TW201930464A - Heat curable resin composition, insulation film, interlayer insulation film, multilayer wiring board and semiconductor apparatus - Google Patents

Abstract

An object of present invention is to provide a polyphenylene ether (PPE) type heat curable resin composition that has high frequency characteristics, excellent heat resistance reliability (change amount of dielectric loss tangent (tan [delta]) is small) and excellent solder heat resistance. Provided is a heat curable resin composition having (A) a polyphenylene ether having an unsaturated double bond at its terminal and having a number average molecular weight of 800 to 4500; (B) phenolic antioxidant having a melting point of 200 DEG C or higher; and (C) thermoplastic elastomer.

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 is a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device which can correspond to high frequency.

Today, electronic devices such as various communication devices require high frequency. For example, a multilayer printed wiring board for high-frequency applications such as millimeter wave communication requires low transmission loss. It is known that a polyphenylene ether (PPE) having excellent high-frequency characteristics is used as an adhesive layer or a coating layer of the multilayer printed wiring board for high-frequency use or a material used for the substrate itself.

On the other hand, it has been reported that the use of a hardening component such as an epoxy resin or an elastomer makes the resin composition have high-frequency characteristics comparable to PPE (Patent Document 1), and the phenol-based antioxidant contained in the epoxy resin can be prevented from being The high-frequency characteristics of the resin composition are deteriorated and used.

 [Previous Technical Literature]    [Patent Literature]  

Patent Document 1: Japanese Laid-Open Patent Publication No. 2014-201642.

Further, from the viewpoint of reactivity and solubility in a solvent, the thermosetting PPE is preferably low in molecular weight.

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

In view of the above, it is an object of the present invention to provide a PPE-based thermosetting resin composition which is excellent in high-frequency characteristics and heat-resistance reliability (the amount of change in dielectric loss tangent (tan δ) is small) and which is excellent in solder heat resistance.

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 the following configuration.

[1] A thermosetting resin composition comprising: (A) a polyphenylene ether having an average number of molecular weights of 800 to 4,500 having an unsaturated double bond at a terminal, and (B) a phenolic antioxidant having a melting point of 200 ° C or more And (C) a thermoplastic elastomer.

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

[3] The thermosetting resin composition according to the above [1], wherein the component (D) contains a cerium oxide filler surface-treated with a decane coupling agent represented by the formula (10). .

(wherein R ²¹ to R ²³ are each independently an alkyl group having 1 to 3 carbon atoms, and R ²⁴ is a functional group having an unsaturated double bond at least at the terminal, and n is 3 to 9).

[4] The thermosetting resin composition according to any one of the above [1], wherein R ²⁴ of the formula (10) is a vinyl group or a (meth) acrylonitrile group.

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

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

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

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

(9) A cured product of the thermosetting resin composition according to any one of the above [1] to [4], the insulating film according to [5], or the above [6] A cured product of an interlayer insulating film.

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

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

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

According to the invention [7], the cured product of the thermosetting resin composition, the insulating film or the cured product of the interlayer insulating film can provide a multilayer wiring board excellent in high frequency characteristics and heat resistance reliability. According to the invention [8], the cured product of the thermosetting resin composition, the insulating film or the cured product of the interlayer insulating film can provide a multilayer wiring board excellent in high frequency characteristics and heat resistance reliability. According to the invention [9], it is possible to provide a semiconductor device excellent in high-frequency characteristics and heat-resistance reliability by the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film.

[thermosetting resin composition]

The thermosetting resin composition of the present invention contains: (A) a polyphenylene ether having a number average molecular weight of 800 to 4,500 having an unsaturated double bond at the terminal, and (B) a phenolic antioxidant having a melting point of 200 ° C or more, and (C) Thermoplastic elastomer.

The component (A) is a polyphenylene ether having a number average molecular weight of 800 to 4,500, which has an unsaturated double bond at the terminal, and can impart adhesion to the thermosetting resin composition (hereinafter referred to as a thermosetting resin composition) of the present invention. , high frequency characteristics, heat resistance. Here, the high frequency characteristic means a property of reducing transmission loss in the high frequency range. From the viewpoint of high-frequency characteristics, the component (A) preferably has a specific dielectric constant (ε) of 10 GHz of 3.5 or less and a dielectric loss tangent (tan δ) of 0.003 or less. The component (A) is preferably a polyphenylene ether having a styryl group at the terminal.

The polyphenylene ether (PPE) having a styryl group at the terminal is preferably a compound represented by the formula (1) because of its high frequency characteristics and temperature dependence of dielectric properties (especially tan δ) (relative to normal temperature (25) °C) The measured value is small in the change in the measured value at high temperature (120 ° C).

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

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

(In the 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 are a hydrogen atom, an alkyl group having 6 or less carbon atoms or a benzene group. -A- is a linear, branched or cyclic divalent hydrocarbon group having a carbon number of 20 or less.)

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

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

(In the formula (1), a and b represent an integer of 0 to 100, and at least either of them is not 0.)

(-A- in the formula (3) may, for example, be a methylene group, an ethylene group, a 1-methylethylene group, a 1,1-propylene group, a 1,4-phenylene bis(1-methyl group) Ethylene), 1,3-phenylene bis(1-methylethylidene), cyclohexylene, phenylmethylene, naphthylmethylene, 1-phenylethylene, etc. Base, but not limited to these.)

(The compound represented by the formula (1) is preferably R ¹ , R ² , R ³ , R ⁷ , R ⁸ , R ¹⁷ and R ¹⁸ are an alkyl group having 3 or less carbon atoms, and R ⁴ , R ⁵ and R ⁶ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁹ and R ²⁰ are each a hydrogen atom or an alkyl group having 3 or less carbon atoms, particularly preferably a formula (2). Or -(OXO)- represented by the formula (3) is a formula (5), a formula (6), or a formula (7), and a formula (4)-(YO)- is a formula (8) or a configuration in which (9) or (8) and (9) are randomly arranged.)

The method for producing the compound represented by the formula (1) is not particularly limited. For example, the bifunctional phenol compound and the monofunctional phenol compound may be oxidatively coupled, and the terminal phenolic hydroxyl group of the obtained bifunctional phenyl ether oligomer may be subjected to vinyl benzophenone. It is produced by 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 1,000 to 3,500, to reduce the oxidative degradation starting point due to polymerization and to From the standpoint of low viscosity, it is more preferably in the range of 1,500 to 2,500. When the number average molecular weight is 800 or more, the thermosetting resin composition of the present invention is less likely to be adhered when it is formed into a coating film shape, and when it is 4,500 or less, the solubility in a solvent can be prevented from being lowered. The component (A) may be used singly or in combination of two or more.

The component (B) is a phenol-based antioxidant having a melting point of 200 ° C or higher, and the solder heat resistance can be imparted 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 is insufficient. The phenol-based antioxidant having a melting point of (B) of 200 ° C or higher may be 1,3,5-gin(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5- Triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-gin (3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4, 6-trimethylbenzene, 6,6'-di-tert-butyl-4,4'-butylene-di-cresol, and the like.

The commercially available product of the component (B) may, for example, be 1,3,5-gin(3,5-di-t-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-parade (3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene (made by ADEKA, product name: AO-330, melting point: 243 To 245 ° C).

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

The component (C) exhibits a function of imparting flexibility to the thermosetting resin composition to impart flexibility. From the viewpoint of dielectric properties, the thermoplastic elastomer of the component (C) is preferably a styrene-based thermoplastic elastomer, and has a temperature dependence of dielectric properties (especially tan δ) (measured relative to a normal temperature (25 ° C)). From the viewpoint of a small change in the measured value at a high temperature (120 ° C), a hydrogenated styrene-based thermoplastic elastomer is more preferable. Further, although the polybutadiene is hydrogenated, the heat resistance is good, but the temperature dependency is increased.

The hydrogenated styrene-based thermoplastic elastomer which is preferably a component (C) is a hydrogenated styrene block copolymer having a main chain unsaturated double bond in the molecule, and the hydrogenated styrene block copolymer may be styrene. -ethylene/butylene-styrene block copolymer (SEBS), styrene-(ethylene-ethylene/propylene)/styrene block copolymer (SEEPS), styrene-ethylene/propylene-styrene block copolymer (SEPS), etc., preferably SEBS, SEEPS. Since SEBS or SEEPS is excellent in dielectric properties, and has good compatibility with polyphenylene ether (PPE) or modified PPE which is an option of the component (A), a heat-resistant thermosetting resin composition can be formed. In addition, since the styrene-based block copolymer contributes to the low elasticity of the thermosetting resin composition, flexibility can be imparted to the insulating film, and it is suitable for the cured product of the thermosetting resin composition to be 3 GPa or less. The use of low elasticity.

The weight average molecular weight of the component (C) is preferably from 30,000 to 200,000, more preferably from 80,000 to 120,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. The component (C) may be used singly 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, more preferably 20 to 60 parts by mass, per 100 parts by mass of the total of the components (A) and (C). .

When the amount of the component (A) is small, the curing of the cured product of the thermosetting resin composition is insufficient, and the peeling strength is lowered, the thermal expansion coefficient (CTE) is increased, and the heat resistance is lowered. When the amount of the component (A) is large, the film made of the thermosetting resin composition is hard, brittle, and easily broken, and the film property is impaired, and the cured product of the thermosetting resin composition is hard and brittle. It is easy to cause a decrease in peel strength, cracking due to thermal shock, and a problem such as reduction in heat resistance reliability due to oxidation at a high temperature.

As the resin other than the component (A) and the component (C), for example, an epoxy resin, a maleimide resin, a cyanate resin, or a polyimide resin can 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, more preferably 0.3 to 5 parts by mass, based on 100 parts by mass of the resin component in the thermosetting resin composition, from the viewpoint of high-frequency characteristics. 0.5 to 2 parts by mass.

The thermosetting resin preferably further contains (D) an inorganic filler from the viewpoint of lowering the CTE of the cured product of the thermosetting resin. From the viewpoint of high frequency characteristics, the component (D) is preferably a cerium oxide filler. From the viewpoint of moisture resistance reliability, the inorganic filler of the component (D) is preferably surface-treated. The surface treatment agent is preferably a decane coupling agent represented by the general formula (10) from the viewpoint of improving moisture resistance:

(wherein R ²¹ to R ²³ are each independently an alkyl group having 1 to 3 carbon atoms, and R ²⁴ is a functional group having an unsaturated double bond at least at the terminal, and n is 3 to 9). Further, it is more preferable that n in the formula is 5 to 9. Further, R ^{24 of the} general formula (10) is preferably a vinyl group or a (meth)acryl fluorenyl group from the viewpoint of reactivity and the adhesion to (A), and from the viewpoint of peel strength, Good for vinyl.

The decane coupling agent which can be used for the component (D) may, for example, be an octenyltrialkoxydecane or a (meth)acryloxyalkyltrialkoxy alkane or a 3-methylpropenyloxypropyltrimethoxy group. Base decane. The octenyltrialkoxide may, for example, be octenyltrimethoxydecane or octenyltriethoxydecane. Examples of the (meth)acryloxyalkyltrial alkoxy decane include (meth) propylene oxime octyl trimethoxy decane, (meth) propylene decyl octyl triethoxy decane, and the like. From the viewpoint of improving the peel strength of the thermosetting resin composition, octenyltrimethoxydecane is more preferable. A commercially available product of a decane coupling agent which can be used as the component (D) is exemplified by octyl methoxy decane (product name: KBM-1083) manufactured by Shin-Etsu Chemical Co., Ltd., and methacryl oxime manufactured by Shin-Etsu Chemical Co., Ltd. Oxyoctyltrimethoxydecane (product name: KBM-5803), 3-methylpropenyloxypropyltrimethoxydecane manufactured by Shin-Etsu Chemical Co., Ltd. (product name: KBM-503). The decane coupling agent which can be used for the component (D) may be singly or in combination of two or more.

The cerium oxide filler used in the component (D) is, for example, a molten cerium oxide, a common vermiculite, a spherical cerium oxide, a crushed cerium oxide, a crystalline cerium oxide, or an amorphous cerium oxide, and is not particularly limited. The spherical fused cerium oxide is preferred from the viewpoints of dispersibility of the cerium oxide filler, fluidity of the thermosetting resin composition, surface smoothness of the cured product, dielectric properties, low thermal expansion ratio, and adhesion. Further, the average particle diameter of the cerium oxide filler (the average longest diameter when it is not spherical) is not particularly limited, but it is preferably from the viewpoint of improving the moisture resistance after curing due to a small specific surface area. It is 0.05 to 20 μm, more preferably 0.1 to 10 μm, still more preferably 1 to 10 μm. Here, the average particle diameter of the cerium oxide filler refers to a volume-based median diameter measured by a laser scattering diffraction type particle size distribution measuring apparatus.

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

In the dry method, the cerium oxide filler and the cerium coupling agent having a suitable surface area relative to the surface area of the cerium oxide filler are added to the stirring device, stirred under appropriate conditions, or the cerium oxide filler is added to the stirring device in advance and stirred under appropriate conditions. At the same time, a suitable amount of the decane coupling agent relative to the surface area of the cerium oxide filler is added to the stock solution or solution by dropping or spraying, and the decane coupling agent is uniformly attached to the surface of the cerium oxide filler by stirring (by The surface is hydrolyzed) to be surface treated (by hydrolysis). The stirring device may, for example, be a mixer that can be stirred and mixed at a high speed, such as a Henschel mixer, but is not limited thereto.

In the wet method, after a sufficient amount of the decane coupling agent is dissolved in water or an organic solvent with respect to the surface area of the cerium oxide filler to be surface-treated, a cerium oxide filler is added to the obtained surface treatment solution, and the mixture is stirred and mixed. In the form of a slurry, the cerium coupling agent is sufficiently reacted with the cerium oxide filler, and the cerium oxide filler is separated from the surface treatment solution by filtration, centrifugation or the like, and dried by heating to perform surface treatment.

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

From the viewpoint of low CTE, the component (D) is preferably 45 to 75 vol% in the thermosetting resin composition (but not including the solvent) (if the solid cerium oxide filler is 64 to 88% by mass) More preferably, it is 50 to 70% by volume (69 to 85% by mass in the case of a solid cerium oxide filler). When the component (D) is small, the CTE of the thermosetting resin composition to be obtained cannot be achieved, and if the component (D) is large, the peel strength of the thermosetting resin composition is likely to be lowered.

In addition, the thermosetting resin composition may contain an organic peroxide as a curing accelerator of the component (A) or a coupling agent such as a decane coupling agent (integrally blended), insofar as the effect of the present invention is not impaired. Additives such as flame retardants, adhesion imparting agents, defoamers, flow regulators, shakers, dispersants, antioxidants, and flame retardants. Examples of the decane coupling agent include p-styryl trimethoxy decane (KBM-1403 manufactured by Shin-Etsu Chemical Co., Ltd.) and bis(triethoxymethyl propyl) tetrasulfide (KBE manufactured by Shin-Etsu Chemical Co., Ltd.) -846), polysulfide decane coupling agent (CABRUS 4 manufactured by Osaka Soda Co., Ltd.), octenyl trimethoxy decane (KBM-1083 manufactured by Shin-Etsu Chemical Co., Ltd.), methacrylic acid oxime octyl Trimethoxydecane (KBM-5803, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxydecane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methylpropene oxime Oxypropyltriethoxydecane (KBE-503, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxydecane (KBM-403, Shin-Etsu Chemical Co., Ltd.), 3- Glycidoxypropyltriethoxydecane (KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The flame retardant may, for example, be a phosphonic acid metal salt (OP-935 manufactured by CLARIANT JAPAN).

A material such as the components (A), (B), and (C) constituting the resin composition can be dissolved or dispersed in an organic solvent to prepare a thermosetting resin composition. The apparatus for dissolving or dispersing the raw materials is not particularly limited, and a stirrer having a heating device, a dissolver, a pulverizer, a three-roll mill, a ball mill, a planetary mixer, a bead mill, or the like can be used. Moreover, it is suitable to use these apparatuses in combination.

Examples of the organic solvent include, for example, toluene and xylene. Examples of the ketone solvent include methyl ethyl ketone and methyl isobutyl ketone. The organic solvents may be used singly 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 was measured using an E-type viscometer at a rotation number of 50 rpm at 25 °C.

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 excellent in solder heat resistance.

[insulating film]

The insulating film of the present invention contains the above thermosetting resin composition. The insulating film is formed into a desired shape from a thermosetting resin composition. Specifically, the thermosetting resin composition is applied onto a support and dried, whereby an insulating film can be obtained. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, organic resins such as polyester resins, polyethylene resins, and polyethylene terephthalate resins (PET). The support may be subjected to a release treatment by a polyoxo compound or the like. Further, 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 from the viewpoint of film formation and control of the film thickness, a concave plate method, a slit mold method, or a doctor blade method is preferable. By the slit 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 kind or amount of the organic solvent used in the thermosetting resin composition, the coating thickness, and the like, and can be, for example, about 50 to 120 ° C for about 1 to 60 minutes. The insulating film thus obtained has good storage stability. Further, the insulating film can be peeled off from the support at a desired timing.

The hardening of the insulating film can be carried out, 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 be cured. When the insulating film is used as the interlayer insulating film, the interlayer insulating film may be cured by sandwiching the interlayer insulating film between the substrates formed by the copper foil or the like, or may be formed between the layers formed by the copper foil or the like. The insulating film is suitably laminated. Further, the insulating film may be used as a coating layer for protecting the wiring on the substrate, and the curing conditions at this time are also the same. Further, the thermosetting resin composition can be cured in the same manner. Further, it is also possible to carry out extrusion hardening at a pressure of, for example, 1 to 5 MPa at the time of hardening.

[Multilayer wiring board]

The multilayer wiring board of the present invention has a cured product of the above thermosetting resin composition, a cured product of the above insulating film or an interlayer insulating film. The printed wiring board of the present invention is produced by curing and curing the thermosetting resin composition, the insulating film, or the interlayer insulating film. The printed wiring board is excellent in high-frequency characteristics and heat-resistance reliability (dielectric loss tangent (tan δ) change by the cured product of the thermosetting resin composition, the insulating film, or the cured film of the interlayer insulating film. The amount is small) and the solder is excellent in heat resistance. The multilayer wiring board may be a substrate for microwave or millimeter wave communication, in particular, a printed wiring board for high frequency use such as a millimeter wave radar substrate for a vehicle. The method for producing the multilayer wiring board is not limited, and the same method as in the case of producing a printed wiring board using a general prepreg can be employed.

[semiconductor device]

The semiconductor device of the present invention is produced by curing and curing the thermosetting resin composition, the insulating film or the interlayer insulating film. The semiconductor device is excellent in high frequency characteristics and heat resistance reliability (change in dielectric loss tangent (tan δ) by the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film. small). Here, the semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules in which these are incorporated, electronic devices, and the like.

 (Example)  

The invention is illustrated by the examples, but the invention is not limited thereto. In the following examples, the parts and % represent parts by mass and mass% unless otherwise specified.

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

<Production of Thermosetting Resin Composition>

In the formulation shown in Tables 1 to 2, each component was weighed and mixed in a spinning/revolving mixer (product name: MAZERUSTAR (registered trademark), Kurashiki Textile Co., Ltd.) for 3 minutes, and then dispersed using a bead mill. The viscosity was adjusted with toluene to adjust the thermosetting resin composition. Next, the thermosetting resin composition is applied onto a polyethylene terephthalate (PET) substrate in a thickness of 50 to 100 μm by a coater, and dried at 100 to 120 ° C for 10 to 20 minutes to carry out. Membrane.

Here, the OPE-2St 2200 described in Tables 1 to 2 used a styrene-terminated PPE (molecular weight (Mn): 2,200) 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.

The AO-20 system uses a hindered phenol-based antioxidant (melting point: 220 to 222 ° C) manufactured by ADEKA.

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

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

G1652 uses SEBS (styrene to 30% elastomer) made of Kraton Polymer.

G1657 uses SEBS (styrene ratio 13% elastomer) manufactured by Kraton Polymer.

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

The CABRUS 4 system uses a thioether-based coupling agent from Osaka Soda.

SFP-130MC M treatment was carried out using SiO ₂ filler (average particle size: 0.7 μm) manufactured by DENKA to carry out a methacrylic coupling agent (3-methacryloxypropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Base decane, product name: KBM-503) treated.

FB-3SDX M treatment was carried out using SiO ₂ filler (average particle size: 3.4 μm) manufactured by DENKA to carry out a methacrylic coupling agent (3-methacryloxypropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Base decane, product name: KBM-503) treated.

FB-3SDX O treatment was carried out using SiO ₂ filler (average particle diameter: 3.4 μm) manufactured by DENKA to carry out an octenyl coupling agent (7-octenyltrimethoxydecane manufactured by Shin-Etsu Chemical Co., Ltd., product name) :KBM-1083) Processed.

The untreated FB-3SDX was a SiO ₂ filler (average particle diameter: 3.4 μm) manufactured by DENKA.

[Evaluation method]

<Dielectric properties>

The film peeled from the PET substrate was extruded and hardened at 200 ° C for 1 hour and 1 MPa, and then cut into 70 × 50 mm, and dielectric resonance was performed by a split-type dielectric resonator (SPDR). The ratio of dielectric constant (ε) and dielectric loss tangent (tan δ) at room temperature to normal humidity was measured at a frequency of 10 GHz. It is preferable that the specific dielectric constant is 3.5 or less and the dielectric loss tangent is 0.0030 or less. The results are shown in Tables 1 to 2.

<heat resistance reliability (tan δ change)>

After the cured film having the above dielectric properties was allowed to stand at 125 ° C for 200 hours, tan δ was measured by SPDR method (10 GHz) at normal temperature and normal humidity to determine the amount of change and the rate of change of tan δ. It is preferred if the rate of change is 80% or less. The results are shown in Tables 1 to 2.

<Solder heat resistance>

Two sheets of Cu foil (manufactured by Fukuda Metal Foil Powder Co., Ltd., product name: CF-T9FZSV) were sandwiched between the film peeled off from the PET substrate, and subjected to extrusion hardening at 200 ° C for 1 hour and 1 MPa, and then cut out. 3 cm × 3 cm, which was used as a test piece, was floated in a solder bath at 270 ° C for 60 seconds to visually confirm the presence or absence of expansion. It was judged as "OK" (passed) when there was no change in appearance such as expansion, and it was judged as "NG" (failed) when expansion was observed. The results are shown in Tables 1 to 2.

<moisture resistance reliability (tan δ change)>

After the cured film having the above dielectric properties was placed in a constant temperature and humidity chamber at 85 ° C / 85% RH for 200 hours, tan δ was measured by SPDR method (10 GHz) at room temperature and humidity to determine the amount of change and rate of change of tan δ. . The rate of change is preferably 55% or less, more preferably 45% or less, and even more preferably 40% or less. The results are shown in Table 3.

As is apparent from Tables 1 to 3, Examples 1 to 11 are in the specific dielectric constant (ε), dielectric loss tangent (tan δ), heat resistance reliability (change amount of tan δ, rate of change), solder heat resistance, and moisture resistance reliability. All of them are good results. Further, in Examples 1 to 10, the results of the moisture resistance reliability (the amount of change in tan δ, the rate of change) were more excellent. Further, the moisture resistance reliability of Example 11 using a cerium oxide filler which was not treated with a decane coupling agent was 53%. The reason for this is as follows: Since the cerium oxide filler itself has poor moisture resistance, if only the cerium oxide filler is added, the moisture resistance reliability is lowered, whereas the surface treatment of the cerium oxide filler can be prevented. Reduced humidity resistance. Further, in Comparative Example 1 and Example 6 in which the molecular weights of the components (A) were different, it was found that the results of heat resistance reliability of the smaller molecular weight were inferior, and oxidative degradation occurred. On the other hand, the rate of change in the moisture resistance reliability of Comparative Example 1 and Comparative Example 2 in which the component (B) was not used was large. Further, the solder of Comparative Example 3 using the component (B') was inferior in heat resistance.

 (industrial availability)  

The thermosetting resin composition of the present invention is excellent in high-frequency characteristics and heat-resistance reliability (the amount of change in dielectric loss tangent (tan δ) is small), and the insulating film or the interlayer insulating film excellent in solder heat resistance is extremely Have users. The multilayer wiring board of the present invention is excellent in high frequency characteristics and heat resistance reliability by the cured product of the above-mentioned thermosetting resin composition, the above-mentioned insulating film or the cured film 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 (dielectric loss tangent (tan δ) by the cured product of the thermosetting resin composition, the insulating film or the cured film of the interlayer insulating film. It is suitable for high frequency applications because of the small amount of change.

Claims (9)

 A thermosetting resin composition comprising: (A) a polyphenylene ether having a number average molecular weight of 800 to 4,500 having an unsaturated double bond at a terminal, and (B) a phenolic antioxidant having a melting point of 200 ° C or more, and C) Thermoplastic elastomer.    The thermosetting resin composition according to claim 1, further comprising (D) an inorganic filler.   The thermosetting resin composition according to claim 1 or 2, wherein the component (D) contains a cerium oxide filler which is surface-treated with a decane coupling agent represented by the formula (10). Wherein R ²¹ to R ²³ are each independently an alkyl group having 1 to 3 carbon atoms, and R ²⁴ is a functional group having an unsaturated double bond at least at the terminal, and n is 3 to 9. The thermosetting resin composition according to any one of claims 1 to 3, wherein R ²⁴ of the formula (10) is a vinyl group or a (meth) acrylonitrile group.  An insulating film comprising the thermosetting resin composition according to any one of claims 1 to 4.    An interlayer insulating film comprising the thermosetting resin composition according to any one of claims 1 to 4.    A cured product of the thermosetting resin composition according to any one of claims 1 to 4, the insulating film of claim 5 or the sixth application of the patent application. A cured product of an interlayer insulating film.    A multilayer wiring board comprising: a cured product of a thermosetting resin composition according to any one of claims 1 to 4, an insulating film according to claim 5 or a patent application scope A cured product of the interlayer insulating film according to item 6.    A semiconductor device comprising: a cured product of a thermosetting resin composition according to any one of claims 1 to 4, an insulating film according to claim 5, or a patent application scope 6 A cured product of the interlayer insulating film according to the item.