Resin-metal composite

Abstract

To provide a resin-metal composite comprising a resin component and a metal component that exhibits excellent heat resistance, dimensional stability, tracking resistance, and suppression of metal corrosion. [Solution] A resin-metal composite comprising a resin member made of a resin composition and a metal member, wherein the melting endothermic peak temperature when differential scanning calorimetry is performed on the resin composition from 0°C to 350°C at a heating rate of 30°C / min is 190°C or more and 250°C or less, the melting enthalpy of the peak is 15.0 J / g or more and 35.0 J / g or less, the total content of phosphorus atoms and nitrogen atoms (P+N) of the resin composition is 0.90 mass% or more and 3.40 mass% or less, and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) is 0.20 or more and 3.50 or less.

Description

Technical Field

[0001] The present invention relates to a resin-metal composite including a resin member made of a resin composition and a metal member.

Background Art

[0002] Many electrical and electronic components use a resin-metal composite composed of a resin member and a metal member. Since resin members generally have insulating properties, they are suitably used for coating metal members such as terminals.

[0003] Among electrical and electronic components, especially those for electric vehicles, resin members are required to have excellent moldability, high dimensional accuracy, and heat resistance to withstand use in a high-temperature environment.

[0004] Generally, crystalline resins are suitably used as resin members because they are excellent in moldability and heat resistance. However, because they are crystalline, they have a large molding shrinkage rate, and dimensional deviation of molded products is likely to occur. To improve dimensional accuracy, methods of blending various amorphous resins have been proposed. However, there is a problem that when the blending amount of the amorphous resin increases, the heat resistance and mechanical properties decrease.

[0005] Also, as a method of improving the mechanical properties of resin members, a method of blending an inorganic filler such as a fibrous reinforcing material into a resin composition can be mentioned. However, when the blending amount of the fibrous reinforcing material is increased, problems such as dimensional deviation due to the anisotropy of the reinforcing material and deterioration of the appearance of the product, such as roughness of the resin member surface and decrease in gloss due to a decrease in the fluidity of the resin composition, become problems.

[0006] In Patent Document 1, as a method of improving the dimensional stability and heat resistance of a polyester resin composition, with respect to a total of 100 parts by mass of (A) 15 to 45 parts by mass of a polybutylene terephthalate resin having an intrinsic viscosity IV of 0.3 to 0.8 and (B) 55 to 85 parts by mass of a styrene-based polymer, (C) 10 to 150 parts by mass of glass fiber is contained, and the (B) styrene-based polymer is (B-1) 250°C, 912 sec -1A thermoplastic resin composition is disclosed, characterized by comprising a polystyrene-based resin having a melt viscosity in the range of 70 to 500 Pa·s and a (B-2) styrene-based elastomer.

[0007] Furthermore, Patent Document 2 describes a method for improving mechanical strength and shrinkage anisotropy, comprising: (A) 100 parts by weight of resin components in the following proportions: (A-1) 100-40% by weight of a resin mainly composed of a thermoplastic resin selected from thermoplastic polyester resins and polyamide resins; (A-2) 0-50% by weight of a polystyrene resin; (A-3) 0-10% by weight of a compatibilizer; (B) 25-125 parts by weight of a total of the following flame retardant combination components: (B-1) 10-60 parts by weight of a phosphorus-based flame retardant selected from the group consisting of phosphazene compounds, phosphate ester compounds, and phosphinates; (B-2) 10-80 parts by weight of a nitrogen-based flame retardant consisting of a salt of an amino group-containing triazine; (B-3) metal borate salt A resin composition for high-voltage insulating material components is disclosed, comprising at least 0 to 45 parts by weight (C) of a fibrous reinforcing material having a flattened cross-sectional shape with a ratio of the major axis to the minor axis (flatness ratio) of the cross-section perpendicular to the fiber length of 1.5 to 10, wherein the content of each of the polyphenylene ether resin, polyphenylene sulfide resin, and phenolic resin is 1% by weight or less. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2022-69942 [Patent Document 2] Japanese Patent Publication No. 2010-24324 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] With the increasing power output of electric vehicles in recent years, the voltage of electrical systems has been rising to over 400V. As a result, resin components of resin-metal composites that are subjected to high voltages, such as connectors and busbars that connect batteries and inverters, and power module cases, now require greater tracking resistance, which is resistance to tracking breakdown (conductivity due to carbonization degradation) under high voltage conditions.

[0010] Furthermore, for applications involving metal-to-metal contacts, resin-metal composites require that the metal contacts remain free from contamination in the operating environment to ensure product reliability.

[0011] Although the invention disclosed in Patent Document 1 has excellent dimensional stability, further improvements are needed in terms of heat resistance.

[0012] Although the invention disclosed in Patent Document 2 has excellent tracking resistance, there is a concern that corrosive gases generated from phosphorus-containing compounds may corrode and contaminate metals, and further improvements are needed for application to resin-metal composites as a resin component.

[0013] Therefore, the object of the present invention is to provide a resin-metal composite comprising a resin member and a metal member that are excellent in heat resistance, dimensional stability, tracking resistance, and suppression of metal corrosion. [Means for solving the problem]

[0014] To solve the above problems, the present invention provides the following means. (1) A resin-metal composite comprising a resin member and a metal member made of a resin composition, wherein the endothermic melting peak temperature when differential scanning calorimetry is performed on the resin composition from 0°C to 350°C at a heating rate of 30°C / min is 190°C or more and 250°C or less, the enthalpy of melting of the peak is 15.0 J / g or more and 35.0 J / g or less, the total content of phosphorus atoms and nitrogen atoms (P+N) of the resin composition is 0.90 mass% or more and 3.40 mass% or less, and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) is 0.20 or more and 3.50 or less. (2) The resin-metal composite according to (1), which is used as an electrical / electronic component having a contact portion between metals. (3) The resin-metal composite according to (1) or (2), wherein the resin composition contains polybutylene terephthalate. (4) The resin-metal composite according to any one of (1) to (3), wherein the resin composition contains at least one selected from phosphoric esters and phosphazenes. [Advantages of the Invention]

[0015] According to the present invention, it is possible to provide a resin-metal composite including a resin member and a metal member, which is excellent in heat resistance, dimensional stability, tracking resistance, and suppression of metal corrosion.

[0016] Therefore, the resin-metal composite of the present invention can be suitably used for electrical and electronic devices, particularly electrical contact materials such as electrical components, connectors, bus bars, relays, and switches for hybrid vehicles and electric vehicles. [Brief Description of the Drawings]

[0017] [Figure 1] It is a schematic diagram of a box-shaped molded product for evaluating the dimensional stability of the resin composition constituting the present invention. [Figure 2] It is a schematic diagram of a resin-metal composite for evaluating the metal corrosion resistance of the resin-metal composite of the present invention. [Modes for Carrying Out the Invention]

[0018] The resin-metal composite of the present invention is a resin-metal composite including a resin member made of a resin composition and a metal member.

[0019] Details of each element constituting the resin-metal composite of the present invention will be described.

[0020] [Resin Composition] The resin composition used in the present invention is a composition containing a resin. When differential scanning calorimetry is performed on the resin composition at a heating rate of 30°C / min from 0°C to 350°C, the melting endothermic peak temperature is 190°C or higher and 250°C or lower, the enthalpy of the peak is 15.0 J / g or higher and 35.0 J / g or lower, the total content of phosphorus atoms and nitrogen atoms (P+N) in the resin composition is 0.90 mass% or higher and 3.40 mass% or lower, and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) is 0.20 or higher and 3.50 or lower. Details will be described below.

[0021] (Melting endothermic peak temperature and melting enthalpy in differential scanning calorimetry) When differential scanning calorimetry is performed on the resin composition used in the present invention at a heating rate of 30°C / min from 0°C to 350°C, a melting endothermic peak derived from a crystalline resin is confirmed in the range of 190°C or higher and 250°C or lower, and the melting enthalpy thereof is 15.0 J / g or higher and 35.0 J / g or lower.

[0022] If the peak top temperature of the melting endothermic peak (hereinafter referred to as the melting endothermic peak temperature) is less than 190°C, the heat resistance of the resin composition and the resin member made of the resin composition is poor. If it exceeds 250°C, since it is necessary to increase the processing temperature of the resin member, thermal decomposition of the resin composition progresses, and when it is combined with a metal member to form a resin-metal composite, metal corrosion progresses. When the melting endothermic peak temperature is 190°C or higher and 250°C or lower, the heat resistance is excellent and metal corrosion is suppressed. The melting endothermic peak temperature is more preferably 200°C or higher and 240°C or lower, and even more preferably 210°C or higher and 230°C or lower.

[0023] If the melting enthalpy of the melting endothermic peak is less than 15.0 J / g, the heat resistance of the resin composition and the resin member made of the resin composition is poor. If it exceeds 35.0 J / g, the molding shrinkage rate when molding the resin composition becomes large, and the dimensional stability of the resin member made of the resin composition is poor. When the melting enthalpy is 15.0 J / g or higher and 35.0 J / g or lower, the heat resistance and dimensional stability of the resin member are excellent. The melting enthalpy is more preferably 19.0 J / g or higher and 26.0 J / g or lower, and even more preferably 20.0 J / g or higher and 22.0 J / g.

[0024] In differential scanning calorimetry, small endothermic peaks with an enthalpy of less than 1.0 J / g, originating from components other than crystalline resin, may be present in the measurement range from 0°C to 350°C.

[0025] (Total content of phosphorus atoms and nitrogen atoms (P+N) and their mass ratio (P / N)) The resin composition used in the present invention has a total phosphorus atom content and nitrogen atom content (P+N) of 0.90% by mass or more and 3.40% by mass or less, and a mass ratio of phosphorus atoms to nitrogen atoms (P / N) of 0.20 or more and 3.50 or less.

[0026] If the sum of phosphorus and nitrogen atoms (P+N) is less than 0.90 mass%, the tracking resistance improvement effect of phosphorus and nitrogen atoms is small, resulting in poor tracking resistance. If it exceeds 3.40 mass%, corrosive gases are generated, causing metal corrosion. When it is between 0.90 mass% and 3.40 mass%, both tracking resistance and suppression of metal corrosion are excellent. The range of P+N is more preferably between 1.20 mass% and 2.20 mass%, and even more preferably between 1.50 mass% and 2.00 mass%.

[0027] If the mass ratio of phosphorus atoms to nitrogen atoms (P / N) is less than 0.20, the heat-resistance-improving effect of phosphorus atoms is reduced, resulting in poor heat resistance. If it exceeds 3.50, corrosive gases are generated, causing metal corrosion. If it is 0.20 or higher, the heat-resistance-improving effect of phosphorus atoms can be fully exerted, and if it is 3.50 or lower, the generation of corrosive gases can be suppressed by the interaction of phosphorus atoms and nitrogen atoms, resulting in excellent heat resistance and suppression of metal corrosion of the resin component. The range of P / N is more preferably 0.50 to 3.00, and even more preferably 0.80 to 2.50.

[0028] Furthermore, if the total content of phosphorus and nitrogen atoms (P+N) exceeds 3.40 mass%, the phosphorus and nitrogen content is too high, resulting in poor inhibition of metal corrosion even if the mass ratio of phosphorus and nitrogen atoms (P / N) is 3.50 or less. When the total content of phosphorus and nitrogen atoms (P+N) is 3.40 mass% or less, and the mass ratio of phosphorus and nitrogen atoms (P / N) is 3.50 or less, excellent inhibition of metal corrosion is achieved.

[0029] Furthermore, since phosphorus atoms have a superior tracking resistance-improving effect compared to nitrogen atoms, if the mass ratio of phosphorus atoms to nitrogen atoms (P / N) is less than 0.20, tracking resistance will be poor even if the total content of phosphorus atoms and nitrogen atoms (P+N) is 0.90 mass% or more. When the total content of phosphorus atoms and nitrogen atoms (P+N) is 0.90 mass% or more and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) is 0.20 or more, a superior tracking resistance-improving effect is exhibited.

[0030] The nitrogen atom content (N) is quantified by organic elemental analysis (CHN analysis).

[0031] The mass ratio of phosphorus atoms to nitrogen atoms (P / N) is measured by EDX analysis.

[0032] The total content of phosphorus and nitrogen atoms (P+N) is calculated from the mass ratio of phosphorus atoms to nitrogen atoms (P / N) and the nitrogen atom content (N) obtained by the above method, based on the following formula. The sum of phosphorus and nitrogen atom content (P+N)(mass%) = (N) × (P / N) + (N)

[0033] While the composition of the resin composition is not limited as long as the above requirements are met, from the viewpoint of moldability and recyclability, the resin included in the resin composition is preferably a thermoplastic resin. Furthermore, from the viewpoint of heat resistance and dimensional stability, it is preferable that the thermoplastic resin includes both crystalline and amorphous resins. It is preferable that the amorphous resin contains nitrogen atoms, as this makes it easier to control the nitrogen atom content. It is preferable that the resin composition includes a phosphorus-containing compound in addition to the crystalline and amorphous resins, as this makes it easier to control the phosphorus atom content. From the viewpoint of heat resistance and mechanical properties, it is preferable that the resin composition further includes an inorganic filler.

[0034] [Crystalline resin] Crystalline resins are resins that possess crystalline properties. Here, "crystalline" means that in differential scanning calorimetry at a heating rate of 30°C / min, at least one crystalline melting endothermic peak with a melting enthalpy of 1 J / g or more is observed in the range of 0 to 350°C.

[0035] Examples of crystalline resins include crystalline polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, and polybutylene terephthalate resin; polyamide resins; polyolefin resins such as polyethylene resin, polypropylene resin, and cycloolefin resin; polyacetal resins; polyimide resins; polyphenylene sulfide resins, polyetheretherketone resins (PEEK), and polytetrafluoroethylene resins. Among these, crystalline polyester resin is preferred as the crystalline resin from the viewpoint of obtaining high-performance resin-metal composites with excellent heat resistance, moldability, and electrical properties.

[0036] The content of the crystalline resin used in the present invention is preferably 30% by mass or more and 65% by mass or less, when the resin composition is considered as 100% by mass. A content of 30% by mass or more is preferable because it makes it easier to control the enthalpy of melting of the endothermic melting peak between 190°C and 250°C to 15.0 J / g or more when differential scanning calorimetry is performed on the resin composition at a heating rate of 30°C / min from 0°C to 350°C. A content of 65% by mass or less is preferable because it makes it easier to control the enthalpy of melting to 35.0 J / g or less. The range of the crystalline resin content is more preferably 35% by mass or more and 60% by mass or less, even more preferably 35% by mass or more and 55% by mass or less, and particularly preferably 35% by mass or more and 50% by mass or less.

[0037] (Crystalline polyester resin) The crystalline polyester resin used in the present invention is a polymer or copolymer having at least one residue selected from the group consisting of (1) dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative, (2) hydroxycarboxylic acid or its ester-forming derivative, and (3) lactone as the main structural unit. Here, "having as the main structural unit" means that at least one residue selected from the group consisting of (1) to (3) is present in an amount of 50 mol or more of the total structural units, and it is preferable that these residues are present in an amount of 80 mol or more. Among these, polymers or copolymers having residues of (1) dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit are preferred in terms of superior mechanical properties and heat resistance.

[0038] Examples of the above-mentioned dicarboxylic acids or their ester-forming derivatives include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, 1,4-anthracenedicarboxylic acid, 1,5-anthracenedicarboxylic acid, 1,8-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 9,10-anthracenedicarboxylic acid, 4,4'-diphenyl etherdicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, and 5-sodium sulfisoisophthalic acid; aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedionic acid, malonic acid, glutaric acid, and dimer acid; alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and their ester-forming derivatives. Two or more of these may be used.

[0039] Examples of the above-mentioned diols or their ester-forming derivatives include aliphatic or alicyclic glycols having 2 to 20 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, and dimergol; long-chain glycols with molecular weights of 200 to 100,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol; aromatic dioxy compounds such as 4,4'-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, and bisphenol F; and their ester-forming derivatives. Two or more of these may be used.

[0040] Polymers or copolymers having dicarboxylic acids or their ester-forming derivatives and diols or their ester-forming derivatives as structural units include, for example, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene isophthalate, polybutylene isophthalate, polybutylene naphthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decanedicarboxylate, polypropylene terephthalate / 5-sodium sulfoisophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene Aromatic polyester resins such as polyethylene glycol, polypropylene terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / succinate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polypropylene terephthalate / sevacate, polybutylene terephthalate / sevacate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, and polybutylene terephthalate / isophthalate / sevacate are examples. These polymers and copolymers may be used individually or in combination of two or more. Here, " / " represents a copolymer.

[0041] Among these, polymers or copolymers having residues of aromatic dicarboxylic acids or their ester-forming derivatives and residues of aliphatic diols or their ester-forming derivatives as the main structural units are more preferred from the viewpoint of further improving mechanical properties and heat resistance, and polymers or copolymers having residues of terephthalic acid, naphthalenedicarboxylic acid or its ester-forming derivative and residues of aliphatic diols selected from propylene glycol and 1,4-butanediol or their ester-forming derivatives as the main structural units are even more preferred.

[0042] Among these, at least one aromatic polyester resin selected from polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene naphthalate, polybutylene naphthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polypropylene terephthalate / naphthalate, polybutylene adipate / terephthalate, polybutylene terephthalate / sevacate, and polybutylene terephthalate / naphthalate is particularly preferred, and at least one selected from polyethylene terephthalate, polybutylene terephthalate, polybutylene isophthalate / terephthalate, polybutylene decanedicarboxylate / terephthalate, polybutylene terephthalate / naphthalate, and polybutylene / ethylene terephthalate is more preferred. Furthermore, two or more of these can be used in any desired content.

[0043] Using polybutylene terephthalate is particularly preferable because it makes it easy to control the melting endothermic peak temperature between 190°C and 250°C when differential scanning calorimetry is performed on the resin composition at a heating rate of 30°C / min from 0°C to 350°C.

[0044] The acid value of the crystalline polyester resin used in the present invention is preferably 50 eq / t or less, from the viewpoint of suppressing the deterioration of the mechanical properties of the resin composition obtained by the present invention during melt kneading and retention, as well as moldability. More preferably, it is 30 eq / t or less, even more preferably 20 eq / t or less, and particularly preferably 10 eq / t or less. The lower limit of the acid value is 0 eq / t. The acid value referred to here is the value measured by dissolving the crystalline polyester resin in o-cresol / chloroform solvent and then titrating it with ethanolic potassium hydroxide.

[0045] The crystalline polyester resin used in the present invention preferably has an intrinsic viscosity of 0.36 dL / g or higher, and more preferably 0.50 dL / g or higher, when measured with an o-chlorophenol solution at 25°C, in order to further improve its mechanical properties. Furthermore, in order to improve fluidity, it is preferably 1.60 dL / g or lower, and more preferably 1.50 dL / g or lower.

[0046] The crystalline polyester resin used in the present invention can be produced by known polycondensation methods, ring-opening polymerization methods, etc. The production method may be either batch polymerization or continuous polymerization, and either transesterification or direct polymerization can be applied, but from the viewpoint of productivity, continuous polymerization is preferred, and direct polymerization is more preferred.

[0047] If the crystalline polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction mainly composed of a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative, it can be produced by esterifying or transesterifying the dicarboxylic acid or its ester-forming derivative and the diol or its ester-forming derivative, followed by a polycondensation reaction.

[0048] To effectively advance esterification, transesterification, and polycondensation reactions, it is preferable to add polymerization catalysts during these reactions. Specific examples of polymerization catalysts include organotitanium compounds such as methyl esters of titanic acid, tetra-n-propyl esters, tetra-n-butyl esters, tetraisopropyl esters, tetraisobutyl esters, tetra-tert-butyl esters, cyclohexyl esters, phenyl esters, benzyl esters, tolyl esters, or mixed esters thereof, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethyldisin oxide, cyclohexahexyldisin oxide, didodecyltin oxide, and triethyltin oxide. Examples include tin compounds such as hydrooxides, triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, alkyl stannon acids such as methyl stannon acid, ethyl stannon acid, and butyl stannon acid, zirconia compounds such as zirconium tetra-n-butoxide, and antimony compounds such as antimony trioxide and antimony acetate. Two or more of these may be used.

[0049] Among these polymerization catalysts, organotitanium compounds and tin compounds are preferred, and tetra-n-butyl ester of titanic acid is even more preferred. The amount of polymerization catalyst added is preferably in the range of 0.01 parts by mass or more and 0.2 parts by mass or less per 100 parts by mass of crystalline polyester resin.

[0050] After polycondensation, the polyester resin is removed from the reaction vessel and cooled to solidify. Generally, it is granulated into pellets by methods such as removing it in strand form and solidifying or semi-solidifying it in cooling water before cutting it with a strand cutter, or by extruding it into water and cutting it with an underwater cutter.

[0051] [Amorphous resin] Amorphous resins are resins that do not possess crystalline properties. Here, "crystalline properties" refer to the presence of at least one crystalline melting endothermic peak with an enthalpy of fusion of 1 J / g or more in differential scanning calorimetry at a heating rate of 30°C / min within the range of 0 to 350°C. In other words, amorphous resins are resins in which no crystalline melting endothermic peak with an enthalpy of fusion of 1 J / g or more is observed under the above conditions.

[0052] The amorphous resin used in the present invention is not particularly limited as long as it meets the above criteria, and various known resins can be used. Specific examples of amorphous resins include (meth)acrylate resins, styrene resins, polycarbonate resins, polyolefin resins, vinyl cyanide resins, polyester resins, polyamide resins, polyarylene sulfide resins, polyacetal resins, polyurethane resins, aromatic or aliphatic polyketone resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, poly-4-methylpentene-1, polyetherimide resins, cellulose acetate resins, polyvinyl alcohol resins, and the like. Two or more of these may be used. From the viewpoint of improving dimensional stability and heat resistance, vinyl cyanide resins and styrene resins are preferred. Furthermore, since it becomes easier to control the total content of phosphorus atoms and nitrogen atoms (P+N) in the resin composition to be between 0.90% and 3.40% by mass, and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) to be between 0.20 and 3.50, an acrylonitrile-styrene copolymer, which is a polymer containing a vinyl cyanide skeleton containing nitrogen atoms and a styrene skeleton, is more preferable.

[0053] (Acrylonitrile-styrene copolymer) The content of units derived from acrylonitrile monomers in the acrylonitrile-styrene copolymer is preferably 5% by mass or more and 50% by mass or less, and more preferably 8% by mass or more and 35% by mass or less. Furthermore, the content of units derived from styrene monomers is preferably 50% by mass or more and 95% by mass or less, and more preferably 65% ​​by mass or more and 92% by mass or less.

[0054] In this invention, the content of units derived from acrylonitrile monomers and units derived from styrene monomers in the acrylonitrile-styrene copolymer is 1 This is performed by 1H-NMR measurement.

[0055] Furthermore, the melt flow rate (MFR) of the acrylonitrile-styrene copolymer is preferably in the range of 5 g / 10 min to 100 g / 10 min at 220°C and a load of 10 kg, and more preferably 5 g / 10 min to 80 g / 10 min.

[0056] Furthermore, the weight-average molecular weight (Mw) of the acrylonitrile-styrene copolymer is preferably in the range of 60,000 to 2,200,000, and more preferably in the range of 80,000 to 200,000.

[0057] In this invention, the weight-average molecular weight (Mw) of the acrylonitrile-styrene copolymer is measured by GPC (gel permeation chromatography).

[0058] The acrylonitrile-styrene copolymer is preferably either acrylonitrile-styrene copolymer (AS resin) or acrylonitrile-styrene-glycidyl methacrylate copolymer. Using these two in combination is particularly preferable from the viewpoint of mechanical properties because it improves compatibility with crystalline polyester resins.

[0059] There are no particular restrictions on the method for producing the acrylonitrile-styrene copolymer; commonly known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. Furthermore, the above composition can also be obtained by blending resins that have been separately (graft) copolymerized.

[0060] The amorphous resin content used in the present invention is preferably 10% by mass or more and 50% by mass or less, when the resin composition is considered to be 100% by mass. A content of 10% by mass or more is preferable because it makes it easier to control the enthalpy of melting of the endothermic melting peak between 190°C and 250°C to 350°C when differential scanning calorimetry is performed on the resin composition at a heating rate of 30°C / min from 0°C to 350°C, and a content of 65% by mass or less is preferable because it makes it easier to control the enthalpy of melting to 15.0 J / g or more. The amorphous resin content is more preferably 10% by mass or more and 45% by mass or less, even more preferably 10% by mass or more and 40% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.

[0061] Furthermore, when the amorphous resin is an acrylonitrile-styrene copolymer, it is preferable because it becomes easier to control the total content of phosphorus atoms and nitrogen atoms (P+N) and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) in the resin composition. When the content of the acrylonitrile-styrene copolymer is 10% by mass or more, it is preferable because it becomes easier to control the total content of phosphorus atoms and nitrogen atoms (P+N) in the resin composition to be 0.90% by mass or more and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) to be 3.50 or less. When the content of the acrylonitrile-styrene copolymer is 50% by mass or less, it is preferable because it becomes easier to control the total content of phosphorus atoms and nitrogen atoms (P+N) in the resin composition to be 3.40% by mass or less and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) to be 0.20 or more. The content of the acrylonitrile-styrene copolymer is more preferably 10% by mass or more and 45% by mass or less, even more preferably 10% by mass or more and 40% by mass or less, and particularly preferably 10% by mass or more and 35% by mass or less.

[0062] [Phosphorus-containing compounds] The phosphorus-containing compounds used in the present invention are compounds containing phosphorus atoms. Examples of phosphorus-containing compounds include phosphate esters, phosphazenes, and metal phosphinate salts. These phosphorus-containing compounds may be used individually or in combination of two or more. Among the phosphorus-containing compounds, phosphate esters and phosphazenes are preferred, and phosphate esters are more preferred, from the viewpoint of heat resistance, tracking resistance, and suppression of metal corrosion of the resin component.

[0063] Examples of phosphate esters include triphenyl phosphate, tris(dimethylphenyl) phosphate, trixylenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl dixylenyl phosphate, trimethyl phosphate, triethyl phosphate, condensed phosphate esters, acidic phosphate esters, and phosphate ester amides.

[0064] From the viewpoint of heat resistance, tracking resistance, and suppression of metal corrosion of resin components, condensed phosphate esters are more preferred. Examples of condensed phosphate esters include resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, bisphenol A diphenyl phosphate, and biphenyl diphenyl phosphate. Commercially available products include PX-202, CR-741, PX-200, PX-201 from Daihachi Chemical Industry Co., Ltd., and FP-500, FP-600, FP-700, and PFR from Adeka Corporation.

[0065] In the present invention, a phosphazene is any compound having a -P=N- bond in its molecule, and examples include chain-like or cyclic phosphazene compounds having the structure shown in the following general formula (1).

[0066] [ka]

[0067] In the general formula (1) above, m represents an integer between 1 and 1000. R3 and R4 each independently represent a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, a linear, branched, or cyclic alkoxy group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryloxy group having 6 to 30 carbon atoms.

[0068] In the above general formula (1), examples of alkyl groups include methyl and ethyl groups. Examples of alkoxy groups include methoxy and ethoxy groups. Examples of aryl groups include phenyl groups. Examples of aryloxy groups include phenyloxy groups. m is preferably 3 to 30, and it is preferable to include at least a cyclic phosphazene compound in which the structure represented by the above general formula (1) is cyclically bonded.

[0069] Phosphazenes can be synthesized or commercially available. Phosphazenes can be synthesized by known methods described in books such as "Synthesis and Application of Phosphazene Compounds" (by Meisetsu Kajiwara, CMC Publishing, 1986). For example, they can be synthesized by reacting phosphorus pentachloride or phosphorus trichloride as a phosphorus source and ammonium chloride or ammonia gas as a nitrogen source using known methods (the cyclic product may be purified), and then substituting the resulting substance with alcohols, phenols, and amines. As a commercially available product, Rabitol (registered trademark) FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd. is preferably used.

[0070] In this invention, the phosphinate is a compound having the structure shown in the following formula (2).

[0071] [ka]

[0072] In the formula, R1 and R2 may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or an aryl group, and may be linear or branched. Also, M is sodium, magnesium, nickel, manganese, calcium, aluminum, or zinc. Also, n is an integer between 1 and 4.

[0073] As for the metal component, aluminum is preferred from the viewpoint of heat resistance, and specifically, aluminum hypophosphite, aluminum ethylmethylphosphinate, or aluminum diethylphosphinate are preferred, with aluminum diethylphosphinate being more preferred. Commercially available phosphinate metal salts include aluminum hypophosphite "Phoslite" (registered trademark) IP-A from Italmatch Chemicals, and "Exolit" (registered trademark) OP1230 and OP1240 from Clariant Japan.

[0074] The phosphorus-containing compound used in the present invention is preferably 2% by mass or more and 30% by mass or less, when the resin composition is considered to be 100% by mass. A phosphorus-containing compound content of 2% by mass or more is preferable because it makes it easy to control the total content of phosphorus atoms and nitrogen atoms (P+N) of the resin composition to be 0.90% by mass or more and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) to be 0.20 or more. A phosphorus-containing compound content of 30% by mass or less is preferable because it makes it easy to control the total content of phosphorus atoms and nitrogen atoms (P+N) of the resin composition to be 3.40% by mass or less and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) to be 3.50 or less.

[0075] [Inorganic fillers] The resin composition of the present invention preferably further contains an inorganic filler. Further addition of an inorganic filler can improve heat resistance and mechanical properties. The inorganic filler may be a fibrous, plate-like, granular, or amorphous inorganic compound.

[0076] Fibrous inorganic fillers are preferred from the viewpoint of mechanical properties, and specific examples include glass fibers, aramid fibers, carbon fibers, alumina fibers, silicon carbide fibers, and cellulose fibers. Glass fibers are more preferred from the viewpoint of mechanical properties.

[0077] Plate-shaped inorganic fillers exhibit functions that reduce anisotropy and warping, and examples include talc, glass flakes, mica, kaolin, and metal foil. Among plate-shaped inorganic fillers, glass flakes are preferred.

[0078] Other granular or amorphous inorganic fillers include ceramic beads, clay, zeolite, barium sulfate, titanium dioxide, silicon dioxide, aluminum oxide, magnesium hydroxide, and zinc sulfide.

[0079] The glass fibers mentioned above include chopped strand type and roving type glass fibers, and glass fibers treated with a sizing agent containing a silane coupling agent such as an aminosilane compound or epoxysilane compound and / or a copolymer made of acrylic acid such as urethane, acrylic acid / styrene copolymer, a copolymer made of maleic anhydride such as methyl acrylate / methyl methacrylate / maleic anhydride copolymer, vinyl acetate, bisphenol A diglycidyl ether, or one or more epoxy compounds such as novolac epoxy compounds are preferably used. Glass fibers treated with a copolymer made of maleic anhydride or a sizing agent containing an epoxy compound are even more preferable because they can further improve mechanical properties and hydrolysis resistance during high-temperature molding. The silane coupling agent and / or sizing agent may be mixed with the emulsion liquid before use. The fiber diameter of the glass fibers is usually preferably in the range of 1 μm to 30 μm, with the lower limit preferably being 5 μm from the viewpoint of dispersibility of the glass fibers in the resin and the upper limit preferably being 15 μm from the viewpoint of mechanical properties.

[0080] Furthermore, the inorganic filler content is preferably 1% by mass or more and 50% by mass or less, when the resin composition is considered as 100% by mass. An inorganic filler content of 1% by mass or more is preferable because it can further improve mechanical properties and heat resistance, and an inorganic filler content of 50% by mass or less is preferable because it can further improve mechanical properties and fluidity. More preferably, the inorganic filler content is 5% by mass or more and 45% by mass or less, even more preferably 10% by mass or more and 40% by mass or less, and particularly preferably 15% by mass or more and 35% by mass or less.

[0081] Two or more inorganic fillers can be used in combination. The number and content of the components used in combination are not particularly limited.

[0082] [Other ingredients] The resin composition of the present invention may contain one or more optional additives, such as a thermosetting resin like epoxy resin, an antioxidant, a heat stabilizer, an ultraviolet absorber, an infrared absorber, a light stabilizer, a fluorescent whitening agent, a plasticizer, a mold release agent, an antistatic agent, an anti-drip agent, a flame retardant, an anti-coloring agent, and various colored pigments and dyes such as carbon black, to the extent that the objectives of the present invention are not impaired.

[0083] The resin composition of the present invention can be obtained, for example, by melt-kneading a crystalline resin, an amorphous resin, and a phosphorus-containing compound, and optionally an inorganic filler and other components.

[0084] Examples of melt-mixing methods include pre-mixing crystalline resin, amorphous resin, and phosphorus-containing compound, along with inorganic fillers and other components as needed, and supplying them to an extruder for melt-mixing; or supplying predetermined amounts of each component to an extruder using a weight feeder or similar quantitative feeder and then melt-mixing them.

[0085] Examples of the above pre-mixing include dry blending, and mixing using mechanical mixing equipment such as tumblers, ribbon mixers, and Henschel mixers. In addition, the inorganic filler may be added by installing a side feeder between the loading section and the vent section of a multi-screw extruder, such as a twin-screw extruder.

[0086] The above composition is preferably granulated before molding. As a granulation method, it is preferable to extrude the polyester resin and other additives into strands using a single-screw extruder, twin-screw extruder, tri-screw extruder, conical extruder, or kneader-type kneader equipped with, for example, a "Unimelt" or "Dalmege" type screw, and then cut them, or to extrude and cut them in water to form pellets with a length of 1.5-5.0 mm and a diameter of 1.5-5.0 mm, but the granulation method is not limited to these.

[0087] The resin composition of the present invention is preferably kneaded using a twin-screw extruder in order to uniformly mix the contained components and, from the viewpoint of productivity, to improve the dispersibility of each component. For the twin-screw extruder, it is preferable to have one or more kneading sections, and more preferably two or more, in order to improve the dispersibility of each component. For example, when adding an inorganic filler from a side feeder, it is preferable to have at least one kneading section upstream of the side feeder to promote the plasticization and dispersion of the crystalline resin, amorphous resin, and phosphorus-containing compound, and at least one kneading section downstream of the side feeder to disperse the inorganic filler in the resin composition while suppressing breakage, for a total of two or more kneading sections.

[0088] Various shapes of resin members can be obtained by melt-molding the resin composition of the present invention. Examples of melt-molding methods include injection molding, extrusion molding, and blow molding, with injection molding being particularly preferred.

[0089] In addition to conventional injection molding methods, other known injection molding methods include gas-assisted molding, two-color molding, sandwich molding, in-mold molding, insert molding, and injection press molding, and any of these molding methods can be applied.

[0090] When melt molding is performed, it is preferable to mold at 300°C or below, more preferably 280°C or below, and even more preferably 270°C or below, from the viewpoint of suppressing deterioration of the resin composition and suppressing metal corrosion of the resin-metal composite. It is also preferable that the temperature is above the melting temperature of the resin composition.

[0091] [Resin metal composite] The resin-metal composite of the present invention comprises a resin component made of a resin composition and a metal component. It may also include components made of other materials. Furthermore, there are no particular limitations on the method for compounding the resin component and the metal component. Examples include the outsert method, in which a molded product of the resin composition (sometimes referred to as the resin component) and a molded product of metal (sometimes referred to as the metal component) are manufactured separately and then press-fitted, or the insert method, in which the metal component is embedded in a mold when the resin component is melt-molded. Both methods can be used suitably. Furthermore, there are no limitations on the material of the metal component used in the present invention. Examples include copper, silver, gold, aluminum, nickel, palladium, tin, and platinum. Alloys of these materials are also acceptable, and the surface may be plated.

[0092] The resin-metal composite of the present invention exhibits excellent heat resistance, dimensional stability, tracking resistance, and suppression of metal corrosion, and can therefore be used in various applications such as mechanical components, electrical components, electronic components, and automotive components, taking advantage of these features. Specific examples of mechanical components, electrical components, electronic components, and automotive components include circuit breakers, flyback transformers, molded products for fusers in copiers and printers, general household electrical appliances, various terminal boards, transformers, printed circuit boards, terminal blocks, coil bobbins, connectors, relays, switch components, outlet components, motor components, sockets, plugs, capacitors, resistors, electrical and electronic components incorporating metal terminals and wires, computer-related components, audio components such as acoustic components, lighting components, telegraph equipment-related components, telephone equipment-related components, air conditioner components, home appliance components such as VTRs and televisions, copier components, facsimile components, optical equipment components, automotive ignition system components, automotive connectors, and various automotive electrical components.

[0093] In particular, the resin-metal composite of the present invention is excellent at suppressing metal corrosion and can therefore be preferably used in electrical and electronic components having metal-to-metal contact points. Here, "having metal-to-metal contact points" means that the metal members of the resin-metal composite have a structure that is exposed for the purpose of contacting the metals of other components. If corrosion of the metal members progresses in the operating environment, the conductivity decreases, making it difficult to use as an electrical or electronic component. Therefore, the resin-metal composite of the present invention, which is excellent at suppressing metal corrosion, can be preferably used in electrical and electronic components having metal-to-metal contact points, and more preferably in connectors, busbars, relays, and switches. [Examples]

[0094] Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[0095] [Examples of Acrylonitrile-Styrene Copolymer Production] · AS Acrylonitrile and styrene were suspended and polymerized to prepare bead-shaped AS (acrylonitrile-styrene copolymer, acrylonitrile / styrene = 28 / 72 (mass ratio), MFR = 24.5 g / 10 min). The acrylonitrile / styrene mass ratio was determined by preparing a 1% by mass solution of AS with deuterated dimethyl sulfoxide. 1 1H-NMR measurements were performed, and the results were calculated based on the following formula. Acrylonitrile mass ratio = (Proton integral ratio of proton peaks derived from β-methylene in acrylonitrile units at 1.6-2.3 ppm) / 2 × (Molecular weight of acrylonitrile) / ((Proton integral ratio of proton peaks derived from β-methylene in acrylonitrile units at 1.6-2.3 ppm) / 2 × (Molecular weight of acrylonitrile) + (Proton integral ratio of proton peaks derived from the aromatic skeleton of styrene units at 6.0-7.5 ppm) / 5 × (Molecular weight of styrene)) × 100 (mass%) Styrene mass ratio = (Proton integral ratio of proton peaks derived from the aromatic skeleton of styrene units at 6.0-7.5 ppm) / 5 × (Molecular weight of styrene) / ((Proton integral ratio of proton peaks derived from β-methylene of acrylonitrile units at 1.6-2.3 ppm) / 2 × (Molecular weight of acrylonitrile) + (Proton integral ratio of proton peaks derived from the aromatic skeleton of styrene units at 6.0-7.5 ppm) / 5 × (Molecular weight of styrene)) × 100 (mass%) MFR was measured according to ISO 1133-1 (2011) under conditions of 220°C and a load of 10 kg.

[0096] Epoxy-modified AS Acrylonitrile, styrene, and glycidyl methacrylate were suspended and polymerized to prepare bead-shaped epoxy-modified AS (acrylonitrile-styrene-glycidyl methacrylate copolymer, acrylonitrile / styrene / glycidyl methacrylate = 25 / 74.7 / 0.3 (mass ratio), MFR = 5.5 g / 10 min). The acrylonitrile / styrene / glycidyl methacrylate mass ratio was determined by preparing a 1% by mass solution of the epoxy-modified AS with deuterated dimethyl sulfoxide. 1 1H-NMR measurements were performed, and the results were calculated based on the following formula. Acrylonitrile mass ratio = (Proton integral ratio of proton peaks derived from β-methylene in acrylonitrile units at 1.6-2.3 ppm) / 2 × (Molecular weight of acrylonitrile) / ((Proton integral ratio of proton peaks derived from β-methylene in acrylonitrile units at 1.6-2.3 ppm) / 2 × (Molecular weight of acrylonitrile) + (Proton integral ratio of proton peaks derived from the aromatic skeleton of styrene units at 6.0-7.5 ppm) / 5 × (Molecular weight of styrene) + (Proton integral ratio of proton peaks derived from the methyl group of glycidyl methacrylate units at 0.8-1.2 ppm) / 3 × (Molecular weight of glycidyl methacrylate)) × 100 (mass%) Styrene mass ratio = (Proton integral ratio of proton peaks derived from the aromatic skeleton of styrene units at 6.0-7.5 ppm) / 5 × (Molecular weight of styrene) / ((Proton integral ratio of proton peaks derived from β-methylene of acrylonitrile units at 1.6-2.3 ppm) / 2 × (Molecular weight of acrylonitrile) + (Proton integral ratio of proton peaks derived from the aromatic skeleton of styrene units at 6.0-7.5 ppm) / 5 × (Molecular weight of styrene) + (Proton integral ratio of proton peaks derived from methyl groups of glycidyl methacrylate units at 0.8-1.2 ppm) / 3 × (Molecular weight of glycidyl methacrylate)) × 100 (mass%) Glycidyl methacrylate mass ratio = (Proton integral ratio of proton peaks derived from methyl groups of glycidyl methacrylate units at 0.8-1.2 ppm) / 3 × (Molecular weight of glycidyl methacrylate) / ((Proton integral ratio of proton peaks derived from β-methylene of acrylonitrile units at 1.6-2.3 ppm) / 2 × (Molecular weight of acrylonitrile) + (Proton integral ratio of proton peaks derived from aromatic skeletons of styrene units at 6.0-7.5 ppm) / 5 × (Molecular weight of styrene) + (Proton integral ratio of proton peaks derived from methyl groups of glycidyl methacrylate units at 0.8-1.2 ppm) / 3 × (Molecular weight of glycidyl methacrylate)) × 100 (mass%) MFR was measured according to ISO 1133-1 (2011) under conditions of 220°C and a load of 10 kg.

[0097] [Measurement methods for each characteristic] In each example and comparative example, the characteristics were evaluated using the measurement method described below.

[0098] 1. Endothermic peak temperature and enthalpy of fusion of resin composition When 10 mg of the resin composition was heated from 0°C to 350°C at a heating rate of 30°C / min using differential scanning calorimetry (DSC, TA-Q200, TA Instruments), the temperature at the peak of the observed endothermic peak was defined as the melting endothermic peak temperature (°C), and the integral value of this peak was defined as the melting enthalpy (J / g).

[0099] 2. The total content of phosphorus atoms and nitrogen atoms in the resin composition (P+N) and their mass ratio (P / N) Organic elemental analysis (CHN analysis) was performed on the resin composition to obtain the nitrogen atom content (N).

[0100] The resin composition was cut into 1.0 to 1.6 mm squares, and EDX spectra were obtained by EDX measurement under the following conditions. • Acceleration voltage: 15kV ·EDX acquisition time: 100s ·Magnification: 1000x The mass ratio (P / N) of phosphorus atoms to nitrogen atoms in the resin composition was obtained from the EDX spectrum.

[0101] From the mass ratio of phosphorus atoms to nitrogen atoms (P / N) and the nitrogen atom content (N) obtained by the above method, the sum of the phosphorus atom content and nitrogen atom content (P+N) was calculated based on the following formula. The sum of phosphorus and nitrogen atom content (P+N)(mass%) = (N) × (P / N) + (N)

[0102] 3.Heat resistance Using a NEX1000 injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., test specimens with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm were obtained under the molding cycle conditions of a molding temperature of 260°C (280°C for Comparative Example 6), a mold temperature of 80°C (100°C for Comparative Example 6), an injection speed of 50 mm / s, a combined injection and holding pressure time of 10 seconds, and a cooling time of 10 seconds. Using the obtained test specimens, the deflection temperature under load conditions of 1.8 MPa was measured according to ISO 75 (2013), and the value was taken as the average of three measured values. It was determined that materials with higher deflection temperatures had superior heat resistance.

[0103] 4. Dimensional stability Using a NEX1000 injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., a box-shaped molded product with a width of 30 mm, a height of 30 mm, a depth of 30 mm, and a thickness of 1.5 mm, as shown in Figure 1(A), was obtained under the molding cycle conditions of a molding temperature of 260°C (280°C for Comparative Example 6), a mold temperature of 80°C (100°C for Comparative Example 6), an injection speed of 100 mm / s, a combined injection time and holding pressure time of 10 seconds, and a cooling time of 10 seconds. For 10 of the obtained molded products, the distance from the center of the line connecting points a and b in Figure 1(B) to point c extending perpendicularly was recorded, and the average value was defined as the amount of internal warp. It was determined that a smaller amount of internal warp indicated superior dimensional stability.

[0104] 5. Tracking resistance Using a NEX1000 injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., a rectangular plate measuring 80 mm × 80 mm × 3 mm thick was obtained under the molding cycle conditions of a molding temperature of 260°C (280°C for Comparative Example 6), a mold temperature of 80°C (100°C for Comparative Example 6), an injection speed of 50 mm / s, a combined injection and holding pressure time of 10 seconds, and a cooling time of 10 seconds. Using the obtained rectangular plate, the comparative tracking index was measured in accordance with the measurement method of the comparative tracking index in IEC 60112:2003, using a 0.1% aqueous ammonium chloride solution as the electrolyte solution. A higher comparative tracking index value was considered to indicate superior tracking resistance.

[0105] 6. Metal corrosion A strip-shaped copper plate measuring 10 mm x 50 mm x 1 mm thick was placed in the center of the mold, and using a NEX1000 injection molding machine manufactured by Nissei Plastic Industrial Co., Ltd., the following molding cycle conditions were used: molding temperature 260°C (280°C for Comparative Example 6), mold temperature 80°C (100°C for Comparative Example 6), injection speed 50 mm / s, injection time and holding time combined 10 seconds, and cooling time 10 seconds. As a result, a resin-metal composite as shown in Figure 2 was obtained, in which the copper plate was exposed at both ends (10 mm x 10 mm x 1 mm thick), and the central part of the copper plate (30 mm x 10 mm x 1 mm thick) was covered with a 1.5 mm thick resin.

[0106] The resulting resin-metal composite was heat-treated at 190°C for 24 hours using a hot air dryer. The presence or absence of metallic luster, discoloration, and rust on the copper plate was visually inspected, and it was determined that the following materials showed superior suppression of metal corrosion in the order of A, B, C, and D. A: Has a metallic luster, no discoloration. B: No metallic luster, no discoloration. C: No metallic luster, slightly discolored. D: No metallic luster, rust present.

[0107] <Materials used in the examples and comparative examples> (1) Crystalline resin PBT (polybutylene terephthalate, melting point 225°C, manufactured by Toray Industries, Inc., acid value 22 eq / t, intrinsic viscosity 0.85 dL / g) • PET (polyethylene terephthalate, melting point 254°C, manufactured by Toray Industries, Inc., acid value 40 eq / t, intrinsic viscosity 0.63 dL / g) • HDPE (High-density polyethylene, "Hyzex" (registered trademark) 1300J, manufactured by Prime Polymer Co., Ltd., melting point 130℃) (2) Amorphous resin AS (Acrylonitrile-styrene copolymer, acrylonitrile / styrene = 28 / 72 (mass ratio), MFR = 24.5g / 10min) • Epoxy-modified AS (acrylonitrile-styrene-glycidyl methacrylate copolymer, acrylonitrile / styrene / glycidyl methacrylate = 25 / 74.7 / 0.3 (mass ratio), MFR = 5.5g / 10min) (3) Phosphorus-containing compounds • PX-200 (phosphate ester, manufactured by Daihachi Chemical Industry Co., Ltd., melting point 92°C, phosphorus content 9% by mass) • "Rabitol" (registered trademark) FP-110 (phosphazene, manufactured by Fushimi Pharmaceutical Co., Ltd., melting point 90°C, phosphorus content 13% by mass) • “Exolit” (registered trademark) OP1240 (metal phosphinate salt, manufactured by Clariant Chemical Co., Ltd., phosphorus content 23% by mass) (4) Inorganic fillers T-187 (glass fiber, manufactured by Nippon Electric Glass Co., Ltd., average fiber diameter 13 μm, average fiber length 3 mm).

[0108] [Examples 1-15, Comparative Examples 1-7] A resin composition was prepared using the following procedure, and its various physical properties were evaluated.

[0109] Using a twin-screw extruder with a screw diameter of 30 mm and an L / D ratio of 35, and equipped with a co-rotating vent (manufactured by Japan Steel Works, TEX-30α), crystalline resin, amorphous resin, and phosphorus-containing compound were mixed in the compositions shown in Tables 1 and 2 and added from the main loading section of the twin-screw extruder. Inorganic fillers were added by installing a side feeder between the main loading section and the vent section. Melt-kneading was performed under extrusion conditions of a kneading temperature of 250°C (280°C for Comparative Example 6) and a screw rotation of 200 rpm. The discharge rate of the resin composition was set to 30 kg / h, and it was discharged in strand form, passed through a cooling bath, and granulated using a strand cutter.

[0110] The obtained pellets were dried in a hot air dryer at 110°C for 6 hours (comparative example 7 was dried at 80°C for 6 hours), and then evaluated using the method described above. The results are shown in Tables 1 and 2.

[0111] Examples 1 to 15, which had a melting endothermic peak temperature of 190°C to 250°C, a melting enthalpy of 15.0 J / g to 35.0 J / g, a total phosphorus and nitrogen content (P+N) of 0.90 mass% to 3.40 mass%, and a phosphorus to nitrogen mass ratio (P / N) of 0.20 to 3.50, exhibited excellent heat resistance, dimensional stability, tracking resistance, and suppression of metal corrosion.

[0112] Comparing Examples 1 to 6, it was found that the higher the endothermic enthalpy, the higher the load deflection temperature and the better the heat resistance, while the lower the endothermic enthalpy, the smaller the internal warping and the better the dimensional stability.

[0113] Comparing Examples 1, 5, and 6, the smaller the sum of phosphorus and nitrogen atom content (P+N), the less the gloss and color change of the copper plate portion, and the better the suppression of metal corrosion.

[0114] Comparing Examples 1, 7, and 11, it was found that the smaller the mass ratio of phosphorus atoms to nitrogen atoms (P / N), the less the luster and color change of the copper plate portion, and the better the suppression of metal corrosion. Conversely, the larger the mass ratio of phosphorus atoms to nitrogen atoms (P / N), the higher the load deflection temperature, the better the heat resistance, and the better the tracking resistance.

[0115] Comparing Examples 1 and 12-15, Example 1, which used phosphate ester, was the most superior in terms of heat resistance, dimensional stability, and suppression of metal corrosion.

[0116] Comparative Example 1, which had an endothermic enthalpy of less than 15.0 J / g, exhibited a low load deflection temperature and poor heat resistance.

[0117] Comparative Example 2, in which the sum of phosphorus and nitrogen atom content (P+N) exceeded 3.50 mass%, showed a loss of luster and rust on the copper plate portion, indicating inferior suppression of metal corrosion.

[0118] Comparative Example 3, which had an endothermic enthalpy exceeding 35.0 J / g and a total phosphorus and nitrogen content (P+N) of less than 0.90 mass%, exhibited significant internal warping, poor dimensional stability, and poor tracking resistance.

[0119] Comparative Example 4, in which the mass ratio of phosphorus atoms to nitrogen atoms (P / N) exceeded 3.50, lost its luster and rusted on the copper plate portion, demonstrating poor suppression of metal corrosion.

[0120] Comparative Example 5, in which the mass ratio of phosphorus atoms to nitrogen atoms (P / N) was less than 0.20, had a low load deflection temperature and poor heat resistance.

[0121] Comparative Example 6, where the endothermic peak temperature exceeded 250°C, showed that the copper plate lost its luster and rusted, indicating poor suppression of metal corrosion.

[0122] Comparative Example 7, which had an endothermic peak temperature of less than 190°C, had a low load deflection temperature and poor heat resistance.

[0123] [Table 1]

[0124] [Table 2] [Explanation of Symbols]

[0125] a, b Two vertices on the opening side of the face opposite to the surface where g of the box-shaped molded product exists. c. The intersection of the member and a line perpendicular to the center of the line connecting points a and b. g Submarine single-point gate, which is the resin injection port during injection molding.

Claims

1. A resin-metal composite comprising a resin member made of a resin composition and a metal member, wherein the endothermic melting peak temperature when differential scanning calorimetry is performed on the resin composition from 0°C to 350°C at a heating rate of 30°C / min is 190°C or more and 250°C or less, the enthalpy of melting of the peak is 15.0 J / g or more and 35.0 J / g or less, the total content of phosphorus atoms and nitrogen atoms (P+N) of the resin composition is 0.90% by mass or more and 3.40% by mass or less, and the mass ratio of phosphorus atoms to nitrogen atoms (P / N) is 0.20 or more and 3.50 or less.

2. The resin-metal composite according to claim 1, used as an electrical or electronic component having metal-to-metal contact points.

3. The resin-metal composite according to claim 1, wherein the resin composition comprises polybutylene terephthalate.

4. The resin-metal composite according to any one of claims 1 to 3, wherein the resin composition comprises at least one selected from phosphate esters and phosphazenes.

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