阅读说明：本技术 酚化合物、活性酯树脂及其制造方法、以及热固性树脂组合物及其固化物 (Phenol compound, active ester resin and method for producing same, and thermosetting resin composition and cured product thereof ) 是由 迫雅树 林弘司 于 2019-09-12 设计创作，主要内容包括：提供一种热固性树脂组合物,其能够获得即使对于高速化、高频化的信号也维持充分低的介电常数且表现充分低的介电损耗角正切的固化物。具体而言,提供一种具有乙烯基苄氧基的酚化合物、含有该酚化合物的活性酯树脂制造用原料组合物、使用该原料组合物而成的含有乙烯基苄氧基结构的活性酯树脂、在两末端具有乙烯基苄氧基结构的活性酯树脂、含有活性酯树脂和固化剂的热固性树脂组合物。(Provided is a thermosetting resin composition which can obtain a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for signals of higher speeds and higher frequencies. Specifically disclosed are a phenol compound having a vinylbenzyloxy group, a raw material composition for producing an active ester resin containing the phenol compound, an active ester resin having a vinylbenzyloxy structure obtained by using the raw material composition, an active ester resin having vinylbenzyloxy structures at both terminals, and a thermosetting resin composition containing the active ester resin and a curing agent.)

1. A phenol compound having 1 or more vinylbenzyloxy structures.

2. The phenol compound according to claim 1, which is a compound represented by any one of formulae (1-1) to (1-8),

in the formula, R₁Is a hydrogen atom or a vinylbenzyl group, 1 molecule of which has at least one R₁Is vinylbenzyl; r₂Is a hydrogen atom, an alkyl group or an aryl group; n in the formulas (1-1), (1-4), (1-5), (1-6) and (1-8) is an integer of 0-4, n in the formula (1-2) is an integer of 0-3, and n in the formulas (1-3) and (1-7) is an integer of 0-6; plural R's present₂R in the formulae (1-3), (1-7), which are optionally the same or different₂Represents any ring optionally bonded to a naphthalene ring.

3. A raw material composition for producing an active ester resin, which contains the phenol compound according to claim 1 or 2.

4. An activated ester resin containing a vinylbenzyloxy structure, which is obtained by using the raw material composition according to claim 3.

5. The active ester resin according to claim 4, which has a vinylbenzyloxy structure at both ends.

6. The active ester resin according to claim 4 or 5, which has a structure represented by formula (I),

in the formula (I), n represents an integer of 0-20; x represents a reactive residue of a vinylbenzyloxy-containing phenol compound; y represents a reactive residue of a polyfunctional phenol compound.

7. The active ester resin according to claim 6, which is a resin having a structure represented by the following formula (I-1),

8. a process for producing an active ester resin, wherein the phenol compound according to claim 1 or 2 and an aromatic polycarboxylic acid or a derivative thereof are reacted as essential reaction raw materials.

9. A thermosetting resin composition comprising the active ester resin according to any one of claims 4 to 7 and a curing agent.

10. The thermosetting resin composition according to claim 9, which is used for an electronic component substrate.

11. A cured product of the thermosetting resin composition according to claim 9 or 10.

12. A packaging substrate using the thermosetting resin composition according to claim 8 or 10.

13. The package substrate of claim 12, which is a semiconductor package substrate.

Technical Field

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.

Background

Curable resin compositions represented by epoxy resins are widely used for electronic parts such as semiconductors and multilayer printed boards because cured products thereof exhibit excellent heat resistance and insulation properties. In the application of electronic components, the semiconductor package substrate is gradually thinned, and the warpage of the package substrate at the time of mounting becomes a problem. High heat resistance is required to suppress the warpage of the package substrate.

In addition, in recent years, the speed and frequency of signals have been increased in semiconductor package substrates. Accordingly, it is desired to provide a thermosetting resin composition capable of obtaining a cured product which exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for signals of high speed and high frequency. 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 (for example, see patent document 1). However, although a low dielectric constant and a low dielectric loss tangent are achieved, the heat resistance is insufficient.

As another technique for producing a thermosetting resin composition having a low dielectric constant and a low dielectric loss tangent, 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 are used. However, when these methods are simply combined, it is sometimes difficult to satisfy various requirements such as low dielectric constant and low dielectric loss tangent, high heat resistance, reliability, and no halogen.

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

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2004-16901921

Patent document 2: japanese patent laid-open publication No. 2018-70564

Patent document 3: japanese patent laid-open publication No. 2018-44040

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a phenol compound, an active ester resin, a method for producing the same, a thermosetting resin composition containing an active ester resin, and a cured product thereof, which are capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for signals at high speeds and high frequencies.

Means for solving the problems

The inventors of the present invention have repeated intensive studies and found that: the above problems can be solved by using an active ester resin having a vinylbenzyloxy group at the terminal (a resin having an ester structure formed from a phenol group and an aromatic carboxylic acid group), and the present invention has been completed.

Namely, the present invention provides a phenol compound having 1 or more vinylbenzyloxy structures, an active ester resin using the phenol compound as a raw material, a curable resin composition containing the active ester resin, and a cured product thereof.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided a phenol compound capable of giving an active ester resin capable of forming a cured product excellent in dielectric characteristics, 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.

Drawings

FIG. 1 is a GPC chart showing the product obtained in example 1.

FIG. 2 is a GPC chart showing the product obtained in example 2.

Detailed Description

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 within a range not impairing the effects of the present invention.

[ phenol Compound ]

The phenol compound described in this embodiment is a phenol compound having 1 or more vinylbenzyloxy groups. The vinylbenzyloxy group is preferably bonded to the vinylbenzyl group via a phenol compound and an ether bond.

Examples of the vinylbenzyl group include vinylbenzyl group, isopropenylbenzyl group, and n-propenylbenzyl group. Among them, from the viewpoint of industrial availability and curability, a vinylbenzyl group is preferable.

The phenol compound of the present invention may have 1 or more substituents such as an alkyl group and an aryl group in addition to the vinylbenzyloxy group. Examples of the alkyl group include alkyl groups 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 n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a n-hexyl group, and a cyclohexyl group. Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl.

The phenol compound having 1 or more vinylbenzyloxy groups includes 1 or more selected from monocyclic or polycyclic aromatic compounds having one or more phenolic hydroxyl groups. Examples of the phenol compound having 1 or more vinylbenzyloxy groups include compounds represented by the following formulae.

In the formula, R₁Is a hydrogen atom or a vinylbenzyl group, 1 molecule of which has at least one R₁Is vinylbenzyl. R₂Is a hydrogen atom, an alkyl group or an aryl group, n in the formulae (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 formulae (1-3) and (1-7) is an integer of 0 to 6. Plural R's present₂Optionally the same or different. R in the formulae (1-3) and (1-7)₂Represents an arbitrary ring optionally bonded to a naphthalene ring。

Examples of the alkyl group include alkyl groups 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 n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a n-hexyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group, a benzyl group, a naphthyl group, and a methoxynaphthyl group.

Further, the phenol compound having 1 or more vinylbenzyloxy groups may be a compound represented by the following formula (2).

[ in the formula (2), m is an integer of 0 to 20 ]

In the above formula (2), Ar¹Each independently represents a substituent containing a phenolic hydroxyl group or a vinylbenzyloxy group, wherein at least one of the vinylbenzyloxy group and the phenolic hydroxyl group is present, and each Z independently represents an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, 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.

As Ar¹Examples of the residue include, but are not particularly limited to, residues of aromatic hydroxy compounds represented by the following formulas (3-1) and (3-2).

In the formulae (3-1) and (3-2), R₁Is a hydrogen atom or a vinylbenzyl group, at least one R in the formula (2)₁Is vinylbenzyl, at least one R₁Is a hydrogen atom. R₂The alkyl group 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 to 5. The substituent in the formula (3-2) represents an arbitrary ring optionally bonded to a naphthalene ring.

Examples of the alkyl group include alkyl groups 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 n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a n-hexyl group, and a cyclohexyl group. Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl.

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

The cycloalkylene group having 3 to 20 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and cycloalkylene groups represented by the following formulae (4-1) to (4-4).

In the above formulae (4-1) to (4-4), "+" represents the same as Ar¹The site of bonding.

The 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).

In the above formula (5), "+" represents the same as Ar¹The site of bonding.

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

In the formulae (6-1) to (6-5), "+" indicates the presence of Ar¹The site of bonding.

Among the above, Z in the formula (2) is preferably a 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, and more preferably a group represented by the formula (4-3), (4-4), (5), (6-1) to (6-5) from the viewpoints of adhesion and dielectric characteristics. 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 a structure represented by the following formula (7).

[ in formula (7), R₁Is vinylbenzyl, l represents an integer of 1 or more, R₂Represents a hydrogen atom, an alkyl group or an aryl group. Angle (c)

In the formula (7), l is preferably an integer of 1 to 20, more preferably 1 to 15, and further preferably 1 to 12. Examples of the alkyl group include alkyl groups 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 n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a n-hexyl group, and a cyclohexyl group. Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl.

Among the above, from the viewpoint of the solvent solubility of the obtained active ester resin and the dielectric characteristics of the cured product, the compounds represented by the formulae (1-3), (1-7), (2) and (7) are preferably used, and further, Ar in the formulae (1-3), (1-7) and (2) is more preferably used¹Is a residue of phenol, o-cresol, dimethylphenol, phenylphenol, alpha-naphthol, beta-naphthol, and Z is a compound of the formulae (4-3), (5), (6-1) to (6-5), and a compound of the formula (7). Particularly preferred compounds include those represented by the following structural formulae.

In the formula, one R₁Is a hydrogen atom, another R₁Is vinylbenzyl, R₂Each independently represents a hydrogen atom, an alkyl group or an aryl group, and n is an integer of 0 to 4. In this case, examples of the alkyl group and the aryl group include the same groups as described above.

By using the phenol compound having 1 or more vinylbenzyloxy groups as described above for the production of an activated ester resin, an activated ester resin having an aryloxycarbonyl group in which a vinylbenzyloxy group is bonded to a molecular terminal can be obtained.

Therefore, the above phenol compound having 1 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 may contain an aromatic carboxylic acid or an acid halide thereof which can react with a phenol compound to form an ester structure. The aromatic carboxylic acid or an acid halide thereof is preferably an aromatic polycarboxylic acid or an acid halide thereof. The aromatic polycarboxylic acid or acid halide thereof is as described later.

[ Process for producing phenol Compound having a vinylbenzyloxy group ]

The method for producing a phenol compound having a vinylbenzyloxy group is not particularly limited, and conventionally known Williamson ether synthesis methods and the like can be used. The catalyst can be produced by dissolving a vinylbenzyl halide compound, a polyphenol compound, and a phase transfer catalyst such as an ammonium salt in an organic solvent such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, adding an aqueous sodium hydroxide solution thereto, and mixing them while heating. In this case, when the stoichiometric ratio of the halogen group of the vinylbenzyl halide compound to the phenolic hydroxyl group of the phenol compound to be used is less than 1.0, a compound containing both the phenolic hydroxyl group and the vinylbenzyloxy group can be synthesized.

[ active ester resin ]

The active ester resin according to the present embodiment has a vinylbenzyloxy structure derived from the phenol compound having a vinylbenzyloxy group at the terminal of the main skeleton. Vinylbenzyloxy structures are preferably present at both ends of the main backbone. As described above, in the present specification, the "active ester resin" refers to a compound or a resin having an ester structure derived from a phenol group and an aromatic carboxylic acid group.

The activated ester resin may be one obtained by using a compound selected from the group consisting of the above-mentioned phenol compound having a vinylbenzyloxy group (a1) and the aromatic polycarboxylic acid or the acid halide thereof (a2) as a reaction raw material. The reaction raw materials may contain a compound (a3) having 2 or more phenolic hydroxyl groups, an aromatic monocarboxylic acid or an acid halide thereof (a4) in addition to the above (a1) and (a 2).

The vinylbenzyloxy-containing phenol compound (a1) is not described here because it is as described above. The phenol compound (a1) having a vinylbenzyloxy group may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Examples of the aromatic polycarboxylic acid or acid halide thereof (a2) include aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid and 2, 6-naphthalenedicarboxylic acid; aromatic tricarboxylic acids such as trimesic acid and trimellitic acid; pyromellitic acid; and acid chlorides thereof. They may be used alone or in combination. Among them, isophthalic acid or a mixture of isophthalic acid and terephthalic acid is preferable from the viewpoint of excellent melting point of the reactant and solvent solubility.

Examples of the compound (a3) having 2 or more phenolic hydroxyl groups include the following compounds.

In the formulae (8-1) to (8-7), R₂Each independently represents a hydrogen atom, an alkyl group or an aryl group; n in (8-1), (8-4), (8-5) and (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 an integer of 0 to 6. Examples of the alkyl group include alkyl groups having 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 and iso-propylPropyl, n-butyl, t-butyl, pentyl, n-hexyl, cyclohexyl and the like. Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl. In the formula (8-7), the hydroxyl group and R₂Represents any ring optionally bonded to a naphthalene ring.

The compound having 2 or more phenolic hydroxyl groups may be a compound represented by the following formula (9).

Wherein m in formula (9) is an integer of 0 to 20. Angle (c)

In the above formula (9), Ar¹Each independently represents a substituent containing a phenolic hydroxyl group; z is each independently an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, 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.

As Ar¹Examples of the residue include, but are not particularly limited to, residues of aromatic hydroxy compounds represented by the following formulae (10-1) and (10-2).

In the formulae (10-1) and (10-2), R₂Each independently is 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 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 alkyl groups 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 n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a n-hexyl group, and a cyclohexyl group. Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl.

The alkylene group having 1 to 20 carbon atoms in Z is not particularly limited, and examples thereof include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a1, 1-dimethylmethylene group, a 1-methylethylene group, a1, 1-dimethylethylene group, a1, 2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, and a hexylene group.

The cycloalkylene group having 3 to 20 carbon atoms is not particularly limited, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cycloheptyl group, and cycloalkylene groups represented by the following formulae (11-1) to (11-4).

In the above formulae (11-1) to (11-4), "+" represents the same as Ar¹The site of bonding.

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

In the above formula (12), "+" indicates the presence of Ar¹The site of bonding.

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

In the formulae (13-1) to (13-5), "+" indicates the presence of Ar¹The site of bonding.

Among the above, Z in the formula (9) is preferably a 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, and more preferably a group represented by the formula (11-3), (11-4), (12), (13-1) to (13-5) from the viewpoints of adhesion and dielectric characteristics. 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.

The compound (a3) having 2 or more phenolic hydroxyl groups may have a structure represented by the following formula (14).

(wherein, in the formula (14), l represents an integer of 1 or more; R₂Represents a hydrogen atom, an alkyl group or an aryl group. )

In the formula (14), l is preferably an integer of 1 to 20, more preferably 1 to 15, and further preferably 1 to 12. Examples of the alkyl group include alkyl groups 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 n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a pentyl group, a n-hexyl group, and a cyclohexyl group. Examples of the aryl group include benzyl, naphthyl, and methoxynaphthyl.

Among the above, from the viewpoint of the solvent solubility and dielectric properties of the reaction product, compounds represented by the formulae (8-7), (9) and (14) are preferable, and further, Ar in the formula (9) is preferable¹Is a residue of phenol, o-cresol, dimethylphenol, phenylphenol or α -naphthol, β -naphthol, and Z is a compound of the formulae (11-3), (12-1), (13-1) to (13-5), and more preferably a compound represented by the formula (16).

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

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

The glass transition temperature of the active ester resin is not particularly limited, but is preferably 200 ℃ or lower, more preferably 150 ℃ or lower, and further preferably 120 ℃ or lower, from the viewpoint of solvent solubility.

[ Process for producing 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 polycarboxylic acid or an acid halide thereof. The step of reacting the vinylbenzyloxy-containing phenol compound with the aromatic polycarboxylic acid or its acid halide is not particularly limited, and the compound can be produced by a known and conventional synthesis method such as an acetic anhydride method, an interfacial polymerization method, or a solution method. Among them, in order to prevent gelation during synthesis due to polymerization of vinylbenzyloxy group, it is preferable to use an acid halide compound 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 active ester resin and a curing agent. The active ester resin is as described above, and therefore, the description thereof is omitted here.

(curing agent)

The curing agent is not particularly limited as long as it is a compound capable of reacting with the active ester resin, and various compounds can be used. Examples of the curing agent include a radical polymerization initiator and an epoxy resin. Typical examples of the radical polymerization initiator include an azo compound and an organic peroxide, and among these, an organic peroxide is preferred because a gas is not generated as a by-product. The epoxy resin may be a known one. Examples thereof include epoxy resins having an epoxy group of 2 or more members, such as bisphenol a type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, phenol biphenyl aralkyl type epoxy resins, epoxy compounds of aralkyl resins based on a xylylene bond such as phenol and naphthol, epoxy compounds of dicyclopentadiene modified phenol resins, glycidyl ether type epoxy resins such as dihydroxynaphthalene type epoxy resins and triphenylphenolmethane type epoxy resins, glycidyl ester type epoxy resins, and glycidyl amine type epoxy resins. These epoxy resins may be used alone, or 2 or more kinds may be used in combination. Among these epoxy resins, resins having a large epoxy equivalent such as phenol biphenyl aralkyl type epoxy resins, epoxides of aralkyl resins based on a xylylene bond such as phenol and naphthol, and epoxides of dicyclopentadiene-modified phenol resins are preferably used.

(compounding amount)

The amount of the active ester resin and the radical polymerization initiator to be blended is preferably adjusted to a blending amount whose curing time is suitable for the molding conditions of the cured product, and is preferably 0 to 1 part per 100 parts of the resin from the viewpoint of the properties of the cured product. When the amount is set as described above, the active ester resin is sufficiently cured, and a resin composition which can provide a cured product having excellent heat resistance and dielectric properties can be easily obtained. Further, regarding the blending ratio of the active ester resin and the epoxy resin, the equivalent ratio of the ester group contained in the active ester resin to the epoxy group contained in the epoxy resin is preferably in the range of 0.5 to 1.5, and particularly preferably in the range of 0.8 to 1.2.

(curing accelerators)

The resin composition may contain a curing accelerator as required. Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, lewis acids, and ammonia complexes. In particular, when used as a build-up material or a circuit board, dimethylaminopyridine and imidazole are preferable from the viewpoint of excellent heat resistance, dielectric properties, solder resistance, and the like. In particular, when used as a semiconductor sealing material, triphenylphosphine is preferable as the phosphorus compound, and 1, 8-diazabicyclo- [5.4.0] -undecene (DBU) is preferable as the tertiary amine, from the viewpoint of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.

(other additional ingredients)

The resin composition may further contain other resin components. Examples of the other resin components include vinyl group-containing compounds such as styrene, acrylic acid, methacrylic acid, and esters thereof; cyanate ester resin; bismaleimide resin; a benzoxazine resin; allyl group-containing resins represented by triallyl isocyanurate; polyphosphates, phosphate-carbonate copolymers, and the like. These may be used alone or in combination of 2 or more.

The blending ratio of these other resin components is not particularly limited, and may be appropriately adjusted according to the desired properties of the cured product and the like. The compounding ratio may be in the range of 1 to 50% by mass of the total resin composition.

The resin composition may contain various additives such as a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, as required. Examples of the flame retardant include ammonium phosphates such as red phosphorus, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium orthophosphate, and ammonium polyphosphate; inorganic phosphorus compounds such as phosphoric acid amide; a cyclic organic phosphorus compound such as a phosphate compound, a phosphonic acid compound, a phosphinic acid compound, a phosphine oxide compound, a phosphane compound, an organic nitrogen-containing phosphorus compound, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, or 10- (2, 7-dihydroxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, or an organic phosphorus compound such as a derivative obtained by reacting the cyclic organic phosphorus compound with a compound such as an epoxy resin or a phenol resin; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, and the like; silicone flame retardants such as silicone oil, silicone rubber, and silicone resin; inorganic flame retardants such as metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When these flame retardants are used, the amount of the flame retardants is preferably in the range of 0.1 to 20% by mass based on the total resin composition.

The inorganic filler is compounded when the resin composition is used for a semiconductor sealing material, for example. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among these, fused silica is preferable because more inorganic filler can be blended. As the fused silica, any of crushed and spherical fused silica can be used, but it is preferable to mainly use a spherical material in order to increase the amount of the fused silica to be blended and to suppress an increase in melt viscosity of the resin composition. Further, in order to increase the amount of the spherical silica to be blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass per 100 parts by mass of the resin component.

The method for producing the resin composition is not particularly limited, and can be obtained by uniformly mixing the above components at, for example, 0 to 200 ℃ using a stirring apparatus, a three-roll mill, or the like.

[ cured product ]

The resin composition can be molded by heating and curing it by a known and conventional heat curing method at a temperature of, for example, about 20 to 250 ℃.

The cured product of the resin composition according to the present embodiment has heat resistance of 160 ℃ or higher, and can exhibit a dielectric loss tangent of as low as 3.0X 10 at 10GHz^-3The following dielectric loss tangent. In summary, the present invention can be preferably 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 package substrates, it is generally preferable to use the resin composition diluted with an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The type and amount of the organic solvent can be suitably adjusted depending on the use environment of the resin composition, and for example, in the use for a semiconductor package substrate, a polar solvent having a boiling point of 160 ℃ or less such as methyl ethyl ketone, acetone, or dimethylformamide is preferably used in such a proportion that the nonvolatile content is 40 to 80 mass%.

Examples of a method for producing a semiconductor package substrate using the resin composition include a method in which a reinforcing base material is impregnated with the resin composition and cured to obtain a prepreg. Examples of the reinforcing base material include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnation amount of the resin composition is not particularly limited, and it is usually preferably prepared so that the resin component in the prepreg is 20 to 80 mass%.

Examples

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

(1) Measurement of Heat resistance

The cured product was cut into a size of 5mm in width and 54mm in length to prepare a test piece. The heat resistance of the test piece was evaluated by using a viscoelasticity measuring apparatus (DMA: solid viscoelasticity measuring apparatus "RSAII" manufactured by Rheometric corporation) and a normal tension (rectangular tension) method with a frequency of 1Hz and a temperature rise rate of 3 ℃/min.

(2) Dielectric loss tangent measurement

The dielectric loss tangent at 1GHz of the test piece after being dried under heating and vacuum and stored in a room at 23 ℃ and a humidity of 50% for 24 hours was measured by a cavity resonance method using a network analyzer E8362C manufactured by Agilent Technologies.

Example 1 (Synthesis of a phenol resin containing a vinylbenzyloxy group)

Into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer were charged 200 parts of an addition polymer of dicyclopentadiene and phenol (hydroxyl equivalent: 165g/eq), 98.0 parts of CMS-P (a mixture of m-chloromethyl styrene and P-chloromethyl styrene manufactured by AGC SEIMI CHEMICAL Co., Ltd.), 298 parts of methyl isobutyl ketone (MIBK), 11.9 parts of tetrabutylammonium bromide and 0.28 part of 2, 4-dinitrophenol, and the mixture was heated to 60 ℃ with stirring. Then, 104.9 parts of 49% NaOH was added dropwise over 30 minutes. After keeping at 60 ℃ for 1 hour, the temperature was raised to 80 ℃ and then kept for 2 hours. The reaction mixture 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 mixture was concentrated under reduced pressure by heating to obtain a vinylbenzyloxy-containing phenol resin (A-1 which was a brown solid having a hydroxyl group equivalent of 406 g/eq). From the results, it was confirmed that the following structures were contained. GPC data of the product is shown in fig. 1.

Example 2 (Synthesis of an active ester resin having a vinylbenzyloxy structure)

A flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer was charged with (A-1)65.0 parts, isophthaloyl dichloride 16.2 parts, toluene 322 parts and tetrabutylammonium bromide 0.16 part to dissolve them. The temperature in the system was controlled to 60 ℃ or lower, and 33.0 parts of a 20% aqueous solution of sodium hydroxide was added dropwise over 3 hours. Subsequently, stirring was continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand for liquid separation to remove the water layer. Further, water was poured into the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for about 15 minutes, and then the mixture was allowed to stand for liquid separation to remove the water layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, the resultant was dried under reduced pressure and heat to synthesize an active ester resin (A-2) having the following structure. GPC data of the product is shown in fig. 2.

Comparative example 1

80.1g (0.5 mol) of 1, 6-dihydroxynaphthalene, 156g of hydrotalcite (KYOWAAD 500SH, manufactured by Kyowa chemical industries, Ltd.) and 624g of toluene were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and heated to 70 ℃. Then, after CMS-P76.3g (0.5 mol) was added dropwise, the mixture was heated to 110 ℃. After the reaction was continued for 5 hours, the insoluble matter was removed by cooling and filtration to obtain a reaction liquid (B-1) containing a compound represented by the following formula. As a result of analysis of the reaction mixture, the hydroxyl equivalent was 177g/eq and the nonvolatile matter was 16.0%.

Comparative example 2

442g of the reaction liquid (B-1) obtained in comparative example 1, 57.6g of alpha-naphthol, and 80.8g of isophthaloyl dichloride were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve the reaction liquid. Thereafter, 0.27g of tetrabutylammonium bromide was dissolved, and the temperature in the system was controlled to 60 ℃ or lower while purging with nitrogen gas, and 164.8g of a 20% aqueous solution of sodium hydroxide was added dropwise over 3 hours. Subsequently, stirring was continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was allowed to stand for liquid separation and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for about 15 minutes to carry out liquid separation by standing, but the lower layer was liquefied and had poor liquid separation properties. This operation was repeated until the pH of the emulsion layer reached 7. Thereafter, the reaction mixture was dried under reduced pressure and heat, and an active ester resin (B-2) containing a compound having the following structure was synthesized. The resultant flask was adhered with a gel-like insoluble substance insoluble in a solvent/water.

Comparative example 3

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, 488.7 parts of 2, 6-xylenol, 281.7 parts of p-xylylene glycol dimethyl ether and 7.7 parts of p-toluenesulfonic acid were charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve them. Then, the temperature in the system was raised to 180 ℃ over 3 hours while purging with nitrogen gas. At this time, the volatile components generated are appropriately removed. After 3.3 parts of 49% NaOH were added, the mixture was washed with water to remove catalyst salts. After heating at 190 ℃ under reduced pressure, residual monomers were removed by steam distillation to obtain 2, 6-xylenol aralkyl resin (B-3). The hydroxyl equivalent of the resin (B-3) was 199 g/eq.

Comparative example 4

130 parts of (B-3), 105 parts of CMS-P, 235 parts of methyl isobutyl ketone, 9.39 parts of tetrabutylammonium bromide and 0.11 part of 2, 4-dinitrophenol were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and heated to 50 ℃ with stirring. Subsequently, 107 parts of 49% aqueous NaOH solution were added dropwise over 60 minutes. The internal temperature rose to 70 ℃ due to the exotherm. Thereafter, the mixture was held at 70 to 75 ℃ for 5 hours. After the lower layer was neutralized with phosphoric acid until the pH reached 7, the lower layer was washed with water by a liquid separation operation, but the lower layer was milk-liquefied, and the liquid separation property was poor. The catalyst is removed from the organic layer by removing the lower layer which has been emulsified. The reaction mixture was concentrated under reduced pressure by heating, to obtain a xylenol aralkyl resin (B-4) having a vinylbenzyloxy group. According to the results of GPC analysis, the raw material chloromethyl styrene was not confirmed to remain.

Comparative example 5

In a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube, and a stirrer, 433 parts of α -naphthol, 315 parts of p-xylene dichloride, and 703 parts of toluene were charged, and the inside of the system was replaced with nitrogen under reduced pressure to dissolve the compounds. Subsequently, the temperature in the system was raised to 90 ℃ while purging with nitrogen gas. 294 parts of 49% aqueous NaOH solution were added dropwise over 1 hour and the mixture was kept as it was for 8 hours. 430 parts of water was added thereto, and the mixture was allowed to stand for liquid separation to remove the lower layer. 15.0 parts of p-toluenesulfonic acid was charged, and the temperature was raised to 150 ℃ while removing volatile components. After 1 hour of holding, the catalyst was removed by washing with water. Thereafter, the resulting mixture was dried under reduced pressure at 180 ℃ to obtain an α -naphthol aralkyl resin (B-5). The hydroxyl equivalent of the resin (B-5) was 217 g/eq.

Comparative example 6

130 parts of (B-5), 96.0 parts of CMS-P, 226 parts of methyl isobutyl ketone, 9.04 parts of tetrabutylammonium bromide and 0.20 part of 2, 4-dinitrophenol were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and heated to 45 ℃ with stirring. Then, 97.8 parts of 49% aqueous NaOH solution was added dropwise over 60 minutes. The internal temperature rose to 60 ℃ due to the exotherm. Thereafter, the mixture was held at 55 to 65 ℃ for 8 hours. After neutralization with phosphoric acid until the lower layer had reached pH 7, water washing was performed by a liquid separation operation to remove salts from the organic layer. The reaction mixture was concentrated under reduced pressure by heating to obtain a vinylbenzyloxy-containing naphthol aralkyl resin (B-6). According to the results of GPC analysis, the raw material chloromethyl styrene was not confirmed to remain.

Curable composition using resin obtained in example 2 and comparative examples 2,4, and 6, and curing thereof

The curable composition was obtained by compounding the components having the compositions shown in table 1 below. The mixture was poured into a 1.6mm thick mold, and cured by heating at 120 ℃ for 120 minutes and 180 ℃ for 60 minutes.

[ Table 1]

As shown in Table 1, the cured product obtained from the resin composition using the resin obtained in example 2 had heat resistance as high as 167 ℃ and exhibited a dielectric loss tangent at 1GHz as low as 2.8X 10^-3The dielectric loss tangent of (1).

On the other hand, the cured product obtained from the resin composition using the resin obtained in comparative example 2 showed a dielectric loss tangent at 1GHz as low as 2.9X 10^-3But has heat resistance as low as 120 ℃.

Furthermore, the resin composition using the resin obtained by comparative example 4 obtained the cured product with high heat resistance of 173 ℃, but showed a dielectric loss tangent at 1GHz as high as 5.1X 10^-3The dielectric loss tangent of (1).

Furthermore, the cured product obtained from the resin composition using the resin obtained in comparative example 6 had not so high heat resistance as 150 ℃ and exhibited a dielectric loss tangent at 1GHz as high as 7.5X 10^-3The dielectric loss tangent of (1).