Fiber-reinforced thermoplastic resin composition and resin-metal composite

Abstract

This fiber-reinforced thermoplastic resin composition comprises a thermoplastic resin composition (T) and a glass fiber (G) having a flat-shaped cross section, wherein: the thermoplastic resin composition (T) contains 100 parts by mass of a styrene-based resin composition (S) having a specific constitution and 0.6-2.0 parts by mass of a crystal nucleating agent (C); and the content of the glass fiber (G) is 33.0-65.0 mass% with respect to the total amount of the thermoplastic resin composition (T) and the glass fiber (G). Moreover, this resin-metal composite comprises: a resin member composed of a reinforced thermoplastic resin composition containing a thermoplastic resin composition (T2) and a glass filler (G2); and a metal member, wherein the difference between the linear expansion coefficient of the resin member in TD and the linear expansion coefficient of the metal member is at most 6.0×10-5 / ºC, and the bending fracture strain of a parallel flow weld test piece composed of the reinforced thermoplastic resin composition is at least 1.15%.

Description

Fiber-reinforced thermoplastic resin composition and resin-metal composite

[0001] The present invention relates to a fiber-reinforced thermoplastic resin composition and a reflow-resistant resin material comprising the resin composition, more particularly to a syndiotactic polystyrene resin composition and a reflow-resistant resin material comprising the resin composition. The present invention also relates to a resin-metal composite, more particularly to a resin-metal composite comprising a syndiotactic polystyrene resin composition and a metal member.

[0002] Conventionally, a reflow method has been used as a method for mounting electronic components and electrical components on a substrate, etc., in which the electronic components are temporarily fixed onto a member on which solder paste has been previously applied in predetermined locations, and then this member is heated by means of infrared rays, hot air, etc. to melt the solder and fix the electronic components, etc. The reflow method can improve the mounting density of electronic components, etc. on the surface of the substrate.

[0003] In recent years, with the development of surface mounting technology in the fields of electronic devices and automotive electrical components, the reflow method, which offers superior mounting density, has become increasingly popular. Furthermore, due to the recent increase in environmental awareness, lead-free reflow soldering has become mainstream. However, due to the rising price of silver, low-silver, lead-free solder, which reduces the amount of silver added, which lowers the melting point of lead-free solder, has attracted attention. Resins used in substrates, connectors, housings, etc., which secure electronic components, require heat resistance sufficient to withstand the low-silver, lead-free reflow soldering process. Practically, examples of resins with heat resistance suitable for the low-silver, lead-free reflow soldering process include liquid crystal polymers, polyphenylene sulfides, and aromatic polyamides. However, due to their high specific gravity and poor dimensional stability due to water absorption, these materials are not necessarily suitable for use in electronic devices or automotive electrical components.

[0004] Styrenic polymers having a syndiotactic structure are known to have excellent mechanical strength, heat resistance, electrical properties, dimensional stability upon water absorption, and chemical resistance, and are expected to have many applications. In particular, the excellent chemical resistance, heat resistance, electrical properties, and dimensional stability upon water absorption of styrenic polymers having a syndiotactic structure have attracted attention in electronic devices, automotive and electrical components, transformer / coil power modules, relays, sensors, and the like. For example, Patent Document 1 discloses a thermoplastic resin composition containing a styrenic polymer primarily having a syndiotactic structure, various polymers, a thermoplastic resin and / or a rubber-like elastomer, a fiber reinforcing agent, and an organic or inorganic filler. Furthermore, Patent Document 2 discloses a styrenic resin having a syndiotactic structure, in which the proportion of the endothermic heat obtained in the range of 175 to 260°C is less than 30% when the total endothermic heat measured by differential scanning calorimetry at a heating rate of 20°C / min is taken as 100%.

[0005] In addition, technologies for integrating dissimilar materials, such as metal and resin, have been developed, primarily in the fields of electronics and electromechanics, automobiles, and home appliances. Products in these fields are often used in harsh environments, such as being alternately exposed to high and low temperatures depending on the usage conditions and environment. Therefore, materials used in these fields are required to have durability, or heat shock resistance, that prevents cracking or other damage even when alternately exposed to high and low temperatures. For example, Patent Document 3 discloses an insert-molded product having a metal or other insert member and a resin composition containing a polyarylene sulfide-based resin, an inorganic filler, and an olefin-based copolymer. Patent Document 4 also discloses an insert-molded product having a metal or other insert member and a resin composition containing a polyarylene sulfide-based resin, a fibrous inorganic filler, a non-fibrous inorganic filler, and an olefin-based copolymer. Furthermore, Patent Document 5 discloses an insert-molded product obtained by insert-molding a resin composition containing a polyarylene sulfide resin, a fibrous reinforcing agent having a flat cross-sectional shape, and a thermoplastic elastomer with a metal or the like.

[0006] Japanese Patent Application Laid-Open No. 2004-155928 International Publication No. 2019 / 107526 International Publication No. 2019 / 208706 Japanese Patent Application Laid-Open No. 2020-109135 Japanese Patent Application Laid-Open No. 2005-161693

[0007] Patent Document 1 discloses a thermoplastic resin composition containing a styrene-based polymer having a specific syndiotactic structure, which is said to have excellent mechanical strength. However, since the resin components constituting substrates, connectors, etc. are exposed to high temperatures during the reflow soldering process, when the thermoplastic resin composition of Patent Document 1 is used for the resin components, it is still not sufficient in terms of "reflow resistance." Furthermore, Patent Document 2 discloses a styrene-based polymer having a syndiotactic structure, which has a specific ratio of heat absorption required under specific conditions. However, since the resin components are exposed to high temperatures during the reflow soldering process, the resin components are prone to deformation, and in some cases, they are unable to exhibit sufficient performance. Therefore, the styrene-based resin having a syndiotactic structure of Patent Document 2, which simply has specific thermal properties, is not sufficiently practical in terms of the reflow soldering process. Furthermore, Patent Document 2 also discloses specific resin compositions, but these compositions are not sufficient, particularly in terms of heat resistance, as resin members to be applied to surface mount technology (SMT) in the fields of recent electronic devices and automotive electrical components.

[0008] A first object of the present invention is to provide a fiber-reinforced thermoplastic resin composition having excellent heat resistance and dimensional stability at high temperatures, and a reflow-resistant resin material made of the resin composition.

[0009] In addition, Patent Document 3 discloses that by using a polyarylene sulfide-based resin in combination with an olefin copolymer and three types of inorganic fillers (plate-shaped, fibrous, and granular) in a resin member, heat shock resistance and low warpage can be achieved even when the weld (counterflow weld) of the resin member is formed to coincide with the stress concentration area. However, Patent Document 3 does not sufficiently consider the difference in expansion coefficients between the metal member and the resin member in the insert molded product, and does not sufficiently consider the physical properties of the parallel flow weld, and the heat shock resistance of the parallel flow weld in particular cannot be said to be sufficient. Patent Document 4 discloses that the heat shock resistance of an insert molded product can be improved by using a resin composition containing a fibrous inorganic filler and a non-fibrous inorganic filler having a predetermined diameter ratio in a predetermined ratio as the inorganic filler to be blended with a polyarylene sulfide-based resin. Furthermore, Patent Document 5 discloses that by using a resin composition containing a polyarylene sulfide resin as a main component and blending a flat fibrous reinforcing agent having a specific cross-sectional shape and a thermoplastic elastomer, it is possible to improve heat shock resistance without significantly reducing mechanical properties. However, Patent Documents 4 and 5 do not sufficiently consider the difference in expansion coefficients between the metal member and the resin member in the insert-molded product, and do not consider the physical properties of the weld portion, so it cannot be said that the heat shock resistance of the weld portion is sufficient.

[0010] A second object of the present invention is to provide a resin-metal composite having excellent heat shock resistance.

[0011] As a result of extensive investigation, the present inventors have found that the first problem can be solved by using a fiber-reinforced thermoplastic resin composition containing a thermoplastic resin composition including a styrene-based polymer having a specific syndiotactic structure, a rubber-like elastomer, and a crystal nucleating agent, and glass fibers having a flat cross section. That is, the first invention relates to the following [1] to

[13] .

[0012] [1] A fiber-reinforced thermoplastic resin composition comprising a thermoplastic resin composition (T) and glass fibers (G) having a flat cross section, wherein the thermoplastic resin composition (T) comprises 100 parts by mass of a styrene-based resin composition (S) consisting of 83 to 100 parts by mass of a styrene-based polymer (A) having a syndiotactic structure and a weight-average molecular weight of less than 230,000, 0 to 17 parts by mass of a rubber-like elastomer (B), and 0.6 to 2.0 parts by mass of a crystal nucleating agent (C), wherein the content of the glass fibers (G) relative to the total of the thermoplastic resin composition (T) and the glass fibers (G) is 33.0 to 65.0% by mass. [2] The fiber-reinforced thermoplastic resin composition according to [1] further comprises 0.1 to 5.0 parts by mass of a modified polyphenylene ether (D) relative to 100 parts by mass of the styrene-based resin composition (S). [3] The fiber-reinforced thermoplastic resin composition according to [1] or [2], wherein the weight-average molecular weight of the styrene polymer (A) is less than 200,000. [4] The fiber-reinforced thermoplastic resin composition according to any one of [1] to [3], wherein the glass fiber (G) has an irregularity ratio of 3.5 to 4.5. [5] The fiber-reinforced thermoplastic resin composition according to any one of [1] to [4], wherein the glass fiber (G) has a fiber diameter of 10 μm or more. [6] The fiber-reinforced thermoplastic resin composition according to any one of [1] to [5], wherein a test piece made of the fiber-reinforced thermoplastic resin composition is treated in accordance with IEC 60068-2-58 and measured, and the TD reflow shrinkage is 0.20% or less, and the anisotropy of the reflow shrinkage (TD / MD) is 4.5 or less. [7] The fiber-reinforced thermoplastic resin composition according to any one of [1] to [6], wherein a test piece made of the fiber-reinforced thermoplastic resin composition has a deflection temperature under load of 255°C or higher, as measured in accordance with Method A of ISO 75-1, 2 (2020). [8] A reflow-resistant resin material made of the fiber-reinforced thermoplastic resin composition according to any one of [1] to [7]. [9] A molded product for reflow soldering made of the reflow-resistant resin material according to [8].

[10] A resin-metal composite made of the molded product for reflow soldering according to [9] and a metal member.

[11] A connector made of the resin-metal composite according to

[10] .

[12] The connector according to

[11] , which is used in a reflow soldering process.

[13] The connector according to

[11] , which is used in a surface mounting reflow soldering process.

[0013] Furthermore, as a result of intensive research, the present inventors have found that the second problem can be solved by using a resin-metal composite including a resin member made of a reinforced thermoplastic resin composition and a metal member, in which the difference between the TD linear expansion coefficient of the resin member and the linear expansion coefficient of the metal member is within a certain range and the bending fracture strain in a parallel flow weld test piece made of the reinforced thermoplastic resin composition is a specific value or more. That is, the second present invention relates to the following

[14] to

[25] .

[0014]

[14] A resin-metal composite including a resin member made of a reinforced thermoplastic resin composition containing a thermoplastic resin composition (T2) and a glass filler (G2), and a metal member, wherein the coefficient of linear expansion (CTE) of the resin member in the TD ＴＤ ) and the coefficient of linear expansion (CTE) of the metal member Ｍ ) difference (CTE ＴＤ -CTE Ｍ ) is 6.0 x 10 －５ / °C or less, and a parallel flow weld test piece made of the reinforced thermoplastic resin composition has a bending fracture strain of 1.15% or more.

[15] The resin-metal composite according to

[14] , wherein the thermoplastic resin composition (T2) comprises a styrene-based resin composition (S2) consisting of 75 to 94 parts by mass of a styrene-based polymer (A) having a syndiotactic structure and a weight-average molecular weight of less than 230,000 and 6 to 25 parts by mass of a rubber-like elastomer (B).

[16] The resin-metal composite according to

[14] or

[15] , wherein the glass filler (G2) is at least one selected from glass fibers and glass flakes having a flat cross section.

[17] The resin-metal composite according to

[16] , wherein the glass fibers having a flat cross section have an irregularity ratio of 3.5 to 4.5.

[18] The resin-metal composite according to

[16] or

[17] , wherein the glass fibers having a flat cross section have a fiber diameter of 10 μm or more.

[19] The resin-metal composite according to any one of

[16] to

[18] , wherein the glass flakes are scaly particles.

[20] The resin-metal composite according to any one of

[14] to

[19] , wherein the content of the glass filler (G2) relative to the total of the thermoplastic resin composition (T2) and the glass filler (G2) is 20.0 to 65.0 mass%.

[21] The resin-metal composite according to any one of

[15] to

[20] , wherein the thermoplastic resin composition (T2) further contains 0.6 to 2.0 parts by mass of a nucleating agent (C) relative to 100 parts by mass of the styrene-based resin composition (S2).

[22] The resin-metal composite according to any one of

[15] to

[21] , wherein the thermoplastic resin composition (T2) further contains 0.1 to 15.0 parts by mass of a modified polyphenylene ether (D) relative to 100 parts by mass of the styrene-based resin composition (S2).

[23] The resin-metal composite according to any one of

[15] to

[22] , wherein the thermoplastic resin composition (T2) further contains 0.05 to 3.0 parts by mass of a release agent (F) relative to 100 parts by mass of the styrene-based resin composition (S2).

[24] The resin-metal composite according to any one of

[15] to

[23] , wherein the weight average molecular weight of the styrene-based polymer (A) is less than 200,000.

[25] The resin-metal composite according to any one of

[14] to

[24] , wherein the metal member is at least one selected from the group consisting of aluminum, stainless steel, copper, titanium, and alloys thereof.

[0015] According to the first aspect of the present invention, it is possible to obtain a fiber-reinforced thermoplastic resin composition having excellent heat resistance and dimensional stability at high temperatures, and a reflow-resistant resin material comprising the resin composition.

[0016] According to the second invention, it is possible to provide a resin-metal composite having excellent heat shock resistance.

[0017] 1 is a schematic diagram showing a cut-out portion of a test piece for measuring bending fracture strain in a parallel flow weld test piece made of a reinforced thermoplastic resin composition according to the second invention. FIG. 2 is a schematic cross-sectional view of a mold for a parallel flow weld test piece made of a reinforced thermoplastic resin composition according to the second invention. FIG. 3 is a schematic plan view of a cavity portion of a mold for a parallel flow weld test piece made of a reinforced thermoplastic resin composition according to the second invention, viewed from the upper side of the mold. FIG. 4 is a schematic diagram showing the coefficient of linear expansion (CTE) in the TD of a resin member according to the second invention. ＴＤ 1 is a schematic diagram showing a cut-out portion of a test piece for measuring the heat shock resistance of a resin-metal composite of the second invention. FIG. 2 is a schematic diagram of a test piece for evaluating the heat shock resistance of a resin-metal composite of the second invention. FIG. 3 is a schematic cross-sectional view of a test piece for evaluating the heat shock resistance of a resin-metal composite of the second invention. FIG. 4 is a schematic diagram of a mold for a test piece for evaluating the heat shock resistance of a resin-metal composite of the second invention.

[0018] [First fiber-reinforced thermoplastic resin composition of the present invention] The first fiber-reinforced thermoplastic resin composition of the present invention is a fiber-reinforced thermoplastic resin composition comprising a thermoplastic resin composition (T) and a glass fiber (G) having a flat cross section, wherein the thermoplastic resin composition (T) comprises 83 to 100 parts by mass of a styrene-based polymer (A) having a syndiotactic structure having a weight average molecular weight of less than 230,000 and 0 to 17 parts by mass of a rubber-like elastomer (B). 100 parts by mass of a styrene-based resin composition (S), and 0.6 to 2.0 parts by mass of a crystal nucleating agent (C), and the content of the glass fiber (G) relative to the total of the thermoplastic resin composition (T) and the glass fiber (G) is 33.0 to 65.0% by mass. Each item will be described in detail below.

[0019] <Thermoplastic resin composition (T)> The thermoplastic resin composition (T) contains 100 parts by mass of a styrene-based resin composition (S) comprising 83 to 100 parts by mass of a styrene-based polymer (A) having a syndiotactic structure and a weight-average molecular weight of less than 230,000 and 0 to 17 parts by mass of a rubber-like elastomer (B), and 0.6 to 2.0 parts by mass of a crystal nucleating agent (C).

[0020] <Styrene-based resin composition (S)> The styrene-based resin composition (S) comprises 83 to 100 parts by mass of a styrene-based polymer (A) having a syndiotactic structure and 0 to 17 parts by mass of a rubber-like elastomer (B).

[0021] <Styrenic polymer (A) having syndiotactic structure> The styrene polymer (A) having a syndiotactic structure (hereinafter also referred to as SPS (A)) is a styrene resin having a highly syndiotactic structure. In this specification, "syndiotactic" means that the phenyl rings in adjacent styrene units are arranged alternately with respect to the plane formed by the main chain of the polymer block (hereinafter referred to as syndiotacticity) at a high rate. The tacticity can be determined by nuclear magnetic resonance spectroscopy using carbon isotopes ( 13 Quantitative identification can be performed using 1C-NMR. 13By C-NMR, the proportion of a plurality of consecutive structural units, for example, two consecutive monomer units as a diad, three consecutive monomer units as a triad, and five consecutive monomer units as a pentad, can be quantified.

[0022] In the first aspect of the present invention, the term "styrene resin having a highly syndiotactic structure" refers to a styrene polymer such as polystyrene, poly(hydrocarbon-substituted styrene), poly(halogenated styrene), poly(halogenated alkylstyrene), poly(alkoxystyrene), or poly(vinyl benzoate ester), a hydrogenated polymer or mixture thereof, or a copolymer having any of these as the main component, having a syndiotacticity of usually 75 mol % or more, preferably 85 mol % or more in racemic diad (r), or usually 30 mol % or more, preferably 50 mol % or more in racemic pentad (rrrr).

[0023] Examples of poly(hydrocarbon-substituted styrenes) include poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(tert-butylstyrene), poly(phenylstyrene), poly(vinylnaphthalene), and poly(vinylstyrene). Examples of poly(halogenated styrenes) include poly(chlorostyrene), poly(bromostyrene), and poly(fluorostyrene), and examples of poly(halogenated alkylstyrenes) include poly(chloromethylstyrene). Examples of poly(alkoxystyrenes) include poly(methoxystyrene) and poly(ethoxystyrene).

[0024] Examples of comonomer components of copolymers containing the structural units include, in addition to the monomers of the styrene polymers, olefin monomers such as ethylene, propylene, butene, hexene, and octene; diene monomers such as butadiene and isoprene; and polar vinyl monomers such as cyclic olefin monomers, cyclic diene monomers, methyl methacrylate, maleic anhydride, and acrylonitrile. Copolymers that are preferably used as SPS (A) include copolymers of styrene and p-methylstyrene, copolymers of styrene and p-tert-butylstyrene, and copolymers of styrene and divinylbenzene, with a copolymer of styrene and p-methylstyrene being preferred.

[0025] Among the SPS (A), one or more selected from polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), poly(p-fluorostyrene), and a copolymer of styrene and p-methylstyrene are preferred, one or more selected from polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), and a copolymer of styrene and p-methylstyrene are more preferred, polystyrene and a copolymer of styrene and p-methylstyrene are even more preferred, and polystyrene is most preferred.

[0026] When the melt flow rate (MFR) of SPS (A) is measured under conditions of a temperature of 300° C. and a load of 1.2 kg, the MFR is preferably 8 g / 10 min or more, more preferably 10 g / 10 min or more, even more preferably 13 g / 10 min or more, and preferably 50 g / 10 min or less, more preferably 35 g / 10 min or less. If the MFR value of SPS (A) is 8 g / 10 min or more, there will be no problem with the flowability of the resin during molding, and if it is 50 g / 10 min or less, preferably 35 g / 10 min or less, a molded product having sufficient strength can be obtained.

[0027] In the first aspect of the present invention, the weight average molecular weight of SPS (A) is less than 230,000. Having a weight average molecular weight of SPS (A) of less than 230,000 improves the heat resistance and dimensional stability at high temperatures of the fiber-reinforced thermoplastic resin composition of the first aspect of the present invention, ensures the flowability of the fiber-reinforced thermoplastic resin composition during molding, and ensures sufficient strength of the resulting molded article. From the viewpoints of improving heat resistance and dimensional stability at high temperatures and the flowability of the resin during molding, the weight average molecular weight of SPS (A) is preferably less than 200,000, preferably less than 190,000, and more preferably less than 185,000. Furthermore, from the viewpoints of improving heat resistance and dimensional stability at high temperatures and the strength of the resulting molded article, the weight average molecular weight of SPS (A) is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more. In this specification, unless otherwise specified, the weight average molecular weight is a value measured by gel permeation chromatography using a GPC apparatus (HLC-8321GPC / HT) manufactured by Tosoh Corporation and a GPC column (GMHHR-H(S)HTC / HT) manufactured by Tosoh Corporation, using 1,2,4-trichlorobenzene as an eluent, at 145°C, and converted using a calibration curve of standard polystyrene. Methods for adjusting the weight average molecular weight of SPS (A) include a method of appropriately selecting the type, amount used, and polymerization temperature of each catalyst component, and a method of introducing hydrogen.

[0028] The content of the styrene polymer (A) having a syndiotactic structure per 100 parts by mass of the styrene resin composition (S) is 83 to 100 parts by mass. When the content of the styrene polymer (A) having a syndiotactic structure is 83 parts by mass or more, the heat resistance and dimensional stability at high temperatures of the obtained fiber-reinforced thermoplastic resin composition can be improved. The content of the styrene polymer (A) having a syndiotactic structure per 100 parts by mass of the styrene resin composition (S) is preferably 85 to 99 parts by mass, more preferably 86 to 98 parts by mass, and even more preferably 88 to 96 parts by mass.

[0029] SPS (A) can be produced, for example, by polymerizing a styrene-based monomer (a monomer corresponding to the above-mentioned styrene-based polymer) in an inert hydrocarbon solvent or in the absence of a solvent, using a titanium compound and a condensation product (aluminoxane) of water and trialkylaluminum as catalysts (for example, JP 2009-068022 A).

[0030] <Rubber-like elastomer (B)> The fiber-reinforced thermoplastic resin composition of the first invention may or may not contain a rubber-like elastomer (B). When the fiber-reinforced thermoplastic resin composition of the first invention contains the rubber-like elastomer (B), it is possible to improve toughness while maintaining dimensional stability.

[0031] The rubber-like elastomer (B) is not limited as long as it contains a structural unit derived from styrene, but is preferably at least one selected from the group consisting of a styrene-diene block copolymer, a hydrogenated styrene-diene block copolymer, a styrene-diene random copolymer, a hydrogenated styrene-diene random copolymer, and a styrene-olefin random copolymer. Here, dienes copolymerized with styrene include butadiene and isoprene, and olefins copolymerized with styrene include ethylene, propylene, and butylene.

[0032] The rubber-like elastomer (B) is more preferably at least one selected from the group consisting of styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, and styrene-ethylene-butylene random copolymer, and is further preferably at least one selected from the group consisting of styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (S

[0039] The copolymer is at least one selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-isoprene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), even more preferably at least one selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), even more preferably at least one selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), and even more preferably hydrogenated styrene-butadiene-styrene block copolymer (SEBS).

[0033] The mass ratio of the styrene-derived structural units to the total of the diene, hydrogenated diene, and olefin-derived structural units constituting the rubbery elastomer (B) [(styrene) / (diene, hydrogenated diene, olefin)] is preferably 20 / 80 to 70 / 30, more preferably 25 / 75 to 60 / 40, and even more preferably 25 / 75 to 45 / 55. The styrene content of the rubbery elastomer (B) is preferably in the range of 25 to 60% by mass, and more preferably 25 to 45% by mass. By achieving such a mass ratio, compatibility with SPS (A) can be improved, and toughness can be improved while maintaining heat resistance and dimensional stability at high temperatures.

[0034] The content of the rubber-like elastomer (B) in 100 parts by mass of the styrene-based resin composition (S) is 0 to 17 parts by mass. By having the amount of the rubber-like elastomer (B) be 17 parts by mass or less, the heat resistance and dimensional stability at high temperatures of the obtained fiber-reinforced thermoplastic resin composition can be maintained while improving toughness. The content of the rubber-like elastomer (B) in 100 parts by mass of the styrene-based resin composition (S) is preferably 1 to 15 parts by mass, more preferably 2 to 14 parts by mass, and even more preferably 4 to 12 parts by mass.

[0035] <Crystalline Nucleating Agent (C)> The thermoplastic resin composition (T) contains a crystalline nucleating agent (C). By containing the crystalline nucleating agent (C) in the thermoplastic resin composition (T), the crystallization temperature can be increased, allowing a wider range of temperature conditions for crystallization to be set, and improving productivity.

[0036] The crystal nucleating agent is preferably at least one selected from the group consisting of inorganic crystal nucleating agents and organic crystal nucleating agents. Of these, organic crystal nucleating agents are preferred. Examples of organic crystal nucleating agents include alkali metal salts of organic carboxylic acids, alkaline earth metal salts of organic carboxylic acids, organic compounds of phosphoric acid or phosphorous acid and their metal salts, phthalocyanine derivatives, and sorbitol derivatives. More specific examples include metal salts of carboxylic acids such as aluminum di(p-tert-butylbenzoate), sodium salt of benzoic acid, hydroxyaluminum salt of p-tert-butylbenzoic acid, and aluminum hydroxy-di(p-tert-butylbenzoate), sodium methylenebis(2,4-di-tert-butylphenol)phosphate, sodium-2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, and [2,2'-methylenebis(4,6-di-tert-butylphenyl)]phosphate. Metal salts of phosphoric acid such as lithium, [2,2'-methylenebis(4,6-di-tert-butylphenyl)]]phosphate, potassium bis(4-tert-butylphenyl)phosphate, sodium methylene(2,4-tert-butylphenyl)phosphate, aluminum bis(4,6',6,6'-tetra-tert-butyl-2,2'-methylenediphenyl phosphate) hydroxide, and ammonium [2,2'-methylenebis(4,6-di-tert-butylphenyl)]]phosphate can be selected and used. Complexes containing these can also be used. Among these, from the viewpoint of increasing the crystallization temperature, it is preferable to use a lithium salt of an organic compound of phosphoric acid or phosphorous acid, and it is more preferable to use lithium [2,2'-methylenebis(4,6-di-tert-butylphenyl)]]phosphate.

[0037] In the thermoplastic resin composition (T), the content of the crystal nucleating agent (C) per 100 parts by mass of the styrene-based resin composition (S) is 0.6 to 2.0 parts by mass. By having a content of the crystal nucleating agent (C) of 0.6 parts by mass or more, the crystallization temperature of the resulting fiber-reinforced thermoplastic resin composition can be increased. Therefore, the temperature conditions for crystallization of the fiber-reinforced thermoplastic resin composition can be set widely, so that conditions that shorten the molding cycle can be selected, and productivity can be improved when used as a reflow-resistant resin material. Furthermore, when the content of the crystal nucleating agent (C) per 100 parts by mass of the styrene-based resin composition (S) is 2.0 parts by mass or less, a crystallization temperature of the fiber-reinforced thermoplastic resin composition sufficient for use as a reflow-resistant resin material can be obtained. The content of the crystal nucleating agent (C) per 100 parts by mass of the styrene-based resin composition (S) is preferably 0.7 to 1.8 parts by mass, more preferably 0.8 to 1.5 parts by mass.

[0038] The total content of the styrene-based resin composition (S) and the crystal nucleating agent (C) in 100% by mass of the thermoplastic resin composition (T) is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and is preferably 100% by mass or less.

[0039] <Modified Polyphenylene Ether (D)> The thermoplastic resin composition (T) contains a modified polyphenylene ether (D). By including the modified polyphenylene ether (D) in the thermoplastic resin composition (T), the interfacial strength between the thermoplastic resin composition (T) and the glass fiber (G) described below is increased, thereby increasing the strength of the fiber-reinforced thermoplastic resin composition. In the thermoplastic resin composition (T), the content of the modified polyphenylene ether (D) is preferably 0.1 to 5.0 parts by mass, more preferably 0.3 to 4.0 parts by mass, even more preferably 0.5 to 3.5 parts by mass, and even more preferably 1.0 to 3.0 parts by mass, relative to 100 parts by mass of the styrene-based resin composition (S).

[0040] The modified polyphenylene ether (D) used in the first aspect of the present invention is compatible with the SPS (A) and improves compatibility with other components, and preferably has a polar group reactive with the glass fiber (G). The modified polyphenylene ether (D) is blended to improve the compatibility between the SPS (A) and other components, particularly the glass fiber (G), and to enhance the interfacial strength between the components. More specifically, the modified polyphenylene ether (D) is preferably an acid-modified polyphenylene ether. The polar group reactive with the glass fiber (G) refers to a functional group reactive with the polar group contained in the glass fiber (G). Specific examples include an acid anhydride group, a carboxylic acid group, a carboxylic acid ester group, a carboxylic acid halide group, a carboxylic acid amide group, a carboxylic acid salt group, a sulfonic acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonate salt group, an epoxy group, an amino group, an imide group, and an oxazoline group. A carboxylic acid group is preferred.

[0041] As the modified polyphenylene ether (D), fumaric acid-modified polyphenylene ether and maleic anhydride-modified polyphenylene ether are preferred, and fumaric acid-modified polyphenylene ether is more preferred.

[0042] The modification amount (modifier content) of the modified polyphenylene ether (D) is preferably 0.1 to 20 mass%, more preferably 0.2 to 15 mass%, even more preferably 0.3 to 10 mass%, and even more preferably 0.5 to 5.0 mass%. When the modification amount is within this range, a styrene-based resin composition and a molded article having good strength and heat resistance can be obtained. The modification amount (modifier content) of the modified polyphenylene ether can be determined by the neutralization titer measured in accordance with JIS K 0070-1992.

[0043] Examples of polyphenylene ethers include poly(2,6-dimethyl-1,4-phenylene ether), poly(2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-chloromethyl-1,4-phenylene ether), poly(2-methyl-6-hydroxyethyl-1,4-phenylene ether), poly(2-methyl-6-n-butyl-1,4-phenylene ether), poly(2-ethyl-6-isopropyl-1,4-phenylene ether), poly(2-ethyl-6-n-propyl-1,4-phenylene ether), poly(2,3,6-trimethyl-1,4-phenylene ether), poly[2-(4'-methylphenyl)-1,4-phenylene ether], poly(2-bromo-6-phenyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly( 2-phenyl-1,4-phenylene ether), poly(2-chloro-1,4-phenylene ether), poly(2-methyl-1,4-phenylene ether), poly(2-chloro-6-ethyl-1,4-phenylene ether), poly(2-chloro-6-bromo-1,4-phenylene ether), poly(2,6-di-n-propyl-1,4-phenylene ether), poly(2-methyl-6-isopropyl-1,4-phenylene ether), poly(2-chloro-6-methyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2,6-dibromo-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), and the like are mentioned, and poly(2,6-dimethyl-1,4-phenylene ether) is preferred.

[0044] Modifiers used to modify polyphenylene ether include compounds having an ethylenic double bond and a polar group in the same molecule, specifically, for example, maleic anhydride, maleic acid, fumaric acid, maleic acid esters, fumaric acid esters, maleimide and its N-substituted derivatives, maleates, fumarates, acrylic acid, acrylic acid esters, acrylic acid amides, acrylic acid salts, methacrylic acid, methacrylic acid esters, methacrylic acid amides, methacrylic acid salts, and glycidyl methacrylate. Among these, maleic anhydride, fumaric acid, and glycidyl methacrylate are particularly preferred, and fumaric acid is more preferred. The above-mentioned various modifiers may be used alone or in combination of two or more.

[0045] The modified polyphenylene ether (D) is obtained by reacting the polyphenylene ether with a modifier. There are no particular limitations on the modification method, and known methods can be used. Preferred modification methods include melt modification and solution modification, and among these, melt modification is more preferred because a higher modification amount can be obtained and productivity is high. That is, the modified polyphenylene ether (D) is preferably a modified polyphenylene ether produced by melt modification or a modified polyphenylene ether produced by solution modification, and more preferably a modified polyphenylene ether produced by melt modification.

[0046] Melt modification is a method of obtaining a modified polyphenylene ether by melt-kneading polyphenylene ether and a modifier in the presence or absence of a radical generator. Specifically, this is a method of melt-kneading and reacting at a temperature in the range of 150 to 350°C using a roll mill, Banbury mixer, extruder, or the like. Specifically, a method is preferred in which polyphenylene ether, a modifier, and an optional radical generator are uniformly dry-blended at room temperature, and then the melt reaction is carried out at a temperature in the range of 300 to 350°C, which is essentially the kneading temperature of polyphenylene ether. If the temperature is 300°C or higher, the melt viscosity can be appropriately maintained, and if the temperature is 350°C or lower, decomposition of the polyphenylene ether can be suppressed.

[0047] The amount of the modifier used in the melt modification is preferably 0.1 to 22 parts by mass, more preferably 0.2 to 17 parts by mass, even more preferably 0.3 to 12 parts by mass, and still more preferably 0.5 to 7.0 parts by mass, relative to 100 parts by mass of polyphenylene ether. When the amount of the modifier used is within this range, a styrene-based resin composition and a molded article having good strength and heat resistance can be obtained.

[0048] The radical generator used in the melt modification is preferably one having a temperature showing a half-life of 1 minute of 300°C or higher. Specific examples include 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylhexane, and 2,3-dimethyl-2,3-di(p-methylphenyl)butane. Of these, 2,3-dimethyl-2,3-diphenylbutane, which has a temperature showing a half-life of 1 minute of 330°C, is preferably used. The proportion of the radical generator used is preferably selected from the range of 0.1 to 3 parts by mass, more preferably 0.5 to 2 parts by mass, per 100 parts by mass of polyphenylene ether. If the amount is 0.1 part by mass or more, a high modification effect can be obtained, and if the amount is 3 parts by mass or less, the polyphenylene ether can be efficiently modified and insoluble components are less likely to be generated.

[0049] <Antioxidant (E)> From the viewpoint of heat resistance, the thermoplastic resin composition (T) preferably further contains an antioxidant (E). The antioxidant (E) is preferably one or more selected from a phenolic compound, a phosphorus-based compound, and a sulfur-based compound, and from the viewpoint of heat resistance, a phenolic compound is more preferred.

[0050] Specific examples of phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-diphenyl-4-methoxyphenol, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(4-methyl-6-nonylphenol), 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, and 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane. ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)-3-(n-dodecylthio)-butane, 4,4'-thiobis(6-tert-butyl-3-methylphenol), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonic acid dioctadecyl ester, n-octadecyl-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate, pentaerythritol tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate}, and the like. In particular, pentaerythritol tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate} is preferred.

[0051] Examples of the phosphorus-based antioxidant include monophosphites and diphosphites such as tris(2,4-di-tert-butylphenyl)phosphite and tris(mono- and di-nonylphenyl)phosphite.

[0052] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], di(tridecyl) 3,3'-thiodipropionate, and 3,3'-thiodipropionate.

[0053] In the thermoplastic resin composition (T), the content of the antioxidant (E) per 100 parts by mass of the styrene-based resin composition (S) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.15 parts by mass or more. Also, it is preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less, and even more preferably 0.7 parts by mass or less. When the amount of the antioxidant is within the above range, the heat discoloration resistance during processing is good, long-term heat resistance can be obtained, antioxidant bleeding can be suppressed, and the appearance is not adversely affected.

[0054] <Release Agent (F)> From the viewpoint of improving heat resistance and dimensional stability at high temperatures, the thermoplastic resin composition (T) preferably further contains a release agent (F). The release agent (F) can be arbitrarily selected from known agents such as polyethylene wax, silicone oil, and long-chain carboxylic acids. In the thermoplastic resin composition (T), the content of the release agent (F) relative to 100 parts by mass of the styrene-based resin composition (S) is preferably 0.05 to 3.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, even more preferably 0.1 to 1.0 part by mass, and even more preferably 0.1 to 0.5 parts by mass.

[0055] <Glass fiber (G)> The fiber-reinforced thermoplastic resin composition of the first invention contains a glass fiber (G) having a flat cross section. By containing the glass fiber (G) in the fiber-reinforced thermoplastic resin composition of the first invention, it is possible to improve heat resistance and dimensional stability at high temperatures.

[0056] In the first aspect of the present invention, the glass fiber (G) has a flat cross section perpendicular to the fiber axis. The flat shape refers to a shape in which the irregularity ratio of the glass fiber (G) is greater than 1. In the first aspect of the present invention, the irregularity ratio refers to the ratio of the major axis to the minor axis of the cross section perpendicular to the fiber axis of the glass fiber (G), i.e., major axis / minor axis. The major axis is the linear distance between two points on the outer edge of the cross section perpendicular to the fiber axis, where the distance is the longest, and the minor axis is the linear distance between two points where a line perpendicular to the major axis intersects with the outer edge of the cross section. Note that both the line representing the major axis and the line representing the minor axis pass through the center of gravity of the cross section. The flat cross section of the glass fiber (G) can improve the heat resistance of the fiber-reinforced thermoplastic resin composition and can also improve dimensional stability at high temperatures. Without being bound by theory, it is presumed that the reason why the heat resistance and dimensional stability at high temperatures can be improved by having the glass fiber (G) have a flat cross section is that when the cross section of the glass fiber (G) is flat, it is more likely to be oriented in the flow direction (MD) of the resin generated by the screw rotation of the extrusion kneader, suppressing breakage of the glass fiber, and also obtaining the effect of suppressing shrinkage due to the influence of an increased aspect ratio of the fiber in the direction perpendicular to the flow direction (TD). From the viewpoint of improving both heat resistance and dimensional stability at high temperatures, the irregularity ratio of the glass fiber (G) is preferably 2 to 6, more preferably 3 to 5, and even more preferably 3.5 to 4.5. The minor axis is preferably 3 μm to 10 μm, more preferably 5 μm to 8 μm. The major axis and minor axis of the glass fiber are both number averages, and are calculated as number averages by measuring 50 or more arbitrarily selected glass fibers by image analysis using a digital microscope.

[0057] From the viewpoint of improving dimensional stability at high temperatures, the fiber diameter of the glass fiber (G) is preferably 10 μm or more, more preferably 10.5 μm or more, even more preferably 11 μm or more, and even more preferably 12 μm or more. Furthermore, from the viewpoint of ensuring the fluidity of the fiber-reinforced thermoplastic resin composition during molding, the fiber diameter of the glass fiber (G) is preferably 20 μm or less, more preferably 18 μm or less. In the first aspect of the present invention, the fiber diameter of the glass fiber (G) means the diameter of a circle obtained by converting a cross section perpendicular to the fiber axis into a circle having the same area as the area of ​​that cross section. The fiber diameter of the glass fiber is a number average, and is measured and calculated by performing image analysis using a digital microscope on 50 or more arbitrarily selected glass fibers.

[0058] The fiber length of the glass fiber (G) used in the fiber-reinforced thermoplastic resin composition of the first invention is preferably 1 to 50 mm, more preferably 1.5 to 15 mm, and even more preferably 2 to 8 mm, from the viewpoint of ensuring the fluidity of the fiber-reinforced thermoplastic resin composition during molding and handling. Furthermore, the fiber length of the glass fiber (G) contained in the fiber-reinforced thermoplastic resin composition is preferably 300 to 600 μm due to breakage during extrusion kneading, etc. The fiber length of the glass fiber is a number average, and is measured and calculated by performing image analysis using a digital microscope on 50 or more arbitrarily selected glass fibers.

[0059] In order to enhance adhesion to the SPS (A), the glass fiber (G) is preferably surface-treated with a coupling agent, more preferably with a silane-based coupling agent or a titanium-based coupling agent, and even more preferably with a silane-based coupling agent from the viewpoint of compatibility with the resin component.

[0060] Specific examples of silane coupling agents include triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(1,1-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. Examples of suitable silanes include hydroxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltris(2-methoxyethoxy)silane, N-methyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-4,5-dihydroimidazolepropyltriethoxysilane, hexamethyldisilazane, N,N-bis(trimethylsilyl)urea, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine. Among these, aminosilanes and epoxysilanes such as γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are preferred.

[0061] Specific examples of titanium-based coupling agents include isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(1,1-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, and bis(dioctyl pyrophosphate)oxyacetate. titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate)titanate, isopropyl tricumyl phenyl titanate, isopropyl tri(N-amidoethyl, aminoethyl)titanate, dicumyl phenyloxyacetate titanate, diisostearoyl ethylene titanate, etc. Among these, isopropyl tri(N-amidoethyl, aminoethyl)titanate is preferred.

[0062] The content of glass fiber (G) in the fiber-reinforced thermoplastic resin composition of the first invention is 33.0% by mass or more and 65.0% by mass or less, based on a total of 100% by mass of the thermoplastic resin composition (T) and the glass fiber (G). By having a glass fiber (G) content of 33.0% by mass or more, heat resistance and dimensional stability at high temperatures can be improved, and the toughness required for a molded product for reflow soldering or a connector for reflow soldering can be obtained. By having a glass fiber (G) content of 65.0% by mass or less, the fluidity of the fiber-reinforced thermoplastic resin composition during molding can be ensured, and the tensile breaking strain is 1.0% or more, thereby obtaining the toughness required for a molded product for reflow soldering or a connector for reflow soldering. The content of the glass fiber (G) in the fiber reinforced thermoplastic resin composition is preferably 33.0% by mass or more and 65.0% by mass or less, more preferably 35.0% by mass or more and 58.0% by mass or less, and 38.0% by mass or more and 55.0% by mass or less is even more preferable.

[0063] <Other Components> Any other components can be added to the fiber-reinforced thermoplastic resin composition of the first invention as long as the object of the first invention is not impaired. Examples of other components include colorants, crosslinking agents, crosslinking aids, dispersants, plasticizers, antifouling agents, UV absorbers, light stabilizers, flame retardants, flame retardant aids, and antistatic agents.

[0064] <Coloring Agent> Any coloring agent can be selected from known coloring agents such as carbon black, inorganic coloring agents, and organic coloring agents. Examples of inorganic coloring agents include inorganic pigments, and examples of organic coloring agents include organic pigments and organic dyes. Examples of inorganic pigments include titanium dioxide, iron oxide, nickel titanium yellow, zinc sulfide, barium sulfate, and ultramarine. Examples of organic pigments include at least one selected from the group consisting of monoazo pigments, perylene pigments, quinacridone pigments, and phthalocyanine pigments. Specific preferred examples of the organic pigment include monoazo pigments such as Pigment Yellow 183 and Pigment Yellow 150, perylene pigments such as Pigment Red 178 and Pigment Red 149, quinacridone pigments such as Pigment Violet 19, Pigment Red 122, Pigment Red 209, Pigment Red 202, Pigment Orange 48 and Pigment Orange 49, and phthalocyanine pigments such as Pigment Blue 15, Pigment Blue 16, Pigment Green 7 and Pigment Green 36.

[0065] <<Dispersant>> The dispersant can be arbitrarily selected from known dispersants such as methylene bisstearic acid amide, polyacrylic acid, sodium polyacrylate, sodium carboxylate, ammonium polyacrylate, polyacrylic acid copolymers, sodium polycarboxylate, carboxylic acid copolymers, and sulfonic acid copolymers.

[0066] <<Ultraviolet absorber>> Examples of ultraviolet absorbers include 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2 Any known hydroxybenzoates can be selected and used, such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and [2-hydroxy-4-(octyloxy)phenyl](phenyl)methane.

[0067] <<Light stabilizer>> As the light stabilizer, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)butane-1,2,3,4-tetracarboxylate, 1,2,3,4-butanetetracarboxylic acid, tetramethyl ester, reaction products with 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β’,β’-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diol, 1,2,3,4-butanetetracarboxylic acid, tetramethyl ester, reaction products with 2,2,6,6-tetramethyl-4-piperidinol and β,β,β’,β’-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diol, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethylpiperidin-4-yl hexadecanoate, 2,2,6,6-tetramethylpiperidin-4-yl octadecanoate, etc. can be arbitrarily selected from known ones and used.

[0068] <Flame Retardant> The flame retardant can be arbitrarily selected from known flame retardants such as brominated polystyrene, ethylene bis(pentabromophenyl), ethylene bis(tetrabromophthalimide), pentabromobenzyl polyacrylate, tetrabromobisphenol A, condensed phosphate esters, ammonium polyphosphate, phosphinates, phosphites, melamine cyanurate, magnesium hydroxide, and boehmite.

[0069] <Flame Retardant Auxiliary> The flame retardant auxiliary can be arbitrarily selected from known ones such as diantimony trioxide, sodium antimonate, diantimony pentoxide, zinc borate, and hydrotalcite.

[0070] [Physical properties of fiber-reinforced thermoplastic resin composition] In the fiber-reinforced thermoplastic resin composition of the first invention, the deflection temperature under load is preferably 255 ° C or higher, more preferably 258 ° C or higher, even more preferably 260 ° C or higher, and even more preferably 262 ° C or higher. When the deflection temperature under load is 255 ° C or higher, the heat resistance of the obtained molded body can be sufficiently achieved. The deflection temperature under load can be adjusted by the content of the glass fiber (G), the deformation ratio of the glass fiber (G), the mass ratio of the styrene-derived structural unit constituting the rubber-like elastomer (B) to the total of other structural units, the content of the rubber-like elastomer (B), etc. In the first invention, the deflection temperature under load is measured by a method in accordance with Method A of ISO 527-1,2 (2020), and can be measured by the method described in the examples.

[0071] In the fiber-reinforced thermoplastic resin composition of the first invention, the MD reflow shrinkage is preferably 0.10% or less, more preferably 0.08% or less. The TD reflow shrinkage is preferably 0.20% or less, more preferably 0.16% or less. Furthermore, the anisotropy of the reflow shrinkage (TD / MD) is preferably 4.5 or less, more preferably 3.0 or less, even more preferably 2.2 or less, and even more preferably 1.8 or less. If the reflow shrinkage in each direction and the anisotropy of the reflow shrinkage are within the above ranges, it can be said that the dimensional stability at high temperatures is high. When a connector using the fiber-reinforced thermoplastic resin composition of the first invention is used in a reflow soldering process, the dimensional stability at high temperatures is high, so that dimensional changes and warping of the connector can be suppressed, preventing poor fitting with the wire harness connector. It is also possible to suppress changes in the distance between the solder paste-coated portion of the board and the metal terminals of the connector, thereby preventing poor joining. The reflow shrinkage in each direction and the anisotropy of the reflow shrinkage can be adjusted, for example, by the content of glass fiber (G) and the deformation ratio of glass fiber (G). In the first invention, the anisotropy of the reflow shrinkage (TD / MD) is determined as the ratio (TD reflow shrinkage / MD reflow shrinkage) of the dimensional change in the MD of a test piece before and after reflow soldering (MD reflow shrinkage) to the dimensional change in the TD (TD reflow shrinkage). MD refers to the direction of resin flow during molding, and TD refers to the direction perpendicular to the flow direction. In addition, the reflow shrinkage in each direction in the first invention is measured using a test piece by the method described in the Examples. The test piece can be treated and measured in accordance with IEC 60068-2-58 as described in the Examples. The test piece used to measure the reflow treatment shrinkage in each direction may be, for example, a square plate test piece measuring 80 mm x 80 mm x 2 mm thick.

[0072] In the fiber-reinforced thermoplastic resin composition of the first invention, the SFL (Spiral Flow Length) when molded in a spiral flow mold having a flow path thickness of 1 mm and a width of 10 mm at an injection pressure setting of 100 MPa is preferably 100 mm or more, more preferably 130 mm or more, even more preferably 140 mm or more, and even more preferably 150 mm or more. By having an SFL of 100 mm or more, the fluidity of the fiber-reinforced thermoplastic resin composition during molding can be sufficiently ensured. Moreover, it is preferable that the SFL is 185 mm or less. The SFL can be adjusted, for example, by the content of glass fiber (G) or the weight average molecular weight of the styrene-based polymer (A) having a syndiotactic structure. In the first invention, the SFL can be measured by the method described in the examples.

[0073] In the fiber-reinforced thermoplastic resin composition of the first invention, the tensile stress at break is preferably 110 MPa or more, more preferably 120 MPa or more, and even more preferably 130 MPa or more. The tensile strain at break is preferably 1.0% or more, more preferably 1.2% or more, even more preferably 1.3% or more, and even more preferably 1.4% or more. When the tensile stress at break is 110 MPa or more and the tensile strain at break is 1.0% or more, the toughness of the obtained molded body can be sufficiently achieved. The tensile stress at break and the tensile strain at break can be adjusted, for example, by the content of the glass fiber (G), the mass ratio of the styrene-derived structural unit constituting the rubber-like elastomer (B) to the total of other structural units, the content of the rubber-like elastomer (B), etc. In addition, in the first invention, the tensile stress at break and the tensile strain at break can be measured by a method conforming to ISO 527-1,2:2019, and can be measured by the method described in the examples.

[0074] In the fiber-reinforced thermoplastic resin composition of the first invention, the crystallization temperature is preferably 246 ° C or higher. When the crystallization temperature is within the above range, the productivity can be improved when producing a molded body using the fiber-reinforced thermoplastic resin composition of the first invention as a reflow-resistant resin material. The crystallization temperature can be adjusted, for example, by the content and type of the crystal nucleating agent (C). In the first invention, the crystallization temperature can be measured by the method described in the examples.

[0075] [Production of Fiber-Reinforced Thermoplastic Resin Composition] The fiber-reinforced thermoplastic resin composition of the first invention is prepared by blending and kneading a styrene-based resin (A) having a syndiotactic structure, a rubber-like elastomer (B), a crystal nucleating agent (C), and glass fiber (G), and, if necessary, the modified polyphenylene ether (D), an antioxidant (E), a release agent (F), and other components. Blending and kneading can be carried out by premixing using commonly used equipment such as a ribbon blender, a drum tumbler, a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a co-kneader, or the like. The melt-kneaded fiber-reinforced thermoplastic resin composition of the first invention is preferably stored in pellet form and used as a reflow-resistant resin material.

[0076] [Reflow-resistant resin material] In the first invention, reflow resistance means having sufficient reflow heat resistance to withstand the reflow soldering process, and the reflow heat resistance can be evaluated by the deflection temperature under load and the above-mentioned reflow treatment shrinkage rate. The reflow-resistant resin material of the first invention comprises the above-mentioned fiber-reinforced thermoplastic resin composition. That is, the first reflow-resistant resin material of the present invention is a fiber-reinforced thermoplastic resin composition containing a thermoplastic resin composition (T) and glass fibers (G) having a flat cross section, wherein the thermoplastic resin composition (T) is a styrene-based polymer (A) having a syndiotactic structure having a weight average molecular weight of less than 230,000. 83 to 100 parts by mass and a rubber-like elastomer (B) 0 to 17 parts by mass. 100 parts by mass of a styrene-based resin composition (S) consisting of, and 0.6 to 2.0 parts by mass of a crystal nucleating agent (C), and the content of the glass fibers (G) relative to the total of the thermoplastic resin composition (T) and the glass fibers (G) is 33.0 to 65.0% by mass. The fiber-reinforced thermoplastic resin composition includes:

[0077] Examples of reflow soldering processes include "insertion mount technology (IMT)," typified by through-hole reflow, in which a hole (through-hole) formed in a metal circuit portion of a printed circuit board is filled with solder paste, a metal terminal of a connector or the like is inserted therethrough, and then the soldering is performed by heating in a reflow furnace; and "surface mount technology (SMT)," in which solder paste is applied to a metal circuit portion on a printed circuit board, a metal terminal of a connector or the like is placed on the solder paste, and then the soldering is performed by heating in a reflow furnace. Of these, surface mount in particular involves soldering by placing a metal terminal of a connector or the like on solder paste applied to the surface of the printed circuit board, and therefore, there have been cases where poor joints have occurred due to changes in the dimensions of the printed circuit board or connector, etc., at high temperatures, which can cause changes in the distance between the surface of the printed circuit board and the metal terminal of the connector, etc.

[0078] On the other hand, since the reflow-resistant resin material of the first invention is made of the above-mentioned fiber-reinforced thermoplastic resin composition, it has excellent heat resistance and dimensional stability at high temperatures. Therefore, the reflow-resistant resin material of the first invention can be suitably used in reflow soldering processes, and is particularly excellent in dimensional stability in reflow soldering processes using surface mounting. Furthermore, using the reflow-resistant resin material of the first invention as part of a printed circuit board, connector, etc. can suppress dimensional changes therein and prevent poor adhesion, making it more suitable.

[0079] The reflow-resistant resin material of the first invention may contain other thermoplastic resins, etc., as long as the effects of the first invention are not impaired. However, the reflow-resistant resin material of the first invention essentially consists of the above-mentioned fiber-reinforced thermoplastic resin composition. Specifically, the content of the above-mentioned fiber-reinforced thermoplastic resin composition in the reflow-resistant resin material of the first invention is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more. There is no upper limit, and it is sufficient as long as it is 100% by mass or less, preferably 100% by mass. It may consist only of the above-mentioned fiber-reinforced thermoplastic resin composition.

[0080] As described above, the reflow-resistant resin material of the first invention has excellent heat resistance and dimensional stability at high temperatures, and therefore can be suitably used for molding a molded body. The shape of the molded body is not particularly limited, and examples thereof include injection-molded products and extrusion-molded products, but since the resin member made of the reflow-resistant resin material of the first invention can be suitably used in a reflow soldering process as described above, the reflow-resistant resin material of the first invention can be particularly suitably used for molded bodies for reflow soldering and connectors.

[0081] The molded article for reflow soldering of the first aspect of the present invention is made of the above-mentioned reflow-resistant resin material. Therefore, as described above, it has excellent heat resistance and dimensional stability at high temperatures, and therefore can be suitably used as a resin-metal composite, particularly consisting of the molded article for reflow soldering of the first aspect of the present invention and a metal member.

[0082] The resin-metal composite of the first invention comprises the above-mentioned molded body for reflow soldering and a metal member. The connector of the first invention comprises the resin-metal composite. As described above, the molded body for reflow soldering, resin-metal composite, and connector of the first invention have excellent heat resistance and dimensional stability at high temperatures. Therefore, when the molded body for reflow soldering, resin-metal composite, and connector of the first invention are used in a reflow soldering process, the bonding strength with the substrate can be improved. Therefore, even when stress is unevenly applied to one or the end of the bonding surface, the bonding portion can be made less likely to break.

[0083] As the metal member of the resin-metal composite of the first invention, it is preferable to use at least one selected from the group consisting of aluminum, stainless steel, copper, titanium, and alloys thereof. These metals can be selected according to the intended application and physical properties, and it is more preferable to use copper or a copper alloy. The shape of the metal member is not particularly limited as long as it can be joined to the molded body for reflow soldering, and can be, for example, a flat plate, a curved plate, a rod, a cylinder, a block, etc. A structure consisting of a combination of these may also be used. The shape of the joining surface of the metal member to be joined to the molded body for reflow soldering of the first invention is not particularly limited, and examples include a flat surface and a curved surface. On the other hand, in order to maintain the joining strength, it is more preferable to use a shape that is less likely to concentrate stress.

[0084] [Reflow soldering process] The reflow soldering process of the first invention involves passing the pin of the chip component of the connector of the first invention through a hole (through hole) formed in the joint portion of the printed circuit board, filling the hole with a reflow material, and then heating and soldering in a reflow furnace. An "insertion mounting" reflow soldering process, or a "surface mounting" reflow soldering process in which a solder paste is applied to the joint portion on a printed circuit board where there is no hole, and then the connector of the first invention is placed on the joint portion. As described above, the molded product for reflow soldering of the first invention has excellent heat resistance and dimensional stability at high temperatures. Therefore, when it is formed into a resin-metal composite, it is possible to suppress uneven stress application to a portion of the joint surface between the resin member and the metal member, and the joint portion is less likely to break. Therefore, a resin-metal composite comprising a molded body for reflow soldering of the first invention and a metal member, and a connector comprising the resin-metal composite, can suppress misalignment and stress concentration at the joint due to dimensional changes in the molded body, particularly in a reflow soldering process by "surface mounting", thereby preventing poor adhesion. Therefore, the resin-metal composite of the first invention is preferably used in a reflow soldering process, and more preferably in a reflow soldering process by surface mounting. Furthermore, as described above, the molded body for reflow soldering of the first invention has excellent heat resistance and dimensional stability at high temperatures. Therefore, the resin-metal composite of the first invention and the connector of the first invention can also be used in a low-silver, lead-free reflow soldering process using a low-silver, lead-free solder with a reduced amount of silver added, which lowers the melting point of the lead-free solder.

[0085] [Resin-metal composite of the second invention] The resin-metal composite of the second invention is a resin-metal composite including a resin member made of a reinforced thermoplastic resin composition containing a thermoplastic resin composition (T2) and a glass filler (G2), and a metal member, wherein the coefficient of linear expansion (CTE) of the resin member in the TD is ＴＤ ) and the coefficient of linear expansion (CTE) of the metal member Ｍ ) difference (CTE ＴＤ -CTE Ｍ ) is 6.0 x 10 －５ / °C or less, and the bending strain at break in a parallel flow weld test piece made of the reinforced thermoplastic resin composition (hereinafter also referred to as "parallel flow weld bending strain at break") is 1.15% or more.

[0086] Generally, when a resin-metal composite is exposed to an environment with large temperature changes, if the difference between the linear expansion coefficient of the resin member and the linear expansion coefficient of the metal member is large, strain increases between the resin member and the metal member, making it more likely to suffer damage such as cracks. In other words, the resin-metal composite has insufficient heat shock resistance. Typically, the linear expansion coefficient of a resin molded body reinforced with fibers or the like differs significantly between the direction of resin flow (MD) during molding and the direction perpendicular to the resin flow (TD), with the TD having a larger linear expansion coefficient than the MD. Therefore, when comparing the linear expansion coefficients of the resin member and the metal member in a resin-metal composite, the difference between the linear expansion coefficient of the TD of the resin member and the linear expansion coefficient of the metal member is particularly large compared to the difference between the linear expansion coefficient of the MD and the linear expansion coefficient of the metal member. As a result, when a resin-metal composite is exposed to an environment with large temperature changes, strain in the TD becomes particularly large, making it more likely to suffer damage such as cracks. Therefore, the inventors have investigated the linear expansion coefficient (CTE) of the TD of the resin member in a resin-metal composite. ＴＤ ) and the coefficient of linear expansion (CTE) of the metal member Ｍ ) difference (CTE ＴＤ -CTE Ｍ ) to a certain range or less, the heat shock resistance can be improved.

[0087] On the other hand, CTE ＴＤ -CTE Ｍ It was confirmed that even if the CTE is reduced to a certain range or less, damage may occur when exposed to an environment with large temperature changes. As a result of extensive research, the inventors have found that parallel flow welds in particular are involved in heat shock resistance, and ＴＤ -CTE Ｍ It has been found that excellent heat shock resistance can be obtained by reducing the CTE to a certain range or less and setting the bending fracture strain of the parallel flow weld to a specific value or more. ＴＤ -CTE ＭAlthough it is unclear why excellent heat shock resistance can be obtained by reducing the strain at break of parallel flow welds to a certain range or less and setting the bending fracture strain of parallel flow welds to a specific value or more, the inventors speculate as follows. Welds are formed where resin flows meet and are known to be weaker than other areas. Depending on the formation process, they can be classified as counterflow welds and parallel flow welds. Counterflow welds are welds formed in areas where the resin flow directions are opposite each other during molding, and are thought to be susceptible to the effects of MD expansion and contraction of the resin component during heat shock testing (or when the environmental temperature changes). On the other hand, parallel flow welds are welds formed in areas where the resin flow directions are parallel during molding, and are thought to be susceptible to the effects of TD expansion and contraction of the resin component during heat shock testing (or when the environmental temperature changes). In resin-metal composites, parallel flow welds, where the resin flow directions meet in parallel during molding, are significantly affected by TD expansion and contraction. Since the linear expansion coefficient of the resin member in the TD is larger than that in the MD, it is thought that the parallel flow welds in the resin-metal composite cause large strain with the metal member, making the resin member more susceptible to breakage. ＴＤ -CTE Ｍ 6.0 x 10 －５ / °C or less, and further, by setting the bending fracture strain of the parallel flow weld to a range of 1.15% or more, the resin-metal composite can withstand the strain between the resin member and the metal member even when exposed to an environment with large temperature changes, so the stress on the easily breakable parallel flow weld is alleviated, and as a result, it is thought that a resin-metal composite with excellent heat shock resistance was obtained. As described above, the second invention is a resin-metal composite with excellent heat shock resistance. ＴＤ ) and the coefficient of linear expansion (CTE) of the metal member Ｍ ) difference (CTE ＴＤ -CTE Ｍ ) to 6.0 x 10 －５ By setting the temperature range to 1.15% or less and the bending breaking strain of a parallel flow weld test piece made of the reinforced thermoplastic resin composition to 1.15% or more, the heat shock resistance is excellent. Each item will be explained in detail below.

[0088] [Linear expansion coefficient] In the resin-metal composite of the second aspect of the present invention, the linear expansion coefficient (CTE) of the resin member in the TD ＴＤ ) and the coefficient of linear expansion (CTE) of the metal member Ｍ ) difference (CTE ＴＤ -CTE Ｍ ) is 6.0 x 10 －５ / °C or less, preferably 5.9 × 10 －５ / °C or less. ＴＤ -CTE Ｍ is 6.0 x 10 －５ / °C or less, the strain between the resin member and the metal member can be reduced, and the heat shock resistance can be increased. ＴＤ -CTE Ｍ The lower limit of is not particularly limited, but is preferably 0 / °C or more from the viewpoint of reducing the strain between the resin member and the metal member and suppressing the fracture of the resin-metal composite, and more preferably 1.5 × 10 from the viewpoint of achieving both the heat shock resistance of the resin-metal composite and the elongation at break, moldability, and kneading stability of the resin member. －５ / °C or more, more preferably 2.0 x 10 －５ / °C or more, and even more preferably 2.5 x 10 －５ / °C or more. In the second invention, the linear expansion coefficient can be measured by the method described in the Examples.

[0089] The coefficient of linear expansion (CTE) of the resin member in the TD ＴＤ ) is due to the combination with the metal member, but the CTE ＴＤ -CTE Ｍ From the viewpoint of reducing the heat shock resistance of the resin-metal composite, it is preferable to reduce the －５ / °C or less, and more preferably 8.0 × 10 －５ / °C or less. ＴＤ Although there is no particular limitation on the lower limit of －５ / °C or more. The coefficient of linear expansion (CTE) of the resin member in the TD ＴＤThe present inventors have found that the CTE can be adjusted by adjusting the type and content of the glass filler (G2) contained in the resin member. ＴＤ It was also found that by increasing the content of the glass filler (G2) in the resin member, the CTE ＴＤ It was found that there is a tendency for

[0090] Coefficient of linear expansion (CTE) of metal members Ｍ ) is not particularly limited, but is preferably 0.5 × 10 －５ ~3.0 x 10 －５ / °C, and more preferably 1.0 × 10 －５ ~2.8 x 10 －５ / °C, and more preferably 1.5 × 10 －５ ~2.5 x 10 －５ / °C. The coefficient of linear expansion (CTE) of the metal member Ｍ ) can be adjusted depending on the type of metal used in the metal member.

[0091] [Bending fracture strain in parallel flow weld test piece made of reinforced thermoplastic resin composition] In the resin-metal composite of the second invention, the bending fracture strain in the parallel flow weld test piece made of the reinforced thermoplastic resin composition (bending fracture strain of parallel flow weld) is 1.15% or more, preferably 1.20% or more. By having a bending fracture strain of 1.15% or more of the parallel flow weld, the stress between the resin member and the metal member can be alleviated, and heat shock resistance can be improved. In addition, the upper limit of the bending fracture strain of the parallel flow weld is not particularly limited, but is preferably 2.00% or less from the viewpoint of achieving both the heat shock resistance of the resin-metal composite and the elastic modulus and heat resistance of the resin member. The bending fracture strain of the parallel flow weld can be adjusted by the content of the rubber-like elastomer (B) and the release agent (F) contained in the resin member. Increasing the content of the rubber-like elastic material (B) contained in the resin member tends to increase the bending fracture strain of the parallel flow weld.

[0092] In the second aspect of the present invention, the bending fracture strain of the parallel flow weld can be measured using a test piece obtained from a test molded article having a parallel flow weld formed from a reinforced thermoplastic resin composition. The test piece is 10 mm wide, 80 mm long, and 2 mm thick and is cut out from the test molded article at a position 50-60 mm in the MD from the gate of the test molded article. Specifically, the test piece is cut out from the cutout portion 11 of the test piece for measuring the bending fracture strain of the parallel flow weld, as shown in Figure 1. The test molded article 1 is fabricated using a test mold 2 for the test molded article shown in Figures 2 and 3. The mold 2 is equipped with a partition wall 25, as shown in Figure 3. The partition wall 25 allows the reinforced thermoplastic resin composition introduced through the resin inlet 24 to flow through flow paths A and B within the cavity 23. The reinforced thermoplastic resin composition that flows separately into flow paths A and B then merges at resin junction 26 in cavity 23, forming a weld. At this time, the converging resin flows are opposed to each other at the weld near partition 25, resulting in a counterflow weld. On the other hand, at positions away from partition 25, more specifically, at positions more than 50 mm away from partition 25 in the MD, the converging resin flows run parallel to each other, resulting in a parallel flow weld. Therefore, the parallel flow weld test piece made of the reinforced thermoplastic resin composition of the second invention has a parallel flow weld, and therefore the bending fracture strain of the parallel flow weld targeted by the second invention can be measured.

[0093] In the second invention, the bending fracture strain of the parallel flow weld is measured in accordance with ISO 178:2010 using a parallel flow weld test piece made of the above-mentioned reinforced thermoplastic resin composition, and specifically, it is measured by the method described in the examples.

[0094] [Resin Member] In the resin-metal composite of the second aspect of the present invention, the resin member is made of a reinforced thermoplastic resin composition containing the thermoplastic resin composition (T2) and the glass filler (G2).

[0095] <Thermoplastic resin composition (T2)> In the resin-metal composite of the second present invention, the thermoplastic resin composition (T2) contains 75 to 94 parts by mass of a styrene-based polymer (A) having a syndiotactic structure and a weight average molecular weight of less than 230,000. It is preferable to include a styrene-based resin composition (S2) consisting of 6 to 25 parts by mass of a rubber-like elastomer (B).

[0096] <Styrenic polymer (A) having syndiotactic structure> In the resin-metal composite of the second invention, the styrene-based polymer (A) having a syndiotactic structure (hereinafter also referred to as SPS (A)) is a styrene-based resin having a high syndiotactic structure, and is preferably the same as the SPS (A) exemplified in the above-mentioned first invention.

[0097] As SPS (A), one or more types selected from polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tert-butylstyrene), poly(p-chlorostyrene), poly(m-chlorostyrene), poly(p-fluorostyrene), and a copolymer of styrene and p-methylstyrene are preferred, one or more types selected from polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), and a copolymer of styrene and p-methylstyrene are more preferred, polystyrene and a copolymer of styrene and p-methylstyrene are even more preferred, and polystyrene is most preferred.

[0098] When the melt flow rate (MFR) of SPS (A) is measured under conditions of a temperature of 300 ° C. and a load of 1.2 kg, it is preferably 8 g / 10 min or more, more preferably 10 g / 10 min or more, even more preferably 13 g / 10 min or more, preferably 50 g / 10 min or less, and more preferably 35 g / 10 min or less. If the MFR value of SPS (A) is 8 g / 10 min or more, there is no problem with the fluidity of the resin during molding of the resin metal composite, and if it is 50 g / 10 min or less, the strength of the resin metal composite can be made sufficient and the heat shock resistance can be increased.

[0099] In the resin-metal composite of the second invention, the weight average molecular weight of SPS (A) is preferably less than 230,000, more preferably less than 200,000, even more preferably less than 190,000, and even more preferably less than 185,000, and is preferably 10,000 or more, more preferably 50,000 or more, and even more preferably 100,000 or more. If the weight average molecular weight of SPS (A) is less than 230,000, there is no problem with the fluidity of the resin during molding of the resin-metal composite, and if it is 10,000 or more, the strength of the resin-metal composite can be made sufficient and the heat shock resistance can be increased. Methods for adjusting the weight average molecular weight of SPS (A) include the same methods as those for SPS (A) exemplified in the first invention described above.

[0100] The content of SPS (A) in 100 parts by mass of the styrene-based resin composition (S2) is preferably 75 to 94 parts by mass, more preferably 77 to 93 parts by mass, even more preferably 78 to 92 parts by mass, and still more preferably 79 to 91 parts by mass. When the content of SPS (A) is within the above range, the heat shock resistance of the resin-metal composite can be increased.

[0101] SPS (A) can be produced by polymerizing styrene monomers and the like in the same manner as in the method exemplified in the first aspect of the present invention.

[0102] <Rubber-like elastic material (B)> In the resin-metal composite of the second invention, the thermoplastic resin composition (T2) contains the rubber-like elastic material (B), which can improve the toughness of the resin member, and in particular, can increase the bending fracture strain of the parallel flow weld, thereby increasing the heat shock resistance of the resin-metal composite.

[0103] The rubber-like elastic material (B) is preferably the same as the rubber-like elastic material (B) exemplified in the first aspect of the present invention.The rubber-like elastomer (B) is more preferably at least one selected from the group consisting of styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block copolymer (SEPS), styrene-butadiene random copolymer, hydrogenated styrene-butadiene random copolymer, styrene-ethylene-propylene random copolymer, and styrene-ethylene-butylene random copolymer, and is further preferably at least one selected from the group consisting of styrene-butadiene block copolymer (SBR), hydrogenated styrene-butadiene block copolymer (SEB), styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (S

[0039] The copolymer is at least one selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-isoprene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIR), hydrogenated styrene-isoprene block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), even more preferably at least one selected from the group consisting of styrene-butadiene-styrene block copolymer (SBS), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), even more preferably at least one selected from the group consisting of hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene-styrene block copolymer (SIS), and hydrogenated styrene-isoprene-styrene block copolymer (SEPS), and even more preferably hydrogenated styrene-butadiene-styrene block copolymer (SEBS).

[0104] The mass ratio of the styrene-derived structural units constituting the rubber-like elastomer (B) to the total of the diene, hydrogenated diene, and olefin-derived structural units [(styrene) / (diene, hydrogenated diene, olefin)] is preferably 20 / 80 to 70 / 30, more preferably 25 / 75 to 60 / 40, and even more preferably 25 / 75 to 45 / 55. The styrene content of the rubber-like elastomer (B) is preferably in the range of 25 to 60% by mass, more preferably 25 to 45%. By setting such a mass ratio, compatibility with SPS (A) can be improved, and the heat shock resistance of the resin-metal composite can be improved.

[0105] The content of the rubber-like elastomer (B) in 100 parts by mass of the styrene-based resin composition (S2) is preferably 6 to 25 parts by mass, more preferably 7 to 20 parts by mass, even more preferably 8 to 15 parts by mass, and still more preferably 8 to 12 parts by mass. By having the content of the rubber-like elastomer (B) within the above range, the heat shock resistance of the resin-metal composite can be increased.

[0106] <Crystal nucleating agent (C)> In the resin-metal composite of the second invention, the thermoplastic resin composition (T2) preferably further contains a crystal nucleating agent (C). By containing the crystal nucleating agent (C) in the thermoplastic resin composition (T2), the crystallization temperature can be increased, allowing a wide range of temperature conditions for crystallization to be set, and productivity can be improved. In addition, in the thermoplastic resin composition (T2), the content of the crystal nucleating agent (C) is preferably 0.6 to 2.0 parts by mass, more preferably 0.7 to 1.8 parts by mass, and even more preferably 0.8 to 1.5 parts by mass. By having the content of the crystal nucleating agent (C) be 0.6 parts by mass or more, it is possible to set a wide range of temperature conditions for crystallization, and productivity can be improved. In addition, by having the content be 2.0 parts by mass or less, the amount of gas components generated during molding can be suppressed, and a good appearance can be obtained.

[0107] The nucleating agent (C) is preferably the same as the nucleating agent (C) exemplified in the first aspect of the present invention. Among these, from the viewpoint of increasing the crystallization temperature, it is preferable to use a lithium salt of an organic compound of phosphoric acid or phosphorous acid, and it is more preferable to use lithium [2,2'-methylenebis(4,6-di-tert-butylphenyl)]phosphate.

[0108] <Modified polyphenylene ether (D)> In the resin-metal composite of the second invention, the thermoplastic resin composition (T2) preferably further contains a modified polyphenylene ether (D). By including the modified polyphenylene ether (D) in the thermoplastic resin composition (T2), the interfacial strength between the thermoplastic resin composition (T2) and the glass filler (G) described below can be increased, thereby increasing the strength of the resin portion as a structure and improving the heat shock resistance of the resin-metal composite. Further, in the thermoplastic resin composition (T2), the content of the modified polyphenylene ether (D) is preferably 0.1 to 15.0 parts by mass, more preferably 0.1 to 10.0 parts by mass, and even more preferably 0.1 to 6.0 parts by mass relative to 100 parts by mass of the styrene-based resin composition (S2). When the content of the modified polyphenylene ether (D) is 0.1 parts by mass or more, the interfacial strength between the thermoplastic resin composition (T2) and the glass filler (G) described later can be increased, so that the strength of the resin part as a structure is increased and the heat shock resistance of the resin-metal composite can be improved. Furthermore, when the content is 15 parts by mass or less, sufficient crystallinity can be ensured, making it easier to ensure heat resistance and rigidity.

[0109] The modified polyphenylene ether (D) used in the resin-metal composite of the second invention is compatible with SPS (A) and improves compatibility with other components, and preferably has a polar group reactive with the glass filler (G2). In this way, the modified polyphenylene ether (D) is blended with the aim of improving the compatibility between SPS (A) and other components, particularly the glass filler (G2), and improving the interfacial strength between the components. More specifically, the modified polyphenylene ether (D) is preferably an acid-modified polyphenylene ether. The polar group reactive with the glass filler (G2) refers to a functional group reactive with the polar group possessed by the glass filler (G2). Specific examples thereof are preferably the same as the functional groups exemplified in the first invention described above, and more preferably a carboxylic acid group. As the modified polyphenylene ether (D), fumaric acid-modified polyphenylene ether and maleic anhydride-modified polyphenylene ether are preferred, with fumaric acid-modified polyphenylene ether being more preferred.

[0110] The modification amount (modifier content) of the modified polyphenylene ether (D) is preferably 0.1 to 20 mass %, more preferably 0.2 to 15 mass %, even more preferably 0.3 to 10 mass %, and still more preferably 0.5 to 5.0 mass %. When the modification amount is within the above range, the interfacial strength between the thermoplastic resin composition (T2) and the glass filler (G2) described below can be increased, and the strength of the resin portion as a structure can be increased.

[0111] Examples of polyphenylene ethers are preferably the same as those exemplified in the first aspect of the present invention.Modifiers used to modify polyphenylene ethers include compounds having an ethylenic double bond and a polar group in the same molecule, and specifically include the same modifiers as those exemplified in the first aspect of the present invention.In particular, maleic anhydride, fumaric acid, and glycidyl methacrylate are preferably used, and fumaric acid is more preferably used.The above-mentioned various modifiers may be used alone or in combination of two or more.

[0112] The modified polyphenylene ether (D) is obtained by reacting the polyphenylene ether with a modifier. There are no particular limitations on the modification method, and examples thereof include the same modification methods as those exemplified in the first invention described above, preferably melt modification and solution modification, and more preferably melt modification. That is, the modified polyphenylene ether (D) is preferably a modified polyphenylene ether produced by melt modification or a modified polyphenylene ether produced by solution modification, and more preferably a modified polyphenylene ether produced by melt modification. In addition, the specific various conditions for melt modification are preferably the same as those for melt modification exemplified in the first invention described above.

[0113] <Antioxidant (E)> From the viewpoint of heat resistance, the thermoplastic resin composition (T2) preferably further contains an antioxidant (E). The antioxidant (E) is preferably one or more selected from a phenolic compound, a phosphorus-based compound, and a sulfur-based compound, and from the viewpoint of heat resistance, a phenolic compound is more preferred.

[0114] Specific examples of phenolic antioxidants include those exemplified in the first aspect of the present invention, with pentaerythritol tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate} being particularly preferred. Phosphorus-based antioxidants include monophosphites and diphosphites such as tris(2,4-di-tert-butylphenyl)phosphite and tris(mono- and di-nonylphenyl)phosphite. Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], di(tridecyl)3,3'-thiodipropionate, and 3,3'-thiodipropionate.

[0115] In the thermoplastic resin composition (T2), the content of the antioxidant (E) per 100 parts by mass of the styrene-based resin composition (S2) is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.15 parts by mass or more. It is also preferably 2.0 parts by mass or less, more preferably 1.0 part by mass or less, and even more preferably 0.7 parts by mass or less. When the amount of the antioxidant is within the above range, the heat discoloration resistance during processing is good, long-term heat resistance can be obtained, and bleeding of the antioxidant can be suppressed, without adversely affecting the appearance.

[0116] <Release Agent (F)> The thermoplastic resin composition (T2) preferably further contains a release agent (F). The release agent (F) can be arbitrarily selected from known agents such as polyethylene wax, silicone oil, and long-chain carboxylic acids. In the thermoplastic resin composition (T2), the content of the release agent (F) relative to 100 parts by mass of the styrene-based resin composition (S2) is preferably 0.05 to 3.0 parts by mass, more preferably 0.1 to 2.0 parts by mass, even more preferably 0.1 to 1.5 parts by mass, and even more preferably 0.1 to 1.0 part by mass.

[0117] <Glass Filler (G2)> In the second invention, the reinforced thermoplastic resin composition contains a glass filler (G2), thereby ＴＤ and CTE ＴＤ -CTE Ｍ This can reduce the coefficient of linear expansion of the resin-metal composite, thereby improving the heat shock resistance of the resin-metal composite. In the present invention, the glass filler (G2) is preferably at least one selected from glass fibers and glass flakes having a flat cross section. When the glass filler (G2) is at least one selected from glass fibers and glass flakes having a flat cross section, the linear expansion coefficient of the resin member can be easily reduced. In particular, by using a glass filler (G2) selected from the above, it is possible to reduce not only the MD linear expansion coefficient but also the TD linear expansion coefficient (CTE ＴＤ ) can also be effectively reduced, so that CTE ＴＤ -CTE Ｍ This is preferable because it can reduce the heat shock resistance of the resin-metal composite.

[0118] (Glass fiber having a flat cross section) In glass fibers having a flat cross section, the flat shape refers to a shape in which the irregularity ratio of the glass fiber is greater than 1. In the present invention, the irregularity ratio refers to the ratio of the major axis to the minor axis of a cross section perpendicular to the fiber axis of a glass fiber having a flat cross section, i.e., major axis / minor axis. The major axis is the linear distance between the longest point on the cross section perpendicular to the fiber axis, which passes through the center of gravity, and the outer edge of the cross section, and the minor axis is the linear distance between the two points on the outer edge of the cross section, which passes through the center of gravity and intersects perpendicularly to the major axis. By using glass fibers having a flat cross section, the CTE can be increased. ＴＤ Since it is possible to reduce the CTE ＴＤ -CTE Ｍ The deformation ratio of the glass fiber having a flat cross section can be reduced, and the CTE of the resin-metal composite can be improved. ＴＤ -CTE Ｍ From the viewpoint of reducing the diameter and improving the heat shock resistance of the resin-metal composite, the diameter is preferably 2.0 to 6.0, more preferably 3.0 to 5.0, and even more preferably 3.5 to 4.5. The minor axis is preferably 3 μm to 10 μm, more preferably 5 μm to 8 μm. The major axis and minor axis of the glass fiber are both number averages, and are measured by performing image analysis using a digital microscope on 50 or more arbitrarily selected glass fibers and calculated as the number average.

[0119] The fiber diameter of the glass fiber having a flat cross section is ＴＤ -CTE ＭFrom the viewpoint of reducing the diameter and improving the heat shock resistance of the resin-metal composite, it is preferably 10 μm or more, more preferably 10.5 μm or more, even more preferably 11 μm or more, and even more preferably 12 μm or more. Furthermore, from the viewpoint of ensuring the fluidity of the reinforced thermoplastic resin composition during molding, the fiber diameter of the glass fiber having a flat cross section is preferably 20 μm or less, more preferably 18 μm or less. In the present invention, the fiber diameter of the glass fiber having a flat cross section means the diameter of a circle obtained by converting a cross section perpendicular to the fiber axis into a circle having the same area as the area of ​​the cross section. The fiber diameter of the glass fiber is a number average and is measured and calculated by performing image analysis using a digital microscope on 50 or more arbitrarily selected glass fibers.

[0120] The fiber length of the glass fiber having a flat cross section is preferably 1 to 50 mm, more preferably 1.5 to 15 mm, and even more preferably 2 to 8 mm, from the viewpoint of ensuring the fluidity of the reinforced thermoplastic resin composition during molding and ease of handling. Furthermore, the fiber length of the glass fiber having a flat cross section is preferably 300 to 600 μm, due to breakage during extrusion kneading or the like, and is contained in the resin composition pellets. The fiber length of the glass fiber is a number average, and is measured and calculated by performing image analysis using a digital microscope on 50 or more arbitrarily selected glass fibers.

[0121] (Glass flakes) The glass flakes are preferably scaly particles. Here, scaly refers to a flat particle shape with an average thickness smaller than the average minor axis. By using glass flakes, the CTE ＴＤ Since it is possible to reduce the CTE ＴＤ -CTE Ｍ This can reduce the heat shock resistance of the resin-metal composite.

[0122] The aspect ratio of the average major axis to the average minor axis of the glass flakes (average major axis / average minor axis) is ＴＤ -CTE ＭFrom the viewpoint of reducing the CTE and improving the heat shock resistance of the resin-metal composite, the aspect ratio is preferably 3.0 or less, more preferably 2.0 or less, and even more preferably 1.6 or less. ＴＤ -CTE Ｍ From the viewpoint of reducing the value of the molecular weight and improving the heat shock resistance of the resin-metal composite, the molecular weight is preferably 5 or more, more preferably 10 or more, and even more preferably 30 or more.

[0123] The average major axis of the glass flakes is preferably 1000 μm or less, more preferably 1 to 500 μm, and even more preferably 1 to 200 μm, from the viewpoints of ensuring the fluidity of the reinforced thermoplastic resin composition during molding and handling. The average minor axis of the glass flakes is preferably 1000 μm or less, more preferably 1 to 500 μm, and even more preferably 1 to 200 μm, from the viewpoints of ensuring the fluidity of the reinforced thermoplastic resin composition during molding and handling.

[0124] The average major axis, average minor axis and average thickness of the glass flakes are all number averages, and are measured and calculated by performing image analysis using a digital microscope on 50 or more arbitrarily selected glass flakes.

[0125] To enhance adhesion to the SPS (A), the glass filler (G2) is preferably surface-treated with a coupling agent, more preferably with a silane coupling agent or a titanium coupling agent, and even more preferably with a silane coupling agent from the viewpoint of compatibility with the resin component. Specific examples of the silane coupling agent include those exemplified in the first aspect of the present invention, with aminosilanes and epoxysilanes such as γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane being preferred. Specific examples of the titanium coupling agent include those exemplified in the first aspect of the present invention, with isopropyltri(N-amidoethyl, aminoethyl)titanate being preferred.

[0126] The content of the glass filler (G2) in the reinforced thermoplastic resin composition of the second invention is preferably 20.0 to 65.0 mass%, more preferably 23.0 to 55.0 mass%, and even more preferably 25.0 to 45.0 mass%, based on 100 mass% of the total of the thermoplastic resin composition (T2) and the glass filler (G2). ＴＤ and CTE ＴＤ -CTE Ｍ When the content of the glass filler (G2) is 65.0 mass% or less, the flowability of the reinforced thermoplastic resin composition during molding can be ensured.

[0127] <Other Components> Any other components can be added to the reinforced thermoplastic resin composition of the second invention as long as the object of the invention is not impaired. The other components can include any optional components such as colorants, crosslinking agents, crosslinking aids, dispersants, plasticizers, antifouling agents, UV absorbers, light stabilizers, flame retardants, flame retardant aids, and antistatic agents. Specific examples of the colorants, dispersants, UV absorbers, light stabilizers, flame retardants, and flame retardant aids include the same colorants, dispersants, UV absorbers, light stabilizers, flame retardants, and flame retardant aids as exemplified in the first invention described above.

[0128] (Production of reinforced thermoplastic resin composition) In the resin-metal composite of the second invention, the reinforced thermoplastic resin composition is a styrene-based resin having a syndiotactic structure (A), a rubber-like elastomer (B) and a glass filler (G2), and, if necessary, the above-mentioned crystal nucleating agent (C) modified polyphenylene ether (D), an antioxidant (E), a mold release agent (F) and other components are blended and kneaded to obtain a composition. Blending and kneading can be performed by pre-mixing using commonly used equipment such as a ribbon blender, a drum tumbler, a Henschel mixer, etc., and then using a Banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a co-kneader, etc.

[0129] <Metal member> The metal member of the resin-metal composite of the second invention is preferably at least one selected from the group consisting of aluminum, stainless steel, copper, titanium, and alloys thereof, and more preferably at least one selected from aluminum, stainless steel, and copper. These metals can be selected according to the intended use and physical properties, and it is more preferable to use copper or a copper alloy. The shape of the metal member is not particularly limited and can be, for example, a flat plate, a curved plate, a rod, a cylinder, a block, etc. A structure consisting of a combination of these may also be used.

[0130] <Applications> The resin-metal composite of the second invention is resistant to cracking and other damage even when exposed alternately to high-temperature and low-temperature environments, and has excellent durability, or heat shock resistance. Therefore, it can be used in harsh environments, such as in the electronics / electrical machinery, automotive, and household appliance fields, as a component integrating dissimilar materials such as metal and resin, where the component is alternately exposed to high-temperature and low-temperature environments. The operating temperature range can be, for example, from 110°C to 150°C as a high-temperature environment and from -50°C to -30°C as a low-temperature environment. It can also be used in environments where the temperature difference is 140°C or more, or even 160°C or more. Specifically, the resin-metal composite of the second invention can be used as terminal blocks and busbar members used in control circuit wiring for automotive lithium-ion batteries and electric vehicles, terminal blocks and busbar members used in panels such as switchboards, distribution boards, and control panels, terminal blocks and busbar members used in relay boxes for electrical wires used in large machinery, solenoid valves, and the like.

[0131] The present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples.

[0132] The raw materials used in the examples and comparative examples are as follows: <SPS (syndiotactic polystyrene) (A)> SPS-30: syndiotactic polystyrene resin, weight average molecular weight: 150,000, MFR: 30 g / 10 min, manufactured by Idemitsu Kosan Co., Ltd. SPS-13: syndiotactic polystyrene resin, weight average molecular weight: 180,000, MFR: 13 g / 10 min, manufactured by Idemitsu Kosan Co., Ltd. SPS-09: syndiotactic polystyrene resin, weight average molecular weight: 200,000, MFR: 9 g / 10 min, manufactured by Idemitsu Kosan Co., Ltd. SPS-06: syndiotactic polystyrene resin, weight average molecular weight: 230,000 to 250,000, MFR: 6 g / 10 min, manufactured by Idemitsu Kosan Co., Ltd. <Rubber-like elastomer (B)> SEPTON 8006: SEPTON 8006, hydrogenated styrene-butadiene-styrene block copolymer, styrene content 33%, manufactured by Kuraray Co., Ltd. <Nucleating agent (C)> NA-70: Adeka STAB NA-70, lithium [2,2'-methylenebis(4,6-di-tert-butylphenyl)] phosphate, manufactured by ADEKA Corporation NA-11: Adeka STAB NA-11, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, manufactured by ADEKA Corporation <Modified polyphenylene ether (D)> Fumaric acid-modified polyphenylene ether, manufactured by Idemitsu Kosan Co., Ltd., modification amount 1.5 mass% <Antioxidant (E)> Antioxidant, Irganox 1010: Irganox 1010, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation <Release agent (F)> KF-53: methylphenyl silicone oil,Manufactured by Shin-Etsu Silicone Co., Ltd. <Glass fiber (G) having a flat cross section (glass filler (G2))> 3PA-820: CSG 3PA-820, cross section: flat (minor diameter: 7 μm, irregularity ratio: 4), fiber length: 3 mm, manufactured by Nitto Boseki Co., Ltd. 3J-820: CSG 3J-820, cross section: flat, fiber diameter: 10.5 μm (minor diameter: 5 μm, irregularity ratio: 4), fiber length: 3 mm, manufactured by Nitto Boseki Co., Ltd. T-249-FGF: ECS 03 T-249-FGF, cross section: flat (minor diameter: 7 μm, irregularity ratio: 4), fiber length: 3 mm, manufactured by Nippon Electric Glass Co., Ltd. <Glass fiber not having a flat cross section> T-249H: ECS 03 T-249H, cross section: circular, fiber diameter: 10.5 μm, fiber length: 3 mm, manufactured by Nippon Electric Glass Co., Ltd. <Glass flakes (glass filler (G2))> ・REFG315: FLEKA REFG-315, average major axis: 160 μm, average minor axis: 160 μm, average thickness: 5 μm, aspect ratio (average major axis / average minor axis): 1, aspect ratio (average major axis / average thickness): 32, manufactured by Nippon Sheet Glass Co., Ltd.

[0133] [Examples of the first fiber-reinforced thermoplastic resin composition of the present invention] Examples 1-1 to 1-14, Comparative Examples 1-1 to 1-11 (Production of fiber-reinforced thermoplastic resin composition) Each component other than the glass fiber (G) was blended in the proportions shown in Tables 1 and 2 and dry-blended using a Henschel mixer. Subsequently, using a twin-screw extruder TEM37SS (manufactured by Shibaura Machine Co., Ltd.), the resin composition was kneaded while side-feeding the glass fiber (G) in the proportions shown in Tables 1 and 2 at a screw rotation speed of 220 rpm and a barrel temperature of 270 to 290 ° C. to produce pellets. The obtained pellets were dried at 120 ° C. for 5 hours using a hot air dryer to obtain pellets of a fiber-reinforced thermoplastic resin composition. Evaluations were performed using the obtained pellets of the fiber-reinforced thermoplastic resin composition.

[0134] (1) SFL (Spiral Flow Length) The SFL (unit: mm) of the obtained fiber reinforced thermoplastic resin composition was measured using an injection molding machine MD100Xi2.7 (manufactured by Niigata Machine Techno Co., Ltd.). The injection conditions during measurement were a cylinder temperature of 290 ° C, a mold temperature of 150 ° C, an injection pressure setting of 100 MPa, and a spiral flow mold with a flow path thickness of 1 mm, a width of 10 mm, and an Archimedes spiral shape. The larger the SFL value, the better the fluidity. The results are shown in Tables 1 and 2.

[0135] (2) Tensile Test Using an injection molding machine SH100A (manufactured by Sumitomo Heavy Industries, Ltd.), a resin temperature of 290 ° C. and a mold surface temperature of 150 ° C. were used to prepare 4 mm thick dumbbell-shaped test pieces made from pellets of the obtained fiber-reinforced thermoplastic resin composition. Here, the dumbbell-shaped test pieces were prepared as multipurpose test pieces (Type A1) in accordance with JIS K7139:2009. Using the obtained dumbbell-shaped test pieces, the tensile stress at break and the tensile strain at break were measured in accordance with ISO 527-1,2:2019. The higher the tensile stress at break and the tensile strain at break, the better the toughness. The results are shown in Tables 1 and 2.

[0136] (3) Reflow Heat Resistance Using an injection molding machine MD100Xi2.7 (manufactured by Niigata Machine Techno Co., Ltd.), a resin temperature of 290 ° C. and a mold surface temperature of 150 ° C. were used to prepare 80 mm x 80 mm x 2 mm thick square plate test pieces made from pellets of the obtained fiber-reinforced thermoplastic resin composition. The solder heat resistance of the prepared square plate test pieces was determined using a reflow furnace UNI-5016F (manufactured by Nippon Antom Co., Ltd.) according to IEC 60068-2-58 (2015, 4th edition). In the reflow temperature profile of the reflow method, the peak temperature was set to 260 ° C. and the time exceeding 255 ° C. was set to 25 seconds, and the reflow treatment was performed. The dimensional changes of the test pieces before and after the reflow treatment in the resin flow direction (MD) and the direction perpendicular to the resin flow direction (TD) were measured, and the reflow treatment shrinkage in MD and TD was determined. Furthermore, the anisotropy of reflow shrinkage (TD / MD) was calculated from the reflow shrinkage in MD and the reflow shrinkage in TD using the following formula. The smaller the reflow shrinkage in each direction and the closer to 1 the anisotropy of reflow shrinkage is, the better the reflow heat resistance is. The results are shown in Tables 1 and 2. The values ​​of the anisotropy of reflow shrinkage (TD / MD) in Tables 1 and 2 were calculated based on the values ​​of the reflow shrinkage in MD and the reflow shrinkage in TD before being rounded off. (Anisotropy of reflow shrinkage) = (Reflow shrinkage in TD / Reflow shrinkage in MD)

[0137] (4) Deflection Temperature Under Load Using an injection molding machine SH100A (manufactured by Sumitomo Heavy Industries, Ltd.), a resin temperature of 290 ° C. and a mold surface temperature of 150 ° C., strip test pieces of 80 mm x 10 mm x 4 mm thick were prepared from the obtained fiber reinforced thermoplastic resin composition. Using the obtained strip test pieces, the deflection temperature under load (load 1.8 MPa) was measured in accordance with ISO 75-1, 2: 2020. The higher the deflection temperature under load, the better the heat resistance. The results are shown in Tables 1 and 2.

[0138] (5) Crystallization temperature The crystallization temperature was measured using a differential scanning calorimetry DSC8500 (manufactured by PerkinElmer, Inc.). The pellets of the obtained fiber-reinforced thermoplastic resin composition were sealed in an aluminum pan and heated from room temperature to 300 ° C. at a rate of 20 ° C. / min under a nitrogen gas atmosphere, held at 300 ° C. for 1 minute, and then cooled to room temperature at a rate of 20 ° C. / min. The peak top temperature of the crystallization peak measured was taken as the crystallization temperature. The higher the crystallization temperature, the wider the temperature conditions for crystallization can be set, improving productivity. The results are shown in Tables 1 and 2.

[0139] The evaluation results of the fiber-reinforced thermoplastic resin compositions are shown in Tables 1 and 2.

[0140]

[0141]

[0142] From the results in Tables 1 and 2, it can be seen that the fiber-reinforced thermoplastic resin composition of the first invention has excellent heat resistance and dimensional stability at high temperatures. For this reason, the fiber-reinforced thermoplastic resin composition of the present invention can be suitably used, particularly as a reflow-resistant resin material.

[0143] [Examples of the resin-metal composite of the second present invention] Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-10 Each component other than the glass filler (G2) was blended in the proportions shown in Tables 3 and 4 and dry-blended using a Henschel mixer. Subsequently, using a twin-screw extruder TEM37SS (manufactured by Shibaura Machine Co., Ltd.), the resin composition was kneaded while side-feeding the glass filler (G2) at the proportions shown in Tables 3 and 4 at a screw rotation speed of 250 rpm and a barrel temperature of 290 ° C. to produce pellets. The obtained pellets were dried at 120 ° C. for 5 hours using a hot air dryer to obtain pellets of a reinforced thermoplastic resin composition. Evaluations were performed using the pellets of the obtained reinforced thermoplastic resin composition.

[0144] (1) Linear expansion coefficient (1-1) TD linear expansion coefficient (CTE) of resin member ＴＤUsing an injection molding machine SE100-EV (manufactured by Sumitomo Heavy Industries, Ltd.), a cylinder temperature of 290°C and a mold temperature of 150°C were used to prepare 4 mm thick dumbbell-shaped test pieces from pellets of the obtained reinforced thermoplastic resin composition. Here, the dumbbell-shaped test pieces were prepared as multipurpose test pieces (Type A1) in accordance with JIS K7139:2009. The coefficient of linear expansion (CTE) in the TD direction of the obtained dumbbell-shaped tensile test pieces was measured as shown in Figure 4. ＴＤ A test piece was cut out at the position of the cutout portion 32 of the test piece for measurement. The size of the test piece was 4 mm × 4 mm × 10 mm. Using the obtained test piece, the coefficient of linear expansion (CTE) of the resin member in the TD was measured using a thermomechanical analyzer (TMA7100, manufactured by Hitachi High-Technologies Corporation) under the following measurement conditions: ＴＤ ) was measured. <<Measurement conditions>> Test equipment: Thermomechanical analyzer (Hitachi High-Tech Corporation, TMA7100) Measurement mode: Compression Measurement temperature: -60 to 270°C Heating rate: 5°C / min Evaluation range: -40 to 120°C

[0145] (1-2) Coefficient of linear expansion (CTE) of metal members Ｍ ) Coefficient of linear expansion (CTE) of metal member Ｍ The coefficient of linear expansion (CTE) of the metal member (made of stainless steel (SUS304)) used in the examples was measured in accordance with JIS Z2285:2003. Ｍ ) is 1.73 x 10 －５ / ℃.

[0146] (2) Bending fracture strain in parallel flow weld test specimens made of reinforced thermoplastic resin composition (Preparation of test specimens) Using an injection molding machine SE100-EV (manufactured by Sumitomo Heavy Industries, Ltd.), a measurement molded body 1 shown in FIG. 1 was produced using a mold having the shape shown in FIGS. 2 and 3 at a cylinder temperature of 290°C and a mold temperature of 150°C. The thickness of the measurement molded body 1 was 2 mm. From the obtained test molded body, a test specimen for measuring bending fracture strain of parallel flow welds, measuring 10 mm wide, 80 mm long, and 2 mm thick, was cut out at a position 50 to 60 mm in the MD from the gate portion 13A of flow path A and the gate portion 13B of flow path B, as shown in FIG. Using the obtained parallel flow weld bending strain measurement test piece, a bending test was performed under the following measurement conditions in accordance with ISO178:2010 to measure the bending strain at break of the parallel flow weld test piece made of a reinforced thermoplastic resin composition. The test piece was placed so that the center part (the location of the parallel flow weld 12 in Figure 1) was pressed by the indenter. <Measurement conditions> - Support distance: 30 mm - Support radius: 2 mm - Indenter radius: 5 mm - Test speed: 1 mm / min

[0147] (3) Heat Shock Resistance Using an injection molding machine SE50-EV (manufactured by Sumitomo Heavy Industries, Ltd.), a metal member (made of stainless steel (SUS304), size: 6 mm x 6 mm x 103 mm) was set in the cavity of the mold as shown in FIG. 7, and a test piece for evaluating heat shock resistance was prepared at a cylinder temperature of 290 ° C. and a mold temperature of 150 ° C. In the test piece for evaluating heat shock resistance, the resin member was coated on the metal member in a shape with a radius of 10 mm and a length of 85 mm, as shown in FIG. 5. In addition, in the cross section shown in FIG. 6, the minimum thickness of the resin member was 0.76 mm. In the resin member of the test piece for evaluating heat shock resistance, a weld line was present in the longitudinal direction on the side opposite the gate portion. Using the obtained test piece for evaluating heat shock resistance, a heat shock test was performed using a small thermal shock apparatus TES-12-A (manufactured by Espec Corporation) under the following measurement conditions. For three test pieces for evaluating heat shock resistance, the minimum number of cycles at which cracks occurred at the weld line was measured, and the heat shock resistance was evaluated based on the following evaluation criteria. <Measurement conditions> - 1 cycle condition: 45 minutes at -40°C → 45 minutes at 120°C <Evaluation criteria> A: The minimum number of cycles at which cracks occurred was greater than 250 cycles. B: The minimum number of cycles at which cracks occurred was greater than 200 cycles and not more than 250 cycles. C: The minimum number of cycles at which cracks occurred was greater than 100 cycles and not more than 200 cycles. D: The minimum number of cycles at which cracks occurred was not more than 100 cycles.

[0148] The evaluation results of the resin-metal composites are shown in Tables 3 and 4.

[0149]

[0150] From the results in Tables 3 and 4, it can be seen that the resin-metal composite of the second invention has excellent heat shock resistance.

[0151] 1: Molded article for measuring bending fracture strain of parallel flow weld 11: Cut-out portion of test piece 12: Parallel flow weld portion 13A: Gate portion of flow path A 13B: Gate portion of flow path B 2: Mold for molded article for measuring bending fracture strain of parallel flow weld 21: Upper portion of mold 22: Lower portion of mold 23: Cavity 24: Resin inlet 25: Partition wall 26: Resin junction 31: Dumbbell-shaped test piece 32: Coefficient of linear expansion (CTE) of TD ＴＤ ) Cut-out portion of test piece for measurement 4: Test piece for evaluating heat shock resistance 41: Resin member 42: Metal member 43: Gate portion 44: Position of weld line 5: Mold for test piece for evaluating heat shock resistance 51: Cavity 52: Resin inlet

Claims

1. A fiber-reinforced thermoplastic resin composition comprising a thermoplastic resin composition (T) and glass fibers (G) having a flattened cross-section, The thermoplastic resin composition (T) comprises 100 parts by mass of a styrene-based resin composition (S) consisting of 83 to 100 parts by mass of a styrene-based polymer (A) having a syndiotactic structure with a weight-average molecular weight of less than 230,000 and 0 to 17 parts by mass of a rubbery elastic body (B), and 0.6 to 2.0 parts by mass of a crystal nucleating agent (C). A fiber-reinforced thermoplastic resin composition in which the content of glass fibers (G) relative to the total of the thermoplastic resin composition (T) and the glass fibers (G) is 33.0 to 65.0% by mass.

2. Furthermore, the fiber-reinforced thermoplastic resin composition according to claim 1, comprising 0.1 to 5.0 parts by mass of modified polyphenylene ether (D) per 100 parts by mass of the styrene-based resin composition (S).

3. The fiber-reinforced thermoplastic resin composition according to claim 1 or 2, wherein the weight-average molecular weight of the styrene polymer (A) is less than 200,000.

4. The fiber-reinforced thermoplastic resin composition according to claim 1 or 2, wherein the ratio of the glass fibers (G) is 3.5 to 4.

5.

5. The fiber-reinforced thermoplastic resin composition according to claim 1 or 2, wherein the fiber diameter of the glass fiber (G) is 10 μm or more.

6. The fiber-reinforced thermoplastic resin composition according to claim 1 or 2, wherein a test specimen made of the fiber-reinforced thermoplastic resin composition is treated in accordance with IEC 60068-2-58 and measured, the reflow shrinkage rate of TD is 0.20% or less, and the anisotropy of the reflow shrinkage rate (TD / MD) is 4.5 or less.

7. The fiber-reinforced thermoplastic resin composition according to claim 1 or 2, wherein the load deflection temperature of a test specimen made of the fiber-reinforced thermoplastic resin composition, measured in accordance with Method A of ISO 75-1,2 (2020), is 255°C or higher.

8. A reflow-resistant resin material comprising the fiber-reinforced thermoplastic resin composition according to claim 1 or 2.

9. A molded body for reflow soldering, made of the reflow-resistant resin material described in claim 8.

10. A resin-metal composite comprising a reflow soldering molded body and a metal member as described in claim 9.

11. A connector made of the resin-metal composite according to claim 10.

12. The connector according to claim 11, for use in a reflow soldering process.

13. The connector according to claim 11, for use in a surface-mount reflow soldering process.

14. A resin member comprising a reinforced thermoplastic resin composition containing a thermoplastic resin composition (T2) and a glass filler (G2), A resin-metal composite including a metal component, The coefficient of linear expansion of the TD of the resin member (CTE) ＴＤ ) and the coefficient of linear expansion of the metal member (CTE) Ｍ ) difference (CTE ＴＤ - CTE Ｍ ) is 6.0 x 10 －５ / ℃ or lower, A resin-metal composite having a bending fracture strain of 1.15% or more in a parallel flow weld test specimen made of the reinforced thermoplastic resin composition.

15. The resin-metal composite according to claim 14, wherein the thermoplastic resin composition (T2) comprises a styrene-based resin composition (S2) consisting of 75 to 94 parts by mass of a styrene-based polymer (A) having a syndiotactic structure with a weight-average molecular weight of less than 230,000 and 6 to 25 parts by mass of a rubbery elastic body (B).

16. The resin-metal composite according to claim 14 or 15, wherein the glass filler (G2) is one or more selected from glass fibers and glass flakes having a flattened cross-section.

17. The resin-metal composite according to claim 16, wherein the ratio of the shape differences of the glass fibers having the flattened cross-section is 3.5 to 4.

5.

18. The resin-metal composite according to claim 16, wherein the fiber diameter of the glass fiber having the flattened cross-section is 10 μm or more.

19. The resin-metal composite according to claim 16, wherein the glass flakes are flaky particles.

20. The resin-metal composite according to claim 14 or 15, wherein the content of the glass filler (G2) relative to the total of the thermoplastic resin composition (T2) and the glass filler (G2) is 20.0 to 65.0% by mass.

21. The resin-metal composite according to claim 15, wherein the thermoplastic resin composition (T2) further comprises 0.6 to 2.0 parts by mass of a crystal nucleating agent (C) per 100 parts by mass of the styrene-based resin composition (S2).

22. The resin-metal composite according to claim 15, wherein the thermoplastic resin composition (T2) further comprises 0.1 to 15.0 parts by mass of a modified polyphenylene ether (D) per 100 parts by mass of the styrene-based resin composition (S2).

23. The resin-metal composite according to claim 15, wherein the thermoplastic resin composition (T2) further comprises a release agent (F) in an amount of 0.05 to 3.0 parts by mass per 100 parts by mass of the styrene-based resin composition (S2).

24. The resin-metal composite according to claim 15, wherein the weight-average molecular weight of the styrene-based polymer (A) is less than 200,000.

25. The resin-metal composite according to claim 14 or 15, wherein the metal member is at least one selected from the group consisting of aluminum, stainless steel, copper, titanium, and alloys thereof.