JPS62121758A - Polyphenylene oxide resin composition and sheet composed of said resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which gives laminated sheets having excellent high-frequency characteristics, dimensional accuracy and resistance to heat and solvents, consisting of a polyphenylene oxide, a crosslinking polymer and/or a crosslinking monomer and an inorg. filler. CONSTITUTION:10-95pts.wt. polyphenylene oxide (A) of the formula (wherein R is H, a 1-3C hydrocarbon group) is blended with 1-50pts.wt. crosslinking polymer (e.g., 1,2-polybutadiene) and/or crosslinking monomer (e.g., triallyl cyanurate) (B), 1-200pts.wt. inorg. filler (C) having an average thickness of 3mum or below and an aspect ratio of 10-100 (e.g., Al2O3) and 0.1-5pts.wt. initiator (e.g., dicumyl peroxide) to obtain a polyphenylene oxide resin compsn. A soln. having a resin solid content of 5-50wt% obtd. by dissolving the compsn. in a solvent is cast into a carrier film for casting and the film is dried to obtain a sheet of 5-700mum in thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a polyphenylene oxide resin composition used for laminates and the like that exhibits excellent dielectric properties in a high frequency range, and a sheet made of this resin composition.

[Background technology]

Polyphenylene oxide is a low dielectric constant material with a relatively high glass transition point, and has attracted attention in recent years because of its excellent high frequency characteristics. However, depending on the application, it is necessary to improve physical properties such as heat resistance, chemical resistance, and physical strength (rigidity). One way to meet these demands is to crosslink resins. Modification of a resin composition by crosslinking is an effective and reliable means. However, polyphenylene oxide cannot be crosslinked (cured) by simple procedures like conventional thermosetting resins.

Furthermore, when designing high-frequency circuits, dimensional accuracy such as circuit width is a major problem. However, with conventional laminates,
4-
There is a proposal in which fluorinated ethylene resin or the like is combined with alumina powder, reinforcing fibers, etc. (Japanese Patent Application Laid-Open No. 130008/1983). However, this proposal has the disadvantage that process control is complicated because slurry is manufactured and then the slurry is made into paper.

When designing high-frequency circuits, it is naturally necessary to use low-loss materials to reduce circuit loss, but due to factors such as circuit size and frequency band, there are certain A specific magnitude of dielectric constant is often required.

In such cases, it is currently not easy to obtain a laminate with a desired dielectric constant.

For these reasons, conventionally it has not been possible to easily obtain a metal foil-clad laminate that has excellent high frequency characteristics, heat resistance, and dimensional stability.

[Purpose of the invention]

The present invention was made in view of the above circumstances, and provides a polyphenylene oxide resin composition that has excellent high frequency characteristics and heat resistance, and is capable of producing laminates and the like that have good dimensional stability and solvent resistance. The present invention also aims to provide a sheet made of this resin composition.

[Disclosure of the Invention] In order to achieve the above object, the present invention provides a polyphenylene oxide-based resin composition containing polyphenylene oxide, a crosslinkable polymer and/or a crosslinkable monomer, and a polyphenylene oxide-based resin composition containing an inorganic filler. The first gist is a polyphenylene oxide-based resin composition characterized in that the resin is The second aspect is a sheet characterized in that the composition contains an inorganic filler.

The present invention will be explained in detail below.

Here, polyphenylene oxide (also referred to as polyphenylene ether, hereinafter referred to as rPPOJ) is represented by the following general formula, for example, poly(2.
6-dimethyl-1,4-phenylene oxide).

Such PPOs are, for example, USP 4059
It can be synthesized by the method disclosed in No. 568. For example, 2,6-xylenol is subjected to an oxidative coupling reaction with an oxygen-containing gas and methanol in the presence of a catalyst to produce poly(2,6-dimethyl-1,4
-phenylene oxide), but is not limited to this method. Here, the catalyst includes a copper(1) compound, N-N'-di-tert-butylethylenedi7mine, butyldimethylamine, and hydrogen bromide. Based on this methanol, add 2 to 15% water to the reaction mixture system, so that the total of methanol and water is 5 to 2%.
It is used in such a way that it becomes a polymerization solvent of 5% by weight. Although not particularly limited, for example, weight average molecule i (M
W) is 50,000, molecular weight distribution M w / M n =
A polymer having a molecular weight of 4.2 (Mn is number average molecular weight) is preferably used.

Examples of crosslinkable polymers include, but are not limited to, 1,2-polybutadiene, 1,4
- Polybutadiene, styrene-butadiene copolymer, modified 1.2-polybutadiene (maleic modification, acrylic modification, epoxy modification).

Examples include rubbers, and each may be used alone or in combination of two or more. The polymer state may be an elastomer or a rubber, but a high molecular weight rubber state is particularly preferred since it improves film forming properties.

From the viewpoint of improving the film-forming properties of the PPO resin composition, it is preferable to use polystyrene within a range that does not impede achievement of the objectives of the present invention.

Note that polystyrene with a high molecular weight is desirable because it improves film-forming properties.

Examples of crosslinkable monomers include (1) ester acrylates, epoxy acrylates, urethane acrylates, and ether acrylates.

Acrylic acids such as melamine acrylates, alkyd acrylates, silicone acrylates, ■Triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, polyfunctional monomers such as divinylbenzene, diallyl phthalate, ■vinyltoluene, ethylvinylbenzene, Examples include monofunctional monomers such as styrene and paramethylstyrene, and polyfunctional epoxies (2), which may be used alone or in combination of two or more, but are not particularly limited to these.

As the crosslinking monomer, triallyl cyanurate and/or triallyl isocyanurate are used.
It is good because it has good compatibility with PO and is preferable in terms of film formability, crosslinkability, heat resistance, and dielectric properties.

The crosslinkable polymer and/or crosslinkable monomer are used to improve heat resistance and the like without impairing the properties of PPO by crosslinking (curing) it. These may be used alone or in combination, but their combined use is more effective in improving characteristics.

Inorganic fillers include alumina, aluminum oxide (A
lz03), silicon dioxide (Sing), titanium dioxide (TiO□), glass fiber, glass chips, etc., each of which may be used alone or in combination of two or more, but is not limited to these. The inorganic filler preferably has a size that does not cause any disadvantage to the properties of products such as molded articles made of the PPO resin composition containing the inorganic filler, and is preferably used in the form of fine particles. The particle size is preferably about 50 μm or less, and if it is too small, handling may become difficult, so it is more preferably in the range of 1 to 20 μm (more preferably 1 to 10 μm). . If aluminum oxide, titanium dioxide, silica, or other well-known dielectric materials with a high dielectric constant are used as inorganic fillers, the dielectric constant of the resulting solidified PPO resin composition will be relatively high (and the dielectric material will have a high dielectric constant). By adjusting the type and amount of the dielectric material, the dielectric constant of the solidified PPO resin composition can be adjusted over a wide range. Yes, it is possible.In other words, inorganic fillers also act as dielectric constant adjusters.For the purpose of increasing the dielectric constant, other types of fillers with high dielectric constants can be used instead of inorganic fillers. The upper limit of the blending ratio of the inorganic filler in the PPO-based resin composition is set at the point at which the solidified product of the PPO-based resin composition begins to exhibit unfavorable tendencies such as becoming porous or losing strength. It is.

The blending ratio of the above raw materials is not particularly limited, but PP
0IO to 95 parts by weight (more preferably 20 to 90 parts by weight), 1 to 50 parts by weight of crosslinkable polymer and/or crosslinkable monomer, 1 to 200 parts by weight of inorganic filler (preferably as a dielectric constant regulator, 1 to 160 parts by weight). In addition, although not particularly limited, crosslinking monomer 1
It is preferable to use the crosslinkable polymer at a ratio of 20 parts by weight or less to parts by weight. However, when PPO is used in combination with polystyrene and/or styrene-butadiene copolymer, it is preferable to use the following blending weight ratio.

Adjustment of the dielectric constant using an inorganic filler is performed as follows. That is, the inventors have confirmed that, for example, PP
The dielectric constant of the organic binder containing 070 parts by weight, 15 parts by weight of styrene-butadiene copolymer, 14 parts by weight of triallyl isocyanurate, and 1 part by weight of dicumyl peroxide was 2.6, and the dielectric loss was 0.002 (at 23°C, IMHz
).

Here, the dielectric constant of a composition in which 340 parts by weight of aluminum oxide is blended with 100 parts by weight of this organic binder is 4.9, the dielectric loss is 0.001 (23°C, IMH2), and the dielectric constant of aluminum oxide is 9. Considering .4, it can be seen that it is related to the blending ratio of aluminum oxide, that is, the blending ratio of the inorganic filler. Therefore, the blending ratio of the inorganic filler can be adjusted to match the desired dielectric constant. In this case, from the viewpoint of uniformity of the PPO resin composition to be adjusted, the blending ratio of the inorganic filler is more preferably 20 to 130 parts by weight at the above blending ratio.

As an inorganic filler, especially in the form of flakes (inorganic substances)
When used, the dimensional stability, solvent resistance 2, warping, etc. of the solidified product of the PPO resin composition are further improved.

Examples of the flaky inorganic filler include glass flakes and mica, each of which may be used alone or in combination of two or more, but is not limited thereto. For example, with a flat piece of glass such as the micro glass flakes manufactured by Nippon Glass Fiber ■, the thickness is 2 to 3 μm, the particle size is 10 to 32
Examples include glass flakes of 5 mesh and/or fine mica particles of 5 to 100 mesh, such as Daimonite manufactured by Topie Corporation. From the viewpoint of electrical properties, mica is preferably muscovite, but is not particularly limited thereto.

Note that the flaky inorganic filler preferably has a size of 80 mesh or less. If the size exceeds 80 meshes, when the PPO resin composition of the present invention is made into a solution as described below, the flaky inorganic filler tends to settle, and the storage stability in the solution may deteriorate. be. The flaky inorganic filler preferably has an average thickness of 3 μm or less and/or an aspect ratio of 100 or less.

The average thickness is greater than 3 μm and the aspect ratio is 1.
If it is larger than 00, the PP of this invention is
When forming an O-based resin composition into a sheet by casting, the drying speed becomes slow, resulting in poor work efficiency.
There is a risk that the physical properties of the sheet will deteriorate. Further, from the viewpoint of improving the dimensional stability of a molded article made of the PPO resin composition of the present invention, it is preferable that the aspect ratio of the flaky inorganic filler is 10 or more.

Moreover, the thickness of the flaky inorganic filler is preferably 1 μm or more.

In the solidified product of the PPO resin composition of the present invention, the flake-like inorganic filler plays the role of a skeleton that connects the resins and improves the strength of the solidified product. It also works to prevent chemicals from entering. Of course, it also contributes to dimensional stability.

The blending ratio of the above raw materials is not particularly limited, but PP
0IO to 95 parts by weight (more preferably 20 to 80 parts by weight), 5 to 50 parts by weight of crosslinkable polymer (more preferably 5 to 45 parts by weight) and/or 1 to 20 parts by weight of crosslinkable monomer 1 to 80 parts by weight of the flaky inorganic filler. Although not particularly limited, 2 parts by weight of the crosslinkable polymer may be added to 1 part by weight of the crosslinkable monomer.
It is preferable to use it in a proportion of 0 parts by weight or less.

In addition, an initiator is usually used in PPO resin compositions. As an initiator, dicumyl peroxide,
tert-butylcumyl peroxide, tert.
t-Butyl peroxide, 2,5-dimethyl-2.
5-di(tert-butylperoxy)hexyne-3
, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, α·α′-bis(tert-butylperoxy-m-isopropyl)benzene [1,4
(Also referred to as l.3)-bis(ter t-butylperoxyisopropyl)benzene]9
Nippon Oil &Fats' Biscumyl and the like can be mentioned, and each can be used alone or in combination of two or more, but is not limited thereto. The blending ratio of the initiator is 0.1 to 5 parts by weight (more preferably 0.1 parts by weight) relative to the above two blending ratios.
~3 parts by weight).

The raw materials according to the above formulation are usually dissolved and dispersed in a solvent (inorganic fillers usually do not dissolve) and mixed (solution mixing). In this case, 5 to 5 of the PPO resin composition
A 50% by weight solution (or a resin solid content in the range of 10 to 30!II% with respect to the solvent) is preferable. After mixing, a PPO resin composition is obtained by removing the solvent. Examples of the solvent include halogenated hydrocarbons such as trichloroethylene, trichloroethane, chloroform, methylene chloride, and chlorobenzene, and aromatic compounds such as benzene, toluene, and xylene. Examples include hydrocarbons, acetone, and carbon tetrachloride, with trichlorethylene being particularly preferred.
These can be used alone or in combination of two or more, but are not limited thereto. Note that the mixing may be performed by other methods.

The PPO resin composition according to the present invention can be prepared by, for example, dissolving and mixing the raw materials in a solvent as described above, forming a thin layer by casting or coating on an appropriate object, and then drying the solvent. can be made into a solidified product by removing (casting method). According to this casting method, a solidified product of the PPO resin composition can be produced at a low temperature without using the costly calendar method. Usually, in such a casting method, the solidified product becomes a sheet (film), but the solidified product is not limited to a sheet. In addition, the solidified product is 1, and the cured product is also included.

The PPO resin composition of the present invention is used for, for example, printed wiring boards. In such cases, a sheet made of the PPO resin composition and/or a base material impregnated with the PPO resin composition (hereinafter referred to as "prepreg") is easy to handle and can be used to obtain the desired thickness. It becomes easier to form a laminate.

A sheet made of the PPO resin composition of the present invention can be produced, for example, by the above-mentioned casting method, but methods other than this method may also be used.

To describe the casting method in detail, please refer to the above P.
Dissolve the PO-based resin composition or its raw materials in a solvent (
Inorganic fillers usually do not dissolve) The mixed solution is placed on a mirror-treated iron plate or a carrier film for casting, etc. at a density of 5 to 700 (preferably 5
A sheet is obtained by casting (or coating) to a thickness of ~500 μm and thoroughly drying to remove the solvent. Note that sheet here refers to film,
Including what are called membranes, tapes, etc., there are no particular limitations on the extent or length of the surface perpendicular to the thickness direction.
The thickness can also be set in various ways depending on the application. The above-mentioned carrier film for casting is not particularly limited, but may include polyethylene terephthalate (hereinafter abbreviated as JfETJ) film, polyethylene film, polypropylene film, and
'Those insoluble in the above-mentioned solvents, such as polyester films and polyimide films, are preferred, and those that have been subjected to mold release treatment are preferred. The solvent is removed from the PPO resin composition solution cast (or coated) on the carrier film for casting by air drying and/or drying with hot air. The upper limit of the set temperature during drying is preferably lower than the boiling point of the solvent or lower than the heat-resistant temperature of the carrier film for casting (when drying is performed on the carrier film for casting),
The lower limit is determined by drying time, processability, etc. For example, when trichlorethylene is used as a solvent and PET film is used as a carrier film for casting, a range from room temperature to 80°C is preferable, and the temperature can be increased within this range. This makes it possible to shorten the drying time.

The solidified product (for example, a sheet) of the PPO resin composition produced in this way can be further subjected to tensile strength by thermal crosslinking using a radical initiator, photocrosslinking, crosslinking using radiation, etc. Strength, impact strength, bursting strength, heat resistance, etc. can be increased.

A sheet made of the PPO resin composition of the present invention can be used for various purposes such as a laminate and an adhesive sheet.

The prepreg may be produced by any method, but generally, it can be produced by the following method.

That is, the PPO resin composition or its raw material is completely dissolved (for example, in a proportion of 5 to 50% by weight) in the above-mentioned solvent.
Inorganic fillers usually do not dissolve), and the base material is immersed (dipped) in this solution to impregnate and adhere these PPO-based resin compositions to the base material. In this case, the solvent may be simply removed by drying or the like, or the B stage may be obtained by semi-curing. The resin content of the prepreg produced in this way is not particularly limited, but is
It is preferable to set it as 0-50 heavy background%. The base material is a resin-impregnated or loss-like material such as glass cloth, aramid cloth, polyester cloth, or nylon cloth, a mat-like material made of these materials and/or a fibrous material such as nonwoven fabric, or kraft paper.

Paper such as linter paper is used, but is not limited to these. If prepreg is produced in this way,
Since the resin does not need to be melted, it can be carried out more easily at relatively low temperatures.

The PPO-based resin composition of the present invention and a laminate using a sheet made from the same (one side or both sides covered with metal foil, without metal foil on both sides) can be produced, for example, as follows:
It is not limited to this. If the sheet of this invention is a cast sheet made as described above, the starting point of the formulation.

Dry thoroughly at a temperature lower than the decomposition temperature of the agent and higher than the boiling point of the solvent used to eliminate residual solvent. The sheets produced in this way and/or the prepregs produced as described above are combined in a predetermined manner so as to have a predetermined design thickness, and if necessary, metal foil is also combined and laminated, followed by heat pressing, etc. By melting the resin, the sheets are bonded together.
Sheet and prepreg, prepreg together, sheet and metal foil.

A laminate is obtained by bonding the prepreg and metal foil to each other.

Strong adhesion can be obtained by this fusion, but if a crosslinking reaction using a radical initiator is performed during heating at this time, even stronger adhesion can be obtained. The crosslinking reaction may be carried out by ultraviolet irradiation or the like. When thermal crosslinking and photocrosslinking are not performed, crosslinking by radiation irradiation may be performed. Further, after thermal crosslinking and photocrosslinking, crosslinking by radiation irradiation may be performed. Therefore, adhesion with excellent heat resistance can be achieved between sheets, between prepregs, between sheets and prepreg, between sheets and metal foil, and between prepreg and metal foil.

Here, the combination of the sheet and the prepreg is not particularly limited, but a vertically symmetrical combination is preferred from the viewpoint of preventing warping after molding and secondary processing (etching, etc.).

Further, from the viewpoint of adhesive strength, it is preferable to combine the sheets so that they are on the adhesive interface with the metal foil. Since the adhesiveness of the sheet can be used to bond the metal foil and the sheet, the lamination pressing temperature is above the glass transition point of the sheet, and is approximately l.
A range of about 60 to 300°C is preferable. In a solidified product of a PPO resin composition, the resin flows slightly before curing, so it exhibits good fusion properties to metals. However, an adhesive may be used in combination.

As the metal foil, copper foil, aluminum foil, etc. are used.

Pressing is performed to bond sheets to each other, sheets to prepreg, prepregs to prepreg, metal foil to sheet, metal foil to prepreg, and to adjust the thickness of the laminate, so the pressing conditions are selected as necessary.

In addition, when the PPO resin composition of the present invention is crosslinked by heating, such as by heating it in a dryer, the crosslinking reaction depends on the reaction temperature of the initiator used, so it depends on the type of initiator. It is recommended that you select the heating temperature. The heating time may also be selected depending on the type of initiator, etc. For example, temperature 15
The temperature is 0 to 300°C and the time is about 10 to 60 minutes. In the case of heat-pressing, a pressure of about 50 kg/cd is selected, for example. A predetermined number of sheets and/or prepregs may be heated and laminated in advance, metal foil may be superimposed on one or both sides of the sheets, and the sheets and/or prepregs may be heat-pressed again.

The PPO of this invention, such as the laminate thus obtained,
The solidified product of the based resin composition does not impair the properties of PPO,
This results in excellent high frequency properties such as dielectric properties and heat resistance, as well as excellent dimensional stability.

If flakes are used as the inorganic filler, in addition to these properties, chemical resistance, solvent resistance, and rigidity (strength) will be excellent, and warpage will be reduced. The manufacturing operation is also simple as described above.

Next, Examples and Comparative Examples will be shown.

(Example 1) 27! Into a reactor equipped with a pressure reduction device, 100 g of PP0, 40 g of styrene-butadiene copolymer (Asahi Kasei ■: Solblen T406), ) realyl isocyanurate (Nippon Kasei ■)
: 40 g of TA r C) and 2 g of dicumyl peroxide were added, followed by 750 g of trichlorethylene (Toagosei Kagaku Kogyo ■: Trichlene), and the mixture was thoroughly stirred until a homogeneous solution was obtained. After this, the average particle size is 1 to 2 IIm.
260 g of aluminum oxide powder was added and further stirred to uniformly disperse the mixture. After that, defoaming was performed, and the obtained P
The PO-based resin composition solution was coated onto a PET film using a coating machine to a thickness of 500 mm.

After drying this at 50°C for about 10 minutes, the resulting film was
The mold was released from the ET film and further dried at 120° C. for 30 minutes to completely remove trichlorethylene to obtain a sheet made of a PPO resin composition. The thickness of this sheet was about 150 pm.

Stack 4 of these sheets, 190℃, 50kg/
It was pressed for 30 minutes under cni conditions to completely cure, and a laminate was produced.

The physical properties of this laminate are shown in Table 1.

(Example 2) 670g of aluminum oxide powder under the blending conditions of Example 1
A laminate was produced under the same conditions except that 850 g of trichlorethylene was used, and the physical properties thereof are shown in Table 1.

(Example 3) 1350g of aluminum oxide powder under the blending conditions of Example 1
A laminate was produced under the same conditions except that 950 g of trichlorethylene was used, and its physical properties are shown in Table 1.

(Example 4) Under the blending conditions of Example 1, 50 g of aluminum oxide powder,
Titanium dioxide (manufactured by Fuji Titanium Industries, average particle size 1-2u)
) and 750 g of trichlorethylene, a laminate was produced under the same conditions, and its physical properties are shown in Table 1.

(Example 5) 100g of aluminum oxide powder under the blending conditions of Example 1
, 330 g of titanium dioxide and 85 g of trichlorethylene
A laminate was produced under the same conditions except that the weight was 0g,
Its physical properties are shown in Table 1 (Comparative Example 1) A sheet containing only resin without adding any inorganic filler was prepared under the compounding conditions of Example 1, and a laminate was prepared under the same conditions. The physical properties of this laminate are shown in Table 1 (Example 6) 140 g of polyphenylene oxide, 40 g of styrene-butadiene copolymer (Asahi Kasei Corporation ■: Solprene T406), triallyl isocyanurate (Japanese) were placed in a reactor equipped with a pressure reduction device. 40 g of TAIC) and 3 g of dicumyl peroxide were added, followed by 850 g of trichlorethylene (Toagosei Chemical Industry Co., Ltd. (Jll)) and thoroughly stirred until a homogeneous solution was obtained. - Alumina powder (resident aluminum smelting ■:
280 g of fine alumina AM-21) was added and further stirred to uniformly disperse the mixture. After that, defoaming was performed, and the obtained P
The PO-based resin composition solution was coated onto a PET film using a coating machine to a thickness of 500 mm.

After drying this at 50°C for about 10 minutes, the formed film was released from the PET film and dried at 120°C for an additional 30 minutes to completely remove trichlorethylene to obtain a sheet made of a PPO resin composition. . The thickness of this sheet was about 120 μm. 8 sheets were stacked together and 3
5 μm electrolytic copper foil was laminated on both sides and heated at 200°C.
A laminate was produced by pressing for 30 minutes at 0 kg/cJ.

The physical properties of this laminate are shown in Table 1.

(Example 7) A laminate was produced under the same conditions as in Example 6 except that 500 g of fine alumina powder and 1200 g of trichlorethylene were used, and the physical properties thereof are shown in Table 1.

(Example 8) A laminate was produced under the same conditions as in Example 6 except that 1100 g of fine alumina powder and 1400 g of trichlorethylene were used, and the physical properties thereof are shown in Table 1.

(Example 9) A laminate was produced under the same conditions as in Example 6, except that 1700 g of fine alumina powder and 1600 g of trichloroethylene were used, and the physical properties thereof are shown in Table 1.

(Example 10) A laminate was produced under the same conditions as in Example 6 except that 2000 g of fine alumina powder and 1800 g of trichlorethylene were used, and the physical properties thereof are shown in Table 1.

(Comparative Example 2) A sheet containing only resin was produced under the compounding conditions of Example 6 without adding fine alumina particles, and a laminate was produced under the same conditions.

The physical properties of this laminate are shown in Table 1.

As shown in Table 1, the laminates using sheets made of the PPO resin compositions of Examples 1 to 10 have excellent high-frequency characteristics of dielectric constant and dielectric loss, and have excellent peel strength and alkali resistance at room temperature. is almost the same as that of the comparative example, and the solder heat resistance and thermal expansion coefficient are better than those of the comparative example. That is, the laminates of Examples 1 to 10 have excellent high frequency characteristics and heat resistance, and also have excellent dimensional stability. When the inorganic fillers are the same, the dielectric constant increases as the blending ratio increases. Titanium dioxide is more effective in increasing the dielectric constant than aluminum oxide or fine alumina. In this way, by changing the type and amount of the inorganic filler, a wide range of dielectric constants can be imparted to the PPO resin composition.

(Example 11 - IT) Each of the raw material formulations shown in Table 2 was dissolved in trichlorethylene (Toagosei Chemical Industry Co., Ltd. + trichlorethylene manufactured by Kiku) in a reactor equipped with a defoaming device (the inorganic filler was dispersed), and the mixture was uniformly dissolved. After stirring sufficiently until it becomes a solution, defoaming was performed to obtain a 25% by weight solution of the PPO resin composition.The obtained solution blend was coated on a PET film with a thickness of 50% using a coating machine.
It was coated so that the thickness was 0 μm. After air-drying this, it was dried in a dryer at 50°C for 10 minutes, and the resulting sheet was made of PE.
The mold was released from the T film and further dried at 120° C. for 30 minutes. After stacking 10 of these sheets (approximately 100 μm in thickness) and forming them into a size of 3001 m x 3 oomm, one sheet of copper foil (35 μm in thickness) was layered on both sides and pressed at 240°C and 50 kg/cm for 30 minutes. Separately, the sheet dried at 120°C for 30 minutes was baked at 220°C for 30 minutes to obtain a crosslinked (cured) sheet.

(Comparative Example 3.4) A laminate was obtained in the same manner as in Example 11 using the formulation shown in Table 2 without adding any filler.

Table 2 shows the characteristics of each of the above laminates.

In Table 2, SBS stands for styrene-butadiene copolymer, 1.2-PBu stands for 1.2-polybutadiene, and TA stands for styrene-butadiene copolymer.
IC is triallylisocyanurate, A is 2,5-dimethyl-2,5-di(tert-butylperoxy)
Hail hexine-3 respectively. The styrene-butadiene copolymer was Asaprene from Asahi Kasei A1, the 1,2-polybutadiene was from Nippon Soda, the triallyl isocyanurate was from Nippon Kasei, and the 2,5-dimethyl-2,5-dimethyl (tert-butylperoxy) hexine-3 is Nippon Oil's perhexine 25B, and the glass flakes are from Nippon Glass Fiber ■ (average thickness 2-3
μm, aspect ratio 300 to 500,150 mesos.
~15 μm and an aspect ratio of 50 to 100.150 mS or less) were used, respectively.

Among the characteristics, regarding warpage, after removing the entire copper foil on one side of a laminate formed to 3QOmm x 3001 by etching, each corner of the laminate is placed on a flat surface with the side with the copper foil removed facing upward. It shows the average distance between the part and the plane.

As shown in Table 2, the laminates using sheets made of each of the Ppo resin compositions of Examples 11-17 have excellent high-frequency characteristics of dielectric constant and dielectric loss tangent (dielectric loss), and have excellent soldering heat resistance. , trichlorethylene resistance, coefficient of thermal expansion, and warpage are better than those of Comparative Example 3.4. That is, the laminates of Examples 11 to 17 have excellent high frequency characteristics and heat resistance, and are also excellent in dimensional stability, solvent resistance, and warpage. This is because a flaky inorganic filler is used. Furthermore, the dielectric constant changes when the blending amount of the flaky inorganic filler changes.

〔Effect of the invention〕

The PPO-based resin composition of the present invention comprises PPO and
It contains a crosslinkable polymer and/or a crosslinkable monomer, and also contains an inorganic filler, so if it is used, a molded product with excellent high frequency characteristics, heat resistance, and dimensional stability can be obtained. be able to. Since the inorganic filler also functions as a dielectric constant adjusting agent, various dielectric constants can be set by adjusting the type and amount of the inorganic filler.

Since the sheet of this invention is made of the above resin composition,
By using this, it is possible to obtain a laminate having excellent high frequency properties and heat resistance, and also excellent dimensional stability. By adjusting the type and amount of the inorganic filler, the dielectric constant of the sheet can be set in various ways.

Agent: Patent Attorney Takehiko Matsumoto Hand □ Fu Seisho January 18, 1986

Claims (23)

[Claims] (1) A polyphenylene oxide resin composition containing polyphenylene oxide, a crosslinkable polymer and/or a crosslinkable monomer, and characterized in that it contains an inorganic filler. (2) The inorganic filler is alumina, aluminum oxide (A
1_2O_3), silicon dioxide (SiO_2), titanium dioxide (TiO_2), glass fiber, and glass chips. (3) The polyphenylene oxide resin composition according to claim 1 or 2, wherein the inorganic filler has a particle size of 1 to 20 μm. (4) 10 to 95 parts by weight of polyphenylene oxide;
The polyphenylene oxide system according to any one of claims 1 to 3, which contains a crosslinkable polymer and/or a crosslinkable monomer in a proportion of 1 to 50 parts by weight, and an inorganic filler in a proportion of 1 to 200 parts by weight, respectively. Resin composition. (5) The polyphenylene oxide resin composition according to claim 1, wherein the inorganic filler is in the form of flakes. (6) The polyphenylene oxide resin composition according to claim 5, wherein the inorganic filler is glass flakes and/or mica. (7) The polyphenylene oxide resin composition according to claim 5 or 6, wherein the inorganic filler has a size of 80 mesh or less. (8) The polyphenylene oxide resin composition according to any one of claims 5 to 7, wherein the inorganic filler has an average thickness of 3 μm or less and/or an aspect ratio of 10 to 100. (9) 10 to 95 parts by weight of polyphenylene oxide,
Any one of claims 5 to 8, which contains a crosslinkable polymer in a proportion of 5 to 50 parts by weight, a crosslinkable monomer in a proportion of 1 to 20 parts by weight, and an inorganic filler in a proportion of 1 to 80 parts by weight, respectively. The polyphenylene oxide resin composition described in . (10) The crosslinkable polymer is 1,2-polybutadiene, 1
・4-polybutadiene, styrene-butadiene copolymer,
The polyphenylene oxide resin composition according to any one of claims 1 to 9, which is at least one member selected from the group consisting of modified 1,2-polybutadiene and rubbers. (11) The crosslinking monomer is ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate , divinylbenzene, diallylphthalate, vinyltoluene, ethylvinylbenzene, styrene, paramethylstyrene, and polyfunctional epoxies. Any polyphenylene oxide resin composition. (12) A sheet made of polyphenylene oxide and a polyphenylene oxide resin composition containing a crosslinkable polymer and/or a crosslinkable monomer, characterized in that the resin composition contains an inorganic filler. . (13) The inorganic filler is alumina, aluminum oxide (A
1_2O_3), silicon dioxide (SiO_2), titanium dioxide (TiO_2), glass fiber, and glass chips. (14) The sheet according to claim 12 or 13, wherein the inorganic filler has a particle size of 1 to 20 μm. (15) The polyphenylene oxide resin composition contains 10 to 95 parts by weight of polyphenylene oxide, 1 to 50 parts by weight of a crosslinkable polymer and/or a crosslinkable monomer, and 1 to 200 parts by weight of an inorganic filler. A sheet according to any one of claims 12 to 14. (16) The sheet according to claim 12, wherein the inorganic filler is in the form of flakes. (17) The sheet according to claim 16, wherein the inorganic filler is glass flakes and/or mica. (18) The sheet according to claim 16 or 17, wherein the inorganic filler has a size of 80 mesh or less. (19) Claim 1, wherein the inorganic filler has an average thickness of 3 μm or less and/or an aspect ratio of 10 to 100.
The sheet according to any one of Items 6 to 18. (20) The polyphenylene oxide resin composition contains 10 to 95 parts by weight of polyphenylene oxide, 5 to 50 parts by weight of a crosslinkable polymer, and/or 1 part by weight of a crosslinkable monomer.
20 parts by weight of the sheet and the inorganic filler in a proportion of 1 to 80 parts by weight, respectively. (21) The crosslinkable polymer is 1,2-polybutadiene, 1
・4-polybutadiene, styrene-butadiene copolymer,
Claim 12, which is at least one member selected from the group consisting of modified 1,2-polybutadiene and rubbers.
The sheet according to any one of Items 20 to 20. (22) The crosslinkable monomer is ester acrylates, epoxy acrylates, urethane acrylates, ether acrylates, melamine acrylates, alkyd acrylates, silicone acrylates, triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate , divinylbenzene, diallylphthalate, vinyltoluene, ethylvinylbenzene, styrene, paramethylstyrene, and polyfunctional epoxies. Sheet listed in either. (23) The sheet according to any one of claims 12 to 22, which is a casting sheet.