JP2021091214A - Resin-metal composite body - Google Patents

Abstract

To provide a resin-metal composite body having a configuration such that a PBT resin member and a metal member are coupled with each other, in which the bonded state can be made sufficiently stable and further generation of gas during production can be suppressed.SOLUTION: There is provided a resin-metal composite body that comprises: a metal member (X) having surface irregularities; and a resin member (Y) made of a polyester resin composition (A), and that has a structure obtained by coupling a surface side having surface irregularities of the metal member (X) with the resin member (Y), in which the polyester resin composition (A) contains polybutylene terephthalate (also referred to as a homo PBT), a copolymer of polybutylene terephthalate (also referred to as a copolymerized PBT) or a mixed resin thereof as a polyester (a), and further contains an epoxy group-containing compound (b) and a low molecular weight compound (c), and the low molecular weight compound contains polyethylene oxide wax.SELECTED DRAWING: Figure 2

Description

The present invention relates to a resin-metal composite having a structure in which a PBT resin member containing polybutylene terephthalate (also referred to as "PBT") as a main component resin and a metal member are joined.

In recent years, in the fields of automobile parts and consumer parts, development has been promoted in the direction of changing metal products to resin products in consideration of environmental aspects such as weight reduction and recycling. Among resin products, polyester products have excellent mechanical strength, chemical resistance, electrical insulation, etc., and also have excellent heat resistance, moldability, and recyclability, so they can be used for various equipment parts. Widely used. In particular, thermoplastic polyester resins typified by polybutylene terephthalate have excellent mechanical strength and moldability, and can be flame-retardant, so they are widely used in electrical and electronic equipment parts that require fire safety. ing.

However, in the case of resin products, heat dissipation is inferior, so in the fields of electrical and electronic equipment parts, automobile parts, etc., the development of resin-metal composites in which metal members such as aluminum and iron and resin members are joined has been developed. It is being advanced. This type of resin-metal composite can generally be superior to resin products in terms of strength, antistatic property, thermal conductivity, heat dissipation, and electromagnetic wave shielding property.

Regarding such a resin-metal composite, for example, Patent Document 1 discloses a method of integrally molding a metal and a thermoplastic resin by in-molding a thermoplastic resin on a metal substrate.
Further, Patent Document 2 discloses, as another method for manufacturing a composite of a resin member and a metal member, a method of joining a resin by injection molding to a part that has been subjected to surface treatment by chemical etching to a metal part. Has been done.
In Patent Document 3, as a method of surface treatment of a metal that exhibits excellent adhesiveness when adhering a metal to an organic polymer substance or the like, a chemical etching treatment accompanied by a film formation is performed on the surface of the metal, and the film is chemically etched. The method of removing the metal is disclosed.
Further, in Patent Document 4, as a manufacturing method for a bonded body of a metal base material and a cured resin product, a zincate film is formed on the surface of an aluminum base material, and then the surface is roughened with an etching agent. A method of inserting the resin composition into the recess formed by the roughening is disclosed.

Japanese Unexamined Patent Publication No. 6-29669 Japanese Unexamined Patent Publication No. 2008-173967 Japanese Unexamined Patent Publication No. 11-293476 Japanese Unexamined Patent Publication No. 2019-99864

With respect to the conventionally known resin-metal composite, it has been difficult to expand its use because the bonding state between the metal member and the resin member is not sufficiently stable. In particular, there was a problem in using it for automobile applications.
By the way, as disclosed in Patent Documents 2 to 4 described above, a metal member is immersed in a chemical solution to roughen the surface of the metal member to provide unevenness, and a resin is applied thereto by injection molding or the like. If filled, not only can the metal member and the resin member be joined by utilizing the anchor effect due to the unevenness, but also the treatment can be performed regardless of the size and shape of the metal member, so that the application can be expanded. For example, it can also be used for automobile applications.
However, it has been found that continuous injection molding as described above for industrial production produces gas of unknown cause.

Therefore, the present invention relates to a resin-metal composite having a structure in which a PBT resin member made of a resin composition containing PBT or a copolymer thereof as a main component resin and a metal member are bonded to each other. It is intended to provide a new resin-metal composite that can be sufficiently stable and that can suppress the generation of gas during production.

The present invention comprises a metal member (X) having a surface having surface irregularities, and a resin member (Y) made of a polyester resin composition (A) containing polyester (a) as a main component resin. It is a resin-metal composite having a structure in which the surface side of the manufacturing member (X) having surface irregularities and the resin member (Y) are joined.
The polyester resin composition (A) contains, as the polyester (a), polybutylene terephthalate (also referred to as "homo PBT"), a copolymer of polybutylene terephthalate (also referred to as "copolymerized PBT"), or a mixed resin thereof. Including, further containing an epoxy group-containing compound (b) and a low molecular weight compound (c).
The low molecular weight compound proposes a resin metal composite characterized by containing polyethylene oxide wax.

The resin-metal composite proposed by the present invention is a resin member (Y) suitable for the surface state of the metal member (X), that is, the surface state having surface irregularities, and is a PBT or PBT copolymer or a PBT copolymer as a main component resin. A resin member (Y) made of a polyester resin composition (A) containing these mixed resins and further containing a bisphenol A type epoxy compound (b) is selected and bonded to the metal member (X). Therefore, the bonded state can be made sufficiently stable. Further, by including the polyethylene oxide wax as the low molecular weight compound (c), gas generation during production, particularly gas generation when the polyester resin composition (A) is heated can be suppressed.
Therefore, the resin-metal composite proposed by the present invention can be widely used, can be widely and suitably used from consumer products to automobile applications, and can be industrially produced.

It is a partial cross-sectional perspective view of the resin metal complex which concerns on an example of this invention. It is a partially enlarged sectional view of FIG. (A) to (e) are cross-sectional views illustrating the joining mode of the metal member (X) and the resin member (Y). It is sectional drawing which showed the example which applied this resin metal composite as a part of the housing of the electric component for a vehicle. It is a top perspective view of the metal member produced in the reference example. It is a figure of the resin metal composite produced in the reference example, that is, the resin metal composite as a test body for airtightness evaluation, the upper figure is a metal member before the composite is made, and the lower left figure is a top perspective view thereof. The figure and the lower right figure are cross-sectional views. It is an exploded perspective view of the pressure vessel used for the above-mentioned airtightness evaluation.

Next, the present invention will be described based on examples of embodiments. However, the present invention is not limited to the embodiments described below.

<<< This Resin Metal Complex >>>
The resin-metal composite (referred to as “the present resin-metal composite”) according to an example of the embodiment of the present invention includes a metal member (X) having a surface having surface irregularities on at least one side, and polyester (a). The resin member (Y) made of the polyester resin composition (A) containing the above as the main component resin is provided, and the surface side of the metal member (X) having surface irregularities and the resin member (Y) are joined. It is a resin-metal composite having such a structure.

<< Metallic member (X) >>
The metal member (X) is a metal member (X) provided with a surface having surface irregularities (also referred to as “uneven surface”) on the entire surface or a part thereof.

Examples of the metal constituting the metal member (X) include various metals such as aluminum, iron, copper, magnesium, tin, nickel, and zinc, and alloys containing these metals. Among these, it is preferable to contain at least one of aluminum, iron, copper and magnesium, and an alloy containing these metals, and more preferably to contain aluminum and an alloy containing aluminum.

The shape of the metal member (X) is not particularly limited. For example, a flat plate shape, a curved plate shape, a plate shape, a rod shape, a tubular shape, a lump shape, a sheet shape, a film shape, or the like, or one manufactured in a specific desired shape is preferable. It is not limited to a single flat surface or curved surface, and may have various shapes such as a stepped portion, a concave portion, and a convex portion.

The thickness of the metal member (X) is not particularly limited. However, from the viewpoint of product design, the range is preferably 0.05 mm to 50 mm, more preferably 0.10 mm or more or 10 mm or less, and more preferably 0.12 mm or more or 5 mm or less. In particular, the thickness of the aluminum plate and the iron plate is preferably 0.10 mm to 10 mm, and more preferably 0.2 mm or more or 5 mm or less.
The "thickness" at this time is the thickness because the thickness is uniform when the metal member is flat, and on the other hand, when the metal member is other than flat, that is, when the thickness is non-uniform. Is the thickness of the thinnest portion of the metal member (X) to be joined to the resin member (Y).

<Uneven surface>
When the surface of a metal member is roughened with a chemical solution or the like and joined to a resin member, it has gradually become clear that there is compatibility between the surface condition and the type of the resin member. In particular, with respect to a PBT resin member composed of a resin composition containing PBT or a copolymer thereof as a main component resin, it was found that there is a special compatibility between the composition of the resin composition and the surface state of the metal member. I came.

From this point of view, the surface of the metal member (X), that is, the surface to be joined to the resin member (Y), has an arithmetic mean roughness (Ra) of 0.05 μm measured in accordance with JIS B 0601: 2001. It is preferably 0.1 μm or more, particularly 0.2 μm or more, 0.3 μm or more, further 0.4 μm or more, and 0.5 μm or more, most preferably 1 μm or more. The upper limit of the arithmetic mean roughness (Ra) is preferably 200 μm or less, more preferably 180 μm or less, further 150 μm or less, particularly 120 μm or less, 100 μm or less, especially 80 μm or less, and 50 μm or less, especially 30 μm or less. Most preferably, it is 10 μm or less.
Further, the maximum height (Rz) is preferably 0.01 μm or more, more preferably 0.05 μm or more, and thereafter, 0.1 μm or more, 0.3 μm or more, 0.5 μm or more, 1 μm or more, sequentially. 3 μm or more, 5 μm or more, 7 μm or more, most preferably 10 μm or more, and the upper limit of the maximum height (Rz) is preferably 200 μm or less, more preferably 180 μm or less, particularly 150 μm or less, and 120 μm or less, among others. It is 100 μm or less, and 80 μm or less, most preferably 50 μm or less.

It has been found that when the surface of the metal member (X) has irregularities in such a rough surface state, strong bonding strength can be exhibited by selecting a resin composition having a specific composition. .. On the other hand, if the surface roughness is out of the above range, the composition of the resin composition having good compatibility will be different. For example, when the surface roughness is out of the above range, the effect of the epoxy group-containing compound (b) cannot be confirmed even if the predetermined polyester (a) is blended with the predetermined epoxy group-containing compound (b) in combination. In some cases.

The arithmetic average roughness (Ra) and maximum height (Rz) of the metal member (X) are such that the uneven surface of the surface-treated metal member (X) is an objective lens of a hybrid laser microscope (OPTELICS HYBRID manufactured by LASERTEC). Arithmetic mean roughness (Arithmetic Mean Roughness (Arithmetic Mean Roughness) by observing at 20x, observing with the attached analysis software (Lasertec Microscope Solution LMeye7) at 20x objective lens, and measuring the surface roughness in accordance with JIS B 0601: 2001. Ra) and maximum height (Rz) can be calculated.
For specific measurement in the examples, an FZ image is obtained by using the measurement algorithm Fine Peak to measure the average uneven surface at the center of a strip-shaped metal plate having a length of 45 mm, a width of 12 mm, and a thickness of 1.5 mm. It was. The measurement range was 4.2 mm in the vertical direction of 45 mm. The cutoff value λc is 0.8000 mm. The same operation was repeated 30 times at arbitrary different places, and the average value was calculated.
Further, when measuring the uneven surface of the metal member (X) in the present resin-metal composite, the portion where the uneven surface of the metal member (X) surface is not affected by the joining is similarly measured. When there is no unbonded region, the cross section of the resin-metal composite bonded to the resin member (Y) is observed and measured with an optical microscope or a scanning electron microscope to obtain the arithmetic mean roughness (Ra). It is possible to obtain a value corresponding to the numerical value of the maximum height (Rz).

The recesses existing on the surface of the metal member (X) need not have a uniform opening diameter and depth thereof. Concavities of several sizes (roughness, height, etc.) may be combined and distributed. Specifically, for example, when the arithmetic average roughness Ra is 1 μm to 10 μm and the maximum height Rz is 10 μm to 50 μm, it has only recesses having a uniform opening diameter and / or depth. Higher bonding strength is obtained on a surface in which recesses having an opening diameter and / or depth of 50 μm or more and 200 μm or less and recesses having an opening diameter and / or depth of 0.5 μm or more and 10 μm or less coexist and are distributed. Is preferable from the viewpoint of obtaining.

The metal member (X) and the resin member (Y) may be joined to the metal member (X) on the entire surface of the uneven surface of the metal member (X), or may be joined by a part of the uneven surface. You may be doing it.
Further, it is not necessary that the surface of the metal member (X) has irregularities at all the locations where the resin member (Y) and the metal member (X) are in contact with each other. That is, the surface of the metal member (X) may have irregularities at a part of the portion where the metal member (X) and the resin member (Y) are joined.

(Roughening method)
The method of roughening the entire surface or a part of the surface of the metal member (X) to provide unevenness is not particularly limited, and a known method can be adopted. Above all, from the viewpoint that the metal member (X) can be treated regardless of the size and shape, it is preferable to adopt a chemical chemical solution treatment method in which the metal member (X) is immersed in a chemical chemical solution or coated with the chemical chemical solution.
Further, the roughening method may be carried out by a single method, or may be carried out by combining a plurality of methods. By combining a plurality of methods, it may be possible to find effects such as optimization of the uneven structure and cost reduction.

Various known chemical chemical treatment methods are known depending on the type of metal, and known methods can be used. When the metal member (X) is aluminum, an aluminum alloy, or cast aluminum, it is preferable that a film is formed on the metal surface before the unevenness is formed, and then the unevenness is formed by removing the film. Further, it is preferable to apply a chemical conversion film after forming the unevenness from the viewpoint of increasing the bonding strength.

Among them, as a chemical chemical treatment method for forming the uneven surface, if necessary, a zincate film is formed on the surface of the metal member (X), and then an etching agent containing peroxodisulfate ion and chloride ion is used. Examples thereof include a method of contacting the surface of the metal member (X).

The etching agent may be an aqueous solution containing at least peroxodisulfate ion and chloride ion. Elements such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc derived from the base material may be present in the etching agent. Further, an element such as zinc may be mixed by dissolving the film formed in the zincate step described later.

The etching agent preferably contains peroxodisulfate ion at a ratio of 0.02 mol / L or more and 0.90 mol / L or less, particularly 0.10 mol / L or more or 0.50 mol / L or less, and 0.15 mol among them. It is more preferably contained at a ratio of / L or more or 0.40 mol / L or less.
The etching agent preferably contains chloride ion (Cl ⁻ ) at a ratio of 0.40 mol / L or more and 2.50 mol / L or less, particularly 0.80 mol / L or more or 2.00 mol / L or less, among which. It is more preferably contained at a ratio of 1.20 mol / L or more or 1.70 mol / L or less.
As the chloride ion source, for example, one or more suitable chlorine compounds such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, and ammonium chloride can be selected.

The etching agent may be substantially free of phosphoric acid. Substantially not included means that it is below the detection limit.

The pH of the etching agent is preferably in the range of 6.0 or less, and more preferably in the range of 2.0 to 4.0. The pH of the etching agent is not limited to commercially available pH measuring instruments and electrodes, and can be measured using these. Also, use a pH measuring device and a device whose electrode has a temperature compensation function, adjust the internal solution of the pH electrode and a commercially available pH standard solution to the same temperature as the etching agent, etc., and calibrate the pH measuring device. For example, the pH at the temperature at which the etching agent or the like is used can be measured.

At the time of etching, the etching agent may have a liquid temperature of 10 to 70 ° C., and the metal member (X) may be immersed therein.

When forming a zincate film on the surface of the metal member (X), for example, an aqueous solution of sodium hydroxide in which zinc oxide is dissolved is used, the bath temperature is maintained at 40.0 ° C. or lower, and the metal member (X) is set to 1. By immersing for about 0.0 seconds to 5.0 minutes, the natural oxide film can be removed and a zinc oxide film can be formed at the same time. Further, the operation of dissolving the formed film with the etching agent or nitric acid and forming the film again may be performed once or more. In addition to the essential components, the treatment liquid used in these zincating steps may contain metals such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper and zinc derived from the base material. ..
The pH of the treatment liquid used for forming the zincate film is not limited as long as it is within a known range. For example, in the case of a treatment liquid showing a pH on the alkaline side, it may be 10.0 or more, 13.0. It may be the above. It is preferably in the range of 11.0 to 13.0. To adjust the pH of the zincate solution, sodium hydroxide or potassium hydroxide can be used to raise the pH.

Before the treatment with the etching agent or the formation of the zincate film, the surface of the metal member (X) may be cleaned in advance. For example, it may be degreased using a solvent-based, water-based or emulsion-based degreasing agent. Moreover, you may perform alkaline washing treatment.

<Surface layer>
The uneven surface of the metal member (X) is an oxide film, a chemical conversion film (phosphate film, chromate film, silicate film, lithium chemical conversion film, calcium chemical conversion film, zirconium oxide film, etc.), alumite film, and others. It may be coated with a film, a plating layer, a silane coupling agent treatment layer, a primer layer, a resin layer, or other layers may be formed, or fine particles or the like may be immobilized.
Next, the outermost surface layer of the uneven surface of the metal member (X) will be described in detail.

(Oxide film)
The uneven surface of the metal member (X) may not be oxidized or may be oxidized.

(Chemical conversion coating)
The uneven surface of the metal member (X) may be subjected to a chemical conversion treatment and may be provided with a chemical conversion treatment film.
By performing such a treatment, the adhesiveness (adhesiveness or adhesive strength) between the metal member (X) and the resin member (Y) can be further improved.
Examples of the chemical conversion treatment method include chemical conversion treatment with phosphoric acid chromate and the like, zirconium phosphate treatment, boehmite treatment, zincate treatment, anodization treatment and the like.
Examples of the anodization treatment include a treated thin film using phosphoric acid, phosphoric acid-sulfuric acid, phosphoric acid-oxalic acid, and phosphoric acid-chromic acid as the electrolytic solution. Of these, treatment with alumite phosphate is preferable.

The thickness of the chemical conversion coating is not particularly limited. For example, it is preferably 1 nm to 300 nm, and more preferably 5 nm or more from the viewpoint of maintaining good processability.
When a chemical conversion treatment film is formed by anodization treatment, the thickness thereof is preferably in the range of 0.05 μm to 2 μm, particularly 0.1 μm or more or 2 μm or less, from the viewpoint of more effectively improving the adhesion. Is more preferable.
The thickness of the chemical conversion treatment layer by the anodic oxidation treatment can be adjusted to the thickness in the above range by adjusting the treatment conditions, particularly the energization condition and the energization time.

(Plating layer)
The uneven surface of the metal member (X) may be subjected to a treatment of forming a plating layer by a plating treatment such as single-layer plating, multi-layer plating or alloy plating. Immersion chromic acid treatment and chromic phosphate treatment may be performed before these plating treatments.
The plating treatment method may be either electroplating or electroless plating. For example, when the metal substrate is iron, zinc, tin, nickel, and copper plating are preferable, and zinc plating is more preferable.

(Silane coupling agent treated layer)
When the uneven surface of the metal member (X), particularly the metal member (X) is made of aluminum, iron, or the like, it is preferable to perform treatment with a silane coupling agent to form a silane coupling agent-treated layer.
The silane coupling agent is not particularly limited. Examples thereof include compounds having a methoxy group, an ethoxy group, a silanol group and the like, and examples of the silane coupling agent include vinyltrimethoxysilane, chloropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-methacry. Loxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) ) Poxytrimethoxysilane hydrochloride, ureidoaminopropylethoxysilane and the like can be preferably mentioned. In particular, the aluminum substrate or the iron substrate and the silane coupling agent form a bond of Al—O—Si or Fe—O—Si to form a strong bond, and the polyester (a) of the polyester resin composition (A) also has a strong bond. And the organic functional group of the silane coupling agent react to form a strong bond, and a stronger bond can be achieved.

(Primer layer)
A primer layer may be provided on the uneven surface of the metal member (X).
Examples of the material used for the primer layer include an acrylic material, an epoxy material, a urethane material, a polyamide material and the like.
Examples of commercially available materials used for the primer layer include Aronmelt PPET manufactured by Toagosei Co., Ltd.

<< Resin member (Y) >>
The resin member (Y) is a member made of a polyester resin composition (A) containing polyester (a) as a main component resin.
The "main component resin" means a resin or a group of resins having the largest content mass ratio among the resins constituting the polyester resin composition (A), and the resin constituting the polyester resin composition (A). Among them, the case where the polyester (a) accounts for 50% by mass or more, particularly 75% by mass or more, and 90% by mass or more (including 100% by mass) among them is included. However, the polyester (a) may be two or more kinds of polyesters (resin group).

The resin member (Y) may have a structure made of the polyester resin composition (A) and only the polyester resin composition (A), or the back surface of the member or layer made of the polyester resin composition (A). It may have a structure made of a plurality of materials in which another resin layer or the like is bonded to the side.

The size, shape, thickness, etc. of the resin member (Y) are not particularly limited, and may be, for example, plate-shaped (disk, polygon, etc.), columnar, box-shaped, bowl-shaped, tray-shaped, or the like. You may. One of the features of this resin-metal composite is that the resin member (Y) can be formed into an arbitrary shape.
The resin member (Y) does not have to have a uniform thickness in all parts, and may be provided with a portion having an arbitrary shape such as a reinforcing rib, if necessary.

<Polyester resin composition (A)>
The polyester resin composition (A) contains, as the polyester (a), polybutylene terephthalate (also referred to as "homo PBT"), a copolymer of polybutylene terephthalate (also referred to as "copolymerized PBT"), or a mixed resin thereof. It is preferable that the resin composition contains the epoxy group-containing compound (b) and the low molecular weight compound (c), and further contains the reinforcing filler (d), if necessary. Further, an impact modifier may be contained.
The resin of the resin member (Y) and the metal member (X) is formed by reacting the terminal functional group (carboxyl group) of the homo PBT and / or the copolymerized PBT with the epoxy group of the epoxy group-containing compound (b). It can be inferred that the airtightness of the metal composite after the thermal shock test is enhanced.

In the polyester resin composition (A), the ratio of the homo PBT and the copolymerized PBT to the polymer components (excluding the elastomer and the flame retardant) constituting the polyester resin composition (A) is preferably 80 to 100% by mass.
When the homo PBT and the copolymerized PBT occupy most of them, that is, when the content ratio thereof is 80% by mass or more, the basic physical properties are improved, which is preferable.
From this point of view, the ratio of the homo PBT and the copolymerized PBT is preferably 80% by mass or more, more preferably 85% by mass or more, particularly 90% by mass or more, and more preferably 95% by mass or more.

The intrinsic viscosity of the polyester resin composition (A) is preferably 0.30 to 2.00 dl / g from the viewpoint of moldability, particularly 0.40 dl / g or more, and among them 0.60 dl / g or more. While it is more preferable, it is more preferably 1.80 dl / g or less, and more preferably 1.50 dl / g or less.
In the present invention, the intrinsic viscosity is a value measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol.
The intrinsic viscosity of the polyester resin composition (A) can be adjusted by changing the molecular weight of the polyester (a). However, the present invention is not limited to this.

<Polyester (a)>
The polyester (a) as the main component resin is preferably polybutylene terephthalate (also referred to as "homo PBT"), a copolymer of polybutylene terephthalate (also referred to as "copolymer PBT"), or a mixed resin thereof. ..

The intrinsic viscosity of the polyester (a) is preferably 0.30 to 2.00 dl / g, particularly 0.40 dl / g or more, and among them 0.60 dl / g or more, from the viewpoint of moldability. On the other hand, it is more preferably 1.80 dl / g or less, and more preferably 1.50 dl / g or less.
The intrinsic viscosity of the polyester (a) can be adjusted by changing the molecular weight of the polyester (a). However, the present invention is not limited to this.

(Homo PBT)
Homo PBT is a polymer having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded, and is a polymer composed of a terephthalic acid unit and a 1,4-butanediol unit.

The amount of the terminal carboxyl group of the homo PBT is preferably 60 eq / ton or less, more preferably 50 eq / ton or less, and more preferably 30 eq / ton or less.
The amount of terminal carboxyl groups of the polybutylene terephthalate homopolymer can be determined by dissolving 0.5 g of the resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide. it can.
As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method for adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, and the depressurization method, and a method for reacting the terminal sequestering agent can be used. Just do it.

The number average molecular weight of the homo PBT is preferably 7,000 or more, more preferably 8,000 or more, and further preferably 9000 or more. On the other hand, it is preferably 20000 or less, more preferably 19000 or less, and further preferably 17000 or less.

The intrinsic viscosity of homo PBT is preferably 0.30 to 2.00 dl / g.
If the intrinsic viscosity is 0.30 dl / g or more, the mechanical strength of the welded body does not become too low, and if it is 2.00 dl / g or less, the fluidity decreases and the moldability deteriorates. It is possible to prevent the joint strength from decreasing.
From this point of view, the intrinsic viscosity of homo PBT is preferably 0.30 to 2.00 dl / g, more preferably 0.40 dl / g or more, and particularly preferably 0.60 dl / g or more. It is more preferably 1.80 dl / g or less, and more preferably 1.50 dl / g or less.

(Copolymerization PBT)
The copolymerized PBT is a polybutylene terephthalate copolymer containing other copolymerizing components other than the terephthalic acid unit and the 1,4-butanediol unit.

Specific examples of other dicarboxylic acid units other than terephthalic acid include, for example, isophthalic acid, orthophthalic 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 (4,5'-carboxyphenyl) methane, anthracendicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid Aromatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 4,4'-dicyclohexyldicarboxylic acid, and aliphatics such as adipic acid, sebacic acid, azelaic acid, dimer acid. Examples thereof include dicarboxylic acids.

Examples of the diol unit other than 1,4-butanediol include aliphatic or alicyclic diols having 2 to 20 carbon atoms, bisphenol derivatives and the like. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, and 4,4'-dicyclohexylhydroxymethane. , 4,4'-Dicyclohexylhydroxypropane, ethylene oxide-added diol of bisphenol A, and the like.

From the viewpoint of mechanical properties and heat resistance, the copolymerized PBT preferably has a ratio of terephthalic acid in the dicarboxylic acid unit of 70 mol% or more, and more preferably 90 mol% or more.
The ratio of 1,4-butanediol in the diol unit is preferably 70 mol% or more, and more preferably 90 mol% or more.

Since the copolymerized PBT introduces a branched structure in addition to the bifunctional monomer as described above, for example, trifunctional ester formation such as tricarbaryl acid, trimeric acid, trimellitic acid or tetrafunctional ester formation such as pyromellitic acid is formed. A small amount of a polyfunctional monomer such as an acid having a function or an alcohol having a trifunctional or tetrafunctional ester-forming ability such as glycerin, trimethylolpropane, or pentaerythritol, or a monofunctional compound such as a fatty acid for adjusting the molecular weight is used in combination. You can also do it.

Copolymerized PBT can be modified by the copolymerization component.
For example, as the copolymerization component, a polybutylene terephthalate resin obtained by copolymerizing polyalkylene glycols (particularly polytetramethylene glycol (PTMG)), a dimer acid copolymer polybutylene terephthalate resin, and particularly an isophthalic acid copolymer polybutylene terephthalate. Resin can be mentioned.

In the copolymerized PBT copolymerized with polytetramethylene glycol (PTMG), the proportion of the tetramethylene glycol component in the copolymer is preferably 3 to 40% by mass, and more than 5% by mass or 30% by mass or less. Among them, it is more preferably 10% by mass or more or 25% by mass or less. It is preferable to use such a copolymerization ratio because the balance between the bonding strength and the heat resistance tends to be excellent.
On the other hand, in the case of a copolymerized PBT obtained by copolymerizing dimer acid, the ratio of the dimer acid component to the total carboxylic acid component is preferably 0.5 to 30 mol% as the carboxylic acid group, and more than 1 mol% among them. Alternatively, it is more preferably 20 mol% or less, particularly preferably 3 mol% or more or 15 mol% or less. It is preferable to use such a copolymerization ratio because the balance between bonding strength, long-term heat resistance and toughness tends to be excellent.
Further, in the case of a copolymerized PBT obtained by copolymerizing isophthalic acid, the ratio of the isophthalic acid component to the total carboxylic acid component is preferably 1 to 30 mol% as the carboxylic acid group, and more than 2 mol% or more. It is more preferably 20 mol% or less, more preferably 3 mol% or more or 15 mol% or less. Such a copolymerization ratio tends to have an excellent balance between bonding strength, heat resistance, injection moldability and toughness, which is preferable.
As the copolymerized PBT, a copolymerized PBT in which polytetramethylene glycol is copolymerized or a copolymerized PBT in which isophthalic acid is copolymerized is particularly preferable from the viewpoint of moldability.

The number average molecular weight of the copolymerized PBT is preferably 5000 or more, more preferably 6000 or more, and further preferably 8000 or more. On the other hand, it is preferably 20000 or less, more preferably 19000 or less, and further preferably 17000 or less.

The intrinsic viscosity of the copolymerized PBT is preferably 0.30 to 2.00 dl / g.
If the intrinsic viscosity is 0.30 dl / g or more, the mechanical strength of the welded body does not become too low, and if it is 2.00 dl / g or less, the fluidity decreases and the moldability deteriorates. It is possible to prevent the joint strength from decreasing.
From this point of view, the intrinsic viscosity of the copolymerized PBT is preferably 0.30 to 2.00 dl / g, more preferably 0.40 dl / g or more, and more preferably 0.60 dl / g or more. Above all, it is more preferably 1.80 dl / g or less, and more preferably 1.50 dl / g or less.

The amount of terminal carboxyl groups in the copolymerized PBT is preferably 60 eq / ton or less.
When the amount of the terminal carboxyl group is 60 eq / ton or less, it is possible to suppress the generation of gas during melt molding of the resin composition.
From this point of view, the amount of terminal carboxyl groups of the copolymerized PBT is preferably 60 eq / ton or less, more preferably 50 eq / ton or less, and more preferably 30 eq / ton or less.
On the other hand, the lower limit of the amount of terminal carboxyl groups is not particularly defined. Usually, it is 5 eq / ton or more.
The amount of terminal carboxyl groups in the copolymerized PBT can be determined by dissolving 0.5 g of a resin in 25 mL of benzyl alcohol and titrating with a 0.01 mol / l benzyl alcohol solution of sodium hydroxide.
As a method for adjusting the amount of the terminal carboxyl group, a conventionally known arbitrary method such as a method for adjusting the polymerization conditions such as the raw material charging ratio at the time of polymerization, the polymerization temperature, and the depressurization method, and a method for reacting the terminal sequestering agent can be used. Just do it.

(Homo PBT + Copolymerized PBT)
The polyester (a) may be a mixed resin of homo PBT and copolymer PBT.
At this time, the mixing ratio of the copolymer PBT to the mixed resin is preferably 0.1 mol% or more and 30 mol% or less, particularly 1 mol% or more or 25 mol% or less, based on all the monomers. Among them, it is more preferably 5 mol% or more or 20 mol% or less.
As for the mass ratio, the mixing ratio of the homo PBT / copolymer is preferably 99/1 to 1/99 (mass ratio), particularly 95/5 to 5/95 (mass ratio), and 90 / of which. It is more preferably in the range of 10 to 10/90 (mass ratio).

<Epoxy group-containing compound (b)>
The epoxy group-containing compound (b) does not necessarily contribute to the initial bonding strength, but improves the durability required by the bonding strength after the durability test. When the epoxy group-containing compound (b) is contained, the durability is greatly improved. This durability does not decrease even if the low molecular weight compound (c) is contained.

Examples of the epoxy group-containing compound (b) include bisphenol A type epoxy compound, bisphenol F type epoxy compound, resorcin type epoxy compound, novolac type epoxy compound, alicyclic compound type diepoxide compound, glycidyl ethers, epoxidized polybutadiene, and more specifically. Specifically, alicyclic compound type epoxy compounds such as bisphenol A type epoxy compound, bisphenol F type epoxy compound, resorcin type epoxy compound, novolac type epoxy compound, vinylcyclohexendioxide, and dicyclopentadiene oxide can be preferably mentioned.

Among them, 2,2-bis (4-hydroxyphenyl) -propane type epoxy compound (also referred to as "bisphenol A type epoxy compound") or novolak type epoxy compound in terms of compatibility with homo PBT and / and copolymerized PBT. It is preferably present, and a bisphenol A type epoxy compound is particularly preferable.

Among them, the epoxy equivalents of the bisphenol A type epoxy compound and the novolak type epoxy compound (mass (g) per mol of epoxy group contained in the epoxy compound) are 50 to 1000 g / eq. It is preferably 70 g / eq. As mentioned above, among them, 100 g / eq. The above is more preferable, while 900 g / eq. Hereinafter, among them, 800 g / eq. The following is more preferable.

The number average molecular weight of the bisphenol A type epoxy compound and the novolak type epoxy compound is preferably 100 to 2000, particularly preferably 150 or more, and more preferably 200 or more in terms of fluidity. Above all, it is more preferably 1800 or less, and more preferably 1600 or less.

From the viewpoint of improving bonding strength and fluidity, the epoxy group-containing compound (b) is preferably contained in a proportion of 0.001 to 35 parts by mass with respect to 100 parts by mass of the polyester (a), particularly 0.01 parts by mass. As mentioned above, it is more preferable to include 0.1 parts by mass or more, particularly 0.3 parts by mass or more, while 25 parts by mass or less, 15 parts by mass or less, 10 parts by mass or less, and the like. Above all, it is more preferable to contain it in a ratio of 6 parts by mass or less.

Further, from the viewpoint of improving the bonding strength, the epoxy group-containing compound (b) has 0.1 to 10 equivalents of the epoxy group with respect to the amount of terminal carboxyl groups in the homo PBT and / or the copolymerized PBT which is the polyester (a). It is preferable to contain the epoxy group in a proportion of 0.15 equivalent or more, and it is more preferable to contain the epoxy group in a proportion of 0.2 equivalent or more, while it is contained in an amount of 8.0 equivalent or less, among which. It is more preferable to contain the epoxy group in a proportion of 7.0 equivalents or less, particularly 6.0 equivalents or less.

<Low molecular weight compound (c)>
If the polyester resin composition (A) further contains the low molecular weight compound (c) having a number average molecular weight of less than 6000, the bonding strength of the present resin metal composite can be further increased.

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 4200 or less.

Examples of the low molecular weight compound (c) 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 silicone compounds. be able to.

Examples of the polyolefin compound include compounds selected from paraffin wax and polyethylene wax. It may be a modified polyolefin compound in which a hydroxyl group, a carboxyl group, a non-hydroxyl group, an epoxy group or the like is introduced into the side chain.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, the preferred aliphatic carboxylic acid is a monovalent or divalent carboxylic acid having 6 to 36 carbon atoms, and an aliphatic saturated monovalent carboxylic acid having 6 to 36 carbon atoms is more preferable.
Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, and adipine. Acids, azelaic acid and the like can be mentioned.

As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, for example, the same one as the aliphatic carboxylic acid can be used.
On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic term also contains an alicyclic compound.
Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol and the like. Can be mentioned.

The ester of the aliphatic carboxylic acid and the alcohol may contain the aliphatic carboxylic acid and / or the alcohol as impurities. Further, the above ester may be a pure substance or a mixture of a plurality of compounds. Further, as the aliphatic carboxylic acid and the alcohol which are combined to form one ester, one kind may be used, or two or more kinds may be used in any combination and ratio.

Specific examples of esters of aliphatic carboxylic acid and alcohol include montanic acid ester wax, beeswax (a mixture containing myricyl palmitate as a main component), stearic acid stearate, behenyl behenate, stearyl behenate, and glycerin mono. Palmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc. be able to.

Examples of the aliphatic hydrocarbon compound include polyolefin waxes such as liquid paraffin, paraffin wax, microcrystalline wax and polyethylene wax, fisher-tropus wax, α-olefin oligomers having 3 to 12 carbon atoms and the like.
Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Moreover, these hydrocarbons may be partially oxidized. The aliphatic hydrocarbon compound may be a single substance or a mixture of various constituents and molecular weights, and can be used as long as the main component is within the above range.

Examples of the silicone-based compound include silicone oil in which an organic group is introduced into the side chain of polysiloxane, silicone oil in which an organic group is introduced into both ends and / or one end of polysiloxane, and the like. .. At this time, examples of the organic group to be introduced include an epoxy group, an amino group, a carboxyl group, a carbinol group, a methacryl group, a mercapto group, a phenol group and the like, and an epoxy group is preferable.
As the modified silicone oil, a silicone oil in which an epoxy group is introduced into the side chain of polysiloxane is particularly preferable.

As the low molecular weight compound, polyolefin wax is particularly preferable from the viewpoint of low gas and suppression of generated gas.
As the polyolefin wax, any conventionally known polyolefin wax can be used, for example, preferably a type of olefin having 2 to 30 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 10 carbon atoms, or any proportion of the polyolefin wax. Examples thereof include (co) polymers containing more than one species (meaning polymerization or copolymerization; the same shall apply hereinafter).

Examples of the olefin having 2 to 30 carbon atoms include ethylene, propylene, α-olefin having 4 to 30 carbon atoms (preferably 4 to 12, more preferably 4 to 10), and 4 to 30 carbon atoms (preferably 4 to 10). 18, and more preferably 4 to 8) diene and the like can be mentioned.
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene.
Examples of the diene include butadiene, isoprene, cyclopentadiene, 11-dodecadiene and the like.

As the polyolefin wax, polyethylene wax is preferable from the viewpoints of low gas, suppression of generated gas, improvement of bonding strength and heat resistance.
The method for producing polyethylene wax is arbitrary, and for example, it can be produced by polymerization of ethylene or thermal decomposition of polyethylene.

As the low molecular weight compound, a compound having an acid value of 0.01 to 40 mgKOH / g is preferable because the effect of improving the bonding strength is remarkable and the volatile content is small. The acid value is more preferably 0.01 to 35 mgKOH / g, still more preferably 0.5 to 32 mgKOH / g.
When the acid value is in the range of 0.01 to 40 mgKOH / g, those having an acid value of less than 0.01 mgKOH / g and those having an acid value of more than 40 mgKOH / g may be used in combination, and a plurality of types of low molecular weight compounds as a whole may be used. The acid value of is 0.01 to 40 mgKOH / g.

Examples of the low molecular weight compound having an acid value of 0.01 to 40 mgKOH / g include the above-mentioned ester of an aliphatic carboxylic acid and an alcohol having an acid value of 0.01 to 40 mgKOH / g, and the above-mentioned aliphatic compound. A carboxyl group (representing a carboxylic acid (anhydrous) group, that is, a carboxylic acid group and / or a carboxylic acid anhydride group; the same applies hereinafter), a haloformyl group, an ester group, and a metal carboxylate in a hydrocarbon compound, preferably a polyolefin wax. A modified polyolefin wax having a functional group compatible with the polyester resin, such as a base, a hydroxyl group, an alcoholic group, an epoxy group, an amino group, and an amide group, is preferable.

Examples of the carboxyl group used for the modification of the polyolefin wax include low molecular weight compounds containing carboxylic acid groups such as maleic acid, maleic anhydride, acrylic acid, and methacrylic acid, and low molecular weight compounds containing sulfo groups such as sulfonic acid. Examples thereof include low molecular weight compounds containing a phospho group such as phosphonic acid. Among these, low molecular weight compounds containing a carboxylic acid group are preferable, and maleic acid, maleic anhydride, acrylic acid, methacrylic acid and the like are particularly preferable. These carboxylic acids may be used alone or in combination of two or more at any ratio.
The amount of acid added to the modified polyolefin wax is usually 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the modified polyolefin wax.

Specific examples of the haloformyl group include a chloroformyl group and a bromoformyl group. The means for imparting these functional groups to the polyolefin wax may be any conventionally known method, and specifically, for example, copolymerization with a compound having a functional group, post-processing such as oxidation, or the like. Method may be used.
The type of the functional group is preferably a carboxyl group because it has an appropriate affinity with the polyester resin.

The concentration of the carboxyl group in the modified polyolefin wax may be appropriately selected and determined, but if it is too low, the affinity with the polyester resin is small, the effect of suppressing volatile matter is small, and the bonding strength may be lowered. is there. On the contrary, if the concentration is too high, for example, the polymer main chain constituting the polyolefin wax is excessively cleaved at the time of modification, and the molecular weight of the modified polyolefin wax is excessively lowered, so that volatile matter is generated more and the polyester is used. Fogging may occur on the surface of the resin molded product.
As the modified polyolefin wax, polyethylene oxide wax is preferable.

Among the above, the low molecular weight compound (c) preferably has a melting point of 40 to 140 ° C., more preferably 45 ° C. or higher, more preferably 50 ° C. or higher, while 135 ° C. or lower, particularly 130 ° C. More preferably, it is below ° C.

In addition, 1 type may be contained in the low molecular weight compound, and 2 or more types may be contained in arbitrary combinations and ratios.

The low molecular weight compound (c) is preferably contained in a proportion of 0 to 1.5 parts by mass, more preferably 0.001 to 1.5 parts by mass, particularly preferably 0.001 to 1.5 parts by mass, based on 100 parts by mass of the polyester resin composition (A). It is more preferably 0.01 parts by mass or more, particularly 0.1 parts by mass or more, and more preferably 0.2 parts by mass or more, while it is 1.4 parts by mass or less, and 1.2 parts by mass or less among them. Is even more preferable.

(Polyethylene oxide wax)
Among the low molecular weight compounds (c), polyethylene oxide wax is most preferable from the viewpoint of suppressing gas generation when the polyester resin composition (A) is heated.

Polyethylene oxide wax is a compound obtained by oxidizing polyethylene and introducing a polar group.
Examples of the polar group include a carboxyl group, an amino group, and a hydroxyl group.

From the viewpoint of suppressing gas generation when the polyester resin composition (A) is heated, the number average molecular weight of the polyethylene oxide wax is 1500 or more, 2000 or more among them, 2500 or more among them, and 3000 or more among them. Among them, it is more preferably 3500 or more. On the other hand, from the viewpoint of improving the bonding strength, it is more preferably 5000 or less, particularly 4500 or less, and among them, 4200 or less.

The acid value of the polyethylene oxide wax is preferably 0.01 to 40 mgKOH / g, particularly 0.1 mgKOH / g, from the viewpoint of suppressing gas generation when the polyester resin composition (A) is heated. It is more preferably 30 mgKOH / g or less, more preferably 0.5 mgKOH / g or more or 20 mgKOH / g or less, and more preferably 0.7 mgKOH / g or more or 10 mgKOH / g or less.

The polyethylene oxide wax as the low molecular weight compound (c) is 0 with respect to 100 parts by mass of the polyester resin composition (A) from the viewpoint of suppressing gas generation when the polyester resin composition (A) is heated. It is preferably contained in a proportion of .001 to 1.5 parts by mass, particularly preferably 0.01 to 1.5 parts by mass, particularly 0.1 parts by mass or more or 1.0 parts by mass or less, and 0.2 parts by mass among them. It is more preferably more than parts or 0.7 parts by mass or less.

<Other resin components>
The polyester resin composition (A) may contain other resins in addition to the above. For example, one or a combination of two or more selected from the group consisting of a carbodiimide compound, a compound having an oxazoline group (ring), a compound having an oxazoline group (ring), a compound having a carboxylic acid, and a compound having an amide group. Can be mentioned.
Further, for example, a polyamide resin, a polyphenylene oxide resin, a polyphenylene sulfide resin, a polysulfone resin, a polyether sulphon resin, a polyetherimide resin, a polyetherketone resin, a fluorine resin and the like can be included.
However, the proportion of the other resin in the polyester resin composition (A) is preferably 20% by mass or less, and more preferably 10% by mass or less.

(Carbodiimide compound)
The carbodiimide compound is a compound containing a carbodiimide group (-N = C = N-) in the molecule.
As the carbodiimide compound, any of an aliphatic aliphatic carbodiimide compound having an aliphatic main chain, an alicyclic carbodiimide compound having an alicyclic main chain, and an aromatic carbodiimide compound having an aromatic main chain can be used. Above all, the use of an alicyclic carbodiimide compound is preferable in that the hydrolysis resistance of the present resin-metal complex can be improved.
The type of the carbodiimide compound may be a monomer type or a polymer type, but in the present invention, the polymer type is preferable.
In the case of the polymer type carbodiimide, the preferable number average molecular weight is preferably 10,000 or less, more preferably 4000 or less, and the lower limit is preferably 100 or more, more preferably 500 or more.

The content of the carbodiimide group contained in the carbodiimide compound is the carbodiimide equivalent (weight [g] of the carbodiimide compound for giving 1 mol of the carbodiimide group), and is preferably 100 to 1000 (g / 1 mol), particularly 200. It is more preferably (g / 1 mol) or more or 800 (g / 1 mol) or less, and more preferably 235 (g / 1 mol) or more or 650 (g / 1 mol) or less.

Examples of the aliphatic carbodiimide compound include diisopropylcarbodiimide and dioctyldecylcarbodiimide.
Examples of the alicyclic carbodiimide compound include dicyclohexylcarbodiimide, poly (4,4′-dicyclohexylmethanecarbodiimide), and the like, and poly (4,4′-dicyclohexylmethanecarbodiimide) is particularly preferable.
Examples of commercially available products include "Carbodilite" (trade name; manufactured by Nisshinbo Chemical Co., Ltd.).

Examples of the aromatic carbodiimide compound include diphenylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, N-triyl-N'-phenylcarbodiimide, di-p-nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, and di-p. -Hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-p-methoxyphenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide , P-Phenylene-bis-di-o-triylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene-bis-di-p-chlorophenylcarbodiimide, ethylene-bis-diphenylcarbodiimide and the like Compounds and poly (4,5'-diphenylmethanecarbodiimide), poly (3,5'-dimethyl-4,4'-biphenylmethanecarbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide), poly ( 3,5'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylene carbodiimide), poly (1,3-diisopropylphenylene carbodiimide), poly (1-methyl-3,5-diisopropylphenylene carbodiimide), poly Examples thereof include polycarbodiimide compounds such as (1,3,5-triethylphenylene carbodiimide) and poly (triisopropylphenylene carbodiimide), and these can be used in combination of two or more. Of these, di-2,6-dimethylphenylcarbodiimide, poly (4,4'-diphenylmethanecarbodiimide), poly (phenylene carbodiimide) and poly (triisopropylphenylene carbodiimide) are particularly preferably used.
Examples of commercially available products include "Stavaxol P" (trade name; manufactured by BASF) and the like.

(Compound having an oxazoline group (ring))
Examples of the compound having an oxazoline group (ring) include oxazoline, alkyloxazoline (C1-4 alkyloxazoline such as 2-methyloxazoline and 2-ethyloxazoline), and bisoxazoline compound.

Examples of the bisoxazoline compound include 2,2'-bis (2-oxazoline), 2,2'-bis (alkyl-2-oxazoline) [2,2'-bis (4-methyl-2-oxazoline), and the like. 2,2'-bis (C1-6 alkyl-2-oxazoline) such as 2,2'-bis (4-ethyl-2-oxazoline), 2,2'-bis (4,4-dimethyl-2-oxazoline), etc. ) 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-benzyl-2-oxazoline), etc.] , 2,2'-alkylene bis (2-oxazoline) [2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), etc. 2,2'-C1-10 Alkylene bis (2-oxazoline), etc.], 2,2'-alkylene bis (alkyl-2-oxazoline) [2,2'-ethylene bis (4-methyl-2-oxazoline), 2,2'-tetramethylene bis 2,2'-C1-10 alkylenebis (C1-6 alkyl-2-oxazoline), etc. such as (4,4-dimethyl-2-oxazoline)], 2,2'-allylenebis (2-oxazoline) [2 , 2'-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,4-phenylene) -bis (2-oxazoline), 2,2'-(1,2-foxazoline) )-Bis (2-oxazoline), 2,2'-diphenylenebis (2-oxazoline), etc.], 2,2'-allylenbis (alkyl-2-oxazoline) [2,2'-(1,3-xazoline) 2,2'-Phenylene-bis (4-methyl-2-oxazoline), 2,2'-(1,4-phenylene) -bis (4,4-dimethyl-2-oxazoline), etc. C1-6 alkyl-2-oxazoline), etc.], 2,2'-allyloxyalkambis (2-oxazoline) [2,2'-9,9'-diphenoxyetambis (2-oxazoline), etc.], 2 , 2'-Cycloalkylene bis (2-oxazoline) [2,2'-cyclohexazoline (2-oxazoline), etc.], N, N'-alkylene bis (2-carbamoyl-2-oxazoline) [N, N' -Ethethylene bis (2) -Carbamoyl-2-oxazoline), N, N'-tetramethylenebis (2-carbamoyl-2-oxazoline), etc. N, N'-C1-10 alkylenebis (2-carbamoyl-2-oxazoline), etc.], N , N'-alkylene bis (2-carbamoyl-alkyl-2-oxazoline) [N, N'-ethylenebis (2-carbamoyl-4-methyl-2-oxazoline), N, N'-tetramethylene bis (2- N, N'-C1-10 alkylenebis (2-carbamoyl-C1-6 alkyl-2-oxazoline), etc.], N, N'-allylenebis (2), such as carbamoyl-4,4-dimethyl-2-oxazoline) -Carbamoyl-2-oxazoline) [N, N'-phenylenebis (2-carbamoyl-oxazoline), etc.] and the like can be mentioned.

The compound having an oxazoline group also includes a vinyl polymer containing an oxazoline group [manufactured by Nippon Shokubai Co., Ltd., Epocross RPS series, RAS series, RMS series, etc.]. Of these oxazoline compounds, a bisoxazoline compound is preferable.

(Compound having an oxazine group (ring))
As the compound having an oxazine group (ring), oxazine, a bisoxazine compound, or the like can be used.

Examples of the bisoxazine compound include 2,2'-bis (5,6-dihydro-4H-1,3-oxazine) and 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) and other 2,2'-bis (C1-6 alkyl-5) , 6-dihydro-4H-1,3-oxazine), etc.], 2,2'-alkylene bis (5,6-dihydro-4H-1,3-oxazine) [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) 2,2'-C1-10 alkylenebis (5,6-dihydro-4H-1,3-oxazine), etc.], 2,2'-allylenebis (5,6-dihydro), etc. -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-phenylene) -bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-diphenylenebis (5,6-dihydro-4H-1,3-oxazine), etc.], N, N'-alkylene bis (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) and other N, N'-C1-10 alkylenebis (2-carbamoyl-5,6- Dihydro-4H-1,3-oxazine), etc.], N, N'-alkylene bis (2-carbamoyl-alkyl-5,6-dihydro-4H-1,3-oxazine) [N, N'-ethylenebis (2-carbamoyl-alkyl-5,6-dihydro-4H-1,3-oxazine) 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) and the like, N, N'-C1-10 alkylenebis (2-carbamoyl-C1-6 alkyl-5,6-dihydro-4H-1,3-oxazine) and the like. ], N, N'-allylenbis (2-carbamoyl-5,6-dihydro-4H-1,3-oxazine) [N, N'-phenylenebis (2-carbamoyl-oxazine), etc.] it can. Of these oxazine compounds, bisoxazine compounds are preferred.

(Compound with carboxylic acid)
Examples of the compound having a carboxylic acid 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 and terephthalic acid. Lactic acid, malic acid, tartaric acid, diphenolic acid benzenesulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, nonylbenzenesulfonic acid, nitrobenzenesulfonic acid, cyanobenzenesulfonic acid, hydroxybenzenesulfonic acid, methylsulfonic acid, trifluoromethanesulfonic acid , Trifluoroacetic acid, nitrobenzenecarboxylic acid, cyanobenzenecarboxylic acid, hydroxybenzenecarboxylic acid, hydroxyacetic acid and salts thereof.

(Compound having an amide group)
Examples of the compound having an amide group include (meth) acrylamide, N-methylmethacrylamide, methylolated acrylamide, methylolated methacrylamide, ureidovinyl ether, β-ureidoisobutylvinyl ether, ureidoethyl acrylate and the like.

<Reinforced filler (d)>
The polyester resin composition (A) preferably contains a reinforcing filler (d) such as glass fiber. By containing the reinforced filler (d), the strength, rigidity, and dimensional stability of the polyester resin composition (A) or the present resin metal composite can be improved.

Hereinafter, the case of glass fiber, which is particularly preferable as the reinforcing filler (d), will be mainly described.
The polyester resin composition (A) preferably contains glass fibers in a ratio of 10 to 100 parts by mass with respect to 100 parts by mass of the polyester resin composition (A). If the content is too small, the reinforcing effect may not be sufficient, and if it is too large, the appearance and impact resistance may be poor, and the fluidity may not be sufficient.
From this point of view, the particularly preferable content of the glass fiber is 15 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 25 parts by mass or more with respect to 100 parts by mass of the polyester resin composition (A). Further, it is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, and particularly 50 parts by mass or less.

The type of glass fiber is not particularly limited, and examples thereof include glass fibers such as E glass, C glass, A glass, and S glass. Among these, the fibers of the non-alkali glass (E glass) are preferable in that they do not adversely affect the thermal stability of the polyester resin composition (A).

Two or more types of glass fibers may be used in combination depending on the required properties.

The average fiber diameter of the glass fiber is not particularly limited. It is preferable to select in the range of 1 to 100 μm. When the average fiber diameter of the glass fiber is 1 μm or more, the production is easy and the high cost can be suppressed. On the other hand, if it is 100 μm or less, the tensile strength of the glass fiber can be maintained.
Above all, from the viewpoint of increasing the bonding strength, the average fiber diameter of the glass fiber is more preferably 4 μm or more or 9 μm or less, particularly preferably 5 μm or more or 8 μm or less, and more preferably 6 μm or more or 7 μm or less.
The fiber cross section may be circular or flat.

The average fiber length of the glass fiber after molding the resin-metal composite is not particularly limited. However, if the average fiber length of the glass fiber is too short, the reinforcing effect may not be sufficiently exhibited, and if it is too long, the bonding strength between the metal member (X) and the resin member (Y) of the resin metal composite is high. May decrease. From this point of view, the average fiber length is preferably 50 μm to 800 μm, more preferably 100 μm or more or 750 μm or less, particularly preferably 150 μm or more or 700 μm or less, and particularly preferably 200 μm or more or 650 μm or less.
As for the average fiber length, 2000 glass fibers of the filler residue collected by high-temperature ashing of the molded product, dissolution with a solvent, decomposition with a chemical, etc. were observed with an optical microscope (B201 manufactured by OLYMPUS). It is an average value calculated from an image by an image analyzer (WinROOF2015 manufactured by Mitani Shoji Co., Ltd.).
Further, the method of forming long fiber pellets by the electric wire coating method in which the polyester resin composition (A) is impregnated around the roving of the glass fiber is not preferable because the bonding strength of the resin metal composite may be lowered.

The glass fiber used in the present invention can be surface-treated with a coupling agent such as aminosilane or epoxysilane for the purpose of improving the adhesion to the polyester resin composition (A).
Examples of the coupling agent include chlorosilane compounds such as vinyltrichlorosilane and methylvinyldichlorosilane, and alkoxysilane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and γ-methacryloxypropyltrimethoxysilane. Compounds, epoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, acrylic compounds, isocyanate compounds, titanate compounds, epoxy compounds, etc. Can be mentioned.

Further, as the glass fiber used in the present invention, it is usually preferable to use a bundle of a large number of these fibers as a chopped strand (chopped glass fiber) cut to a predetermined length, and at this time, the glass fiber is used. It is preferable to add a converging agent. By blending the converging agent, in addition to the advantage of increasing the production stability of the polyester resin composition (A), good mechanical properties can be obtained.
The sizing agent for glass fibers is not particularly limited, and examples thereof include resin emulsions such as vinyl acetate resin, ethylene-vinyl acetate copolymer, acrylic resin, epoxy resin, polyurethane resin, and polyester resin, and acrylic is preferable. Resin, epoxy resin, polyurethane resin.

The polyester resin composition (A) preferably contains other inorganic fillers in the form of plates, granules or amorphous, in addition to the above-mentioned glass fibers.
The plate-shaped inorganic filler exhibits a function of reducing anisotropy and warpage, and examples thereof include talc, glass flakes, mica, mica, kaolin, and metal leaf. Among the plate-shaped inorganic fillers, glass flakes are preferable.
Examples of other granular or amorphous fillers include ceramic beads, clay, zeolite, barium sulfate, titanium oxide, silicon oxide, aluminum oxide, magnesium hydroxide, zinc sulfide and the like.
As other inorganic fillers, talc, titanium oxide and zinc sulfide are particularly preferable.

The polyester resin composition (A) preferably contains an inorganic filler at a ratio of 10 to 100 parts by mass with respect to 100 parts by mass of the polyester resin composition (A). If the content is too small, the reinforcing effect may not be sufficient, and if it is too large, the appearance and impact resistance may be poor, and the fluidity may not be sufficient.
From this point of view, the content of the inorganic filler is particularly preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and particularly 25 parts by mass or more with respect to 100 parts by mass of the polyester resin composition (A). It is preferably, preferably 80 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 60 parts by mass or less, and particularly 50 parts by mass or less.

<Other ingredients>
The polyester resin composition (A) may contain other components in addition to the above.
For example, stabilizers, mold release agents, colorants, elastomers, flame retardants, flame retardants, dripping inhibitors, UV absorbers, antistatic agents, antifogging agents, lubricants, antiblocking agents, plasticizers, dispersants, antibacterial agents. Agents and the like can be mentioned.
As the elastomer, those described in paragraphs 0050 to 0076 of Japanese Patent No. 6604977 can be used.
As the flame retardant, those described in paragraphs 0071 to 0076 of Japanese Patent No. 6518479 can be applied.

<< Manufacturing method of this resin-metal complex >>
Next, a method for producing the present resin-metal composite will be described.
The method for producing the resin-metal composite is not particularly limited. For example, it can be performed by insert molding.

<Insert molding>
In the case of insert molding as described above, a metal member (X) having an uneven surface is mounted in advance in a molding die, and a molten polyester resin composition (A) is placed in the die. It may be filled and cooled.
By insert molding in this way, at the same time as molding the resin member (Y), the surface side of the metal member (X) having surface irregularities can be joined to the resin member (Y), which is strong. The metal member (X) and the resin member (Y), which were difficult to join and weld, can be joined firmly and stably.

As for the method for preparing the polyesul resin composition (A), the resin composition may be prepared according to a conventional method. Usually, each component and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Further, the resin composition of the present invention can be prepared without premixing each component or by premixing only a part thereof and supplying the components to an extruder using a feeder for melt kneading.
When a fibrous reinforcing filler such as glass fiber is used, it is also preferable to supply it from a side feeder in the middle of the cylinder of the extruder.

The melting temperature of the polyester resin composition (A), in other words, the heating temperature at the time of melt-kneading, is usually preferably appropriately selected from the range of 220 to 300 ° C. If this temperature is too high, decomposition gas is likely to be generated. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation and the like.

Examples of the molding method for filling the polyester resin composition (A) in the mold include an injection molding method, an extrusion molding method, a compression molding method, and the like. Among them, the injection molding method is common.

On the other hand, the size and shape of the metal member (X) to be mounted in the mold may be appropriately determined depending on the size, structure and the like of the present resin metal composite.

The size, shape, thickness, etc. of the resin-metal composite are not particularly limited, and may be plate-shaped (disk, polygon, etc.), columnar, box-shaped, bowl-shaped, tray-shaped, or the like. These shapes may be formed after shaping the metal member (X) by casting, press molding, or the like before mounting the metal member (X) in the molding die in advance, or may be shaped after compounding. Alternatively, it may be shaped in the mold at the same time as or immediately before injection molding by a composite molding machine having a pressing function. In the case of a large complex or a complex complex, the thickness of all parts of the complex does not have to be uniform, and the complex may be provided with reinforcing ribs.
The metal member (X) does not have to cover the entire resin-metal composite, and may be a part thereof.

When insert molding, it is useful to optimize the temperature of the molten polyester resin composition (A) and the temperature of the metal member (X) by combining them in order to improve the bonding strength.
Examples of the method include a method of preheating the metal member (X) to be mounted in the mold and a method of heating the mold.

As a method of preheating the metal member (X) to be mounted in the mold, a method of induction heating the metal member (X) before insert molding, heating with an IH heater, a hot plate, a heating furnace, etc. After inserting the metal member (X) into the mold, the method of heating the vicinity of the joint area with the polyester resin composition from the outside with a halogen lamp, dryer, etc., after inserting the metal member (X) into the mold. , A method of heating with a cartridge heater or the like inside the mold can be mentioned. Above all, it is most useful to locally heat only the bonding region with the polyester resin composition (A).
The term "local heating" includes that, depending on the heating means, the periphery including the joint region is heated, but the portion of the metal member (X) farther than the joint region is not heated.

When heating the mold, if the temperature of the mold is too low, the inserted metal member (X) is not sufficiently heated, so that sufficient joint strength may not be obtained. In particular, in the case of this resin-metal composite, it is necessary to solidify after the resin has sufficiently penetrated into the unevenness of the surface of the metal member (X). It is preferable that the temperature is higher than that. On the other hand, if the temperature is too high, a good composite may not be obtained due to the influence on the resin itself.
From this point of view, in the method for producing the resin-metal composite, the surface temperature of the mold with which the metal member (X) mounted on the mold comes into contact is set to 60 to 60 to higher than the glass transition temperature of the polyester (a). It is preferable to set the temperature to be 100 ° C. higher, and it is more preferable to set the temperature to be 65 to 95 ° C. higher, particularly 68 to 95 ° C. higher, and 70 to 93 ° C. higher.

<< Form of this resin-metal complex >>
The present resin-metal composite can be formed in any form.
As an example of the form of the resin-metal composite, as shown in FIGS. 1 and 2, the resin member (Y) having a shape as an in-vehicle component is a peripheral end of a metal member (X) having a plate shape. A form in which the peripheral wall portion Y1 is provided so as to surround the portion can be mentioned.

The metal member (X) is formed by subjecting a plate-shaped joint region of a metal substrate to an uneven surface to form an uneven surface. As shown in FIG. 2, the peripheral end portion of the metal member (X) is formed. In, the resin member (Y) covers the edge portion on the back surface side from the edge portion on the front surface side of the metal member (X) via the end surface, and the metal member (X) is on the front surface side. At the edge portion and the edge portion on the back surface side, the front surface side of the metal member (X) and the polyester resin composition (A) of the resin member (Y) are joined (joint portion (J)). ..

The forms shown in FIGS. 1 and 2 are merely examples. The shape of the metal member (X) and the shape of the resin member (Y) can be arbitrarily changed. Further, the present resin-metal composite can be formed by combining various forms of the metal member (X) and various forms of the resin member (Y).

Further, as illustrated in FIGS. 3A to 3E, the joining state of the metal member (X) and the resin member (Y) can be arbitrarily changed.
For example, as shown in FIG. 3A, as the metal member (X), one surface of the metal substrate is roughened to form irregularities on the metal surface, and the metal member (X) is used. At the peripheral end portion of X), the resin member (Y) covers the end edge portion on the back surface side from the end edge portion on the front surface side of the metal member (X) via the end face, and the metal member (X). The uneven surface of the metal member (X) and the resin member (Y) may be joined only on one side of the edge portion of X) (joint portion (J)).
As shown in FIG. 3B, as the metal member (X), one surface of the metal substrate is subjected to unevenness treatment to form unevenness on the metal surface, and the metal member (X) is used. At the peripheral end portion of the metal member (X), the resin member (Y) covers from the end edge portion to the end face on the surface side of the metal member (X), and only one side of the end edge portion of the metal member (X). In the case, the uneven surface of the metal member (X) and the resin member (Y) may be joined (joined portion (J)).

As shown in FIG. 3C, as the metal member (X), one surface of the metal substrate is subjected to unevenness treatment to form unevenness on the metal surface, and the metal member (X) is used. The edge portion of the one side surface of the metal member (Y) and the edge portion of the one side surface of the resin member (Y) are overlapped so as to have an appropriate width, and at this portion, the uneven surface of the metal member (X) and the resin member ( It may be joined with Y) (joint portion (J)).
As shown in FIG. 3 (d), as the metal member (X), a member obtained by performing unevenness treatment on both sides of a metal substrate to form irregularities on the metal surface is used, and the metal member (X) is used. At the peripheral end portion of the metal member (X), the resin member (Y) covers from the end edge portion to the end face on the surface side of the metal member (X), and only one side of the end edge portion of the metal member (X). In the case, the uneven surface of the metal member (X) and the resin member (Y) may be joined (joined portion (J)).
As shown in FIG. 3 (e), as the metal member (X), a member obtained by performing unevenness treatment on both sides of the metal substrate to form unevenness on the metal surface is used, and the metal member (X) is used. The edge portion of the one side surface of the metal member (Y) and the edge portion of the one side surface of the resin member (Y) are overlapped so as to have an appropriate width, and at this portion, the uneven surface of the metal member (X) and the resin member ( It may be joined with Y) (joint portion (J)).

The ratio of the joint area (S1) between the metal member (X) and the resin member (Y) to the area (S2) of the metal member (X) exposed without being covered by the resin member (Y) (S2). The larger S1 / S2) is preferable because the adhesion is stable and the airtightness can be improved. Specifically, the ratio (S1 / S2) is preferably 0.01 or more, more preferably 0.1 or more, and sufficient airtightness can be obtained if 0.5 or more. Especially preferable.
Further, in order to secure heat dissipation from the exposed portion of the metal, it is preferable that the size is small to some extent. Specifically, the ratio (S1 / S2) is preferably 8 or less, more preferably 4 or less, further preferably 2 or less, and particularly preferably 1 or less because sufficient heat dissipation can be ensured.

By joining the ratio of S1 / S2 in this way, the joining strength and airtightness are further enhanced, and even when used as a member of the housing, the heat trapped in the housing is sufficiently released to dissipate heat. Can be secured.
When the uneven surface of the metal surface is provided on both sides, the joint area between the uneven surface of the metal member (X) and the resin member (Y), that is, the area of the joint portions (J) (J) is the same on both sides. No need.

<< Bonding strength of this resin-metal composite >>
The resin-metal composite can have excellent bonding strength by forming a structure in which the uneven surface of the metal member (X) and the resin member (Y) are bonded. Specifically, an initial bonding strength of 20 MPa or more can be realized.

In the present invention, the term "bonding strength" refers to a metal member (X) and a resin material using the bonding conditions for preparing a bonding strength test test piece having the shape described in the examples and producing a resin metal composite. It means a value obtained by joining the members (Y) and performing a tensile test described in Examples on the obtained composite and measuring the result.

(air tightness)
The resin-metal composite has a treatment step of treating at -40 ° C. for 1 hour and then treating at 150 ° C. for 1 hour as one cycle, and the airtightness after performing a heat shock test in which this treatment step is performed for 100 cycles is 0. It can be 5 MPa or more, preferably 0.6 MPa or more, particularly preferably 0.8 MPa or more, and particularly preferably 1.0 MPa or more.

<< Applications of this resin-metal complex >>
In this resin-metal composite, a metal member and a resin member can be strongly and stably bonded to each other, and excellent bonding strength can be obtained. Moreover, the properties of both, such as heat dissipation, heat resistance, and insulation, can be obtained. Since it can have both properties and antistatic properties, it can be suitably used for various purposes. Above all, it can be suitably used for automobile applications in which joint strength and heat dissipation are particularly required.

Specifically, if a container is formed using the present resin-metal composite, such a container can be made into a container having excellent airtightness, heat dissipation, heat resistance, insulation, antistatic property, and the like. Because it can be done, electrical and electronic parts (housing, case, cover, etc.) incorporated in OA equipment, including general household appliances, mechanical parts, electrical parts for vehicles (various control units, ignition coil parts, sensor parts, motor parts, power) Modules, step-up DC / DC converters, step-down DC / DC converters, capacitors, insulators, motor terminal blocks, batteries, electric compressors, battery current sensors, junction blocks, etc.) , It can be suitably used for applications that require bonding strength as a function.

FIG. 4 shows an example in which the resin metal composite is applied as a part of the housing of the electrical components for the vehicle.
When this resin-metal composite is used as a part of a product, that is, when it is used in combination with another member (Z) (resin molded product, aluminum die-cast, metal, etc.), another member (Z). ) And the present resin-metal composite, for example, any method can be used for the method of joining the resin member (Y) and the other member (Z). For example, laser welding, ultrasonic welding, vibration welding, heat welding, mechanical bonding using bolts and tapping screws, adhesives, and the like can be mentioned.

<< Explanation of words >>
In the present invention, when "X to Y" (X, Y are arbitrary numbers) is described, it means "X or more and Y or less" and "preferably larger than X" or "preferably Y". It also includes the meaning of "smaller".
Further, when "X or more" (X is an arbitrary number) is described, it includes the meaning of "preferably larger than X" and is described as "Y or less" (Y is an arbitrary number) unless otherwise specified. In this case, unless otherwise specified, it also includes the meaning of "preferably smaller than Y".

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

<Surface treatment of metal parts>
A metal plate made of a strip-shaped aluminum alloy (JIS H4000 "A5052") having a length of 45 mm, a width of 12 mm, and a thickness of 1.5 mm was immersed in the following zincate solution (40.0 ° C.) for 60 seconds. Next, the surface of the metal plate was roughened by immersing it in the following etching agent (50 ° C.) for 480 seconds to obtain an uneven surface. Next, the metal plate material was immersed in a commercially available zirconium chemical conversion treatment agent (“Pulseed (registered trademark)” manufactured by Nihon Parkerizing Co., Ltd., concentration 50 g / L, temperature 45 ° C., pH 4.0) for 120 seconds, and the metal member ( X) was obtained.

<Ginkate liquid component>
-Water / zinc oxide: 0.25 mol / L
-Sodium hydroxide: 3.80 mol / L
-Tartaric acid: 0.07 mol / L
・ PH: 12.5

<Etching agent component>
・ Water ・ Sodium peroxodisulfate: 0.35 mol / L
-Sodium chloride: 1.70 mol / L
・ PH: 3.0

The uneven surface of the metal member (X) treated as described above is observed with an objective lens of a hybrid laser microscope (OPTELICS HYBRID manufactured by LASERTEC) at a magnification of 20 times, and an objective is used with the attached analysis software (Lasertec Microscope Solution LMeye7). The surface roughness was measured according to JIS B 0601: 2001 by observing with a lens of 20 times.
The measurement uses the measurement algorithm Fine Peak to measure the average uneven surface in the center of a metal plate made of an aluminum alloy (JIS H4000 "A5052") having a strip shape of 45 mm in length, 12 mm in width, and 1.5 mm in thickness. An FZ image was obtained. The measurement range was 4.2 mm in the vertical direction of 45 mm. The cutoff value λc is 0.8000 mm.
As a result of repeating the same operation 30 times at arbitrary different places and calculating the average value, the arithmetic mean roughness (Ra) was 5.2 μm and the maximum height (Rz) was 34.7 μm. Further, it had a size distribution in which a large recess having an opening diameter and / or a depth of 80 to 150 μm and a small recess having an opening diameter and / or a depth of 1 to 5 μm were combined. The small recesses were distributed in and around the large recesses.

(Preparation of polyester resin compositions α1 to 7)
Of the components shown in Table 1, each component excluding the reinforcing filler (D) is uniformly mixed with a tumbler mixer at the ratio shown in Table 2 (all by mass), and then a meshing type isodirectional twin-screw extruder. (“TEX-30α” manufactured by Japan Steel Works, Ltd., screw diameter 32 mm, L / D = 52) was used, and the reinforced filler (D) was supplied from the side feeder at 40 kg / hr. Melting and kneading under the conditions of the barrel set temperature C1 to C15 of the extruder at 260 ° C, the die at 250 ° C, and the screw rotation speed of 200 rpm, the number of nozzles is 4 (circular (φ4 mm), length 1.5 cm), and the shear rate (γ). ) Extruded as a strand under the condition of ^211sec-1. The strand temperature immediately after extrusion was 270 ° C. The extruded strands were introduced into a water tank adjusted to a temperature in the range of 30 to 50 ° C. and rapidly cooled. The strand surface temperature (T) is cooled to 65 ° C. at the temperature measured by an infrared thermometer (γ · T = 1.4 × 10 ⁴ ), inserted into a pelletizer and cut to form a polybutylene terephthalate resin composition. Pellets of substances α1 to 7 were obtained.
Then, the obtained pellets of the polyester resin compositions α1 to 7 were dried at 120 ° C. for 5 hours and then used for insert molding.

<Examples 1 to 5 and Comparative Examples 1 to 2>
The metal member (X) produced as described above was mounted in the mold cavity, and the pellets of the polyester resin compositions α1 to α13 obtained above were injection-molded under the conditions shown below, and FIG. As shown, a resin-metal composite (evaluation sample) was obtained in which a metal member (X) and a resin member (Y) made of a polyester resin composition (A) were joined. At this time, the joint area between the metal member (X) and the resin member (Y) was 5 mm × 10 mm.
Injection molding conditions: Using "J85AD" manufactured by Japan Steel Works as an injection molding machine, cylinder temperature 270 ° C, mold temperature 140 ° C, injection speed 60 mm / sec, filling time 0.2 seconds, holding pressure 110 MPa, holding time 10 The procedure was performed under the conditions of seconds and cooling time of 30 seconds.
The mold temperature indicates the temperature of the mold surface with which the metal member (X) comes into contact.

<Evaluation / measurement method>
The resin-metal composites (evaluation samples) obtained in Examples and Comparative Examples were measured and evaluated by the following methods.

(Initial joint strength)
Using the resin-metal composites (evaluation samples) obtained in Examples, Comparative Examples, and Reference Examples, the initial bonding strength was measured as follows in accordance with ISO19095.
Using a tensile tester (Instron's "5544 type"), perform a tensile test (tensile speed 5 mm / min) in the direction perpendicular to the joint surface at the end of the obtained resin-metal composite (evaluation sample). This was carried out, and the maximum tensile stress of the joint surface, that is, the joint strength was measured. The obtained strengths are listed in the “Initial Bond Strength” column of Table 3.

(Fracture stress test)
The resin composition pellets obtained above are dried at 120 ° C. for 5 hours, and then used in an injection molding machine (“NEX80” manufactured by Nissei Resin Industry Co., Ltd.) under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. , ISO dumbbell piece (4 mm thick) was injection molded.
The breaking stress (unit: MPa) of the ISO dumbbell piece obtained above was measured in accordance with ISO standards 527-1 and ISO527-2.

(Flexural strength test)
The pellets of the polyester resin compositions α1 to α7 obtained by the above method are dried at 70 ° C. for 3 hours, and then molded by an injection molding machine (manufactured by Toshiba Machine Co., Ltd., “EC75SX”) at a cylinder temperature of 300 ° C. An ISO tensile test piece (4 mm thick) was injection-molded under the conditions of a temperature of 130 ° C. and a molding cycle of 50 seconds.
In accordance with ISO178, the flexural strength (unit: MPa) was measured at a temperature of 23 ° C. using the ISO tensile test piece (4 mm thick).

(Gas generation test)
Using the pellets of the polyester resin compositions α1, α3 and α6 obtained by the above method, a gas generation amount test was carried out by the following mold deposit evaluation.

[Mold deposit evaluation]
The molding machines and conditions used for the evaluation are as follows.
Injection molding machine SE18 manufactured by Sumitomo Heavy Industries, Ltd.
Injection pressure 50MPa Injection speed 80mm / sec
Cylinder temperature 270 ° C
Injection time 3 sec
Cooling 8 sec
Mold temperature 35 ° C
Sackback 3mm
Molded product Length 35 mm Width 14 mm, Thickness 2 mm
Mold Pingate mold

After performing injection molding continuously under the above conditions and performing 300 shots, the state of the mold deposit adhering to the mold (mold contamination) is observed with the naked eye, and the state of the mold deposit is the best with a maximum of 10 points. Good ones were given 10 points and evaluated.
The above evaluation results are shown in Table 3 below. "-" In the table indicates that it has not been measured.

(Evaluation of mold releasability during continuous molding)
During the mold deposit evaluation test, continuous molding of 300 shots was carried out, and the mold releasability during continuous molding was evaluated according to the following criteria.
◯ (good): There was little sticking to the mold at the time of mold release, and automatic continuous molding was possible.
× (poor): Sticking to the mold occurred frequently at the time of mold release, and automatic continuous molding was difficult.

(Discussion)
As is clear from the above results, it was found that the resin composition of the present invention has a small amount of gas. In particular, since the amount of gas was reduced in Example 1, it was found that the amount of gas could be reduced by using polyethylene oxide wax. Further, it was found that Examples 1 to 5 had higher releasability during continuous molding as compared with Comparative Example 2, and the releasability was improved by the low molecular weight compound.
Further, Example 1 using glass fibers having an average fiber diameter of 6.5 μm has improved breaking stress and bending strength as compared with Example 2 using glass fibers having an average fiber diameter of 13 μm, and has a smaller diameter. It was found that the physical properties of the resin were improved when glass was used. From this, the average fiber diameter of the glass fiber is preferably at least 13 μm, and it is expected that the physical characteristics of the resin will be improved particularly in the range of plus or minus 2.5 μm of the average fiber diameter of 6.5 μm.

(Preparation of polyester resin compositions α8 to 13)
Similar to the polyester resin compositions α1 to 7, the polyester resin compositions α8 to 13 were prepared with the components and proportions (all by mass) shown in Table 4.

<Examples 6 to 9, Comparative Examples 3 to 4>
A resin metal composite (evaluation sample) was prepared in the same manner as in Example 1 except that the polyester resin compositions α8 to 13 were used instead of the polyester resin compositions α1 to 7, and evaluated in the same manner as in Example 1 and the like. did.

(Discussion)
Even when the amount of glass is reduced, Examples 6 and 8 using glass fibers having an average fiber diameter of 6.5 μm have a breaking stress as compared with Examples 7 and 9 using glass fibers having an average fiber diameter of 13 μm. , Bending strength has improved. From this, it is preferable that the average fiber diameter of the glass fiber is at least 13 μm, and it is expected that the fracture stress and the bending strength will be improved particularly in the range of plus or minus 2.5 μm of the average fiber diameter of 6.5 μm. To.

<< Reference Example >>
Hereinafter, specific examples (referred to as “reference examples”) referred to in the present invention will be described.

<Surface treatment of metal parts>
A metal plate made of a strip-shaped aluminum alloy (JIS H4000 "A5052") having a length of 45 mm, a width of 12 mm, and a thickness of 1.5 mm was immersed in the following zincate solution (40.0 ° C.) for 60 seconds. Next, the surface of the metal plate was roughened by immersing it in the following etching agent (50 ° C.) for 480 seconds to obtain an uneven surface. Next, the metal plate material was immersed in a commercially available zirconium chemical conversion treatment agent (“Pulseed (registered trademark)” manufactured by Nihon Parkerizing Co., Ltd., concentration 50 g / L, temperature 45 ° C., pH 4.0) for 120 seconds, and the metal member ( X) was obtained.

<Ginkate liquid component>
-Water / zinc oxide: 0.25 mol / L
-Sodium hydroxide: 3.80 mol / L
-Tartaric acid: 0.07 mol / L
・ PH: 12.5

<Etching agent component>
・ Water ・ Sodium peroxodisulfate: 0.35 mol / L
-Sodium chloride: 1.70 mol / L
・ PH: 3.0

The uneven surface of the metal member (X) treated as described above is observed with an objective lens of a hybrid laser microscope (OPTELICS HYBRID manufactured by LASERTEC) at a magnification of 20 times, and an objective is used with the attached analysis software (Lasertec Microscope Solution LMeye7). The surface roughness was measured according to JIS B 0601: 2001 by observing with a lens of 20 times.
The measurement uses the measurement algorithm Fine Peak to measure the average uneven surface in the center of a metal plate made of an aluminum alloy (JIS H4000 "A5052") having a strip shape of 45 mm in length, 12 mm in width, and 1.5 mm in thickness. An FZ image was obtained. The measurement range was 4.2 mm in the vertical direction of 45 mm. The cutoff value λc is 0.8000 mm.
As a result of repeating the same operation 30 times at arbitrary different places and calculating the average value, the arithmetic mean roughness (Ra) was 5.2 μm and the maximum height (Rz) was 34.7 μm. Further, it had a size distribution in which a large recess having an opening diameter and / or a depth of 80 to 150 μm and a small recess having an opening diameter and / or a depth of 1 to 5 μm were combined. The small recesses were distributed in and around the large recesses.

(Preparation of Polyester Resin Composition α101-113)
Of the components shown in Table 6, each component excluding the reinforcing filler (D) is uniformly mixed with a tumbler mixer at the ratio shown in Table 7 (all by mass), and then a meshing type isodirectional twin-screw extruder. (“TEX-30α” manufactured by Japan Steel Works, Ltd., screw diameter 32 mm, L / D = 52) was used, and the reinforced filler (D) was supplied from the side feeder at 40 kg / hr. The extruder barrel set temperature C1 to C15 is 260 ° C., the die is 250 ° C., and the screw rotation speed is 200 rpm. ) Extruded as a strand under the condition of ^211sec-1. The strand temperature immediately after extrusion was 270 ° C. The extruded strands were introduced into a water tank adjusted to a temperature in the range of 30 to 50 ° C. and rapidly cooled. The strand surface temperature (T) is cooled to 65 ° C. at the temperature measured by an infrared thermometer (γ · T = 1.4 × 10 ⁴ ), inserted into a pelletizer and cut to form a polybutylene terephthalate resin composition. Pellets of article α101-113 were obtained.
Then, the obtained pellets of the polyester resin composition α101 to 113 were dried at 120 ° C. for 5 hours and then used for insert molding.

<Reference Examples 1 to 2, 4 to 10, Reference Comparative Examples 1 to 4, Reference Reference Example 1>
The metal member (X) produced as described above was mounted in the mold cavity, and the pellets of the polyester resin compositions α101 to α113 obtained above were injection-molded under the conditions shown below, and FIG. As shown, a resin-metal composite (evaluation sample) was obtained in which a metal member (X) and a resin member (Y) made of a polyester resin composition (A) were joined. At this time, the joint area between the metal member (X) and the resin member (Y) was 5 mm × 10 mm.
Injection molding conditions: Using "J85AD" manufactured by Japan Steel Works as an injection molding machine, cylinder temperature 270 ° C, mold temperature 140 ° C, injection speed 60 mm / sec, filling time 0.2 seconds, holding pressure 110 MPa, holding time 10 The procedure was performed under the conditions of seconds and cooling time of 30 seconds.
In the local heating of Reference Example 2, the cartridge heater arranged inside the mold was locally heated so that only the joint region with the metal member (X) was 160 ° C.
The mold temperature indicates the temperature of the mold surface with which the metal member (X) comes into contact.

<Reference Example 3>
A resin-metal composite (evaluation sample) was obtained in the same manner as in Reference Example 1 except that a plate material of cast aluminum (ADC12) was used as the metal member.

<Evaluation / measurement method>
The resin-metal complex (evaluation sample) obtained in the reference example and the reference comparative example was measured and evaluated by the following method.

(Joint strength test)
Using the resin-metal composites (evaluation samples) obtained in Reference Examples, Reference Comparative Examples, and Reference Reference Examples, a joint strength test was conducted in accordance with ISO19095.
Using a tensile tester (Instron's "5544 type"), perform a tensile test (tensile speed 5 mm / min) in the direction perpendicular to the joint surface at the end of the obtained resin-metal composite (evaluation sample). This was carried out, and the maximum tensile stress of the joint surface, that is, the joint strength was measured. The obtained strength is described in the column of "joint strength" of 0 hr in Table 8 as the joint strength before the durability evaluation is carried out.

In the evaluation of bondability, all of Reference Examples 1 to 10 showed higher bonding strength than Reference Comparative Example. This is because the epoxy group-containing compound, which is a polyester terminal-reactive compound, is added to the polyester resin composition (A), so that the reactive compound on the metal surface reacts with the polyester-terminal reactive compound, and the anchor effect is stronger. Therefore, it is considered that the bonding strength was improved.

Furthermore, based on this result and the test results conducted by the inventor so far, as an epoxy group-containing compound to be combined with homo-PBT or copolymerized PBT, 2,2-bis (4-hydroxy) is required to increase the bonding strength. It was found that it is optimal to select phenyl) -propane (bisphenol A type epoxy compound).

(Preparation of polyester resin compositions α114 to 120)
Similar to the polyester resin compositions α101 to 113, the polyester resin compositions α114 to 120 were prepared at the ratios shown in Table 9 (all by mass).

<Reference Examples 11 to 15, Reference Comparative Examples 5 to 6>
A resin metal composite (evaluation sample) was prepared in the same manner as in Reference Example 1 except that the polyester resin compositions α114 to 120 were used instead of the polyester resin compositions α101 to 113.
The results of the joint strength test are shown in Table 10.

From this result and the test results conducted by the inventor so far, a low molecular weight compound having a melting point of 40 to 140 ° C. and a number average molecular weight of less than 6000 is further added to the polyester resin composition (A). It was found that the joint strength can be increased.

<Reference Examples 16 to 18, Reference Comparative Examples 6 and 7>
As shown in FIG. 6, the metal plate material made of an aluminum alloy (JIS H4000 “A5052”), which is cut into a disk shape having a diameter of 55 mm and a thickness of 2 mm and has a hole with a diameter of 20 mm in the center, is described in The surface was treated in the same manner as in Surface Treatment> to prepare a metal member (X).
The metal member (X) produced as described above is mounted in the mold cavity, and the pellets of the polyester resin composition α1 or α13 obtained above are injection-molded under the conditions shown below, and are shown in FIG. As described above, the polyester resin composition (A) has a disk shape having a diameter of 24 mm and a thickness of 2 mm, partially overlaps the metal member (X), and covers the central hole of the metal member (X). ) Was arranged to obtain a resin-metal composite (evaluation sample) in which the metal member (X) and the resin member (Y) made of the polyester resin composition (A) were joined. In this case, bonding width of the metal member (X) and the resin member (Y) is 2 mm, the bonding area was 0.00013816m ^2.
Injection molding conditions: Using "J85AD" manufactured by Japan Steel Works as an injection molding machine, cylinder temperature 270 ° C, mold temperature 140 ° C, injection speed 60 mm / sec, filling time 0.2 seconds, holding pressure 110 MPa, holding time 10 The procedure was performed under the conditions of seconds and cooling time of 30 seconds.

<Evaluation / measurement method>
The resin-metal complex (evaluation sample) obtained in the reference example and the reference comparative example was measured and evaluated by the following method.

(Airtightness test)
An airtightness test was conducted using the resin-metal complex (evaluation sample) obtained in the reference example and the reference comparative example.
The test was conducted using the evaluation pressure vessel shown in FIG. 7.
The evaluation pressure device was created with the following shape.
Using a metal made of SUS304 having a diameter of 90 mm, a hole having a diameter of 30 mm and a depth of 20 mm was drilled in the center and filled with water. Furthermore, a hole with a diameter of 56 mm and a depth of 0.5 mm is drilled in the peripheral part, and the disk-shaped resin-metal composite (evaluation sample) obtained in the reference example / reference comparative example is attached via an O-ring made by Viton. Then, it was fixed with bolts using a holding plate made of SUS304, having a diameter of 90 mm and a thickness of 8 mm, and immersed in water at 25 ° C. Next, using a test pump (TP50N manufactured by Asada Co., Ltd.) inside the welded body, water supply was started at 16 mL / 5 seconds, the internal pressure of the welded body was gradually increased, and when the pressure was released from the joint (pressure). The pressure of water at the point of decrease) was measured using a pressure sensor (GP-M025 manufactured by Keyence Co., Ltd.).
The obtained pressures are listed in the “0 hr” column of Table 11 as airtightness before performing the durability evaluation.

(Durability evaluation)
The disk-shaped resin-metal composite (evaluation sample) obtained in Reference Example / Reference Comparative Example was treated at -40 ° C for 1 hour using a thermal shock tester (TSA-103ES-W manufactured by Espec Co., Ltd.). After that, 60 cycles and 100 cycles of heat shock resistance test were carried out with the treatment step of treating at 150 ° C. for 1 hour as one cycle, and the samples after each exposure were airtight (water at the time when the pressure was released from the joint). Maximum pressure) was measured. The results are shown in Table 11.

In the evaluation of airtightness, all of Reference Examples 16 to 18 showed higher airtightness than the comparative examples. This is because the polyester terminal-reactive compound was added to the polyester resin composition (A), so that the reactive compound on the metal surface reacted with the polyester-terminal reactive compound, and the anchor effect became stronger, so that the airtightness became stronger. It is considered to have improved.

(X) ・ ・ Metal member (Y) ・ ・ Resin member Y1 ・ ・ Peripheral wall part (J) ・ ・ Joint part (Z) ・ ・ Other members

Claims (17)

A metal member (X) having a surface having surface irregularities and a resin member (Y) made of a polyester resin composition (A) containing polyester (a) as a main component resin are provided, and the metal member (X) is provided. ) Is a resin-metal composite having a structure in which a surface side having surface irregularities and a resin member (Y) are joined.
The polyester resin composition (A) contains, as the polyester (a), polybutylene terephthalate (also referred to as "homo PBT"), a copolymer of polybutylene terephthalate (also referred to as "copolymerized PBT"), or a mixed resin thereof. Including, further containing an epoxy group-containing compound (b) and a low molecular weight compound (c).
The low molecular weight compound is a resin metal complex containing polyethylene oxide wax. The polyester resin composition (A) is characterized in that the ratio of the homo PBT and the copolymerized PBT to the polymer components (excluding the elastomer and the flame retardant) constituting the polyester resin composition (A) is 80 to 100% by mass. Item 2. The resin-metal composite according to Item 1. The polyester (a) is claimed to have an intrinsic viscosity of 0.30 to 2.00 dl / g measured at 30 ° C. in a 1: 1 (mass ratio) mixed solvent of tetrachloroethane and phenol. Item 2. The resin-metal composite according to Item 1 or 2. The invention according to any one of claims 1 to 3, wherein the low molecular weight compound (c) is contained in a proportion of 0.001 to 1.5 parts by mass with respect to 100 parts by mass of the polyester resin composition (A). Resin metal composite. The resin metal composite according to any one of claims 1 to 4, wherein the polyethylene oxide wax is a polyethylene oxide wax having a number average molecular weight of 1500 to 5000. The resin-metal complex according to claim 1, wherein the acid value of the low-molecular-weight compound (c) is 0.01 to 40 mg / KOH. The resin-metal complex according to any one of claims 1 to 5, wherein the low molecular weight compound (c) has an acid value of 0.5 to 20 mg / KOH. The resin-metal composite according to any one of claims 1 to 7, wherein the polyester resin composition (A) further contains a reinforcing filler (d). The resin-metal composite according to claim 8, wherein the reinforcing filler (d) is a glass fiber having an average fiber diameter of 4 μm to 9 μm. The uneven surface of the metal member (X) has an arithmetic mean roughness (Ra) of 0.05 μm or more and 200 μm or less and a maximum height (Rz) measured in accordance with JIS B 0601: 2001. The resin-metal composite according to any one of claims 1 to 9, wherein the resin metal composite is 0.01 μm or more and 200 μm or less. The surface of the metal member (X) is provided with an oxide film, a chemical conversion coating film, a plating layer, a silane coupling agent treatment layer, a primer layer or another resin layer, or fine particles are immobilized. The resin-metal composite according to any one of claims 1 to 10. The resin member (Y) covers the end edge portion on the back surface side from the end edge portion on the front surface side of the metal member (X) via the end surface, and the end on the front surface side of the metal member (X). Claims 1 to 2 include a structure in which the front surface side of the metal member (X) and the polyester resin composition (A) of the resin member (Y) are joined to each other at the edge portion and the end edge portion on the back surface side. 11. The resin-metal composite according to any one of 11. The method for producing a resin-metal composite according to any one of claims 1 to 12.
The metal member (X) is mounted on the molding die in advance, and then the molten polyester resin composition (A) is filled in the die and cooled to have surface irregularities of the metal member (X). It is a method of manufacturing a resin metal composite for joining a resin member (Y) with a surface side having a resin.
A resin metal characterized in that the surface temperature of the mold with which the metal member (X) mounted on the mold comes into contact is set to a temperature 60 to 100 ° C. higher than the glass transition temperature of the polyester (a). Method for producing the complex. A vehicle member made of the resin-metal composite according to any one of claims 1 to 12. An electrical component made of the resin-metal composite according to any one of claims 1 to 12. A housing member made of the resin-metal composite according to any one of claims 1 to 12. A housing member for an electrical component for a vehicle, which comprises the resin-metal composite according to any one of claims 1 to 12.

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