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WO2016000574A1 - Composite métal-résine et son procédé de préparation - Google Patents

Composite métal-résine et son procédé de préparation Download PDF

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Publication number
WO2016000574A1
WO2016000574A1 PCT/CN2015/082541 CN2015082541W WO2016000574A1 WO 2016000574 A1 WO2016000574 A1 WO 2016000574A1 CN 2015082541 W CN2015082541 W CN 2015082541W WO 2016000574 A1 WO2016000574 A1 WO 2016000574A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
oxide layer
resin
corrosion pores
metal substrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2015/082541
Other languages
English (en)
Inventor
Jian Sun
Yanqin Wu
Yunxia ZHANG
Liang Chen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BYD Co Ltd
Original Assignee
BYD Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BYD Co Ltd filed Critical BYD Co Ltd
Publication of WO2016000574A1 publication Critical patent/WO2016000574A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/542—Shear strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion

Definitions

  • the present disclosure relates to the field of metal-resin integrally molding, and more particularly to a method for producing a composite of a metal and a resin, and a metal-resin composite obtainable by the same.
  • metal-resin composites formed with the adhesion agent may have a poor adhesion force between the metal and the resin composition, and the adhesion agent between the metal and the resin composition has poor acid resistance and alkali resistance, which may limit the use field of the metal-resin composites.
  • the adhesion agent has a certain thickness, which may affect the size of the final product.
  • Embodiments of the present disclosure seek to solve at least one of the problems existing in the prior art to at least some extent, for example, a poor adhesion force between the substrate made of copper or copper alloy and the resin layer in the current metal-resin composite.
  • a method of preparing a metal-resin composite includes: providing a metal substrate including a metal base made of copper or copper alloy and an oxide layer attached to at least a part of a surface of the metal base; chemically etching the metal substrate to form corrosion pores on a surface of the oxide layer to obtain a surface-treated metal substrate; and providing a resin composition on a surface with corrosion pores of the surface-treated metal substrate and molding the resin composition to obtain the metal-resin composite.
  • the method may include: providing a metal substrate, the metal substrate including a metal base made of copper or copper alloy and an oxide layer attached to at least a part of a surface of the metal base; chemically etching the metal substrate to form corrosion pores on a surface of the oxide layer to obtain a surface-treated metal substrate with a treated surface; and injecting a resin composition to fill in the corrosion pores, then molding to obtain a resin layer.
  • a metal-resin composite obtainable by the fore-mentioned method is provided.
  • a metal-resin composite includes: a metal substrate, and a resin layer attached to at least a part of a surface of the metal substrate, wherein the metal substrate includes: a metal base made of copper or copper alloy; and an oxide layer attached to at least a part of a surface of the metal base, corrosion pores formed in the oxide layer and filled with a part of the resin from the resin layer.
  • the metal-resin composite may include: a metal substrate, and a resin layer, attached to at least a part of a surface of the metal substrate, wherein the metal substrate includes a metal base made of copper or copper alloy and an oxide layer attached to at least a part of a surface of the metal base; the oxide layer has a surface thereof formed with corrosion pores, and the corrosion pores are filled with a part of the resin from the resin layer.
  • the metal-resin composite according to embodiments of the present disclosure may have a strong adhesion force between the resin and the metal substrate, and the resin layer may be not easy to fall off from the metal substrate, which may enhance a high structure stability of the metal-resin composite, and meet the requirements of using occasions with high structure stability.
  • the method of preparing the metal-resin composite according to embodiments of the present disclosure may have good applicability, and is suitable to combine a variety of resins and metal substrates, thus meeting the requirements of a variety of using occasions.
  • the metal base is made of copper or copper alloy.
  • the copper alloy refers to an alloy using copper as the essential element, and with a combination of other elements.
  • the copper alloy may be some common copper alloys, such as brass.
  • the metal base may be a variety of forming bodies made of copper or copper alloy, which can be any shape according to special requirements.
  • a method of preparing a metal-resin composite includes steps of proving a metal substrate.
  • the metal substrate includes a metal base and an oxide layer attached to at least a part of a surface of the metal base.
  • the oxide layer may be a copper oxide layer, or an oxide layer using copper oxide as a main component.
  • the oxide layer when the metal substrate is made of copper alloy, the oxide layer contains not only copper oxide, but also some oxides of other elements existed in the copper alloy.
  • the oxide layer has a thickness of about 0.1 ⁇ m to about 50 ⁇ m. In some embodiments of the present disclosure, the oxide layer has a thickness of about 1 ⁇ m to about 25 ⁇ m. In some embodiments of the present disclosure, the oxide layer has a thickness of about 5 ⁇ m to about 10 ⁇ m. From the viewpoint of further improving the structure stability of the metal-resin composite, a ratio of the thickness of the oxide layer and the metal base may be about 0.001: 1 to about 1: 1. In some embodiments of the present disclosure, the ratio of the thickness of the oxide layer and the metal base is about 0.005: 1 to about 0.5: 1. In some embodiments of the present disclosure, the ratio of the thickness of the oxide layer and the metal base is about 0.005: 1 to about 0.01: 1.
  • the oxide layer may be formed by a variety of methods.
  • the oxide layer is formed by anodizing a surface of the metal base.
  • the oxide layer is an oxide layer formed by anodic oxidation, which ensure a higher structure stability of the metal-resin composite.
  • the method for anodizing is well known to the skilled person in the art, without special limiting.
  • the anodic oxidation method comprises: the metal base is placed in an electrolyte solution, and the metal base is used as an anode, a conductive material which may not react with the electrolyte solution is used as a cathode, the anode and the cathode are electrically connected with the negative electrode and the positive electrode of a power respectively, after turning on the power, an oxide layer may be formed on the metal base.
  • the electrolyte solution may be any conventional electrolyte solution that may form an oxide layer on the surface of a copper or a copper alloy under the anodizing conditions.
  • the electrolyte solution includes at least one alkaline compound.
  • the term “at least one” refers to one or more than one.
  • the alkaline compound may be an alkali or an alkaline salt.
  • the alkaline compound may be selected from alkali metal hydroxides (e.g. sodium hydroxide and/or potassium hydroxide) , alkali metal carbonate and alkali metal phosphate.
  • the alkali metal may be sodium and/or potassium.
  • the alkaline compound may be selected from sodium hydroxide, sodium carbonate and sodium phosphate.
  • the alkaline compound may have a concentration of about 1 wt%to about 50 wt%in the electrolyte solution. In some embodiments of the present disclosure, the alkaline compound may have a concentration of about 10 wt%to about 30 wt%in the electrolyte solution. In some embodiments of the present disclosure, the alkaline compound may have a concentration of about 20 wt%to about 30 wt%in the electrolyte solution.
  • the electrolyte solution further comprises at least a molybdate, which may improve the speed of the anodic oxidation thus improving the production efficiency, and may provide higher structure stability to the metal-resin composite.
  • the molybdate may be a water-soluble molybdate.
  • the molybdate may be an alkali metal molybdate, such as sodium molybdate or potassium molybdate, preferably sodium molybdate.
  • the concentration of the molybdate is determined based on the content of the alkaline compound. In some embodiments of the present disclosure, the content of the molybdate is about 1 wt%to about 10 wt%, based on the total weight of the electrolyte solution. In some embodiments of the present disclosure, the content of the molybdate is about 1 wt%to about 5 wt%, based on the total weight of the electrolyte solution.
  • anodizing the surface of the metal base is performed under a voltage of about 10 Volts to about 100 Volts for about 1 minute to about 60 minutes. And in some embodiments of present disclosure, anodizing the surface of the metal base is performed at a temperature of about -20 Celsius degrees to about 80 Celsius degrees. In other words, the electrolyte solution used to perform anodizing the surface of the metal base may have a temperature of about -20 Celsius degrees to about 80 Celsius degrees.
  • the conditions for anodic oxidation may be any conventional conditions which may form an oxide layer with a suitable thickness to meet the actual requirements.
  • anodizing the surface of the metal base is performed under a voltage of about 10 Volts to about 100 Volts for about 1 minute to about 60 minutes.
  • the temperature of the electrolyte solution is about minus 20 Celsius degrees to about 80 Celsius degrees.
  • anodizing the surface of the metal base is performed under a voltage of about 10 Volts to about 50 Volts for about 5 minutes to about 30 minutes. And the temperature of the electrolyte solution is about 20 Celsius degrees to about 60 Celsius degrees.
  • anodizing the surface of the metal base is performed under a voltage of about 15 Volts to about 30 Volts for about 5 minutes to about 20 minutes.
  • the temperature of the electrolyte solution is about 40 Celsius degrees to about 60 Celsius degrees.
  • the method further includes steps of chemically etching the metal substrate to form corrosion pores on the surface of the oxide layer to obtain a surface-treated metal substrate with a treated surface.
  • a part of the resin from the resin composition may fill in the corrosion pores, which may improve the adhesion force between the resin layer and the metal substrate in the metal-resin composite.
  • the condition to perform the chemical etching may be selected depending on the desired properties of the corrosion pores on the metal substrate.
  • chemically etching the metal substrate is performed until the corrosion pores have a pore diameter of about 200 nm to about 2000 nm, and a ratio of the depth of the corrosion pores and the thickness of the oxide layer is about 0.1-1 to about 1: 1.
  • chemically etching the metal substrate is performed until the corrosion pores have a pore diameter of about 800 nm to about 1500 nm, and a ratio of the depth of the corrosion pores and the thickness of the oxide layer is about 0.1: 1 to about 0.5: 1.
  • a metal-resin composite obtained may have higher structure stability between the resin layer and the metal substrate.
  • chemically etching the metal substrate is performed until the corrosion pores have a pore diameter of about 1000 nm to about 15000 nm, and a ratio of the depth of the corrosion pores and the thickness of the oxide layer is about 0.2: 1 to about 0.4: 1.
  • the pore diameter of the corrosion pores refers to the maximum radial dimension of an upper port of the corrosion pores (i.e. the port of the corrosion pores located at the surface of the oxide layer) .
  • the depth of the corrosion pores refers to the vertical distance between the two ends of a corrosion hole.
  • the pore diameter and depth of the corrosion pores may be determined by electron microscopy.
  • chemically etching the metal substrate may be performed by any conventional methods which may form corrosion pores on the surface of the oxide layer.
  • chemically etching the metal substrate is performed by immersing the metal substrate in an acidic etching solution.
  • the acidic etching solution is an aqueous solution comprising at least an acid.
  • the acid may be selected from a group consisting of hydrohalic acid, phosphoric acid, sulfuric acid and nitric acid.
  • the hydrohalic acid may be hydrochloric acid.
  • the acid has a concentration of about 0.1 wt%to about 50 wt%. In some embodiments of the present disclosure, the acid has a concentration of about 1 wt%to about 30 wt%. In some embodiments of the present disclosure, the acid has a concentration of about 20 wt%to about 50 wt%. Thereby the corrosion pores may be formed on the surface of the oxide layer, with more uniform size and more uniform distribution, which may provide a metal-resin composite with higher structure stability.
  • the acid etching solution further comprises at least a soluble salt, which may improve the stability of the chemically etching, thus ensuring a higher structure stability between the resin layer and the metal base of the metal-resin composite.
  • the content of the soluble salt may be determined by the content of the acid.
  • the soluble salt and the acid have a molar ratio of about 0.1: 1 to about 1: 1.
  • the soluble salt may be at least one selected from a group consisting of hydrohalide, phosphate, sulfate and nitrate.
  • Specific examples of the soluble salt may include, but without no limitation: NaCl, KCl, AlCl 3 , NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 , KH 2 PO 4 , K 2 HPO 4 , K 3 PO 4 , Na 2 SO 4 , K 2 SO 4 , NaNO 3 , and KNO 3 .
  • the soluble salt may be one or more selected from NaCl, NaH 2 PO 4 , Na 2 HPO 4 , NaNO 3 , and Na 2 SO 4 .
  • the soluble salt has the same acid radicals to the acid of the acid etching solution.
  • the soluble salt is one selected from hydrohalide.
  • the temperature of the acid etching solution may be a conventional choice in the art. Usually, the temperature of the acid etching solution is about 10 Celsius degrees to about 60 Celsius degrees. In some embodiments of the present disclosure, the temperature of the acid etching solution is about 20 Celsius degrees to about 40 Celsius degrees.
  • the time for chemically etching the metal substrate varies with the type and the concentration of the acid in the acid etching solution. Generally, chemically etching the metal substrate is performed for about 1 minute to about 60 minutes. From the viewpoint of further improving the dimension uniformity of the corrosion pores, chemically etching the metal substrate is performed for about 10 minutes to about 30 minutes.
  • chemically etching the metal substrate may be carried out for one time or more than one time, such as for 2 times, as long as the total time for chemically etching meet the requirements. While chemically etching the metal substrate may be carried out for more than one time, the etching solution used may be the same or different each time. And, while chemically etching the metal substrate may be carried out for more than one time, the metal substrate should be cleaned to remove the residual etching solution after completion of each chemically etching.
  • the method further includes steps of injecting a resin composition to fill in the corrosion pores, then molding to obtain a resin layer.
  • the resin from the resin composition may be selected according to specific requirements, as long as the resin can be combined with the copper or copper alloy.
  • the main resin may use any conventional thermoplastic resin, such as polyphenylene sulfide (PPS) , polyesters (PE) , polyamides (PA) , polycarbonates (PC) , polyolefins and combinations thereof.
  • the polyesters (PE) may be a variety of polymers by polycondensation of a dicarboxylic acid with a diol, such as polyethylene terephthalate and/or polybutylene terephthalate (PBT) , but without limits.
  • the polyamides (PA) may be a variety of polymers by polycondensation of a diamine with a dicarboxylic acid, such as polyhexamethylene adipamide, poly-azelaic-methylene adipamide, poly-tetra-methylene adipamide, poly-dodecane-methylene adipamide, poly (hexamethylene sebacamide) (PA-610) , poly-sebacamide-decamethylenediamine (PA-1010) , polyundecamide, polydodecamide, poly octanamide, poly 9-amino-nonanoic acid, polycaprolactam, poly-p-phenylene isophthalamide, poly-m-phenylene adipamide, poly-p-phenylene adipamide, and poly terephthaloyl nonanediamine, but without limits.
  • the polyolefins may be at least one selected from a group consisting of polystyrene (PS) , polypropylene (PP) , polymethyl methacrylate (PMMA) and poly (acrylonitrile-butadiene-styrene) (ABS) , but without limits.
  • PS polystyrene
  • PP polypropylene
  • PMMA polymethyl methacrylate
  • ABS poly (acrylonitrile-butadiene-styrene)
  • the resin composition further comprises at least one filler and/or at least one fluidity modifier.
  • the filler may be any type of fillers selected according to specific requirements.
  • the filler may be a fiber filler and/or a powder filler.
  • the fiber filler is at least one selected from a group consisting of glass fiber, carbon fiber and aromatic polyamide fiber.
  • the powder filler is at least one selected from a group consisting of calcium carbonate, magnesium carbonate, silicon dioxide, heavy barium sulfate, talcum powder, glass and clay.
  • the size of the filler may be conventional choice in the art, as long as a compact resin layer can be formed.
  • the fiber filler may have a length of about 1 mm to about 10mm.
  • the powder filler may have a particle diameter of about 1 ⁇ m to about 200 ⁇ m.
  • the content of the filler may be conventional choice in the art. Usually, based on 100 weight parts of the main resin, the content of the filler is about 20 weight parts to 150 weight parts. In some embodiments of the present disclosure, based on 100 weight parts of the main resin, the content of the filler is about 30 weight parts to 60 weight parts.
  • the fluidity modifier is used to improve the flowing capability of the main resin, further improve the adhesion between the metal substrate and the resin and the processing properties of the resin.
  • the fluidity modifier may be any materials which are able to achieve the above-mentioned effects.
  • the fluidity modifier is a cyclic polyester.
  • the content of the fluidity modifier is determined to ensure the flowing capability of the main resin. In some embodiments of the present disclosure, based on 100 weight parts of the main resin, the content of the fluidity modifier is about 1 weight part to about 5 weight parts.
  • the resin composition may further comprise other additives according to practical requirements, without special limitations.
  • the additives may comprise a colorant or an antioxidant, which may modify the performance of the resin layer of the metal-resin composite or provide a new performance to the resin layer of the metal-resin composite.
  • the resin composition used in present disclosure may be prepared by uniformly mixing the main resin, the filler, the fluidity modifier and other additives.
  • the resin composition may be prepared by mixing evenly the main resin, the filler, the fluidity modifier and other additives, then granulating and extruding.
  • injecting a resin composition to the treated surface of the metal substrate may use a conventional method well known in the art, then molding to obtain a resin layer, such as cast molding or injection molding.
  • the metal substrate is placed in a mold, and then the resin composition is injected into the mold.
  • the conditions for injecting may be selected according to the types of the main resin of the resin composition.
  • the injecting is performed under conditions of: a mold temperature of about 50 Celsius degrees to about 300 Celsius degrees, a nozzle temperature of about 200 Celsius degrees to about 450 Celsius degrees, an injection pressure of about 50 MPa to about 300 MPa, a pressure maintaining time of about 1 s to about 50 s, an injection time of about 1 s to about 30 s, and a delay time of about 1 s to about 30 s.
  • the injecting is performed under conditions of: a mold temperature of about 100 Celsius degrees to about 180 Celsius degrees (such as about 120 Celsius degrees to 160 Celsius degrees) , a nozzle temperature of about 280 Celsius degrees to about 350 Celsius degrees (such as about 290 Celsius degrees to 320 Celsius degrees) , thereby the resin composition may sufficiently fill in the corrosion pores, ensure a higher adhesion force between the resin layer and the metal substrate on one hand; on the other hand, the mold temperature may be easily controlled.
  • the amount of the injecting of the resin composition may be selected according to the desired thickness of the resin layer.
  • the resin composition has an injecting amount for that the resin layer has a thickness of about 0.5 mm to about 10 mm.
  • the thickness of the resin layer refers to a vertical distance between the upper surface of the oxide layer and the upper surface of the resin layer, for which the upper surface of the oxide layer refers to a surface contacted to the resin layer.
  • the surface without the formation of the resin layer may be treated to remove the surface pores and the color changes of the surface caused by chemically etching. These treatments may be carried out before or after the steps of molding, without special limitations.
  • the metal-resin composite obtained by the method has a higher adhesion force between the resin layer and the metal substrate, which may meet the requirements of using occasions with high structure stability.
  • a metal-resin composite includes: a metal substrate, and a resin layer attached to at least a part of a surface of the metal substrate, wherein the metal substrate comprises: a metal base made of copper or copper alloy; and an oxide layer attached to at least a part of a surface of the metal base, corrosion pores formed in the oxide layer and filled with a part of the resin from the resin layer.
  • the metal-resin composite may include: a metal substrate, and a resin layer, attached to at least a part of a surface of the metal substrate, wherein the metal substrate includes a metal base made of copper or copper alloy and an oxide layer attached to at least a part of a surface of the metal base; the oxide layer has a surface thereof formed with corrosion pores, and the corrosion pores are filled with a part of the resin from the resin layer.
  • the oxide layer has a thickness of about 0.1 ⁇ m to about 50 ⁇ m. In some embodiments of the present disclosure, the oxide layer has a thickness of about 1 ⁇ m to about 25 ⁇ m. In some embodiments of the present disclosure, the oxide layer has a thickness of about 5 ⁇ m to about 10 ⁇ m.
  • a ratio of the thickness of the oxide layer and the metal base is about 0.001: 1 to about 1: 1. In some embodiments of the present disclosure, the ratio of the thickness of the oxide layer and the metal base is about 0.005: 1 to about 0.5: 1. In some embodiments of the present disclosure, the ratio of the thickness of the oxide layer and the metal base is about 0.005: 1 to about 0.01: 1.
  • the corrosion pores have a pore diameter of about 200 nm to about 2000 nm, and a ratio of the depth of the corrosion pores and the thickness of the oxide layer is about 0.1-1 to about 1: 1.
  • the corrosion pores have a pore diameter of about 800 nm to about 1500 nm, and a ratio of the depth of the corrosion pores and the thickness of the oxide layer is about 0.1: 1 to about 0.5: 1.
  • the corrosion pores have a pore diameter of about 1000 nm to about 15000 nm, and a ratio of the depth of the corrosion pores and the thickness of the oxide layer is about 0.2: 1 to about 0.4: 1.
  • the main resin may be selected according to specific requirements, as long as the resin can be combined with the copper or copper alloy.
  • the main resin may use any conventional thermoplastic resin, such as polyphenylene sulfide (PPS) , polyesters (PE) , polyamides (PA) , polycarbonates (PC) , polyolefins and combinations thereof.
  • the polyesters (PE) may be a variety of polymers by polycondensation of a dicarboxylic acid with a diol, such as polyethylene terephthalate and/or polybutylene terephthalate, but without limits.
  • the polyamides (PA) may be a variety of polymers by polycondensation of a diamine with a dicarboxylic acid, such as polyhexamethylene adipamide, poly-azelaic-methylene adipamide, poly-tetra-methylene adipamide, poly-dodecane-methylene adipamide, poly (hexamethylene sebacamide) (PA-610) , poly-sebacamide-decamethylenediamine (PA-1010) , polyundecamide, polydodecamide, poly octanamide, poly 9-amino-nonanoic acid, polycaprolactam, poly-p-phenylene isophthalamide, poly-m-phenylene adipamide, poly-p-phenylene adipamide, and poly terephthaloyl nonanediamine, but without limits.
  • the polyolefins may be at least one selected from a group consisting of polystyrene (PS) , polypropylene (PP) , polymethyl methacrylate (PMMA) and poly (acrylonitrile-butadiene-styrene) (ABS) , but without limits.
  • PS polystyrene
  • PP polypropylene
  • PMMA polymethyl methacrylate
  • ABS poly (acrylonitrile-butadiene-styrene)
  • the resin composition further comprises at least one filler.
  • the filler may be any type of fillers selected according to specific requirements.
  • the filler may be a fiber filler and/or a powder filler.
  • the fiber filler is at least one selected from a group consisting of glass fiber, carbon fiber and aromatic polyamide fiber.
  • the powder filler is at least one selected from a group consisting of calcium carbonate, magnesium carbonate, silicon dioxide, heavy barium sulfate, talcum powder, glass and clay.
  • the content of the filler may be conventional choice in the art. Usually, based on 100 weight parts of the main resin, the content of the filler is about 20 weight parts to 150 weight parts. In some embodiments of the present disclosure, based on 100 weight parts of the main resin, the content of the filler is about 30 weight parts to 60 weight parts.
  • the size of the filler may be conventional choice in the art, as long as a compact resin layer can be formed.
  • the fiber filler may have a length of about 1 mm to about 10mm.
  • the powder filler may have a particle diameter of about 1 ⁇ m to about 200 ⁇ m.
  • the thickness of the resin layer may be selected according to specific using occasions.
  • the resin layer has a thickness of about 0.5 mm to about 10 mm.
  • the thickness of the oxide layer and the depth of the corrosion pores were tested by a metallographic microscope Axio Imager Alm, purchased from ZEISS. Every sample was tested at five different positions thereof, and recorded the depth of the corrosion pores appearing in sight.
  • the pore diameter of the corrosion pores was tested by a scan electron microscope JSM-7600F, purchased from Japan Electronics Co., Ltd. Every sample was tested at five different positions thereof, and recorded the depth of the corrosion pores appearing in sight.
  • Examples 1-10 were for instruction of the metal-resin composite and the method of preparing the same According to embodiments of the present disclosure.
  • a commercially available brass plate with a thickness of 1 mm was cut into 15mm ⁇ 80mm rectangular sheets, which were then polished in a polishing machine, and cleaned with water-free ethanol, and then immersed in a 2 wt%NaOH aqueous solution. After 2 minutes, the rectangular sheets were washed with water and dried to obtain pretreated brass sheets
  • step (3) The brass sheet after step (2) was immersed in an etching solution containing a hydrochloric acid having a concentration of 30 wt%at 20 °C, taken out after 10 min, and placed in a beaker containing water to be immersed for 1minute. Then the brass sheet was blow-dried.
  • the dried brass sheet after step (3) was inserted into an injection mold.
  • a resin composition containing a polyphenylene sulfide (PPS) resin and fiberglass (length of 5 mm) was injection molded, for which the content of the fiberglass was 30 weight parts, based on 100 weight parts of the PPS, then demolded and cooled.
  • the conditions for injection molding included: a mold temperature of 120 Celsius degrees, a nozzle temperature of 305 Celsius degrees, an injection pressure of 120 MPa, a pressure maintaining time of 5 s, an injection time of 5 s, and a delay time of 5 s.
  • the cooled product was placed into an oven thermostat keeping 120 Celsius degrees for 1.5h, then cooled to room temperature in the furnace.
  • a metal-resin composite having an oxide layer (the thickness of the oxide layer was 2 mm) was obtained, the average shear strength and fracture mode were listed in Table 1.
  • the brass sheet was immersed in an etching solution which was an aqueous solution containing 3 wt%H 2 SO 4 and 3 wt%H 2 O 2 at 30 Celsius degrees for 15 minutes, and placed in a beaker containing water to be immersed for 1minute, then blow-dried.
  • the brass sheet was immersed in a aqueous solution containing 10 wt%NaOH and 5 wt%Na 2 SO 3 at 70 Celsius degrees for 1 minute to form oxidation on the surface of the brass, then placed in a beaker containing water to be immersed for 1minute, a brass sheet with a treated surface was obtained.
  • step (3) The brass sheet after step (2) was immersed in an etching solution containing a hydrochloric acid having a concentration of 30 wt%at 20 °C, taken out after 10 min, and placed in a beaker containing water to be immersed for 1minute. Then the brass sheet was blow-dried.
  • a commercially available brass plate with a thickness of 1 mm was cut into 15mm ⁇ 80mm rectangular sheets, which were then polished in a polishing machine, and cleaned with water-free ethanol, and then immersed in a 2 wt%NaOH aqueous solution. After 2 minutes, the rectangular sheets were washed with water and dried to obtain pretreated brass sheets
  • step (3) The brass sheet after step (2) was immersed in an etching solution containing a sulfuric acid having a concentration of 25 wt%at 30 °C, taken out after 10 min, and placed in a beaker containing water to be immersed for 1minute. Then the brass sheet was blow-dried.
  • the dried brass sheet after step (3) was inserted into an injection mold.
  • a resin composition containing a polybutylene terephthalate (PBT) resin and talcum powder (average particle diameter was 4 ⁇ m) was injection molded, for which the content of the talcum powder was 40 weight parts, based on 100 weight parts of the PBT, then demolded and cooled.
  • the conditions for injection molding included: a mold temperature of 120 Celsius degrees, a nozzle temperature of 305 Celsius degrees, an injection pressure of 120 MPa, a pressure maintaining time of 5 s, an injection time of 5 s, and a delay time of 3 s.
  • the cooled product was placed into an oven thermostat keeping 120 Celsius degrees for 1.5h, then cooled to room temperature in the furnace.
  • a metal-resin composite having an oxide layer (the thickness of the oxide layer was 4 mm) was obtained, the average shear strength and fracture mode were listed in Table 1.
  • a commercially available brass plate with a thickness of 1 mm was cut into 15mm ⁇ 80mm rectangular sheets, which were then polished in a polishing machine, and cleaned with water-free ethanol, and then immersed in a 2 wt%NaOH aqueous solution. After 2 minutes, the rectangular sheets were washed with water and dried to obtain pretreated brass sheets
  • step (3) The brass sheet after step (2) was immersed in an etching solution containing a phosphoric acid having a concentration of 20 wt%at 30 °C, taken out after 30 min, and placed in a beaker containing water to be immersed for 1minute. Then the brass sheet was blow-dried.
  • the dried brass sheet after step (3) was inserted into an injection mold.
  • a resin composition containing a nylon 66 (PA-66) resin and fiberglass (length of 5 mm) was injection molded, for which the content of the fiberglass was 50 weight parts, based on 100 weight parts of the PA-66, then demolded and cooled.
  • the conditions for injection molding included: a mold temperature of 150 Celsius degrees, a nozzle temperature of 305 Celsius degrees, an injection pressure of 120 MPa, a pressure maintaining time of 5 s, an injection time of 5 s, and a delay time of 3 s.
  • the cooled product was placed into an oven thermostat keeping 120 Celsius degrees for 1.5h, then cooled to room temperature in the furnace.
  • a metal-resin composite having an oxide layer (the thickness of the oxide layer was 5 mm) was obtained, the average shear strength and fracture mode were listed in Table 1.
  • Example 1 23 A Comparative Example 1 0.2 B Comparative Example 2 5 B Comparative Example 3 11 B Example 2 20.2 A Example 3 26.8 A Example 4 18.1 A Example 5 20 A Example 6 23.4 A Example 7 27 A Example 8 30.6 A Example 9 21 A Example 10 24.5 A
  • the fracture mode A referred to that the fracture place was located at the resin layer.
  • the fracture mode B referred to that the fracture place was located at the combination part of the resin layer and the metal substrate.
  • the metal-resin composites prepared from the method according to embodiments of the present disclosure showed higher average shear strength, and the fracture place thereof were located at the resin layer, which demonstrated that the metal-resin composites prepared from the method according to embodiments of the present disclosure had a strong adhesion force between the resin layer and the metal substrate.
  • the raw materials used in the method according to embodiments of the present disclosure have good applicability and can be used to form various types of resin layers on the surface of the metal substrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

La présente invention concerne un composite métal-résine et son procédé de fabrication. Le procédé consiste en : la fourniture d'un substrat métallique, le substrat métallique comprenant une base métallique composée de cuivre ou d'un alliage de cuivre et une couche d'oxyde fixée à au moins une partie d'une surface de la base métallique ; l'attaque chimique du substrat métallique afin de former des pores de corrosion sur une surface de la couche d'oxyde afin d'obtenir un substrat métallique traité en surface doté d'une surface traitée ; et l'injection d'une composition de résine pour remplir les pores de corrosion, puis moulage afin d'obtenir une couche de résine.
PCT/CN2015/082541 2014-06-30 2015-06-26 Composite métal-résine et son procédé de préparation Ceased WO2016000574A1 (fr)

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CN107187143B (zh) * 2017-05-11 2019-12-17 歌尔股份有限公司 一种金属和塑料的复合体及其制备方法
CN107779931A (zh) * 2017-12-08 2018-03-09 博罗县东明化工有限公司 阳极氧化电解液及镁合金与树脂复合体的制造方法
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CN112440430A (zh) * 2019-08-30 2021-03-05 比亚迪股份有限公司 树脂-铝合金复合体和制备方法，以及壳体
CN114851465B (zh) * 2021-02-04 2025-01-14 比亚迪股份有限公司 一种镁合金-树脂复合体及其制备方法、以及电子产品壳体
CN114293056B (zh) * 2021-12-20 2022-12-23 富联裕展科技(深圳)有限公司 金属工件、金属制品、蚀刻液以及金属工件的制作方法

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