WO2019020065A1 - Bonded body of thermoplastic resin composition and metal, and manufacturing method therefor - Google Patents

Abstract

Provided are a bonded body of a thermoplastic resin composition and a metal, which bonded body has excellent bonding properties, and a manufacturing method therefor. The thermoplastic resin composition contains a terminally modified polyamide resin. The content of the terminally modified polyamide resin in the thermoplastic resin composition is 5-100 wt% of the total weight of the thermoplastic resin composition, and the terminally modified polyamide resin has a terminal structure shown in formula I, -X-(R1-O)n-R2, formula I. In formula I above, n is an integer from 2 to 100; R1 is identical or different, and is an alkylene group having 2-10 carbon atoms; R2 is an alkyl group having 1-30 carbon atoms; and -X- is any one of -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or-CH(OH)-CH2-. The content of the structure shown in formula I in the terminally modified polyamide resin is 0.05-20 wt% of the total weight of the terminally modified polyamide resin.

Description

Bonded body of thermoplastic resin composition and metal and method of producing the same Technical field

The present invention belongs to the field of composites of polymers and metals, and specifically discloses a bonded body of a thermoplastic resin composition and a metal and a method for producing the same.

Background technique

With the three major problems of energy, safety and environmental protection becoming more and more prominent, the lightweight of automobiles has received more and more attention. Because the proportion is much smaller than that of metal, the application of engineering plastics in automobiles is gradually increasing. However, in some structural components, the mechanical strength of engineering plastics is still difficult to meet the demand. The metal/plastic hybrid composite combines the high strength of metal with the light weight of plastic, while meeting the mechanical strength requirements and lightweight requirements of automotive structural components.

At present, the joint between the metal member and the plastic is mainly joined by mechanical riveting and adhesive bonding to form a hybrid composite material, but in these joining methods, the plastic component and the metal component need to be processed separately, and then riveted and glued. They are joined together to form a complete part. The above bonding method has problems such as complicated process and easy deterioration of the adhesive.

In recent years, more and more research has been conducted on a method in which a resin is directly joined to a metal by injection molding. International Patent Application Publication No. WO 2012/132639 discloses a composite of a thermoplastic resin and a metal, which contains an inorganic filler capable of increasing the crystallization temperature of the resin, but the composite obtained by the method has a bond between the resin and the metal. Sex is still insufficient. International Patent Application Publication No. WO 2015/022955 discloses a composite of a thermoplastic resin and a metal, which may be a polyether copolymer modified polyamide elastomer or a thermoplastic resin composed of a water-absorbing thermoplastic resin and a metal hydroxide. combination. However, the mechanical properties of polyamide elastomers are significantly reduced compared to polyamide homopolymers. On the other hand, the polyamide elastomer has a lower glass transition temperature than the polyamide homopolymer, and the curing speed is slower at the time of injection molding, and the molding cycle is lengthened. At the same time, the polyamide elastomer has poor adhesion to metals.

Chinese Patent Application Publication No. CN105479659A discloses a composite of a plastic material and a metal material comprising a polyether block amide. Although the plastic material and the metal have excellent bonding strength and provide a certain degree of sealing property, due to the polyether block amide The content of the polyether structure is high, and the mechanical properties of the polyether block amide are degraded compared with the polyamide homopolymer, and the bonding property of the polyether block amide with the metal is insufficient.

Prior art literature

Patent Document 1: International Patent Application Publication No. WO2012/132639

Patent Document 2: International Patent Application Publication No. WO2015/022955

Patent Document 3: Chinese Patent Application Publication No. CN105479659A

Summary of the invention

An object of the present invention is to solve the above problems and to provide a bonded body of a thermoplastic resin composition containing a polyamide resin having a polyether chain introduced at its end, thereby enhancing the thermoplastic resin composition and the metal. The bonding strength while the thermoplastic resin composition itself still maintains high mechanical properties.

The present invention also provides a method for producing a bonded body of the thermoplastic resin composition and a metal, which is capable of efficiently preparing a joint of a metal and a resin, and laying a foundation for continuous production.

The invention consists of the following:

A joint of a thermoplastic resin composition comprising a terminal-modified polyamide resin, the terminal-modified polyamide resin being contained in an amount of from 5 to 100% by weight based on the total weight of the thermoplastic resin composition. The terminal modified polyamide resin has an end structure represented by Formula I,

-X-(R ₁ -O)nR ₂ Formula I

In the above formula I, n is an integer of 2 to 100, R _{1 is the} same or different, and is an alkylene group having 2 to 10 carbon atoms, R 2 is an alkyl group having 1 to 30 carbon atoms, and -X- is - Among NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH(OH)-CH ₂ - Any one of the structures of Formula I in the terminally modified polyamide resin is 0.05 to 20% by weight based on the total weight of the terminally modified polyamide resin.

2. The bonded body according to the above 1, wherein in the terminal structure represented by the above formula I, n is an integer of from 16 to 50.

3. The bonded body according to the above 1, wherein in the terminal structure represented by the above formula I, n is an integer of from 16 to 25.

4. The joined body according to the above 1, wherein, in the terminal structure represented by the above formula I, R _{1 is the} same or different and is an alkylene group having 2 to 4 carbon atoms.

5. The joined body according to the above 1, wherein in the terminal structure represented by the formula I, R ₂ is an alkyl group having 1 to 20 carbon atoms.

6. The joined body according to the above 1, wherein in the terminal structure represented by the formula I, R ₂ is a methyl group.

7. The joined body according to the above 1, wherein -X- is -NH- in the terminal structure represented by the above formula I.

8. The joined body according to the above 1, wherein the terminal structure represented by the above formula I is contained in the terminal-modified polyamide resin in an amount of from 0.1 to 15% by weight based on the total weight of the terminal-modified polyamide resin. 9. The joined body according to the above 1, wherein the terminal structure represented by the above formula I is contained in the terminal-modified polyamide resin in an amount of from 0.1 to 10% by weight based on the total weight of the terminal-modified polyamide resin. 10. The joined body according to the above 1, wherein the thermoplastic resin composition has a tensile shear strength of ≥ 10 MPa measured at a tensile speed of 5 mm/min according to the joint test strip specified in ISO19095.

11. The joined body according to the above 1, wherein the joined body is obtained by directly bonding a thermoplastic resin composition to a metal.

12. The joined body according to the above 1, wherein the terminal modified polyamide resin having the terminal structure represented by Formula I is formulated into a 0.01 g/ml polyamide resin solution using 96 wt% sulfuric acid as a solvent, and is measured at 25 ° C. The relative viscosity ηr is from 1.1 to 5.0.

13. The joined body according to the above 1, wherein the terminal modified polyamide resin having the terminal structure represented by Formula I has a weight average molecular weight Mw measured by gel permeation chromatography in the range of 10,000 to 400,000.

14. The joined body according to the above 1, wherein the terminal modified polyamide resin having the terminal structure represented by Formula I has a melting point of 215 ° C or higher.

15. The joined body according to the above 1, wherein the thermoplastic resin composition further comprises an inorganic filler in an amount of from 5 to 80% by weight based on the total mass of the thermoplastic resin composition.

The method for producing a joined body according to any one of the above 1 to 15, wherein the joined body is heated and melted by a thermoplastic resin composition, and then injection-molded with a metal previously placed in a mold.

17. The manufacturing method according to the above 16, wherein the joint body has a mold temperature of between 60 and 180 ° C during the injection molding process.

The method of producing a joined body according to any one of the above 1 to 15, wherein the joined body is obtained by welding a molded article of a thermoplastic resin composition and a metal by laser irradiation.

The bonded body of the thermoplastic resin composition of the present invention and metal can be used for automobile parts, electronic parts, electrical product parts, structural materials, and the like.

The above summary of the invention is described in detail below:

The thermoplastic resin composition used in the joined body of the present invention comprises a terminal-modified polyamide resin having an end structure represented by Formula I, and the content of the terminal-modified polyamide resin is 5 to 100% by weight based on the total weight of the thermoplastic resin composition. ,

-X-(R ₁ -O)nR ₂ Formula I

In the above formula I, n is an integer of 2 to 100, R _{1 is the} same or different, and is an alkylene group having 2 to 10 carbon atoms, and R ₂ is an alkyl group having 1 to 30 carbon atoms, and -X- is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH(OH)-CH ₂ - Any of the structures of Formula I in the terminally modified polyamide resin is 0.05 to 20% by weight based on the total weight of the terminally modified polyamide resin.

In the present invention, when the thermoplastic resin composition contains only a single component of the terminal-modified polyamide resin, it is also defined as a thermoplastic resin composition.

The present invention is not particularly limited to the kind of the terminal-modified polyamide resin main chain structure to be used. The monomer raw material constituting the main chain structure of the terminal-modified polyamide resin may be a diacid, a diamine, an amino acid or a lactam, etc., and specific examples thereof are exemplified but are not limited to the following examples: 6-aminocaproic acid, 11-amino-10- An acid, an amino acid such as 12-aminododecanoic acid or 4-aminomethylbenzoic acid; a lactam such as ε-caprolactam, ω-undecanolactam or ω-laurolactam; ethylenediamine, propylenediamine, and butyl Diamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetradecanediamine , pentadecanediamine, hexadecanediamine, heptadecanediamine, stearyldiamine, nonadecanediamine, eicosanediamine, 2-methyl-1,5-pentanediamine or An aliphatic diamine such as 2-methyl-1,8-octanediamine; cyclohexanediamine or 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclo) An alicyclic diamine such as hexylamine; an aromatic diamine such as xylylenediamine; an aliphatic oxalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid or dodecanedioic acid Carboxylic acid; terephthalic acid, isophthalic acid, 2-chloro-1 An aromatic dicarboxylic acid such as 4-phthalic acid, 2-methyl-1,4-phthalic acid or 5-methylisophthalic acid or sodium 5-sulfonate isophthalic acid; cyclohexanedicarboxylic acid Alicyclic dicarboxylic acid. The alkyl diester and diacid chloride derived from a dicarboxylic acid are also exemplified as a monomer raw material constituting the main chain structure of the polyamide resin. The main chain of the terminal-modified polyamide resin used in the present invention may specifically be a homopolymer structure prepared from the above monomers, or a copolymerization structure prepared from the above monomers.

The polyamide backbone structure for the terminal-modified polyamide resin may be exemplified by, but not limited to, the following examples: polycaprolactam (nylon 6), polyundecanolactam (nylon 11), polydodelactam (nylon 12), poly Adipyl hexamethylenediamine (nylon 66), polyadipyl butanediamine (nylon 46), polyhexamethylene diamylamine (nylon 56), polysebacyl diamine (nylon 410), polyfluorene Acylpentanediamine (nylon 510), polyphthalamide (nylon 610), polydodecanoyldiamine (nylon 612), polysebacyldiamine (nylon 1010), polydodecanoylhydrazide Diamine (nylon 1012), polycaprolactam/polyhexamethylene adipamide (nylon 6/66), poly(m-xylylenediamine) (MXD6), poly(m-xylylenediamine) (MXD10) ), poly(p-xylylenediamine) (PXD10), poly(p-phenylene terephthalamide) (nylon 9T), poly(p-phenylene terephthalamide) (nylon 10T), poly(p-phenylene terephthalate) Monoamine (nylon 11T), poly(p-phenylene terephthalamide) (nylon 12T), poly(p-phenylene glutamine)/poly(p-phenylene terephthalamide) (nylon 5T/6T), poly Terephthaloyl-2-methylpentanediamine/poly(p-phenylene hexamethylenediamine copolymer (nylon M5T) /6T), polyhexamethylene adipamide/poly(p-phenylene hexamethylene diamine copolymer (nylon 66/6T), polyhexamethylene adipamide/poly(m-phenylene diamine) copolymer Nylon 66/6I), polyhexamethylene adipamide/poly(p-phenylene hexamethylenediamine/poly-m-phenylene hexamethylenediamine copolymer (nylon 66/6T/6I), polyparaphenylene 4,4'-methylenebis(2-methylcyclohexylamine) (nylon MACMT), polyisophthaloyl 4,4'-methylenebis(2-methylcyclohexylamine) (nylon MACMI ), polydodecanoyl 4,4'-methylenebis(2-methylcyclohexylamine) (nylon MACM12), polyparaphenyl 4,4'-methylenebiscyclohexylamine (nylon PACMT) , polyisophthaloyl 4,4'-methylenebiscyclohexylamine (nylon PACMI), polydodecanoyl 4,4'-methylenebiscyclohexylamine (nylon PACM12) or a copolymer of the above polymers.

In order to obtain a terminally modified polyamide resin having good crystallinity, the polyamide main chain structure of the above terminal modified polyamide resin is preferably polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene. Acetyl pentane diamine (nylon 56), polysebacyl diamine (nylon 410), polysebacyl pentane diamine (nylon 510), polyphthalamide (nylon 610), polyparaphenylene A hydrazide diamine (nylon 9T) or a poly(p-phenylene terephthalamide) (nylon 10T).

The main chain structure of the terminal-modified polyamide resin may be composed of one of the above-described main chain structures, or may be composed of two or more of the above-described main chain structures. The main chain repeating unit of the terminal-modified polyamide resin used in the present invention is preferably composed of 80 mol% or more of the structural unit derived from the above-mentioned monomer raw material (the number of repeating units of the polyamide main chain structure is 100 mol%). In view of heat resistance and crystallinity, it is preferably 90 mol% or more, and most preferably 100 mol%.

The terminally modified polyamide resin used in the present invention increases the mobility of the entire molecular chain by introducing a flexible polyether structure represented by Formula I at the terminal of the polyamide, thereby lowering the melt viscosity. Therefore, when the thermoplastic resin containing the terminal-modified polyamide resin is brought into contact with the metal in a molten state, the resin melt is more effectively infiltrated into minute pores of the metal surface, so that it can be better bonded to the metal surface.

In the above formula I, n is an integer of from 2 to 100. When n is less than 2, the effect of lowering the melt viscosity of the thermoplastic resin composition is deteriorated. Preferably, n is 4 or more, and further preferably n is 8 or more, and most preferably n is 16 or more. On the other hand, when n is more than 100, the heat resistance of the terminal structure represented by Formula I is deteriorated. Preferably, n is 70 or less, more preferably n is 50 or less, and most preferably n is 25 or less.

In the above formula I, R _{1 is the} same or different and is an alkylene group having 2 to 10 carbon atoms. Specific examples of R ₁ include -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH(CH ₃ )-CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -CH ₂ -. In view of affinity with the polyester main chain structure, R ₁ is preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms. R ₁ may be a combination of different alkylene groups, preferably at least one of -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, -CH(CH ₃ )-CH ₂ -.

In the above formula I, R ₂ is an alkyl group having 1 to 30 carbon atoms. The smaller the number of carbon atoms in R ₂ , the higher the affinity with the polyamide main chain structure. Therefore, R ₂ is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group is more preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group.

In the above formula I, -X- is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or - Any one of CH(OH)-CH ₂ -, in order to make the thermoplastic resin composition used in the present invention have a lower melt viscosity, the affinity of the polyether end to the polyamide main chain is preferably higher, -X- Preferred is -NH-.

The terminal modified polyamide resin used in the present invention has a terminal structure represented by the formula I in an amount of 0.05 to 20% by weight based on the total weight of the terminal-modified polyamide resin, and the terminal structure is considered for the purpose of lowering the melt viscosity and improving moldability. The content in the terminally modified polyamide resin is preferably 0.1% by weight or more, further preferably 0.5% by weight or more, still more preferably 1.5% by weight or more, and most preferably 2% by weight or more; on the other hand, by making the terminal of Formula I The content of the structure is 20% by weight or less, and the crystallinity and mechanical properties of the terminal-modified polyamide resin can be more preferably maintained, and are preferably 15% by weight or less, further preferably 10% by weight or less, and still more preferably 5% by weight or less. Here, the content (wt%) of the polyether segment represented by the above formula I with respect to the terminal-modified polyamide resin was obtained by ¹ H-NMR (nuclear magnetic resonance) test.

The terminal modified polyamide resin having the terminal structure represented by Formula I in the present invention is preferably prepared at a concentration of 0.01 g/ml in a solution of 96 wt% concentrated sulfuric acid as a solvent at a relative viscosity ηr measured at 25 ° C. It is 1.1 to 5.0. When ηr is less than 1.1, the mechanical properties and metal bonding properties of the thermoplastic resin composition tend to decrease. Preferably, ηr is 1.2 or more, and more preferably 1.4 or more. On the other hand, when ηr is more than 5.0, the molecular weight is too high, and thus the melt viscosity is too high, which tends to lower the metal bonding performance. ηr is preferably 4 or less, and more preferably ηr is 3 or less.

The weight-average molecular weight (Mw) of the terminal-modified polyamide resin having the terminal structure represented by Formula I in the present invention is preferably 10,000 or more. When the Mw reaches 10,000 or more, the mechanical properties and metal bonding properties are improved. Mw is further preferably 20,000 or more, and still more preferably 30,000 or more. Further, Mw is preferably 400,000 or less. When the Mw is 400,000 or less, the melt viscosity is low, and during the process of manufacturing the joined body, the resin melt can sufficiently wet the minute holes of the metal surface, thereby bringing the thermoplastic resin composition into close contact with the metal surface, and improving the metal bonding property. Mw is more preferably 300,000 or less, still more preferably 250,000 or less. The weight average molecular weight (Mw) can be determined by gel permeation chromatography (GPC).

The present invention is intended to obtain a joined body having good heat resistance, and therefore the melting point (Tm) of the terminal-modified polyamide resin having the terminal structure represented by Formula I is preferably 215 ° C or higher, and further preferably the melting point of the terminal-modified polyamide resin. (Tm) is above 218 °C. In general, the introduction of a flexible structure into a polyamide resin by copolymerization causes a decrease in the melting point of the polyamide resin, but the present invention selectively introduces a polyether having a specific structure at the end of the resin to a polyamide phase which does not contain a polyether end structure. The decrease in the melting point of the polyamide resin into which the polyether end is introduced is controlled to the minimum. The melting point is preferably not more than 5 ° C, and further preferably the melting point is not more than 3 ° C. The melting point of the polyamide resin described herein is determined by differential scanning calorimetry (DSC): the polyamide resin is accurately weighed 5 to 7 mg, and the temperature is raised from 20 ° C at a heating rate of 20 ° C / min under a nitrogen atmosphere. Up to a temperature of 30 ° C higher than the temperature T0 of the endothermic peak, at this temperature for 2 min, then cooling to 20 ° C at a temperature drop rate of 20 ° C / min, and then heating up to a temperature increase rate of 20 ° C / min to The temperature of the endothermic peak appearing during the second temperature rise is defined as the melting point (Tm) at a temperature 30 ° C higher than T0.

In the thermoplastic resin composition used in the present invention, other kinds of polymers, fillers, and various additives may be added in addition to the terminal-modified polyamide resin.

The other types of polymers in the thermoplastic resin composition may be, but not limited to, the following examples: polyolefins such as polyethylene and polypropylene; modified polyolefins such as copolymers obtained by polymerizing olefins and/or conjugated diene compounds; Ester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, polyunsity other than the terminal unmodified polyamide resin of the present invention Amide resin and the like.

As the above-mentioned other kinds of polymers, in order to improve the impact resistance of the molded article obtained by the thermoplastic resin composition used in the present invention and to reduce the shrinkage ratio, it is preferred to use a polymer obtained by polymerizing an olefin and/or a conjugated diene compound (or copolymerization). An impact agent such as a modified polyolefin.

The polymer (or copolymer) may, but not limited to, the following examples: an ethylene-based copolymer, a conjugated diene-based polymer, or a conjugated diene-aromatic ethylene copolymer.

The ethylene-based copolymer means a copolymer of ethylene and another monomer. Other monomers copolymerized with ethylene may be exemplified by, but not limited to, the following examples: an α-olefin having 3 or more carbon atoms, a non-conjugated diene, a vinyl acetate, a vinyl alcohol, an α,β-unsaturated carboxylic acid or a derivative thereof. Things. Two or more kinds of the above monomers may be copolymerized with ethylene.

The α-olefin having 3 or more carbon atoms may, but not limited to, the following examples: propylene, 1-butene, 1-pentene or 3-methyl-1-pentene, preferably propylene or 1-butene. The non-conjugated diene may be exemplified by, but not limited to, the following examples: 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5 -propenyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-butenyl-2-norbornene, 5-(2-methyl-2-butenyl)-2 -norbornene compound such as norbornene, 5-(2-ethyl-2-butenyl)-2-norbornene or 5-methyl-5-vinylnorbornene; dicyclopentadiene, A Tetrahydroindole, tetrahydroanthracene, 1,5-cyclooctadiene, 1,4-hexadiene, 6-methyl-1,5-heptadiene or 11-tridecadiene, etc., preferably 5 -methylene-2-norbornene, 5-ethylidene-2-norbornene, dicyclopentadiene or 1,4-hexadiene. The α,β-unsaturated carboxylic acid may be exemplified by, but not limited to, the following examples: acrylic acid, methacrylic acid, ethacrylic acid, 2-butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or butyl Oleic acid and the like. The derivative of the α,β-unsaturated carboxylic acid may, but not limited to, the following examples: an alkyl ester, an aryl ester, a glyceride, an acid anhydride or an imide of the above α,β-unsaturated carboxylic acid.

The conjugated diene polymer refers to a polymer obtained by polymerizing at least one conjugated diene. The conjugated diene described herein may be exemplified by, but not limited to, the following examples: 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl Base-1,3-butadiene or 1,3-pentadiene. The conjugated diene may be copolymerized in two or more types. Additionally, the unsaturated bonds of the polymer can be partially or completely reduced by hydrogenation.

The conjugated diene-aromatic ethylene copolymer refers to a copolymer of a conjugated diene and an aromatic ethylene, and may be a block copolymer or a random copolymer. Examples of the conjugated diene may be the same as those of the above-mentioned conjugated diene-based polymer, and 1,3-butadiene and isoprene are preferable. The aromatic vinyl may, for example, be styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene or vinylnaphthalene or the like, preferably styrene. Further, the unsaturated bond other than the double bond of the aromatic ring of the conjugated diene-aromatic ethylene copolymer may be partially or completely reduced by hydrogenation.

Specific examples of the impact agent include an ethylene/propylene copolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/propylene/dicyclopentadiene copolymer, and an ethylene/propylene/5-Asian Base-2-norbornene copolymer, unhydrogenated or hydrogenated styrene/isoprene/styrene triblock copolymer, unhydrogenated or hydrogenated styrene/butadiene/styrene triblock a salt of a part or all of a carboxylic acid group of a copolymer, an ethylene/methacrylic acid copolymer or a copolymer with sodium, lithium, potassium, zinc or calcium, an ethylene/methyl acrylate copolymer, an ethylene/ethyl acrylate copolymer , ethylene / methyl methacrylate copolymer, ethylene / ethyl acrylate - g - maleic anhydride copolymer (here "g" means grafting, the same below), ethylene / methyl acrylate - g - maleic anhydride copolymerization , ethylene/ethyl acrylate-g-maleimide copolymer, ethylene/ethyl acrylate-gN-phenylmaleimide copolymer or partial saponification of the copolymer, ethylene/methacrylic acid Glycidyl ester copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/methyl methacrylate /glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, ethylene/glycidyl ether copolymer, ethylene/propylene-g-maleic anhydride copolymerization , ethylene/propylene-g-maleic anhydride copolymer, ethylene/butene-1-g-maleic anhydride copolymer, ethylene/propylene/1,4-hexadiene-g-maleic anhydride copolymer, ethylene /propylene/dicyclopentadiene-g-maleic anhydride copolymer, ethylene/propylene/2,5-norbornadiene-g-maleic anhydride copolymer, ethylene/propylene-gN-phenylmaleimide Copolymer, ethylene/butene-1-gN-phenylmaleimide copolymer, hydrogenated (styrene/butadiene/styrene-g-maleic anhydride) copolymer, hydrogenated (styrene/isoprene) Diene/styrene-g-maleic anhydride) copolymer, ethylene/propylene-g-glycidyl methacrylate copolymer, ethylene/butene-1-g-glycidyl methacrylate copolymer, ethylene/ Propylene/1,4-hexadiene-g-glycidyl methacrylate copolymer, ethylene/propylene/dicyclopentadiene-g-glycidyl methacrylate copolymer, hydrogenation (styrene/butadiene) Ethylene/styrene-g-glycidyl methacrylate copolymer, nylon 12/polytetrahydrofuran copolymer, nylon 12/polypropylene glycol copolymer, polybutylene terephthalate/polytetrahydrofuran copolymer or polyparaphenylene Butylene dicarboxylate/polypropylene glycol copolymer and the like. The above copolymer is preferably an ethylene/methacrylic acid copolymer and a salt of a part or all of a carboxylic acid group of the copolymer with sodium, lithium, potassium, zinc or calcium, an ethylene/propylene-g-maleic anhydride copolymer, ethylene/ Butene-1-g-maleic anhydride copolymer.

The polymer other than the terminal-modified polyester resin in the above thermoplastic resin composition may be added singly or in combination of two or more kinds. The addition amount is preferably 0% by weight or more and 80% by weight or less (100% by weight of the thermoplastic resin composition), and by controlling the amount of addition to the above range, the fluidity at the time of melting the thermoplastic resin composition can be further improved. It is further preferably 60% by weight or less, and still more preferably 50% by weight or less.

The thermoplastic resin composition of the present invention may further contain a filler, and the filler may be exemplified by, but not limited to, the following examples: glass fiber, carbon fiber, titanic acid whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, Fibrous inorganic or organic fillers such as alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers or metal fibers; wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, Montmorillonite, asbestos, silicate, alumina, silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide Non-fibrous inorganic fillers such as aluminum hydroxide, glass microspheres, ceramic microbeads, boron nitride, silicon carbide or silicon dioxide. The filler may be hollow, and the filler may be treated with a coupling agent such as an isocyanate compound, an organosilane compound, an organic titanate compound, an organoborane compound or an epoxy compound. The above montmorillonite may also be an organic montmorillonite obtained by cation exchange of interlamellar ions through an organic ammonium salt. In view of improvement in mechanical properties of the thermoplastic resin composition and reduction in mold shrinkage, the above filler is preferably a fibrous inorganic filler, and more preferably glass fiber or carbon fiber. Further, the above fillers may be added singly or in combination of two or more.

The content of the above filler in the thermoplastic resin composition is preferably from 5 to 80% by weight based on the total weight of the thermoplastic resin composition, and when the filler is added in an amount of 5% by weight or more, the shrinkage ratio of the thermoplastic resin composition is reduced, and the joint body is produced. After the melt of the thermoplastic resin composition is brought into contact with the metal and cooled, the interface peeling of the thermoplastic resin composition with the metal is suppressed, so that the bondability of the thermoplastic resin composition to the metal is enhanced, and it is further preferred that the filler is added in a total amount of the thermoplastic resin composition. The weight is 10% by weight or more, more preferably 20% by weight or more, and most preferably 30% by weight or more. On the other hand, when the amount of the filler added is 80% by weight or less, the melt of the thermoplastic resin composition has good fluidity, more preferably 60% by weight or less, still more preferably 50% by weight or less.

The thermoplastic resin composition used in the present invention may further contain various additives. For example, antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites, phosphates and substituted products, copper halides, iodine compounds, etc.), weathering agents (resorcinol, water) Salicylic acid, benzotriazole, diphenyl ketone or sterically hindered amines, mold release agents and lubricants (fatty alcohols, aliphatic amides, aliphatic diamides or diureas or polyethylene waxes, etc.) ), pigment (calcium sulfide, phthalocyanine or carbon black, etc.), dye (aniline black, etc.), plasticizer (n-octyl p-hydroxybenzoate or N-butylbenzenesulfonamide), antistatic agent (alkyl sulfate) a salt type anionic antistatic agent, a 4-stage ammonium salt type cationic antistatic agent, a nonionic antistatic agent such as polyoxyethylene sorbitan monostearate or a trimethylglycine amphoteric antistatic agent) Flame retardant (melamine cyanurate, hydroxide such as magnesium hydroxide or aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin A bromine-based flame retardant or a combination of the above bromine-based flame retardant and antimony trioxide). These additives may be used singly or in combination of two or more.

The present invention is intended to obtain a joined body having excellent bonding properties between a thermoplastic resin composition and a metal, and therefore it is preferred to use a stretched shear bonded to aluminum using a thermoplastic resin composition comprising a terminally modified polyamide resin having an end structure of the formula I. A thermoplastic resin composition having a shear strength of 10 MPa or more. The tensile shear strength is defined as a value measured at a tensile speed of 5 mm/min according to the joint test strip (Fig. 1) specified in IS019095. The surface of the aluminum used herein has a microporous structure having an average pore diameter of 10 to 100 nm, and the uneven structure of the aluminum surface can be observed by an electron scanning microscope. Further preferably, the tensile shear strength is 15 MPa or more, and most preferably the thermoplastic resin composition having a tensile shear strength of 20 MPa or more, and the tensile shear strength of the thermoplastic resin composition bonded to the metal herein is prepared according to ISO 19095. It was tested at a tensile speed of 5 mm/min.

The joined body in the present invention can be obtained by directly bonding a thermoplastic resin composition to a metal, that is, the thermoplastic resin composition and the metal can be directly joined without passing through an intermediate layer such as another bonding material. The metal may be surface-treated or not surface-treated, and the type of the metal is not particularly limited, and examples thereof include iron, copper, silver, gold, aluminum, zinc, lead, tin, magnesium, and the like. An alloy of metals, such as stainless steel. The metal surface may have an oxide layer, or may have a surface structure to form an uneven structure, or an organic functional group or a low molecular weight organic compound may be introduced into the metal surface to form a chemical structure layer.

The surface treatment method of the above metal may be exemplified by immersing the metal surface in a corrosive liquid, immersing the fine concavo-convex structure on the surface, immersing it in an aqueous solution of the nitrogen-containing compound, or fumigation using a nitrogen-containing compound gas to make the metal surface a method of attaching a chemical substance; immersing a metal surface in a corrosive liquid, and forming a fine uneven structure on the surface of the metal by anodization on the surface of the metal, and attaching a chemical substance to the surface of the metal; etching the groove by laser processing The method of the slot, etc. Specifically, the NMT surface treatment method of Dacheng PLAS Corporation and the TRI surface treatment method of the East Asia Electrochemical Company can be exemplified.

The corrosive liquid used for the surface treatment may, for example, be an alkaline aqueous solution (pH>7), an acidic aqueous solution (pH<7), an aqueous solution containing a nitrogen compound, or the like, wherein the alkaline aqueous solution may, for example, be sodium hydroxide or hydroxide. An aqueous solution of potassium or sodium carbonate; an acidic aqueous solution may, for example, be an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid or hydrofluoric acid; the nitrogen-containing compound may be ammonia, hydrazine or a water-soluble amine, and the water-soluble amine may specifically be methylamine. Dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, allylamine, ethanolamine, diethanolamine, triethanolamine, aniline, and other amines.

The metal surface anodizing treatment method may be exemplified by using a metal as an anode and passing an electric current in the electrolytic solution to form an oxide film on the metal surface. For example, the water-soluble amine composition may be used as an electrolytic solution for anodizing the metal surface.

Examples of the chemical substance to be attached to the metal surface include ammonia, hydrazine, a water-soluble amine, and a triazine dithiol compound.

The above method of etching the groove by laser processing can specifically exemplify the technique of manufacturing micropores by metal surface etching by the DLAMP technology developed by Daicel Corporation of Japan and Daicel Plastics Co., Ltd.

The nano-scale uneven structure of the above metal surface is a nano-scale microporous structure under an electron scanning microscope, and preferably has an average pore diameter of 10 to 100 nm, and more preferably has a pore diameter of 10 to 80 nm.

The present invention also provides a process for producing a bonded body of a thermoplastic resin composition of the present invention and a metal. The method for producing the joined body of the present invention is not particularly limited, and the method for producing the joined body will be exemplified below.

It is considered to improve the bonding property of the thermoplastic resin composition and the metal and the efficiency in the actual manufacturing process, and it is preferable to perform injection molding or welding by laser irradiation.

The method of injection molding can specifically exemplify a method in which a thermoplastic resin composition is heated and melted and then injection-molded into a mold placed in advance in a metal to obtain a joined body. In the above injection molding process, the mold temperature is not particularly limited, but is preferably 60° C. or higher and 180° C. or lower. The moldability of the thermoplastic resin composition to the metal can be further improved by controlling the mold temperature to 60° C. or higher, more preferably 80° C. or higher, and still more preferably 100° C. or higher. On the other hand, the thermoplastic resin combination when the mold temperature is 180° C. or lower. The material can be more effectively cured and formed, and is more preferably 160 ° C or lower, still more preferably 150 ° C or lower.

Specifically, the method of welding by laser irradiation may be carried out by laminating and fixing a molded article obtained by using a thermoplastic resin composition, and then irradiating with a laser from the resin side or the metal side to melt the resin in the vicinity of the interface between the resin and the metal material. Thus, a method of joining a resin molded article and a metal material.

The thermoplastic resin composition of the present invention has high bonding property with a metal joined body, and is suitable for fields such as automobile parts requiring metal joining, electronic parts, electrical product parts, structural materials, and the like.

DRAWINGS

Fig. 1 is a resin-metal bonded spline used for testing the adhesion of a resin to a metal in an embodiment of the present invention.

Detailed ways

The invention is further illustrated by the following examples, which are not intended to limit the invention.

The description of the tests involved in the examples and comparative examples is as follows:

(1) Relative viscosity ηr: The polyamide resin sample used in each of the examples and the comparative examples was dissolved in 96 wt% of concentrated sulfuric acid to prepare a solution having a polyamide resin concentration of 0.01 g/ml, and was used at 25 ° C. The viscometer measures the relative viscosity.

(2) The terminal structure content represented by Formula I: the polyamide resin having the terminal structure represented by the above formula I used in each of the Examples and Comparative Examples, dissolved in deuterated concentrated sulfuric acid at a concentration of 50 mg/ml, in scanning The ¹ H-NMR nuclear magnetic test was carried out using Japanese electronic JEOL ECX400P under the conditions of 256 times. a peak corresponding to hydrogen on -CH ₂ - adjacent to the oxygen of the ether bond in the terminal structure of the above formula I in the ¹ H-NMR spectrum, and hydrogen corresponding to the repeating unit of the polyamide main chain as a main component After the peaks were assigned, the terminal structure content of the formula (I) in the polyamide resin was calculated by calculating the peak area obtained by integrating the peaks and the number of hydrogen atoms contained in each structure.

(3) Thermal properties

The thermoplastic resin composition used in each of the examples and the comparative examples was accurately weighed 5 to 7 mg by a differential scanning calorimeter (DSC Q2000) of TA Corporation, and the temperature was raised from 20 ° C at a heating rate of 20 ° C / min under a nitrogen atmosphere. Start heating up to a temperature 30 ° C higher than the temperature T0 of the endothermic peak that appears, and then thermostat at this temperature for 2 min, then cool down to 20 ° C at a temperature drop rate of 20 ° C / min, and then thermostatically at 20 ° C for 2 min. The temperature increase rate of 20 ° C / min was raised to a temperature 30 ° C higher than T0 to obtain a melting point T _m . T _m is the temperature corresponding to the peak tip of the endothermic peak during the secondary temperature rise.

(4) Molecular weight

The polyamide resin particles obtained in each of the preparation examples or the resin portion of the joined body obtained after the injection molding in each of the examples and the comparative examples were dissolved in 4 ml of hexafluoroisopropanol containing 0.0075 N of sodium trifluoroacetate. After the filtration, the number average molecular weight Mn and the weight average molecular weight Mw were measured by filtration through a 0.45 μm filter, and the measurement conditions were as follows:

Pump: e-Alliance GPC system (made by Waters)

Detector: Differential detector Waters 2414 (manufactured by Waters)

Column: Shodex HFIP-806M (2) + HFIP-LG

Solvent: hexafluoroisopropanol (adding 0.0075N sodium trifluoroacetate)

Flow rate: 0.5ml/min

Sample injection amount: 0.1ml

Temperature: 40 ° C

Molecular weight correction: polymethyl methacrylate.

(5) Melt viscosity

The polyamide resin obtained in Preparation Examples 1 to 12 was dried in a vacuum drying oven at 80 ° C for 12 hours or more, and then formed into a film (film thickness: 0.7 mm) by a laminator and then cut into a circle having a diameter of 25 mm. The sheet was measured for melt viscosity by a rotary rheometer (manufactured by Antonpaar, MCR302, φ25 parallel plate) by the following method: at 260 ° C (preparation examples 1 to 7, 10 to 12) or 280 ° C under a nitrogen atmosphere. (Preparation Examples 8 and 9) Molten for 5 minutes, parallel plate pitch of 0.5 mm, vibration mode measurement, frequency of 0.5 to 6.88 Hz, measurement of 50 points (0.5 minutes), and amplitude of 1%. The complex viscosity measurement at a frequency of 1 Hz was used as the melt viscosity.

(6) Tensile strength / tensile modulus

Tested according to ASTM D638, the spline size is Type IV in ASTM D638, the terminal modified polyamide obtained in Preparation Example 3 using Shimadzu AG-IS 1 KN, and the commercial polyamide elastomer used in Comparative Examples 4 and 5. The tensile modulus, test temperature 23 ° C, humidity 50% RH, tensile speed 10 mm / min, clamp spacing 60 mm. The tensile modulus results are taken as the average of the five spline test results. The injection molding conditions for the spline are as follows:

Injection molding machine: ST10S2V (manufactured by NISSEI)

Screw temperature: 250 ° C

Mold temperature: 80 ° C

(7) Metal sheet

Aluminum sheet A6061 (45mm*10mm*1.5mm) Kunshan Xinda Mould Co., Ltd.

Entrusted aluminum sheet processing company: Shenzhen Baoyuanjin Co., Ltd. (NMT);

Shenzhen Jinhongxin Technology Co., Ltd. (TRI processing).

(8) Joint injection molding

The metal piece was placed in a cavity of the mold, and after the mold was held for 1 minute, the melt of the thermoplastic resin composition was metered and injected into the mold. After the melt is cooled and solidified, the mold is opened to obtain a joined body.

Injection molding machine: ST10S2V (manufactured by NISSEI)

Screw temperature: 260 ° C (Examples 1 to 11, Comparative Examples 1 to 6)

280 ° C (Example 12, Comparative Example 7)

Mold temperature: 60 ~ 120 ° C

(9) splicability

The bondability between resin and metal is characterized by tensile shear strength, tested according to ISO 19095, the spline size is the specified size in ISO 19095 shown in Figure 1, and the joint area is 0.5 cm ² using Shimadzu AG-IS 1 KN test tensile modulus, test temperature 23 ° C, humidity 50% RH, tensile speed 5 mm / min, clamp spacing 3 mm. The tensile shear strength results are taken as the average of the five spline test results.

For the preparation method of the terminal-modified polyamide resin without the terminal-modified polyamide resin and the structure containing the formula I, the description is as follows:

Raw materials used in the preparation examples:

Caprolactam: BASF

Polyetheramine: Huntsman's JEFFAMINE M1000 (Mn = 1000), the structure is shown in Formula II

Adipic acid: Alfa

1,6-hexanediamine: TCI

Preparation Example 1

500 g of caprolactam, 0.19 g of adipic acid, 2.6 g of JEFFAMINE M1000 (Mn = 1000), and 150 g of deionized water were placed in the reaction vessel, and the reaction vessel was sealed and replaced with nitrogen three times. Heating was started after the heater temperature of the reaction vessel was set to 290 °C. After the pressure in the reactor reached 1 MPa, the water vapor in the reactor was discharged through a bleed valve while maintaining the pressure in the vessel at 1 MPa until the temperature in the vessel was raised to 250 °C. When the temperature in the autoclave reached 250 ° C, the heater set temperature was lowered to 260 ° C, and the pressure in the autoclave was gradually lowered from 1 MPa to normal pressure within 1 hour (the temperature in the autoclave was 260 ° C when the pressure was reached). After the pressure was reduced to normal pressure, a nitrogen gas flow was introduced into the autoclave, and after 30 minutes of melt polymerization under a nitrogen stream (up to a temperature of 263 ° C), the polymer melt was discharged through a discharge valve and cooled by cooling water. The pellets are obtained to obtain product particles. The obtained particles were subjected to removal of small molecules in the polymer using methanol as a solvent in a Soxhlet extractor, and dried in a vacuum oven at 80 ° C for 24 hours to obtain a terminal modified N6 containing the structure represented by Formula I.

Preparation Examples 2 to 7

The other operations were the same as in Preparation Example 1, except that the raw materials were changed as shown in Table 1 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 1.

Preparation Example 8

381.64 g of adipic acid, 302.11 g of 1,6-hexanediamine, 23.6 g of JEFFAMINE M1000 (Mn = 1000), and 180 g of deionized water were placed in the reaction vessel, and the reaction vessel was sealed and replaced with nitrogen three times. Heating was started after the heater temperature of the reaction vessel was set to 210 °C. After 1.5 hours of reaction, the heater temperature of the reaction vessel was set to 300 ° C. After the pressure in the reactor reached 1.75 MPa, the water vapor in the reactor was discharged through a gas release valve while maintaining the pressure in the reactor at 1.75 MPa until the kettle was maintained. The internal temperature rose to 250 °C. When the temperature in the autoclave reached 250 ° C, the pressure in the autoclave was gradually decreased from 1.75 MPa to normal pressure within 1 hour (the temperature in the autoclave at normal pressure was 270 ° C). After the pressure was reduced to normal pressure, a nitrogen gas flow was introduced into the autoclave, and after 20 minutes of melt polymerization under a nitrogen stream (up to a temperature of 283 ° C), the polymer melt was discharged through a discharge valve and cooled by cooling water. The pellets are obtained to obtain product particles. The resulting particles were dried in a vacuum oven at 80 ° C for 24 h to give a terminal modified N66 of the formula I.

Preparation Example 9

The other operations were the same as in Preparation 8 except that the raw materials were changed as shown in Table 1 and the pressure in the autoclave reached the normal pressure and the nitrogen-passing time was as shown in Table 1.

Table 1

In Preparation Example 6, when the terminal-modified polyamide resin was discharged from the reactor, the product was not stretched and the product particles could not be obtained. It is presumed that the molecular weight of the polymer could not be increased because the amount of the polyetheramine added was too high.

Preparation Examples 10 to 12

The raw materials were weighed as shown in Table 2. After the raw materials were mixed in a high-speed mixer, they were fed from a main feed port of a TEX30α-type twin-screw extruder (L/D=45.5) manufactured by Nippon Steel Works Co., Ltd., and melt-kneaded at a screw temperature of 250 ° C and a screw rotation speed of 200 rpm. . The extruded tow was subjected to pelletization, and vacuum dried at 80 ° C for 24 hours to obtain a polyamide resin composition.

Table 2

Example 1

The surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in a ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the end-modification of the structure containing the I obtained by the measurement preparation example 1. The polyamide resin was poured into the mold, and the cooling time was 15 s. The mold was opened to obtain a joined body. During the molding, the screw temperature was 260 ° C and the mold temperature was 120 ° C. The joined body obtained by the above method was subjected to metal bonding performance test at a tensile speed of 5 mm/min in accordance with ISO 19095, and the results are shown in Table 3.

Examples 2-7

Except for the modification of the type of the terminally modified polyamide shown in Table 3, the other operations were the same as in Example 1, and the properties of the obtained joined body were as shown in Table 3.

Comparative example 1

The surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in a ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the measurement of the unmodified polyamide obtained in Preparation Example 7. The resin melt was injected into the mold, the cooling time was 15 s, and the mold was opened to obtain a joined body. During the molding process, the screw temperature was 260 ° C and the mold temperature was 120 ° C. The obtained joined body of the above method was subjected to metal bonding performance test at a tensile speed of 5 mm/min in accordance with ISO 19095, and the results are shown in Table 3.

table 3

Comparing Examples 1 to 7 with Comparative Example 1, it can be seen that the thermoplastic resin composition containing the structurally modified polyamide of the structure represented by Formula I has a tensile shear strength superior to that of the metal without the structural polyamide represented by Formula I. The resin, Examples 2 to 6 metal joint tensile shear strength was significantly higher than Examples 1 and 7 having a lower structural content as shown in Formula I. For Example 4, a higher content of the structure of Formula I has an effect on the mechanical strength of the end-modified polyamide resin body such that the metal bond tensile shear strength ratio is 2 wt% and 4 wt% of the end of the structure shown in Formula I. The examples are low. For Examples 5 and 6, the obtained thermoplastic resin composition has a lower content by blending a structurally modified polyamide resin having a higher content of the formula I and a structural polyamide resin not containing the formula I. The melt viscosity (Table 2) was such that the resulting joined body had a higher metal bond tensile shear strength.

Examples 8 to 10

Except that the mold temperature during the injection molding process was changed as shown in Table 4, the other operations were the same as in Example 3, and the properties of the resulting joined body were as shown in Table 4.

Comparative Examples 2 and 3

Except that the mold temperature during the injection molding process was changed as shown in Table 4, the other operations were the same as in Comparative Example 1, and the properties of the obtained joined body were as shown in Table 4.

Table 4

Comparing Example 8 with Comparative Example 2, Example 9 and Comparative Example 3, it is understood that 4% by weight of the structure-modified polyamide resin of the formula I has a higher tensile shear strength and higher mold temperature. The metal bonded tensile shear strength of Examples 3 and 8 molded under the conditions was higher than that of Example 9 and Example 10 which were molded under the mold temperature conditions.

Comparative example 4

The surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in a ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the measurement of the commercial polyamide elastomer (PEBAX 5533SP01, manufactured by Arkema). The resin melt was poured into a mold, the cooling time was 15 s, and the mold was opened to obtain a joined body. During the molding, the screw temperature was 260 ° C and the mold temperature was 60 ° C. The obtained joined body of the above method was subjected to metal bonding performance test at a tensile speed of 5 mm/min in accordance with ISO 19095, and the results are shown in Table 5.

Comparative Example 5

Other operations were in accordance with Comparative Example 4 except that the mold temperature during the injection molding process was changed to 120 ° C as shown in Table 5. However, the resin could not be sufficiently cured in the mold, and deformation occurred during demolding, so that test strips could not be obtained.

table 5

*Data from Shannon Armstrong, Benny Freeman, Anne Hiltner, Eric Baer. Polymer; 2012: 1383-1392.

Compared with Comparative Example 5, Example 3 was excellent in high-temperature molding properties and had higher metal bond tensile shear strength. Meanwhile, in Example 10, the tensile strength of the metal joint tensile shear of Example 10 was higher than that of Comparative Example 4. Further, the tensile strength and tensile modulus of the thermoplastic resin composition body in Example 3 and Example 10 were significantly superior to those of Comparative Example 4 and Comparative Example 5.

Example 11

Except as shown in Table 6, the metal sheets treated by different surface treatment methods (TRI treatment, Shenzhen Jinhongxin Technology Co., Ltd.) were subjected to the same operations as in Example 3, and the properties of the obtained joined bodies were as shown in Table 6.

Comparative Example 6

Except as shown in Table 6, the metal sheets treated by different surface treatment methods (TRI treatment, Shenzhen Jinhongxin Technology Co., Ltd.) were used, and the other operations were the same as in Comparative Example 1, and the properties of the obtained joined bodies were as shown in Table 6.

Table 6

It can be seen from Example 3 and Example 11 that the tensile shear strength of the joint containing 4 wt% of the terminal modified polyamide resin of the formula I and the NMT and TRI treatments was 20 MPa or more. In Comparative Example 1 and Comparative Example 6 in which a polyamide resin which was not subjected to terminal modification was used, the tensile shear strength of the joint of the resin and the NMT and TRI treatments was less than 10 MPa.

Example 12

The surface-treated metal sheet (NMT treatment, Shenzhen Baoyuanjin Co., Ltd.) was placed in a ST10S2V (NISSEI) injection molding machine mold, and the injection molding machine completed the measurement of the terminal modification of the structure I obtained by the preparation of Example 8. The polyamide resin was poured into the mold, and the cooling time was 15 s. The mold was opened to obtain a joined body. During the molding, the screw temperature was 280 ° C and the mold temperature was 120 ° C. The joined body obtained by the above method was subjected to metal bonding performance test at a tensile speed of 5 mm/min in accordance with ISO 19095, and the results are shown in Table 7.

Comparative Example 7

Except for the modification of the type of the terminally modified polyamide shown in Table 7, the other operations were the same as in Example 12, and the properties of the obtained joined body were as shown in Table 7.

Table 7

In Example 12, as compared with Comparative Example 7, it can be seen that the thermoplastic resin composition containing the terminal-modified polyamide of the formula I represented by the structure has a tensile shear strength superior to that of the metal bonded structure of the formula I.

Claims (18)

A bonded body of a thermoplastic resin composition and a metal, characterized in that the thermoplastic resin composition contains a terminal-modified polyamide resin, and the content of the terminal-modified polyamide resin is 5 to the total weight of the thermoplastic resin composition. 100% by weight, the terminal modified polyamide resin has an end structure represented by Formula I, -X-(R ₁ -O)nR ₂ Formula I In the above formula I, n is an integer of 2 to 100, R _{1 is the} same or different, and is an alkylene group having 2 to 10 carbon atoms, and R ₂ is an alkyl group having 1 to 30 carbon atoms, and -X- is -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- or -CH(OH)-CH ₂ - Any of the structures of Formula I in the terminally modified polyamide resin is 0.05 to 20% by weight based on the total weight of the terminally modified polyamide resin. The bonded body according to claim 1, wherein in the terminal structure represented by the above formula I, n is an integer of from 16 to 50. The bonded body according to claim 1, wherein in the terminal structure represented by the above formula I, n is an integer of from 16 to 25. The joined body according to claim 1, wherein in the terminal structure represented by the above formula I, R _{1 is the} same or different and is an alkylene group having 2 to 4 carbon atoms. The bonded body according to claim 1, wherein in the terminal structure represented by the formula I, R ₂ is an alkyl group having 1 to 20 carbon atoms. The joined body according to claim 1, wherein in the terminal structure represented by the above formula I, R ₂ is a methyl group. The joined body according to claim 1, wherein -X- is -NH- in the terminal structure represented by the above formula I. The joined body according to claim 1, wherein the terminal structure represented by the above formula I is contained in the terminal-modified polyamide resin in an amount of from 0.1 to 15% by weight based on the total weight of the terminal-modified polyamide resin. The joined body according to claim 1, wherein the terminal structure represented by the above formula I is contained in the terminal-modified polyamide resin in an amount of from 0.1 to 10% by weight based on the total weight of the terminal-modified polyamide resin. The joined body according to claim 1, wherein the thermoplastic resin composition has a tensile shear strength of ≥ 10 MPa measured at a tensile speed of 5 mm/min according to the joint test strip specified in ISO19095. The joined body according to claim 1, wherein the joined body is obtained by directly bonding a thermoplastic resin composition to a metal. The joined body according to claim 1, wherein the terminal modified polyamide resin having the terminal structure represented by Formula I is formulated into a polyamide resin solution of 0.01 g/ml with 96 wt% sulfuric acid as a solvent, at 25 The relative viscosity ηr measured at ° C was 1.1 to 5.0. The joined body according to claim 1, wherein the terminal modified polyamide resin having the terminal structure represented by Formula I has a weight average molecular weight Mw measured by gel permeation chromatography in the range of 10,000 to 400,000. The joined body according to claim 1, wherein the terminal modified polyamide resin having the terminal structure represented by Formula I has a melting point of 215 ° C or higher. The joined body according to claim 1, wherein the thermoplastic resin composition further comprises a filler in an amount of from 5 to 80% by weight based on the total mass of the thermoplastic resin composition. The method for producing a joined body according to any one of claims 1 to 15, wherein the joined body is heated and melted by a thermoplastic resin composition, and then injection-molded with a metal previously placed in a mold. The manufacturing method according to claim 16, wherein in the injection molding, the mold temperature is between 60 and 180 °C. The method for producing a joined body according to any one of claims 1 to 15, wherein the joined body is obtained by welding a molded article of a thermoplastic resin composition and a metal by laser irradiation.

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