JP2018177867A - Polyamide resin composition for metal conjugation, metal resin composite, and manufacturing method of metal resin composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a polyamide resin composition for metal conjugation capable of providing a metal resin composite having strong conjugation strength and excellent rigidity; and the metal resin composite and a manufacturing method of the metal resin composite, using the polyamide resin composition for metal conjugation.SOLUTION: There is provided a polyamide resin composition for metal conjugation containing 30 to 90 pts.mass of a polyamide resin, 70 to 10 pts.mass of a reinforced filler, and talc of 0.1 to 10 mass%, in which the polyamide resin has Tm≤290°C, Tm-Tcc≥28°C, and 0 J/g<ΔHm≤55 J/g, where Tm, Tcc and ΔHm are melting point of the polyamide resin, crystallization temperature during temperature fall, and melting enthalpy, respectively.SELECTED DRAWING: Figure 1

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 and the like which are excellent in the bonding property of a metal member and a resin member.

  In recent years, in automobile parts and consumer parts, from the viewpoint of weight reduction and recycling, plasticization of parts using metal and miniaturization of resin products are progressing. On the other hand, polyamide resins are excellent in chemical resistance, heat resistance and the like, and in particular, have high mechanical strength and rigidity, and thus are widely used in various device parts.

In recent years, metal-resin composites in which a resin member and a metal member such as aluminum or iron are combined are often used in electric / electronic equipment parts, automobile parts and the like. The compounding of the resin member with the metal member is advantageous also from the viewpoints of electrostatic prevention, thermal conductivity, and electromagnetic wave shielding, in addition to the improvement of the strength of the resin member.
In order to produce such a metal-resin composite, for example, as described in Patent Document 1, integral molding with a metal is carried out by in-molding a thermoplastic resin on a metal member. However, a composite in which a thermoplastic polyamide resin is simply in-mold molded to a metal member has a disadvantage that the bonding property between the thermoplastic polyamide resin and the metal member is poor.

  In addition, as a method of obtaining a composite of resin and metal, there is a method of joining a resin to a metal component which has been subjected to chemical treatment on the metal surface or surface treated with ammonia, hydrazine, pyridine, amine or the like by insert molding etc. References 2 and 3) have been proposed. In addition, a method (Patent Document 4) in which the concavo-convex shape of the metal surface is set to a specific Rsm (average length) and Rz (maximum height roughness) is also proposed.

  Furthermore, Patent Document 5 has a metal layer and a polyamide resin layer having a carbon fiber reinforced polyamide resin layer on the surface of the metal layer, wherein the carbon fiber reinforced polyamide resin layer comprises a diamine unit and a dicarboxylic acid unit ( A) 5 to 300 parts by weight of carbon fiber (B) per 100 parts by weight, 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 Derived laminates are disclosed.

In Patent Document 6, a resin composition (A) containing an aromatic polyamide resin (a) as a main component, or 100 parts by mass of the inorganic composition (F) with respect to 100 parts by mass of the resin composition (A) The filler-containing resin composition (B) comprising a part by mass or less is a bonded structure having a craving surface fixed to the fine asperity surface of the metal member (M) having the fine asperity surface, comprising the resin composition ( A metal / resin composite structure is disclosed in which A) or (B) meets the following requirement 1 and requirements at the same time.
[Requirement 1] The melting point (Tm) observed using a differential scanning calorimeter (DSC) is 230 ° C. or more.
[Requirement 2] Melting enthalpy ΔHf (J / g) observed using DSC and semicrystallization in isothermal crystallization at a temperature (Tc + 15 ° C) 15 ° C higher than the crystallization temperature (Tc) observed in DSC The 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 when the surface treatment is carried out, to always stably secure strong bonding strength between the metal member and the polyamide resin member. There is an uneasy side. In addition, even if the bonding strength is high, it is required that the automobile parts and the electronic and electric equipment parts and the like be excellent in mechanical strength, particularly rigidity.

Japanese Patent Application Publication No. 06-29669 JP 2001-225352 A JP, 2006-315398, A International Publication WO2015 / 037718 JP, 2016-43526, A JP, 2016-190411, A

  The present invention is intended to solve the above-mentioned problems, and has a strong bonding strength and can provide a metal resin composite excellent in rigidity, and a polyamide resin composition for metal bonding, and the above An object of the present invention is to provide a method for producing a metal resin composite and a metal resin composite using a polyamide resin composition for metal bonding.

Based on the above problems, as a result of investigations by the present inventor, the problems are solved by the following means <1>, preferably by <2> to <16>.
A polyamide resin composition for metal bonding comprising 30 to 90 parts by weight of a <1> polyamide resin, 70 to 10 parts by weight of a reinforcing filler, and talc, wherein the polyamide resin composition for metal bonding is the talc 0 A polyamide resin composition for metal bonding, containing at a ratio of 1 to 10% by mass, wherein the polyamide resin has Tm ≦ 290 ° C., Tm-Tcc ≧ 28 ° C., and 0 J / g <ΔHm ≦ 55 J / g; , Tm, Tcc, and ΔHm are the melting point, crystallization temperature upon cooling, and enthalpy of melting, respectively, of the polyamide resin.
<2> The metal bonding according to <1>, wherein the melt viscosity of the polyamide resin composition for metal bonding at a holding time of 6 minutes, melting point + 40 ° C. and shear rate of 1000 (1 / sec) is ηa ≦ 400 Pa · s Polyamide resin composition.
The polyamide resin composition for metal joining as described in <1> or <2> in which the <3> above-mentioned polyamide resin contains semi-aromatic polyamide resin.
The polyamide resin composition for metal joining as described in any one of <1>-<3> whose bending elastic modulus according to ISO527 of <4> said polyamide resin composition for metal joining is 9 GPa or more.
The melt viscosity of 粘度 a 前 記 350 Pa · s at a retention time of 6 minutes, a melting point of + 40 ° C and a shear rate of 1000 (1 / sec) of the polyamide resin composition for <5> metal bonding of <1> to <4> The polyamide resin composition for metal joining as described in any one.
The polyamide resin composition for metal joining as described in any one of <1>-<5> in which the <6> above-mentioned reinforcement filler contains glass fiber.
<7> The polyamide resin is composed of a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid, and 70 mol% or more of the constituent unit derived from the diamine is derived from xylylene diamine, and a composition derived from the dicarboxylic acid For metal bonding according to any one of <1> to <6>, wherein 70 mol% or more of the units include a polyamide resin derived from a C 4 to C 20 α, ω-linear aliphatic dicarboxylic acid Polyamide resin composition.
The metal member which has an unevenness | corrugation in the <8> surface, and the resin member which is in contact with the said metal member and the surface side which has the said unevenness | corrugation are included, The said resin member is 30-90 mass parts of polyamide resin, The reinforcement filler 70- The polyamide resin composition for metal joining containing 10 parts by mass and talc, wherein the polyamide resin composition for metal joining contains 0.1% to 10% by mass of the talc, and the polyamide resin has Tm ≦ 290. C., Tm-Tcc.gtoreq.28.degree. C., and 0 J / g <.DELTA.Hm.ltoreq.55 J / g; however, Tm, Tcc and .DELTA.Hm are respectively the melting point of polyamide resin, crystallization temperature upon cooling and melting, and melting It is an enthalpy.
The metal resin composite as described in <8> in which <9> said polyamide resin contains semi-aromatic polyamide resin.
In <8> or <9>, the melt viscosity of the <10> polyamide resin composition for metal bonding is ηa ≦ 400 Pa · s at a holding time of 6 minutes, a melting point of + 40 ° C. and a shear rate of 1000 (1 / sec). Metal resin composite as described.
The metal resin complex as described in any one of <8>-<10> whose bending elastic modulus according to ISO527 of the <11> above-mentioned polyamide resin composition for metal joining is 9 GPa or more.
The metal resin composite as described in any one of <8>-<11> in which the <12> above-mentioned reinforcement filler contains glass fiber.
<13> The polyamide resin is composed of a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid, and 70 mol% or more of the constituent unit derived from the diamine is derived from xylylene diamine, and a composition derived from the dicarboxylic acid The metal resin composite according to any one of <8> to <12>, wherein 70 mol% or more of the unit comprises a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms body.
The polyamide resin composition for metal joining which contains 30-90 mass parts of polyamide resin, 70-10 mass parts of reinforcement fillers, and talc on the surface side which has the said unevenness of the metal member which has an unevenness | corrugation in <14> surface Injection molding, the polyamide resin composition for metal bonding contains the talc at a ratio of 0.1 to 10% by mass, the polyamide resin has Tm ≦ 290 ° C., Tm-Tcc ≧ 28 ° C., and A method for producing a metal resin complex, wherein 0 J / g <ΔHm ≦ 55 J / g, provided that Tm, Tcc and ΔHm are the melting point, crystallization temperature upon cooling and melting enthalpy, respectively, of the polyamide resin.
The metal resin composite as described in <14> whose melt viscosity in the holding time 6 minutes, melting | fusing point +40 degreeC, and shear rate 1000 (1 / sec) of <15> said polyamide resin composition for metal joining is eta a <= 400 Pa.s. How to make the body.
The manufacturing method of the metal resin complex as described in <14> or <15> whose <16> metal resin complex is a metal resin complex as described in any one of <8>-<13>.

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

It is the schematic of the metal resin complex produced in the Example. (A) is the figure which looked at the complex from the top, (b) is the figure 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 meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

The polyamide resin composition for metal bonding of the present invention (hereinafter sometimes referred to simply as "the resin composition of the present invention") comprises 30 to 90 parts by mass of a polyamide resin, 70 to 10 parts by mass of a reinforcing filler, and talc A polyamide resin composition for metal bonding, wherein the polyamide resin composition for metal bonding contains the talc in a ratio of 0.1 to 10% by mass, and the polyamide resin has Tm-Tcc ≧ 28 ° C., And 0 J / g <ΔHm ≦ 55 J / g. However, Tm, Tcc and ΔHm are the melting point, crystallization temperature at the time of temperature decrease and melting enthalpy, respectively, of the polyamide resin.
By adopting such a configuration, it is possible to provide a metal resin composite which has strong bonding strength and is excellent in rigidity when it is bonded to a metal member. In particular, it also becomes possible to produce a metal-resin composite which always achieves stable bonding strength.
That is, the crystallization rate of the polyamide resin is adjusted by blending talc with a polyamide resin having Tm ≦ 290 ° C., Tm-Tcc ≧ 28 ° C. and ΔHm ≦ 55 J / g as the polyamide resin. The resin composition of the present invention is adjusted so that it can be solidified in a state where the resin is sufficiently intruded into the concave portion 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 is deteriorated by retention during molding, and a deteriorated material is mixed in the bonding surface of the metal and the resin, thereby inhibiting the bonding. Furthermore, by setting the melt viscosity to a predetermined value or less, the resin can more sufficiently enter the recess 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 (hereinafter sometimes referred to as "specific polyamide resin") having Tm ≦ 290 ° C., Tm-Tcc ≧ 28 ° C., and 0 J / g <ΔHm ≦ 55 J / g. . However, Tm, Tcc and ΔHm are the melting point, crystallization temperature at the time of temperature decrease and melting enthalpy, respectively, of the polyamide resin.
The specific polyamide resin used in the present invention is preferably Tm-Tcc ≧ 30, more preferably Tm-Tcc ≧ 32, still more preferably Tm-Tcc ≧ 33, and Tm-Tcc ≧ 35. Or Tm-Tcc3838 or more, or Tm-Tcc ≧ 40. The upper limit of Tm-Tcc is not particularly limited, but may be, for example, 5555Tm-Tcc, 50 ≧ Tm-Tcc, or 45 ≧ Tm-Tcc.
The specific polyamide resin used in the present invention preferably has 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 as such a range, crystallinity can be made higher.
The ΔHm in the present invention is measured according to the method described in the examples described later. When the devices described in the embodiments are difficult to obtain due to disuse, etc., other devices having similar performance can be used. The same applies to the other measurement methods below.

The lower limit of the Tm (melting point) of the specific polyamide resin used in the present invention is preferably 175 ° C. or more, more preferably 190 ° C. or more, and still more preferably 205 ° C. or more. 290 degrees C or less is preferable, 285 degrees C or less is more preferable, 280 degrees C or less is further more preferable, and the upper limit of said Tm may be 270 degrees C or less. By setting it as such a range, deterioration of resin can be effectively suppressed at the time of shaping | molding.
Tm in the present invention is measured according to the method described in the examples described later.
The lower limit of Tcc of the specific polyamide resin used in the present invention is preferably 140 ° C. or more, more preferably 150 ° C. or more, and still more preferably 175 ° C. or more. 250 degrees C or less is preferable and, as for the upper limit of said Tcc, 230 degrees C or less is more preferable. With such a range, a better metal surface transferability tends to be obtained.
Tcc in the present invention is measured according to the method described in the examples below.

The relative viscosity of the specific polyamide resin used in the present invention is preferably 1.5 to 3.0. The lower limit value 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 value of the relative viscosity is more preferably 2.8 or less, further preferably 2.5 or less, and still more preferably 2.3 or less. Within such a range, higher mechanical properties of the molded article and better flowability at the time of molding can be obtained.
The relative viscosity in the present invention is measured according to the description of the examples described later.

  The lower limit of the number average molecular weight (Mn) of the specific polyamide resin used in the present invention is preferably 6,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more. Is more preferably 15,000 or more, still more preferably 20,000 or more, and even more preferably 22,000 or more. 35,000 or less is preferable, 30,000 or less is more preferable, 28,000 or less is more preferable, and 26,000 or less is still more preferable. Within such a range, the heat resistance, modulus of elasticity, dimensional stability, and moldability of the resulting molded article become better.

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

The type of specific polyamide resin used in the present invention is not particularly limited, and preferably contains at least one of an aliphatic polyamide resin and a semiaromatic polyamide resin, and more preferably contains a semiaromatic polyamide resin. Use of a semiaromatic polyamide resin can further improve the mechanical strength of the resulting molded article.
Specific examples of the aliphatic polyamide resin include polyamide 610, polyamide 12, polyamide 46, polyamide 11 and the like, and polyamide 610 and polyamide 12 are more preferable.
On the other hand, a semi-aromatic polyamide resin is composed of a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid, and 30 to 70 mol% of the total constituent unit of the constituent unit derived from a diamine and the constituent unit derived from a dicarboxylic acid 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 structural unit derived from a diamine and the structural unit derived from a dicarboxylic acid is a structural unit containing an aromatic ring. By using such a semiaromatic polyamide resin, the mechanical strength of the resin molded product obtained can be further improved.
Examples of semi-aromatic polyamide resins include polyamide 6T / 66, polyamide 6I / 66, and xylylenediamine-based polyamide resin described later, and the like, and xylylenediamine-based polyamide resin is preferable.

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

  As a diamine other than metaxylylenediamine and paraxylylenediamine which can be used as a raw material diamine component of xylylenediamine-based polyamide resin, tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylene can be used. Aliphatic diamines such as diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 1,3-butadiene Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) meta Alicyclic diamines such as 2, 2-bis (4-aminocyclohexyl) propane, bis (aminomethyl) decalin, bis (aminomethyl) tricyclodecane, bis (4-aminophenyl) ether, paraphenylene diamine, bis Examples thereof include aromatic diamines such as (aminomethyl) naphthalene and the like, and one or more types can be mixed and used.

  Examples of preferred α, ω-linear aliphatic dicarboxylic acids having 4 to 20 carbon atoms for use as raw material dicarboxylic acid components of xylylene diamine-based polyamide resins include, for example, succinic acid, glutaric acid, pimelic acid, suberic acid and azelaic acid And aliphatic dicarboxylic acids such as adipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc., and one or two or more thereof may be mixed and used. Among these, the melting point of the polyamide resin is molded and processed. Adipic acid or sebacic acid is more preferable because it is in the range appropriate for

  Examples of the dicarboxylic acid component other than α, ω- straight chain 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, 1, 3 -Naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 1,7-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 2,3-naphthalene Examples thereof include naphthalene dicarboxylic acids such as dicarboxylic acids, isomers such as 2,6-naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid, and the like, and one kind or a mixture of two or more kinds can be used.

  In addition, although it comprises as a main component the structural unit derived from diamine and the structural unit derived from dicarboxylic acid, it does not exclude completely the structural units other than these, Lactams, such as (epsilon) -caprolactam and lauro lactam, aminocaproic acid It goes without saying that a structural unit derived from aliphatic aminocarboxylic acids such as aminoundecanoic acid may be contained. Here, the main component means that the total number of the structural unit derived from a diamine and the structural unit derived from a dicarboxylic acid among the structural units constituting the xylylene diamine-based polyamide resin is the largest among all the structural units. In the present invention, in the xylylenediamine-based polyamide resin, the total of the constituent unit derived from a diamine and the constituent unit derived from a dicarboxylic acid preferably accounts for 90% or more of the total constituent units, and more preferably 95% or more. .

The resin composition of the present invention preferably contains 31% by mass or more of the specific polyamide resin, more preferably 35% by mass or more, and still more preferably 40% by mass or more of the resin composition. Moreover, it is preferable that the resin composition of this invention contains 89 mass% or less of specific polyamide resins of a resin composition.
The specific polyamide resin may contain only one kind, or two or more kinds. When it contains 2 or more types, it is preferable that a total amount becomes said range.

<Polyamide resin other than specified polyamide resin>
The resin composition of the present invention may contain a polyamide resin other than the specific polyamide resin. In particular, it is mentioned as an example of a preferred embodiment that other polyamide resin is included as a crystallization accelerator.
As a polyamide resin used as a crystallization promoter, the polyamide resin which satisfy | fills Tm-Tcc <28 degreeC is illustrated. 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 polyamide resin include polyamide 66, polyamide 6, polyamide PXD10 and the like.
When the polyamide resin satisfying Tm-Tcc <28 ° C. is contained, the content is preferably 1 to 20% by mass of the specific polyamide resin, more preferably 1 to 15% by mass, and 5 to 15% by mass. It is further preferred that
The polyamide resin satisfying Tm-Tcc <28 ° C. may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

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

<Reinforcing filler>
The resin composition of the present invention comprises a reinforcing filler. The reinforcing filler referred to here does not include talc.
As the reinforcing filler, a conventional plastic reinforcing filler can be used. Preferably, fibrous fillers such as glass fibers, carbon fibers, basalt fibers, wollastonite and potassium titanate fibers can be used.
Among them, in view of the bonding property of the metal-resin composite, mechanical strength, rigidity and heat resistance, a fibrous filler is preferable, and glass fiber is more preferably used.

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

The glass fiber is also preferably a glass fiber having an anisotropic cross-sectional shape in which the ratio of the major axis to the minor axis in the cross section is 1.5 to 10, from the viewpoint of the bonding property of the metal resin composite.
The cross-sectional shape is preferably an oval, oval, or cocoon-shaped cross section, and particularly preferably an oval cross section. In addition, it is preferable that the major axis / minor axis ratio is in the range of 2.5 to 8, more preferably 3 to 6. Furthermore, when the major axis of the cross section of the glass fiber in the molded article 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. .
When such flat glass fibers are used, warpage is suppressed, which is particularly effective in producing a box-shaped metal resin composite.

The reinforcing filler contains 70 to 10 parts by mass of the reinforcing filler with respect to 30 to 90 parts by mass of the specific polyamide resin, and includes 65 to 20 parts by mass of the reinforcing filler with respect to 35 to 80 parts by mass of the specific polyamide resin Preferably, 60 to 25 parts by mass of the reinforcing filler is more preferably contained with respect to 40 to 75 parts by mass of the specific polyamide resin. The resin composition of the present invention preferably contains a reinforcing filler in a proportion of 20 to 50% by mass of the composition, and more preferably in a proportion of 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. When it contains 2 or more types, it is preferable that a total amount becomes said range.

<Talc>
The resin composition of the present invention contains talc. In the present invention, by blending talc, the crystallization rate can be adjusted, and as a result of the resin composition solidifying in a state of being sufficiently intruded in the unevenness of the metal member, the anchor effect of 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 content of the talc is preferably 0.15% by mass or more, and more preferably 0.2% by mass or more, based on the resin composition. The upper limit of the content of the talc is preferably 5% by mass or less, and more preferably 3% by mass or less, based on the resin composition. Talc may be used alone or in combination of two or more. In the case of two or more types, the total amount is preferably in the above range.

<Release agent>
The resin composition of the present invention may further contain a release agent. The mold release agent is mainly used to improve the productivity at the time of molding of the resin composition. As the releasing agent, for example, aliphatic carboxylic acid amide type, aliphatic carboxylic acid, ester of aliphatic carboxylic acid and alcohol, aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15000, polysiloxane silicone oil, etc. It can be mentioned. Among these releasing agents, in particular, carboxylic acid amide compounds are preferable.

Examples of aliphatic carboxylic acid amides include compounds obtained by the dehydration reaction of higher aliphatic monocarboxylic acids and / or polybasic acids with diamines.
The details of the release agent can be referred to the description of paragraphs 0037 to 0042 of JP-A-2016-196563 and the description of paragraphs 0048-0058 of JP-A-2016-078318, the contents of which are incorporated herein. .

  The lower limit of the content of the releasing agent to the resin composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and the upper limit is Preferably it is 2 mass% or less, More preferably, it is 1.5 mass% or less. By setting it in such a range, releasability can be improved, and mold contamination at the time of injection molding can be prevented. The mold release agent may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes said range.

<Other ingredients>
The resin composition of the present invention may contain other components without departing from the spirit of the present invention. As such additives, light stabilizers, antioxidants, flame retardants, ultraviolet light absorbers, fluorescent whitening agents, anti-drip agents, antistatic agents, anti-fogging agents, lubricants, anti-blocking agents, fluidity improvers , Plasticizers, dispersants, antibacterial agents and the like. One of these components may be used alone, or two or more thereof may be used in combination.
In the resin composition of the present invention, the contents of the resin component, the reinforcing filler, and other additives are adjusted so that the total of each component is 100% by mass.

<Characteristics of polyamide resin composition for metal bonding>
The flexural modulus according to ISO 527 of the resin composition of the present invention is preferably 5 GPa or more, more preferably 9 GPa or more, can be 10 GPa or more, and can be 11 GPa or more. The upper limit of the elastic modulus is not particularly limited, but for example, 20 GPa or less, and even 15 GPa or less is sufficiently practical level. 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 retention 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, and 380 Pa · s or less It is more preferable that the pressure be 350 Pa · s or less. By setting the melt viscosity to 400 Pa · s or less, the resin flows more effectively to the metal asperities, and higher adhesion strength can be obtained. The lower limit of the melt viscosity of the specific polyamide resin is not particularly limited, but may be, for example, 40 Pa · s or more. The melt viscosity in the present invention is measured in accordance with the description of examples described later.

<Method for Producing Resin Composition>
The production of the resin composition of the present invention can be carried out according to a conventional method of preparation of a resin composition. Usually, the components and optionally added various additives are combined and intimately mixed, and then melt-kneaded in a single- or twin-screw extruder. Alternatively, the resin composition of the present invention can be prepared without mixing each component in advance, or mixing only a part of each component in advance, supplying it to an extruder using a feeder, and melt-kneading it. .
In addition, when using fibrous reinforcement fillers, such as glass fiber, it is also preferable to supply from the side feeder in the middle of the cylinder of an extruder.

  The heating temperature at the time of melt-kneading can be appropriately selected usually from the range of 220 to 300 ° C. If the temperature is too high, decomposition gas may be easily generated, and it is desirable to select a screw configuration considering shear heat generation and the like.

<Metal resin composite>
The metal resin composite of the present invention includes a metal member having irregularities on the surface, and a resin member in contact with the metal member on the surface side having the irregularities, and the resin member contains 30 to 90 parts by mass of polyamide resin And 70 to 10 parts by mass of a reinforcing filler and a polyamide resin composition for metal bonding containing talc, wherein 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 0 J / g <ΔHm ≦ 55 J / g. The polyamide resin composition for metal bonding here is synonymous with the above-mentioned polyamide resin composition for metal bonding, and the preferable range is also the same.

  The metal resin composite of the present invention can have a tensile strength of 1100 N or more when it is pulled under the conditions of a tensile speed of 5 mm / minute and a distance between chucks of 80 mm using a tensile jig in accordance with ISO19095. The metal-resin composite of the present invention can be base material-broken 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 side having the asperities, but it is preferable that the resin member is in contact with the surface on the side having the asperities. However, as described later in detail, when fine particles and the like are fixed by the surface roughening treatment of the metal member, or when a primer layer is provided on the surface of the metal member, the resin member is applied to the surface after such treatment. The aspect provided is also included in the aspect which is in contact with the metal member on the side having the unevenness.
Further, in the present invention, it is not necessary that the resin member is in contact with all the surface side of the metal member having the unevenness, and it is needless to say that the resin member may be in contact with a part of the surface side with the unevenness.

As a metal which comprises a metallic member, various metals, such as aluminum, iron, copper, magnesium, tin, nickel, zinc, and the alloy containing these metals are mentioned. Among these, the metal member preferably contains at least one of aluminum, iron, copper and magnesium, and more preferably contains aluminum. Aluminum includes pure Al and various Al alloys. Examples of iron include iron such as iron, steel, stainless steel, and various iron alloys. Magnesium includes pure magnesium and magnesium alloys.
Moreover, the metal member is a member plated with a metal, such as nickel, chromium, zinc, gold or the like, in addition to the one in which the whole is made of metal, the surface on the uneven side of the member made of a part other than metal. It may be.

The shape of the metal member is not particularly limited, but flat plate, curved plate, plate, rod, cylinder, block, sheet, film and the like, or those manufactured in a desired specific shape are preferable. . The shape of the surface of the raw metal member surface before the roughening treatment is not particularly limited, and is not limited to a single flat surface or a 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 still more preferably 0.12 to 10 mm. . In particular, in the case of an aluminum plate and an iron plate, the thickness is preferably 0.1 to 20 mm, and more preferably 0.2 to 10 mm. The thickness means the thickness when the metal member is flat, and when the metal member is other than flat, among the metal members, among the metal portions which are in contact with the resin member on the side having the unevenness. The thinnest thickness is preferably in the above range.

The metal member has irregularities at least on the surface in contact with the resin member (resin composition). The unevenness can be formed by applying an unevenness treatment (also referred to as roughening treatment) to a metal member. By such a concavo-convex treatment, the metal member can have a fine concavo-convex surface.
The concavo-convex treatment (also referred to as roughening treatment) for forming fine concavities and convexities on the surface of the metal member is not particularly limited, and various known methods can be adopted, for example, chemical conversion treatment or chemical etching, The processing by laser etching, blast etching, etc. is mentioned. By this treatment, fine irregularities are formed on the surface of the metal member, and the resin composition described above intrudes into the recesses of the fine asperity structure, penetrates the depth of the recess wall, and solidifies as it is. It is thought that strong joint strength can be expressed by fixing without fixing the recess.

  In addition to the etching method, the surface of the metal member is not only an etching method, but fine particles of metal oxide, ceramics, etc., for example, titanium oxide, silicon oxide fine particles or powders dispersed in various solvents. And may be made uneven by physically forming a convex portion. 10 nm-1 mm are preferable, as for the number weight average particle diameter of microparticles | fine-particles, 20 nm-500 micrometers are more preferable, and 30 nm-200 micrometers are more preferable.

With regard to chemical conversion treatment and chemical etching, various methods are known depending on the type of metal, and known methods can be used.
When the metal member is aluminum or an aluminum alloy, etching is performed with an acidic aqueous solution and / or a basic aqueous solution, or an oxide film is formed on the surface, then the oxide film is removed, and then ammonia, hydrazine, water-soluble amine compound, etc. The method of processing etc. are mentioned preferably. In addition, according to alumite treatment which is a general surface treatment method applied to aluminum, it is possible to form a concavo-convex structure by electrolyzing aluminum with an acid using an acid.

The laser etching is formed by irradiating the surface of the metal member with a laser beam and processing the metal surface under the conditions of grooving, melting and resolidification. For example, it is formed by repeating laser scanning in the same scanning direction or cross direction a plurality of times after performing laser scanning processing in a certain scanning direction.
The conditions for laser scanning include output, scan speed, scan frequency, number of scans, hatching width (processing pitch), patterning shape, etc. With these combinations, a fine uneven surface is formed from the desired recesses and protrusions be able to.

  Further, the type of laser used for processing may be appropriately selected from solid laser, fiber laser, semiconductor laser, gas laser, and various wavelengths of liquid laser, and the oscillation form is also a concavo-convex shape that expects continuous wave or pulse wave. It can be selected together. Moreover, when a continuous wave is used, it is possible to set it as a more complicated uneven structure.

As the blast etching, there are shot blasting treatment for projecting a blasting material by utilizing centrifugal force of an impeller (impeller), and air blasting treatment for projecting a blasting material by compressed air using an air compressor. It is possible to provide an uneven shape on the surface. As a blasting material, materials such as silica sand, alumina, aluminum cut wire, steel grid, steel shot and the like can be mentioned.
In addition, wet blast etching is performed by causing water mixed with abrasive particles such as resin particles and metal particles to be directed to the surface of the metal member together with processing air at a high pressure of several tens m / s to about 300 m / s and etching processing The law is also possible.

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

  The roughening treatment (roughening treatment) exemplified above is used singly 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 on 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, still more preferably 30 nm or more, more preferably 50 nm or more, still more preferably 1 μm or 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, and still more preferably 50 μm or less. The ten-point average roughness is measured as described in the examples below.

It is also useful to surface-treat the metal member which has an unevenness | corrugation in the above-mentioned surface by a silane coupling agent.
Although it does not specifically limit as a silane coupling agent, For example, the compound which has a methoxy group, an ethoxy group, a silanol group etc. is mentioned, As a silane coupling agent, vinyl trimethoxysilane, chloropropyl trimethoxysilane, 3-gly Cidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- ( Preferred examples include N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane hydrochloride and ureidoaminopropylethoxysilane. In particular, the aluminum base, the iron base and the silane coupling agent form a bond of Al-O-Si or Fe-O-Si to form a strong bond, and the organic functional group of the resin composition and the silane coupling agent React to form a tight bond, and a stronger bond can be achieved.

  Further, by forming a film of the triazinethiol derivative on the surface of the metal which has been roughened by a wet method using a solution containing the triazinethiol derivative, it is possible to achieve further improvement in bonding strength by chemical bonding. ※

In bonding the metal member and the resin member, it is also preferable to form a chemical bond by effectively acting a polar group as well as the anchor effect by the unevenness. For example, in order to add CO, COO, NH ₂ group, etc. as acidic and basic functional groups, ozone treatment, plasma treatment, flame treatment, corona discharge treatment, chemical solution treatment, etc. are applied to the metal surface that has been roughened. It is also useful to apply.

  Furthermore, it is also preferable to provide a primer layer on the metal member. As a material to be 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. As a commercial item of the material used for a primer layer, Aon melt PPET by Toagosei Co., Ltd. is illustrated.

<Method of Manufacturing Metal-Resin Complex>
In this invention, it can form by applying the said polyamide resin composition for metal joining 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, and, for example, an injection molding machine, an extrusion molding machine, a heating press molding machine, a compression molding machine, a transfer molding machine Although various molding machines such as cast molding machines and reaction injection molding machines can be used, among these, injection molding machines are particularly preferable.
More specifically, the method for producing a metal-resin composite according to the present invention comprises: 30 to 90 parts by mass of a polyamide resin and a reinforcing filler 70 to 10 on the surface side of the metal member having irregularities on the surface. Injection molding of a polyamide resin composition for metal bonding containing talc and a mass part, the polyamide resin composition for metal bonding containing the talc in a proportion of 0.1 to 10% by mass, the polyamide resin Tm ≦ 290 ° C., Tm−Tcccc28 ° C., and 0 J / g <ΔHm ≦ 55 J / g. The polyamide resin composition for metal bonding here is synonymous with the above-mentioned polyamide resin composition for metal bonding, and the preferable range is also the same. Moreover, a metal resin complex is synonymous with the above-mentioned metal resin complex, and its 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 portion of an injection mold and the resin composition is injected into the mold. Specifically, a mold for molding is prepared, the mold is opened, and a metal member is installed (inserted) on a part of the mold, 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 is formed. Thereafter, 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 determined appropriately depending on the size, structure, etc. of the target metal-resin complex. The metal member to be inserted does not have to extend over the entire metal-resin composite to be obtained, and may be a part of the metal-resin composite.

In order to improve the bonding strength, it is preferable to make the temperature of the molten resin composition and the temperature of the metal member as close as possible at the time of insert molding. Although the method is not particularly limited, it is desirable to heat the metal member in advance. Although the heating method is not particularly limited, for example, a method of inserting one heated by induction heating, infrared heating, a hot plate, a heating furnace, a laser, etc. before insert molding a metal member, a metal member after insertion into a mold A method of heating from the outside with a halogen lamp, a dryer or the like from the outside, a method of heating with a cartridge heater or the like disposed inside the mold, etc. may be mentioned. In particular, it is useful to heat only the bonding region with the resin composition locally. Note that “locally heating” includes that heating is performed to the periphery including the bonding area depending on the heating means, but heating is not performed to a portion farther than the bonding area of the metal member.
The heating temperature is preferably as high as possible, but 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 more effectively exhibited, and by setting the heating temperature to 350 ° C. or lower, the temperature rising time can be shortened. Tends to improve, and retention of the resin is less likely to occur, which is preferable in terms of molding.

  As a method of obtaining a metal-resin composite, in addition to the above, a composite is formed by heating a metal member or a resin member (resin composition) such as a laser welding method, a vibration welding method, an ultrasonic welding method or the like. It is also possible to choose the method. An optimal method may be selected according to the shape, cost and the like 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 and the like of the metal-resin composite of the present invention obtained in this manner are not particularly limited, and may be plate-like (disc, polygon, etc.), columnar, box-like, wedge-like, Any shape such as a tray may be used. Further, the thickness of all parts of the composite does not have to be uniform, and the composite may be provided with a reinforcing rib or the like.

  In the metal-resin composite of the present invention, the metal member and the resin member are firmly joined, and the mechanical strength is excellent. Therefore, general household appliances, office automation equipment (copiers, printers, facsimiles, etc.) and various portable terminals Electrical and electronic components (housings, etc.) (PCs etc.) (housings, cases, covers etc.), automotive parts such as automobiles (structural parts for vehicles or brake pedals etc.), mechanical parts, bicycles and other parts materials It is preferably used.

  Hereinafter, the present invention will be more specifically described by way of examples. The materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below.

<Surface treatment of aluminum plate>
After degreasing, the aluminum plate (JIS A1050) with a thickness of 1.5 mm is chemically etched with an aqueous solution (aluminum etching solution manufactured by Kanto Chemical Co., Ltd., made of Kanto Chemical Co., Ltd.) and cleaned. An aluminum plate having an uneven surface was obtained. The surface of the obtained aluminum plate was observed with a 20 × objective lens of a laser microscope (KEYENCE VK-X100), and the surface roughness was measured. The ten-point average roughness Rz was 27.96 μm.

<Polyamide resin>
Polyamide resin A: manufactured by Mitsubishi Gas Chemical Co., Ltd., MXD6 6000
Polyamide resin B: Prepared according to the following synthesis example.
<< Composition example >>
In a 3-liter flask equipped with a stirrer, thermometer, reflux condenser, raw material dropping device, heating device, etc., 730 g of sebacic acid is charged, and the temperature inside the flask is raised to 160 ° C. under a nitrogen atmosphere to carry out sebacine. The acid was allowed to melt. Into the flask, 680 g of mixed xylylene diamine containing 30 mol% of p-xylylene diamine and 70 mol% of meta-xylylene diamine was dropped successively over about 2.5 hours. During this time, the reaction was continued under stirring while maintaining the internal temperature always above the melting point of the product, and the temperature was raised to 270 ° C. at the end of the reaction. Water generated by the reaction was discharged out of the reaction system by a partial condenser. After completion of the dropwise addition, the reaction was continued by stirring at a temperature of 275 ° C., and after 1 hour, the reaction was completed. The product was removed from the flask, water cooled and pelletized. The relative viscosity (measured at a concentration of 1 g / 100 mL in a 96 mass% sulfuric acid solution at 23 ° C.) of the obtained polyamide resin was 2.20.

Polyamide resin C: Prepared according to the following synthesis example.
<< Composition example >>
In a 3-liter flask equipped with a stirring device, thermometer, reflux condenser, raw material dropping device, heating device, etc., 730 g of adipic acid is charged, and the temperature inside the flask is raised to 160 ° C. under a nitrogen atmosphere, The acid was allowed to melt. Into the flask, 680 g of mixed xylylenediamine containing 30 mol% of paraxylylenediamine and 70 mol% of metaxylylenediamine was sequentially dropped over about 2.5 hours. During this time, the reaction was continued under stirring while maintaining the internal temperature always above the melting point of the product, and the temperature was raised to 270 ° C. at the end of the reaction. Water generated by the reaction was discharged out of the reaction system by a partial condenser. After completion of the dropwise addition, the reaction was stirred at a temperature of 275 ° C., and the reaction was continued, and after 1 hour, the reaction was completed. The product was removed from the flask, water cooled and pelletized. The relative viscosity (measured at a concentration of 1 g / 100 mL in a 96 mass% sulfuric acid solution at 23 ° C.) of the obtained polyamide resin was 2.10.

Polyamide resin D: manufactured by EMS, PA12 Grivory L20G

Polyamide resin E: Prepared according to the following preparation example.
In a 3-liter flask equipped with a stirrer, thermometer, reflux condenser, raw material dropping device, heating device, etc., 730 g of sebacic acid is charged, and the temperature inside the flask is raised to 160 ° C. under a nitrogen atmosphere to carry out sebacine. The acid was allowed to melt. Into the flask, 680 g of paraxylylenediamine was dropped successively over about 2.5 hours. During this time, the reaction was continued while maintaining the internal temperature constantly above the melting point of the product under stirring, and the temperature was raised to 300 ° C. at the end of the reaction. Water generated by the reaction was discharged out of the reaction system by a partial condenser. After completion of the dropwise addition, the reaction was continued by stirring at a temperature of 300.degree. The product was removed from the flask, water cooled and pelletized. The relative viscosity (measured at a concentration of 1 g / 100 mL in a 96 mass% sulfuric acid solution at 23 ° C.) of the obtained polyamide resin was 2.20.

Polyamide resin F: manufactured by Solvay, PA6 Stabamid 26 AE 1 K
Reinforcing filler B: Glass fiber, ECS03T-289H, manufactured by Nippon Electric Glass Co., Ltd., fiber length 3.0 mm, fiber diameter 10 μm
Talc: Hayashi Kasei Co., Ltd., micron white # 5000 S
Release agent: Nitto Kasei Kogyo Co., Ltd. CS-8 CP

<Method of measuring 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 in a Cannonfence-type viscometer, and after standing for 10 minutes in a thermostat at 25 ° C., a drop time (t) was measured. Moreover, the fall time (t0) of the 96 mass% sulfuric acid aqueous solution itself was also measured similarly. The relative viscosity was calculated from t and t0 by the following equation.
Relative viscosity = t / t0

<Method of measuring melting point (Tm), crystallization temperature (Tcc) and melting enthalpy (ΔHm)>
The measurement of the differential scanning heat quantity was performed according to JIS K7121 and K7122. Using a differential scanning calorimeter, charge the polyamide resin into the measurement pan of the differential scanning calorimeter, raise the temperature to 30 to 300 ° C at a heating rate of 20 ° C / minute under a nitrogen atmosphere, and hold for 3 minutes at 300 ° C Then, 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.) The melting enthalpy (ΔHm, unit: J / g) was determined.
As a differential scanning calorimeter, “DSC 7020 AUTO” manufactured by SII Nanotechnology Inc. was used.
The results are shown in Table 1 below.

<Compound>
Each component is weighed to obtain the composition shown in Table 2 described later (the ratio of each component in Table 2 is a mass ratio), and the components except glass fiber are blended with a tumbler to obtain a twin-screw extruder ( After charging from the base of TEM26SS (manufactured by Toshiba Machine Co., Ltd.) and melting, glass fibers were side-fed to produce resin pellets. The temperature setting of the extruder was carried out at 300 ° C. for Comparative Example 1 and 280 ° C. for the others.

<Flexural modulus>
After drying the obtained resin pellet at 120 ° C. for 4 hours, Comparative Example 1 has a cylinder temperature of 300 ° C., others 280 ° C., and a mold temperature of 130 ° C. using a FANUC injection molding machine (100 T). Under the conditions, ISO test pieces (4 mm thick) were injection molded. The flexural modulus (unit: GPa) was measured at a temperature of 23 ° C. using the above-mentioned ISO tensile test piece (4 mm thick) in accordance with ISO 178.

Melt viscosity
The melt viscosity was measured according to JIS K7199 after drying the obtained resin pellet at 120 ° C. for 4 hours. The capillary used was 1 × x 20 mm, and was performed under the conditions of a shear rate of 1000 (1 / sec), a melting point of + 40 ° C, and a holding time of 6 minutes.

Examples 1 to 7 and Comparative Examples 1 to 3
In accordance with ISO 19095, the aluminum plate obtained above was cut into a size of length 45 mm × width 12 mm × thickness 1.5 mm, and was mounted in a mold cavity.
The resin pellet (resin composition) obtained above was dried at 120 ° C. for 4 hours on the uneven surface side of the mounted aluminum plate, and the bonding area of the aluminum plate and the resin composition was 5 mm long × 10 mm wide Insert molding (length 45 mm × width 10 mm × thickness 3 mm) to form a metal-resin composite in which an aluminum plate (metal member) 1 and a resin composition (resin member) 2 as shown in FIG. did.
For molding, “Funak α-100” manufactured by FANUC CO., LTD. Is used as an injection molding machine, and in Comparative Example 1, the cylinder temperature is 300 ° C., others are 280 ° C., the mold temperature is 130 ° C., the injection speed is 30 mm / sec, the filling time is 0. It carried out on condition of 58 seconds, holding pressure 80MPa, holding time 6 seconds, and cooling time 20 seconds.

<Evaluation of bondability>
The bonding property was evaluated using the obtained metal resin composite in accordance with ISO19095.
The measurement is carried out using a tensile tester (Instron's "5544 type") and bonding and integrating the aluminum plate 1 and the resin composition portion 2 using a tension jig conforming to ISO 19095. The bonding strength (unit: N) was measured by clamping both ends in the long axis direction with a clamp and pulling at a tensile speed of 5 mm / min and a distance between chucks of 80 mm. A: 1100 N or more (base material was broken by tension).
B: Bonded but less than 1100 N (partially base material fractured by tension).
C: It did not join.

The results are shown in Table 2 below

As is clear from the above results, the metal resin composite molded using the resin composition of the present invention was excellent in the bonding 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 is 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), bonding was not performed. When talc was not blended (Comparative Example 3), molding could not be performed.

  The metal-resin composite of the present invention is preferably used as a material of parts such as general household appliances, OA equipment, electric and electronic products, parts for vehicles such as automobiles, and mechanical parts because the resin member and the metal member are firmly joined. Used.

1: Aluminum member 2: Resin composition

Claims (16)

A polyamide resin composition for metal bonding comprising 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 contains the talc in a proportion of 0.1 to 10% by mass,
A polyamide resin composition for metal bonding, wherein the polyamide resin has Tm ≦ 290 ° C., Tm-Tcc ≧ 28 ° C., and 0 J / g <ΔHm ≦ 55 J / g; provided that Tm, Tcc and ΔHm are polyamides respectively They are the melting point of the resin, the crystallization temperature upon cooling, and the melting enthalpy. The polyamide resin composition for metal bonding according to claim 1, wherein the melt viscosity at a holding time of 6 minutes, a melting point + 40 ° C and a shear rate of 1000 (1 / sec) of the polyamide resin composition for metal bonding is ηa 400 400 Pa · s. object. The polyamide resin composition for metal joining of Claim 1 or 2 in which the said polyamide resin contains semi-aromatic polyamide resin. The polyamide resin composition for metal joining according to any one of claims 1 to 3, wherein a bending elastic modulus according to ISO 527 of the polyamide resin composition for metal joining is 9 GPa or more. 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. The polyamide resin composition for metal joining as described. The polyamide resin composition for metal joining according to any one of claims 1 to 5, wherein the reinforcing filler contains glass fiber. The polyamide resin is composed of a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid,
70 mol% or more of the constituent units derived from the diamine are derived from xylylene diamine,
The resin according to any one of claims 1 to 6, wherein 70 mol% or more of the constituent units derived from dicarboxylic acid include a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Polyamide resin composition for metal bonding. A metal member having irregularities on the surface, and a resin member in contact with the metal member on the side having the irregularities,
The resin member comprises 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,
The polyamide resin composition for metal bonding contains the talc in a proportion of 0.1 to 10% by mass,
A metal resin composite wherein the polyamide resin has Tm ≦ 290 ° C., Tm-Tcccc28 ° C., and 0 J / g <ΔHm ≦ 55 J / g; where Tm, Tcc and ΔHm are the melting point of the polyamide resin, respectively It is crystallization temperature and melting enthalpy at the time of cooling. The metal resin composite according to claim 8, wherein the polyamide resin comprises a semiaromatic polyamide resin. 10. The metal resin composite according to claim 8, 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. . The metal resin composite according to any one of claims 8 to 10, wherein the flexural modulus according to ISO 527 of the polyamide resin composition for metal bonding is 9 GPa or more. The metal resin composite according to any one of claims 8 to 11, wherein the reinforcing filler comprises glass fiber. The polyamide resin is composed of a constituent unit derived from a diamine and a constituent unit derived from a dicarboxylic acid,
70 mol% or more of the constituent units derived from the diamine are derived from xylylene diamine,
The resin according to any one of claims 8 to 12, wherein 70 mol% or more of the constituent units derived from dicarboxylic acid include a polyamide resin derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Metal resin complex. Injection molding of 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 on the surface side of the uneven surface of the metal member having irregularities on the surface Including
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 complex, wherein the polyamide resin has Tm ≦ 290 ° C., Tm-Tcc ≧ 28 ° C., and 0 J / g <ΔHm ≦ 55 J / g, provided that Tm, Tcc and ΔHm are respectively polyamide resin Melting point, crystallization temperature at melting and enthalpy of melting. 15. The metal-resin composite according to claim 14, 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 ≦ a ≦ 400 Pa · s. Method. The manufacturing method of the metal resin composite of Claim 14 or 15 whose said metal resin composite is a metal resin composite of any one of Claims 8-13.

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