KR102583421B1 - Raw material composition for producing active ester resin, active ester resin and method for producing the same, and thermosetting resin composition and cured product thereof - Google Patents

Abstract

A thermosetting resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for signals with increased speed and high frequency is provided. Specifically, 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 containing a vinylbenzyloxy structure made using the raw material composition, and a vinylbenzyloxy structure at both ends. A thermosetting resin composition containing an active ester resin, an active ester resin, and a curing agent is provided.

Description

Raw material composition for producing active ester resin, active ester resin and method for producing the same, and thermosetting resin composition and cured product thereof

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

Curable resin compositions represented by epoxy resins exhibit excellent heat resistance and insulation properties in their cured products, and are therefore widely used in electronic components such as semiconductors and multilayer printed circuit boards. Among electronic component applications, semiconductor package substrates are becoming thinner, and bending of the package substrate during mounting is becoming a problem. In order to suppress warping of this package substrate, high heat resistance is required.

In addition, in recent years, signal speeds and higher frequencies have been progressing in semiconductor package substrates. Therefore, there is a demand for a thermosetting resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even for signals with increased speed and high frequency. As a material capable of realizing low dielectric constant and low dielectric loss tangent, a technology using an active ester compound as a curing agent for epoxy resin is known (see, for example, Patent Document 1). However, although low dielectric constant and low dielectric loss tangent were achieved, heat resistance was insufficient.

As other techniques for making thermosetting resin compositions with low dielectric constant and low dielectric loss tangent, methods of incorporating an epoxy resin with low dielectric constant and low dielectric loss tangent, methods of introducing cyanate groups, methods of incorporating polyphenylene ether, etc. have been used. . However, by simply combining these methods, it may be difficult to satisfy various requirements such as low dielectric constant and low dielectric loss tangent, high heat resistance, reliability, and halogen-free.

In this situation, vinylbenzyl-modified active ester resin is being studied as a resin composition capable of forming a cured product having dielectric properties and heat resistance (for example, see Patent Documents 2 to 3).

Japanese Patent Application Publication No. 2004-169021 Japanese Patent Application Publication No. 2018-70564 Japanese Patent Application Publication No. 2018-44040

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

As a result of repeated studies, the present inventors have found that the above problems can be solved by using an active ester resin (a resin having an ester structure created from a phenol group and an aromatic carboxylic acid group) containing a vinylbenzyloxy group at the terminal. This led to completion of the present invention.

That is, the present invention provides a phenolic hydroxyl group-containing compound having at least one vinylbenzyloxy structure, an active ester resin using the compound as a raw material, a curable resin composition containing the active ester resin, and a cured product thereof.

According to the present invention, a phenolic hydroxyl group-containing compound capable of forming an active ester resin capable of forming a cured product with excellent dielectric properties, an active ester resin and a method for producing the same, a thermosetting resin composition containing the active ester resin, and a cured product thereof are provided. can be provided.

1 shows a GPC chart of the product obtained in Example 1.
Figure 2 shows a GPC chart of the product obtained in Example 2.

Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and may be implemented with appropriate changes within the range that does not impair the effect of the present invention.

[Phenolic hydroxyl group-containing compounds]

The phenolic hydroxyl group-containing compound according to the present embodiment is a phenolic hydroxyl group-containing compound having one or more vinylbenzyloxy groups. The vinylbenzyloxy group is preferably bonded to a phenolic hydroxyl group-containing compound via an ether bond.

Examples of the vinylbenzyl group include ethenylbenzyl group, isopropenylbenzyl group, and normal propenylbenzyl group. Among them, an ethenylbenzyl group is preferable from the viewpoint of industrial availability and curability.

The phenolic hydroxyl group-containing compound of the present invention may have one or more substituents such as an alkyl group and an aryl group in addition to the vinylbenzyloxy group. Examples of the alkyl group include 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 group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, and cyclohexyl group. Examples of the aryl group include benzyl group, naphthyl group, and methoxynaphthyl group.

Examples of the phenolic hydroxyl group-containing 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 phenolic hydroxyl group-containing compound having one or more vinylbenzyloxy groups include compounds of the following formula.

In the formula, R ₁ is a hydrogen atom or a vinylbenzyl group, and at least one molecule is a vinylbenzyl group. R ₂ is a hydrogen atom, an alkyl group, or an aryl group, n in formulas (1-1), (1-4), (1-5), and (1-6) is an integer of 0 to 4, and 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. Multiple R ₂ may be the same or different. R ₂ in formulas (1-3) and (1-7) indicates that it may be bonded to any ring of the 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 methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, and cyclohexyl group. Examples of the aryl group include phenyl group, benzyl group, naphthyl group, and methoxynaphthyl group.

In addition, the phenolic hydroxyl group-containing compound having one or more vinylbenzyloxy groups may be a compound represented by the following formula (2).

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

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

Ar ¹ is not particularly limited, but examples include the residues of aromatic hydroxy compounds shown in the following formulas (3-1) and (3-2).

In formulas (3-1) and (3-2), R ₁ is a hydrogen atom or a vinylbenzyl group, and in formula (2), at least one is a vinylbenzyl group and at least one is a hydrogen atom. R ₂ is one of a hydroxy group, an alkyl group with 1 to 20 carbon atoms, and an aryl group with 6 to 20 carbon atoms. n is an integer from 0 to 5. The substituent in formula (3-2) may be bonded to any ring of the 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 methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, and cyclohexyl group. Examples of the aryl group include benzyl group, naphthyl group, and methoxynaphthyl group.

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

The cycloalkylene having 3 to 20 carbon atoms is not particularly limited, but includes cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following formula (4-1). Cycloalkylene represented by (4-4), etc. can be mentioned.

In addition, in the above formulas (4-1) to (4-4), “*” represents a site that binds to Ar ¹ .

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

In addition, in the above formula (5), “*” represents a site that binds to Ar ¹ .

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

Additionally, in formulas (6-1) to (6-5), “*” represents a site that bonds to Ar ¹ .

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

The phenolic hydroxyl group-containing compound having a vinylbenzyloxy group may have a structure represented by the following formula (7).

[In formula (7), R ₁ is a vinylbenzyl group, l is an integer of 1 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 still more 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 methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, and cyclohexyl group. Examples of the aryl group include benzyl group, naphthyl group, and methoxynaphthyl group.

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

In the formula, one R ₁ is a hydrogen atom, the other R ₁ is a vinylbenzyl group, R ₂ is each independently a hydrogen atom, an alkyl group, or an aryl group, and n is an integer of 0 to 4. At this time, the alkyl group and the aryl group include those similar to those described above.

By using the phenolic hydroxyl group-containing compound having at least one vinylbenzyloxy group in the production of an active ester resin, an active ester resin having an aryloxycarbonyl group bonded to a vinylbenzyloxy group at the molecule end can be obtained.

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

[Method for producing a phenolic hydroxyl group-containing compound having a vinylbenzyloxy group]

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

[Activated ester resin]

The active ester resin according to the present embodiment has a vinylbenzyloxy structure derived from a phenolic hydroxyl group-containing compound having the vinylbenzyloxy group described above at the terminal of the main skeleton. The vinylbenzyloxy structure is preferably present at both ends of the main skeleton. 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 as reaction raw materials a compound selected from the above-mentioned phenolic hydroxyl group-containing compound (a1) having a vinylbenzyloxy group and aromatic polycarboxylic acid or its acid halide (a2). In addition to the above-mentioned (a1) and (a2), the reaction raw material may contain a compound (a3) having two or more phenolic hydroxyl groups, an aromatic monocarboxylic acid, or an acid halide thereof (a4).

Since the phenolic hydroxyl group-containing compound (a1) having a vinylbenzyloxy group is as described above, description thereof is omitted here. The phenolic hydroxyl group-containing compound (a1) having a vinylbenzyloxy group may be used alone or in combination of two or more types.

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

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

In formulas (8-1) to (8-7), R ₂ each independently represents a hydrogen atom, an alkyl group, or an aryl group, and is represented by (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 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 group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, and cyclohexyl group. Examples of the aryl group include benzyl group, naphthyl group, and methoxynaphthyl group. In addition, the hydroxyl group in Formula (8-7) and R ₂ may be bonded to any ring on the naphthalene ring.

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

[However, in equation (9), m is an integer between 0 and 20]

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

Ar ¹ is not particularly limited, but examples include residues of aromatic hydroxy compounds shown in 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 with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms. n in formula (10-1) is an integer from 0 to 5, and n in formula (10-2) is an integer from 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 methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, and cyclohexyl group. Examples of the aryl group include benzyl group, naphthyl group, and methoxynaphthyl group.

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

The cycloalkylene having 3 to 20 carbon atoms is not particularly limited, but includes cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following formula (11-1). Cycloalkylene represented by (11-4), etc. can be mentioned.

In addition, in the above formulas (11-1) to (11-4), “*” represents a site that binds to Ar ¹ .

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

In addition, in the above formula (12), “*” represents a site that binds to Ar ¹ .

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

Additionally, in formulas (13-1) to (13-5), “*” represents a site that bonds to Ar ¹ .

In the above, Z in formula (9) is preferably cycloalkylene with 3 to 20 carbon atoms, arylene with 6 to 20 carbon atoms, or aralkylene with 8 to 20 carbon atoms, and is represented by the formula (11- 3), (11-4), (12), (13-1) to (13-5) are more preferable from the viewpoint of adhesion and dielectric properties. m in 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.

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

In formula (14), l is an integer of 1 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 still more 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 methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, pentyl group, normal hexyl group, and cyclohexyl group. Examples of the aryl group include benzyl group, naphthyl group, and methoxynaphthyl group.

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

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

Specific examples of the active ester resin include, for example, the active resin represented by the following formula.

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 still more preferably 120°C or lower.

[Method for producing activated ester resin]

The method for producing an active ester resin according to the present embodiment includes a step of reacting a phenolic hydroxyl group-containing compound having a vinylbenzyloxy group with an aromatic polyhydric carboxylic acid or an acid halide thereof. The process of reacting a phenolic hydroxyl group-containing compound having a vinylbenzyloxy group with an aromatic polyhydric carboxylic acid or its acid halide is not particularly limited, and can be produced by known and common synthetic methods such as acetic anhydride method, interfacial polymerization method, and solution method. You can. Among these, in order to prevent gelation during synthesis due to polymerization of the vinylbenzyloxy group, it is preferable to produce it using an acid halide that allows synthesis at a lower temperature.

[Thermosetting resin composition]

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

(hardener)

As a curing agent, any compound that can react with the above-described active ester resin is sufficient, and various compounds can be used without particular limitation. Examples of the curing agent include a radical polymerization initiator and an epoxy resin. Representative examples of the radical polymerization initiator include azo compounds and organic peroxides. Among these, organic peroxides are preferable because they do not generate gas as a by-product. Known epoxy resins can be used. For example, 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 type epoxy resin, phenol, naphthol, etc. Epoxidized products of aralkyl resins via rylene bonds, epoxidized products of dicyclopentadiene-modified phenol resins, dihydroxynaphthalene-type epoxy resins, glycidyl ether-type epoxy resins such as triphenolmethane-type epoxy resins, and glycidyl esters. Epoxy resins having a divalent or higher epoxy group such as type epoxy resin and glycidylamine type epoxy resin can be mentioned. These epoxy resins may be used alone or in combination of two or more types. Among these epoxy resins, resins with a large epoxy equivalent weight such as phenolbiphenyl aralkyl type epoxy resins, epoxides of aralkyl resins with xylylene bonds such as phenol and naphthol, and epoxides of dicyclopentadiene-modified phenol resins are used. It is desirable.

(Blending amount)

The mixing amount of the active ester resin and the radical polymerization initiator is preferably adjusted to a mixing amount that provides a curing time suitable for the molding conditions of the cured product. However, from the viewpoint of the properties of the cured product, a mixing amount of 0 to 1 part per 100 parts of resin is preferable. . If the above mixing amount is used, the active ester resin can be sufficiently cured, and a resin composition that provides a cured product with excellent heat resistance and dielectric properties can be easily obtained. In addition, the mixing ratio of the active ester resin and the epoxy resin is preferably in the range of 0.5 to 1.5, and especially preferably in the range of 0.8 to 1.2. do.

(curing accelerator)

The resin composition may contain a curing accelerator as needed. Examples of the curing accelerator include phosphorus-based compounds, tertiary amines, imidazole, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a build-up material or circuit board, dimethylaminopyridine or imidazole is preferable because it has excellent heat resistance, dielectric properties, solder resistance, etc. In particular, when used as a semiconductor encapsulation material, triphenylphosphine is used as a phosphorus compound and 1,8-diazabicyclo is used as a tertiary amine because of its excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc. -[5.4.0]-undecene (DBU) is preferred.

(Other added ingredients)

The resin composition may further contain other resin components. Other resin components include, for example, vinyl group-containing compounds such as styrene, acrylic acid, methacrylic acid and their esters, and cyanate ester resin; Bismaleimide resin; benzoxazine resin; Allyl group-containing resins such as triallyl isocyanurate; Examples include polyphosphoric acid ester and phosphoric acid ester-carbonate copolymer. These may be used individually, or two or more types may be used together.

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

The resin composition may, if necessary, contain various additives such as flame retardants, inorganic fillers, silane coupling agents, mold release agents, pigments, and emulsifiers. Examples of flame retardants include inorganic phosphorus compounds such as ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphate amides; Phosphoric acid ester compound, phosphonic acid compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 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 -Organophosphorus compounds such as cyclic organic phosphorus compounds such as phosphaphenanthrene-10-oxide and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins; Nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, and phenothiazine; Silicone-based 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 point glass can be mentioned. When using these flame retardants, it is preferable that they are in the range of 0.1 to 20 mass% of the total resin composition.

Inorganic fillers are blended, for example, when the resin composition is used as a semiconductor encapsulation material. Examples of inorganic fillers include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Among them, fused silica is preferable because it makes it possible to mix more inorganic fillers. Fused silica can be either crushed or spherical, but in order to increase the amount of fused silica and suppress an increase in melt viscosity of the resin composition, it is preferable to mainly use spherical silica. In addition, in order to increase the compounding amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filling rate is preferably in the range of 0.5 to 95 parts by mass per 100 parts by mass of the resin component.

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

[Hardened product]

The resin composition can be molded by heat-curing at a temperature range of about 20 to 250°C using a known and common heat curing method, for example.

The cured product of the resin composition according to the present embodiment has heat resistance of 160°C or higher and can exhibit a low dielectric loss tangent of 3.0×10 ^-3 or less at 10 GHz. From the above, it can be suitably used for electronic materials such as semiconductor package substrates.

[Semiconductor package substrate, etc.]

When using a resin composition for substrate applications such as semiconductor package substrates, it is generally preferable to dilute it by mixing it with an organic solvent. Examples of organic solvents include methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The type and mixing amount of the organic solvent can be appropriately adjusted depending on the usage environment of the resin composition, but for example, in semiconductor package substrate applications, it is preferable to use a polar solvent such as methyl ethyl ketone, acetone, or dimethylformamide with a boiling point of 160°C or lower. It is preferable to use the non-volatile content in a ratio of 40 to 80% by mass.

A method of manufacturing a semiconductor package substrate using a resin composition includes, for example, a method of obtaining a prepreg by impregnating the resin composition into a reinforcing base material and curing the resin composition. Examples of the reinforcing base material include paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, and glass rubbing cloth. The impregnated amount of the resin composition is not particularly limited, but it is generally preferable to prepare the resin content in the prepreg to be 20 to 80% by mass.

(Example)

The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples. In the following, “part” and “%” are based on mass unless otherwise specified. In addition, heat resistance measurements and dielectric loss tangent measurements were conducted under the following conditions.

(1) Heat resistance measurement

The cured product was cut to a size of 5 mm in width and 54 mm in length, and this was used as a test piece. The heat resistance of this test piece was evaluated using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Rheomatrix Corporation, rectangular tension method: frequency of 1 Hz, temperature increase rate of 3°C/min).

(2) Dielectric loss tangent measurement

Using a network analyzer "E8362C" manufactured by Agilent Technology Co., Ltd., the dielectric loss tangent at 1 GHz was measured using the cavity resonance method of a test piece that was heated and vacuum dried and stored for 24 hours in a room at 23°C and 50% humidity.

Example 1 (Synthesis of phenol resin containing vinylbenzyloxy group)

In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a dividing tube, and a stirrer, 200 parts of the polyadduct of dicyclopentadiene and phenol (hydroxyl equivalent 165 g/eq) and CMS-P (manufactured by AGC Semichemical Co., Ltd.) , a mixture of metachloromethylstyrene and parachloromethylstyrene), 298 parts of methyl isobutyl ketone (MIBK), 11.9 parts of tetrabutylammonium bromide, and 0.28 parts of 2,4-dinitrophenol were added and stirred at 60°C. heated with Then, 104.9 parts of 49% NaOH was added dropwise over 30 minutes. After maintaining the temperature 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, 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 the salt from the organic layer. The reaction solution was concentrated by heating and reducing pressure to obtain a phenol resin containing a vinylbenzyloxy group (brown solid A-1 with a hydroxyl group equivalent weight of 406 g/eq). From this result, it was confirmed that it contains the following structure. Additionally, GPC data of the product is shown in Figure 1.

Example 2 (Synthesis of active ester resin containing vinylbenzyloxy structure)

65.0 parts of (A-1), 16.2 parts of isophthalic acid chloride, 322 parts of toluene, and 0.16 parts of tetrabutylammonium bromide were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer and dissolved. The inside of the system was controlled to 60°C or lower, and 33.0 parts of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hours under these conditions. After completion of the reaction, the liquid was separated while standing and the aqueous layer was removed. Additional water was added to the toluene layer in which the reactant was dissolved, stirred and mixed for about 15 minutes, and the water layer was removed by standing liquid separation. This operation was repeated until the pH of the water layer reached 7. Afterwards, it was dried under reduced heat pressure to synthesize an active ester resin (A-2) containing the following structure. Additionally, GPC data of the product is shown in Figure 2.

Comparative Example 1

In a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer, 80.1 g (0.5 mole) of 1,6-dihydroxynaphthalene and hydrotalcite (Kyowad, manufactured by Kyowa Chemical Co., Ltd.) 500SH) 156g and toluene 624g were added and heated to 70°C. Next, 76.3 g (0.5 mol) of CMS-P was added dropwise and heated to 110°C. After continuing the reaction for 5 hours, it was cooled and filtered to remove insoluble matter, thereby obtaining a reaction solution (B-1) containing the compound represented by the following formula. When the reaction solution was analyzed, the hydroxyl equivalent weight was 177 g/eq and the non-volatile matter was 16.0%.

Comparative Example 2

442 g of the reaction solution (B-1) obtained in Comparative Example 1, 57.6 g of α-naphthol, and 80.8 g of isophthalic acid chloride were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer, and the inside of the system was depressurized. It was dissolved by nitrogen substitution. After that, 0.27 g of tetrabutylammonium bromide was dissolved, the inside of the system was controlled to 60°C or lower while purging nitrogen gas, and 164.8 g of 20% sodium hydroxide aqueous solution was added dropwise over 3 hours. Stirring was then continued for 1.0 hours under these conditions. After completion of the reaction, the liquid was separated while standing and the aqueous layer was removed. Additional water was added to the toluene layer in which the reactant was dissolved, stirred and mixed for about 15 minutes, and the liquid was separated while standing, but the lower layer was emulsified and the liquid separation was poor. This operation was repeated until the pH of the emulsion layer reached 7. Afterwards, it was dried under reduced heat pressure to synthesize an active ester resin (B-2) containing a compound having the following structure. A gel-like insoluble matter that did not dissolve in solvent or water was attached to the flask after synthesis.

Comparative Example 3

488.7 parts of 2,6-xylenol, 281.7 parts of para-xylene glycol dimethyl ether, and 7.7 parts of para-toluenesulfonic acid were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer, and the system was filled with reduced pressure nitrogen. It was dissolved by substitution. Next, while purging nitrogen gas, the temperature inside the system was raised to 180°C over 3 hours. At this time, the volatile matter generated was removed. After adding 3.3 parts of 49% NaOH, it was washed with water to remove the catalyst salt. After heating to 190°C and reducing pressure, the remaining monomer was removed by steam distillation to obtain 2,6-xylenolaralkyl resin (B-3). The hydroxyl equivalent of this resin (B-3) was 199 g/eq.

Comparative Example 4

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

Comparative Example 5

433 parts of α-naphthol, 315 parts of para-xylene dichloride, and 703 parts of toluene were added to a flask equipped with a thermometer, dropping funnel, cooling tube, flow distribution tube, and stirrer, and the system was dissolved by purging with reduced pressure nitrogen. Next, while purging nitrogen gas, the temperature inside the system was raised to 90°C. 294 parts of 49% NaOH aqueous solution were added dropwise over 1 hour and kept as is for 8 hours. 430 parts of water were added, and the lower layer was removed by static separation. 15.0 parts of p-toluenesulfonic acid was added, and the temperature was raised to 150°C while removing volatile matter. After holding for 1 hour, the catalyst was removed by washing with water. Afterwards, 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) was 217 g/eq.

Comparative Example 6

In a flask equipped with a thermometer, dropping funnel, cooling tube, dividing tube, and stirrer, 130 parts of (B-5), 96.0 parts of CMS-P, 226 parts of methyl isobutyl ketone, 9.04 parts of tetrabutylammonium bromide, 2,4- 0.20 part of dinitrophenol was added and heated to 45°C while stirring. Next, 97.8 parts of 49% NaOH aqueous solution was added dropwise over 60 minutes. The internal temperature rose to 60℃ due to fever. Afterwards, it was maintained at 55-65°C for 8 hours. After neutralizing the lower layer with phosphoric acid until the pH reached 7, it was washed with water through a liquid separation operation to remove the salt from the organic layer. The reaction solution was concentrated by heating and reducing pressure to obtain naphthol aralkyl resin (B-6) having a vinylbenzyloxy group. From the results of GPC analysis, no residual chloromethylstyrene, which was the raw material, was confirmed.

Curable composition using the resin obtained in Example 2 and Comparative Examples 2, 4, and 6, and curing thereof

A curable composition was obtained by mixing the compositions shown in Table 1 below. This was poured into a 1.6 mm thick mold and heated at 120°C for 120 minutes and at 180°C for 60 minutes to cure.

[Table 1]

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

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

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

In addition, the cured product obtained from the resin composition using the resin obtained in Comparative Example 6 did not have very high heat resistance at 150°C, and showed a high dielectric loss tangent of 7.5 × 10 ^-3 at 1 GHz.

Claims (13)

A raw material composition for producing an active ester resin containing a phenolic hydroxyl group-containing compound having at least one vinylbenzyloxy structure and one phenolic hydroxyl group and an aromatic polycarboxylic acid or an acid halide thereof,
A raw material composition for producing an active ester resin, wherein the phenolic hydroxyl group-containing compound is a compound represented by any one of the following formulas (1-1) to (1-8), (2), and (7).


[In the formula, one of R ₁ is a hydrogen atom and the others are vinylbenzyl groups. R ₂ is a hydrogen atom, an alkyl group, or an aryl group, and n in formulas (1-1), (1-4), (1-5), (1-6), and (1-8) is an integer of 0 to 4. , n in formulas (1-2) is an integer from 0 to 3, and n in formulas (1-3) and (1-7) is an integer from 0 to 6. Multiple R ₂ may be the same or different. R ₂ in formulas (1-3) and (1-7) indicates that it may be bonded to any ring of the naphthalene ring]

[In formula (2), m is an integer of 0 to 20, Ar ¹ each independently represents a substituent containing a phenolic hydroxyl group or a vinylbenzyloxy group, and in formula (2), the number of vinylbenzyloxy groups is 1 or more, There is one phenolic hydroxyl group, and Z is each independently an oxygen atom, a sulfur atom, a ketone group, a sulfonyl group, a substituted or unsubstituted alkylene having 1 to 20 carbon atoms, or a substituted or unsubstituted alkylene having 3 to 20 carbon atoms. Cycloalkylene of 20, arylene of 6 to 20 carbon atoms, or aralkylene of 8 to 20 carbon atoms]

[In formula (7), R ₁ is a vinylbenzyl group, l is an integer of 1 or more, and R ₂ represents a hydrogen atom, an alkyl group, or an aryl group] According to paragraph 1,
A raw material composition for producing an active ester resin, wherein the phenolic hydroxyl group-containing compound is a compound represented by any one of formulas (1-1) to (1-8).

[In the formula, one of R ₁ is a hydrogen atom and the others are vinylbenzyl groups. R ₂ is a hydrogen atom, an alkyl group, or an aryl group, and n in formulas (1-1), (1-4), (1-5), (1-6), and (1-8) is an integer of 0 to 4. , n in formulas (1-2) is an integer from 0 to 3, and n in formulas (1-3) and (1-7) is an integer from 0 to 6. Multiple R ₂ may be the same or different. R ₂ in formulas (1-3) and (1-7) indicates that it may be bonded to any ring of the naphthalene ring] The raw material composition for producing an active ester resin according to claim 1, wherein the phenolic hydroxyl group-containing compound is a compound represented by any one of formulas (1-3), (1-7), (2) and (7). An active ester resin containing a vinylbenzyloxy structure, comprising the raw material composition according to any one of claims 1 to 3. According to paragraph 4,
An active ester resin having a vinylbenzyloxy structure at both ends. According to paragraph 4,
An active ester resin having a structure represented by formula (I).

(In formula (I), n represents an integer of 0 to 20, ) According to clause 6,
An active ester resin, which is a resin having a structure represented by the following formula (I-1).

A method for producing an active ester resin, comprising reacting the raw material composition according to claim 1 as an essential reaction raw material. A thermosetting resin composition containing the active ester resin and a curing agent according to claim 4. According to clause 9,
Thermosetting resin composition for electronic component substrates. A cured product of the thermosetting resin composition according to claim 9. A package substrate using the thermosetting resin composition according to claim 9. According to clause 12,
A semiconductor package substrate, a package substrate.

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