Resin metal composite

Abstract

A resin metal composite having excellent joint strength, which is configured by joining a resin member (Y) formed of a thermoplastic resin composition (A) in which a thermoplastic resin is a main component to a metal member (X). More specifically, a resin metal composite characterized by being configured by joining a surface side of a metal member (X) having surface irregularities to a resin member (Y), the aforementioned thermoplastic resin composition (A) containing a thermoplastic resin and a fibrous reinforcing filler, the resin metal composite satisfying the following relational expression (1). Ra / (Fd x Wr) ≥ 0.5 … (1) (Note that in the aforementioned relational expression (1), Ra refers to the arithmetic average roughness (μm) of the surface of the aforementioned metal member (X) as measured in accordance with JIS B 0601:2001; Fd refers to the average fiber diameter (μm) of the aforementioned fibrous reinforcing filler; and Wr refers to the amount (parts by mass) of the fibrous reinforcing filler in the thermoplastic resin composition (A) per the total amount (parts by mass) of all the constituent components in the thermoplastic resin composition (A)).

Description

Technical Field

[0001] The present invention relates to a resin-metal composite comprising a thermoplastic resin component, preferably a thermoplastic resin component with polybutylene terephthalate (PBT) as the main component, and a metal component. Background Technology

[0002] In recent years, in the automotive and consumer parts industries, development has been driven by considerations such as lightweighting and environmental reusability, with a focus on replacing metal products with resin products. Among resin products, polyester products, in particular, possess excellent mechanical strength, chemical resistance, and electrical insulation, as well as superior heat resistance, formability, and reusability, making them widely used in various machine parts. Thermoplastic polyester resins, especially polybutylene terephthalate (PET), exhibit excellent mechanical strength and formability, and can be flame-retardant, thus being widely used in electrical and electronic equipment components requiring fire safety.

[0003] However, resin products suffer from poor heat dissipation. Therefore, in fields such as electrical and electronic equipment components and automotive parts, resin-metal composites are being developed, combining metal components such as aluminum and iron with resin components. Generally speaking, these resin-metal composites are superior to resin products in terms of strength, antistatic properties, thermal conductivity, heat dissipation, and electromagnetic wave shielding.

[0004] Regarding such resin-metal composites, for example, Patent Document 1 discloses a method for integrally molding metal and thermoplastic resin by in-mold molding thermoplastic resin onto a metal matrix.

[0005] In addition, Patent Document 2 discloses another method for manufacturing a composite of resin and metal components, which involves bonding resin to a component by injection molding, wherein the component is formed by performing a chemical etching-based surface treatment on a metal component.

[0006] Patent document 3 discloses a method for surface treatment of metals that exhibits excellent adhesion when bonding metals with organic polymers, etc., which involves chemical etching of the metal surface with the formation of a coating and removing the coating by chemical means.

[0007] Furthermore, in Patent Document 4, as a method for manufacturing a bond between a metal substrate and a resin-cured product, the following method is disclosed: after forming a zincate coating on the surface of an aluminum substrate, the surface is roughened using an etchant, and a resin composition is inserted into the depressions formed by the roughening.

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Application Publication No. 6-29669

[0011] Patent Document 2: Japanese Patent Application Publication No. 2008-173967

[0012] Patent Document 3: Japanese Patent Application Publication No. 11-293476

[0013] Patent Document 4: Japanese Patent Application Publication No. 2019-99864 Summary of the Invention

[0014] The problem the invention aims to solve

[0015] Regarding existing resin-metal composites, their applications are limited because the bonding between the metal and resin components is not sufficiently stable. This is particularly problematic when used in automotive applications.

[0016] However, as disclosed in the aforementioned Patent Documents 2 to 4, if a metal component is pre-formed with unevenness by immersing it in a liquid to roughen its surface, and then filled with resin by injection molding or the like, not only can the metal component and the resin component be joined by utilizing the anchoring effect based on the aforementioned unevenness, but it can also be processed regardless of the size or shape of the metal component, thus expanding its applications and making it suitable for applications such as automobiles.

[0017] In recent years, when joining metal components with resin components, there has been a growing demand to further improve the strength of the joint while simultaneously increasing the strength of the resin components.

[0018] Therefore, the present invention relates to a resin-metal composite comprising a thermoplastic resin component formed by bonding a metal component with a resin composition, and provides a novel resin-metal composite capable of sufficiently stabilizing the bonding state, thereby improving the bonding strength while also improving the strength of the resin component.

[0019] Solution for solving the problem

[0020] The inventors have solved the above-mentioned problems by means of the following methods.

[0021] <1> A resin-metal composite, characterized in that it comprises a metal component (X) and a resin component (Y), wherein the metal component (X) has a surface with unevenness, and the resin component (Y) is formed of a thermoplastic resin composition (A).

[0022] The resin-metal composite has a structure in which a metal component (X) with an uneven surface is joined to a resin component (Y), the aforementioned thermoplastic resin composition (A) comprises a thermoplastic resin and a fibrous reinforcing filler, and the resin-metal composite satisfies the following relationship (1).

[0023] Ra / (Fd×Wr)≥0.5…(1)

[0024] (It should be noted that in the above relationship (1), Ra refers to the arithmetic mean roughness (μm) of the surface of the aforementioned metal component (X) measured according to JISB 0601:2001; Fd refers to the average fiber diameter (μm) of the aforementioned fibrous reinforcing filler material; Wr refers to the amount (parts by mass) of the fibrous reinforcing filler material in the thermoplastic resin composition (A) / the total amount (parts by mass) of all the constituent components in the thermoplastic resin composition (A).)

[0025] <2> according to <1> The resin-metal composite wherein the content of thermoplastic resin is 30-80% by mass.

[0026] <3> according to <1> or <2> The resin-metal composite according to any one of the following, wherein the aforementioned thermoplastic resin composition (A) comprises a polyester (a-1) and a thermoplastic resin (a-2), wherein the polyester (a-1) comprises polybutylene terephthalate (also known as "homopolymer PBT") or a copolymer of polybutylene terephthalate (also known as "copolymer PBT") or a mixture thereof, wherein the thermoplastic resin (a-2) is miscible with the polyester (a-1) and comprises the aforementioned polyester (a-1) and the aforementioned thermoplastic resin (a-2) in a mass ratio of (a-1):(a-2) = 20:80 to 80:20.

[0027] <4> according to <1> ~ <3> The resin-metal composite as described in any one of the following, wherein the bonding strength between the aforementioned metal component (X) and the resin component (Y), as measured according to ISO 19095, is 26 MPa or more.

[0028] <5> according to <1> ~ <4> The resin-metal composite as described in any one of the following, wherein the arithmetic mean roughness (Ra) of the aforementioned surface of the aforementioned metal component (X), as measured according to JIS B 0601:2001, is 0.01 to 100 μm.

[0029] <6> according to <1> ~ <5> In any one of the resin-metal composites, the aforementioned average fiber diameter (Fd) is 4–9 μm.

[0030] <7> according to <1> ~ <6> In any one of the resin-metal composites, the surface irregularities of the aforementioned metal component (X) are formed by a chemical solution-based treatment.

[0031] <8> according to <1> ~ <7> The resin-metal composite as described in any one of the following, wherein the surface of the aforementioned metal component (X) has a coating based on a chemical solution as its outermost layer.

[0032] <9> according to <1> ~ <8> In any one of the resin-metal composites, the surface irregularities of the aforementioned metal component (X) are formed by laser-based processing.

[0033] <10> according to <1> ~ <9> The resin-metal composite according to any one of the following, wherein the aforementioned thermoplastic resin composition (A) contains a low molecular weight compound (c), which contains oxidized polyethylene wax.

[0034] <11> according to <1> ~ <10> The resin-metal composite according to any one of the following, wherein the aforementioned thermoplastic resin composition (A) contains a low molecular weight compound (c) having an acid value of 0.01 to 40 mg / KOH.

[0035] <12> according to <1> ~ <11> The resin-metal composite according to any one of the above-mentioned thermoplastic resin compositions contains a low molecular weight compound (c) having an acid value of 0.5 to 20 mg / KOH.

[0036] <13> according to <1> ~ <12> In any one of the resin-metal composites, the average fiber length of the aforementioned fibrous reinforcing filler material is 50 to 800 μm.

[0037] <14> according to <1> ~ <13> The resin-metal composite according to any one of the following, wherein the aforementioned thermoplastic resin composition (A) further comprises a compound (b) containing an epoxy group.

[0038] <15> according to <1> ~ <14> The resin-metal composite as described in any one of the following statements, wherein the aforementioned thermoplastic resin (a-2) is polyethylene terephthalate.

[0039] <16> according to <1> ~ <15> The resin-metal composite according to any one of the following configurations, wherein the resin-metal composite comprises a resin member (Y) extending from the edge end of the surface side of a metal member (X) having an uneven surface to the edge end of the back side via a side end face, and wherein the uneven portion of the metal member (X) is bonded to the thermoplastic resin composition of the resin member (Y) at the edge end of the surface side and the edge end of the back side of the metal member.

[0040] <17> according to <1> ~ <16> The method for manufacturing the resin-metal composite as described in any one of the following steps includes: applying a molten resin composition to a metal component (X) having an uneven surface by injection molding.

[0041] <18> A component for a vehicle, comprising <1> ~ <16> The resin-metal composite as described in any one of the following.

[0042] <19> An electrical component comprising <1> ~ <16> The resin-metal composite as described in any one of the following.

[0043] <20> A housing component comprising <1> ~ <16> The resin-metal composite as described in any one of the following.

[0044] <21> A component for a smartphone casing, comprising <1> ~ <16> The resin-metal composite as described in any one of the following.

[0045] <22> A housing component for an electrical component in a vehicle, comprising: <1> ~ <16> The resin-metal composite as described in any one of the following.

[0046] <23> A resin-metal composite, characterized in that it comprises a metal component (X) and a resin component (Y), wherein the metal component (X) has a surface with unevenness, and the resin component (Y) is formed of a polyester resin composition (A).

[0047] The resin-metal composite is formed by joining a metal component (X) with a surface side having irregularities to a resin component (Y).

[0048] The aforementioned polyester resin composition (A) comprises a polyester (a-1), a thermoplastic resin (a-2), an epoxy-containing compound (b), and a reinforcing filler (d), wherein the polyester (a-1) comprises polybutylene terephthalate (also known as "homopolymer PBT") or a copolymer of polybutylene terephthalate (also known as "copolymer PBT") or a mixture thereof, wherein the thermoplastic resin (a-2) is miscible with the polyester (a-1).

[0049] The aforementioned polyester resin composition (A) comprises the aforementioned polyester (a-1) and the aforementioned thermoplastic resin (a-2) in a mass ratio of (a-1):(a-2) = 50:50 to 20:80.

[0050] The aforementioned reinforcing filler material (d) is glass fiber with an average fiber diameter of 4 to 9 μm.

[0051] <24> according to <23> The resin-metal composite wherein the arithmetic mean roughness (Ra) of the aforementioned surface of the aforementioned metal component (X), as measured according to JIS B 0601:2001, is 0.01 to 100 μm.

[0052] <25> according to <23> or <24> The resin-metal composite wherein the surface irregularities of the aforementioned metal component (X) are formed by a chemical solution-based treatment.

[0053] <26> according to <23> ~ <25> The resin-metal composite as described in any one of the following, wherein the surface of the aforementioned metal component (X) has a coating based on a chemical solution as its outermost layer.

[0054] <27> according to <23> ~ <26> The resin-metal composite according to any one of the following is characterized in that the aforementioned polyester resin composition contains a low molecular weight compound (c), which contains oxidized polyethylene wax.

[0055] <28> according to <23> ~ <27> The resin-metal composite according to any one of the following is characterized in that the aforementioned polyester resin composition contains a low molecular weight compound (c) having an acid value of 0.01 to 40 mg / KOH.

[0056] <29> according to <23> ~ <27> The resin-metal composite according to any one of the following is characterized in that the aforementioned polyester resin composition contains a low molecular weight compound (c) having an acid value of 0.5 to 20 mg / KOH.

[0057] <30> according to <23> ~ <29> The resin-metal composite according to any one of the following configurations, wherein the resin-metal composite comprises a resin member (Y) extending from the edge end of the surface side of a metal member (X) having an uneven surface to the edge end of the back side via a side end face, and wherein the uneven portion of the metal member (X) is bonded to the polyester resin composition of the resin member (Y) at the edge end of the surface side and the edge end of the back side of the metal member.

[0058] <31> according to <23> ~ <29> The method for manufacturing a resin-metal composite according to any one of the following is characterized in that the step of applying a molten resin composition to the aforementioned metal component (X) having an uneven surface is performed by injection molding.

[0059] <32> A component for a vehicle, comprising <23> ~ <30> The resin-metal composite as described in any one of the following.

[0060] <33> An electrical component comprising <23> ~ <30> The resin-metal composite as described in any one of the following.

[0061] <34> A housing component comprising <23> ~ <30> The resin-metal composite as described in any one of the following.

[0062] <35> A housing component for an electrical component in a vehicle, comprising: <23> ~ <30> The resin-metal composite as described in any one of the following.

[0063] The effects of the invention

[0064] In the resin-metal composite proposed in this invention, a resin component (Y) formed of a thermoplastic resin composition (A) is selected as the resin component (Y) that corresponds to the surface state of the metal component (X), i.e., the surface state having unevenness. Furthermore, a resin component (Y) formed of a thermoplastic resin composition (A) containing a fibrous reinforcing filler is selected. Furthermore, the arithmetic mean roughness (Ra) of the surface of the aforementioned metal component (X) measured according to JIS B 0601:2001, the average fiber diameter (Fd) of the aforementioned fibrous reinforcing filler, and the ratio of the amount (parts by mass) of the fibrous reinforcing filler in the thermoplastic resin composition (A) to the total amount (parts by mass) of all constituent components satisfy the following relationship (1), thereby improving the bonding strength with the aforementioned metal component (X).

[0065] Ra / (Fd×Wr)≥0.5…(1)

[0066] Therefore, the resin-metal composite proposed in this invention can expand its applications and can be widely and appropriately used in applications ranging from consumer goods to automotive applications. Attached Figure Description

[0067] Figure 1 This is a partial cross-sectional perspective view of a resin-metal composite as described in an example of the present invention.

[0068] Figure 2 yes Figure 1 A partially enlarged sectional view.

[0069] Figure 3 (a) through (e) are cross-sectional views illustrating the joining method between a metal component (X) and a resin component (Y).

[0070] Figure 4 This is a cross-sectional view showing an example of the application of this resin-metal composite as part of the housing of an electrical component for a vehicle.

[0071] Figure 5Figure (a) and cross-sectional view (b) show a resin-metal composite (evaluation sample) formed by joining a metal component (X) and a resin component (Y) in the above observation embodiment. Detailed Implementation

[0072] Next, the present invention will be described with reference to exemplary embodiments. However, the present invention is not limited to the embodiments described below.

[0073] <<<This resin-metal composite>>>

[0074] The resin-metal composite described in one embodiment of the present invention (referred to as "this resin-metal composite") is characterized in that it comprises a metal component (X) and a resin component (Y), wherein the metal component (X) has a surface with unevenness on at least one side, and the resin component (Y) is formed of a thermoplastic resin composition (A) comprising a thermoplastic resin and a fibrous reinforcing filler material, and the resin-metal composite is configured such that the surface side of the metal component (X) with unevenness is joined to the resin component (Y), and satisfies the following relationship (1).

[0075] Ra / (Fd×Wr)≥0.5…(1)

[0076] (It should be noted that in the above relationship (1), Ra refers to the arithmetic mean roughness (μm) of the surface of the aforementioned metal component (X) measured according to JISB 0601:2001; Fd refers to the average fiber diameter (μm) of the aforementioned fibrous reinforcing filler material; Wr refers to the amount (parts by mass) of the fibrous reinforcing filler material in the thermoplastic resin composition (A) / the total amount (parts by mass) of all the constituent components in the thermoplastic resin composition (A).)

[0077] When the aforementioned relationship (1) is satisfied, the balance between the embedding depth and amount of glass fiber in the unevenness of the metal surface becomes good, and the bonding strength with the metal is improved.

[0078] From this perspective, the value of Ra / (Fd×Wr), i.e. Ra÷Fd÷Wr, is preferably 0.8 or more, more preferably 1.0 or more, more preferably 2.0 or more, even more preferably 5.0 or more, preferably 10 or more, preferably 20 or more, and particularly preferably 30 or more.

[0079] It should be noted that there is no particular limitation on the upper limit of the value of Ra / (Fd×Wr). From the viewpoint of the bonding strength with metal components, it is preferably 70 or less, more preferably 65 or less, more preferably 60 or less, and particularly preferably 50 or less.

[0080] <<Metal Components (X)>>

[0081] A metal component (X) is a metal component (X) having a surface with unevenness (also called "uneven surface") on its entire surface or part of its surface.

[0082] Examples of metals constituting the metallic component (X) include aluminum, iron, copper, magnesium, tin, nickel, zinc, and alloys containing these metals. Preferably, the metals include at least one of aluminum, iron, copper, and magnesium, and alloys containing these metals; more preferably, the metals include aluminum and alloys containing aluminum.

[0083] The shape of the metal component (X) is not particularly limited. Examples of preferred shapes include flat plates, curved plates, plates, rods, cylinders, blocks, sheets, films, etc., or components of a desired specific shape. It is not limited to a single plane or curved surface, and can have various shapes such as stepped portions, concave portions, and convex portions.

[0084] The thickness of the metal component (X) is not particularly limited. However, from the viewpoint of product design, a range of 0.05 mm to 50 mm is preferred, more preferably 0.10 mm or more or 10 mm or less, and even more preferably 0.12 mm or more or 5 mm or less. In particular, the thickness of aluminum and iron plates is preferably 0.10 mm to 10 mm, and more preferably 0.2 mm or more or 5 mm or less.

[0085] It should be noted that, regarding the "thickness" at this time, when the metal component is flat, it is its thickness because the thickness is uniform. On the other hand, in cases other than flat, that is, when the thickness is not uniform, it is the thickness of the thinnest part of the metal component (X) that is joined to the resin component (Y).

[0086] <Uneven Surface>

[0087] Regarding the aforementioned surface of the metal component (X), i.e., the surface joined with the resin component (Y), from the viewpoint of bonding strength, the arithmetic mean roughness (Ra) measured according to JIS B 0601:2001 is preferably 0.3 μm or more, more preferably 0.5 μm or more, more preferably 5 μm or more, and more preferably 30 μm or more. On the other hand, from the viewpoint of bonding strength after long-term testing, it is preferably 100 μm or less, more preferably 80 μm or less, more preferably 70 μm or less, and more preferably 60 μm or less.

[0088] Furthermore, from the same viewpoint, the maximum height (Rz) of the aforementioned surface of the metal component (X), i.e., the surface bonded to the resin component (Y), as measured according to JIS B 0601:2001, is preferably 5 μm or more, more preferably 10 μm or more, more preferably 30 μm or more, and more preferably 100 μm or more. On the other hand, from the viewpoint of bonding strength and airtightness, it is preferably 500 μm or less, more preferably 400 μm or less, more preferably 300 μm or less, and more preferably 250 μm or less.

[0089] In this way, as a method to adjust the arithmetic mean roughness (Ra) of the aforementioned surface of the metal component (X) to 0.3 μm or more and 100 μm or less, or to adjust the maximum height (Rz) to 5 μm or more and 500 μm or less, the roughening methods such as metal surface treatments A and C described later are preferred. However, it is not limited to this method.

[0090] The arithmetic mean roughness (Ra) and maximum height (Rz) of the metal component (X) were obtained by observing the uneven surface of the surface-treated metal component (X) using a hybrid laser microscope (LASERTEC OPTELICS HYBRID) with a 20x objective lens. The surface roughness was measured according to JIS B 0601:2001 using the accompanying analysis software (Lasertec Microscope Solution Software LMeye7).

[0091] It should be noted that, in the specific measurement of this embodiment, the Fine Peak measurement algorithm was used to obtain the FZ image for the average uneven surface of the center of a strip of metal sheet with a length of 45mm, a width of 12mm, and a thickness of 1.5mm. The measurement range was set to a length of 4.2mm in the 45mm direction. The cutoff value λc was 0.8000mm. The same operation was repeated 30 times at randomly selected different locations, and the average value was calculated.

[0092] Furthermore, when measuring the uneven surface of the metal component (X) in this resin-metal composite, the areas on the surface of the metal component (X) that are not affected by the bonding are also measured. In the absence of unbonded areas, the cross-section of this resin-metal composite bonded to the resin component (Y) is observed and measured using an optical microscope or a scanning electron microscope, thereby obtaining values ​​corresponding to the arithmetic mean roughness (Ra) and maximum height (Rz).

[0093] The opening diameter and depth of the recesses present on the surface of the metal component (X) do not need to be uniform. Recesses of various sizes (thickness, height, etc.) can be combined and distributed. Specifically, in the case of unevenness, for example, with an arithmetic mean roughness Ra of 1 μm to 10 μm and a maximum height Rz of 10 μm to 50 μm, it is preferable from the viewpoint of obtaining high bonding strength and airtightness when a surface with a combination of recesses with an opening diameter and / or depth of 50 μm or more and 200 μm or less, and recesses with an opening diameter and / or depth of 0.5 μm or more and 10 μm or less, is distributed, compared to recesses with only uniform opening diameter and / or depth.

[0094] Regarding the metal component (X) and the resin component (Y), they can be joined to the entire surface of the uneven surface of the metal component (X), or they can be joined to a portion of the uneven surface.

[0095] Furthermore, it is not necessary for the surface of the metal component (X) to be uneven at all points of contact between the resin component (Y) and the metal component (X). That is, it is sufficient for the surface of the metal component (X) to be uneven only at a portion of the joint between the metal component (X) and the resin component (Y).

[0096] (Roughening method)

[0097] There are no particular limitations on the method of roughening the entire surface or a portion of the metal component (X) to create unevenness; known methods can be used. From the viewpoint that the metal component (X) can be processed regardless of its size or shape, a chemical treatment method involving immersion in or coating with a chemical solution is preferred. Furthermore, from the viewpoint of achieving mass production and high design flexibility, a laser treatment method is also preferred.

[0098] Furthermore, roughening methods can be implemented individually or in combination. Combining multiple methods can sometimes yield results such as optimized surface texture and reduced costs.

[0099] Regarding chemical treatment methods, various methods are known depending on the type of metal, and known methods can be used. When the metal component (X) is aluminum, an aluminum alloy, or cast aluminum, the following treatment is preferred: a coating is formed on the metal surface before creating the unevenness, and then the coating is removed, thereby creating the unevenness. Furthermore, from the viewpoint of improving bonding strength, it is preferable to apply the chemical conversion coating after the unevenness is formed.

[0100] Among them, the chemical treatment method for forming the aforementioned uneven surface can be exemplified by: on the basis of forming a zincate coating on the surface of the metal component (X) as needed, contacting the surface of the metal component (X) with an etchant containing persulfate ions and chloride ions.

[0101] The aforementioned etchant only needs to be an aqueous solution containing at least disulfide ions and chloride ions. The aforementioned etchant may contain elements derived from the aforementioned substrate, such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc. Furthermore, elements such as zinc can be incorporated through the dissolution of the coating formed in the zincate process described later.

[0102] The aforementioned etchant preferably contains persulfate ions at a ratio of 0.02 mol / L or more and 0.90 mol / L or less, more preferably at a ratio of 0.10 mol / L or more or 0.50 mol / L or more, and even more preferably at a ratio of 0.15 mol / L or more or 0.40 mol / L or less.

[0103] The aforementioned etchant preferably contains chloride ions (Cl) in a proportion of 0.40 mol / L or more and 2.50 mol / L or less. - (), wherein it is further preferably contained in a proportion of 0.80 mol / L or more or 2.00 mol / L or less, and further preferably in a proportion of 1.20 mol / L or more or 1.70 mol / L or less.

[0104] As a chloride ion source, one or more suitable substances can be selected from chlorides such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, and ammonium chloride.

[0105] The aforementioned etchant may be substantially free of phosphoric acid. "Substantially free" means below the detection limit.

[0106] The pH of the aforementioned etchant is preferably in the range of 6.0 or below, and more preferably in the range of 2.0 to 4.0. Commercially available pH measuring devices and electrodes can be used without limitation. Furthermore, if a device with temperature compensation is used for the pH measuring device and electrode, and the internal liquid of the pH electrode and a commercially available pH standard solution are adjusted to the same temperature as the etchant, etc., and the pH measuring device is calibrated, then the pH of the aforementioned etchant, etc., at the operating temperature can also be measured.

[0107] During etching, the liquid temperature of the aforementioned etchant is set to 10–70°C, and the metal component (X) is immersed in it.

[0108] Laser processing is the process of creating irregularities on the surface of a metal component (X) by irradiating it with a laser. Examples include grooving the metal surface and laser etching, which involves melting and resolidifying the metal. For instance, this can be achieved by repeatedly performing the following operation: after laser scanning in a certain scanning direction, laser scanning is performed along the same or intersecting scanning directions. During laser processing, it is preferable to irradiate the surface with an angle. Specifically, the laser is irradiated at an angle of 15–85°, more preferably 25–75°, relative to the surface of the metal component. This configuration results in a wider bottom for the recess than for the opening, leading to better bonding between the metal component (X) and the thermoplastic resin component (Y).

[0109] The conditions for laser scanning include output power, scanning speed, scanning frequency, number of scans, shadow width (processing spacing), patterned shape, etc. Through the combination of these, it is possible to form a fine uneven surface from the desired concave and convex parts.

[0110] Furthermore, the type of laser used in the processing can be any wavelength from solid-state lasers, fiber lasers, semiconductor lasers, gas lasers, and liquid lasers. The vibration mode can also be selected as continuous wave or pulsed wave according to the desired surface texture of the metal component. In addition, using continuous wave allows for the fabrication of more complex textured structures.

[0111] Furthermore, based on the aforementioned laser treatment, other treatment methods such as sandblasting and chemical treatment can be combined.

[0112] When forming a zincate coating on the surface of a metal component (X), for example, an aqueous solution of sodium hydroxide containing dissolved zinc oxide can be used. The bath temperature is maintained below 40.0°C, and the metal component (X) is immersed for approximately 1.0 second to 5.0 minutes. This removes the natural oxide film while forming the zincate coating. Alternatively, the following operation can be performed more than once: the formed coating is dissolved using the aforementioned etchant and nitric acid, and a coating is formed again. In addition to the necessary components, the treatment solutions used in these zincate processes may also contain metals derived from the aforementioned substrate, such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc.

[0113] The pH of the treatment solution used to form the zincate coating is not limited as long as it is within a known range. For example, in the case of a treatment solution exhibiting an alkaline pH, it can be 10.0 or higher, or 13.0 or higher. A range of 11.0 to 13.0 is preferred. To adjust the pH of the zincate solution, sodium hydroxide or potassium hydroxide can be used to raise the pH.

[0114] It should be noted that the surface of the metal component (X) can be pre-treated to clean it before etchant-based processing or zincate coating formation. For example, degreasing can be performed using solvent-based, water-based, or emulsion-based degreasing agents. Alternatively, alkaline washing can be performed.

[0115] <Outermost layer>

[0116] The uneven surface of the metal component (X) can be covered by anodizing, chemical conversion coating (phosphate coating, chromate coating, silicate coating, lithium chemical conversion coating, calcium chemical conversion coating, zirconium oxide coating, etc.), aluminum anodizing (Alumite) coating, and other coatings. It can also form a plating layer, silane coupling agent treatment layer, primer layer, resin layer, other layers, and can also fix microparticles, etc.

[0117] Next, the outermost layer of the uneven surface of the metal component (X) will be described in detail.

[0118] (Oxidation coating)

[0119] The uneven surface of a metal component (X) may be unoxidized or oxidized.

[0120] (Chemical conversion treatment coating)

[0121] The uneven surfaces of the metal component (X) can be chemically converted to have a chemical conversion coating.

[0122] By implementing this treatment, the adhesion (bonding strength) between the metal component (X) and the resin component (Y) can be further improved.

[0123] Examples of chemical conversion treatment methods include chemical conversion treatment based on chromate phosphate, zirconium phosphate treatment, boehmite treatment, zincate treatment, and anodizing treatment.

[0124] Examples of the above-mentioned anodizing treatments include processed films using phosphoric acid, phosphoric acid-sulfuric acid, phosphoric acid-oxalic acid, and phosphoric acid-chromic acid as electrolytes. Among these, anodizing based on phosphoric acid-aluminum is preferred.

[0125] The thickness of the chemical conversion coating is not particularly limited. For example, it is preferably 1 nm to 300 nm, and from the viewpoint of maintaining processability well, it is further preferably 5 nm or more.

[0126] It should be noted that, when a chemical conversion coating is formed by anodizing, from the viewpoint of more effectively improving adhesion, its thickness is preferably in the range of 0.05 μm to 2 μm, and more preferably 0.1 μm or more or 2 μm or less.

[0127] The thickness of the chemical conversion treatment layer based on anodic oxidation can be adjusted to the above-mentioned range by adjusting the treatment conditions, especially the energizing conditions and energizing time.

[0128] (Coating)

[0129] The uneven surfaces of a metal component (X) can be coated by single-layer plating, multi-layer plating, or alloy plating. Prior to these plating processes, chromic acid immersion treatment or chromic phosphate treatment can be performed.

[0130] The plating process can be either electroplating or electroless plating. For example, when the metal substrate is iron, zinc plating, tin plating, nickel plating, or copper plating are preferred, with zinc plating being more preferred.

[0131] (Silane coupling agent treated layer)

[0132] When the uneven surface of a metal component (X) is particularly such that the metal component (X) is made of aluminum, iron, or the like, it is preferable to perform a silane coupling agent-based treatment to form a silane coupling agent-treated layer.

[0133] There are no particular limitations on the silane coupling agent. Examples include compounds having methoxy, ethoxy, or silanol groups. Preferred silane coupling agents include vinyltrimethoxysilane, chloropropyltrimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane hydrochloride, and acylureaaminopropylethoxysilane. In particular, aluminum or iron matrices form Al-O-Si or Fe-O-Si bonds with the silane coupling agent for strong bonding. Furthermore, the polyester (a-1) of the thermoplastic resin composition (A) reacts with the organic functional groups of the silane coupling agent for strong bonding, achieving an even stronger bond.

[0134] (Primer layer)

[0135] A primer layer can be applied to the uneven surface of the metal component (X).

[0136] Materials used in the primer layer include, for example, acrylic materials, epoxy materials, urethane materials, and polyamide materials.

[0137] Commercially available materials used in primer layers include ARON MELT PPET manufactured by Toa Gosei Corporation.

[0138] <<Resin Components (Y)>>

[0139] The resin component (Y) is a component formed from a thermoplastic resin composition (A). The aforementioned thermoplastic resin composition (A) is preferably a resin composition comprising a thermoplastic resin and a fibrous reinforcing filler (d), and further comprising, if necessary, an epoxy-containing compound (b), and further comprising, if necessary, a low-molecular-weight compound (c).

[0140] Regarding the content of thermoplastic resin in the thermoplastic resin composition (A) of this embodiment, it is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 37% by mass or more, and even more preferably 40% by mass or more. By setting it to the aforementioned lower limit or above, there is a tendency for further improvement in chemical resistance.

[0141] Furthermore, the content of the aforementioned thermoplastic resin is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 72% by mass or less, even more preferably 66% by mass or less, and still more preferably 60% by mass or less, and further preferably 55% by mass or less, 50% by mass or less, or 47% by mass or less. By setting it to the aforementioned upper limit value or less, there is a tendency to more effectively reduce the warpage of the molded article.

[0142] The thermoplastic resin composition (A) of this embodiment may contain only one thermoplastic resin or two or more. When two or more are contained, the total amount is preferably within the range described above.

[0143] The resin component (Y) is formed from a thermoplastic resin composition (A). It can be a structure formed solely from the thermoplastic resin composition (A), or it can be a structure formed from multiple materials by bonding a different resin layer to the back side of a component or layer formed from the thermoplastic resin composition (A).

[0144] The size, shape, and thickness of the resin component (Y) are not particularly limited, and it can be any of the following shapes: plate-shaped (circular plate, polygonal plate, etc.), column-shaped, box-shaped, bowl-shaped, tray-shaped, etc. The ability to mold the resin component (Y) into any shape is one of the characteristics of this resin-metal composite.

[0145] The thickness of all parts of the resin component (Y) does not need to be uniform. In addition, parts of arbitrary shapes such as reinforcing ribs can be provided as needed.

[0146] Examples of thermoplastic resins used in this embodiment include polyester resin (thermoplastic polyester resin); polyamide resin; polycarbonate resin; polystyrene resin; polyolefin resins such as polyethylene resin, polypropylene resin, and cyclic olefin resin; polyacetal resin; polyimide resin; polyetherimide resin; polyurethane resin; polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; and polymethacrylate resin. More preferably, it includes at least one of polyolefin resin (preferably polypropylene resin), polycarbonate resin, polyphenylene ether resin, polyester resin, polyphenylene sulfide resin, and polyamide resin. More preferably, it includes at least one of polycarbonate resin, polyphenylene ether resin, polyester resin, polyphenylene sulfide resin, and polyamide resin. More preferably, it includes either polyester resin or polyphenylene sulfide resin.

[0147] One example of the thermoplastic resin in this embodiment includes polyester resin, wherein 90% by mass or more (preferably 95% by mass or more) of the thermoplastic resin is polyester resin.

[0148] Another example of the thermoplastic resin in this embodiment includes polyphenylene sulfide resin, wherein 90% by mass or more (preferably 95% by mass or more) of the thermoplastic resin is polyphenylene sulfide resin.

[0149] Another example of the thermoplastic resin in this embodiment includes polycarbonate resin, wherein 90% by mass or more (preferably 95% by mass or more) of the thermoplastic resin is polycarbonate resin.

[0150] Another example of the thermoplastic resin in this embodiment includes polyphenylene ether resin, wherein 90% by mass or more (preferably 95% by mass or more) of the thermoplastic resin is polyphenylene ether resin.

[0151] Another example of the thermoplastic resin in this embodiment includes a polyolefin resin (preferably a polypropylene resin), wherein 90% or more (preferably 95% or more by mass) of the thermoplastic resin is a polyolefin resin (preferably a polypropylene resin).

[0152] Another example of the thermoplastic resin in this embodiment includes a polyamide resin, wherein 90% or more (preferably 95% or more) of the thermoplastic resin is a polyamide resin.

[0153] Examples of polyamide resins used in this embodiment include phenylenediamine-based polyamide resins and aliphatic polyamide resins (preferably polyamide 1010).

[0154] In this embodiment, a preferred example of the thermoplastic resin includes polyphenylene sulfide resin, wherein 90% or more (preferably 95% or more) of the thermoplastic resin is polyphenylene sulfide resin. Furthermore, a particularly preferred example of the thermoplastic resin includes polyester resin, wherein 90% or more (preferably 95% or more) of the thermoplastic resin group is polyester resin.

[0155] The following provides details about each thermoplastic resin.

[0156] <<Polyester Resin>>

[0157] As the polyester resin, known thermoplastic polyester resins can be used, preferably polyethylene terephthalate resin and polybutylene terephthalate resin, more preferably including at least polybutylene terephthalate resin.

[0158] The polybutylene terephthalate resin used in the thermoplastic resin composition (A) of this embodiment is a polyester resin having a structure obtained by ester bonding of terephthalic acid units and 1,4-butanediol units. In addition to polybutylene terephthalate (homogene), it also includes a mixture of polybutylene terephthalate copolymer, homopolymer, and polybutylene terephthalate copolymer containing other copolymer components besides terephthalic acid units and 1,4-butanediol units.

[0159] Polybutylene terephthalate resins may contain one or more dicarboxylic acid units other than terephthalic acid.

[0160] Other specific examples of dicarboxylic acids include isophthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis(4,4'-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, etc.; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 4,4'-dicyclohexyl dicarboxylic acid; and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dimer acid, etc.

[0161] In the polybutylene terephthalate resin used in this embodiment, the terephthalic acid unit preferably accounts for more than 80 mol% of all dicarboxylic acid units, and more preferably more than 90 mol%.

[0162] As a diol unit, in addition to 1,4-butanediol, it may also contain one or more other diol units.

[0163] Specific examples of other diol units include aliphatic or alicyclic diols with 2 to 20 carbon atoms, bisphenol derivatives, etc. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, decamethyldiol, cyclohexanediol, 4,4'-dicyclohexylhydroxymethane, 4,4'-dicyclohexylhydroxypropane, and ethylene oxide addition diols of bisphenol A. In addition to the difunctional monomers mentioned above, to introduce branched structures, small amounts of trifunctional monomers such as trimellitic acid, pyromellitic acid, pyromellitic tetracarboxylic acid, pentaerythritol, and trimethylolpropane can be used in combination. To adjust the molecular weight, small amounts of monofunctional compounds such as fatty acids can also be used in combination.

[0164] In the polybutylene terephthalate resin used in this embodiment, the 1,4-butanediol unit preferably accounts for more than 80 mol% of all diol units, and more preferably more than 90 mol%.

[0165] As described above, the polybutylene terephthalate resin is preferably a polybutylene terephthalate homopolymer obtained by polycondensation of terephthalic acid and 1,4-butanediol. Alternatively, it can be a polybutylene terephthalate copolymer containing one or more dicarboxylic acids other than terephthalic acid as carboxylic acid units and / or containing one or more diols other than 1,4-butanediol as diol units. When the polybutylene terephthalate resin is a polybutylene terephthalate resin modified by copolymerization, preferred copolymers include polyester ether resins copolymerized with polyalkylene glycols, especially polytetramethylene glycol, dimer acid copolymerized polybutylene terephthalate resins, and isophthalic acid copolymerized polybutylene terephthalate resins. Polyester ether resins copolymerized with polytetramethylene glycol are preferred.

[0166] It should be noted that these copolymers refer to substances with a copolymer content of 1 mol% or more and less than 50 mol% of all segments of polybutylene terephthalate resin. Preferably, the copolymer content is 2 mol% or more and less than 50 mol%, more preferably 3 to 40 mol%, and even more preferably 5 to 20 mol%. By setting this copolymerization ratio, there is a tendency to easily improve flowability, toughness, and traceability, and therefore it is preferred.

[0167] The amount of terminal carboxyl groups in polybutylene terephthalate (PET) resin can be determined by appropriate selection, typically below 60 eq / ton, preferably below 50 eq / ton, and more preferably below 30 eq / ton. By setting it below the above upper limit, there is a tendency to improve alkali resistance and hydrolysis resistance. The lower limit of the terminal carboxyl group amount is not particularly limited, but considering the manufacturing productivity of PET resin, it is typically above 10 eq / ton.

[0168] It should be noted that the amount of terminal carboxyl groups in the polybutylene terephthalate resin was determined by dissolving 0.5 g of polybutylene terephthalate resin in 25 mL of benzyl alcohol and titrating it with a 0.01 mol / L benzyl alcohol solution containing sodium hydroxide. As a method for adjusting the amount of terminal carboxyl groups, any existing known method can be used, such as adjusting the polymerization conditions (e.g., feed ratio, polymerization temperature, reduced pressure method) or reacting the end-capping agent.

[0169] The intrinsic viscosity of the polybutylene terephthalate resin is preferably 0.5 to 2 dL / g. From the viewpoint of formability and mechanical properties, an intrinsic viscosity in the range of 0.6 to 1.5 dL / g is more preferred. By setting the intrinsic viscosity to 0.5 dL / g or higher, there is a tendency to further improve the mechanical strength of the resulting resin composition. Furthermore, by setting it to 2 dL / g or lower, there is a tendency to further improve the flowability and formability of the resin composition.

[0170] It should be noted that the intrinsic viscosity of polybutylene terephthalate resin was measured at 30°C in a 1:1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

[0171] Polybutylene terephthalate (PET) resin can be manufactured by melt polymerization of a dicarboxylic acid component, with terephthalic acid as the main component, or its ester derivatives, with a diol component, with 1,4-butanediol as the main component, using either batch or continuous methods. Alternatively, after manufacturing a low molecular weight PET resin using melt polymerization, further solid-state polymerization under nitrogen gas flow or reduced pressure can increase the degree of polymerization (or molecular weight) to the desired value.

[0172] Polybutylene terephthalate resin is preferably obtained by a manufacturing method in which a dicarboxylic acid component with terephthalic acid as the main component undergoes continuous melt polycondensation with a diol component with 1,4-butanediol as the main component.

[0173] The catalyst used in the esterification reaction can be any known catalyst, such as titanium compounds, tin compounds, magnesium compounds, and calcium compounds. Among these, titanium compounds are particularly suitable catalysts. Specific examples of titanium compounds used as esterification catalysts include titanium alkoxides such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; and titanium phenolates such as tetraphenyl titanate.

[0174] As for the polyester resin, in addition to the above, reference can be made to paragraphs 0013 to 0016 of Japanese Patent Application Publication No. 2010-174223, the contents of which are incorporated herein by reference.

[0175] Regarding the content of polybutylene terephthalate resin in the thermoplastic resin composition (A) of this embodiment, when the thermoplastic resin composition (A) contains polybutylene terephthalate resin, the content is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, even more preferably 37% by mass or more, and even more preferably 40% by mass or more. By setting it to the aforementioned lower limit or above, there is a tendency to further improve chemical resistance. Furthermore, when the thermoplastic resin composition (A) contains polybutylene terephthalate resin, the aforementioned content of polybutylene terephthalate resin is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 72% by mass or less, even more preferably 66% by mass or less, and even more preferably 60% by mass or less, and can be 55% by mass or less, 50% by mass or less, or 47% by mass or less. By setting it to the aforementioned upper limit or less, there is a tendency to more effectively reduce the warpage of the molded article.

[0176] The thermoplastic resin composition (A) of this embodiment may contain only one type of polybutylene terephthalate resin, or it may contain two or more types. When it contains two or more types, the total amount is preferably within the range described above.

[0177] <<Polycarbonate resin>>

[0178] Polycarbonate resin is an optionally branched homopolymer or copolymer obtained by reacting a dihydroxy compound or a mixture thereof and a small amount of a polyhydroxy compound with phosgene or diester carbonate. There are no particular limitations on the manufacturing method of polycarbonate resin; resins manufactured using the well-known phosgene process (interfacial polymerization) or melt process (transesterification) can be used.

[0179] Regarding the dihydroxy compound used as a raw material, aromatic dihydroxy compounds are preferred, and examples include 2,2-bis(4-hydroxyphenyl)propane (= bisphenol A), tetramethylbisphenol A, bis(4-hydroxyphenyl)p-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxybiphenyl, etc., with bisphenol A being a preferred example. Alternatively, compounds having one or more tetraalkylphosphonium sulfonate bonds to the aforementioned aromatic dihydroxy compounds may also be used.

[0180] Of the polycarbonate resins described above, aromatic polycarbonate resins derived from 2,2-bis(4-hydroxyphenyl)propane are preferred, as are aromatic polycarbonate copolymers derived from 2,2-bis(4-hydroxyphenyl)propane and other aromatic dihydroxy compounds. Alternatively, copolymers with an aromatic polycarbonate resin as the main component, such as copolymers with polymers or oligomers having a siloxane structure, may also be used. Furthermore, two or more of the above-mentioned polycarbonate resins may be used in combination.

[0181] To adjust the molecular weight of polycarbonate resin, only monovalent aromatic hydroxyl compounds are needed, such as m-methylphenol and p-methylphenol, m-propylphenol and p-propylphenol, p-tert-butylphenol, p-long-chain alkyl-substituted phenols, etc.

[0182] The viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 13,000 or more. By using a resin with a viscosity-average molecular weight of 5,000 or more, the mechanical strength of the resulting resin composition tends to be further improved. Furthermore, the viscosity-average molecular weight (Mv) of the polycarbonate resin is preferably 6,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. By using a resin with a viscosity-average molecular weight of 60,000 or less, the flowability and formability of the resin composition tend to be improved.

[0183] It should be noted that, in this embodiment, the viscosity-average molecular weight (Mv) of the polycarbonate resin is expressed as follows: the intrinsic viscosity ([η]) is obtained by measuring the viscosity of the polycarbonate resin dichloromethane solution at 20°C using an Ubbelohde viscometer, and the value is calculated according to the following Schnell viscosity formula.

[0184] [η] = 1.23 × 10 -4 Mv 0.83

[0185] There are no particular limitations on the manufacturing method of polycarbonate resin; polycarbonate resins manufactured using either the phosgene method (interfacial polymerization) or the melt method (transesterification) can be used. Furthermore, it is preferable to form a polycarbonate resin by subjecting the polycarbonate resin manufactured by the melt method to a post-treatment to adjust the amount of terminal OH groups.

[0186] <<Polystyrene-based resins>>

[0187] Examples of polystyrene-based resins include homopolymers of styrene monomers and copolymers of styrene monomers with other copolymerizable monomers.

[0188] More specifically, polystyrene-based resins include polystyrene resin, acrylonitrile-styrene copolymer (AS resin), high-impact polystyrene resin (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene-propylene rubber-styrene copolymer (AES resin), and styrene-IPN type rubber copolymer, among others.

[0189] When a polystyrene-based resin contains a rubber component, the content of the rubber component in the polystyrene-based resin is preferably 3 to 70% by mass, more preferably 5 to 50% by mass, and even more preferably 7 to 30% by mass. Setting the rubber component content to 3% by mass or more tends to improve impact resistance, while setting it to 50% by mass or less tends to improve flame retardancy, and is therefore preferred. Furthermore, the average particle size of the rubber component is preferably 0.05 to 10 μm, more preferably 0.1 to 6 μm, and even more preferably 0.2 to 3 μm. If the average particle size is 0.05 μm or more, there is a tendency to easily improve impact resistance; if it is 10 μm or less, there is a tendency to improve appearance, and is therefore preferred.

[0190] The weight-average molecular weight of polystyrene-based resins is typically 50,000 or more, preferably 100,000 or more, more preferably 150,000 or more, and typically 500,000 or less, preferably 400,000 or less, more preferably 300,000 or less. Furthermore, the number-average molecular weight is typically 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and more preferably 500,000 or less, more preferably 300,000 or less.

[0191] The melt flow rate (MFR) of the polystyrene resin, measured according to JIS K7210 (temperature 200°C, load 5 kgf), is preferably 0.1 to 30 g / 10 min, more preferably 0.5 to 25 g / 10 min. If the MFR is 0.1 g / 10 min or more, there is a tendency for improved fluidity; if it is 30 g / 10 min or less, there is a tendency for improved impact resistance.

[0192] Commonly known methods for manufacturing polystyrene-based resins include emulsion polymerization, solution polymerization, suspension polymerization, and bulk polymerization.

[0193] <<Polyphenylene ether resin>>

[0194] In this embodiment, a known polyphenylene ether resin can be used, and examples include polymers having structural units in the main chain as shown in the following formula (preferably polymers in which the structural units shown in the following formula occupy more than 90 mol% of all structural units except for the terminal groups). The polyphenylene ether resin can be either a homopolymer or a copolymer.

[0195]

[0196] In the formula, the two R a Each independently represents a hydrogen atom, halogen atom, primary or secondary alkyl group, aryl group, aminoalkyl group, haloalkyl group, alkyl group, or haloalkyloxy group; two R groups bEach of these independently represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, or a hydroxyl or halohydroxyl group. Among them, the two R's... a They are not both hydrogen atoms.

[0197] As R a and R b Each of these is preferably a hydrogen atom, a primary or secondary alkyl group, or an aryl group. Suitable examples of primary alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopentyl, 2-methylbutyl, 2,3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, or 4-methylpentyl, or heptyl. Suitable examples of secondary alkyl groups include, for example, isopropyl, sec-butyl, or 1-ethylpropyl. In particular, R a Preferably, it is a primary or secondary alkyl group or a phenyl group having 1 to 4 carbon atoms. b Hydrogen atoms are preferred.

[0198] Suitable homopolymers of polyphenylene ether resins include polymers of 2,6-dialkylphenylene ethers such as poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-diethyl-1,4-phenylene ether), poly(2,6-dipropyl-1,4-phenylene ether), poly(2-ethyl-6-methyl-1,4-phenylene ether), and poly(2-methyl-6-propyl-1,4-phenylene ether). Examples of copolymers include 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymers, 2,6-dimethylphenol / 2,3,6-triethylphenol copolymers, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymers, 2,6-dipropylphenol / 2,3,6-trimethylphenol copolymers, 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers, graft copolymers obtained by grafting poly(2,6-dimethyl-1,4-phenylene ether) onto styrene, and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymers. As the polyphenylene ether resin in this embodiment, poly(2,6-dimethyl-1,4-phenylene) ether and random copolymers of 2,6-dimethylphenol / 2,3,6-trimethylphenol are particularly preferred.

[0199] Alternatively, polyphenylene ether resins with specified end groups and copper content, as described in Japanese Patent Application Publication No. 2005-344065, may also be used.

[0200] The intrinsic viscosity of the polyphenylene ether resin at 30°C, measured in chloroform, is preferably 0.2–0.8 dL / g, more preferably 0.3–0.6 dL / g. Setting the intrinsic viscosity to 0.2 dL / g or higher tends to further improve the mechanical strength of the resin composition, while setting it to 0.8 dL / g or lower tends to further improve flowability and facilitate molding and processing. Alternatively, two or more polyphenylene ether resins with different intrinsic viscosities can be used in combination within this range.

[0201] The manufacturing method of the polyphenylene ether resin used in this embodiment is not particularly limited, and can be carried out according to known methods, such as oxidative polymerization of monomers such as 2,6-dimethylphenol in the presence of a copper amine catalyst. In this case, by selecting the reaction conditions, the intrinsic viscosity can be controlled to the desired range. The intrinsic viscosity can be controlled by selecting conditions such as polymerization temperature, polymerization time, and catalyst amount.

[0202] <<Polyolefin Resins>>

[0203] Polyolefin resins include, for example, polyethylene, polypropylene, polybutene-1 and poly-4-methylpentene, and their copolymers.

[0204] Examples of polyethylene include low-density polyethylene and high-density polyethylene.

[0205] Examples of polypropylene include crystalline and amorphous polypropylene.

[0206] Examples of the aforementioned copolymers include, for instance, random, block, or graft copolymers of ethylene and propylene, copolymers of α-olefins with ethylene or propylene, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, and ethylene-acrylic acid copolymers.

[0207] Among these, crystalline or amorphous polypropylene, random, block, or graft copolymers of ethylene and propylene are preferred, with propylene-ethylene block copolymers being more preferred. Furthermore, from the viewpoint that polypropylene resin can achieve lightweighting of molded articles due to its low cost and low specific gravity, polypropylene resin is preferred.

[0208] The melt flow rate (MFR) of the polyolefin resin is preferably 0.1 to 5.0 g / 10 min.

[0209] <<Polyamide Resin>>

[0210] Polyamide resins are polymers whose structural units are acid amides obtained through ring-opening polymerization of lactams, condensation polymerization of aminocarboxylic acids, and condensation polymerization of diamines and diacids. Specifically, examples include polyamides 6, 11, 12, 46, 66, 610, 612, 6I, 6 / 66, 6T / 6I, 6 / 6T, 66 / 6T, 66 / 6T / 6I, 1010, phthalamide-based polyamide resins (see below for details), poly(trimethylhexamethylene terephthalamide), poly(4-aminocyclohexyl)methanedodecanoamide, poly(3-methyl-4-aminocyclohexyl)methanedodecanoamide, and polyhexahydroterephthalamide undecanediamine. It should be noted that "I" in the above examples represents isophthalic acid, and "T" represents terephthalic acid. In addition, as for polyamide resin, the contents of paragraphs 0011 to 0013 of Japanese Patent Application Publication No. 2011-132550 are cited in this specification.

[0211] The polyamide resin used in this embodiment is composed of structural units derived from diamines and structural units derived from dicarboxylic acids. Preferably, it is a phenylenediamine-based polyamide resin in which at least 50 mol% of the structural units derived from diamines are derived from phenylenediamine. More preferably, at least 70 mol% of the structural units derived from diamines in the phenylenediamine-based polyamide resin is derived from at least one of m-phenylenediamine and p-phenylenediamine. Preferably, at least 50 mol% of the structural units derived from dicarboxylic acids in the phenylenediamine-based polyamide resin is derived from α,ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms. α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms, such as adipic acid, sebacic acid, octanoic acid, dodecanoic acid, and eicosidine, are suitable, with adipic acid and sebacic acid being more preferred.

[0212] Examples of diamines other than m-phenylenediamine and p-phenylenediamine that can be used as raw material diamines for diphenylenediamine-based polyamide resins include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, and 2,4,4-trimethylhexamethylenediamine, etc. (aliphatic diamines); 1,3-bis(phenylenediamine) Alicyclic diamines such as (aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(aminomethyl)decahydronaphthalene, and bis(aminomethyl)tricyclodecane; and diamines with aromatic rings such as bis(4-aminophenyl)ether, p-phenylenediamine, and bis(aminomethyl)naphthalene, may be used, either one or a mixture of two or more.

[0213] Examples of dicarboxylic acid components other than the aforementioned α,ω-linear aliphatic dicarboxylic acids with 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid, and phthalic acid; and naphthalenedicarboxylic acid isomers such as 1,2-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid, one or more of these compounds may be used.

[0214] <<Polyphenylene sulfide resin>>

[0215] In this embodiment, a known polyphenylene sulfide resin can be used, and examples include polymers having repeating units as shown in the following structural formula.

[0216] From the viewpoint of heat resistance, polymers containing repeating units as shown in the following structural formula are preferred, with a content of 70 mol% or more, and further 90 mol% or more. The polyphenylene sulfide (PPS) resin has the above-described chemical structure, and the melt flow rate specified in ASTM D1238-86 at 315°C and a 5000g load is preferably 1000g / 10min or more, and more preferably 3000g / 10min or more.

[0217]

[0218] As the thermoplastic resin composition (A) of this embodiment, a polyester resin composition comprising a polyester (a-1) and a thermoplastic resin (a-2) that is compatible with the polyester (a-1) as the main component resin is particularly preferred.

[0219] The term "main component resin" refers to the resin or resin group that constitutes the thermoplastic resin composition (A) and has the largest mass proportion, including the following situations: in the resin constituting the thermoplastic resin composition (A), polyester (a-1) and thermoplastic resin (a-2) account for more than 50% by mass, more than 75% by mass, and more than 90% by mass (including 100% by mass). Sometimes, polyester (a-1) and thermoplastic resin (a-2) are also two or more types of polyesters (resin groups).

[0220] In the aforementioned thermoplastic resin composition (A), the ratio of the aforementioned polyester (a-1) to the aforementioned thermoplastic resin (a-2) is preferably a mass ratio of (a-1):(a-2) = 20:80 to 80:20 from the viewpoint of formability and bonding strength with metal components.

[0221] Furthermore, if polyester (a-1) is included in a ratio of (a-1):(a-2) = 50:50 or higher, it is preferable from the viewpoint of improved bond strength and improved basic physical properties of the resin. If thermoplastic resin (a-2) is included in a ratio of (a-1):(a-2) = 50:50 to 80:20, it is preferable from the viewpoint of improved bond strength. From this viewpoint, a ratio of (a-1):(a-2) of 50:50 to 80:20 is preferred, more preferably 55:45 to 80:20, and even more preferably 60:40 to 80:20.

[0222] From the viewpoint of formability, the intrinsic viscosity of the thermoplastic resin composition (A) is preferably 0.30 to 2.00 dl / g, more preferably 0.40 dl / g or more, more preferably 0.60 dl / g or more, and more preferably 1.80 dl / g or less, more preferably 1.50 dl / g or less.

[0223] It should be noted that, in this invention, the intrinsic viscosity is a value measured at 30°C in a 1:1 (mass ratio) mixed solvent of tetrachloroethane and phenol.

[0224] The intrinsic viscosity of the thermoplastic resin composition (A) can be adjusted by changing the molecular weight of the polyester (a-1), but is not limited thereto.

[0225] <Polyester (a-1)>

[0226] The polyester (a-1) used as the main component resin is preferably polybutylene terephthalate (also known as "homopolymer PBT") or a copolymer of polybutylene terephthalate (also known as "copolymer PBT") or a mixture thereof.

[0227] From the viewpoint of formability, the intrinsic viscosity of polyester (a-1) is preferably 0.30 to 2.00 dl / g, more preferably 0.40 dl / g or more, more preferably 0.60 dl / g or more, and on the other hand, more preferably 1.80 dl / g or less, more preferably 1.50 dl / g or less.

[0228] The intrinsic viscosity of polyester (a-1) can be adjusted by changing the molecular weight of polyester (a-1), but it is not limited to this.

[0229] (Homopolymer PBT)

[0230] Homopolymer PBT is a polymer with a structure obtained by ester bonding of terephthalic acid units and 1,4-butanediol units. It is a polymer formed by terephthalic acid units and 1,4-butanediol units.

[0231] The amount of terminal carboxyl groups in homopolymer PBT is preferably 60 eq / ton or less, more preferably 50 eq / ton or less, and even more preferably 30 eq / ton or less.

[0232] It should be noted that the amount of terminal carboxyl groups in polybutylene terephthalate homopolymer can be determined by dissolving 0.5 g of resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

[0233] As a method to adjust the amount of terminal carboxyl groups, any existing known method can be used, such as adjusting the polymerization conditions during polymerization, including the feed ratio, polymerization temperature, and reduced pressure method, or causing the end-capping agent to react.

[0234] The number average molecular weight of homopolymer PBT is preferably 7,000 or more, more preferably 8,000 or more, and more preferably 9,000 or more. On the other hand, it is preferably 20,000 or less, more preferably 19,000 or less, and more preferably 17,000 or less.

[0235] The intrinsic viscosity of homopolymer PBT is preferably 0.30 to 2.00 dl / g.

[0236] If the intrinsic viscosity is above 0.30 dl / g, the mechanical strength of the weld will not become too low; if it is below 2.00 dl / g, it can prevent reduced fluidity, deterioration of formability, or reduction of bond strength.

[0237] From this perspective, the intrinsic viscosity of homopolymer PBT is preferably 0.30 to 2.00 dl / g, more preferably 0.40 dl / g or more, more preferably 0.60 dl / g or more, and more preferably 1.80 dl / g or less, more preferably 1.50 dl / g or less.

[0238] (Copolymer PBT)

[0239] Copolymer PBT is a polybutylene terephthalate copolymer containing copolymer components other than terephthalic acid units and 1,4-butanediol units.

[0240] Specific examples of other dicarboxylic acid units besides terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis(4,4'-carboxyphenyl)methane, anthracene dicarboxylic acid, and 4,4'-diphenyl ether dicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and 4,4'-dicyclohexyldicarboxylic acid; and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dimer acids.

[0241] Other diol units besides 1,4-butanediol can include aliphatic or alicyclic diols with 2 to 20 carbon atoms, bisphenol derivatives, etc. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, decamethyldiol, cyclohexanediol, 4,4'-dicyclohexylhydroxymethane, 4,4'-dicyclohexylhydroxypropane, and ethylene oxide addition diols of bisphenol A.

[0242] Regarding PBT copolymer, from the viewpoint of mechanical properties and heat resistance, the proportion of terephthalic acid in the dicarboxylic acid unit is preferably 70 mol% or more, and more preferably 90 mol% or more.

[0243] Furthermore, the proportion of 1,4-butanediol in the diol unit is preferably 70 mol% or more, and more preferably 90 mol% or more.

[0244] In PBT copolymers, in addition to introducing difunctional monomers as described above, small amounts of trifunctional acids with ester-forming ability, such as tricarboxylic acid, pyromellitic acid, trimellitic acid, etc., or tetrafunctional acids with ester-forming ability, such as pyromellitic acid, etc., or polyfunctional alcohols with ester-forming ability, such as glycerol, trimethylolpropane, pentaerythritol, etc., can also be used to introduce branched structures. In order to adjust the molecular weight, small amounts of monofunctional compounds such as fatty acids can also be used.

[0245] Copolymer PBT can be modified using copolymer components.

[0246] For example, as a copolymer component, polybutylene terephthalate resin copolymerized with polyalkylene glycols (especially polytetramethylene glycol (PTMG)) and dimer acid copolymerized polybutylene terephthalate resin can be listed, and isophthalic acid copolymerized polybutylene terephthalate resin can be specifically listed.

[0247] In the copolymerized PBT containing polytetramethylene glycol (PTMG), the proportion of tetramethylene glycol in the copolymer is preferably 3 to 40% by mass, more preferably 5% or more by mass or 30% or less by mass, and more preferably 10% or more by mass or 25% or less by mass. This copolymerization ratio tends to exhibit an excellent balance between bond strength and heat resistance, and is therefore preferred.

[0248] On the other hand, in the case of copolymerized PBT containing dimer acid, the proportion of dimer acid component in the total carboxylic acid component, calculated by carboxylic acid groups, is preferably 0.5 to 30 mol%, more preferably 1 mol% or more or 20 mol% or less, and more preferably 3 mol% or more or 15 mol% or less. This copolymerization ratio tends to exhibit an excellent balance of bond strength, long-term heat resistance, and toughness, and is therefore preferred.

[0249] Furthermore, in the case of PBT copolymerized with isophthalic acid, the proportion of isophthalic acid in the total carboxylic acid composition, calculated by carboxylic acid groups, is preferably 1 to 30 mol%, more preferably 2 mol% or more or 20 mol% or less, and more preferably 3 mol% or more or 15 mol% or less. By setting this copolymerization ratio, an excellent balance of bond strength, heat resistance, injection molding properties, and toughness is achieved, and therefore it is preferred.

[0250] From a formability point of view, copolymer PBT is particularly preferred as a copolymer of polytetramethylene glycol or copolymer of isophthalic acid.

[0251] The number average molecular weight of the copolymerized PBT is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more. On the other hand, it is preferably 20,000 or less, more preferably 19,000 or less, and even more preferably 17,000 or less.

[0252] The intrinsic viscosity of the copolymer PBT is preferably 0.30 to 2.00 dl / g.

[0253] If the intrinsic viscosity is above 0.30 dl / g, the mechanical strength of the weld will not become too low; if it is below 2.00 dl / g, it can prevent reduced fluidity, deterioration of formability, or reduction of bond strength.

[0254] From this perspective, the intrinsic viscosity of the copolymer PBT is preferably 0.30 to 2.00 dl / g, more preferably 0.40 dl / g or more, more preferably 0.60 dl / g or more, and more preferably 1.80 dl / g or less, more preferably 1.50 dl / g or less.

[0255] The amount of terminal carboxyl groups in the copolymer PBT is preferably below 60 eq / ton.

[0256] If the amount of terminal carboxyl groups is less than 60 eq / ton, gas generation can be suppressed during melt molding of the resin composition.

[0257] From this perspective, the amount of terminal carboxyl groups in the copolymer PBT is preferably 60 eq / ton or less, more preferably 50 eq / ton or less, and more preferably 30 eq / ton or less.

[0258] On the other hand, there is no specific lower limit for the amount of terminal carboxyl groups. It is usually above 5 eq / ton.

[0259] It should be noted that the amount of terminal carboxyl groups in the copolymer PBT can be determined by dissolving 0.5g of resin in 25mL of benzyl alcohol and titrating it with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

[0260] As a method to adjust the amount of terminal carboxyl groups, any existing known method can be used, such as adjusting the polymerization conditions during polymerization, including the feed ratio, polymerization temperature, and reduced pressure method, or causing the end-capping agent to react.

[0261] (Homopolymer PBT + Copolymer PBT)

[0262] Polyester (a-1) can be a mixture of homopolymer PBT and copolymer PBT resin.

[0263] At this point, the amount of copolymer component (monomer) in the copolymer PBT resin is preferably 0.1 mol% or more and 30 mol% or less relative to all monomers, more preferably 1 mol% or more or 25 mol% or less, and more preferably 5 mol% or more or 20 mol% or less.

[0264] As a mass ratio, the mixing ratio of homopolymer PBT / polymer is preferably 99 / 1 to 1 / 99 (mass ratio), more preferably 95 / 5 to 5 / 95 (mass ratio), and more preferably in the range of 90 / 10 to 10 / 90 (mass ratio).

[0265] <Thermoplastic Resin (a-2)>

[0266] The thermoplastic resin (a-2) can be any thermoplastic resin that is compatible with the polyester (a-1) mentioned above.

[0267] From the viewpoint that the two are miscible, the difference in solubility parameter (also known as "SP value") between the thermoplastic resin (a-2) and the polyester (a-1) is preferably 2 or less, more preferably 1 or less, and more preferably 0.5 or less.

[0268] Incidentally, the solubility parameter of polybutylene terephthalate resin is 12.1 (cal / cm³). 3 The SP value of polyethylene terephthalate resin is 11.5 (cal / cm). 3 The SP value of CHDM-modified polyethylene terephthalate resin (CHDM content in glycol = 30 mol%) is 11.5 (cal / cm). 3 The SP value of polycarbonate resin is 11.6 (cal / cm). 3 ).

[0269] It should be noted that the SP value in this invention is a value that can be calculated according to the FEDORS method (R. FEDORS, POLYMERENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol 14, No. 2).

[0270] Examples of thermoplastic resins (a-2) include, for example, polyesters, polycarbonates, and polystyrene resins other than homopolymer PBT and copolymer PBT.

[0271] Examples of polyesters other than homopolymer PBT and copolymer PBT include 1,3-propylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene terephthalate. Of these, polyethylene terephthalate is preferred from the viewpoint of improved bonding strength.

[0272] The aforementioned polycarbonate and polystyrene-based resins can be cited as examples of polycarbonate and polystyrene-based resins.

[0273] <Compounds containing epoxy groups (b)>

[0274] The thermoplastic resin composition (A) of the present invention may, as needed, contain an epoxy-containing compound (b).

[0275] Compounds containing epoxy groups (b) may not contribute to initial bond strength, but they improve the desired durability through bond strength after durability testing. The presence of epoxy-containing compounds (b) significantly enhances durability. Even the presence of low-molecular-weight compounds (c) does not reduce this durability.

[0276] It can be inferred that the hydrolysis resistance of the resin component (Y) is improved by reacting the terminal functional groups (carboxyl groups) of homopolymer PBT and / or copolymer PBT with the epoxy groups of the compound (b) containing epoxy groups.

[0277] As for compounds (b) containing epoxy groups, preferred examples include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, resorcinol type epoxy compounds, phenolic varnish type epoxy compounds, alicyclic type diesters, glycidyl ethers, and epoxidized polybutadiene. More specifically, preferred examples include alicyclic type epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, resorcinol type epoxy compounds, phenolic varnish type epoxy compounds, vinylcyclohexene dioxide, and dicyclopentadiene oxide.

[0278] From the viewpoint of compatibility with homopolymer PBT and / or copolymer PBT, 2,2-bis(4-hydroxyphenyl)propane type epoxy compounds (also known as "bisphenol A type epoxy compounds") and phenolic varnish type epoxy compounds are preferred.

[0279] From the viewpoint of improving bonding strength, the epoxy equivalent (relative to the mass (g) of 1 mole of epoxy group contained in the epoxy compound) of the aforementioned bisphenol A type epoxy compound and phenolic varnish type epoxy compound is preferably 50 to 1000 g / eq., more preferably 70 g / eq. or more, more preferably 100 g / eq. or more, and on the other hand, more preferably 900 g / eq. or less, more preferably 800 g / eq. or less.

[0280] Furthermore, from the viewpoint of fluidity, the number average molecular weight of the aforementioned bisphenol A type epoxy compound and phenolic varnish type epoxy compound is preferably 100 to 2000, more preferably 150 or more, more preferably 200 or more, and on the other hand, more preferably 1800 or less, more preferably 1600 or less.

[0281] From the viewpoint of improved bonding strength and flowability, the epoxy-containing compound (b) is preferably contained in a proportion of 0.001 to 35 parts by mass relative to 100 parts by mass of polyester (a-1), more preferably in a proportion of 0.01 parts by mass or more, more preferably in a proportion of 0.1 parts by mass or more, more preferably in a proportion of 0.3 parts by mass or more, and on the other hand, more preferably in a proportion of 25 parts by mass or less, more preferably in a proportion of 15 parts by mass or less, more preferably in a proportion of 10 parts by mass or less, more preferably in a proportion of 6 parts by mass or less.

[0282] Furthermore, from the viewpoint of improving bond strength, it is preferable to include the epoxy-containing compound (b) in a proportion of 0.1 to 10 equivalents of epoxy groups relative to the amount of terminal carboxyl groups in the homopolymer PBT and / or copolymer PBT that is the polyester (a-1). It is even more preferable to include epoxy groups in a proportion of 0.15 equivalents or more, and even more preferably in a proportion of 0.2 equivalents or more. On the other hand, it is even more preferable to include epoxy groups in a proportion of 8.0 equivalents or less, even more preferably in a proportion of 7.0 equivalents or less, and even more preferably in a proportion of 6.0 equivalents or less.

[0283] <Low molecular weight compound (c)>

[0284] If the thermoplastic resin composition (A) of the present invention further contains a low molecular weight compound (c) with a number average molecular weight of less than 6000, the bonding strength of the resin-metal composite can be further improved.

[0285] The number average molecular weight of the low molecular weight compound (c) is preferably less than 6000, more preferably 50 or more, and even more preferably 100 or more. On the other hand, it is more preferably 5000 or less, 4500 or less, and even more preferably 4200 or less.

[0286] As a low molecular weight compound (c), examples include one or more low molecular weight compounds selected from polyolefin compounds, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds and organosilicon compounds.

[0287] Examples of the aforementioned polyolefin compounds include compounds selected from paraffin wax and polyethylene wax. These can be modified polyolefin compounds obtained by introducing hydroxyl, carboxyl, anhydride, or epoxy groups into the side chains.

[0288] Examples of aliphatic carboxylic acids include, for instance, saturated or unsaturated aliphatic monocarboxylic acids, dicarboxylic acids, or tricarboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Preferred aliphatic carboxylic acids are monocarboxylic or dicarboxylic acids having 6 to 36 carbon atoms, and more preferably are saturated aliphatic monocarboxylic acids having 6 to 36 carbon atoms.

[0289] Specific examples of this aliphatic carboxylic acid include palmitic acid, stearic acid, hexanoic acid, decanoic acid, lauric acid, arachidic acid, behenic acid, ceric acid, ceric acid, bermuda acid, triacontanic acid, limonitic acid, adipic acid, and azelaic acid.

[0290] As the aliphatic carboxylic acid in the aforementioned ester of aliphatic carboxylic acid and alcohol, the same substance as the aforementioned aliphatic carboxylic acid can be used, for example.

[0291] On the other hand, examples of alcohols include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have substituents such as fluorine atoms or aryl groups. Among these, monohydric or polyhydric saturated alcohols with 30 or fewer carbon atoms are preferred, and aliphatic saturated monohydric or polyhydric alcohols with 30 or fewer carbon atoms are more preferred. It should be noted that aliphatic compounds here also include alicyclic compounds.

[0292] Specific examples of this alcohol include octanol, decanol, dodecanol, stearyl alcohol, behenol, ethylene glycol, diethylene glycol, glycerol, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentyl glycol, bis(trimethylolpropane), dipentaerythritol, etc.

[0293] It should be noted that the aforementioned esters of aliphatic carboxylic acids and alcohols may contain aliphatic carboxylic acids and / or alcohols as impurities. Furthermore, the aforementioned esters may be pure substances or mixtures of multiple compounds. Moreover, the aliphatic carboxylic acid and alcohol that form an ester by bonding may each be one type, or two or more types may be used in any combination and ratio.

[0294] Specific examples of esters of aliphatic carboxylic acids and alcohols include, for example, tannin ester wax, beeswax (a mixture with myristyl palmitate as the main component), stearate stearate, behenate behenate, behenate stearate, glyceryl monopalmitate, glyceryl monostearate, glyceryl distearate, glyceryl tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc.

[0295] Examples of the aforementioned aliphatic hydrocarbon compounds include, for example, liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax and other polyolefin waxes; Fischer-Tropsch wax, α-olefin oligomers with 3 to 12 carbon atoms, etc.

[0296] Here, aliphatic hydrocarbons also include alicyclic hydrocarbons. Furthermore, these hydrocarbons can be partially oxidized. Aliphatic hydrocarbon compounds can be single substances or mixtures with diverse constituents and molecular weights, as long as the main component falls within the aforementioned range.

[0297] As for the aforementioned organosilicon compounds, examples of modified silicone oils include silicone oils obtained by introducing organic groups into the side chains of polysiloxanes, and silicone oils obtained by introducing organic groups into both ends and / or a single end of a polysiloxane. In this case, examples of the introduced organic groups include, for instance, epoxy groups, amino groups, carboxyl groups, methanol groups, methacryloyl groups, mercapto groups, phenolic groups, etc., with epoxy groups being preferred.

[0298] As a modified silicone oil, silicone oil obtained by introducing epoxy groups into the side chains of polysiloxanes is particularly preferred.

[0299] As a low-molecular-weight compound, polyolefin waxes are particularly preferred from the viewpoint of minimizing gas production and suppressing gas generation.

[0300] As a polyolefin wax, any known material can be used, such as, preferably, one of an olefin having 2 to 30 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 10 carbon atoms, or containing two or more (co)polymers (meaning polymerization or copolymerization. The same applies hereinafter).

[0301] Examples of olefins with 2 to 30 carbon atoms include ethylene, propylene, α-olefins with 4 to 30 carbon atoms (preferably 4 to 12, more preferably 4 to 10), and dienes with 4 to 30 carbon atoms (preferably 4 to 18, more preferably 4 to 8).

[0302] Examples of α-olefins include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, and 1-dodecene.

[0303] Examples of dienes include butadiene, isoprene, cyclopentadiene, and 11-dodecadiene.

[0304] From the viewpoints of low gas content, suppression of gas production, improved bonding strength, and heat resistance, polyethylene wax is preferred as a polyolefin wax.

[0305] The manufacturing method of polyethylene wax is arbitrary and can be achieved through, for example, the polymerization of ethylene or the thermal decomposition of polyethylene.

[0306] From the viewpoint of significantly improving bonding strength and having low volatile components, a low-molecular-weight compound with an acid value of 0.01 to 40 mg KOH / g is preferred. More preferably, the acid value is 0.01 to 35 mg KOH / g, even more preferably 0.5 to 32 mg KOH / g, and particularly preferably 0.5 to 20 mg KOH / g.

[0307] As long as the acid value is in the range of 0.01 to 40 mg KOH / g, substances with an acid value less than 0.01 mg KOH / g and substances with an acid value greater than 40 mg KOH / g can be used in combination. The total acid value of the various low molecular weight compounds should be in the range of 0.01 to 40 mg KOH / g.

[0308] As a low molecular weight compound with an acid value of 0.01 to 40 mg KOH / g, the preferred options are: low molecular weight compounds belonging to the esters of the above-mentioned aliphatic carboxylic acids and alcohols with an acid value of 0.01 to 40 mg KOH / g; the preferred options are the above-mentioned aliphatic hydrocarbon compounds; and the preferred options are modified polyolefin waxes obtained by endowing polyolefin waxes with functional groups that have affinity for polyester resins, such as carboxyl groups (representing carboxylic acid (anhydride) groups, i.e., carboxylic acid groups and / or carboxylic acid anhydride groups. The same applies hereinafter), haloformyl groups, ester groups, carboxylic acid metal salts, hydroxyl groups, alkoxy groups, epoxy groups, amino groups, amide groups, etc.

[0309] Examples of low molecular weight compounds containing carboxylic acid groups, such as maleic acid, maleic anhydride, acrylic acid, and methacrylic acid, can be used as the carboxyl group in the modification of this polyolefin wax; low molecular weight compounds containing sulfonic acid groups, such as sulfonic acid; and low molecular weight compounds containing phosphoric acid groups, such as phosphonic acid. Among these, low molecular weight compounds containing carboxylic acid groups are preferred, and maleic acid, maleic anhydride, acrylic acid, and methacrylic acid are particularly preferred. One of these carboxylic acids may be used, or two or more may be used in any proportion.

[0310] The amount of acid added to the modified polyolefin wax is typically 0.01 to 10% by mass, and preferably 0.05 to 5% by mass, relative to the modified polyolefin wax.

[0311] It should be noted that, specifically, examples of the aforementioned haloformyl groups include chloroformyl and bromoformyl groups. The means of imparting these functional groups to polyolefin waxes can be any method known to the public, specifically, any method such as copolymerization with compounds having functional groups, post-processing such as oxidation, etc.

[0312] From the perspective of having a suitable affinity for polyester resin, carboxyl groups are preferred as the type of functional group.

[0313] The concentration of carboxyl groups in modified polyolefin waxes can be determined by appropriate selection. If it is too low, the affinity with polyester resin may be low, the effect of suppressing volatile components may be reduced, and the bonding strength may decrease. Conversely, if the concentration is too high, the polymer backbone constituting the polyolefin wax may be excessively broken during modification, resulting in an excessive decrease in the molecular weight of the modified polyolefin wax. This leads to an increase in the generation of volatile components and fogging on the surface of the polyester resin molded body.

[0314] As a modified polyolefin wax, oxidized polyethylene wax is preferred.

[0315] In the above, the melting point of the low molecular weight compound (c) is preferably 40 to 140°C, more preferably 45°C or higher, more preferably 50°C or higher, and more preferably 135°C or lower, more preferably 130°C or lower.

[0316] It should be noted that low molecular weight compounds may contain one type, or two or more types in any combination and ratio.

[0317] The low molecular weight compound (c) is preferably contained in a ratio of 0 to 1.5 parts by weight relative to 100 parts by weight of the thermoplastic resin composition (A), more preferably in a ratio of 0.001 to 1.5 parts by weight, and even more preferably in a ratio of 0.01 parts by weight or more, especially more preferably in a ratio of 0.1 parts by weight or more, and even more preferably in a ratio of 0.2 parts by weight or more. On the other hand, it is even more preferably contained in a ratio of 1.4 parts by weight or less, and even more preferably in a ratio of 1.2 parts by weight or less.

[0318] (Polyolefin wax)

[0319] From the viewpoint of being able to suppress gas generation when heating the thermoplastic resin composition (A), polyolefin wax is preferably selected as the low molecular weight compound (c).

[0320] Examples of polyolefins include polyethylene, polypropylene, polyisobutylene, polyisoprene, polybutadiene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, and ethylene-vinyl chloride copolymer.

[0321] From the viewpoint of being able to suppress gas generation when heating the thermoplastic resin composition (A), oxidized polyolefin wax is preferred, and oxidized polyethylene wax is most preferred.

[0322] Oxidized polyethylene wax refers to compounds that have been oxidized to polyethylene to introduce polar groups.

[0323] Examples of polar groups include carboxyl, amino, and hydroxyl groups.

[0324] From the viewpoint of suppressing gas generation when heating the thermoplastic resin composition (A), the number average molecular weight of the oxidized polyethylene wax is further preferably 1500 or more, more preferably 2000 or more, more preferably 2500 or more, more preferably 3000 or more, and more preferably 3500 or more. On the other hand, from the viewpoint of improving bonding strength, it is further preferably 5000 or less, more preferably 4500 or less, and more preferably 4200 or less.

[0325] From the viewpoint of suppressing gas generation when heating the thermoplastic resin composition (A), the acid value of the above-mentioned oxidized polyethylene wax is preferably 0.01 to 40 mg KOH / g, more preferably 0.1 mg KOH / g or more or 30 mg KOH / g or less, more preferably 0.5 mg KOH / g or more or 20 mg KOH / g or less, and more preferably 0.7 mg KOH / g or more or 10 mg KOH / g or less.

[0326] From the viewpoint of suppressing gas generation when heating the thermoplastic resin composition (A), it is preferable to include polyolefin wax as a low molecular weight compound (c) in a proportion of 0.01 to 1.5 parts by mass relative to 100 parts by mass of the aforementioned thermoplastic resin composition (A), more preferably 0.1 parts by mass or more or 1.0 parts by mass or less, and more preferably 0.2 parts by mass or more or 0.7 parts by mass or less.

[0327] <Other Resin Components>

[0328] In addition to the above-mentioned components, the thermoplastic resin composition (A) may also contain other resins and compounds. Examples include one or more combinations of compounds selected from the group consisting of carbodiimide compounds, compounds having an oxazoline group (ring), compounds having an oxazine group (ring), compounds having a carboxylic acid group, and compounds having an amide group.

[0329] Alternatively, it may contain, for example, polysulfone resin, polyethersulfone resin, polyetherimide resin, polyetherketone resin, fluororesin, etc.

[0330] The proportion of other resins in the thermoplastic resin composition (A) is preferably 20% by mass or less, more preferably 10% by mass or less.

[0331] (Carbodiimide compound)

[0332] The aforementioned carbodiimide compounds are compounds containing a carbodiimide group (-N=C=N-) in their molecules.

[0333] As carbodiimide compounds, aliphatic carbodiimide compounds with an aliphatic main chain, alicyclic carbodiimide compounds with an alicyclic main chain, and aromatic carbodiimide compounds with an aromatic main chain can all be used. Among them, from the viewpoint of improving the hydrolysis resistance of the resin-metal composite, alicyclic carbodiimide compounds are preferred.

[0334] The type of carbodiimide compound can be either monomeric or polymeric, and polymeric compounds are preferred in this invention.

[0335] When the carbodiimide is a polymeric type, the preferred number-average molecular weight is 10,000 or less, more preferably 4,000 or less, and as a lower limit, it is preferably 100 or more, more preferably 500 or more.

[0336] The content of carbodiimide groups in the carbodiimide compound is preferably 100 to 1000 (g / 1mol) in terms of carbodiimide equivalent (the weight [g] of the carbodiimide compound used to impart 1 mol of carbodiimide groups), more preferably 200 (g / 1mol) or more or 800 (g / 1mol) or less, and more preferably 235 (g / 1mol) or more or 650 (g / 1mol) or less.

[0337] Examples of the aforementioned aliphatic carbodiimide compounds include diisopropylcarbodiimide and dioctyldecylcarbodiimide.

[0338] Examples of the aforementioned alicyclic carbodiimide compounds include dicyclohexylcarbodiimide and poly(4,4'-dicyclohexylmethanecarbodiimide), with poly(4,4'-dicyclohexylmethanecarbodiimide) being particularly preferred.

[0339] As commercially available products, examples include "CARBODILITE" (trade name; manufactured by Nisshinbo Chemical Co., Ltd.).

[0340] Examples of the aforementioned aromatic carbodiimide compounds include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, N-tolyl-N'-phenylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-p-methoxyphenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, p-phenylenebisdi-o-tolylcarbodiimide, p-phenylenebisdicyclohexylcarbodiimide, p-phenylenebisdi-p-chlorophenylcarbodiimide, and ethylenebisdiphenylcarbodiimide, among other single-carbodiimide compounds. Or dicarbodiimide compounds; and polycarbodiimide compounds such as poly(4,4'-diphenylmethane carbodiimide), poly(3,5'-dimethyl-4,4'-biphenylmethane carbodiimide), poly(p-phenylene carbodiimide), poly(m-phenylene carbodiimide), poly(3,5'-dimethyl-4,4'-diphenylmethane carbodiimide), poly(naphthalene carbodiimide), poly(1,3-diisopropylphenylene carbodiimide), poly(1-methyl-3,5-diisopropylphenylene carbodiimide), poly(1,3,5-triethylphenylene carbodiimide), and poly(triisopropylphenylene carbodiimide), which may also be used in combination of two or more. Among these, di-2,6-dimethylphenylcarbodiimide, poly(4,4'-diphenylmethanecarbodiimide), poly(phenylenecarbodiimide), and poly(triisopropylphenylenecarbodiimide) are particularly suitable.

[0341] As commercially available products, examples include "Stabaxol P" (trade name; manufactured by BASF).

[0342] (Compounds containing an oxazoline group (ring))

[0343] Examples of compounds containing an oxazoline group (ring) include oxazoline, alkyl oxazoline (such as 2-methyloxazoline, 2-ethyloxazoline, etc., C1-4 alkyloxazoline), and bisoxazoline compounds.

[0344] Examples of the aforementioned bisoxazoline compounds include, for example, 2,2'-bis(2-oxazoline), 2,2'-bis(alkyl-2-oxazoline) [2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(4-ethyl-2-oxazoline), 2,2'-bis(4,4-dimethyl-2-oxazoline), etc., 2,2'-bis(C1-6alkyl-2-oxazoline), etc.], 2,2'-bis(aryl-2-oxazoline) [2,2'-bis(4-phenyl-2-oxazoline), etc.], 2,2'-bis(cycloalkyl-2-oxazoline) [2,2'-bis(4-cyclohexyl-2-oxazoline), etc.], 2,2'-bis(aralkyl-2-oxazoline) [2,2'-bis(4-cyclohexyl-2-oxazoline), etc.], 2,2'-bis(aralkyl-2-oxazoline) [2,2'-bis(4-benzyl-2-oxazoline), etc.], 2,2'-bis(aralkyl-2-oxazoline), etc. ) etc., 2,2'-alkylenebis(2-oxazoline) [2,2'-ethylenebis(2-oxazoline), 2,2'-tetramethylenebis(2-oxazoline), etc. 2,2'-C1-10 alkylenebis(2-oxazoline), etc.], 2,2'-alkylenebis(alkyl-2-oxazoline) [2,2'-ethylenebis(4-methyl-2-oxazoline), 2,2'-tetramethylenebis(4,4-dimethyl-2-oxazoline), etc. 2,2'-C1-10 alkylenebis(C1-6 alkyl-2-oxazoline), etc.], 2,2'-arylenebis(2-oxazoline) [2,2'-(1,3-phenylene)-bis(2-oxazoline), 2,2'-(1,4-phenylene)-bis(2-oxazoline), 2, 2'-(1,2-phenylene)-bis(2-oxazoline), 2,2'-diphenylenebis(2-oxazoline), etc.; 2,2'-arylenebis(alkyl-2-oxazoline) [2,2'-(1,3-phenylene)-bis(4-methyl-2-oxazoline), 2,2'-(1,4-phenylene)-bis(4,4-dimethyl-2-oxazoline), etc., 2,2'-phenylene-bis(C1-6alkyl-2-oxazoline), etc.]; 2,2'-aryloxyalkanebis(2-oxazoline) [2,2'-9,9'-diphenoxyethanebis(2-oxazoline), etc.]; 2,2'-cycloalkylenebis(2-oxazoline) [2,2'-cyclohexylenebis(2-oxazoline), etc.]; N,N'-alkylenebis(2-oxazoline), etc. -carbamoyl-2-oxazoline) [N,N'-ethylidene bis(2-carbamoyl-2-oxazoline), N,N'-tetramethylene bis(2-carbamoyl-2-oxazoline), etc. N,N'-C1-10 alkylidene bis(2-carbamoyl-2-oxazoline), etc.], N,N'-alkylidene bis(2-carbamoyl-alkyl-2-oxazoline) [N,N'-ethylidene bis(2-carbamoyl-4-methyl-2-oxazoline), N,N'-tetramethylene bis(2-carbamoyl-4,4-dimethyl-2-oxazoline), etc. N,N'-C1-10 alkylidene bis(2-carbamoyl-C1-6 alkyl-2-oxazoline), etc.], N,N'-arylidene bis(2-carbamoyl-2-oxazoline) [N,[N'-Phenylidene bis(2-carbamoyl-oxazoline), etc.]

[0345] In addition, compounds containing an oxazoline group also include vinyl polymers containing an oxazoline group [manufactured by Nippon Shokubai Co., Ltd.; EPOCROS RPS series, RAS series, and RMS series, etc.]. Among these oxazoline compounds, bisoxazoline compounds are preferred.

[0346] (Compounds containing an oxazine group (ring))

[0347] As compounds containing the oxazine group (ring), oxazine, bioxazine, and other compounds can be used.

[0348] Examples of the aforementioned bisoxazine compounds include, for example, 2,2'-bis(5,6-dihydro-4H-1,3-oxazine), 2,2'-bis(alkyl-5,6-dihydro-4H-1,3-oxazine) [2,2'-bis(4-methyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-bis(4,4-dimethyl-5,6-dihydro-4H-1,3-oxazine), 2,2'-bis(4,5-dimethyl-5,6-dihydro-4H-1,3-oxazine), etc., 2,2'-bis(C1-6alkyl-5,6-dihydro-4H-1,3-oxazine), etc.], 2,2'-alkylenebis(5,6-dihydro-4H-1,3-oxazine) [2 2,2'-Methylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-Ethylenebis(5,6-dihydro-4H-1,3-oxazine), 2,2'-Hexanemethylenebis(5,6-dihydro-4H-1,3-oxazine), etc., 2,2'-C1-10 alkylenebis(5,6-dihydro-4H-1,3-oxazine), etc., 2,2'-arylenebis(5,6-dihydro-4H-1,3-oxazine) [2,2'-(1,3-phenylene)-bis(5,6-dihydro-4H-1,3-oxazine), 2,2'-(1,4-phenylene)-bis(5,6-dihydro-4H-1,3-oxazine), 2,2'-(1,2 ... Phenyl)-bis(5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthobis(5,6-dihydro-4H-1,3-oxazine), 2,2'-diphenylenebis(5,6-dihydro-4H-1,3-oxazine), etc., N,N'-alkylenebis(2-carbamoyl-5,6-dihydro-4H-1,3-oxazine) [N,N'-ethylenebis(2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), N,N'-tetramethylenebis(2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), etc., N,N'-C1-10 alkylenebis(2-carbamoyl-5,6-dihydro-4H-1,3-oxazine), etc.], N,N'-alkylenebis(2-carbamoyl-alkyl-5,6-dihydro-4H-1,3-oxazine) [N,N'-ethylenebis(2-carbamoyl-4-methyl-5,6-dihydro-4H-1,3-oxazine), N,N'-hexamethylenebis(2-carbamoyl-4,4-dimethyl-5,6-dihydro-4H-1,3-oxazine), etc., N,N'-C1-10 alkylenebis(2-carbamoyl-C1-6 alkyl-5,6-dihydro-4H-1,3-oxazine), etc.], N,N'-arylenebis(2-carbamoyl-5,6-dihydro-4H-1,3-oxazine) [N,N'-phenylenebis(2-carbamoyl-oxazine), etc.], etc. Among these oxazine compounds, bioxazine compounds are preferred.

[0349] (Compounds containing carboxylic acids)

[0350] Examples of compounds containing carboxylic acids include formic acid, acetic acid, propionic acid, acrylic acid, methacrylic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, lactic acid, malic acid, tartaric acid, bisphenol A benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, nonylbenzenesulfonic acid, nitrobenzenesulfonic acid, cyanobenzenesulfonic acid, hydroxybenzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, nitrobenzenecarboxylic acid, cyanobenzenecarboxylic acid, hydroxybenzenecarboxylic acid, glycolic acid, and their salts.

[0351] (Compounds containing amide groups)

[0352] Examples of compounds containing an amide group include (meth)acrylamide, N-methylmethacrylamide, hydroxymethylated acrylamide, hydroxymethylated methacrylamide, acrylamide vinyl ether, β-acrylamide isobutyl vinyl ether, and acrylamide ethyl acrylate.

[0353] <Fiber-reinforced filler material (d)>

[0354] The thermoplastic resin composition (A) contains fibrous reinforcing filler (d) such as glass fiber. By including the fibrous reinforcing filler (d), the bonding strength between the metal component (X) and the resin component (Y) is improved. Furthermore, the strength, rigidity, and dimensional stability of the thermoplastic resin composition (A) or the resin-metal composite can be improved.

[0355] The average fiber diameter (Fd) of the fibrous reinforcing filler is not particularly limited, but is preferably selected in the range of 1 to 100 μm. If the average fiber diameter of the fibrous reinforcing filler is 1 μm or more, it is easy to manufacture and the cost can be controlled. On the other hand, if it is 100 μm or less, the tensile strength of the fibrous reinforcing filler can be maintained.

[0356] From the viewpoint of improving bonding strength, the average fiber diameter of the fibrous reinforcing filler is more preferably 4 to 9 μm, more preferably 5 to 8 μm, and more preferably 6 to 7 μm.

[0357] It should be noted that the fiber cross-section can be circular or flat.

[0358] The thermoplastic resin composition (A) preferably contains fibrous reinforcing filler (d) in a ratio of 10 to 100 parts by weight relative to 100 parts by weight of the thermoplastic resin composition (A). If the content is too low, the reinforcing effect may be insufficient; if the content is too high, the appearance, impact resistance, and flowability may be poor.

[0359] From this perspective, the particularly preferred content of the fibrous reinforcing filler (d) relative to 100 parts by weight of the thermoplastic resin composition (A) is 15 parts by weight or more, more preferably 20 parts by weight or more, particularly preferably 25 parts by weight or more, and preferably 80 parts by weight or less, more preferably 70 parts by weight or less, more preferably 60 parts by weight or less, and especially 50 parts by weight or less.

[0360] As a fibrous reinforcing filler (d), glass fiber is particularly preferred. The type of glass fiber is not particularly limited, and examples include E-glass, C-glass, A-glass, and S-glass. Among these, E-glass fibers are preferred from the viewpoint of not adversely affecting the thermal stability of the thermoplastic resin composition (A).

[0361] Two or more types of glass fiber can be used in combination depending on the required properties.

[0362] Furthermore, the ratio (Fd / Rz) of the average fiber diameter (Fd) of the aforementioned fibrous reinforcing filler (d) to the maximum height (Rz) of the surface of the metal component (X) as measured according to JIS B 0601:2001 is preferably 0.1 or more.

[0363] If the ratio (Fd / Rz) of the average fiber diameter (Fd) of the fibrous reinforcing filler material to the maximum height (Rz) of the surface of the metal component (X) is 1.0 or less, the probability of the glass fiber entering the unevenness of the metal surface increases, and the bonding strength with the metal increases, which is therefore preferred.

[0364] From this perspective, the ratio (Fd / Rz) is preferably 1.0 or less, more preferably 0.8 or less, more preferably 0.5 or less, more preferably 0.3 or less, and more preferably 0.1 or less.

[0365] The lower limit of the ratio (Fd / Rz) is not particularly limited, but from the viewpoint of the bonding strength with metal components, it is preferably 0.01 or more, and more preferably 0.02 or more.

[0366] As described above, the opening diameter and depth of the recess on the surface of the metal component (X) do not necessarily need to be uniform. However, by immersing the fibrous reinforcing filler material into the recess, the rigidity of the joint interface can be strengthened, resulting in high joint strength and airtightness. Therefore, the opening diameter of the recess is preferably greater than or equal to the average fiber diameter (Fd) of the fibrous reinforcing filler material. In this case, the opening diameter is preferably 10 μm or more and 300 μm or less, more preferably 20 μm or more and 250 μm or less, and even more preferably 40 μm or more and 200 μm or less. Furthermore, its depth is preferably 10 μm or more and 500 μm or less, more preferably 30 μm or more and 300 μm or less, and even more preferably 40 μm or more and 250 μm or less. Furthermore, regarding the presence ratio of such recesses, when observing the cross-section of the joint using a scanning electron microscope (manufactured by Hitachi High-Tech Co., Ltd., S3400) at 100x magnification, it is preferable that there are two or more recesses within a 1mm length range on the metal surface, and more preferably four or more recesses, as this results in higher joint strength, and is therefore preferred.

[0367] The average fiber length of the fibrous reinforcing filler material after molding the resin-metal composite is not particularly limited. However, if the average fiber length of the fibrous reinforcing filler material is too short, it may not sufficiently exhibit a reinforcing effect; if it is too long, the bonding strength between the metal component (X) and the resin component (Y) of the resin-metal composite may be reduced. From this point of view, the average fiber length is preferably 50–800 μm, more preferably 100–750 μm, more preferably 150–700 μm, and especially preferably 200–650 μm.

[0368] It should be noted that the average fiber length is as follows: 2000 fibrous reinforcing filler fibers collected from filler material residues after high-temperature ashing of molded articles, solvent-based dissolution, and chemical decomposition were observed using an optical microscope (OLYMPUS B201) and the average value was calculated based on the images using an image analysis device (Mitani Corporation WinROOF2015).

[0369] Furthermore, the method of achieving long fiber granulation by impregnating the thermoplastic resin composition (A) into the wire covering around the roving of the fibrous reinforcing filler material may reduce the bonding strength of the resin-metal composite, and is therefore not preferred.

[0370] For the purpose of improving adhesion to the thermoplastic resin composition (A), the fibrous reinforcing filler material used in this invention can be surface-treated using coupling agents such as aminosilanes and epoxysilanes.

[0371] Examples of coupling agents include chlorosilane compounds such as vinyltrichlorosilane and methylvinyldichlorosilane; alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloyloxypropyltrimethoxysilane; epoxysilane compounds such as β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-epoxypropoxypropyltrimethoxysilane; acrylic compounds, isocyanate compounds, titanate compounds, and epoxy compounds.

[0372] Furthermore, the fibrous reinforcing filler material (d) such as glass fiber used in this invention is generally preferably used in the form of chopped filaments (chopped glass fiber, etc.) obtained by bundling multiple of these fibers together and cutting them to a specified length. In this case, it is preferable to mix a bundling agent into the fibrous reinforcing filler material. By mixing in a bundling agent, good mechanical properties can be obtained on the basis of the advantage of improved production stability of the thermoplastic resin composition (A).

[0373] The binder used as a fibrous reinforcing filler is not particularly limited, and examples include resin emulsions such as vinyl acetate resin, ethylene-vinyl acetate copolymer, acrylic resin, epoxy resin, polyurethane resin, and polyester resin, with acrylic resin, epoxy resin, and polyurethane resin being preferred.

[0374] In addition to the aforementioned fibrous reinforcing filler, the thermoplastic resin composition (A) preferably contains other inorganic fillers in the form of plates, granules, or irregular shapes.

[0375] Plate-shaped inorganic fillers function to reduce anisotropy and warpage; examples include talc, glass flakes, mica, kaolin, and metal foil. Among plate-shaped inorganic fillers, glass flakes are preferred.

[0376] Other inorganic filler materials that can be granular or irregularly shaped include, for example, ceramic beads, clay, zeolite, barium sulfate, titanium dioxide, silicon dioxide, aluminum oxide, magnesium hydroxide, zinc sulfide, etc.

[0377] Talc, titanium dioxide, and zinc sulfide are particularly preferred as other inorganic filler materials.

[0378] <Other Ingredients>

[0379] In addition to the above-mentioned components, the thermoplastic resin composition (A) may contain other components.

[0380] Examples include stabilizers, release agents, colorants, elastomers, flame retardants, flame retardant additives, anti-drip agents, ultraviolet absorbers, antistatic agents, antifogging agents, lubricants, antiblocking agents, plasticizers, dispersants, and antibacterial agents.

[0381] The elastomer may use the substances described in paragraphs 0050 to 0076 of Japanese Patent No. 6604977.

[0382] Flame retardants may be substances described in paragraphs 0071 to 0076 of Japanese Patent No. 6518479.

[0383] <<Manufacturing Method of This Resin-Metal Composite>>

[0384] Next, the manufacturing method of this resin-metal composite will be described.

[0385] The manufacturing method of this resin-metal composite is not particularly limited, and methods such as filling a thermoplastic resin composition (A) into a mold for molding can be listed. Specifically, injection molding, extrusion molding, compression molding, etc. are examples. Among these, injection molding, such as insert molding, is commonly used.

[0386] <Insert Forming>

[0387] In the case of insert molding, a metal component (X) with a concave-convex surface is pre-installed in a molding mold, and a molten thermoplastic resin composition (A) is filled into the mold and cooled.

[0388] If insert molding is performed in this way, the surface side of the metal component (X) with uneven surface can be joined to the resin component (Y) while the resin component (Y) is being molded, thus enabling a firm and stable connection between the metal component (X) and the resin component (Y), which are difficult to firmly join / weld.

[0389] The thermoplastic resin composition (A) can be prepared using conventional methods. Typically, the components and various additives, added as desired, are mixed together, and then melt-blended using a single-screw or twin-screw extruder. Alternatively, the components may not be pre-mixed, or only a portion of them may be pre-mixed and fed into the extruder for melt blending, thereby also preparing the thermoplastic resin composition (A) of the present invention.

[0390] It should be noted that, in the case of compounding fibrous reinforcing filler (d), it is also preferable to supply it from a side feeder in the middle of the extruder barrel.

[0391] The melting temperature of the thermoplastic resin composition (A), in other words, the heating temperature during melt mixing, is preferably selected from the range of 220 to 300°C. If this temperature is too high, decomposition gases are easily generated; therefore, it is desirable to select the screw configuration taking into account factors such as shear exothermics.

[0392] On the other hand, the size and shape of the metal component (X) installed into the mold can be appropriately determined according to the size, structure, etc. of the resin metal composite.

[0393] The size, shape, and thickness of this resin-metal composite are not particularly limited, and it can be any of the following: plate-shaped (circular, polygonal, etc.), column-shaped, box-shaped, bowl-shaped, tray-shaped, etc. Regarding these shapes, the metal component (X) can be pre-shaped by casting, pressure molding, etc., before being installed in the molding die, or it can be shaped after composite molding. Alternatively, it can be shaped in the mold during injection molding or just before injection molding using a composite molding machine equipped with pressure molding capabilities. In the case of large or complex composites, it is not necessary for all parts of the composite to have uniform thickness; additionally, reinforcing ribs can be provided to the composite.

[0394] It should be noted that the metal component (X) does not necessarily have to be distributed throughout the entire resin-metal composite; it can be a part of it.

[0395] In insert molding, it is useful to optimize the combination of the temperature of the molten thermoplastic resin composition (A) and the temperature of the metal component (X) to improve the bonding strength.

[0396] As examples of methods, methods such as preheating the metal component (X) installed in the mold and heating the mold can be listed.

[0397] Methods for preheating the metal component (X) installed in the mold include: induction heating before insert molding of the metal component (X); heating using an IH heater, heating plate, heating furnace, etc.; heating the area near the thermoplastic resin composition from the outside using a halogen lamp, dryer, etc. after the metal component (X) is inserted into the mold; and heating inside the mold using a cylindrical heater, etc., after the metal component (X) is inserted into the mold. Among these, localized heating of only the area in contact with the thermoplastic resin composition (A) is most useful.

[0398] It should be noted that "local heating" refers to the situation where heating is applied to the surrounding area, including the joint area, but the joint area away from the metal component (X) is not heated.

[0399] When heating the mold, if the mold temperature is too low, the embedded metal component (X) will not be sufficiently heated, and therefore, adequate bonding strength may not be achieved. Especially in the case of this resin-metal composite, it is necessary to cure the resin after it has fully penetrated the surface irregularities of the metal component (X). Therefore, it is preferable to set a temperature higher than usual, such as by localized heating as needed. On the other hand, if the temperature is too high, the resin itself may be affected, and a product that is not good for the composite may not be obtained.

[0400] From this perspective, in the manufacturing method of this resin-metal composite, it is preferable to set the surface temperature of the mold that is in contact with the metal component (X) in the mold state to a temperature 60 to 100°C higher than the glass transition temperature of the thermoplastic resin, such as polyester (a-1), more preferably to a temperature 65 to 95°C higher, more preferably to a temperature 68 to 95°C higher, and more preferably to a temperature 70 to 93°C higher.

[0401] <<Morphology of this resin-metal composite>>

[0402] This resin-metal composite can be formed into any shape.

[0403] As an example of the form of this resin-metal composite, such as Figure 1 and Figure 2 As shown, an example can be given: a resin component (Y) having the shape of a vehicle component is provided with a peripheral wall portion Y1 that surrounds the edge end of a plate-shaped metal component (X).

[0404] Metal components (X) are obtained by roughening the joint areas of a plate-shaped metal substrate to create a textured surface, such as... Figure 2 As shown, at the edge end of the metal component (X), the resin component (Y) covers the end edge of the metal component (X) from the surface side end edge to the back side end edge via the side end face, and the aforementioned uneven portion of the surface side of the metal component (X) is joined with the thermoplastic resin composition (A) of the resin component (Y) at the surface side end edge and the back side end edge (joint portion (J)).

[0405] It should be noted that, Figure 1 and Figure 2 The shapes shown are merely illustrative. The shapes of the metal component (X) and the resin component (Y) can be arbitrarily changed. Furthermore, various shapes of metal components (X) and resin components (Y) can be combined to form this resin-metal composite.

[0406] In addition, such as Figure 3 As illustrated in (a) to (e), the joining state between the metal component (X) and the resin component (Y) can also be arbitrarily changed.

[0407] For example, such as Figure 3 As shown in (a), as a metal component (X), a component with unevenness formed on the metal surface can be formed by roughening one side of the metal substrate. At the edge end of the metal component (X), a resin component (Y) covers the end edge of the metal component (X) from the end edge on the surface side to the end edge on the back side. Furthermore, the uneven surface of the metal component (X) is joined to the resin component (Y) only on one side of the end edge of the metal component (X) (joint part (J)).

[0408] like Figure 3 As shown in (b), as a metal component (X), a component with an uneven surface formed on the metal surface can be formed by processing one side of the metal substrate. At the edge end of the metal component (X), a resin component (Y) covers the end face from the surface side of the metal component (X). The uneven surface of the metal component (X) is joined to the resin component (Y) only on one side of the end edge of the metal component (X) (joint part (J)).

[0409] like Figure 3 As shown in (c), as a metal component (X), a component with an uneven surface is formed on the metal surface by performing an uneven surface treatment on one side of the metal substrate. The end edge of one side surface of the metal component (X) overlaps with the end edge of one side surface of the resin component (Y) in a manner with an appropriate width. In this part, the uneven surface of the metal component (X) and the resin component (Y) are joined (joint part (J)).

[0410] like Figure 3 As shown in (d), as a metal component (X), a component with an uneven surface formed by processing both sides of a metal substrate is used. At the edge end of the metal component (X), a resin component (Y) covers the end face from the surface side of the metal component (X). Furthermore, the uneven surface of the metal component (X) is joined to the resin component (Y) only on one side of the end edge of the metal component (X) (joint part (J)).

[0411] like Figure 3As shown in (e), as a metal component (X), a component with unevenness formed on the metal surface by unevenness treatment of both sides of the metal substrate can be used. The end edge of one side surface of the metal component (X) overlaps with the end edge of one side surface of the resin component (Y) in a manner with an appropriate width. In this part, the uneven surface of the metal component (X) and the resin component (Y) are joined (joint part (J)).

[0412] When the ratio (S1 / S2) of the bonding area (S1) between the metal component (X) and the resin component (Y) to the area (S2) of the exposed metal component (X) not covered by the resin component (Y) is large, the sealing performance is stable and the airtightness is improved, which is therefore preferred. Specifically, this ratio (S1 / S2) is preferably 0.01 or higher, more preferably 0.1 or higher, and especially preferred when it is 0.5 or higher to achieve sufficient airtightness.

[0413] Furthermore, to ensure sufficient heat dissipation from the exposed portion of the metal, the ratio (S1 / S2) is preferably small to a certain extent. Specifically, this ratio is preferably 8 or less, more preferably 4 or less, even more preferably 2 or less, and if it is 1 or less, sufficient heat dissipation can be ensured, so it is particularly preferred.

[0414] By setting the S1 / S2 ratio in this way for bonding, the bonding strength and airtightness can be further improved, and when used as a component of the housing, the heat contained in the housing can be fully dissipated, ensuring heat dissipation.

[0415] It should be noted that when the metal surfaces on both sides are uneven, the contact area between the uneven surface of the metal component (X) and the resin component (Y), i.e., the area of ​​the joint (J), does not necessarily have to be the same on both sides.

[0416] <<The bonding strength of this resin-metal composite>>

[0417] This resin-metal composite exhibits excellent bonding strength by bonding the uneven surface of the metal component (X) to the resin component (Y).

[0418] Regarding this resin-metal composite, the bonding strength between the aforementioned metal component (X) and resin component (Y) is preferably 26 MPa or more, more preferably 27 MPa or more, further preferably 28 MPa or more, even more preferably 29 MPa or more, and particularly preferably 30 MPa or more. Higher bonding strength results in better airtightness, and is therefore preferred.

[0419] In this invention, "bonding strength" refers to the value measured according to ISO 19095, that is, the value obtained by making a bonding strength test piece of the shape described in the embodiment, using the bonding conditions for manufacturing resin-metal composites, bonding a metal component (X) and a resin component (Y), and performing a tensile test on the resulting composite as described in the embodiment.

[0420] <<Applications of this resin-metal composite>>

[0421] This resin-metal composite can firmly and stably bond metal components to resin components, achieving excellent bond strength, and combining the properties of both, such as heat dissipation, heat resistance, insulation, and antistatic properties. Therefore, it is suitable for a variety of applications. In particular, it is suitable for automotive applications where bond strength and heat dissipation are especially important.

[0422] Specifically, if this resin-metal composite is used to form containers, such containers can be made with excellent airtightness, heat dissipation, heat resistance, insulation, and antistatic properties. Therefore, they can be used in vehicle components, electrical components, and housing components. Specifically, they are suitable for use as components assembled into electrical and electronic components (housings, shells, covers, etc.) in office automation equipment, primarily household appliances; components constituting mechanical mechanisms; and components in the housings of some or all of the electrical components in vehicles (various control units, ignition coil components, sensor components, motor components, power modules, boost DC / DC converters, buck DC / DC converters, capacitors, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, and bonding blocks, etc.); and for applications requiring strong bonding in terms of function, such as smartphone housings.

[0423] In particular, the relative permittivity of the resin component of the present invention is 3.3 to 3.7, especially 3.4 to 3.6, and the dielectric loss tangent is around 0.01, for example 0.005 to 0.015. Therefore, it can be suitable for use in automotive sensor components, fairing components, ECU housings, millimeter-wave radar housings, etc.

[0424] Figure 4 The image shows an example of using this resin-metal composite as part of the housing for electrical components in a vehicle.

[0425] When this resin-metal composite is used as part of an article, that is, when it is used in combination with other components (Z) (resin molded body, aluminum die casting, metal, etc.), the joining method between the other components (Z) and this resin-metal composite, for example, the joining method between the resin component (Y) and the other component (Z), can be any method. Examples include laser welding, ultrasonic welding, vibration welding, thermal welding, mechanical joining using bolts or self-tapping screws, adhesives, etc.

[0426] <<Explanation of Terms>>

[0427] In this invention, when referred to as "X~Y" (where X and Y are arbitrary numbers), unless otherwise specified, it includes the meaning of "X or more and Y or less", as well as the meaning of "preferably greater than X" or "preferably less than Y".

[0428] Furthermore, when it is written as "X or above" (where X is any number), unless otherwise specified, it includes the meaning of "preferably greater than X". When it is written as "Y or below" (where Y is any number), unless otherwise specified, it includes the meaning of "preferably less than Y".

[0429] Example

[0430] The present invention will now be described in more detail through embodiments. However, the present invention is not limited to the following embodiments as long as it does not depart from its spirit.

[0431] <Metal Components (X1)>

[0432] As follows, metal surface treatment method A is applied to the metal component to obtain a metal component (X1) as a metal component (X).

[0433] Metal Surface Treatment Method A: A strip of aluminum alloy (JISH4000 "A5052") measuring 45mm in length, 12mm in width, and 1.5mm in thickness is immersed in a zincate solution (40.0°C) for 60 seconds. Next, it is immersed in an etchant (50°C) for 480 seconds to roughen the surface of the metal sheet, creating an uneven surface. Then, the metal sheet is immersed in a commercially available zirconium chemical conversion treatment agent ("PALLUCID" (registered trademark) manufactured by Nihon Parkerizing, 50g / L, 45°C, pH 4.0) for 120 seconds to obtain a metal component (X1).

[0434] <Zincate Liquid Composition>

[0435] ·water

[0436] Zinc oxide: 0.25 mol / L

[0437] Sodium hydroxide: 3.80 mol / L

[0438] Tartaric acid: 0.07 mol / L

[0439] pH: 12.5

[0440] <Etching Agent Ingredients>

[0441] ·water

[0442] Sodium persulfate: 0.35 mol / L

[0443] Potassium chloride: 1.40 mol / L

[0444] pH: 3.0

[0445] The uneven surface of the metal component (X1) treated as described above was observed using a hybrid laser microscope (LASERTEC OPTELICS HYBRID) with a 20x objective lens. The surface roughness was measured according to JIS B0601:2001 using the accompanying analysis software (Lasertec Microscope Solution Software LMeye7) with a 20x objective lens.

[0446] For the measurement, the FZ image was obtained using the Fine Peak measurement algorithm on the average uneven surface of the center of a strip-shaped metal sheet made of aluminum alloy (JIS H4000 "A5052"), which is 45 mm long, 12 mm wide, and 1.5 mm thick. The measurement range was set to 4.2 mm in the 45 mm length direction. The cutoff value λc was 0.8000 mm.

[0447] The same operation was repeated 30 times at different locations, and the average values ​​were calculated. The arithmetic mean roughness (Ra) was 5.2 μm, and the maximum height (Rz) was 34.7 μm. Furthermore, surface and cross-sectional observations using an electron microscope (Hitachi High-Tech S3400) revealed a size distribution consisting of large recesses with opening diameters of 40–190 μm and depths of 10–80 μm, combined with small recesses with opening diameters of 0.1–5 μm and depths of 0.1–5 μm. The small recesses are distributed inside and around the large recesses.

[0448] <Metal components (X2)>

[0449] The following operation is performed to apply metal surface treatment method B to the metal component to obtain a metal component (X2) as a metal component (X).

[0450] Metal surface treatment method B: For a strip of aluminum alloy (JISH4000 "A5052") with a length of 45mm, a width of 12mm and a thickness of 1.5mm, as the first step, the metal sheet is immersed in the following treatment solution (1) for 300 seconds, then as the second step, it is immersed in the following treatment solution (2) for 180 seconds, and as the third step, it is immersed in the following treatment solution (3) for 120 seconds to obtain a metal component (X2).

[0451] Treatment solution (1): Lithium chloride (3.0 mol / L) and magnesium nitrate hexahydrate (0.1 mol / L) were added to the ion-exchange water according to the target volume. While measuring the pH using a handheld pH meter (portable pH meter HM-30P manufactured by DKK Corporation) and a pH measuring electrode (GST-2739C manufactured by DKK Corporation), the pH was adjusted to 10.0 using nitric acid and sodium hydroxide, and adjusted to the target volume. The temperature of treatment solution (1) was set to 60°C.

[0452] Treatment solution (2): Nitric acid was added at a concentration of 6.5 mol / L relative to the ion-exchanged water. In this example, no pH adjustment was performed. The temperature of treatment solution (2) was set to 50°C.

[0453] Treatment solution (3): A commercially available zirconium chemical conversion treatment agent (PALLUCID (registered trademark), manufactured by Nihon Parkerizing) was added at a concentration of 50 g / L relative to the ion-exchanged water. The pH was adjusted to 4.0 using sodium hydroxide, and the solution was adjusted to the target volume. The temperature of the treatment solution (3) was set to 50°C.

[0454] The uneven surface of the metal component (X2) treated as described above was observed using a hybrid laser microscope (LASERTEC OPTELICS HYBRID) with a 20x objective lens. The surface roughness was measured according to JIS B0601:2001 using the accompanying analysis software (Lasertec Microscope Solution Software LMeye7) with a 20x objective lens.

[0455] For the measurement, the FZ image was obtained using the Fine Peak measurement algorithm on the average uneven surface of the center of a strip-shaped metal sheet made of aluminum alloy (JIS H4000 "A5052"), which is 45 mm long, 12 mm wide, and 1.5 mm thick. The measurement range was set to 4.2 mm in the 45 mm length direction. The cutoff value λc was 0.8000 mm.

[0456] The same operation was repeated 30 times at different locations, and the average value was calculated. The arithmetic mean roughness (Ra) was 0.4 μm, and the maximum height (Rz) was 4.8 μm. In addition, the surface and cross-section observations using an electron microscope (Hitachi High-Tech S3400) showed that the aperture diameter was 10–150 nm and the depth was 300–800 μm.

[0457] <Metal Components (X3)>

[0458] The following operation is performed to apply metal surface treatment method C to the metal component to obtain a metal component (X3) as a metal component (X).

[0459] Metal surface treatment method C: Using a fiber laser with a wavelength of 1064nm (Panasonic LP-M500), the surface is raised and recessed on a strip of aluminum alloy (JIS H4000 "A5052") with a length of 45mm, a width of 12mm and a thickness of 1.5mm.

[0460] It should be noted that the above laser processing is performed as follows: the output power of 40W, the scanning speed of 1500mm / s, the pulse period of 20μs, and the shadow line width of 0.10mm are combined with the scanning speed of 1000mm / s, the pulse period of 20μs, and the shadow line width of 0.12mm in a grid pattern, and the vertical and horizontal scans are performed 10 times each.

[0461] The uneven surface of the metal component (X3) obtained as described above was observed using a hybrid laser microscope (LASERTEC OPTELICS HYBRID) with a 20x objective lens. The surface roughness was measured according to JIS B0601:2001 using the accompanying analysis software (Lasertec Microscope Solution Software LMeye7) with a 20x objective lens.

[0462] For the measurement, the FZ image was obtained using the Fine Peak measurement algorithm on the average uneven surface of the center of a strip-shaped metal sheet made of aluminum alloy (JIS H4000 "A5052"), which is 45 mm long, 12 mm wide, and 1.5 mm thick. The measurement range was set to 4.2 mm in the 45 mm length direction. The cutoff value λc was 0.8000 mm.

[0463] The same operation was repeated 30 times at different locations, and the average values ​​were calculated. The arithmetic mean roughness (Ra) was 58 μm, and the maximum height (Rz) was 228 μm. In addition, the surface and cross-section observations using an electron microscope (Hitachi High-Tech S3400) showed that the opening diameter ranged from 50 to 190 μm, and the depth ranged from 40 μm to 180 μm.

[0464] [Table 1]

[0465]

[0466] [Table 2]

[0467]

[0468] (Preparation of polyester resin compositions α1-17)

[0469] All components shown in Table 1, except for the fibrous reinforcing filler (d), were uniformly mixed using a rotary drum mixer at the proportions shown in Table 2 (all parts by weight). The fibrous reinforcing filler (d) was then fed from the side feeder at a rate of 40 kg / hr using a meshing co-rotating twin-screw extruder (Nippon Steel's "TEX-30α", screw diameter = 32 mm, L / D = 52). Melt mixing was performed at extruder barrel temperatures (C1-C15) of 260°C, die temperature of 250°C, and screw speed of 200 rpm. The nozzles were set to 4 holes (circular (φ4 mm), length 1.5 cm), and the shear rate (γ) was 211 sec. -1 The extruded yarn was spun into strands under specific conditions. The temperature of the extruded strands was 270°C immediately after extrusion. The extruded strands were then rapidly cooled in a water bath with a temperature range of 30–50°C. The surface temperature (T) of the strands was measured using an infrared thermometer until it reached 65°C (γ·T = 1.4 × 10⁻⁶). 4 The granules are inserted into a granulator for cutting to obtain granules of polybutylene terephthalate resin composition α1-17.

[0470] Furthermore, the granules of the obtained polyester resin compositions α1 to 17 were dried at 120°C for 5 hours and then used for insert molding.

[0471] <Examples 1-22, Comparative Examples 1-15>

[0472] Metal components X1, X2, and X3 (hereinafter collectively referred to as "X") manufactured as described above are installed in the mold cavity, and the granules of the polyester resin compositions α1 to 17 obtained above are injection molded under the conditions shown below. Figure 5 As shown, a resin-metal composite (evaluation sample) was obtained by bonding a metal component (X) with a resin component (Y) formed from a polyester resin composition (A). The bonding area between the metal component (X) and the resin component (Y) was 5 mm × 10 mm.

[0473] Injection molding conditions: The injection molding machine used was the "J85AD" manufactured by Nippon Steel, with the following conditions: barrel temperature 270°C, mold temperature 140°C, injection speed 60 mm / s, filling time 0.2 seconds, holding pressure 110 MPa, holding time 10 seconds, and cooling time 30 seconds.

[0474] <Evaluation / Measurement Methods>

[0475] The resin-metal composites (evaluation samples) obtained in the examples / comparative examples were measured and evaluated using the following methods.

[0476] (Joint strength)

[0477] Using the resin-metal composites (evaluation samples) obtained in the examples / comparative examples, the bond strength was determined in accordance with ISO 19095 as follows.

[0478] Using a tensile testing machine (Instron Model 5544), a tensile test was performed on the joint surfaces at the ends of the obtained resin-metal composite (evaluation sample) in the vertical direction (tensile speed 5 mm / min) to determine the maximum tensile stress at the joint surfaces, i.e., the joint strength. The obtained strengths are recorded in the "Joint Strength" column of Tables 3-1 and 3-2.

[0479] (Tensile strength retention rate after 100 hours of PCT test)

[0480] Using granules of polyester resin compositions α1 to 17 obtained by the above method, the tensile strength retention rate after 100 hours of PCT testing was determined as follows.

[0481] After drying the granules at 120°C for 5 hours, an ISO multi-object test piece (4 mm thick) was injection molded using an injection molding machine (NEX80 manufactured by Nissei Resin Kogyo Co., Ltd.) at a barrel temperature of 250°C and a mold temperature of 80°C.

[0482] Using ISO multi-object test specimens, tensile strength (before treatment) was determined according to ISO 527 at a tensile speed of 5 mm / min (unit: MPa). Using a pressure cooker (PCT) testing machine (manufactured by Hirayama Manufacturing Co.), the ISO multi-object test specimens were treated for 100 hours at a temperature of 121°C, relative humidity of 100%, and pressure of 2 atm. Tensile strength was then measured similarly, and the strength retention rate (unit: %) after treatment relative to before treatment was calculated.

[0483] (Gas production after 300 consecutive forming cycles)

[0484] Gas production tests were conducted using granules of polyester resin compositions α2, α4, and α7 obtained by the above method, based on the following mold fouling evaluation.

[0485] [Mold Scale Evaluation]

[0486] The molding machine, conditions, etc. used for evaluation are as follows.

[0487] Injection molding machine: SE18 manufactured by Sumitomo Heavy Industries, Ltd.

[0488] Injection pressure: 50 MPa

[0489] Injection speed: 80 mm / sec

[0490] Barrel temperature: 270℃

[0491] Injection time: 3 seconds

[0492] Cooldown: 8 seconds

[0493] Mold temperature: 35℃

[0494] Suck back: 3mm

[0495] Molded part: Length 35mm, Width 14mm, Thickness 2mm

[0496] Mold: Needle-point gate mold

[0497] Under the above conditions, injection molding was performed continuously for 300 cycles. The state of the mold fouling (mold contamination) was observed with the naked eye. 10 points is the maximum score. The best state of mold fouling was set as 10 points for evaluation.

[0498] The evaluation results are shown in Tables 3-1 and 3-2 below.

[0499] (Evaluation of demolding performance during continuous forming)

[0500] In the mold fouling evaluation test, 300 continuous molding cycles were performed, and the demolding performance during continuous molding was evaluated according to the following criteria. The results are shown in Tables 3-1 and 3-2.

[0501] ○(Good): Less adhesion to the mold during demolding, enabling automatic continuous forming.

[0502] ×(poor): Frequent adhesion to the mold during demolding makes it difficult to automatically perform continuous forming.

[0503] [Table 3-1]

[0504]

[0505] [Table 3-2]

[0506]

[0507] (Inspection)

[0508] As clearly shown by the above results, Examples 1 to 22, with Ra / (Fd×Wr) of 0.5 or higher, exhibited improved bonding strength compared to Comparative Examples 1 to 15, which had Ra / (Fd×Wr) of less than 0.5.

[0509] Furthermore, by comparing Examples 3, 6, and 9, it can be seen that by using oxidized polyethylene wax as a low molecular weight compound (c), the amount of gas during continuous molding is reduced. As in Example 3, if low molecular weight compound c1, i.e., oxidized polyethylene wax with a molecular weight of 4000 and an acid value of 1 mgKOH / g, is used, the amount of gas is further reduced.

[0510] <Examples 23-29>

[0511] (Relative permittivity, dielectric loss tangent)

[0512] After drying the granules of polybutylene terephthalate resin compositions α1 to 7 obtained by the above method at 120°C for 5 hours, a flat molded body with a length of 100mm × width of 100mm × thickness of about 2mm was obtained using an injection molding machine "NEX80-9E" manufactured by Nissei Resin Kogyo Co., Ltd., with a barrel temperature of 250°C and a mold temperature of 80°C.

[0513] The resulting molded body was placed on a Φ80mm diameter sample stage. Using a KEYCOM DPS10 millimeter-wave / microwave measurement system equipped with a VirginiaDiodes WR10-VNAX millimeter-wave module, a KEYSIGHT N5227A network analyzer, and a KEYCOM DPS10 millimeter-wave / microwave measurement tool with a dielectric lens, the transmission attenuation and phase change were measured at 25°C and a measurement frequency of 70–90 GHz using the free space frequency variation method. Furthermore, the accurate thickness of the molded body was measured using a SHINWA digital micrometer. Based on the measured results of transmission attenuation, phase change, and thickness, the relative permittivity and dielectric loss tangent at 76.5 GHz were determined.

[0514] [Table 4]

[0515] Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Resin component (Y) α1 α2 α3 α4 α5 α6 α7 Relative permittivity (77 GHz) 3.40 3.62 3.62 3.63 3.39 3.41 3.63 Dielectric loss tangent (77GHz) 0.010 0.011 0.011 0.011 0.009 0.009 0.011

[0516] (Inspection)

[0517] It is known that the compositions of Examples 23 to 29 have a relative permittivity of around 3.4 to 3.6 and a dielectric loss tangent of around 0.01, and are therefore suitable for use in automotive sensor components, fairing components, ECU housings, millimeter-wave radar housings, etc.

[0518] Explanation of reference numerals in the attached figures

[0519] (X)··Metal components

[0520] (Y)··Resin components

[0521] Y1··Peripheral Part

[0522] (J)··Joint

[0523] (Z)··Other Components

Claims

1. A resin-metal composite, characterized in that, It comprises a metal component (X) and a resin component (Y), wherein the metal component (X) has a surface with unevenness, and the resin component (Y) is formed of a thermoplastic resin composition (A). The resin-metal composite comprises a metal component (X) having a surface side with uneven surface joined to a resin component (Y), the thermoplastic resin composition (A) comprising a thermoplastic resin and a fibrous reinforcing filler, and the resin-metal composite satisfies the following relationship (1). 70≥Ra / (Fd×Wr)≥1.0 …(1) It should be noted that in the above relationship (1), Ra refers to the arithmetic mean roughness of the surface of the metal component (X) measured according to JIS B0601:2001, in μm; Fd refers to the average fiber diameter of the fibrous reinforcing filler material, in μm; Wr refers to the amount of fibrous reinforcing filler material in the thermoplastic resin composition (A) by mass / the total amount of all components in the thermoplastic resin composition (A) by mass.

2. The resin-metal composite according to claim 1, wherein, The content of thermoplastic resin is 30-80% by mass.

3. The resin-metal composite according to claim 1 or 2, wherein, The thermoplastic resin composition (A) comprises a polyester (a-1) and a thermoplastic resin (a-2), wherein the polyester (a-1) comprises polybutylene terephthalate or a copolymer of polybutylene terephthalate or a mixture thereof, and the thermoplastic resin (a-2) is miscible with the polyester (a-1). The polyester (a-1) and the thermoplastic resin (a-2) are contained in a mass ratio of (a-1):(a-2) = 20:80~80:

20.

4. The resin-metal composite according to claim 1 or 2, wherein, The bonding strength between the metal component (X) and the resin component (Y), as measured according to ISO 19095, is 26 MPa or more.

5. The resin-metal composite according to claim 1 or 2, wherein, The surface roughness Ra of the metal component (X), as measured according to JIS B 0601:2001, is 0.01~100 μm.

6. The resin-metal composite according to claim 1 or 2, wherein, The average fiber diameter Fd is 4~9 μm.

7. The resin-metal composite according to claim 1 or 2, wherein, The surface irregularities of the metal component (X) are formed by a chemical-based treatment.

8. The resin-metal composite according to claim 1 or 2, wherein, The surface of the metal component (X) has an uneven surface with a chemical coating as the outermost layer.

9. The resin-metal composite according to claim 1 or 2, wherein, The surface irregularities of the metal component (X) are formed by laser-based processing.

10. The resin-metal composite according to claim 1 or 2, wherein, The thermoplastic resin composition (A) contains a low molecular weight compound (c), which contains oxidized polyethylene wax.

11. The resin-metal composite according to claim 1 or 2, wherein, The thermoplastic resin composition (A) contains a low molecular weight compound (c) with an acid value of 0.01 to 40 mg / KOH.

12. The resin-metal composite according to claim 1 or 2, wherein, The thermoplastic resin composition contains a low molecular weight compound (c) with an acid value of 0.5 to 20 mg / KOH.

13. The resin-metal composite according to claim 1 or 2, wherein, The average fiber length of the fibrous reinforcing filler material is 50~800μm.

14. The resin-metal composite according to claim 1 or 2, wherein, The thermoplastic resin composition (A) further comprises a compound (b) containing an epoxy group.

15. The resin-metal composite according to claim 3, wherein, The thermoplastic resin (a-2) is polyethylene terephthalate.

16. The resin-metal composite according to claim 1 or 2, wherein, The resin-metal composite has the following configuration: a resin member (Y) extends from the edge end of the surface side of a metal member (X) with an uneven surface to the edge end of the back side via a side end face, and the uneven portion of the metal member (X) is bonded to the thermoplastic resin composition of the resin member (Y) at the edge end of the surface side and the edge end of the back side of the metal member.

17. A method for manufacturing a resin-metal composite according to any one of claims 1 to 16, comprising: The process of applying a molten resin composition to a metal component (X) with an uneven surface by injection molding.

18. A component for a vehicle comprising the resin-metal composite of any one of claims 1 to 16.

19. An electrical component comprising the resin-metal composite of any one of claims 1 to 16.

20. A housing component comprising the resin-metal composite of any one of claims 1 to 16.

21. A component for a smartphone casing comprising the resin-metal composite as described in any one of claims 1 to 16.

22. A housing component for an electrical component for a vehicle, comprising the resin-metal composite as described in any one of claims 1 to 16.

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