TW202021938A - Phenol compound, active ester resin, production method for active ester resin, thermosetting resin composition, and cured product of thermosetting resin composition - Google Patents

Abstract

Provided is a thermosetting resin composition that makes it possible to obtain a cured product that maintains a substantially low dielectric constant but also has a substantially low dielectric loss tangent, even for high-speed, high-frequency signals. Specifically provided are: a phenol compound that has a vinylbenzyloxy group; a raw material composition that contains the phenol compound and is for producing an active ester resin; an active ester resin that contains a vinylbenzyloxy structure and is formed using the raw material composition; an active ester resin that has a vinylbenzyloxy structure at either end; and a thermosetting resin composition that contains an active ester resin and a curing agent.

Description

Phenolic compound, active ester resin and manufacturing method thereof, and thermosetting resin composition and cured product thereof

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

The curable resin composition represented by epoxy resin exhibits excellent heat resistance and insulation properties in its cured product, so it is widely used in electronic parts such as semiconductors and multilayer printed circuit boards. Among the uses of electronic parts, semiconductor packaging substrates are becoming thinner, and the bending of the packaging substrate during mounting becomes a problem. In order to suppress the bending of the package substrate, high heat resistance is pursued.

In addition, in recent years, semiconductor packaging substrates have also developed high-speed and high-frequency signals. Therefore, it is desired to provide a thermosetting resin composition that can obtain a cured product that exhibits a sufficiently low dielectric tangent while maintaining a sufficiently low dielectric constant for high-speed and high-frequency signals. As a material that can realize low dielectric constant and low dielectric tangent, a technique of using an active ester compound as a hardener for epoxy resin is known (for example, refer to Patent Document 1). However, although low dielectric constant and low dielectric tangent are achieved, heat resistance is insufficient.

As other technologies for making thermosetting resin compositions with low dielectric constant and low dielectric tangent, methods that contain epoxy resins with low dielectric constant and low dielectric tangent, methods of introducing isocyanate groups, and methods containing poly The method of phenyl ether, etc. However, sometimes a simple combination of these methods is difficult to meet various requirements such as low dielectric constant and low dielectric tangent, high heat resistance, reliability, and halogen-free.

Under such circumstances, a vinylbenzyl modified active ester resin is considered as a resin composition capable of forming a cured product having dielectric properties and heat resistance (for example, refer to Patent Documents 2 to 3). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2004-169021 A [Patent Document 2] Japanese Patent Application Publication No. 2018-70564 [Patent Document 3] Japanese Patent Application Publication No. 2018-44040

[The problem to be solved by the invention]

The subject of the present invention is to provide a phenol compound, an active ester resin and a method for producing the same, and a thermosetting resin composition containing an active ester resin and a cured product thereof. The cured product exhibits a sufficiently low dielectric tangent while maintaining a sufficiently low dielectric rate. [Means to solve the problem]

The inventors of the present invention have conducted intensive research and found that the above-mentioned problems can be solved by using an active ester resin containing a vinylbenzyloxy group at the end (resin having an ester structure formed from a phenol group and an aromatic carboxylic acid group). To complete the present invention.

That is, the present invention provides a phenol compound having one or more vinylbenzyloxy structures, an active ester resin using this as a raw material, a curable resin composition containing the active ester resin, and a cured product thereof. [Effect of invention]

According to the present invention, it is possible to provide a phenol compound, an active ester resin and a method for producing the same, and a thermosetting resin composition containing an active ester resin and a cured product thereof. The phenol compound can form a cured product with excellent dielectric properties. Active ester resin.

Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented by adding appropriate changes within a range that does not impair the effects of the present invention.

[Phenolic compound] The phenol compound of this embodiment is a phenol compound having one or more vinylbenzyloxy groups. The vinylbenzyloxy group is preferably bonded to a vinylbenzyl group via a phenol compound and an ether bond.

Examples of the vinyl benzyl group include vinyl benzyl, isopropenyl benzyl, n-propenyl benzyl, and the like. From the viewpoints of industrial availability and hardening properties, among them, vinylbenzyl is preferred.

In addition to the vinylbenzyloxy group, the phenol compound of the present invention may have one or more substituents such as an alkyl group and an aryl group. Examples of the alkyl group include: 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. As an aryl group, a benzyl group, a naphthyl group, a methoxynaphthyl group, etc. are mentioned.

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 of the following formula.

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

Examples of the aforementioned alkyl group include an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. As said aryl group, a phenyl group, a benzyl group, a naphthyl group, a methoxynaphthyl group, etc. are mentioned.

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

[式(2)中，m為0～20之整數]。

[In formula (2), m is an integer of 0-20].

In the above formula (2), Ar ¹ each independently represents a substituent containing a phenolic hydroxyl group or a vinylbenzyloxy group, where at least one vinylbenzyloxy group and a phenolic hydroxyl group each exist, and Z is each independently Oxygen atom, sulfur atom, ketone group, sulfonyl group, substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, 6 to carbon atoms 20 arylene groups, or aralkylene groups with 8 to 20 carbon atoms.

There are no particular limitations on Ar ¹ , and examples include residues of aromatic hydroxy compounds described in the following formulas (3-1) and (3-2).

In the formulas (3-1) and (3-2), R ₁ is a hydrogen atom or a vinyl benzyl group, and in the formula (2), at least one is a vinyl benzyl group, and at least one is a hydrogen atom. R ₂ is any one of a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. n is an integer of 0-5. The substituent in the formula (3-2) represents any ring that can be bonded to the naphthalene ring.

Examples of the aforementioned alkyl group include an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. As an aryl group, a benzyl group, a naphthyl group, a methoxynaphthyl group, etc. are mentioned.

The alkylene group having 1 to 20 carbon atoms in Z in the aforementioned formula (2) is not particularly limited, and examples thereof include methylene, ethylene, propylene, and 1-methylmethylene , 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-Methyl propylene, 2-methyl propylene, pentylene, hexylene, etc.

The cycloalkylene having 3 to 20 carbon atoms is not particularly limited, and examples include cyclopropylidene, cyclobutylene, cyclopentyl, cyclohexyl, cyclopentyl, and heptene Group, and cycloalkylene groups represented by the following formulas (4-1) to (4-4).

此外，在上述式(4-1)～(4-4)中，「*」表示與Ar¹ 鍵結之部位。

Further, the ~ (4-4), a "*" represented by the above formula (4-1) bond and Ar ¹ knot site.

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

此外，在上述式(5)中，「*」表示與Ar¹ 鍵結之部位。

In addition, in the above-mentioned formula (5), "*" represents a site bonded to Ar ¹ .

The aralkylene having 8 to 20 carbon atoms is not particularly limited, but aralkylene represented by the following formulas (6-1) to (6-5) and the like can be mentioned.

此外，在式(6-1)～(6-5)中，「*」表示與Ar¹ 鍵結之部位。

Further, in the formula (6-1) to (6-5), the "*" portion indicates ^a bond to Ar knot.

Among the above, Z in 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. From the viewpoint of adhesion and dielectric properties, the formulas (4-3), (4-4), (5), (6-1) to (6-5) are more preferable. In formula (2), m is preferably 0 or an integer of 1-10, more preferably 0-8, and more preferably 0-5 from the viewpoint of solvent solubility.

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

[式(7)中，R₁ 為乙烯基苄基，l為1個以上之整數，R₂ 表示氫原子、烷基、芳基]。

[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 1-20, more preferably 1-15, and still more preferably an integer of 1-12. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is mentioned, preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. As an aryl group, a benzyl group, a naphthyl group, a methoxynaphthyl group, etc. are mentioned.

From the standpoint of the solvent solubility of the resulting active ester resin and the dielectric properties of the cured product, the above are expressed by using formulas (1-3), (1-7), (2), (7) The compound is preferred. Furthermore, in formulas (1-3), (1-7), (2), Ar ¹ is phenol, o-cresol, dimethylphenol, phenylphenol, or α-naphthol , The residue of β-naphthol, and Z is more preferably those of formula (4-3), (5), (6-1) to (6-5), and formula (7). 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} each independently a hydrogen atom, an alkyl group or an aryl group, and n is an integer of 0-4. In this case, examples of the alkyl group and aryl group are the same as those described above.

By using the above-mentioned phenol compound having one or more vinylbenzyloxy groups in the manufacture of active ester resins, an active ester having an aryloxycarbonyl group with a vinylbenzyloxy group bonded to the molecular end can be obtained Resin.

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

[Production method of phenol compound having vinylbenzyloxy group] The production method of 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, it is possible to dissolve vinylbenzyl halide compounds, polyphenol compounds, and phase transfer catalysts such as ammonium salts in organic solvents such as toluene, methyl isobutyl ketone, and methyl ethyl ketone. It is manufactured by adding sodium hydroxide aqueous solution and mixing while heating. At this time, by setting the stoichiometric ratio of the halogenated group of the vinylbenzyl halide compound to the phenolic hydroxyl group of the phenol compound to be less than 1.0, it is possible to synthesize containing both phenolic hydroxyl group and vinylbenzyloxy group. The compound.

[Active Ester Resin] The active ester resin of this embodiment has a vinylbenzyloxy structure derived from the phenol compound having a vinylbenzyloxy group at the end of the main skeleton. The vinylbenzyloxy structure is preferably present at both ends of the main skeleton. In addition, as described above, in this specification, "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 active resins using a compound selected from the above-mentioned vinylbenzyloxy-containing phenol compound (a1) and aromatic polycarboxylic acid or its acid halide (a2) as a reaction 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).

Since the phenol compound (a1) having a vinylbenzyloxy group is as described above, the description is omitted here. The phenol compound (a1) which has a vinylbenzyloxy group may use only 1 type, and may use 2 or more types together.

The aromatic polycarboxylic acid or its acid halide (a2) includes, for example, aromatics such as isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid Dicarboxylic acids; aromatic tricarboxylic acids such as trimesic acid and trimellitic acid; pyromellitic acid; and these acyl chlorides. These can be used alone or in combination. From the viewpoint of the melting point of the reactant and the excellent solvent solubility, isophthalic acid or a mixture of isophthalic acid and terephthalic acid is preferred.

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

In formulas (8-1) to (8-7), R ₂ each independently represents a hydrogen atom, an alkyl group, or an aryl group, (8-1), (8-4), (8-5), (8- 6) n 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 an integer of 0 to 6. Examples of the aforementioned alkyl group include an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. As said aryl group, a benzyl group, a naphthyl group, a methoxynaphthyl group, etc. are mentioned. In addition, the hydroxyl group and R ₂ in formula (8-7) represent any ring that can be bonded to the naphthalene ring.

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

[其中，式(9)中，m為0～20之整數]。

[Wherein, in formula (9), m is an integer of 0-20].

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

There are no particular limitations on Ar ¹ , and examples include residues of aromatic hydroxy compounds described in the following formulas (10-1) and (10-2).

In formulas (10-1) and (10-2), R _{2 is} each independently any 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 formula (10-1) is an integer of 0 to 5, and n in formula (10-2) is an integer of 0 to 7. Examples of the aforementioned alkyl group include an alkyl group having 1 to 20 carbon atoms, and preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. As said aryl group, a benzyl group, a naphthyl group, a methoxynaphthyl group, etc. are mentioned.

The alkylene group having 1 to 20 carbon atoms in Z is not particularly limited, and examples include methylene, ethylene, propylene, 1-methylmethylene, 1,1-di Methyl methylene, 1-methyl ethylene, 1,1-dimethyl ethylene, 1,2-dimethyl ethylene, propylene, butyl, 1-methyl ethylene Group, 2-methylpropylene, pentylene, hexylene, etc.

The cycloalkylene having 3 to 20 carbon atoms is not particularly limited, and examples include cyclopropylidene, cyclobutylene, cyclopentyl, cyclohexyl, cyclopentyl, and heptene Groups, and cycloalkylene groups represented by the following formulas (11-1) to (11-4).

此外，在上述式(11-1)～(11-4)中，「*」表示與Ar¹ 鍵結之部位。

Further, in the - (11-4), the "*" represented by the above formula (11-1) with Ar ¹ bond sites knot.

The aforementioned arylene group having 6 to 20 carbon atoms is not particularly limited, but an arylene group represented by the following formula (12) and the like can be mentioned.

此外，在上述式(12)中，「*」表示與Ar¹ 鍵結之部位。

In addition, in the above-mentioned formula (12), "*" represents a site bonded to Ar ¹ .

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

此外，在式(13-1)～(13-5)中，「*」表示與Ar¹ 鍵結之部位。

Further, in the formula (13-1) - (13-5), the "*" portion indicates ^a bond to Ar knot.

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

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

其中，式(14)中，l為1個以上之整數，R₂ 表示氫原子、烷基、或芳基)。

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

In the formula (14), l is preferably 1-20, more preferably 1-15, and still more preferably an integer of 1-12. As the alkyl group, an alkyl group having 1 to 20 carbon atoms is mentioned, preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, n-hexyl, and cyclohexyl. As an aryl group, a benzyl group, a naphthyl group, a methoxynaphthyl group, etc. are mentioned.

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

As aromatic monocarboxylic acid or its acid halide (a4), specifically, benzoic acid, chlorinated benzoic acid, etc. are mentioned.

As a specific example of an active ester resin, the active resin represented by the following formula is mentioned, for example.

The glass transition temperature of the active ester resin is not particularly limited, but from the standpoint of solvent solubility, it is preferably 200°C or less, more preferably 150°C or less, and more preferably 120°C or less.

[Manufacturing method of active ester resin] The manufacturing method of the active ester resin of this embodiment has a step of reacting a phenol compound having a vinylbenzyloxy group with an aromatic polycarboxylic acid or its acid halide. The step of reacting a phenol compound having a vinylbenzyloxy group with an aromatic polycarboxylic acid or its acid halide is not particularly limited, and it can be obtained by well-known and customary synthesis methods such as acetic anhydride method, interfacial polymerization method, and solution method. manufacture. Among them, in order to prevent gelation during synthesis due to polymerization of vinylbenzyloxy groups, it is preferable to use acid halides that can be synthesized at lower temperatures.

[Thermosetting resin composition] The thermosetting resin composition of the present embodiment (hereinafter also simply referred to as "resin composition") contains the above-mentioned active ester resin and curing agent. The description of the active ester resin is omitted here because it is as described above.

(hardener) As the curing agent, any compound can be used as long as it can react with the above-mentioned active ester resin, and various compounds can be used without particular limitation. As an example of a curing agent, a radical polymerization initiator and an epoxy resin can be mentioned. As the radical polymerization initiator, azo compounds and organic peroxides can be cited as representative examples. Among them, organic peroxides are preferred because they do not generate gas as a by-product. Known epoxy resins can be used. Examples include: bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, phenol biphenyl aralkyl Type epoxy resin, phenol, naphthol and other aralkyl resin epoxides, dicyclopentadiene-modified phenol resin epoxides, dihydroxy naphthalene type epoxy resins, three Glycidyl ether type epoxy resins such as phenolmethane type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and other epoxy resins having an epoxy group having a valence of more than two. These epoxy resins may be used alone or in combination of two or more kinds. Among these epoxy resins, epoxides of aralkyl resins such as phenol biphenyl aralkyl type epoxy resins, phenol, naphthol and other aralkyl resins are modified by epoxides and dicyclopentadiene. Resins with large epoxy equivalents such as epoxides of phenol resins are preferred.

(Blending amount) The blending amount of the active ester resin and the radical polymerization initiator is preferably adjusted to the blending amount of the curing time suitable for the molding conditions of the cured product, and from the viewpoint of the characteristics of the cured product, it is relative to The blending amount of 100 parts of resin is preferably 0 to 1 part. If set to the above blending amount, curing of the active ester resin proceeds sufficiently, and a resin composition that provides a cured product with excellent heat resistance and dielectric properties can be easily obtained. In addition, the blending 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 to the epoxy group contained in the epoxy resin is in the range of 0.5 to 1.5, preferably 0.8 to 1.2 The range is particularly good.

(Hardening accelerator) The resin composition may contain a hardening accelerator as needed. Examples of hardening accelerators include phosphorus-based compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acid, and amine salts. Especially when used as build-up materials and circuit boards, from the viewpoint of excellent heat resistance, dielectric properties, solder resistance, etc., dimethylaminopyridine and imidazole are preferred . Especially when used as a semiconductor sealing material, from the standpoint of excellent curability, heat resistance, electrical properties, and humidity resistance, the phosphorus-based compound is preferably triphenylphosphine, and the tertiary amine is preferably 1 , 8-Diazibicyclo-[5.4.0]-undecene (DBU) is preferred.

樹脂；異三聚氰酸三烯丙酯所代表之含有烯丙基之樹脂；多磷酸酯、磷酸酯-碳酸酯共聚物等。此等可分別單獨使用，亦可併用2種以上。(Other additional components) The resin composition may further contain other resin components. As other resin components, for example, vinyl-containing compounds such as styrene, acrylic acid, methacrylic acid, and esters thereof, cyanate resin; bismaleimide resin; benzo

Resin; allyl-containing resin represented by triallyl isocyanurate; polyphosphate, phosphate-carbonate copolymer, etc. These may be used individually, respectively, and may use 2 or more types together.

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

化合物、三聚氰酸化合物、異三聚氰酸化合物、啡噻

等氮系阻燃劑；聚矽氧油、聚矽氧橡膠、聚矽氧樹脂等聚矽氧系阻燃劑；金屬氫氧化物、金屬氧化物、金屬碳酸鹽化合物、金屬粉、硼化合物、低熔點玻璃等無機阻燃劑等。當使用此等阻燃劑時，係以全樹脂組成物中0.1～20質量%的範圍為較佳。The resin composition can contain various additives such as flame retardants, inorganic fillers, silane coupling agents, mold release agents, pigments, emulsifiers, etc. as needed. Examples of flame retardants include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; inorganic phosphorus compounds such as amide phosphate; phosphate ester compounds, phosphonic acid compounds, and phosphinic acid. Compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5 -Dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene -10-Oxide and other cyclic organophosphorus compounds, and organic phosphorus compounds such as derivatives that react with compounds such as epoxy resin and phenol resin;

Compounds, cyanuric acid compounds, isocyanuric acid compounds, phenanthrene

And other nitrogen-based flame retardants; silicone oil, silicone rubber, silicone resin and other silicone-based flame retardants; metal hydroxides, metal oxides, metal carbonate compounds, metal powder, boron compounds, Inorganic flame retardants such as low melting point glass. When these flame retardants are used, the range of 0.1-20% by mass in the entire resin composition is preferred.

The inorganic filler is blended, for example, when the resin composition is used for semiconductor sealing materials. Examples of inorganic fillers include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, fused silica is preferred because more inorganic fillers can be blended. The fused silica can be crushed or spherical. In order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the resin composition, it is preferable to mainly use the spherical shape. Furthermore, in order to increase the blending amount of the spherical silica, it is better to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably blended in the range of 0.5 to 95 parts by mass relative to 100 parts by mass of the resin component.

The preparation method of the resin composition is not particularly limited, and for example, it can be obtained by uniformly mixing the above-mentioned components using a stirring device, a three-roller, etc., for example, at 0°C to 200°C.

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

[Semiconductor package substrate, etc.] When the resin composition is used for substrate applications such as semiconductor packaging substrates, it is usually preferable to dilute and use by blending an organic solvent. Examples of organic solvents include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxy propanol, cyclohexanone, methyl cyrus, and diethylene glycol ethyl ether. Acetate, propylene glycol monomethyl ether acetate, etc. The type and blending amount of organic solvents can be adjusted appropriately according to the environment in which the resin composition is used. For example, for semiconductor packaging substrates, polar solvents with boiling points below 160°C such as methyl ethyl ketone, acetone, and dimethylformamide are used. Preferably, it is more preferable to use the non-volatile component in a ratio of 40 to 80% by mass.

The method of manufacturing a semiconductor package substrate using a resin composition includes, for example, a method of impregnating a reinforcing base material with a resin composition and curing it to obtain a prepreg. Examples of the reinforcing base material include paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, and glass fiber gauze cloth. The amount of impregnation of the resin composition is not particularly limited, but it is usually preferably prepared so that the resin component of the prepreg becomes 20 to 80% by mass. [Example]

Examples are disclosed below to explain the present invention more specifically, but the present invention is not limited by these examples. The following "parts" and "%" are quality standards unless otherwise specified. In addition, the heat resistance measurement and the dielectric tangent measurement were performed under the following conditions.

(1) Heat resistance measurement The cured product was cut into a size of 5 mm in width and 54 mm in length, and used as a test piece. A viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheometric Co., Ltd., rectangular tension method: frequency 1 Hz, heating rate 3°C/min) was used for this test piece to evaluate the heat resistance. (2) Dielectric tangent measurement Using a network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd., and using the cavity resonance method, the dielectric tangent at 1 GHz of a test piece stored in a room at 23° C. and a humidity of 50% for 24 hours was measured by the cavity resonance method.

Example 1 (Synthesis of phenol resin containing vinylbenzyloxy) Put 200 parts of the complex adduct of dicyclopentadiene and phenol (hydroxy equivalent 165g/eq) and 98.0 parts of CMS-P into the flask equipped with thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. (AGC SEIMI CHEMICAL Co., Ltd., a mixture of m-chloromethylstyrene and p-chloromethylstyrene), 298 parts of methyl isobutyl ketone (MIBK), 11.9 parts of tetrabutylammonium bromide, 0.28 Part of 2,4-dinitrophenol was heated to 60°C while stirring. Next, 104.9 parts of 49% NaOH was dropped in 30 minutes. After keeping at 60°C for 1 hour, after raising the temperature to 80°C, keeping it for 2 hours. After diluted with 275 parts of MIBK and neutralized with phosphoric acid until the pH of the lower layer became 7, it was washed with water by a liquid separation operation to remove salt from the organic layer. The reaction liquid was concentrated by heating and decompression operation to obtain a vinylbenzyloxy-containing phenol resin (brown solid A-1 with a hydroxyl equivalent of 406 g/eq). From this result, it was confirmed that the following structure was included. In addition, the GPC data of the product is shown in Fig. 1.

Example 2 (Synthesis of active ester resin containing vinylbenzyloxy structure) Put 65.0 parts of (A-1), 16.2 parts of chlorinated isophthalic acid, 322 parts of toluene, and 0.16 parts of tetrabutyl in a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. Ammonium bromide to dissolve it. The system was controlled to below 60°C, and 33.0 parts of 20% sodium hydroxide aqueous solution was dropped in 3 hours. Next, continue stirring for 1.0 hour under these conditions. After the completion of the reaction, the liquid was separated and the water layer was removed. Furthermore, water was poured into the toluene layer in which the reactant was dissolved, stirred and mixed for about 15 minutes, and left to stand for liquid separation to remove the water layer. Repeat this operation until the pH of the water layer reaches 7. Thereafter, it was dried under heat and reduced pressure to synthesize an active ester resin (A-2) containing the following structure. In addition, the GPC data of the product is shown in FIG. 2.

Comparative example 1 Put 80.1 g (0.5 mol) of 1,6-dihydroxynaphthalene and 156 g of hydrotalcite (made by Kyowa Chemical Industry Co., Ltd.) into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. KYOWAAD 500SH), 624g of toluene, heated to 70°C. Next, after dripping 76.3 g (0.5 mol) of CMS-P, it heated to 110 degreeC. After continuing the reaction for 5 hours, it was cooled and filtered to remove insoluble materials, and a reaction liquid (B-1) containing a compound represented by the following formula was obtained. The reaction solution was analyzed, and the hydroxyl equivalent was 177g/eq and the non-volatile content was 16.0%.

Comparative example 2 Put 442g of the reaction solution (B-1) obtained in Comparative Example 1, 57.6g of α-naphthol, and 80.8g of chlorinated metabenzene into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. Diformic acid is substituted with nitrogen under reduced pressure in the system to dissolve it. Thereafter, 0.27 g of tetrabutylammonium bromide was dissolved, and while nitrogen flushing was performed, the system was controlled to 60° C. or lower, and 164.8 g of 20% sodium hydroxide aqueous solution was dropped in 3 hours. Next, continue stirring for 1.0 hour under these conditions. After the completion of the reaction, the liquid was separated and the water layer was removed. Furthermore, water was poured into the toluene layer in which the reactant was dissolved, stirred and mixed for about 15 minutes, and allowed to stand for liquid separation. However, the lower layer was emulsified, resulting in poor liquid separation. Repeat this operation until the pH of the emulsion layer becomes 7. Thereafter, it was dried under heat and reduced pressure to synthesize an active ester resin (B-2) containing a compound having the following structure. After the synthesis of the flask, there is a gel-like insoluble matter that does not dissolve in solvent or water.

Comparative Example 3 Put 488.7 parts of 2,6-xylenol, 281.7 parts of p-xylene glycol dimethyl ether, and 7.7 parts of p-toluene sulfonate into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. Acid dissolves by replacing the pressure with nitrogen in the system. Next, while performing nitrogen purge, it took 3 hours to raise the temperature in the system to 180°C. At this time, appropriately remove the generated volatile components. After adding 3.3 parts of 49% NaOH, wash with water to remove the catalyst salt. After heating and reducing pressure to 190°C, residual monomers were removed by steam distillation to obtain 2,6-xylenol aralkyl resin (B-3). The hydroxyl equivalent of this resin (B-3) was 199 g/eq.

Comparative Example 4 Put 130 parts of (B-3), 105 parts of CMS-P, 235 parts of methyl isobutyl ketone, 9.39 parts of tetramethyl ketone into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. Butylammonium bromide and 0.11 part of 2,4-dinitrophenol were heated to 50°C while stirring. Secondly, 107 parts of 49% NaOH aqueous solution were dropped in 60 minutes. The internal temperature rises to 70°C due to heat. After that, keep it at 70-75°C for 5 hours. After the pH of the lower layer was neutralized with phosphoric acid to 7 and then washed with water by a liquid separation operation, the lower layer was emulsified and the liquid separation property was poor. The catalyst is removed from the organic layer by extracting the emulsified lower layer. The reaction liquid was concentrated by heating and decompression operation to obtain a xylenol aralkyl resin (B-4) having a vinylbenzyloxy group. As a result of GPC analysis, no residue of chloromethylstyrene as the raw material was confirmed.

Comparative example 5 Put 433 parts of α-naphthol, 315 parts of p-xylene dichloride, and 703 parts of toluene into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionation tube, and stirrer, and depressurize the system with nitrogen. Replace to dissolve. Next, the temperature in the system was increased to 90°C while performing nitrogen purge. It took 1 hour to drop 294 parts of 49% NaOH aqueous solution, and keep it for 8 hours. Put in 430 parts of water and let it stand for liquid separation to remove the lower layer. 15.0 parts of p-toluenesulfonic acid was added, and the temperature was raised to 150°C while removing volatile components. After keeping for 1 hour, wash with water to remove the catalyst. Thereafter, the α-naphthol aralkyl resin (B-5) was obtained by drying under reduced pressure at 180°C. The hydroxyl equivalent of this resin (B-5) was 217 g/eq.

Comparative Example 6 Put 130 parts of (B-5), 96.0 parts of CMS-P, 226 parts of methyl isobutyl ketone, 9.04 parts of tetramethyl ketone into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. Butylammonium bromide and 0.20 parts of 2,4-dinitrophenol were heated to 45°C while stirring. Next, 97.8 parts of 49% NaOH aqueous solution was dropped over 60 minutes. The internal temperature rises to 60°C due to heat. After that, keep it at 55-65°C for 8 hours. After neutralizing with phosphoric acid until the pH of the lower layer became 7, it was washed with water by a liquid separation operation to remove salt from the organic layer. The reaction liquid was concentrated by heating and decompression operation to obtain a naphthol aralkyl resin (B-6) having a vinylbenzyloxy group. As a result of GPC analysis, no residue of chloromethylstyrene as the raw material was confirmed.

The curable composition of the resin obtained in Example 2 and Comparative Examples 2, 4, and 6 and its curing The composition shown in Table 1 below was blended to obtain a curable composition. This was poured into a 1.6 mm thick template, heated at 120°C for 120 minutes, and heated at 180°C for 60 minutes to harden it.

[Table 1]

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

In contrast, the cured product obtained from the resin composition using the resin obtained in Comparative Example 2 exhibits a low dielectric tangent of 2.9×10 ^-3 at 1 GHz, but has a low heat resistance of 120°C.

In addition, although the cured product obtained from the resin composition using the resin obtained in Comparative Example 4 has a high heat resistance of 173°C, it exhibits a high dielectric tangent of 5.1×10 ^-3 at 1 GHz.

Furthermore, the cured product obtained from the resin composition using the resin obtained in Comparative Example 6 has not so high heat resistance at 150°C, and exhibits a high dielectric tangent of 7.5×10 ^-3 at 1 GHz.

no.

Fig. 1 is a diagram showing a GPC chart of the product obtained in Example 1. FIG. 2 is a diagram showing a GPC chart of the product obtained in Example 2. FIG.

no.

Claims (13)

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

[In the formula, R ₁ is a hydrogen atom or a vinyl benzyl group, and at least one of a molecule is a vinyl benzyl group; R ₂ is a hydrogen atom, an alkyl group or an aryl group, and the formula (1-1), (1-4 ), (1-5), (1-6), (1-8), n is an integer from 0 to 4, n in formula (1-2) is an integer from 0 to 3, formula (1-3 ), in (1-7) n is an integer of 0 to 6; a plurality of R ₂ may be the same or is different; the formula (1-3), in (1-7) may be bonded to R ₂ represents In any ring of the naphthalene ring]. A raw material composition for producing an active ester resin, which contains a phenol compound as claimed in claim 1 or 2. An active ester resin containing a vinylbenzyloxy structure, which is formed by using the raw material composition of claim 3. The active ester resin of claim 4 has a vinylbenzyloxy structure at both ends. Such as the active ester resin of claim 4 or 5, which has the structure shown in formula (I),

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

. A method for producing an active ester resin, which involves reacting the phenol compound of claim 1 or 2 as an essential reaction material with an aromatic polycarboxylic acid or its derivative. A thermosetting resin composition containing the active ester resin according to any one of claims 4 to 7 and a hardener. Such as the thermosetting resin composition of claim 9, which is used for electronic component substrates. A cured product which is a cured product of the thermosetting resin composition of claim 9 or 10. A package substrate using the thermosetting resin composition of claim 9 or 10. Such as the package substrate of claim 12, which is a semiconductor package substrate.

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