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CN109715393A - A kind of conjugant and its manufacturing method of thermoplastic resin composition and metal - Google Patents

A kind of conjugant and its manufacturing method of thermoplastic resin composition and metal Download PDF

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Publication number
CN109715393A
CN109715393A CN201880003557.7A CN201880003557A CN109715393A CN 109715393 A CN109715393 A CN 109715393A CN 201880003557 A CN201880003557 A CN 201880003557A CN 109715393 A CN109715393 A CN 109715393A
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conjugant
thermoplastic resin
resin composition
terminal
modified polyamide
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CN109715393B (en
Inventor
左璞晶
宋婷婷
陈斌
加藤公哉
大久保拓郎
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Toray Advanced Materials Research Laboratories China Co Ltd
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Toray Advanced Materials Research Laboratories China Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Abstract

The present invention provides the conjugants and its manufacturing method of a kind of thermoplastic resin composition with excellent Joint Properties and metal.The thermoplastic resin composition contains terminal-modified polyamide, content of the terminal-modified polyamide in thermoplastic resin composition is 5~100wt% of thermoplastic resin composition's total weight, the terminal-modified polyamide has end structure shown in formula I ,-X- (R1‑O)n‑R2In the above-mentioned formula I of formula I, the integer that n is 2~100, R1It is identical or different, it is the alkylidene that carbon atom number is 2~10, R2The alkyl for being 1~30 for carbon atom number ,-X- are-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)-NH- or-CH (OH)-CH2Any one of；Content of the structure shown in formula I in terminal-modified polyamide is 0.05~20wt% of terminal-modified polyamide total weight.

Description

A kind of conjugant and its manufacturing method of thermoplastic resin composition and metal Technical field
The invention belongs to the complex fields of polymer and metal, specifically disclose the conjugant and its manufacturing method of a kind of thermoplastic resin composition and metal.
Background technique
As the energy, safe and environment-friendly three major issues become increasingly conspicuous, automotive light weight technology is increasingly taken seriously.Since specific gravity is much smaller than metal, application of the engineering plastics on automobile is gradually increased, but in certain structure members, itself mechanical strength of engineering plastics is still difficult to meet demand.Metal/plastic hybrid composite material has both the characteristics of metal high intensity and plastics lightweight, while meeting the mechanical strength requirements and lightweight demand of structural partsof automobiles.
At present, engagement between metal component and plastics mainly passes through machine riveting, adhesive adhesive joint to constituting hybrid composite material together, but after plastic components and metal parts need to process respectively in these junctures, then by riveting, be glued etc. and to be joined together composition whole parts.Above-mentioned juncture has the problems such as complex process, adhesive easily deteriorate.
In recent years, resin is directly passed through to the method that injection molding is engaged with metal and has also obtained more and more researchs.International Patent Application Publication bulletin WO2012/132639 discloses the complex of a kind of thermoplastic resin and metal, containing the inorganic filler that increase Resin crystallization temperature in the thermoplastic resin, but the zygosity between obtained its resin of complex of this method and metal is still insufficient.International Patent Application Publication bulletin WO2015/022955 discloses the complex of a kind of thermoplastic resin and metal, the thermoplastic resin composition which can be the polyamide elastomer of polyethers modification by copolymerization or be made of water imbibition thermoplastic resin and metal hydroxides.But compared with polyamide homopolymer, the mechanical performance of polyamide elastomer is remarkably decreased.On the other hand, compared to polyamide homopolymer, polyamide elastomer glass transition temperature is lower, and curing rate is slower when injection moulding, and molding cycle lengthens.Meanwhile the zygosity of polyamide elastomer and metal is bad.
Chinese patent application Publication CN105479659A discloses the complex of a kind of plastic material comprising polyether block amide and metal material, although plastic material and metallic cohesion are excellent and provide a degree of sealing characteristics, but since polyether structure content is higher in polyether block amide, compared with polyamide homopolymer, the decline of polyether block amide mechanical performance, and the Joint Properties of polyether block amide and metal are insufficient.
Existing technical literature
Patent document 1: International Patent Application Publication bulletin WO2012/132639
Patent document 2: International Patent Application Publication bulletin WO2015/022955
Patent document 3: Chinese patent application Publication CN105479659A
Summary of the invention
Present invention aim to address the above subject, the conjugant of a kind of thermoplastic resin composition and metal are provided, the thermoplastic resin composition contains the polyamide that end has imported polyether chain, to improve the bond strength of thermoplastic resin composition and metal, while thermoplastic resin composition itself still keeps higher mechanical performance.
The present invention also provides the manufacturing method of the thermoplastic resin composition and the conjugant of metal, this method can efficiently prepare the conjugant of metal and resin, lay the foundation for continuous production.
The present invention is made of the following contents:
1, the conjugant of a kind of thermoplastic resin composition and metal, the thermoplastic resin composition contains terminal-modified polyamide, the content of the terminal-modified polyamide is 5~100wt% of thermoplastic resin composition's total weight, the terminal-modified polyamide has end structure shown in Formulas I
-X-(R 1-O)n-R 2Formulas I
In above-mentioned Formulas I, the integer that n is 2~100, R 1It is identical or different, the alkylidene for being 2~10 for carbon atom number, R2 is the alkyl that carbon atom number is 1~30, and-X- is-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)-NH- or-CH (OH)-CH 2Any one of；Content of the structure shown in Formulas I in terminal-modified polyamide is 0.05~20wt% of terminal-modified polyamide total weight.
2, the conjugant according to above-mentioned 1, in end structure shown in above-mentioned Formulas I, integer that n is 16~50.
3, the conjugant according to above-mentioned 1, in end structure shown in above-mentioned Formulas I, integer that n is 16~25.
4, the conjugant according to above-mentioned 1, in end structure shown in above-mentioned Formulas I, R 1It is identical or different, it is the alkylidene that carbon atom number is 2~4.
5, the conjugant according to above-mentioned 1, in end structure shown in above-mentioned Formulas I, R 2The alkyl for being 1~20 for carbon atom number.
6, the conjugant according to above-mentioned 1, in end structure shown in above-mentioned Formulas I, R 2For methyl.
7, the conjugant according to above-mentioned 1, in end structure shown in above-mentioned Formulas I ,-X- is-NH-.
8, the conjugant according to above-mentioned 1, content of the end structure shown in above-mentioned Formulas I in terminal-modified polyamide are 0.1~15wt% of terminal-modified polyamide total weight.9, the conjugant according to above-mentioned 1, content of the end structure shown in above-mentioned Formulas I in terminal-modified polyamide are 0.1~10wt% of terminal-modified polyamide total weight.10, the conjugant according to above-mentioned 1, tensile shear strength >=10MPa that thermoplastic resin composition conjugant according to as defined in ISO19095 test batten measures under the tensile speed of 5mm/min.
11, the conjugant according to above-mentioned 1, the conjugant are directly engaged to obtain by thermoplastic resin composition with metal.
12, the conjugant according to above-mentioned 1, the terminal-modified polyamide with end structure shown in Formulas I are configured to the polyamide resin lipoprotein solution of 0.01g/ml using 96wt% sulfuric acid as solvent, and the relative viscosity η r measured at 25 DEG C is 1.1~5.0.
13, the conjugant according to above-mentioned 1, the range for the weight average molecular weight Mw that the terminal-modified polyamide with end structure shown in Formulas I is measured with gel permeation chromatography are 10,000~400,000.
14, the conjugant according to above-mentioned 1, the fusing point of the terminal-modified polyamide with end structure shown in Formulas I are 215 DEG C or more.
15, the conjugant according to above-mentioned 1, the thermoplastic resin composition further include inorganic filler, and the content of the inorganic filler is 5~80wt% of thermoplastic resin composition's total weight.
16, the manufacturing method of conjugant described in one kind above-mentioned any one of 1~15, the conjugant by after thermoplastic resin composition's heating melting be placed in advance in the metal injection molded molding of mold.
17, the manufacturing method according to above-mentioned 16, the conjugant is in injection molding process, and mold temperature is between 60~180 DEG C.
18, the manufacturing method of conjugant described in one kind above-mentioned any one of 1~15, it is characterised in that: the conjugant is welded to obtain by the molded product and metal of thermoplastic resin composition by laser irradiation.
The conjugant of thermoplastic resin composition and metal of the invention can be used for automobile component, electronics, electric equipment products component, structural material etc..
Foregoing invention content is described in detail below:
Thermoplastic resin composition used in conjugant of the present invention includes the terminal-modified polyamide with end structure shown in Formulas I, and the content of the terminal-modified polyamide is 5~100wt% of thermoplastic resin composition's total weight,
-X-(R 1-O)n-R 2Formulas I
In above-mentioned Formulas I, the integer that n is 2~100, R 1It is identical or different, it is the alkylidene that carbon atom number is 2~10, R 2The alkyl for being 1~30 for carbon atom number ,-X- are-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)-NH- or-CH (OH)-CH 2Any one of；Content of the structure shown in Formulas I in terminal-modified polyamide is 0.05~20wt% of terminal-modified polyamide total weight.
In the present invention, when thermoplastic resin composition contains only this single component of terminal-modified polyamide, it is also defined as thermoplastic resin composition.
The present invention does not have special limitation to the type of used terminal-modified polyamide backbone structure.The raw material monomer for constituting terminal-modified polyamide backbone structure can be diacid, diamines, amino acid or lactams etc., can specifically enumerate following instance but be not limited only to following instance: the amino acid such as 6-aminocaprolc acid, 11- aminoundecanoic acid, 12-aminolauric acid or Aminomethylbenzoic Acid；The lactams such as epsilon-caprolactams, ω-ten lactams or omega-lauric lactam；Ethylenediamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, octamethylenediamine, nonamethylene diamine, decamethylene diamine, hendecane diamines, dodecamethylene diamine, tridecane diamine, tetradecane diamines, pentadecane diamines, hexadecane diamines, heptadecane diamines, octadecamethylene diamine, nonadecane diamines, eicosane diamines, 2- methyl-1,5- pentanediamine or 2- methyl-1, the aliphatic diamines such as 8- octamethylenediamine；Cyclohexanediamine or 4,4 '-diamino-dicyclohexyl methanes, 4, the alicyclic diamines such as 4 '-di-2-ethylhexylphosphine oxides (2- methyl cyclohexylamine)；The aromatic diamines such as benzene dimethylamine；The aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, azelaic acid, decanedioic acid or dodecanedioic acid；The aromatic dicarboxylic acids such as the chloro- Isosorbide-5-Nitrae-phthalic acid of terephthalic acid (TPA), M-phthalic acid, 2-, 2- methyl-1,4- phthalic acid or oreinol dioctyl phthalate, 5- sodium sulfonate M-phthalic acid；The alicyclic dicarboxylic acids such as cyclohexane cyclohexanedimethanodibasic.Alkyl diester and diacid chloride derived from dicarboxylic acids, which similarly can be used as, to be constituted the raw material monomer of polyamide backbone structure and is enumerated.The main chain of terminal-modified polyamide used in the present invention can specifically include the equal poly structure prepared by above-mentioned monomer, be also possible to the copolymeric structure prepared by above-mentioned monomer.
The polyamide backbone structure of terminal-modified polyamide can be enumerated but be not limited only to following instance: polycaprolactam (nylon 6), poly- 11 lactams (nylon 11), nylon 12 (nylon 12), polyhexamethylene adipamide (nylon66 fiber), nylon 46 (nylon 46), poly hexamethylene adipamide pentanediamine (nylon 56), polytetramethylene sebacamide (nylon 410), poly- decanedioyl pentanediamine (nylon 510), polyhexamethylene sebacamide (nylon 610), poly- dodecanoamide (nylon 612), nylon 1010 (nylon 1010), poly- lauroyl decamethylene diamine (Nylon 1012), polycaprolactam/polyhexamethylene adipamide copolymer (nylon 6/66), poly-meta-xylylene adipamide (MXD6), poly- decanedioyl m-xylene diamine ( MXD10), poly- decanedioyl p dimethylamine (PXD10), poly-paraphenylene terephthalamide's nonamethylene diamine (nylon 9 T), poly- paraphenylene terephthalamide's decamethylene diamine (nylon 10T), poly- paraphenylene terephthalamide's undecylamine (nylon 11 T), poly- paraphenylene terephthalamide's lauryl amine (nylon 12T), poly- paraphenylene terephthalamide's pentanediamine/poly- hexamethylene terephthalamide copolymer (nylon 5T/6T), poly- paraphenylene terephthalamide -2 methyl pentamethylenediamine/poly- hexamethylene terephthalamide copolymer (nylon M5T/6T), polyhexamethylene adipamide/poly- hexamethylene terephthalamide copolymer (nylon66 fiber/6T), phenyl-diformyl ` diamine copolymer (nylon66 fiber/6I) between polyhexamethylene adipamide/poly-, polyhexamethylene adipamide/poly- hexamethylene terephthalamide/poly-6I hexamethylene isoterephalamide copolymer (nylon66 fiber / 6T/6I), poly- paraphenylene terephthalamide 4, 4 '-di-2-ethylhexylphosphine oxides (2- methyl cyclohexylamine) (nylon MACMT), phenyl-diformyl 4 between poly-, 4 '-di-2-ethylhexylphosphine oxides (2- methyl cyclohexylamine) (nylon MACMI), poly- lauroyl 4, 4 '-di-2-ethylhexylphosphine oxides (2- methyl cyclohexylamine) (nylon MACM12), poly- paraphenylene terephthalamide 4, 4 '-methylenebiscyclohexylamines (nylon PACMT), phenyl-diformyl 4 between poly-, 4 '-methylenebiscyclohexylamines (nylon PACMI), poly- lauroyl 4, the copolymer of 4 '-methylenebiscyclohexylamines (nylon PACM12) or above-mentioned polymer.
The preferably terminal-modified polyamide of crystallinity in order to obtain, the preferred polycaprolactam of the polyamide backbone structure of above-mentioned end modified polyamide resin (nylon 6), polyhexamethylene adipamide (nylon66 fiber), poly hexamethylene adipamide pentanediamine (nylon 56), polytetramethylene sebacamide (nylon 410), poly- decanedioyl pentanediamine (nylon 510), polyhexamethylene sebacamide (nylon 610), poly-paraphenylene terephthalamide's nonamethylene diamine (nylon 9 T) or poly- paraphenylene terephthalamide's decamethylene diamine (nylon 10T).
The backbone structure of the terminal-modified polyamide can be separately formed by one of above-mentioned backbone structure, can also be made of the two or more combinations in above-mentioned backbone structure.The preferred 80mol% or more of backbone repeat unit of terminal-modified polyamide used in the present invention is made of the structural unit of enumerated raw material monomer origin (with the number of repeat unit of polyamide backbone structure for 100mol%).In view of heat resistance and crystallinity, preferably 90mol% or more, most preferably 100mol%.
Terminal-modified polyamide used in the present invention improves the motility of strand entirety by the flexible polyether structure shown in polyamides amine end introduction-type I, to reduce melt viscosity.Therefore, when the thermoplastic resin containing terminal-modified polyamide is contacted with metal in the molten state, resin melt is more effectively impregnated into the small hole in metal surface, so as to preferably be tightly engaged into metal surface.
In above-mentioned Formulas I, n be 2~100 integer.When n is less than 2, thermoplastic resin composition's melt viscosity reducing effect is deteriorated.It is preferred that n is 4 or more, further preferred n is 8 or more, and most preferably n is 16 or more.On the other hand, when n is greater than 100, the heat resistance of end structure shown in Formulas I is deteriorated.It is preferred that n is 70 hereinafter, further preferably n is 50 hereinafter, most preferably n is 25 or less.
In above-mentioned Formulas I, R 1It is identical or different, it is the alkylidene of carbon atom number 2~10.R 1- CH can specifically be enumerated 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 2Or-CH 2-CH 2-CH 2-CH 2-CH 2-CH 2Etc..In view of the compatibility with polyester backbone structure, preferably R 1For the alkylidene of carbon atom number 2~6, the alkylidene of further preferred carbon atom number 2~4.R 1It can be composed of different alkylidenes, preferably-CH 2-CH 2-、-CH 2-CH 2-CH 2-、-CH(CH 3)-CH 2At least one of.
In above-mentioned Formulas I, R 2For the alkyl of carbon atom number 1~30.R 2Middle carbon atom number is fewer, also higher with the compatibility of polyamide backbone structure, therefore R 2It is preferred that the alkyl that carbon atom number is 1~20, the alkyl that the alkyl that further preferred carbon atom number is 1~10, still more preferably carbon atom number are 1~5, most preferable.
In above-mentioned Formulas I ,-X- is-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)-NH- or-CH (OH)-CH 2Any one of, in order to make thermoplastic resin composition used in the present invention have lower melt viscosity, the affinity of polyethers end and polyamide skeleton is higher preferably ,-X- preferably-NH-.
The content of end structure shown in Formulas I is 0.05~20wt% of terminal-modified polyamide total weight in terminal-modified polyamide used in the present invention, in view of the purpose for reducing melt viscosity, improving molding processibility, content preferred 0.1wt% or more of the end structure in the terminal-modified polyamide, further preferred 0.5wt% or more, still more preferably 1.5wt% or more, most preferably 2wt% or more；On the other hand, by making the content 20wt% of end structure shown in Formulas I hereinafter, the crystallinity of terminal-modified polyamide and mechanical performance can be made preferably to be kept, preferably 15wt% or less, further preferably 10wt% is hereinafter, be still more preferably 5wt% or less.Herein, polyether segment shown in above-mentioned Formulas I passes through relative to the content (wt%) of the terminal-modified polyamide 1H-NMR (nucleus magnetic hydrogen spectrum) test obtains.
Terminal-modified polyamide with end structure shown in Formulas I in the present invention is when using the 96wt% concentrated sulfuric acid as solvent, being configured to solution that concentration is 0.01g/ml, preferably 1.1~5.0 under the relative viscosity η r measured at 25 DEG C.When η r is less than 1.1, thermoplastic resin composition's mechanical property and metal bonding performance have a declining tendency.It is preferred that η r is 1.2 or more, further preferably 1.4 or more.On the other hand, when η r is higher than 5.0, molecular weight is excessively high, thus melt viscosity is excessively high that metal bonding performance is caused to have a declining tendency, and preferably η r is 4 hereinafter, further preferably η r is below 3.
The weight average molecular weight (Mw) of terminal-modified polyamide with end structure shown in Formulas I in the present invention is preferably 10,000 or more.When Mw reaches 10,000 or more, mechanical performance and metal bonding performance are improved.Mw further preferred 20,000 or more, still more preferably 30,000 or more.In addition, Mw preferably 400,000 or less.When Mw is 400,000 or less, melt viscosity is lower, and during manufacturing conjugant, resin melt can sufficiently infiltrate the small hole in metal surface, so that thermoplastic resin composition is tightly engaged into metal surface, improves metal bonding performance.Mw further preferred 300,000 is hereinafter, still more preferably 250,000 or less.Weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC).
The present invention is directed to obtain heat-resist conjugant, therefore the fusing point (Tm) of the terminal-modified polyamide with end structure shown in Formulas I is preferably 215 DEG C or more, and the fusing point (Tm) of further preferred terminal-modified polyamide is at 218 DEG C or more.In general introducing flexible structure to polyamide by copolymerization can be such that the fusing point of polyamide declines, but the present invention imports the polyethers of specific structure in resinous terminal by selectivity, so that the decline for having imported the polyamide fusing point of polyethers end is controlled in the smallest range compared with the polyamide without containing polyethers end structure.Preferably more than 5 DEG C of fusing point decline, further preferred fusing point decline is no more than 3 DEG C.The fusing point of polyamide described here is obtained by differential scanning calorimeter (DSC) measurement: by 5~7mg of polyamide accurate weighing, it is started to warm up in a nitrogen atmosphere from 20 DEG C to the temperature T0 of the endothermic peak than occurring with the heating rate of 20 DEG C/min and is higher by 30 DEG C of temperature, constant temperature 2min at this temperature, it is then cooled to the rate of temperature fall of 20 DEG C/min and is warming up to the temperature for being higher by 30 DEG C than T0 after 20 DEG C with the heating rate of 20 DEG C/min again, the temperature of the endothermic peak occurred in second of temperature-rise period is defined as fusing point (Tm).
In the thermoplastic resin composition that the present invention uses, other kinds of polymer, filler and various additives can also be added in addition to terminal-modified polyamide and are compounded.
Other kinds of polymer can be enumerated but be not limited only to following example in above-mentioned thermoplastic resin composition: the polyolefin such as polyethylene, polypropylene；The improved polyalkenes such as the copolymer that alkene and/or conjugated diene hydrocarbon compound polymerize；Polyamide etc. other than polyester, polycarbonate, polyphenylene oxide, polyphenylene sulfide, liquid crystal polymer, polysulfones, polyether sulfone, ABS resin, SAN resin, polystyrene, the unmodified polyamide in end of the invention.
As above-mentioned other kinds of polymer, in order to improve the thermoplastic resin composition's obtained molded product impact resistance of the invention used and reduce shrinking percentage, it is preferable to use the anti-impact agents such as improved polyalkenes such as polymer (or copolymer) that alkene and/or conjugated diene hydrocarbon compound polymerize.
Above-mentioned polymer (or copolymer) can enumerate but be not limited only to following instance: vinyl copolymer, conjugated diene based polymer or conjugated diene-aromatic vinyl copolymer etc..
Vinyl copolymer refers to the copolymer of ethylene and other monomers.It can be enumerated with the other monomers of ethylene copolymer but be not limited only to following instance: alpha-olefin, non-conjugated diene hydrocarbon, vinyl acetate, the vinyl alcohol, α of 3 or more carbon atom number, beta-unsaturated carboxylic acid or derivatives thereof.Above-mentioned monomer also can choose two or more and is copolymerized with ethylene.
The alpha-olefin of 3 or more carbon atom number can be enumerated but be not limited only to following instance: propylene, 1- butylene, 1- amylene or 3- Methyl-1-pentene, preferably propylene or 1- butylene.Non-conjugated diene hydrocarbon can be enumerated but be not limited only to following instance: 5- methylene -2- norbornene, 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene, 5- acrylic -2- norbornene, 5- isopropenyl -2- norbornene, 5- cyclobutenyl -2- norbornene, 5- (2- methyl-2-butene base) -2- norbornene, 5- (2- ethyl -2- cyclobutenyl) norbornene compounds such as -2- norbornene or 5- methyl -5- vinyl norbornene；Dicyclopentadiene, methyl tetrahydroquinone, tetrahydroindene, 1,5- cyclo-octadiene, Isosorbide-5-Nitrae-hexadiene, 6- methyl-1,5- heptadiene or 11- oleatridecadiene etc., it is preferred that 5- methylene -2- norbornene, 5- ethylidene -2- norbornene, dicyclopentadiene or Isosorbide-5-Nitrae-hexadiene.α, beta-unsaturated carboxylic acid can be enumerated but be not limited only to following instance: acrylic acid, methacrylic acid, ethylacrylic acid, 2- butenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid or butene dioic acid etc..The derivative of α, beta-unsaturated carboxylic acid can be enumerated but be not limited to following instance: above-mentioned α, Arrcostab, aryl ester, glyceride, acid anhydrides or acid imide of beta-unsaturated carboxylic acid etc..
Conjugated diene based polymer refers to the polymer obtained by least one conjugate diene polymerization.Conjugated diene described here can be enumerated but be not limited only to following instance: 1,3-butadiene, isoprene (2- methyl-1,3- butadiene), 2,3- dimethyl -1,3-butadiene or 1,3-pentadiene etc..Above-mentioned conjugated diene also can choose two or more and is copolymerized.In addition, the unsaturated bond of the polymer can carry out reduction partially or completely by hydrogenation.
Conjugated diene-aromatic vinyl copolymer refers to the copolymer of conjugated diene and aromatic vinyl, can be block copolymer, is also possible to random copolymer.The adducible example of conjugated diene is identical as the above-mentioned raw material for preparing conjugated diene based polymer, preferably 1,3-butadiene and isoprene.Aromatic vinyl can enumerate following instance: styrene, o-methyl styrene, m-methyl styrene, p-methylstyrene, 1,3- dimethyl styrene or vinyl naphthalene etc., optimization styrene.In addition, unsaturated bond of the conjugated diene-aromatic vinyl copolymer in addition to the double bond of aromatic rings can also pass through hydrogenated fractions or complete reduction.
Anti-impact agent can specifically be enumerated: ethylene/propene copolymer, Ethylene/1-butene copolymer, ethylene/1- hexene copolymer, ethylene/propylene/dicyclopentadiene copolymer, ethylene/propene/5- ethylidene -2- norbornene copolymer, not plus hydrogen or add hydrogen styrene/isoprene/styrene triblock copolymer, not plus hydrogen or add hydrogen styrene/butadiene/styrene triblock copolymer, some or all of carboxylic acid group and sodium in ethylene/methacrylic acid or copolymer, lithium, potassium, the salt that zinc or calcium are formed, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/methacrylic acid methyl terpolymer, (" g " indicates grafting to ethylene/ethyl acrylate-g- copolymer-maleic anhydride herein, similarly hereinafter), ethylene/methyl acrylate-g- maleic anhydride is total Polymers, ethylene/ethyl acrylate-g- maleimide copolymer, the partially saponified matter of ethylene/ethyl acrylate-g-N- phenyl maleimide copolymers or the copolymer, ethylene/methacrylic acid glycidyl ester copolymer, Ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/methacrylic acid methyl esters/glycidyl methacrylate copolymer, ethylene/acrylic acid glycidyl ester copolymer, Ethylene/vinyl acetate/glycidyl acrylate copolymer, ethylene/glycidyl ether copolymers, ethylene/propene-g- copolymer-maleic anhydride, ethylene/propene-g- copolymer-maleic anhydride, ethylene/butylene -1-g- copolymer-maleic anhydride, ethylene/propene/1, 4- hexadiene-g- copolymer-maleic anhydride, ethylene/propene/bicyclic penta Diene-g- copolymer-maleic anhydride, ethylene/propene/2, 5- norbornadiene-g- copolymer-maleic anhydride, ethylene/propene-g-N- phenyl maleimide copolymers, ethylene/butylene -1-g-N- phenyl maleimide copolymers, hydrogenate (styrene/butadiene/styrene-g- maleic anhydride) copolymer, hydrogenate (styrene/isoprene/styrene-g- maleic anhydride) copolymer, ethylene/propene-g- glycidyl methacrylate copolymer, ethylene/butylene -1-g- glycidyl methacrylate copolymer, ethylene/propene/1, 4- hexadiene-g- glycidyl methacrylate copolymer, ethylene/propylene/dicyclopentadiene-g- glycidyl methacrylate copolymer, hydrogenate (styrene/butadiene/styrene- G- glycidyl methacrylate) copolymer, 12/ polytetrahydrofuran copolymer of nylon, 12/ polypropylene glycol copolymers of nylon, polybutylene terephthalate/polytetrahydrofuran copolymer or polybutylene terephthalate/polypropylene glycol copolymers etc..Salt, the ethylene/propene-g- copolymer-maleic anhydride, ethylene/butylene -1-g- copolymer-maleic anhydride that part or all of carboxylic acid group and sodium, lithium, potassium, zinc or calcium are formed in above-mentioned copolymer optimal ethylene/methacrylic acid copolymer and copolymer.
Polymer in above-mentioned thermoplastic resin composition in addition to terminal-modified polyester resin can be added individually, can also choose two or more cooperation additions.Its additive amount is preferably 0wt% or more, 80wt% or less (being 100wt% with thermoplastic resin composition), and by controlling additive amount in above range, mobility when thermoplastic resin composition can be made to melt is more preferable.Further preferred 60wt% is hereinafter, still more preferably 50wt% or less.
Filler can also be contained in thermoplastic resin composition of the invention, filler can be enumerated but be not limited only to following instance: the inorganic or organic filler of the threadiness such as glass fibre, carbon fiber, titanium potassium acid crystals palpus, ZnOw, aluminium borate whisker, aromatic polyamide fibre, alumina fibre, silicon carbide fibre, ceramic fibre, asbestos fibre, gypsum fiber or metallic fiber；The Non-fibrous inorganic filler such as wollastonite, zeolite, sericite, kaolin, mica, talcum, clay, pyrophyllite, bentonite, montmorillonite, asbestos, silicate, aluminium oxide, silica, magnesia, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminium hydroxide, glass microballoon, ceramic microbead, boron nitride, silicon carbide or silica.Above-mentioned filler can be to be hollow, in addition, above-mentioned filler can also be through coupling agent treatments such as isocyanic acid based compound, organic silane compound, organic titanate based compound, organoborane compounds or epoxides.Above-mentioned montmorillonite is also possible to piece interlayer ion and carries out the organic montmorillonite after cationic exchange by organic ammonium salt.Mechanical performance raising, shaping shrinkage rate reduction in view of thermoplastic resin composition, the inorganic filler of the preferred threadiness of above-mentioned filler, further preferred glass fibre or carbon fiber.In addition, above-mentioned filler can be added individually, two or more cooperation additions can also be chosen.
Content of the above-mentioned filler in thermoplastic resin composition is preferably 5~80wt% of thermoplastic resin composition's total weight, when the additive amount of filler is in 5wt% or more, since thermoplastic resin composition's shrinking percentage is reduced, during manufacturing conjugant, after thermoplastic resin composition's melt is contacted and is cooled down with metal, the interface peel of thermoplastic resin composition and metal is suppressed, so that the zygosity of thermoplastic resin composition and metal enhances, further preferred filler additive amount is the 10wt% or more of thermoplastic resin composition's total weight, still more preferably 20wt% or more, most preferably 30wt% or more.On the other hand, for the additive amount of filler in 80wt% or less, thermoplastic resin composition's melt has good mobility, and further preferred 60wt% is hereinafter, still more preferably 50wt% or less.
In the thermoplastic resin composition that the present invention uses, various additives can also be contained.Such as, antioxidant and heat stabilizer (hindered phenolic, hydroquinone system, phosphite ester system, phosphate system and its substitution product, copper halide, iodine compound etc.), weather resisting agent (resorcinol system, salicylic acid system, enumerate BTA system, diphenylmethanone system or steric hindrance amine system etc.), release agent and lubricant (fatty alcohol, aliphatic amide, aliphatic diamides or two ureas or polyethylene wax etc.), pigment (calcium sulfide, phthalocyanine or carbon black etc.), dyestuff (nigrosine etc.), plasticiser (P-hydroxybenzoic acid n-octyl or N-butylbenzenesulfonamide), antistatic agent (alkyl sulphate type anionic system antistatic agent, 4 grades of ammonium salt type cationic system antistatic agents, the nonionic systems such as polyoxyethylene sorbitan monostearate antistatic agent or trimethylglycine system both sexes antistatic agent), fire retardant (melamine cyanurate Salt, the hydroxide such as magnesium hydroxide, aluminium hydroxide, polyvinyl ammonium, the composition of the bromide fire retardants such as brominated Polystyrene, brominated polyphenylether, brominated polycarbonate, brominated epoxy resin or above-mentioned bromide fire retardant and antimony oxide).Above-mentioned additive can be used alone, and also can choose two or more compounding.
The present invention is directed to obtain the conjugant between thermoplastic resin composition and metal with excellent Joint Properties, therefore the thermoplastic resin composition that the tensile shear strength engaged it is preferable to use the thermoplastic resin composition comprising the terminal-modified polyamide with end structure shown in Formulas I with aluminium is 10MPa or more.The tensile shear strength is defined as the value that the test of the conjugant according to as defined in IS019095 batten (Fig. 1) measures under the tensile speed of 5mm/min.It is the microcellular structure of 10~100nm that the surface of aluminium used herein, which has average pore size, and the concaveconvex structure of aluminium surface can be observed by electronic scanner microscope.Further preferred tensile shear strength 15MPa or more, most preferably tensile shear strength be 20MPa or more thermoplastic resin composition, test batten is made according to ISO19095 in the tensile shear strength of thermoplastic resin composition and metal bonding described here, tests and obtains under the tensile speed of 5mm/min.
Conjugant in the present invention can directly be engaged to obtain by thermoplastic resin composition with metal, that is, can also not engaged directly by middle layers such as other adhesives between thermoplastic resin composition and metal.The metal can be by surface treatment, be also possible to no surface treated, is not particularly limited simultaneously for the type of metal, can enumerate the alloy of tapping, copper, silver, gold, aluminium, zinc, lead, tin, magnesium and above-mentioned metal, such as stainless steel.The metal surface may exist oxide layer, its surface can also be made to form concaveconvex structure by surface treatment, can also import organo-functional group in metal surface or low molecular weight organic compound forms chemical structure layer.
Above-mentioned metallic surface processing method can be included carries out metal surface impregnation in corrosive liquids, it immerses in nitrogenous compound aqueous solution after going out fine concaveconvex structure in surface etch or is fumigated using nitrogenous compound gas, make the method for metal surface attachment chemical substance；Metal surface is subjected to impregnation in corrosive liquids, and so that metal surface is formed fine concaveconvex structure by anodic oxidation in metal surface, in the method for metal surface attachment chemical substance；By laser machining the method etc. for etching groove.NMT surface treatment method and the TRI surface treatment method of East Asia electrification company etc. of great achievement PLAS company can specifically be included.
The above-mentioned corrosive liquids for surface treatment can include alkaline aqueous solution (pH > 7), acidic aqueous solution (pH < 7), nitrogenous compound aqueous solution etc., wherein alkaline aqueous solution can include the aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate etc.；Acidic aqueous solution can include the aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid etc.；Nitrogenous compound can be ammonia, hydrazine or water-soluble amine, and water-soluble amine can specifically enumerate methylamine, dimethylamine, trimethylamine, ethamine, diethylamine, triethylamine, ethylenediamine, allylamine, ethanol amine, diethanol amine, triethanolamine, aniline and other amines.
Above-mentioned metal surface anode oxidative treatment method can be included using metal as anode, in the electrolytic solution by electric current, form oxidation film in metal surface, such as water-soluble amine composition can be used as anodized of the electrolyte for metal surface.
The chemical substance of metal surface attachment can enumerate ammonia, hydrazine, water-soluble amine, two mercaptan compound of triazine etc..
The Daicel company of Japan and the DLAMP technology of Daicel Plastics Company exploitation can be specifically included above by the method for laser processing etching groove, and the technology of micropore is manufactured by metal surface etching.
The nanoscale concaveconvex structure of above-mentioned metal surface is nano micropore structure under electronic scanner microscope, and preferably average pore size is in 10~100nm, and further preferred aperture is in 10~80nm.
The present invention also provides the preparation methods of the conjugant of a kind of thermoplastic resin composition and metal of the invention.The present invention is not particularly limited the manufacturing method of conjugant, in the following, the preparation method to the conjugant is illustrated.
Consider to improve the zygosity of thermoplastic resin composition and metal and efficient in practical manufacturing process, preferably injection molding or is welded by laser irradiation.
The method of injection molding can specifically be included after thermoplastic resin composition's heating melting in injection molding to the mold for being placed in advance in metal, thus the method for obtaining conjugant.In above-mentioned injection molding process, mold temperature is not particularly limited, but preferably 60 DEG C or more, 180 DEG C or less.The zygosity of thermoplastic resin composition and metal can be made more preferable at 60 DEG C or more by controlling mold temperature, further preferred 80 DEG C or more, still more preferably 100 DEG C or more；On the other hand, mold temperature at 180 DEG C or less thermoplastic resin composition can more effectively curing molding, further preferred 160 DEG C hereinafter, still more preferably 150 DEG C or less.
The method welded as laser irradiation can specifically include molded product made from thermoplastic resin composition and metal are overlapped and are fixed after, from resin side or metal side laser irradiation, so that the method that resin engages synthetic resin and metal material with the resin melting near metal material contact interface.
The conjugant of thermoplastic resin composition and metal of the invention have higher zygosity, are suitble to need the automobile component of metal bonding, electronics, electric equipment products component, the fields such as structural material.
Detailed description of the invention
Fig. 1: the engagement batten of resin and metal used in the zygosity of resin and metal is tested in the embodiment of the present invention.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but this does not illustrate that present invention is limited only to these embodiments.
Test involved in embodiment and comparative example is described as follows:
(1) relative viscosity η r: polyamide sample used in each Examples and Comparative Examples is dissolved in the concentrated sulfuric acid of 96wt%, is configured to the solution that polyamide resin lipid concentration is 0.01g/ml, is measured relative viscosity with Ubbelohde viscometer at 25 DEG C.
(2) end structure content shown in Formulas I: the polyamide with end structure shown in above-mentioned Formulas I used in each embodiment and comparative example, it is dissolved in the deuterated concentrated sulfuric acid with the concentration of 50mg/ml, is carried out under conditions of scanning times are 256 times using Japan Electronics JEOL ECX400P 1The test of H-NMR nuclear-magnetism.It is right 1- the CH adjacent with the oxygen of ehter bond on end structure in H-NMR spectrum in above-mentioned Formulas I 2On the corresponding peak of hydrogen and after being belonged to as the corresponding peak of hydrogen on the polyamide skeleton repetitive unit of main composition, end structure content shown in formula (I) is calculated in polyamide by the number of hydrogen atoms for integrate contained by resulting peak area and each structure to each peak.
(3) hot property
Using the differential scanning calorimeter (DSC Q2000) of TA company, 5~7mg of thermoplastic resin composition's accurate weighing used in each Examples and Comparative Examples, it is started to warm up in a nitrogen atmosphere from 20 DEG C to the temperature T0 of the endothermic peak than occurring with the heating rate of 20 DEG C/min and is higher by 30 DEG C of temperature, and constant temperature 2min at this temperature, then 20 DEG C are cooled to the rate of temperature fall of 20 DEG C/min, it is warming up to again with the heating rate of 20 DEG C/min after constant temperature 2min at 20 DEG C and is higher by 30 DEG C of temperature than T0, obtain fusing point T m。T mFor the corresponding temperature of peak point of endothermic peak during secondary temperature elevation.
(4) molecular weight
After taking the resin portion 2.5mg of obtained conjugant after injection molded in obtained polyamide particle in each preparation example or each embodiment and comparative example to be dissolved in the hexafluoroisopropanol of sodium trifluoroacetate of the 4ml containing 0.0075N, it is as follows with measurement number-average molecular weight Mn after 0.45 μm of filter filtering and weight average molecular weight Mw, determination condition:
Pump: e-Alliance GPC system (Waters system)
Detector: Composition distribution Waters 2414 (Waters system)
Chromatographic column: Shodex HFIP-806M (2)+HFIP-LG
Solvent: hexafluoroisopropanol (sodium trifluoroacetate of addition 0.0075N)
Flow velocity: 0.5ml/min
Sample injection rate: 0.1ml
Temperature: 40 DEG C
Molecular weight calibration: polymethyl methacrylate.
(5) melt viscosity
Polyamide obtained in preparation example 1~12 is placed in a vacuum drying oven at 80 DEG C after drying 12 hours or more, with the disk for being cut into diameter 25mm after film laminator hot pressing film forming (film thickness 0.7mm), with rotational rheometer (Antonpaar system, MCR302, 25 parallel-plate of φ) using the following method measurement melt viscosity: under nitrogen atmosphere, by above-mentioned sample in 260 DEG C of (preparation examples 1~7, 10~12) or 280 DEG C of (preparation examples 8, 9) it melts 5 minutes, parallel plate spacing 0.5mm, vibration mode measurement, 0.5~6.88Hz of frequency, measure 50 points (0.5 minute), amplitude 1%.Use complex viscosity measured value of the frequency for 1Hz when as melt viscosity.
(6) tensile strength/stretch modulus
According to ASTM D638 standard testing, batten is having a size of the TypeIV in ASTM D638, the stretch modulus of polyamide elastomer is commercialized used in the terminal-modified polyamide and comparative example 4,5 obtained using 1 KN of Shimadzu AG-IS test preparation example 3,23 DEG C of test temperature, humidity 50%RH, 10 mm/min of tensile speed, fixture spacing 60mm.The result of stretch modulus takes the average value of 5 batten test results.The injecting condition of batten is as follows:
Injection moulding machine: ST10S2V (NISSEI system)
Extruder temperature: 250 DEG C
Mold temperature: 80 DEG C
(7) sheet metal
The Kunshan aluminium flake A6061 (45mm*10mm*1.5mm) is prosperous to reach mold Co., Ltd.
Aluminium flake is entrusted to handle company: Shenzhen Bao Yuanjin limited liability company (NMT` reason)；
Shenzhen Jin Hongxin Science and Technology Ltd. (TRI processing).
(8) conjugant is injection moulded
Sheet metal is placed in the die cavity of mold, after molding is kept for 1 minute, the melt of thermoplastic resin composition be metered and injected into mold.After melt cooling and solidifying, mold is opened, obtains conjugant.
Injection moulding machine: ST10S2V (NISSEI system)
Extruder temperature: 260 DEG C (embodiment 1~11, comparative example 1~6)
280 DEG C (embodiment 12, comparative example 7)
Mold temperature: 60~120 DEG C
(9) zygosity
The zygosity of resin and metal is characterized using tensile shear strength, and according to 19095 standard testing of ISO, batten is having a size of the predetermined size in ISO 19095 shown in attached drawing 1, bonding area 0.5cm 2, using 1 KN of Shimadzu AG-IS test stretch modulus, 23 DEG C of test temperature, humidity 50%RH, tensile speed 5mm/min, fixture spacing 3mm.The result of tensile shear strength takes the average value of 5 batten test results.
For the preparation method of the terminal-modified polyamide without terminal-modified polyamide and containing structure shown in Formulas I, it is described as follows:
Raw material used in preparation example:
Caprolactam: BASF
Polyetheramine: the JEFFAMINE M1000 (Mn=1000) of Huntsman, structure is as shown in Formula II
Adipic acid: Alfa
1,6- hexamethylene diamine: TCI
Preparation example 1
By 500g caprolactam, 0.19g adipic acid, 2.6g JEFFAMINE M1000 (Mn=1000), 150g deionized water be added reaction kettle in, by reaction kettle it is closed after with nitrogen displacement three times.It is begun to warm up after the heter temperature of reaction kettle is set as 290 DEG C.After reacting kettle inner pressure reaches 1MPa, pressure in kettle is maintained into 1MPa until temperature in the kettle is increased to 250 DEG C while releasing by vapor in vent valve goalkeeper's reaction kettle.After temperature in the kettle reaches 250 DEG C, heater setpoint temperatures are reduced to 260 DEG C, and pressure in kettle is gradually decreased to normal pressure from 1MPa in 1 hour (temperature in the kettle is 260 DEG C when reaching normal pressure).Nitrogen stream is passed through into kettle after being down to normal pressure, and under nitrogen flowing after the melt polymerization (263 DEG C of maximum temperature reached) of progress 30 minutes, polymer melt carries out pelletizing after discharge valve discharge growth strip and by cooling water cooling and obtains product particles.Gained particle removes the small molecule in polymer by solvent of methanol in Soxhlet extractor, in 80 DEG C of vacuum drying ovens after drying for 24 hours, obtains containing the modified N6 of structure end shown in Formulas I.
Preparation example 2~7
In addition to leading to the change as shown in Table 1 of nitrogen time after raw material reaches normal pressure according to pressure in change shown in table 1 and kettle, other operations are as preparation example 1.
Preparation example 8
By 381.64g adipic acid, 302.11g 1,6- hexamethylene diamine, 23.6g JEFFAMINE M1000 (Mn=1000), 180g deionized water are added in reaction kettle, by reaction kettle it is closed after with nitrogen displacement three times.It is begun to warm up after the heter temperature of reaction kettle is set as 210 DEG C.The heter temperature of reaction kettle is set as 300 DEG C after reaction 1.5 hours, after reacting kettle inner pressure reaches 1.75MPa, pressure in kettle is maintained into 1.75MPa until temperature in the kettle is increased to 250 DEG C while releasing by vapor in vent valve goalkeeper's reaction kettle.After temperature in the kettle reaches 250 DEG C, pressure in kettle is gradually decreased to normal pressure from 1.75MPa in 1 hour (temperature in the kettle is 270 DEG C when reaching normal pressure).Nitrogen stream is passed through into kettle after being down to normal pressure, and under nitrogen flowing after the melt polymerization (283 DEG C of maximum temperature reached) of progress 20 minutes, polymer melt carries out pelletizing after discharge valve discharge growth strip and by cooling water cooling and obtains product particles.Gained particle after drying for 24 hours, is obtained containing the modified N66 of structure end shown in Formulas I in 80 DEG C of vacuum drying ovens.
Preparation example 9
In addition to leading to the change as shown in Table 1 of nitrogen time after raw material reaches normal pressure according to pressure in change shown in table 1 and kettle, other operations are as preparation example 8.
Table 1
For preparation example 6, when terminal-modified polyamide spues from reaction kettle, strip can not be drawn into be unable to get product particles, thus it is speculated that due to polyetheramine adding too much, cause polymer molecular weight that can not rise.
Preparation example 10~12
Raw material weighs as shown in table 2.After raw material mixes in a high speed mixer, it is added from the main spout of Nippon Steel Works corporation TEX30 α type biaxial extruder (L/D=45.5), carries out melting mixing under 250 DEG C of extruder temperature and screw speed 200rpm.The tow of extrusion is dried in vacuo 24 hours at 80 DEG C after pelletizing and obtains Amilan polyamide resin composition.
Table 2
Embodiment 1
By (the NMT processing of surface treated sheet metal, Shenzhen Bao Yuanjin limited liability company) it is placed in ST10S2V (NISSEI system) injection (mo(u)lding) machine mold, injection molding machine completion metering preparation example 1 is obtained to be injected in mold containing structure end modified polyamide resin shown in I and by resin melt, cooling time is 15s, die sinking, obtains conjugant, in forming process, extruder temperature is 260 DEG C, and mold temperature is 120 DEG C.By conjugant obtained by the above method, according to ISO19095, metal bonding performance test is carried out under 5mm/min tensile speed, the results are shown in Table 3.
Embodiment 2~7
In addition to the type according to the terminal-modified polyamide of change shown in table 3, as embodiment 1, gained conjugant performance is as shown in table 3 for other operations.
Comparative example 1
By (the NMT processing of surface treated sheet metal, Shenzhen Bao Yuanjin limited liability company) it is placed in ST10S2V (NISSEI system) injection (mo(u)lding) machine mold, injection molding machine complete metering preparation example 7 obtain without after terminal-modified polyamide will resin melt inject mold in, cooling time is 15s, die sinking, obtains conjugant, in forming process, extruder temperature is 260 DEG C, and mold temperature is 120 DEG C.By the obtained conjugant of the above method, according to ISO19095, metal bonding performance test is carried out under 5mm/min tensile speed, the results are shown in Table 3.
Table 3
Examples 1 to 7 is compared with comparative example 1, it can be seen that the thermoplastic resin composition containing structure end modified polyamide shown in Formulas I and metal bonding tensile shear strength are better than without structure polyamide shown in Formulas I, 2~6 metal bonding tensile shear strength of embodiment is apparently higher than the embodiment 1,7 with structural content shown in lower Formulas I.For embodiment 4, structure shown in the Formulas I of high level has an impact the mechanical strength of terminal-modified polyamide ontology, so that metal bonding tensile shear strength is lower than the embodiment containing structure end shown in 2wt% and 4wt% Formulas I.For embodiment 5,6, by that will contain structure end modified polyamide resin shown in high level Formulas I and be free of structure polyamide resin blends shown in Formulas I, make obtained thermoplastic resin composition that there is lower melt viscosity (table 2), so that obtained conjugant has higher metal to engage tensile shear strength.
Embodiment 8~10
In addition to according to mold temperature in change process of injection molding shown in table 4, as embodiment 3, gained conjugant performance is as shown in table 4 for other operations.
Comparative example 2 and 3
In addition to according to mold temperature in change process of injection molding shown in table 4, as comparative example 1, gained conjugant performance is as shown in table 4 for other operations.
Table 4
It will be known to embodiment 8 and comparative example 2, embodiment 9 and the comparison of comparative example 3, it is higher containing structure end modified polyamide resin shown in 4wt% Formulas I and metal bonding tensile shear strength, also, molding embodiment 9 and embodiment 10 are higher under the conditions of the relatively low mold temperature of metal bonding tensile shear strength of molding embodiment 3,8 under the conditions of higher die temperature.
Comparative example 4
By (the NMT processing of surface treated sheet metal, Shenzhen Bao Yuanjin limited liability company) it is placed in ST10S2V (NISSEI system) injection (mo(u)lding) machine mold, injection molding machine completes metering commercialization polyamide elastomer (PEBAX 5533SP01, Arkema system) after by resin melt inject mold in, cooling time 15s, die sinking, obtain conjugant, in forming process, extruder temperature is 260 DEG C, and mold temperature is 60 DEG C.By the obtained conjugant of the above method, according to ISO19095, metal bonding performance test is carried out under 5mm/min tensile speed, the results are shown in Table 5.
Comparative example 5
According to change process of injection molding shown in table 5 mold temperature to 120 DEG C it is outer, other operations are equal consistent with comparative example 4.But resin is unable to fully solidify in mold, when demoulding, deforms, to be unable to get test batten.
Table 5
* data are derived from Shannon Armstrong, Benny Freeman, Anne Hiltner, Eric Baer.Polymer；2012:1383-1392.
Compared with comparative example 5,3 high-temperature molding function admirable of embodiment, and there is higher metal bonding tensile shear strength.For embodiment 10 compared with comparative example 4,10 metal bonding tensile shear strength of embodiment is higher simultaneously.In addition, the tensile strength and stretch modulus of thermoplastic resin composition's ontology are substantially better than the polyamide elastomer in comparative example 4 and comparative example 5 in embodiment 3 and embodiment 10.
Embodiment 11
In addition to according to shown in table 6, using the sheet metal by different surface treatment method (TRI processing, Shenzhen Jin Hongxin Science and Technology Ltd.) processing, as embodiment 3, gained conjugant performance is as shown in table 6 for other operations.
Comparative example 6
In addition to according to shown in table 6, using the sheet metal by different surface treatment method (TRI processing, Shenzhen Jin Hongxin Science and Technology Ltd.) processing, as comparative example 1, gained conjugant performance is as shown in table 6 for other operations.
Table 6
From embodiment 3 and embodiment 11 as it can be seen that the engagement tensile shear strength containing structure end modified polyamide resin shown in 4wt% Formulas I and the metal of two kinds of processing modes of NMT and TRI has reached 20MPa or more.And comparative example 1 and comparative example 6 without terminal-modified polyamide have been used, the engagement tensile shear strength of the metal of resin and two kinds of processing modes of NMT and TRI is below 10MPa.
Embodiment 12
By (the NMT processing of surface treated sheet metal, Shenzhen Bao Yuanjin limited liability company) it is placed in ST10S2V (NISSEI system) injection (mo(u)lding) machine mold, injection molding machine completion metering preparation example 8 is obtained to be injected in mold containing structure end modified polyamide resin shown in I and by resin melt, cooling time is 15s, die sinking, obtains conjugant, in forming process, extruder temperature is 280 DEG C, and mold temperature is 120 DEG C.By conjugant obtained by the above method, according to ISO19095, metal bonding performance test is carried out under 5mm/min tensile speed, the results are shown in Table 7.
Comparative example 7
In addition to the type according to the terminal-modified polyamide of change shown in table 7, as embodiment 12, gained conjugant performance is as shown in table 7 for other operations.
Table 7
Embodiment 12 is compared with comparative example 7, it can be seen that the thermoplastic resin composition containing structure end modified polyamide shown in Formulas I and metal bonding tensile shear strength are better than without structure polyamide shown in Formulas I.

Claims (18)

  1. A kind of conjugant of thermoplastic resin composition and metal, it is characterized by: the thermoplastic resin composition contains terminal-modified polyamide, the content of the terminal-modified polyamide is 5~100wt% of thermoplastic resin composition's total weight, the terminal-modified polyamide has end structure shown in Formulas I
    -X-(R 1-O)n-R 2Formulas I
    In above-mentioned Formulas I, the integer that n is 2~100, R 1It is identical or different, it is the alkylidene that carbon atom number is 2~10, R 2The alkyl for being 1~30 for carbon atom number ,-X- are-NH- ,-O- ,-C (=O)-,-NH-C (=O)-O- ,-NH-C (=O)-NH- or-CH (OH)-CH 2Any one of；Content of the structure shown in Formulas I in terminal-modified polyamide is 0.05~20wt% of terminal-modified polyamide total weight.
  2. Conjugant according to claim 1, it is characterised in that: in end structure shown in above-mentioned Formulas I, n be 16~50 integer.
  3. Conjugant according to claim 1, it is characterised in that: in end structure shown in above-mentioned Formulas I, n be 16~25 integer.
  4. Conjugant according to claim 1, it is characterised in that: in end structure shown in above-mentioned Formulas I, R 1It is identical or different, it is the alkylidene that carbon atom number is 2~4.
  5. Conjugant according to claim 1, it is characterised in that: in end structure shown in above-mentioned Formulas I, R 2The alkyl for being 1~20 for carbon atom number.
  6. Conjugant according to claim 1, it is characterised in that: in end structure shown in above-mentioned Formulas I, R 2For methyl.
  7. Conjugant according to claim 1, it is characterised in that: in end structure shown in above-mentioned Formulas I ,-X- is-NH-.
  8. Conjugant according to claim 1, it is characterised in that: content of the end structure shown in above-mentioned Formulas I in terminal-modified polyamide is 0.1~15wt% of terminal-modified polyamide total weight.
  9. Conjugant according to claim 1, it is characterised in that: content of the end structure shown in above-mentioned Formulas I in terminal-modified polyamide is 0.1~10wt% of terminal-modified polyamide total weight.
  10. Conjugant according to claim 1, it is characterised in that: tensile shear strength >=10MPa that thermoplastic resin composition conjugant according to as defined in ISO19095 test batten measures under the tensile speed of 5mm/min.
  11. Conjugant according to claim 1, it is characterised in that: the conjugant is directly engaged to obtain by thermoplastic resin composition with metal.
  12. Conjugant according to claim 1, it is characterized by: the terminal-modified polyamide with end structure shown in Formulas I is configured to the polyamide resin lipoprotein solution of 0.01g/ml using 96wt% sulfuric acid as solvent, the relative viscosity η r measured at 25 DEG C is 1.1~5.0.
  13. Conjugant according to claim 1, it is characterised in that: the range for the weight average molecular weight Mw that the terminal-modified polyamide with end structure shown in Formulas I is measured with gel permeation chromatography is 10,000~400,000.
  14. Conjugant according to claim 1, it is characterised in that: the fusing point of the terminal-modified polyamide with end structure shown in Formulas I is 215 DEG C or more.
  15. Conjugant according to claim 1, it is characterised in that: the thermoplastic resin composition further includes filler, and the content of the filler is 5~80wt% of thermoplastic resin composition's total weight.
  16. A kind of manufacturing method of conjugant described in any one of claim 1~15, it is characterised in that: the conjugant by after thermoplastic resin composition's heating melting with the metal injection molded molding that is placed in advance in mold.
  17. The manufacturing method according to claim 16, it is characterised in that: the conjugant is in injection molding process, and mold temperature is between 60~180 DEG C.
  18. The manufacturing method of conjugant described in a kind of any one of claim 1~15, it is characterised in that: the conjugant is welded to obtain by the molded product and metal of thermoplastic resin composition by laser irradiation.
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