 parts of a vinyl resin (V11) that was semi-solid at room temperature. The obtained vinyl resin (V11) had a hydroxyl equivalent of 27,300, a vinyl equivalent of 530, and a total chlorine content of 810 ppm. １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, X is (1b) and Ar is a benzene ring. As measured by GPC, Mw was 600, Mn was 370, the content of n=0 isomer was 60.8 area%, the content of n=1 isomer was 18.0 area%, and the content of n=2 or more isomers was 21.2 area%, and the average value of n was 0.71.

[0127] Example 12: Into an apparatus similar to that of Synthesis Example 1, 100 parts of hydroxy resin (P6), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged, and the mixture was heated to 60°C and dissolved. 14.8 parts of 86% potassium hydroxide was added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, 35 parts of chloromethylstyrene (AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula above) (1.13 equivalents relative to the hydroxyl group equivalent of P6) was added dropwise over 1 hour, and the mixture was further reacted at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 150 parts of toluene and washed with 180 parts of water until the pH of the aqueous layer reached 7. The solvent was then distilled off under reduced pressure, yielding 99 parts of a vinyl resin (V12) that was semi-solid at room temperature. The obtained vinyl resin (V12) had a hydroxyl equivalent of 32,300, a vinyl equivalent of 600, and a total chlorine content of 780 ppm. １ is a methyl group, R ２ is a group (1c) or (1d), R ３ and R ４ is a methyl group or a hydrogen atom, X is (1b) and Ar is a benzene ring. As measured by GPC, Mw was 570, Mn was 360, the content of n=0 isomer was 64.3 area%, the content of n=1 isomer was 18.6 area%, and the content of n=2 or more isomers was 17.1 area%, and the average value of n was 0.63.

[0128] Comparative Example 3: In a similar apparatus to that used in Synthesis Example 1, 100 parts of hydroxy resin (P7), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged and heated to 60°C for dissolution. 36.8 parts of 86% potassium hydroxide were added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, 88 parts of chloromethylstyrene (manufactured by AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula above) (1.13 equivalents relative to the hydroxyl group equivalent of P7) were added dropwise over 1 hour, and the mixture was further reacted at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 330 parts of toluene and washed with 250 parts of water until the pH of the aqueous layer reached 7. The solvent was then distilled off under reduced pressure to obtain 128 parts of vinyl resin (VH3). The obtained vinyl resin (VH3) had a hydroxyl equivalent of 13,000, a vinyl equivalent of 310, and a total chlorine content of 1,200 ppm. １ is a methyl group, R ２ is a hydrogen atom, R ３ and R ４ is a hydrogen atom, X is (1b), and Ar is a benzene ring. As measured by GPC, Mw was 530, Mn was 500, the content of n=0 isomer was 3.8 area%, the content of n=1 isomer was 84.2 area%, and the content of n=2 or more isomers was 12.0 area%, and the average value of n was 1.08.

[0129] Comparative Example 4 Into an apparatus similar to that used in Synthesis Example 1, 100 parts of hydroxy resin (P8), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were charged and heated to 60°C for dissolution. 31.0 parts of 86% potassium hydroxide was added, and the mixture was further reacted at 60°C for 1 hour. After cooling to 20°C, 74 parts of chloromethylstyrene (AGC Seimi Chemical Co., Ltd., CMS-P, 3-position / 4-position = 50 / 50) (structural formula above) (1.13 equivalents relative to the hydroxyl group equivalent of P8) was added dropwise over 1 hour, and the mixture was further reacted at 60°C for 3 hours. The absence of chloromethylstyrene was confirmed by gas chromatography, and the solvent was recovered under reduced pressure. The resulting resin was dissolved in 280 parts of toluene and washed with 230 parts of water until the pH of the aqueous layer reached 7. The solvent was then distilled off under reduced pressure to obtain 121 parts of vinyl resin (VH4). The obtained vinyl resin (VH4) had a hydroxyl equivalent of 15,400, a vinyl equivalent of 350, and a total chlorine content of 1,050 ppm. １ is a methyl group, R ２ is a hydrogen atom, R ３ and R ４ is a methyl group or a hydrogen atom, X is (1b) and Ar is a benzene ring. As measured by GPC, Mw was 700, Mn was 530, the content of n=0 isomer was 17.1 area%, the content of n=1 isomer was 53.8 area%, and the content of n=2 or more isomers was 29.1 area%, and the average value of n was 1.16.

[0130] Examples 13-24 and Comparative Examples 5-12: The components were mixed in the blending ratios (parts) shown in Tables 1 to 3 and dissolved in toluene to obtain a uniform vinyl resin composition varnish with a non-volatile content of 50%. The obtained vinyl resin composition varnish was applied to a PET film, dried at 130°C for 5 minutes, and peeled off from the PET film to obtain a resin composition. The resin composition was sandwiched between mirror plates and cured under reduced pressure at 130°C for 30 minutes and at 220°C for 100 minutes while applying a pressure of 2 MPa to obtain a cured product. The measurement results of the relative dielectric constant and dielectric loss tangent of the obtained cured product are shown in Tables 1 to 3.

[0131]

[0132]

[0133]

[0134] The vinyl resins of the Examples had lower viscosity than the Comparative Examples, and furthermore exhibited excellent physical properties such as low dielectric constant and low dielectric loss tangent.

[0135] The vinyl resin of the present invention is useful as an electronic material for high-speed communication equipment, and as a material with low signal loss for electronic parts.

Claims

1. A vinyl resin represented by the following general formula (1): (where R １ R independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. ２ R independently represent a hydrogen atom or a dicyclopentenyl group which may have a hydrocarbon group having 1 to 8 carbon atoms, and at least one of them is a dicyclopentenyl group which may have a hydrocarbon group having 1 to 8 carbon atoms. ３ , R ４ R independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and a and b are each an integer of 0 to 2. X independently represent a hydrogen atom or a vinyl group-containing group represented by the above formula (1a) or (1b), and at least one X is the vinyl group-containing group. ５ is a hydrogen atom or an alkyl or alkenyl group having 1 to 8 carbon atoms. Ar represents an aromatic ring. n represents the number of repetitions, the average value of which is a number smaller than 1.

2. A method for producing the vinyl resin described in claim 1, comprising reacting a phenol represented by the following general formula (2) with dicyclopentadiene, which may have a hydrocarbon group having 1 to 8 carbon atoms, in the presence of a Lewis acid catalyst to obtain a hydroxy resin represented by the following general formula (3), and then reacting the resulting hydroxy resin with one or more acid anhydrides represented by the following general formula (4a) or acid halides represented by the following general formula (4b), or a halogenated methyl group-containing aromatic vinyl compound represented by the following general formula (5), wherein the Lewis acid catalyst is used in an amount of 0.1 to 8 parts by mass per 100 parts by mass of the cyclopentadiene, and the dicyclopentadiene is used in a molar ratio of 0.5 to 2 times the phenol. (where R １ , R ２ , R ３ , R ４ , R ５ , a, b, and n are each defined as in the general formula (1). ６ , R ７ indicates halogen.) 3. A vinyl resin composition comprising the vinyl resin of claim 1 and a radical polymerization initiator as essential components.

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

5. A prepreg comprising the vinyl resin composition or semi-cured product thereof according to claim 3 and a fibrous substrate.

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

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

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