Polyphenylene ether-based resin composition, injection-molded body, electronic member, and antenna member

Abstract

The present invention relates to a polyphenylene ether-based resin composition, an injection-molded body, an electronic member, and an antenna member. The object of the present invention is to provide a polyphenylene ether-based resin composition which is excellent in balance of heat resistance, mechanical properties, dielectric properties, molding fluidity, and oil resistance. In order to achieve the above object, the polyphenylene ether-based resin composition of the present invention is a thermoplastic resin composition comprising (A) a polyphenylene ether-based resin or a mixed resin of a polyphenylene ether-based resin and a styrene-based resin, (B) a cyclic olefin-based resin having neither an aromatic group nor an aromatic alkyl group, and (C) a styrene-based thermoplastic elastomer, characterized in that the glass transition temperature of the above-mentioned (B) component is 105°C or higher, and the weight average molecular weight of the above-mentioned (C) component is 50,000 to 220,000.

Description

Technical Field

[0001] This invention relates to polyphenylene ether resin compositions, injection molded articles, electronic components, and antenna components. Background Technology

[0002] Polyphenylene ether (PPE) resins, such as poly(2,6-dimethyl-1,4-phenylene ether), are resins with excellent properties including high heat resistance, lightweight, low water absorption, hydrolysis resistance, dimensional stability, acid / alkali resistance, flame retardancy, high volume resistivity, low dielectric constant, and low dielectric loss. Therefore, PPE resins are widely used in automotive parts, electrical and electronic components, OA equipment, and water supply and drainage components. However, PPE resins have a high melt viscosity, resulting in poor molding flowability. Therefore, alloying with other resins such as polystyrene, polyamide, and polypropylene has been developed to improve molding flowability.

[0003] In recent years, polyphenylene ether (PPE) resins have been increasingly used as polymer insulating materials for circuit boards and other electronic components, such as antenna parts, due to their excellent heat resistance and dielectric properties. For such applications, a low dielectric loss tangent is preferred to reduce signal transmission loss in the high-frequency band of communication / electronic equipment. Therefore, the application of PPE resins alloyed with polyolefins such as polyethylene and polypropylene, or polystyrene, which have low dielectric loss tangents, has been studied. However, since polyolefins and polystyrene have lower heat resistance than PPE resins, resin compositions formulated with these resins and PPE resins suffer from reduced heat resistance.

[0004] Furthermore, it is known that cyclic olefin resins containing cyclic olefins such as norbornene as polymerization components possess both excellent heat resistance and dielectric properties compared to polyolefins such as polyethylene or polystyrene. Additionally, resin compositions prepared by blending such cyclic olefin resins with polyphenylene ether resins are already known. For example, Patent Document 1 discloses a method for obtaining a polyphenylene ether resin composition with excellent heat resistance, dielectric properties, and molding flowability by blending a cyclic olefin resin formed from a copolymer of ethylene and cyclic olefins such as 1,4,5,8-dimethylbridged-1,2,3,4,4a,5,8,8a-octahydronaphthalene with a polyphenylene ether resin.

[0005] In addition, Patent Document 2 discloses the following: a resin composition containing a polyphenylene ether resin, a cyclic olefin resin containing a specific cyclic olefin with aromatic substituents such as 5-phenyl-bicyclo[2.2.1]hept-2-ene as a monomer component, and a styrene thermoplastic elastomer, for the purpose of improving mechanical properties such as impact resistance, and a resin composition with significantly improved mechanical properties is obtained.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2-115248

[0009] Patent Document 2: Japanese Patent Application Publication No. 5-186682 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] However, the cyclic olefin resins disclosed in Patent Document 1 have a rigid and brittle skeleton. Furthermore, the compatibility between polyphenylene ether resins and cyclic olefin resins is low, resulting in resin compositions with low mechanical properties such as impact resistance. In particular, when using cyclic olefin resins with high heat resistance and a glass transition temperature of 130°C or higher, the mechanical properties tend to decrease further.

[0012] Furthermore, while the resin composition described in Patent Document 2 exhibits excellent impact resistance, its heat resistance and molding flowability are insufficient, leaving room for improvement. Additionally, cyclic olefin resins with aromatic substituents lack sufficient oil resistance to organic solvents such as toluene and greases such as lubricating oils; therefore, resin compositions blended with polyphenylene ether resins suffer from insufficient oil resistance.

[0013] As mentioned above, resin compositions made by blending cyclic olefin resins into polyphenylene ether resins suffer from insufficient balance in terms of heat resistance, impact resistance, molding flowability, and oil resistance. Therefore, they are difficult to use in applications requiring both heat resistance and impact resistance, such as components for electrical / electronic devices (MIDs, which are circuit components formed by forming electrical circuits or electrodes on the surface of a resin molded article).

[0014] Such components are exposed to high temperatures due to heat generated by electronic devices, etc., and therefore require high heat resistance.

[0015] In addition, from the perspective of extending the product's lifespan, the impact resistance of the resin itself, which constitutes the components, plays an important role in resisting external impacts after installation. If the impact resistance is insufficient, cracks may occur, or the circuits formed on the resin surface may experience problems such as broken wires.

[0016] Furthermore, in components used in communication / electronic equipment, the increasing frequency of electromagnetic waves in recent years has led to a demand for excellent dielectric properties in the high-frequency region.

[0017] Furthermore, from the perspective of easily molding into the desired shape, it is required that it can be molded by injection molding, and in order to manufacture parts with complex shapes, it is required that it has excellent molding flowability.

[0018] Therefore, the present invention was made in view of the above circumstances, and its object is to provide a polyphenylene ether resin composition with excellent balance of heat resistance, mechanical properties, dielectric properties, molding flowability and oil resistance.

[0019] In addition, the present invention aims to provide an injection molded article that can be suitably used as an electrical circuit component, electronic device housing, antenna component, antenna housing, etc., which uses a polyphenylene ether resin composition with excellent balance of heat resistance, mechanical properties, dielectric properties, molding flowability and oil resistance.

[0020] Methods for solving problems

[0021] In order to solve the above problems, the inventors conducted in-depth research and found that by blending a cyclic olefin resin with a specific glass transition temperature and a styrene thermoplastic elastomer with a specific molecular weight into a polyphenylene ether resin or a mixture of polyphenylene ether resin and styrene resin, a resin composition with excellent balance of heat resistance, mechanical properties, dielectric properties, molding flowability and oil resistance can be obtained, thus completing the present invention.

[0022] This invention is based on the above-mentioned technical concept, and its key points are as follows. [1]

[0024] A polyphenylene ether-based resin composition, which is a thermoplastic resin composition, comprising:

[0025] (A) Polyphenylene ether resin, or a mixture of polyphenylene ether resin and styrene resin;

[0026] (B) Cyclic olefin resins that do not have either an aryl or an aralkyl group; and

[0027] (C) Styrene-based thermoplastic elastomers,

[0028] The composition is characterized in that,

[0029] The glass transition temperature of component (B) above is 105°C or higher.

[0030] The weight-average molecular weight of component (C) above is 50,000 to 220,000. [2]

[0032] The polyphenylene ether resin composition as described in [1] above is characterized in that,

[0033] The mass ratio ((A) / (B)) of the content of component (A) to the content of component (B) is 98 / 2 to 40 / 60, and

[0034] The mass ratio of the total content of component (A) and component (B) to the content of component (C) (((A)+(B)) / (C)) is 98 / 2 to 75 / 25. [3]

[0036] The polyphenylene ether resin composition as described in [1] or [2] above is characterized in that the (B) component comprises at least one selected from the group consisting of an addition (co)polymer of a cyclic olefin represented by general formula [II], an addition copolymer of a cyclic olefin and an α-olefin represented by general formula [II], a ring-opening (co)polymer of a cyclic olefin represented by general formula [II] and its hydrides.

[0037] [Chemistry 1]

[0038]

[0039] (In general formula [II], R) 1 ~R 12 Each group can be the same or different, and can be selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, alkoxycarbonyl groups, alkenyl groups, alkynyl groups, and alkylidene groups. 9 With R 10 R 11 With R 12 They can be integrated to form a divalent hydrocarbon group, R 9 or R 10 With R 11 or R 12 They can form cycles. Additionally, n represents 0 or a positive integer; when n is 2 or greater, R... 5 ~R 8 Each repeating unit may be the same or different. [4]

[0041] The polyphenylene ether resin composition described in [3] above is characterized in that component (B) comprises an addition copolymer of ethylene and norbornene. [5]

[0043] The polyphenylene ether resin composition as described in any one of [1] to [4] above is characterized in that the glass transition temperature of component (B) is 155°C or higher. [6]

[0045] The polyphenylene ether resin composition as described in any one of [1] to [5] above is characterized in that the weight-average molecular weight of component (C) is 50,000 to 150,000. [7]

[0047] The polyphenylene ether resin composition as described in any one of [1] to [6] above is characterized in that the content of the blocks in component (C) above, which are mainly composed of structural units derived from aromatic vinyl compounds, is 30 to 50% by mass. [8]

[0049] The polyphenylene ether resin composition as described in any one of [1] to [7] above is characterized in that it is manufactured by melt mixing. [9]

[0051] The polyphenylene ether resin composition as described in any one of [1] to [8] above is characterized in that the weight-average molecular weight of component (A) is 35,000 to 60,000.

[10]

[0053] The polyphenylene ether resin composition as described in any one of [1] to [9] above is characterized in that,

[0054] According to ISO 1133, the melt flow rate at 300℃ and a load of 5.00 kg is greater than 10 g / 10 min.

[0055] According to ISO 75, the load deformation temperature under 1.80 MPa conditions is above 125℃.

[0056] The Chevalier impact strength, as measured according to ISO 179 / 1eA, is 20 kJ / m. 2 above,

[0057] The dielectric loss tangent at 1.1 GHz, as measured by the resonator method, is below 0.001.

[11]

[0059] An injection-molded article, characterized in that it comprises the polyphenylene ether resin composition described in any one of [1] to

[10] above.

[12]

[0061] An electronic component, characterized in that it has the injection-molded body described in

[11] above.

[13]

[0063] An antenna component, characterized in that it has the injection-molded body described in

[11] above.

[0064] The effects of the invention

[0065] According to the present invention, a polyphenylene ether resin composition with excellent balance of heat resistance, mechanical properties, dielectric properties, molding flowability and oil resistance can be provided.

[0066] Furthermore, according to the present invention, injection-molded articles suitable for use as electrical circuit components, electronic device housings, antenna components, antenna housings, etc., can be provided. Detailed Implementation

[0067] The following provides a detailed description of specific embodiments of the present invention (hereinafter referred to as "this embodiment"). It should be noted that this embodiment is merely an illustration of the present invention, and the present invention is not limited to this embodiment. That is, the present invention can be modified in various ways without departing from its essential points.

[0068] <Polyphenylene ether resin composition>

[0069] The polyphenylene ether-based resin composition of this embodiment is a thermoplastic resin composition comprising the following components:

[0070] (A) Polyphenylene ether resin, or a mixture of polyphenylene ether resin and styrene resin.

[0071] (B) Cyclic olefin resins that do not contain aryl or aralkyl groups, and

[0072] (C) Styrene-based thermoplastic elastomers.

[0073] ((A) Polyphenylene ether resin, or a mixture of polyphenylene ether resin and styrene resin)

[0074] The polyphenylene ether resin composition of this embodiment includes (A) a polyphenylene ether resin, or a mixture of a polyphenylene ether resin and a styrene resin (hereinafter also referred to as "(A) component").

[0075] As the polyphenylene ether resin used in this embodiment, homopolymers and copolymers formed from structural units of the following general formula [I], as well as copolymers having structural units of the following general formula [I] and other structural units, may be used.

[0076] [Chemistry 2]

[0077]

[0078] (In general formula [Ⅰ], O is an oxygen atom, R) 1 ~R 4Each of the following groups is independently selected from: hydrogen atoms, halogen atoms, alkyl groups having 1 to 7 carbon atoms, cycloalkyl groups having 1 to 7 carbon atoms, phenyl groups (with or without substituted aromatic hydrocarbon groups), haloalkyl groups, aminoalkyl groups, hydroxyl groups, and halohydroxyl groups (where at least two carbon atoms separate the halogen atom from the oxygen atom).

[0079] Examples of polyphenylene ether resins used in this embodiment include, but are not limited to, homopolymers of poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), etc.; copolymers of 2,6-dimethylphenol with other phenols such as 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, and 3-methyl-6-tert-butylphenol.

[0080] Among these, from the perspective of the balance of mechanical properties and productivity, poly(2,6-dimethyl-1,4-phenylene ether), copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and 3-methyl-6-tert-butylphenol, or mixtures thereof are preferred.

[0081] It should be noted that, as a method for manufacturing the polyphenylene ether resin used in this embodiment, examples include, but are not limited to, known manufacturing methods described in, for example, U.S. Patent No. 3,306,874, U.S. Patent No. 3,306,875, U.S. Patent No. 3,257,357, and U.S. Patent No. 3,257,358, Japanese Patent Application Publication No. 50-51,197, Japanese Patent Application Publication No. 52-17,880, and Japanese Patent Application Publication No. 63-152,628.

[0082] In addition, the polyphenylene ether resin in this embodiment may include a modified polyphenylene ether resin.

[0083] The modified polyphenylene ether resin mentioned here refers to a polyphenylene ether resin in which a portion of the main chain and / or side chain is modified by using at least one functional group selected from the group consisting of carboxyl, anhydride, amino, hydroxyl and glycidyl groups.

[0084] From the perspective of adjusting the weight-average molecular weight of the polyphenylene ether resin after melt mixing to the range described later, the specific viscosity of the polyphenylene ether resin used in this embodiment is preferably in the range of 0.20 to 0.80 dL / g, more preferably 0.30 to 0.70 dL / g, and most preferably 0.35 to 0.55 dL / g.

[0085] It should be noted that the specific viscosity is a value obtained using an Ubbelohde viscometer for a 0.5 g / dL chloroform solution (30°C) through existing known methods.

[0086] Furthermore, in this embodiment, a substance made by blending two or more polyphenylene ether resins with different specific viscosities can also be preferably used.

[0087] Typically, polyphenylene ether resins undergo a molecular weight jump through melt mixing at approximately 300°C or higher. Therefore, unlike typical thermoplastic resins, their molecular weight can be significantly changed through melt mixing.

[0088] In this embodiment, the weight-average molecular weight of the polyphenylene ether resin in the polyphenylene ether resin composition, i.e., the weight-average molecular weight of the polyphenylene ether resin after melt mixing, is preferably in the range of 20,000 to 90,000, more preferably 30,000 to 80,000, and even more preferably 35,000 to 60,000. When the weight-average molecular weight of the polyphenylene ether resin after melt mixing is within the above range, a resin composition with excellent mechanical properties and, consequently, excellent balance between heat resistance and molding flowability can be obtained.

[0089] It should be noted that the weight-average molecular weight of the polyphenylene ether resin after melt mixing can be determined as follows: After separating the polyphenylene ether resin and other resin components in the polyphenylene ether resin composition using an appropriate organic solvent based on their solubility difference, the weight-average molecular weight is determined by gel permeation chromatography (mobile phase: chloroform, standard substance: polystyrene) using existing known methods.

[0090] In addition, in this embodiment, component (A) may also be a mixture of polyphenylene ether resin and styrene resin.

[0091] In this case, from the perspective of improving the heat resistance of the resin composition, the content of polyphenylene ether resin in the above-mentioned component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may also be 100% by mass, relative to 100% by mass of component (A).

[0092] The styrene-based resin used in this embodiment is a homopolymer or copolymer obtained by polymerizing a styrene-based compound, or a styrene-based compound and a compound capable of copolymerizing with a styrene-based compound, in the presence or absence of a rubbery polymer, excluding substances that fall within the scope of (C) styrene-based thermoplastic elastomers described later.

[0093] Examples of the aforementioned styrene compounds include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, etc., with styrene being preferred.

[0094] Examples of compounds capable of copolymerizing with the aforementioned styrene-based compounds include, but are not limited to, (meth)acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylonitrile, methyl maleate, ethyl maleate, (meth)acrylamide, and 2-hydroxyethyl (meth)acrylate. It should be noted that "(meth)acrylic acid" refers to "acrylic acid" or "methacrylic acid," "(meth)acryloyl" refers to "acryloyl" or "methacryloyl," and "(meth)acrylate" refers to "acrylate" or "methacrylate."

[0095] Regarding the amount of the compound that can copolymerize with the styrene-based compounds, it is preferably 20% by mass or less, more preferably 15% by mass or less, relative to 100% by mass of the total amount of the compound and the styrene-based compounds.

[0096] Examples of the aforementioned rubbery polymers include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Among these, polybutadiene, styrene-butadiene random copolymers, styrene-butadiene block copolymers, and rubber components formed by partially or substantially completely hydrogenating them (e.g., rubber components with a hydrogenation rate of 50 to 100%) are preferred.

[0097] It should be noted that the aforementioned styrene-based resins may include, but are not limited to, homopolymers with stereoregularity selected from atactic, syndiotactic, and isotactic structures, rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymers (AS resin), styrene-rubber polymer-acrylonitrile copolymers (ABS resin), and other styrene-based copolymers. Among these, from the perspective of compatibility with polyphenylene ether-based resins, homopolymers and rubber-modified polystyrene (HIPS) are preferred.

[0098] (B) Cyclic olefin resins)

[0099] In addition to component (A) described above, the polyphenylene ether resin composition of this embodiment also includes (B) a cyclic olefin resin that does not have an aryl or aralkyl group (hereinafter also referred to as "component (B)").

[0100] In this embodiment, the (B) component is not particularly limited as long as it is a resin that does not have an aryl or aralkyl group and has a cyclic olefin structure in its structure. Preferably, it includes at least one selected from the group consisting of an addition (co)polymer of a cyclic olefin represented by general formula [II], an addition copolymer of a cyclic olefin and an α-olefin represented by general formula [II], a ring-opening (co)polymer of a cyclic olefin represented by general formula [II], and their hydrides. It is particularly preferred that it includes an addition copolymer of ethylene and norbornene. It should be noted that "(co)polymer" means "polymer" or "copolymer".

[0101] [Chemistry 3]

[0102]

[0103] (In general formula [II], R) 1 ~R 12 Each group can be the same or different, and can be selected from the group consisting of hydrogen atoms, halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, alkoxycarbonyl groups, alkenyl groups, alkynyl groups, and alkylidene groups. 9 With R 10 R 11 With R 12 They can be integrated to form a divalent hydrocarbon group, R 9 or R 10 With R 11 or R 12 They can form cycles. Additionally, n represents 0 or a positive integer; when n is 2 or greater, R... 5 ~R 8 Each repeating unit may be the same or different.

[0104] Here, as R 1 ~R 8 Specific examples include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; and lower alkyl groups such as methyl, ethyl, propyl, and butyl. They can be different from each other, partially different, or completely the same.

[0105] Additionally, as R 9 ~R 12Specific examples include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, and stearyl; cycloalkyl groups such as cyclohexyl; alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and phenoxy; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, and propoxycarboxyl; alkenyl groups such as vinyl, allyl, propenyl, butenyl, and hexenyl; and alkynyl groups such as ethynyl, propynyl, butynyl, and hexynyl. From the perspective of dielectric properties and oil resistance, hydrogen atoms, fluorine atoms, alkyl groups, and cycloalkyl groups are preferred. Furthermore, these groups can be different individually, partially different, or all the same.

[0106] In addition, as R 9 With R 10 Or R 11 With R 12 Specific examples of the formation of divalent hydrocarbon groups through integration include alkylidenes such as ethoxylide, propionylide, and isopropionylide.

[0107] It should be noted that R 9 or R 10 With R 11 or R 12 When rings are formed, the resulting rings can be monocyclic or polycyclic, can be bridging polycyclic rings or rings with double bonds, or can be a combination of these rings. Furthermore, these rings can also have substituents such as methyl groups.

[0108] Specific examples of cyclic alkenes represented by general formula [II] include, but are not limited to, bicyclo[2.2.1]hept-2-ene (common name: norbornene), 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethimide-bicyclo[2.2.1]hept-2-ene, and 5-hexyl-bicyclo[2.2.1]hept-2-ene. Bicyclic cyclic alkenes such as hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methoxy-bicyclo[2.2.1]hept-2-ene, 5-methylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene, 5-ethynyl-bicyclo[2.2.1]hept-2-ene; tricyclic [4.3.0.1] 2,5 ] Dec-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 ] Dec-3-ene; Tricyclic [4.4.0.1 2,5Undecyl-3,7-diene or tricyclic [4.4.0.1] 2,5 Undecyl-3,8-diene or as a partial hydride of them (or an adduct of cyclopentadiene and cyclohexene) in tricyclic [4.4.0.1] 2,5 Undecyl-3-ene; tricyclic cyclic alkenes such as 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, and 5-cyclohexenylbicyclo[2.2.1]hept-2-ene; tetracyclic [4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene (also simply tetracyclic dodecylene), 8-methyltetracyclo[4.4.0.1] 2,5 .1 7,10 [Dodecyl-3-ene, 8-ethyltetracyclo[4.4.0.1]] 2,5 .1 7,10 [Dodecyl-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1]] 2,5 .1 7,10 [Dodecyl-3-ene, 8-methylenetetracyclo[4.4.0.1]] 2,5 .1 7,10 [Dodecyl-3-ene, 8-ethide tetracyclo[4.4.0.1]] 2,5 .1 7,10 [dodecyl-3-ene, 8-vinyltetracyclo[4,4.0.1]] 2,5 .1 7,10 [dodecyl-3-ene, 8-propenyl-tetracyclo[4.4.0.1]] 2,5 .1 7,10 Tetracyclic cyclic alkenes such as dodecyl-3-ene; 8-cyclopentyl-tetracyclic [4.4.0.1] 2,5 .1 7,10 [Dodecyl-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1]] 2,5 .1 7,10 [Dodecyl-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1]] 2,5 .1 7,10 [Dodecyl-3-ene, pentacyclic [6.6.1.1]] 3,6 .0 2,7 .0 9,14 ]-4-Hexadecene, Pentane [6.5.1.1 3,6 .0 2,7 .0 9,13 ]-4-Pentadecene, Pentane [7.4.0.0] 2,7 .1 3,6 .1 10,13 ]-4-pentadene; heptacyclic [8.7.0.1 2,9 .1 4,7.1 11,17 .0 3,8 .0 12,16 ]-5-Eicosene, heptacyclic [8.7.0.1 2,9 .0 3,8 .1 4,7 .0 12,17 .1 13,l6 14-eicosene; tetramers of cyclopentadiene and other polycyclic cyclic alkenes, etc.

[0109] These cyclic olefins can be used alone or in combination of two or more. Among them, from the perspective of ease of acquisition and processing, bicyclo[2.2.1]hept-2-ene (common name: norbornene) is preferred, but norbornene can also be used alone.

[0110] As the aforementioned α-olefins, α-olefins with 2 to 20 carbon atoms are preferred, but not limited to. Examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Furthermore, one α-olefin component may be used alone, or two or more may be used in combination.

[0111] Among these α-olefins, ethylene is preferred from the perspective of ease of acquisition and processing, but ethylene can also be used alone.

[0112] As specific examples of addition (co)polymers of cyclic olefins represented by general formula [II], addition (co)polymers of norbornene without substitution or with alkyl substitution having 1 to 20 carbon atoms, and addition (co)polymers of tetracyclododecene without substitution or with alkyl substitution having 1 to 20 carbon atoms are preferred, but not limited to.

[0113] As an addition copolymer of cyclic olefins and α-olefins represented by general formula [II], preferred, but not limited, is an addition copolymer of norbornene and ethylene with unsubstituted or alkyl-substituted carbon atoms of 1 to 20, or an addition copolymer of tetracyclododecene and ethylene with unsubstituted or alkyl-substituted carbon atoms of 1 to 20.

[0114] As the open-ring (co)polymer of cyclic olefins represented by general formula [II] and its hydrides, preferably, but not limited to, the hydrides of open-ring (co)polymers of norbornene without substitution or with alkyl substitution having 1 to 20 carbon atoms, and the hydrides of open-ring (co)polymers of tetracyclododecene without substitution or with alkyl substitution having 1 to 20 carbon atoms.

[0115] The copolymerization method of component (B) and the hydrogenation method of the resulting copolymer in this embodiment are not particularly limited, and can be carried out according to known methods. When component (B) is a copolymer, it can be random copolymer or block copolymer, and random copolymer is preferred.

[0116] There are no particular limitations on the polymerization catalyst used; known catalysts such as Ziegler-Natta catalysts, metathesis catalysts, and metallocene catalysts can be used. For example, metallocene catalysts are preferably used to produce addition copolymers of α-olefins and cyclic olefins.

[0117] Furthermore, ring-opening (co)polymers of cyclic olefins are preferably manufactured using metathesis catalysts. Additionally, from the perspective of thermal stability and dielectric properties, polymers obtained from metathesis catalysts are preferably hydrogenated using transition metal catalysts supported on inorganic supports.

[0118] Examples of metathesis catalysts include molybdenum or tungsten-based metathesis catalysts known for their role in the ring-opening polymerization of cyclic olefins (e.g., catalysts described in Japanese Patent Application Publication Nos. 58-127728 and 58-129013). Furthermore, the polymer obtained from the metathesis catalyst preferably utilizes a transition metal catalyst supported on an inorganic support to hydrogenate at least 90% of the double bonds in the main chain and at least 98% of the carbon-carbon double bonds in the aromatic rings of the side chains.

[0119] As a preferred component (B) in the resin composition of this embodiment, in addition to the cyclic olefin represented by general formula [II], other copolymerizable unsaturated monomer components may be included as needed, within a range that does not impair the purpose of this embodiment.

[0120] In addition, the glass transition temperature of component (B) used in this embodiment needs to be 105°C or higher, preferably 130°C or higher, and more preferably 155°C or higher.

[0121] By setting the glass transition temperature of component (B) to 105°C or higher, there is a tendency to improve the heat resistance of polyphenylene ether resin compositions.

[0122] It should be noted that there is no particular upper limit to the glass transition temperature of component (B), but it is preferably below 220°C. By setting the glass transition temperature of component (B) to below 220°C, there is a tendency to further improve the molding fluidity of the polyphenylene ether resin composition.

[0123] In this embodiment, because the glass transition temperature, mechanical properties, etc. can be easily adjusted by using the copolymerization ratio, component (B) is preferably an addition copolymer of α-olefin and cyclic olefin represented by general formula [ⅠⅠ].

[0124] Additionally, component (B) used in this embodiment may include a modified cyclic olefin resin grafted and / or copolymerized with an unsaturated compound having a polar group. Examples of polar groups include carboxyl groups, anhydride groups, epoxy groups, amide groups, ester groups, and hydroxyl groups. Examples of unsaturated compounds having polar groups include (meth)acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, methyl maleate, ethyl maleate, (meth)acrylamide, and 2-hydroxyethyl (meth)acrylate.

[0125] It should be noted that in this embodiment, component (B) can be used alone or in combination with two or more components.

[0126] Alternatively, commercially available resins may be used as component (B) in this embodiment. Examples of commercially available cyclic olefin resins include TOPAS (registered trademark, manufactured by TOPAS Advanced Polymers Co., Ltd.), APEL (registered trademark, manufactured by Mitsui Chemicals Co., Ltd.), ZEONEX (registered trademark, manufactured by Zeon Corporation of Japan), ZEONOR (registered trademark, manufactured by Zeon Corporation of Japan), and ARTON (registered trademark, manufactured by JSR Corporation).

[0127] Here, in the resin composition of this embodiment, the mass ratio ((A) / (B)) of component (A) to component (B) is preferably 98 / 2 to 2 / 98, more preferably 98 / 2 to 40 / 60, even more preferably 95 / 5 to 40 / 60, and particularly preferably 90 / 10 to 50 / 50. By mixing component (A) and component (B) in the above mass ratio, the resin composition tends to have better heat resistance and mechanical properties.

[0128] (C) Styrene-based thermoplastic elastomers

[0129] In addition to components (A) and (B) described above, the polyphenylene ether resin composition of this embodiment also contains (C) a styrene-based thermoplastic elastomer (hereinafter also referred to as "component (C)").

[0130] The component (C) in this embodiment is a non-hydrogenated block copolymer and / or a hydrogenated form of the block copolymer comprising at least one aromatic vinyl polymer block (X) based on structural units from an aromatic vinyl compound and at least one conjugated diene polymer block (Y) based on structural units from a conjugated diene compound, referring to a component containing styrene in the aforementioned aromatic vinyl compound.

[0131] It should be noted that the phrase "mainly composed of structural units derived from aromatic vinyl compounds" in the aforementioned aromatic vinyl polymer block (X) means that at least 50% by mass of the block is formed from structural units derived from aromatic vinyl compounds. More preferably, the percentage of structural units derived from aromatic vinyl compounds is 70% or more, further preferably 80% or more, and most preferably 90% or more.

[0132] There are no particular limitations on the aromatic vinyl compounds used to form the aromatic vinyl polymer block (X) described above. Examples include styrene, α-methylstyrene, vinyltoluene, etc., and one or more compounds selected from them can be used, with styrene being particularly preferred.

[0133] Furthermore, the phrase "mainly composed of structural units derived from conjugated diene compounds" in the aforementioned conjugated diene polymer block (Y) also refers to the fact that it is formed by structural units derived from conjugated diene compounds at a rate of 50% by mass or more. More preferably, the structural units derived from conjugated diene compounds are 70% by mass or more, further preferably 80% by mass or more, and most preferably 90% by mass or more.

[0134] There are no particular limitations on the conjugated diene compound used to form the conjugated diene polymer block (Y) described above. Examples include butadiene, isoprene, isoprene, 1,3-pentadiene, etc. One or more compounds selected from these compounds may be used, with butadiene, isoprene, and combinations thereof being preferred.

[0135] Furthermore, the aforementioned aromatic vinyl polymer block (X) can be, for example, a copolymer block in which a small amount of conjugated diene compound is randomly bonded within the aromatic vinyl polymer block. Similarly, in the case of the aforementioned conjugated diene polymer block, it can also be, for example, a copolymer block in which a small amount of aromatic vinyl compound is randomly bonded within the conjugated diene polymer block.

[0136] In the component (C) used in this embodiment, the aromatic vinyl polymer block (X) preferably contains 10 to 90% by mass in 100% by mass of component (C), more preferably 20 to 60% by mass, and most preferably 30 to 50% by mass.

[0137] The bonding mode of the aforementioned conjugated diene polymer block (Y) is not particularly limited and can be chosen arbitrarily. The vinyl binding amount (the proportion introduced by the 1,2-bonding and 3,4-bonding modes among the 1,2-bonding, 3,4-bonding, and 1,4-bonding modes of the conjugated diene compound) is preferably 2% to 90%. For example, when the conjugated diene compound is mainly composed of 1,3-butadiene, the vinyl binding amount is preferably 30% to 90%; when it is mainly composed of isoprene, the vinyl binding amount is preferably 2% to 80%. It should be noted that the vinyl binding amount can be determined using an infrared spectrophotometer or a nuclear magnetic resonance (NMR) apparatus.

[0138] In addition, component (C) used in this embodiment can be at least a portion of a hydrogenated block copolymer (hydrogenated block copolymer).

[0139] Here, a hydrogenated block copolymer refers to a copolymer in which the aliphatic double bonds of the polymer portion of the conjugated diene compound that may be included in the aromatic vinyl polymer block (X) and the polymer portion of the conjugated diene compound included in the conjugated diene polymer block (Y) are reduced by hydrogenation treatment of the aforementioned non-hydrogenated block copolymer. The hydrogenation rate of the hydrogenated block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more, relative to the total amount of aliphatic double bonds from the polymer portion of the conjugated diene compound.

[0140] In this embodiment, component (C) is preferably a block copolymer of aromatic vinyl polymer block (X) and conjugated diene polymer block (Y) having a combination form selected from XY type, XYX type, and XYXY type. Block copolymers with different combination forms may also be used in combination. Among these, a combination form selected from XYX type and XYXY type is more preferred, and a combination form of XYX type is even more preferred.

[0141] There are no particular limitations on the specific examples of component (C) used in this embodiment, and examples include styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, styrene-isoprene-styrene block copolymer, styrene-(ethylene-butene) block copolymer, styrene-(ethylene-butene)-styrene block copolymer, styrene-(ethylene-propylene) block copolymer, styrene-(ethylene-propylene)-styrene block copolymer, styrene-(ethylene-ethylene-propylene)-styrene block copolymer, etc.

[0142] In this embodiment, the weight-average molecular weight of component (C) is 50,000 to 220,000. When the weight-average molecular weight is within this range, the compatibility between component (A) and component (B) is improved, and a resin composition with excellent balance of heat resistance, mechanical properties, and molding flowability, especially with significantly improved impact resistance, can be obtained.

[0143] Similarly, the weight-average molecular weight of component (C) is preferably 50,000 to 200,000, more preferably 50,000 to 150,000, and most preferably 50,000 to 100,000. It should be noted that the weight-average molecular weight of component (C) can be determined using gel permeation chromatography (mobile phase: chloroform, standard substance: polystyrene) by existing known methods.

[0144] For component (C) that can be used in this embodiment, as long as it does not violate the purpose of this embodiment, two or more substances can be mixed, such as substances with different binding forms, substances with different types of aromatic vinyl compounds, substances with different types of conjugated diene compounds, substances with different amounts of vinyl compounds, substances with different contents of aromatic vinyl compounds, and substances with different hydrogenation rates.

[0145] Alternatively, component (C) used in this embodiment can also be a modified block copolymer.

[0146] The modified block copolymers referred to herein are block copolymers formed by modifying a portion of the main chain and / or side chain of a block copolymer using at least one functional group selected from the group consisting of carboxyl, anhydride, amino, hydroxyl and glycidyl groups.

[0147] As a method for manufacturing the modified block copolymer described above, examples include (1) a method of reacting the block copolymer and the modified compound by melt mixing in a temperature range of 250°C above and below the softening point of the block copolymer, with or without a free radical initiator; (2) a method of reacting the block copolymer and the modified compound in solution at a temperature below the softening point of the block copolymer; (3) a method of reacting the block copolymer and the modified compound at a temperature below the softening point of the block copolymer without melting; etc. Any of these methods can be used, with method (1) being preferred. Furthermore, in (1), the method carried out in the presence of a free radical initiator is most preferred.

[0148] Furthermore, the mass ratio of the total content of component (A) and component (B) to the content of component (C) in the polyphenylene ether resin composition of this embodiment (((A)+(B)) / (C)) is preferably 98 / 2 to 75 / 25, more preferably 95 / 5 to 80 / 20, and even more preferably 95 / 5 to 85 / 15.

[0149] When the mass ratio of the total content of component (A) and component (B) to the content of component (C) is within the above range, a resin composition with excellent balance of heat resistance, mechanical properties and molding flowability can be obtained.

[0150] (Other ingredients)

[0151] In the polyphenylene ether resin composition of this embodiment, in addition to components (A), (B) and (C) above, other thermoplastic resins, thermoplastic elastomers other than styrene-based thermoplastic elastomers, inorganic fillers, colorants, flame retardants, other additives, etc. (hereinafter collectively referred to as "other components") may be included, without impairing the effects of this embodiment.

[0152] The preferred content of the other components mentioned above is not particularly limited. When the total content of the polyphenylene ether resin composition of this embodiment is 100% by mass, the content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. It can also be 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, 1% by mass or less, or even 0% by mass.

[0153] Examples of other thermoplastic resins mentioned above include polyphenylene sulfide, polyethersulfone, polysulfone, polycarbonate, polyacetal, etc.; polyester resins such as liquid crystal polymers, aromatic polyesters, polyarylates, polyethylene terephthalate, and polybutylene terephthalate; polyolefin resins such as polyethylene, polypropylene, α-olefin copolymers, and polymethylpentene; polyamide resins such as nylon 6, nylon 66, and aromatic nylon; and acrylic resins such as polymethyl methacrylate. Other thermoplastic resins do not include thermoplastic elastomers.

[0154] Examples of thermoplastic elastomers other than styrene-based thermoplastic elastomers include urethane-based, polyester-based, polyamide-based, fluorinated, vinyl chloride-based, polyolefin-based, polybutadiene-based, polyisoprene-based, and polyethylene-based thermoplastic elastomers. These thermoplastic elastomers can be used alone or in combination of two or more.

[0155] By adding inorganic fillers as the other components mentioned above, the heat resistance, mechanical properties, and dimensional stability of the polyphenylene ether resin composition of this embodiment can be improved.

[0156] Examples of inorganic fillers include glass fibers, potassium titanate fibers, barium titanate fibers, gypsum fibers, brass fibers, ceramic fibers, boron whisker fibers, mica, talc, silicon dioxide, calcium carbonate, kaolin, calcined kaolin, wollastonite, diaspore, apatite, glass beads, hollow glass beads, glass flakes, and other fibrous, needle-like, granular, spherical, hollow, or plate-like inorganic reinforcing materials. Two or more of these inorganic fillers can be used in combination. Alternatively, inorganic fillers can be substances that have undergone surface treatment using known methods with surface treatment agents such as silane coupling agents.

[0157] There are no particular limitations on the aforementioned coloring agents; for example, one or more coloring agents selected from known organic dyes / pigments and inorganic pigments may be used.

[0158] Examples of the aforementioned organic dyes / pigments include azo lake dyes / pigments, benzimidazolone dyes / pigments, benzidine dyes / pigments, condensed azo dyes / pigments, phthalocyanine blue, phthalocyanine green, isoindolineone dyes / pigments, quinolineone dyes / pigments, quinacridone dyes / pigments, perylene dyes / pigments, anthraquinone dyes / pigments, violet ketone dyes / pigments, dioxazine violet, azazine dyes / pigments, and carbon black.

[0159] Examples of inorganic pigments mentioned above include metal oxides such as titanium oxide, zinc oxide, and chromium oxide, as well as composite metal oxides such as titanium yellow, cobalt blue, and ultramarine.

[0160] Examples of flame retardants include phosphate ester compounds, phosphinates, phosphazenes, hydrated metal compounds, and silicones, with phosphate ester compounds and phosphinates being preferred.

[0161] Examples of the aforementioned phosphate ester compounds include monophosphates such as triphenyl phosphate, tricresyl phosphate, diphenyltoluene phosphate, and tri(xylene) phosphate; condensed phosphates such as resorcinol bis(xylene) phosphate, resorcinol bis(di(xylene)) phosphate, biphenyl bis(xylene) phosphate, bisphenol A bis(xylene) phosphate, and bisphenol A bis(xylene) phosphate; and so on. Among these, condensed phosphates are preferred due to their low gas generation during processing and excellent thermal stability.

[0162] Examples of the aforementioned phosphines include calcium dimethylphosphines, aluminum dimethylphosphines, zinc dimethylphosphines, calcium ethylmethylphosphines, aluminum ethylmethylphosphines, zinc ethylmethylphosphines, calcium diethylphosphines, aluminum diethylphosphines, and zinc diethylphosphines.

[0163] The above flame retardants can be used in one or in combination of two or more.

[0164] In addition to the above-mentioned components, other ingredients may also include organic or metallic heat stabilizers (antioxidants), ultraviolet absorbers, light stabilizers, anti-dripping agents, plasticizers, flow improvers, lubricants, crystal nucleating agents, release agents, anti-blocking agents, antistatic agents, spreading agents, etc., as other additives.

[0165] Additionally, it may contain various laser direct forming (LDS) additives such as copper-chromium composite oxide, copper-chromium-manganese composite oxide, and copper-manganese-iron composite oxide. The polyphenylene ether resin composition of this embodiment containing LDS additives can be suitably used in MID (molded circuit components), etc.

[0166] The polyphenylene ether resin composition of this embodiment is characterized by its particularly excellent balance of molding flowability, heat resistance, mechanical properties, and dielectric properties. More specifically, the polyphenylene ether resin composition of this embodiment satisfies the conditions of each of the following properties (1) to (4).

[0167] (1) Melt Flow Rate (MFR)

[0168] The melt flow rate (MFR) of the polyphenylene ether resin composition of this embodiment, measured according to ISO 1133 at a temperature of 300°C and a load of 5.00 kg, is preferably 10 g / 10 min or more, more preferably 15 g / 10 min or more, and even more preferably 20 g / 10 min or more.

[0169] MFR is one of the indicators of the molding flowability of a resin composition. When the MFR is low, it tends to be difficult to obtain molded parts with complex shapes by injection molding.

[0170] (2) Load Deformation Temperature (DTUL)

[0171] The polyphenylene ether resin composition of this embodiment preferably has a load deflection temperature (DTUL) of 120°C or higher, more preferably 130°C or higher, and even more preferably 140°C or higher, when measured by the flat tensile method under a load of 1.80 MPa according to ISO 75-1 and 75-2. DTUL is one of the indicators of the heat resistance of the resin composition. When the DTUL is low, it tends to soften or deform easily due to heat during use.

[0172] (3) Impact strength

[0173] The polyphenylene ether resin composition of this embodiment preferably has a Chebel impact strength of 20 kJ / m² when measured according to ISO 179 / 1eA. 2 The above, and more preferably 25 kJ / m 2 The above, and more preferably 30 kJ / m 2 The above. Chappey impact strength is one of the indicators of the impact resistance of a resin composition. When the Chappey impact strength is low, the molded part is prone to breakage during assembly or breakage due to impact during use.

[0174] (4) Dielectric loss tangent

[0175] The dielectric loss tangent of the polyphenylene ether resin composition of this embodiment, as measured by the resonator method at 1.1 GHz, is preferably 0.001 or less. The dielectric loss tangent is one of the indicators representing the energy loss when an alternating electric field is applied to a dielectric. The larger the dielectric loss tangent of the resin composition, the greater the energy loss from the electric field. In particular, the higher the frequency of the electric field, the stronger the influence of dielectric loss; therefore, lower dielectric loss of the resin composition used in high-frequency communication devices is preferred.

[0176] <Method for manufacturing polyphenylene ether resin compositions>

[0177] The method for manufacturing the polyphenylene ether resin composition of this embodiment is not particularly limited, and it can be manufactured by melt-blending the above-mentioned components (A), (B) and (C), and other components as necessary.

[0178] There are no particular limitations on the melt mixing machine used for melt mixing. Examples include single-screw extruders, twin-screw extruders (including twin-screw extruders), and heated melt mixing machines that utilize rollers, kneaders, Brayburn plasticizers, and Banbury mixers. Among these, a twin-screw extruder is preferred from the perspective of mixability. Examples of such twin-screw extruders include the ZSK series manufactured by WERNER & PFLEIDERER, the TEM series manufactured by TOSHIBA MACHINE CO.,LTD, and the TEX series manufactured by Nippon Steel Corporation.

[0179] One specific method for manufacturing the polyphenylene ether resin composition of this embodiment using a twin-screw extruder is, for example, the following melt-blending method: Each component is supplied to the first feed port of the twin-screw extruder, the heating and melting zone is set above the melting temperature of the thermoplastic resin, and melt-blending is performed at a screw speed of 100–1200 rpm, preferably 200–500 rpm. Furthermore, regarding the location of supplying each component to the twin-screw extruder, as described above, it can be supplied uniformly from the first feed port of the extruder, or it can be supplied separately by providing a second, third, and fourth feed port.

[0180] Furthermore, to reduce the formation of crosslinks or carbides in the resin due to the thermal history of oxygen, it is preferable to maintain the oxygen concentration in each process line at less than 1.0% by volume during the addition path of each raw material to the extruder. The addition path is not particularly limited, but a specific example is a configuration consisting of piping, a weight-type feeder with a replenishment tank, piping, a feed hopper, and a twin-screw extruder, arranged sequentially from the storage tank. The method for maintaining such a low oxygen concentration is not particularly limited; introducing an inert gas into each process line with improved airtightness is effective. Generally, introducing nitrogen is preferred to maintain the oxygen concentration at less than 1.0% by volume.

[0181] <Injection molded parts, electronic components, antenna components>

[0182] The injection-molded article of this embodiment comprises the polyphenylene ether resin composition of this embodiment described above. The manufacturing method of the injection-molded article of this embodiment is not particularly limited except for the use of injection molding.

[0183] Furthermore, the injection-molded articles of this embodiment exhibit particularly excellent balance in heat resistance, mechanical properties, and dielectric properties, thus making them suitable for use as electronic components and antenna components. The electronic components and antenna components may have one or more injection-molded articles as described above. The electronic components and antenna components may also have a structure formed by the interlocking of multiple molded articles.

[0184] Example

[0185] The present invention is illustrated by specific embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0186] [Composition of each sample]

[0187] The components contained in each sample of the Examples and Comparative Examples are shown below.

[0188] (A) Polyphenylene ether resin, or a mixture of polyphenylene ether resin and styrene resin.

[0189] (A-1) Specific viscosity (0.5 g / dL chloroform solution, 30°C, measured using an Ubbelohde viscometer): 0.52 dL / g of poly(2,6-dimethyl-1,4-phenylene ether).

[0190] (A-2) Specific viscosity (measured in the same manner as (A-1) above): 0.40 dL / g of poly(2,6-dimethyl-1,4-phenylene ether)

[0191] (A-3) Randomized homopolymer styrene (trade name: 685, manufactured by PS Japan)

[0192] (B) Cyclic olefin resins

[0193] (B-1) Glass transition temperature (Tg): 178℃ for ethylene-norbornene addition copolymer (trade name: TOPAS6017S-04, manufactured by TOPAS Advanced Polymers).

[0194] (B-2) Glass transition temperature (Tg): 138℃ for ethylene-norbornene addition copolymer (trade name: TOPAS6013S-04, manufactured by TOPAS Advanced Polymers).

[0195] (B-3) Glass transition temperature (Tg): 136℃ cyclic olefin ring-opening polymer hydride (trade name: ZEONOR1420R, manufactured by ZEON Corporation, Japan)

[0196] (C) Styrene-based thermoplastic elastomers

[0197] (C-1) Styrene-(ethylene-butene)-styrene block copolymer (SEBS) with 42% by mass, number average molecular weight: 66,000, and weight average molecular weight: 72,000.

[0198] (C-2) Styrene-(ethylene-butene)-styrene block copolymer (SEBS) with styrene as the main component: 15% by weight, number average molecular weight: 166,000, weight average molecular weight: 204,000

[0199] (C-3) Styrene-(ethylene-ethylene-propylene)-styrene block copolymer (SEEPS) with styrene as the main component: 30% by weight, number average molecular weight: 87,000, weight average molecular weight: 92,000

[0200] (C-4) Styrene-(ethylene-ethylene-propylene)-styrene copolymer (SEEPS) with styrene as the main component: 32% by weight, number average molecular weight: 140,000, weight average molecular weight: 158,000

[0201] (C'-5) Styrene-(ethylene-butene)-styrene block copolymer (SEBS) with styrene as the main component: 32% by weight, number average molecular weight: 235,000, weight average molecular weight: 259,000

[0202] (C'-6) Styrene-(ethylene-ethylene-propylene)-styrene copolymer (SEEPS) with 30% by weight of styrene-based blocks, number-average molecular weight of 221,000, and weight-average molecular weight of 291,000.

[0203] It should be noted that the molecular weight of component (C) was determined using gel permeation chromatography (model: LC2030S, manufactured by Shimadzu Corporation), with a calibration curve prepared using the following standard polystyrene, and the determination was performed under the following conditions using this calibration curve.

[0204] Molecular weights of standard polystyrene: 3,650,000, 2,170,000, 1,090,000, 681,000, 204,000, 52,000, 30,200, 13,800, 3,360, 1,300, 550

[0205] Column: Use two K-805L (manufactured by Showa Denko) wires connected in series.

[0206] Solvent: Chloroform

[0207] Flow rate: 1.0 mL / min

[0208] Column temperature: 40℃

[0209] Detection wavelength: 254nm

[0210] Based on the above determination conditions, the number-average molecular weight and weight-average molecular weight are calculated from the proportion of peak areas of the curve representing the molecular weight distribution obtained by gel permeation chromatography.

[0211] [Examples 1-10, Comparative Examples 1-7]

[0212] Samples of resin compositions comprising the components (A) to (C) of the examples and comparative examples were prepared.

[0213] A twin-screw extruder (model: ZSK-25, manufactured by WERNER & PFLEIDERER) was used as the apparatus for manufacturing the resin composition. Regarding the flow direction of the raw materials, the first raw material supply port, the first kneading section, the second kneading section, the third kneading section, and the first vacuum exhaust port were sequentially arranged from the upstream side. In the twin-screw extruder configured as described above, components (A), (B), and (C) were supplied according to the compositions shown in Table 1. Melt mixing was performed under conditions of an extruder barrel temperature of 280°C, a screw speed of 200 rpm, and a discharge rate of 10 kg / h to produce granules of the resin composition.

[0214] [evaluate]

[0215] The resin compositions of each sample obtained by the above method were evaluated as follows.

[0216] (1) Melt Flow Rate (MFR)

[0217] After drying the resin composition granules of each sample at 80°C for 2 hours, the melt flow rate (MFR) was determined using a semi-automatic melt flow index tester (model: 2A, manufactured by Toyo Seiki Co., Ltd.) according to ISO 1133. It should be noted that the test conditions were a temperature of 300°C and a load of 5.00 kg.

[0218] The evaluation results are shown in Table 1. It should be noted that the higher the MFR value, the better the molding flowability.

[0219] (2) Weight-average molecular weight of polyphenylene ether resins

[0220] Regarding the weight-average molecular weight of the polyphenylene ether resin in the granules of the resin composition for each sample, the polyphenylene ether resin in the resin composition was separated using cold chloroform (-15°C), and after drying under reduced pressure, the sample was determined using gel permeation chromatography. It should be noted that, except that the detection wavelength was set to 283 nm, the calculation was performed using the same method as described in component (C) above.

[0221] The measurement results are shown in Table 1.

[0222] (3) Load Deformation Temperature (DTUL)

[0223] After drying the resin composition granules of each sample at 80°C for 2 hours, they were fed into an injection molding machine (model: IS100GN, manufactured by TOSHIBA MACHINE) with the barrel temperature set to 280-300°C. A multi-purpose test piece of JIS K7139 type A1 was formed according to JIS K7152-1 and K7313-2 at a mold temperature of 80°C. A strip-shaped test piece of type B2 was then cut from the central parallel section of this test piece using an automatic cutting machine (model: Notching Tool A-3, manufactured by Toyo Seiki Co., Ltd.). The DTUL was determined using a fully automatic HDT testing device (model: 6A-2, manufactured by Toyo Seiki Co., Ltd., heat medium: silicone oil) according to ISO 75-1 and 75-2, under a load of 1.80 MPa, using the flat tensile method.

[0224] The test results are shown in Table 1. It should be noted that the DTUL value is calculated as the average of the three test pieces. The higher the value, the better the heat resistance.

[0225] (4) Impact strength

[0226] Using the same automatic cutting machine as described in (3) above, notched test pieces were prepared from the multipurpose test pieces obtained in (3) above, in accordance with JIS K7111-1. The chevron impact strength was determined in an atmosphere of 23°C × 50% RH using a digital chevron impact testing machine (model: DG-CB, manufactured by Toyo Seiki Co., Ltd.) in accordance with ISO 179 / 1eA.

[0227] Let the impact strength of the test specimens be the average value of the five specimens (kJ / m). 2 The values ​​are shown in Table 1. The higher the impact strength value, the better the impact resistance. If the sample is not damaged when measured with a 4J hammer, it is denoted as NB.

[0228] (5) Tensile strength

[0229] Using the multi-purpose test piece obtained in (3) above, a tensile test was conducted at a tensile speed of 50 mm / min according to ISO 527-1 and 527-2 under an atmosphere of 23℃×50%RH, using a fully automatic tensile testing machine (model: AG-X, manufactured by Shimadzu Corporation) to evaluate the tensile strength.

[0230] The tensile strength is defined as the average value (MPa) of the five test specimens, as shown in Table 1. A higher tensile strength value indicates a better overall performance.

[0231] (6) Bending strength - bending modulus

[0232] Using the long strip test piece of type B2 obtained in (3) above, the bending strength and bending modulus were evaluated by using a fully automatic bending testing machine (model: Bendograph B-2, manufactured by Toyo Seiki Co., Ltd.) at a test speed of 2 mm / min according to ISO178 under an atmosphere of 23℃×50%RH.

[0233] The flexural strength and flexural modulus are set as the average values ​​(MPa) of the three test specimens, and are shown in Table 1. Higher values ​​for flexural strength and flexural modulus indicate better performance.

[0234] (7) Dielectric constant - dielectric loss tangent

[0235] After drying the resin composition granules of each sample at 80°C for 2 hours, they were fed into an injection molding machine (model: SE180EV-HP, manufactured by Sumitomo Heavy Industries, Ltd.) with a barrel temperature set at 320°C. Flat test pieces of 150×150×2mm were produced at a mold temperature of 130°C. The test pieces were then left to stand at 23°C and 50% RH for at least 24 hours. The dielectric constant-dielectric loss tangent was then measured using a network analyzer (model: N5224B, manufactured by Keysight Technologies) under the following conditions at 23°C and 50% RH. The dielectric constant-dielectric loss tangent was calculated from the average of the three test pieces; lower values ​​indicated better dielectric properties.

[0236] Resonator: Split Post dielectric resonator (Model: N1501AE19, manufactured by Keysight Technologies)

[0237] Frequency: 1.1GHz

[0238] (8) Oil resistance

[0239] The resin composition granules for each sample were dried at 80°C for 2 hours and then fed into an injection molding machine (model: EC75SXIII, manufactured by TOSHIBA MACHINE) with a barrel temperature set to 300°C. A 70mm × 70mm × 3mm plate was formed at a mold temperature of 80°C. A strip shape (70mm × 12.5mm × 3mm) was cut from this plate, with its length perpendicular to the flow direction. The strip was then mounted using a fixture, ensuring no gaps between the rod and the strip. The strip was shaped as follows: x-axis horizontal, y-axis vertical, with a vertical cross-section formed by y... 2The parabola represented by the equation 6x (x≧0, y≧0) is on the curved surface of the bending member. Furthermore, in the bending member, the position where x=0, y=0 on its vertical section is used as the placement position of the starting end of the test piece, and the position where x>0 and y>0 is used as the placement position of the ending end of the test piece.

[0240] After mounting the test piece onto the bending member as described above, apply processing oil G-6280 (made by Japanese processing oil) to the surface of the test piece and place it at 40°C for 24 hours. After 24 hours, if cracks appear on the surface of the test piece, record the critical position where the cracks occur (the position where the x-value of the bending member is the largest in the x-axis direction). It should be noted that cracks refer to flow-direction cracks larger than 200 μm observed when the surface of the test piece is examined under a microscope.

[0241] When reading the critical position where a crack occurs, the x-axis coordinate scale of the bending member is transferred to the test piece while it is installed in the bending member. After removing the test piece from the bending member, the presence of the crack is confirmed, and the location of the crack is compared with the transferred scale and read (since the critical position is the position corresponding to the x-axis coordinate of the bending member, it is not the circumferential length of the test piece).

[0242] The critical deformation (%) is calculated using the following formula based on the thickness of the test piece and the critical location where cracks occur. When the critical deformation is above 0.5%, the oil resistance is considered good.

[0243] Critical deformation (%) = d × 3 1 / 2 / 2(3+2x) 3 / 2 ×100

[0244] d: Thickness of the test piece (inches)

[0245] x: Crack stop position (inches)

[0246]

[0247] As shown in Table 1, compared with the resin compositions of the comparative examples, the resin compositions of the examples have significantly improved impact resistance, and also exhibit excellent balance in heat resistance, mechanical properties, dielectric properties, molding flowability, and oil resistance.

[0248] Industrial applicability

[0249] The polyphenylene ether resin composition of the present invention exhibits excellent balance in heat resistance, mechanical properties, dielectric properties, molding flowability, and oil resistance. Therefore, it can be suitable for use as components in automotive parts, electrical / electronic equipment parts, industrial parts, household electrical products, etc. In particular, due to its excellent heat resistance and dielectric properties, it can be suitable for use as components in high-frequency communication / electronic equipment; specifically, it can be used in housings, antennas, connectors, switches, filters, converters, couplers, circulating fans, isolators, capacitors, inductors, coils, resonators, FPCs, etc.

Claims

1. A polyphenylene ether-based resin composition, which is a thermoplastic resin composition, comprising: (A) Polyphenylene ether resin, or a mixture of polyphenylene ether resin and styrene resin; (B) Cyclic olefin resins that do not have either an aryl or an aralkyl group; and (C) Styrene-based thermoplastic elastomers, The composition is characterized in that, The polyphenylene ether resin after melt mixing has a weight-average molecular weight of 20,000 to 90,000. The glass transition temperature of component (B) is above 105°C. The weight-average molecular weight of component (C) is 50,000 to 220,000. The mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 98 / 2 to 40 / 60, and The mass ratio of the total content of component (A) and component (B) to the content of component (C) ((A)+(B)) / (C) is 98 / 2 to 75 / 25. The (B) component comprises at least one selected from the group consisting of addition polymers of cyclic olefins represented by general formula [II], addition copolymers of cyclic olefins and α-olefins represented by general formula [II], ring-opening polymers of cyclic olefins represented by general formula [II], and their hydrides. [Chemistry 1] In general formula [II], R 1 ~R 12 Whether they are the same or different, they are selected from the group consisting of hydrogen atoms, halogen atoms, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkenyl, alkynyl, and alkylidene groups, R 9 With R 10 R 11 With R 12 They can be integrated to form a divalent hydrocarbon group, R 9 or R 10 With R 11 or R 12 They can form cycles; additionally, n represents 0 or a positive integer, and when n is 2 or more, R 5 ~R 8 Each repeating unit may be the same or different.

2. The polyphenylene ether-based resin composition according to claim 1, characterized in that, said R 1 ~R 8 is selected from the group consisting of a hydrogen atom, fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, The R 9 ~R 12 The group consisting of hydrogen atom, fluorine, chlorine, bromine, methyl, ethyl, propyl, butyl, hexyl, stearyl, cyclohexyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, methoxycarbonyl, ethoxycarbonyl, propoxycarboxyl, vinyl, allyl, propenyl, butenyl, hexenyl, ethynyl, propynyl, butynyl, and hexynyl.

3. The polyphenylene ether-based resin composition according to Claim 1, wherein The α-olefin is an α-olefin with 2 to 20 carbon atoms.

4. The polyphenylene ether-based resin composition according to Claim 1, wherein Component (B) comprises an addition copolymer of ethylene and norbornene.

5. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, The glass transition temperature of component (B) is above 155°C.

6. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, The weight-average molecular weight of component (C) is 50,000 to 150,000.

7. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, The content of the blocks in component (C) that are mainly composed of structural units derived from aromatic vinyl compounds is 30% to 50% by mass, and more than 50% by mass of the blocks that are mainly composed of structural units derived from aromatic vinyl compounds are formed from structural units derived from aromatic vinyl compounds.

8. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, It is manufactured through melt mixing.

9. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, The weight-average molecular weight of component (A) is 35,000 to 60,000.

10. The polyphenylene ether resin composition according to any one of claims 1 to 4, characterized in that, According to ISO 1133, the melt flow rate at 300℃ and a load of 5.00 kg is greater than 10 g / 10 min. According to ISO 75, the load deformation temperature under 1.80 MPa conditions is above 125℃. Charpy impact strength of 20 kJ / m determined according to ISO 179 / 1 eA 2 The above, The dielectric loss tangent at 1.1 GHz, as measured by the resonator method, is below 0.

001.

11. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, The content of polyphenylene ether resin in component (A) is 70% or more, relative to 100% by mass of component (A).

12. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, The glass transition temperature of component (B) is above 130°C and below 220°C.

13. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, wherein The mass ratio (A) / (B) of the content of component (A) to the content of component (B) is 90 / 10 to 50 / 50.

14. The polyphenylene ether-based resin composition according to any one of claims 1 to 4, characterized by, The mass ratio of the total content of component (A) and component (B) to the content of component (C) ((A)+(B)) / (C) is 95 / 5 to 80 / 20.

15. An injection molded body characterized by, It comprises the polyphenylene ether resin composition according to any one of claims 1 to 14.

16. An electronic component, characterized by It has the injection-molded body as described in claim 15.

17. An antenna structure, characterized by It has the injection-molded body as described in claim 15.

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