JPH0841362A - High frequency resin composition - Google Patents

Abstract

(57) [Summary] [Object] To provide a resin composition having small reflection loss and transmission loss in a wide range of high frequencies and suitable for molding. [Structure] 100 parts by weight of a polymer component containing (A) at least one kind of polyetherimide and polyester and (B) at least one kind of polyphenylene ether, polyolefin and polycarbonate, and (1) 0.1 to 50 parts by weight of A maleic anhydride compound-vinyl compound copolymer or (2) a resin composition containing 0.1 to 1.0 part by weight of an epoxy-modified styrene copolymer.
One side of a 50 × 7 mm surface of a 0 × 7 × 1 mm test piece 100 is copper-plated, and a microstrip line 110 having a width of 1.86 mm and a thickness of 10 μm or more and an impedance of 50 Ω is provided on the opposite side longitudinal center line. When formed over the entire length in the longitudinal direction, 950 MHz or more and 100 GHz
The reflection loss of the electric signal in the frequency range below is 30.0d
When B or less, the transmission loss is 5.0 dB or less.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for high frequencies, which has a small reflection loss and a small transmission loss in a wide range of a high frequency band (950M to 300GHz) and is particularly suitable for molding.

[0002]

2. Description of the Related Art In recent years, with the development of high-frequency related technology, the signal frequency tends to gradually increase. However, depending on the equipment, the signal in the frequency range from several hundred MHz to maximum 100 GHz is used. There is also a need to handle. In electronic devices that handle such high frequencies, materials such as packages, circuit boards, sockets, connectors, and other devices and connecting members that have low permittivity and loss tangent and low loss, that is, have excellent electrical characteristics, are used. To be done.

Further, as a material for electronic members, particularly electronic members used in a high frequency band, it is necessary to have a material having not only excellent electric characteristics but also moldability and plating property.

Polyether imides, polyesters, polyimides and the like are used in many applications as engineering plastics because they have excellent properties such as heat resistance, electrical insulation and mechanical properties. Further, due to its excellent heat resistance and electric insulation, it is often used as an electric insulation material for IC substrates, printed wiring boards and the like.

However, such a condensed aromatic heat-resistant polymer generally has a relatively high dielectric constant, so that it is used as an insulating material for high-density / multilayer integration or high-speed / high-frequency circuits. , Its performance is limited.

On the other hand, polyphenylene ether, polyolefin, polycarbonate, aromatic polyvinyl compounds, etc. are inferior in mechanical strength, moldability and heat resistance,
It has a low dielectric constant and relatively excellent electrical characteristics.

By blending two or more polymers having different properties, a polymer blend having the characteristics of each polymer is actively designed. However, many polymers are incompatible systems, and in the case of incompatible polymer blends, properties,
Especially, there is a problem in mechanical properties.

Conventionally, the compatibility of a polymer blend when a poly (phenylene ether) having the above-mentioned characteristics is mixed with a polyetherimide having the above-mentioned characteristics is mixed with an epoxy-modified aromatic vinyl resin. In some cases, this has been solved (Japanese Patent Laid-Open No. 5-328)
No. 80, hereinafter referred to as "known art").

However, although the compatibilizing agent used in this polymer blend, that is, the epoxy-modified aromatic vinyl resin of the known art generally interacts with other components, it has poor heat resistance by itself. Therefore, when used in a large amount, there is a great possibility that the heat resistance originally possessed by the polyetherimide and polyphenylene ether will be impaired.

Moreover, since the compatibilizer generally has a lower crystallization temperature or glass transition temperature than polyetherimide and polyphenylene ether, these 3
If a large amount of compatibilizer is used when forming a molded product of a polymer blend consisting of three components, the compatibilizer may appear as a layer on the surface of the molded product, resulting in a problem in uniformity as a molded product. . That is, due to this non-uniformity, particularly the heat resistance of the molded body after repeated melting, electrical characteristics,
The drawback is that mechanical properties are reduced.

On the other hand, in the case of an electric insulating material such as a printed circuit board of an electronic member such as an IC board, in addition to the above-mentioned various characteristics such as heat resistance, mechanical characteristics, electric insulation, dielectric characteristics and moldability. In order to dissipate the heat generated during use, a material having a high thermal conductivity is preferable. However, in general, a polymer has a low thermal conductivity, and it is difficult to improve it only by blending the polymers with each other, and even a known technique still has an insufficient thermal conductivity.

The present invention solves the above-mentioned problem of compatibility in polymer blends without causing the above-mentioned problem of non-uniformity of the molded body, and thus has electrical insulation, dielectric properties, heat resistance and mechanical properties. Etc., it is also compatible with repeated molding, and has excellent thermal characteristics such as thermal conductivity. Especially, reflection loss and transmission loss are small when used in the high frequency band. Therefore, it is suitable for use in this field. An object is to provide a suitable resin composition for electronic members.

[0013]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to achieve the above object, (A) at least one selected from the polyetherimide represented by the general formula (a) and the polyester represented by the general formula (b), and (B) the polyphenylene ether represented by the general formula (c), As a compatibilizer, (1) 0.1 to 100 parts by weight of a polymer component containing a polyolefin represented by the formula (d) and at least one selected from a polycarbonate represented by the general formula (e). 50 parts by weight of maleic anhydride compound-vinyl compound copolymer, or (2) 0.1-1.0 part by weight of epoxy-modified styrene copolymer, especially this graft copolymer. 1. The resin composition is excellent in compatibility, heat resistance and mechanical properties, and has small reflection loss and transmission loss (excellent electrical properties), and is also excellent in plating property and moldability. In addition, in the resin composition using (2) as the compatibilizer, the compatibility problem can be sufficiently solved even if the amount of the compatibilizer is reduced, and the amount of the compatibilizer is As a result of the extremely small amount, surprisingly, even when repeatedly molding, not only the compatibility does not decrease, the problem of non-uniformity of the molded body does not occur at all, was found, The present invention has been completed.

That is, the present invention comprises (A) at least one selected from polyetherimide and polyester,
(B) 0.1 to 50 parts by weight of a maleic anhydride compound-vinyl compound copolymer, based on 100 parts by weight of a polymer component containing at least one selected from polyphenylene ether, polyolefin and polycarbonate. Or a resin composition containing (2) 0.1 to 1.0 part by weight of an epoxy-modified styrene-based copolymer, and one of 50 mm × 7 mm × 1 mm test pieces made of the resin composition. Of 50 mm x 7 mm surface is plated with copper, and a microstrip line with a width of 1.86 mm and a thickness of 10 μm or more and an impedance of 50 Ω is provided over the entire length in the longitudinal direction on the longitudinal center line of the other 50 mm x 7 mm surface. When formed, 950MHz or more 100
A gist of the resin composition for high frequencies is that the reflection loss of an electric signal is 30.0 dB or less and the transmission loss is 5.0 dB or less in a frequency region of less than GHz.

The composition of the present invention comprises a polymer component
At least one selected from polyetherimide (general formula (a)) and polyester (general formula (b)) as component (A), and polyphenylene ether (general formula (c)) and polyolefin as component (B). (General formula (d)) and at least one selected from polycarbonate (general formula (e)).

[0016]

Embedded image

[0017]

[1 of chemical formula 2]

[0018]

[Chemical 2-2]

[0019]

[Chemical 3]

[0020]

[Chemical 4]

[0021]

[Chemical 5]

The polyetherimide, polyester, polyphenylene ether, polyolefin and polycarbonate represented by the above general formulas (a) to (e) have the following properties:
From the viewpoint of production or cost, those represented by the following structural formulas are particularly preferably used.

[0023]

[Chemical 6]

Polyester: General formula (b) shown in Chemical formula 2
(Vii), (viii), (ix), (x),
(Xi)

[0025]

[Chemical 7]

The polyphenylene ether is preferably one having a low degree of modification or unmodified in terms of heat resistance, while it is preferably one having a high degree of modification in terms of molding processability. They can be used properly or can be used in combination with each of these modification degrees or unmodified ones.

Polyolefin; polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-
Butene, polybutadiene, polystyrene, syndiotactic polystyrene, polyparamethylstyrene, polyparafluorostyrene, polyparachlorostyrene, polyparabromostyrene, etc.

Polycarbonate: (xii) in the general formula (e) shown in Chemical formula 5

The content ratio of the above components (A) and (B) is (A) / (B) = 10/90 to 90/1 in weight ratio.
It is 0, preferably 20/80 to 80/20.

When the amount of the component (A) is small, the mechanical strength, moldability, heat resistance, etc. are lowered, but the dielectric constant and dielectric loss tangent are lowered, and the electrical characteristics are improved. On the other hand, when the amount of the component (A) is large, mechanical strength, moldability, heat resistance, etc. are improved, but the dielectric constant and the dielectric loss tangent are increased, and the electrical characteristics are deteriorated.

On the other hand, when the amount of the component (B) is small,
Mechanical strength, moldability, heat resistance, etc. are improved, but the dielectric constant and dielectric loss tangent are increased, and the electrical characteristics are deteriorated. On the contrary, when the amount of the component (B) is large, mechanical strength, moldability,
Although the heat resistance and the like are lowered, the dielectric constant and the dielectric loss tangent are lowered and the electric characteristics are improved.

As described above, since the component (A) and the component (B) have contradictory properties, the dielectric constant and the arbitrary dielectric constant can be adjusted by appropriately adjusting the mixing ratio of these two components within the above range. A composition having mechanical strength and the like can be obtained.

In the composition of the present invention, Table 1 shows preferable combinations of the component (A) and the component (B) constituting the polymer component.

[0034]

[Table 1]

One of the compositions of the present invention uses a maleic anhydride compound-vinyl compound copolymer as a compatibilizer. This maleic anhydride compound-vinyl compound copolymer is a maleic anhydride-styrene copolymer, a maleic anhydride-ethylene copolymer, a maleic anhydride, as a preferred specific example in terms of its performance, production, cost and the like. Acid-propylene copolymer, maleic anhydride-methyl methacrylate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-α-methylstyrene copolymer, maleic anhydride-p-methylstyrene copolymer, Examples thereof include maleic anhydride-N-phenylmaleimide copolymers, and maleic anhydride-styrene copolymers are particularly desirable. These can be used alone or in admixture of two or more.

In the maleic anhydride compound-vinyl compound copolymer as described above, the maleic anhydride compound portion is the polyetherimide or polyester as the component (A) and the vinyl compound portion is (B). Since they have excellent compatibility with polyphenylene ether, polyolefin and polycarbonate as the component), these two polymers can be well compatibilized with each other.

As another compatibilization of the composition of the present invention, an epoxy-modified styrene copolymer is used in place of the above maleic anhydride compound-vinyl compound copolymer for compatibilization. it can. Specific examples of the epoxy-modified styrene-based copolymer that are preferable in terms of performance, production, cost, etc. include an epoxy-modified styrene-styrene copolymer and an epoxy-modified styrene-methyl methacrylate copolymer. These may be used alone or in combination of two or more.

In the composition of the present invention, the epoxy-modified styrene-based graft copolymer may be any other epoxy-modified styrene-based alternating copolymer, epoxy-modified styrene-based block copolymer, or epoxy-modified styrene-based random copolymer. In comparison with the above-mentioned component (A) and component (B), it tends to have an intermolecular interaction with the component (A) and component (B) so as to have a higher three-dimensional network structure. It has no inconvenience and has excellent durability for remolding.
Therefore, it is preferable to use the epoxy-modified styrene-based graft copolymer in the composition of the present invention.

In the composition of the present invention, the above (A),
A filler may be added to the three components of the component (B) and the compatibilizer to improve mechanical properties, thermal properties (thermal conductivity) and the like. This filler is a glass, aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, aluminum nitride, silicon nitride, boron nitride, titanium nitride, silicon carbide, titanic acid, as a preferable specific example in terms of its performance, production, cost and the like. Inorganic fillers such as potassium, aluminum borate, calcium carbonate and the like can be mentioned. Above all,
Preferred are silicon carbide, silicon nitride, aluminum oxide, potassium titanate, glass, beryllium oxide, aluminum nitride, aluminum borate and calcium carbonate.

These fillers can be used in any shape such as whiskers, fibres, spheres, powders and the like, but whiskers and single fibers are particularly preferable.
It has desirable physical properties in order to improve properties such as mechanical properties, thermal properties, and electrical properties. When using whiskers or single fibers as a filler, silicon carbide, silicon nitride, aluminum oxide, potassium titanate, aluminum borate, aluminum nitride, and calcium carbonate are particularly suitable.

When used as a whisker shape, if it is too short or too thin, the characteristics of the whisker shape will not be fully exhibited, and conversely if it is too long or too thick, the whisker shape will break during blending, As described below, when a surface-treated one with a silane coupling agent is used in advance, the number of untreated surfaces may increase and the physical properties may deteriorate. Therefore, the length is about 5 to 50 μm, and the diameter is Suitable is within the range of about 0.1 to 1.8 μm,
More preferably, those having a length of about 20 to 40 μm and a diameter of about 0.3 to 0.9 μm are suitable.

When it is used as a single fiber, if it is too short or too thin, the mechanical strength of the composite material decreases, and if it is too long or too thick, it has the same physical properties as in the whisker shape. The length may be about 2000-4000 μm and the diameter may be about 4-1.
The range of 5 μm is suitable, and more preferably the length is about 2000 to 2600 μm and the diameter is about 8 to 1.
It is preferably within the range of 1 μm.

The filler used is one treated with a silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane. Good.

The compounding ratio of each component in the composition of the present invention is summarized in Table 2.

[0045]

[Table 2]

If the amount of the maleic anhydride compound-vinyl compound copolymer blended is too small, the compatibility will decrease.
The mechanical strength is reduced, and on the contrary, if it is too large, not only the compatibility may be reduced, but also the heat resistance may be reduced. Therefore, in the composition of the present invention, the content is within the above range. Is.

If the amount of the epoxy-modified styrene copolymer used in place of the maleic anhydride compound-vinyl compound copolymer is too small, the compatibility will decrease and the mechanical strength will decrease. On the contrary, if the amount is too large, a problem occurs in repeated molding. Therefore, the composition of the present invention has the above range.

The composition of the present invention may contain components other than the above-mentioned three components, for example, a filler, a heat stabilizer, a flame retardant, a coloring agent, a reinforcing agent and the like.

As a method for producing the composition of the present invention comprising the above components, a melt blending method, a solution blending method or the like can be adopted. The solution blending method can be blended at a low temperature and does not require complicated equipment, but requires a large amount of solvent and has an economical problem. On the other hand, the melt blending method requires high temperature and requires equipment such as an extractor,
The method of producing the composition of the present invention is preferably a melt blending method because the steps are simple and the productivity and economy are excellent.

In the case of the hot melt blending method, the above-mentioned polymer component and compatibilizer, or these and filler,
Further, these and the above-mentioned various additives may be kneaded at once, but may be melt-kneaded by heating in any order. The filler may be kneaded with the polymer component and the compatibilizer at the same time, or before or after,
It is also possible to knead a polymer blend composition obtained by kneading the polymer component and the compatibilizer in advance.

Examples of the mixer used for blending the above components include a conventional kneading mixer having a heating function and a mixing function, a single-screw or twin-screw extruder, and the like.

Preferred blending conditions are, for example, when a kneading mixer is used, the rotation speed of the rotor is about 10 to 200 rpm, preferably about 30 to 100 rp.
m, the blending temperature is about 200 to 400 ° C., preferably about 250 to 350 ° C., and the blending time is about 1 to 60.
Minutes, preferably about 2-10 minutes.

No good blends are obtained with rotor speeds below about 10 rpm or above about 200 rpm. When the blending temperature is less than about 200 ° C, the component (A) among the polymer components is not completely melted, and the temperature is about 400 ° C.
If it exceeds, decomposition of components is caused, which is not preferable.
When the blending time is less than about 1 minute, sufficient mixing is not performed,
Even if blending is continued for more than about 60 minutes, no further effect is obtained.

When a twin-screw extruder is used, for example, the twin-screw extruder has a shaft diameter of about 40 m.
m, L / D≅33.5 co-rotating type, the screw rotation speed is about 50 to 400 rpm, preferably about 100 to 300 rpm, and the blending temperature is about 200.
It is preferably in the range of to 400 ° C, preferably about 250 to 350 ° C.

When the screw speed is less than about 50 rpm or more than about 400 rpm, a good blend is not obtained. If the blending temperature is lower than about 200 ° C., the component (A) of the polymer components will not be completely melted, and
If the temperature exceeds 0 ° C, the components are decomposed, which is not preferable.

The composition of the present invention obtained by kneading as described above can be pelletized by a molding machine depending on the purpose.
It can be formed into a film or any other suitable shape.

[0057]

In the present invention, the components (A) and (B), which are originally poorly compatible polymer components, are maleic anhydride compound-vinyl compound copolymer and epoxy-modified styrene which are compatibilizing agents. The copolymer (in particular, the epoxy-modified styrene-based graft copolymer) exhibits good compatibility, and the interface between the component (A) and the component (B) or the interface between the polymer component and the filler has a good affinity. It is a polymer blend that exhibits excellent properties and bonding properties, is in an intimately mixed state, and is therefore excellent in mechanical properties.

Moreover, a very small amount of the epoxy-modified styrenic copolymer does not deteriorate the compatibility of the above-mentioned polymers even when the composition of the present invention is repeatedly subjected to molding. However, the problem of non-uniformity of this repeated molding does not occur at all.

Further, the epoxy-modified styrene type copolymer and the maleic anhydride type compound-vinyl type compound copolymer are originally possessed by the component (A) and the component (B) which are polymer components. Does not impair heat resistance, moldability, electrical properties, mechanical properties, etc.

In addition, when whiskers or single-fiber inorganic fillers are used as the filler, heat resistance, moldability, compatibility, compatibility between the filler and the polymer component and bondability are not impaired. Mechanical properties, thermal conductivity, etc. can be improved.

Since the composition of the present invention has excellent electrical characteristics, it is suitable as a material for electronic members used in a high frequency band. That is, the composition of the present invention,
When the reflection loss and the transmission loss of the electric signal are measured according to the test method described later, the frequency range is 950 MHz or more 100 G
The reflection loss is 30.0 dB or less, preferably 25.
0 dB or less, more preferably 20.0 dB or less, and transmission loss is 5.0 dB or less, preferably 3.0 dB
Hereafter, 1.0 dB or less is more preferable, and the reflection loss and the transmission loss are small.

FIG. 1 shows the 50 m used in the present invention.
mΩ7mm × 1mm 50Ω scale measurement test piece 100
FIG. In this way, 50 mm x 7 mm x 1 m
Copper plating (hatched portion in FIG. 1) is applied to the entire surface of one 50 mm × 7 mm surface of the test piece 100 of m, and the width is 1.8 on the center line in the longitudinal direction of the other 50 mm × 7 mm surface.
A microstrip line 110 having a 6 mm thickness and a thickness of 10 μm or more and an impedance of 50Ω is formed over the entire length in the longitudinal direction, and measurement is performed.

The test piece 100 is housed in the holder 200 for electromagnetic shielding shown in FIG. 2 in order to eliminate external noise, and the reflection loss and the transmission loss are measured.

The reflection loss and the transmission loss of this test piece 100 can be easily obtained by measuring the S parameter. At high frequencies, the signal line of the electric circuit is the microstrip line 110 having an impedance of 50Ω. Therefore, if the test piece 100 is used, the reflection loss and the transmission loss of the DUT are uniquely specified.

Even when nickel plating, gold plating or silver plating is further applied on the copper plating, the measurement results of the reflection loss and the transmission loss do not change. Therefore, it goes without saying that the plating applied to the test piece of the composition of the present invention is not limited to the case of copper plating alone, but also includes the case of applying nickel plating, gold plating or silver plating on copper plating.

The composition of the present invention is suitable as a material for electronic members such as printed circuit boards, various housings, sockets, antennas and waveguides, and is particularly excellent in moldability. Or extrusion molding), an electronic member of any shape can be made.

Further, the composition of the present invention comprises a dry plating method,
The surface treatment can be performed by a well-known technique such as wet plating.

[0068]

【Example】

Examples 1 to 17 Polymers and fillers were blended by an omni mixer in a mixing ratio shown in Tables 3 to 7, and the resulting mixture was continuously heated and melt blended at 300 ° C. and 200 rpm by a twin-screw extruder,
Resin compositions having the compositions shown in Tables 3 to 7 were obtained. The following tests were performed on these compositions.

As the polyether imide, the product name "Ultem1010-" manufactured by General Electric Company of the United States of America is used.
1000 "as polyester, Sumitomo Chemical Co., Ltd. trade name" Rod Run LC-5000 ", and polyphenylene ether as Unitika Co. Ltd. trade name" Zylon PX "
L9102 "is a syndiotactic polystyrene as a polyolefin (trade name" Idemitsu SP manufactured by Idemitsu Kosan Co., Ltd. "
S ”) was used as the polycarbonate, and the product name“ Novarex ”manufactured by Mitsubishi Kasei Co., Ltd. was used. Also, the product name“ ZE4 ”manufactured by BERSTORFF of Germany was used as the twin-screw extruder.
0A ″ (L / D = 33.5) was used.

[Preparation Procedure of Test Pieces]: Mechanical properties (tensile strength, tensile modulus, bending strength, flexural modulus, Izod impact strength), dielectric properties (dielectric constant, dielectric loss tangent) and heat resistance of the above resin composition In order to evaluate the property (deflection temperature under load), the above resin composition was injection-molded and strips (127 mm
X12.7 mm x 3 mm), ASTM No. 1 dumbbell (thickness 3 mm) and a disc (φ100 mm x 1.6 mm) were molded.

A strip, ASTM No. 1 dumbbell, was molded by an injection molding machine (trade name "N40" manufactured by Japan Steel Works, Ltd.).
-BII ") at a nozzle temperature of 340 ° C, and the disk is molded using an injection molding machine manufactured by Crockner (trade name" Clockner F85 ") at a nozzle temperature of 325.
Performed at ° C.

In the high frequency range (100 MHz or more, 10
In order to evaluate the electrical characteristics (reflection loss and transmission loss) at less than 0 GHz, the test piece 100 shown in FIG. 1 was prepared by two-color molding. That is, the primary side (a part of the main body of the test piece 100 in FIG. 1-for example, 50 mm × 7 mm ×
Cylinder temperature of 260 ° C., mold temperature of 10
Injection molded at 0 ° C. and injection pressure of 650 kgf / cm ² ,
After the whole surface was surface-treated (etching treatment with chromic acid mixed solution, and palladium catalyst was applied), the secondary side (test piece 1 in FIG. 1)
The remaining part of the main body of No. 00) was injection molded at a cylinder temperature of 370 ° C., a mold temperature of 95 ° C., and an injection pressure of 250 kgf / cm ² with the microstrip line portion exposed.

This two-color molded product was plated with electroless copper to obtain a 50Ω scale measurement test piece test piece 100 in which the surface of the microstrip line 110 was flush with the surface of the test piece 100.

[Evaluation Procedure of Physical Properties]: The tensile test is AST
It carried out by the method according to MD638. Instron 4302 manufactured by Instron Co., Ltd. is used as a tester, and the pulling speed is 5 mm / min and the chuck distance is 115 m.
m, and the temperature was 23 ° C., and the average value of 5 measurements was calculated.

The bending test was carried out by a method according to ASTM D790. The same "Instron 4302" used in the above tensile test was used as a tester, and the bending speed was 2 mm /
The measurement was performed at min, the distance between fulcrums was 50 mm, and the temperature was 23 ° C., and the average value of 5 measurements was calculated.

Izod impact test (with notch) is AS
It carried out by the method according to TM D256. As a tester, a trade name “Izod impact tester” manufactured by Toyo Seiki Seisaku-sho, Ltd. was used, and measurement was performed at a temperature of 23 ° C., and an average value of 5 measurements was calculated.

The dielectric constant (ε) and the dielectric loss tangent (tan δ) are
Impedance made by Hewlett-Packard, USA
/ Gain-phase analyzer (trade name "HP-4194A") and a dielectric measuring electrode manufactured by the same company (trade name "HP-16451B") are used, and the frequencies are measured at 1 MHz and 10 MHz at a temperature of 25 ° C. The average value of 5 measurements was calculated.

The deflection temperature under load (HDT) is measured by AS
It carried out by the method according to TM D648. As a testing machine, a product name “Heat Distortion Tester Model S3-MH” manufactured by Toyo Seiki Seisakusho, Ltd. is used, and a test stress is 18.6 k.
The measurement was performed at gf / cm ² , and the average value of 5 times of measurement was calculated.

Next, a method of evaluating electric characteristics (high frequency characteristics) will be described. First, the overall configuration of an electrical characteristic evaluation device for measuring reflection loss and transmission loss will be described with reference to FIG. In the evaluation apparatus shown in the figure, a high frequency signal is applied to a DUT (measurement target) 3 attached to a connector 2 by a synthesized sweeper 1 via a bridge circuit 4, and its response is sent to a scalar network analyzer 6 via a detector 5. To measure reflection loss and transmission loss.

FIG. 4 is a circuit block diagram of the electric characteristic evaluation apparatus. A signal from the millimeter wave sweep oscillator 11 incorporated in the sweeper 1 of FIG. 3 is passed through a frequency meter 12, a variable attenuator 13 and an isolator 14. The DUT mounted between the directional couplers 21 and 22 built in the connector 2.
3 is applied.

Of the response signal of the DUT 3, the reflected wave is the directional coupler 21 built in the connector 2 of FIG.
The network analyzer 6 via the isolator 23 and the detector 41 (corresponding to the detector 4 in FIG. 3).
The transmitted wave is captured by the network analyzer 6 via the directional coupler 22, the isolator 24, and the detector 42 (corresponding to the detector 4 in FIG. 3) built in the connector 2. In FIG. 4, the end of the DUT 3 on the side opposite to the sweeper 1 is terminated by the resistor R _T.

FIG. 5 is a diagram showing the reflection coefficient measuring circuit extracted from the circuit block diagram of FIG. As shown in the figure, a signal proportional to the signal (incident wave) applied to the DUT 3 and the response signal (reflected wave) is detected, and the reflection coefficient is obtained from the ratio of the measured values of both signals.

FIG. 6 is a diagram showing a circuit for measuring the transmission coefficient extracted from the circuit block diagram of FIG. As shown in the figure, a signal proportional to the signal (corresponding to the incident wave to the DUT) and the response signal (transmitted wave) that is taken into the network analyzer 6 by bypassing the DUT 3 is detected,
The transmission coefficient is calculated from the ratio of the measured values of both signals.

As a network analyzer, a product name "HP8757A SCARA NETWORK ANALYZER" manufactured by Hewlett-Packard Company, USA, as a synthesized sweeper, a "HP8341B synthesized sweeper", a bridge circuit, a "bridge", and a detector as well. The "HP11664E Detector" is used as the connector, the product name "Wiltron K Connector" manufactured by Anritsu Corporation.

Further, the measurement at a frequency of 100 GHz or more is slightly different from the above-mentioned measurement at 100 MHz or more and less than 100 GHz, 220 mm × 200 mm × 1 mm,
Using a test piece with a maximum surface roughness (Rmax) of 0.05 μm or less (no microstrip line is required), a quasi-confocal open resonator consisting of a spherical mirror and a plane mirror on which the test piece is mounted allows a temperature of 25 ° C. I went. The composition of the present invention has a frequency of 100 GHz or higher, preferably 10 GHz.
Also in 0 GHz to 300 GHz, the condition of the measurement test piece is slightly different, but as in the case of 950 MHz or more and less than 100 GHz, the reflection loss of the electric signal is 30.0 dB or less,
It is preferably 25.0 dB or less, more preferably 20.
The transmission loss is 0 dB or less, the transmission loss is 5.0 dB or less, preferably 3.0 dB or less, and more preferably 1.0 dB or less.

Using the above-mentioned measuring device, 50 shown in FIG.
mm x 7 mm x 1 mm or 220 mm x 200 mm x
The 1 mm 50 Ω scale measurement test piece 100 was housed in the holder 200 shown in FIG. 2 for eliminating external noise, and the reflection loss and the transmission loss were measured.

[Evaluation of heat resistance]: Deflection temperature under load is 19
Those having a temperature of 0 ° C or higher were evaluated as ◯, those having a temperature of 180 ° C or more and less than 190 ° C were evaluated as Δ, and those having a temperature of less than 180 ° C were evaluated as x.

[Evaluation of Plating Property]: Regarding the plating property, the resin composition was plated with copper and evaluated in the following manner. That is, a new adhesive surface of a tape (cellophane adhesive tape having a width of 12 mm specified in JIS Z 1522) is crimped with a length of 50 mm or more so that air bubbles do not remain by finger pressure, and after about 10 seconds, it is vertically aligned with the plating surface. The tape was peeled off, and the plating film was lifted up and the presence of plating on the tape was examined. None was evaluated as ◯, plating film partially lifted was evaluated as Δ, and plating film peeling was observed (having tape adhesion on the tape side) as x.

[Evaluation of moldability (melt flowability)]: The rod flow length was measured and used as an index. That is, using an injection molding machine, the cylinder temperature is 340 ° C and the mold temperature is 150 ° C.
Then, the resin composition was melt-injected into the mold, and the distance (flow length) through which the melted resin composition flows was measured. This mold is T
It is of a letter shape, the T-shaped vertical bar part is the introduction gate with a diameter of 1.5 mm, and the horizontal bar part is the tip part, 0.4 mm x 2
It has a square shape of mm. Further, the flow length means a distance flowing out to the tip of the mold. ○ with a flow length of 25 mm or more, △ with a flow length of 20 mm or more and less than 25 mm
Those having a size of less than 0 mm were evaluated as x.

[Evaluation of Recyclability Moldability]: The composition to be tested is kneaded and molded as it is (initial molding).
Then, the appearance was observed and comparative evaluation was carried out on a product (repeated molding) obtained by melting and molding this sample again. When the appearance of the repeated molded article was the same as that of the initial molded article, it was evaluated as ◯, slightly inferior was evaluated as Δ, and inferior was evaluated as x.

[Electrical characteristics]: A reflection loss of 25.0 dB or less and a transmission loss of 3.0 dB or less is good, and a reflection loss of 30.0 dB or less and a transmission loss of 5.0 dB or less is Δ. A reflection loss of 30.0 dB or more and a transmission loss of 5.0 dB or more was evaluated as x.

The above evaluation results are shown in Tables 3 to 7.

Comparative Examples 1 to 6 Polyetherimide (“Ultem1010-
1000 "), modified polyphenylene ether (Example" Zylon PXL "), liquid crystalline polyester (Example" Rod Run LC-5000 "), Teflon, and these polymers with glass filler (glass fiber) 30.
A test was conducted on the composition filled with wt% under the same conditions as in Examples 1 to 17. The results are shown in Tables 8-9.

In Tables 3 to 9 below, each component is shown by the following abbreviations, and the units of each characteristic are as follows. <Abbreviations> Polyetherimide = PEI, Aromatic polyester = LCP, Polyphenylene ether = PPE, Syndiotactic polystyrene = SPS, Polycarbonate = PC, Maleic anhydride compound-Styrene copolymer = St-
MAnh, Epoxy-modified styrene-styrene copolymer = EpSt
-St, -epoxy-modified styrene-methyl methacrylate copolymer = EpSt-MMA, -potassium titanate whiskers = Ti acid K-w, -aluminum borate whiskers = B-acid Al-w, <unit> -tensile strength = kgf / Cm ² , ・ Tensile elastic modulus = kgf / cm ² , ・ Bending strength = kgf / cm ² , ・ Bending elastic modulus = kgf / cm ² , ・ Izod impact strength (abbreviated as impact strength) = kgf ・ c
m / cm, dielectric constant = ε, dielectric loss tangent = tan δ, reflection loss = / − dB, transmission loss = / − dB, deflection temperature under load = ° C., thermal conductivity = cal / cm · sec ℃ 、 ・ Thermal expansion coefficient ＝ ppm / ℃

[0095]

[Table 3]

[0096]

[Table 4]

[0097]

[Table 5]

[0098]

[Table 6]

[0099]

[Table 7]

[0100]

[Table 8]

[0101]

[Table 9]

[0102]

[Table 10]

As is clear from the above table, in all the examples, the reflection loss is 30 dB or less and the transmission loss is 5 dB or less, which shows better electrical characteristics than the comparative examples.
In addition, all of the examples also show good performances in terms of moldability, and examples 3 to 9, 11, 14, 15, in which inorganic fillers such as potassium titanate whiskers and aluminum borate whiskers were added. No. 17 shows better electric characteristics.

On the other hand, as shown in Comparative Examples 1 and 2, P which is a super engineering plastic excellent in heat resistance.
EI and LCP have a relatively high dielectric constant and also have large reflection loss and transmission loss at high frequencies. Further, as shown in Comparative Example 3, Teflon, which is a typical low-dielectric polymer, has excellent electrical properties, but has significantly poor moldability and plating properties. Furthermore, Comparative Example 4 is excellent in moldability, electrical characteristics, and plating properties, but is insufficient in heat resistance. Comparative Example 5 is excellent in heat resistance and mechanical characteristics, but inferior in electrical characteristics. Comparative Examples 6 and 7 are excellent in plating property, heat resistance, and electric characteristics, but inferior in recyclability.

As is clear from the above evaluation results, the composition of the present invention is excellent in heat resistance, plating property and moldability, has a low dielectric constant and a low dielectric loss tangent, and has a reflection loss of an electric signal at a high frequency. It can be seen that the transmission loss is small.

[0106]

As described above, according to the present invention, in the present invention, the reflection loss of the electric signal in the frequency range of a wide range of high frequencies (in particular, 950 MHz or more and less than 100 GHz) is 30.0 dB or less and Transmission loss is 5.0d
It is possible to provide a resin composition for electronic members, which is B or less and has a small loss. As a result, the degree of freedom in selecting a material for a high-frequency substrate and the like has increased.

Moreover, since they are excellent in moldability, they can be easily molded by molding to form electronic members such as packages, connectors, printed circuit boards, sockets, various housings and devices. Can be manufactured. This diversifies the application to device design, circuit design of electronic components, and package design.

Furthermore, since the above characteristics are hardly deteriorated even when the filler is filled, it becomes possible to provide a resin composition for electronic members which is also excellent in mechanical characteristics.

[Brief description of drawings]

FIG. 1 is a diagram showing a shape of a pellet used in the present invention,

FIG. 2 is a view showing a holder for electromagnetic shielding.

FIG. 3 is a diagram showing an overall configuration of an electrical characteristic evaluation apparatus for measuring reflection loss and transmission loss in the present invention.

FIG. 4 is a circuit block diagram of the electrical characteristic evaluation apparatus.

5 is a diagram showing a reflection coefficient measurement circuit extracted from the circuit block diagram of FIG. 4;

FIG. 6 is a diagram showing a circuit for measuring a transmission coefficient extracted from the circuit block diagram of FIG.

[Explanation of symbols]

 1 Synthesized sweeper 2 Connector 3 DUT (measurement target) 4 Detector 5 Bridge circuit 6 Scalar network analyzer 100 Test piece 110 Microstrip line 200 Holder

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location C08L 71/12 LQP 79/08 LRC (72) Inventor Seitoshi Iwafune Gongendo, Satte City, Saitama Prefecture 1134-2 Cosmo Research Institute Co., Ltd. R & D Center (72) Inventor ▲ Ryo ▼ 7-3-21 Ikegami, Ota-ku, Tokyo Premier No. 201 Ikegami

Claims (2)

[Claims] 1. A polymer component containing 100 parts by weight of at least one selected from (A) polyether imide and polyester and at least one selected from (B) polyphenylene ether, polyolefin and polycarbonate. A resin composition containing 1 to 50 parts by weight of a maleic anhydride-based compound-vinyl-based compound copolymer, wherein a 50 mm × 7 mm surface of a 50 mm × 7 mm × 1 mm test piece of the resin composition When copper plating is applied to the entire surface and a microstrip line with a width of 1.86 mm and a thickness of 10 μm or more and an impedance of 50 Ω is formed over the entire length in the longitudinal direction on the center line of the other 50 mm × 7 mm surface in the longitudinal direction, 950 MHz. 100G or more
The reflection loss of the electric signal in the frequency range below Hz is 3
A resin composition for high frequencies, which has a transmission loss of 5.0 dB or less at 0.0 dB or less. 2. A polymer component containing at least one selected from the group consisting of (A) polyether imide and polyester and at least one selected from (B) polyphenylene ether, polyolefin and polycarbonate is 100 parts by weight. A resin composition containing 1 to 1.0 part by weight of an epoxy-modified styrene-based copolymer, wherein copper is provided on the entire surface of one 50 mm × 7 mm surface of a 50 mm × 7 mm × 1 mm test piece made of the resin composition. 950 MHz or more and less than 100 GHz when plated and formed on the other 50 mm × 7 mm plane in the longitudinal direction center line, a microstrip line having a width of 1.86 mm and a thickness of 10 μm or more and an impedance of 50 Ω is formed over the entire length in the longitudinal direction. The reflection loss of the electric signal in the frequency region of 30.0 dB or less, the transmission loss High-frequency resin composition characterized by .0dB or less.