TWI813767B - Raw material composition for producing active ester resin, active ester resin and production method thereof, thermosetting resin composition and cured product thereof - Google Patents

Abstract

The present invention provides a thermosetting resin composition that can obtain a cured product that exhibits a sufficiently low dielectric tangent while maintaining a sufficiently low dielectric constant in response to high-speed and high-frequency signals. Specifically, the invention provides a phenol compound having a vinylbenzyloxy group, a raw material composition for producing an active ester resin containing the phenolic compound, and an active ester containing a vinylbenzyloxy structure produced using the raw material composition. Resin, an active ester resin having a vinyl benzyloxy group structure at both ends, and a thermosetting resin composition containing an active ester resin and a hardener.

Description

Raw material composition for producing active ester resin, active ester resin and its manufacturing method, and thermosetting resin composition and its cured product

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

Curable resin compositions represented by epoxy resins are widely used in electronic components such as semiconductors and multilayer printed circuit boards because their cured products exhibit excellent heat resistance and insulation properties. Among electronic component applications, semiconductor package substrates are becoming thinner, and bending of the package substrate during mounting has become 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 provide 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 using an active ester compound as a hardener for epoxy resin is known (for example, see Patent Document 1). However, although low dielectric constant and low dielectric tangent are achieved, the heat resistance is insufficient.

As other technologies for producing thermosetting resin compositions with low dielectric constant and low dielectric tangent, methods using epoxy resins containing low dielectric constant and low dielectric tangent, methods of introducing isocyanate groups, methods containing polyethylene Methods of phenylene ether, etc. However, sometimes it is difficult to simply combine these methods to meet various requirements such as low dielectric constant and low dielectric tangent, high heat resistance, reliability, and halogen-free.

Under such circumstances, 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). [Prior technical literature] [Patent Document]

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

[Problem to be solved by the invention]

The subject of the present invention is to provide a phenolic compound, an active ester resin and a manufacturing method thereof, as well as a thermosetting resin composition containing an active ester resin and a cured product thereof. The phenolic compound can obtain high-speed and high-frequency signals. It also maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric tangent in a hardened material. [Means used to solve problems]

The inventors of the present invention conducted extensive research and found that the above problems can be solved by using an active ester resin (a resin having an ester structure composed of a phenol group and an aromatic carboxylic acid group) containing a vinyl benzyloxy group at the terminal end. To complete the present invention.

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

According to the present invention, it is possible to provide a phenolic compound capable of forming a cured product having excellent dielectric properties, an active ester resin and a method for producing the same, as well as a thermosetting resin composition containing an active ester resin and a cured product thereof. Active ester resin.

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 implemented by adding appropriate changes within a range that does not hinder 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 the vinylbenzyl group through the phenol compound and the ether bond.

Examples of the vinyl benzyl group include vinyl benzyl group, isopropenyl benzyl group, n-propenyl benzyl group, and the like. Among them, vinyl benzyl group is preferred from the viewpoint of industrial availability and curability.

The phenolic compound of the present invention may have one or more substituents such as an alkyl group and an aryl group in addition to the vinyl benzyloxy group. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 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, cyclohexyl, and the like. Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group, and the like.

Examples of the phenolic compound having one or more vinylbenzyloxy groups include one or more types 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 represented by the following formulas.

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

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 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, cyclohexyl, and the like. Examples of the aryl group include phenyl, benzyl, naphthyl, methoxynaphthyl, and the like.

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

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

In the above formula (2), Ar ¹ independently represents a substituent containing a phenolic hydroxyl group or a vinyl benzyloxy group. In the formula, there is at least one vinylbenzyloxy group and a phenolic hydroxyl group, and Z independently represents Oxygen atom, sulfur atom, ketone group, styrene group, substituted or unsubstituted alkylene group with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkylene group with 3 to 20 carbon atoms, 6 to 6 carbon atoms 20 arylyl group, or arylalkyl group with 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 (3-1) and (3-2).

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

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 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, cyclohexyl, and the like. Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group, and the like.

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, and 1-methylmethylene. , 1,1-dimethylmethylene, 1-methylethylidene, 1,1-dimethylethylidene, 1,2-dimethylethylidene, propylene, butylene, 1-methyl propylene group, 2-methyl propylene group, pentylene group, hexylene group, etc.

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

In addition, in the above formulas (4-1) to (4-4), "*" represents a site bonded to Ar ¹ .

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

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

The 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 addition, in formulas (6-1) to (6-5), "*" represents a site bonded to Ar ¹ .

Among the above, Z in the formula (2) is preferably a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 8 to 20 carbon atoms. , from the viewpoint of adhesion and dielectric properties, those represented by formulas (4-3), (4-4), (5), (6-1) to (6-5) are better. m in 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 described in the following formula (7).

[In the formula (7), R ₁ is a vinyl benzyl group, l is an integer of one or more, and R ₂ represents 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 an integer of 1 to 12. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 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, cyclohexyl, and the like. Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group, and the like.

From the viewpoint of the solvent solubility of the obtained active ester resin and the dielectric properties of the cured product, among the above, the formulas (1-3), (1-7), (2), and (7) are used The compound is preferred. Furthermore, Ar ¹ in formulas (1-3), (1-7), and (2) is phenol, o-cresol, dimethylphenol, phenylphenol, or α-naphthol. , a residue of β-naphthol, and those where Z is formula (4-3), (5), (6-1) to (6-5), and formula (7) are more preferred. Particularly preferred 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 vinyl benzyl group, R ₂ is independently a hydrogen atom, an alkyl group or an aryl group, and n is an integer from 0 to 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 for the production of an active ester resin, an active ester having an aryloxycarbonyl group bonded to a vinylbenzyloxy group at the molecular terminal can be obtained. resin.

Therefore, the above-mentioned phenolic compound having one or more vinylbenzyloxy groups can be preferably used as a raw material composition for producing active ester resin. The raw material composition for producing an active ester resin may contain an aromatic carboxylic acid or an acid halide thereof that reacts with a phenolic 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 method for producing the phenol compound having a vinylbenzyloxy group is not particularly limited, and the conventionally known Williamson ether synthesis method, etc. can be used. For example, a vinyl benzyl halide compound, a polyphenol compound, and a phase transfer catalyst such as an ammonium salt can be dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, etc. A sodium hydroxide aqueous solution is added and mixed while heating to produce it. In this case, by setting the chemical equivalent ratio of the halogenated group of the vinylbenzyl halide compound used to the phenolic hydroxyl group of the phenolic compound to less than 1.0, it is possible to synthesize a compound containing both a phenolic hydroxyl group and a vinylbenzyloxy group. of compounds.

[Active ester resin] The active ester resin of this embodiment has a vinylbenzyloxy group structure derived from the above-mentioned phenol compound having a vinylbenzyloxy group at the end of the main skeleton. It is preferable to have a vinylbenzyloxy structure at both ends of the main skeleton. In addition, as mentioned 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-described phenol compound (a1) having a vinyl benzyloxy group and an aromatic polycarboxylic acid or its acid halide (a2) as a reaction raw material. In addition to the above (a1) and (a2), the reaction raw materials may include a compound (a3) having two or more phenolic hydroxyl groups, an aromatic monocarboxylic acid, or its acid halide (a4).

Since the phenol compound (a1) having a vinylbenzyloxy group is as described above, description thereof is omitted here. Only one type of phenol compound (a1) having a vinylbenzyloxy group may be used, or two or more types may be used in combination.

Examples of the aromatic polycarboxylic acid or its acid halide (a2) include isophthalic acid, terephthalic acid, 1,4-, 2,3-, or 2,6-naphthalenedicarboxylic acid and other aromatic acids. Dicarboxylic acids; aromatic tricarboxylic acids such as trimesic acid and trimellitic acid; pyromellitic acid; and their acyl chlorides, etc. These can be used alone or in combination. Among them, isophthalic acid or a mixture of isophthalic acid and terephthalic acid is preferred from the viewpoint of excellent melting point of the reactant and excellent 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, (8-1), (8-4), (8-5), (8- n in 6) is an integer from 1 to 4, n in (8-2) is an integer from 0 to 3, and n in (8-3) and (8-7) is an integer from 0 to 6. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 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, cyclohexyl, and the like. Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group, and the like. In addition, the hydroxyl group and R ₂ in the 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).

[Wherein, in formula (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 styrene group, or a substituted or unsubstituted extension of 1 to 20 carbon atoms. Alkyl group, substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, arylyl group having 6 to 20 carbon atoms, or aralkyl group 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 each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. n in the formula (10-1) is an integer from 0 to 5, and n in the formula (10-2) is an integer from 0 to 7. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 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, cyclohexyl, and the like. Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group, and the like.

The alkylene group having 1 to 20 carbon atoms in Z is not particularly limited, and examples thereof include: methylene, ethylene, propylene, 1-methylmethylene, 1,1-di Methylmethylene, 1-methylethylidene, 1,1-dimethylethylidene, 1,2-dimethylethylidene, propylene, butyl, 1-methylpropylene base, 2-methyl propylene group, pentylene group, hexylene group, etc.

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

In addition, in the above formulas (11-1) to (11-4), "*" represents a site bonded to Ar ¹ .

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

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

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

In addition, in formulas (13-1) to (13-5), "*" represents a site bonded to Ar ¹ .

Among the above, Z in the formula (9) is preferably a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 8 to 20 carbon atoms. , from the viewpoint of adhesion and dielectric properties, those represented by 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 to 10, preferably 0 to 8, and from the viewpoint of solvent solubility, 0 to 5 is preferred.

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

Among them, 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 formula (14), l is preferably an integer of 1 to 20, more preferably 1 to 15, and even more preferably an integer of 1 to 12. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, 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, cyclohexyl, and the like. Examples of the aryl group include benzyl group, naphthyl group, methoxynaphthyl group, and the like.

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

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

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 from the viewpoint of solvent solubility, it is preferably 200°C or lower, more preferably 150°C or lower, and further preferably 120°C or lower.

[Production method of active ester resin] The method for producing an active ester resin according to this embodiment includes the step of reacting a phenol compound having a vinyl benzyloxy group with an aromatic polycarboxylic acid or an acid halide thereof. The step of reacting a phenolic compound having a vinyl benzyloxy group with an aromatic polycarboxylic acid or its acid halide is not particularly limited, and can be produced by a well-known and commonly used synthesis method such as an acetic anhydride method, an interfacial polymerization method, or a solution method. manufacturing. Among them, in order to prevent gelation during synthesis due to polymerization of vinyl benzyloxy groups, it is preferable to use an acid halide that can be synthesized at a lower temperature.

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

(hardener) The curing agent may be any compound that can react with the above-mentioned active ester resin, and various compounds may be used without particular limitation. Examples of the hardener include radical polymerization initiators and epoxy resins. Typical examples of the radical polymerization initiator include azo compounds and organic peroxides. Among them, organic peroxides are preferred because they do not generate gas as by-products. Epoxy resin can be used by well-known manufacturers. Examples include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl epoxy resins, epoxides of aralkyl resins bonded with stubble groups such as phenol and naphthol, epoxides of dicyclopentadiene-modified phenol resins, dihydroxynaphthalene-type epoxy resins, trihydroxynaphthalene-type epoxy resins, etc. Epoxy resins with an epoxy group having a divalent or higher value, such as phenolmethane type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, and glycidylamine type epoxy resin. These epoxy resins may be used individually or in combination of 2 or more types. Among these epoxy resins, epoxides and dicyclopentadiene modified aralkyl resins such as phenol-biphenyl aralkyl epoxy resin, phenol, naphthol and other aralkyl resins bonded with stubble groups are used. Resins with large epoxy equivalents, such as epoxides, are preferred.

(Blending amount) The blending amount of the active ester resin and the radical polymerization initiator is preferably adjusted to a curing time that is suitable for the molding conditions of the cured product, and from the viewpoint of the characteristics of the cured product, the blending amount is The optimal blending amount is 0 to 1 part for 100 parts of resin. If the blending amount is the above, 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, and is preferably in the range of 0.8 to 1.2 The range is particularly good.

(hardening accelerator) The resin composition may contain a hardening accelerator if necessary. Examples of the hardening accelerator include phosphorus compounds, tertiary amines, imidazole, organic acid metal salts, Lewis acids, amine salts, and the like. Especially when used as a build-up material or a circuit board, dimethylaminopyridine and imidazole are preferred from the viewpoint of excellent heat resistance, dielectric properties, soldering resistance, etc. . Especially when used as a semiconductor sealing material, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., triphenylphosphine is preferred as a phosphorus compound, and 1 is preferred as a tertiary amine compound. , 8-diazine bicyclo-[5.4.0]-undecene (DBU) is preferred.

(Other additive components) The resin composition may further contain other resin components. Examples of other resin components include vinyl-containing compounds such as styrene, acrylic acid, methacrylic acid and their esterified products, cyanate ester resin; bismaleimide resin; benzo Resin; allyl-containing resin represented by triallyl isocyanate; polyphosphate, phosphate-carbonate copolymer, etc. These may be used individually, or 2 or more types may be used 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, the blending ratio 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 flame retardants, inorganic fillers, silane coupling agents, release agents, pigments, and emulsifiers as needed. Examples of the flame retardant include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and inorganic phosphorus compounds such as ammonium 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 Cyclic organophosphorus compounds such as -10-oxides, and organophosphorus compounds such as derivatives reacted with compounds such as epoxy resin and phenol resin; 3 Compounds, cyanuric acid compounds, isocyanuric acid compounds, phenanthrene nitrogen-based flame retardants; polysilicone flame retardants such as polysilicone oil, polysilicone rubber, and polysilicone resin; metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, Low melting point glass and other inorganic flame retardants. When using such a flame retardant, the range of 0.1 to 20% by mass in the total resin composition is preferred.

The inorganic filler is blended, for example, when the resin composition is used as a semiconductor sealing material. Examples of the inorganic filler include fused silica, crystallized silica, alumina, silicon nitride, aluminum hydroxide, and the like. Among them, fused silica is preferred because it can be blended with more inorganic fillers. The fused silica may be either crushed or spherical. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the resin composition, it is preferable to mainly use spherical silica. Furthermore, in order to increase the blending amount of spherical silica, it is better to appropriately adjust the particle size distribution of 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 method of producing the resin composition is not particularly limited. For example, the above-mentioned components can be uniformly mixed at 0° C. to 200° C. using a stirring device, a three-roller machine, or the like.

[Cured material] The resin composition can be cured by heating and molding in a well-known and commonly used thermosetting method, for example, in a temperature range of about 20 to 250°C. The cured product of the resin composition of this embodiment has heat resistance of 160° C. or higher and can exhibit 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 packaging substrates.

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

An example of a method of manufacturing a semiconductor packaging substrate using a resin composition is a method of impregnating a reinforcing base material with the resin composition and then hardening the resin composition to obtain a prepreg. Examples of reinforcing base materials include: paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass fiber gauze cloth, etc. The impregnation amount of the resin composition is not particularly limited, but it is usually preferably prepared so that the resin component in the prepreg becomes 20 to 80% by mass. [Example]

The following examples are disclosed to illustrate the present invention in more detail, but the present invention is not limited by these examples. The following "parts" and "%" are based on mass 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 hardened material was cut into a size of 5 mm in width and 54 mm in length, and this was 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, temperature rise rate 3° C./min) was used on this test piece to evaluate heat resistance. (2) Dielectric tangent measurement Using the network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd., the cavity resonance method was used to measure the dielectric tangent at 1 GHz of the test piece after heating and vacuum drying, and then storing it in a room at 23°C and 50% humidity for 24 hours.

Example 1 (Synthesis of phenol resin containing vinyl benzyloxy groups) Put 200 parts of the complex adduct of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g/eq) and 98.0 parts of CMS-P into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. (Made by 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 of 2,4-dinitrophenol, and heat to 60°C while stirring. Next, 104.9 parts of 49% NaOH was added dropwise over 30 minutes. After maintaining at 60°C for 1 hour, the temperature was raised to 80°C and maintained for 2 hours. It was diluted with 275 parts of MIBK and neutralized with phosphoric acid until the pH of the lower layer became 7, and then washed with water by a liquid separation operation to remove salt from the organic layer. The reaction liquid was concentrated by a heating and pressure-reducing operation to obtain a phenol resin containing vinyl benzyloxy groups (brown solid A-1 with a hydroxyl equivalent weight of 406 g/eq). From this result, it was confirmed that the following structures were included. In addition, the GPC data of the product are shown in Figure 1 .

Example 2 (Synthesis of active ester resin containing vinyl benzyloxy 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 into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. ammonium bromide to dissolve. The system was controlled below 60°C, and 33.0 parts of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Next, continue stirring under these conditions for 1.0 hours. After the reaction is completed, let it stand for liquid separation and remove the water layer. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes. The mixture was allowed 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 are shown in Figure 2 .

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

Comparative example 2 Into a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 442 g of the reaction liquid (B-1) obtained in Comparative Example 1, 57.6 g of α-naphthol, and 80.8 g of chlorinated isophthalic acid were placed. Diformic acid replaces the system with decompressed nitrogen and dissolves it. Thereafter, 0.27 g of tetrabutylammonium bromide was dissolved, and while purging with nitrogen, the system was controlled to be 60° C. or lower, and 164.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Next, continue stirring under these conditions for 1.0 hours. After the reaction is completed, let it stand for liquid separation and remove the water layer. Further, water was added to the toluene layer in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the mixture was left to stand for liquid separation. However, the lower layer was emulsified and had poor liquid separation properties. Repeat this operation until the pH of the emulsion layer reaches 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. The synthesized flask has gel-like insoluble matter that is insoluble in solvent and 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 sulfon into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. Acid is used to replace the pressure-reduced nitrogen in the system to dissolve it. Next, while performing nitrogen purge, it took 3 hours to raise the temperature inside the system to 180°C. At this time, the generated volatile components are appropriately removed. After adding 3.3 parts of 49% NaOH, wash with water to remove the catalytic salt. After heating and reducing the pressure to 190°C, residual monomers were removed by steam distillation to obtain 2,6-xylenol aralkyl resin (B-3). The hydroxyl equivalent weight of this resin (B-3) is 199 g/eq.

Comparative example 4 Put 130 parts of (B-3), 105 parts of CMS-P, 235 parts of methyl isobutyl ketone, and 9.39 parts of Tetrahydrofuran into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer. Butylammonium bromide and 0.11 parts of 2,4-dinitrophenol were heated to 50°C while stirring. Next, 107 parts of 49% NaOH aqueous solution was dripped over 60 minutes. The internal temperature rises to 70°C due to heat generation. Thereafter, the temperature is maintained at 70 to 75°C for 5 hours. After neutralizing the pH of the lower layer to 7 using phosphoric acid, water washing was performed by a liquid separation operation. However, the lower layer was emulsified and had poor liquid separation properties. The catalyst is removed from the organic layer by extracting the emulsified lower layer. The reaction liquid was concentrated by heating and pressure-reducing operation to obtain xylenol aralkyl resin (B-4) having a vinyl benzyloxy group. From the results of GPC analysis, no residual chloromethylstyrene in the raw material was confirmed.

Comparative example 5 Put 433 parts of α-naphthol, 315 parts of paraxylene dichloride, and 703 parts of toluene into a flask equipped with a thermometer, dropping funnel, cooling tube, fractionating tube, and stirrer, and depressurize the system with nitrogen. Displace it and dissolve it. Next, while performing nitrogen purging, the temperature inside the system was raised to 90°C. 294 parts of the 49% NaOH aqueous solution was added dropwise over 1 hour, and this was maintained for 8 hours. Add 430 parts of water and let it stand to separate the liquid 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, α-naphthol aralkyl resin (B-5) was obtained by drying under reduced pressure at 180°C. The hydroxyl equivalent weight of this resin (B-5) is 217 g/eq.

Comparative example 6 Put 130 parts of (B-5), 96.0 parts of CMS-P, 226 parts of methyl isobutyl ketone, and 9.04 parts of Tetrahydrofuran 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 added dropwise over 60 minutes. The internal temperature rises to 60°C due to heat generation. Thereafter, the temperature is maintained at 55 to 65°C for 8 hours. After neutralizing the lower layer with phosphoric acid until the pH of the lower layer reaches 7, the solution is washed with water by a liquid separation operation to remove salt from the organic layer. The reaction liquid was concentrated by heating and pressure-reducing operation to obtain a naphthol aralkyl resin (B-6) having a vinyl benzyloxy group. From the results of GPC analysis, no residual chloromethylstyrene in the raw material was confirmed.

Curable composition using the resin obtained in Example 2 and Comparative Examples 2, 4, and 6 and its curing The compositions shown in Table 1 below were blended to obtain a curable composition. Flow it into a 1.6mm thick template and heat it at 120°C for 120 minutes and 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.

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

Furthermore, 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 showed 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 a not so high heat resistance of 150° C. and shows a high dielectric tangent of 7.5×10 ^-3 at 1 GHz.

without.

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.

Claims (13)

A raw material composition for producing active ester resin, which contains a phenolic compound having one or more vinyl benzyloxy structures and one phenolic hydroxyl group and an aromatic polycarboxylic acid or an acid halide thereof, which has one The above phenolic compound with a vinyl benzyloxy structure and one phenolic hydroxyl group is a compound represented by any one of the following formulas (1-1) to (1-8), (2), and (7),

[In the formula, R ₁ is a hydrogen atom or a vinyl benzyl group, and at least one in 1 molecule is a vinyl benzyl group; R ₂ is a hydrogen atom, an alkyl group or an aryl group, formulas (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 ), n in (1-7) is an integer from 0 to 6; multiple R ₂ can be the same or different; R ₂ in formulas (1-3) and (1-7) means that it can be bonded in any ring of the naphthalene ring]

[In formula (2), m is an integer from 0 to 20, and Ar ¹ independently represents a substituent containing a phenolic hydroxyl group or a vinyl benzyloxy group. In the formula, at least a vinyl benzyloxy group and a phenolic hydroxyl group exist respectively. 1, Z is independently an oxygen atom, a sulfur atom, a ketone group, a styrene group, a substituted or unsubstituted alkylene group with 1 to 20 carbon atoms, and a substituted or unsubstituted cycloalkylene group with 3 to 20 carbon atoms. group, an aryl group with 6 to 20 carbon atoms, or an aralkyl group with 8 to 20 carbon atoms]

[In the formula (7), R ₁ is a vinyl benzyl group, l is an integer of one or more, and R ₂ represents a hydrogen atom, an alkyl group, or an aryl group]. The raw material composition for producing active ester resin according to claim 1, wherein the phenolic compound having one or more vinyl benzyloxy structures and one phenolic hydroxyl group is formula (1-1)~(1-8 ), a compound represented by any one of

[In the formula, R ₁ is a hydrogen atom or a vinyl benzyl group, and at least one in 1 molecule is a vinyl benzyl group; R ₂ is a hydrogen atom, an alkyl group or an aryl group, formulas (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 ), n in (1-7) is an integer from 0 to 6; multiple R ₂ can be the same or different; R ₂ in formulas (1-3) and (1-7) means that it can be bonded in any ring of the naphthalene ring]. The raw material composition for producing active ester resin according to claim 1, wherein the phenolic compound having one or more vinyl benzyloxy structures and one phenolic hydroxyl group is formula (1-3), (1-7 ), (2), (7) any one of the compounds represented. An active ester resin containing a vinyl benzyloxy group structure is produced by using the raw material composition according to any one of claims 1 to 3. The active ester resin of claim 4 has at both ends Vinyl benzyloxy structure. The active ester resin of claim 4 or 5 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 phenol compound containing a vinylbenzyloxy group, and Y represents a reaction residue of a polyfunctional phenol compound). The active ester resin of claim 6 is a resin having a structure represented by the following formula (I-1),

A method for manufacturing an active ester resin, which uses the raw material composition of claim 1 as necessary reaction raw materials to carry out the reaction. A thermosetting resin composition containing the active ester resin according to any one of claims 4 to 7 and a hardener. For example, the thermosetting resin composition of claim 9 is used for electronic component substrates. A cured product of the thermosetting resin composition according to claim 9 or 10. A packaging substrate using the thermosetting resin composition according to claim 9 or 10. Such as the packaging substrate of claim 12, which is a semiconductor packaging substrate.