WO2019189773A1 - Substrat ayant une surface entièrement ou au moins partiellement constituée d'un matériau métallique, la surface dudit matériau métallique ayant des trous, et composite de substrat et de produit durci en résine contenant ledit substrat et ledit produit durci en résine - Google Patents

Substrat ayant une surface entièrement ou au moins partiellement constituée d'un matériau métallique, la surface dudit matériau métallique ayant des trous, et composite de substrat et de produit durci en résine contenant ledit substrat et ledit produit durci en résine Download PDF

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Publication number
WO2019189773A1
WO2019189773A1 PCT/JP2019/014029 JP2019014029W WO2019189773A1 WO 2019189773 A1 WO2019189773 A1 WO 2019189773A1 JP 2019014029 W JP2019014029 W JP 2019014029W WO 2019189773 A1 WO2019189773 A1 WO 2019189773A1
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Prior art keywords
resin
base material
substrate
metal material
hole
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PCT/JP2019/014029
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English (en)
Japanese (ja)
Inventor
太一 永井
益代 西村
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日本パーカライジング株式会社
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Publication of WO2019189773A1 publication Critical patent/WO2019189773A1/fr

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    • 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
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention provides a base material-resin comprising a base material in which at least all or a part of the surface is made of a metal material, the surface of the metal material having specific holes, and the base material and a cured resin product. It relates to a composite of a cured product.
  • Patent Document 1 describes as follows.
  • (1) Includes one or more straight line portions with a load length ratio (Rmr) of a roughness curve at a cutting level of 20% and an evaluation length of 4 mm of 30% or less.
  • the bonding strength of the metal / resin composite structure obtained by the method disclosed in Patent Document 1 may be insufficient.
  • the present invention solves the above-mentioned problems of the prior art, that is, a base material having a metal material having a specific hole excellent in bonding strength with a resin, and a base material-resin curing containing the base material and a resin cured product.
  • the object is to provide a composite of objects.
  • the present inventors have found a base material in which at least all or a part of the surface is made of a metal material, and the surface of the metal material has a specific hole.
  • the headline and the present invention were completed. That is, the gist of the present invention is as follows.
  • the load length ratio (Pmr) of the cross-sectional curve is 40% or more at a cutting level of 30% and an evaluation length of 10 ⁇ m.
  • the average value (a) of the diameter at the inlet of the hole and the average of the hole depth is 2 or more and 50 or less [2] A substrate-resin composite containing a substrate and a cured resin, wherein the substrate is described in [1] A composite of a base material and a resin cured product, wherein a resin cured product is contained in pores on the surface of the metal material of the base material.
  • the base material is excellent in bonding strength with a resin, and at least all or part of the surface is made of a metal material, and the surface of the metal material has a specific hole and the base material.
  • a substrate-resin cured product composite containing a cured resin product can be provided.
  • hole means not a through hole but a recess.
  • the base material applied to the embodiment of the present invention is not particularly limited as long as at least the whole or a part of the surface is a base material made of a metal material.
  • the metal material present on all or a part of at least the surface of the substrate include iron, iron alloy, titanium, titanium alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, and copper alloy. It is not limited.
  • the base material is not particularly limited, and includes wrought material, extruded material, cast material, and die-cast material.
  • the said metal material may be used independently and may be used in combination of 2 or more types of metal materials.
  • aluminum or an aluminum alloy is preferable from the viewpoint of light weight and high strength.
  • aluminum or an aluminum alloy may be simply referred to as “aluminum material”.
  • the iron or iron alloy is not particularly limited, and examples include industrially used ordinary steel, chrome molybdenum steel, and stainless steel. Specifically, S45C, SCM415, SUS304, SUS316, SUS430, etc. standardized by JISG4051, JISG4053, JISG4304, etc. are mentioned.
  • the titanium or titanium alloy is not particularly limited, and includes pure titanium, ⁇ - ⁇ alloy, ⁇ alloy and the like used in the industry. Specifically, one to four kinds of pure titanium, Ti-6Al-4V, Ti-22V-4Al, and other titanium alloys specified in JISH-4600 are listed.
  • Aluminum or aluminum alloy is not particularly limited, and any aluminum material used in the industry can be applied.
  • An aluminum material refers to a material containing 60% or more of aluminum, and examples of alloy components other than aluminum include magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc.
  • alloy components other than aluminum include magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc.
  • A1050, A2014, A2024, A3003, A5052, A5N01, A6061, A6063, A7075, AC4A, ADC12 and the like specified in JIS HH 5302 and JIS HH 5202 are listed.
  • the magnesium alloy is not particularly limited, and any magnesium alloy used in the industry can be applied. Specific examples of the magnesium alloy include AZ92, AZ91, AZ80, AZ63, AZ61, AZ31, AM100, AM60, AM50, AM20, AS41, AS21, AE42, ACM522, and the like.
  • Copper or copper alloy is not particularly limited, and any copper or copper alloy used in the industry can be applied. Specific examples of copper or copper alloy include C1020, C1100, C1220, C2801, C4621, C6140, etc., which are standardized in JIS H3100.
  • the shape of the base material having at least all or part of the surface made of a metal material is not particularly limited as long as the resin can be joined to the base material. May be. Moreover, the structure which combined these may be sufficient.
  • the base material includes all intermediate products and finished products in the category of the base material according to the embodiment of the present invention. If at least all or a part of the surface of the base material is a metal material, the other part may be a material other than the metal material.
  • a base material may be comprised only from a metal material. Examples of the material other than the metal material include, but are not limited to, metals other than the base material, resin, rubber, wood, ceramic, composite material, and the like.
  • the joining method of materials other than the said base material is not specifically limited.
  • the shape of the surface of the joint portion of the metal material of the base material to be joined to the resin may be a flat surface or a curved surface, but is not particularly limited.
  • the base material may be subjected to plastic processing, cutting processing, blast processing, polishing processing, electric discharge processing, drilling processing, heat treatment (age hardening processing, solution treatment, etc.).
  • the base material may be subjected to surface treatment (chemical conversion treatment, plating treatment, anodizing treatment, etc.), but these film components may be polished or chemically treated before forming the holes described below. Is preferably removed.
  • the surface is made of a metal material, the surface of the metal material has pores, and satisfies the following requirements (1) and (2).
  • the load length ratio (Pmr) of the cross-sectional curve is 40% or more at a cutting level of 30% and an evaluation length of 10 ⁇ m.
  • the average value (a) of the diameter at the inlet of the hole and the average of the hole depth is 2 or more and 50 or less
  • the load length ratio of the cross-sectional curve is less than the lower limit value, the strength is lowered, so that the bonding strength with the resin is lowered.
  • the load length ratio of the cross-sectional curve is more preferably 45% or more, and further preferably 50% or more.
  • the upper limit of the load length ratio of the cross-sectional curve is 95% or less.
  • the aspect ratio is less than 2, the bonding strength with the resin decreases. Even when the load length ratio of the cross-sectional curve is equal to or more than the above lower limit value, when the aspect ratio is less than 2, excellent bonding strength with the resin cannot be obtained. Further, even when the aspect ratio is 2 or more, when the load length ratio of the cross-sectional curve is less than the lower limit value, the strength is lowered, so that excellent bonding strength cannot be obtained. Therefore, in order to obtain excellent bonding strength with the resin, it is necessary to satisfy the two requirements (1) and (2) at the same time.
  • the load length ratio (Pmr (c)) of the cross-sectional curve represents the ratio of the load length Ml (c) of the contour curve element at the cutting level c to the evaluation length (ln) as shown in the equation (A).
  • the measuring method is defined in JIS B 0601.
  • (A) Pmr (c) Ml (c) / ln
  • the load length ratio of the cross-sectional curve in the embodiment of the present invention is determined by observing the cross-sectional structure appearing at the cut surface by electron microscope observation when cut in the direction perpendicular to the actual surface of the base material having the metal material having holes. Measure from the photograph taken.
  • a method for preparing a sample for observing the cross-sectional structure is not particularly limited, and examples thereof include a mechanical polishing method, a focused ion beam method, an ion milling method, and a microtome method. In short, it is only necessary to observe the structure of the holes.
  • the distance be Rt.
  • the cutting level c is set to 30%. That is, the cutting level is 30% from the top line with respect to Rt.
  • the evaluation length is set to 10 ⁇ m.
  • the load length Ml (c) is obtained by measuring the sum of the actual lengths (Ml 1 to Ml 9 in FIG. 1) of the contour curve elements cut at a cutting level of 30% from a photograph taken with an electron microscope. It can ask for.
  • the load length ratio of the cross-sectional curve in the embodiment of the present invention means that the cross-sectional structure that appears at the cut surface when the substrate is cut in the direction perpendicular to the actual surface of the base material having the metal material with holes is measured with an electron microscope.
  • the ratio of the load length Ml (c) at the height of 30% from the top line to Rt with respect to the evaluation length of 10 ⁇ m is shown.
  • the magnification is 10,000 times or more in observation with an electron microscope.
  • the aspect ratio according to the embodiment of the present invention is calculated by the ratio (b / a) of the average value (a) of the diameters at the hole entrance and the average value (b) of the hole depth.
  • An aspect ratio of 2 or more means that there is a hole in which (b) has an average value of hole depths twice or more that of (a).
  • the average value of the diameter at the entrance of the hole can be measured from a photograph of the surface of the base material having the metal material having the hole taken with an electron microscope. As shown in FIG. 2, circular or elliptical holes are observed on the surface of the metal material of the base material according to the embodiment of the present invention.
  • the average value of the diameter at the entrance of the hole is the average value of the diameter (a in FIG. 2) or the short diameter (b in FIG. 2) of the circular or elliptical opening formed on the surface.
  • the average value of the diameters at the entrances of the holes was taken with an electron microscope when a large number of holes were to be measured, and the cross-sectional structure that appeared at the cut ends when cut in a direction perpendicular to the actual surface of the substrate. It can also be measured from photographs.
  • the average value of the diameter at the entrance of the hole is the average value of the opening width of the uppermost part of the formed hole (c in FIG. 3).
  • the total length is divided and divided by 10 to obtain the average value of the diameters at the hole entrances.
  • the magnification is 10,000 times or more in observation with an electron microscope.
  • the average diameter measurement method at the entrance of the hole is more preferably obtained from a photograph of the surface of the base material having the metal material having the hole taken with an electron microscope.
  • the average value of the hole depth is measured from a photograph taken by observing an electron microscope of a cross-sectional structure that appears at the cut edge when cut in a direction perpendicular to the actual surface of the substrate. In order to obtain the hole depth, it is preferable that the magnification is 10,000 times or more in observation with an electron microscope.
  • the average value of the hole depth is an average value of the length (d in FIG. 3) between the uppermost part and the deepest part in the formed hole, and the top 10 are selected from the longest hole depths, The length from the top to the deepest part is measured, and all are integrated and divided by 10 to obtain the average value of the hole depth.
  • the diameter range at the hole entrance of the base material is preferably 50 nm or more and 4000 nm or less. More preferably, it is 60 nm or more and 2000 nm or less, More preferably, it is 70 nm or more and 1000 nm or less.
  • the range of the hole depth of the base material is preferably 100 nm or more and 10 ⁇ m or less, More preferably, it is 200 nm or more and 9 micrometers or less, More preferably, it is 300 nm or more and 8 micrometers or less.
  • the aspect ratio defined in (2) above according to the embodiment of the present invention is 2 or more and 50 or less. From the viewpoint of further improving the bonding strength between the base material having the metal material having holes and the resin according to the embodiment of the present invention, the range of the aspect ratio is 2 or more, preferably 3 or more, Preferably it is 4 or more. When the aspect ratio exceeds 50, the strength of the metal material itself decreases.
  • the hole should just confirm one or more places by observing arbitrary 10 places on the surface and cross section of the base material. More specifically, in the embodiment of the present invention, the number of holes having the aspect ratio on the surface of the metal material preferably has one or more per 1 ⁇ m 2 of the surface area of the metal material. It is more preferable to have the above. The hole does not need to be present on the entire surface of the base material, and it is sufficient that the hole has at least a portion to be bonded to a resin described later.
  • the method for producing the substrate having the metal material having the holes is not particularly limited, and examples thereof include known methods such as an imprint method, a laser processing method, and a chemical etching method.
  • the imprint method is a method of forming a hole by pressing a substrate or a roll having a plurality of protrusions against a base material having a metal material, and examples thereof include a transfer method and a press patterning method.
  • the laser processing method is a method of forming holes by irradiating the surface of a metal material with laser light.
  • the chemical etching method is a method in which a substrate having a metal material is brought into contact with a treatment liquid using a chemical to cause corrosion to form holes.
  • a method for producing holes by film formation is excluded.
  • the coating include an anodic oxide coating, chemical conversion coating (phosphate coating, zirconium coating, chromium coating, silicate coating, lithium conversion coating), plating film, and the like.
  • the following chemical etching method is suitable as a method for producing the substrate having the holes.
  • This chemical etching method is particularly suitable for the production of a substrate having an aluminum material on at least all or part of its surface.
  • a surface treating agent (zinc ions and an alkali source) containing a lithium ion source and an alkali source on the surface of the substrate whose whole or part of the surface is made of a metal material.
  • a manufacturing method including a process is suitable.
  • the surface treatment agent of the first step is applied to the surface of the substrate made of at least all or part of the surface of the metal material.
  • a film containing lithium element is formed.
  • at least all or part of the surface is accompanied by a dissolution reaction of a passive film including an oxide film on the surface of the base material made of a metal material.
  • the film containing lithium element can be formed using a known method. Examples include boehmite treatment and chemical conversion treatment, but are not limited thereto.
  • the film containing lithium element includes a hydroxide film, an oxide film, a hydrated oxide film and the like containing a metal derived from a base material.
  • the treatment method for example, the methods described in JP-A-48-89138, JP-A-53-11841 and the like can be used.
  • the surface treatment agent in the first step contains a lithium ion source and an alkali source as components.
  • the form of the lithium ion source is not particularly limited, and is suitable from hydroxide, chloride, carbonate, bicarbonate, nitrate, nitrite, sulfate, persulfate, bromide, bromate, etc. Can be selected from one or more.
  • the treatment liquid used in the first step according to the embodiment of the present invention preferably contains lithium ions in the range of 0.001 mol / L to 5.00 mol / L, more preferably 0.10 mol / L to 4.00 mol / L, More preferably, it contains 0.50 mol / L or more and 3.50 mol / L or less.
  • the lithium salt concentration may exceed the saturation solubility.
  • the surface treatment agent in the first step contains an alkali source.
  • the alkali source include hydroxides of alkali metals or alkaline earth metals, magnesium hydroxides, or water-soluble amine compounds.
  • the alkali metal or alkaline earth metal hydroxide is not particularly limited, and one or more suitable ones can be selected from lithium, sodium, potassium, calcium and the like.
  • the surface treatment agent in the first step is usually 0.001 mol / L or more and 5.00 mol / L or less, more preferably 0.005 mol / L or more and 4.00 mol / L or less, more preferably as an alkali source. Includes 0.01 mol / L or more and 3.00 mol / L or less. Further, the hydroxide concentration of the alkali metal, alkaline earth metal and magnesium may exceed the saturation solubility.
  • the water-soluble amine compound includes a primary amine to which an alkyl group having 1 to 12 carbon atoms is bonded, a secondary amine to which an alkyl group having 1 to 12 carbon atoms is bonded, and an alkyl group having 1 to 12 carbon atoms.
  • any of the bound tertiary amines can be used, and in addition to these water-soluble amines, aromatic amines in which a part or all of the alkyl group or hydroxyalkyl group is substituted with a phenol group are also used.
  • at least one methylene of the alkyl group having 1 to 12 carbon atoms may be substituted with —NH—.
  • water-soluble amine compounds include monoethylamine, diethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, dimethylaminoethanol, triethylenetetraamine, hexamethylenetetraamine, ethylenediamine, and ammonia.
  • One type or two or more types can be selected.
  • the treatment liquid used in the first step according to the embodiment of the present invention is preferably a water-soluble amine compound of 0.001 mol / L to 1.00 mol / L, more preferably 0.005 mol / L to 0.90 mol / L.
  • the following can be mentioned, More preferably, 0.01 mol / L or more and 0.80 mol / L or less are included.
  • the surface treatment agent in the first step among the alkali metal or alkaline earth metal hydroxide, magnesium hydroxide, and water-soluble amine compound, even if one component is used alone, several components are used in combination. It can also be used.
  • the surface treatment agent in the first step does not contain zinc ions and silicate ions.
  • zinc ions when zinc ions are present, when a base material having an aluminum material is used as the metal material, a desired hole cannot be obtained because a zinc-substituted film is formed on the surface of the aluminum material.
  • silicate ions when silicate ions are present, a film containing silicon is formed on the surface of the aluminum material, so that desired holes cannot be obtained.
  • transition metal ions such as copper, iron, nickel and tin. Alkali metal, alkaline earth metal, magnesium hydroxide, sodium, potassium, magnesium, calcium and the like supplied from these salts may be included in the film.
  • the surface treatment agent in the first step can be easily prepared by dissolving a lithium ion source and an alkali source in ion exchange water, industrial water, tap water and the like.
  • elements such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc derived from the base material and water may be present.
  • An organic solvent, a surfactant, and a chelating agent may be added to the surface treatment agent in the first step.
  • the total content is preferably 50.0% by mass or less based on the total amount of the surface treatment agent.
  • a film containing lithium element By contacting the surface treatment agent in the first step, a film containing lithium element can be formed on the surface of the base material in which at least all or part of the surface is made of a metal material.
  • the adhesion amount of the film is not particularly limited, and the film may be a continuous film or a discontinuous film.
  • Examples of the method of bringing the surface treatment agent in the first step into contact with a base material having at least all or part of the surface made of a metal material include treatment methods by dipping and spraying. By contacting the surface treatment agent, a film containing lithium element can be formed on the substrate, but an electrolytic treatment can be used in combination.
  • the liquid temperature of the surface treatment agent when used in the first step is preferably 20.0 ° C to 100.0 ° C.
  • the pH is preferably adjusted from 8.0 to 13.0.
  • the contact time is preferably 5 seconds to 1800 seconds.
  • a water washing step and a drying step may be performed as necessary.
  • the acidic aqueous solution in the second step contains an inorganic acid.
  • the inorganic acid one or more suitable ones can be selected from sulfuric acid, nitric acid, hydrochloric acid, amidosulfuric acid and the like, but are not limited thereto.
  • the aqueous solution may contain an organic acid, an inorganic acid salt, an organic acid salt, or the like, but it is preferable that the aqueous solution does not contain a transition metal.
  • the organic acid one or more suitable ones can be selected from formic acid, citric acid, oxalic acid, malic acid, succinic acid, malonic acid, ethylenediaminetetraacetic acid, gluconic acid, and the like. It is not limited.
  • the inorganic acid salt and organic acid salt can be selected from one or more suitable ones from alkali metal salts, alkaline earth metal salts and ammonium salts of the inorganic acids and organic acids. It is not limited to.
  • the said aqueous solution can mix
  • the total content of the components including the inorganic acid is preferably 0.1% by mass to 70.0% by mass, and preferably 0.5% by mass to 50.0% by mass with respect to the total amount of the acidic aqueous solution. Is more preferable, and it is further more preferable that it is 1.0 mass% to 45.0 mass%.
  • a surfactant or chelating agent may be added to the acidic aqueous solution in the second step.
  • the total content is 10.0 mass% or less with respect to the whole quantity of acidic aqueous solution.
  • the acidic aqueous solution in the second step can be easily prepared by dissolving each of the above components in ion exchange water, industrial water, tap water or the like.
  • elements such as aluminum, magnesium, silicon, titanium, chromium, manganese, iron, nickel, copper, and zinc derived from the base material and water may be present.
  • membrane containing the lithium element formed by said 1st process may mix.
  • Examples of the method of bringing the acidic aqueous solution containing the inorganic acid in the second step into contact with a substrate having at least a part of the surface made of a metal material include a treatment method by dipping and spraying. It is also possible to use electrolytic treatment in combination.
  • the acidic aqueous solution used in the second step preferably has a liquid temperature of 10.0 ° C to 80.0 ° C.
  • the pH may be acidic, and for example, it is preferably adjusted to pH 6.0 or lower.
  • the contact time is preferably about 1 to 1800 seconds, more preferably 900 seconds or less.
  • a water washing step and a drying step are usually performed. In the water washing step, ultrasonic waves may be used in combination. In the drying step, natural drying may be used, and a dryer, air blow, oven, or the like may be used.
  • the whole surface of the base material which has a metallic material may be processed, and it processes partially. May be. In order to obtain an excellent bonding strength with the resin, it is only necessary to treat only the portion bonded to the resin.
  • the base material having a metal material used for the base material manufacturing method according to the embodiment of the present invention is shot blasted, sandblasted, or ground before the manufacturing method (hole forming step) according to the embodiment of the present invention.
  • Mechanical roughening treatment such as processing, physical roughening treatment such as laser processing or plasma processing, or roughening treatment may be performed in advance by a chemical method.
  • corrugated shape formed after these processes is not ask
  • the base material having a metal material used in the base material manufacturing method according to the embodiment of the present invention cleans the surface of the metal material before the manufacturing method (hole forming step) according to the embodiment of the present invention. Therefore, a pretreatment consisting of a degreasing treatment, an acid treatment with an acid aqueous solution, and / or an alkali treatment with an alkali solution may be performed.
  • the method of the degreasing treatment is not particularly limited, and for example, a solvent-based, aqueous-based or emulsion-based degreasing agent can be used, and an alkali salt, a surfactant or the like may be included.
  • inorganic acids such as sulfuric acid, nitric acid, phosphoric acid and hydrofluoric acid, organic acids such as citric acid and gluconic acid, and those prepared by mixing these can be used.
  • organic acids such as citric acid and gluconic acid
  • alkali treatment those prepared with an alkali reagent such as sodium hydroxide or potassium hydroxide, or those prepared by mixing them can be used.
  • a film may be formed on the surface of the metal material having holes.
  • the film formation method may be a coating type or a reaction type.
  • the film to be formed include a natural oxide film, an anodized film, a chemical conversion film (phosphate-based film, zirconium-based film, chromium-based film). Film), a silane coupling agent cured film, a plating film, and the like, but are not limited thereto.
  • the film thickness is not particularly limited, but is preferably 100 nm or less. When the thickness of the film is thicker than 100 nm, the bonding strength with the resin may decrease. The thickness of the film can be appropriately adjusted according to the shape of the hole.
  • the water washing step may be performed before and after all the steps (for example, a surface processing step, a surface cleaning step, a hole forming step, a post-treatment step, etc.).
  • you may perform a drying process suitably after each water washing process.
  • the substrate-resin cured product composite according to an embodiment of the present invention is a substrate-resin composite including a substrate and a resin cured product, and the substrate is the substrate described above,
  • the cured resin in the composite of the substrate and the cured resin according to the embodiment of the present invention includes a thermoplastic resin, a thermosetting resin, a thermoplastic elastomer, a resin paint cured to a coating film, an adhesive It may be any resin such as a cured agent.
  • the substrate-resin cured product composite manufacturing method includes a hole forming step, which is a step included in the substrate manufacturing method according to the embodiment of the present invention, and the hole forming step. And putting the resin into the holes of the surface of the metal material. After the step of putting the resin into the holes, the resin is cured by cooling, leaving, or heating to form a base material-cured resin composite.
  • the composite of the base material-resin cured product may be composed only of the base material and the resin cured product, or in addition to the base material having the metal material having the holes and the resin cured product, You may include the other party material which contacts the resin cured material.
  • the counterpart material may be not only a resin material but also any material including metal, rubber, wood, ceramic, and composite material.
  • the shape of the counterpart material is not particularly limited, and may be a plate, a rod, a band, a tube, a wire, a film, or the like.
  • an adhesive is applied to the surface of a base material having a metal material having pores or the surface of the base material.
  • a method of bonding materials together and bonding a method of applying a resin to the surface or surface of a base material having a metal material having holes and bonding by thermocompression bonding, a surface or surface of a base material having a metal material having holes
  • the surface or surface of the substrate is made by insert molding and joining (hereinafter referred to as injection molding joining), the surface of the substrate having the holes or the surface of the substrate by curing the resin paint after contacting the surface. Form a coating on top And a method of, and the like.
  • the thermoplastic resin can be selected from known thermoplastic resins depending on the application.
  • polyamide resin, polycarbonate resin, polyvinyl resin, polyphenylene sulfide resin, polyacrylic resin, polyester resin, polyacetal resin, acrylonitrile / butadiene / styrene copolymer resin, polystyrene resin, polyimide resin, etc. 1 type or 2 or more types can be selected from, but is not limited thereto.
  • thermosetting resin can be selected from known thermosetting resins depending on the application.
  • one or two or more suitable ones can be selected from a phenol resin, an epoxy resin, a urea resin, a melamine resin, etc., but is not limited thereto.
  • thermoplastic elastomer can be selected from known thermoplastic elastomers according to applications.
  • one or two or more suitable materials can be selected from polyester elastomers, vinyl chloride elastomers, polyamide elastomers and the like, but the invention is not limited thereto.
  • the resin paint can be selected from known resin paints according to the application.
  • one or two or more suitable resins can be selected from an epoxy resin, an acrylic resin, a polyester resin, a urethane resin, and the like, but the invention is not limited thereto.
  • the paint may optionally contain components such as a pigment, a dispersant, a plasticizer, and a solvent.
  • the adhesive examples include a vinyl chloride resin adhesive, a vinyl acetate resin adhesive, a polyvinyl alcohol adhesive, a polyacryl adhesive, a polyamide adhesive, a cellulose adhesive, a urea resin adhesive, and a melamine.
  • Resin adhesives phenol resin adhesives, epoxy resin adhesives, silicon resin adhesives, polyester adhesives, polyurethane adhesives, chloroprene rubber adhesives, nitrile rubber adhesives, styrene / butadiene rubber adhesives
  • One or two or more suitable adhesives can be selected from, but not limited to, adhesives, silicone rubber adhesives, acrylic rubber adhesives, urethane rubber adhesives, hot melt adhesives, etc. is not.
  • thermoplastic resin thermosetting resin
  • thermoplastic elastomer thermoplastic elastomer
  • resin paint and adhesive
  • one or more suitable materials can be selected from glass fiber, carbon fiber, metal fiber, ceramic fiber, glass bead, carbon powder, metal powder, ceramic powder, aluminum oxide powder, etc. It is not limited to.
  • the type, content and shape of the filler are not particularly limited.
  • a composite of a base material having a metal material having holes according to an embodiment of the present invention and a cured resin is an automotive member, an aircraft member, an electronic device member, a mobile device member, an OA device member, It is useful as a material for members for home appliances and medical devices.
  • the base material having the metal material having the holes can improve not only the bonding strength with the resin but also the adhesion of the plating film and the like.
  • the base material having a metal material having holes and the composite of the base material and the resin cured product according to the embodiment of the present invention are not limited to the above-mentioned usage.
  • the composite of the base material-resin cured product according to Examples 1 to 3 and Comparative Examples 1 to 3 is a surface cleaning process ⁇ a hole forming process (first process ⁇ second process) ⁇ injection molding joining. It manufactured through each process. Hereinafter, each process of the said process process is demonstrated.
  • the surface cleaning step is alkali degreasing ⁇ Fine Cleaner 315E manufactured by Nippon Parkerizing Co., Ltd., 30 g / L (solid content concentration), 70 ° C., immersion time 1 minute ⁇ , followed by alkaline washing (sodium hydroxide 1.0 mol / L, 40 C., immersion time 1 minute), and water washing was performed after each step.
  • the substrate was immersed in a surface treatment agent containing lithium ions, and then washed with water.
  • the pH was adjusted using an aqueous nitric acid solution and an aqueous sodium hydroxide solution.
  • the substrate was immersed in an acidic aqueous solution containing an inorganic acid, and then washed with water and dried.
  • injection molding joining process In the injection molding joining process, a polyphenylene sulfide resin (PPS resin) containing 30% glass fiber was injection molded to the base material after the hole forming process.
  • An electric servo injection molding machine Si-50III manufactured by Toyo Machine Metal Co., Ltd. was used for the injection molding.
  • the injection molding conditions were preheat 125 ° C., molding temperature 320 ° C., mold temperature 135 ° C., injection speed 30 mm / second, injection pressure 1000 kgf, holding pressure 1200 kgf, and cooling time 15 seconds.
  • the dimension of the molded PPS resin is 10 mm wide ⁇ 45 mm long ⁇ 3 mm thick.
  • the joining area of a base material and PPS resin is 10 mm x 5 mm.
  • Example 1 As the base material, A2017 standardized by JIS H 4000 was used. As a 1st process, the base material was immersed for 300 second using the following process liquids (1). As a second step, the substrate was immersed for 180 seconds using the following treatment liquid (2). Thus, the base material-cured resin composite according to Example 1 was obtained.
  • the treatment liquid (1) has a target volume of 3.0 mol / L (mol / L) lithium chloride and 0.1 mol / L magnesium nitrate hexahydrate added to ion-exchanged water, While measuring the pH with a handy pH meter (portable pH meter HM-30P manufactured by Toa DKK Co., Ltd.) and a pH measuring electrode (GST-2739C manufactured by the same company), it was adjusted to pH 10.0 using nitric acid and sodium hydroxide. Adjusted and adjusted to the target capacity.
  • the temperature of the treatment liquid (1) was 60 ° C.
  • the treatment liquid (2) was added so that nitric acid was 6.5 mol / L (mol / L) with respect to ion-exchanged water. In this example, pH adjustment was not performed.
  • the temperature of the treatment liquid (2) was 50 ° C.
  • Example 2 A substrate-resin cured product composite of [Example 2] was produced in the same manner as in [Example 1] except that the substrate was changed to A3003 standardized by JIS H4000.
  • Example 3 A substrate-resin cured product composite of [Example 3] was produced in the same manner as in [Example 1] except that the substrate was changed to A5052 standardized by JIS H4000.
  • the base material was A2017 standardized by JIS H4000.
  • a base material-cured resin composite was produced in the same manner as in [Example 1] except that the treatment conditions in the first step and the second step were changed. Specifically, as a first step, the substrate was immersed for 60 seconds using the following treatment liquid (3). As a second step, the substrate was immersed for 300 seconds using the following treatment liquid (4).
  • the treatment liquid (3) has a target volume of 4.20 mol / L (mol / L) sodium hydroxide, 0.66 mol / L zinc nitrate, and 0.06 mol / L sodium thiosulfate. Were added to ion-exchanged water and adjusted to the target volume. The temperature of the treatment liquid (3) was 35 ° C.
  • the treatment liquid (4) has a target volume of sulfuric acid at 0.84 mol / L (mol / L), ferric chloride at 0.96 mol / L, and ferric chloride at 0.03 mol / L. Copper and manganese sulfate monohydrate at 0.05 mol / L were added to ion-exchanged water. In this example, pH adjustment was not performed.
  • the temperature of the treatment liquid (4) was 30 ° C.
  • the aspect ratio was calculated by the ratio (b / a) of the average value (a) of the diameters at the inlets of the holes and the average value (b) of the hole depths.
  • the average value (a) of the diameter at the entrance of the hole was measured from a photograph obtained by photographing the surface of the base material after the treatment in Examples 1 to 3 and Comparative Examples 1 to 3 with the electron microscope at a magnification of 50,000 times.
  • the top 10 were selected from those having a long diameter or short diameter of the opening of the hole, their lengths were measured, and all of them were integrated and divided by 10 to obtain the average value of the diameters at the inlet of the hole.
  • the average value (b) of the hole depth was measured from photographs obtained by photographing the cross sections of the substrates after the treatments of Examples 1 to 3 and Comparative Examples 1 to 3 with the electron microscope at a magnification of 30,000 times.
  • the top 10 were selected from those having the longest hole depth, the length of the deepest part was measured from the uppermost part, and the total was divided by 10 to obtain the average value of the hole depth.
  • a case where the aspect ratio (b / a) was 2 or more was evaluated as good (“A”), and a case where the aspect ratio (b / a) was less than 2 or not calculated was determined as bad (“B”).
  • the results are shown in Table 1.

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

Abstract

L'invention concerne un substrat ayant une surface entièrement ou au moins partiellement constituée d'un matériau métallique, la surface du matériau métallique ayant des trous, et les exigences (1) et (2) ci-dessous étant satisfaites. (1) Le rapport entre longueur et charge (Pmr) d'une courbe de section transversale est d'au moins 40 % à un niveau de coupe de 30 % et à une longueur d'évaluation de 10 µm. (2) Le rapport de forme (b/a) entre le diamètre d'entrée de trou moyen (a) et la profondeur de trou moyenne (b) est compris entre 2 et 50.
PCT/JP2019/014029 2018-03-30 2019-03-29 Substrat ayant une surface entièrement ou au moins partiellement constituée d'un matériau métallique, la surface dudit matériau métallique ayant des trous, et composite de substrat et de produit durci en résine contenant ledit substrat et ledit produit durci en résine WO2019189773A1 (fr)

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JP2018068521A JP7123605B2 (ja) 2018-03-30 2018-03-30 少なくとも表面の全部又は一部が金属材料からなる基材であって、該金属材料の表面が孔を有する基材及び該基材と樹脂硬化物を含む基材－樹脂硬化物の複合体

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CN112522706A (zh) * 2020-11-27 2021-03-19 山东泰宝包装制品有限公司 一种精密刻蚀隐藏式防伪工艺
WO2023243190A1 (fr) * 2022-06-13 2023-12-21 メック株式会社 Procédé de production de composite aluminium-résine, et agent de traitement de surface

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WO2007114261A1 (fr) * 2006-03-31 2007-10-11 Kabushiki Kaisha Kobe Seiko Sho Feuille d'acier haute resistance laminee a froid d'excellente compatibilite avec un traitement chimique
JP2008189914A (ja) * 2007-01-10 2008-08-21 Mitsubishi Rayon Co Ltd 成形体およびその製造方法
JP2010137475A (ja) * 2008-12-12 2010-06-24 Furukawa-Sky Aluminum Corp 樹脂密着性に優れた樹脂塗装アルミニウム板
JP2016142119A (ja) * 2015-02-05 2016-08-08 三井化学株式会社 ドアチェッカー用アームおよびドアチェッカー
JP2017019164A (ja) * 2015-07-09 2017-01-26 三井化学株式会社 金属／樹脂複合構造体および金属／樹脂複合構造体の製造方法

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Publication number Priority date Publication date Assignee Title
WO2007114261A1 (fr) * 2006-03-31 2007-10-11 Kabushiki Kaisha Kobe Seiko Sho Feuille d'acier haute resistance laminee a froid d'excellente compatibilite avec un traitement chimique
JP2008189914A (ja) * 2007-01-10 2008-08-21 Mitsubishi Rayon Co Ltd 成形体およびその製造方法
JP2010137475A (ja) * 2008-12-12 2010-06-24 Furukawa-Sky Aluminum Corp 樹脂密着性に優れた樹脂塗装アルミニウム板
JP2016142119A (ja) * 2015-02-05 2016-08-08 三井化学株式会社 ドアチェッカー用アームおよびドアチェッカー
JP2017019164A (ja) * 2015-07-09 2017-01-26 三井化学株式会社 金属／樹脂複合構造体および金属／樹脂複合構造体の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112522706A (zh) * 2020-11-27 2021-03-19 山东泰宝包装制品有限公司 一种精密刻蚀隐藏式防伪工艺
WO2023243190A1 (fr) * 2022-06-13 2023-12-21 メック株式会社 Procédé de production de composite aluminium-résine, et agent de traitement de surface

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