JP6025952B1 - Vinyl benzylated phenol compound, method for producing vinyl benzylated phenol compound, active ester resin, method for producing active ester resin, thermosetting resin composition, cured product of thermosetting resin composition, interlayer insulating material, Prepreg and method for producing prepreg - Google Patents

Abstract

Provided is a raw material for producing an active ester resin useful as a component of a thermosetting resin composition capable of forming a cured product having excellent dielectric properties and excellent heat resistance. A vinylbenzylated phenol compound represented by formula (1) is provided. (Ar0 is a bifunctional phenol compound residue, R1 to R5 are hydrogen or a methyl group, p is 0.1 to 4) [Selection] FIG.

Description

  The present invention relates to an active ester resin useful as a component of a thermosetting resin composition, a method for producing the active ester resin, a vinylbenzylated phenol compound which is one of raw materials for producing the active ester resin, and vinyl Method for producing benzylated phenol compound, thermosetting resin composition containing active ester resin as described above, cured product of thermosetting resin composition, interlayer insulating material formed using thermosetting resin composition, The present invention relates to a prepreg using a thermosetting resin composition and a method for producing the prepreg.

  In accordance with recent improvements in performance of information communication equipment such as higher functionality and higher density, printed wiring boards are also required to have performance adapted to them. A cured product of a thermosetting resin composition is used as an insulating material for forming a printed wiring board. Among thermosetting resin compositions, an epoxy resin composition containing an epoxy compound from the viewpoint of price and adhesiveness. Goods are widely used. In particular, in recent years, multilayered wiring boards have been developed in accordance with the reduction in thickness, size, and performance of electronic devices.

  As a curing agent in such an epoxy resin composition, for example, Patent Document 1 describes using an active ester resin. By using the ester resin disclosed in Patent Document 1, a thermosetting resin composition having both excellent heat resistance and flame retardancy while having a low dielectric constant and low dielectric loss tangent in the cured product is obtained. It is supposed to be done.

  Patent Document 1 describes that the ester resin is produced by reacting a substance containing a phenolic hydroxyl group with an aromatic dicarboxylic acid or an aromatic dicarboxylic acid chloride.

  On the other hand, Patent Document 2 gives a cured product having excellent dielectric properties (low dielectric constant and low dielectric loss tangent) even after moisture absorption in a high temperature and high humidity environment, and having a high glass transition temperature and flame retardancy. Aromatic vinyl benzyl ether compounds are described.

Japanese Patent No. 5120520 JP 2014-62243 A

  The present invention relates to an active ester resin useful as a component of a thermosetting resin composition capable of forming a cured product having excellent dielectric properties and excellent heat resistance, a method for producing the active ester resin, and producing the active ester resin. A vinylbenzylated phenol compound, a method for producing the vinylbenzylated phenol compound, a thermosetting resin composition containing the above active ester resin, and a cured product of the thermosetting resin composition It is an object of the present invention to provide an interlayer insulation material using the thermosetting resin composition, a prepreg using the thermosetting resin composition, and a method for producing the prepreg.

The present invention provided to solve the above-described problems is as follows.
[1] A vinylbenzylated phenol compound represented by the following general formula (1).
(In the above general formula (1), Ar ⁰ is a bifunctional phenol compound residue having one or more monocyclic or polycyclic aromatic nuclei, and R ^{1 to} R ⁵ may be the same or different, hydrogen or methyl And p is an integer of 1 to 4. )

[2] The vinylbenzylated phenol compound according to the above [1], wherein Ar ⁰ in the general formula (1) is a structure represented by the following general formula (2) or the following general formula (3).

(Y in the general formula (3) is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, an ether bond, a fluorenyl group, a sulfone group, and a cyclohexylidene group. , 3,3,5-trimethyl cyclohexylidene _{radical, -C (CF 3) 2 -} , - C (CH 3) (Ph) -, 1,3- phenylene isopropylidene or 1,4-phenylene, An isopropylidene group.)

[3] A method for producing a vinylbenzylated phenol compound as described in [1] or [2] above, wherein the bifunctional phenol compound and vinylbenzyl halide compound have one or more monocyclic or polycyclic aromatic nuclei. Is reacted with hydrotalcite as a dehydrohalogenating agent, and a method for producing a vinylbenzylated phenol compound is characterized.

[4] The bifunctional phenol compound having one or more monocyclic or polycyclic aromatic nuclei is represented by the following general formula (4) or the following general formula (5), and is vinylbenzylated according to the above [3] A method for producing a phenol compound.

(Y in the general formula (5) is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, an ether bond, a fluorenyl group, a sulfone group, a cyclohexylidene group. , 3,3,5-trimethyl cyclohexylidene _{radical, -C (CF 3) 2 -} , - C (CH 3) (Ph) -, 1,3- phenylene isopropylidene or 1,4-phenylene, An isopropylidene group.)

[5] An active ester resin represented by the following general formula (6):

(In the general formula (6), X is a structure represented by the following general formula (7) or the following general formula (8), Ar ¹ and Ar ² may be the same or different, A phenyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms, a naphthyl group, or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, and the average number of repetitions n is 0.5-30.)

(In the general formula (7) and the general formula (8), R ^{1 to} R ¹⁵ may be the same or different, are hydrogen or a methyl group, and the average repeating number m is 0.1 to 4, The average repeating number 1 and the average repeating number k are each independently 0.1 to 2. Y in the general formula (8) is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, — CH (CH ₃ ) —, ether bond, fluorenyl group, sulfone group, cyclohexylidene group, 3,3,5-trimethylcyclohexylidene group, —C (CF ₃ ) ₂ —, —C (CH ₃ ) (Ph )- , 1,3-phenylene diisopropylidene group, or 1,4-phenylene diisopropylidene group.)

[6] The active ester resin according to the above [5], wherein X in the general formula (6) is a structure represented by the general formula (7).

[7] One or more selected from the group consisting of the vinylbenzylated phenol compound described in [1] or [2] above, a monofunctional phenol compound, an aromatic nucleus-containing dicarboxylic acid and a halide compound thereof, A process for producing an active ester resin, characterized by reacting.

[8] A thermosetting resin composition comprising the active ester resin described in [5] or [6] above and an epoxy resin.

[9] The thermosetting resin composition according to [8], further including a curing accelerator.

[10] The thermosetting resin composition according to [8] or [9], further including an inorganic filler.

[11] A cured product of the thermosetting resin composition according to any one of [8] to [10].

[12] An interlayer insulating material comprising the thermosetting resin composition according to any one of [8] to [10].

[13] A prepreg comprising a semi-cured body of the thermosetting resin composition described in any one of [8] to [10] above and a fibrous reinforcing member.

[14] The thermosetting resin impregnated in the fibrous reinforcing material by impregnating the thermosetting resin composition described in any of [8] to [10] above into a fibrous reinforcing material and heating. A method for producing a prepreg, comprising semi-curing the composition.
[15] A composition comprising a plurality of types of compounds in which the number of bonds to the aromatic nucleus of the structural moiety shown in parentheses in the general formula (1) of [1] above is different, wherein the average number of repetitions of the structural moiety is The composition which is 0.1-4.

  According to the present invention, there is provided a thermosetting resin composition capable of forming a cured product having excellent dielectric properties (dielectric constant, dielectric loss tangent) and excellent heat resistance (glass transition temperature, weight loss under high temperature environment). Active ester resin useful as a component, method for producing the active ester resin, vinylbenzylated phenol compound as one of raw materials for producing the active ester resin, method for producing the vinylbenzylated phenol compound, the above-mentioned activity A thermosetting resin composition containing an ester resin, a cured product of the thermosetting resin composition, an interlayer insulating material using the thermosetting resin composition, and a prepreg using the thermosetting resin composition And a method for producing the prepreg.

1 is a GPC chart of a vinyl benzylated solution (A-1) obtained in Example 1. 2 is an FD-MS spectrum of the vinylbenzylated solution (A-1) obtained in Example 1. 6 is a GPC chart of a vinyl group-containing active ester resin solution (B-1) obtained in Example 5. FIG. 4 is an FD-MS spectrum of a vinyl group-containing active ester resin solution (B-1) obtained in Example 5.

  Embodiments of the present invention will be described below.

The vinylbenzylated phenol compound (a) according to one embodiment of the present invention is represented by the following general formula (1).

In the general formula (1), Ar ⁰ is a bifunctional phenol compound residue having one or more monocyclic or polycyclic aromatic nuclei. R ^{1 to} R ⁵ may be the same or different and are hydrogen or a methyl group. p is an integer of 1 to 4. The composition according to an embodiment of the present invention includes a plurality of types of compounds in which the number of bonds to the aromatic nucleus of the structural site shown in parentheses in the general formula (1) is different, and the average number of repetitions of the structural site is 0.1-4. The average number of repetitions is non-integer because the vinylbenzylated phenol compound (a) is a compound of a plurality of types having different numbers of bonds to the aromatic nucleus at the structural site shown in parentheses in the general formula (1). It is because it may consist of a composition containing. The same applies to the average number of repetitions in other general formulas.

Specific examples of Ar ⁰ include structures represented by the following general formula (2) or the following general formula (3).

The positions of the two hydroxyl groups on the aromatic nucleus in the general formula (2) and the general formula (3) are arbitrary. Y in the general formula (3) is a direct bond (in this case, the structure represented by the general formula (3) is a biphenylylene group), —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, ether bond, fluorenyl group, sulfone group, cyclohexylidene group, 3,3,5-trimethylcyclohexylidene group, —C (CF ₃ ) ₂ —, or —C (CH ₃ ) (Ph)-, 1,3-phenylenediisopropylidene group, 1,4-phenylenediisopropylidene group.

  The method for producing the vinylbenzylated phenol compound (a) according to one embodiment of the present invention is not limited. The vinylbenzylated phenol compound (a) can be efficiently produced by the production method described below.

  In the method for producing a vinylbenzylated phenol compound (a) according to an embodiment of the present invention, a bifunctional phenol compound (α) having at least one monocyclic or polycyclic aromatic nucleus and a vinylbenzyl halide compound (β) are prepared. Hydrotalcite (γ) is reacted as a dehydrohalogenating agent.

The specific kind of said bifunctional phenol compound ((alpha)) is not limited. Specific examples include compounds represented by the following general formula (4) or the following general formula (5).

Here, Y in the general formula (5) is a direct bond (in this case, the compound represented by the general formula (5) includes biphenol), —CH ₂ — (in this case, the general formula The compound represented by (5) includes bisphenol F.), —C (CH ₃ ) ₂ — (in this case, the compound represented by the general formula (5) includes bisphenol A), —CH (CH ₃ )-(in this case, the compound represented by the general formula (5) includes bisphenol E), an ether bond, a fluorenyl group, a sulfone group (in this case, the compound represented by the general formula (5) is Bisphenol S.), a cyclohexylidene group (in this case, the compound represented by the general formula (5) contains bisphenol Z), a 3,3,5-trimethylcyclohexylidene group (in this case) In general formula (5) .) The compounds containing bisphenol _{TMC, - C. (CF 3} ) 2 - ( in this case, the general formula (5) compounds represented by include bisphenol AF), or -C _(CH 3) ( Ph)-(in this case, the compound represented by the general formula (5) includes bisphenol AP), 1,3-phenylenediisopropylidene group (in this case, the compound represented by the general formula (5)) Includes bisphenol M.) and 1,4-phenylenediisopropylidene group (in this case, the compound represented by the general formula (5) includes bisphenol P).

  The vinyl benzyl halide compound (β) is not limited as long as the vinyl group and the halogenated methyl group are bonded to the aromatic nucleus, and the positional relationship between the vinyl group and the halogenated methyl group is not limited.

In the production method according to an embodiment of the present invention, hydrotalcites (γ) are used as a dehydrohalogenating agent in the reaction of the bifunctional phenol compound (α) and the vinylbenzyl halide compound (β). Hydrotalcite (γ) is a hydrate of a complex of magnesium and aluminum carbonate and hydroxide, and the general formula thereof is Mg ₆ Al ₁₂ (OH) ₁₆ (CO ₃ ) · 4H ₂ O, _{mg 4.5 Al 2 (OH) 13} CO 3 · qH 2 O (q is 3 to 3.5) is. Moreover, Mg _0.7 Al _0.3 O _1.15 is mentioned as an example of those anhydrides. Specific examples of hydrotalcites (γ) include KW-500SH, KW-500SN, KW-500PL, KW-500G-7, KW-1000, KW-1015, KW-2000, KW-2100 ( Both are manufactured by Kyowa Chemical Industry Co., Ltd.). By using hydrotalts (γ) as a dehydrohalogenating agent, residues based on the vinylbenzyl halide compound (β) can be used as the skeleton of the aromatic nucleus while leaving the phenolic hydroxyl group of the bifunctional phenol compound (α). Direct coupling is realized.

  In this regard, for example, the aromatic vinyl benzyl ether compound described in Patent Document 2 is formed from a polyhydric phenol compound and vinyl benzyl halide, and an alkali metal hydroxide such as sodium hydroxide is used as a dehydrohalogenating agent. As a result, the phenolic hydroxyl group in the polyhydric phenol compound reacts with the halogen of vinylbenzyl halide to form an ether bond. In such a reaction, a vinyl group is introduced in a form that consumes a part of the polyhydric phenol compound, and the structure controllability of the active ester resin thereafter is lowered. On the other hand, according to the production method according to one embodiment of the present invention, the phenolic hydroxyl group of the bifunctional phenol compound (α) is converted to the carboxylic acid halide during the reaction for forming the active ester resin. Since it can be a reaction point, the molecular design of the active ester resin is facilitated.

  Depending on the structure of the desired reaction product, the raw material charge amount and reaction conditions in the reaction between the bifunctional phenol compound (α) and the vinylbenzyl halide compound (β) are dehalogenated with hydrotalcites (γ). It is suitably set so that the hydrogen reaction proceeds appropriately. The molar ratio (β / α) of the charged amount of the vinylbenzyl halide compound (β) to the charged amount of the bifunctional phenol compound (α) may be preferably 0.1 to 2.0. The molar ratio (γ / β) of the usage amount of the hydrotalcite (γ) to the charged amount of the vinylbenzyl halide compound (β) may preferably be 0.70 to 1.50. When hydrotalcite (γ) is used as a dehydrohalogenating agent, the dehydrohalogenation reaction involves the generation of carbon dioxide and water, so the generation of carbon dioxide gas during the reaction is appropriately controlled, It is preferable to set reaction conditions such as heating temperature in consideration of appropriately discharging moisture out of the system.

  As a non-limiting example, the dehydrohalogenation reaction is carried out using a slurry-like reaction solution containing a bifunctional phenol compound (α) and hydrotalcites (γ) within a range of 50 ° C. to 80 ° C., preferably 60 While maintaining the temperature within a range of from ℃ to 70 ℃, drastic generation of carbon dioxide can be suppressed by dropping the vinylbenzyl halide compound (β). Further, the solvent in the slurry-like reaction solution is toluene or methyl isobutyl ketone, and after all the vinylbenzyl halide compound (β) is dropped, the temperature of the reaction solution is heated to 100 ° C. or higher, and the reaction solution is heated. It is preferable to remove the moisture.

  Specific examples of the bifunctional phenol (α) include 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7 -Dihydroxynaphthalenes such as dihydroxynaphthalene, bisphenol F, bisphenol A, bisphenol E, bisphenol S, bisphenol fluorene, bisphenol Z, bisphenol TMC, bisphenols such as bisphenol AF, bisphenol M, bisphenol P, 4,4'-oxydi Examples include phenol. From the viewpoint of heat resistance, dielectric properties, and raw material availability, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, bisphenolfluorene, and bisphenol TMC are preferable.

  Examples of the solvent used for the reaction between the bifunctional phenol compound (α) and the vinylbenzyl halide compound (β) include toluene, xylene, mesitylene, ethylbenzene, methyl isobutyl ketone, methyl n-amyl ketone, and methyl isoamyl ketone.

The active ester resin (A) according to one embodiment of the present invention has a structure represented by the following general formula (6).

In the general formula (6), X is a structure represented by the following general formula (7) or the following general formula (8). Ar ¹ and Ar ² may be the same or different, and a phenyl group, a phenyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, a naphthyl group, or 1 carbon atom on the aromatic nucleus. A naphthyl group having 1 to 3 alkyl groups of ˜4. The average repetition number n is 0.5-30.

In the general formula (7) and the general formula (8), R ^{1 to} R ¹⁵ may be the same or different and are hydrogen or a methyl group. The average repeating number m is 0.1-4. The average repetition number 1 and the average repetition number k are each independently 0.1-2. Y in the general formula (8) is the same as Y in the general formula (3) and the general formula (5), and is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, — CH (CH ₃ ) —, ether bond, fluorenyl group, sulfone group, cyclohexylidene group, 3,3,5-trimethylcyclohexylidene group, —C (CF ₃ ) ₂ —, or —C (CH ₃ ) ( Ph)-, 1,3-phenylenediisopropylidene group, 1,4-phenylenediisopropylidene group.

  Unlike the active ester resin disclosed in Patent Document 1, the active ester resin (A) according to an embodiment of the present invention has a vinyl group capable of polymerization reaction in the aromatic nucleus of the benzyl group. For this reason, when the reaction using the double bond of the vinyl group proceeds, the relative position between the carbon chain formed by the reaction and the main chain containing the ester bond of the active ester resin (A) changes. Hard to do. Therefore, the cured product of the thermosetting resin composition containing the active ester resin (A) according to an embodiment of the present invention is not easily deformed or decomposed when heated, has a high glass transition temperature, and is heat resistant and stable. It is easy to become a material with excellent properties. From the viewpoint of more stably increasing the difficulty of movement of the main chain of the active ester resin (A) (such as the difficulty of rotation using the main chain as the rotation axis), the active ester resin (A ) May preferably have a structure in which X in the general formula (6) is represented by the general formula (7).

  The manufacturing method of active ester resin (A) which concerns on one Embodiment of this invention is not limited. For example, an aromatic composed of one kind selected from the group consisting of a vinylbenzylated phenol compound (a), a monofunctional phenol compound (b), an aromatic nucleus-containing dicarboxylic acid and a halide compound thereof according to an embodiment of the present invention. The active ester resin (A) can be obtained by reacting the carboxylic acid compound (c) or higher.

  Specific examples of the monofunctional phenol compound (b) include unsubstituted monofunctional phenol compounds such as phenol and naphthol, and alkyl-substituted monofunctional phenol compounds such as cresol, dimethylphenol, and ethylphenol. In the alkyl-substituted monofunctional phenolic compound, the number of substitution of the alkyl group is 3 or less, and the number of carbon atoms of the alkyl group is 4 or less, from the viewpoint of balance between curability and dielectric properties with the epoxy resin (B) described later. It may be preferable.

  Specific examples of the aromatic carboxylic acid compound (c) include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl ether 4, Examples include 4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and acid chlorides thereof.

  The reaction conditions are arbitrary as long as the active ester resin (A) can be appropriately generated. An active ester resin is obtained by reacting a polyfunctional phenol compound (the phenolic hydroxyl group-containing resin in Patent Document 1 is exemplified), a monofunctional phenol compound (b), and an aromatic carboxylic acid compound (c). Since this is well-known, you may refer to the manufacturing method.

  The thermosetting resin composition according to an embodiment of the present invention contains an active ester resin (A) and an epoxy resin (B) according to an embodiment of the present invention.

  A well-known thing can be used for an epoxy resin (B). For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, aralkyl resin epoxy with xylylene bonds such as phenol and naphthol Epoxides of dicyclopentadiene-modified phenolic resins, dihydroxynaphthalene type epoxy resins, glycidyl ether type epoxy resins such as triphenolmethane type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins and other bivalent or more epoxies An epoxy resin having a group can be mentioned. These epoxy resins may be used alone or in combination of two or more.

  Among these epoxy resins (B), resins having a large epoxy equivalent, such as phenol biphenyl aralkyl type epoxy resins, epoxidized aralkyl resins by xylylene bonds such as phenol and naphthol, and epoxidized products of dicyclopentadiene-modified phenol resins are used. Is preferred. This is from the viewpoint of obtaining good dielectric properties.

  In the thermosetting resin composition according to one embodiment of the present invention, the compounding ratio of the active ester resin (A) and the epoxy resin (B) is the ester group contained in the active ester resin (A) and the epoxy resin (B). The equivalent ratio (B / A) of the epoxy groups contained in is preferably in the range of 0.5 to 1.5, particularly preferably in the range of 0.8 to 1.2.

The thermosetting resin composition according to one embodiment of the present invention may further contain a curing accelerator. Examples of such curing accelerators include organic peroxides such as hydroperoxides and dialkyl peroxides, azo compounds, and organic borons such as trialkylboranes from the viewpoint of promoting the reaction of vinyl groups contained in the active ester resin (A). Compound etc. are mentioned. Moreover, a well-known substance can be used as a hardening accelerator of the ester group and epoxy resin (B) which are contained in active ester resin (A). Examples of such curing accelerators include tertiary amine compounds, quaternary ammonium salts, imidazoles, phosphine compounds, and phosphonium salts. More specifically, triethylamine, triethylenediamine, benzyldimethylamine, 4-dimethylaminopyridine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 Tertiary amine compounds such as 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, triphenylphosphine, Phosphonium compounds such as tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphoniumtetranaphthoic acid borate, etc. It can be mentioned bets, betaine-like organic phosphorus compounds such as the reaction product of benzoquinone and triphenyl phosphine - salt, triphenylphosphonio phenolate la.

  The usage-amount of said hardening accelerator is not limited. It should be appropriately set according to the function of the curing accelerator.

  The thermosetting resin composition according to one embodiment of the present invention may further contain an inorganic filler. Examples of the inorganic filler include amorphous silica, crystalline silica, alumina, glass, calcium silicate, gypsum, calcium carbonate, magnesite, clay, talc, mica, magnesia, or barium sulfate. Among these, amorphous silica and crystalline silica are preferable.

  In order to increase the blending amount of the filler while maintaining excellent moldability, it is preferable to use a spherical filler having a wide particle size distribution that enables fine packing. In that case, a small inorganic particle size spherical filler having a particle size of 0.1 to 3 μm is mixed in a proportion of 5 to 40% by weight, and a large particle size spherical inorganic filler having a particle size of 5 to 30 μm is mixed in a proportion of 95 to 60% by weight. And preferably used.

  In the case where the thermosetting resin composition according to one embodiment of the present invention contains an inorganic filler, the blending amount of the inorganic filler is appropriately set according to the type and application of the inorganic filler. As an example which is not limited, it is mentioned that the compounding quantity of an inorganic filler shall be 60 mass%-93 mass% of the whole thermosetting resin composition.

  To the thermosetting resin composition according to an embodiment of the present invention, a solvent, a coupling agent, a release agent, a colorant, a flame retardant, a low stress agent, a thickener, and the like are further added as necessary. Or it can react and use beforehand. Examples of the coupling agent include silane coupling agents such as vinyl silane, amino silane, and epoxy silane, titanium coupling, and the like. Examples of the mold release agent include carnauba wax, paraffin wax, stearic acid, montanic acid, carboxyl group-containing polyolefin wax, and the like. Examples of the colorant include carbon black. Examples of the flame retardant include halogenated epoxy resins, halogen compounds, and phosphorus compounds, and examples of the flame retardant aid include antimony trioxide. Examples of the low stress agent include silicon rubber, modified nitrile rubber, modified butadiene rubber, and modified silicone oil.

  A cured product can be obtained by heating the thermosetting resin composition according to one embodiment of the present invention. Such a cured product according to one embodiment of the present invention has a structural portion derived from the active ester resin (A) having a vinyl group, and therefore has excellent dielectric properties such as low dielectric constant and low dielectric loss tangent.

  In addition, since the active ester resin (A) has a structure in which a vinylbenzyl group is directly bonded to an aromatic nucleus, a carbon chain formed when the vinyl group undergoes a polymerization reaction is a vinyl benzyl ether introduced using a hydroxyl group and Compared to molecular movement is difficult. For this reason, even if the hardened | cured material which concerns on one Embodiment of this invention is heated, the structure part derived from active ester resin (A) in hardened | cured material does not produce a rotational motion etc. easily. Therefore, the cured product according to an embodiment of the present invention tends to have a high glass transition temperature and excellent heat stability.

  The temperature at which the thermosetting resin composition according to one embodiment of the present invention is cured is appropriately set according to the composition of the cured product. A non-limiting example is heating in a temperature range of 100 to 250 ° C.

  The specific operation for curing is not limited. For example, the thermosetting resin composition according to one embodiment of the present invention is diluted with a solvent as necessary, the obtained diluted solution is applied to a substrate, and dried and cured by heating. By removing the obtained cured coating film from the substrate, a cured product (cured product film) according to one embodiment of the present invention can be obtained. A molding material can be obtained by curing the thermosetting resin composition according to an embodiment of the present invention in a mold. The cured product of the thermosetting resin composition according to one embodiment of the present invention may be used as a binder, may be used as a coating material, or a member including the cured product may be used as a laminated material.

  The interlayer insulation material which concerns on one Embodiment of this invention consists of a thermosetting resin composition which concerns on one Embodiment of this invention. For example, by dissolving the thermosetting resin composition according to one embodiment of the present invention in a solvent, an interlayer insulating varnish for applying to a circuit board to form an insulating layer can be obtained.

  If the obtained interlayer insulating varnish is spread on a support film and then heat-treated to form a film, an adhesive sheet for use as an interlayer insulating material can be obtained. This adhesive sheet can be used as an interlayer insulating material in a multilayer printed wiring board. When using the interlayer insulation material which concerns on one Embodiment of this invention for semiconductor sealing, it is preferable that a thermosetting resin composition contains an inorganic filler as mentioned above.

  A prepreg according to an embodiment of the present invention includes a semi-cured body of a thermosetting resin composition according to an embodiment of the present invention and a fibrous reinforcing member such as glass fiber. This prepreg can be used as an interlayer insulating material in a multilayer printed wiring board. The manufacturing method of the prepreg which concerns on one Embodiment of this invention is not limited. The thermosetting resin composition according to one embodiment of the present invention is made into a varnish by adding a solvent as necessary, and impregnated into a fibrous reinforcing member, and subjected to heat treatment, thereby achieving one embodiment of the present invention. Such a prepreg can be manufactured.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

<Hydroxyl equivalent>
The sample was acetylated with pyridine and excess acetic anhydride, and acetic acid produced from acetic anhydride consumed by hydroxyl groups present in the sample was determined by titration with a potassium hydroxide alcohol solution.

<GPC analysis conditions>
(1) Equipment used: “HLC-8320 GPC” manufactured by Tosoh Corporation
(2) Column: All manufactured by Tosoh Corporation, “TSKgel superHZ4000” (1) + “TSKgel superHZ3000” (1) + “TSKgel superHZ2000” (2) + “TSKgel superHZ1000” (1) (each 6) (Connect a column of 0mm x 15cm)
(3) Solvent: Tetrahydrofuran (4) Flow rate: 0.6 ml / min
(5) Temperature: 40 ° C
(6) Detector: differential refractive index (RI) meter (RI detector with built-in measuring device “HLC-8320 GPC”)

<FD-MS analysis conditions>
(1) Equipment: “JMS-T100GCV” manufactured by JEOL
(2) Cathode voltage: -10 kV
(3) Emitter current: 0 mA → 35 mA (51.2 mA / min.)
(4) Measurement mass range: m / z = 10 to 2000 (Example 1)
m / z = 10 to 3000 (Example 5)

Example 1
In a four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 160.2 g of 2,7-dihydroxynaphthalene, 311.0 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and toluene 1251.3 g was charged and the temperature was raised to 60 to 70 ° C. Next, 152.6 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was added dropwise while paying attention to sudden foaming with carbon dioxide gas. did. Furthermore, it heated up to the temperature of 100-110 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. After removing hydrotalcite from the obtained reaction solution by filtration, the hydrotalcite was washed with toluene to obtain 1606.6 g of a vinylbenzylated solution (A-1) of 2,7-dihydroxynaphthalene. . The solid content yield was 78.5%, the solid content was 13.5%, and the hydroxyl group equivalent was 144.5 g / eq. A GPC chart of the resulting vinylbenzylated solution (A-1) is shown in FIG.

FIG. 2 shows the FD-MS spectrum of the resulting vinylbenzylated solution (A-1). 2,7-dihydroxynaphthalene (Mw: 160) the vinylbenzyl group (Mw: 116) is one additional peaks ^(M + = 276), vinylbenzyl group (Mw: 116) Two additional peaks ^{(M +} = 392), a peak (M ⁺ = 508) with three vinylbenzyl groups (Mw: 116) added was detected.

  Therefore, it was confirmed that the compound was obtained by bonding 1 to 3 mol of vinylbenzyl group to 1 mol of 2,7-dihydroxynaphthalene.

  Further, when 1 mol of 2,7-dihydroxynaphthalene reacts with 1 mol of chloromethylstyrene in total with a hydroxyl group, the theoretical hydroxyl equivalent is 276 g / eq. On the other hand, when 1 mol of chloromethylstyrene is reacted with the aromatic nucleus side of 1 mol of 2,7-dihydroxynaphthalene, the theoretical hydroxyl equivalent is 138 g / eq. Since the measured hydroxyl equivalent of vinylbenzylated product (A-1) was close to 138 g / eq, it was confirmed that most of chloromethylstyrene was added to the aromatic nucleus side.

(Example 2)
In a four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 160.2 g of 1,6-dihydroxynaphthalene, 311.0 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and toluene 1251.3 g was charged and the temperature was raised to 60 to 70 ° C. Next, 152.6 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was added dropwise while paying attention to sudden foaming with carbon dioxide gas. did. Furthermore, it heated up to the temperature of 100-110 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. After removing hydrotalcite from the obtained reaction solution by filtration, the hydrotalcite was washed with toluene to obtain 1646.1 g of 1,6-dihydroxynaphthalene vinylbenzylated solution (A-2). . The solid content yield was 79.0%, the solid content was 13.3%, and the hydroxyl group equivalent was 150.1 g / eq.

Example 3
To a four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 208.3 g of 1,6-dihydroxynaphthalene, 412.2 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and methyl 948.9 g of isobutyl ketone was charged, and the temperature was raised to 60 to 70 ° C. Next, 198.4 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was added dropwise while paying attention to rapid foaming by carbon dioxide gas. And added. Furthermore, it heated up to the temperature of 100-115 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. After removing hydrotalcite from the obtained reaction solution by filtration, the hydrotalcite was washed with methyl isobutyl ketone, whereby 1401.4 g of a vinylbenzylated solution of 1,6-dihydroxynaphthalene (A-3) was obtained. Obtained. The solid content yield was 83.1%, the solid content was 21.3%, and the hydroxyl group equivalent was 153.7 g / eq.

Example 4
In a four-necked 2 L flask equipped with a nitrogen gas introduction tube, a thermometer and a stirrer, 128.2 g of 1,6-dihydroxynaphthalene, 157.0 g of hydrotalcite (“KW-500SH” manufactured by Kyowa Chemical Industry Co., Ltd.), and methyl 385.4 g of isobutyl ketone was charged, and the temperature was raised to 60 to 70 ° C. Next, 79.4 g of chloromethylstyrene (“CMS-P” manufactured by AGC Seimi Chemical Co., Ltd.) was dropped while paying attention to sudden foaming by carbon dioxide gas. And added. Furthermore, it heated up to the temperature of 100-115 degreeC, and was made to react for 5 hours, discharging | emitting a carbon dioxide gas and water out of the system. Hydrotalcite was removed by filtration from the resulting reaction solution, and then hydrotalcite was washed with methyl isobutyl ketone to obtain 665.5 g of 1,6-dihydroxynaphthalene vinylbenzylated solution (A-4). Obtained. The solid content yield was 92.8%, the solid content was 26.3%, and the hydroxyl group equivalent was 127.3 g / eq.

(Example 5)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 190.0 g of vinylbenzylated solution (A-1), 20.9 g of 1-naphthol, and 0.6 g of tetra n-butylammonium bromide Was dissolved at room temperature. Next, 32.5 g of isophthalic acid chloride was charged and dissolved, and 64.1 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 60 ° C., and then reacted at a temperature of 50 to 60 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, the resultant was concentrated by distillation under reduced pressure to obtain a vinyl group-containing active ester resin solution (B-1) having a solid content of 67.7% and a theoretical functional group equivalent of 209 g / eq. A GPC chart of the resulting vinyl group-containing active ester resin solution (B-1) is shown in FIG.

The spectrum of FD-MS of the obtained vinyl group-containing active ester resin solution (B-1) is shown in FIG. In the following general formula (9), a peak corresponding to i = 0 (M ⁺ = 418) and a peak corresponding to i = 1 and j = 1 (M ⁺ = 824) were detected.

(Example 6)
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer, 190.0 g of vinylbenzylated solution (A-2), 19.8 g of 1-naphthol, and 0.6 g of tetra-n-butylammonium bromide Was dissolved at room temperature. Next, 30.8 g of isophthalic acid chloride was charged and dissolved, and 60.7 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 60 ° C., and then reacted at a temperature of 50 to 60 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, the resultant was concentrated by distillation under reduced pressure to obtain a vinyl group-containing active ester resin solution (B-2) having a solid content of 65.2% and a theoretical functional group equivalent of 212 g / eq.

(Example 7)
A four-necked 2 L flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer was charged with 400.0 g of vinylbenzylated solution (A-3), 120.0 g of 1-naphthol, and 233.4 g of methyl isobutyl ketone. And dissolved. Next, 140.2 g of isophthalic acid chloride was charged and dissolved, and 290.0 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 40 ° C., and then reacted at a temperature of 30 to 40 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure while gradually adding 158.9 g of cyclohexanone, and a vinyl group-containing active ester resin solution (B-3) having a solid content of 61.3% and a theoretical functional group equivalent of 213 g / eq. Got.

(Example 8)
A four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 40.0 g of vinylbenzylated solution (A-4), 22.1 g of 1-naphthol, and 50.8 g of methyl isobutyl ketone at room temperature. And dissolved. Next, 23.7 g of isophthalic acid chloride was charged and dissolved, and 49.1 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 40 ° C., and then reacted at a temperature of 30 to 40 ° C. for 6 hours. Furthermore, after draining and separating the separated aqueous layer, it was washed with pure water until the pH became neutral. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure while gradually adding 25.8 g of cyclohexanone to give a vinyl group-containing active ester resin solution (B-4) having a solid content of 79.1% and a theoretical functional group equivalent of 205 g / eq. Got.

(Comparative Example 1)
A 4-neck 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer and a stirrer was charged with 1-naphthol (36.1 g), isophthalic acid chloride (25.3 g), and toluene (183.5 g) and dissolved at room temperature. Next, 52.0 g of a 20% aqueous sodium hydroxide solution was added dropwise at a temperature in the range of 20 to 60 ° C, and then reacted at a temperature of 50 to 60 ° C for 6 hours. Thereafter, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration. Further, the obtained crystal was washed with pure water, dried under reduced pressure at 80 ° C., and dissolved in dimethylacetamide to obtain an active ester compound solution (B-5) having a solid content of 30%. The theoretical functional group equivalent was 209 g / eq.

(Comparative Example 2)
Biphenylaralkylphenol resin (“HE200C-17” manufactured by Air Water, ICI viscosity at 150 ° C. 150 mPa · s, hydroxyl group equivalent 210 g / eq) was dissolved in methyl ethyl ketone (MEK) to obtain a resin solution (B -6).

(Examples 9 to 12 and Comparative Examples 3 and 4)
In each of the resin solutions (B-1 to B-6) produced in Examples 5 to 8 and Comparative Examples 1 and 2, a biphenyl aralkyl type epoxy resin (“NC-3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 290 g / A methyl ethyl ketone (MEK) solution having a solid content of 75% of eq) and dimethylaminopyridine (DMAP) were mixed to prepare a resin composition varnish. The blending amount for producing each resin composition varnish was as shown in Table 1. Each resin composition varnish was applied to the glossy surface of the copper foil, dried at 100 ° C. for 8 minutes, and cured at 200 ° C. for 6 hours. After curing, it was peeled off from the copper foil to obtain a cured film (cured product) having a film thickness of about 80 μm.

(Measurement of glass transition temperature Tg)
The cured product films obtained in Examples 9 to 12 and Comparative Examples 3 and 4 were cut (cut out) to a predetermined size to obtain glass transition temperature measurement samples. The glass transition temperature Tg of the sample was measured under the following conditions.
Measuring instrument: Rigaku's thermomechanical analyzer "TMA8310evo"
Sample dimensions: width 5 mm x length 15 mm x thickness 0.080 mm (80 μm)
Atmosphere: In nitrogen Measurement temperature: 25-300 ° C
Temperature increase rate: 10 ° C / min Measurement mode: Tensile

(Evaluation of dielectric properties)
The cured product films obtained in Examples 9 to 12 and Comparative Examples 3 and 4 were cut into a predetermined size and used as measurement samples. The dielectric properties of the samples were measured using the following measuring equipment under the following conditions.
Measuring equipment: “Network Analyzer E5071C” manufactured by Keysight Technology
Cavity resonator perturbation method dielectric constant measuring device manufactured by Kanto Electronics Application Development Company Frequency: 1 GHz
Sample dimensions: width 2 mm x length 100 mm x thickness 0.080 mm (80 μm)

  The evaluation results are shown in Table 1.

Claims (15)

A vinylbenzylated phenol compound represented by the following general formula (1).
(In the above general formula (1), Ar ⁰ is a bifunctional phenol compound residue having one or more monocyclic or polycyclic aromatic nuclei, and R ^{1 to} R ⁵ may be the same or different, hydrogen or methyl And p is an integer of 1 to 4. ) Ar ⁰ in the general formula (1) is a vinylbenzylated phenol compound according to claim 1, which has a structure represented by the following general formula (2) or the following general formula (3).

(Y in the general formula (3) is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, an ether bond, a fluorenyl group, a sulfone group, and a cyclohexylidene group. , 3,3,5-trimethyl cyclohexylidene _{radical, -C (CF 3) 2 -} , - C (CH 3) (Ph) -, 1,3- phenylene isopropylidene or 1,4-phenylene, An isopropylidene group.) A method for producing a vinylbenzylated phenol compound according to claim 1 or claim 2,
A method for producing a vinylbenzylated phenol compound, comprising reacting a bifunctional phenol compound having one or more monocyclic or polycyclic aromatic nuclei and a vinylbenzyl halide compound with hydrotalcites as a dehydrohalogenating agent . The production of the vinylbenzylated phenol compound according to claim 3, wherein the bifunctional phenol compound having one or more monocyclic or polycyclic aromatic nuclei is represented by the following general formula (4) or the following general formula (5). Method.

(Y in the general formula (5) is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, —CH (CH ₃ ) —, an ether bond, a fluorenyl group, a sulfone group, a cyclohexylidene group. , 3,3,5-trimethyl cyclohexylidene _{radical, -C (CF 3) 2 -} , - C (CH 3) (Ph) -, 1,3- phenylene isopropylidene or 1,4-phenylene, An isopropylidene group.) An active ester resin represented by the following general formula (6):

(In the general formula (6), X is a structure represented by the following general formula (7) or the following general formula (8), Ar ¹ and Ar ² may be the same or different, A phenyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms, a naphthyl group, or a naphthyl group having 1 to 3 alkyl groups having 1 to 4 carbon atoms on the aromatic nucleus, and the average number of repetitions n is 0.5-30.)

(In the general formula (7) and the general formula (8), R ^{1 to} R ¹⁵ may be the same or different, are hydrogen or a methyl group, and the average repeating number m is 0.1 to 4, The average repeating number 1 and the average repeating number k are each independently 0.1 to 2. Y in the general formula (8) is a direct bond, —CH ₂ —, —C (CH ₃ ) ₂ —, — CH (CH ₃ ) —, ether bond, fluorenyl group, sulfone group, cyclohexylidene group, 3,3,5-trimethylcyclohexylidene group, —C (CF ₃ ) ₂ —, —C (CH ₃ ) (Ph )- , 1,3-phenylenediisopropylidene group, or 1,4-phenylenediisopropylidene group)   The active ester resin according to claim 5, wherein X in the general formula (6) is a structure represented by the general formula (7).   A vinylbenzylated phenol compound according to claim 1 or 2, a monofunctional phenol compound, and at least one selected from the group consisting of an aromatic nucleus-containing dicarboxylic acid and a halide compound thereof are reacted. And a method for producing an active ester resin.   A thermosetting resin composition comprising the active ester resin according to claim 5 or 6 and an epoxy resin.   Furthermore, the thermosetting resin composition of Claim 8 containing a hardening accelerator.   Furthermore, the thermosetting resin composition of Claim 8 or Claim 9 containing an inorganic filler.   Hardened | cured material of the thermosetting resin composition as described in any one of Claims 8-10.   An interlayer insulating material comprising the thermosetting resin composition according to any one of claims 8 to 10.   A prepreg comprising a semi-cured body of the thermosetting resin composition according to any one of claims 8 to 10 and a fibrous reinforcing member.   A thermosetting resin composition according to any one of claims 8 to 10 is impregnated in a fibrous reinforcing material and heated to heat the thermosetting resin composition impregnated in the fibrous reinforcing material. A method for producing a prepreg characterized by semi-curing.   A composition comprising a plurality of types of compounds in which the number of bonds to the aromatic nucleus of the structural moiety shown in parentheses in the general formula (1) of claim 1 is different, wherein the average number of repetitions of the structural moiety is 0.1 to 4. The composition which is 4.