JP2017082200A - Resin composition, prepreg, metal-clad laminate, and wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of reducing a dielectric constant and a dielectric loss tangent. A resin composition comprises (A) a polyphenylene ether in which the hydroxyl group present at the end of the main chain is modified with an ethylenically unsaturated compound, and (B) at least one of triallyl isocyanurate and triallyl cyanurate. It contains (C) a copolymer of butadiene and styrene and (D) an organic peroxide. The component (C) is 0.5 to 20% by mass when the total amount of the component (A), the component (B), the component (C), and the component (D) is 100% by mass. [Selection diagram] None

Description

  The present invention relates to a resin composition capable of reducing a dielectric constant and a dielectric loss tangent. Furthermore, the present invention relates to a prepreg, a metal-clad laminate, and a wiring board using such a resin composition.

  In recent years, LSIs have been increased in speed, integration, memory capacity, etc., and along with this, various electronic components have been rapidly reduced in size, weight, thickness, and the like. For this reason, in terms of materials, more excellent heat resistance, dimensional stability, electrical characteristics, and the like are required.

  Conventionally, thermosetting resins such as phenol resins, epoxy resins, and polyimide resins have been used for printed wiring boards. Although these resins have various performances in a well-balanced manner, the dielectric properties in the high frequency region are insufficient. As a new material for solving this problem, polyphenylene ether has attracted attention, and its application to a copper-clad laminate has been attempted (for example, see Patent Document 1).

JP 2005-8829 A

  In recent years, there has been a demand for lower dielectric constant and dielectric loss tangent in a higher frequency region. For this reason, polyphenylene ether is also required to have a reduced dielectric constant and dielectric loss tangent in such a high frequency region.

  An object of this invention is to provide the resin composition which can reduce a dielectric constant and a dielectric loss tangent. Another object of the present invention is to provide a prepreg, a metal-clad laminate, and a wiring board using such a resin composition.

  The resin composition of the embodiment includes (A) a polyphenylene ether in which a hydroxyl group present at the terminal of the main chain is modified with an ethylenically unsaturated compound, and (B) at least one of triallyl isocyanurate and triallyl cyanurate. And (C) a copolymer of butadiene and styrene, and (D) an organic peroxide.

  A component (C) is 0.5-20 mass% when the total amount of a component (A), a component (B), a component (C), and a component (D) is 100 mass%.

（一般式（Ｉ）中、Ｒ_１〜Ｒ_１１は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数が１〜８個の直鎖または分岐アルキル基、置換基を有していてもよい炭素数が２〜８個の直鎖または分岐アルケニル基、置換基を有していてもよい炭素数が２〜８個の直鎖または分岐アルキニル基、または置換基を有していてもよい炭素数が６〜１０個のアリール基である。Ｚは、カルボニル基、チオカルボニル基、メチレン基、エチレン基、トリメチレン基またはテトラメチレン基を示す。ｎは１〜２００の整数である。） The component (A) contains polyphenylene ether represented by the following general formula (I).

(In the general formula (I), R _{1 to} R ₁₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituent. A linear or branched alkenyl group having 2 to 8 carbon atoms which may have, a linear or branched alkynyl group having 2 to 8 carbon atoms which may have a substituent, or a substituent. And an optionally substituted aryl group having 6 to 10 carbon atoms, Z represents a carbonyl group, a thiocarbonyl group, a methylene group, an ethylene group, a trimethylene group or a tetramethylene group, and n is an integer of 1 to 200. .)

  According to the resin composition of the embodiment, the dielectric constant and the dielectric loss tangent can be reduced. Thereby, excellent high frequency characteristics can be obtained.

Hereinafter, modes for carrying out the present invention will be described.
The resin composition of the embodiment includes (A) a polyphenylene ether in which a hydroxyl group present at the terminal of the main chain is modified with an ethylenically unsaturated compound, and (B) at least one of triallyl isocyanurate and triallyl cyanurate. And (C) a copolymer of butadiene and styrene, and (D) an organic peroxide.

  Component (C) is included in a proportion of 0.5 to 20% by mass, where the total amount of component (A), component (B), component (C), and component (D) is 100% by mass.

（一般式（Ｉ）中、Ｒ_１〜Ｒ_１１は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数が１〜８個の直鎖または分岐アルキル基、置換基を有していてもよい炭素数が２〜８個の直鎖または分岐アルケニル基、置換基を有していてもよい炭素数が２〜８個の直鎖または分岐アルキニル基、または置換基を有していてもよい炭素数が６〜１０個のアリール基である。Ｚは、カルボニル基、チオカルボニル基、メチレン基、エチレン基、トリメチレン基またはテトラメチレン基を示す。ｎは１〜２００の整数である。） The component (A) contains polyphenylene ether represented by the following general formula (I).

(In the general formula (I), R _{1 to} R ₁₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituent. A linear or branched alkenyl group having 2 to 8 carbon atoms which may have, a linear or branched alkynyl group having 2 to 8 carbon atoms which may have a substituent, or a substituent. And an optionally substituted aryl group having 6 to 10 carbon atoms, Z represents a carbonyl group, a thiocarbonyl group, a methylene group, an ethylene group, a trimethylene group or a tetramethylene group, and n is an integer of 1 to 200. .)

  Hereinafter, each component will be specifically described.

  Component (A) is a compound represented by the general formula (I). The compound represented by the general formula (I) is described in, for example, Japanese Patent No. 4913970.

（一般式（Ｉ）中、Ｒ_１〜Ｒ_１１は、それぞれ独立して、水素原子、置換基を有していてもよい炭素数が１〜８個の直鎖または分岐アルキル基、置換基を有していてもよい炭素数が２〜８個の直鎖または分岐アルケニル基、置換基を有していてもよい炭素数が２〜８個の直鎖または分岐アルキニル基、または置換基を有していてもよい炭素数が６〜１０個のアリール基である。Ｚは、カルボニル基（＞Ｃ＝Ｏ）、チオカルボニル基（＞Ｃ＝Ｓ）、メチレン基（−ＣＨ_２−）、エチレン基（ジメチレン基）（−ＣＨ_２−ＣＨ_２−）、トリメチレン基（−ＣＨ_２−ＣＨ_２−ＣＨ_２−）またはテトラメチレン基（−ＣＨ_２−ＣＨ_２−ＣＨ_２−ＣＨ_２−）を示す。ｎは１〜２００の整数である。）

(In the general formula (I), R _{1 to} R ₁₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituent. A linear or branched alkenyl group having 2 to 8 carbon atoms which may have, a linear or branched alkynyl group having 2 to 8 carbon atoms which may have a substituent, or a substituent. And optionally substituted aryl group having 6 to 10 carbon atoms, Z is carbonyl group (> C═O), thiocarbonyl group (> C═S), methylene group (—CH ₂ —), ethylene Represents a group (dimethylene group) (—CH ₂ —CH ₂ —), trimethylene group (—CH ₂ —CH ₂ —CH ₂ —) or tetramethylene group (—CH ₂ —CH ₂ —CH ₂ —CH ₂ —). N is an integer from 1 to 200.)

Examples of the substituent include a carboxyl group, an aldehyde group, a hydroxyl group, and an amino group. R _{1 to} R ₁₁ are each independently preferably a hydrogen atom, a methyl group, an ethyl group, or an optionally substituted phenyl group.

  Component (A) is preferably 29.9 to 90% by mass when the total amount of component (A), component (B), component (C), and component (D) is 100% by mass. When the content is 29.9 to 90% by mass, the dielectric constant and dielectric loss tangent can be further reduced. The component (A) is more preferably 40 to 75% by mass.

  Component (B) acts as a crosslinking agent, and one kind selected from triallyl isocyanurate and triallyl cyanurate may be used alone, or these may be used in combination. By using at least one selected from triallyl isocyanurate and triallyl cyanurate, excellent dielectric properties and heat resistance can be obtained. Among these, triallyl isocyanurate is preferably used.

  From the viewpoint of suppressing a decrease in heat resistance, diallyl isocyanurate as an impurity contained in triallyl isocyanurate is preferably 500 ppm or less. A commercially available product can be used as triallyl isocyanurate. Examples of commercially available products include TAICROS (manufactured by Evonik Degussa, trade name, diallyl isocyanurate content: 100 to 400 ppm).

  Component (B) is preferably 9.9 to 70% by mass when the total amount of component (A), component (B), component (C) and component (D) is 100% by mass. When it is 9.9-70 mass%, high heat resistance can be obtained. As for a component (B), it is more preferable that it is 20-50 mass%.

  Component (C) is a copolymer of butadiene and styrene. Component (C) reacts with component (A) and component (B) to form a polymer (crosslinked product). Specifically, the double bond present in the copolymer of component (C) reacts with the double bond present in component (A) and component (B).

  Component (C) is preferably one obtained by polymerizing butadiene and styrene at a mass ratio of 50/50 to 90/10 (butadiene / styrene). When mass ratio is 50 / 50-90 / 10, adhesiveness with metal foil can be improved. The mass ratio is more preferably 50/50 to 80/20, and even more preferably 50/50 to 70/30, from the viewpoint of dielectric loss tangent and the like.

  The weight average molecular weight and number average molecular weight of the component (C) are not particularly limited. As the component (C), an oligomer having a relatively low degree of polymerization (low molecular weight) can also be used. As a component (C), what has a weight average molecular weight of about 1,000-100,000 normally can be used.

  A component (C) is 0.5-20 mass% when the total amount of a component (A), a component (B), a component (C), and a component (D) is 100 mass%. When the content is 0.5 to 20% by mass, the dielectric constant and dielectric loss tangent can be lowered and the adhesion to the metal foil can be increased. As for a component (C), it is more preferable that it is 3-15 mass%.

  Component (D) acts as a radical initiator. That is, the component (D) is a radical reaction of the component (A), the component (B), and the component (C) to produce a polymer (crosslinked product) of the component (A), the component (B), and the component (C). obtain.

  The component (D) is not particularly limited as long as it is an organic peroxide. Examples of such a compound include di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide) hexane, 2,5-dimethyl-2,5-di (t -Butyl peroxide) hexyne-3, t-butylcumyl peroxide, α, α'-di- (t-butylperoxy) diisopropylbenzene, t-butylperoxybenzoate and the like.

  A commercial item can be used as a component (D). Examples of such include “Perbutyl D”, “Perhexa 25B”, “Perhexine 25B”, “Perbutyl C”, “Perbutyl P”, “Perbutyl Z” (all manufactured by NOF Corporation). .

  The organic peroxide of component (D) preferably has no benzene ring. When it does not have a benzene ring, the dielectric loss tangent can be reduced more efficiently.

  Component (D) is preferably 0.1 to 7% by mass when the total amount of component (A), component (B), component (C), and component (D) is 100% by mass. When the content is 0.1 to 7% by mass, higher heat resistance can be obtained. As for a component (D), it is more preferable that it is 1-6 mass%.

The resin composition of the embodiment can include a core-shell structure containing at least a part of (E) a silicone-based polymer as necessary and within the limits not departing from the spirit of the present invention. The component (E) imparts elasticity and can improve the adhesion with the metal foil, particularly the adhesion with the metal foil at a high temperature.

  The core-shell structure of component (E) has a core-shell structure, and includes a silicone polymer at least in part. As such, for example, it has a particulate core portion and a shell portion formed outside the core portion, and at least one selected from the core portion and the shell portion is a silicone polymer. The thing which consists of is mentioned.

  The manufacturing method of a core-shell structure will not be specifically limited if a shell part can be formed in the outer side of a core part. For example, the core-shell structure can be obtained by polymerizing monomer components that form the shell part in the presence of the core part. The shell part can be formed from a monomer component different from the monomer component forming the core part.

  As a monomer component which forms a shell part, what has reactivity with the silicone type polymer which forms a core part is mentioned, for example. By using such a monomer component, the monomer component is grafted on the outside of the core portion, and a core portion formed of a silicone polymer, and a shell portion formed of a graft polymer on the outside of the core portion, The core-shell structure comprised by this can be obtained.

  The average particle diameter of the core-shell structure is preferably 0.1 to 5 μm, and more preferably 0.5 to 2.0 μm. The average particle size means a particle size (d50) at which the cumulative volume from 0 μm becomes 50% in the particle size distribution. The average particle diameter can be measured using a laser diffraction / scattering type particle size distribution measuring apparatus.

  A commercial item can be used as such a core-shell structure. As such a thing, KMP-600, X-52-7030 (made by Shin-Etsu Silicone Co., Ltd.) etc. are mentioned, for example.

  The component (E) is preferably 0.05 to 5 parts by mass when the total amount of the component (A), the component (B), the component (C), and the component (D) is 100 parts by mass. When the component (E) is 0.05 parts by mass or more, sufficient elasticity can be imparted. As for a component (E), 0.1 mass part or more is more preferable, and 1 mass part or more is further more preferable. Moreover, when a component (E) is 5 mass parts or less, the dielectric constant, a dielectric loss tangent, and the fall of other characteristics can be suppressed. As for a component (E), 4 mass parts or less are more preferable, and 3 mass parts or less are still more preferable.

  The resin composition of the embodiment may further contain (F) toluene (component (F)) as necessary and within the limits not departing from the gist of the present invention. The component (F) is used as a solvent for dissolving or dispersing the resin, that is, the polymer (crosslinked product) of the components (A) to (C).

  The component (F) is preferably 70 to 140 parts by mass when the total amount of the component (A), component (B), component (C), and component (D) is 100 parts by mass, More preferably, it is 130 parts by mass.

  In addition to the component (F) toluene, aromatic solvents such as benzene and xylene, ketone solvents such as acetone and methyl ethyl ketone, and solvents such as tetrahydrofuran and chloroform can be used in the resin composition of the embodiment.

The resin composition of the embodiment may further contain silica, a flame retardant, a stress relaxation agent, and the like as necessary and within the limits not departing from the spirit of the present invention.

  Examples of the silica include pulverized silica and fused silica. These may be used alone or in combination of two or more. A commercially available product can be used as the silica. Examples thereof include methacrylsilane-treated fused silica: SFP-130 MHM (manufactured by Denki Kagaku Kogyo Co., Ltd.), FUSELEX E-2, Adma FineSO-C5, and PLV-3 (all manufactured by Tatsumori Co., Ltd.). It is done.

  The average particle diameter of silica is preferably 10 μm or less. In the case of 10 micrometers or less, adhesiveness with metal foil can be improved more.

  Silica is preferably 5 to 40 parts by mass when the total amount of component (A), component (B), component (C), and component (D) is 100 parts by mass. When the amount is 5 to 40 parts by mass, the melt fluidity of the resin composition is improved, the adhesion to the metal foil is increased, and the connection reliability of the through-hole conductor is also increased. Silica is more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more. Silica is more preferably 35 parts by mass or less.

  Flame retardants include melamine phosphate, melam polyphosphate, melem polyphosphate, melamine pyrophosphate, ammonium polyphosphate, red phosphorus, aromatic phosphate ester, phosphonate ester, phosphinate ester, phosphine oxide, phosphazene, melamine cyanolate Etc. These flame retardants may be used alone or in combination of two or more. Among these, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and ammonium polyphosphate are preferable from the viewpoints of dielectric properties, flame resistance, heat resistance, adhesion, moisture resistance, chemical resistance, reliability, and the like.

  The flame retardant is preferably 15 to 45 parts by mass when the total amount of the component (A), the component (B), the component (C), and the component (D) is 100 parts by mass. In the case of 15 to 45 parts by mass, the flame resistance and heat resistance can be further improved without substantially affecting the dielectric properties, adhesion, and moisture resistance.

  Examples of the stress relaxation agent include silicone resin particles having no core-shell structure. As such silicone resin particles, for example, X-52-875, X-52-854 (manufactured by Shin-Etsu Chemical Co., Ltd.), MSP-1500 (manufactured by Nikko Rica Co., Ltd.), MSP-3000 (Nikko Rica Co., Ltd.). Manufactured)) and the like. These stress relaxation agents may be used individually by 1 type, and may use 2 or more types together.

  The average particle size of the stress relaxation agent is preferably 10 μm or less. When it is 10 μm or less, the adhesion to the metal foil can be further enhanced.

  When the total amount of the component (A), the component (B), the component (C), and the component (D) is 100 parts by mass, the stress relaxation agent is preferably 1 to 10 parts by mass. When it is 1-10 mass parts, adhesiveness with metal foil and moisture absorption resistance can be improved more, and the connection reliability of a through-hole conductor can also be improved more.

  The resin composition of the embodiment can further contain fillers, additives and the like other than those described above. Examples of the filler include carbon black, titanium oxide, barium titanate, glass beads, and glass hollow spheres. Examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, and a colorant. Specific examples of the additive include R-42 (manufactured by Sakai Chemical Co., Ltd.) and IRGANOX 1010 (manufactured by BASF). A filler and an additive may be used individually by 1 type, and may use 2 or more types together.

  Furthermore, the resin composition of the embodiment can include at least one of a thermoplastic resin and a thermosetting resin. Examples of the thermoplastic resin include GPPS (general purpose polystyrene) and HIPS (impact resistant polystyrene). As a thermosetting resin, an epoxy resin etc. are mentioned, for example. These resins may be used alone or in combination of two or more.

  The resin composition of the embodiment is obtained, for example, by mixing components (A) to (D) that are essential components and other components that are added as necessary. Examples of the mixing method include a solution mixing method in which all components are uniformly dissolved or dispersed in a solvent, a melt blending method in which heating is performed with an extruder or the like, and the like.

Next, the prepreg of the embodiment will be described.
The prepreg of the embodiment includes a base material and the resin composition contained in the base material. Examples of the substrate include woven or non-woven fabric made of fibers such as glass and polyimide, and paper. Examples of the glass material include normal E glass, D glass, S glass, NE glass, L glass, T glass, and quartz glass.

  The prepreg of the embodiment preferably contains 20 to 80% by mass of a base material. When the prepreg of the embodiment includes a base of 20 to 80% by mass, the dimensional stability and strength after curing are increased, and the dielectric properties are also excellent. For the prepreg of the embodiment, a coupling agent such as a silane coupling agent and a titanate coupling agent can be used as necessary.

  The prepreg of the embodiment can be produced by applying or impregnating a resin composition to a substrate and then drying. In this case, the resin composition can be used by being dissolved or dispersed in a solvent as necessary.

  Examples of the application method include a method in which a solution or dispersion of the resin composition is applied using a spray, a brush, a bar coater, or the like. Moreover, as an impregnation method, the method (dipping) etc. which immerse a base material in the solution or dispersion liquid of a resin composition are mentioned.

  Application or impregnation can be repeated multiple times as required. Moreover, application | coating or impregnation can also be repeated using the some solution or dispersion liquid from which resin concentration differs. The resin composition may be melted and impregnated in the base material.

  The prepreg of the embodiment preferably contains 0.5% by mass or less of toluene. In particular, the prepreg of the embodiment is manufactured using a resin composition containing the component (F) of toluene, and contains 0.5% by mass or less of toluene, that is, 0% of toluene. It is preferable that 5% by mass or less remain.

  When toluene is contained, the fluidity of the resin composition is improved and the adhesion with the metal foil is improved. The content of toluene is preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. On the other hand, when the content of toluene is 0.5% by mass or less, a glass transition point and a decrease in heat resistance are suppressed. The content of toluene is more preferably 0.4% by mass or less, and more preferably 0.3% by mass.

  The content of toluene can be measured using a gas chromatograph. Specifically, prepreg is dissolved in ethylbenzene, and this solution is introduced into a gas chromatograph. And the amount of toluene in this solution is measured, and the mass of toluene in the whole prepreg is calculated. The content of toluene can be adjusted by, for example, drying conditions after application or impregnation of the resin composition.

  The prepreg of the embodiment is processed into a laminated plate by, for example, heating and pressing after a plurality of prepregs are overlapped. Furthermore, a thicker laminated board can also be obtained by combining the laminated board and another prepreg.

  In heat-pressure molding, for example, molding and curing are simultaneously performed using a hot press machine. The hot pressing is preferably performed at 80 to 300 ° C. under a pressure of 0.1 to 50 MPa for 1 minute to 10 hours, and at 150 to 250 ° C. under a pressure of 0.5 to 6 MPa for 60 minutes to 5 hours. More preferably. Note that molding and curing may be performed separately. For example, after a laminated sheet in a semi-cured state is formed, it may be completely cured by being processed by a heat treatment machine.

Next, the metal-clad laminate of the embodiment will be described.
The metal-clad laminate includes the prepreg and a conductive metal foil provided on the surface of the prepreg. Examples of the conductive metal foil include copper foil such as electrolytic copper foil and rolled copper foil, aluminum foil, and composite foil obtained by superimposing these metal foils. Among these conductive metal foils, copper foil is preferable. The thickness of the conductive metal foil is preferably 5 to 105 μm.

  The metal-clad laminate can be obtained, for example, by superposing a prepreg and a conductive metal foil and performing heat and pressure molding. In addition, the metal-clad laminate can be obtained, for example, by superposing a desired number of prepregs and conductive metal foils, followed by heating and pressing. The metal-clad laminated board of embodiment is used suitably for manufacture of a printed circuit board etc.

Next, the wiring board of the embodiment will be described.
The wiring board according to the embodiment includes a plurality of insulating layers and a conductor layer disposed between these insulating layers, and the insulating layer is formed of a base material and the resin composition. Such a wiring board can be manufactured as follows, for example.

  First, an inner layer plate is manufactured by forming a circuit and a through-hole conductor on the metal-clad laminate. Thereafter, a prepreg and a conductive metal foil are laminated in this order on the surface of the inner layer plate and heated and pressed. Thereby, the wiring board by which the conductor layer is arrange | positioned between several insulating layers can be obtained. Furthermore, a circuit and a through hole may be formed in a conductive metal foil provided on the surface of the wiring board to form a multilayer printed wiring board.

  In the wiring board of the embodiment, for example, by using the resin composition of the embodiment that includes the core-shell structure of the component (E), it can be made excellent in elasticity. For this reason, an insulating layer can be made to follow the thermal expansion of the longitudinal direction of a through-hole conductor, the cutting | disconnection with a through-hole conductor and a conductor layer can be suppressed, and connection reliability can be improved.

  In recent years, the diameter of through-hole conductors has been reduced due to higher circuit density, and there is a need to improve connection reliability. According to the wiring board of the embodiment, even when the ratio (L / D) of the length (L) to the diameter (D) of the through-hole conductor is 12 or more, the connection reliability can be improved.

Embodiments of the present invention will be specifically described below with reference to examples.
The embodiments of the present invention are not limited to these examples.

Below, the component used for preparation of the resin composition of an Example and a comparative example is shown.
Ingredient (A)
A1. Methacryl-modified polyphenylene ether: SA9000 (product name, number average molecular weight Mn: 2,000 to 3,000, manufactured by Savix Corporation, represented by the general formula (I))
A2. Methacryl-modified polyphenylene ether: SA6000 (manufactured by Savix, trade name, number average molecular weight Mn: 3,000 to 5,000, represented by general formula (I))
Ingredient (B)
B1. Triallyl isocyanurate: TAICROS (manufactured by Evonik Co., Ltd., trade name, diallyl isocyanurate amount 300 ppm)
B2. Triallyl cyanurate: TAC (trade name, manufactured by Evonik)
B3. Triallyl isocyanurate: Trialic (manufactured by Kawaguchi Chemical Co., Ltd., trade name, diallyl isocyanurate amount 700 ppm)
Ingredient (C)
C1. Butadiene-styrene copolymer: RICON 100 (manufactured by CRAY VALLEY, trade name, mass ratio (butadiene / styrene): 75/25)
C2. Butadiene-styrene copolymer: RICON184 (manufactured by CRAY VALLEY, trade name, mass ratio (butadiene / styrene): 72/28)
C3. Butadiene-styrene copolymer: RICON257 (manufactured by CRAY VALLEY, trade name, mass ratio (butadiene / styrene): 65/35)
Ingredient (D)
D1. Di-t-butyl peroxide: Perbutyl D (trade name, manufactured by NOF Corporation)
D2. α, α'-di- (t-butylperoxy) diosopropylbenzene: perbutyl P (trade name, manufactured by NOF Corporation)
Ingredient (E)
Core shell structure containing silicone polymer in at least part: X-52-7030 (manufactured by Shin-Etsu Silicone Co., Ltd., trade name, average particle size: 0.5 μm)
Ingredient (F)
Toluene: Triol (Daishin Chemical Co., Ltd., trade name)
Others・ Polybutadiene: B-1000 (made by Nippon Soda Co., Ltd., trade name)
Polystyrene: PS685 (made by Japan PS Co., Ltd., trade name)
・ Polydivinylbenzene: DVB960 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
・ Silicone with core-shell structure ・ Acrylic rubber: S-2001 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.)
Acrylic rubber having a core-shell structure: W-450A (Mitsubishi Rayon Co., Ltd., trade name)
-Butadiene rubber having a core-shell structure: C-223A (Mitsubishi Rayon Co., Ltd., trade name)
・ Xylene: Xylol (Daishin Chemical Co., Ltd., trade name)
Silica: SFP-130MC (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name, average particle size 0.5 μm)

(Examples 1-12)
Component (A) polyphenylene ether, component (B) triallyl isocyanurate or triallyl cyanurate, component (C) butadiene and styrene copolymer, component (D) so as to have the ratio shown in Table 1. The organic peroxide and silica were mixed. Furthermore, “SAYTEX 8010” (manufactured by Albemarle Asano Co., Ltd.) was added to this mixture as a flame retardant and stirred at room temperature (25 ° C.) to obtain a resin composition. In addition, the flame retardant was 30 mass parts with respect to 100 mass parts of total amounts of component (A)-(D).

  Next, the resin composition was dissolved in toluene to obtain a resin varnish. A glass woven fabric having a thickness of 100 μm was immersed in this resin varnish, and the glass woven fabric was impregnated with the resin varnish. Thereafter, the glass woven fabric impregnated with the resin varnish was dried at 130 ° C. for 7 minutes to obtain a prepreg having a thickness of 100 μm. In addition, the ratio of the base material in a prepreg is 60 mass%.

  Eight prepregs were stacked to produce a laminate. Further, a copper foil having a thickness of 18 μm was laminated on both surfaces of the laminate. Thereafter, heating at 195 ° C. for 75 minutes was performed under a pressure of 4 MPa to cure the resin in the prepreg to obtain a copper-clad laminate having a thickness of 0.8 mm.

(Comparative Example 1)
Production of resin composition and copper-clad laminate in the same manner as in Example 1 except that the polyphenylene ether of component (A) is 60 parts by mass and the copolymer of butadiene and styrene of component (C) is not used. Went.

(Comparative Example 2)
Except that the polyphenylene ether of the component (A) was 40 parts by mass, the triallyl isocyanurate of the component (B) was 25 parts by mass, and the copolymer of butadiene and styrene of the component (C) was 30 parts by mass. In the same manner as in Example 1, a resin composition and a copper clad laminate were produced.

(Comparative Example 3)
Example 1 except that the polyphenylene ether of component (A) is 50 parts by mass, the copolymer of butadiene and styrene of component (C) is not used, and 10 parts by mass of polybutadiene is used instead. Thus, a resin composition and a copper clad laminate were produced.

(Comparative Example 4)
The same procedure as in Example 1 except that the polyphenylene ether of component (A) was 50 parts by mass, the copolymer of butadiene and styrene of component (C) was not used, and 10 parts by mass of polystyrene was used instead. Thus, a resin composition and a copper clad laminate were produced.

(Comparative Example 5)
The component (A) polyphenylene ether is 50 parts by mass, the component (B) triallyl isocyanurate is 35 parts by mass, the copolymer of component (C) butadiene and styrene is not used, and 2 parts of polybutadiene is used instead. A resin composition and a copper clad laminate were produced in the same manner as in Example 1 except that 8 parts by mass of polydivinylbenzene was used.

  Next, the following evaluation was performed about the copper clad laminated board of Examples 1-12 and Comparative Examples 1-5. The results are shown in Table 2. Table 2 also shows the glass transition point (Tg) of the cured product of the resin composition.

(Dielectric constant, dielectric loss tangent)
The copper foil of the copper clad laminate was peeled off, and the dielectric constant and dielectric loss tangent at 10 GHz were measured by the cavity resonator method.

(Peel strength)
The peel strength was measured by performing a 90-degree peel test of the copper foil on the copper-clad laminate.

(Heat-resistant)
The copper clad laminate was immersed in solder at 288 ° C., 300 ° C., or 320 ° C. for 5 minutes, and the heat resistance was evaluated by observing the swelling of the copper foil. In the evaluation, three copper clad laminates were observed, and “AAA” was defined as “AAA” in which no three blisters were generated at 320 ° C., and “AA” was defined as “AA” in which all three blisters were not generated at 300 ° C. “A” was the case where no blistering occurred at all three sheets at 288 ° C., and “B” was the one where even one sheet was swollen at 288 ° C.

  As apparent from Tables 1 and 2, when a specific polyphenylene ether, triallyl isocyanurate or triallyl cyanurate, a copolymer of butadiene and styrene, and an organic peroxide are contained, the dielectric constant in the high frequency region In addition, the dielectric loss tangent can be lowered, and the glass transition point (Tg), peel strength, and heat resistance can be increased.

(Examples 21 to 25)
Component (A) polyphenylene ether, component (B) triallyl isocyanurate, component (C) butadiene and styrene copolymer, component (D) organic peroxide so that the proportions shown in Table 3 are obtained. The core-shell structure containing at least a part of the silicone polymer of component (E) and silica were mixed. Furthermore, “SAYTEX 8010” (manufactured by Albemarle Asano Co., Ltd.) was added to this mixture as a flame retardant and stirred at room temperature (25 ° C.) to obtain a resin composition. In addition, the flame retardant was 30 mass parts with respect to 100 mass parts of total amounts of component (A)-(D). Thereafter, using this resin composition, a copper clad laminate was produced in the same manner as in Example 1.

(Example 26)
A resin composition and a copper clad laminate were produced in the same manner as in Example 21 except that the core / shell structure of component (E) was not used.

(Example 27)
A resin composition and a copper clad laminate were produced in the same manner as in Example 21 except that the core / shell structure of the component (E) was 7 parts by mass.

(Example 28)
A resin composition and a copper clad laminate were produced in the same manner as in Example 21, except that the core / shell structure of component (E) was not used and the silicone-acrylic rubber having the core / shell structure was changed to 3 parts by mass. went.

(Example 29)
A resin composition and a copper clad laminate were produced in the same manner as in Example 21, except that the core-shell structure of component (E) was not used and the acrylic rubber having the core-shell structure was changed to 3 parts by mass. .

(Example 30)
A resin composition and a copper clad laminate were produced in the same manner as in Example 21 except that the core / shell structure of component (E) was not used and the butadiene rubber having the core / shell structure was changed to 3 parts by mass. .

  Next, the copper clad laminates of Examples 21 to 30 were evaluated for dielectric constant, dielectric loss tangent, peel strength, heat resistance, and connectivity. The connectivity was evaluated as follows. The results are shown in Table 4. Table 4 also shows the glass transition point (Tg) of the cured product of the resin composition.

(Connectivity)
After a through hole was formed in the copper clad laminate, a circuit (wiring layer) and a through hole conductor were formed to obtain an inner layer plate. A prepreg was overlaid on the inner layer plate, and heated and pressurized at 190 ° C. and 4 MPa to obtain a wiring board. Thereafter, the connectivity between the through-hole conductor and the wiring layer was confirmed by observing a cross section of the wiring board using a scanning electron microscope. The case where the through-hole conductors and the wiring layers were connected without problems was designated as “A”, and the case where some of the through-hole conductors and the wiring layers were not connected was designated as “B”.

  As is apparent from Tables 3 and 4, by using the core-shell structure of component (E), heat resistance and connection are maintained while maintaining the dielectric constant, dielectric loss tangent, and glass transition point (Tg) in the high-frequency region. Can be improved.

(Examples 31-36)
Component (A) polyphenylene ether, component (B) triallyl isocyanurate, component (C) butadiene and styrene copolymer, component (D) organic peroxide so as to have the ratio shown in Table 5 , And silica were mixed. “SAYTEX 8010” (manufactured by Albemarle Asano Co., Ltd.) was added to the mixture as a flame retardant and stirred at room temperature (25 ° C.). In addition, the flame retardant was made into the ratio of 30 mass parts with respect to 100 mass parts of total amounts of component (A)-(D). Furthermore, the component (F) toluene was added to the ratio shown in Table 5 and stirred at room temperature (25 ° C.) to obtain a resin composition (resin varnish).

  A glass woven fabric having a thickness of 100 μm was immersed in the resin varnish, and the glass woven fabric was impregnated with the resin varnish. Thereafter, the glass woven fabric impregnated with the resin varnish was dried at 130 ° C. for 7 minutes to obtain a prepreg having a thickness of 100 μm. The ratio of the base material in a prepreg is 60 mass%. In addition, drying adjusted the content of toluene by adjusting an air volume as shown in Table 6. Further, the content of toluene was measured by a gas chromatograph.

  Thereafter, eight prepregs were stacked to produce a laminate. Further, a copper foil having a thickness of 18 μm was laminated on both surfaces of the laminate. Thereafter, heating at 195 ° C. for 75 minutes was performed under a pressure of 4 MPa to cure the resin in the prepreg to obtain a copper-clad laminate having a thickness of 0.8 mm.

(Example 37)
A resin composition and a copper clad laminate were produced in the same manner as in Example 31, except that the air volume when drying the prepreg was 20 N / m.

(Example 38)
A resin composition and a copper clad laminate were produced in the same manner as in Example 31, except that the air volume when drying the prepreg was 100 N / m.

(Example 39)
The resin composition and the copper clad laminate were produced in the same manner as in Example 31, except that the component (F) toluene was 150 parts by mass and the air volume when drying the prepreg was 60 N / m. .

(Example 40)
In the same manner as in Example 31, except that the component (F) toluene was not used, but xylene was used instead, and the air volume when drying the prepreg was 60 N / m, the resin composition and the copper-clad A laminate was produced.

  Next, the following evaluation was performed about the copper clad laminated board of Examples 31-40. The results are shown in Table 6. Table 6 also shows the glass transition point (Tg) of the cured product of the resin composition.

  As is clear from Tables 5 and 6, by adjusting the content of toluene in the prepreg, the dielectric constant and dielectric loss tangent in the high frequency region can be reduced, and the glass transition point (Tg), peel Strength and heat resistance can be increased.

Claims (9)

(A) a polyphenylene ether in which the hydroxyl group present at the end of the main chain is modified with an ethylenically unsaturated compound;
(B) at least one of triallyl isocyanurate and triallyl cyanurate;
(C) a copolymer of butadiene and styrene;
(D) an organic peroxide and
When the total amount of the component (A), the component (B), the component (C), and the component (D) is 100% by mass, the component (C) is 0.5 to 20% by mass. The resin composition, wherein the component (A) contains a polyphenylene ether represented by the following general formula (I).

(In the general formula (I), R _{1 to} R ₁₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a substituent. A linear or branched alkenyl group having 2 to 8 carbon atoms which may have, a linear or branched alkynyl group having 2 to 8 carbon atoms which may have a substituent, or a substituent. And an optionally substituted aryl group having 6 to 10 carbon atoms, Z represents a carbonyl group, a thiocarbonyl group, a methylene group, an ethylene group, a trimethylene group or a tetramethylene group, and n is an integer of 1 to 200. .)   The component (C) includes a copolymer of butadiene and styrene obtained by polymerizing butadiene and styrene at a mass ratio of 50/50 to 90/10 (butadiene / styrene). The resin composition as described.   The resin composition according to claim 1 or 2, wherein the component (B) contains at least triallyl isocyanurate, and the triallyl isocyanurate has a diallyl isocyanate content of 500 ppm or less.   And (E) a core-shell structure containing at least a part of a silicone-based polymer, and the component (E) is the component (A), the component (B), the component (C), and the component The resin composition according to any one of claims 1 to 3, wherein the total amount of the component (D) is 0.05 to 5 parts by mass when the total amount is 100 parts by mass.   Furthermore, (F) Toluene is included, and the component (F) has a total amount of the component (A), the component (B), the component (C), and the component (D) as 100 parts by mass. The resin composition according to claim 1, wherein the resin composition is 70 to 140 parts by mass.   A prepreg comprising a base material and the resin composition according to claim 1 contained in the base material.   The prepreg according to claim 6, wherein the prepreg contains 0.5% by mass or less of toluene.   A metal-clad laminate comprising the prepreg according to claim 7 and a conductive metal foil provided on a surface of the prepreg. A plurality of insulating layers and a conductor layer disposed between these insulating layers;
The wiring board, wherein the insulating layer is formed of a base material and the resin composition according to any one of claims 1 to 5.