JP3289534B2 - Polyphenylene oxide resin composition and prepreg and laminate using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-resistant polyphenylene oxide resin composition useful as an insulating material for printed wiring boards and the like, a prepreg using the polyphenylene oxide resin composition, and a laminated board using the prepreg. About.

[0002]

2. Description of the Related Art In recent years, electronic equipment has made great progress with the increase in the degree of integration of semiconductor devices to be mounted, the refinement of packages, the increase in the density of printed wiring boards, the joining, and the improvement of mounting techniques. In particular, progress has been remarkable in electronic devices using a high frequency band such as mobile communication.

[0003] In printed wiring boards constituting such electronic equipment, multilayering and fine wiring are progressing simultaneously, but printed wiring boards are required to have a higher signal transmission speed required for faster information processing. Is indispensable, and the higher the frequency band, the higher the demand. The quality of the impedance control of the printed wiring board depends on dimensional accuracy such as a circuit width and a circuit interval. However, in the case of a conventional laminate made of a resin composition containing a flame retardant, the dimensional stability is poor due to a large coefficient of thermal expansion.Therefore, the circuit width and the circuit interval vary, and the design dimensional accuracy cannot be secured. Impedance control was not enough.

[0004] A printed wiring board of an electronic device utilizing such a high frequency band is required to have a polyphenylene oxide resin [also referred to as a polyphenylene ether (PPE) resin] because of its excellent high frequency characteristics such as dielectric constant and dielectric loss. ]
However, heat resistance and dimensional stability were not sufficient.

[0005]

Accordingly, the present inventors have disclosed in Japanese Patent Application No. Hei 5-236893 a polyphenylene oxide resin composition which has improved heat resistance and dimensional stability, and a polyphenylene oxide resin composition. A method for producing a prepreg using the composition and a method for producing a laminate using the prepreg have been disclosed. That is, polyphenylene oxide, triallyl isocyanurate, a polyphenylene oxide resin composition containing a reactive brominated compound having a monomaleimide group that reacts with triallyl isocyanurate, and a prepreg using the polyphenylene oxide resin composition. And a method for producing a laminate using this prepreg.
However, when such a brominated compound such as a reaction type or an addition type is contained as a flame retardant in a polyphenylene oxide-triallyl isocyanurate system, there is an effect on heat resistance and dimensional stability. However, the water resistance, moisture resistance, moisture absorption heat resistance, glass transition point (Tg) and the like of the laminate were not at a satisfactory level.
In other words, the heat resistance to moisture absorption and the glass transition point (Tg) are low, and the water absorption and the moisture absorption are large.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyphenylene oxide resin composition having improved water resistance, moisture resistance, moisture absorption heat resistance, and glass transition point. An object of the present invention is to provide a prepreg using an oxide resin composition and a laminate using the prepreg.

[0007]

According to a first aspect of the present invention, there is provided a polyphenylene oxide resin composition comprising a polyphenylene oxide, a triallyl isocyanurate, a compatibilizer, and a flame retardant. in the varnish was added, triallyl
Its monomer and its prepoly as isocyanurate
If you are using mer, the flame retardant is a brominated organic compound nonreactive to polyphenylene oxide and triallyl isocyanurate, and not dissolved in the solvent, characterized in that it dispersed.

[0008] The polyphenylene oxide resin composition according to claim 2 of the present invention is characterized in that the brominated organic compound has a true specific gravity of 3.0 or less.

The polyphenylene oxide resin composition according to claim 3 of the present invention is characterized in that the brominated organic compound is decabromodiphenylethane represented by the following general formula [1] or represented by the following general formula [2]: 4,4-dibromobiphenyl to be used.

[0010]

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[0011]

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[0012] The polyphenylene oxide resin composition according to claim 4 of the present invention comprises polyphenylene oxide containing 3
0-60 parts by weight, triallyl isocyanurate 35-
Content of 62 parts by weight, and the content of bromine is 8 to 20 with respect to the total amount of the polyphenylene oxide resin composition.
It is characterized by containing the above-mentioned brominated organic compound by weight.

A prepreg according to a fifth aspect of the present invention is obtained by impregnating a base material with the polyphenylene oxide resin composition according to any one of the first to fourth aspects, drying by heating and semi-curing.

A laminate according to a sixth aspect of the present invention is obtained by laminating a predetermined number of the prepregs according to the fifth aspect by heating and pressing.

Hereinafter, the present invention will be described in detail. The polyphenylene oxide (hereinafter referred to as PP) used in the present invention
O) [also referred to as polyphenylene ether (PPE)] is represented, for example, by the following general formula [3].

[0016]

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An example of the PPO represented by the above general formula [3] is poly (2,6) represented by the following general formula [4].
-Dimethyl-1,4-phenylene oxide) and the like.

[0018]

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Such PPO is, for example, USP4,
It can be synthesized by the method disclosed in the specification of US Pat. No. 059,568. Although not particularly limited, for example,
Weight average molecular weight (Mw) of 46,000-53,000
PPO having a ratio to the number average molecular weight (Mn), that is, a molecular weight distribution (Mw / Mn) of 4.0 to 4.5 is preferable. Originally, PPO is a thermoplastic resin. In order to improve heat resistance and dimensional stability, PPO and styrene-butadiene block copolymer, styrene-isoprene block copolymer, 1,2-polybutadiene, 1,4-
It is used as a PPO resin composition containing at least one compatibilizer selected from the group consisting of polybutadiene, malein-modified polybutadiene, acrylic-modified polybutadiene and epoxy-modified polybutadiene, and triallyl isocyanurate (hereinafter referred to as TAIC). TAI
For C, its monomer (hereinafter referred to as m-TAIC) and its prepolymer (hereinafter referred to as p-TAIC) are used.

The feature of the PPO resin composition of the present invention is that
In order to improve the water resistance, moisture resistance, moisture absorption heat resistance, and glass transition point of a laminate using the O resin composition,
Comprising a compatibilizer and a flame retardant in TAIC and TAIC
In a varnish obtained by adding a solvent to a resin composition, the flame retardant is a brominated organic compound that is not reactive to PPO and TAIC, and is not dissolved in the solvent but is dispersed. That is, thermoplastic PPO and thermosetting TAI
When mixed with C and cured, an interpenetrating network structure [IP
N (Interpenetrating Polymer Net Work)]
It has an extremely excellent structure as a laminate having high heat resistance. However, when the flame retardant is a reactive flame retardant having an unsaturated bond or a soluble flame retardant that dissolves in the solvent, the flame retardant penetrates into the IPN of the PPO-TAIC and enters the IPN. Formation, and as a result, many unpolymerized residues of TAIC are generated, and the prepreg using this PPO resin composition and the laminated board using this prepreg have water resistance, moisture resistance, moisture absorption heat resistance and glass transition point. (Hereinafter, referred to as Tg).

Therefore, the flame retardant is composed of PPO and TAI.
C is a brominated organic compound that does not react with C, and is not dissolved in the solvent but is dispersed, so that the flame retardant is present as a filler in the resin.
It is presumed that the water resistance, moisture resistance, moisture absorption heat resistance, and Tg are improved because the TAIC hardens almost completely and forms a good IPN without inhibiting the formation of. Further, the true specific gravity of the brominated organic compound is preferably 3.0 or less. That is, when the true specific gravity of the brominated organic compound, which is a flame retardant, exceeds 3.0, the flame retardant tends to settle in the varnish of the PPO resin composition. Is not obtained, and workability deteriorates.

For example, as the brominated organic compound,
Examples include decabromodiphenylethane represented by the general formula [1] or 4,4-dibromobiphenyl represented by the general formula [2].

30 to 60 parts by weight of PPO and 3 of TAIC
It is preferable to contain it in a proportion of 5 to 62 parts by weight. That is, when PPO is less than 30 parts by weight and TAIC is more than 62 parts by weight, the laminate becomes brittle. When PPO is more than 60 parts by weight and TAIC is less than 35 parts by weight, A sufficient IPN cannot be formed. Further, it is preferable to contain the brominated organic compound having a bromine content of 8 to 20% by weight based on the total amount of the PPO resin composition. That is, when the bromine content is less than 8% by weight with respect to the total amount of the PPO resin composition, the flame retardancy of the laminate decreases, and the flame retardancy of the UL standard of 94V-0 cannot be maintained. If it exceeds 20% by weight, bromine (Br) is dissociated during the heat and pressure molding for producing the laminate, and tends to precipitate on the surface of the laminate, so that the heat resistance tends to decrease.

In order to obtain a prepreg by impregnating a substrate with the PPO resin composition of the present invention, first, PPO, TAIC and the above-mentioned brominated organic compound and the above-mentioned compatibilizer added as necessary are mixed with an organic solvent. Are mixed to prepare a varnish for use. The organic solvent is not particularly limited as long as it does not dissolve the brominated organic compound, dissolves the resin component, and does not adversely affect the reaction.Examples include ketones such as methyl ethyl ketone and ethers such as dibutyl ether. , An amide such as dimethylformamide, a chlorinated hydrocarbon such as trichloroethylene, or a mixture of two or more suitable organic solvents. The concentration of the resin solid content of the varnish may be appropriately adjusted according to the operation of impregnating the base material with the varnish, and for example, 50 to 90% by weight is appropriate.

The varnish prepared as described above is impregnated into a substrate, dried by heating, and the organic solvent is evaporated to obtain a prepreg. As the base material, a woven or nonwoven fabric of organic fibers or glass fibers is used. The amount of impregnation into this substrate is
It is preferable that the weight ratio of the resin solid content in the prepreg is 35% by weight or more. In general, the dielectric constant of the base material is higher than that of the resin, and therefore, in order to reduce the dielectric constant of the laminate obtained by using this prepreg, the content of the resin solid content in the prepreg should be larger than the weight ratio. Good to be more. For example, a prepreg using an E glass cloth as a base material can achieve a dielectric constant of 3.7 or less at a resin solid content of 37% by weight or more, and a prepreg using a D glass cloth as a base material has a dielectric constant of 45% or less. A dielectric constant of 3.2 or less can be achieved with a resin solid content of not less than weight%.

In the present invention, a laminated board can be manufactured using the prepreg. More specifically, one or more prepregs of the present invention are stacked, and further, a metal foil such as a copper foil is stacked on the upper and lower surfaces or one surface of the prepreg by heating and pressing to form a laminated and integrated double-sided metal. A foil-clad or one-sided metal foil-clad laminate can be made. A printed wiring board can be obtained by forming a circuit by etching the metal foil of the laminated board or the like.Furthermore, this printed wiring board is used as an inner layer printed wiring board, with a prepreg of the present invention interposed therebetween. A multilayer printed wiring board can be produced by stacking a plurality of sheets and forming a metal foil on the outermost layer by heating and pressing. The molding conditions vary depending on the mixing ratio of the raw materials of the resin composition of the present invention, and are not particularly limited. Generally, the temperature is 170 ° C or higher and 230 ° C or lower.
It is preferable to heat and pressurize under conditions of a pressure of 10 kg / cm ² or more and 50 kg / cm ² or less for an appropriate time. Curing can be further accelerated.
The PPO resin composition thus obtained does not impair the properties of the PPO, has excellent high-frequency properties such as dielectric properties, and has improved water resistance, moisture resistance, moisture absorption heat resistance and glass transition point. It was excellent.

As described above, the prepreg obtained by impregnating the substrate with the PPO resin composition of the present invention, drying by heating and semi-curing, and laminating and molding a predetermined number of prepregs by heating and pressing. According to the laminated plate, the water resistance, the moisture resistance, the heat resistance to moisture absorption and the glass transition point are high and excellent.

[0028]

The PPO resin composition according to claim 1 of the present invention comprises a varnish prepared by adding a solvent to a PPO resin composition containing PPO, TAIC, a compatibilizer and a flame retardant.
Since the flame retardant is a brominated organic compound that does not react with PPO and TAIC and is not dissolved but dispersed in the solvent, it is cured by mixing thermoplastic PPO and thermosetting TAIC. Then, the interpenetrating network structure [IPN (In
terpenetrating Polymer Net Work)], resulting in an extremely excellent structure as a laminate having high heat resistance. However, when the flame retardant is a reactive flame retardant having an unsaturated bond or a soluble flame retardant that dissolves in the solvent, the flame retardant penetrates the IPN of PPO-TAIC and causes
The formation of PN is inhibited, and as a result, a large amount of unpolymerized residue of TAIC is generated. Thus, the prepreg using the PPO resin composition and the laminate using the prepreg have water resistance, moisture resistance, moisture absorption heat resistance, and glass transition. Point (hereinafter referred to as Tg)
Decrease. Therefore, the flame retardant is PPO and TAI
C is a brominated organic compound that does not react with C, and is not dissolved in the solvent but is dispersed, so that the flame retardant is present as a filler in the resin.
It is presumed that the TAIC hardens almost completely and does not inhibit the formation of, forming a good IPN.

In the PPO resin composition according to the second aspect of the present invention, the true specific gravity of the brominated organic compound as a flame retardant is 3.0.
Because of the following, the flame retardant hardly settles in the varnish of the PPO resin composition, and a uniform varnish can be obtained without constantly stirring during the work of impregnating the base material.

In the PPO resin composition according to claim 3 of the present invention, the brominated organic compound is represented by decabromodiphenylethane represented by the general formula [1] or represented by the general formula [2]. 4,4-dibromobiphenyl, does not inhibit the formation of IPN of PPO-TAIC,
It is presumed that the IC hardened almost completely and formed a good IPN.

In the PPO resin composition according to the fourth aspect of the present invention, 30 to 60 parts by weight of PPO and 35 to 6 parts of TAIC are used.
Since it is contained at a ratio of 2 parts by weight, an IPN is formed, so that it is excellent in heat resistance. That is, when the PPO is less than 30 parts by weight and the TAIC is more than 62 parts by weight,
The laminate becomes brittle, PPO exceeds 60 parts by weight, TAI
When C is less than 35 parts by weight, a sufficient IPN cannot be formed. Furthermore, since the brominated organic compound having a bromine content of 8 to 20% by weight based on the total amount of the PPO resin composition is contained, flame retardancy is excellent. That is, when the bromine content is less than 8% by weight with respect to the total amount of the PPO resin composition, the flame retardancy of the laminate is reduced, and the UL standard is 9%.
If the flame retardancy at the level of 4V-0 cannot be maintained and exceeds 20% by weight, bromine (Br) is dissociated at the time of heat and pressure molding for producing a laminate, and precipitates on the surface of the laminate. The heat resistance tends to decrease.

In the prepreg according to claim 5 of the present invention,
Since the substrate is impregnated with the PPO resin composition according to any one of claims 1 to 4, and is semi-cured by heating and drying, it has excellent water resistance, moisture resistance, moisture absorption heat resistance, and a high glass transition point.

In the laminate according to the sixth aspect of the present invention, since a predetermined number of the prepregs according to the fifth aspect are laminated under pressure by heating and pressurizing, they are excellent in water resistance, moisture resistance, moisture absorption heat resistance and glass transition point. high.

[0034]

The present invention will be specifically described below with reference to examples.

(Example 1) As shown in the composition of Table 1, PPO (Noryl PX9701 manufactured by Nippon GE Plastics Co., Ltd.) represented by the above general formula [4] 4
0 parts by weight, m-TAIC (manufactured by Nippon Kasei Co., Ltd.) 45 parts by weight, p-TAIC (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: trade name P-TAIC-1000C) 10 parts by weight, styrene-butadiene 5 parts by weight of a block copolymer (trade name: Tufprene A manufactured by Asahi Kasei Kogyo Co., Ltd.), decabromodiphenylethane represented by the above general formula [1] which is a brominated organic compound as a flame retardant (manufactured by Mitsui Toatsu Fine Co., Ltd.) : Trade name: Planelon BDE, 82.3Br
%) And 1.5 parts by weight of α, α 'bis (t-butylperoxy-m-isopropyl) benzene (manufactured by NOF Corporation, trade name: PB-P) as an initiator. This was mixed, dispersed and dissolved in trichlorethylene as a solvent to obtain a varnish of the PPO resin composition.
Since the flame retardant is a brominated organic compound that does not react with PPO and TAIC, the flame retardant was not dissolved in the solvent but dispersed in the varnish of the PPO resin composition. The varnish was impregnated with E glass cloth (trade name: 216L, manufactured by Asahi Schabel Co., Ltd.),
The resultant was dried by heating under the conditions of 5 ° C. for 5 minutes, and the solvent was removed to obtain a prepreg having a resin content of 35% by weight. Copper foil (DT foil) is stuck on both sides of this one prepreg, and the temperature is 170 ° C.
Heating and pressurizing under pressure of 50 kg / cm ² for 180 minutes,
Then, it was reheated at a temperature of 230 ° C. for 2 hours with a dryer under pressure release to obtain a double-sided copper-clad laminate for an inner printed wiring board. A pattern is formed on the double-sided copper-clad laminate for the inner layer printed wiring board to form a core, and two prepregs are laminated on both sides of the core, and a 70 μm thick copper foil (ST foil) is placed on the upper and lower sides. Again, temperature 170
C., pressure 50 kg / cm ² , heating and pressurizing under the molding conditions of 180 minutes, and then 230 ° C.
Reheating was performed under the conditions of time to obtain a double-sided copper-clad laminate for a printed wiring board. 50 mm × 5
It was cut to 0 mm to obtain a sample for heat resistance to moisture absorption of the laminate.

Five prepregs were stacked, copper foil (ST foil) having a thickness of 70 μm was stacked on both the upper and lower sides, and the temperature was 170
C., pressure 50 kg / cm ² , heating and pressurizing under the molding conditions of 180 minutes, and then 230 ° C.
Reheating was performed under the conditions of time to obtain a double-sided copper-clad laminate for a printed wiring board. The copper foil on the surface of the obtained double-sided copper-clad laminate was removed by etching, and cut into 50 mm x 50 mm to obtain samples for glass transition point (Tg), water absorption and moisture absorption.

Using the above samples, the heat resistance to moisture absorption, the glass transition point (Tg), the water absorption and the moisture absorption of the laminate were measured.

(Comparative Example 1) In Example 1, a reactive brominated compound which is a reactive flame retardant having an unsaturated bond is represented by the following general formula [5] instead of decabromodiphenylethane. In the same manner as in Example 1 except that 35 parts by weight of N- (2,4,6-tribromophenyl) maleimide (trade name: TBP-MI, manufactured by Mitsui Toatsu Fine Co., Ltd., 58.5 Br%) was used. Thus, a PPO resin composition, a prepreg and a laminate were obtained, and the heat resistance to moisture absorption, the glass transition point (Tg), the water absorption and the moisture absorption of the laminate were measured.

[0039]

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(Comparative Example 2) In Example 1, instead of decabromodiphenylethane, an addition type flame retardant represented by the following general formula [6], which is a soluble flame retardant soluble in the solvent (trichloroethylene): Flame retardant (Nissan Chemical Co., Ltd .:
A PPO resin composition, a prepreg, and a laminate were obtained in the same manner as in Example 1, except that 29.1 parts by weight of trade name SR-245, 67.4 Br%) was used. The transition point (Tg), water absorption and moisture absorption were measured and are shown in Table 1.

[0041]

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The glass transition point (Tg) of the PPO resin composition was determined using TMA according to the thermodynamic analysis method of IPC-TM-650, 2.4.24.

The heat resistance to moisture absorption is 50 mm × 50 m obtained.
m-sided copper-clad laminates are boiled at 100 ° C for 2 hours.
Performed by a pressure cooker test (PCT) at 2/100 and 135 ° C., 2 atmospheres, and 2 hours. Each of the five samples was immersed in a solder bath at 260 ° C. for 20 seconds, and the presence or absence of blisters was visually observed. Observed. For example, 5
In the case where no blisters were generated, 0/5,
For 5 of the 5 out of 5 blisters, 5 /
The results are shown in Table 1 below.

The water absorption is determined according to JIS-C6481.
It measured by E-24 / 50 + D-24 / 23. That is, by drying at 50 ° C. for 24 hours and immersing in water at 23 ° C. for 24 hours, the water absorption was measured. The moisture absorption rate is E
It measured by -24 / 50 + C-24 / 60/95. That is, by drying at 50 ° C. for 24 hours, controlling the humidity at 23 ° C. for 24 hours, the relative humidity at 95% and the temperature at 60 ° C. for 24 hours,
The moisture absorption was measured. The sample used for the measurement of the water absorption and the moisture absorption was obtained by etching the surface copper foil of the obtained laminate 5.
What was cut to 0 mm x 50 mm was used.

[0045]

[Table 1]

From Table 1, it can be seen that in Example 1, the glass transition point of the obtained PPO resin composition was higher than that of Comparative Examples 1 and 2, and in addition, the water resistance, moisture resistance and heat resistance of the laminated board were high. It was confirmed that the properties were good.

[0047]

According to the PPO resin composition according to claim 1 of the present invention, the flame retardant is a brominated organic compound that is not reactive with PPO and TAIC, and does not dissolve in the solvent.
Because it is dispersed, thermoplastic PPO and thermosetting TA
When mixed with IC and cured, an interpenetrating network structure [I
PN (Interpenetrating Polymer Net Work)], and has an extremely excellent structure as a laminate with high heat resistance. Therefore, prepregs and laminates with a high glass transition point and excellent water resistance, moisture resistance and moisture absorption heat resistance are available. can get.

According to the PPO resin composition according to the second aspect of the present invention, the flame retardant hardly settles in the varnish of the PPO resin composition, so that even when the substrate is impregnated, it is not necessary to constantly stir the mixture. Since varnish is obtained, workability is improved.

According to the PPO resin composition according to claim 3 of the present invention, the brominated organic compound is decabromodiphenylethane or 4,4-dibromobiphenyl.
A prepreg and a laminate having a high glass transition point and excellent in water resistance, moisture resistance and moisture absorption heat resistance because the TAIC hardens almost completely and forms a good IPN without inhibiting the formation of the IPN of PO-TAIC. Is obtained.

According to the PPO resin composition of claim 4 of the present invention, 30 to 60 parts by weight of PPO and 35 of TAIC are used.
６２62 parts by weight and the brominated organic compound in a proportion of 8 to 20 parts by weight, so that the prepreg has a high glass transition point, and is excellent in flame retardancy, heat resistance and water resistance, moisture resistance and moisture absorption heat resistance. A laminate is obtained.

According to the prepreg according to the fifth aspect of the present invention, the substrate is impregnated with the PPO resin composition according to any one of the first to fourth aspects, and is heated and dried to be semi-cured.
A prepreg used for a laminate having excellent water resistance, moisture resistance, and heat resistance to moisture absorption can be obtained.

According to the laminate according to the sixth aspect of the present invention, since a predetermined number of the prepregs according to the fifth aspect are laminated under heat and pressure, the laminate is excellent in water resistance, moisture resistance and heat resistance to moisture absorption. Is obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-258537 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 71/00-71/14

Claims (6)

(57) [Claims] 1. A varnish obtained by adding a solvent to a polyphenylene oxide resin composition containing a polyphenylene oxide, triallyl isocyanurate, a compatibilizer and a flame retardant, as triallyl isocyanurate.
Using a monomer and a prepolymer thereof, wherein the flame retardant is a brominated organic compound that is non-reactive with polyphenylene oxide and triallyl isocyanurate, and is not dissolved but dispersed in the solvent. Characteristic polyphenylene oxide resin composition. 2. The brominated organic compound has a true specific gravity of 3.0.
The polyphenylene oxide resin composition according to claim 1, wherein: 3. The brominated organic compound is decabromodiphenylethane represented by the following general formula [1] or 4,4-dibromobiphenyl represented by the following general formula [2]. The polyphenylene oxide resin composition according to claim 1 or 2, wherein Embedded image Embedded image 4. A polyphenylene oxide of 30 to 60.
Parts by weight, 35 to 62 parts by weight of triallyl isocyanurate, and the brominated organic compound having a bromine content of 8 to 20% by weight based on the total amount of the polyphenylene oxide resin composition. The polyphenylene oxide resin composition according to any one of claims 1 to 3, wherein: 5. A prepreg obtained by impregnating a substrate with the polyphenylene oxide resin composition according to any one of claims 1 to 4, drying by heating and semi-curing. 6. A laminate formed by laminating a predetermined number of the prepregs according to claim 5 by heating and pressing.