JPH10101931A - Low-dielectric resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a low-dielectric resin compsn. excellent in electrical properties (low dielectric properties), heat resistance, and moldability by thermally melt blending polyphenylene ether with a specific styrene-vinyl compd. copolymer and thermally melt blending the resultant resin compsn. with a polyetherimide. SOLUTION: This compsn. is prepd. by thermally melt blending 10 pts.mass polyphenylene ether with 5-40 pts.mass styrene-vinyl compd. copolymer obtd. by copolymerizing a styrenic compd. represented by formula I (wherein R<1> to R<4> are each H, a halogen, a hydrocarbon group, an alkoxy, cyano, phenoxy, nitro, or phenyl) and a vinyl compd. represented by formula II or III (wherein R<5> to R<7> and R<9> are each H, a halogen, a hydrocarbon group, an alkoxy, cyano, phenoxy, nitro, or phenyl; and R<8> is a hydrocarbon group, carbonyl, an alkoxycarbonyl, or phenoxycarbonyl) and thermally melt blending 10 pts.mass the resultant resin compsn. with 2-30 pts.mass polyetherimide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention has excellent electrical properties (low dielectric properties), precision moldability, and heat resistance.
High frequency electronic components (wiring boards, connectors, housings,
Low dielectric resin composition useful for insulating materials and the like). More specifically, it is thermoplastic and is suitable for manufacturing electronic components using injection molding technology, particularly electronic components used for high-frequency circuits. In particular, injection molded circuit components (Molded
interconnection device (MI
D)), an injection molded circuit board (Molded circuit)
The present invention relates to a low dielectric resin composition suitable for manufacturing a three-dimensional circuit component such as an it board (MCB).

[0002]

2. Description of the Related Art Conventionally, many thermoplastic resins are easily molded by injection molding or extrusion molding.
Dimensional molding is possible, and it has been widely used for various electronic / electric parts, automobile parts, machine parts and decorative articles.
On the other hand, a thermoplastic resin used for an electronic component, for example, a printed wiring board, a connector, or an insulating board, is required to be capable of being molded and to have strict performance in electrical characteristics. In particular, in recent years, in the information communication field, the use of high-frequency signals in a frequency band exceeding 1 GHz has been progressing in response to an increase in the amount of transmitted information. Since the amount of information that can be transmitted per unit time of a high-frequency signal can be increased in proportion to the frequency of a high-frequency signal compared to a low-frequency signal, electronic devices and communication devices can be speeded up as a result. Further, by using a high-frequency signal having a short wavelength, components such as an antenna can be reduced in size, and the size and weight of electronic and electric products can be reduced. Currently, communication devices using high-frequency signals have been put into practical use, and specific products include mobile phones, PHS, pagers, satellite terminal devices, navigation systems, BS broadcast devices, and the like. In the future, wireless L
It is expected that electronic devices utilizing higher frequency signals than AN (local area network) systems, automobile collision prevention systems, IC cards, etc. will be put to practical use. However, high-frequency signals have a disadvantage that signal energy loss (dielectric loss) due to insulators is large,
This may be a problem in practical use or in the design of equipment. In general, the magnitude of the dielectric loss is represented by a function (formula-1) depending on the signal frequency (λ) and the dielectric constant (ε) and the dielectric loss tangent (tan δ) of an insulating material used for a device or the like.

[0003]

(Equation 1)

A: Dielectric loss (dB / cm) C: Speed of light f: Frequency (Hz) k ¹ : Constant Therefore, a high dielectric insulating material having a large value of dielectric constant (ε) and dielectric loss tangent (tan δ) is used. Then, the signal energy loss increases, and a low dielectric insulating material having a small value of the dielectric constant (ε) and the dielectric loss tangent (tan δ) can reduce the dielectric loss of a high-frequency signal. Further, the magnitude of the dielectric constant also affects the electric signal propagation speed (Equation-
2).

[0005]

(Equation 2)

V: Electric signal propagation speed (cm / sec.) C: Light speed k ² : Constant That is, the use of an insulating material having a high dielectric constant lowers the electric signal propagation speed, and as a result, the calculation speed of electronic equipment and Reduce the processing speed. In general, the higher the heat-resistant temperature of engineering plastics, the higher both the dielectric constant and the dielectric loss tangent, and it is difficult to achieve both heat resistance and low dielectric constant.

For example, typical heat-resistant engineering plastics include polyimide (PI), polyetherimide (PEI), polyphenylene sulfide (PPS), polyarylate (PAR), liquid crystal polymer (LCP), and polyether sulfone. (PES), polyketone (PK), polyetheretherketone (PEE)
K) etc. have high heat resistance and excellent mechanical properties and are used for various applications, but these polymers have high dielectric constant and dielectric loss tangent especially in the high frequency range, and are used for high frequency electronic equipment. There are limits to what you can do. In addition, polyacetal (POM), polyethylene terephthalate (PE
Engineering plastics such as T), polybutylene terephthalate (PBT), and polyamide (PA) are insufficient in heat resistance and have high dielectric properties. on the other hand,
Among engineering plastics, general-purpose plastics such as modified polyphenylene ether (PPE), polycarbonate (PC) and polyethylene (PE), polypropylene (PP) and polystyrene (PSt), which have low heat resistance, have low dielectric constants and dielectric loss tangents. Although it can be said that the insulating material is suitable for an electronic device using a high-frequency signal, the use environment is greatly limited due to the low heat-resistant temperature.
Therefore, it can be said that there is no polymer having both heat resistance and low dielectric properties at present. Among them, polyetherimide is a thermoplastic resin having high heat resistance and is widely used for electronic parts requiring heat resistance, but has poor electric characteristics especially in a high frequency signal region (high dielectric constant, high dielectric constant). It cannot be used as an insulating material for high-frequency electronic components because of its dielectric loss tangent.

On the other hand, polyphenylene ether is generally commercially available as a modified polyphenylene ether (mPPE) obtained by blending and modifying polystyrene and polyphenylene ether, and is used for various applications including electronic parts because of its excellent electrical properties. Have been. In particular, modified polyphenylene ether has attracted attention as an insulating material for high-frequency electronic components because it has excellent electrical characteristics (low dielectric constant and low dielectric loss tangent) in the high-frequency signal region. There is a problem. In the past, Japanese Patent No. 1864864 reports a resin composition using polyetherimide and polyphenylene ether having relatively high heat resistance as raw materials. The polyetherimide / polyphenylene ether resin composition reported here uses unmodified polyphenylene ether as a constituent. A polyetherimide / polyphenylene ether resin composition using an unmodified polyphenylene ether is industrially high in value as a heat-resistant resin composition, but has low melt fluidity and extremely poor moldability. There is a disadvantage of saying. Further, JP-A-5-179140, JP-A-5-179132, JP-A-7-11122, JP-A-7-82469, JP-A-8-41362, and the like also disclose a polyetherimide having a relatively high heat resistance temperature, A resin composition using polyphenylene ether having a relatively low dielectric constant and a low dielectric loss tangent has been reported. These resin compositions are reported to have high heat resistance, a low dielectric constant and a low dielectric loss tangent in the high-frequency region, and are low-dielectric resin compositions, and are industrially used as insulating materials for electronic devices utilizing high-frequency signals. The utility value is extremely high.

Further, the polyetherimide / polyphenylene ether resin composition reported here includes, in addition to unmodified polyphenylene ether as a constituent,
It is stated that a modified polyphenylene ether can be used. The modified polyphenylene ether in this report is obtained by melt-blending polystyrene and polyphenylene ether, and is generally called polystyrene-modified polyphenylene ether. It is described that when polystyrene-modified polyphenylene ether is used, the melt fluidity is higher and the moldability is improved as compared with the case where unmodified polyphenylene ether is used. However, polystyrene-modified polyphenylene ether is basically incompatible with polyetherimide, and when a resin composition blended with these is molded at a high temperature, phase separation occurs, resulting in deterioration of mechanical properties and discoloration. Occurs. Furthermore, here, it is also reported that a compatibilizer (third component) is blended in order to solve the compatibility problem between polyetherimide and polyphenylene ether or modified polyphenylene ether, and that MID and MCB can be produced. There is also a description that it is a resin composition having excellent moldability. As a compatibilizer for improving the compatibility between polyetherimide and polyphenylene ether, epoxy-modified styrene-styrene copolymer, epoxy-modified styrene-methyl methacrylate copolymer, styrene-
It is described that a maleic anhydride copolymer or the like is suitable. The compatibilizer used here is for the purpose of compatibilizing the polyetherimide and the polyphenylene ether, and the amount of the compatibilizer is merely an amount that is usually blended as an additive. Further, by blending the respective components simultaneously, the effect of compatibilization becomes the most remarkable.

[0010]

However, the resin composition of polyetherimide and polyphenylene ether obtained by blending a compatibilizer here, when subjected to molding at high temperature, changes color and mechanical properties. In some cases, and the moldability required by the inventor cannot be sufficiently achieved. That is, although the resin composition shown in the report has no problem in terms of low dielectric properties, it cannot be molded at high temperatures sufficiently, and therefore has a sufficiently high precision moldability (melt fluidity) that we aim for. Difficult to get.
In other words, these are ordinary electronic components or specific MI
D and MCB can be molded and can be used for electronic parts that use low frequency and high dielectric constant. However, there is still a problem in moldability, that is, fluidity, and precise and high molding precision is required. However, it has been difficult to use it as an electronic component that requires the above, or as a material for MID and MCB having a more precise and dense shape.

[0011]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on polyetherimide / polyphenylene ether-based polymer alloys in order to solve the drawbacks in molding processability and heat resistance. And a resin composition prepared by heating and melting a styrene-vinyl compound copolymer capable of forming a bond by chemically reacting with the polyetherimide at a specific ratio, and thereafter, the resin composition and the polyetherimide are mixed. A resin composition obtained by heating and melt-blending a specific amount, and a resin composition in which a specific amount of a styrene-vinyl compound copolymer having a specific molar ratio, a polyphenylene ether, and a polyetherimide are blended are formed and processed. Excellent in heat resistance, heat resistance, and found that a resin composition having a low dielectric constant can be obtained,
The present invention has been reached. That is, the present invention is obtained by copolymerizing 10 parts by mass of polyphenylene ether, a styrene-based compound represented by the general formula (1), and a vinyl-based compound represented by the general formula (2) or (3). 10 to 40 parts by mass of a resin composition obtained by heat-melting and blending 5 to 40 parts by mass of a styrene-vinyl compound copolymer,
An object of the present invention is to provide a low dielectric resin composition characterized in that 30 parts by mass are produced by heating and blending.

[0012]

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(Wherein, R ¹ , R ² , R ³ , and R ⁴ each represent hydrogen, halogen, a hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group, a nitro group, or a phenyl group)

[0014]

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(Wherein R ⁵ , R ⁶ and R ⁷ are each hydrogen, halogen, hydrocarbon, alkoxy, cyano,
Represents a phenoxy group, a nitro group, or a phenyl group. R ⁸ represents a substituent in which one or more epoxy groups are bonded to any of a hydrocarbon group, a carbonyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, or an aromatic group.

[0016]

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(Wherein R ⁹ represents hydrogen, halogen, a hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group, a nitro group, or a phenyl group) Further, the present invention relates to 10 parts by mass of polyphenylene ether,
A copolymer obtained by copolymerizing a styrene compound represented by the general formula (1) and a vinyl compound represented by the general formula (2) or (3), wherein the styrene compound is When the molar ratio of the vinyl compound is 10
0 to 0 to 5 to 40 parts by mass of a styrene-vinyl compound copolymer which is a vinyl compound 1 to 30, and 10 parts by mass of the total amount of the polyphenylene ether and the styrene-vinyl compound copolymer, Imides 2-30
An object of the present invention is to provide a low dielectric resin composition containing parts by mass. Further, the present invention provides an article obtained by molding the above low dielectric resin composition. Hereinafter, the present invention will be described in detail.

In the styrene compound of the general formula (1) used for the styrene-vinyl compound copolymer used in the present invention, R ¹ , R ² , R ³ and R ⁴ are each hydrogen, halogen, It is selected from a hydrogen group, an alkoxy group, a cyano group, a phenoxy group, a nitro group, and a phenyl group. Halogen may be any of fluorine, chlorine, bromine and iodine, and as the hydrocarbon group, methyl, ethyl, propyl, phenyl,
Benzyl is preferred, and methoxy as the alkoxy group,
Ethoxy and propoxy are preferred. Preferred specific examples of the styrene compound include styrene, α-methylstyrene, p-methylstyrene, p-fluorostyrene,
Examples thereof include p-cyanostyrene and p-methoxystyrene, and styrene is particularly preferable.

In the vinyl compound of the general formula (2) used in the styrene-vinyl compound copolymer used in the present invention, R ⁵ , R ⁶ and R ⁷ are each hydrogen, halogen, a hydrocarbon group, It is selected from an alkoxy group, a cyano group, a phenoxy group, a nitro group, and a phenyl group. R ⁸ is a hydrocarbon group, a carbonyl group, an alkoxycarbonyl group,
It is selected from a substituent in which one or more epoxy groups are bonded to either a phenoxycarbonyl group or an aromatic group. Halogen may be any of fluorine, chlorine, bromine and iodine, and the hydrocarbon group is preferably methyl, ethyl, propyl, phenyl or benzyl, and the alkoxy group is preferably methoxy, ethoxy or propoxy. Preferred specific examples of the vinyl compound of the general formula (2) include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, allyl glycidyl ether,
Styrene-p-glycidyl ether is mentioned, and glycidyl methacrylate and styrene-p-glycidyl ether are particularly preferable.

In the vinyl compound of the general formula (3) used in the styrene-vinyl compound copolymer used in the present invention, R ⁹ represents hydrogen, halogen, hydrocarbon group, alkoxy group, cyano group, phenoxy group. Group, nitro group or phenyl group. Halogen may be any of fluorine, chlorine, bromine and iodine, and the hydrocarbon group is preferably methyl, ethyl, propyl, phenyl or benzyl, and the alkoxy group is preferably methoxy, ethoxy or propoxy. Preferred specific examples of the vinyl compound of the general formula (3) include maleic anhydride, methyl maleic anhydride,
Fluoro-maleic anhydride and the like can be mentioned, and among them, maleic anhydride is particularly preferable. The styrene-vinyl compound copolymer used in the present invention may be a random copolymer, an alternating copolymer, a block copolymer or a graft copolymer, or may be any of the general formulas (1) and ( 2), the monomer of the general formula (3) does not need to be one kind each,
Each may be a copolymer of a plurality of monomers selected from the group of monomers having the structures shown above.

In the styrene-vinyl compound copolymer, the molar ratio of the styrene compound represented by the general formula (1) to the vinyl compound represented by the general formula (2) or (3) is Preferably, the vinyl compound is 1 to 30 with respect to the styrene compound 100, more preferably the vinyl compound is 3 to 20 with respect to the styrene compound 100, particularly preferably the vinyl compound with respect to the styrene compound 100. 4 to 15. When the molar ratio of the styrene compound and the vinyl compound is in a preferable range,
The object of the present invention can be achieved without observing the above-described order of the hot melt blending. The number average molecular weight of the styrene-vinyl compound copolymer is not particularly limited,
3,000 to 1,000,000 are preferable, and in particular,
000 to 100,000 is preferred. The styrene-vinyl compound copolymer can form a bond by chemically reacting with a terminal amino group of polyetherimide, a phthalic anhydride group, or the like. In general, just like polystyrene is completely compatible with polyphenylene ether, the styrene-vinyl compound copolymer used in the present invention is compatible with polyphenylene ether. The polyphenylene ether used in the present invention is a polymer having a repeating structural unit represented by the general formula (4).

[0022]

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(Wherein R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxyl group, or a halogenated hydrocarbon group). And iodine; the hydrocarbon group is preferably methyl, ethyl, propyl, phenyl and benzyl; the alkoxyl group is preferably methoxy, ethoxy and propoxy; and the halogenated hydrocarbon group is preferably chloromethyl and bromomethyl. Among them, polyphenylene ether having a repeating structural unit represented by the general formula (5) is most preferable in terms of economy.

[0024]

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Although the number average molecular weight of the polyphenylene ether is not particularly limited, it is 5,000 to 1,000,000.
Is preferred, and 10,000 to 500,000 is particularly preferred. On the other hand, the polyetherimide resin used in the present invention is a polymer having a repeating unit represented by the general formula (6).

[0026]

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Wherein R ¹⁴ is a divalent aromatic group having 6 to 30 carbon atoms, and R ¹⁵ is an aromatic group having 6 to 20 carbon atoms, an alkylene group or a cycloalkylene group. Most preferred is a polyetherimide having the structure of formula (7).

[0028]

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The number average molecular weight of the polyetherimide is not particularly limited, but is preferably from 1,000 to 1,000,000, and particularly preferably from 3,000 to 100,000. The low-dielectric resin composition of the present invention is obtained by first heating and melt-blending polyphenylene ether and a styrene-vinyl compound copolymer to form a resin composition, and then heat-blending the resin composition with polyetherimide. It is characterized by being manufactured. Here, when the order of the heat-melt blending is different from the order specified in the present invention, for example, heat-melt blending of polyphenylene ether, styrene-vinyl-based compound copolymer and polyetherimide at once, or polyphenylene ether and polyether When the imide is heat-melted and blended with the styrene-vinyl compound copolymer, or the styrene-vinyl compound copolymer and the polyetherimide are heat-melted and then blended with the polyetherimide. As a result, discoloration is observed during high-temperature molding or the performance after molding is reduced. For hot melt blending,
General melt blending methods such as a twin-screw extruder, a single-screw extruder, a masterbatch, and a lab plastomill can be applied. However, a heat-melt blend using a twin-screw extruder or the like can be easily mass-produced. Yes, it is economically advantageous.

Next, preferred conditions for producing the low dielectric resin composition of the present invention when a twin-screw extruder is used will be described. Heat-melt blending using a twin-screw extruder has a higher kneading stress than the production using a masterbatch, injection molding or press molding, so that the resin generates heat and tends to undergo thermal decomposition. Therefore, in general, in order to produce a resin composition by a twin-screw extruder, it is important to control the number of rotations of the screw, though it depends on the resin temperature and the apparatus (type) at the time of the hot melt blending. The preferred temperature range for hot melt blending the polyphenylene ether and the styrene-vinyl compound copolymer is from 250 to 300C. At this time, when the temperature is 25
When the temperature is 0 ° C or lower, the polyphenylene ether and the styrene-vinyl compound copolymer are not sufficiently melted and may not be completely mixed. When the temperature is 300 ° C or higher, the heat of the styrene-vinyl compound copolymer may be reduced. Decomposition is likely to occur. Further, a preferred temperature range when the resin composition obtained by heating and melting the polyphenylene ether and the styrene-vinyl compound copolymer and the polyetherimide is heated and melt-blended is a temperature of 250 to 320 ° C.
At this time, when the temperature is 250 ° C. or lower, the polyetherimide is hardly melted. As a result, sufficient kneading may not be performed. When the temperature is 320 ° C. or higher, the polyphenylene ether and the styrene-vinyl-based compound Thermal decomposition of the resin composition composed of the coalesce is likely to occur, and discoloration of the pellet may occur.

On the other hand, when the rotation speed is 50 rpm. In the following cases, kneading may not be performed sufficiently, and 400 rpm
m. If it is above, unnecessary stress or heat is applied to the resin during melt-kneading, and as a result, the mechanical strength of the product may be reduced. The mixing ratio of each of the above components in the low dielectric resin composition of the present invention is such that the polyphenylene ether is 10 parts by mass and the styrene-vinyl compound copolymer is 5 parts by mass.
2 to 30 parts by mass, preferably 3 to 30 parts by mass, preferably 10 to 35 parts by mass, and 10 to 30 parts by mass of the polyphenylene ether and the styrene-vinyl compound copolymer in total. 20 parts by mass.

Further, the low dielectric resin composition of the present invention contains basic properties of the resin, for example, mechanical properties, electrical properties, heat resistance, moldability, flowability, flame retardancy, and UV resistance. Various additives may be blended for the purpose of improving the chemical resistance, the appearance of the molded article, etc., coloring, and imparting gloss. Examples of the additive include a plasticizer, a heat stabilizer, an oxidation stabilizer, a cross-linking agent, a flame retardant, an ultraviolet absorber, a gloss-imparting agent, and a pigment. In addition, for the purpose of improving mechanical strength, heat resistance, thermal conductivity, coefficient of thermal expansion, and imparting electroless plating property, an inorganic filler may be blended within a range in which moldability, electrical properties, and mechanical properties are not reduced. . Examples of inorganic fillers that can be blended include quartz, quartz glass, glass, short glass fiber, glass fiber,
Glass balloon, shirasu balloon, chopped strand, carbon fiber, carbon, carbon black, aramid, potassium titanate, aluminum borate, magnesium borate, calcium carbonate, magnesium carbonate, magnesium sulfate, calcium sulfate, aluminum sulfate,
Pyrophosphate, silicon nitride, aluminum nitride, boron nitride, silicon carbide, alumina, alumina fiber, silica, mica, talc, diatomaceous earth, clay, volcanic ash, limestone, bentonite, titanium oxide, magnesium oxide, calcium oxide, disulfide Molybdenum and the like. The shape of these inorganic fillers is preferably selected depending on the purpose of blending, and may be any of powder, sphere, fiber, and whisker. For the purpose of improving mechanical strength, heat resistance, thermal conductivity, and coefficient of thermal expansion, fibrous inorganic fillers, such as glass fibers, whiskers of aluminum borate and potassium titanate, are preferred. For the purpose of imparting the electroless plating property, a shape close to a sphere, in other words, a shape having a relatively small aspect ratio is particularly preferable.

Among them, high-purity quartz glass powder is dielectric,
It is suitable from the viewpoint of plating properties. The SiO ₂ purity of the high-purity quartz glass powder is preferably as high as possible from the viewpoint of low dielectric properties, and preferably the purity of SiO ₂ is 99% or more, more preferably 99.5% or more. When the SiO ₂ purity is 99% or less, the dielectric constant and the dielectric loss tangent of the product increase. Furthermore, from the viewpoint of imparting electroless plating properties, the shape is preferably close to spherical, and the average particle size is in the range of 0.1 to
It is preferably 100 μm. If the average particle size of the high-purity quartz glass powder is smaller than 0.1 μm, the adhesion strength of the electroless plating film is low, and if it is larger than 100 μm, the moldability is remarkably deteriorated. The amount of the high-purity quartz glass powder is preferably from 10 to 150 parts by mass, more preferably from 20 to 100 parts by mass, per 100 parts by mass of the low dielectric resin composition. If the amount of the high-purity quartz powder is small, the electroless plating property cannot be imparted, and if it is too large, the moldability deteriorates.

Various coupling agents and the like may be blended for the purpose of improving the interfacial adhesion between the inorganic filler and the resin composition. Preferred examples of the coupling agent include vinyl trichlorosilane, vinyl tris (β-
Methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-
β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
-Chloropropyltrimethoxysilane, di (3-triethoxysilylpropyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) Silane coupling agents such as -3-aminopropyltrimethoxysilane, vinyltri (2-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, and 3-glycidyloxypropyltrimethoxysilane; triisostearoyl isopropyl titanate; Titanate couplings such as di (dioctyl phosphate) diisopropyl titanate, didodecylbenzenesulfonyl diisopropyl titanate, diisostearyl diisopropyl titanate ; And the like. The coupling agent can be used in an amount that does not deteriorate heat resistance, electrical characteristics, and moldability, and is usually preferably in the range of 0.0001 to 1 part by mass with respect to 100 parts by mass of the inorganic filler to be mixed. The timing of addition of the various additives is not particularly limited, but it is preferable to add them at the time when the resin composition composed of polyphenylene ether and a styrene-vinyl compound copolymer and polyetherimide are melted by heating.
The addition at the preferable addition timing can minimize the heat generation during kneading and the thermal decomposition of the resin due to the addition of the inorganic filler.

The resin having a different structure may be added to the low dielectric resin composition of the present invention as long as the mechanical strength, electrical properties, moldability and heat resistance are not significantly reduced. Specifically, polyethylene (PE), polypropylene (PP),
Polystyrene (PS), polymethyl methacrylate (P
MMA), general-purpose resins such as ABS resin and AS resin, polyacetate (POM), polycarbonate (PC), polyamide (PA: nylon), polyethylene terephthalate (PET), polybutylene terephthalate (PB)
T) and other engineering plastics, as well as polyphenylene sulfide (PPS), polyethersulfone (PES), and polyetheretherketone (PEE).
K), polyketone (PK), polyimide (PI), polycyclohexanedimethanol terephthalate (PC
T), thermoplastic resins such as polyarylate (PAR) and various liquid crystal polymers (LCP), and thermosetting resins such as epoxy resins, phenol resins, and novolak resins. The low dielectric resin composition according to the present invention can be molded without decomposing the resin, deteriorating mechanical properties, discoloration, etc., even at a high molding temperature at which high melt fluidity can be obtained. In other words, the low-dielectric resin composition can be molded at a higher temperature than the polyetherimide / polyphenylene ether-based resin composition reported in the previous report, and can produce more precise molded products. It becomes possible. Therefore,
The low-dielectric resin composition is thermoplastic, has high fluidity when melted, and can be injection-molded, extruded or pressed, and is suitable for production of MID and MCB which require more precise molding accuracy. it can. The timing of adding the above various resins is not particularly limited, but it is preferable to add them at the time when the resin composition composed of polyphenylene ether and styrene-vinyl compound copolymer and polyetherimide are blended by heating and melting. The addition at this preferred timing is styrene-
The reaction between the vinyl compound copolymer and the added resin can be suppressed.

The low dielectric resin composition of the present invention is a resin composition exhibiting low dielectric properties particularly in a high frequency region, and has a dielectric constant (ε) of 3.5 or less in a high frequency band of 100 KHz to 300 GHz, and in the same frequency band. Dielectric loss tangent (tan
δ) is 0.01 or less, more preferably, the dielectric constant is 3.0 or less, and the dielectric loss tangent is 0.007 or less. When a resin having a dielectric constant in the above frequency band of more than 3.5 or a dielectric loss tangent of more than 0.01 is used for electronic components and electric insulating materials (particularly, those components and materials used in a high frequency band of 1 GHz or more). In addition, since the loss of the signal becomes large, not only will excessive force be caused in circuit design and the like, but also it becomes impossible to use in some cases (applications).

[0037]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. The present invention is not limited by these examples. The resin raw materials, inorganic fillers, and additives (compatibilizers) used in Examples and Comparative Examples are shown below. (1) Polyphenylene ether PPE-N: unmodified polyphenylene ether having a number average molecular weight of 13,500 (in terms of polystyrene). (2) Styrene-vinyl compound copolymer St-GMA: styrene-glycidyl methacrylate copolymer, number average molecular weight 18,000 (in terms of polystyrene), styrene / glycidyl methacrylate (molar ratio 1)
00/10). St-MMA: styrene-maleic anhydride copolymer, number average molecular weight 19,800 (in terms of polystyrene), styrene / maleic anhydride (molar ratio 100/10). (3) Polyetherimide PEI: Polyetherimide / Ultem 1010-1000 manufactured by GE Plastics Japan.

(4) Other additives LCP: Liquid crystal polymer / Sumitomo Super E6000 manufactured by Sumitomo Chemical Co., Ltd. PC: polycarbonate / manufactured by Teijin Chemicals Ltd., Panlite L1250. Compatibilizer: epoxy-modified styrene-styrene copolymer,
Reseda GP500 manufactured by Toagosei Chemical Industry Co., Ltd. SiO ₂ : high-purity silica / Fuselex ZE30A manufactured by Tatsumori Co., Ltd., shape: pulverized product, average particle size: 5 μm, purity: 99.8%.

Examples 1 to 12 and Comparative Examples 1 to 1
2] <Production of Resin Composition> In Examples 1 to 12, a styrene-vinyl compound copolymer having a predetermined composition was blended with the unmodified polyphenylene ether (PPE-N) by heating and melting. Those (mPPE-1 to 6) were used. A twin screw extruder (made by Kobe Steel Co., Ltd.)
Using KTX46), the mixture was heated and melt-blended at a predetermined rotation speed and a predetermined temperature, and then the strand was cut by a strand pelletizer to obtain a pellet (material before molding). Also,
Comparative examples also show the results obtained when unmodified polyphenylene ether (PPE-N) and polyphenylene ether (PPE-7) obtained by heat-melting and blending a predetermined polystyrene with unmodified polyphenylene ether. (1) PPE-1: number average molecular weight 15900 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound random copolymer (styrene / glycidyl methacrylate molar ratio: 100/10) 35 parts by mass, Conditions: 160 rpm. 270 ° C. (2) PPE-2: number average molecular weight 15100 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound random copolymer (styrene / glycidyl methacrylate molar ratio: 100/10) 12 parts by mass, Conditions: 160 rpm. 270 ° C. (3) PPE-3: number average molecular weight 14000 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound random copolymer (styrene / glycidyl methacrylate molar ratio: 100/10) 6 parts by mass, Conditions: 160 rpm. 270 ° C.

(4) PPE-4: number average molecular weight 16200 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound random copolymer (styrene / glycidyl methacrylate molar ratio: 100/5) 12 Parts by mass, conditions: 160 rpm. 270 ° C. (5) PPE-5: number average molecular weight 14,800 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound random copolymer (styrene / glycidyl methacrylate molar ratio: 100/20) 12 parts by mass, conditions : 160 rpm. 280 ° C. (6) PPE-6: number-average molecular weight 13600 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound random copolymer (styrene / maleic anhydride molar ratio: 100/12) 10 parts by mass, Conditions: 160 rpm. 280 ° C.

(7) PPE-7: number average molecular weight 16000 (in terms of polystyrene), PPE-N 10 parts by mass, polystyrene 20 parts by mass, Condition: 160 rpm. 270 ° C. (8) PPE-8: number average molecular weight 15600 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound copolymer 3 parts by mass, styrene / glycidyl methacrylate molar ratio: 100/10, condition: 160 rpm . 270 ° C. (9) PPE-9: number average molecular weight 15,600 (in terms of polystyrene), PPE-N 10 parts by mass, styrene-vinyl compound copolymer 45 parts by mass, styrene / glycidyl methacrylate molar ratio: 100/10, condition: 160 rpm . 270 ° C.

<Preparation of Low Dielectric Resin Composition> Pre-blend of predetermined raw materials at the raw materials and composition ratios shown in Table 1, and then using a quantitative feeder at a feed rate of 40 kg / h, a twin-screw extruder (Kobe) -KTX46) manufactured by Steel Works, and heated and melt-kneaded at the same temperature and screw speed as shown in Table 1. After cooling with water, the strand was cut by a strand pelletizer to obtain pellets (material before molding). <Molding> The obtained pellets were passed through a ventilated incubator for 120 hours.
After drying at 5 ° C for 5 hours, injection molding machine (Clockner “F”)
−85 ″) and the nozzle temperatures 320 and 33, respectively.
Injection molding was performed at 0 and 340 ° C. to prepare test pieces for evaluation of mechanical properties, thermal properties, and electrical properties. The shape of the test piece is as follows. Test piece 1 ASTM No. 1 dumbbell: Test piece 2 for mechanical property evaluation Strip: Load deflection temperature (HDT) test piece 3 Disc 1 φ100 mm × 1.6 mm: 1 to 15 MHz dielectric property evaluation Test piece 4 Disk 2 φ100 mm × 0.8mm: 1 to 25GHz for dielectric property evaluation

<Evaluation of Dielectric Properties> Under the following conditions, the dielectric constant (ε) and the dielectric loss tangent (tan δ) of the resin composition were measured. The measurement results are shown in Tables 3 and 4. Measurement frequency: 1MHz, 10MHz, 1GHz, 10G
Hz, 20 GHz Measurement temperature: 25 ° C. Measurement method: Parallel plate electrode method (1, 10 MHz), Petri plate line resonator method (loss separation method) (1, 10, 20)
<Evaluation of moldability (melt fluidity)> The pellets were dried in a ventilated thermostat at 120 ° C. for 5 hours, and melt flow was performed using a semi-automatic melt indexer 2A manufactured by Toyo Seiki Seisakusho under the following conditions The late (MFR) was measured. M
FR is represented by an extrusion amount (g / 10 min.) Of the molten resin per 10 minutes at each temperature, and the measurement results are shown in Tables 5 and 6. Further, changes in the color tone of the pellet surface before and after the measurement and after the measurement (after heating and melting at a predetermined temperature) were also evaluated, and the results are shown in Tables 5 and 6. Standard: in accordance with JIS-K7212 Measurement temperature: 300, 310, 320, 330, 340 ° C. Load: 5 kgf / cm 2 · Strand color tone evaluation (standard) Evaluation was made by comparison with the color tone of the pellet before measurement. ○: no change in color tone △: slight change ×: change in color tone

<Evaluation of Heat Resistance During Molding> Evaluation of the heat resistance of the resin composition during molding was performed at nozzle temperatures 320, 330, and 3
Using test pieces injection molded at 40 ° C,
Measurement of mechanical strength (tensile test), deflection temperature under load (HD
T) was measured and evaluated by the color tone (appearance) of the molded article after injection molding. The results are shown in Tables 7 and 8. The respective measurement conditions are shown below. -Deflection temperature under load (HDT) Standard: compliant with ASTM D638 Measurement temperature: 320 ° C Load: 18.6 kgf / cm2-Mechanical strength measurement Standard: compliant with ASTM D638-Evaluation of color tone of molded product (standard) Comparison with color tone of pellet before molding It was evaluated by comparison. ○: no change in color tone △: slight change ×: change in color tone

[0045]

[Table 1]

[0046]

[Table 2]

[0047]

[Table 3] In Tables 3 and 4, the upper row shows the dielectric constant (ε), and the lower row shows the dielectric loss tangent (tan δ).

[0048]

[Table 4]

[0049]

[Table 5] In Tables 5 and 6, () shows the color tone of the surface of the strand. ○: no change in color tone △: slight change ×: change in color tone

[0050]

[Table 6]

[0051]

[Table 7]

[0052]

[Table 8] In Tables 7 and 8, the color tone is a comparison between the surface of the molded article and the pellet before molding. ○: no change in color tone △: slight change ×: change in color tone

Examples 1 to 12 and Comparative Examples 1 to 6
Each is a resin composition obtained by heat-melting and blending a resin composition comprising a styrene-vinyl compound copolymer and polyphenylene ether and a polyetherimide. In Example 10, polycarbonate, liquid crystal polymer in Example 11, and high-purity silica in Example 12 were compounded as third components, respectively. All of the resin compositions obtained in the examples were measured for the dielectric constant and the dielectric loss tangent (Table 3).
5 or less, a dielectric loss tangent of 0.01 or less, and low dielectric properties.
On the other hand, Comparative Example 2 is a resin composition obtained by heating and melt-blending a resin composition comprising a styrene-vinyl compound copolymer and polyphenylene ether and a polyetherimide. The difference from the embodiment in many points is that both the dielectric constant and the dielectric loss tangent are high and the dielectric is high. Similarly, the polyetherimide (PEI) shown in Comparative Example 10 also shows high values for both the dielectric constant and the dielectric loss tangent, and has high dielectric properties. Further, the resin compositions obtained in the examples melted in the temperature range of 300 to 340 ° C. from the results of the melt flow rate measurement in Table 5, and showed a high melt flow rate at 340 ° C. There is no change in color tone due to. Further, the resin composition of the comparative example also melts in a temperature range up to 340 ° C. However, in Comparative Example 1, which is different from the example in that the amount of PEI to PPE-1 is small, a change in color tone is observed after the measurement of the melt flow rate, suggesting that the resin is degraded by heat.

Comparative Example 4 is an example using PPE-8 in which the amount of the styrene-vinyl compound copolymer is small with respect to the polyphenylene ether, and Comparative Example 5 is the case where the styrene-vinyl compound copolymer is mixed with the polyphenylene ether. This is an example using a large amount of PPE-9. Comparative Example 6 is an example in which a small amount of a compatibilizer was added. In each of Comparative Examples 4 to 6, a change in color tone is observed at the time of melt flow measurement at a high temperature, and when injection molding is performed at a high temperature of 340 ° C, a decrease in performance is observed. Furthermore, in Comparative Examples 7 and 8, in which unmodified polyphenylene ether, styrene-vinyl compound copolymer, and polyetherimide, which are components used in the low dielectric resin composition of the present invention, were simultaneously heated and melt-blended. , As well,
A change in color tone is observed at the time of melt flow measurement at a high temperature, and when injection molding is performed at a high temperature of 340 ° C., performance is reduced. Comparative Example 9 using only PPE-7 in which polystyrene was blended with unmodified polyphenylene ether, Comparative Example 10 using only unmodified PPE-N, PPE-
Similarly, in Comparative Example 11 having only 1 color tone, the color tone changes and the performance decreases. From the above, the low dielectric resin composition of the present invention can be obtained only when the mixing ratio of each component, the order and the conditions of the hot melt blending of each component are all the same. The resin compositions shown in Examples 1 to 12 have low dielectric properties, and do not show a decrease in color tone and performance due to thermal degradation even when molded at a high temperature. Is a low dielectric resin composition that can be formed by molding, and is a high-frequency electronic component, especially a MID that requires precise molding accuracy
And MCB.

[0055]

The low dielectric resin composition of the present invention has not only excellent electrical properties (low dielectric properties) and heat resistance, but also excellent moldability, in other words, high melt fluidity. That is, MID and MCB, among them, parts formed by the two-shot method, precision electronic parts for micromachines, small electronic parts for mobile terminals, high-frequency antenna parts, housing-integrated antennas for mobile terminals, and the like. It has high melt fluidity required for insulating materials for electronic components.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Seitoshi Iwafune 1134-2 Gongendo, Satte City, Saitama Prefecture, Cosmo Research Institute R & D Center

Claims (6)

[Claims] 1. A polyphenylene ether (10 parts by mass), a styrene compound represented by the general formula (1), and a styrene compound represented by the general formula (2):
Alternatively, a polystyrene is added to 10 parts by mass of a resin composition obtained by heat-melting and blending 5 to 40 parts by mass of a styrene-vinyl compound copolymer obtained by copolymerizing a vinyl compound represented by the general formula (3). A low dielectric resin composition characterized by being produced by heating and melting 2 to 30 parts by mass of imide. Embedded image (In the formula, R ¹ , R ² , R ³ , and R ⁴ each represent hydrogen, halogen, a hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group, a nitro group, or a phenyl group.) (Wherein R ⁵ , R ⁶ and R ⁷ are each hydrogen, halogen,
Hydrocarbon group, alkoxy group, cyano group, phenoxy group,
Represents a nitro group or a phenyl group. R ⁸ represents a substituent in which one or more epoxy groups are bonded to any of a hydrocarbon group, a carbonyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, or an aromatic group. (Wherein, R ⁹ represents hydrogen, halogen, a hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group, a nitro group, or a phenyl group) 2. In the styrene-vinyl compound copolymer, the molar ratio of the styrene compound represented by the general formula (1) to the vinyl compound represented by the general formula (2) or (3) is The low dielectric resin composition according to claim 1, wherein the ratio of the vinyl compound to the styrene compound is 100 to 100. 3. A hot-melt blend of a polyphenylene ether and a styrene-vinyl compound copolymer at a temperature of 250 to 300 ° C., and a hot melt blend of the resin composition and a polyetherimide at a temperature of 250 to 320 ° C. The low dielectric resin composition according to claim 1, wherein the resin composition is manufactured by the following method. 4. A polyphenylene ether (10 parts by mass), a styrene compound represented by the general formula (1), and a styrene compound represented by the general formula (2):
Or a copolymer obtained by copolymerizing a vinyl compound represented by the general formula (3), wherein the molar ratio of the styrene compound to the vinyl compound is such that the ratio of the styrene compound 100 to the vinyl compound 1 5 to 40 parts by mass of a styrene-vinyl compound copolymer which is from 30 to 30, and 2 to 30 parts by mass of a polyetherimide based on a total amount of 10 parts by mass of the polyphenylene ether and the styrene-vinyl compound copolymer. A low dielectric resin composition characterized by containing. Embedded image (Wherein, R ¹ , R ² , R ³ , and R ⁴ each represent hydrogen, halogen, a hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group, a nitro group, or a phenyl group) (Wherein R ⁵ , R ⁶ and R ⁷ are each hydrogen, halogen,
Hydrocarbon group, alkoxy group, cyano group, phenoxy group,
Represents a nitro group or a phenyl group. R ⁸ represents a substituent in which one or more epoxy groups are bonded to any of a hydrocarbon group, a carbonyl group, an alkoxycarbonyl group, a phenoxycarbonyl group, or an aromatic group. (Wherein, R ⁹ represents hydrogen, halogen, a hydrocarbon group, an alkoxy group, a cyano group, a phenoxy group, a nitro group, or a phenyl group) 5. The low-molecular-weight copolymer according to claim 1, wherein the styrene-vinyl compound copolymer is a styrene-glycidyl methacrylate copolymer or a styrene-maleic anhydride copolymer. Dielectric resin composition. 6. An article obtained by molding the low dielectric resin composition according to claim 1.