JP2022138952A - Metal resin joined body - Google Patents

Abstract

To provide a metal resin joined body which is obtained by strongly joining a resin member obtained by molding a polyamide resin composition and a copper member, and has enhanced airtightness.SOLUTION: A metal resin joined body has a copper member whose surface is roughened, and a resin member containing a polyamide resin (A) joined to the roughened surface of the copper member, wherein a joint strength of the copper member and the resin member obtained by dividing a breaking load (N) measured at a room temperature (23°C) by a tensile testing machine under conditions of a distance between chucks of 60 mm and tensile speed of 10 mm/min by a joined area of the copper member and the resin member is 40 MPa or more, and a leak amount of helium measured by a method according to ISO 19095 in a joined part between the copper member and the resin member is 1×10-6 Pa m3/s or less.SELECTED DRAWING: None

Description

The present invention relates to a metal-resin joined body.

Conventionally, polyamide resin compositions have been widely used as materials for various parts such as industrial materials, automobiles, electrical/electronics, and industrial applications because of their excellent moldability, mechanical properties, and chemical resistance. It is

When the polyamide resin composition is used for these applications, it is required to firmly bond the resin member formed by molding the polyamide resin composition and the metal member. Further, when the polyamide resin composition is used for vehicle-mounted electrical/electronic equipment, etc., it is required that the resin member be firmly bonded to a metal member containing copper as a main component.

For example, Patent Literature 1 describes a composite of copper and resin in which a polyamide-based resin composition is bonded to a surface-treated copper member.

JP 2017-132243 A

However, according to the findings of the present inventors, even with the composite described in Patent Document 1, it was difficult to obtain the desired bonding strength. In addition, when the polyamide resin composition is used for in-vehicle electrical and electronic equipment, for example, in order to suppress leakage of oil such as automatic transmission fluid (ATF), high adhesion between the resin member and the copper member (Airtightness) is required, but it was difficult to obtain the desired airtightness even with the composite described in Patent Document 1.

In view of these circumstances, it is an object of the present invention to provide a metal-resin joined body in which a resin member formed by molding a polyamide resin composition and a copper member are firmly joined together and airtightness is improved. for that purpose.

A metal-resin bonded body according to an embodiment of the present invention comprises a copper member having a roughened surface, and a resin member containing a polyamide resin (A) bonded to the roughened surface of the copper member. , The breaking load (N) of the copper member and the resin member measured by a tensile tester at room temperature (23 ° C.) at a chuck distance of 60 mm and a tensile speed of 10 mm / min, The bonding strength obtained by dividing the bonding area between the copper member and the resin member is 40 MPa or more, and the amount of helium measured by a method in accordance with ISO 19095 at the bonding portion between the copper member and the resin member. A leak amount is 1×10 ⁻⁶ Pa·m ³ /s or less.

A metal-resin joined body according to another embodiment of the present invention is a resin member comprising a copper member having a roughened surface and a polyamide resin (A) bonded to the roughened surface of the copper member. And, the resin member has a polyamide resin (A) having a melting point (Tm) of 280 ° C. or higher as measured by differential scanning calorimetry (DSC), and 0.1 with respect to the total mass of the resin member The modified polyolefin resin (C) is contained in an amount of not less than 10% by mass and not more than 10% by mass.

According to the present invention, it is possible to provide a metal-resin joined body in which a resin member formed by molding a polyamide resin composition and a copper member are firmly joined together and airtightness is improved.

1. First Embodiment A first embodiment of the present invention is a polyamide containing a copper member having a roughened surface and a polyamide resin (A) bonded to the roughened surface of the copper member. The present invention relates to a metal-resin joined body having a resin member.

1-1. Copper Member The surface of the copper member is roughened. The roughening treatment method is not particularly limited, and the surface is roughened by chemical treatment such as immersion in a treatment solution containing a base or acid, etching, or physical treatment such as laser or blasting. Just do it.

On the roughened surface of the copper member, the center-to-center distance (pitch) of the plurality of protrusions formed by the roughening treatment is preferably 5 nm or more and 500 μm or less. When the center-to-center distance between the plurality of protrusions is 5 nm or more, the recesses between the protrusions are appropriately large, so that the resin composition can be sufficiently penetrated into the recesses during bonding, and the copper member and the resin member can be easily bonded. Bonding strength can be further improved. Further, when the center-to-center distance of the plurality of protrusions is 500 μm or less, the recesses do not become too large, so that the formation of gaps at the metal-resin interface of the metal-resin bonded body is further suppressed, and the airtightness is further improved. be able to. From the same point of view, it is more preferable that the center-to-center distance between the plurality of protrusions is 5 μm or more and 250 μm or less. The center-to-center distance of a plurality of protrusions is the average value of the distances between the center of one protrusion and the centers of adjacent protrusions.

The center-to-center distance of a plurality of protrusions is measured by removing the resin member from the metal-resin joint by mechanical peeling, solvent cleaning, etc., and observing the surface of the exposed copper member with an electron microscope or laser microscope, or using a surface roughness measuring device. can be observed and measured using

Specifically, when the center-to-center distance of the plurality of protrusions is less than 0.5 μm, it is possible to observe with an electron microscope, and when the center-to-center distance of the plurality of protrusions is 0.5 μm or more. can be observed with a laser microscope or a surface roughness measuring device. For example, in a photograph of the surface of a copper member taken with an electron microscope or a laser microscope, 50 arbitrary convex portions are selected and the center-to-center distances of the convex portions are measured. Then, after accumulating all the measured values of the center-to-center distances of the convex portions, the value obtained by dividing by 50 (the average value) is defined as "the center-to-center distances of the plurality of convex portions."

The average value of the ten-point average roughness (Rz) of the roughened surface of the copper member at an evaluation length of 4 mm is not particularly limited, but preferably exceeds 2 μm, and is greater than 2 μm and 50 μm or less. is more preferable, and more preferably greater than 2.5 μm and 45 μm or less.

The average value of ten-point average roughness (Rz) can be measured according to JIS B0601 (ISO 4287). Specifically, measure the ten-point average roughness (Rz) on a total of six straight lines, any three straight lines parallel to each other and any three straight lines orthogonal to them, and average these be the average value of Rz.

The average length (RSm) of the roughness curve element of the roughened surface of the copper member is preferably 0.5 μm or more and 500 μm or less. In particular, from the viewpoint of further increasing the bonding strength, the center-to-center distance of the plurality of protrusions is less than 0.5 μm, and the average length (RSm) of the roughness curve elements is 0.5 μm or more and 500 μm or less. is preferred. The average length of roughness curve elements can also be measured according to JIS B0601 (ISO 4287) as described above.

1-2. Resin Member The resin member is a resin composition in which the main component of the resin component is the polyamide resin (A). Being the main component means that the polyamide resin (A) accounts for 50% by mass or more of the resin components. The proportion of the polyamide resin (A) in the resin component is preferably 60% by mass or more, more preferably 70% by mass or more. The upper limit of the ratio of the polyamide resin (A) in the resin component is not particularly limited, but may be 100% by mass or less, may be 90% by mass or less, or may be 80% by mass or less.

1-2-1. Polyamide resin (A)
The polyamide resin may be a polyamide resin containing component units (Aa) derived from a dicarboxylic acid and component units (Ab) derived from a diamine. At this time, in order to increase the melting point (Tm) and glass transition temperature (Tg) of the polyamide resin, the component unit (Aa) derived from a dicarboxylic acid contains a component unit derived from an aromatic dicarboxylic acid or an alicyclic dicarboxylic acid. is preferred. The polyamide resin (A) has a role of bonding the resin member to the copper member. Moreover, from the viewpoint of further increasing bonding strength and airtightness, the polyamide resin (A) is preferably a crystalline polyamide resin.

[Component unit (Aa) derived from dicarboxylic acid]
Examples of aromatic dicarboxylic acids include terephthalic acid, naphthalenedicarboxylic acid and their esters. Examples of cycloaliphatic dicarboxylic acids include cyclohexanedicarboxylic acid and its esters. Among them, from the viewpoint of obtaining a polyamide resin having high crystallinity and high heat resistance, the component unit (Aa) derived from a dicarboxylic acid preferably contains a component unit derived from an aromatic dicarboxylic acid, and is derived from terephthalic acid. It is more preferable to include a component unit that

The content of component units derived from aromatic dicarboxylic acid or alicyclic dicarboxylic acid (preferably component units derived from aromatic dicarboxylic acid, more preferably component units derived from terephthalic acid) is not particularly limited, but dicarboxylic acid It is preferably 50 mol % or more and 100 mol % or less with respect to the total number of moles of component units (Aa) derived from an acid. When the content of the component unit is 50 mol % or more, the crystallinity of the polyamide resin can be easily increased. From the same viewpoint, the content of the component unit is more preferably 70 mol % or more and 100 mol % or less.

In the present embodiment, the component unit (Aa) derived from dicarboxylic acid preferably contains a component unit (a1) derived from terephthalic acid, naphthalenedicarboxylic acid or cyclohexanedicarboxylic acid. These component units (Aa1) can increase the crystallinity of the polyamide, unlike isophthalic acid, for example. From the viewpoint of ensuring the crystallinity of the polyamide resin, the content of these component units (Aa1) is more than 20 mol% and 100 mol% or less with respect to the total number of moles of the component units (Aa) derived from dicarboxylic acid. do. From the viewpoint of further increasing the crystallinity of the polyamide resin, the content of these component units (Aa1) is 45 mol% or more and 100 mol% or less with respect to the total number of moles of the component units (Aa) derived from dicarboxylic acid. more preferably 50 mol % or more and 99 mol % or less, and even more preferably more than 60 mol % and 80 mol % or less.

The component unit (Aa) derived from a dicarboxylic acid is an aromatic carboxylic acid component unit (Aa2) other than the above component unit (Aa1) or an aliphatic having 4 to 20 carbon atoms, within a range that does not impair the effects of the present invention. It may contain a component unit (Aa3) derived from a dicarboxylic acid.

Examples of component units (Aa2) derived from aromatic dicarboxylic acids other than terephthalic acid include component units derived from isophthalic acid and 2-methylterephthalic acid. Among these, component units derived from isophthalic acid are preferred. When the polyamide resin (A) contains the component unit (Aa2), the content of these component units (Aa2) is, from the viewpoint of ensuring the crystallinity of the polyamide resin, the total amount of the component units (Aa) derived from dicarboxylic acid. It is preferably 1 mol% or more and 50 mol% or less, more preferably 10 mol% or more and 40 mol% or less, further preferably 15 mol% or more and 40 mol% or less, based on the number of moles. It is particularly preferable that it is mol % or more and 40 mol % or less.

The component unit (Aa3) derived from an aliphatic dicarboxylic acid is a component unit derived from an aliphatic dicarboxylic acid having an alkylene group having 4 to 20 carbon atoms, and has an alkylene group having 6 to 12 carbon atoms. A component unit derived from an aliphatic dicarboxylic acid is preferred. Examples of the above aliphatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3 - includes diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid component units, etc. Among these, adipic acid and sebacic acid are preferred. When the polyamide resin (A) contains the component unit (Aa3), the content of these component units (Aa3) is, from the viewpoint of ensuring the crystallinity of the polyamide resin, the total amount of the component units (Aa) derived from dicarboxylic acid. It is preferably 0 mol% or more and 40 mol% or less, more preferably 0 mol% or more and 20 mol% or less, further preferably 1 mol% or more and 10 mol% or less, relative to the number of moles. It is particularly preferable that it is mol % or more and 5 mol % or less.

The polyamide resin (A) includes, in addition to the component units (Aa1), (Aa2), and (Aa3) described above, a small amount of tribasic or higher polyvalent such as trimellitic acid or pyromellitic acid. It may further contain a carboxylic acid component unit. The content of such polyvalent carboxylic acid component units can be 0 mol % or more and 5 mol % or less with respect to the total number of moles of component units (Aa) derived from dicarboxylic acids.

[Component unit (Ab) derived from diamine]
The component unit (Ab) derived from a diamine preferably contains a component unit (Ab1) derived from a straight-chain alkylenediamine having 4 to 18 carbon atoms, and has a side chain alkyl group having 4 to 18 carbon atoms. It may further contain a component unit (Ab2) derived from an alkylenediamine and a component unit (Ab3) derived from an alicyclic diamine having 4 to 20 carbon atoms.

The diamine-derived component unit (Ab) is a linear alkylenediamine having 4 to 18 carbon atoms when the total number of moles of the diamine-derived component units contained in the polyamide resin (A) is 100 mol%. The amount of the derived component unit (Ab1) is preferably 20 mol % or more and 100 mol % or less, more preferably 20 mol % or more and 80 mol % or less. When the content of the above component unit is 20 mol % or more, the crystallization rate does not become too slow, so the crystallinity and mechanical strength of the polyamide resin (A) can be moderately increased. When the content of the component unit is 100 mol % or less, preferably 80 mol % or less, the crystallization rate of the polyamide resin (A) does not become too high, and the fluidity during molding is less likely to be impaired. From the same point of view, the content of component units derived from linear aliphatic diamines is more preferably 30 mol % or more and 60 mol % or less of the above total.

In addition, the component unit (Ab) derived from a diamine is derived from a component unit (Ab2) derived from an alkylenediamine having 4 to 18 carbon atoms having a side chain alkyl group or an alicyclic diamine having 4 to 20 carbon atoms. It may contain a component unit (Ab3) that At this time, when the total number of moles of the component units derived from the diamine contained in the polyamide resin (A) is 100 mol%, the component units derived from the alkylenediamine having 4 to 18 carbon atoms having a side chain alkyl group ( The amount of Ab2) or the component unit (Ab3) derived from an alicyclic diamine having 4 to 20 carbon atoms is preferably 20 mol % or more and 80 mol % or less. When the content of the component unit is 20 mol % or more, the crystallization speed of the polyamide resin (A) tends to be moderately slowed, so that the fluidity during molding can be easily improved. When the content of the component unit is 80 mol % or less, the crystallinity and mechanical strength of the polyamide resin (A) are less likely to be impaired. From the same point of view, the content of component units derived from a branched aliphatic diamine is more preferably 40 mol % or more and 70 mol % or less with respect to the above total.

Examples of component units (Ab1) derived from linear alkylenediamines having 4 to 18 carbon atoms include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Included are component units derived from diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and the like. Among these, component units derived from 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane are preferred, with 1,6-diaminohexane component units being more preferred. preferable. A plurality of types of these component units may be contained in the polyamide resin (A).

Examples of component units (Ab2) derived from alkylenediamines having 4 to 18 carbon atoms with side chain alkyl groups include 1-butyl-1,2-diamino-ethane, 1,1-dimethyl-1,4- Diamino-butane, 1-ethyl-1,4-diamino-butane, 1,2-dimethyl-1,4-diamino-butane, 1,3-dimethyl-1,4-diamino-butane, 1,4-dimethyl- 1,4-diamino-butane, 2,3-dimethyl-1,4-diamino-butane, 2-methyl-1,5-diaminopentane, 2,5-dimethyl-1,6-diamino-hexane, 2,4 -dimethyl-1,6-diamino-hexane, 3,3-dimethyl-1,6-diamino-hexane, 2,2-dimethyl-1,6-diamino-hexane, 2,2,4-trimethyl-1,6 -diamino-hexane, 2,4,4-trimethyl-1,6-diamino-hexane, 2,4-diethyl-1,6-diamino-hexane, 2,3-dimethyl-1,7-diamino-heptane, 2 ,4-dimethyl-1,7-diamino-heptane, 2,5-dimethyl-1,7-diamino-heptane, 2,2-dimethyl-1,7-diamino-heptane, 2-methyl-4-ethyl-1 ,7-diamino-heptane, 2-ethyl-4-methyl-1,7-diamino-heptane, 2,2,5,5-tetramethyl-1,7-diamino-heptane, 3-isopropyl-1,7- Diamino-heptane, 3-isooctyl-1,7-diamino-heptane, 1,3-dimethyl-1,8-diamino-octane, 1,4-dimethyl-1,8-diamino-octane, 2,4-dimethyl- 1,8-diamino-octane, 3,4-dimethyl-1,8-diamino-octane, 4,5-dimethyl-1,8-diamino-octane, 2,2-dimethyl-1,8-diamino-octane, 3,3-dimethyl-1,8-diamino-octane, 4,4-dimethyl-1,8-diamino-octane, 3,3,5-trimethyl-1,8-diamino-octane, 2,4-diethyl- Included are component units derived from 1,8-diamino-octane, and 5-methyl-1,9-diamino-nonane. Among these, a component unit derived from a side chain alkyldiamine having 1 to 2 side chain alkyl groups having 1 to 2 carbon atoms and a main chain having 4 to 10 carbon atoms is preferable. Methyl-1,5-diaminopentane component units are more preferred. A plurality of types of these component units may be contained in the polyamide resin (A).

Examples of component units (Ab3) derived from alicyclic diamines having 4 to 20 carbon atoms include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1 ,4-bis(aminomethyl)cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis(4-aminocyclohexyl)methane, bis(4-aminocyclohexyl)propane, 4,4′-diamino-3,3 '-dimethyldicyclohexylpropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'- Diamino-3,3′-dimethyl-5,5′-dimethyldicyclohexylpropane, α,α′-bis(4-aminocyclohexyl)-p-diisopropylbenzene, α,α′-bis(4-aminocyclohexyl)-m -diisopropylbenzene, α,α'-bis(4-aminocyclohexyl)-1,4-cyclohexane, and α,α'-bis(4-aminocyclohexyl)-1,3-cyclohexane. be Among these, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, and 4,4′-diamino-3,3′-dimethyldicyclohexylmethane Component units derived from are preferred and are 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis(4-aminocyclohexyl)methane, 1,3-bis(aminocyclohexyl)methane, and 1,3-bis( More preferred are constituent units derived from aminomethyl)cyclohexane.

In the present specification, unless otherwise specified, the number of carbon atoms in a component unit derived from an alkylenediamine having a side chain alkyl group is equal to the number of carbon atoms in the main chain alkylene group and the number of carbon atoms in the side chain alkyl group. Total.

The polyamide resin (A) includes a component unit (Ab1) derived from the linear alkylenediamine having 4 to 18 carbon atoms described above, and a component unit derived from an alkylenediamine having 4 to 18 carbon atoms having a side chain alkyl group. In addition to (Ab2) and component units (Ab3) derived from alicyclic diamines having 4 to 20 carbon atoms, component units derived from other diamines such as component units derived from a small amount of metaxylylenediamine are included. may contain. The content of component units derived from other diamines may be 50 mol % or less, preferably 40 mol % or less, relative to the total amount of component units (Ab) derived from diamines.

Polyamide resin (A), from the viewpoint of increasing the thermal stability during compounding and molding, and further increasing the mechanical strength, at least part of the terminal groups of the molecules are blocked with a terminal blocking agent. good. The terminal blocking agent is preferably a monoamine when the molecular terminal is a carboxyl group, and is preferably a monocarboxylic acid when the molecular terminal is an amino group.

Examples of monoamines include aliphatic monoamines such as methylamine, ethylamine, propylamine, and butylamine, cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine, and aromatic monoamines such as aniline and toluidine. is included. Examples of monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. aliphatic monocarboxylic acids having 2 to 30 atoms, aromatic monocarboxylic acids including benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid; and alicyclic monocarboxylic acids including cyclohexanecarboxylic acid and the like. Contains carboxylic acids. Aromatic monocarboxylic acids and alicyclic monocarboxylic acids may have a substituent on the cyclic structure portion.

[Physical properties]
The polyamide resin (A) can have a melting point (Tm) of 280° C. or higher and 340° C. or lower. When the melting point (Tm) of the polyamide resin (A) is 280° C. or higher, the mechanical strength and heat resistance of the resin composition and the molded article are unlikely to be impaired in a high temperature range, and when it is 340° C. or lower, the molding temperature is reduced. Since there is no need to make the temperature excessively high, the moldability of the resin composition tends to be good. From the above viewpoint, the melting point (Tm) of the polyamide resin is more preferably 290° C. or higher and 340° C. or lower, and further preferably 300° C. or higher and 340° C. or lower.

The polyamide resin (A) can have a glass transition temperature (Tg) of 80°C or higher and 150°C or lower.

The heat of fusion (ΔH) of the polyamide resin (A) is preferably 20 J/g or more. When the heat of fusion (ΔH) of the polyamide resin (A) is 20 J/g or more, the heat resistance of the resin member can be easily improved because of the crystallinity. Although the upper limit of the heat of fusion (ΔH) of the polyamide resin (A) is not particularly limited, it can be 130 J/g from the viewpoint of not impairing moldability. The heat of fusion (ΔH) of the polyamide resin (A) is preferably 30 J/g or more and 130 J/g or less, more preferably 30 J/g or more and 100 J/g or less.

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

Specifically, about 5 mg of crystalline polyamide resin is sealed in an aluminum pan for measurement and heated from room temperature to 350°C at 10°C/min. Hold at 350°C for 3 minutes to completely melt the resin, then cool to 30°C at 10°C/min. After 5 minutes at 30°C, heat a second time to 350°C at 10°C/min. The endothermic peak temperature (° C.) in this second heating is taken as the melting point (Tm) of the crystalline polyamide resin, and the displacement point corresponding to the glass transition is taken as the glass transition temperature (Tg). The heat of fusion (ΔH) is determined according to JIS K7122 from the area of the endothermic peak during melting during the first heating process.

The melting point (Tm), glass transition temperature (Tg) and heat of fusion (ΔH) of the polyamide resin (A) depend on, for example, the composition of the component unit (Aa1) derived from the dicarboxylic acid described above and the component unit (Ab1 ) can be adjusted by the number of carbon atoms per one. In order to raise the melting point of the polyamide resin (A), for example, the content ratio of component units derived from terephthalic acid may be increased.

The intrinsic viscosity [η] of the polyamide resin (A) measured in 96.5% sulfuric acid at a temperature of 25° C. is preferably 0.6 dl/g or more and 1.5 dl/g or less. When the intrinsic viscosity [η] of the polyamide resin (A) is 0.6 dl/g or more, the mechanical strength (such as toughness) of the molded body can be sufficiently increased, and when it is 1.5 dl/g or less, the resin composition Fluidity during molding is less likely to be impaired. From the same viewpoint, the intrinsic viscosity [η] of the polyamide resin (A) is more preferably 0.8 dl/g or more and 1.2 dl/g or less. The intrinsic viscosity [η] can be adjusted by the amount of terminal blocking of the polyamide resin (A) and the like.

The intrinsic viscosity of the polyamide resin (A) can be measured according to JIS K6810 (1977). Specifically, 0.5 g of polyamide resin (A) is dissolved in 50 ml of 96.5% sulfuric acid solution to prepare a sample solution. The number of seconds the sample solution flows down can be measured using an Ubbelohde viscometer under the condition of 25±0.05° C., and the obtained value can be applied to the following formula for calculation.
[η]=ηSP/[C(1+0.205ηSP)]

In the above formula, each algebra or variable represents:
[η]: Intrinsic viscosity (dl/g)
ηSP: specific viscosity C: sample concentration (g/dl)

ηSP is obtained by the following formula.
ηSP=(t−t0)/t0
t: number of seconds for the sample solution to flow down (seconds)
t0: Number of seconds for blank sulfuric acid to flow down (seconds)

[Production method]
The polyamide resin can be produced, for example, by polycondensing the aforementioned dicarboxylic acid and the aforementioned diamine in a uniform solution. Specifically, a dicarboxylic acid and a diamine are heated in the presence of a catalyst as described in WO 03/085029 to obtain a lower condensate, and then the lower condensate is It can be produced by subjecting a melt to polycondensation by applying shear stress.

From the viewpoint of adjusting the intrinsic viscosity of the polyamide resin, etc., the aforementioned end blocking agent may be added to the reaction system. The intrinsic viscosity [η] (or molecular weight) of the polyamide resin can be adjusted by the amount of the terminal blocker added.

A terminal blocking agent is added to the reaction system of the dicarboxylic acid and the diamine. The amount added is preferably 0.07 mol or less, more preferably 0.05 mol or less, per 1 mol of the total amount of dicarboxylic acid.

The content of the polyamide resin (A) is preferably 35% by mass or more and 80% by mass or less, and 40% by mass or more and 80% by mass or less, relative to the total mass of the resin composition constituting the resin member. is more preferable, and more preferably 50% by mass or more and 80% by mass or less. As the content of the polyamide resin (A) is increased, the bonding strength of the resin member to the copper member can be increased. On the other hand, the upper limit of the polyamide resin (A) is in the above range in order to leave room for further improving the bonding strength and improving the airtightness by delaying the crystallization rate by adding other components. can be

1-2-2. Polyamide resin (B)
The resin member preferably contains, in addition to the polyamide resin (A), a polyamide resin (B) whose heat of fusion (ΔH) measured by a differential scanning calorimeter (DSC) is lower than that of the polyamide resin (A). Moreover, it is preferable that the melting point (Tm) of the polyamide resin (B) is not substantially measured in differential scanning calorimetry (DSC). Since the polyamide resin (B) has lower crystallinity than the polyamide resin (A), the crystallization speed of the resin composition during molding of the resin member can be retarded. As a result, the resin composition constituting the resin member can be caused to sufficiently flow along the unevenness of the surface of the roughened copper member, and the resin composition can be sufficiently adhered to the unevenness. Therefore, it is considered that the polyamide resin (B) can further increase the bonding strength between the copper member and the resin member, and further improve the airtightness.

"The melting point (Tm) is not substantially measured" means that the displacement point corresponding to the glass transition is not substantially observed in the above-described measuring method.

That is, the heat of fusion (ΔH) of the polyamide resin (B) is preferably 5 J/g or less, more preferably 0 J/g. When the heat of fusion (ΔH) of the polyamide resin (B) is 5 J/g or less, the crystallinity is moderately low, so that the crystallization rate of the resin composition during molding of the resin member can be sufficiently retarded. can. The polyamide resin (B) preferably exhibits amorphousness. The heat of fusion (ΔH) can be measured by the same method as described above.

The polyamide resin (B) may be a polyamide resin containing component units (Ba) derived from dicarboxylic acid and component units (b) derived from diamine.

[Component unit (Ba) derived from dicarboxylic acid]
The component unit (Ba) derived from dicarboxylic acid preferably contains at least a component unit derived from isophthalic acid. Component units derived from isophthalic acid can lower the crystallinity of the polyamide resin (B).

The content of component units derived from isophthalic acid is preferably 40 mol % or more, more preferably 50 mol % or more, relative to the total amount of component units (Ba) derived from dicarboxylic acid. When the content of component units derived from isophthalic acid is 40 mol % or more, the polyamide resin (B) tends to be amorphous. Although the upper limit of the content of component units derived from isophthalic acid is not particularly limited, it can be 100 mol % or less, preferably 90 mol % or less.

The component unit (Ba) derived from dicarboxylic acid may further contain component units derived from dicarboxylic acids other than component units derived from isophthalic acid, as long as the effects of the present invention are not impaired. Examples of other dicarboxylic acids include aromatic dicarboxylic acids other than isophthalic acid, such as terephthalic acid, 2-methylterephthalic acid and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. The aliphatic dicarboxylic acid and alicyclic dicarboxylic acid can be the same as the aliphatic dicarboxylic acid and alicyclic dicarboxylic acid described above, respectively. Among them, aromatic dicarboxylic acids other than isophthalic acid are preferred, and terephthalic acid is more preferred.

In the component unit (Ba) derived from dicarboxylic acid, the molar ratio of the component unit derived from isophthalic acid to the component unit derived from an aromatic dicarboxylic acid other than isophthalic acid (preferably terephthalic acid) is the component derived from isophthalic acid. Unit/component unit derived from an aromatic dicarboxylic acid other than isophthalic acid (preferably terephthalic acid) = preferably 55/45 to 100/0 (molar ratio), 60/40 to 90/10 (molar ratio) is more preferable. When the amount of component units derived from isophthalic acid is a certain amount or more, the polyamide resin (B) tends to be amorphous, and the crystallization speed of the resin composition during molding of the resin member is retarded, resulting in a copper member. It is easy to increase the bonding strength of the resin member and to increase the airtightness.

[Component unit (Bb) derived from diamine]
The component unit (Bb) derived from a diamine preferably contains a component unit derived from an aliphatic diamine having 4 to 15 carbon atoms.

The aliphatic diamine having 4 to 15 carbon atoms is the same as the aforementioned aliphatic diamine having 4 to 15 carbon atoms, preferably 1,6-hexanediamine.

The content of component units derived from aliphatic diamines having 4 to 15 carbon atoms is preferably 50 mol% or more, and preferably 60 mol% or more, relative to the total amount of component units (Bb) derived from diamines. It is more preferable to have

The component unit (Bb) derived from a diamine may further contain a component unit derived from another diamine other than the component unit derived from an aliphatic diamine having 4 to 15 carbon atoms, as long as it does not impair the effects of the present invention. good. Examples of other diamines include cycloaliphatic diamines and aromatic diamines. The cycloaliphatic diamine and aromatic diamine can be the same as the cycloaliphatic diamine and aromatic diamine described above, respectively. The content of other diamine component units may be 50 mol % or less, preferably 40 mol % or less.

Specific examples of the polyamide resin (B) include polycondensates of isophthalic acid/terephthalic acid/1,6-hexanediamine/bis(3-methyl-4-aminocyclohexyl)methane, isophthalic acid/bis(3-methyl- 4-aminocyclohexyl)methane/ω-laurolactam polycondensate, isophthalic acid/terephthalic acid/1,6-hexanediamine polycondensate, isophthalic acid/2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1,6-hexanediamine polycondensate, isophthalic acid / terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1 ,6-hexanediamine polycondensates, isophthalic acid/bis(3-methyl-4-aminocyclohexyl)methane/ω-laurolactam polycondensates, isophthalic acid/terephthalic acid/other diamine component polycondensates, etc. is included. Among them, a polycondensate of isophthalic acid/terephthalic acid/1,6-hexanediamine is preferred. Only one kind of polyamide resin (B) may be contained, or two or more kinds thereof may be contained.

The intrinsic viscosity [η] of the polyamide resin (B) measured in 96.5% sulfuric acid at a temperature of 25° C. is preferably 0.6 to 1.6 dl/g, and 0.65 to 1.2 dl. /g is more preferred. The intrinsic viscosity [η] of the polyamide resin (B) can be measured by the same method as the intrinsic viscosity [η] of the polyamide resin (A) described above.

The polyamide resin (B) can be produced in the same manner as the polyamide resin (A) described above.

The proportion of the polyamide resin (B) in the resin component is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. By setting the proportion of the polyamide resin (B) within the above range, the effect of improving the bonding strength and the airtightness due to the delay in crystallization can be more sufficiently exhibited. The upper limit of the ratio of the polyamide resin (B) in the resin component is not particularly limited, but from the viewpoint of blending a sufficient amount of the polyamide resin (A) in the resin composition, it can be 30% by mass or less, It may be 25% by mass or less.

1-2-3. Modified polyolefin resin (C)
The resin member may contain a modified polyolefin resin (C) in addition to the polyamide resin (A). The modified polyolefin resin (C) can retard the crystallization rate of the resin composition during molding of the resin member. As a result, the resin composition constituting the resin member can be caused to sufficiently flow along the unevenness of the surface of the roughened copper member, and the resin composition can be sufficiently adhered to the unevenness. Therefore, it is considered that the modified polyolefin resin (C) can further increase the bonding strength between the copper member and the resin member, and further improve the airtightness.

Modified polyolefin resin (C) is an olefin polymer having polyolefin units and functional group structural units. Examples of functional groups possessed by the functional group structural units include heteroatom-containing functional groups and aromatic hydrocarbon groups. Preferably, the modified polyolefin resin (C) is a modified olefin polymer having polyolefin units and structural units containing functional groups containing heteroatoms (functional group structural units).

The heteroatom is preferably oxygen. Functional groups containing heteroatoms include ester groups, ether groups, carboxylic acid groups (including carboxylic anhydride groups), aldehyde groups, ketone groups, and the like.

The modified polyolefin resin (C) contains 0.1 to 5.0% by mass of functional group structural units with respect to 100% by mass of the modified polyolefin resin (C). The content of functional group structural units contained in the modified polyolefin resin (C) is preferably 0.2 to 3.0% by mass, preferably 0.2 to 2.0% by mass, more preferably 0.2 to 1.0% by mass. .2 mass %. When the amount of functional group structural units is within the above range, the impact resistance and elongation of the resin composition are likely to increase.

The content of the functional group structural unit contained in the modified polyolefin resin (C) is determined by the feed ratio when the olefin polymer and the functional group-containing compound are reacted in the presence of a radical initiator or the like, ¹³ C NMR measurement, It is identified by known means such as ¹ H NMR measurement. As specific NMR measurement conditions, the following conditions can be exemplified.

¹ H NMR measurement was performed using an ECX400 type nuclear magnetic resonance instrument manufactured by JEOL Ltd. The solvent was deuterated ortho-dichlorobenzene, the sample concentration was 20 mg/0.6 mL, the measurement temperature was 120° C., and the number of observation nuclei was ¹ . H (400 MHz), the sequence is a single pulse, the pulse width is 5.12 μs (45° pulse), the repetition time is 7.0 seconds, and the number of integrations is 500 or more. The standard chemical shift is 0 ppm for hydrogen in tetramethylsilane, but similar results can be obtained by setting the peak derived from residual hydrogen in deuterated ortho-dichlorobenzene to 7.10 ppm as the standard value for the chemical shift. be done. A peak such as ¹ H derived from a functional group-containing compound is assigned by a conventional method.

¹³ C NMR measurement was performed using a nuclear magnetic resonance apparatus ECP500 manufactured by JEOL Ltd. as a measuring apparatus, using a mixed solvent of ortho-dichlorobenzene/heavy benzene (80/20% by volume) as a solvent, measuring temperature at 120° C., observation nucleus can be performed under the conditions of ¹³ C (125 MHz), single pulse proton decoupling, 45° pulse, repetition time of 5.5 seconds, accumulation number of 10,000 or more, and chemical shift reference value of 27.50 ppm. Assignment of various signals is performed based on a conventional method, and quantification can be performed based on the integrated value of signal intensity.

On the other hand, the skeleton portion of the modified polyolefin resin (C) preferably has a structure derived from polyolefin, such as an ethylene-based polymer, a propylene-based polymer, a butene-based polymer, and copolymers of these olefins. A known olefin polymer is preferred. The skeleton portion of the olefin polymer is more preferably a copolymer of ethylene and an α-olefin having 3 or more carbon atoms (hereinafter also simply referred to as “ethylene/α-olefin copolymer”).

Examples of the α-olefins having 3 or more carbon atoms include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. Specific examples of the ethylene/α-olefin copolymer include ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/1-hexene copolymer, ethylene/1-octene copolymer, and ethylene. - 4-methyl-1-pentene copolymer and the like are included. Among these, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/4-methyl-1-pentene copolymer, ethylene/1-hexene copolymer, and ethylene/1-octene copolymer coalescence is preferred.

The above ethylene/α-olefin copolymer contains 70 to 99.5 mol% of ethylene-derived structural units when the total number of moles of the structural units contained in the ethylene/α-olefin copolymer is 100 mol%. It is preferably contained in an amount of 80 to 99 mol %, more preferably in an amount of 80 to 99 mol %. Further, the ethylene/α-olefin copolymer has a structural unit derived from α-olefin of 0.5 to 100 mol%, when the total number of moles of the structural units contained in the ethylene/α-olefin copolymer is 100 mol%. It is preferably contained in an amount of 30 mol %, more preferably in an amount of 1 to 20 mol %.

The ethylene/α-olefin copolymer preferably has a melt flow rate (MFR) of 0.01 to 20 g/10 minutes at 190° C. under a load of 2.16 kg according to ASTM D1238, and preferably 0.05 to 20 g/10 minutes. 10 minutes is more preferable, and 0.1 to 10 g/10 minutes is even more preferable.

The modified polyolefin resin (C) can be obtained, for example, by reacting the above-mentioned olefin polymer and the compound having the functional group at a specific ratio.

Preferred examples of functional group-containing compounds to be reacted with the olefin polymer include unsaturated carboxylic acids or derivatives thereof. Specific examples of the functional group-containing compounds include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2, 2,1]hepto-5-ene-2,3-dicarboxylic acid (nadic acid (trademark)) and other unsaturated carboxylic acids, and derivatives thereof such as acid halides, amides, imides, acid anhydrides and esters. be Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferred, and maleic acid, nadic acid (trademark), or acid anhydrides thereof are particularly preferred.

Preferably, the functional group-containing compound is maleic anhydride. Maleic anhydride has a relatively high reactivity with the above-mentioned olefin polymer, and itself tends to be stable as a basic structure with little major structural change due to polymerization or the like. Therefore, there are various advantages such as the ability to obtain modified polyolefin resin (C) with stable quality.

An example of a method for obtaining a modified polyolefin resin (C) using an ethylene/α-olefin copolymer is the so-called grafting of an ethylene/α-olefin copolymer with a functional group-containing compound corresponding to the functional group structural unit. Methods of denaturation are included.

The density of the modified polyolefin resin (C) is preferably 0.80-0.96 g/cm ³ , more preferably 0.85-0.95 g/cm ³ , still more preferably 0.89-0.94 g/cm ³ . be.

Furthermore, the intrinsic viscosity [η] of the modified polyolefin resin (C) measured in a decalin (decahydronaphthalene) solution at 135° C. is preferably 1.5 to 4.5 dl/g, more preferably 1.6 to 3 dl/g. is g. When [η] is within the above range, both mechanical strength and injection fluidity of the resin composition can be achieved at a high level.

[η] in decalin at 135° C. of the modified polyolefin resin (C) is measured as follows according to a conventional method. 20 mg of a sample is dissolved in 15 ml of decalin, and the specific viscosity (ηsp) is measured at 135° C. using an Ubbelohde viscometer. 5 ml of decalin is further added to this decalin solution for dilution, and the same specific viscosity measurement is performed. Based on the measurement results obtained by repeating this dilution operation and the viscosity measurement twice, the "ηsp/C" value when the concentration (C) is extrapolated to zero is defined as the intrinsic viscosity [η].

The melt flow rate (MFR, compliant with JIS K7210, temperature 190°C, load 21.2N) of the modified polyolefin resin (C) of the present invention is preferably 0.01 to 20 g/10 minutes, and is preferably 0.05. It is more preferably ~20 g/10 minutes, and even more preferably 0.1 to 10 g/10 minutes. If the MFR is less than 0.01 g/10 minutes, the fluidity is poor, and if it exceeds 20 g/10 minutes, the impact strength may be low depending on the shape of the molded product.

The proportion of the modified polyolefin resin (C) in the resin component is preferably 0.1% by mass or more, more preferably 0.8% by mass or more, and preferably 1.0% by mass or more. More preferred. By setting the proportion of the polyamide resin (B) within the above range, the effect of improving the bonding strength and the airtightness due to the delay in crystallization can be more sufficiently exhibited. The upper limit of the ratio of the polyamide resin (B) in the resin component is not particularly limited, but from the viewpoint of blending a sufficient amount of the polyamide resin (A) in the resin composition, it can be 10% by mass or less, It is preferably 5% by mass or less, more preferably 4% by mass or less.

1-2-4. Heat resistant stabilizer (D)
The resin member may contain a copper-based heat resistant stabilizer (D) in addition to the polyamide resin (A). The copper-based heat resistant stabilizer (D) can improve the fluidity of the resin composition during molding of the resin member. As a result, the resin composition constituting the resin member can be caused to sufficiently flow along the unevenness of the surface of the roughened copper member, and the resin composition can be sufficiently adhered to the unevenness. Therefore, it is considered that the copper-based heat resistant stabilizer (D) can further increase the bonding strength between the copper member and the resin member, and further improve the airtightness. In addition, the copper-based heat resistant stabilizer (D) improves the heat aging resistance of the resin composition. As a result, it is thought that deterioration in airtightness can be suppressed when the metal-resin joined body is used under conditions in which heating and cooling are repeatedly performed.

The copper-based heat resistant stabilizer (D) contains (i) a salt of a halogen and a group 1 or group 2 metal element of the periodic table (halogen metal salt), and (ii) a copper compound, and optionally and (iii) a higher fatty acid metal salt.

(i) Examples of metal halide salts include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride. Among them, potassium iodide and potassium bromide are preferred. Only one type of halogen metal salt may be contained, or two or more types may be contained.

(ii) Examples of copper compounds include copper halides, copper salts (sulphates, acetates, propionates, benzoates, adipates, terephthalates, salicylates, nicotinates and stearates). acid salts, etc.), and copper chelate compounds (compounds of copper with ethylenediamine or ethylenediaminetetraacetic acid, etc.). Among them, copper iodide, cuprous bromide, cupric bromide, cuprous chloride, and copper acetate are preferred. Only one type of copper compound may be contained, or two or more types may be contained.

The content mass ratio of (i) the halogen metal salt and (ii) the copper compound is such that the molar ratio of the halogen and copper is 0.1 from the viewpoint of facilitating the improvement of the heat resistance of the molded body and the corrosiveness during production. /1 to 200/1, preferably 0.5/1 to 100/1, more preferably 2/1 to 40/1.

(iii) Examples of higher fatty acid metal salts include higher saturated fatty acid metal salts and higher unsaturated fatty acid metal salts.

The higher saturated fatty acid metal salt is a metal salt of a saturated fatty acid having 6 to 22 carbon atoms and a metal element (M1) such as an element of groups 1, 2, and 3 of the periodic table, zinc, and aluminum. preferable. Such a higher saturated fatty acid metal salt is represented by the following formula (1).
_CH3 ( _CH2 ) _nCOO (M1). . . (1)
(In formula (1), the metal element (M1) is an element of Groups 1, 2, and 3 of the periodic table, zinc or aluminum, and n can be 8 to 30.)

Examples of higher saturated fatty acid metal salts include capric acid, uradecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanic acid, arachidic acid, behenic acid, lignoceric acid, and serotin. Lithium, sodium, magnesium, calcium, zinc and aluminum salts of acids, heptacosanoic acid, montanic acid, melissic acid, laxelic acid.

The higher unsaturated fatty acid metal salt is a metal salt of an unsaturated fatty acid having 6 to 22 carbon atoms and a metal element (M1) such as an element of groups 1, 2 and 3 of the periodic table, zinc, and aluminum. is preferred.

Examples of higher unsaturated fatty acid metal salts include undecylenic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, 2-hexadecenoic acid, Included are the lithium, sodium, magnesium, calcium, zinc and aluminum salts of 7-hexadecenoic acid, 9-hexadecenoic acid, gadoleic acid, gadoelaidic acid and 11-eicosenoic acid.

Examples of the copper-based heat resistant stabilizer (D) include a mixture of 10% by mass of copper (I) iodide and 90% by mass of potassium iodide, and 14.3% by mass of copper (I) iodide and 85 .7% by weight of potassium iodide/calcium distearate (98:2 weight ratio).

The content of the copper-based heat resistant stabilizer (D) in the resin composition constituting the resin member can be 0.01% by mass or more and 3% by mass or less with respect to the total mass of the resin composition. 0.1% by mass or more and 3% by mass or less, and more preferably 0.1% by mass or more and 0.5% by mass. When the amount of the copper-based heat resistant stabilizer (D) is 0.01% by mass or more with respect to the total mass of the resin composition, the bonding strength and airtightness are sufficiently increased, and heating or cooling is repeatedly performed. A decrease in airtightness when the metal-resin bonded body is used under such conditions can be more sufficiently suppressed. Moreover, the mechanical strength of a resin member is hard to be impaired as it is 3 mass % or less.

1-2-5. Other Components The resin member may contain other known components.

Examples of other components include reinforcing agents, crystal nucleating agents, fluidity improvers, colorants, corrosion resistance improvers, anti-drip agents, ion scavengers, elastomers (rubber), antistatic agents, release agents, Antioxidants (phenols, amines, sulfurs, phosphorus, etc.), heat stabilizers other than the above (lactone compounds, vitamin E, hydroquinones, etc.), light stabilizers (benzotriazoles, triazines, benzophenones) , benzoates, hindered amines and oxanilides, etc.), other polymers (polyolefins, olefin copolymers such as ethylene/propylene copolymers and ethylene/1-butene copolymers, propylene/1-butene copolymers olefin copolymers such as polystyrene, polyamide, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesin, silicone resin and LCP). Above all, it is preferable that the resin composition constituting the resin member further contains a reinforcing material from the viewpoint of increasing the mechanical strength of the molded article.

The reinforcing material can impart high mechanical strength to the resin composition. Examples of reinforcements include fibrous reinforcements such as glass fibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, zinc oxide whiskers, milled and cut fibers, and granular Includes reinforcement. Among these, one type may be used alone, or two or more types may be used in combination. Among them, wollastonite, glass fiber, and potassium titanate whiskers are preferred, and wollastonite or glass fiber are more preferred, because they tend to increase the mechanical strength of the molded article.

The average fiber length of the fibrous reinforcing material can be, for example, 1 μm or more and 20 mm or less, preferably 5 μm or more and 10 mm or less, from the viewpoints of the moldability of the resin composition and the mechanical strength and heat resistance of the obtained molded article. Also, the aspect ratio of the fibrous reinforcing material can be, for example, 5 or more and 2000 or less, preferably 30 or more and 600 or less.

The average fiber length and average fiber diameter of the fibrous reinforcing material can be measured by the following methods.
1) After dissolving the resin composition in a hexafluoroisopropanol/chloroform solution (0.1/0.9% by volume), the solution is filtered and collected.
2) The filtrate obtained in 1) above is dispersed in water, and the fiber length (Li) and fiber diameter (di) of each of 300 arbitrary fibers are measured with an optical microscope (magnification: 50 times). Let qi be the number of fibers whose fiber length is Li, and the weight average length (Lw) is calculated based on the following equation, which is taken as the average fiber length of the fibrous reinforcing material.
Weight average length (Lw)=(Σqi×Li ² )/(Σqi×Li)
Similarly, the number of fibers having a fiber diameter of Di is defined as ri, and the weight average diameter (Dw) is calculated based on the following equation, and is defined as the average fiber diameter of the fibrous reinforcing material.
Weight average diameter (Dw)=(Σri×Di ² )/(Σri×Di)

The content of the fibrous reinforcing material is not particularly limited, but can be, for example, 15% by mass or more and 70% by mass or less with respect to the total mass of the resin composition.

A crystal nucleating agent can increase the crystallinity of a molded body. Examples of nucleating agents include 2,2-methylenebis(4,6-di-t-butylphenyl)sodium phosphate, tris(pt-butylbenzoate)aluminum, and metals such as stearates. Salt compounds, sorbitol compounds including bis(p-methylbenzylidene)sorbitol and bis(4-ethylbenzylidene)sorbitol, and inorganic substances including talc, calcium carbonate, hydrotalcite, and the like are included. Among these, talc is preferable from the viewpoint of increasing the degree of crystallinity of the molded product. One type of these crystal nucleating agents may be used alone, or two or more types may be used in combination.

The content of the crystal nucleating agent is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less, relative to the total mass of the resin composition. . When the content of the crystal nucleating agent is within the above range, the degree of crystallinity of the molded body can be sufficiently increased, and sufficient mechanical strength can be easily obtained.

The fluidity improver enhances the injection fluidity of the resin composition and improves the appearance of the resulting molded product. Fluidity improvers can be fatty acid metal salts such as oxycarboxylic acid metal salts and higher fatty acid metal salts.

The oxycarboxylic acid constituting the oxycarboxylic acid metal salt may be either an aliphatic oxycarboxylic acid or an aromatic oxycarboxylic acid. Examples of the above aliphatic oxycarboxylic acids include α-hydroxymyristic acid, α-hydroxypalmitic acid, α-hydroxystearic acid, α-hydroxyeicosanoic acid, α-hydroxydocosanoic acid, α-hydroxytetraeicosanoic acid. , α-hydroxyhexaeicosanoic acid, α-hydroxyoctaeicosanoic acid, α-hydroxytriacontanoic acid, β-hydroxymyristic acid, 10-hydroxydecanoic acid, 15-hydroxypentadecanic acid, 16-hydroxyhexadecanoic acid, 12- Aliphatic oxycarboxylic acids having 10 to 30 carbon atoms such as hydroxystearic acid and ricinoleic acid are included. Examples of the aromatic oxycarboxylic acids include salicylic acid, m-oxybenzoic acid, p-oxybenzoic acid, gallic acid, mandelic acid, and trobaic acid.

Examples of metals constituting the metal oxycarboxylate include alkali metals such as lithium and alkaline earth metals such as magnesium, calcium and barium.

Among these, the metal oxycarboxylic acid salt is preferably a metal salt of 12-hydroxystearate, more preferably magnesium 12-hydroxystearate and calcium 12-hydroxystearate.

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

Examples of metals constituting the higher fatty acid metal salt include calcium, magnesium, barium, lithium, aluminum, zinc, sodium and potassium.

Among these, the higher fatty acid metal salt is preferably calcium stearate, magnesium stearate, barium stearate, calcium behenate, sodium montanate, calcium montanate, or the like.

The content of the fluidity improver is preferably 0.01% by mass or more and 1.3% by mass or less with respect to the total mass of the resin composition. When the content of the fluidity improver is 0.01% by mass or more, the fluidity during molding tends to increase, and the appearance of the resulting molded product tends to improve. When the content of the fluidity improver is 1.3% by mass or less, gas due to decomposition of the fluidity improver is less likely to be generated during molding, and the appearance of the product tends to be good.

The coloring agent imparts a desired color tone to the molded article. Colorants may be, but are not limited to, pigments. Examples of pigments include inorganic pigments such as carbon black, alumina, titanium oxide, chromium oxide, iron oxide, zinc oxide, barium sulfate; azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, anthraquinone pigments. , thioindigo-based pigments, and indanthrene-based pigments.

The content of the colorant is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less, relative to the total mass of the resin composition.

1-2-6. Production method The resin composition is prepared by mixing the above-described polyamide resin and, if necessary, other components with a known resin kneading method, such as a Henschel mixer, V blender, ribbon blender, or tumbler blender, or after mixing Furthermore, after melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, or a Banbury mixer, it can be produced by a method of granulating or pulverizing.

1-3. Method for producing a metal-resin bonded body The method for producing a metal-resin composite structure is not particularly limited, but for example, (1) a step of preparing a copper member having a roughened surface; and a step of injecting a molten resin composition onto the roughened surface and solidifying to join the resin members.

1-3-1. Preparation of surface-roughened copper member First, a copper member having an uneven structure on at least a part of its surface is prepared.

A method for obtaining a copper member having a fine uneven structure is not particularly limited. For example, a method using laser processing, a method of immersing a copper member in an inorganic base aqueous solution such as NaOH or an inorganic acid aqueous solution such as HCl or _HNO3 , a method of treating a copper member by an anodizing method, an acid etching agent (preferably , inorganic acid, ferric ions, cupric ions and, if necessary, acid-based etchant aqueous solution containing manganese ions, aluminum chloride hexahydrate, sodium chloride, etc.) substitution crystallization method, hydrazine hydrate , a method of immersing the copper member in an aqueous solution of ammonia and a water-soluble amine compound, and a hot water treatment method can be used.

1-3-2. Bonding of Resin Member The prepared copper member having a roughened surface is placed in a cavity (space) in an injection mold.

Then, the resin composition is injected into the cavity of the mold so that at least part of the resin composition is in contact with the roughened surface of the copper member. After that, it is cooled and solidified to join the copper member and the resin member.

The temperature of the mold for injection molding is not particularly limited as long as it is a temperature at which the resin composition can be melted to a state suitable for injection molding.

After injection and holding pressure, the mold is cooled, then the mold is opened, and if necessary, an ejector pin is used to eject the molded product, whereby a metal-resin joined body can be obtained.

As the mold, a known injection mold, such as a mold for high-speed heat cycle molding (RHCM, heat & cool molding) or a core-back mold for foam molding, can be used.

2. Second Embodiment In a second embodiment of the present invention, a copper member having a roughened surface and a resin member containing a polyamide resin bonded to the roughened surface of the copper member are provided. The present invention relates to a metal-resin bonded body having the following characteristics.

It should be noted that it is possible to realize a metal-resin bonded body having the following characteristics by using the copper member and the resin member according to the first embodiment described above. However, the metal-resin bonded body according to this embodiment is not limited to the metal-resin bonded body according to the first embodiment. and the blending amount are not limited to those of the resin member of the first embodiment.

The above-mentioned metal-resin joined body is a breaking load (N) measured between the above-mentioned copper member and the above-mentioned resin member by a tensile tester at room temperature (23° C.) under the conditions of a chuck distance of 60 mm and a tensile speed of 10 mm/min. is divided by the bonding area between the copper member and the resin member, and the bonding strength is 40 MPa or more. The bonding strength is preferably 45 MPa or more, more preferably 50 MPa or more, still more preferably 55 MPa or more, and particularly preferably 60 MPa or more. A metal-resin bonded body having the above properties has a high bonding strength between a copper member and a resin member.

Further, in the metal-resin joined body, a helium leak amount measured by a method conforming to ISO19095 at the joint between the copper member and the resin member is 1×10 ⁻⁶ Pa·m ³ /s or less. be. The leak amount is preferably 9×10 ⁻⁷ Pa·m ³ /s or less, more preferably 8×10 ⁻⁷ Pa·m ³ /s or less. A metal-resin bonded body having the above characteristics has high adhesion (airtightness) between a copper member and a resin member, and hardly causes gas or liquid (oil, water, etc.) leakage.

Further, the metal-resin joined body was subjected to a thermal shock test under the following conditions, and the helium leak amount measured by a method conforming to ISO 19095 at the joint between the copper member and the resin member was Less than twice the amount of helium leaked before the thermal shock test was performed. The leak amount is preferably less than 1.5 times, preferably less than 1.2 times.
(Conditions for thermal shock test)
Temperature range: -40°C to 150°C
Cycle conditions: -40°C and 150°C, holding for 30 minutes each cycle once Cycle number: 500 times

In the metal-resin joined body, the resin member is processed into a test piece of 100 mm × 100 mm × 3 mm, and the tracking resistance of the test piece evaluated according to IEC60112 is preferably greater than 200 V. , more preferably greater than 400V, even more preferably greater than 600V.

3. Uses of Resin Composition The resin composition of the present invention is used as various molded articles by molding by known molding methods such as compression molding, injection molding, and extrusion molding.

Furthermore, the above-mentioned metal-resin bonded body is suitably used for various uses in which the metal-resin bonded body is applied or its application is being considered.

Examples of the above applications include structural parts for vehicles, vehicle-mounted items, housings for electronic equipment, housings for home appliances, structural parts, mechanical parts, parts for various automobiles, parts for electronic equipment, furniture, and kitchen utensils. household goods applications, medical devices, building material parts, other structural parts, and exterior parts.

More specifically, examples of the above applications include instrument panels, console boxes, door knobs, door trims, shift levers, pedals, glove boxes, bumpers, bonnets, fenders, trunks, doors, roofs, and more. Pillars, seats, steering wheels, bus bars, terminals, motors, power converters (inverters, converters), ECU boxes, electrical parts, engine peripheral parts, drive system/gear peripheral parts, intake/exhaust system parts, and cooling system parts and so on. Also, precision electronic parts include connectors, relays, gears, and the like.

In addition, the metal-resin bonded body combines the high thermal conductivity of the copper member and the heat insulating properties of the resin member, and is used for parts used in equipment designed for optimal heat management, such as various home appliances. be able to. Examples of the above applications include home appliances such as refrigerators, washing machines, vacuum cleaners, microwave ovens, air conditioners, lighting equipment, electric water heaters, televisions, clocks, ventilators, projectors, speakers, personal computers, mobile phones, smartphones, and digital cameras. , tablet PCs, portable music players, portable game machines, chargers, and electronic information devices such as batteries.

Examples of other applications include parts for lithium-ion secondary batteries, robots, and the like.

In the following, the invention is illustrated with reference to examples. The examples should not be construed as limiting the scope of the present invention.

In the experiments below, the melting point (Tm) and glass transition temperature (Tg) of the polyamide resin were measured by the following methods.

(Melting point (Tm), glass transition temperature (Tg))
The melting point (Tm) and glass transition temperature (Tg) of the polyamide resin were measured using differential scanning calorimetry (DSC220C model, manufactured by Seiko Instruments Inc.). Specifically, approximately 5 mg of polyamide resin was sealed in an aluminum measuring pan and set for differential scanning calorimetry. Then, it was heated from room temperature to 350°C at 10°C/min. To completely melt the resin, it was held at 360°C for 3 minutes and then cooled to 30°C at 10°C/min. After 5 minutes at 30°C, it was heated a second time to 360°C at 10°C/min. The endothermic peak temperature (°C) in this second heating was taken as the melting point (Tm) of the polyamide resin, and the displacement point corresponding to the glass transition was taken as the glass transition temperature (Tg).

(Intrinsic viscosity [η])
The intrinsic viscosity [η] of the polyamide resin is obtained by dissolving 0.5 g of the polyamide resin in 50 ml of a 96.5% sulfuric acid solution, and the number of seconds the resulting solution flows down under the conditions of 25 ° C. ± 0.05 ° C. It was measured using an Ubbelohde viscometer and calculated based on the formula: [η]=ηSP/(C(1+0.205ηSP)).
[η]: Intrinsic viscosity (dl/g)
ηSP: specific viscosity C: sample concentration (g/dl)
t: number of seconds for the sample solution to flow down (seconds)
t0: Number of seconds for blank sulfuric acid to flow down (seconds)
ηSP=(t−t0)/t0

(heat of fusion (ΔH))
The heat of fusion (ΔH) of the polyamide resin was determined according to JIS K 7122 (2012) from the area of the exothermic peak of crystallization during the first heating process.

(composition)
The composition of the modified polyolefin resin, specifically, the content of ethylene and α-olefins having 3 or more carbon atoms (mol%) and the content of functional group structural units (mass%) were measured by ¹³ C-NMR. The measurement conditions are as follows.
Measuring device: Nuclear magnetic resonance device (ECP500 type, manufactured by JEOL Ltd.)
Observation nuclei: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μs (45° pulse)
Repeat time: 5.5 seconds Accumulation times: 10,000 times or more Solvent: ortho-dichlorobenzene/deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg/0.6 mL
Measurement temperature: 120°C
Chemical shift reference value: 27.50 ppm

(density)
The density of the modified polyolefin resin was measured at a temperature of 23° C. using a density gradient tube according to JIS K7112.

(Melt flow rate (MFR))
The melt flow rate (MFR: Melt Flow Rate) of the modified polyolefin resin was measured at 190°C under a load of 2.16 kg according to ASTM D1238. The unit is g/10min.

1. Synthesis/preparation of materials 1-1. Synthesis of polyamide resin (A) 2800 g (24.1 mol) of 1,6-hexanediamine, 2774 g (16.7 mol) of terephthalic acid, 1196 g (7.2 mol) of isophthalic acid, 36.6 g (0.30 mol) of benzoic acid mol), 5.7 g of sodium hypophosphite monohydrate and 545 g of distilled water were placed in an autoclave having an internal volume of 13.6 L and purged with nitrogen. Stirring was started from 190° C., and the internal temperature was raised to 250° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.03 MPa. After the reaction was continued for 1 hour, the autoclave was vented to the atmosphere through a spray nozzle installed at the bottom of the autoclave to extract low order condensates. Then, after cooling the low condensate to room temperature, the low condensate was pulverized with a pulverizer to a particle size of 1.5 mm or less and dried at 110° C. for 24 hours. The resulting low-order condensate had a water content of 4100 ppm and an intrinsic viscosity [η] of 0.15 dl/g.

Next, this low-order condensate was placed in a tray-type solid-phase polymerization apparatus, and after purging with nitrogen, the temperature was raised to 180° C. over about 1 hour and 30 minutes. After that, the reaction was allowed to proceed for 1 hour and 30 minutes, and the temperature was lowered to room temperature. The intrinsic viscosity [η] of the resulting prepolymer was 0.20 dl/g.
Thereafter, the obtained prepolymer is melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and L/D = 36 at a barrel setting temperature of 330°C, a screw rotation speed of 200 rpm, and a resin feed rate of 6 kg/h. , to obtain a polyamide resin (A-1).
The resulting polyamide resin (A-1) had an intrinsic viscosity of 1.0 dl/g, a melting point (Tm) of 330°C, a glass transition temperature (Tg) of 125°C, and a heat of fusion (ΔH) of 50 J/g. .

1-2. Synthesis of polyamide resin (B) 2800 g (24.1 mol) of 1,6-hexanediamine, 1390 g (8.4 mol) of terephthalic acid, 2581 g (15.5 mol) of isophthalic acid, 109.5 g (0.9 mol) of benzoic acid mol), 5.7 g of sodium hypophosphite monohydrate and 545 g of distilled water were placed in an autoclave having an internal volume of 13.6 L and purged with nitrogen. Stirring was started from 190° C., and the internal temperature was raised to 250° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.02 MPa. After the reaction was continued for 1 hour, the low order condensate was extracted by discharging into the atmosphere from a spray nozzle installed at the bottom of the autoclave. Thereafter, the low order condensate was cooled to room temperature, pulverized with a pulverizer to a particle size of 1.5 mm or less, and dried at 110° C. for 24 hours. The obtained low order condensate had a water content of 3000 ppm and an intrinsic viscosity [η] of 0.14 dl/g.

Next, this low-order condensate is melt-polymerized in a twin-screw extruder with a screw diameter of 30 mm and L/D = 36 at a barrel setting temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply rate of 6 kg / h. , to obtain a polyamide resin (B-1).
The resulting polyamide resin (B-1) had an intrinsic viscosity [η] of 0.68 dl/g, a melting point (Tm) not measured, a glass transition temperature (Tg) of 125° C., and a heat of fusion (ΔH) of 0 J/ was g.

1-3. Synthesis of Modified Polyolefin Resin (C) 0.63 mg of bis(1,3-dimethylcyclopentadienyl)zirconium dichloride was placed in a sufficiently nitrogen-substituted glass flask, and a toluene solution of methylaluminoxane (Al; A catalyst solution was obtained by adding 1.57 ml of 13 mmol/l) and 2.43 ml of toluene. Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a 2-liter stainless steel autoclave that was sufficiently purged with nitrogen, and the temperature in the system was raised to 80°C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml of the catalyst solution prepared above (0.0005 mmol as Zr) were injected into the system with ethylene to initiate the polymerization reaction. Polymerization was carried out at 80° C. for 30 minutes while maintaining the total pressure at 8.0 kg/cm 2 -G by continuously supplying ethylene. A small amount of ethanol was introduced into the system to terminate the polymerization, and then unreacted ethylene was purged. A white solid was precipitated by dropping the resulting solution into a large excess of methanol. This white solid was recovered by filtration and dried overnight under reduced pressure to obtain a white solid (ethylene/1-butene copolymer).

The ethylene content of the ethylene/1-butene copolymer was 96 mol %. Also, the density was 0.920 g/cm ³ , the MFR (ASTM D 1238, 190°C, 2.16 kg load) was 1.0 g/10 minutes, and the melting point was 124°C.

To 100 parts by mass of the obtained ethylene/1-butene copolymer, 0.5 parts by mass of maleic anhydride and 0.04 parts by mass of peroxide (Perhexyne 25B, manufactured by NOF Corporation, trademark) were mixed. A modified polyolefin resin (C-1) was obtained by subjecting the resulting mixture to melt-graft modification in a single-screw extruder set at 230°C.

The amount of maleic anhydride grafted to the modified polyolefin resin (C-1) measured by IR analysis was 0.8% by mass. Also, the density was 0.916 g/cm ³ , the MFR (ASTM D 1238, 190°C, 2.16 kg load) was 0.27 g/10 minutes, and the melting point (Tm) was 121°C.

1-4. Copper-based heat resistant stabilizer (D)
A mixture of 10% by mass of copper (I) iodide and 90% by mass of potassium iodide was used as a copper-based heat resistant stabilizer (D).

1-5. Reinforcement Glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-251H) was used as a reinforcement.

1-6. Crystal Nucleating Agent Talc (High Filler #5000PJ, manufactured by Matsumura Sangyo Co., Ltd.) was used as a crystal nucleating agent.

1-7. Fluidity improver The following fluidity improver was used.
・ Fluidity improver 1: sodium montanate (manufactured by Clariant, LICOMONT NAV101 “LICOMNT” is a registered trademark of the company))
・ Fluidity improver 2: 12-hydroxy calcium stearate (manufactured by Nitto Kasei Kogyo Co., Ltd., CS-6CP)

1-8. Colorants Masterbatches containing pigments were used as colorants.

2. Production of metal-resin joined body 2-1. Preparation of polyamide resin composition The above materials are mixed in a tumbler blender at the composition ratio (unit: parts by mass) shown in Table 1, and the cylinder temperature is 300 to 335 ° C. using a 30 mmφ vented twin screw extruder. It was melt-kneaded under the following conditions. After that, the kneaded product was extruded into strands and cooled in a water bath. After that, the strand was collected by a pelletizer and cut to obtain a polyamide resin composition in the form of pellets.

2-2. Production of surface-roughened copper member A copper alloy plate (thickness: 2 mm) of alloy number C1100 specified in JIS H3100:2012 was cut into a length of 45 mm and a width of 18 mm to produce a copper member. The degreased copper member was immersed in a chemical etchant (AMALFA A-10201H manufactured by MEC Co., Ltd.), washed with water, and immersed in a chemical etchant in this order. Immediately thereafter, the member was immersed in a chemical etchant for 4 minutes. Next, water washing, alkali washing (5 mass% NAOH, immersion for 20 seconds), water washing, neutralization treatment (5 mass% H ₂ SO ₄ , 20 seconds immersion), water washing, rust prevention treatment (A-10290, 1 minute) and washing with water in this order.

2-3. Production of Metal-Resin Joined Body The roughened copper member was placed in a small dumbbell metal insert mold attached to an injection molding machine (manufactured by Japan Steel Works, Ltd., J55-AD). Next, the above various polyamide resin compositions are injection molded in a mold under the conditions of a cylinder temperature of 335 ° C., a mold temperature of 170 ° C., a primary injection pressure of 90 MPa, a holding pressure of 80 MPa, and an injection speed of 25 mm / sec. A test piece was prepared in which a resin member made of polyamide resin was bonded to the surface of . The bonding area between the copper member and the resin member of this test piece was 50 mm ² .

3. Evaluation The obtained metal-resin joined bodies were evaluated according to the following criteria.

3-1. Bond strength The shear bond strength (MPa) of the prepared test piece was measured by a method conforming to ISO19095. Specifically, a tensile tester (manufactured by Aikoh Engineering Co., Ltd., model 1323) was attached with a special jig, and fractured under the conditions of room temperature (23°C), a distance between chucks of 60 mm, and a tensile speed of 10 mm/min. A load (N) was measured. The shear bond strength (MPa) was obtained by dividing the measured breaking load (N) by the area (50 mm ² ) of the bonded portion between the copper member and the resin member.

3-2. Air tightness (initial)
The helium leak property of the prepared test piece was evaluated by a method based on ISO19095. Specifically, the test piece is set in a special jig that can be sealed, He gas is applied to the sealed space at a pressure of 0.1 MPa, and the He gas that has passed through the test piece is detected by a He gas detector (Canon Anelva Co., Ltd.). It was measured by the sniffer method with HELEN M-222LD manufactured by the company. Based on the detected He gas flow rate (leak amount) 5 minutes after the start of detection, the airtightness was evaluated according to the following criteria.

〇 Detected He gas flow rate is 1×10 ⁻⁶ Pa・m ³ /s or less △ Detected He gas flow rate is more than 1×10 ⁻⁶ Pa・m ³ /s and 1×10 ⁻⁵ Pa・m ³ /s x Detected He gas flow rate is greater than 1×10 ⁻⁵ Pa·m ³ /s

3-3. Airtightness (after thermal shock test)
The He leak property of the produced test piece after the thermal shock test was evaluated by a method conforming to ISO19095. Specifically, the prepared test piece was subjected to a thermal shock test with a cooling and heating cycle under the following conditions, and the subsequent helium leak amount was measured in the same manner as the initial airtightness evaluation. The airtightness after the thermal shock test was evaluated according to the following criteria based on the ratio of the change in the leak amount after the thermal shock test to the initial leak amount.

(Conditions for thermal shock test)
Temperature range: -40°C to 150°C
Cycle conditions: -40°C and 150°C, holding for 30 minutes each cycle once Cycle number: 500 times

〇 The amount of change in the detected He gas flow rate is less than 1.2 times. △ The amount of change in the detected He gas flow rate is 1.2 times or more and less than 2 times. × The amount of change in the detected He gas flow rate is 2 times or more.

3-4. Tracking Resistance Using each synthesized polyamide resin, a test piece of 100 mm×100 mm×3 mm was produced. The tracking resistance of this test piece was evaluated according to IEC60112.

Table 1 shows the composition of the prepared polyamide resin composition, the bonding strength, airtightness (initial), airtightness (after the thermal shock test), and tracking resistance of the metal-resin bonded body.

According to the polyamide resin composition of the present invention, the resin member formed by molding the polyamide resin composition and the copper member can be strongly bonded together, and airtightness can be improved. Therefore, the present invention is expected to expand the applicability of metal-resin bonded bodies to vehicle body parts where leakage of gas, liquid, etc. is a problem, and contribute to the further spread of metal-resin bonded bodies.

Claims (7)

a resin member including a copper member having a roughened surface and a polyamide resin (A) bonded to the roughened surface of the copper member;
The breaking load (N) of the copper member and the resin member was measured by a tensile tester at room temperature (23° C.) under the conditions of a chuck distance of 60 mm and a tensile speed of 10 mm/min. The joint strength obtained by dividing by the joint area with the resin member is 40 MPa or more,
A helium leak amount measured by a method conforming to ISO19095 at the joint between the copper member and the resin member is 1×10 ⁻⁶ Pa·m ³ /s or less.
Metal-resin joint. After performing a thermal shock test under the following conditions at the joint between the copper member and the resin member, the amount of helium leakage measured by a method based on ISO 19095 is the amount of helium before the thermal shock test. 2. The metal-resin joined body according to claim 1, which is less than 1.2 times the leakage amount.
(Conditions for thermal shock test)
Temperature range: -40°C to 150°C
Cycle conditions: -40°C and 150°C, holding for 30 minutes each cycle once Cycle number: 500 times A copper member having a roughened surface, and a resin member containing a polyamide resin (A) bonded to the roughened surface of the copper member,
The resin member is
A polyamide resin (A) having a melting point (Tm) of 280° C. or higher as measured by differential scanning calorimetry (DSC), and an amount of 0.1% by mass or more and 10% by mass or less with respect to the total mass of the resin member, including modified polyolefin resin (C),
Metal-resin joint. The resin member is
A copper-based heat resistant stabilizer (D) in an amount of 0.01% by mass or more and 3% by mass or less with respect to the total mass of the resin member,
A metal-resin joined body according to any one of claims 1 to 3. The polyamide resin (A) contains a component unit (Aa) derived from a dicarboxylic acid and a component unit (Ab) derived from a diamine,
The component unit (Aa) derived from dicarboxylic acid includes a component unit derived from terephthalic acid and a component unit derived from isophthalic acid.
A metal-resin joined body according to any one of claims 1 to 4. The resin member includes the polyamide resin (A),
A polyamide resin (B) having a heat of fusion (ΔH) of 5 J/g or less as measured by differential scanning calorimetry (DSC),
A metal-resin joined body according to any one of claims 1 to 5. is a car part,
A metal-resin joined body according to any one of claims 1 to 6.