JP7011898B2 - Polyamide resin composition for metal bonding, metal resin complex and method for producing metal resin composite - Google Patents

Description

The present invention relates to a polyamide resin composition for metal bonding, a metal resin composite, and a method for producing a metal resin composite. In particular, the present invention relates to a polyamide resin composition for metal bonding, which has excellent bondability between a metal member and a resin member.

In recent years, in automobile parts and consumer parts, from the environmental aspect such as weight reduction and recycling, resinization of parts using metal and miniaturization of resin products are progressing. On the other hand, polyamide resins are excellent in chemical resistance, heat resistance, etc., and have particularly high mechanical strength and rigidity, and are therefore widely used in various equipment parts.

In recent years, in electrical and electronic equipment parts, automobile parts, and the like, a metal-resin composite in which a resin member and a metal member such as aluminum or iron are composited is often used. Combining the resin member with the metal member is advantageous not only in improving the strength of the resin member but also in terms of antistatic property, thermal conductivity, and electromagnetic wave shielding property.
In order to produce such a metal-resin composite, for example, as described in Patent Document 1, a thermoplastic resin is in-molded on a metal member to be integrally molded with the metal. However, a composite obtained by in-molding a thermoplastic polyamide resin with respect to a metal member has a drawback that the bondability between the thermoplastic polyamide resin and the metal member is poor.

Further, as a method for obtaining a composite of a resin and a metal, a method of bonding the resin to a metal part whose surface is treated with chemical etching or surface treatment with ammonia, hydrazine, pyridine, amine or the like by insert molding or the like (for example, patent). References 2 and 3) have been proposed. Further, a method (Patent Document 4) has been proposed in which the uneven shape of the metal surface is set to a specific Rsm (average length) and Rz (maximum height roughness).

Further, Patent Document 5 describes a polyamide resin having a metal layer and a carbon fiber reinforced polyamide resin layer on the surface of the metal layer, and the carbon fiber reinforced polyamide resin layer is composed of a diamine unit and a dicarboxylic acid unit. A) It contains 5 to 300 parts by weight of carbon fiber (B) with respect to 100 parts by weight, and 70 mol% or more of the diamine unit is derived from xylylene diamine and 70 mol% or more of the dicarboxylic acid unit is sebacic acid. The derived laminate is disclosed.

Patent Document 6 describes a resin composition (A) containing an aromatic polyamide resin (a) as a main component, or an inorganic filler (F) exceeding 0 parts by mass with respect to 100 parts by mass of the resin composition (A). The filler-containing resin composition (B) containing parts by mass or less is a bonded structure having a coveted surface fixed to the fine concavo-convex surface of a metal member (M) having a fine concavo-convex surface, and the resin composition ( A metal / resin composite structure in which A) or (B) satisfies the following requirement 1 and the requirement at that time is disclosed.
[Requirement 1] The melting point (Tm) observed using a differential scanning calorimeter (DSC) is 230 ° C. or higher.
[Requirement 2] Melting enthalpy ΔHf (J / g) observed using DSC and semi-crystallization in isothermal crystallization at a temperature (Tc + 15 ° C.) 15 ° C higher than the crystallization temperature (Tc) observed in DSC. Time (τ _1/2 ) satisfies the relationship of the following equation (1).

However, these methods themselves require a high degree of surface treatment on the metal surface, and even if the surface treatment is applied, the strong bonding strength between the metal member and the polyamide resin member is always stably ensured. Has an uneasy side. Further, even if the joint strength is high, it is required to have excellent mechanical strength, particularly rigidity, in automobile parts, electronic electric machine parts, and the like.

Japanese Unexamined Patent Publication No. 06-29669 Japanese Unexamined Patent Publication No. 2001-225352 Japanese Unexamined Patent Publication No. 2006-315398 International release WO2015 / 037718 Japanese Unexamined Patent Publication No. 2016-43526 Japanese Unexamined Patent Publication No. 2016-190411

The present invention is intended to solve the above problems, and is a polyamide resin composition for metal bonding capable of providing a metal resin composite having strong bonding strength and excellent rigidity, and the above-mentioned polyamide resin composition. It is an object of the present invention to provide a metal resin composite and a method for producing a metal resin composite using a polyamide resin composition for metal bonding.

As a result of the examination by the present inventor based on the above problems, the above problems have been solved by the following means <1>, preferably <2> to <16>.
<1> A polyamide resin composition for metal bonding containing 30 to 90 parts by mass of a polyamide resin, 70 to 10 parts by mass of a reinforcing filler, and talc, wherein the polyamide resin composition for metal bonding has 0 parts of the talc. . Polyamide resin composition for metal bonding, which is contained in a proportion of 1 to 10% by mass, and the polyamide resin is Tm ≤ 290 ° C., Tm-Tcc ≥ 28 ° C., and 0 J / g <ΔHm ≤ 55 J / g; , Tm, Tcc and ΔHm are the melting point of the polyamide resin, the crystallization temperature at lower temperature and the melting enthalpy, respectively.
<2> The metal bonding polyamide resin composition according to <1>, wherein the melt viscosity of the polyamide resin composition for metal bonding at a holding time of 6 minutes, a melting point of + 40 ° C. and a shear rate of 1000 (1 / sec) is ηa ≦ 400 Pa · s. Polyamide resin composition.
<3> The polyamide resin composition for metal bonding according to <1> or <2>, wherein the polyamide resin contains a semi-aromatic polyamide resin.
<4> The polyamide resin composition for metal bonding according to any one of <1> to <3>, which has a flexural modulus of 9 GPa or more according to ISO527 of the polyamide resin composition for metal bonding.
<5> The melt viscosity of the polyamide resin composition for metal bonding at a holding time of 6 minutes, a melting point of + 40 ° C. and a shear rate of 1000 (1 / sec) is ηa ≦ 350 Pa · s, <1> to <4>. The polyamide resin composition for metal bonding according to any one.
<6> The polyamide resin composition for metal bonding according to any one of <1> to <5>, wherein the reinforcing filler contains glass fiber.
<7> The polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylene diamine and the dicarboxylic acid-derived constitution. The metal bonding according to any one of <1> to <6>, wherein 70 mol% or more of the unit contains a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Polyamide resin composition.
<8> A metal member having an uneven surface and a resin member in contact with the metal member on the surface side having the unevenness are included, and the resin member includes 30 to 90 parts by mass of a polyamide resin and 70 to 70 to a reinforcing filler. The polyamide resin composition for metal bonding comprises 10 parts by mass and a polyamide resin composition for metal bonding containing talc, and the polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass, and the polyamide resin has Tm ≦ 290. A metal resin composite in which ° C., Tm-Tcc ≧ 28 ° C. and 0 J / g <ΔHm ≦ 55 J / g; where Tm, Tcc and ΔHm are the melting point of the polyamide resin, the crystallization temperature at lower temperature and melting, respectively. It is enthalpy.
<9> The metal resin complex according to <8>, wherein the polyamide resin contains a semi-aromatic polyamide resin.
<10> In <8> or <9>, the melt viscosity of the polyamide resin composition for metal bonding at a holding time of 6 minutes, a melting point of + 40 ° C. and a shear rate of 1000 (1 / sec) is ηa ≦ 400 Pa · s. The metal resin composite described.
<11> The metal-resin composite according to any one of <8> to <10>, which has a flexural modulus of 9 GPa or more according to ISO527 of the polyamide resin composition for metal bonding.
<12> The metal-resin composite according to any one of <8> to <11>, wherein the reinforcing filler contains glass fiber.
<13> The polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from xylylenediamine and the dicarboxylic acid-derived constitution. The metal resin composite according to any one of <8> to <12>, wherein 70 mol% or more of the unit contains a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. body.
<14> A polyamide resin composition for metal bonding containing 30 to 90 parts by mass of a polyamide resin, 70 to 10 parts by mass of a reinforcing filler, and talc is placed on the surface side of the metal member having irregularities on the surface. Including injection molding, the polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass, and the polyamide resin has Tm ≦ 290 ° C., Tm-Tcc ≧ 28 ° C., and A method for producing a metal resin composite in which 0 J / g <ΔHm ≦ 55 J / g; where Tm, Tcc and ΔHm are the melting point of the polyamide resin, the crystallization temperature at lower temperature and the melting enthalpy, respectively.
<15> The metal-resin composite according to <14>, wherein the polyamide resin composition for metal bonding has a holding time of 6 minutes, a melting point of + 40 ° C., and a melt viscosity at a shear rate of 1000 (1 / sec) of ηa ≦ 400 Pa · s. How to make a body.
<16> The method for producing a metal resin complex according to <14> or <15>, wherein the metal resin complex is the metal resin complex according to any one of <8> to <13>.

INDUSTRIAL APPLICABILITY According to the present invention, a polyamide resin composition for metal bonding capable of providing a metal resin composite having strong bonding strength and excellent rigidity, a metal resin composite using the polyamide resin composition for metal bonding, and a metal resin composite. It has become possible to provide a method for producing a metal-resin composite.

It is a schematic diagram of the metal resin complex produced in the Example. (A) is a view of the complex seen from above, and (b) is a view seen from the side.

Hereinafter, the contents of the present invention will be described in detail. In addition, in this specification, "-" is used in the sense that the numerical values described before and after it are included as the lower limit value and the upper limit value.

The polyamide resin composition for metal bonding of the present invention (hereinafter, may be simply referred to as “resin composition of the present invention”) includes 30 to 90 parts by mass of a polyamide resin, 70 to 10 parts by mass of a reinforcing filler, and talc. The polyamide resin composition for metal bonding, wherein the polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass, and the polyamide resin has Tm-Tcc ≥ 28 ° C. , 0J / g <ΔHm ≦ 55J / g. However, Tm, Tcc and ΔHm are the melting point of the polyamide resin, the crystallization temperature at lower temperature and the melting enthalpy, respectively.
With such a configuration, it is possible to provide a metal-resin composite having strong bonding strength and excellent rigidity when bonded to a metal member. In particular, it is also possible to produce a metal-resin composite that always and stably achieves strong bonding strength.
That is, as the polyamide resin, a polyamide resin having Tm ≦ 290 ° C., Tm−Tcc ≧ 28 ° C., and ΔHm ≦ 55 J / g is used, and the crystallization rate of the polyamide resin is adjusted by blending talc. The resin composition of the present invention can be adjusted so as to be solidified in a state where the resin is sufficiently contained in the recesses of the metal member, and the anchor effect can be effectively achieved. On the other hand, when the polyamide resin has a Tm> 295 ° C., the resin deteriorates due to retention during molding, and a deteriorated substance is mixed in the bonding surface between the metal and the resin, which hinders the bonding. Further, by setting the melt viscosity to a predetermined value or less, the resin can more sufficiently penetrate into the recesses of the metal member, and higher adhesion between the metal member and the polyamide resin composition can be achieved.

<Polyamide resin>
The resin composition of the present invention contains a polyamide resin having Tm ≤ 290 ° C., Tm-Tcc ≥ 28 ° C., and 0 J / g <ΔHm ≤ 55 J / g (hereinafter, may be referred to as "specific polyamide resin"). .. However, Tm, Tcc and ΔHm are the melting point of the polyamide resin, the crystallization temperature at lower temperature and the melting enthalpy, respectively.
The specific polyamide resin used in the present invention preferably has Tm-Tcc ≧ 30, more preferably Tm-Tcc ≧ 32, further preferably Tm-Tcc ≧ 33, and Tm-Tcc ≧ 35. It may be present, Tm-Tcc ≧ 38 or more, or Tm-Tcc ≧ 40. The upper limit of Tm-Tcc is not particularly defined, but may be, for example, 55 ≧ Tm-Tcc, 50 ≧ Tm-Tcc, or 45 ≧ Tm-Tcc.
The specific polyamide resin used in the present invention is preferably ΔHm ≦ 52 J / g. Further, 1 J / g ≦ ΔHm is preferable, 10 J / g ≦ ΔHm is more preferable, 20 J / g ≦ ΔHm is more preferable, and 28 J / g ≦ ΔHm is more preferable. By setting it in such a range, the crystallinity can be further increased.
ΔHm in the present invention is measured according to the method described in Examples described later. If the equipment described in the examples is difficult to obtain due to discontinuation of numbers or the like, other equipment having equivalent performance can be used. Hereinafter, the same applies to other measurement methods.

The lower limit of the Tm (melting point) of the specific polyamide resin used in the present invention is preferably 175 ° C. or higher, more preferably 190 ° C. or higher, and even more preferably 205 ° C. or higher. The upper limit of Tm is preferably 290 ° C or lower, more preferably 285 ° C or lower, further preferably 280 ° C or lower, and may be 270 ° C or lower. Within such a range, deterioration of the resin during molding can be effectively suppressed.
Tm in the present invention is measured according to the method described in Examples described later.
The lower limit of Tcc of the specific polyamide resin used in the present invention is preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and even more preferably 175 ° C. or higher. The upper limit of Tcc is preferably 250 ° C. or lower, more preferably 230 ° C. or lower. Within such a range, better transferability of the metal surface tends to be obtained.
Tcc in the present invention is measured according to the method described in Examples described later.

The relative viscosity of the specific polyamide resin used in the present invention is preferably 1.5 to 3.0. The lower limit of the relative viscosity is more preferably 1.6 or more, further preferably 1.8 or more, and particularly preferably 1.9 or more. The upper limit of the relative viscosity is more preferably 2.8 or less, further preferably 2.5 or less, and even more preferably 2.3 or less. Within such a range, higher mechanical properties of the molded product and better fluidity during molding can be obtained.
The relative viscosity in the present invention is measured according to the description of Examples described later.

The specific polyamide resin used in the present invention preferably has a lower limit of the number average molecular weight (Mn) of 6,000 or more, more preferably 8,000 or more, and further preferably 10,000 or more. , 15,000 or more, more preferably 20,000 or more, and even more preferably 22,000 or more. The upper limit of Mn is preferably 35,000 or less, more preferably 30,000 or less, further preferably 28,000 or less, and even more preferably 26,000 or less. Within such a range, the heat resistance, elastic modulus, dimensional stability, and molding processability of the obtained molded product become better.

The number average molecular weight (Mn) referred to here is the following formula from the terminal amino group concentration [NH ₂ ] (μ equivalent / g) and the terminal carboxyl group concentration [COOH] (μ equivalent / g) of the polyamide resin. It is calculated.
Number average molecular weight (Mn) = 2,000,000 / ([COOH] + [NH ₂ ])

The type of the specific polyamide resin used in the present invention is not particularly specified, and preferably contains at least one of an aliphatic polyamide resin and a semi-aromatic polyamide resin, and more preferably contains a semi-aromatic polyamide resin. When a semi-aromatic polyamide resin is used, the mechanical strength of the obtained molded product can be further improved.
Specific examples of the aliphatic polyamide resin include polyamide 610, polyamide 12, polyamide 46, and polyamide 11, with polyamide 610 and polyamide 12 being more preferred.
On the other hand, the semi-aromatic polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 30 to 70 mol% of the total structural unit of the diamine-derived structural unit and the dicarboxylic acid-derived structural unit is aromatic. It means that it is a structural unit containing a ring, and it is preferable that 40 to 60 mol% of the total structural unit of the diamine-derived structural unit and the dicarboxylic acid-derived structural unit is a structural unit containing an aromatic ring. By using such a semi-aromatic polyamide resin, the mechanical strength of the obtained resin molded product can be further improved.
Examples of the semi-aromatic polyamide resin include polyamide 6T / 66, polyamide 6I / 66, and a xylylenediamine-based polyamide resin described later, and a xylylenediamine-based polyamide resin is preferable.

Next, the xylylenediamine-based polyamide resin will be described.
The xylylene diamine-based polyamide resin in the present invention is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit, and 70 mol% or more of the diamine-derived structural unit is derived from the xylylene diamine. A polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms in which 70 mol% or more of the constituent unit derived from the dicarboxylic acid is used.
The diamine-derived constituent unit of the xylylenediamine-based polyamide resin is more preferably 80 mol% or more, further preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more. Derived from. The constituent unit derived from the dicarboxylic acid of the xylylene diamine-based polyamide resin is more preferably 80 mol% or more, further preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and carbon. It is derived from α, ω-linear aliphatic dicarboxylic acid having a number of 4 to 20.
The xylylenediamine is preferably paraxylylenediamine and metaxylylenediamine, and more preferably contains at least metaxylylenediamine. In the xylylenediamine-based polyamide resin used in the present invention, it is preferable that 30 mol% or more of the diamine-derived constituent units are derived from m-xylylenediamine, and 30 to 100 mol% of the diamine-derived constituent units are methylylenediamine. It is more preferable that 70 to 0 mol% is derived from paraxylylenediamine.

Examples of diamines other than metaxylylenediamine and paraxamethylenediamine that can be used as the raw material diamine component of the xylylenediamine-based polyamide resin include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, and heptamethylene. An aliphatic diamine such as diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3- Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-amino) Arocyclic diamines such as cyclohexamethylene) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane, aromatic diamines such as bis (4-aminophenyl) ether, paraphenylenediamine, bis (aminomethyl) naphthalene, etc. Etc. can be exemplified, and one kind or a mixture of two or more kinds can be used.

Examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms preferable to be used as the raw material dicarboxylic acid component of the xylylene diamine-based polyamide resin include succinic acid, glutaric acid, pimelic acid, suberic acid and adipic acid. , Adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids can be exemplified, and one kind or a mixture of two or more kinds can be used, but among these, the melting point of the polyamide resin is molded. Adipic acid or sebacic acid is more preferable because it is in an appropriate range.

Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include phthalic acid compounds such as isophthalic acid, terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid and 1,3. -Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Examples of naphthalenedicarboxylic acids such as isomers such as dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid can be exemplified, and one kind or a mixture of two or more kinds can be used.

Although the constituent units derived from diamine and the constituent units derived from dicarboxylic acid are the main components, the constituent units other than these are not completely excluded, and lactams such as ε-caprolactam and laurolactam, aminocaproic acid. Needless to say, it may contain a constituent unit derived from an aliphatic aminocarboxylic acid such as aminoundecanoic acid. Here, the main component means that among the constituent units constituting the xylylenediamine-based polyamide resin, the total number of the constituent units derived from diamine and the constituent units derived from dicarboxylic acid is the largest among all the constituent units. In the present invention, the total of the diamine-derived constituent units and the dicarboxylic acid-derived constituent units in the xylylenediamine-based polyamide resin preferably occupies 90% or more of all the constituent units, and more preferably 95% or more. ..

The resin composition of the present invention preferably contains the specific polyamide resin in an amount of 31% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more. Further, the resin composition of the present invention preferably contains the specific polyamide resin in an amount of 89% by mass or less of the resin composition.
The specific polyamide resin may contain only one kind, or may contain two or more kinds. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<Polyamide resin other than specific polyamide resin>
The resin composition of the present invention may contain a polyamide resin other than the specific polyamide resin. In particular, as an example of an embodiment, it is preferable to include another polyamide resin as the crystallization accelerator.
Examples of the polyamide resin used as the crystallization accelerator include polyamide resins satisfying Tm-Tcc <28 ° C. The polyamide resin satisfying Tm-Tcc <28 ° C. is preferably Tm-Tcc <25 ° C., and more preferably 10 ° C. <Tm-Tcc <25 ° C.
Examples of such a polyamide resin include polyamide 66, polyamide 6, and polyamide PXD10.
When a polyamide resin satisfying Tm-Tcc <28 ° C. is contained, the content is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and 5 to 15% by mass of the specific polyamide resin. Is more preferable.
As the polyamide resin satisfying Tm-Tcc <28 ° C., only one kind may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount is within the above range.

<Other resin components>
The resin composition of the present invention may contain a resin component other than the polyamide resin.
As other resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and thermoplastic resins such as polycarbonate resin and polyacetal resin can be used.
Further, an impact resistance improving agent or the like may be blended. When the resin composition of the present invention contains an impact resistance improving agent, it is preferably 1 to 20% by mass of the resin composition.
The resin composition of the present invention may be configured so as to substantially not contain a resin component other than the polyamide resin, for example, 5% by mass or less, further 1% by mass or less of the total amount of the resin component contained in the resin composition. In particular, it can be 0.4% by mass or less.

<Reinforced filler>
The resin composition of the present invention contains a reinforced filler. The reinforced filler referred to here does not include talc.
As the reinforced filler, a conventional reinforced filler for plastics can be used. Fibrous fillers such as glass fiber, carbon fiber, basalt fiber, wollastonite, and potassium titanate fiber can be preferably used.
Among them, a fibrous filler is preferable, and glass fiber is more preferable, from the viewpoint of the bondability, mechanical strength, rigidity and heat resistance of the metal resin composite.

It is more preferable to use a reinforcing filler that has been surface-treated with a surface-treating agent such as a coupling agent. The glass fiber to which the surface treatment agent is attached is preferable because it is excellent in durability, moisture heat resistance, hydrolysis resistance, and heat shock resistance.

From the viewpoint of the bondability of the metal resin composite, the glass fiber is preferably a glass fiber having an irregular cross-sectional shape in which the ratio of the major axis to the minor axis in the cross section is 1.5 to 10.
The cross-sectional shape is preferably oval, elliptical, or eyebrows, and particularly preferably an oval cross-section. Further, it is preferable that the major axis / minor axis ratio is in the range of 2.5 to 8, more preferably 3 to 6. Further, when the major axis of the cross section of the glass fiber in the molded product is D2, the minor axis is D1, and the number average fiber length is L, the aspect ratio ((L × 2) / (D2 + D1)) is preferably 10 or more. ..
The use of such flat glass fibers suppresses warpage and is particularly effective in producing a box-shaped metal-resin composite.

The reinforced filler may contain 70 to 10 parts by mass of the reinforced filler with respect to 30 to 90 parts by mass of the specific polyamide resin, and 65 to 20 parts by mass of the reinforced filler with respect to 35 to 80 parts by mass of the specific polyamide resin. It is preferable to include 60 to 25 parts by mass of the reinforcing filler with respect to 40 to 75 parts by mass of the specific polyamide resin. Further, the resin composition of the present invention preferably contains the reinforcing filler in a proportion of 20 to 50% by mass, more preferably 20 to 40% by mass.
The resin composition of the present invention may contain only one type of reinforcing filler, or may contain two or more types of reinforcing filler. When two or more kinds are contained, it is preferable that the total amount is within the above range.

<Talc>
The resin composition of the present invention contains talc. In the present invention, the crystallization rate can be adjusted by blending talc, and as a result of the resin composition solidifying in a state where it sufficiently penetrates into the unevenness of the metal member, the anchor effect between the metal member and the resin member is effective. Can be achieved.
The content of talc in the resin composition of the present invention is 0.1 to 10% by mass with respect to the resin composition. The lower limit of the talc content is preferably 0.15% by mass or more, more preferably 0.2% by mass or more, based on the resin composition. The upper limit of the talc content is preferably 5% by mass or less, more preferably 3% by mass or less, based on the resin composition. Only one type of talc may be used, or two or more types may be used in combination. In the case of two or more types, it is preferable that the total amount is within the above range.

<Release agent>
The resin composition of the present invention may further contain a mold release agent. The mold release agent is mainly used to improve the productivity of the resin composition during molding. Examples of the release agent include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils. Can be mentioned. Among these mold release agents, carboxylic acid amide compounds are particularly preferable.

Examples of the aliphatic carboxylic acid amide system include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine.
For details of the release agent, the description of paragraphs 0037 to 0042 of JP-A-2016-196563 and the description of paragraphs 0048-0058 of JP-A-2016-0783818 can be referred to, and these contents are incorporated in the present specification. ..

When blended, the lower limit of the content of the release agent is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and the upper limit is set with respect to the resin composition. It is preferably 2% by mass or less, more preferably 1.5% by mass or less. Within such a range, the mold releasability can be improved, and mold contamination during injection molding can be prevented. As the release agent, one type may be used alone or two or more types may be used in combination. When two or more types are used, it is preferable that the total amount is within the above range.

<Other ingredients>
The resin composition of the present invention may contain other components as long as it does not deviate from the gist of the present invention. Such additives include light stabilizers, antioxidants, flame retardants, UV absorbers, optical brighteners, anti-dripping agents, antistatic agents, anti-fog agents, lubricants, anti-blocking agents, and fluidity improvers. , Plasticizers, dispersants, antibacterial agents and the like. Only one kind of these components may be used, or two or more kinds thereof may be used in combination.
In the resin composition of the present invention, the contents of the resin component, the reinforcing filler, other additives, and the like are adjusted so that the total of each component is 100% by mass.

<Characteristics of polyamide resin composition for metal bonding>
The flexural modulus of the resin composition of the present invention according to ISO527 is preferably 5 GPa or more, more preferably 9 GPa or more, 10 GPa or more, or 11 GPa or more. The upper limit of the elastic modulus is not particularly defined, but for example, even if it is 20 GPa or less, further 15 GPa or less, it is a sufficiently practical level. The flexural modulus is measured according to the method described in the examples.

The melt viscosity of the polyamide resin composition for metal bonding used in the present invention at a holding time of 6 minutes, a melting point of + 40 ° C. and a shear rate of 1000 (1 / sec) is preferably 400 Pa · s or less, preferably 380 Pa · s or less. It is more preferable that there is, and it is further preferable that it is 350 Pa · s or less. By setting the melt viscosity to 400 Pa · s or less, the resin flows more effectively on the unevenness of the metal, and higher adhesion strength can be obtained. The lower limit of the melt viscosity of the specific polyamide resin is not particularly defined, but may be, for example, 40 Pa · s or more. The melt viscosity in the present invention is measured according to the description of Examples described later.

<Manufacturing method of resin composition>
The resin composition of the present invention can be produced according to a conventional method for preparing a resin composition. Usually each component and various additives added as desired are mixed well together and then melt-kneaded in a single-screw or twin-screw extruder. Further, it is also possible to prepare the resin composition of the present invention without mixing each component in advance or by mixing only a part of each component in advance and supplying the mixture 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 heating temperature for melt-kneading can usually be appropriately selected from the range of 220 to 300 ° C. If the temperature is too high, decomposition gas may be easily generated, so it is desirable to select a screw configuration in consideration of shear heat generation.

<Metal resin complex>
The metal-resin composite of the present invention includes a metal member having an uneven surface and a resin member in contact with the metal member on the surface side having the unevenness, and the resin member comprises 30 to 90 parts by mass of a polyamide resin. The polyamide resin composition for metal bonding comprises 70 to 10 parts by mass of a reinforcing filler and a polyamide resin composition for metal bonding containing talc, and the polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass. The polyamide resin has Tm ≦ 290 ° C., Tm—Tcc ≧ 28 ° C., and 0J / g <ΔHm ≦ 55J / g. Here, the polyamide resin composition for metal bonding has the same meaning as the above-mentioned polyamide resin composition for metal bonding, and the preferred range is also the same.

The metal-resin composite of the present invention can have a tensile strength of 1100 N or more when pulled under the conditions of a tensile speed of 5 mm / min and a chuck-to-chuck distance of 80 mm using a tensioning jig compliant with ISO19095. Further, the metal-resin composite of the present invention can be made to break the base metal by tension when the above-mentioned tensile test is performed.

In the present invention, the resin member is in contact with the metal member on the surface side having the unevenness, but it is preferable that the resin member is in contact with the metal member on the surface side having the unevenness. However, as will be described in detail later, when fine particles or the like are immobilized by the unevenness treatment on the surface of the metal member, or when a primer layer is provided on the surface of the metal member, the resin member is placed on the surface after the treatment or the like. The aspect of providing the metal member is also included in the aspect of being in contact with the metal member on the surface side having the unevenness.
Further, in the present invention, it is not necessary that the resin member is in contact with all the surface sides having the unevenness of the metal member, and it is needless to say that the resin member may be in contact with a part of the surface side having the unevenness.

Examples of the metal constituting the metal member include various metals such as aluminum, iron, copper, magnesium, tin, nickel, and zinc, and alloys containing these metals. Among these, the metal member preferably contains at least one of aluminum, iron, copper and magnesium, and more preferably contains aluminum. Examples of aluminum include pure Al and various Al alloys. Examples of iron include iron such as iron, steel and stainless steel, and various iron alloys. Examples of magnesium include pure magnesium and magnesium alloys.
In addition to the metal members that are all made of metal, the surface of the member made of parts other than metal on the uneven side is plated with metal such as nickel, chromium, zinc, and gold. There may be.

The shape of the metal member is not particularly limited, but a flat plate, a curved plate, a plate, a rod, a cylinder, a lump, a sheet, a film, or the like, or a metal member manufactured into a specific desired shape is preferable. .. The shape of the surface of the raw material metal member before the unevenness treatment is not particularly limited, and is not limited to a single flat surface or curved surface, and may have various shapes such as stepped portions, concave portions, and convex portions.
The thickness of the metal member is not particularly limited, but is preferably in the range of 0.05 to 100 mm, more preferably 0.1 to 50 mm, and even more preferably 0.12 to 10 mm. .. In particular, the thickness of the aluminum plate and the iron plate is preferably 0.1 to 20 mm, more preferably 0.2 to 10 mm, respectively. The above-mentioned thickness means the thickness when the metal member has a flat plate shape, and when the metal member has a non-flat plate shape, the thickness is among the metal parts in contact with the resin member on the surface side having irregularities. The thinnest thickness is preferably in the above range.

The metal member has irregularities on at least the surface in contact with the resin member (resin composition). The unevenness can be formed by subjecting a metal member to an unevenness treatment (also referred to as a roughening treatment). By such unevenness treatment, the metal member can be made to have a surface having a fine uneven shape.
The unevenness treatment (also referred to as roughening treatment) for forming fine irregularities on the surface of the metal member is not particularly limited, and various known methods can be adopted. Processing by laser etching, blast etching, etc. can be mentioned. By performing such a treatment, fine irregularities are formed on the surface of the metal member, and the above-mentioned resin composition invades into the recesses of the fine irregularities structure, penetrates deep into the recessed wall, and solidifies as it is. It is considered that strong bonding strength can be developed by fixing the metal so that it does not come off from the recess.

Further, the unevenness treatment is not limited to the etching method, in which fine particles such as metal oxides and ceramics, for example, titanium oxide and silicon oxide fine particles are dispersed on the surface of a metal member in powder or in various solvents. May be made uneven by immobilizing and physically forming a convex portion. The average particle size by weight of the fine particles is preferably 10 nm to 1 mm, more preferably 20 nm to 500 μm, and even more preferably 30 nm to 200 μm.

Various methods are known for chemical conversion treatment and chemical etching depending on the type of metal, and known methods can be used.
When the metal member is aluminum or an aluminum alloy, it is etched with an acidic aqueous solution and / or a basic aqueous solution, or an oxide film is formed on the surface, and then the oxide film is removed, and then with ammonia, hydrazine, a water-soluble amine compound, or the like. A method of processing and the like are preferably mentioned. Further, according to the alumite treatment, which is a general surface treatment method applied to aluminum, it is possible to form an uneven structure by electrolyzing aluminum at an anode using an acid.

Laser etching is formed by irradiating the surface of a metal member with laser light to perform grooving and processing under the conditions of melting and resolidifying the metal surface. For example, it is formed by repeating laser scanning in a certain scanning direction and then laser scanning in the same scanning direction or in a crossing direction a plurality of times.
Laser scanning conditions include output, scan speed, scan frequency, number of scans, hatching width (processing pitch), patterning shape, etc., and a combination of these conditions forms a fine uneven surface from the desired concave and convex parts. be able to.

The type of laser used for processing may be appropriately selected from solid-state lasers, fiber lasers, semiconductor lasers, gas lasers, and liquid lasers with various wavelengths, and the oscillation form may be a concavo-convex shape that expects continuous waves and pulse waves. It can be selected together. Further, when a continuous wave is used, a more complicated uneven structure can be obtained.

Blast etching includes shot blasting, which uses the centrifugal force of an impeller (impeller) to project blasting material, and air blasting, which uses an air compressor to project blasting material with compressed air, both of which are made of metal members. It is possible to give an uneven shape to the surface. Examples of the blast material include materials such as silica sand, alumina, aluminum cut wire, steel grid, and steel shot.
In addition, wet blast etching is performed by injecting water mixed with abrasive grains such as resin grains and metal grains toward the surface of the metal member at a high speed of several tens of m / sec to about 300 m / sec together with the processing air. It is also possible by law.

Alternatively, metal plating (for example, zinc plating) and then heating to a temperature higher than the melting point of the plated metal (zinc) to evaporate a part or most of the metal (zinc) in the plating layer. Therefore, it is also possible to obtain a metal member having a roughened surface.

The unevenness treatment (roughening treatment) exemplified above is used alone or in combination of two or more. Depending on the combination method, effects such as optimization of the uneven structure and cost reduction may be found.

The unevenness of the surface of the metal member is preferably 10 nm to 300 μm as a ten-point average roughness Rz, more preferably 20 nm or more, further preferably 30 nm or more, still more preferably 50 nm or more, still more preferably 1 μm or more, and further more. It is preferably 10 μm or more, more preferably 250 μm or less, still more preferably 200 μm or less, still more preferably 180 μm or less, still more preferably 100 μm or less, still more preferably 50 μm or less. The ten-point average roughness is measured according to the description of Examples described later.

It is also useful to surface-treat the above-mentioned metal member having irregularities on the surface with a silane coupling agent.
The silane coupling agent is not particularly limited, and 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, and 3-glyceride. Sidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-( N-Stylylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride, ureidoaminopropylethoxysilane and the like are preferably mentioned. In particular, the aluminum substrate, the iron substrate and the silane coupling agent form a bond of Al—O—Si or Fe—O—Si and are firmly bonded, and the organic functional group of the resin composition and the silane coupling agent. React and bond tightly, and a stronger bond can be achieved.

Further, by forming a film of the triazine thiol derivative on the surface of the metal having been subjected to the unevenness treatment by a wet method using a solution containing the triazine thiol derivative, further improvement of the bonding strength by chemical bonding can be achieved. *

In joining a metal member and a resin member, it is preferable not only to have an anchor effect due to unevenness but also to effectively act a polar group to form a chemical bond. For example, in order to impart CO, COO, NH ₂ groups, etc. as acidic and basic functional groups, ozone treatment, plasma treatment, flame treatment, corona discharge treatment, chemical chemical treatment, etc. are performed on the uneven metal surface. It is also useful to apply.

Further, it is also preferable to provide a primer layer on the metal member. As the material used for the primer layer, it is preferable to use an acrylic material, an epoxy material, a urethane material, a polyamide material or the like. Examples of commercially available materials used for the primer layer include Aronmelt PPET manufactured by Toagosei Co., Ltd.

<Manufacturing method of metal resin complex>
In the present invention, it can be formed by applying the above-mentioned polyamide resin composition for metal bonding to a metal member. The molding machine to be used is not particularly limited as long as it can form a metal-resin composite of a metal member and a resin composition. For example, an injection molding machine, an extrusion molding machine, a heat press molding machine, a compression molding machine, or a transfer molding machine. , Various molding machines such as a casting molding machine and a reaction injection molding machine can be used, but among these, an injection molding machine is particularly preferable.
More specifically, in the method for producing a metal resin composite of the present invention, 30 to 90 parts by mass of a polyamide resin and 70 to 10 parts of a reinforcing filler are provided on the surface side of a metal member having irregularities on its surface. A part by mass and injection molding of a polyamide resin composition for metal bonding containing talc are included, and the polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass, and the polyamide resin. Is Tm ≦ 290 ° C., Tm—Tcc ≧ 28 ° C., and 0J / g <ΔHm ≦ 55J / g. Here, the polyamide resin composition for metal bonding has the same meaning as the above-mentioned polyamide resin composition for metal bonding, and the preferred range is also the same. Further, the metal resin complex has the same meaning as the above-mentioned metal resin complex, and the preferable range is also the same.

In the case of the injection molding method, specifically, it is preferable to manufacture by an insert molding method in which a metal member is inserted into a cavity of an injection molding die and a resin composition is injected into the mold. Specifically, a mold for molding is prepared, the mold is opened, a metal member is installed (inserted) in a part thereof, and then the mold is closed, and at least a part of the resin composition is a metal member. The resin composition is injected into the mold and solidified so as to be in contact with the surface on which the uneven shape of the above is formed. After that, the metal resin composite can be obtained by opening the mold and releasing the mold.
The size of the metal member to be inserted may be appropriately determined depending on the size, structure, etc. of the target metal-resin composite. The metal member to be inserted does not have to cover the entire obtained metal-resin composite, and may be a part of the metal-resin composite.

At the time of insert molding, it is preferable to make the temperature of the molten resin composition and the temperature of the metal member as close as possible in order to improve the bonding strength. Although the method is not particularly limited, it is desirable to preheat the metal member. The heating method is not particularly limited, but for example, induction heating before insert molding of a metal member, a method of inserting a material heated by an infrared heater, a hot plate, a heating furnace, a laser, or the like, or after inserting a metal member into a mold. Examples thereof include a method of heating the vicinity of the bonding region of the metal member with the resin composition from the outside with a halogen lamp, a dryer or the like, a method of heating with a cartridge heater or the like arranged inside the mold, and the like. In particular, it is useful to locally heat only the bonding region with the resin composition. The term "local heating" includes that, depending on the heating means, the periphery including the joint region is heated, but the portion far from the joint region of the metal member is not heated.
The higher the heating temperature, the better, but it is usually 100 to 350 ° C, preferably 120 to 250 ° C, and more preferably 130 to 200 ° C.
By setting the heating temperature to 100 ° C or higher, the difference from the mold temperature can be increased, the effect of heating can be exhibited more effectively, and by setting it to 350 ° C or lower, the heating time can be shortened. Is more likely to improve, and the resin is less likely to stay, which is preferable in terms of molding.

In addition to the above, as a method for obtaining a metal-resin composite, a metal member or a resin member (resin composition) such as a laser welding method, a vibration welding method, or an ultrasonic welding method, or any of them is heated to form a composite. It is also possible to choose the method. The optimum method may be selected according to the shape and cost of the complex. In particular, the laser welding method is preferable because it can weld a local region and can also serve as local heating.

The size, shape, thickness, etc. of the metal-resin composite of the present invention thus obtained are not particularly limited, and may be plate-shaped (disk, polygon, etc.), columnar, box-shaped, bowl-shaped, etc. It may be in the shape of a tray. Further, the thickness of all parts of the complex does not have to be uniform, and the complex may be provided with reinforcing ribs or the like.

Since the metal-resin composite of the present invention has a strong bond between the metal member and the resin member and has excellent mechanical strength, it includes general household appliances, OA equipment (copiers, printers, facsimiles, etc.) and various mobile terminals. As a material for electrical and electronic parts (housings, cases, covers, etc.) such as (mobile phones, etc.) and personal computers, vehicle parts (vehicle structural parts, for example, brake pedals, etc.), mechanical parts, bicycles, and other parts such as automobiles. It is preferably used.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Aluminum plate unevenness treatment>
After degreasing, an aluminum plate (JIS A1050) with a thickness of 1.5 mm is chemically etched with an aqueous solution (manufactured by Kanto Chemical Co., Inc., aluminum etching solution) consisting of several types of mixed acids (hydrogen, sulfuric acid and other components) to perform the cleaning process. After that, an aluminum plate having an uneven surface was obtained. When the surface of the obtained aluminum plate was observed with a laser microscope (KEYENCE VK-X100) with an objective lens of 20 times and the surface roughness was measured, the ten-point average roughness Rz was 27.96 μm.

<Polyamide resin>
Polyamide resin A: Mitsubishi Gas Chemical Co., Ltd., MXD6 6000
Polyamide resin B: Manufactured according to the following synthetic example.
<< Synthesis example >>
730 g of sebacic acid is placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a raw material dropping device, a heating device, etc., and the temperature inside the flask is raised to 160 ° C. under a nitrogen atmosphere. The acid was melted. Into the flask, 680 g of mixed xylylenediamine containing 30 mol% of paraxylylenediamine and 70 mol% of metaxylylenediamine was sequentially added dropwise over about 2.5 hours. During this period, the reaction was continued by maintaining the internal temperature at a temperature always higher than the melting point of the product under stirring, and the temperature was raised to 270 ° C. at the end of the reaction. The water generated by the reaction was discharged out of the reaction system by a splitter. After completion of the dropping, the reaction was continued by stirring at a temperature of 275 ° C., and the reaction was completed after 1 hour. The product was removed from the flask, cooled with water and pelletized. The obtained polyamide resin had a relative viscosity (measured at a concentration of 1 g / 100 mL at 23 ° C. in a 96 mass% sulfuric acid solution) of 2.20.

Polyamide resin C: Manufactured according to the following synthetic example.
<< Synthesis example >>
730 g of adipic acid is charged in a flask equipped with a stirrer, a thermometer, a reflux condenser, a raw material dropping device, a heating device, etc., and the temperature inside the flask is raised to 160 ° C. under a nitrogen atmosphere. The acid was melted. Into the flask, 680 g of mixed xylylenediamine containing 30 mol% of paraxylylenediamine and 70 mol% of methylylenediamine was sequentially added dropwise over about 2.5 hours. During this period, the reaction was continued by maintaining the internal temperature at a temperature always higher than the melting point of the product under stirring, and the temperature was raised to 270 ° C. at the end of the reaction. The water generated by the reaction was discharged out of the reaction system by a splitter. After completion of the dropping, the mixture was stirred at a temperature of 275 ° C., the reaction was continued, and the reaction was completed after 1 hour. The product was removed from the flask, cooled with water and pelletized. The obtained polyamide resin had a relative viscosity (measured at a concentration of 1 g / 100 mL at 23 ° C. in a 96 mass% sulfuric acid solution) of 2.10.

Polyamide resin D: EMS, PA12 Grivory L20G

Polyamide resin E: Manufactured according to the following production example.
730 g of sebacic acid is placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a raw material dropping device, a heating device, etc., and the temperature inside the flask is raised to 160 ° C. under a nitrogen atmosphere. The acid was melted. Into the flask, 680 g of paraxylylenediamine was sequentially added dropwise over about 2.5 hours. During this period, the reaction was continued by maintaining the internal temperature at a temperature always higher than the melting point of the product under stirring, and the temperature was raised to 300 ° C. at the end of the reaction. The water generated by the reaction was discharged out of the reaction system by a splitter. After completion of the dropping, the reaction was continued by stirring at a temperature of 300 ° C., and the reaction was completed after 1 hour. The product was removed from the flask, cooled with water and pelletized. The obtained polyamide resin had a relative viscosity (measured at a concentration of 1 g / 100 mL at 23 ° C. in a 96 mass% sulfuric acid solution) of 2.20.

Polyamide resin F: manufactured by Solvay, PA6 Tabamid26AE1K
Reinforced filler B: glass fiber, ECS03T-289H, manufactured by Nippon Electric Glass Co., Ltd., fiber length 3.0 mm, fiber diameter 10 μm
Talc: Micron White # 5000S manufactured by Hayashi Kasei Co., Ltd.
Release agent: Nitto Kasei Kogyo Co., Ltd., CS-8CP

<Measurement method of relative viscosity>
1.0 g of the polyamide resin was precisely weighed and dissolved in 100 mL of a 96 mass% sulfuric acid aqueous solution with stirring at 23 ° C. After the polyamide resin was completely dissolved, 5 mL of the solution was immediately taken into a Canon Fenceke type viscometer, left in a constant temperature bath at 25 ° C. for 10 minutes, and then the drop time (t) was measured. Further, the drop time (t0) of the 96% by mass sulfuric acid aqueous solution itself was also measured in the same manner. The relative viscosity was calculated from t and t0 by the following equation.
Relative viscosity = t / t0

<Measuring method of melting point (Tm), crystallization temperature (Tcc) and melting enthalpy (ΔHm)>
The differential scanning calorimetry was measured according to JIS K7121 and K7122. Using a differential scanning calorimeter, charge the polyamide resin in the measuring pan of the differential scanning calorimeter, raise the temperature from 30 to 300 ° C. at a heating rate of 20 ° C./min, and hold at 300 ° C. for 3 minutes. After that, the peak temperature of the exothermic peak observed when the temperature is lowered at a temperature lowering rate of 10 ° C./min is measured, and the crystallization temperature (Tcc, unit: ° C.), melting point (Tm, unit: ° C.) and melting point (Tm, unit: ° C.) at the time of lowering temperature are measured. The melting enthalpy (ΔHm, unit: J / g) was determined.
As the differential scanning calorimeter, "DSC7020 AUTO" manufactured by SII Nanotechnology Inc. was used.
The results are shown in Table 1 below.

<Compound>
Each component is weighed so as to have the composition shown in Table 2 described later (the ratio of each component in Table 2 is a mass ratio), and the components other than the glass fiber are blended with a tumbler, and a twin-screw extruder ( It was charged from the root of TEM26SS manufactured by Toshiba Machinery Co., Ltd., and after melting, glass fibers were side-fed to prepare resin pellets. The temperature of the extruder was set at 300 ° C. for Comparative Example 1 and 280 ° C. for the others.

<Bending modulus>
The obtained resin pellets were dried at 120 ° C. for 4 hours, and then using an injection molding machine (100T) manufactured by FANUC, Comparative Example 1 had a cylinder temperature of 300 ° C., the others had a cylinder temperature of 280 ° C., and a mold temperature of 130 ° C. Under the conditions, an ISO test piece (4 mm thick) was injection molded. In accordance with ISO178, the flexural modulus (unit: GPa) was measured at a temperature of 23 ° C. using the ISO tensile test piece (thickness of 4 mm).

<Melting viscosity>
The melt viscosity was measured by drying the obtained resin pellets at 120 ° C. for 4 hours and then according to JIS K7199. The capillary was used under the conditions of a shear rate of 1000 (1 / sec), a melting point of + 40 ° C., and a holding time of 6 minutes using 1Φ × 20 mm.

Examples 1 to 7 and Comparative Examples 1 to 3
According to ISO19095, the aluminum plate obtained above was cut into a size of 45 mm in length × 12 mm in width × 1.5 mm in thickness, and mounted in a mold cavity.
The resin pellets (resin composition) obtained above were dried at 120 ° C. for 4 hours on the uneven surface side of the mounted aluminum plate, and the bonding area between the aluminum plate and the resin composition was 5 mm in length × 10 mm in width. Insert molding (length 45 mm × width 10 mm × thickness 3 mm) is performed so as to be, and a metal resin composite in which an aluminum plate (metal member) 1 and a resin composition (resin member) 2 are bonded as shown in FIG. 1 is formed. did.
For molding, "FANUC α-100" manufactured by FANUC was used as an injection molding machine. In Comparative Example 1, the cylinder temperature was 300 ° C., the others were 280 ° C., the mold temperature was 130 ° C., the injection speed was 30 mm / sec, and the filling time was 0. The procedure was carried out under the conditions of 58 seconds, holding pressure of 80 MPa, holding time of 6 seconds, and cooling time of 20 seconds.

<Evaluation of bondability>
Using the obtained metal-resin composite, the bondability was evaluated in accordance with ISO19095.
For the measurement, a tensile tester ("5544 type" manufactured by Instron) was used, and the aluminum plate 1 and the resin composition portion 2 that were joined and integrated were used for a tensile jig compliant with ISO19095. , Both ends in the long axis direction were clamped, and the joint strength (unit: N) was measured by pulling under the conditions of a tensile speed of 5 mm / min and a chuck distance of 80 mm. A: It was 1100 N or more (the base metal was broken by tension).
B: Joined but less than 1100N (partially broken base metal due to tension).
C: Not joined.

The results are shown in Table 2 below.

As is clear from the above results, the metal resin composite formed by using the resin composition of the present invention was excellent in the bondability between the resin composition (resin member) and the aluminum member (metal member) (Example 1). ~ 7). In particular, by setting the melt viscosity of the resin composition of the present invention to 400 Pa · s or less, the bonding strength was further improved (Examples 1 to 6).
On the other hand, when the polyamide resin did not satisfy Tm—Tcc ≧ 28 ° C. (Comparative Example 1, Comparative Example 2), no bonding was performed. When talc was not blended (Comparative Example 3), molding could not be performed.

Since the metal member and the metal member are firmly bonded to each other, the metal-resin composite of the present invention is suitable as a material for general household appliances, OA equipment, electrical and electronic products, vehicle parts such as automobiles, and mechanical parts. Used.

1: Aluminum member 2: Resin composition

Claims (19)

A polyamide resin composition for metal bonding, which is used for bonding 30 to 90 parts by mass of a polyamide resin, 70 to 10 parts by mass of a reinforcing filler , and a metal containing talc and having irregularities on the surface .
The polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass.
Polyamide resin composition for metal bonding, wherein the polyamide resin is Tm ≤ 290 ° C, Tm-Tcc ≥ 28 ° C, and 0 J / g <ΔHm ≤ 55 J / g; however, Tm, Tcc, and ΔHm are polyamides, respectively. The melting point of the resin, the crystallization temperature at lower temperature, and the melting enthalpy. The polyamide resin composition for metal bonding according to claim 1, wherein the polyamide resin composition for metal bonding has a holding time of 6 minutes, a melting point of + 40 ° C., and a melt viscosity at a shear rate of 1000 (1 / sec) of ηa ≦ 400 Pa · s. thing. The polyamide resin composition for metal bonding according to claim 1 or 2, wherein the polyamide resin contains a semi-aromatic polyamide resin. The polyamide resin composition for metal bonding according to any one of claims 1 to 3, wherein the polyamide resin composition for metal bonding has a flexural modulus of 9 GPa or more according to ISO527. The invention according to any one of claims 1 to 4, wherein the polyamide resin composition for metal bonding has a holding time of 6 minutes, a melting point of + 40 ° C., and a melt viscosity at a shear rate of 1000 (1 / sec) of ηa ≦ 350 Pa · s. The polyamide resin composition for metal bonding according to the above. The polyamide resin composition for metal bonding according to any one of claims 1 to 5, wherein the reinforcing filler contains glass fiber. The polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit.
More than 70 mol% of the constituent units derived from the diamine are derived from xylylenediamine.
The invention according to any one of claims 1 to 6, wherein 70 mol% or more of the constituent unit derived from the dicarboxylic acid contains a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Polyamide resin composition for metal bonding. The above-mentioned polyamide resin composition for metal bonding contains the polyamide resin having Tm ≤ 290 ° C., Tm-Tcc ≥ 28 ° C., and 0 J / g <ΔHm ≤ 55 J / g in a proportion of 31% by mass or more. The polyamide resin composition for metal bonding according to any one of 1 to 7. A metal member having an uneven surface and a resin member in contact with the metal member on the surface side having the unevenness are included.
The resin member comprises 30 to 90 parts by mass of a polyamide resin, 70 to 10 parts by mass of a reinforcing filler, and a polyamide resin composition for metal bonding containing talc.
The polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass.
The metal resin composite in which the polyamide resin is Tm ≦ 290 ° C., Tm—Tcc ≧ 28 ° C., and 0 J / g <ΔHm ≦ 55 J / g; where Tm, Tcc and ΔHm are the melting points of the polyamide resin, respectively. Crystallization temperature and melting enthalpy at lower temperature. The metal resin complex according to claim 9 , wherein the polyamide resin contains a semi-aromatic polyamide resin. The metal resin composite according to claim 9 or 10 , wherein the polyamide resin composition for metal bonding has a holding time of 6 minutes, a melting point of + 40 ° C., and a melt viscosity at a shear rate of 1000 (1 / sec) of ηa ≦ 400 Pa · s. .. The metal-resin composite according to any one of claims 9 to 11 , wherein the polyamide resin composition for metal bonding has a flexural modulus of 9 GPa or more according to ISO527. The metal-resin composite according to any one of claims 9 to 12 , wherein the reinforcing filler contains glass fiber. The polyamide resin is composed of a diamine-derived structural unit and a dicarboxylic acid-derived structural unit.
More than 70 mol% of the constituent units derived from the diamine are derived from xylylenediamine.
The invention according to any one of claims 9 to 13 , wherein 70 mol% or more of the constituent unit derived from the dicarboxylic acid contains a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Metal resin composite. The above-mentioned polyamide resin composition for metal bonding contains the polyamide resin having Tm ≤ 290 ° C., Tm-Tcc ≥ 28 ° C., and 0 J / g <ΔHm ≤ 55 J / g in a proportion of 31% by mass or more. The metal resin composite according to any one of 9 to 14. A polyamide resin composition for metal bonding containing 30 to 90 parts by mass of a polyamide resin, 70 to 10 parts by mass of a reinforcing filler, and talc is injection-molded on the surface side of the metal member having irregularities on the surface. Including that
The polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass.
A method for producing a metal resin composite in which the polyamide resin is Tm ≦ 290 ° C., Tm—Tcc ≧ 28 ° C., and 0 J / g <ΔHm ≦ 55 J / g; however, Tm, Tcc and ΔHm are polyamide resins, respectively. Melting point, crystallization temperature at lower temperature and melting enthalpy. The production of the metal resin composite according to claim 16 , wherein the polyamide resin composition for metal bonding has a holding time of 6 minutes, a melting point of + 40 ° C., and a melt viscosity at a shear rate of 1000 (1 / sec) of ηa ≦ 400 Pa · s. Method. The method for producing a metal-resin composite according to claim 16 or 17 , wherein the metal-resin composite is the metal-resin composite according to any one of claims 8 to 13. The above-mentioned polyamide resin composition for metal bonding contains the polyamide resin having Tm ≤ 290 ° C., Tm-Tcc ≥ 28 ° C., and 0 J / g <ΔHm ≤ 55 J / g in a proportion of 31% by mass or more. The method for producing a metal resin composite according to any one of 16 to 18.

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