JPWO2020059625A1 - Phenolic compounds, active ester resins and methods for producing them, and thermosetting resin compositions and cured products thereof. - Google Patents

Abstract

Provided is a thermosetting resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for a signal having a high speed and a high frequency. Specifically, a phenol compound having a vinylbenzyloxy group, a raw material composition for producing an active ester resin containing the phenol compound, a vinylbenzyloxy structure-containing active ester resin using the raw material composition, at both ends. Provided is a thermosetting resin composition containing an active ester resin having a vinylbenzyloxy structure, an active ester resin, and a curing agent.

Description

The present invention relates to a phenol compound, an active ester resin and a method for producing the same, and a thermosetting resin composition and a cured product thereof.

Curable resin compositions typified by epoxy resins are widely used in electronic component applications such as semiconductors and multilayer printed circuit boards because they exhibit excellent heat resistance and insulating properties in the cured products. Among electronic component applications, semiconductor package substrates are becoming thinner, and warpage of the package substrate during mounting has become a problem. High heat resistance is required to suppress the warpage of this package substrate.

In addition, in recent years, the speed and frequency of signals have been increasing in semiconductor package substrates as well. Therefore, it is possible to provide a thermosetting resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for a signal having a high speed and a high frequency. It is desired. As a material capable of achieving a low dielectric constant and a low dielectric loss tangent, a technique of using an active ester compound as a curing agent for an epoxy resin is known (see, for example, Patent Document 1). However, although low dielectric constant and low dielectric loss tangent are realized, heat resistance is insufficient.

Other techniques for producing a thermosetting resin composition having a low dielectric constant and a low dielectric loss tangent include a method of containing an epoxy resin having a low dielectric constant and a low dielectric loss tangent, a method of introducing a cyanate group, a method of containing a polyphenylene ether, and the like. Has been used. However, it may be difficult to satisfy various requirements such as low dielectric constant and low dielectric loss tangent, high heat resistance, reliability, and halogen-free by simply combining these methods.

Under such circumstances, a vinyl benzyl-modified active ester resin has been studied as a resin composition capable of forming a cured product having dielectric properties and heat resistance (see, for example, Patent Documents 2 and 3).

Japanese Unexamined Patent Publication No. 2004-169021 Japanese Unexamined Patent Publication No. 2018-70564 JP-A-2018-44040

The present invention is a phenol compound and an active ester resin capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for a signal having a high speed and a high frequency. An object of the present invention is to provide a thermosetting resin composition containing an active ester resin and a method for producing the same, and a cured product thereof.

As a result of diligent studies, the present inventors have solved the above problems by using an active ester resin containing a vinylbenzyloxy group at the terminal (a resin having an ester structure generated from a phenol group and an aromatic carboxylic acid group). We have found that it can be solved and have completed the present invention.

That is, the present invention provides a phenol compound having one or more vinyl benzyloxy structures, an active ester resin using the active ester resin as a raw material, a curable resin composition containing the active ester resin, and a cured product thereof.

According to the present invention, a phenol compound capable of obtaining an active ester resin capable of forming a cured product having excellent dielectric properties, an active ester resin and a method for producing the same, a thermosetting resin composition containing the active ester resin, and a thermosetting resin composition. The cured product can be provided.

It is a figure which shows the GPC chart of the product obtained in Example 1. FIG. It is a figure which shows the GPC chart of the product obtained in Example 2. FIG.

Hereinafter, one embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications as long as the effects of the present invention are not impaired.

[Phenol compound]
The phenol compound according to this embodiment is a phenol compound having one or more vinylbenzyloxy groups. The vinylbenzyloxy group preferably has a vinylbenzyl group bonded to the phenol compound via an ether bond.

Examples of the vinylbenzyl group include an ethenylbenzyl group, an isopropenylbenzyl group, a normalpropenylbenzyl group and the like. Of these, an ethenylbenzyl group is preferable in terms of industrial availability and curability.

The phenol compound of the present invention may have one or more substituents such as an alkyl group and an aryl group in addition to the vinylbenzyloxy group. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

Examples of the phenol compound having one or more vinylbenzyloxy groups include one or more selected from monocyclic or polycyclic aromatic compounds having one or more phenolic hydroxyl groups. Examples of the phenol compound having one or more vinylbenzyloxy groups include compounds as shown in the following formula.

In the formula, R ₁ is a hydrogen atom or a vinylbenzyl group, and at least one in one molecule is a vinylbenzyl group. R ₂ is a hydrogen atom, an alkyl group or an aryl group, and n in the formulas (1-1), (1-4), (1-5) and (1-6) is an integer of 0 to 4. N in the formula (1-2) is an integer of 0 to 3, and n in the formulas (1-3) and (1-7) is an integer of 0 to 6. A plurality of R _2s may be the same or different. _{It is shown that R 2} in the formulas (1-3) and (1-7) may be bonded to any ring of the naphthalene ring.

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a phenyl group, a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

Further, the phenol compound having one or more vinylbenzyloxy groups may be a compound represented by the following formula (2).

〔式（２）中、ｍは０〜２０の整数である〕

[In equation (2), m is an integer from 0 to 20]

In the above formula (2), Ar ¹ independently represents a phenolic hydroxyl group or a substituent containing a vinylbenzyloxy group, and at least one vinylbenzyloxy group and one phenolic hydroxyl group are present in the formula. Z is an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, an alkylene having 1 to 20 substituted or unsubstituted carbon atoms, a cycloalkylene having 3 to 20 substituted or unsubstituted carbon atoms, and carbon, respectively. It is an arylene having 6 to 20 atoms or an aralkylene having 8 to 20 carbon atoms.

The Ar ¹ is not particularly limited, and examples thereof include residues of aromatic hydroxy compounds represented by the following formulas (3-1) and (3-2).

In formulas (3-1) and (3-2), R ₁ is a hydrogen atom or a vinylbenzyl group, and in the formula (2), at least one is a vinylbenzyl group and at least one is a hydrogen atom. R ₂ is either a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms. n is an integer from 0 to 5. It is shown that the substituent in the formula (3-2) may be bonded to any ring of the naphthalene ring.

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

The alkylene having 1 to 20 carbon atoms in Z in the formula (2) is not particularly limited, but is methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1, Examples thereof include 1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene and hexylene.

The cycloalkylene having 3 to 20 carbon atoms is not particularly limited, but cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following formulas (4-1) to (4). Examples thereof include cycloalkylene represented by -4).

なお、上記式（４−１）〜（４−４）において、「＊」はＡｒ^１と結合する部位を表す。

In the above formulas (4-1) to (4-4), "*" represents a site that binds to ^{Ar 1.}

The arylene having 6 to 20 carbon atoms is not particularly limited, and examples thereof include an arylene represented by the following formula (5).

なお、上記式（５）において、「＊」はＡｒ^１と結合する部位を表す。

In the above formula (5), "*" represents a site that binds to ^{Ar 1.}

The aralkylene having 8 to 20 carbon atoms is not particularly limited, and examples thereof include aralkylene represented by the following formulas (6-1) to (6-5).

なお、式（６−１）〜（６−５）において、「＊」はＡｒ^１と結合する部位を表す。

In the formulas (6-1) to (6-5), "*" represents a site that binds to ^{Ar 1.}

Of the above, Z in the formula (2) is preferably cycloalkylene having 3 to 20 carbon atoms, arylene having 6 to 20 carbon atoms, and aralkylene having 8 to 20 carbon atoms, and is preferably formula (4-4). It is more preferable that it is represented by 3), (4-4), (5), (6-1) to (6-5) from the viewpoint of adhesion and dielectric properties. M in the formula (2) is preferably 0 or an integer of 1 to 10, more preferably 0 to 8, and further preferably 0 to 5 from the viewpoint of solvent solubility.

The phenol compound having a vinylbenzyloxy group may have the structure described in the following formula (7).

〔式（７）中、Ｒ_１はビニルベンジル基であり、ｌは１以上の整数、Ｒ_２は水素原子、アルキル基、アリール基を示す。〕

[In formula (7), R ₁ is a vinylbenzyl group, l is an integer of 1 or more, and R ₂ is a hydrogen atom, an alkyl group, or an aryl group. ]

In formula (7), l is preferably an integer of 1 to 20, more preferably 1 to 15, and even more preferably 1 to 12. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

Among the above, the compounds represented by the formulas (1-3), (1-7), (2) and (7) are used in terms of the solvent solubility of the obtained active ester resin and the dielectric properties of the cured product. Further, among the formulas (1-3), (1-7) and (2), Ar ¹ is a residue of phenol, orthocresol, dimethylphenol, phenylphenol, or α-naphthol or β-naphthol. And Z is of the formulas (4-3), (5), (6-1) to (6-5), and the formula (7) is more preferable. Particularly preferable ones include those represented by the following structural formulas.

In the formula, one R ₁ is a hydrogen atom, the other R ₁ is a vinylbenzyl group, R ₂ is an independent hydrogen atom, an alkyl group or an aryl group, and n is an integer of 0 to 4. Is. At this time, the alkyl group and the aryl group may be the same as described above.

By using the above-mentioned phenol compound having one or more vinylbenzyloxy groups in the production of an active ester resin, an active ester resin having an aryloxycarbonyl group having a vinylbenzyloxy group bonded to the molecular terminal can be obtained.

Therefore, the phenol compound having one or more vinylbenzyloxy groups can be suitably used as a raw material composition for producing an active ester resin. The raw material composition for producing an active ester resin can contain an aromatic carboxylic acid or an acid halide thereof that reacts with a phenol compound to form an ester structure. The aromatic carboxylic acid or its acid halide is preferably an aromatic polycarboxylic acid or an acid halide thereof. Aromatic polycarboxylic acids or acid halides thereof will be described later.

[Method for producing phenol compound having vinylbenzyloxy group]
The method for producing the phenol compound having a vinylbenzyloxy group is not particularly limited, and a conventionally known Williamson ether synthesis method or the like can be used. For example, a phase transfer catalyst such as a vinylbenzyl halide compound, a polyvalent phenol compound, and an ammonium salt is dissolved in an organic solvent such as toluene, methyl isobutyl ketone, or methyl ethyl ketone, and an aqueous sodium hydroxide solution is added thereto while heating. It can be produced by mixing. At this time, by setting the chemical equivalent ratio of the halide group of the vinylbenzyl halide compound to be used and the phenolic hydroxyl group of the phenol compound to less than 1.0, a compound containing both the phenolic hydroxyl group and the vinylbenzyloxy group can be synthesized. Is.

[Active ester resin]
The active ester resin according to the present embodiment has a vinylbenzyloxy structure derived from the phenol compound having the vinylbenzyloxy group at the end of the main skeleton. The vinylbenzyloxy structure is preferably provided at both ends of the main skeleton. As described above, in the present specification, the "active ester resin" means a compound or resin having an ester structure derived from a phenol group and an aromatic carboxylic acid group.

Examples of the active ester resin include an active resin using the above-mentioned phenol compound (a1) having a vinyl benzyloxy group and a compound selected from an aromatic polycarboxylic acid or an acid halide thereof (a2) as a reaction raw material. .. In addition to the above (a1) and (a2), the reaction raw material may contain a compound (a3) having two or more phenolic hydroxyl groups, an aromatic monocarboxylic acid or an acid halide (a4) thereof.

Since the phenol compound (a1) having a vinylbenzyloxy group is as described above, the description thereof is omitted here. As the phenol compound (a1) having a vinylbenzyloxy group, only one kind may be used, or two or more kinds may be used in combination.

Examples of the aromatic polycarboxylic acid or the acid halide (a2) thereof include an aromatic dicarboxylic acid such as isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid; trimesin. Examples include aromatic tricarboxylic acids such as acids and trimellitic acids; pyromellitic acids; and acidified products thereof. These may be used alone or in combination. Of these, isophthalic acid or a mixture of isophthalic acid and terephthalic acid is preferable because the reaction product has an excellent melting point and solvent solubility.

Examples of the compound (a3) having two or more phenolic hydroxyl groups include the following.

In formulas (8-1) to (8-7), R ₂ independently represents a hydrogen atom, an alkyl group, or an aryl group, respectively, and represents (8-1), (8-4), (8-5). , (8-6) is an integer of 1 to 4, n in (8-2) is an integer of 0 to 3, and n in (8-3) and (8-7) is. It is an integer from 0 to 6. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like. The hydroxyl in formula (8-7), R ₂ indicates that may be attached to either ring of the naphthalene ring.

The compound having two or more phenolic hydroxyl groups may be a compound represented by the following formula (9).

〔但し、式（９）中、ｍは０〜２０の整数である。〕

[However, in equation (9), m is an integer from 0 to 20. ]

In the above formula (9), Ar ¹ independently represents a substituent containing a phenolic hydroxyl group, and Z independently represents an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, a substituted or unsubstituted group. It is an alkylene having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene having 3 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or an aralkylene having 8 to 20 carbon atoms.

Ar ¹ is not particularly limited, and examples thereof include residues of aromatic hydroxy compounds represented by the following formulas (10-1) and (10-2).

In formulas (10-1) and (10-2), R ₂ is independently one of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. N in the formula (10-1) is an integer of 0 to 5, and n in the formula (10-2) is an integer of 0 to 7. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

The alkylene having 1 to 20 carbon atoms in Z is not particularly limited, but is methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1 , 2-Dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, hexylene and the like.

The cycloalkylene having 3 to 20 carbon atoms is not particularly limited, but cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following formulas (11-1) to (11). Examples thereof include cycloalkylene represented by -4).

なお、上記式（１１−１）〜（１１−４）において、「＊」はＡｒ^１と結合する部位を表す。

In the above formulas (11-1) to (11-4), "*" represents a site that binds to ^{Ar 1.}

The arylene having 6 to 20 carbon atoms is not particularly limited, and examples thereof include an arylene represented by the following formula (12).

なお、上記式（１２）において、「＊」はＡｒ１と結合する部位を表す。

In the above formula (12), "*" represents a site that binds to Ar1.

The aralkylene having 8 to 20 carbon atoms is not particularly limited, and examples thereof include aralkylene represented by the following formulas (13-1) to (13-5).

なお、式（１３−１）〜（１３−５）において、「＊」はＡｒ^１と結合する部位を表す。

In the formulas (13-1) to (13-5), "*" represents a site that binds to ^{Ar 1.}

Of the above, Z in the formula (9) is preferably a cycloalkylene having 3 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, and an aralkylene having 8 to 20 carbon atoms, preferably from the formula (11-). 3), (11-4), (12), (13-1) to (13-5) are more preferable from the viewpoint of adhesion and dielectric properties. M in the formula (9) is 0 or an integer of 1 to 10, preferably 0 to 8, and preferably 0 to 5 from the viewpoint of solvent solubility.

Further, the compound (a3) having two or more phenolic hydroxyl groups may have the structure described in the following formula (14).

但し式（１４）中、ｌは１以上の整数、Ｒ_２は水素原子、アルキル基、又はアリール基を示す。）

However, in the formula (14), l is an integer of 1 or more, and R ₂ is a hydrogen atom, an alkyl group, or an aryl group. )

In formula (14), l is preferably an integer of 1 to 20, more preferably 1 to 15, and even more preferably 1 to 12. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, a cyclohexyl group and the like. .. Examples of the aryl group include a benzyl group, a naphthyl group, a methoxynaphthyl group and the like.

Among the above, the compounds represented by the formulas (8-7), (9) and (14) are preferable in terms of the solvent solubility and the dielectric properties of the reaction product, and among the formulas (9), Ar. ¹ is a residue of phenol, orthocresol, dimethylphenol, phenylphenol, or α-naphthol, β-naphthol, and Z is a residue of the formulas (11-3), (12-1), (13-1) to (13-1) to (1). 13-5) is preferable, and the compound represented by the formula (16) is more preferable.

Specific examples of the aromatic monocarboxylic acid or its acid halide (a4) include benzoic acid and benzoic acid chloride.

Specific examples of the active ester resin include active resins represented by the following formulas.

The glass transition temperature of the active ester resin is not particularly limited, but is preferably 200 ° C. or lower, more preferably 150 ° C. or lower, and even more preferably 120 ° C. or lower in terms of solvent solubility.

[Manufacturing method of active ester resin]
The method for producing an active ester resin according to the present embodiment includes a step of reacting a phenol compound having a vinylbenzyloxy group with an aromatic polyvalent carboxylic acid or an acid halide thereof. The step of reacting a phenol compound having a vinylbenzyloxy group with an aromatic polyvalent carboxylic acid or an acid halide thereof is not particularly limited, and a known and commonly used synthetic method such as an acetic acid anhydride method, an interfacial polymerization method, or a solution method is used. Can be manufactured. Of these, in order to prevent gelation during synthesis due to polymerization of the vinylbenzyloxy group, it is preferable to produce using an acid halide that can be synthesized at a lower temperature.

[Thermosetting resin composition]
The thermosetting resin composition according to the present embodiment (hereinafter, also simply referred to as “resin composition”) contains the above-mentioned active ester resin and curing agent. Since the active ester resin is as described above, the description thereof is omitted here.

(Hardener)
The curing agent may be any compound that can react with the above-mentioned active ester resin, and various compounds can be used without particular limitation. Examples of the curing agent include a radical polymerization initiator and an epoxy resin. Typical examples of the radical polymerization initiator include azo compounds and organic peroxides, but among them, organic peroxides are preferable because gas is not generated as a by-product. A known epoxy resin can be used. 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, phenol, epoxy of aralkyl resin by xylylene bond such as naphthol. Dicyclopentadiene-modified phenolic resin epoxies, dihydroxynaphthalene-type epoxies, glycidyl ether-type epoxies such as triphenol methane-type epoxies, glycidyl ester-type epoxies, glycidylamine-type epoxies, and other divalent or higher epoxies. Epoxy resins having a group can be mentioned. These epoxy resins may be used alone or in combination of two or more. Among these epoxy resins, it is preferable to use a resin having a large epoxy equivalent, such as a phenolbiphenyl aralkyl type epoxy resin, an epoxidized aralkyl resin having a xylylene bond such as phenol or naphthol, or an epoxidized dicyclopentadiene-modified phenol resin. ..

(Mixing amount)
The blending amount of the active ester resin and the radical polymerization initiator is preferably adjusted to a blending amount that gives a curing time suitable for the molding conditions of the cured product, but from the viewpoint of the cured product characteristics, it is 0 with respect to 100 parts of the resin. The blending amount of about 1 part is preferable. With the above blending amount, the active ester resin is sufficiently cured, and a resin composition that gives a cured product having excellent heat resistance and dielectric properties can be easily obtained. The compounding ratio of the active ester resin and the epoxy resin is preferably such that the equivalent ratio of the ester group contained in the active ester resin and the epoxy group contained in the epoxy resin is in the range of 0.5 to 1.5. It is particularly preferably in the range of 8 to 1.2.

(Curing accelerator)
The resin composition may contain a curing accelerator, if necessary. Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts and the like. In particular, when used as a build-up material or a circuit board, dimethylaminopyridine or imidazole is preferable from the viewpoint of excellent heat resistance, dielectric properties, solder resistance and the like. Especially when used as a semiconductor encapsulant material, it is excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc., so it is triphenylphosphine for phosphorus compounds and 1,8-diazabicyclo for tertiary amines. -[5.4.0] -Undesen (DBU) is preferred.

(Other additive ingredients)
The resin composition may further contain other resin components. Other resin components include, for example, vinyl group-containing compounds such as styrene, acrylic acid, methacrylic acid and their esterified products, cyanate ester resin; bismaleimide resin; benzoxazine resin; allyl represented by triallyl isocyanurate. Group-containing resin: Polyphosphate ester, phosphoric acid ester-carbonate copolymer and the like can be mentioned. Each of these may be used alone, or two or more types may be used in combination.

The blending ratio of these other resin components is not particularly limited, and can be appropriately adjusted according to the desired cured product performance and the like. As an example of the blending ratio, it can be in the range of 1 to 50% by mass in the total resin composition.

The resin composition may contain various additives such as a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, and an emulsifier, if necessary. Examples of the flame retardant include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, and inorganic phosphorus compounds such as phosphoric acid amide; phosphoric acid ester compounds and phosphonic acid. Compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) -10H-9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic organic phosphorus Organophosphorus compounds such as compounds and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazine; silicone oils, silicone rubbers and silicones. Silicone-based flame retardants such as resins; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low melting point glass can be mentioned. When these flame retardants are used, it is preferably in the range of 0.1 to 20% by mass in the total resin composition.

The inorganic filler is blended, for example, when the resin composition is used as a semiconductor encapsulant material. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide and the like. Among them, molten silica is preferable because it is possible to blend a larger amount of the inorganic filler. The molten silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the molten silica and suppress an increase in the melt viscosity of the resin composition, a spherical one is mainly used. preferable. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass with respect to 100 parts by mass of the resin component.

The method for producing the resin composition is not particularly limited, and can be obtained, for example, by uniformly mixing the above-mentioned components at 0 ° C. to 200 ° C. using a stirrer, three rolls, or the like.

[Cured product]
The resin composition can be heat-cured and molded in a temperature range of, for example, about 20 to 250 ° C. by a known and commonly used thermosetting method.
The cured product of the resin composition according to the present embodiment has a heat resistance of 160 ° C. or higher, and can exhibit a low dielectric loss tangent of 3.0 × 10-3 or less at 10 GHz. From the above, it can be preferably used for electronic material applications such as semiconductor package substrates.

[Semiconductor package substrate, etc.]
When the resin composition is used for a substrate such as a semiconductor package substrate, it is generally preferable to add an organic solvent to dilute the resin composition. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. The type and blending amount of the organic solvent can be appropriately adjusted according to the usage environment of the resin composition. For example, in the case of semiconductor package substrate applications, polar solvents having a boiling point of 160 ° C. or lower such as methyl ethyl ketone, acetone, and dimethylformamide may be used. It is preferable to use the non-volatile content at a ratio of 40 to 80% by mass.

As a method of manufacturing a semiconductor package substrate using a resin composition, for example, a method of impregnating a reinforcing base material with a resin composition and curing it to obtain a prepreg can be mentioned. Examples of the reinforcing base material include paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnation amount of the resin composition is not particularly limited, but it is usually preferable to prepare the resin composition so that the resin content in the prepreg is 20 to 80% by mass.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following, "part" and "%" are based on mass unless otherwise specified. The heat resistance measurement and the dielectric loss tangent measurement were performed under the following conditions.

(1) Heat resistance measurement A cured product was cut into a size of 5 mm in width and 54 mm in length, and this was used as a test piece. The heat resistance of this test piece was evaluated using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Leometric Co., Ltd., rectangular tension method: frequency 1 Hz, heating rate 3 ° C./min).
(2) Dissipation factor measurement Dielectric at 1 GHz of a test piece stored in a room at 23 ° C and 50% humidity for 24 hours after being heated and vacuum dried by a cavity resonance method using a network analyzer "E8632C" manufactured by Agilent Technologies, Inc. The loss factor was measured.

Example 1 (Synthesis of vinylbenzyloxy group-containing phenol resin)
200 parts of dicyclopentadiene and phenol heavy addition (hydroxyl equivalent 165 g / eq) and CMS-P (made by AGC Seimicelcal Co., Ltd.) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 98.0 parts of a mixture of metachloromethylstyrene and parachloromethylstyrene), 298 parts of methylisobutylketone (MIBK), 11.9 parts of tetrabutylammonium bromide, and 0.28 parts of 2,4-dinitrophenol were added and stirred. While heating to 60 ° C. Then, 104.9 parts of 49% NaOH was added dropwise over 30 minutes. After holding at 60 ° C. for 1 hour, the temperature was raised to 80 ° C., and then the temperature was maintained for 2 hours. It was diluted with 275 parts of MIBK, neutralized with phosphoric acid until the pH of the lower layer reached 7, and then washed with water by a liquid separation operation to remove salts from the organic layer. The reaction solution was concentrated by heating and reducing pressure to obtain a vinylbenzyloxy group-containing phenol resin (brown solid A-1 having a hydroxyl group equivalent of 406 g / eq). From this result, it was confirmed that the following structures were included. The GPC data of the product is shown in FIG.

Example 2 (Synthesis of vinylbenzyloxy structure-containing active ester resin)
65.0 parts of (A-1), 16.2 parts of isophthalic acid chloride, 322 parts of toluene, 0.16 parts of tetrabutylammonium bromide in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. Was charged and dissolved. The inside of the system was controlled to 60 ° C. or lower, and 33.0 parts of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, stirring was continued for 1.0 hour under this condition. After completion of the reaction, the liquid was separated by standing and the aqueous layer was removed. Further, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, and the solution was allowed to be separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Then, it was dried under hot and reduced pressure to synthesize an active ester resin (A-2) containing the following structure. The GPC data of the product is shown in FIG.

Comparative Example 1
80.1 g (0.5 mol) of 1,6-dihydroxynaphthalene and hydrotalcite (Kyoward manufactured by Kyowa Chemical Industry Co., Ltd.) in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. 156 g of 500SH) and 624 g of toluene were charged and heated to 70 ° C. Then, 76.3 g (0.5 mol) of CMS-P was added dropwise, and then the mixture was heated to 110 ° C. After continuing the reaction for 5 hours, the mixture was cooled and filtered to remove insoluble matter, and a reaction solution (B-1) containing a compound represented by the following formula was obtained. When the reaction solution was analyzed, it was found that the hydroxyl group equivalent was 177 g / eq and the non-volatile content was 16.0%.

Comparative Example 2
442 g of the reaction solution (B-1) obtained in Comparative Example 1, 57.6 g of α-naphthol, and 80.8 g of isophthalic acid chloride were placed in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractional tube, and a stirrer. The mixture was charged and the inside of the system was replaced with nitrogen under reduced pressure to dissolve it. Then, 0.27 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen gas, the temperature inside the system was controlled to 60 ° C. or lower, and 164.8 g of a 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Then, stirring was continued for 1.0 hour under this condition. After completion of the reaction, the liquid was separated by standing and the aqueous layer was removed. Further, water was added to the toluene layer in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes and separated by standing, but the lower layer was emulsified and the liquid separation property was poor. This operation was repeated until the pH of the emulsion layer reached 7. Then, it was dried under hot and reduced pressure to synthesize an active ester resin (B-2) containing a compound having the following structure. A gel-like insoluble matter insoluble in solvent and water was attached to the flask after synthesis.

Comparative Example 3
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer was charged with 488.7 parts of 2,6-xylenol, 281.7 parts of paraxylene glycol dimethyl ether, and 7.7 parts of paratoluenesulfonic acid. The inside of the system was replaced with reduced pressure nitrogen to dissolve it. Then, while performing nitrogen gas purging, the temperature inside the system was raised to 180 ° C. over 3 hours. At this time, the generated volatile matter was appropriately removed. After charging 3.3 parts of 49% NaOH, it was washed with water to remove the catalyst salt. After heating and reducing the pressure to 190 ° C., the residual monomer was removed by steam distillation to obtain a 2,6-xylenol aralkyl resin (B-3). The hydroxyl group equivalent of this resin (B-3) was 199 g / eq.

Comparative Example 4
(B-3) 130 parts, CMS-P 105 parts, methyl isobutyl ketone 235 parts, tetrabutylammonium bromide 9.39 parts, 2, in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. 0.11 part of 4-dinitrophenol was charged and heated to 50 ° C. with stirring. Then, 107 parts of a 49% NaOH aqueous solution was added dropwise over 60 minutes. The internal temperature rose to 70 ° C due to heat generation. After that, it was kept at 70 to 75 ° C. for 5 hours. After neutralizing the lower layer with phosphoric acid until the pH reached 7, the liquid was washed with water by a liquid separation operation, but the lower layer was emulsified and the liquid separation property was poor. The catalyst was removed from the organic layer by extracting the emulsified lower layer. The reaction mixture was concentrated by heating and reducing pressure to obtain a xylenol aralkyl resin (B-4) having a vinylbenzyloxy group. From the results of GPC analysis, no residue of chloromethylstyrene as a raw material was confirmed.

Comparative Example 5
A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer was charged with 433 parts of α-naphthol, 315 parts of paraxylene chloride, and 703 parts of toluene, and the inside of the system was dissolved by reducing pressure with nitrogen. Next, the temperature inside the system was raised to 90 ° C. while performing nitrogen gas purging. 294 parts of a 49% NaOH aqueous solution was added dropwise over 1 hour, and the mixture was kept as it was for 8 hours. 430 parts of water was charged, and the liquid was statically separated to remove the lower layer. 15.0 parts of paratoluenesulfonic acid was charged, and the temperature was raised to 150 ° C. while removing volatile components. After holding for 1 hour, the catalyst was removed by washing with water. Then, it was dried under reduced pressure at 180 ° C. to obtain α-naphthol aralkyl resin (B-5). The hydroxyl group equivalent of this resin (B-5) was 217 g / eq.

Comparative Example 6
(B-5) 130 parts, CMS-P96.0 parts, methyl isobutyl ketone 226 parts, tetrabutylammonium bromide 9.04 parts, in a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionation tube, and a stirrer. 0.20 parts of 2,4-dinitrophenol was charged and heated to 45 ° C. with stirring. Then, 97.8 parts of a 49% NaOH aqueous solution was added dropwise over 60 minutes. The internal temperature rose to 60 ° C due to heat generation. After that, it was kept at 55 to 65 ° C. for 8 hours. After neutralizing the lower layer with phosphoric acid until the pH reached 7, the mixture was washed with water by a liquid separation operation to remove salts from the organic layer. The reaction solution was concentrated by heating and reducing pressure to obtain a naphthol aralkyl resin (B-6) having a vinylbenzyloxy group. From the results of GPC analysis, no residue of chloromethylstyrene as a raw material was confirmed.

Curable Composition Using Resins Obtained in Example 2 and Comparative Examples 2, 4 and 6 and Curing The Curable Composition was obtained by blending the compositions shown in Table 1 below. This was poured into a 1.6 mm thick mold and heated at 120 ° C. for 120 minutes and 180 ° C. for 60 minutes to cure.

As shown in Table 1, the cured product obtained from the resin composition using the resin obtained in Example 2 had a high heat resistance of 167 ° C., and the dielectric loss tangent at 1 GHz was 2.8 ×. It showed a low dielectric loss tangent of ^10-3.

On the other hand, the cured product obtained from the resin composition using the resin obtained in Comparative Example 2 showed a low dielectric loss ^{tangent of 2.9 × 10 -3 at 1 GHz, but at 120 ° C.} It had low heat resistance.

Further, the cured product obtained from the resin composition using the resin obtained in Comparative Example 4 had a high heat resistance of 173 ° C., but the dielectric loss tangent at 1 GHz was 5.1 × 10 ^-3. It showed a high dielectric loss tangent.

Further, the cured product obtained from the resin composition using the resin obtained in Comparative Example 6 does not have a very high heat resistance of 150 ° C., and the dielectric loss tangent at 1 GHz is 7.5 × 10 ^{−. It} showed a high dielectric loss tangent of 3.

Claims (13)

A phenol compound having one or more vinylbenzyloxy structures. The phenolic compound according to claim 1, which is a compound represented by any of the formulas (1-1) to (1-8).

[In the formula, R ₁ is a hydrogen atom or a vinylbenzyl group, and at least one in one molecule is a vinylbenzyl group. R ₂ is a hydrogen atom, an alkyl group or an aryl group, the formula (1-1), (1-4), (1-5), (1-6), n in (1-8) is 0 It is an integer of 4, n in the equation (1-2) is an integer of 0 to 3, and n in the equations (1-3) and (1-7) is an integer of 0 to 6. A plurality of R _2s may be the same or different. _{It is shown that R 2} in the formulas (1-3) and (1-7) may be bonded to any ring of the naphthalene ring]. A raw material composition for producing an active ester resin, which contains the phenol compound according to claim 1 or 2. A vinylbenzyloxy structure-containing active ester resin using the raw material composition according to claim 3. The active ester resin according to claim 4, which has a vinylbenzyloxy structure at both ends. The active ester resin according to claim 4 or 5, which has a structure represented by the formula (I).

(In the formula (I), n represents an integer of 0 to 20, X represents the reaction residue of the phenol compound containing a vinylbenzyloxy group, and Y represents the reaction residue of the polyfunctional phenol compound.) The active ester resin according to claim 6, which is a resin having a structure represented by the following formula (I-1).

A method for producing an active ester resin, wherein the phenol compound according to claim 1 or 2 is reacted with an aromatic polycarboxylic acid or a derivative thereof as an essential reaction raw material. A thermosetting resin composition containing the active ester resin and the curing agent according to any one of claims 4 to 7. The thermosetting resin composition according to claim 9, which is used for an electronic component substrate. A cured product of the thermosetting resin composition according to claim 9 or 10. A package substrate using the thermosetting resin composition according to claim 8 or 10. The package substrate according to claim 12, which is a semiconductor package substrate.

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