Polyamide resin composition for insert molding, metal resin composite body and method for producing same

Abstract

The present invention provides a polyamide resin composition for insert molding, the polyamide resin composition being capable of enhancing the heat shock resistance of a molded body. A polyamide resin composition for insert molding according to the present invention contains: a polyamide resin (A); a reinforcing material (B), the content of which relative to the total mass of the polyamide resin composition is 10% by mass to 50% by mass; a modified polyolefin resin (C), the content of which relative to the total mass of the polyamide resin composition is 1% by mass to 10% by mass; and scale-like or plate-like inorganic particles (D), the content of which relative to the total mass of the polyamide resin composition is 5% by mass or more but less than 40% by mass. The polyamide resin (A) contains a polyamide resin (A1) which has a melting point (Tm) of 280°C or more as determined by a differential scanning calorimeter (DSC), and the storage elastic modulus E' of the modified polyolefin resin (C) at -40°C is 7.0 × 107 Pa or less.

Description

Polyamide resin composition for insert molding, metal-resin composite, and method for producing the same

[0001] The present invention relates to a polyamide resin composition for insert molding, a metal-resin composite, and a method for producing the same.

[0002] Polyamide resin compositions have been known as molding materials. Polyamide resin compositions are widely used as materials for various parts, such as automotive parts and electrical and electronic parts, and are known to produce molded articles with excellent mechanical strength.

[0003] For example, Patent Document 1 discloses a polyamide resin composition containing polyamide, glass fiber, glass flakes, and an impact modifier. Patent Document 1 states that the rigidity and toughness of the polyamide resin composition can be improved by adjusting the composition ratio in the polyamide resin composition to make the tensile modulus of the polyamide resin composition greater than 9 GPa.

[0004] Furthermore, for example, Patent Document 2 discloses a polyamide resin composition comprising polyamide, glass fiber, glass flake, a heat stabilizer, and additives, and Patent Document 2 states that the polyamide resin composition has good mechanical properties such as elastic modulus.

[0005] JP 2010-510374 A JP 2020-180280 A

[0006]

[0003] Meanwhile, polyamide resin compositions can be used in insert molding, in which a resin member and a metal member are combined and molded. For molded articles (metal-resin composites) obtained by insert molding using a polyamide resin composition, there is a demand for polyamide resin compositions that can suppress cracks that occur immediately after molding. Furthermore, for the metal-resin composites used in, for example, automobile parts, there is a demand for polyamide resin compositions that can withstand thermal shocks (high heat shock resistance) that occur when the environmental temperature changes to lower or higher temperatures.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a polyamide resin composition for insert molding that can suppress cracks that occur immediately after molding and can improve the heat shock resistance of metal-resin composites, and a metal-resin composite using the same.

[0008] To solve the above problems, one aspect of the present invention relates to polyamide resin compositions according to the following items [1] to

[13] . [1] A polyamide resin composition for insert molding, comprising: a polyamide resin (A); a reinforcing material (B) whose content relative to the total mass of the polyamide resin composition is 10% by mass or more and 50% by mass or less; a modified polyolefin resin (C) whose content relative to the total mass of the polyamide resin composition is 1% by mass or more and 10% by mass or less; and scale-like or plate-like inorganic particles (D) whose content relative to the total mass of the polyamide resin composition is 5% by mass or more and less than 40% by mass, wherein the storage modulus E' at -40°C of the modified polyolefin resin (C) is 7.0 x 10 ７[2] The polyamide resin composition for insert molding according to [1], wherein the polyamide resin (A) comprises a polyamide resin (A1) having a melting point (Tm) of 280°C or higher as measured by differential scanning calorimetry (DSC). [3] The polyamide resin composition for insert molding according to [2], wherein the polyamide resin (A1) comprises two or more polyamide resins having different compositions. [4] The polyamide resin composition for insert molding according to [2] or [3], wherein the polyamide resin (A) comprises a polyamide resin (A2) having a heat of fusion (ΔH) of 5 J / g or lower as measured by differential scanning calorimetry (DSC). [5] The polyamide resin composition for insert molding according to [1], wherein the polyamide resin (A) comprises a polyamide resin (A2) having a heat of fusion (ΔH) of 5 J / g or lower as measured by differential scanning calorimetry (DSC). [6] The polyamide resin composition for insert molding according to any one of [1] to [5], wherein the content of the reinforcing material (B) is 20% by mass or more and 40% by mass or less, based on the total mass of the polyamide resin composition. [7] The polyamide resin composition for insert molding according to any one of [1] to [6], wherein the content of the inorganic particles (D) is 10% by mass or more and 30% by mass or less, based on the total mass of the polyamide resin composition. [8] The density of the modified polyolefin resin (C) is 850 kg / m ３ More than 880kg / m ３[9] The polyamide resin composition for insert molding according to any one of [1] to [7], wherein the modified polyolefin resin (C) contains a functional group structural unit whose content relative to the total mass of the modified polyolefin resin (C) is 0.1% by mass or more and 5.0% by mass or less.

[10] The polyamide resin composition for insert molding according to [9], wherein the content of the functional group structural unit relative to the total mass of the modified polyolefin resin (C) is 0.5% by mass or more and 2.0% by mass or less.

[11] The polyamide resin composition for insert molding according to any one of [1] to

[10] , wherein the modified polyolefin resin (C) has a temperature of 335°C or higher at which a mass loss rate of 10% occurs when the modified polyolefin resin (C) is heated at a temperature increase rate of 10°C / min while flowing dry air at a flow rate of 200 mL / min.

[12] The polyamide resin composition for insert molding according to any one of [1] to

[11] , wherein the total content of the reinforcing material (B) and the inorganic particles (D) is 30% by mass or more and 55% by mass or less, based on the total mass of the polyamide resin composition, and the content of the inorganic particles (D) is 20% by mass or more and 60% by mass or less, based on the total mass of the reinforcing material (B) and the inorganic particles (D).

[13] The polyamide resin composition for insert molding according to any one of [1] to

[12] , wherein the polyamide resin (A1) comprises component units (A1a) derived from a dicarboxylic acid and component units (A1b) derived from a diamine, and the component units (A1a) derived from the dicarboxylic acid comprise 55 mol% to 75 mol% of component units derived from terephthalic acid and 25 mol% to 45 mol% of component units derived from isophthalic acid relative to the total number of moles of the component units (A1b) derived from the dicarboxylic acid, and the component units (A1b) derived from the diamine comprise component units derived from an aliphatic diamine having 4 to 15 carbon atoms.

[0009] In order to solve the above problems, one aspect of the present invention relates to the following molded article

[14] :

[14] A metal resin composite comprising a metal member and a resin member composited with the metal member, the resin member comprising the polyamide resin composition for insert molding according to any one of [1] to

[13] .

[0010] One aspect of the present invention for solving the above problems relates to a molded article according to the following item

[15] :

[15] A method for producing a metal resin composite, comprising the steps of: placing a metal member in a mold; and injecting and filling the mold with the metal member placed therein with the polyamide resin composition for insert molding according to any one of items [1] to

[13] .

[0011] According to the present invention, it is possible to provide a polyamide resin composition for insert molding that can suppress cracks that occur immediately after molding and can improve the heat shock resistance of molded articles, and a molded article using the same.

[0012] Fig. 1 is a schematic diagram showing an exemplary form of a metal-resin composite as a busbar unit. Fig. 2 is a structural diagram showing an exemplary configuration of a moving body (vehicle) having a busbar unit. Fig. 3A is a perspective view showing the shape of an insert test piece prepared for evaluating heat shock resistance in the examples, Fig. 3B is a plan view of the insert test piece, and Fig. 3C is a cross-sectional view of the insert test piece taken along line CC' shown in Fig. 3B.

[0013] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.

[0014] 1. Polyamide Resin Composition for Insert Molding The polyamide resin composition for insert molding in this embodiment contains a polyamide resin (A), a reinforcing material (B), a modified polyolefin resin (C), and scale-like or plate-like inorganic particles (D).

[0015] As described above, there is a demand for a polyamide resin composition for insert molding that can suppress cracks that occur immediately after molding. There is also a demand for a polyamide resin composition for insert molding (hereinafter simply referred to as a polyamide resin composition) that has improved heat shock resistance. According to the findings of the present inventors, it is believed that a metal-resin composite obtained by insert molding using a polyamide resin composition is prone to cracks when the environmental temperature changes to a lower temperature, resulting in a decrease in heat shock resistance.

[0016] Immediately after molding, the temperature drops from the high temperature state during molding to room temperature (e.g., 25°C), causing the resin member containing the polyamide resin composition to shrink. Furthermore, when the temperature drops below room temperature, the resin member containing the polyamide resin composition shrinks even more. When the resin member shrinks, the difference in linear expansion coefficient between the resin member and the metal member is large, so the resin member shrinks more than the metal member. At this time, stress related to the shrinkage of the resin member is thought to occur at the interface between the resin member and the metal member. For this reason, it is thought that the metal-resin composite is particularly prone to cracking immediately after molding and when the temperature changes to low temperatures.

[0017] In contrast, the inventors have conducted research and found that a polyamide resin composition containing the reinforcing agent (B) has a storage modulus E' of 7.0 × 10 at −40° C. ７ It has been found that by incorporating a modified polyolefin resin (C) having a modulus of elasticity of 100 Pa or less and scale-like or plate-like inorganic particles (D), it is possible to suppress the occurrence of cracks immediately after molding and improve heat shock resistance.

[0018] When insert molding is performed on a polyamide resin composition, the polyamide resin composition is poured into a mold in a molten state. At this time, the reinforcing agent (B) described later is considered to be aligned so that its long side direction (the length direction in the case of a fibrous form, or the major axis direction in the case of a granular form) is parallel to the flow direction of the polyamide resin composition. Therefore, it is considered that the difference in the linear expansion coefficient between the resin member and the metal member can be reduced, particularly in the flow direction.

[0019] Similarly, it is considered that the inorganic particles (D) are also arranged so that their long sides are aligned along the flow direction. Here, since the inorganic particles (D) have a length in the direction perpendicular to the flow direction compared to the reinforcing agent (B), it is considered that the difference in linear expansion coefficient between the resin member and the metal member can also be reduced in the direction perpendicular to the flow direction. As a result, it is considered that cracks immediately after molding caused by the difference in linear expansion coefficient between the resin member and the metal member can be suppressed.

[0020] Furthermore, the storage modulus E' at -40°C is 7.0 × 10 ７The modified polyolefin resin (C) having a modulus of elasticity of 100 Pa or less can reduce the elastic modulus of the polyamide resin composition even at low temperatures, thereby imparting flexibility to the resin member. Therefore, it is thought that the stress generated by the contraction of the resin member at low temperatures can be alleviated, thereby suppressing the occurrence of cracks. This can alleviate the stress generated by the difference in linear expansion coefficient between the resin member and the metal member when repeatedly subjected to thermal shocks, thereby suppressing the occurrence of cracks in the resin member.

[0021] Furthermore, the scale-like or plate-like inorganic particles (D) have a larger area spread on the plane of the polyamide resin composition than the spherical inorganic particles. Therefore, they can suppress the permeation of oxygen into the polyamide resin composition and suppress the oxidative degradation of the modified polyolefin resin (C). As a result, it is thought that the deterioration of the function of the modified polyolefin resin (C) to impart flexibility to the resin member due to oxidative degradation can be suppressed, and the occurrence of cracks in the resin member can be suppressed.

[0022] For these reasons, it is believed that the occurrence of cracks immediately after molding of a resin member containing a polyamide resin composition can be suppressed, and the heat shock resistance can be improved.

[0023] 1-1. Polyamide Resin (A) In this embodiment, the polyamide resin (A) may contain only a crystalline polyamide resin, only an amorphous polyamide resin, or both, but preferably contains at least a crystalline semi-aromatic polyamide resin. More specifically, the polyamide resin (A) preferably contains at least a polyamide resin (A1) having a melting point (Tm) measured by differential scanning calorimetry (DSC) of 280°C or higher. In this specification, "crystalline polyamide resin" refers to a polyamide resin having a heat of fusion (ΔH) measured by differential scanning calorimetry (DSC) of 5 J / g or higher.

[0024] 1-1-1. Polyamide Resin (A1) The polyamide resin (A1) has crystallinity, which can increase the tensile strength and modulus of elasticity of a resin member containing the polyamide resin composition. The polyamide resin (A1) can be, for example, a polyamide containing a component unit (A1a) derived from a dicarboxylic acid and a component unit (A1b) derived from a diamine. Hereinafter, a case where the polyamide resin (A1) contains a component unit (A1a) derived from a dicarboxylic acid and a component unit (A1b) derived from a diamine will be described.

[0025] (Component Unit (A1a) Derived from Dicarboxylic Acid) The component unit (A1a) derived from a dicarboxylic acid can include, for example, a component unit derived from an aromatic dicarboxylic acid, a component unit derived from an alicyclic dicarboxylic acid, or a component unit derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Of these, from the viewpoint of obtaining a polyamide resin composition having high crystallinity, tensile strength, and elastic modulus, the component unit (A1a) derived from a dicarboxylic acid preferably includes a component unit derived from an aromatic dicarboxylic acid or an alicyclic dicarboxylic acid, and more preferably includes a component unit derived from an aromatic dicarboxylic acid.

[0026] Examples of aromatic dicarboxylic acids include terephthalic acid and aromatic carboxylic acids other than terephthalic acid. From the viewpoint of enhancing the crystallinity of the polyamide resin, the component units (A1a) derived from dicarboxylic acids preferably contain component units derived from terephthalic acid.

[0027] Examples of terephthalic acid include terephthalic acid, terephthalic acid esters, etc. Among these, terephthalic acid is preferred.

[0028] Examples of aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, and naphthalenedicarboxylic acid, etc. Among these, isophthalic acid is preferred.

[0029] Examples of alicyclic dicarboxylic acids include cyclohexanedicarboxylic acid and its esters.

[0030] The aliphatic dicarboxylic acid has 4 to 20 carbon atoms, and preferably has 6 to 12 carbon atoms. Examples of such aliphatic dicarboxylic acids include adipic acid, azelaic acid, and sebacic acid. Of these, adipic acid and sebacic acid are preferred.

[0031] The content of the component units derived from aromatic dicarboxylic acid or alicyclic dicarboxylic acid is preferably 45 mol% or more and 100 mol% or less, and more preferably 55 mol% or more and 100 mol% or less, based on the total number of moles of the component units (A1a) derived from dicarboxylic acid. When the content is 45 mol% or more, the crystallinity of the polyamide resin can be further increased.

[0032] The dicarboxylic acid-derived component units (A1a) preferably contain 45 mol% or more and 100 mol% or less of terephthalic acid-derived component units, and more preferably 90 mol% or more and 100 mol% or less of terephthalic acid-derived component units, relative to the total number of moles of the dicarboxylic acid-derived component units (a1). When the content of terephthalic acid-derived component units is 45 mol% or more, the melting point of the polyamide resin (A) can be easily increased, and the tensile strength and elastic modulus of the resulting molded article can be increased.

[0033] When the dicarboxylic acid-derived component units (A1a) contain component units derived from terephthalic acid, the dicarboxylic acid-derived component units (A1a) preferably further contain component units derived from isophthalic acid. In this case, the dicarboxylic acid-derived component units (A1a) preferably contain 55 mol% to 75 mol% of component units derived from terephthalic acid and 25 mol% to 45 mol% of component units derived from isophthalic acid, and more preferably contain 65 mol% to 75 mol% of component units derived from terephthalic acid and 25 mol% to 35 mol% of component units derived from isophthalic acid. By ensuring that the isophthalic acid content is 25 mol% or more, the crystallinity of the polyamide resin (A1) can be appropriately reduced. This allows the shrinkage rate of the resin member to be appropriately reduced. Therefore, the stress generated between the resin member and the metal member can be reduced, and the heat shock resistance of the polyamide resin composition can be further improved. When the content of isophthalic acid is 45 mol % or less, an extreme decrease in the crystallinity of the polyamide resin (A1) can be suppressed, and an extreme decrease in the tensile strength of the resin member can be suppressed.

[0034] The content of the component units derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferably from 0 mol % to 55 mol % and more preferably from 0 mol % to 45 mol % relative to the total number of moles of the component units (A1a) derived from dicarboxylic acids.

[0035] (Diamine-Derived Component Units (A1b)) The diamine-derived component units (A1b) can include, for example, component units derived from aliphatic diamines having 4 to 18 carbon atoms, component units derived from alicyclic diamines having 4 to 20 carbon atoms, and aromatic diamines. Of these, the diamine-derived component units (A1b) preferably include component units derived from aliphatic diamines having 4 to 18 carbon atoms.

[0036] The polyamide resin (A1) is preferably a semi-aromatic polyamide in which, when the dicarboxylic acid-derived component units (A1a) include component units derived from an aromatic dicarboxylic acid, the diamine-derived component units (A1b) include component units derived from an aliphatic diamine having 4 to 18 carbon atoms.

[0037] The aliphatic diamine has 4 to 18 carbon atoms, and preferably has 4 to 15 carbon atoms. Examples of such aliphatic diamines include linear alkylenediamines having 4 to 18 carbon atoms, and branched alkylenediamines (alkylenediamines having a side chain) having 4 to 18 carbon atoms.

[0038] Examples of the linear alkylenediamine include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane. Of these, 1,6-diaminohexane, 1,9-nonanediamine, and 1,10-diaminodecane are preferred. Only one type of linear alkylenediamine may be contained, or two or more types may be contained.

[0039] The content of the component units derived from the linear alkylenediamine is preferably 40 mol % or more and 100 mol % or less, and more preferably 40 mol % or more and 80 mol % or less, relative to the total number of moles of the component units (A1b) derived from the diamine.

[0040] Examples of the branched alkylenediamine include 1-butyl-1,2-diaminoethane, 2,2-dimethyldiaminopropane, 1,1-dimethyl-1,4-diaminobutane, 1-ethyl-1,4-diaminobutane, 1,2-dimethyl-1,4-diaminobutane, 1,3-dimethyl-1,4-diaminobutane, 1,4-dimethyl-1,4-diaminobutane, 2,3-dimethyl-1,4-diaminobutane, 2-methyl-1,5-diaminopentane, 2,5-dimethyl-1,6 ... Diaminohexane, 2,4-dimethyl-1,6-diaminohexane, 3,3-dimethyl-1,6-diaminohexane, 2,2-dimethyl-1,6-diaminohexane, 2,2,4-trimethyl-1,6-diaminohexane, 2,4,4-trimethyl-1,6-diaminohexane, 2,4-diethyl-1,6-diaminohexane, 2,3-dimethyl-1,7-diaminoheptane, 2,4-dimethyl-1,7-diaminoheptane, 2,5-dimethyl-1,7-diaminohexane butane, 2,2-dimethyl-1,7-diaminoheptane, 2-methyl-4-ethyl-1,7-diaminoheptane, 2-ethyl-4-methyl-1,7-diaminoheptane, 2,2,5,5-tetramethyl-1,7-diaminoheptane, 3-isopropyl-1,7-diaminoheptane, 3-isooctyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, 1,3-dimethyl-1,8-diaminooctane, 1,4-dimethyl-1,8-diaminooctane Examples of suitable diaminopentanes include 2,4-dimethyl-1,8-diaminooctane, 3,4-dimethyl-1,8-diaminooctane, 4,5-dimethyl-1,8-diaminooctane, 2,2-dimethyl-1,8-diaminooctane, 3,3-dimethyl-1,8-diaminooctane, 4,4-dimethyl-1,8-diaminooctane, 3,3,5-trimethyl-1,8-diaminooctane, 2,4-diethyl-1,8-diaminooctane, and 5-methyl-1,9-diaminononane. Among these, 2-methyl-1,5-diaminopentane is more preferred.

[0041] The content of the component units derived from the branched alkylenediamine is preferably 0 mol % or more and 60 mol % or less, and more preferably 20 mol % or more and 60 mol % or less, relative to the total number of moles of the component units (A1b) derived from the diamine.

[0042] When the diamine-derived component units (A1b) contain the linear and branched alkylenediamine-derived component units in the above-mentioned amounts, the melting point of the polyamide resin (A) can be lowered to a level at which the polyamide resin composition does not cause gas burning during molding, and the melt flowability of the polyamide resin composition during molding can be further improved, and the creep resistance of the molded article at high temperatures can be increased.

[0043] When the diamine-derived component units (A1b) contain both component units derived from a linear alkylenediamine having 4 to 18 carbon atoms and component units derived from a branched alkylenediamine having 4 to 18 carbon atoms, the melt fluidity during molding can be further improved if the content of the component units derived from the linear alkylenediamine is 99 mol% or less based on the total number of moles of both. Furthermore, if the content of the component units derived from the branched alkylenediamine is 50 mol% or less based on the total number of moles, the crystallization rate of the polyamide resin (A) is less likely to be slowed, and sufficient heat resistance is likely to be achieved.

[0044] When the dicarboxylic acid-derived component unit (A1a) contains a component unit derived from isophthalic acid, the diamine-derived component unit (A1b) preferably contains a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms.

[0045] In this case, the content of the component units derived from an aliphatic diamine having 4 to 15 carbon atoms is preferably 30 mol % or more and 100 mol % or less, and more preferably 70 mol % or more and 100 mol % or less, relative to the total number of moles of the component units (A1b) derived from the diamine.

[0046] Examples of the alicyclic diamine having 4 to 20 carbon atoms include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 2,5-bisaminomethylnorbornane, and 2,6-bisaminomethylnorbornane, etc. Examples of the aromatic diamine include metaxylylenediamine, etc.

[0047] The content of the component units derived from the alicyclic diamine having 4 to 20 carbon atoms can be from 0 mol % to 75 mol % and preferably from 35 mol % to 65 mol % relative to the total number of moles of the component units (A1b) derived from the diamine.

[0048] The content of the component units derived from aromatic diamine can be 0 mol % or more and 50 mol % or less, and preferably 0 to 30 mol %, based on the total number of moles of the component units derived from diamine.

[0049] The constituent units of the polyamide resin (A1) and their ratios can be calculated from the ratios charged when the polyamide resin (A1) is prepared, or can be measured by NMR.

[0050] １ In the case of H-NMR measurement, for example, a nuclear magnetic resonance apparatus (ECX400 model manufactured by JEOL Ltd.) is used, the solvent is deuterated orthodichlorobenzene, the sample concentration is 20 mg / 0.6 mL, the measurement temperature is 120° C., and the observation nucleus is １ The conditions were H (400 MHz), sequence was a single pulse, pulse width was 5.12 μsec (45° pulse), repetition time was 7.0 sec, and the number of accumulations was 500 or more. The reference chemical shift was set to 0 ppm for hydrogen in tetramethylsilane, but similar results could also be obtained by setting the peak derived from residual hydrogen in deuterated orthodichlorobenzene at 7.10 ppm as the reference value for the chemical shift. １ Peaks such as H can be assigned by conventional methods.

[0051] １３ ​​In the case of C-NMR measurement, for example, a nuclear magnetic resonance apparatus (ECP500 type manufactured by JEOL Ltd.) is used as the measurement apparatus, a mixed solvent of ortho-dichlorobenzene / heavy benzene (80 / 20% by volume) is used as the solvent, the measurement temperature is 120°C, and the observation nucleus is １３ The conditions were: C (125 MHz), single pulse proton decoupling, 45° pulse, repetition time 5.5 seconds, number of integrations 10,000 or more, and chemical shift reference value 27.50 ppm. Assignment of various signals was performed based on standard methods, and quantification could be performed based on the integrated value of signal intensity.

[0052] Specific examples of the polyamide resin (A1) include polyamide 6T6I, polyamide 6T66, polyamide 6TDT, polyamide 9T, and the like.

[0053] The polyamide resin (A1) preferably contains two or more polyamide resins with different compositions. More specifically, it is preferable that the first polyamide resin is contained in an amount of 50% by mass or more relative to the total mass of the polyamide resin (A1), and that the second polyamide resin, which has a melting point (Tm) or heat of fusion ΔH lower than that of the first polyamide resin, is contained in an amount less than that of the first polyamide resin relative to the total mass of the polyamide resin (A1). This makes it possible to appropriately lower the crystallinity of the polyamide resin (A1) compared to when only one polyamide resin is contained. As a result, the difference in the linear expansion coefficient between the resin member and the metal member can be further reduced, thereby improving heat shock resistance.

[0054] In order to improve the thermal stability during compounding or molding and to further increase the mechanical strength, at least some of the molecular terminal groups of the polyamide resin (A1) may be capped with a terminal capping agent. The terminal capping agent is preferably a monoamine when the molecular terminal is a carboxyl group, and is preferably a monocarboxylic acid when the molecular terminal is an amino group, for example.

[0055] Examples of monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, and butylamine, alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, and aromatic monoamines such as aniline and toluidine. Examples of monocarboxylic acids include aliphatic monocarboxylic acids having 2 to 30 carbon atoms such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid, aromatic monocarboxylic acids such as benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid, and alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid. The aromatic monocarboxylic acid and the alicyclic monocarboxylic acid may have a substituent on the ring structure portion.

[0056] (Physical Properties of Polyamide Resin (A1)) The polyamide resin (A1) in this embodiment has a melting point (Tm) measured by a differential scanning calorimeter (DSC) of 280°C or higher, preferably 280°C or higher and 340°C or lower, and more preferably 290°C or higher and 330°C or lower. When the melting point (Tm) is 280°C or higher, the tensile strength and heat resistance of the polyamide resin composition and molded article can be further increased. Furthermore, when the melting point (Tm) is 340°C or lower, the polyamide resin composition can be easily molded without excessively increasing the molding temperature, and molding processability can be further improved.

[0057] The melting point (Tm) of the polyamide resin (A1) can be adjusted to fall within the above range by adjusting the composition of the polyamide resin (A1). For example, the melting point (Tm) can be increased by increasing the content of component units derived from terephthalic acid in the polyamide resin (A1).

[0058] The polyamide resin (A1) preferably has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of 70°C or higher and 145°C or lower, and more preferably 80°C or higher and 145°C or lower. When the glass transition temperature (Tg) is 90°C or higher, the temperature at which molecular mobility becomes active in a high-temperature environment increases, thereby suppressing molecular mobility and further improving the heat resistance of the polyamide resin composition and molded article. When the glass transition temperature (Tg) is 145°C or lower, the fluidity of the resin composition can be easily maintained without excessively increasing the mold temperature during molding, thereby improving molding processability.

[0059] The heat of fusion (ΔH) of the polyamide resin (A1) measured by differential scanning calorimetry (DSC) is preferably 20 J / g or more and 80 J / g or less. When the heat of fusion (ΔH) of the polyamide resin (A1) is 20 J / g or more, the crystallinity is increased, and the heat resistance and bonding strength of the resin member are likely to be improved. Furthermore, when it is 80 J / g or less, the crystallinity of the polyamide resin (A1) can be appropriately reduced, thereby reducing the shrinkage rate of the resin member and reducing the difference in the linear expansion coefficient between the resin member and the metal member. This can further improve the heat shock resistance of the molded product.

[0060] The heat of fusion (ΔH), melting point (Tm) and glass transition temperature (Tg) of the polyamide resin can be measured using a differential scanning calorimeter (DSC220C, manufactured by Seiko Instruments Inc.).

[0061] Specifically, approximately 5 mg of crystalline polyamide resin is sealed in a measuring aluminum pan and heated from room temperature to 350°C at 10°C / min. To completely melt the resin, it is held at 350°C for 3 minutes and then cooled to 30°C at 10°C / min. After leaving it at 30°C for 5 minutes, it is heated a second time to 350°C at 10°C / min. The temperature (°C) of the endothermic peak during this second heating is taken as the melting point (Tm) of the crystalline polyamide resin, and the inflection point corresponding to the glass transition is taken as the glass transition temperature (Tg). The heat of fusion (ΔH) is determined from the area of ​​the endothermic peak during melting during the first heating process in accordance with JIS K7122.

[0062] The intrinsic viscosity [η] of the polyamide resin (A1) measured at 25°C in 96.5% sulfuric acid is preferably 0.6 dl / g or more and 1.5 dl / g or less. When the intrinsic viscosity [η] of the polyamide resin (A1) is 0.6 dl / g or more, the mechanical strength (tensile strength, etc.) of the molded product is easily increased, and when it is 1.5 dl / g or less, the fluidity of the resin composition during molding is less likely to be impaired. From the same viewpoint, the intrinsic viscosity [η] of the polyamide resin (A1) is more preferably 0.8 dl / g or more and 1.2 dl / g or less. The intrinsic viscosity [η] can be adjusted by, for example, the amount of terminal blocking of the polyamide resin (A1).

[0063] The intrinsic viscosity [η] of polyamide resin (A1) can be measured as follows. 0.5 g of polyamide resin (A1) is dissolved in 50 ml of 96.5% sulfuric acid solution to prepare a sample solution. The flow time of the obtained solution at 25°C ± 0.05°C is measured using an Ubbelohde viscometer and calculated based on the following formula: [η] = ηSP / (C*(1 + 0.205ηSP)) [η]: intrinsic viscosity (dl / g) ηSP: specific viscosity C: sample concentration (g / dl) t: flow time of the sample solution (seconds) t ０ : Number of seconds for blank sulfuric acid to flow (seconds) ηSP = (t - t ０ ) / t ０

[0064] The polyamide resin (A1) can be produced by the same method as that for known polyamide resins, for example, by polycondensing a dicarboxylic acid and a diamine in a homogeneous solution. Specifically, the polyamide resin (A1) can be produced by heating a dicarboxylic acid and a diamine in the presence of a catalyst to obtain a low-order condensate, as described in WO 03 / 085029, and then applying shear stress to the melt of the low-order condensate to polycondense it.

[0065] The dicarboxylic acid-derived component units of the polyamide resin (A1) may include component units derived from a biomass-derived dicarboxylic acid, and the diamine-derived component units may include component units derived from a biomass-derived diamine. The polyamide resin (A1) may also be a biomass-derived polyamide resin (A1) obtained by polymerizing raw materials including a biomass-derived raw material.

[0066] The content of polyamide resin (A1) is preferably 25.00% by mass or more and 80.00% by mass or less, preferably 30.00% by mass or more and 80.00% by mass or less, and more preferably 35.00% by mass or more and 80.00% by mass or less, based on the total mass of the polyamide resin composition. When the content is 25.00% by mass or more, the tensile strength of the polyamide resin composition can be further increased. When the content is 80.00% by mass or less, other components such as the modified polyolefin resin (C) described below can be added to the polyamide resin composition, thereby further improving the heat shock resistance of a resin member containing the polyamide resin composition.

[0067] 1-1-2. Polyamide Resin (A2) In this embodiment, the polyamide resin (A) preferably includes a polyamide resin (A2) having a heat of fusion (ΔH) of 5 J / g or less as measured by differential scanning calorimetry (DSC). Because the polyamide resin (A2) has lower crystallinity than the polyamide resin (A1), the degree of crystallinity during molding of the polyamide resin composition can be reduced. This reduces the shrinkage rate of a resin member containing the polyamide resin composition, thereby reducing stress generated between the resin member and the metal member. As a result, cracking of the resin member due to shrinkage of the resin member immediately after insert molding can be suppressed. Furthermore, because the shrinkage rate can be reduced, stress is less likely to accumulate in the molded product when the ambient temperature is lowered, and cracking of the resin member can also be suppressed, which is believed to further enhance the heat shock resistance of the polyamide resin composition.

[0068] The polyamide resin (A2) preferably has a melting point (Tm) that is not substantially measurable by differential scanning calorimetry (DSC). The phrase "having a melting point (Tm) that is not substantially measurable" means that a transition point corresponding to the melting point is not substantially observed in the above-mentioned measurement method.

[0069] The heat of fusion (ΔH) of the polyamide resin (A2) is preferably 5 J / g or less, more preferably 0 J / g. When the heat of fusion (ΔH) of the polyamide resin (A2) is 5 J / g or less, the crystallinity of the polyamide resin (A2) is appropriately low, so that the flexibility of the resin workpiece containing the polyamide resin composition can be further improved. The polyamide resin (A2) preferably exhibits amorphous properties. The heat of fusion (ΔH) can be measured by the same method as that described for the polyamide (A1).

[0070] The polyamide resin (A2) is not particularly limited as long as it is a polyamide resin having a heat of fusion (ΔH) of 5 J / g or less, but may be, for example, a polyamide containing a component unit (A2a) derived from a dicarboxylic acid and a component unit (A2b) derived from a diamine. Hereinafter, a case where the polyamide resin (A2) contains a component unit (A2a) derived from a dicarboxylic acid and a component unit (A2b) derived from a diamine will be described.

[0071] (Component Unit (A2a) Derived from Dicarboxylic Acid) The component unit (A2a) derived from a dicarboxylic acid preferably includes a component unit derived from isophthalic acid. By including a component unit derived from isophthalic acid, the crystallinity of the polyamide resin (A2) can be further reduced.

[0072] The content of the component units derived from isophthalic acid is preferably 40 mol% or more and 100 mol% or less, and more preferably 50 mol% or more and 100 mol% or less, relative to the total number of moles (A2a) of components derived from dicarboxylic acids in the polyamide resin (A2). When the content of the isophthalic acid component units is 40 mol% or more, the crystallinity of the polyamide resin (A2) can be further reduced.

[0073] The dicarboxylic acid-derived component units (A2a) may further contain component units derived from other dicarboxylic acids other than the isophthalic acid-derived component units, as long as the effects of the present invention are not impaired. Examples of other dicarboxylic acids include aromatic dicarboxylic acids other than isophthalic acid, such as terephthalic acid, 2-methylterephthalic acid, and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. The aliphatic dicarboxylic acids and alicyclic dicarboxylic acids may be the same as the above-mentioned aliphatic dicarboxylic acids and alicyclic dicarboxylic acids, respectively. Of these, aromatic dicarboxylic acids other than isophthalic acid are preferred, and terephthalic acid is more preferred.

[0074] When the dicarboxylic acid-derived component units (A2a) further contain terephthalic acid-derived component units, the molar ratio of isophthalic acid-derived component units to terephthalic acid-derived component units (isophthalic acid-derived component units / terephthalic acid-derived component units) is preferably 55 / 45 to 95 / 5, more preferably 60 / 40 to 90 / 10, and even more preferably 60 / 40 to 80 / 20. When the molar ratio is within the above range, the crystallinity of the polyamide resin (A2) can be further reduced, thereby further suppressing cracking that occurs immediately after insert molding of a resin workpiece containing the polyamide resin composition. Furthermore, cracking at low temperatures can be further suppressed, thereby further improving heat shock resistance.

[0075] (Diamine-Derived Component Units (A2b)) The diamine-derived component units (A2b) preferably include component units derived from an aliphatic diamine having 4 to 15 carbon atoms.

[0076] The polyamide resin (A2) is preferably a semi-aromatic polyamide in which, when the dicarboxylic acid-derived component units (A2a) include isophthalic acid-derived component units, the diamine-derived component units (A2b) include C4-C15 aliphatic diamine-derived component units.

[0077] Examples of the aliphatic diamine having 4 to 15 carbon atoms include those mentioned in connection with the polyamide resin (A1). Of these, the aliphatic diamine is preferably 1,6-diaminohexane.

[0078] The content of the component units derived from aliphatic diamine is preferably 50 mol % or more and 100 mol % or less, and more preferably 60 mol % or more and 100 mol % or less, based on the total number of moles of the component units (A2b) derived from diamine.

[0079] The diamine-derived component units (A2b) may further contain component units derived from other diamines in addition to the aliphatic diamine-derived component units, as long as the effects of the present invention are not impaired. Examples of the other diamines include alicyclic diamines and aromatic diamines. Examples of the alicyclic diamines and aromatic diamines include those described for the polyamide resin (A). The content of the other diamine-derived component units can be, for example, 10 mol% or less based on the total number of moles of the diamine-derived component units (A2b).

[0080] The respective structural units of the polyamide resin (A2) and their ratios can be calculated from the charge ratios when preparing the polyamide resin (A2) or measured by the NMR method. For the NMR method, the same method as described for the polyamide resin (A2) can be used.

[0081] Specific examples of the polyamide resin (A2) include a polycondensate of isophthalic acid / terephthalic acid / 1,6-diaminohexane / bis(3-methyl-4-aminocyclohexyl)methane, a polycondensate of isophthalic acid / terephthalic acid / 1,6-diaminohexane (e.g., polyamide 6I6T), and a polycondensate of isophthalic acid / 2,2,4-trimethyl-1,6-diaminohexane / 2,4,4-trimethyl-1,6-diaminohexane. Of these, a polycondensate of isophthalic acid / terephthalic acid / 1,6-diaminohexane is preferred. The polyamide resin (B) may be comprised of one type alone or two or more types.

[0082] The polyamide resin (A2) preferably has an intrinsic viscosity [η] of 0.4 dl / g or more and 1.6 dl / g or less, and more preferably 0.5 dl / g or more and 1.2 dl / g or less, as measured in 96.5% sulfuric acid at 25° C. The intrinsic viscosity [η] of the polyamide resin (A2) can be measured in the same manner as the intrinsic viscosity [η] of the polyamide resin (A1).

[0083] The polyamide resin (A2) can be produced by the same method as that described for the polyamide resin (A1). The dicarboxylic acid-derived component units of the polyamide resin (A2) may include component units derived from a biomass-derived dicarboxylic acid, and the diamine-derived component units may include component units derived from a biomass-derived diamine. The polyamide resin (A2) may also be a biomass-derived polyamide resin (A2) obtained by polymerizing a group of raw materials including a biomass-derived raw material.

[0084] The content of polyamide resin (A2) is preferably 2.0% by mass or more and 20.0% by mass or less, and more preferably 5.0% by mass or more and 15.0% by mass or less, relative to the total mass of polyamide resin (A). A content of 2.0% by mass or more reduces the crystallinity of the polyamide resin (A) as a whole, thereby improving the flexibility of the resin member and further suppressing cracking immediately after insert molding. For the same reason, cracking at low temperatures is further suppressed, thereby further improving the heat shock resistance of the resin member. Furthermore, a content of 20.0% by mass or less allows a sufficient amount of polyamide resin (A1) to be contained in the polyamide resin composition, thereby further increasing the tensile strength and elastic modulus of the resin member containing the polyamide resin composition.

[0085] The heat of fusion ΔH of the polyamide resin (A) is preferably 10 J / g or more and 70 J / g or less, and more preferably 20 J / g or more and 60 J / g or less. When it is 10 J / g or more, the crystallinity of the polyamide resin (A) is further increased, and the tensile strength and elastic modulus of the resin member are easily increased. Furthermore, when it is 70 J / g or less, the crystallinity of the polyamide resin (A) can be appropriately reduced, thereby reducing the shrinkage rate of the resin member and reducing the difference in the linear expansion coefficient between the resin member and the metal member. This can further improve the heat shock resistance of the molded product.

[0086] 1-2. Reinforcing Material (B) The reinforcing material (B) can impart high mechanical strength (such as tensile strength) to the polyamide resin composition. Examples of the reinforcing material (B) include fibrous reinforcing materials such as glass fiber, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, zinc oxide whiskers, milled fiber, and cut fiber, as well as granular reinforcing materials. One of these may be used alone, or two or more may be used in combination. Among these, the reinforcing material (B) is preferably a fibrous reinforcing material, more preferably glass fiber, wollastonite, or potassium titanate whiskers, and even more preferably glass fiber or wollastonite, because they facilitate increasing the mechanical strength of the molded article.

[0087] The average fiber length of the fibrous reinforcing material can be, for example, 1 μm or more and 20 mm or less, and preferably 5 μm or more and 10 mm or less, from the viewpoints of the moldability of the polyamide resin composition and the mechanical strength and heat resistance of a resin part containing the polyamide resin.

[0088] The average fiber length and average fiber diameter of the fibrous reinforcing material can be measured by the following method. 1) A polyamide resin composition is dissolved in a hexafluoroisopropanol / chloroform solution (0.1 / 0.9% by volume), and then filtered to obtain a filtrate. 2) The filtrate obtained in 1) above is dispersed in water, and the fiber length (Li) and fiber diameter (di) of each of 300 randomly selected fibers are measured using an optical microscope (magnification: 50x). The number of fibers with a fiber length of Li is designated as qi, and the weight average length (Lw) is calculated based on the following formula, and this is the average fiber length of the fibrous reinforcing material. Weight average length (Lw) = (Σqi × Li ２ ) / (Σqi × Li) Similarly, the number of fibers with a fiber diameter Di is taken as ri, and the weight average diameter (Dw) is calculated based on the following formula, and this is taken as the average fiber diameter of the fibrous reinforcing material. Weight average diameter (Dw) = (Σri × Di ２ ) / (Σri × Di)

[0089] The content of the reinforcing material (B) is 10% by mass or more and 50% by mass or less, and preferably 20% by mass or more and 40% by mass or less, based on the total mass of the polyamide resin composition. A content of 10% by mass or more can increase the tensile strength of a resin member containing the polyamide resin composition, and a content of 20% by mass or more can further increase the tensile strength. A content of 50% by mass or less can prevent a decrease in the fluidity of the polyamide resin composition during molding, and a content of 40% by mass or less can further prevent a decrease in the fluidity.

[0090] 1-3. Modified Polyolefin Resin (C) The modified polyolefin resin (C) is an olefin polymer having polyolefin units and functional group structural units. The modified polyolefin resin (C) can be obtained by modifying a polyolefin resin before modification with a compound containing a functional group structural unit. The modified polyolefin resin becomes more easily dispersed in the polyamide resin (A), making it easier to impart flexibility to the resin member.

[0091] Examples of polyolefins include ethylene polymers, propylene polymers, butene polymers, and copolymers of these olefins, etc. Among these, ethylene-α-olefin copolymers are preferred.

[0092] Examples of α-olefins other than ethylene that constitute the ethylene-α-olefin copolymer include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene. Among these, 1-butene and 1-octene are preferred, and 1-butene is more preferred. These α-olefins can be used alone or in combination of two or more. The content of component units derived from the α-olefin in the ethylene-α-olefin copolymer is preferably 0.5 mol% or more and 30 mol% or more, and more preferably 1 mol% or more and 20 mol% or less.

[0093] Examples of the functional group structural unit include functional groups containing heteroatoms. Examples of functional groups containing heteroatoms include carboxylic acid groups (including carboxylic acid anhydride groups), ester groups, ether groups, aldehyde groups, and ketone groups. Of these, carboxylic acid groups (including carboxylic acid anhydride groups) are preferred.

[0094] Examples of compounds containing a carboxylic acid group include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and phthalic acid. Examples of compounds containing a carboxylic acid anhydride group include dicarboxylic acid anhydrides having an α,β-unsaturated bond such as maleic anhydride, itaconic anhydride, and phthalic anhydride. Of these, maleic anhydride is preferred.

[0095] The content (modification amount) of the functional group structural unit of the modified polyolefin resin (C) is preferably 0.1% by mass or more and 5.0% by mass or less, more preferably 0.2% by mass or more and 3.0% by mass or less, and even more preferably 0.5% by mass or more and 2.0% by mass or less. When it is 0.1% by mass or more, the modified polyolefin resin (C) is easily dispersed in the polyamide resin (A), thereby further increasing the flexibility of the resin member and further suppressing the occurrence of cracks in the molded article. Furthermore, when it is 5.0% by mass or less, the viscosity of the polyamide resin composition can be appropriately reduced, thereby suppressing a decrease in injection flowability during molding. Furthermore, the amount of gas generated during molding can be reduced, thereby suppressing gas burning of the molded article and mold contamination.

[0096] The content (modification amount) of the functional group structural unit of the modified polyolefin resin (C) can be calculated from the charge ratio when preparing the modified polyolefin resin (C) or can be measured by the NMR method. For the NMR method, the same method as described for the polyamide resin (A) can be used.

[0097] The storage modulus E' of the modified polyolefin resin (C) at -40°C is 7.0 x 10 ７ From the viewpoint of further suppressing the occurrence of cracks in the resin member at low temperatures and further enhancing the heat shock resistance, the storage modulus E′ is 6.5×10 Pa or less. ７ Pa or less, and more preferably 6.0 × 10 ７ The lower limit of the storage modulus E′ is not particularly limited, but is, for example, 7.0×10 ６ Pa.

[0098] The density of the modified polyolefin resin (C) is 800 kg / m ３ More than 1000kg / m ３ Preferably, it is 850 kg / m or less. ３ More than 880kg / m ３ It is more preferable that the density of the modified polyolefin resin (C) is 800 kg / m or less. ３ When the tensile strength is 850 kg / m or more, the tensile strength of the resin member containing the polyamide resin composition is not easily impaired, and３ If the tensile strength is 1000 kg / m or more, the tensile strength is less likely to be impaired. ３ When the compressive strength is 880 kg / m or less, the resin member is given an appropriate flexibility and the occurrence of cracks at low temperatures can be easily suppressed. Therefore, the heat shock resistance of the resin member is easily improved. ３ When the density is not more than 1000 kJ / cm 2 , the heat shock resistance is more likely to be improved. The density of the modified polyolefin resin (C) can be measured in accordance with JIS K7112:1999.

[0099] The modified polyolefin resin (C) preferably has a melt flow rate (MFR) according to ASTM D1238 at 230°C under a load of 2.16 kg of 0.01 g / 10 min or more and 20 g / 10 min or less, more preferably 0.05 g / 10 min or more and 20 g / 10 min or less, and even more preferably 0.1 g / 10 min or more and 10 g / 10 min or less. Having an MFR of 0.01 g / 10 min or more can prevent a decrease in fluidity during molding of the polyamide resin composition. Having an MFR of 20 g / 10 min or less can prevent a decrease in tensile strength of the molded article.

[0100] When the modified polyolefin resin (C) is heated at a temperature increase rate of 10°C / min while flowing dry air at a flow rate of 200 mL / min, the temperature at which the mass loss rate reaches 10% (hereinafter referred to as the 10% mass loss temperature) is preferably 335°C or higher, and more preferably 450°C or lower. A temperature of 335°C or higher is likely to reduce decomposition of the modified polyolefin resin, thereby making it easier to impart flexibility to the resin part and further improving heat shock resistance. Furthermore, the amount of gas generated during molding can be reduced, thereby suppressing gas burning of molded products and mold contamination. The upper limit of the temperature is not particularly limited, but is, for example, 450°C. In this specification, "dry air" refers to air having a dew point of 15°C or lower under pressure at 0.78 to 0.93 MPa.

[0101] The modified polyolefin resin (C) is obtained by graft-modifying an unmodified polyolefin resin with a compound containing a functional group structural unit.

[0102] Graft modification can be carried out by various conventionally known methods. For example, it may be carried out by a melt modification method in which a polyolefin resin before modification is melted using an extruder and a graft monomer is added to carry out graft copolymerization, or it may be carried out by a solution modification method in which a polyolefin resin before modification is dissolved in a solvent and a graft monomer is added to carry out graft copolymerization. In either case, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft copolymerize the graft monomer.

[0103] Specific examples of the modified polyolefin resin (C) include maleic anhydride-modified ethylene-α-olefin copolymers. Commercially available examples of the modified polyolefin resin (C) include TAFMER MH5020 (storage modulus E′=3.4×10 ７ Pa), TAFMER MH5010 (storage modulus E'=3.2×10 ７ Pa), TAFMER MH7010 (storage modulus E'=5.9×10 ７ Pa) (all manufactured by Mitsui Chemicals, Inc.).

[0104] The content of the modified polyolefin resin (C) is 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 8% by mass or less, and even more preferably 3% by mass or more and 7% by mass or less, relative to the total mass of the polyamide resin composition. A content of 1% by mass or more can increase the flexibility of a resin member containing the polyamide resin composition, suppress cracking of the resin member at low temperatures, and improve heat shock resistance. Furthermore, the modified polyolefin resin (C) can undergo a crosslinking reaction with the polyamide resin (A). Here, a content of 10% by mass or less can appropriately reduce the degree of crosslinking between the polyamide resin (A) and the modified polyolefin resin (C), thereby suppressing a decrease in fluidity during molding of the polyamide resin composition. Furthermore, a content of 10% by mass or less can sufficiently contain other components such as the polyamide resin (A) and the reinforcing material (B), thereby further increasing the tensile strength and elastic modulus of a resin member containing the polyamide resin composition.

[0105] 1-4. Inorganic Particles (D) In ​​the present embodiment, the polyamide resin composition contains scaly or plate-like inorganic particles (D).

[0106] In this specification, "scale-like" or "plate-like" inorganic particles refer to inorganic particles whose surface is composed of multiple flat surfaces and whose area when observed from a predetermined angle (when viewed in plan) is larger than the area when observed from an angle perpendicular to the observation direction.

[0107] Examples of the material of the inorganic particles (D) include glass, mica, kaolin, clay, alumina, and the like.

[0108] The weight-average particle size of the inorganic particles (D) is preferably 20 μm or more and 700 μm or less, more preferably 25 μm or more and 180 μm or less, and even more preferably 30 μm or more and 170 μm or less. When the weight-average particle size is 20 μm or more, it is easy to reduce the difference between the linear expansion coefficient of the resin member and the linear expansion coefficient of the metal member in the direction perpendicular to the flow direction of the polyamide resin composition during molding. Therefore, the heat shock resistance of the resin member can be further improved. Furthermore, when the weight-average particle size is 700 μm or less, it is easy to reduce the difference between the linear expansion coefficient of the resin member and the linear expansion coefficient of the metal member in the flow direction. When the material of the inorganic particles (D) is glass, the weight-average particle size of the inorganic particles (D) is preferably 30 μm or more and 700 μm or less, more preferably 40 μm or more and 180 μm or less, and even more preferably 50 μm or more and 170 μm or less. When the material of the inorganic particles (D) is mica, the weight average particle size of the inorganic particles (D) is preferably 20 μm or more and 180 μm or less, more preferably 25 μm or more and 150 μm or less, and even more preferably 30 μm or more and 100 μm or less. The particle size of the inorganic particles (D) can be measured by a laser diffraction method when the weight average particle size is 30 μm or less, and can be measured by a dry sieving method when the weight average particle size is more than 30 μm.

[0109] The aspect ratio (particle size / thickness) of the inorganic particles (D) is preferably 25 to 70, more preferably 30 to 60. The thickness of the inorganic particles (D) refers to the length of the inorganic particles (D) extending in the observation direction when viewed in plan. Having the aspect ratio within the above range increases the surface area of ​​the inorganic particles (D). This increases the length of the inorganic particles (D) in the direction perpendicular to the flow direction of the polyamide resin composition during molding, thereby reducing the difference in linear expansion coefficient between the metal member and the resin member in the perpendicular direction and improving the heat shock resistance of the resin member. The aspect ratio of the inorganic particles (D) can be determined by measuring the average particle size and average thickness and dividing the average particle size by the average thickness.

[0110] The average thickness of the inorganic particles (D) is preferably 0.5 μm or more and 6.0 μm or less, more preferably 1.5 μm or more and 5.0 μm or less. The average thickness of the inorganic particles (D) can be measured by a water surface particle film method or length measurement using a scanning electron microscope. When measuring the average thickness using a scanning electron microscope, for example, length measurements can be performed on any 10 particles, and the average can be used as the average thickness.

[0111] The inorganic particles (D) are preferably surface-treated with a surface treatment agent or sizing agent such as an epoxy compound, an isocyanate compound, an organic silane compound, an organic titanate compound, or an organic borane. By surface-treating the inorganic particles (D), the affinity between the inorganic particles (D) and the polyamide resin (A) can be increased. This increases the interfacial strength between the inorganic particles (D) and the polyamide resin (A), thereby reducing the difference in linear expansion coefficient between the resin member and the metal member and further improving the heat shock resistance of the resin member. The surface treatment agent is preferably an epoxy compound, an isocyanate compound, or an organic silane compound.

[0112] Examples of commercially available inorganic particles (D) include glass flakes (Fleca REFG-315, Fleca REFG-312, Fleca REFG-301, all manufactured by Nippon Sheet Glass Co., Ltd.), mica particles (Repco Mica M-60, Repco Mica M-200, Repco Mica M-400, all manufactured by Repco Corporation), and the like.

[0113] The content of inorganic particles (D) is preferably 5% by mass or more but less than 40% by mass, and 10% by mass or more but 30% by mass or less, relative to the total mass of the polyamide resin composition. A content of 5% by mass or more reduces the difference in linear expansion coefficient between the resin member and the metal member in the perpendicular direction, thereby further suppressing cracking of the resin member immediately after molding. A content of 10% by mass or more further enhances the heat shock resistance. A content of less than 40% by mass allows for a larger content of reinforcing agent (B) to increase the strength of the polyamide resin composition in the flow direction into the mold during molding. This makes it difficult for the strands to break when the polyamide resin composition is extruded into a strand shape, thereby suppressing a decrease in the molding processability of the polyamide resin composition. Furthermore, a content of 30% by mass or less further suppresses a decrease in the molding processability.

[0114] The total content of the reinforcing agent (B) and the inorganic particles (D) is preferably 30% by mass or more and 55% by mass or less, and more preferably 40% by mass or more and 50% by mass or less, based on the total mass of the polyamide resin composition.

[0115] When the total content is within the above range, the content of the inorganic particles (D) is preferably 20% by mass or more and 60% by mass or less, and more preferably 30% by mass or more and 50% by mass or less, relative to the total content. Increasing the content of the inorganic particles (D) among the reinforcing agent (B) and the inorganic particles (D) can further improve the heat shock resistance of the resin member, but the content of the reinforcing agent (B) is reduced, making it difficult to sufficiently increase the tensile strength and elastic modulus of the resin member. Therefore, by keeping the content of the inorganic particles (D) within the above range, the tensile strength and elastic modulus of the resin member can be sufficiently increased while further improving the heat shock resistance.

[0116] 1-5. Other Components The polyamide resin composition may contain other known components.

[0117] Examples of other components include nucleating agents, lubricants, colorants, heat stabilizers, corrosion resistance improvers, anti-drip agents, ion scavengers, elastomers (rubbers), antistatic agents, mold release agents, antioxidants (phenols, amines, sulfurs, phosphorus compounds, etc.), heat stabilizers other than those mentioned above (lactone compounds, vitamin E compounds, hydroquinones, etc.), light stabilizers (benzotriazoles, triazines, benzophenones, benzoates, hindered amines, oxanilides, etc.), other polymers (polyolefins, olefin copolymers such as ethylene-propylene copolymers, ethylene-1-butene copolymers, olefin copolymers such as propylene-1-butene copolymers, polystyrene, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesin, silicone resin, LCP, etc.).

[0118] Nucleating Agent The nucleating agent can promote the crystallization of the polyamide resin (A), thereby further increasing the tensile strength and elastic modulus of the resin member.

[0119] Examples of nucleating agents include metal salt compounds such as sodium 2,2-methylenebis(4,6-di-t-butylphenyl)phosphate, aluminum tris(p-t-butylbenzoate), and stearates; sorbitol compounds such as bis(p-methylbenzylidene)sorbitol and bis(4-ethylbenzylidene)sorbitol; and inorganic substances such as talc, calcium carbonate, and hydrotalcite. Of these, talc is preferred from the viewpoint of further increasing the crystallinity of the molded body. These nucleating agents may be used alone or in combination of two or more.

[0120] Talc is generally a hydrous magnesium silicate (SiO ２ :58~64%, MgO:28~32%, Al ２ O ３ :0.5~5%, Fe ２ O ３: 0.3 to 5%) as a main component. The average particle size of talc is not particularly limited, but is preferably 1 to 15 μm. When the average particle size of talc is within the above range, the talc can be easily dispersed in the polyamide resin (A) without impairing the fluidity of the polyamide resin composition. From the same viewpoint, the average particle size of talc is more preferably 1 to 7.5 μm. The average particle size of talc can be measured by a laser diffraction method, for example, using a Shimadzu particle size distribution analyzer SALD-2000A manufactured by Shimadzu Corporation.

[0121] The content of the nucleating agent is preferably 0.10 parts by mass or more and 5.00 parts by mass or less, and more preferably 0.10 parts by mass or more and 3.00 parts by mass or less, relative to the total mass of the polyamide resin composition. When the content of the nucleating agent is within the above range, the crystallinity of the molded body is easily sufficiently increased, and sufficient mechanical strength is easily obtained.

[0122] The lubricant improves the injection flowability of the polyamide resin composition and improves the appearance of the resulting molded article. The lubricant can be a metal salt of a fatty acid, such as a metal salt of an oxycarboxylic acid or a metal salt of a higher fatty acid.

[0123] The oxycarboxylic acid constituting the oxycarboxylic acid metal salt may be an aliphatic oxycarboxylic acid or an aromatic oxycarboxylic acid. Examples of the aliphatic oxycarboxylic acid include aliphatic oxycarboxylic acids having 10 to 30 carbon atoms, such as α-hydroxymyristic acid, α-hydroxypalmitic acid, α-hydroxystearic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid, α-hydroxyhexaeicosanoic acid, α-hydroxyoctaeicosanoic acid, α-hydroxytriacontanoic acid, β-hydroxymyristic acid, 10-hydroxydecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 12-hydroxystearic acid, and ricinoleic acid. Examples of the aromatic oxycarboxylic acid include salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, gallic acid, mandelic acid, and trovic acid.

[0124] Examples of the metal constituting the metal oxycarboxylic acid salt include alkali metals such as lithium, and alkaline earth metals such as magnesium, calcium and barium.

[0125] Of these, the metal oxycarboxylic acid salt is preferably a metal salt of 12-hydroxystearic acid, and more preferably magnesium 12-hydroxystearate and calcium 12-hydroxystearate.

[0126] Examples of the higher fatty acid that constitutes the higher fatty acid metal salt include higher fatty acids having 15 to 30 carbon atoms, such as stearic acid, oleic acid, behenic acid, behenic acid, and montanic acid.

[0127] Examples of metals constituting the above higher fatty acid metal salts include calcium, magnesium, barium, lithium, aluminum, zinc, sodium, and potassium.

[0128] Of these, the higher fatty acid metal salts are preferably calcium stearate, magnesium stearate, barium stearate, calcium behenate, sodium montanate, and calcium montanate.

[0129] The content of the lubricant is preferably 0.01% by mass or more and 1.30% by mass or less relative to the total mass of the polyamide resin composition. When the content of the lubricant is 0.01% by mass or more, the flowability during molding tends to be improved, and the appearance of the obtained molded product tends to be improved. When the content of the lubricant is 1.30% by mass or less, gas due to decomposition of the lubricant is unlikely to be generated during molding, and the appearance of the product tends to be good.

[0130] 1-5-3. Colorant The colorant imparts a desired color tone to the molded article. The colorant is not particularly limited, but may be a pigment. Examples of pigments include inorganic pigments such as carbon black, alumina, titanium oxide, chromium oxide, iron oxide, zinc oxide, and barium sulfate, and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, thioindigo pigments, and indanthrene pigments.

[0131] The content of the colorant is preferably 0.01% by mass or more and 5.00% by mass or less, and more preferably 0.10% by mass or more and 2.00% by mass or less, relative to the total mass of the polyamide resin composition. The colorant imparts a desired color tone to the molded product. The colorant is not particularly limited, but may be a pigment. Examples of pigments include inorganic pigments such as carbon black, alumina, titanium oxide, chromium oxide, iron oxide, zinc oxide, and barium sulfate, and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, thioindigo pigments, and indanthrene pigments.

[0132] The content of the colorant is preferably 0.01% by mass or more and 5.00% by mass or less, and more preferably 0.10% by mass or more and 2.00% by mass or less, based on the total mass of the polyamide resin composition.

[0133] The polyamide resin composition can be produced by a known resin kneading method, for example, by mixing the above-mentioned polyamide resin and, if necessary, other components in a Henschel mixer, V blender, ribbon blender, or tumbler blender, or by mixing and then melt-kneading the resulting mixture in a single-screw extruder, multi-screw extruder, kneader, or Banbury mixer, followed by granulation or pulverization.

[0134] 2. Metal Resin Composite (Insert Molded Article) The metal resin composite according to this embodiment includes a metal member and a resin member that is composited with the metal member and includes the polyamide resin composition described above.

[0135] 2-1. Resin member The resin member contains the polyamide resin composition described above. The proportion of the polyamide resin composition relative to the total mass of the resin member is preferably 50.00% by mass or more, more preferably 60.00% by mass or more, and even more preferably 70.00% by mass or more. The upper limit of the proportion of the polyamide resin composition relative to the total mass of the resin member is not particularly limited, but can be 100.00% by mass or less, or may be 90.00% by mass or less, or may be 80.00% by mass or less.

[0136] The material and shape of the metal member are not particularly limited as long as it is made of metal. For example, the material of the metal member can be iron, copper, nickel, gold, silver, platinum, cobalt, zinc, lead, tin, titanium, chromium, aluminum, magnesium, manganese, or an alloy such as stainless steel, brass, or phosphor bronze.

[0137] These materials can be selected depending on the application of the metal-resin composite. For example, when thermal conductivity is required, aluminum, aluminum alloys, magnesium, magnesium alloys, copper, and copper alloys are preferred, with copper and copper alloys being more preferred. Furthermore, when weight reduction and strength are required, aluminum, aluminum alloys, magnesium, and magnesium alloys are preferred.

[0138] The metal member preferably has a surface roughened by any method, as long as the surface is roughened by a chemical treatment such as immersion in a treatment solution containing a base or acid or etching, or by a physical treatment such as laser or blasting.

[0139] The surface of the roughened metal member preferably has a center-to-center distance (pitch) of 5 nm or more and 500 μm or less between the multiple convex portions formed by the surface roughening treatment. When the center-to-center distance between the multiple convex portions is 5 nm or more, the recesses between the convex portions are appropriately large, making it easier for the resin member to sufficiently penetrate into the recesses during bonding, thereby further improving the bonding strength between the metal member and the resin member. Furthermore, when the center-to-center distance between the multiple convex portions is 500 μm or less, the recesses do not become too large, thereby further suppressing the formation of gaps at the metal-resin interface of the metal-resin composite and further improving airtightness. From the same perspective, the center-to-center distance between the multiple convex portions is more preferably 5 μm or more and 250 μm or less. The center-to-center distance between the multiple convex portions is the average value of the distance between the center of one convex portion and the center of the adjacent convex portion.

[0140] The center-to-center distance of the multiple convex portions can be measured by removing the resin member from the metal-resin composite by mechanical peeling, solvent washing, or the like, and observing the surface of the exposed metal member using an electron microscope or laser microscope, or a surface roughness measuring device.

[0141] Specifically, when the center-to-center distance between the multiple protrusions is less than 0.5 μm, the protrusions can be observed using an electron microscope, and when the center-to-center distance between the multiple protrusions is 0.5 μm or more, the protrusions can be observed using a laser microscope or a surface roughness measuring device. For example, in a photograph of the surface of a metal member taken with an electron microscope or a laser microscope, 50 random protrusions are selected and the center-to-center distance between each of these protrusions is measured. All the measured values ​​of the center-to-center distance between the protrusions are then added up and divided by 50 (average), which is then used as the "center-to-center distance between the multiple protrusions."

[0142] The average value of the ten-point average roughness (Rz) of the roughened surface of the metal member over an evaluation length of 4 mm is not particularly limited, but is preferably greater than 2 μm, more preferably greater than 2 μm and not greater than 50 μm, and even more preferably greater than 2.5 μm and not greater than 45 μm.

[0143] The average value of the ten-point average roughness (Rz) can be measured in accordance with JIS B0601 (ISO 4287). Specifically, the ten-point average roughness (Rz) is measured on a total of six straight line portions, including three arbitrary straight line portions parallel to each other and three arbitrary straight line portions perpendicular to the three arbitrary straight line portions, and the average value of these is taken as the average Rz value.

[0144] The average length of the roughness curve element (RSm) of the roughened surface of the metal member is preferably 0.5 μm or more and 500 μm or less. In particular, from the viewpoint of further increasing the bonding strength, it is preferable that the center-to-center distance between the plurality of convex portions is less than 0.5 μm and the average length of the roughness curve element (RSm) is 0.5 μm or more and 500 μm or less. The average length of the roughness curve element can also be measured according to JIS B0601 (ISO 4287) as described above.

[0145] 3. Method for Manufacturing a Metal-Resin Composite A third embodiment of the present invention relates to a method for manufacturing the above-mentioned metal-resin composite. The method for manufacturing a metal-resin composite is not particularly limited, but may include, for example, the steps of (1) preparing a metal member, (2) placing the metal member in a mold and injecting a molten polyamide resin composition into the mold, and (3) cooling the polyamide resin composition. The step (1) of preparing a metal member may include a step of roughening the surface of the metal member.

[0146] 3-1. Preparation of Metal Member First, the above-described metal member is prepared. At this time, at least a part of the surface of the metal member may be roughened, or a metal member having an uneven structure on at least a part of the surface may be prepared.

[0147] The method for roughening the surface of the metal member is not particularly limited. For example, a method using laser processing, an aqueous solution of an inorganic base such as NaOH, or HCl or HNO ３ a method of treating a metal member by an anodic oxidation method; a displacement crystallization method in which etching is performed with an acid-based etching agent (preferably an acid-based etching agent aqueous solution containing an inorganic acid, ferric ions, cupric ions, and, if necessary, manganese ions, aluminum chloride hexahydrate, sodium chloride, etc.); a method of immersing a metal member in an aqueous solution of hydrazine hydrate, ammonia, a water-soluble amine compound, etc.; and a hot water treatment method.

[0148] 3-2. Insert molding Next, a metal member is placed in a mold, and the molten polyamide resin composition is injected into the mold to fill it, thereby combining the softened or molten polyamide resin composition with the prepared metal member.

[0149] Specifically, the prepared metal member is first placed in a cavity (space) within an injection mold. Then, the polyamide resin composition is injected and filled into the cavity of the mold so that at least a portion of the polyamide resin composition contacts the metal member. This allows the injected molten polyamide resin composition to come into contact with the surface of the metal member. The temperature of the injection mold at this time is not particularly limited as long as it is a temperature at which the polyamide resin composition can be melted to a state suitable for injection molding, and can be, for example, 100 to 350°C.

[0150] As the mold, a known injection molding mold, for example, a mold for high speed heat cycle molding (RHCM, heat & cool molding) or a core back mold for foam molding can be used.

[0151] 3-3. Cooling Thereafter, the polyamide resin composition in contact with the surface of the metal member is cooled and solidified, thereby obtaining a metal resin composite in which the resin member containing the polyamide resin composition is composited with the metal member.

[0152] 4. Applications The above-described metal-resin composite is suitable for use in various applications where metal-resin composites are currently being used or where their application is being considered.

[0153] Examples of such applications include vehicle structural parts, vehicle mounted items, housings for electronic devices, housings for home appliances, structural parts, machine parts, various automobile parts, electronic device parts, household goods applications such as furniture and kitchen utensils, medical equipment, building material parts, other structural parts, and exterior parts.

[0154] More specifically, examples of the above applications include, in the vehicle field, instrument panels, console boxes, door handles, door trim, shift levers, pedals, glove boxes, bumpers, hoods, fenders, trunks, doors, roofs, pillars, seats, steering wheels, bus bars, terminals, motors, power conversion devices (inverters, converters), ECU boxes, electrical components, engine peripheral components, drivetrain / gear peripheral components, intake / exhaust system components, and cooling system components, etc. Precision electronic components include connectors, relays, gears, etc.

[0155] Furthermore, the metal-resin composite can be used in various home appliances, such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilation fans, projectors, speakers, and other home appliances, as well as electronic information devices such as personal computers, mobile phones, smartphones, digital cameras, tablet PCs, portable music players, portable game consoles, chargers, and batteries, by combining the high thermal conductivity of the copper member with the insulating properties of the resin member.

[0156] Other example applications include components for lithium ion secondary batteries and robots.

[0157] For example, the metal-resin composite can be used in a bus bar unit of a mobile body (vehicle) such as an automobile.

[0158] 1 is a schematic diagram showing an exemplary embodiment of the metal-resin composite as a busbar unit. The busbar unit 100 includes a busbar 110, which is a conductive metal member (e.g., a copper metal member) and serves as a conductor for supplying current to each member, and a holding member 120, which is the resin member described above and serves as a protective member for protecting the busbar 110.

[0159] Of the surfaces of busbar 110, which is a metal member, the surface that comes into contact with retaining member 120 is roughened, and retaining member 120, which is a resin member (a resin member including a molded body of a polyamide resin composition), is joined to this roughened surface.

[0160] The bus bar unit 100 can be used to electrically connect a motor of a moving object and an inverter that controls the power supplied to the motor via the bus bar 110.

[0161] 2 is a diagram showing an exemplary configuration of a mobile body (vehicle) having the busbar unit 100. The mobile body 200 has a body 210, a power supply 220 such as a secondary battery that supplies power to drive the body 210, and a drive unit 230 that drives the body 210 with the power supplied from the power supply 220.

[0162] Drive unit 230 has an inverter 232 that controls the power (current) from power supply 220, a motor 234 that rotates by receiving the power controlled by inverter 232, and a bus bar unit 100 that has bus bars 110 that connect inverter 232 and motor 234. Motor 234 is housed in a motor case 236 together with a reducer 235 that converts the rotational speed obtained by motor 234 into a rotational speed for driving machine body 210. Bus bar unit 100 is attached to motor case 236, and bus bars 110 communicate from the inside to the outside of motor case 236 via bus bar unit 100.

[0163] The motor case 236 stores a coolant (coolant oil) for cooling the motor 234. The connection between the bus bar unit 100 and the motor case 236 is sealed with a sealing member such as an O-ring, thereby preventing oil from leaking from the inside of the motor case 236 to the outside.

[0164] 2 shows an example in which the moving body 200 is a vehicle such as an automobile, but the moving body 200 is not particularly limited as long as it has a body and a drive unit and is capable of moving. For example, the moving body 200 may be a vehicle such as an automobile, a motorcycle, or an electric bicycle, as well as a railroad car, a ship, an airplane, a drone, or a robot.

[0165] The present invention will be described below with reference to examples, which should not be construed as limiting the scope of the present invention.

[0166] 1. Synthesis / preparation of materials 1-1. Synthesis of polyamide resin (A) <Preparation of polyamide resin (A-1) (6T6I)> 2,800 g (24.1 mol) of 1,6-diaminohexane, 2,774 g (16.7 mol) of terephthalic acid, 1,196 g (7.2 mol) of isophthalic acid, 5.7 g (5.4 × 10) of sodium hypophosphite monohydrate as a catalyst. －２36.6 g (0.30 mol) of benzoic acid as a molecular weight modifier, and 545 g of distilled water were placed in a 13.6 L autoclave and purged with nitrogen. Stirring was started at 190°C, and the internal temperature was raised to 250°C over 3 hours. At this time, the internal pressure of the autoclave was raised to 3.03 MPa. After continuing the reaction for 1 hour, the low-order condensate was discharged into the atmosphere through a spray nozzle installed at the bottom of the autoclave and extracted. Thereafter, the low-order condensate was cooled to room temperature, pulverized in a pulverizer to a particle size of 1.5 mm or less, and dried at 110°C for 24 hours. The water content of the obtained low-order condensate was 4100 ppm, and the intrinsic viscosity [η] was 0.15 dl / g.

[0167] Next, this low-order condensate was placed in a tray-type solid-state polymerization reactor, and after purging with nitrogen, the reactor was heated to 180°C over approximately 1 hour and 30 minutes. The reaction was then continued for 1 hour and 30 minutes, and the temperature was then lowered to room temperature. The intrinsic viscosity [η] of the resulting prepolymer was 0.20 dL / g.

[0168] Thereafter, the obtained prepolymer was melt-polymerized in a twin-screw extruder having a screw diameter of 30 mm and an L / D ratio of 36 at a barrel setting temperature of 330°C, a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h to obtain a polyamide resin (A-1).

[0169] The resulting polyamide resin (A-1) had an intrinsic viscosity [η] of 1.00 dl / g, a melting point (Tm) of 330° C., a glass transition temperature (Tg) of 125° C., and a heat of fusion (ΔH) of 50 J / g. The resulting polyamide resin (A-1) had a composition in which the content of component units derived from terephthalic acid among component units derived from dicarboxylic acid was 70 mol %, the content of component units derived from isophthalic acid was 30 mol %, and the content of component units derived from 1,6-diaminohexane among component units derived from diamine was 100 mol %.

[0170] <Synthesis of Polyamide Resin (A-2) (6T66)> Polyamide resin (A-2) was obtained in the same manner as in the synthesis of polyamide resin (A-1), except that the raw materials used were changed to 2,184 g (13.1 mol) of terephthalic acid, 2,800 g (24.1 mol) of 1,6-hexanediamine, and 1,572 g (10.8 mol) of adipic acid.

[0171] The resulting polyamide resin (A-2) had an intrinsic viscosity [η] of 0.80 dl / g, a melting point (Tm) of 310°C, a glass transition temperature (Tg) of 85°C, and a heat of fusion (ΔH) of 50 J / g. The resulting polyamide resin (A-2) had a composition in which the content of component units derived from terephthalic acid among component units derived from dicarboxylic acid was 55 mol%, the content of component units derived from adipic acid was 45 mol%, and the content of component units derived from 1,6-diaminohexane among component units derived from diamine was 100 mol%.

[0172] <Synthesis of Polyamide Resin (A-3) (6T66)> Polyamide resin (A-3) was obtained in the same manner as in the synthesis of polyamide resin (A-1), except that the raw materials were changed to 1720 g (10.4 mol) of terephthalic acid, 2800 g (24.1 mol) of 1,6-hexanediamine, and 1849 g (12.7 mol) of adipic acid.

[0173] The resulting polyamide resin (A-3) had an intrinsic viscosity [η] of 0.90 dl / g, a melting point (Tm) of 295°C, a glass transition temperature (Tg) of 75°C, and a heat of fusion (ΔH) of 60 J / g. The resulting polyamide resin (A-3) had a composition in which the content of component units derived from terephthalic acid among component units derived from dicarboxylic acid was 45 mol%, the content of component units derived from adipic acid was 55 mol%, and the content of component units derived from 1,6-diaminohexane among component units derived from diamine was 100 mol%.

[0174] <Synthesis of Polyamide Resin (A-4) (6TDT)> Polyamide resin (A-4) was obtained in the same manner as in the synthesis of polyamide resin (A-1), except that the raw materials were changed to 3655 g (22.0 mol) of terephthalic acid, 1312 g (11.3 mol) of 1,6-diaminohexane, and 1312 g (11.3 mol) of 2-methyl-1,5-diaminopentane.

[0175] The resulting polyamide resin (A-4) had an intrinsic viscosity [η] of 0.90 dl / g, a melting point (Tm) of 300°C, a glass transition temperature (Tg) of 140°C, and a heat of fusion (ΔH) of 40 J / g. The resulting polyamide resin (A-4) had a composition in which the content of component units derived from terephthalic acid among component units derived from dicarboxylic acid was 100 mol%, and the content of component units derived from 1,6-diaminohexane among component units derived from diamine was 50 mol%, and the content of component units derived from 2-methyl-1,5-diaminopentane was 50 mol%.

[0176] <Synthesis of Polyamide Resin (A-5) (9T)> 4,537.7 g (27.3 mol) of terephthalic acid, 4,385 g (27.5 mol) of a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine (1,9-nonanediamine:2-methyl-1,8-octanediamine (molar ratio) = 80:20), 9.12 g (8.6 × 10) of sodium hypophosphite monohydrate as a catalyst, and －２ 41.5 g (0.34 mol) of benzoic acid as a molecular weight modifier, and 2.5 L of distilled water were placed in a 20.0 L autoclave and purged with nitrogen. The mixture was stirred at 100°C for 30 minutes, and the temperature inside the autoclave was raised to 220°C over 2 hours. At this time, the internal pressure of the autoclave was raised to 2.00 MPa. After continuing the reaction for 2 hours, the temperature inside the autoclave was further raised to 230°C. The reaction was continued for 2 hours while maintaining the temperature at 230°C, and the water vapor inside the autoclave was gradually released to maintain the pressure at 2 MPa. Next, the pressure was reduced to 1 MPa over 30 minutes, and the reaction was continued for another hour, yielding a prepolymer with an intrinsic viscosity [η] of 0.15 dl / g. This prepolymer was dried at 100°C under reduced pressure for 12 hours and pulverized to a particle size of 2 mm or less. This was polymerized in a solid-state polymerization apparatus at 230° C. and 13 Pa (0.1 mmHg) for 10 hours to obtain polyamide resin (A-5).

[0177] The resulting polyamide resin (A-5) had an intrinsic viscosity [η] of 1.20 dl / g, a melting point (Tm) of 300° C., and a glass transition temperature (Tg) of 125° C. The composition of the resulting polyamide resin (A-5) was such that the content of component units derived from terephthalic acid among component units derived from dicarboxylic acid was 100 mol %, the content of component units derived from 1,9-nonanediamine among component units derived from diamine was 80 mol %, and the content of component units derived from 2-methyl-1,8-octanediamine was 20 mol %.

[0178] <Synthesis of Polyamide Resin (A-6) (6I6T)> Polyamide resin (A-6) was obtained in the same manner as in the synthesis of polyamide resin (A-1), except that the raw materials were changed to 2774 g (16.7 mol) of isophthalic acid, 2800 g (24.1 mol) of 1,6-diaminohexane, and 1196 g (7.2 mol) of terephthalic acid.

[0179] The intrinsic viscosity [η] of the obtained polyamide resin (A-6) was 0.54 dl / g, the melting point (Tm) was not measured, the glass transition temperature (Tg) was 125°C, and the heat of fusion (ΔH) was 0 J / g. Furthermore, the composition of the obtained polyamide resin (A-6) was such that the content of component units derived from terephthalic acid among component units derived from dicarboxylic acid was 30 mol%, the content of component units derived from isophthalic acid was 70 mol%, and the content of component units derived from 1,6-diaminohexane among component units derived from diamine was 100 mol%.

[0180] 1-2. Reinforcement (B) Glass fiber (CS 03JA FT2A, manufactured by Owens Corning, average fiber diameter 10.5 μm, average fiber length 3 mm) was used.

[0181] 1-3. Synthesis of Modified Polyolefin Resin (C) <Synthesis of Modified Polyolefin Resin (C-1)> 0.63 mg of bis(1,3-dimethylcyclopentadienyl)zirconium dichloride was placed in a glass flask that had been thoroughly purged with nitrogen, and 1.57 ml of a toluene solution of methylaminoxane (Al; 0.13 mmol / L) and 2.43 ml of toluene were added to obtain a catalyst solution. Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a 2 L stainless steel autoclave that had been thoroughly purged with nitrogen, and the temperature within the system was raised to 80°C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml of the catalyst solution prepared above (0.0005 mmol as Zr) were pressure-injected into the system with ethylene, and the polymerization reaction was initiated. Ethylene was continuously supplied to maintain the total pressure at 8.0 kg / cm. ２ The temperature was kept at -G, and polymerization was carried out at 80°C for 30 minutes. A small amount of ethanol was introduced into the system to terminate the polymerization, and then unreacted ethylene was purged. The resulting solution was dropped into a large excess of methanol to precipitate a white solid. This white solid was recovered by filtration and dried overnight under reduced pressure to obtain a white solid (ethylene-1-butene copolymer).

[0182] The ethylene content of the ethylene-1-butene copolymer was 81 mol %. The density was 860 g / m ３ The MFR (ASTM D 1238, 190°C, 2.16 kg load) was 0.5 g / 10 min, and the melting point was 35°C.

[0183] 100 parts by mass of the obtained ethylene-1-butene copolymer was mixed with 1.0 part by mass of maleic anhydride and 0.04 part by mass of peroxide (Perhexyne 25B, manufactured by NOF Corporation). The obtained mixture was melt-graft-modified in a twin-screw extruder set at 230°C to obtain a modified polyolefin resin (C-1).

[0184] The modification amount of the modified polyolefin resin (C-1) was 0.8% by mass. The density was 866 kg / m ３, MFR (ASTM D 1238, 230°C, 2.16 kg load) is 0.27 g / 10 min, and the storage modulus E' at -40°C is 3.4 × 10 ７ The 10% mass loss temperature was 357°C.

[0185] <Modified Polyolefin Resin (C-2)> Maleic anhydride-modified SEBS (Tuftec M1913, manufactured by Asahi Kasei Corporation) was used. The modification amount of the modified polyolefin resin (C-2) was 1.0% by mass. The density was 920 kg / m ３ , MFR (ASTM D 1238, 230°C, 2.16 kg load) is 5.0 g / 10 min, and the storage modulus E' at -40°C is 2.4 × 10 ８ The 10% mass loss temperature was 340°C.

[0186] <Modified Polyolefin Resin (C-3)> Maleic anhydride-modified EPDM (KEPA 1130, manufactured by Kumho Polychem Co., Ltd.) was used. The density of the modified polyolefin resin (C-3) was 880 kg / m ３ , MFR (ASTM D 1238, 230°C, 2.16 kg load) is 3.0 g / 10 min, and the storage modulus E' at -40°C is 7.9 × 10 ７ The 10% mass loss temperature was 328°C.

[0187] <Synthesis of modified polyolefin resin (C-4)> Linear low-density polyethylene (density: 0.92 g / cm ３ 100 parts by mass of a polyethylene glycol acrylate copolymer (PEG-1400, MFR (190°C / 2.16 kg load) 4 g / 10 min), 1.0 part by mass of maleic anhydride, and 0.07 part by mass of peroxide (Perhexyne 25B, manufactured by NOF Corporation) were mixed in a Henschel mixer. The resulting mixture was melt-graft-modified in a 65 mmφ single-screw extruder set at 230°C to obtain a graft-modified polyethylene.

[0188] The modified polyolefin resin (C-4) obtained had a modification amount of 0.9% by mass and a density of 915 kg / m ３, MFR (ASTM D 1238, 230°C, 2.16 kg load) is 0.7 g / 10 min, and the storage modulus E' at -40°C is 1.5 × 10 ９ The 10% mass loss temperature was 421°C.

[0189] 1-4. Synthesis of Polyolefin Resin A catalyst solution was prepared by adding 0.63 mg of bis(1,3-dimethylcyclopentadienyl)zirconium dichloride to a glass flask thoroughly purged with nitrogen, followed by 1.57 ml of a toluene solution of methylaluminoxane (Al; 0.13 mmol / L) and 2.43 ml of toluene. Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a 2-liter stainless steel autoclave thoroughly purged with nitrogen, and the temperature inside the system was raised to 80°C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml of the catalyst solution prepared above (0.0005 mmol as Zr) were pressure-charged into the system with ethylene to initiate the polymerization reaction. The total pressure was maintained at 8.0 kg / cm2-G by continuously supplying ethylene, and the polymerization was carried out at 80°C for 30 minutes. A small amount of ethanol was introduced into the system to terminate the polymerization, after which the unreacted ethylene was purged. The resulting solution was dropped into a large excess of methanol to precipitate a white solid, which was collected by filtration and dried overnight under reduced pressure to obtain a white solid (ethylene-1-butene copolymer).

[0190] The ethylene content of the ethylene-1-butene copolymer was 81 mol %. The density was 861 g / m ３ The MFR (ASTM D 1238, 230°C, 2.16 kg load) was 0.9 g / 10 min, and the storage modulus E' at -40°C was 3.1 × 10 ７ It was Pa.

[0191] 1-5. Inorganic particles (D) <Inorganic particles (D-1)> Glass flakes (Fleka REFG-315, manufactured by Nippon Sheet Glass Co., Ltd., weight average particle size 160 μm, average thickness 5 μm, aspect ratio: 32, scaly, surface-treated with a urethane-based compound (sizing agent) and an aminosilane-based compound (surface treatment agent)) were used.

[0192] <Inorganic Particles (D-2)> Mica particles 1 (Repco Mica M-60, manufactured by Repco Corporation, weight average particle size 160 μm, average thickness 2.7 μm, aspect ratio: 60, scale-like) were used.

[0193] <Inorganic Particles (D-3)> Mica particles 2 (Repco Mica M-200, manufactured by Repco Corporation, weight average particle size 55 μm, average thickness 1.7 μm, aspect ratio: 33, scale-like) were used.

[0194] <Inorganic Particles (D-4)> Mica particles 3 (Repco Mica M-400, manufactured by Repco Corporation, weight average particle size 24 μm, aspect ratio: 28, scale-like) were used.

[0195] The aspect ratios of inorganic particles (D-1) to (D-4) were calculated by measuring the average particle size and average thickness of each inorganic particle and dividing the average particle size by the average thickness. The average particle sizes of inorganic particles (D-2) to (D-3) were measured by dry sieving, and the average particle size of inorganic particles (D-4) was measured by laser diffraction. The average thickness of inorganic particles (D-1) was measured by length measurement using a scanning electron microscope, and the average thickness of inorganic particles (D-2) to (D-4) was measured by the water surface particle film method.

[0196] 1-6. Other Components 1-6-1. Nucleating Agent Talc (average particle size 6 μm) was used as a nucleating agent.

[0197] 1-6-2. Lubricant Sodium montanate was used as the lubricant.

[0198] 1-6-3. Colorant A masterbatch containing a pigment was used as the colorant.

[0199] 2. Measurement The physical properties of each of the above resins were measured by the following methods.

[0200] <Melting Point (Tm) and Glass Transition Temperature (Tg)> The melting point (Tm) and glass transition temperature (Tg) of the polyamide resin were measured using a differential scanning calorimetry (DSC220C, manufactured by Seiko Instruments Inc.). Specifically, approximately 5 mg of polyamide resin was sealed in an aluminum pan for measurement and set in the differential scanning calorimetry. The polyamide resin was then heated from room temperature to 350°C at 10°C / min. To completely melt the resin, the pan was held at 350°C for 3 minutes and then cooled to 30°C at 10°C / min. After leaving the pan at 30°C for 5 minutes, the pan was heated a second time to 350°C at 10°C / min. The temperature (°C) of the endothermic peak during this second heating was taken as the melting point (Tm) of the polyamide resin, and the inflection point corresponding to the glass transition was taken as the glass transition temperature (Tg).

[0201] <Heat of fusion (ΔH)> The heat of fusion (ΔH) of a polyamide resin was determined from the area of ​​the exothermic peak of crystallization in the first temperature rise process in accordance with JIS K 7122 (2012).

[0202] (Intrinsic Viscosity [η]) The intrinsic viscosity [η] of a polyamide resin was determined by dissolving 0.5 g of the polyamide resin in 50 ml of a 96.5% sulfuric acid solution, measuring the flow time of the resulting solution at 25°C ± 0.05°C using an Ubbelohde viscometer, and calculating the flow time in seconds based on the formula: [η] = ηSP / (C(1 + 0.205ηSP)) [η]: intrinsic viscosity (dl / g) ηSP: specific viscosity C: sample concentration (g / dl) t: flow time in seconds (seconds) of the sample solution t ０ : Number of seconds for blank sulfuric acid to flow (seconds) ηSP = (t - t ０ ) / t ０

[0203] <Composition> The composition of the modified polyolefin resin, specifically the content (mol %) of ethylene and α-olefin having 3 or more carbon atoms, and the content (mass %) of functional group structural units are １３ Measurement was performed by C-NMR under the following conditions: Measurement device: Nuclear magnetic resonance device (ECP500 model, manufactured by JEOL Ltd.) Observation nuclei: １３C (125 MHz) Sequence: Single pulse proton decoupling Pulse width: 4.7 μsec (45° pulse) Repetition time: 5.5 sec Number of accumulations: 10,000 or more Solvent: Orthodichlorobenzene / deuterated benzene (volume ratio: 80 / 20) mixed solvent Sample concentration: 55 mg / 0.6 mL Measurement temperature: 120 °C Reference value of chemical shift: 27.50 ppm

[0204] <Density> The density of the modified polyolefin resin was measured at a temperature of 23°C using a density gradient tube in accordance with JIS K7112.

[0205] <Melt Flow Rate (MFR)> The melt flow rate (MFR) of the modified polyolefin resin was measured in accordance with ASTM D1238 at 230°C under a load of 2.16 kg, in units of g / 10 min.

[0206] <Melting Point> The melting point of the modified polyolefin resin was measured by differential scanning calorimetry (DSC).

[0207] <Storage Modulus E'> The storage modulus E' of each modified polyolefin resin was determined by preparing a 500 μm pressed sheet of the modified polyolefin resin by hot pressing, and measuring the solid viscoelasticity using a solid viscoelasticity measuring device (DVA-225, manufactured by IT Measurement & Control Co., Ltd.) under conditions of a frequency of 1 Hz, a heating rate of 3°C / min, a strain of 0.05%, a chuck distance of 20 mm, a sample width of 2 mm, and a nitrogen atmosphere, while raising the temperature from -100°C to 200°C, and calculating the storage modulus E' at -40°C.

[0208] <10% Mass Loss Temperature> The 10% mass loss temperature of each modified polyolefin resin was determined by placing 10 mg of a sample in an aluminum pan using a differential thermogravimetry and thermogravimetry simultaneous analyzer (TG-DTA7300, manufactured by Seiko Instruments Inc.), heating at a temperature increase rate of 10°C / min while flowing dry air at a flow rate of 200 mL / min, and measuring the temperature at which the mass had decreased by 10% from the initial mass (10 mg).

[0209] 3. Preparation of Polyamide Resin Composition The above materials were mixed in a tumbler blender in the composition ratios (units: parts by mass) shown in Tables 1 to 9, and melt-kneaded using a 30 mmφ vented twin-screw extruder at a cylinder temperature of 300 to 335°C. The kneaded mixture was then extruded into strands and cooled in a water tank. The strands were then taken up in a pelletizer and cut to obtain pellets of polyamide resin compositions.

[0210] 4. Evaluation <Heat shock resistance> An insert member (54 mm × 54 mm × 2 mm) made of S45C as specified in JIS G4051:2016 carbon steel for mechanical structures was placed in a metal insert molding mold attached to an injection molding machine (SE75EV, manufactured by Sumitomo Heavy Industries, Ltd.). Next, the above-mentioned various polyamide resin compositions were injection molded into the mold under conditions of a cylinder setting temperature of 335 ° C, a mold temperature of 160 ° C, and an injection speed of 50 mm / sec to prepare metal insert test pieces.

[0211] FIG. 3A is a perspective view showing the shape of a test piece prepared for evaluating heat shock resistance, FIG. 3B is a plan view of the test piece, and FIG. 3C is a cross-sectional view of the test piece taken along line A-A' in FIG. 3B. The numerical values ​​in FIGS. 3B and 3C indicate dimensions (unit: mm). As shown in FIGS. 3A to 3C, the upper, lower, and side surfaces of the insert member were covered by a 56.4 mm x 57 mm rectangular parallelepiped resin portion (1 mm thick on the upper and lower surfaces and 2 mm thick on the side surfaces (the same thickness as the insert member)) that was 1 mm larger than the four sides of the test piece in a plan view toward the gate portion (the Y direction in FIG. 3B), 2 mm larger in the direction opposite the gate portion (the direction opposite the Y direction in FIG. 3B), and 1.2 mm larger in each of the remaining two outward directions (the X direction and the opposite direction in FIG. 3B). However, in order to hold the insert member in the mold, a cutout portion was provided on each of the four sides of the test piece, in the shape of a right-angled isosceles triangle with two sides of 7 mm each, with the top and bottom surfaces of the test piece not covered with resin. The side surfaces of the test piece at the cutout were covered with resin. A 2 mm (outward direction: X direction and the opposite direction) x 4 mm (opposite the Y direction) x 2 mm (thickness) resin reservoir portion was provided at the end of the resin portion facing the gate portion in the outward direction (X direction and the opposite direction in Figure 3B) perpendicular to the resin flow direction, continuous with the resin portion covering the side surfaces of the test piece at the cutout. Furthermore, a resin reservoir portion was provided at the end of the resin portion facing the gate portion to prevent a weld from forming in the portion of the resin portion adjacent to the insert member.

[0212] A heat shock test was performed on this test piece using a thermal shock tester (manufactured by Espec Corporation), with one cycle consisting of a -40°C / 30 minute hold and a 160°C / 30 minute hold. The presence or absence of cracks was observed every five cycles, and the number of cycles until cracks occurred was measured. This measurement was performed five times for each test piece, and the average of the measured number of cycles was calculated. Note that a calculated number of cycles of 0 indicates that cracks occurred immediately after molding, and a number of cycles of 1 or more indicates that no cracks occurred immediately after molding.

[0213] <Tensile strength and tensile modulus> Each polyamide resin composition was injected under the following conditions to obtain an ISO dumbbell-shaped test piece Type A having a thickness of 4.0 mm: Molding machine: SG50M3 manufactured by Sumitomo Heavy Industries, Ltd. Molding machine cylinder temperature: melting point of polyamide resin + 10°C Mold temperature: 160°C

[0214] The obtained test piece was left for 24 hours in a nitrogen atmosphere at a temperature of 23° C. Then, a tensile test was carried out in accordance with ISO 527 in an atmosphere of a temperature of −40° C. and a relative humidity of 50%, and the tensile strength and tensile modulus were measured.

[0215] <Flowability> Each polyamide resin composition was injected into a bar flow mold having a width of 10 mm and a thickness of 0.5 mm under the following conditions, and the flow length (mm) of the resin composition in the mold was measured: Injection molding machine: Tupearl TR40S3A manufactured by Sodick Plastec Co., Ltd. Injection pressure: 2000 kg / cm ２ Cylinder temperature setting: Polyamide resin melting point + 10°C Mold temperature: 160°C

[0216] The composition and evaluation results of each polyamide resin composition are shown in Tables 1 to 9. The numerical values ​​for the composition in Tables 1 to 9 represent parts by mass.

[0217]

[0218]

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225]

[0226] Comparing Examples 1 to 18, which contain the modified polyolefin resin (C) and the inorganic particles (D), with Comparative Example 1, which does not contain these, it was found that in Examples 1 to 18, the occurrence of cracks immediately after molding was suppressed. In addition, the storage modulus E' at -40°C was 7.0 × 10 ７ In Examples 1 to 18, which used the modified polyolefin resin (C) and scaly or plate-like inorganic particles (D) having a modulus of 0.05 Pa or less, the heat shock resistance of the resin members was better than that of Comparative Examples 1 to 11. This is thought to be because the modified polyolefin resin (C) and the inorganic particles (D) were able to suppress the occurrence of cracks at low temperatures when the resin members were repeatedly subjected to thermal shocks.

[0227] Furthermore, as shown in Comparative Examples 8 to 10, the heat shock resistance of the resin workpiece could not be improved by using only either the modified polyolefin resin (C) or the inorganic particles (D). These results show that the synergistic effect of the modified polyolefin resin (C) and the inorganic particles (D) is necessary to improve the heat shock resistance of the resin workpiece.

[0228] Furthermore, as shown in Examples 1 to 4, it was found that the heat shock resistance improved as the ratio of the content of the inorganic particles (D) to the total amount of the reinforcing agent (B) and the inorganic particles (D) increased.

[0229] It was found that Example 3, which contained an amorphous polyamide resin, had improved heat shock resistance compared to Example 16, which did not contain an amorphous polyamide resin. This is thought to be because the degree of crystallinity of the polyamide resin was reduced, thereby reducing the shrinkage rate of the polyamide resin composition.

[0230] Furthermore, Example 3, which used 6T6I as the polyamide resin (A), had better heat shock resistance than Examples 13 to 15, which used other polyamide resins.

[0231] This application claims priority from Japanese Patent Application No. 2023-017664, filed February 8, 2023. The entire disclosures of the specification, claims, and drawings of that application as originally filed are incorporated herein by reference.

[0232] The polyamide resin composition for insert molding of the present invention can suppress cracks that occur immediately after molding and can improve the heat shock resistance of metal-resin composites. Therefore, insert-molded articles using the polyamide resin composition are useful for parts (e.g., automobile parts) that are used in low-temperature environments.

[0233] REFERENCE SIGNS LIST 100 bus bar unit 110 bus bar 120 holding member 200 moving body 210 machine body 220 power supply 230 drive unit 232 inverter 234 motor 235 reducer 236 motor case

Claims

1. A polyamide resin composition for insert molding, comprising: A polyamide resin (A), a reinforcing material (B) whose content relative to the total mass of the polyamide resin composition is 10% by mass or more and 50% by mass or less; a modified polyolefin resin (C) having a content of 1% by mass or more and 10% by mass or less relative to the total mass of the polyamide resin composition; scaly or plate-like inorganic particles (D) whose content relative to the total mass of the polyamide resin composition is 5% by mass or more and less than 40% by mass; Including, The storage modulus E' of the modified polyolefin resin (C) at -40 ° C. is 7.0 × 10 Pa or less. A polyamide resin composition for insert molding.

2. 2. The polyamide resin composition for insert molding according to claim 1, wherein the polyamide resin (A) comprises a polyamide resin (A1) having a melting point (Tm) measured by a differential scanning calorimeter (DSC) of 280°C or higher.

3. The polyamide resin composition for insert molding according to claim 2, wherein the polyamide resin (A1) contains two or more types of polyamide resins having different compositions.

4. 3. The polyamide resin composition for insert molding according to claim 2, wherein the polyamide resin (A) comprises a polyamide resin (A2) having a heat of fusion (ΔH) measured by differential scanning calorimetry (DSC) of 5 J / g or less.

5. 2. The polyamide resin composition for insert molding according to claim 1, wherein the polyamide resin (A) comprises a polyamide resin (A2) having a heat of fusion (ΔH) measured by differential scanning calorimetry (DSC) of 5 J / g or less.

6. 2. The polyamide resin composition for insert molding according to claim 1, wherein the content of the reinforcing material (B) is 20% by mass or more and 40% by mass or less with respect to the total mass of the polyamide resin composition.

7. 2. The polyamide resin composition for insert molding according to claim 1, wherein the content of the inorganic particles (D) is 10% by mass or more and 30% by mass or less with respect to the total mass of the polyamide resin composition.

8. 2. The polyamide resin composition for insert molding according to claim 1, wherein the density of the modified polyolefin resin (C) is 850 kg / m<3 > or more and 880 kg / m<3 > or less.

9. 2. The polyamide resin composition for insert molding according to claim 1, wherein the modified polyolefin resin (C) contains a functional group structural unit whose content relative to the total mass of the modified polyolefin resin (C) is 0.1 mass% or more and 5.0 mass% or less.

10. 10. The polyamide resin composition for insert molding according to claim 9, wherein the content of the functional group structural unit is 0.5% by mass or more and 2.0% by mass or less based on the total mass of the modified polyolefin resin (C).

11. 2. The polyamide resin composition for insert molding according to claim 1, wherein the modified polyolefin resin (C) has a temperature of 335°C or higher at which a mass loss rate of 10% occurs when the modified polyolefin resin (C) is heated at a temperature increase rate of 10°C / min while dry air is flowing at a flow rate of 200 mL / min.

12. a total content of the reinforcing material (B) and the inorganic particles (D) is 30% by mass or more and 55% by mass or less based on the total mass of the polyamide resin composition, The content of the inorganic particles (D) is 20% by mass or more and 60% by mass or less with respect to the total mass of the reinforcing material (B) and the inorganic particles (D). The polyamide resin composition for insert molding according to claim 1.

13. The polyamide resin (A1) contains a component unit (A1a) derived from a dicarboxylic acid and a component unit (A1b) derived from a diamine, the dicarboxylic acid-derived component units (A1a) contain, relative to the total number of moles of the dicarboxylic acid-derived component units (A1a), 55 mol % to 75 mol % of terephthalic acid-derived component units and 25 mol % to 45 mol % of isophthalic acid-derived component units, 2. The polyamide resin composition for insert molding according to claim 1, wherein the diamine-derived component units (A1b) include component units derived from an aliphatic diamine having 4 to 15 carbon atoms.

14. A metal member; A resin member comprising the polyamide resin composition for insert molding according to any one of claims 1 to 13, which is composited with the metal member. Metal resin composite.

15. placing a metal member in a mold; and a step of injecting and filling the mold in which the metal member is placed with the polyamide resin composition for insert molding according to any one of claims 1 to 13. Method for manufacturing metal-resin composites.