JP2684342B2 - High frequency resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high frequency resin composition which has a small reflection loss and a small transmission loss in a wide range of a high frequency band (950 MHz to 300 GHz) 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 can be obtained. 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, (1) (i) (A) a polyether imide represented by the general formula (a) and a polyester represented by the general formula (b),
And (B) a polyolefin represented by the general formula (c),
A polymer containing 100 parts by weight of a polymer component containing at least one selected from the polycarbonate represented by the general formula (d), or (ii) (A) the above polyetherimide, and (B) the above polyolefin. Ingredient 100
With respect to 100 parts by weight of (2) (i) (A) at least one selected from the above polyether imide and polyester, and (B) 100 parts by weight of a polymer component containing the polyolefin, or ii) 100 parts by weight of a polymer component containing (A) the above polyester, and (B) at least one selected from the above polyolefins and polycarbonates, as a compatibilizer, (i) of the above (1), In the polymer component (ii), 0.1 to 50 parts by weight of the maleic anhydride compound-vinyl compound copolymer, and in the polymer components (i) and (ii) of the above (2), 0.1 to 50 parts by weight are used. 1.0
A resin composition containing parts by weight of an epoxy-modified styrenic copolymer, particularly this graft copolymer, has excellent compatibility, heat resistance, mechanical properties, and small reflection loss and transmission loss (excellent electrical properties. ) In addition, it has excellent plating properties and moldability. Moreover, in the resin composition (2) using the epoxy-modified styrene-based copolymer as the compatibilizing agent, the compatibility problem can be sufficiently solved even if the amount of the compatibilizing agent is reduced. As a result of making the amount of the compatibilizing agent such an extremely small amount, surprisingly, even when repeatedly molding,
The inventors have found that not only the compatibility is not lowered, but also the problem of non-uniformity of the molded body does not occur, and the present invention has been completed.

That is, the present invention includes (1) (i) (A) a polyetherimide represented by the general formula (a) and a polyester represented by the general formula (b), and (B) a general formula (c). ), A polymer represented by the general formula (d), and 100 parts by weight of a polymer component containing at least one selected from the polycarbonates represented by the general formula (d):
Or (ii) with respect to 100 parts by weight of a polymer component containing (A) a polyetherimide represented by the general formula (a) and (B) a polyolefin represented by the general formula (c), or (2) ( i) (A) at least one selected from the polyetherimide represented by the general formula (a), the polyester represented by the general formula (b), and (B) the polyolefin represented by the general formula (c). With respect to 100 parts by weight of the polymer component contained, or (ii) the polyester represented by the general formula (b), and (B) the polyolefin represented by the general formula (c), the polycarbonate represented by the general formula (d). As a compatibilizer, 0.1 to 50 parts by weight of a maleic anhydride compound-vinyl is used as a compatibilizing agent with respect to 100 parts by weight of a polymer component containing at least one selected from A resin composition containing a resin-based compound copolymer, wherein the polymer component (2) is 0.1 to 1.0 part by weight of an epoxy-modified styrene-based copolymer, and the resin composition is 50 mm × 7 mm x 1
A 50 mm x 7 mm surface of one of the 50 mm test pieces is copper-plated, and a microstrip with a width of 1.86 mm and a thickness of 10 pm or more and an impedance of 50 Ω on the center line in the longitudinal direction of the other 50 mm x 7 mm surface. When the line is formed over the entire length in the longitudinal direction, the reflection loss of the electric signal in the frequency region of 950 MHz or more and less than 100 GHz is 30.0 dB or less and the transmission loss is 5.0 dB or less. Is the gist.

In the composition of the present invention, the polymer component (1) comprises polyetherimide (general formula (a)), polyester (general formula (b)), and (B) as components (i) and (A). A) containing at least one selected from the group consisting of polyolefin (general formula (c)) and polycarbonate (general formula (d)),
(Ii) Polyetherimide (general formula (a)) as the component (A) and polyolefin (general formula (c)) as the component (B) are contained, and the polymer component (2) is (I) Polyetherimide as the component (A), at least one selected from polyesters, and polyolefin containing the component (B), or (ii) a polyester as the component (A), and (B) It contains at least one selected from polyolefin and polycarbonate as a component.

[0016]

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[0017]

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[0018]

[Chemical 2-2]

[0019]

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[0020]

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The polyetherimide represented by the general formula (a) ~ (d), polyesters, Po Li olefins, polycarbonates, its performance, manufacturing, or in terms of cost and the like, which is represented by the structure like the following Those used are particularly preferable.

[0022]

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

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 ( d ) shown in Chemical formula 4

The content ratio of the component (A) and the component (B) is (A) / (B) = 10/90 to 90/10 in the weight ratio of the polymer components (1) and (2). , 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, by appropriately adjusting the mixing ratio of these two components within the above range, any dielectric constant or A composition having mechanical strength and the like can be obtained.

In the composition of the present invention, (1),
Table 1 shows preferable combinations of the component (A) and the component (B) constituting the polymer component (2) .

[0031]

[Table 1]

The polymer composition of (1) in the composition of the present invention is
In the case of minutes, a maleic anhydride compound-vinyl compound copolymer is used as a compatibilizer. This maleic anhydride-based compound-vinyl-based copolymer, its performance, production,
Specific examples preferable in terms of cost include maleic anhydride-styrene copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-propylene copolymer, maleic anhydride-methyl methacrylate copolymer, maleic anhydride. -Acrylonitrile copolymers, maleic anhydride-α-methylstyrene copolymers, maleic anhydride-p-methylstyrene copolymers, maleic anhydride-N-phenylmaleimide copolymers, and the like, particularly maleic anhydride -Styrene copolymers are desirable, and they 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). ) and Po Li olefin or polycarbonate as a component, because it has excellent compatibility, respectively, can be favorably compatibilize these two polymers to each other.

In the composition of the present invention, the poly (2)
For mer component, as a compatibilizer, said maleic acid-based compound - instead of a vinyl compound copolymer, Ru using an epoxy-modified styrene-based copolymer. 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 another 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 porosities of (1) and (2) are used.
With respect to the limer component , a filler may be added to the above three components (A) and (B) and the compatibilizer to improve mechanical properties, thermal properties (thermal conductivity) and the like. This filler, as a preferred specific example in terms of its performance, production, cost, etc.,
Examples thereof include inorganic fillers such as glass, aluminum oxide, magnesium oxide, beryllium oxide, titanium oxide, aluminum nitride, silicon nitride, boron nitride, titanium nitride, silicon carbide, potassium titanate, aluminum borate, and calcium carbonate. Of these, silicon carbide, silicon nitride, aluminum oxide, potassium titanate, glass, beryllium oxide, aluminum nitride, aluminum borate, and calcium carbonate are preferable.

These fillers can be used in any shape such as whiskers, fibers, spheres, powders, etc. In particular, whiskers or single fibers can be used.
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 composition of the present invention (of the polymer component of (1)
The case is referred to as composition 1, and the case of the polymer component (2) is
It may be referred to as composition 2 and these may be collectively referred to as a composition.
Table 2 collectively shows the blending ratio of each component in (1 ) .

[0042]

[Table 2]

If the blending amount of the maleic anhydride compound-vinyl compound copolymer is too small, the compatibility decreases,
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 three components, for example, a filler, a heat stabilizer, a flame retardant, a colorant, 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 at 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.

If the screw speed is less than about 50 rpm or more than about 400 rpm, a good blend cannot be 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.

[0054]

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, molding processability, 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 electric 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 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 above 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. Since it is particularly excellent in moldability, it can be molded (injection molded). Or extrusion molding), an electronic member of any shape can be made.

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

[0065]

Example 1 Polymer and filler were blended by an omni mixer in a mixing ratio shown in Table 3 and the blended by a twin-screw extruder.
Continuous heating melt blending at 0 ° C. and 200 rpm,
A resin composition having the composition shown in was obtained. The following tests were performed on these compositions.

As the polyether imide, a trade name "U1tem1010-" manufactured by General Electric Company, USA
1000 "is polyester, Unitika Co., Ltd. trade name" Rod Run LC-5000 ", polyolefin is syndiotactic polystyrene (Idemitsu Kosan Co., Ltd. trade name" Idemitsu SPS "), and polycarbonate is Mitsubishi Kasei Co. The product name "Novarex" was used for each, and the twin-screw extruder was used as German BERSTOR.
The product name "ZE40A" (L / D = 33.5) manufactured by FF was used.

[Preparation Procedure of Specimen]: Mechanical properties (tensile strength, tensile modulus,
In order to evaluate the flexural strength, flexural modulus, Izod impact strength), dielectric properties (dielectric constant, dielectric loss tangent) and heat resistance (deflection temperature under load), the above resin composition was injection molded to obtain strips (127 mm × 12). 0.7 mm x 3 mm), AST
No. M1 dumbbell (thickness 3 mm) and disk (φ100 m)
m × 1.6 mm) was molded.

The strip of 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.
C. was performed.

In the high frequency region (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, on 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.

[Guideline for Evaluation of Physical Properties]: The tensile test was carried out by a method according to ASTM D638. As a tester, a product name “Instron 4302” manufactured by Instron Co., Ltd. was used, measurement was performed at a pulling speed of 5 mm / min, a chuck distance of 115 mm, and a temperature of 23 ° C., and an average value of 5 times of measurement 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-M pressure" manufactured by Toyo Seiki Seisakusho Co., Ltd. is used, and a test stress is 18.6k.
The measurement was performed at gf / cm ² , and the average value of 5 times of measurement was calculated.

Next, a method for 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 built 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 opposite to the sweeper 1 is terminated by the resistor RT.

FIG. 5 is a diagram showing a 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.

The network analyzer is a product name "HP8757A SCARA NETWORK ANALYZER" manufactured by Hewlett-Packard Company of America, the synthetic sweeper is the same as the "HP8341B synthesized sweeper", the bridge circuit is the same "bridge", and the detector is the same. 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 higher is slightly different from the above-mentioned measurement at 100 MHz or higher but lower 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 measuring apparatus, 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]: A product having a deflection temperature under load of 190 ° C. or higher was evaluated as ◯, a product having a deflection temperature under load of 180 ° C. or more and less than 190 ° C. was evaluated as Δ, and a product having a deflection temperature under load of 180 ° C. was evaluated as ×.

[Evaluation of Plating Property]: Regarding the plating property, the resin composition was plated with copper and evaluated in the following manner. That is, tape (JIS Z
1522 cellophane adhesive tape with a specified width of 12 mm)
The new adhesive surface of 50mm or more is pressure-bonded by finger pressure so that air bubbles do not remain, and after about 10 seconds, the tape is peeled off in the direction perpendicular to the plating surface, the plating film floats, and the adhesion of the plating on the tape side Existence was checked. 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 Molding Workability (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.
The resin composition was melt-injected into a mold at 0 ° C., and the distance (flow length) through which the melted resin composition flows was measured. This mold
It is a T-shaped type, the vertical bar of T is the introduction gate, the diameter is 1.5 mm, and the horizontal bar is the tip, 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]: Appearances of the composition to be tested were kneaded and molded (initial molded product) and the sample was remelted and molded (repeated molded product). , Comparative evaluation.
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]: The reflection loss is 25.0 dB or less and the transmission loss is 3.0 dB.
The following are good, the reflection loss is 30.0 dB or less, the transmission loss is 5.0 dB or less, and the reflection loss is 30.0.
Those having a transmission loss of 5.0 dB or more and a dB or more were evaluated as x.

Table 3 shows the above evaluation results.

Comparative Examples 1 to 5 Polyetherimide (“Ultem 1010-
1000 "), liquid crystal polyester (" Rod Run LC-5000 "in the examples), Teflon, and compositions obtained by filling these polymers with 30% by weight of glass filler (glass fiber) under the same conditions as in Examples 1 to 3. test was carried out. the results are shown in tables 4-5.

In Tables 3 to 5 below, each component is shown by the following abbreviations, and the unit of each characteristic is as follows. <Abbreviation> - polyetherimide = PEI), - aromatic polyesters = LCP, & syndiotactic polystyrene = SPS, · Polycarbonate = PC, & maleic acid 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 Kw, 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 · cm / cm, dielectric constant = ε, dielectric loss tangent = tan δ, reflection loss = -dB, · transmission loss = / - dB, · heat deflection temperature = ° C., · thermal conductivity = cal / cm · sec · ℃, · thermal expansion coefficient = ppm / ° C.

[0092]

[Table 3]

[0093]

[Table 4]

[0094]

[Table 5]

[0095]

[Table 6]

As is clear from the above table, in Example 1, the reflection loss is 30 dB or less and the transmission loss is 5 dB or less,
Compared with Comparative Examples 1 to 4, excellent electrical characteristics are shown.
In addition, Example 1 also shows good performance in terms of moldability, and further contains an inorganic filler called aluminum borate whiskers, and shows better electric characteristics.

On the other hand, as shown in Comparative Examples 1 and 2, heat resistance
Excellent super engineering plastic P
EI and LCP have a relatively high dielectric constant and
Reflection loss and transmission loss are also large. In addition, as shown in Comparative Example 3,
Teflon, which is a typical low-dielectric polymer,
It has excellent characteristics, but its moldability and plating are extremely poor.
Heat resistance and recyclability are poor.No. Furthermore, a comparative example4
Has excellent heat resistance and mechanical properties, but electrical propertiesAnd Resai
ClounessIs inferior.

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.

[0099]

As described above, according to the present invention, the reflection loss of an 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 into electronic members such as packages, connectors, printed circuit boards, sockets, various housings and devices, which are made of materials having the above characteristics. 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 the 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 code Internal reference number FI Technical display location C08L 71/12 C08L 71/12 79/08 79/08 (72) Inventor Ito ▲ RYO ▼ Tokyo 7-2 Ikegami 7-21, Ikegami, Ota-ku Premier No. 201 Ikegami 201 (56) Reference JP 5-239348 (JP, A) JP 6-1911 (JP, A) JP 62-209165 (JP, A) ) JP-A-6-73239 (JP, A) JP-A-61-60744 (JP, A) JP-A-6-293849 (JP, A)

Claims (2)

(57) [Claims] 1. A polymer component containing (i) (A) a polyetherimide and polyester, and (B) at least one selected from a polyolefin and a polycarbonate, or (ii) a polyetherimide (A) and (B). With respect to 100 parts by weight of the polymer component containing polyolefin,
A resin composition containing 0.1 to 50 parts by weight of a maleic anhydride compound-vinyl compound copolymer, which is 50 mm x 7 mm of one of 50 mm x 7 mm x 1 mm test pieces made 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 in the longitudinal direction of the other 50 mm × 7 mm surface. , A reflection loss of an electric signal in a frequency range of 950 MHz or more and less than 100 GHz is 30.0 dB or less, a transmission loss is 5.0 dB or less, and is used in a frequency range of 950 MHz to 300 GHz. Stuff. 2. A polymer component containing (i) at least one selected from (A) polyether imide and polyester, and (B) polyolefin, or (ii) (A) polyester, and (B) polyolefin and polycarbonate. 0.1 to 1. 1 with respect to 100 parts by weight of the polymer component containing at least one selected.
A resin composition containing 0 part by weight of an epoxy-modified styrene-based copolymer, wherein a 50 mm × 7 mm × 1 mm test piece made of the resin composition is plated with copper on the entire surface of one side of 50 mm × 7 mm, And, when 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 plane in the frequency direction of 950 MHz or more and less than 100 GHz. A resin composition for high frequencies, which has a reflection loss of an electric signal of 30.0 dB or less and a transmission loss of 5.0 dB or less and is used in a frequency range of 950 MHz to 300 GHz.