KR20200079509A - Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device - Google Patents

Abstract

An object of the present invention is to provide a polyphenylene ether (PPE)-based thermosetting resin composition excellent in high-frequency characteristics and heat-resistance reliability (the amount of change of the dielectric tangent (tanδ) is small) and also excellent in solder heat resistance. A thermosetting resin comprising (A) a polyphenylene ether having a number average molecular weight of 800 to 4500 having an unsaturated double bond at the terminal, (B) a phenolic antioxidant having a melting point of 200°C or higher, and (C) a thermoplastic elastomer. It is a composition.

Description

Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device

The present invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device. In particular, it relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device capable of coping with high frequency.

Currently, high frequency is often required for electronic devices such as various communication devices. For example, low transmission loss is often required for multilayer printed wiring boards for high frequency applications such as millimeter wave communication. It is known to use polyphenylene ether (PPE) having excellent high-frequency properties as a material used for the adhesive layer, coverlay, or substrate itself of this high-frequency multilayer printed wiring board.

On the other hand, it has been reported to use a curing component such as epoxy or an elastomer to have a PPE level high-frequency property in a resin composition (Patent Document 1), and the phenolic antioxidant contained in the epoxy resin exhibits a high-frequency property in the resin composition. It is described that it can be used without deterioration.

Japanese Patent Publication No. 2014-201642

However, it is preferable to make the thermosetting PPE low molecular weight from the viewpoint of reactivity and solubility in a solvent.

However, the present inventors have found that the PPE polymer obtained by polymerizing a low molecular weight thermosetting PPE has a problem that oxidation deterioration at a high temperature is very fast and the dielectric tangent (tanδ) value after the heat resistance reliability test fluctuates when used in a multilayer wiring board. I figured it out. In addition, solder heat resistance is also required for the multilayer wiring board, and this need also needs to be satisfied.

An object of the present invention is to provide a PPE-based thermosetting resin composition excellent in high-frequency characteristics and heat-resistance (the amount of change in the dielectric loss tangent (tanδ) is small) and also excellent in solder heat resistance in view of the above.

The present invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device that solves the above problems by having the following structures.

[1] (A) Polyphenylene ether having a number average molecular weight of 800 to 4500 having an unsaturated double bond at the terminal,

(B) a phenolic antioxidant having a melting point of 200°C or higher, and

(C) Thermoplastic elastomer

Thermosetting resin composition comprising a.

[2] The thermosetting resin composition according to the above [1], further comprising (D) an inorganic filler.

[3] A silica filler whose component (D) is surface-treated with a silane coupling agent represented by formula (10)

(Wherein, R ²¹ to R ²³ are each independently an alkyl group 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 3 to 9). Or the thermosetting resin composition as described in [2].

[4] The thermosetting resin composition according to any one of [1] to [3], wherein R ²⁴ in Formula (10) is a vinyl group or a (meth)acrylic group.

[5] An insulating film comprising the thermosetting resin composition according to any one of [1] to [4].

[6] An interlayer insulating film containing the thermosetting resin composition according to any one of [1] to [4].

[7] A cured product of the resin composition according to any one of [1] to [4], a cured product of the insulating film as described in [5], or an interlayer insulating film as described in [6] above.

[8] A multilayer wiring board having a cured product of the resin composition according to any one of [1] to [4] above, a cured product of the insulating film of [5] or an interlayer insulating film of [6].

[9] A semiconductor device comprising a cured product of the thermosetting resin composition according to any one of [1] to [4], an insulating film as described in [5], or a cured product as the interlayer insulating film as described in [6] above.

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

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

ADVANTAGE OF THE INVENTION According to this invention [7], the multilayer wiring board excellent in high frequency characteristics and heat resistance can be provided by the hardened|cured material of the said thermosetting resin composition, the said insulating film, or the hardened|cured material of the interlayer insulating film. ADVANTAGE OF THE INVENTION According to this invention [8], the multilayer wiring board excellent in high frequency characteristics and heat resistance can be provided by the hardened|cured material of the said thermosetting resin composition, the said insulating film, or the hardened|cured material of the interlayer insulating film. According to the present invention [9], a semiconductor device excellent in high-frequency characteristics and heat resistance can be provided by a cured product of the thermosetting resin composition, a cured product of the insulating film or the interlayer insulating film.

[Thermosetting resin composition]

The thermosetting resin composition of the present invention,

(A) polyphenylene ether having a number average molecular weight of 800 to 4500 having an unsaturated double bond at the terminal,

(B) a phenolic antioxidant having a melting point of 200°C or higher, and

(C) It contains a thermoplastic elastomer.

The component (A) is a polyphenylene ether having a number average molecular weight of 800 to 4500 having an unsaturated double bond at the terminal, and imparting adhesiveness, high-frequency properties, and heat resistance to the thermosetting resin composition (hereinafter referred to as a thermosetting resin composition) of the present invention. do. Here, the high frequency characteristic refers to a property of reducing transmission loss in a high frequency region. The component (A) is preferable from the viewpoint of high-frequency characteristics when the relative dielectric constant (ε) at 10 GHz is 3.5 or less and the dielectric loss tangent (tanδ) is 0.003 or less. 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 terminal, it has excellent high-frequency properties and is measured at a high temperature (120°C) relative to a temperature dependence of dielectric properties (especially tanδ) (measured at room temperature (25°C)). Since the change in value) is small, the compound represented by formula (1) is preferred.

(In formula (1), -(O-X-O)- is represented by 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 an alkyl group or a phenyl group having 6 or less carbon atoms. R ⁴ , R ⁵ , R ⁶ may be the same or different. 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 , R ¹⁶ may be the same or different, and are a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group- A- is a straight, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms)

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

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

(In formula (1), a and b represent an integer of 0 to 100 in which at least one is not 0)

(For -A- in formula (3), for example, methylene, ethylidene, 1-methylethylidene, 1,1-propylidene, 1,4-phenylenebis(1-methylethylidene) , Divalent organic groups such as 1,3-phenylene bis (1-methylethylidene), cyclohexylidene, phenylmethylene, naphthylmethylene, and 1-phenylethylidene, but are not limited to these. )

(As a compound represented by Formula (1), R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹⁷ , 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 , R ²⁰ is preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, and in particular formula (2) or formula (3 -(OXO)- represented by) is a formula (5), a formula (6), or a formula (7), -(YO)- represented by a formula (4) is a formula (8) or a formula (9), or It is more preferable that the structures (8) and (9) are randomly arranged.

The method for producing the compound represented by formula (1) is not particularly limited, and, for example, vinylbenzyl terminal phenolic hydroxyl group of the bifunctional phenylene ether oligomer obtained by oxidative coupling of the bifunctional phenol compound and the monofunctional phenol compound. It can be prepared by etherification.

(A) The number average molecular weight of the thermosetting resin of the component is in the range of 800 to 4,500 in terms of polystyrene by the GPC method, and more preferably in the range of 1000 to 3500, reducing the starting point of oxidation deterioration by polymerization, and achieving low viscosity. From the viewpoint of, the range of 1500-2500 is more preferable. If the number average molecular weight is 800 or more, it is difficult to stick when the thermosetting resin composition of the present invention is formed into a coating film, and if it is 4,500 or less, a decrease in solubility in a solvent can be prevented. (A) Components 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. When the melting point of the component (B) is less than 200°C, the solder heat resistance of the thermosetting resin becomes insufficient. (B) As a phenolic antioxidant having a melting point of 200°C or higher, 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-trimethyl And benzene, 6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, and the like.

As a commercial item of the component (B), 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 Adeca, product name: AO-330, melting point: 243 to 245 ℃)：

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 dielectric properties (especially tanδ) (high temperature (120°C) with respect to the measured value at room temperature (25°C)) Hydrophobic styrene thermoplastic elastomer is more preferable from the viewpoint of small). On the other hand, when the polybutadiene is added, the heat resistance becomes good, but the temperature dependence may increase.

The preferred hydrogenated styrene-based thermoplastic elastomer as component (C) is a styrene-based block copolymer obtained by unsaturated double bonds of a main chain in a molecule, and the hydrogenated styrene-based block copolymer includes styrene-ethylene/butylene-styrene block copolymers ( SEBS), styrene-(ethylene-ethylene/propylene)-styrene block copolymer (SEEPS), styrene-ethylene/propylene-styrene block copolymer (SEPS), and the like, and SEBS and SEEPS are preferred. This is because SEBS and SEEPS have excellent dielectric properties and are compatible with polyphenylene ether (PPE), modified PPE, which is an option for component (A), and can form a thermosetting resin composition having heat resistance. In addition, since the styrenic block copolymer also contributes to low elasticity of the thermosetting resin composition, it is preferable for applications in which flexibility is imparted to the insulating film and low elasticity of 3 GPa or less is required for the cured product of the thermosetting resin composition.

The weight average molecular weight of the component (C) is preferably 30,000 to 200,000, and 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, and 20 to 60 parts by mass with respect to 100 parts by mass of the components (A) and (C) It is more preferable.

(A) When there are few components, hardening of the hardened|cured material of a thermosetting resin composition will not be enough, and problems, such as a fall in peel strength, an increase in thermal expansion coefficient (CTE), and fall in heat resistance, will arise easily. (A) When there are many components, the film produced from a thermosetting resin composition is hard, fragile, brittle, and the film property is damaged, and the hardened|cured material of a thermosetting resin composition is also hard, fragile, and peel strength falls or heat shock It is easy to cause cracks due to or problems such as a decrease in heat resistance due to oxidation at high temperatures.

As the resins 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, more preferably 0.3 to 5 parts by mass, and particularly preferably 0.5 to 2 parts by mass, from the viewpoint of high-frequency properties, with respect to 100 parts by mass of the resin component in the thermosetting resin composition. .

The thermosetting resin is preferred from the viewpoint of lowering the CTE of the cured product of the thermosetting resin when (D) further includes an inorganic filler. (D) As a component, it is preferable that it is a silica filler from a viewpoint of high frequency characteristics. (D) The inorganic filler of a component is more preferable from a viewpoint of moisture resistance reliability, if it is surface-treated. Formula (10):

(In the formula, R ²¹ to R ²³ are each independently an alkyl group 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 3 to 9). It is preferable from the viewpoint of improving moisture resistance, and in the formula, n is more preferably 5 to 9. Moreover, it is preferable that R ²⁴ of Formula (10) is a vinyl group or (meth)acrylic group from a viewpoint of adhesiveness with (A) by reactivity, and if it is a vinyl group, it is more preferable from a peel strength viewpoint.

Examples of the silane coupling agent that can be used in the component (D) include octenyl trialkoxysilane, (meth)acryloxyalkyl trialkoxysilane, and 3-methacryloxypropyl trimethoxysilane. Examples of the octenyl trialkoxysilane include octenyl trimethoxysilane and octenyl triethoxysilane. Examples of the (meth)acryloxyalkyltrialkoxysilane include (meth)acryloxyoctyltrimethoxysilane, (meth)acryloxyoctyltriethoxysilane, and the like. Octenyl trimethoxysilane is more preferable from the viewpoint of improving the peel strength of the thermosetting resin composition. (D) As a commercial product of a silane coupling agent that can be used for the component, octenyl trimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. (Product name: KBM-1083), methacryloxyoctyl trimethoxy manufactured by Shin-Etsu Chemical Co., Ltd. Silane (product name: KBM-5803), 3-methacryloxypropyl trimethoxysilane (product name: KBM-503) manufactured by Shin-Etsu Chemical Industry Co., Ltd. are mentioned. (D) The silane coupling agent which can be used for a component may be individual or 2 or more types may be sufficient as it.

Examples of the silica filler used in the component (D) include fused silica, ordinary silica, 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 coefficient, adhesion, etc., spherical fused silica is preferred. Further, the average particle diameter of the silica filler (if it is not spherical, the average maximum diameter) is not particularly limited, but is preferably 0.05 to 20 µm, and preferably 0.1 to 10 µm, from the viewpoint of improving moisture resistance after curing due to the small specific surface area. It is more preferable than this, and more preferably 1 to 10 µm. Here, the average particle diameter of the silica filler refers to a median diameter based on volume measured by a laser scattering diffraction particle size distribution measuring device.

The method of surface-treating a silica filler using the above-mentioned coupling agent is not specifically limited, For example, a dry method, a wet method, etc. are mentioned.

In the dry method, a suitable amount of the silica filler and the surface area of the silica filler while stirring under suitable conditions by adding an appropriate amount of a silane coupling agent to the surface area of the silica filler and stirring in an agitating device or stirring the silica filler in an appropriate condition beforehand It is a method of adding a silane coupling agent of, by dripping or spraying with a stock solution or a solution, and uniformly adhering the silane coupling agent to the surface of the silica filler by stirring, thereby surface treatment (by hydrolysis). As the stirring device, for example, a mixer capable of stirring and mixing by high-speed rotation such as a Henschel mixer is mentioned, but is not particularly limited.

In the wet method, a silica filler is added to a surface treatment solution in which a sufficient amount of a silane coupling agent is dissolved in water or an organic solvent with respect to the surface area of the silica filler subjected to the surface treatment, and the mixture is stirred to form a slurry, thereby sufficiently providing the silane coupling agent and the silica filler. After the reaction, the silica filler is separated from the surface treatment solution by filtration, centrifugation, or the like, and then heated and dried to perform surface treatment.

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

(D) The component is preferably 45 to 75% by volume (64 to 88% by mass if it is a solid silica filler), and 50 to 70% by volume in the thermosetting resin composition (however, the solvent is excluded) from the viewpoint of low CTE. (If it is a solid silica filler, it is more preferable that it is 69-85 mass %). When there are few (D) components, CTE of a desired thermosetting resin composition cannot be achieved, and if there are many (D) components, peeling strength of a thermosetting resin composition will fall easily.

On the other hand, the thermosetting resin composition is an organic peroxide as a curing accelerator for component (A) or a silane coupling agent (integral blend), flame retardant, tackifier, antifoaming agent, flow, within the range that does not impair the effects of the present invention. Additives such as modifiers, thixotropic agents, dispersants, antioxidants, and flame retardants may be included. As the silane coupling agent, P-styryl trimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-1403), bis(triethoxysilylpropyl) tetrasulfide (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBE-846) , Polysulfide silane coupling agent (Osaka Soda Co., Ltd., Cabrus 4), octenyl trimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM-1083), methacryloxyoctyl trimethoxysilane (Shin-Etsu Chemical Industry) Co., Ltd., KBM-5803), 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Industry Co., Ltd., KBM-503), 3-methacryloxypropyl triethoxysilane (Shin-Etsu Chemical Industry Co., Ltd. ) Preparation, KBE-503), 3-glycidoxypropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-403), 3-glycidoxypropyl triethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) , KBE-403) and the like. Examples of the flame retardant include phosphinic acid metal salt (manufactured by Clariant Japan, OP-935).

The thermosetting resin composition can be produced by dissolving or dispersing raw materials such as components (A), (B), and (C) in an organic solvent. The apparatus for dissolving or dispersing these raw materials is not particularly limited, but a stirrer, a dissolver, a threshing machine, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. with a heating device can be used. Moreover, you may use it combining these apparatus suitably.

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 solvents may be used alone or in combination of two or more. From the viewpoint of workability, the thermosetting resin composition is preferably in the range of viscosity of 200 to 3000 mPa·s. The viscosity is a value measured at 50 rpm and 25°C using an E-type viscometer.

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

[Insulating film]

The insulating film of the present invention includes the above-mentioned thermosetting resin composition. The insulating film is formed into a desired shape from the thermosetting resin composition. Specifically, the insulating film can be obtained by applying the above-mentioned thermosetting resin composition on a support and drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, polyester resins, polyethylene resins, and organic films such as polyethylene terephthalate resins (PET). The support may be subjected to a release treatment with a silicone-based compound or the like. Meanwhile, 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 preferred from the viewpoint of thinning and film thickness control. By the slot die method, an uncured film of 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 depending on 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 about 50 to 120°C for about 1 to 60 minutes. The insulating film thus obtained has good storage stability. On the other hand, the insulating film can be peeled from the support at a desired timing.

The insulating film can be cured, for example, at 150 to 230° C. for 30 to 180 minutes. The interlayer insulating film of the present invention can be produced in the same manner as described above, and can also be cured. When an insulating film is used as an interlayer insulating film, curing of the interlayer insulating film may be performed by sandwiching an interlayer insulating film between substrates on which wirings made of copper foil or the like are formed, and an interlayer insulating film having wirings formed of copper foil or the like is appropriately laminated. You may do it after. Further, the insulating film can also be used as a coverlay film to protect the wiring on the substrate, and the curing conditions at that time are also the same. On the other hand, the thermosetting resin composition can be cured in the same way. Further, during curing, for example, press curing may be performed at a pressure of 1 to 5 MPa.

[Multi-layer wiring board]

The multilayer wiring board of the present invention has a cured product of the above-mentioned thermosetting resin composition, a cured product of the above-described insulating film or an interlayer insulating film. The printed wiring board of the present invention is produced by using the above-mentioned thermosetting resin composition, the above-described insulating film or interlayer insulating film, and curing it. This printed wiring board is excellent in high-frequency characteristics and heat-resistant reliability (the amount of change in the dielectric loss tangent (tanδ) is small) by the cured product of the thermosetting resin composition, the cured product of the insulating film or the interlayer insulating film, and also the solder heat resistance. great. Among the multilayer wiring boards, there may be mentioned printed wiring boards for high-frequency applications such as microwave or millimeter-wave communication substrates, in particular, millimeter-wave radar substrates for automobiles. The manufacturing method of the multilayer wiring board is not particularly limited, and the same method as in the case of manufacturing a 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-described thermosetting resin composition, the above-described insulating film or interlayer insulating film, and curing it. This semiconductor device is excellent in high-frequency characteristics and heat resistance by a cured product of the thermosetting resin composition, a cured product of the insulating film or an interlayer insulating film (the amount of change in the dielectric loss tangent (tanδ) is small). Here, the semiconductor device refers to an overall device capable of functioning by using semiconductor characteristics, and includes electronic components, semiconductor circuits, modules combining them, and electronic equipment.

Example

Although this invention is demonstrated by an Example, this invention is not limited to these. On the other hand, in the following examples, parts and% represent parts by mass and mass% unless otherwise stated.

[Examples 1 to 11 and Comparative Examples 1 to 3]

<Production of a thermosetting resin composition>

With the composition shown in Tables 1 to 2, each component was weighed into a container, stirred and mixed for 3 minutes with a rotating/revolution type stirrer (product name: Magerstar (registered trademark), manufactured by Kurabo Industries), and then used a bead mill. It dispersed and adjusted the viscosity with toluene to adjust the thermosetting resin composition. Subsequently, the thermosetting resin composition was applied on a polyethylene terephthalate (PET) substrate to a thickness of 50 to 100 µm by an applicator, and dried at 100 to 120°C for 10 to 20 minutes to form a film.

Here, the OPE-2St 2200 shown in Tables 1 to 2 is a styrene end-modified PPE (molecular weight (Mn): 2200) manufactured by Mitsubishi Gas Chemical Co., Ltd.,

OPE-2St 1200 is a styrene end-modified PPE (molecular weight (Mn): 1200) manufactured by Mitsubishi Gas Chemical Co., Ltd.,

AO-20 is a hindered phenolic antioxidant (melting point: 220 to 222°C) manufactured by ADEKA.

AO-330 is a hindered phenolic antioxidant (melting point: 243 to 245°C) manufactured by ADEKA.

AO-80 is a hindered phenolic antioxidant manufactured by ADEKA (melting point: 110 to 120°C, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy ]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane:

G1652 is SEBS (Styrene Ratio 30% Elastomer) manufactured by Kraton Polymer,

G1657 is made of Kraton Polymer SEBS (styrene ratio 13% elastomer),

KBM-1403 is a styryl-based coupling agent (p-styryl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.,

Cabrus 4 is a sulfide-based coupling agent manufactured by Osaka Soda,

SFP-130MC M treatment is a methacryl-based coupling agent (3-methacryloxypropyl trimethoxysilane manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name: KBM-503) to an SiO ₂ filler (average particle size: 0.7 µm) manufactured by DENKA. What has been processed,

The FB-3SDX M treatment is a methacrylic coupling agent (a 3-methacryloxypropyl trimethoxysilane manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name: KBM-503) to a SiO ₂ filler (average particle size: 3.4 µm) manufactured by DENKA. What has been processed,

The FB-3SDX O treatment was carried out by treatment with an octenyl-based coupling agent (7-octenyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd., product name: KBM-1083) with an SiO ₂ filler (average particle size: 3.4 µm manufactured by DENKA). Thing,

For the untreated FB-3SDX, a DENKA SiO ₂ filler (average particle size: 3.4 μm) was used.

[Assessment Methods]

<Genetic characteristics>

The film peeled from the PET substrate was press-cured at 200° C. for 1 hour at 1 MPa, and then cut to 70×50 mm, by a split post dielectric resonator (SPDR), at a dielectric resonance frequency of 10 GHz, and relative dielectric constant at normal temperature and humidity ( ε) and dielectric tangent (tanδ) were measured. The dielectric constant is preferably 3.5 or less and the dielectric loss tangent is 0.0030 or less. Tables 1 to 2 show the results.

<Heat resistance (tanδ change)>

After the cured film measuring the dielectric properties described above was left at 125°C for 200 hours, tanδ was measured by SPDR method (10 GHz) at normal temperature and humidity to obtain a change amount and a change rate of tanδ. The rate of change is preferably 80% or less. Tables 1 to 2 show the results.

<Solder heat resistance>

2 sheets of Cu foil (manufactured by Fukuda Metallic Foil Industry Co., Ltd., product name: CF-T9FZSV) were sandwiched by a film peeled from the PET substrate, pressed and cured at 200°C for 1 hour at 1 MPa, and then 3 cm x 3 What was cut into cm was used as a test piece, and floated in a solder bath at 270°C for 60 seconds to check whether or not expansion occurred. The case where there was no change in appearance such as expansion was set to "OK" (pass), and the case where expansion was observed was set to "NG" (pass). Tables 1 to 2 show the results.

<Reliability of moisture resistance (tanδ change)>

After the cured film measuring the dielectric properties described above was left in a constant temperature and humidity tank at 85°C/85%RH for 200 hours, tanδ was measured by SPDR method (10 GHz) at normal temperature and humidity to obtain a change amount and a change rate of tanδ. 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 3, Examples 1 to 11 show good results in terms of relative dielectric constant (ε), dielectric loss tangent (tanδ), heat resistance reliability (change amount of tanδ, change rate), solder heat resistance, and moisture resistance. It was. In addition, in Examples 1 to 10, the results of moisture resistance reliability (change amount of tanδ, rate of change) were also better. On the other hand, in Example 11 using a silica filler not treated with a silane coupling agent, the result of moisture resistance reliability was 53%. This is considered to be because, because the moisture resistance of the silica filler itself is poor, simply adding the silica filler lowers the moisture resistance reliability, and it is possible to prevent the degradation of the moisture resistance by performing the surface treatment of the silica filler. Further, when Examples 1 and 6 in which the molecular weights of the component (A) are different are compared, it can be seen that the smaller the molecular weight is, the worse the results of the heat resistance are, and oxidation deterioration proceeds. 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. In addition, the comparative example 3 using the component (B') had poor solder heat resistance.

The thermosetting resin composition of the present invention is very useful because it is excellent in high-frequency characteristics and heat-resistance reliability (the amount of change in the dielectric loss tangent (tanδ) is small), and also can form an insulating film or an interlayer insulating film excellent in solder heat resistance. The multilayer wiring board of the present invention is excellent in high-frequency characteristics and heat resistance by a cured product of the thermosetting resin composition, a cured product of the insulating film or an interlayer insulating film (the amount of change in the dielectric loss tangent (tanδ) is small). Since the semiconductor device of the present invention is excellent in high frequency characteristics and heat resistance by the cured product of the thermosetting resin composition, the cured product of the insulating film or the interlayer insulating film (because the amount of change in the dielectric loss tangent (tanδ) is small), the high frequency Suitable for use.

Claims (9)

(A) polyphenylene ether having a number average molecular weight of 800 to 4500 having an unsaturated double bond at the terminal,
(B) a phenolic antioxidant having a melting point of 200°C or higher, and
(C) Thermoplastic elastomer
Thermosetting resin composition comprising a. According to claim 1,
(D) A thermosetting resin composition comprising an inorganic filler. The method according to claim 1 or 2,
(D) Silica filler whose component was surface-treated with the silane coupling agent represented by Formula (10)

(In the formula, R ²¹ to R ²³ are each independently an alkyl group having 1 to 3 carbon atoms, R ²⁴ is at least a functional group having an unsaturated double bond at the terminal, and n is 3 to 9). The method according to any one of claims 1 to 3,
A thermosetting resin composition in which R ²⁴ in formula (10) is a vinyl group or a (meth)acrylic group. An insulating film comprising the thermosetting resin composition of any one of claims 1 to 4. An interlayer insulating film comprising the thermosetting resin composition of any one of claims 1 to 4. A cured product of the resin composition according to any one of claims 1 to 4, a cured product of the insulating film of claim 5 or the interlayer insulating film of 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 of claim 5, or a cured product of the interlayer insulating film of claim 6. The semiconductor device which has the hardened|cured material of the thermosetting resin composition of any one of Claims 1-4, the insulating film of Claim 5, or the hardened|cured material of the interlayer insulating film of Claim 6.