JPWO2019103086A1 - Thermosetting resin compositions, insulating films, interlayer insulating films, multilayer wiring boards, and semiconductor devices - Google Patents

Abstract

An object of the present invention is to provide a polyphenylene ether (PPE) -based thermosetting resin composition having excellent high-frequency characteristics and heat resistance (small change in dielectric loss tangent (tan δ)) and excellent solder heat resistance. .. It is characterized by containing (A) a polyphenylene ether having an unsaturated double bond at the terminal and having a number average molecular weight of 800 to 4500, (B) a phenolic antioxidant having a melting point of 200 ° C. or higher, and (C) a thermoplastic elastomer. It is a thermosetting resin composition. [Selection diagram] None

Description

The present invention relates to thermosetting resin compositions, insulating films, interlayer insulating films, multilayer wiring boards, and semiconductor devices. In particular, the present invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device capable of increasing the frequency.

At present, electronic devices such as various communication devices are often required to have high frequencies. For example, a low transmission loss is often required for a multilayer printed wiring board for high frequency applications such as millimeter wave communication. It is known to use polyphenylene ether (PPE) having excellent high frequency characteristics as a material used for an adhesive layer or a coverlay of a multilayer printed wiring board for high frequency applications, or a substrate itself.

On the other hand, it has been reported that a resin composition has high-frequency characteristics comparable to those of PPE by using a curing component such as epoxy or an elastomer (Patent Document 1), and a phenolic antioxidant contained in the epoxy resin. It is stated that the agent can be used without deteriorating the high frequency properties of the resin composition.

Japanese Unexamined Patent Publication No. 2014-201642

By the way, it is preferable that the thermosetting PPE has a low molecular weight from the viewpoint of reactivity and solubility in a solvent.

However, the PPE polymer obtained by polymerizing a low molecular weight thermosetting PPE has very rapid oxidative deterioration at high temperatures, and when used in a multilayer wiring board, it has a dielectric loss tangent (tan δ) after a heat resistance reliability test. ) The present inventors have found that there is a problem that the value fluctuates. In addition, the multilayer wiring plate is also required to have solder heat resistance, and this requirement must be satisfied.

From the above viewpoint, an object of the present invention is to provide a PPE-based thermosetting resin composition having excellent high-frequency characteristics, heat resistance reliability (small change in dielectric loss tangent (tan δ)), and excellent solder heat resistance. The purpose is to do.

The present invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device, which solve the above problems by having the following configurations.
[1] (A) A polyphenylene ether having an unsaturated double bond at the terminal and having a number average molecular weight of 800 to 4500.
A thermosetting resin composition comprising (B) a phenolic antioxidant having a melting point of 200 ° C. or higher, and (C) a thermoplastic elastomer.
[2] The thermosetting resin composition according to the above [1], which further comprises (D) an inorganic filler.
[3] A silica filler in which the component (D) is surface-treated with a silane coupling agent represented by the general formula (10).

(In the formula, R ^{21 to} R ²³ are independently alkyl groups having 1 to 3 carbon atoms, R ²⁴ is a functional group having an unsaturated double bond at least at the terminal, and n is. The thermosetting resin composition according to the above [1] or [2], which comprises (3 to 9).
[4] The thermosetting resin composition according to any one of the above [1] to [3], wherein R ²⁴ of the general formula (10) is a vinyl group or a (meth) acrylic group.
[5] An insulating film containing the thermosetting resin composition according to any one of the above [1] to [4].
[6] An interlayer insulating film containing the thermosetting resin composition according to any one of the above [1] to [4].
[7] A cured product of the resin composition according to any one of the above [1] to [4], a cured product of the insulating film according to the above [5], or a cured product of the interlayer insulating film according to the above [6].
[8] A cured product of the resin composition according to any one of the above [1] to [4], a cured product of the insulating film according to the above [5], or a cured product of the interlayer insulating film according to the above [6]. Multi-layer wiring board.
[9] A cured product of the thermosetting resin composition according to any one of [1] to [4] above, an insulating film according to [5], or a cured product of an interlayer insulating film according to [6] above. Has a semiconductor device.

According to the present invention [1], it is possible to provide a PPE-based thermosetting resin composition having excellent high-frequency characteristics, heat resistance reliability (small change in dielectric loss tangent (tan δ)), and excellent solder heat resistance. it can.

According to the present invention [5], it is possible to provide an interlayer insulating film formed of a PPE-based thermosetting resin composition, which has excellent high-frequency characteristics, heat resistance reliability, and solder heat resistance.
According to the present invention [6], it is possible to provide an interlayer insulating film formed of a PPE-based thermosetting resin composition, which has excellent high-frequency characteristics, heat resistance reliability, and solder heat resistance.

According to the present invention [7], a multilayer wiring board excellent in high frequency characteristics and heat resistance reliability is provided by a cured product of the thermosetting resin composition, the insulating film, or the cured product of the interlayer insulating film. can do. According to the present invention [8], a multilayer wiring board excellent in high frequency characteristics and heat resistance reliability is provided by a cured product of the thermosetting resin composition, the insulating film, or the cured product of the interlayer insulating film. can do. According to the present invention [9], a semiconductor device having excellent high frequency characteristics and heat resistance reliability is provided by the cured product of the thermosetting resin composition, the insulating film, or the cured product of the interlayer insulating film. be able to.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention
(A) Polyphenylene ether having an unsaturated double bond at the terminal and having a number average molecular weight of 800 to 4500.
It contains (B) a phenolic antioxidant having a melting point of 200 ° C. or higher, and (C) a thermoplastic elastomer.

The component (A) is a polyphenylene ether having an unsaturated double bond at the terminal and having a number average molecular weight of 800 to 4500, and is used in the thermosetting resin composition of the present invention (hereinafter referred to as the thermosetting resin composition). Provides adhesiveness, high frequency characteristics, and heat resistance. Here, the high frequency characteristic means a property of reducing the transmission loss in the high frequency region. The component (A) preferably has a relative permittivity (ε) of 3.5 or less and a dielectric loss tangent (tan δ) of 0.003 or less at 10 GHz from the viewpoint of high frequency characteristics. As the component (A), polyphenylene ether having a styrene group at the terminal is preferable.

As a polyphenylene ether (PPE) having a styrene group at the end, it has excellent high frequency characteristics, and the dielectric property (particularly tan δ) is temperature-dependent (measured at high temperature (120 ° C) with respect to the measured value at room temperature (25 ° C). The compound represented by the general formula (1) is preferable because the change) is small.

(In the formula (1),-(OX-O)-is represented by the general formula (2) or (3).)

(In formula (2), R ¹ , R ² , R ³ , R ⁷ , and R ⁸ may be the same or different, and are alkyl or phenyl groups having 6 or less carbon atoms. R ⁴ , R ⁵ , R. ⁶ may be the same or different, and is a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group.)

(In formula (3), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ may be the same or different, and may be the same or different, and may be a hydrogen atom, an alkyl group having 6 or less carbon atoms, or an alkyl group. It is a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.)

(In the formula (1),-(YO)-is represented by the general formula (4), and one type of structure or two or more types of structures are randomly arranged.)

(In the formula (4), R ¹⁷ and R ¹⁸ may be the same or different, and may be an alkyl group or a phenyl group having 6 or less carbon atoms. R ¹⁹ and R ²⁰ may be the same or different and may be hydrogen atoms. , An alkyl group or a phenyl group having 6 or less carbon atoms.)

(In equation (1), a and b represent integers from 0 to 100 in which at least one of them is not 0.)

(For example, -A- in the formula (3) includes methylene, ethylidene, 1-methylethylidene, 1,1-propyridene, 1,4-phenylenebis (1-methylethylidene), and 1,3-phenylenebis (1). -Methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, 1-phenylethylidene, and other divalent organic groups, but are not limited to these.)

(As the compound represented by the formula (1), R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹⁷ , and R ¹⁸ are alkyl groups having 3 or less carbon atoms, and R ⁴ , R ⁵ , R. ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁹ , and R ²⁰ are preferably hydrogen atoms or alkyl groups having 3 or less carbon atoms, and are particularly general. -(OX-O)-represented by the formula (2) or the general formula (3) is the general formula (5), the general formula (6), or the general formula (7), and the general formula (4). ) Is more preferably the formula (8) or the formula (9), or a structure in which the formulas (8) and (9) are randomly arranged. )

The method for producing the compound represented by the formula (1) is not particularly limited, and for example, the terminal phenolic hydroxyl group of the bifunctional phenylene ether oligomer obtained by oxidation-coupling the bifunctional phenol compound and the monofunctional phenol compound. Can be produced by vinyl benzyl etherification.

The number average molecular weight of the thermosetting resin of the component (A) is in the range of 800 to 4,500 in terms of polystyrene by the GPC method, preferably in the range of 1000 to 3500, and has a low viscosity while reducing the origin of oxidative deterioration due to polymerization. The range of 1500 to 2500 is more preferable from the viewpoint of achieving the conversion. When the number average molecular weight is 800 or more, the thermosetting resin composition of the present invention is less sticky when it is formed into a coating film, and when it is 4500 or less, the decrease in solubility in a solvent can be prevented. The component (A) may be used alone or in combination of two or more.

The component (B) is a phenolic antioxidant having a melting point of 200 ° C. or higher, and imparts solder heat resistance to the thermosetting resin. If the melting point of the component (B) is less than 200 ° C., the solder heat resistance of the thermosetting resin becomes insufficient. Examples of the phenolic antioxidant having a component (B) having a melting point of 200 ° C. or higher include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine. -2,4,6 (1H, 3H, 5H) -trione, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, Examples thereof include 6,6'-di-tert-butyl-4,4'-butylidenes-m-cresol and the like.

Commercially available products of the component (B) include 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H,). 3H, 5H) -trione (manufactured by ADEKA, product name: AO-20, melting point: 220 to 222 ° C., molecular weight: 784);

1,3,5-Tris (3,5-di-tert-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene (manufactured by ADEKA, product name: AO-330, melting point: 243 to 245 ° C) :

However, it can be mentioned. The component (B) may be used alone or in combination of two or more.

The component (C) functions as a flexibility-imparting resin that imparts flexibility to the thermosetting resin composition. As the thermoplastic elastomer of the component (C), a styrene-based thermoplastic elastomer is preferable from the viewpoint of dielectric properties, and the temperature dependence of the dielectric properties (particularly tan δ) (high temperature (25 ° C.) with respect to the measured value at room temperature (25 ° C.)) A hydrogenated styrene-based thermoplastic elastomer is more preferable from the viewpoint of small change in the measured value at 120 ° C.). Hydrogenated polybutadiene improves heat resistance, but may increase temperature dependence.

The preferred hydrogenated styrene-based thermoplastic elastomer as the component (C) is a styrene-based block copolymer in which an unsaturated double bond of the main chain in the molecule is hydrogenated, and the hydrogenated styrene-based block copolymer is styrene-. Ethylene / butylene-styrene block copolymer (SEBS), styrene- (ethylene-ethylene / propylene) -styrene block copolymer (SEEPS), styrene-ethylene / propylene-styrene block copolymer (SEPS), etc. SEBS and SEEPS are preferable. This is because SEBS and SEEPS are excellent in dielectric properties, have good compatibility with polyphenylene ether (PPE), modified PPE, etc., which are options of the component (A), and can form a thermosetting resin composition having heat resistance. Furthermore, since the styrene-based block copolymer also contributes to lowering the elasticity of the thermosetting resin composition, it imparts flexibility to the insulating film, and the cured product of the thermosetting resin composition has a low elasticity of 3 GPa or less. Is suitable for applications that require

The weight average molecular weight of the component (C) is preferably 30,000 to 200,000, more preferably 80,000 to 120,000. The weight average molecular weight is set to a value using a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The component (C) may be used alone or in combination of two or more.

The component (A) and the component (C) are resins, and the component (A) is preferably 10 to 70 parts by mass with respect to 100 parts by mass in total of the components (A) and (C), and is 20 to 20 parts by mass. It is more preferably 60 parts by mass.

If the amount of the component (A) is small, the cured product of the thermosetting resin composition is not sufficiently cured, and problems such as a decrease in peel strength, an increase in the coefficient of thermal expansion (CTE), and a decrease in heat resistance are likely to occur. When the amount of the component (A) is large, the film produced from the thermosetting resin composition becomes hard, brittle and easily cracked, the film property is impaired, and the cured product of the thermosetting resin composition also becomes hard and brittle. Problems such as a decrease in peel strength, a tendency for cracks due to heat shock to occur, and a decrease in heat resistance due to oxidation at a high temperature are likely to occur.

As the resin other than the component (A) and the component (C), for example, an epoxy resin, a maleimide resin, a cyanate resin, a polyimide resin, or the like may be used in combination.

The component (B) is preferably 0.1 to 10 parts by mass, preferably 0.3 to 5 parts by mass, with respect to 100 parts by mass of the resin component in the thermosetting resin composition from the viewpoint of high frequency characteristics. It is more preferable, and 0.5 to 2 parts by mass is particularly preferable.

It is preferable that the thermosetting resin further contains (D) an inorganic filler from the viewpoint of lowering the CTE of the cured product of the thermosetting resin. As the component (D), a silica filler is preferable from the viewpoint of high frequency characteristics. It is more preferable that the inorganic filler of the component (D) is surface-treated from the viewpoint of moisture resistance and reliability. As this surface treatment agent, the general formula (10):

(In the formula, R ^{21 to} R ²³ are independently alkyl groups having 1 to 3 carbon atoms, R ²⁴ is a functional group having an unsaturated double bond at least at the terminal, and n is. The silane coupling agent represented by (3 to 9) is preferable from the viewpoint of improving moisture resistance, and n is more preferably 5 to 9 in the formula. Further, R ^{24 of} the general formula (10) is preferably a vinyl group or a (meth) acrylic group from the viewpoint of adhesiveness to (A) due to reactivity, and a vinyl group is preferably from the viewpoint of peel strength. , More preferred.

Examples of the silane coupling agent that can be used as the component (D) include octenyltrialkoxysilane, (meth) acryloxyalkyltrialkoxysilane, and 3-methacryloxypropyltrimethoxysilane. Examples of the octenyltrialkoxysilane include octenyltrimethoxysilane and octenyltriethoxysilane. Examples of the (meth) acryloxyalkyltrialkoxysilane include (meth) acryloxyoctyltriethoxysilane and (meth) acryloxyoctyltrialkoxysilane. From the viewpoint of improving the peel strength of the thermosetting resin composition, octenyltrimethoxysilane is more preferable. Commercially available silane coupling agents that can be used as the component (D) include octenyltrimethoxysilane (product name: KBM-1083) manufactured by Shin-Etsu Chemical Co., Ltd. and methacryoxyoctyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include silane (product name: KBM-5803) and 3-methacryloxypropyltrimethoxysilane (product name: KBM-503) manufactured by Shin-Etsu Chemical Co., Ltd. The silane coupling agent that can be used as the component (D) may be used alone or in combination of two or more.

Examples of the silica filler used for the component (D) include fused silica, ordinary silica stone, spherical silica, crushed silica, crystalline silica, and amorphous silica, and are not particularly limited. From the viewpoints of dispersibility of the silica filler, fluidity of the thermosetting resin composition, surface smoothness of the cured product, dielectric properties, low thermal expansion rate, adhesiveness, and the like, spherical fused silica is desirable. The average particle size of the silica filler (or the average maximum diameter if it is not spherical) is not particularly limited, but is 0.05 to 20 μm from the viewpoint of improving the moisture resistance after curing due to the small specific surface area. It is preferably 0.1 to 10 μm, more preferably 1 to 10 μm, and even more preferably 1 to 10 μm. Here, the average particle size of the silica filler refers to a volume-based median diameter measured by a laser scattering diffraction type particle size distribution measuring device.

The method for surface-treating the silica filler using the above-mentioned coupling agent is not particularly limited, and examples thereof include a dry method and a wet method.

In the dry method, the silica filler and the silane coupling agent in an appropriate amount with respect to the surface area of the silica filler are put into a stirrer and stirred under appropriate conditions, or the silica filler is put in a stirrer in advance and under appropriate conditions. While stirring, an appropriate amount of the silane coupling agent with respect to the surface area of the silica filler is added in a stock solution or a solution by dropping or spraying, and the silane coupling agent is uniformly adhered to the surface of the silica filler by stirring. A method of surface treatment (by hydrolysis). Examples of the stirring device include, for example, a mixer capable of stirring and mixing at high speed rotation such as a Henschel mixer, but the stirring device is not particularly limited.

In the wet method, the silica filler is added to a surface treatment solution in which a sufficient amount of silane coupling agent is dissolved in water or an organic solvent with respect to the surface area of the silica filler to be surface-treated, and the mixture is stirred so as to form a slurry. This is a method in which the silica coupling agent and the silica filler are sufficiently reacted, and then the silica filler is separated from the surface treatment solution by filtration, centrifugation or the like, and then heat-dried to perform the surface treatment.

The component (D) may be used alone or in combination of two or more.

The component (D) is 45 to 75% by volume (64 to 88% by mass in the case of a solid silica filler) in the thermosetting resin composition (excluding the solvent) from the viewpoint of reducing CTE. Is preferable, and 50 to 70% by volume (69 to 85% by mass in the case of a solid silica filler) is more preferable. If the amount of the component (D) is small, the desired CTE of the thermosetting resin composition cannot be achieved, and if the amount of the component (D) is large, the peel strength of the thermosetting resin composition tends to decrease.

The thermosetting resin composition is an organic peroxide as a curing accelerator of the component (A) or a coupling agent (integral blend) such as a silane coupling agent as long as the effect of the present invention is not impaired. , Flame retardants, tackifiers, defoamers, flow regulators, rocking agents, dispersants, antioxidants, flame retardants and other additives can be included. Examples of the silane coupling agent include P-styryltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-1403), bis (triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-846), Polysulfide-based silane coupling agent (Osaka Soda Co., Ltd., Cabras 4), octenyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-1083), metharoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) , KBM-5803), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503), 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-503), Examples thereof include 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) and 3-glycidoxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-403). .. Examples of the flame retardant include a phosphinic acid metal salt (manufactured by Clariant Japan, OP-935) and the like.

The thermosetting resin composition can be produced by dissolving or dispersing the raw materials such as the components (A), (B) and (C) constituting the resin composition in an organic solvent. The device for dissolving or dispersing these raw materials is not particularly limited, but a stirrer, a resolver, a Raikai machine, a three-roll mill, a ball mill, a planetary mixer, a bead mill or the like equipped with a heating device shall be used. Can be done. Moreover, you may use these devices in combination as appropriate.

Examples of the organic solvent include aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. The organic solvent may be used alone or in combination of two or more. From the viewpoint of workability, the thermosetting resin composition preferably has a viscosity in the range of 200 to 3000 mPa · s. The viscosity is a value measured at a rotation speed of 50 rpm and 25 ° C. using an E-type viscometer.

The obtained thermosetting resin composition is excellent in high frequency characteristics and heat resistance reliability (the amount of change in dielectric loss tangent (tan δ) is small), and is also excellent in solder heat resistance.

[Insulating film]
The insulating film of the present invention contains the above-mentioned thermosetting resin composition. The insulating film is formed from the thermosetting resin composition into a desired shape. Specifically, the insulating film can be obtained by applying the above-mentioned thermosetting resin composition on a support and then drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, organic films such as polyester resin, polyethylene resin, and polyethylene terephthalate resin (PET). The support may be mold-released with a silicone compound or the like. The thermosetting resin composition can be used in various shapes, and the shape is not particularly limited.

The method of applying the thermosetting resin composition to the support is not particularly limited, but the gravure method, the slot die method, and the doctor blade method are preferable from the viewpoint of thinning and film thickness control. By the slot die method, an uncured film having a thermosetting resin composition having a thickness of 5 to 300 μm, that is, an insulating film can be obtained.

The drying conditions can be appropriately set according to the type and amount of the organic solvent used in the thermosetting resin composition, the thickness of the coating, and the like. For example, at 50 to 120 ° C. for about 1 to 60 minutes. Can be. The insulating film thus obtained has good storage stability. The insulating film can be peeled off from the support at a desired timing.

The curing of the insulating film can be performed, for example, at 150 to 230 ° C. for 30 to 180 minutes. The interlayer insulating film of the present invention can be produced and cured in the same manner as described above. When the insulating film is used as the interlayer insulating film, the interlayer insulating film may be cured after the interlayer insulating film is sandwiched between the substrates on which the wiring made of copper foil or the like is formed, and the wiring made of copper foil or the like. The interlayer insulating film formed on the above may be laminated as appropriate. Further, the insulating film can also be used as a coverlay film for protecting the wiring on the substrate, and the curing conditions at that time are also the same. The thermosetting resin composition can also be cured in the same manner. Further, at the time of curing, press curing may be performed at a pressure of, for example, 1 to 5 MPa.

[Multilayer wiring board]
The multilayer wiring board of the present invention has a cured product of the above-mentioned thermosetting resin composition, the above-mentioned insulating film, or a cured product of the interlayer insulating film. The printed wiring board of the present invention is produced by using the above-mentioned thermosetting resin composition, the above-mentioned insulating film, or interlayer insulating film and curing the same. This printed wiring board is excellent in high frequency characteristics and heat resistance reliability (change amount of dielectric positive contact (tan δ)) due to the cured product of the thermosetting resin composition, the insulating film, or the cured product of the interlayer insulating film. Is small) and has excellent solder heat resistance. Among the multilayer wiring boards, a substrate for microwave and millimeter wave communication, particularly a printed wiring board for high frequency applications such as an in-vehicle millimeter wave radar substrate, and the like can be mentioned. The method for manufacturing the multilayer wiring board is not particularly limited, and the same method as in the case of manufacturing the printed wiring board using a general prepreg can be used.

[Semiconductor device]
The semiconductor device of the present invention is produced by using the above-mentioned thermosetting resin composition, the above-mentioned insulating film, or interlayer insulating film and curing the same. This semiconductor device is excellent in high frequency characteristics and heat resistance reliability due to the cured product of the thermosetting resin composition, the insulating film, or the cured product of the interlayer insulating film (the amount of change in dielectric loss tangent (tan δ) is changed). small). Here, the semiconductor device refers to all devices that can function by utilizing the semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, and the like.

The present invention will be described with reference to Examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and% by mass unless otherwise specified.

[Examples 1 to 11 and Comparative Examples 1 to 3]
<Preparation of thermosetting resin composition>
With the formulations shown in Tables 1 and 2, each component is measured in a container, stirred and mixed with a rotating / revolving stirrer (product name: Mazellster (registered trademark), manufactured by Kurabou) for 3 minutes, and then dispersed using a bead mill. , The viscosity was adjusted with toluene to prepare a thermosetting resin composition. Next, the thermosetting resin composition was applied onto a polyethylene terephthalate (PET) substrate with a coating machine to a thickness of 50 to 100 μm, and dried at 100 to 120 ° C. for 10 to 20 minutes. It was made into a film.

Here, the OPE-2St 2200 shown in Tables 1 and 2 is a styrene-terminated PPE (molecular weight (Mn): 2200) manufactured by Mitsubishi Gas Chemical Company, Inc.
OPE-2St 1200 is a styrene-terminated PPE (molecular weight (Mn): 1200) manufactured by Mitsubishi Gas Chemical Company, Inc.
AO-20 is a ADEKA hindered phenolic antioxidant (melting point: 220-222 ° C.).
AO-330 is a ADEKA hindered phenolic antioxidant (melting point: 243 to 245 ° C.).
AO-80 is an ADEKA hindered phenolic antioxidant (melting point: 110-120 ° C., 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) pro. Pionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane:

G1652 is a Kraton polymer SEBS (30% styrene ratio elastomer).
G1657 is a Kraton polymer SEBS (13% styrene ratio elastomer).
KBM-1403 is a styryl-based coupling agent (p-styryltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.
Cabras 4 is a sulfide-based coupling agent manufactured by Osaka Soda.
For SFP-130MC M treatment, DENKA SiO ₂ filler (average particle size: 0.7 μm product) and methacrylic coupling agent (3-methacryloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM) -503) The processed product
For FB-3SDX M treatment, DENKA SiO ₂ filler (average particle size: 3.4 μm product) and methacrylic coupling agent (3-methacryloxypropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM) -503) Processed product,
For FB-3SDX O treatment, DENKA SiO ₂ filler (average particle size: 3.4 μm product) and octenyl coupling agent (Shin-Etsu Chemical Co., Ltd. 7-octenyltrimethoxysilane, product name: KBM- 1083) The processed product
For FB-3SDX untreated, use DENKA SiO ₂ filler (average particle size: 3.4 μm product).
used.

〔Evaluation method〕

<Dielectric property>
The film peeled from the PET substrate is press-cured at 200 ° C. for 1 hour at 1 MPa, cut into 70 × 50 mm, and subjected to a dielectric resonance frequency of 10 GHz by a split post dielectric resonator (SPDR) at room temperature. The relative permittivity (ε) and dielectric loss tangent (tan δ) of wetness were measured. The relative permittivity is preferably 3.5 or less, and the dielectric loss tangent is preferably 0.0030 or less. The results are shown in Tables 1 and 2.

<Heat resistance (tan δ change)>
The cured film having the above-mentioned dielectric properties measured was left at 125 ° C. for 200 hours, and then tan δ was measured by the SPDR method (10 GHz) at room temperature and humidity to determine the amount of change and the rate of change of tan δ. The rate of change is preferably 80% or less. The results are shown in Tables 1 and 2.

<Solder heat resistance>
A film peeled from the PET base material was sandwiched between two Cu foils (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., product name: CF-T9FZSV), pressed and cured at 200 ° C. for 1 hour at 1 MPa, and then adhered. A test piece cut into 3 cm × 3 cm was used as a test piece, floated in a solder bath at 270 ° C. for 60 seconds, and the presence or absence of swelling was visually confirmed. When there was no change in the appearance such as swelling, it was evaluated as "OK" (passed), and when swelling was observed, it was evaluated as "NG" (failed). The results are shown in Tables 1 and 2.

<Moisture resistance reliability (tan δ change)>
The cured film whose dielectric properties were measured described above was left in a constant temperature and humidity chamber at 85 ° C./85% RH for 200 hours, and then tanδ was measured by the SPDR method (10 GHz) at room temperature and humidity, and the change in tanδ. The amount and rate of change were calculated. The rate of change is preferably 55% or less, more preferably 45% or less, and even more preferably 40% or less. Table 3 shows the results.

As can be seen from Tables 1 to 11, Examples 1 to 11 have a relative permittivity (ε), a dielectric loss tangent (tan δ), heat resistance reliability (change amount and change rate of tan δ), solder heat resistance, and moisture resistance reliability. Good results in all. Further, in Examples 1 to 10, the result of moisture resistance reliability (change amount of tan δ, change rate) was also better. In Example 11 using a silica filler not treated with a silane coupling agent, the result of moisture resistance reliability was 53%. This is because the moisture resistance of the silica filler itself is poor, and the moisture resistance reliability is lowered by simply adding the silica filler, whereas the surface treatment of the silica filler can prevent the deterioration of the moisture resistance reliability. ,it is conceivable that. Further, when comparing Examples 1 and 6 in which the molecular weights of the component (A) are different, it can be seen that the smaller the molecular weight, the worse the heat reliability result and the more the oxidative deterioration progresses. On the other hand, in Comparative Examples 1 and 2 in which the component (B) was not used, the rate of change in moisture resistance reliability was large. Further, in Comparative Example 3 in which the component (B') was used, the solder heat resistance was poor.

The thermosetting resin composition of the present invention can form an insulating film or an interlayer insulating film having excellent high frequency characteristics and heat resistance (the amount of change in dielectric loss tangent (tan δ) is small) and excellent solder heat resistance. It is very useful. The multilayer wiring board of the present invention is excellent in high frequency characteristics and heat resistance reliability due to the cured product of the thermosetting resin composition, the insulating film, or the cured product of the interlayer insulating film (dielectric loss tangent (tan δ)). The amount of change is small). The semiconductor device of the present invention is excellent in high frequency characteristics and heat resistance reliability due to the cured product of the thermosetting resin composition, the insulating film, or the cured product of the interlayer insulating film (change in dielectric loss tangent (tan δ)). (Small amount), suitable for high frequency applications.

Claims (9)

(A) Polyphenylene ether having an unsaturated double bond at the terminal and having a number average molecular weight of 800 to 4500.
A thermosetting resin composition comprising (B) a phenolic antioxidant having a melting point of 200 ° C. or higher, and (C) a thermoplastic elastomer. The thermosetting resin composition according to claim 1, further comprising (D) an inorganic filler. A silica filler in which the component (D) is surface-treated with a silane coupling agent represented by the general formula (10).

(In the formula, R ^{21 to} R ²³ are independently alkyl groups having 1 to 3 carbon atoms, R ²⁴ is a functional group having an unsaturated double bond at least at the terminal, and n is. The thermosetting resin composition according to claim 1 or 2, which comprises (3 to 9). The thermosetting resin composition according to any one of claims 1 to 3, wherein R ²⁴ of the general formula (10) is a vinyl group or a (meth) acrylic group. An insulating film containing the thermosetting resin composition according to any one of claims 1 to 4. An interlayer insulating film containing the thermosetting resin composition according to any one of claims 1 to 4. A cured product of the resin composition according to any one of claims 1 to 4, an insulating film according to claim 5, or a cured product of an interlayer insulating film according to claim 6. A multilayer wiring board having a cured product of the resin composition according to any one of claims 1 to 4, an insulating film according to claim 5, or a cured product of an interlayer insulating film according to claim 6. A semiconductor device having a cured product of the thermosetting resin composition according to any one of claims 1 to 4, a cured product of the insulating film according to claim 5, or a cured product of the interlayer insulating film according to claim 6.