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WO2018121493A1 - Composition de résine pour coller des métaux, produit formé par collage de métaux avec une composition de résine, et procédé de fabrication - Google Patents

Composition de résine pour coller des métaux, produit formé par collage de métaux avec une composition de résine, et procédé de fabrication Download PDF

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Publication number
WO2018121493A1
WO2018121493A1 PCT/CN2017/118442 CN2017118442W WO2018121493A1 WO 2018121493 A1 WO2018121493 A1 WO 2018121493A1 CN 2017118442 W CN2017118442 W CN 2017118442W WO 2018121493 A1 WO2018121493 A1 WO 2018121493A1
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WIPO (PCT)
Prior art keywords
resin composition
component
weight
parts
metal bonding
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PCT/CN2017/118442
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English (en)
Chinese (zh)
Inventor
祁兴超
郑大蓬
汤先文
加藤公哉
松田政
张新谱
Original Assignee
东丽先端材料研究开发（中国）有限公司
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Priority claimed from CN201710690782.XA external-priority patent/CN108250668A/zh
Application filed by 东丽先端材料研究开发（中国）有限公司 filed Critical 东丽先端材料研究开发（中国）有限公司
Priority to US16/470,857 priority Critical patent/US20190338119A1/en
Priority to JP2019534170A priority patent/JP2020506980A/ja
Priority to CN201780057037.XA priority patent/CN109804001B/zh
Priority to KR1020197020126A priority patent/KR102376660B1/ko
Publication of WO2018121493A1 publication Critical patent/WO2018121493A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/02—Polythioethers; Polythioether-ethers

Definitions

  • the present invention relates to the field of high molecular polymer materials, and mainly relates to a resin composition for metal joining, a metal bonded product thereof, and a method for producing the same.
  • the existing metal-resin bonding technique is mainly to treat the surface of the metal with a chemical agent or to irradiate with a laser (see International Patent Application Publication No. WO2004/041532, WO2013/077277), and the metal-bonding resin composition used in these techniques is polyphenylene sulfide. Ether composition, polybutylene terephthalate composition, polyamide composition, and the like.
  • the resin composition used in this technique is a polyetheretherketone composition or a polyetheretherketone and a polyetherimide alloy composition, and a polyetheretherketone and a polyphenylene sulfide alloy resin composition are not used. .
  • the present inventors have found that (I) at least one of polyether ketone, polyether ether ketone or polyether ketone ketone and (II) polyphenylene sulfide form an alloy polymer than component (I) or component (II) alone Better metal bondability.
  • a resin composition for metal bonding comprising a component (I) and a component (II);
  • component (I) is at least one selected from the group consisting of polyether ketone, polyether ether ketone or polyether ketone ketone; and component (II) is polyphenylene sulfide.
  • the filler (IV) is added in an amount of 5 to 300 parts by weight.
  • inorganic filler (IV) is selected from the group consisting of glass fibers, carbon fibers, glass beads, mica flakes, calcium carbonate, magnesium carbonate, silica, talc or At least one of wollastonite.
  • the resin composition for metal bonding according to the above-mentioned item 2, wherein the component (II) is added in an amount of 1 part by weight or more and less than 66.7 parts by weight based on 100 parts by weight of the component (I).
  • the resin composition for metal bonding according to the above-mentioned item 2, wherein the component (II) is added in an amount of 150 parts by weight or more and 9900 parts by weight or less based on 100 parts by weight of the component (I).
  • the resin composition for metal bonding according to the above-mentioned item 2, wherein the component (II) is added in an amount of 66.7 parts by weight or more and less than 150 parts by weight based on 100 parts by weight of the component (I).
  • a molded article obtained by joining a metal composition for resin bonding according to any one of the above 1 to 13 to a metal.
  • the metal bonding resin composition of the present invention has excellent metal bondability, and is suitable not only for automotive parts that require metal bonding, but also for electronic products such as notebook computers and mobile phones.
  • Fig. 1 is a schematic view showing the front side of a joint molded product of metal and resin.
  • Fig. 2 is a schematic view showing the side surface of a joint molded product of metal and resin.
  • the present invention relates to a resin composition for metal bonding, wherein the material of the metal is not particularly limited, and examples thereof include gold, platinum (platinum), silver, aluminum, magnesium, titanium, iron, tin, zinc, lead, chromium, and manganese. Copper, stainless steel, cobalt or alloys of the above materials are all within the scope of protection.
  • the microporous or concave-convex structure may be etched by chemical treatment on the metal surface by metal surface treatment, or may be formed by anodizing to form micropores, or may be formed by plating, or the metal surface may be irradiated by laser irradiation.
  • the metal is placed in a mold in advance, and the metal bonding resin of the present invention is subjected to injection molding to cause the resin to intrude into the pores or the uneven structure of the metal surface to form a physical bond.
  • the resin composition of the present invention can also be used in a chemical bonding technique in which a metal surface is subjected to an activation treatment with a chemical reagent, and then the resin and the metal are chemically reacted to form a film by the above-described injection molding method.
  • the metal surface treatment method according to the present invention may be a treatment method used in NMT (Nano Molding Technology) technology, for example, T (Dacheng Plas's first letter) processing method developed by Dacheng Plath Co., Ltd. and East Asian electrochemical type Metal surface treatment technology such as the TRI treatment method developed by the company or the C treatment method developed by Japan Corona Industrial Co., Ltd.
  • the corrosive liquid used for the corrosion of the chemical agent includes an alkaline aqueous solution (pH>7), an acidic aqueous solution (pH ⁇ 7), an aqueous solution of a nitrogen-containing compound, and the like.
  • the alkaline aqueous solution may be an aqueous solution of sodium hydroxide, potassium hydroxide or sodium carbonate.
  • the acidic aqueous solution may 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.
  • the water-soluble amine may be methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, propylamine, ethanolamine, diethanolamine, triethanolamine, aniline or other amines. Class of compounds.
  • the anodic oxidation of the metal surface of the present invention refers to a method of forming an oxide film on a metal surface by a current acting on the metal using the metal as an anode.
  • a current acting on the metal using the metal as an anode for example, water-soluble ammonia can be used as an electrolyte to anodize the metal surface.
  • the chemical reagent for forming a reactive coating film between the metal and the resin according to the present invention may be a compound such as ammonia, hydrazine, a water-soluble amine or a triazine thiol derivative.
  • the triazine thiol derivative specifically, 1,3,5-triazine-2,4,6-trithiol (TT), 1,3,5-triazine-2, 4 , 6-trithiol monosodium (TTN), 1,3,5-triazine-2,4,6-trithiol triethanolamine (F-TEA), 6-anilino-1,3,5-three Pyrazine-2,4-dithiol (AF), 6-anilino-1,3,5-triazine-2,4-dithiol monosodium (AFN), 6-dibutylamino-1,3 , 5-triazine-2,4-dithiol (DB), 6-dibutylamino-1,3,5-triazine-2,4-dithiol monosodium (DBN), 6-diene Propylamino-1,3,5-triazine-2,4-dithiol (DA), 6-diallylamino-1,3,5-triazine-2,4-d
  • the present invention relates to a method of plating a metal surface to form micropores, including a method of depositing another metal on a treated metal surface by electrical treatment or a method of forming a deposited layer by chemical treatment, which may be gold or silver. , nickel, chromium and other metals.
  • the laser metal surface etching according to the present invention may be a technique in which micropores are etched on a metal surface by a laser, such as DLAMP technology developed by Daicel Corporation of Daicel and Daicel Plastics.
  • the metal surface nano-scale concavo-convex structure according to the present invention refers to a micron- to nano-scale pore existing on a metal surface observed by a scanning electron microscope.
  • the average pore diameter is preferably from 10 to 100 nm, more preferably from 10 to 80 nm.
  • the component (I) used in the resin composition for metal bonding of the present invention is at least one selected from the group consisting of polyether ketone, polyether ether ketone, and polyether ketone ketone.
  • a typical repeating unit in the chemical structure of the polyether ketone is represented by the formula (1), and the repeating unit represented by the formula (I) accounts for 70 mol% or more, more preferably 90 mol% or more of the polyether ketone polymer.
  • a typical repeating unit in the chemical structure of the polyetheretherketone is represented by the formula (2), and the repeating unit represented by the formula (2) accounts for 70% by mole or more, and more preferably 90% by mole or more of the polyetheretherketone polymer.
  • a typical repeating unit in the chemical structure of the polyetherketoneketone is represented by the formula (3), and the repeating unit represented by the formula (3) accounts for 70% by mole or more, and more preferably 90% by mole or more of the polyetherketoneketone polymer.
  • a polyether ketone, a polyetheretherketone or a polyetherketoneketone having good fluidity is preferred, and a melt volume flow rate (MVR) measured by a melt indexer under a test condition of 380 ° C and a load of 5 Kgf is preferred.
  • MVR melt volume flow rate measured by a melt indexer under a test condition of 380 ° C and a load of 5 Kgf.
  • the polyether ketone, polyether ether ketone or polyether ketone ketone at 5 cm 3 / 10 min or more is more preferably 15 cm 3 /10 min or more, and most preferably 60 cm 3 /10 min or more.
  • the polyether ketone, polyetheretherketone or polyetherketoneketone has a melt volume flow rate (MVR) of 300 cm 3 / 10 min or less.
  • the component (II) used in the resin composition for metal bonding of the present invention is polyphenylene sulfide.
  • the polyphenylene sulfide polymer is a polymer having a repeating unit represented by the following formula (4), and the repeating unit represented by the formula (4) accounts for 70% by mole or more, more preferably 90% by mole based on the polyphenylene sulfide polymer. the above.
  • it can be manufactured by Toray Industries, Inc. Manufactured by SOLVAY Made by American GE Made by Ticona, USA Wait.
  • the repeating unit other than the repeating unit represented by (4) is selected from the repeating units (5), (6), (7), (8), (9), and the following structures.
  • the polyphenylene sulfide polymer has one or more of the above repeating units (5) to (11), the polyphenylene sulfide polymer has a low melting point, which is more advantageous from the viewpoint of molding. At the same time, since the crystallization property is also lowered, the molding shrinkage of the molded article is also lowered.
  • the polyphenylene sulfide polymer used in the present invention is more preferably a high melt index from the viewpoint of obtaining excellent fluidity.
  • the melt index is from 200 g/10 minutes or more, and further preferably 500 g/10 minutes or more
  • the resin composition for metal bonding of the present invention is preferably 5,000 g/10 minutes or less.
  • polyphenylene sulfide a mixture of polyphenylene sulfides having various chemical structures is preferably used.
  • the polyphenylene sulfide used in the present invention is not limited to the production method.
  • the polyphenylene sulfide polymer having a structure of the above (5) to (11) can be used for a method for obtaining high fluidity as described in JP-A-45-3368 or JP-A-52-12240. Prepared by a method that achieves lower fluidity.
  • the former differs from the latter in whether or not there is a polymerization aid alkali metal carboxylate in the polymerization system. In the former method, the alkali metal carboxylate is not added to the polymerization system, and the fluidity is high.
  • the alkali metal carboxylate is added to the polymerization system, and the fluidity is low, thereby contributing to the toughness of the resin. . Therefore, the polyphenylene sulfide polymers prepared by the two methods can be used in combination, thereby balancing the fluidity and toughness of the polyphenylene sulfide resin.
  • a polyphenylene sulfide polymer having a lower chlorine content can be obtained.
  • a blocked polyphenylene sulfide polymer having a lower chlorine content can be obtained.
  • the amount of the component (II) to be added is preferably from 1 to 9,900 parts by weight based on 100 parts by weight of the component (I). In the present invention, it is necessary to suppress shrinkage of the resin which enters the micropores or the uneven structure of the metal surface. In order to achieve this, the components (I) and (II) are mixed, and the two resin components mutually inhibit crystallization.
  • the component (II) is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, and most preferably 15 parts by weight or more based on 100 parts by weight of the component (I).
  • the amount of the component (II) to be added is preferably 1900 parts by weight or less, more preferably 900 parts by weight or less, and most preferably 570 parts by weight or less.
  • the component (III) used in the resin composition for metal bonding of the present invention is at least one of polyetherimide, polyimide, polyamideimide or polysulfone resin.
  • the polyetherimide is a polymer having a repeating unit represented by the following formula (12), and the repeating unit represented by the formula (12) accounts for 70% by mole or more, more preferably 90% by weight of the polyetherimide polymer. More than mol%.
  • R 1 is a divalent aromatic residue having 6 to 30 carbon atoms
  • R 2 is a divalent organic group selected from the group consisting of 6 to 30 carbon atoms a divalent aromatic residue, an alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 2 to 20 carbon atoms, and a polyorganosiloxane terminated by an alkylene group having 2 to 8 carbon atoms Alkyl composition.
  • the above R 1 and R 2 are preferably the chemical groups shown below.
  • the polyimide is a polymer having a repeating unit represented by the following formula (13), and the repeating unit represented by the formula (13) accounts for 70% by mole or more, more preferably 90% by mole based on the polyimide polymer. the above.
  • R 3 is a direct bond or is -SO 2 -, -CO-, -C(CH 3 ) 2 -, C(CF 3 ) 2 -, -S-.
  • R 4 is one or more selected from the following structures.
  • the polyamideimide is a polymer having a repeating unit represented by the following formula (14), and the repeating unit represented by the formula (14) accounts for 70% by mole or more, more preferably 90% by weight of the polyamideimide polymer. More than mol%.
  • R 5 is a divalent aromatic and/or aliphatic group
  • R 6 is hydrogen, a methyl group or a phenyl group
  • Ar is a trivalent aromatic group containing at least one six-membered ring.
  • repeating structural unit represented by the above formula (14) and the repeating structural unit represented by the following formula (15) and/or (16) may be aggregated together.
  • R 7 is also applicable to the above description for R 5
  • Ar′ represents a divalent aromatic group containing one or two or more carbon 6-membered rings or a divalent alicyclic group.
  • R 8 also applies to the above description for R 5
  • Ar represents a tetravalent carbonyl group-containing aromatic group containing one or two carbon 6-membered rings.
  • the imide bond structure of the structural units (14) and (16) may retain the closed-loop front structure as shown in the structural unit (17).
  • the polysulfone resin is a polymer having a repeating unit represented by the following formula (18) or (19), and the repeating unit represented by the formula (18) or (19) accounts for 70% by mole or more, more preferably 90% by weight of the polysulfone resin. More than mol%.
  • the amount of the component (III) to be added is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the components (I) and (II). Since the component (III) may affect the mixing property of the components (I) and (II), and thereby inhibit the crystallization of the components (I) and (II), the component (III) is added in a relative amount (I) and (II) 100 parts by weight is preferably 10 parts by weight or less, more preferably 5 parts by weight or less, most preferably less than 3 parts by weight, and further preferably 0.5 parts by weight or more, more preferably 1 part by weight or more.
  • the ratio of the inorganic filler (IV) of the present invention is preferably 5 to 300 parts by weight based on 100 parts by weight of the components (I) and (II).
  • the resin composition for metal bonding of the present invention can impart a good fluidity to the resin composition while reducing the shrinkage ratio.
  • the inorganic filler (IV) is preferably added in an amount of 10 parts by weight or more, more preferably 20 parts by weight or more, and most preferably 30 parts by weight or more. Further, it is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, and most preferably 70 parts by weight or less.
  • the inorganic filler of the present invention refers to a filler used in the resin which is used in the prior art.
  • a filler used in the resin which is used in the prior art.
  • the inorganic filler is preferably at least one of glass fiber or carbon fiber.
  • the glass fiber is not particularly limited and may be a glass fiber used in the prior art.
  • the glass fiber may be a fiber of a shape such as a chopped strand of a fixed length, a coarse sand, or a ground fiber. In general, it is preferred to use glass fibers having an average diameter of 5 to 15 ⁇ m. In the case of using chopped strands, the length is not particularly limited, and it is preferred to use a standard 3 mm-length fiber suitable for extrusion kneading.
  • At least one of glass beads, mica, calcium carbonate, magnesium carbonate, silica, talc or wollastonite is preferred.
  • the average diameter of the inorganic filler is not particularly limited, and is preferably 0.001 to 20 ⁇ m, and in this range, better fluidity and a better appearance can be obtained.
  • the inorganic filler is preferably an inorganic filler previously 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 dispersion state of each component varies depending on the ratio of the component (I) and the component (II). Further, the addition of the component (III) also changes the morphology of the dispersion.
  • the amount of the component (II) is 1 part by weight or more and less than 66.7 parts by weight based on 100 parts by weight of the component (I)
  • the component (I) is formed as the sea phase and the component (II) as the island phase.
  • the smaller the dispersed particle diameter of the component (II) the higher the bonding property with the metal, which is preferable.
  • the average dispersed particle diameter of the component (II) is preferably 1.0 ⁇ m or less, more preferably 0.50 ⁇ m or less, still more preferably 0.40 ⁇ m or less, and most preferably 0.2 ⁇ m or less.
  • the component (II) is 150 parts by weight or more and 9900 parts by weight or less based on 100 parts by weight of the component (I), the component (I) is formed as an island phase and the component (II) is used as a sea phase. .
  • the average dispersed particle diameter of the component (I) is preferably 5.0 ⁇ m or less, more preferably 3.0 ⁇ m or less, and still more preferably 2.0 ⁇ m or less.
  • the component (II) when the component (II) is 66.7 parts by weight or more and less than 150 parts by weight based on 100 parts by weight of the component (I), the component (I) is formed as the sea phase and the component (II) is used as the island phase.
  • the component (I) has a structure in which the island phase and the component (II) are simultaneously present as a sea phase.
  • the component (II) which is an island phase has a small dispersed particle diameter and tends to have improved metal bonding properties.
  • the dispersed particle diameter of the dispersed phase of the component (II) is preferably 1.0 ⁇ m or less, and the dispersed particle diameter of the component (II) is preferably 1.0 ⁇ m or less, and more preferably, the dispersed particle diameter is 0.6 ⁇ m or less, and more preferably The dispersed particle diameter is 0.40 ⁇ m or less, and most preferably, the dispersed particle diameter is 0.3 ⁇ m or less.
  • the dispersed particle diameter of each component can be tested by the following method.
  • the resin composition for metal bonding of the present invention was cut by an automatic sheet cutter, and then observed with a JEM-2100 transmission electron microscope manufactured by JEOL.
  • the obtained electron microscope photograph was processed using Image-ProPlus, an image analysis software of Media Cybernetics, and the area of 100 dispersed phases was calculated. The area was calculated into the area of a circle, and the diameter was calculated to obtain an average dispersed particle diameter.
  • the component (II) is 150 parts by weight or more and 900 parts by weight or less based on 100 parts by weight of the component (I)
  • 100 PPS dispersed phases are randomly selected from the obtained electron micrograph, and the smallest is measured. Dispersed particle size.
  • the metal bonding resin composition of the present invention may further comprise other thermoplastic polymers in addition to the components (I) to (III), for example, polyamide, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, liquid crystal. Polymer, ABS resin, SAN resin, polystyrene, or polytetrafluoroethylene.
  • a (co)modified polyolefin polymer obtained by polymerizing an olefin compound and/or a conjugated diene compound is preferable.
  • an antioxidant can be added to the resin composition for metal bonding of the present invention in a range that does not impair the effects of the present invention, whereby the heat resistance and thermal stability of the resin composition can be further improved.
  • the antioxidant preferably contains at least one selected from the group consisting of a phenol antioxidant and a phosphorus antioxidant. When a phenolic antioxidant and a phosphorus-based antioxidant are used in combination, heat resistance and heat stability can be efficiently maintained, so that the combination of both is preferable.
  • a hindered phenol compound is preferably used as the phenolic antioxidant.
  • Specific examples are: triethylene glycol bis(3-tert-butyl-(5-methyl-4-hydroxybenzyl)propionate), N,N'-hexamethylene double (3,5-di-tert Butyl-4-hydroxy-hydrocinnamamide), tetrakis(methylene-3-(3',5'-di-tert-butyl-4'-hydroxybenzyl)propionate)methane, pentaerythritol tetrakis(3- (3',5'-di-tert-butyl)-4'-hydroxybenzyl)propionate), 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-s -Triazine-2,4,6-(1H,3H,5H)-trione, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)
  • an ester type polymer is preferably a hindered phenol type, and specifically, tetrakis(methylene-3-(3',5'-di-tert-butyl-4'-hydroxybenzyl)propionate)methane or pentaerythritol IV is preferably used.
  • 3-(3',5'-di-tert-butyl)-4'-hydroxybenzyl)propionate) or 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-)- 5-methylphenyl)propanoyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane and the like.
  • Examples of the phosphorus-based antioxidant include bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol-two.
  • Phosphite bis(2,4-dicumylphenyl)pentaerythritol-diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tetrakis(2,4-di-tert-butyl) Phenyl)-4,4'-bisphenylene phosphite, distearyl pentaerythritol-diphosphite, triphenylphosphite, or 3,5-dibutyl-4-hydroxybenzylphosphoric acid Ethyl ester and the like.
  • the amount of the antioxidant added is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, most preferably 0.1 to 1 part by weight based on 100 parts by weight of the relative components (I) and (II).
  • a release agent (montanic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearic acid amide, amide, biuret or polyethylene wax, etc., in which, in order to reduce during the molding process, can also be used.
  • Gas generation preferably amide
  • pigment cadmium sulfide, phthalocyanine, or colored carbon black masterbatch, etc.
  • dye aniline black, etc.
  • crystallization agent talc, titanium dioxide, kaolin, clay, etc.
  • plasticizer Octyl-p-hydroxybenzoate, or N-butylbenzenesulfonamide, etc.
  • antistatic agent alkyl sulfate type anionic antistatic agent, quaternary ammonium type cationic antistatic agent, polyoxyethylene sorbitan
  • Nonionic antistatic agent such as monostearate or ampicillin amphoteric antistatic agent
  • flame retardant for example, red phosphorus, phosphate, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, more Ammonium phosphate, brominated polystyrene, brominated polyphenylene ether, polycarbonate bromide, brominated epoxy resin or a combination of these bromine-containing flame retardants and antimony
  • the method for producing a metal composition for metal bonding of the present invention is to use the main components (I) and (II) and the components (III) and (IV) to be added as needed in a known melt kneader such as a single screw or a double.
  • a known melt kneader such as a single screw or a double.
  • a screw extruder, a Banbury mixer, a kneader, and a kneader are obtained in accordance with a corresponding melt-kneading method.
  • the metal bonding resin composition is heated and melted, and then injection-molded with a metal previously placed in a mold. details as follows:
  • the mold temperature is preferably in the range of 120 ° C or more and 250 ° C or less, and the molten metal bonding resin composition can intrude into the micropores or the uneven structure of the metal surface under the conditions of 120 ° C or higher.
  • the mold temperature is preferably 130 ° C or higher, more preferably 140 ° C or higher; and for the formulation in which the component (I) is more than the component (II), the mold temperature is preferably 180 ° C or higher, and most preferably 200 ° C or higher.
  • the resin composition for metal bonding can be cured in a mold, and the mold temperature is preferably 240 ° C or lower, more preferably 230 ° C or lower.
  • the mold temperature is preferably 170 ° C or lower, and most preferably 160 ° C or lower.
  • the metal bonding resin composition of the present invention has high bonding strength and is suitable for use in a housing of an electronic component such as an automobile component, a notebook computer, or a mobile phone that requires metal bonding.
  • Aluminum sheet A6061 (45mm*10mm*1.5mm): Kunshan Xinda Mould Co., Ltd.;
  • Polyetheretherketone PEEK1 VICTREX TM 450PF;
  • Polyetheretherketone PEEK2 PFLUON manufactured by Pengfulong Chemical Co., Ltd. 8800G (melt volume flow rate (MVR): 70cm 3 /10min)
  • Polyetheretherketone PEEK3 PFLUON manufactured by Pengfulong Chemical Co., Ltd. 8900G (melt volume flow rate (MVR): 120cm 3 /10min)
  • Polyphenylene sulfide PPS Toray Co., Ltd. M2888;
  • Polyetherimide PEI SABIC ULTEM TM PEI1010;
  • Glass fiber Nitto Spin CSG 3PA-830.
  • a molded article obtained by injection molding of a resin composition and a metal is obtained, and its shape is as shown in FIG.
  • the formulation having a higher PPS content was annealed at 130 ° C for 1 hour.
  • Formulations with a higher PEEK content and formulations with the same PEEK and PPS content were annealed at 170 °C for 1 hour.
  • the test was carried out under the conditions of a temperature of 23 ° C and a humidity of 50% RH using an AG-IS1KN apparatus of Shimadzu Corporation of Japan, and the shearing force was measured at a tensile speed of 5 mm/min and a clamp distance of 3 mm. strength.
  • the resin portion of the molded article in which the resin composition and the T-treated metal were joined was sliced with an automatic sheet slicer, and observed with a JEM-2100 transmission electron microscope manufactured by JEOL.
  • the results of the observation were processed by the processing software of Media Cybernetics, and the area of the 100 particles of the dispersed phase was converted into the area of the circle to calculate the diameter, thereby obtaining the average dispersed particle diameter.
  • the results of Examples 23 to 28 are the smallest dispersed particle diameters calculated by randomly selecting 100 PPS dispersed phase particle diameters from electron micrographs.
  • the raw materials were weighed as shown in Tables 1 to 6.
  • the raw materials other than the glass fiber are mixed in a high-speed mixer, and then added to the main feed port of the extruder, and the glass fiber is fed from the extruder side feed port, and the extruder temperature is set as shown in Tables 1 to 6.
  • Example 14 A comparison of Example 14 and Example 29, Example 20 and Example 30, Example 26 and Example 31 shows that the shear strength is improved in the formulation of PEEK3 which is relatively large in melt volume flow rate (MVR).
  • MVR melt volume flow rate

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  • Manufacturing & Machinery (AREA)
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Abstract

La présente invention concerne une composition de résine pour coller des métaux, un produit formé par collage de métaux avec la composition de résine, et un procédé de fabrication. La composition comprend principalement : un composant (I) (qui est au moins un composant choisi parmi la polyéther cétone, la polyéther éther cétone, ou la polyéther cétone cétone) ; un composant (II) (qui est du sulfure de polyphénylène) ; un composant (III) (qui est au moins un composant choisi parmi le polyétherimide, le polyimide, le polyamideimide ou la résine de polysulfone) qui est ajouté selon les besoins ; et (IV) une charge inorganique. La composition est obtenue au moyen d'un mélange à l'état fondu correspondant dans un mélangeur à fusion connu tel qu'une extrudeuse monovis ou bi-vis, un mélangeur Banbury, un malaxeur et un mélangeur. La composition de résine pour coller des métaux selon la présente invention présente une excellente propriété de collage de métaux, et est appropriée pour être utilisée dans des parties de véhicule à moteur et des produits électroniques, tels que des ordinateurs portables et des téléphones mobiles, qui nécessitent un collage de métaux.
PCT/CN2017/118442 2016-12-28 2017-12-26 Composition de résine pour coller des métaux, produit formé par collage de métaux avec une composition de résine, et procédé de fabrication WO2018121493A1 (fr)

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US16/470,857 US20190338119A1 (en) 2016-12-28 2017-12-26 Resin composition for bonding metal, production formed by bonding metal with resin composition, and manufacturing method thereof
JP2019534170A JP2020506980A (ja) 2016-12-28 2017-12-26 金属接合用樹脂組成物及びそれと金属との接合成形品並びにそれらの製造方法
CN201780057037.XA CN109804001B (zh) 2016-12-28 2017-12-26 金属接合用树脂组合物及其与金属接合成型品和制造方法
KR1020197020126A KR102376660B1 (ko) 2016-12-28 2017-12-26 금속 접합용 수지 조성물, 이와 금속 접합하는 성형품, 및 이의 제조방법

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KR0119913B1 (ko) * 1994-05-19 1997-10-17 조병용 고분자-금속 접합장치 및 접합방법
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WO2016092087A1 (fr) * 2014-12-12 2016-06-16 Solvay Specialty Polymers Usa, Llc Compositions de poly(éther d'aryle) pour des jonctions polymère-métal et jonctions polymère-métal et procédés de fabrication correspondants

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CN1030433A (zh) * 1987-06-30 1989-01-18 埃德朗产品公司 聚合物-金属粘接混合材料及粘接方法
KR0119913B1 (ko) * 1994-05-19 1997-10-17 조병용 고분자-금속 접합장치 및 접합방법
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WO2016092087A1 (fr) * 2014-12-12 2016-06-16 Solvay Specialty Polymers Usa, Llc Compositions de poly(éther d'aryle) pour des jonctions polymère-métal et jonctions polymère-métal et procédés de fabrication correspondants

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Publication number Priority date Publication date Assignee Title
CN109880286A (zh) * 2019-02-28 2019-06-14 武汉材料保护研究所有限公司 一种用于涉水运动副的减摩抗磨复合材料及其制备方法
CN109880286B (zh) * 2019-02-28 2021-09-03 武汉材料保护研究所有限公司 一种用于涉水运动副的减摩抗磨复合材料及其制备方法

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