Polyfunctional vinyl resin and method for producing same

Abstract

Provided is a resin material having a low relative dielectric constant and dielectric loss tangent while having high heat resistance and adhesiveness. A polyfunctional vinyl resin represented by general formula (1). # imgabs0 (In the formula, R1 represents a hydrocarbon group having 1-8 carbon atoms, and R2 represents a hydrogen atom or a group represented by formula (2) or formula (3). And X represents a hydrogen atom or a vinyl group-containing aromatic group represented by formula (1a).

Description

Technical Field

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

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

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

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

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

[0006] In addition, it is known that the phenolic hydroxyl group of the polyfunctional phenylene ether oligomer obtained by reacting a polyphenol having more than 3 and less than 9 phenolic hydroxyl groups in the molecule and a polyphenol having an alkyl or alkylene group at 2 or 6 positions of at least one phenolic hydroxyl group therein and a monophenol compound is vinylbenzylated (patent documentation 7). However, the vinylbenzyl ether resin obtained by adopting this technology has a high molding temperature due to high viscosity, and if exposed to high temperature under air atmosphere, the shortcoming that the dielectric loss tangent greatly deteriorates. In addition, the bonding force with the conductor layer does not meet the demand and needs to be improved.

[0007] Therefore, conventional vinyl benzyl ether compounds and resins do not form cured products that satisfy the heat resistance and low dielectric loss tangent required for use as electrical insulating materials, especially for use as electrical insulating materials for high frequencies, and are also insufficient in terms of adhesion properties to conductor layers, reliability, and processability.

[0008] Prior art literature

[0009] Patent Literature

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

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

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

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

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

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

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

[0017] The present invention aims to provide a vinyl resin and a resin composition which can form a cured product having a low relative dielectric constant, a low dielectric loss tangent, and a high glass transition temperature, and which has excellent adhesion to a conductor layer. The purpose of the present invention is to provide a resin composition, a cured product, or a material containing the same which can be used as a dielectric material, an insulating material, or a heat-resistant material in the fields of the electrical and electronic industries and the aerospace and aircraft industries.

[0018] The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by using a specific polyfunctional vinyl resin represented by the following general formula (1) and a resin composition containing the polyfunctional vinyl resin, thereby completing the present invention.

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

[0020] [Chemistry 1]

[0021]

[0022] -CH2-Ar-CH=CH2 (1a)

[0023]

[0024] in,

[0025] R 1 independently represent a hydrocarbon group having 1 to 8 carbon atoms,

[0026] R 2 They independently represent a hydrogen atom, a group represented by formula (2), or a group represented by formula (3), and at least one of them is formula (2) or formula (3).

[0027] R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms,

[0028] R 4 Each of them independently represents a hydrogen atom or a group represented by the formula (2).

[0029] A is the two R 2 The residue removed, R in the residue 2 are independently a hydrogen atom or a group represented by formula (2).

[0030] Me represents a methyl group.

[0031] X independently represents a hydrogen atom or a vinyl-containing aromatic group represented by the above formula (1a), at least one of which is a vinyl-containing aromatic group,

[0032] Ar represents an aromatic ring.

[0033] i is an integer from 0 to 2.

[0034] n and p1 each represent the number of repetitions, and the average value thereof is a number from 0 to 5.

[0035] Ar in the above formula (1a) is preferably an aromatic ring selected from a benzene ring, a naphthalene ring and a biphenyl ring, and the aromatic ring Ar is unsubstituted or has one or more substituents.

[0036] The above R 1 Methyl or phenyl is preferred, and i is preferably 1 or 2.

[0037] The present invention is a polyfunctional vinyl resin obtained by vinylating a polyhydroxy resin represented by the following general formula (4).

[0038] [Chemistry 2]

[0039]

[0040] in,

[0041] R 1 independently represent a hydrocarbon group having 1 to 8 carbon atoms,

[0042] R 21 Each of them independently represents a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), and at least one of them is formula (5) or formula (6).

[0043] R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms,

[0044] R 4 Each of them independently represents a hydrogen atom or a group represented by the formula (5).

[0045] A 1 To remove the two R from formula (4) 21 The residues, R 21 are independently a hydrogen atom or a group represented by formula (5).

[0046] Me represents a methyl group.

[0047] i is an integer from 0 to 2.

[0048] m and p2 each represent the number of repetitions, and the average value thereof is a number from 0 to 5.

[0049] The present invention is also a polyfunctional vinyl resin composition comprising the above-mentioned polyfunctional vinyl resin and a radical polymerization initiator as essential components.

[0050] The present invention is also directed to a cured product obtained by curing the resin composition, which is a circuit board material, a sealing material, a prepreg material, a resin sheet, or a laminate, characterized in that the resin composition is used.

[0051] The present invention is also a method for producing the polyfunctional vinyl resin, characterized in that the polyvalent hydroxy resin is reacted with a halomethyl group-containing aromatic vinyl compound represented by the following general formula (10).

[0052] [Chemistry 3]

[0053] R 5 -CH2-AR-CH=CH2 (10)

[0054] Where Ar represents an aromatic ring, R 5 Represents halogen.

[0055] The multifunctional vinyl resin and composition of the present invention, and further the cured product obtained by curing the composition, have low relative dielectric constant and dielectric loss tangent and high adhesion to the conductor layer, and can be used as electronic materials for high-speed communication equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 The GPC chart of the multifunctional vinyl resin obtained in Example 1 is shown.

[0057] Figure 2 The IR chart of the multifunctional vinyl resin obtained in Example 1 is shown.

[0058] Figure 3 The GPC chart of the multifunctional vinyl resin obtained in Example 2 is shown.

[0059] Figure 4 The GPC chart of the multifunctional vinyl resin obtained in Example 3 is shown.

[0060] Figure 5 The GPC chart of the multifunctional vinyl resin obtained in Comparative Example 1 is shown. DETAILED DESCRIPTION

[0061] The present invention is described in detail below.

[0062] The polyfunctional vinyl resin of the present invention is represented by the following general formula (1).

[0063] [Chemistry 4]

[0064]

[0065] In the general formula (1), R 1 It independently represents a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, or an allyl group. As the alkyl group, it can be linear, branched, or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, cyclohexyl, and methylcyclohexyl. As the aryl group, phenyl, tolyl, xylyl, and ethylphenyl can be listed. As the aralkyl group, benzyl, α-methylbenzyl, etc. can be listed. Among these substituents, from the viewpoint of ease of acquisition and reactivity when made into a cured product, phenyl and alkyl groups having 1 to 3 carbon atoms are preferred, and methyl is particularly preferred.

[0066] R 1 The substitution position may be any of the ortho, meta, or para position relative to the aryl ether group (-OX), and the ortho position is preferred.

[0067] R 2 represents a hydrogen atom, or a group represented by formula (2) or formula (3), at least one of which is of formula (2) or formula (3). 2 With R as a substituent 1 Different from these, it does not necessarily mean only a substituent but also means a hydrogen atom.

[0068] [Chemistry 5]

[0069]

[0070] The group represented by formula (2) is a group derived from an aromatic monovinyl compound represented by general formula (8a) described later in the aromatic vinyl compound used as a raw material when manufacturing the polyhydroxy resin (4) represented by general formula (4), and the group represented by formula (3) is a group derived from an aromatic divinyl compound represented by general formula (8b) described later in the aromatic vinyl compound.

[0071] X independently represents a hydrogen atom or a vinyl group-containing aromatic group represented by the following formula (1a), and at least one of the vinyl group-containing aromatic groups is a group derived from a halogenated methyl group-containing aromatic vinyl compound as a raw material.

[0072] [Chemistry 6]

[0073] -CH2-Ar-CH=CH2 (1a)

[0074] The aromatic ring Ar in formula (1a) is preferably an aromatic ring selected from a benzene ring, a naphthalene ring and a biphenyl ring, and is unsubstituted or may have one or more substituents. When having a substituent, the number of substituents is preferably 1 to 4, and the substituent is preferably an alkyl group or an aryl group having 1 to 10 carbon atoms, and more preferably an alkyl group or a phenyl group having 1 to 3 carbon atoms.

[0075] i is R 1 The number of substitutions is 0 to 2, preferably 1 or 2, and more preferably 2.

[0076] n is a repetition number and represents a number greater than or equal to 0, and its average value (number average) is 0 to 5, preferably 1.0 to 4.0, more preferably 1.1 to 3.0, and further preferably 1.2 to 2.5.

[0077] In formula (2), R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms include 1 The same hydrocarbon group. 3 Also with R 2 Similarly, with R as a substituent 1 Different from these, it does not necessarily mean only a substituent but also means a hydrogen atom.

[0078] When an aromatic monovinyl compound represented by the formula (8a) described later is used as a raw material of the polyhydroxy resin (4) represented by the general formula (4), R 3 In view of the ease of obtaining and the heat resistance of the cured product, a hydrogen atom, a methyl group, and an ethyl group are preferred, and a hydrogen atom and an ethyl group are particularly preferred. When an aromatic divinyl compound represented by the formula (8b) described later is used as a raw material, R 3 , may contain vinyl. In addition, R 3 The substitution position may be any of the ortho, meta, and para positions, with the meta and para positions being preferred.

[0079] Preferably, R 3 One of the radicals is an ethyl group and the rest are hydrogen atoms.

[0080] In formula (3), A is the two R 2 The residue removed, R in the residue 2 is a hydrogen atom or a group represented by formula (2). In other words, A is a divalent group having the same structure as that of general formula (1), but will not be a group represented by formula (3).

[0081] R 3 With R in formula (2) 3 Synonymous.

[0082] R 4 represents a hydrogen atom or a group represented by formula (2). 4 Also with R 2 , R 3 Similarly, with R as a substituent 1 Different from these, it does not necessarily mean only a substituent but also means a hydrogen atom.

[0083] p1 is a repetition number, which represents a number greater than or equal to 0, and its average value (number average) is 0 to 5, preferably 0.01 to 3, more preferably 0.1 to 2.0, further preferably 0.2 to 1.0, and particularly preferably 0.3 to 0.8.

[0084] The weight average molecular weight (Mw) of the polyfunctional vinyl resin (1) of the present invention is preferably 400 to 5000, more preferably 600 to 4500, and further preferably 800 to 4000. The number average molecular weight (Mn) is preferably 350 to 2000, more preferably 500 to 1500, and further preferably 700 to 1200.

[0085] As the content based on GPC, the molecular weight distribution of the polyhydroxy resin (4) as a raw material is substantially maintained as it is, and in the general formula (1), preferably, the n=0 body is in the range of 10 area % or less, the n=1 body is in the range of 30 to 90 area %, and the n=2 body or more is in the range of 0 to 70 area %. More preferably, the n=0 body is in the range of 1 to 10 area %, the n=1 body is in the range of 30 to 60 area %, and the n=2 body or more is in the range of 35 to 65 area %.

[0086] The phenolic hydroxyl equivalent (g / eq.) is preferably 5000 or more, more preferably 10000 or more, and further preferably 16000 or more. When it exceeds 10000, it exceeds the amount of hydroxyl groups that can be basically measured, indicating that the phenolic hydroxyl groups of the raw material polyhydroxy resin are almost completely vinylized.

[0087] The vinyl equivalent (g / eq.) is preferably 300 or more, more preferably 350 or more, and further preferably 400 or more. On the other hand, the upper limit of the vinyl equivalent is preferably 1000 or less, more preferably 700 or less, and further preferably 500 or less.

[0088] The polyvalent hydroxy resin which is a raw material of the polyfunctional vinyl resin (1) of the present invention is represented by the following general formula (4).

[0089] [Chemistry 7]

[0090]

[0091] In the general formula (4), R 1 and i have the same meanings as in the general formula (1). m has the same meanings as n in the general formula (1), and is also substantially the same in the case of the relationship between the raw material and the product. 21 R independently represents a hydrogen atom, or a group represented by the following formula (5) or (6), and at least one of them is of the formula (5) or (6). 21 R of general formula (1) 2 Likewise, it does not necessarily mean only a substituent but also means a hydrogen atom.

[0092] [Chemistry 8]

[0093]

[0094] In formula (5), R 3 The same meaning as in formula (2).

[0095] In formula (6), R 3 , R 4 and Me are synonymous with those in formula (3). p2 is synonymous with p1 in formula (3), and is also substantially the same in terms of the relationship between the raw material and the product. 1To remove the two R from formula (4) 21 The residues, R 21 is a hydrogen atom or a group represented by formula (5). 1 It is a divalent group having the same structure as that of the general formula (4), but does not become a group represented by the formula (6).

[0096] The weight average molecular weight (Mw) of the polyhydroxy resin represented by the general formula (4) is preferably 400 to 5000, more preferably 500 to 3000, and further preferably 600 to 2500. The number average molecular weight (Mn) is preferably 350 to 2000, more preferably 400 to 1500, and further preferably 450 to 1000.

[0097] The phenolic hydroxyl group equivalent (g / eq.) is preferably 190 to 500, more preferably 220 to 400, further preferably 250 to 350.

[0098] The softening point is preferably 50 to 180°C, more preferably 50 to 120°C.

[0099] The polyhydroxy resin (4) represented by the general formula (4) is obtained by subjecting a dicyclopentadiene type polyhydroxy resin (a) represented by the following general formula (7) to an aromatic electrophilic substitution reaction with an aromatic monovinyl compound represented by the general formula (8a) and / or an aromatic divinyl compound represented by the general formula (8b) in the presence of an acid catalyst. Aromatic monovinyl compounds and aromatic divinyl compounds are collectively referred to as aromatic vinyl compounds. The aromatic vinyl compounds (8a) and (8b) are different from the aromatic vinyl compounds (10) containing halogenated methyl groups and do not have halogenated methyl groups.

[0100] Among them, the polyhydroxy resin (a) represented by the general formula (7) has a structure in which phenols are linked by dicyclopentadiene.

[0101] [Chemistry 9]

[0102]

[0103] [Chemistry 10]

[0104]

[0105] In the general formula (7), R 1 i has the same meaning as in the general formula (1), s has the same meaning as n in the general formula (1), and the relationship between raw materials and products is also substantially the same.

[0106] In the general formulas (8a) and (8b), R 3 The same meaning as in formula (2). 3When it is a substituent, the substitution position may be any of the ortho, meta, and para positions relative to the vinyl group, and the meta and para positions are preferred.

[0107] In the aromatic divinyl compound represented by the general formula (8b), the substitution position of another vinyl group relative to the vinyl group may be any of ortho, meta and para, preferably meta and para, and may be a mixture thereof.

[0108] As for the aromatic vinyl compound used as a raw material, an aromatic monovinyl compound (8a) and an aromatic divinyl compound (8b) are necessary. The more the amount of the aromatic divinyl compound is added, the more the molecular weight of the polyhydroxy resin (4) increases. Therefore, the amount of the polyhydroxy resin (4) can be adjusted while considering the molecular weight of the polyhydroxy resin (4) so ​​as to achieve the target molecular weight. The aromatic monovinyl compound becomes a substituent represented by formula (2) through an addition reaction, further showing the effect of reducing the dielectric properties.

[0109] Examples of the aromatic monovinyl compound (8a) include vinyl aromatic compounds such as styrene, vinyl naphthalene, vinyl biphenyl, and α-methyl styrene, core alkyl-substituted vinyl aromatic compounds such as o-methyl styrene, m-methyl styrene, p-methyl styrene, o-, p-dimethyl styrene, o-ethyl vinyl benzene, m-ethyl vinyl benzene, p-ethyl vinyl benzene, ethyl vinyl biphenyl, and ethyl vinyl naphthalene, and cyclic vinyl aromatic compounds such as indene, acenaphthylene, benzothiophene, and coumarone. Preferred are styrene and ethyl vinyl benzene.

[0110] These can be used alone or in combination of two or more.

[0111] Examples of the aromatic divinyl compound (8b) include divinyl aromatic compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl. Divinylbenzene is preferred. These can be used alone or in combination of two or more.

[0112] The amount of the aromatic monovinyl compound (8a) and the aromatic divinyl compound (8b) to be added may be such that the amount of the aromatic monovinyl compound (8a) is 15 to 50% by mass and the amount of the aromatic divinyl compound (8b) is 50 to 85% by mass relative to the total amount of the aromatic vinyl compound. The amount of the aromatic monovinyl compound (8a) is preferably 15 to 50% by mass, more preferably 17 to 45% by mass. The amount of the aromatic divinyl compound (8b) is preferably 50 to 85% by mass, more preferably 55 to 83% by mass.

[0113] The phenolic hydroxyl equivalent (g / eq.) of the polyhydroxy resin (a) represented by the general formula (7) is preferably 160 to 220, more preferably 165 to 210, and further preferably 170 to 200.

[0114] The content based on GPC is preferably in the range of 10 area % or less for s=0 body, 50 to 90 area % for s=1 body, and 0 to 50 area % for s=2 or more body.

[0115] The polyhydroxy resin (a) represented by the general formula (7) is obtained by reacting dicyclopentadiene with a phenol represented by the following general formula (9) in the presence of a Lewis acid. This reaction includes not only isomers with different substitution positions but also structures in which a dicyclopentadiene structure is bonded to a hydroxyl group of a phenol.

[0116] [Chemistry 11]

[0117]

[0118] In the general formula (9), R 1 and i have the same meanings as in the general formula (1). 1 The substitution position may be any of the ortho, meta, and para positions, and the ortho position is preferred.

[0119] The structure of dicyclopentadiene is shown below.

[0120] [Chemistry 12]

[0121]

[0122] Examples of the phenols represented by the general formula (9) include phenol, cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, tert-butylphenol, hexylphenol, cyclohexylphenol, phenylphenol, cresylphenol, benzylphenol, α-methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(tert-butyl)phenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, xylenolphenol, dibenzylphenol, bis(α-methylbenzyl)phenol, methylethylphenol, methylpropylphenol, methylisopropylphenol, methylbutylphenol, methyltert-butylphenol, methylallylphenol, cresylphenylphenol, and the like. From the viewpoint 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.

[0123] The catalyst used in the above reaction is a Lewis acid, specifically, boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex, aluminum chloride, tin chloride, zinc chloride, ferric chloride, etc. Among them, boron trifluoride-ether complex is preferred from the ease of handling. The amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 15 parts by mass, relative to 100 parts by mass of dicyclopentadiene in the case of boron trifluoride-ether complex.

[0124] The amount of dicyclopentadiene used is 0.08 to 0.80 mol, preferably 0.09 to 0.60 mol, more preferably 0.10 to 0.50 mol, further preferably 0.10 to 0.40 mol, particularly preferably 0.10 to 0.20 mol, based on 1 mol of the phenols.

[0125] The reaction may be carried out by charging a phenol and a catalyst into a reactor, and dropping dicyclopentadiene therein over 0.1 to 10 hours, preferably 0.5 to 8 hours, more preferably 1 to 6 hours.

[0126] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and further preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and further preferably 4 to 8 hours.

[0127] After the reaction is completed, a base such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. Then, a solvent such as aromatic hydrocarbons such as toluene and xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone is added to dissolve the mixture, and after washing with water, the solvent is recovered under reduced pressure to obtain the target polyhydroxy resin represented by the general formula (7). It should be noted that it is preferred to react all of the dicyclopentadiene as much as possible and to recover the unreacted raw material phenol under reduced pressure.

[0128] During the reaction, solvents such as aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether may be used as necessary.

[0129] The reaction method for introducing the aromatic skeleton structure of the formula (5) or (6) into the benzene ring of the polyhydroxy resin (a) represented by the general formula (7) is a method in which an aromatic vinyl compound (8a) or (8b) is reacted with the polyhydroxy resin (a) at a predetermined ratio. The reaction ratio is 0.05 to 2.0 mol, more preferably 0.1 to 1.0 mol, and particularly preferably 0.15 to 0.95 mol, relative to 1 mol of the phenolic hydroxyl group of the polyhydroxy resin (a).

[0130] The reaction is an aromatic electrophilic substitution reaction, and the reaction target is the benzene ring. However, as can be seen from the structure, one OH group corresponds to one benzene ring. Generally, aromatic electrophilic substitution reactions (Friedel Crafts type reactions) proceed rapidly in the case of a phenol skeleton, so the phenolic hydroxyl group is used as the basis.

[0131] [Chemistry 13]

[0132]

[0133] [Chemistry 14]

[0134]

[0135] The catalyst used for the reaction is an acid catalyst, specifically, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, organic acids such as zinc chloride, aluminum chloride, ferric chloride, boron trifluoride, Lewis acids, or solid acids such as activated clay, silica-alumina, zeolite, etc. can be listed. Among them, p-toluenesulfonic acid is preferred from the ease of handling. As for the amount of the catalyst used, in the case of p-toluenesulfonic acid, it is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the polyhydroxy resin (a).

[0136] The reaction can be carried out as follows: after the polyhydroxy resin (a), the catalyst and the solvent are charged into a reactor and dissolved, the aromatic vinyl compound is added dropwise over 0.1 to 10 hours, preferably 0.5 to 8 hours, more preferably 0.5 to 5 hours.

[0137] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and further preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and further preferably 4 to 8 hours.

[0138] After the reaction is completed, a base such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. Then, a solvent such as aromatic hydrocarbons such as toluene and xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone is added to dissolve the catalyst, and after washing with water, the solvent is recovered under reduced pressure to obtain the target polyhydroxy resin.

[0139] As the solvent used in the reaction, there can be mentioned aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more.

[0140] As the polyhydroxy compound (resin) represented by the general formula (4), the polyhydroxy resin obtained by the above reaction is preferably used, but the present invention is not limited thereto.

[0141] As a method for obtaining a multifunctional vinyl resin of the general formula (1), an etherification method is excellent. The following method can be cited: a polyhydroxy resin (4) represented by the general formula (4) is reacted with an aromatic vinyl compound containing a halogenated methyl group represented by the general formula (10) in a solvent and in the presence of an alkaline compound. The etherification reaction referred to here refers to a bimolecular nucleophilic substitution reaction between the phenolic hydroxyl group of the polyhydroxy resin and the halogenated methyl group of the aromatic vinyl compound containing a halogenated methyl group. In this case, the following method can be used: the polyhydroxy resin (4) and a solvent are charged into a reactor, dissolved, and then a solution of the aromatic vinyl compound (10) containing a halogenated methyl group and an alkaline compound are added to react.

[0142] [Chemistry 15]

[0143]

[0144] [Chemistry 16]

[0145] R 5 -CH2-Ar-CH=CH2 (10)

[0146] In the general formula (10), Ar has the same meaning as in the formula (1a), and R 5 represents a halogen atom, and preferably a chlorine atom or a bromine atom.

[0147] The polyhydroxy resin and the halogenated methyl group-containing aromatic vinyl compound can be reacted in a ratio such that the halogenated methyl group of 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 1 equivalent of the phenolic hydroxyl group of the polyhydroxy resin.

[0148] As the aromatic vinyl compound containing a halomethyl group, a halomethylstyrene is preferred. Specific examples of the halomethylstyrene include chloromethylstyrene, bromomethylstyrene and isomers thereof, and halomethylstyrene having a substituent. Regarding the substitution position of the halomethyl compound, for example, in the case of halomethylstyrene, the 3rd position or the 4th position is preferred, and the content ratio of each is preferably in the range of 1 / 99 to 99 / 1. Commercially available products of chloromethylstyrene include CMS-P (manufactured by AGC SEIMI CHEMICAL Co., Ltd., 3rd position / 4th position = 50 / 50) and CMS-14 (manufactured by AGC SEIMI CHEMICAL Co., Ltd., 3rd position / 4th position = 5 / 95).

[0149] As the alkali compound used in the production of the multifunctional vinyl resin of the present invention, alkali metal hydroxides, carbonates, etc. are preferred, and specific examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, and sodium hydroxide and potassium hydroxide are preferred. Such alkali metal hydroxides may be used in the form of a solid or in the form of a solution.

[0150] The amount of the base 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, further preferably 1.0 to 1.3 mol, particularly preferably 1.0 to 1.1 mol, based on 1 mol of the phenolic hydroxyl groups of the polyhydroxy resin.

[0151] The solvent used in the manufacture of the multifunctional vinyl resin of the present invention is not particularly limited, and examples thereof 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 diethylene glycol dimethyl ether, and aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide. One or more of these solvents can be used. In addition, water can also be mixed with the above-mentioned solvents. In addition, in addition to the above-mentioned water and solvents, solvents such as toluene (other organic solvents) can be included. The amount of other organic solvents used is in the range of 0.5 to 400% by mass, preferably in the range of 100 to 300% by mass, and more preferably in the range of 150 to 250% by mass, relative to the amount of the above-mentioned solvents used.

[0152] 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 relative to the total mass of the polyhydroxy resin. In particular, aprotic polar solvents cannot be used for purification such as washing with water, and have a high boiling point and are difficult to remove, so it is not preferred that the amount used exceeds 500% by mass relative to the total mass of the polyhydroxy resin.

[0153] The reaction temperature for producing the polyfunctional vinyl resin of the present invention is usually 30 to 90° C., preferably 35 to 80° C. In order to obtain a polyfunctional vinyl resin with higher purity, it is preferred to raise the reaction temperature in two or more stages, for example, it is particularly preferred to raise the reaction temperature in the first stage to 15 to 50° C. and in the second stage to 45 to 70° C.

[0154] The reaction time for producing the multifunctional vinyl resin of the present invention is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. When the reaction time is 0.5 hours or more, the reaction proceeds sufficiently, and when the reaction time is 10 hours or less, the amount of by-products generated can be suppressed to a low level.

[0155] After the reaction is completed, the solvent is distilled off under heating and reduced pressure, or the mixture is dissolved in a ketone solvent having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.), toluene, etc. without distillation, and washed with water while heating to 40 to 90° C., more preferably 50 to 80° C., until the water layer reaches pH 5 to 8, to remove the by-product salt. During the water washing, an alcohol such as methanol, ethanol, or propanol may be added.

[0156] It should be noted that the production of the multifunctional vinyl resin of the present invention is usually carried out while blowing an inert gas such as nitrogen into the system (in the air or in the liquid). By blowing an inert gas into the system while reacting, the obtained product can be prevented from being colored.

[0157] The amount of the inert gas blown in per unit time also varies depending on the volume of the reactor used in the reaction, and is preferably adjusted so that the volume of the reactor can be replaced in 0.5 to 20 hours.

[0158] When there is a concern about self-polymerization of the halomethyl group-containing aromatic vinyl compound, a polymerization inhibitor such as quinones, nitro compounds, nitrophenols, nitroso compounds, nitrone compounds, phenols, oxygen, or the like may be used.

[0159] The reaction endpoint can be determined by tracking the remaining amount of the halomethyl group-containing aromatic vinyl compound using various chromatograms, and the reaction rate can be adjusted by adjusting the type and amount of the metal hydroxide, adjusting the addition rate, or using an appropriate catalyst.

[0160] The polyfunctional vinyl resin of the present invention can be cured alone, but is preferably used as a polyfunctional resin composition blended with various additives. For example, a radical polymerization initiator can be blended to promote curing.

[0161] As a free radical polymerization initiator (also referred to as a free radical polymerization catalyst), for example, a crosslinking reaction is induced by heating or the like as described later to cure the resin composition of the present invention, and a free radical polymerization initiator may be contained and used in order to lower the reaction temperature at this time or to promote the crosslinking reaction of unsaturated groups. The amount of the free radical polymerization initiator used for this purpose is preferably 0.01 to 12 parts by mass, more preferably 0.1 to 8 parts by mass, relative to 100 parts by mass of the multifunctional vinyl resin.

[0162] Representative examples of the radical polymerization initiator include peroxides such as benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, di-tert-butyl peroxide, tert-butylcumyl peroxide, α,α′-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, dicumyl peroxide, di-tert-butylperoxyisophthalate, tert-butylperoxybenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, bis(trimethylsilyl)peroxide, and trimethylsilyltriphenylsilyl peroxide, but are not limited thereto. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator (or polymerization catalyst). However, the catalyst and radical polymerization initiator used for curing the resin composition are not limited to these examples.

[0163] The polyfunctional vinyl resin composition of the present invention may contain other resin components as long as the effect of the polyfunctional vinyl resin represented by formula (1) as an essential component is not impaired, preferably in an amount of 50% by mass or less based on the total amount of the resin components.

[0164] As other resin components, vinyl resins and other thermoplastic vinyl resins can be added, for example, vinyl ester resins, polyvinyl benzyl resins, epoxy resins, oxetane resins, maleimide resins, acrylate resins, polyester resins, polyurethane resins, polycyanate resins, phenolic resins, benzoxazine resins, etc.

[0165] In addition, thermoplastic resins such as polystyrene resins, polyphenylene ether resins, polyetherimide resins, polyethersulfone resins, PPS resins, polycyclopentadiene resins, and polycycloolefin resins, thermoplastic elastomers such as styrene-ethylene-propylene copolymers, styrene-ethylene-butylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenated styrene-butadiene copolymers, and hydrogenated styrene-isoprene copolymers, and rubbers such as polybutadiene and polyisoprene can also be combined.

[0166] In the multifunctional vinyl resin composition of the present invention, in order to improve the flame retardancy of the cured product obtained, various known flame retardants can be used within the scope of not reducing reliability. As the flame retardant that can be used, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. can be listed. From the viewpoint of the environment, halogen-free flame retardants are preferably used, and phosphorus flame retardants are particularly preferred. These flame retardants can be used alone, and two or more flame retardants of the same system can also be used in combination. In addition, flame retardants of different systems can be used in combination.

[0167] In order to further improve the functionality, the multifunctional vinyl resin composition of the present invention may contain components other than the components listed above (sometimes referred to as "other components" in the present invention). Such other components include fillers, ultraviolet light inhibitors, antioxidants, coupling agents, plasticizers, fluxes, thixotropy-imparting agents, smoothing agents, colorants, pigments, dispersants, emulsifiers, low-elasticity agents, release agents, defoaming agents, ion trapping agents, and the like.

[0168] Examples of fillers include fused silica, crystalline silica, alumina, silicon nitride, boron nitride, aluminum nitride, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, boehmite, talc, mica, clay, calcium carbonate, magnesium carbonate, barium carbonate, zinc oxide, titanium oxide, magnesium oxide, magnesium silicate, calcium silicate, zirconium silicate, barium sulfate, and inorganic fillers such as carbon; fibrous fillers such as carbon fibers, glass fibers, alumina fibers, silica alumina fibers, silicon carbide fibers, polyester fibers, polyamide fibers, cellulose fibers, aramid fibers, and ceramic fibers; and fine-particle rubber.

[0169] As other components, there can be mentioned organic pigments such as quinacridone, azo, and phthalocyanine, inorganic pigments such as titanium oxide, metallic foil pigments, and rust-proof pigments, ultraviolet absorbers such as hindered amine, benzotriazole, and benzophenone, antioxidants such as hindered phenol, phosphorus, sulfur, and hydrazide, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, leveling agents, rheology control agents, pigment dispersants, shrinkage inhibitors, defoaming agents, etc. The amount of these other components is preferably in the range of 0.01 to 20% by mass relative to the total solid content in the resin composition.

[0170] The multifunctional vinyl resin composition of the present invention can be made into a resin varnish by dissolving in a solvent. As a solvent, methyl ethyl ketone, acetone, toluene, xylene, tetrahydrofuran, dioxolane, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, etc. can be listed, and its selection and appropriate usage amount can be appropriately selected according to the purpose. For example, in the use of printed wiring boards, preferably methyl ethyl ketone, acetone, toluene, xylene, 1-methoxy-2-propanol and other solvents with a boiling point of less than 160°C are used, and it is preferably used in a ratio of 20 to 80% by mass of non-volatile components. On the other hand, in the application of adhesive film for increasing the layer, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, acetate cellosolve, propylene glycol monomethyl ether acetate, carbitol acetate, ester compounds such as γ-butyrolactone, cellosolve, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and in addition, it is preferably used in a ratio of 20 to 80% by mass of non-volatile components. It should be noted that for the laminated board of the present invention, the resin varnish is cured to obtain it. Specifically, printed wiring substrates, printed circuit boards, flexible printed wiring boards, increasing layer wiring boards, etc. can be listed.

[0171] The cured product obtained by curing the multifunctional vinyl resin composition of the present invention can be used as a molded product, a laminated product, a casting, an adhesive, a coating, or a film. For example, the cured product of the semiconductor sealing material is a casting or a molded product. As a method for obtaining the cured product for this purpose, the compound can be molded using a casting or transfer molding machine, an injection molding machine, etc., and then heated at 80 to 230° C. for 0.5 to 10 hours to obtain a cured product. In addition, the cured product of the resin varnish is a laminated product. As a method for obtaining the cured product, the resin varnish can be impregnated with the above-mentioned fibrous filler, a substrate such as paper, heated and dried to obtain a prepreg material, which is laminated alone or laminated with a metal foil such as copper foil, and hot-pressed to obtain. In addition, the uncured sheet or partially cured sheet of the multifunctional vinyl resin composition of the present invention can be suitable for use as a build-up film, a bonding sheet, a cover sheet, a bump sheet for a flip-chip bonding machine, an insulating layer for a substrate, and an adhesive layer.

[0172] In addition, by mixing an inorganic high dielectric powder such as barium titanate or an inorganic magnetic material such as ferrite, the composite can be used as an electronic component material, particularly a high-frequency electronic component material.

[0173] Next, the prepreg material of the present invention and its cured product are described. In order to improve the mechanical strength and increase the dimensional stability, a base material is added to the prepreg material of the present invention.

[0174] As such a substrate, various glass cloths such as untwisted gauze, cloth, chopped strand mat, and surface mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloths, woven or non-woven fabrics obtained from liquid crystal fibers such as wholly aromatic polyamide fibers, wholly aromatic polyester fibers, and polybenzoxazole fibers, woven or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, and acrylonitrile fibers, natural fiber cloths such as cotton cloth, linen, and felt, carbon fiber cloth, natural cellulose cloths such as kraft paper, cotton paper, and paper-glass mixed fiber paper, and the like, and paper and the like are used individually or in combination of two or more thereof.

[0175] The proportion of the substrate in the prepreg material can be 5 to 90% by mass, preferably 10 to 80% by mass, and more preferably 20 to 70% by mass. If the substrate is less than 5% by mass, the dimensional stability and strength of the cured product tend to decrease. In addition, if the substrate is more than 90% by mass, the dielectric properties of the cured product tend to decrease.

[0176] In the prepreg material of the present invention, a coupling agent can be used as needed to improve the adhesion at the interface between the resin and the substrate. As the coupling agent, a general coupling agent such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zirconium aluminate coupling agent, etc. can be used.

[0177] As a method for manufacturing the prepreg material of the present invention, for example, the following method can be cited: the multifunctional vinyl resin composition of the present invention and other components as needed are uniformly dissolved or dispersed in the above-mentioned aromatic solvent, ketone solvent, etc., or a mixed solvent thereof, and then impregnated into a substrate, and then dried. The impregnation is performed by dipping (impregnation), coating, etc. As for the impregnation, it can be repeated multiple times as needed. In addition, at this time, it is also possible to use multiple solutions with different compositions and concentrations for repeated impregnation, and finally adjust to the desired resin composition and resin amount.

[0178] By curing the prepreg of the present invention by methods such as heating, a cured product is obtained. There is no particular limitation on its manufacturing method. For example, multiple prepregs can be overlapped, and each layer is bonded under heating and pressure while being thermally cured to obtain a cured product (laminated plate) of the desired thickness. In addition, it is also possible to combine the cured product once bonded and cured with the prepreg to obtain a multilayer laminate of a new layer structure. Stacking molding and curing are usually carried out simultaneously by hot pressing, and both can also be carried out separately. That is, by using heat treatment or another method to process the uncured or semi-cured prepreg obtained by pre-stack molding, it can be cured.

[0179] The molding and curing can be performed at a temperature of 80 to 300°C and a pressure of 0.1 to 1000 kgf / cm 2, time: 1 minute to 10 hours, more preferably, at a temperature of 150 to 250°C and a pressure of 1 to 500 kgf / cm 2 , Time: range from 1 minute to 5 hours.

[0180] The laminate of the present invention is a laminate composed of a layer of the prepreg material of the present invention and a layer of a metal foil. Examples of the metal foil used herein include copper foil and aluminum foil. The thickness thereof is not particularly limited, but is in the range of 3 to 200 μm, more preferably in the range of 3 to 105 μm.

[0181] As a method for manufacturing the laminate of the present invention, for example, the following method can be cited: the prepreg material obtained from the multifunctional vinyl resin composition of the present invention and the substrate described above and the metal foil are stacked in a layer structure consistent with the purpose, and the layers are bonded together under heating and pressure and thermally cured. In the laminate of the multifunctional vinyl resin composition of the present invention, the cured product and the metal foil are stacked in an arbitrary layer structure. The metal foil can be used as a surface layer or as an intermediate layer. In addition to the above, it is also possible to repeat stacking and curing multiple times to make it multilayered.

[0182] In the bonding with the metal foil, an adhesive can also be used. As the adhesive, epoxy, acrylic, phenolic, cyanoacrylate, etc. can be listed, but it is not particularly limited to these. The above-mentioned stacking molding and curing can be carried out under the same conditions as the production of the cured product of the prepreg material of the present invention.

[0183] The polyfunctional vinyl resin composition of the present invention can also be formed into a film. The thickness thereof is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

[0184] The method for producing the film of the present invention is not particularly limited, and examples thereof include a method in which the multifunctional vinyl resin composition and other components used as required are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof, and then applied to a resin film such as a PET film and dried. The coating may be repeated multiple times as required, and in this case, multiple solutions with different compositions and concentrations may be repeatedly coated to ultimately adjust to the desired resin composition and resin amount.

[0185] In addition, when the resin sheet of the present invention is used as a bonding sheet, for example, two substrates can be bonded with a resin sheet. Each of the two substrates is, for example, a laminate or a printed wiring board. Specifically, for example, by heating after the multifunctional vinyl resin composition is formed into a sheet by a coating method on a supporting film, a resin sheet is made by drying or semi-curing it. The resin sheet is overlapped on the substrate (the first substrate), the supporting film is peeled off from the resin sheet, and another substrate (the second substrate) is overlapped. That is, the first substrate, the resin sheet (the multifunctional vinyl resin composition) and the second substrate are stacked in sequence. Then, by heat curing, the first substrate and the second substrate are bonded via the cured product of the multifunctional vinyl resin composition.

[0186] In addition, the multifunctional vinyl resin composition of the present invention and the metal foil can obtain a metal foil with resin. Examples of the metal foil used here include copper foil and aluminum foil. The thickness thereof is not particularly limited, but is in the range of 3 to 200 μm, more preferably in the range of 5 to 105 μm.

[0187] There is no particular limitation on the method for producing the metal foil with resin, and examples thereof include a method in which the multifunctional vinyl resin composition and other components used as required are uniformly dissolved or dispersed in an aromatic solvent, a ketone solvent, or a mixed solvent thereof, applied to the metal foil, and then dried. The application may be repeated multiple times as required, and in this case, multiple solutions with different compositions and concentrations may be repeatedly applied to finally adjust the desired resin composition and resin amount.

[0188] The substrate for electronic materials is formed using the laminate of the present invention. The substrate for electronic materials can be suitable for use as a mobile phone, PHS, notebook personal computer, PDA (portable information terminal), portable video phone, personal computer, supercomputer, server, router, liquid crystal projector, engineering workstation (EWS), pager, word processor, TV, video recorder of viewfinder type or monitor direct view type, electronic notepad, electronic desktop computer, car navigation device, POS terminal, various electrical and electronic equipment such as the device including touch panel, which require reliability in an environment requiring heat resistance and water resistance, and transmission reliability of high-frequency signals. In particular, due to the heat resistance stability of the excellent dielectric properties of the cured product of the present invention and the dimensional stability and formability corresponding to the circuit formation of the fine pattern, it can be suitable for use as a circuit substrate for the above-mentioned electrical and electronic equipment. Specifically, single-sided, double-sided, multi-layer printed substrates, flexible substrates, and build-up substrates can be listed. A multi-layer circuit substrate using a metal plating layer as the above-mentioned conductor layer is also included as a preferred example.

[0189] Example

[0190] The present invention is specifically described by way of examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" represent parts by mass, "%" represents mass %, and "ppm" represents mass ppm. In addition, the following methods are used for determination.

[0191] The test conditions of the polyhydroxy resin, the multifunctional vinyl resin and the cured product are shown.

[0192] (1) Hydroxyl equivalent:

[0193] The measurement is carried out in accordance with JIS K0070, and the unit is expressed as "g / eq." It should be noted that, unless otherwise specified, the hydroxyl equivalent of the polyhydroxy resin means a phenolic hydroxyl equivalent.

[0194] (2) Softening point:

[0195] The softening point was measured by the ring and ball method according to JIS K7234. Specifically, an automatic softening point device (manufactured by Meitech Co., Ltd., ASP-MG4) was used.

[0196] (3) Vinyl equivalent:

[0197] The iodine value is determined according to JIS K0070. Specifically, the sample is reacted with Wijs solution (iodine monochloride solution) and placed in a dark place. Then, the excess iodine chloride is reduced to iodine, and the iodine component is titrated with sodium thiosulfate to calculate the iodine value. The iodine value is converted into vinyl equivalent.

[0198] (4) Total chlorine:

[0199] The determination was carried out in accordance with JIS K7243-3. Specifically, 1.0 g of the sample was dissolved in 25 mL of butyl carbitol, 25 mL of 1N-KOH propylene glycol solution was added, and the mixture was heated under reflux for 10 minutes, cooled to room temperature, and 100 mL of 80% acetone water was added. The mixture was then potentiometrically titrated with 0.002N-AgNO3 aqueous solution to determine the concentration.

[0200] (5) Relative dielectric constant and dielectric loss tangent:

[0201] Measured according to IPC-TM-650 2.5.5.9. Specifically, the relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were obtained and evaluated by a volumetric method using a material analyzer (manufactured by AGILENT Technologies).

[0202] (6) Copper foil peel strength:

[0203] Measured according to JIS C6481 standard.

[0204] (7) Glass transition temperature (Tg):

[0205] The viscosity was measured according to JIS C6481. Specifically, it was expressed by the tan δ peak top when measured using a dynamic viscoelasticity measuring apparatus (manufactured by Hitachi High-Technologies Corporation, EXSTAR DMS6100) under the condition of a temperature increase of 5°C / min.

[0206] (8) GPC (gel permeation chromatography) determination:

[0207] A device having a column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL) in series with a main body (manufactured by Tosoh Corporation, HLC-8220GPC) was used, and the column temperature was set to 40 ° C. In addition, tetrahydrofuran (THF) was used as an eluent, and the flow rate was set to 1 mL / min, and a differential refractive index detector was used as the detector. The sample was measured using 50 μL of a substance obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering with a microfilter. Mw and Mn were calculated based on the calibration line conversion obtained by standard polystyrene (manufactured by Tosoh Corporation, PStQuick Kit-H). It should be noted that data processing uses GPC-8020 Model II Version 6.00 manufactured by Tosoh Corporation.

[0208] (9)IR:

[0209] A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, SpectrumOne FT-IR Spectrometer 1760X) was used. A sample dissolved in toluene was applied to the ATR using diamond ATR, and after drying, the wave number of 650 to 4000 cm was measured. -1 The absorbance.

[0210] The abbreviations used in Examples and Comparative Examples are as follows.

[0211] [Polyhydroxy resin]

[0212] PH1: polyhydroxy resin obtained in Synthesis Example 1

[0213] P1: polyhydroxy resin obtained in Synthesis Example 2

[0214] P2: polyhydroxy resin obtained in Synthesis Example 3

[0215] P3: Biphenyl aralkyl type polyhydroxy resin (produced by Meiwa Chemicals Co., Ltd., MEH-7851, phenolic hydroxyl equivalent 223)

[0216] P4: phenol novolac resin (manufactured by Aica Industries, Ltd., BRG-555, phenolic hydroxyl equivalent 105)

[0217] [Multifunctional vinyl resin]

[0218] V1: Multifunctional vinyl resin obtained in Example 1

[0219] V2: Multifunctional vinyl resin obtained in Example 2

[0220] V3: Multifunctional vinyl resin obtained in Example 3

[0221] VH1: Multifunctional vinyl resin obtained in Comparative Example 1

[0222] VH2: Multifunctional vinyl resin obtained in Comparative Example 2

[0223] VH3: Multifunctional vinyl resin obtained in Comparative Example 3

[0224] VH4: Multifunctional vinyl resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., OPE-2ST, Mn1187, vinyl equivalent 590)

[0225] PO: Organic peroxide (manufactured by NOF Corporation, Perbutyl P)

[0226] AO: Antioxidant (ADK STAB AO-60 manufactured by ADEKA Corporation)

[0227] Synthesis example 1

[0228] 2,6-dimethylphenol (structural formula shown below) was placed in a reaction apparatus including a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel and a condenser.

[0229] [Chemistry 17]

[0230]

[0231] 500 parts, 7.3 parts of 47% BF3 ether complex, heated to 100°C while stirring. While maintaining this temperature, dicyclopentadiene (the following structural formula) was added dropwise over 1 hour.

[0232] [Chemistry 18]

[0233]

[0234] 67.6 parts (0.12 times the mole of 2,6-xylenol). Furthermore, react at a temperature of 115-125°C for 4 hours, and add 11 parts of calcium hydroxide. Furthermore, add 19 parts of a 10% aqueous solution of oxalic acid. Then, heat to 160°C, dehydrate, and heat to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. Add 1320 parts of methyl isobutyl ketone (MIBK), dissolve the product, add 400 parts of warm water at 80°C, wash with water, and separate and remove the water tank at the lower layer. Then, heat to 160°C under a reduced pressure of 5 mmHg, evaporate and remove MIBK, and obtain 164 parts of a reddish-brown polyhydroxy resin (PH1).

[0235] The obtained polyhydroxy resin (PH1) had a hydroxyl equivalent of 195 and a softening point of 73°C. The polyhydroxy resin represented by formula (7) is 1 It is a methyl group, i is 2, Mw obtained by GPC is 470, Mn is 440, s=0 isomer content is 2.8 area %, s=1 isomer content is 86.2 area %, and s=2 or more isomer content is 11.0 area %.

[0236] Synthesis example 2

[0237] Into the same reaction apparatus as in Synthesis Example 1, 400 parts of the polyhydroxy resin (PH1) obtained in Synthesis Example 1, 4.0 parts of p-toluenesulfonic acid monohydrate, and 100 parts of MIBK were placed, and heated to 120° C. while stirring. While maintaining this temperature, divinylbenzene (manufactured by Aldrich, 80% divinylbenzene, 20% ethylvinylbenzene) (the following structural formula) was added dropwise over 1 hour.

[0238] [Chemistry 19]

[0239]

[0240] 240 parts (0.90 times the mole relative to PH1). Further react at a temperature of 120-130°C for 4 hours. Add 1400 parts of MIBK, dissolve the product, neutralize with 5.3 parts of sodium bicarbonate, add 450 parts of warm water at 80°C, wash with water, and separate and remove the water tank at the lower layer. Then, heat to 180°C under a reduced pressure of 5 mmHg, evaporate and remove MIBK, and obtain 608 parts of reddish brown polyhydroxy resin (P1).

[0241] The obtained polyhydroxy resin (P1) had a hydroxyl equivalent of 302 and a softening point of 82°C. The polyhydroxy resin represented by formula (4) is 1is methyl, i is 2, Mw obtained by GPC is 2000, Mn is 670, m=0 isomer content is 3.6 area%, m=1 isomer content is 41.1 area%, and m=2 or more isomer content is 55.3 area%. In formula (4), R 21 For example, the group (R 3 One of which is ethyl) and the group represented by the formula (6) derived from divinylbenzene (R 3 All of them are hydrogen atoms) are mixed in a ratio substantially the same as the mixing ratio (20 / 80) of the raw material divinylbenzene.

[0242] Synthesis example 3

[0243] Into the same reaction apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (PH1) obtained in Synthesis Example 1, 1.0 part of p-toluenesulfonic acid·monohydrate, and 25 parts of MIBK were placed, and heated to 120°C while stirring. While maintaining this temperature, 45 parts of divinylbenzene (manufactured by Aldrich, 55% divinylbenzene, 45% ethylvinylbenzene) (0.67 times the mole relative to PH1) were added dropwise over 1 hour. The reaction was then carried out at a temperature of 120-130°C for 4 hours. 310 parts of MIBK were added, the product was dissolved, neutralized with 1.3 parts of sodium bicarbonate, 100 parts of warm water at 80°C was added, washed with water, and the water tank at the lower layer was separated and removed. Then, the mixture was heated to 180°C under a reduced pressure of 5 mmHg, and MIBK was evaporated and removed to obtain 139 parts of a reddish brown polyhydroxy resin (P2).

[0244] The obtained polyhydroxy resin (P2) had a hydroxyl equivalent of 276 and a softening point of 71°C. The polyhydroxy resin represented by formula (4) is 1 is methyl, i is 2, Mw obtained by GPC is 740, Mn is 540, m=0 isomer content is 4.8 area%, m=1 isomer content is 51.8 area%, and m=2 or more isomer content is 43.4 area%. In formula (4), R 21 For example, the group (R 3 One of which is ethyl) and the group represented by the formula (6) derived from divinylbenzene (R 3 All of them are hydrogen atoms) are mixed in a ratio substantially the same as the mixing ratio (45 / 55) of the raw material divinylbenzene.

[0245] Example 1

[0246] Into the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (P1) obtained in Synthesis Example 2, 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were placed, and the temperature was raised to 60°C to dissolve them. 23.7 parts of 86% potassium hydroxide were added, and the mixture was reacted at 60°C for 1 hour. After cooling to 20°C, chloromethylstyrene (manufactured by AGC SEIMI CHEMICAL, CMS-P, 3-position / 4-position = 50 / 50; structural formula shown below) was added dropwise over 1 hour.

[0247] [Chemistry 20]

[0248]

[0249] 57 parts (1.13 equivalents relative to the hydroxyl equivalent of P1) was added and 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 obtained resin was dissolved in 320 parts of toluene and washed with 240 parts of water until the pH of the water layer reached 7. Then, the solvent was distilled off under reduced pressure to obtain 185 parts of a toluene solution with a non-volatile content of 60%, namely a multifunctional vinyl resin (V1).

[0250] The obtained multifunctional vinyl resin (V1) had a hydroxyl equivalent of 17,200, a vinyl equivalent of 430, and a total chlorine content of 420 ppm. 1 is methyl, i is 2, Mw obtained by GPC is 3020, Mn is 1050, n=0 isomeric content is 1.8 area%, n=1 isomeric content is 36.6 area%, and n=2 or more isomeric content is 61.5 area%. In formula (1), R 2 For example, the group (R 3 One of which is ethyl) and the group represented by the formula (3) derived from divinylbenzene (R 3 All of them are hydrogen atoms) are mixed at a ratio substantially the same as the mixing ratio (20 / 80) of the raw material divinylbenzene. In the formula (1a) representing X, Ar is a benzene ring, and with respect to the position of the vinyl group, the meta-form (3-position) and the para-form (4-position) are mixed at a ratio substantially the same as the mixing ratio (50 / 50) of the raw material chloromethylstyrene.

[0251] The GPC of the multifunctional vinyl resin (V1) is shown in Figure 1 , and IR is shown in Figure 2 .

[0252] Example 2

[0253] Into the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (P2) obtained in Synthesis Example 3, 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were placed, and the temperature was raised to 60°C to dissolve them. 26.0 parts of 86% potassium hydroxide were added, and the mixture was reacted at 60°C for 1 hour. After cooling to 20°C, 62 parts of chloromethylstyrene (CMS-P, 3-position / 4-position = 50 / 50, manufactured by AGC SEIMI CHEMICAL) (1.13 equivalents of hydroxyl group equivalent relative to P2) were added dropwise over 1 hour, and the mixture was 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 obtained resin was dissolved in 320 parts of toluene and washed with 240 parts of water until the pH of the water layer reached 7. Then, the solvent was distilled off under reduced pressure to obtain 190 parts of a toluene solution having a non-volatile component of 60%, i.e., a polyfunctional vinyl resin (V2).

[0254] The obtained multifunctional vinyl resin (V2) had a hydroxyl equivalent of 59400, a vinyl equivalent of 402, and a total chlorine content of 760 ppm. 1 is methyl, i is 2, Mw obtained by GPC is 910, Mn is 750, n=0 isomer content is 3.9 area%, n=1 isomer content is 56.6 area%, and n=2 or more isomer content is 39.5 area%. In formula (1), R 2 For example, the group (R 3 One of which is ethyl) and the group represented by the formula (3) derived from divinylbenzene (R 3 All of them are hydrogen atoms) are mixed at a ratio substantially the same as the mixing ratio (45 / 55) of the raw material divinylbenzene. In the formula (1a) representing X, Ar is a benzene ring, and with respect to the position of the vinyl group, the meta-form (3-position) and the para-form (4-position) are mixed at a ratio substantially the same as the mixing ratio (50 / 50) of the raw material chloromethylstyrene.

[0255] The GPC of the multifunctional vinyl resin (V2) is shown in Figure 2 .

[0256] Example 3

[0257] Into the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (P1) obtained in Synthesis Example 2, 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were placed, and the mixture was heated to 60°C to dissolve. 23.7 parts of 86% potassium hydroxide were added, and the mixture was reacted at 60°C for 1 hour. After cooling to 20°C, chloromethylstyrene (manufactured by AGC SEIMI CHEMICAL, CMS-14, 3-position / 4-position = 5 / 95; structural formula shown below) was added dropwise over 1 hour.

[0258] [Chemistry 21]

[0259]

[0260] 57 parts (1.13 equivalents relative to the hydroxyl equivalent of P1), and then 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 obtained resin was dissolved in 320 parts of toluene and washed with 240 parts of water until the pH of the water layer reached 7. Then, the solvent was distilled off under reduced pressure to obtain 186 parts of a toluene solution with a non-volatile content of 60%, namely a multifunctional vinyl resin (V3).

[0261] The obtained multifunctional vinyl resin (V3) had a hydroxyl equivalent of 23,500, a vinyl equivalent of 429, and a total chlorine content of 550 ppm. 1 is methyl, i is 2, Mw obtained by GPC is 2980, Mn is 1030, n=0 isomeric content is 1.9 area%, n=1 isomeric content is 35.6 area%, and n=2 or more isomeric content is 62.5 area%. In formula (1), R 2 For example, the group (R 3 One of which is ethyl) and the group represented by the formula (3) derived from divinylbenzene (R 3 All of them are hydrogen atoms) are mixed at a ratio substantially the same as the mixing ratio (20 / 80) of the raw material divinylbenzene. In the formula (1a) representing X, Ar is a benzene ring, and with respect to the position of the vinyl group, the meta-form (3-position) and the para-form (4-position) are mixed at a ratio substantially the same as the mixing ratio (5 / 95) of the raw material chloromethylstyrene.

[0262] The GPC of the multifunctional vinyl resin (V3) is shown in Figure 4 .

[0263] Comparative Example 1

[0264] Into the same apparatus as in Synthesis Example 1, 100 parts of the polyhydroxy resin (PH1) obtained in Synthesis Example 1, 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were placed, and the temperature was raised to 60°C to dissolve them. 36.8 parts of 86% potassium hydroxide were added, and the mixture was reacted at 60°C for 1 hour. After cooling to 20°C, 88 parts of chloromethylstyrene (1.13 equivalents of hydroxyl equivalent relative to PH1) were added dropwise over 1 hour, and the mixture was 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 obtained resin was dissolved in 370 parts of toluene and washed with 270 parts of water until the pH of the water layer reached 7. Then, the solvent was distilled off under reduced pressure to obtain a toluene solution with a non-volatile component of 60%, i.e., 213 parts of the polyfunctional vinyl resin (VH1).

[0265] The obtained multifunctional vinyl resin (VH1) had a hydroxyl equivalent of 15500, a vinyl equivalent of 315, and a total chlorine content of 1580 ppm. The Mw obtained by GPC was 700, the Mn was 660, the n=0 body content was 1.5 area%, the n=1 body content was 87.1 area%, and the content of n=2 bodies or more was 11.4 area%.

[0266] The GPC of the multifunctional vinyl resin (VH1) is shown in Figure 5 .

[0267] Comparative Example 2

[0268] In the same apparatus as in Synthesis Example 1, 100 parts of a polyhydroxy resin (P3), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were placed, and the temperature was raised to 60°C to dissolve them. 32.2 parts of 86% potassium hydroxide were added, and the mixture was reacted at 60°C for 1 hour. After cooling to 20°C, 77 parts of chloromethylstyrene (1.13 equivalents relative to the hydroxyl equivalent of P3) were added dropwise over 1 hour, and the mixture was 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 obtained resin was dissolved in 320 parts of toluene and washed with 250 parts of water until the pH of the water layer reached 7. Then, the solvent was distilled off under reduced pressure to obtain a toluene solution with a non-volatile component of 60%, i.e., 203 parts of a polyfunctional vinyl resin (VH2).

[0269] The obtained multifunctional vinyl resin (VH2) had a hydroxyl equivalent of 15,200, a vinyl equivalent of 331, and a total chlorine content of 1,680 ppm.

[0270] Comparative Example 3

[0271] In the same apparatus as in Synthesis Example 1, 100 parts of a polyhydroxy resin (P4), 200 parts of toluene, 100 parts of dimethyl sulfoxide, and 25 parts of methanol were placed, and the temperature was raised to 60°C to dissolve them. 68.4 parts of 86% potassium hydroxide were added, and the mixture was reacted at 60°C for 1 hour. After cooling to 20°C, 164 parts of chloromethylstyrene (1.13 equivalents relative to the hydroxyl equivalent of P4) were added dropwise over 1 hour, and the mixture was 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 obtained resin was dissolved in 490 parts of toluene and washed with 330 parts of water until the pH of the water layer reached 7. Then, the solvent was distilled off under reduced pressure to obtain a toluene solution with a non-volatile component of 60%, i.e., 280 parts of a polyfunctional vinyl resin (VH3).

[0272] The obtained multifunctional vinyl resin (VH3) had a hydroxyl equivalent of 12,200, a vinyl equivalent of 235, and a total chlorine content of 2,700 ppm.

[0273] Example 4

[0274] Mix in the proportions (parts) shown in Table 1, dissolve in a solvent to obtain a uniform vinyl resin composition varnish. The obtained vinyl resin composition varnish is impregnated in glass cloth (manufactured by Nitto Bosho Co., Ltd., WEA 7628XS13, 0.18 mm thick). The impregnated glass cloth is dried in a hot air circulation oven at 130°C for 5 minutes to obtain a prepreg material. 8 sheets of the obtained prepreg material are overlapped with copper foil (manufactured by Mitsui Mining and Smelting Co., Ltd., 3EC-III, 35 μm thick) above and below it, and vacuum pressed at 2 MPa under the temperature conditions of 130°C × 30 minutes + 220°C × 100 minutes to obtain a 1.6 mm thick laminate. The results of the copper foil peel strength and Tg of the laminate are shown in Table 1.

[0275] In addition, the above-mentioned vinyl resin composition varnish was applied to a PET film, dried at 130°C for 5 minutes, and peeled from the PET film to obtain a resin composition. The obtained resin composition was placed in a mold made of fluororesin and vacuum pressed at 2MPa under the temperature conditions of 130°C×30 minutes+220°C×100 minutes to obtain a 50mm square×2mm thick test piece. The results of the relative dielectric constant and dielectric loss tangent of the test piece are shown in Table 1.

[0276] Examples 5 to 7, Comparative Examples 4 to 7

[0277] The same operation as in Example 4 was carried out by mixing the components in the amounts (parts) shown in Table 1 to obtain a vinyl resin composition varnish, a prepreg, a laminate, a vinyl resin composition and a test piece. The same test as in Example 4 was carried out and the results are shown in Table 1.

[0278] [Table 1]

[0279]

[0280] The multifunctional vinyl resins of Examples have higher adhesive strength than Comparative Examples, and exhibit excellent physical properties such as low relative dielectric constant and low dielectric loss tangent. In addition, they have a Tg of 250° C. or higher, and thus exhibit sufficient heat resistance.

[0281] Industrial Applicability

[0282] The multifunctional vinyl resin and composition of the present invention can be used as dielectric materials, insulating materials, and heat-resistant materials in the fields of electrical and electronic industries, aerospace and aircraft industries, and can be used as printed circuit boards, sealing materials, casting materials, etc. for electronic equipment, and can be used especially as electronic materials for high-speed communication equipment.

Claims

1. A multifunctional vinyl resin, characterized in that It is represented by the following general formula (1): [Chemistry 1] -CH2-Ar-CH=CH2 (1a) Among them, R 1 independently represent a hydrocarbon group having 1 to 8 carbon atoms, R 2 independently represent a hydrogen atom, a group represented by formula (2), or a group represented by formula (3), at least one of which is formula (2) or formula (3), R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 4 independently represents a hydrogen atom or a group represented by formula (2), and A is the result of removing two R from formula (1): 2 The residues, R 2 independently a hydrogen atom or a group represented by formula (2), Me represents a methyl group, X independently represents a hydrogen atom or an aromatic group containing a vinyl group represented by the above formula (1a), at least one is an aromatic group containing a vinyl group, Ar represents an aromatic ring, i is an integer of 0 to 2, n and p1 each represent a repetition number, the average value of which is a number of 0 to 5.

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

3. The multifunctional vinyl resin according to claim 1, wherein The R 1 is methyl or phenyl, and i is 1 or 2.

4. The multifunctional vinyl resin according to claim 1, which is a vinylate of a polyhydroxy resin represented by the following general formula (4): [Chemistry 2] in, R 1 independently represent a hydrocarbon group having 1 to 8 carbon atoms, R 21 independently represent a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), at least one of which is formula (5) or formula (6), R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 4 A independently represents a hydrogen atom or a group represented by formula (5), 1 To convert the two R 21 The residue removed, R in the residue 21 They are independently a hydrogen atom or a group represented by the formula (5); Me represents a methyl group; i represents an integer of 0 to 2; m and p2 each represent a repetition number, and the average value thereof is a number of 0 to 5.

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

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

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

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

9. A laminated plate obtained by laminating and molding the prepreg material according to claim 7 and / or the resin sheet according to claim 8.

10. A method for producing a multifunctional vinyl resin, which is the method for producing a multifunctional vinyl resin according to claim 1, characterized in that: A polyhydroxy resin represented by the following general formula (4) is reacted with an aromatic vinyl compound containing a halogenated methyl group represented by the following general formula (10), [Chemistry 3] 【Chemistry 3】 Among them, R 1 independently represent a hydrocarbon group having 1 to 8 carbon atoms, R 21 independently represent a hydrogen atom, a group represented by formula (5), or a group represented by formula (6), at least one of which is formula (5) or formula (6), R 3 independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 4 A independently represents a hydrogen atom or a group represented by formula (5), 1 To remove two R from formula (4) 21 The residues, R 21 are independently a hydrogen atom or a group represented by formula (5), Me represents a methyl group, i represents an integer of 0 to 2, m and p2 each represent a repetition number, the average value of which is a number of 0 to 5, [Chemistry 4] R 5 -CH2-Ar-CH=CH2 (10) Where Ar represents an aromatic ring, R 5 Represents halogen.

11. The method for producing a multifunctional vinyl resin according to claim 10, wherein: Ar in the formula (10) is an aromatic ring selected from a benzene ring, a naphthalene ring and a biphenyl ring, and the aromatic ring Ar is unsubstituted or has one or more substituents.

12. The method for producing a multifunctional vinyl resin according to claim 10, wherein: R of the formula (4) 1 is methyl or phenyl, and i is 1 or 2.

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