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WO2019020065A1 - Corps lié de composition de résine thermoplastique et métal, et procédé de fabrication associé - Google Patents

Corps lié de composition de résine thermoplastique et métal, et procédé de fabrication associé Download PDF

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Publication number
WO2019020065A1
WO2019020065A1 PCT/CN2018/097143 CN2018097143W WO2019020065A1 WO 2019020065 A1 WO2019020065 A1 WO 2019020065A1 CN 2018097143 W CN2018097143 W CN 2018097143W WO 2019020065 A1 WO2019020065 A1 WO 2019020065A1
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Prior art keywords
terminal
polyamide resin
joined body
thermoplastic resin
resin composition
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PCT/CN2018/097143
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English (en)
Chinese (zh)
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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Priority to CN201880003557.7A priority Critical patent/CN109715393B/zh
Publication of WO2019020065A1 publication Critical patent/WO2019020065A1/fr
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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

Definitions

  • 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.
  • 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.
  • 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.
  • polyamide elastomers have mechanical properties significantly reduced compared to polyamide homopolymers.
  • 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.
  • 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
  • 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,
  • 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
  • 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.
  • n is an integer of from 16 to 50.
  • n is an integer of from 16 to 25.
  • R 1 is the same or different and is an alkylene group having 2 to 4 carbon atoms.
  • R 2 is an alkyl group having 1 to 20 carbon atoms.
  • 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 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.
  • 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.
  • thermoplastic resin composition of the present invention can be used for automobile parts, electronic parts, electrical product parts, structural materials, and the like.
  • 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.
  • 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
  • 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.
  • thermoplastic resin composition 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 ⁇ -caprolactam, ⁇ -undecanolactam or ⁇ -laurolactam; ethylenediamine, propylenediamine, and butyl Diamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, decanediamine, decanediamine, undecanediamine, dodecanediamine, tridecanediamine, tetrade
  • 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
  • the polyamide main chain structure of the above terminal modified polyamide resin is preferably polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene.
  • 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.
  • n is an integer of from 2 to 100.
  • n is less than 2, the effect of lowering the melt viscosity of the thermoplastic resin composition is deteriorated.
  • n is 4 or more, and further preferably n is 8 or more, and most preferably n is 16 or more.
  • n is more than 100, the heat resistance of the terminal structure represented by Formula I is deteriorated.
  • n is 70 or less, more preferably n is 50 or less, and most preferably n is 25 or less.
  • R 1 is the same or different and is an alkylene group having 2 to 10 carbon atoms.
  • 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 - or -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -.
  • 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 -.
  • 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.
  • 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.
  • 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 ⁇ r measured at 25 ° C. It is 1.1 to 5.0. When ⁇ r is less than 1.1, the mechanical properties and metal bonding properties of the thermoplastic resin composition tend to decrease. Preferably, ⁇ r is 1.2 or more, and more preferably 1.4 or more. On the other hand, when ⁇ r 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. ⁇ r is preferably 4 or less, and more preferably ⁇ r 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.
  • 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.
  • Tm melting point
  • 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.
  • 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,
  • thermoplastic resin composition used in the present invention 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 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 ⁇ -olefin having 3 or more carbon atoms, a non-conjugated diene, a vinyl acetate, a vinyl alcohol, an ⁇ , ⁇ -unsaturated carboxylic acid or a derivative thereof. Things. Two or more kinds of the above monomers may be copolymerized with ethylene.
  • the ⁇ -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, te
  • the ⁇ , ⁇ -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 ⁇ , ⁇ -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 ⁇ , ⁇ -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.
  • 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.
  • 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 /
  • 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,
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • thermoplastic resin composition used in the present invention may further contain various additives.
  • antioxidants and heat stabilizers hindered phenols, hydroquinones, phosphites, phosphates and substituted products, copper halides, iodine compounds, etc.
  • weathering agents resorcinol, water
  • Salicylic acid resorcinol, water
  • 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 ammoni
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • 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.
  • thermoplastic resin composition 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.
  • 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.
  • 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.
  • 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.
  • a method of joining a resin molded article and a metal material 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.
  • 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.
  • 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.
  • Relative viscosity ⁇ r 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.
  • 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.
  • 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.
  • 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 ⁇ m filter, and the measurement conditions were as follows:
  • 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 Antonpas, MCR302, ⁇ 25 parallel plate) by the following method: at 260 ° C (preparation examples 1 to 7, 10 to 12) or 280 ° C under a nitrogen atmosphere.
  • 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 results are taken as the average of the five spline test results.
  • the injection molding conditions for the spline are as follows:
  • 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.
  • Screw temperature 260 ° C (Examples 1 to 11, Comparative Examples 1 to 6)
  • 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.
  • 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).
  • 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.
  • 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).
  • 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.
  • the extruded tow was subjected to pelletization, and vacuum dried at 80 ° C for 24 hours to obtain a polyamide resin composition.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Example 8 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.
  • 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.
  • 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.
  • 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 3 and Example 11 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.
  • 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.
  • 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.
  • 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.

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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

L'invention concerne un corps lié d'une composition de résine thermoplastique et d'un métal, présentant d'excellentes propriétés de liaison, ainsi qu'un procédé de fabrication associé. La composition de résine thermoplastique selon l'invention contient une résine polyamide à terminaison modifiée. La teneur en résine polyamide à terminaison modifiée de la composition de résine thermoplastique est de 5 à 100% en poids du poids total de la composition de résine thermoplastique, et la résine polyamide à terminaison modifiée présente une structure de terminaison représentée par la formule I, -X-(R1-O)n-R2. Dans cette formule, n est un nombre entier de 2 à 100 ; R1 est identique ou différent et représente un groupe alkylène contenant de 2 à 10 atomes de carbone ; R2 est un groupe alkyle contenant de 1 à 30 atomes de carbone ; et -X- représente l'un des constituants suivants : -NH-, -O-, -C(=O)-, -NH-C(=O)-O-, -NH-C(=O)-NH- ou -CH(OH)-CH2-. La teneur en structure de formule I dans la résine polyamide à terminaison modifiée est de 0,05 à 20% en poids du poids total de la résine polyamide à terminaison modifiée.
PCT/CN2018/097143 2017-07-28 2018-07-26 Corps lié de composition de résine thermoplastique et métal, et procédé de fabrication associé Ceased WO2019020065A1 (fr)

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CN116157472A (zh) * 2021-07-13 2023-05-23 东丽先端材料研究开发（中国）有限公司 末端改性聚酰胺树脂、其制备方法、组合物及成型品
CN115160885B (zh) * 2022-06-01 2023-03-31 安徽登王化工有限公司 一种水性石墨烯散热涂料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040399A1 (fr) * 2009-09-30 2011-04-07 日立化成工業株式会社 Composition de résine, préimprégné utilisant celui-ci, feuille métallique avec résine, film adhésif, et laminé de gaine métallique
CN102911496A (zh) * 2011-08-05 2013-02-06 鸿富锦精密工业（深圳）有限公司 树脂组合物及应用该树脂组合物所制得的复合体
CN103429413A (zh) * 2011-03-25 2013-12-04 宇部兴产株式会社 金属与热塑性树脂的复合体
CN105479659A (zh) * 2015-04-30 2016-04-13 硕尼姆通信技术（深圳）有限公司 金属与塑胶的复合体及其制造方法
CN106280005A (zh) * 2016-08-30 2017-01-04 联泓(江苏)新材料研究院有限公司 一种可用于与金属复合的绝缘热封材料及其制备方法和应用
CN106459408A (zh) * 2014-05-30 2017-02-22 东丽株式会社 末端改性聚酰胺树脂、其制造方法及成型品的制造方法
CN106536187A (zh) * 2014-07-31 2017-03-22 纳幕尔杜邦公司 基于呋喃的聚酰胺及由其制成的制品
WO2017110918A1 (fr) * 2015-12-25 2017-06-29 東レ株式会社 Résine polyamide à extrémité modifiée et son procédé de production

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040399A1 (fr) * 2009-09-30 2011-04-07 日立化成工業株式会社 Composition de résine, préimprégné utilisant celui-ci, feuille métallique avec résine, film adhésif, et laminé de gaine métallique
CN103429413A (zh) * 2011-03-25 2013-12-04 宇部兴产株式会社 金属与热塑性树脂的复合体
CN102911496A (zh) * 2011-08-05 2013-02-06 鸿富锦精密工业（深圳）有限公司 树脂组合物及应用该树脂组合物所制得的复合体
CN106459408A (zh) * 2014-05-30 2017-02-22 东丽株式会社 末端改性聚酰胺树脂、其制造方法及成型品的制造方法
CN106536187A (zh) * 2014-07-31 2017-03-22 纳幕尔杜邦公司 基于呋喃的聚酰胺及由其制成的制品
CN105479659A (zh) * 2015-04-30 2016-04-13 硕尼姆通信技术（深圳）有限公司 金属与塑胶的复合体及其制造方法
WO2017110918A1 (fr) * 2015-12-25 2017-06-29 東レ株式会社 Résine polyamide à extrémité modifiée et son procédé de production
CN106280005A (zh) * 2016-08-30 2017-01-04 联泓(江苏)新材料研究院有限公司 一种可用于与金属复合的绝缘热封材料及其制备方法和应用

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