WO2022130833A1 - 金属部材－樹脂部材接合体の製造方法及びフィルム - Google Patents

金属部材－樹脂部材接合体の製造方法及びフィルム Download PDF

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Publication number
WO2022130833A1
WO2022130833A1 PCT/JP2021/041191 JP2021041191W WO2022130833A1 WO 2022130833 A1 WO2022130833 A1 WO 2022130833A1 JP 2021041191 W JP2021041191 W JP 2021041191W WO 2022130833 A1 WO2022130833 A1 WO 2022130833A1
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WIPO (PCT)
Prior art keywords
resin
layer
group
film
epoxy resin
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/JP2021/041191
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English (en)
French (fr)
Japanese (ja)
Inventor
信行 高橋
正広 佐藤
和男 大谷
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.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
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 Showa Denko KK filed Critical Showa Denko KK
Priority to EP21906197.5A priority Critical patent/EP4265398A1/en
Priority to KR1020237020334A priority patent/KR20230107859A/ko
Priority to CN202180084575.4A priority patent/CN116635219A/zh
Priority to JP2022569767A priority patent/JPWO2022130833A1/ja
Priority to US18/268,036 priority patent/US20240051237A1/en
Publication of WO2022130833A1 publication Critical patent/WO2022130833A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/022—Mechanical pre-treatments, e.g. reshaping
    • B29C66/0224—Mechanical pre-treatments, e.g. reshaping with removal of material
    • B29C66/02245—Abrading, e.g. grinding, sanding, sandblasting or scraping
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/024—Thermal pre-treatments
    • B29C66/0246—Cutting or perforating, e.g. burning away by using a laser or using hot air
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/026—Chemical pre-treatments
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/01—General aspects dealing with the joint area or with the area to be joined
    • B29C66/02—Preparation of the material, in the area to be joined, prior to joining or welding
    • B29C66/028—Non-mechanical surface pre-treatments, i.e. by flame treatment, electric discharge treatment, plasma treatment, wave energy or particle radiation
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the present disclosure relates to a method for manufacturing a metal member-resin member joint and a film that can be used for manufacturing the joint.
  • metal-resin joints in which metal materials such as aluminum and resin are joined and integrated.
  • metal materials such as aluminum and resin are joined and integrated.
  • the aluminum is surface-treated in order to sufficiently secure the joint strength between the metal and the resin.
  • surface treatments physical and chemical surface treatments such as blast treatment, chemical conversion treatment, and anodizing treatment are being studied.
  • polystyrene resin When a polyolefin such as polypropylene is used as a resin in a metal-resin bonded body, since the polyolefin is a low-polarity poorly adhesive material, an acid-modified polyolefin should be used in order to improve the bondability with the metal. Is being considered.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2016-16584
  • an adhesive layer containing a modified polypropylene resin having a polar group introduced is formed on a base treatment film provided on the surface of a base material made of an aluminum alloy.
  • Patent Document 1 also describes a method of providing a modified polypropylene layer having a polar group by using phosphoric acid chromate, chromic acid chromate, zirconium oxide, titanium zirconium or the like for the surface treatment of an aluminum alloy.
  • Patent Document 2 International Publication No. 2016/199339
  • a polypropylene resin layer is bonded to a metal substrate via a hydrophilic surface formed on the metal substrate, and the polypropylene resin layer is compatible with the polypropylene resin layer and has an anchor effect. It is described that the thermoplastic resin molded body is bonded to the polypropylene resin layer.
  • Patent Document 3 International Publication No. 2016/1521178 describes a method for forming an acid-modified polypropylene layer having a melt viscosity, melting point, crystallinity, etc. on an aluminum alloy.
  • Patent Document 4 Japanese Unexamined Patent Publication No. 2018-154034
  • a layer composed of an epoxy resin having a thickness of 15 to 40 ⁇ m and a blocked isocyanate is formed as a first layer on the surface of a metal chemical conversion treatment film, and 4 to 4 as a second layer.
  • a method for providing a 30 ⁇ m acid-modified polyolefin layer is described.
  • the bonding strength of the metal-polyolefin bonded body is not sufficient, and it is desirable to further improve the bonding strength and durability.
  • An object of the present disclosure is to provide a method for easily producing a metal-polyolefin bonded body having high bonding strength in view of the above-mentioned technical background.
  • a method for producing a metal member-resin member joint which comprises joining the resin member on the resin coating layer of the metal member.
  • the joining is performed simultaneously with the molding of the resin member on the resin coating layer of the metal member by an injection molding method, a transfer molding method, a press molding method, a filament winding molding method, or a hand lay-up molding method. 1] The method described in.
  • a method for producing a metal member-resin member bonded body which comprises joining the metal base material and the resin member via the film.
  • the reaction product 1 is formed by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in a solution containing maleic anhydride-modified polyolefin.
  • reaction product 2 is formed by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin.
  • the method described in. [8] The method according to any one of [1] to [5], wherein the mixture is a mixture of polypropylene and a thermoplastic epoxy resin.
  • the film is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer, and at least one layer of the layer other than the modified polyolefin layer is formed from a resin composition containing a thermoplastic epoxy resin.
  • the curable resin is at least one selected from the group consisting of urethane resin, epoxy resin, vinyl ester resin and unsaturated polyester resin.
  • the metal substrate has a functional group-containing layer laminated on the surface in contact with the film.
  • the functional group-containing layer contains at least one functional group selected from the group consisting of the following (1) to (7).
  • At least one functional group derived from the silane coupling agent and selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group (2) An amino group derived from the silane coupling agent.
  • a functional group generated by the reaction of at least one selected from a glycidyl compound and a thiol compound (3) A glycidyl compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and a glycidyl group are added to a mercapto group derived from a silane coupling agent.
  • a functional group produced by the reaction of at least one selected from the group consisting of a compound having a (meth) acryloyl group and a compound having an amino group (4) A thiol compound to a (meth) acryloyl group derived from a silane coupling agent. (5) A glycidyl group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound.
  • a metal-polyolefin joint having high bonding strength can be easily produced.
  • the films of the present disclosure can be advantageously used in the production of metal-polyolefin conjugates.
  • FIG. 1 is an explanatory diagram of a method for manufacturing a metal member-resin member joint according to the first embodiment.
  • FIG. 2 is an explanatory diagram of another manufacturing method of the metal member-resin member bonded body of the first embodiment.
  • FIG. 3 is an explanatory diagram of a method for manufacturing a metal member-resin member joint of the second embodiment.
  • FIG. 4 is a schematic cross-sectional view of a metal member-resin member joint of one embodiment.
  • FIG. 5 is a schematic cross-sectional view of a metal member-resin member joint having a functional group-containing layer.
  • FIG. 6 is a schematic cross-sectional view of a metal member-resin member joint having an adhesive layer.
  • FIG. 7 is an SEM photograph of the boehmite film.
  • metal is meant to include both pure metals consisting of a single metal element and alloys of pure metals mixed with one or more other elements. Used.
  • aluminum includes pure metals of aluminum and alloys thereof.
  • bonding means connecting objects to each other, and adhesion is a subordinate concept thereof, and through organic materials such as tapes and adhesives (curable resin, thermoplastic resin, etc.), It means that two adherends (those to be bonded) are put into a bonded state.
  • the method for producing the metal member-resin member bonded body of the first embodiment is a layer containing a reaction product 1 of a maleic anhydride-modified polyolefin, a bifunctional epoxy resin and a bifunctional phenol compound, a maleic anhydride-modified polyolefin and a thermoplastic epoxy.
  • a film containing at least one modified polyolefin layer selected from the group consisting of a layer containing a reactant 2 with a resin and a layer containing a mixture of a polyolefin and a thermoplastic epoxy resin the modified polyolefin layer is exposed.
  • the film is placed on the surface of at least a part of the metal substrate to form a metal member in which the resin coating layer is laminated on the metal substrate, on the resin coating layer of the metal member. Includes joining resin members.
  • the resin coating layer laminated on the metal base material contained in the metal member is formed by using the film containing the modified polyolefin layer.
  • the film may have one layer or may be composed of a plurality of layers.
  • the film is composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer, and the layer other than the modified polyolefin layer is at least one selected from a thermoplastic epoxy resin layer and a curable resin layer.
  • the modified polyolefin layer of the film is bonded to the resin member, and the layers other than the modified polyolefin layer of the film are bonded to the metal base material or the functional group-containing layer having or not having the surface treatment.
  • the thermoplastic epoxy resin layer, the curable resin layer, the surface treatment and the functional group-containing layer will be described later.
  • Modified polyolefin layer At least one layer of the film is a modified polyolefin layer formed from a resin composition containing a modified polyolefin.
  • the film containing the modified polyolefin layer can bond (bond) the metal base material and the resin member with high bonding strength.
  • the modified polyolefin layer was obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of maleic anhydride-modified polyolefin, and at the same time, reacting with maleic anhydride in the maleic anhydride-modified polyolefin skeleton.
  • Reaction product 2 obtained by reacting a layer containing reaction product 1 with a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with maleic anhydride in a maleic anhydride-modified polyolefin skeleton. It is at least one selected from the group consisting of a layer containing a layer containing maleic anhydride and a layer containing a mixture of a thermoplastic epoxy resin and a polyolefin.
  • reaction product 1 can be obtained by subjecting a bifunctional epoxy resin and a bifunctional phenol compound to a double addition reaction in the presence of a catalyst in a solution of maleic anhydride-modified polyolefin. At this time, the maleic anhydride-modified polyolefin also reacts with the bifunctional epoxy resin, the bifunctional phenol compound, and the thermoplastic epoxy resin produced from the bifunctional epoxy resin and the bifunctional phenol compound described later in the section of the reactant 2. it is conceivable that.
  • the maleic anhydride-modified polyolefin is obtained by grafting maleic anhydride on the polyolefin, and examples thereof include maleic anhydride-modified polyethylene and maleic anhydride-modified polypropylene.
  • Specific examples of the maleic anhydride-modified polyolefin include Kayaku Akzo Corporation's Kayabrid 002PP, 002PP-NW, 003PP, 003PP-NW, and Mitsubishi Chemical Corporation's Modic series.
  • SCONA TPPP2112GA, TPPP8112GA, or TPPP9212GA manufactured by BYK may be used in combination with maleic anhydride-modified polyolefin as a polypropylene additive functionalized with maleic anhydride.
  • bifunctional epoxy resin examples include a bisphenol type epoxy resin and a biphenyl type epoxy resin.
  • the bifunctional epoxy resin may be used alone or in combination of two or more.
  • Specific examples of the bifunctional epoxy resin include "jER (registered trademark) 828”, “jER (registered trademark) 834", “jER (registered trademark) 1001", and “jER (registered trademark)” manufactured by Mitsubishi Chemical Corporation. 1004 ”,“ jER® 1007 ”, and“ jER® YX-4000 ”.
  • bifunctional phenol compound examples include bisphenol and biphenol.
  • the bifunctional phenol compound may be used alone or in combination of two or more.
  • Examples of the combination of the bifunctional phenol compound include bisphenol A type epoxy resin and bisphenol A; bisphenol A type epoxy resin and bisphenol F; biphenyl type epoxy resin and 4,4'-biphenol; and "WPE190" manufactured by Nagase ChemteX Corporation. "And” EX-991L ".
  • a tertiary amine such as triethylamine, 2,4,6-tris (dimethylaminomethyl) phenol
  • a phosphorus-based compound such as triphenylphosphine are preferable.
  • the reaction product 2 can be obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with a maleic anhydride-modified polyolefin.
  • a maleic anhydride-modified polyolefin the bifunctional epoxy resin, and the bifunctional phenol compound used in this reaction, the same ones as those used for producing the reactant 1 can be used.
  • thermoplastic epoxy resin used for producing the reaction product 2 is a resin also called a field-polymerized phenoxy resin, a field-curable phenoxy resin, a field-curable epoxy resin, or the like, and a bifunctional epoxy resin and a bifunctional phenol compound are catalysts.
  • a thermoplastic structure that is, a linear polymer structure is formed.
  • the linear polymer means a polymer that does not contain a crosslinked structure in the polymer molecule and is one-dimensional linear.
  • the thermoplastic epoxy resin has thermoplasticity unlike the curable resin that constitutes a three-dimensional network with a crosslinked structure.
  • the total amount of the bifunctional epoxy resin and the bifunctional phenol compound used in producing the reactant 1 or the reactant 2 is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the maleic anhydride-modified polyolefin. It is more preferably 5 to 60 parts by mass, further preferably 10 to 30 parts by mass.
  • the reaction that occurs when the reactant 1 and the reactant 2 are obtained is the reaction between the maleic anhydride-modified polyolefin and the bifunctional epoxy resin, the reaction between the maleic anhydride-modified polyolefin and the bifunctional phenol compound, and the maleic anhydride.
  • Specifics based on a wide variety of reactions such as the reaction of connecting epoxies, the reaction of the epoxy group at the end of the thermoplastic epoxy resin with maleic anhydride, and the reaction of the secondary hydroxyl group in the skeleton of the thermoplastic epoxy resin with maleic anhydride. It is also not possible to comprehensively express the aspect. Therefore, it can be said that it is impossible or impractical to directly specify the modified polyolefin obtained as the reactant 1 or the reactant 2 by the structure or the property.
  • the mixture of the thermoplastic epoxy resin and the polyolefin can be obtained by mixing the same thermoplastic epoxy resin as that used for producing the above-mentioned reaction product 2 and the polyolefin by a conventional method.
  • the polyolefin used for forming the mixture can be used.
  • the polyolefin is not particularly limited and may be a general synthetic resin. Examples of the polyolefin include polyethylene and polypropylene, and polypropylene is preferable.
  • the film is composed of a plurality of layers including a modified polyolefin layer and a layer other than the modified polyolefin layer, and at least one layer other than the modified polyolefin layer is a thermoplastic formed from a resin composition containing a thermoplastic epoxy resin. It can be composed of an epoxy resin layer.
  • the resin composition containing the thermoplastic epoxy resin preferably contains 40% by mass or more of the thermoplastic epoxy resin, and more preferably 70% by mass or more.
  • thermoplastic epoxy resin Similar to the thermoplastic epoxy resin used for producing the reactant 2, the thermoplastic epoxy resin has a thermoplastic structure, that is, a thermoplastic structure, that is, a double-addition reaction between the bifunctional epoxy resin and the bifunctional phenol compound in the presence of a catalyst. It is a resin that forms a linear polymer structure, and has thermoplasticity unlike curable resins that form a three-dimensional network with a crosslinked structure. Since the thermoplastic epoxy resin has such characteristics, it is possible to form a thermoplastic epoxy resin layer having excellent bondability with the modified polyolefin layer.
  • the composition containing the monomer of the thermoplastic epoxy resin may contain a solvent and, if necessary, an additive such as a colorant in order to sufficiently proceed the double addition reaction of the thermoplastic epoxy resin. ..
  • the monomer of the thermoplastic epoxy resin is the main component among the components other than the solvent of the composition.
  • the main component means that the content of the monomer of the thermoplastic epoxy resin is 50 to 100% by mass.
  • the content of the monomer of the thermoplastic epoxy resin is preferably 60% by mass or more, more preferably 80% by mass or more.
  • the monomer for obtaining the thermoplastic epoxy resin is preferably a combination of a bifunctional epoxy resin and a bifunctional phenolic compound.
  • the double addition reaction is preferably carried out by heating at a temperature of 120 to 200 ° C. for 5 to 90 minutes, although it depends on the type of the reaction compound and the like.
  • the thermoplastic epoxy resin layer can be formed by coating the composition, volatilizing the solvent as appropriate, and then heating to carry out the double addition reaction.
  • the film is composed of a plurality of layers including a modified polyolefin layer and a layer other than the modified polyolefin layer, and the layer other than the modified polyolefin layer is composed of a curable resin layer formed from a resin composition containing a curable resin. You can also do it.
  • the resin composition containing the curable resin may contain a solvent and, if necessary, an additive such as a colorant in order to sufficiently promote the curing reaction of the curable resin.
  • the curable resin is the main component among the components other than the solvent of the resin composition.
  • the main component means that the content of the curable resin is 40 to 100% by mass.
  • the content of the curable resin is preferably 60% by mass or more, more preferably 70% by mass or more, and most preferably 80% by mass or more.
  • curable resin examples include urethane resin, epoxy resin, vinyl ester resin, and unsaturated polyester resin.
  • the curable resin layer may be formed of one of these resins, or may be formed by mixing two or more of them.
  • the curable resin layer may be composed of a plurality of layers, and each layer may be formed of a resin composition containing different types of curable resin.
  • the method for forming the curable resin layer using the resin composition containing the curable resin is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • the curable resin means a resin that is cross-linked and cured, and is not limited to the thermosetting type, but also includes a room temperature curing type and a photocuring type.
  • the photo-curing type can be cured in a short time by irradiation with visible light or ultraviolet rays.
  • the photo-curing type may be used in combination with the heat-curing type and / or the room temperature curing type.
  • Examples of the photocurable type include vinyl ester resins such as "Lipoxy (registered trademark) LC-760" and “Lipoxy (registered trademark) LC-720" manufactured by Showa Denko KK.
  • Urethane resin is a resin usually obtained by the reaction of the isocyanato group of an isocyanate compound with the hydroxyl group of a polyol compound, and is defined in ASTM D16 as "a paint containing 10% by weight or more of a vehicle non-volatile component polyisocyanate".
  • the urethane resin corresponding to the above is preferable.
  • the urethane resin may be a one-component type or a two-component type.
  • Examples of the one-component urethane resin include oil-modified type (cured by oxidative polymerization of unsaturated fatty acid group), moisture-curable type (cured by reaction between isocyanato group and water in air), and block type (cured by reaction between isocyanato group and water in air).
  • Examples thereof include a lacquer type (a type in which a solvent is volatilized and cured by drying) and a lacquer type (a type in which a blocking agent is dissociated by heating and regenerated by reacting with an isocyanato group and a hydroxyl group to be cured).
  • a moisture-curable one-component urethane resin is preferably used from the viewpoint of ease of handling.
  • Specific examples of the moisture-curable one-component urethane resin include "UM-50P" manufactured by Showa Denko KK.
  • Examples of the two-component urethane resin include a catalyst-curable type (a catalyst-curable group in which an isocyanato group reacts with water in the air to cure in the presence of a catalyst) and a polyol-curable type (isocyanato group and a hydroxyl group of a polyol compound). Those that cure by reaction) can be mentioned.
  • a catalyst-curable type a catalyst-curable group in which an isocyanato group reacts with water in the air to cure in the presence of a catalyst
  • a polyol-curable type isocyanato group and a hydroxyl group of a polyol compound
  • polyol compound in the polyol curing type examples include polyester polyols and polyether polyol-phenol resins.
  • Examples of the isocyanate compound having an isocyanato group in the polyol-cured type include aliphatic isocyanates such as hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, and dimerate diisocyanate; 2,4- or 2,6-tolylene diisocyanate (TDI). Or a mixture thereof, aromatic isocyanates such as p-phenylenediisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate (MDI) or a polynuclear mixture thereof, Polymeric MDI; and alicyclic isocyanates such as isophorone diisocyanate (IPDI).
  • HDI hexamethylene diisocyanate
  • TDI dimerate diisocyanate
  • TDI 2,4- or 2,6-tolylene diisocyanate
  • aromatic isocyanates such as p-phenylenediisocyanate,
  • the compounding ratio of the polyol compound and the isocyanate compound in the polyol-curable two-component urethane resin is preferably in the range of 0.7 to 1.5 in the molar equivalent ratio of the hydroxyl group / isocyanato group.
  • Examples of the urethanization catalyst used in the two-component urethane resin include triethylenediamine, tetramethylguanidine, N, N, N', N'-tetramethylhexane-1,6-diamine, dimethyletheramine, N, N.
  • the epoxy resin is a resin having at least two epoxy groups in one molecule.
  • the prepolymer before curing of the epoxy resin include ether-based bisphenol-type epoxy resin, novolak-type epoxy resin, polyphenol-type epoxy resin, aliphatic-type epoxy resin, ester-based aromatic epoxy resin, and cyclic aliphatic epoxy resin. And ether ester type epoxy resin.
  • bisphenol A type epoxy resin is preferably used.
  • the epoxy resin may be used alone or in combination of two or more.
  • bisphenol A type epoxy resin examples include “jER (registered trademark) 828” and “jER (registered trademark) 1001" manufactured by Mitsubishi Chemical Corporation.
  • novolak type epoxy resin examples include "DEN (registered trademark) 438” manufactured by The Dow Chemical Company.
  • Examples of the curing agent used for the epoxy resin include aliphatic amines, aromatic amines, acid anhydrides, phenol resins, thiols, imidazoles, and cationic catalysts.
  • the curing agent in combination with long-chain aliphatic amines and / and thiols, a film having a large elongation rate and excellent impact resistance can be formed.
  • thiols are not particularly limited, and for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40” manufactured by Mitsubishi Chemical Co., Ltd. and “QE-” manufactured by Toray Fine Chemical Co., Ltd. 340M "), ether-based first-class thiol (for example,” Cup Cure 3-800 “manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (for example,” Karenz “manufactured by Showa Denko KK.
  • pentaerythritol tetrakis (3-mercaptopropionate) for example, "QX40" manufactured by Mitsubishi Chemical Co., Ltd. and “QE-” manufactured by Toray Fine Chemical Co., Ltd. 340M "
  • ether-based first-class thiol for example," Cup Cure 3-800 “manufactured by Cognis
  • pentaerythritol tetrakis (3-mercaptobutyrate) for example, "Karensu MT (registered trademark) PE1" manufactured by Showa Denko KK
  • Karensu MT registered trademark
  • PE1 registered trademark
  • the vinyl ester resin is obtained by dissolving a vinyl ester compound in a polymerizable monomer (for example, styrene).
  • the vinyl ester resin is also generally referred to as an epoxy (meth) acrylate resin, but in the present disclosure, the vinyl ester resin also includes a urethane (meth) acrylate resin.
  • vinyl ester resin for example, those described in "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, published in 1988), “Paint Glossary” (Japan Society of Color Material, published in 1993), etc. can be used. can.
  • Specific examples of the vinyl ester resin include “Lipoxy (registered trademark) R-802", “Lipoxy (registered trademark) R-804", and “Lipoxy (registered trademark) R-806" manufactured by Showa Denko KK. Can be mentioned.
  • the urethane (meth) acrylate resin is, for example, radical polymerization obtained by reacting an isocyanate compound with a polyol compound and then reacting with a hydroxyl group-containing (meth) acrylic monomer (and, if necessary, a hydroxyl group-containing allyl ether monomer).
  • examples include sex-unsaturated radical-containing oligomers.
  • Specific examples of the urethane (meth) acrylate resin include "Ripoxy (registered trademark) R-6545" manufactured by Showa Denko KK.
  • Vinyl ester resin can be cured by radical polymerization by heating in the presence of a catalyst such as an organic peroxide.
  • organic peroxides examples include ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. By combining these organic peroxides with a cobalt metal salt or the like, curing at room temperature is also possible.
  • cobalt metal salt examples include cobalt naphthenate, cobalt octylate, and cobalt hydroxide. Among these, cobalt naphthenate and cobalt octylate are preferable.
  • the unsaturated polyester resin dissolves a condensation product (unsaturated polyester) of an esterification reaction between a polyol compound and an unsaturated polybasic acid (and, if necessary, a saturated polybasic acid) in a polymerizable monomer (for example, styrene). It was done.
  • unsaturated polyester resin for example, those described in "Polyester Resin Handbook” (Nikkan Kogyo Shimbun, published in 1988), “Paint Glossary” (Japan Society of Color Material, published in 1993), etc. shall be used. Can be done. Specific examples of the unsaturated polyester resin include “Rigolac (registered trademark)” manufactured by Showa Denko KK.
  • the unsaturated polyester resin can be cured by radical polymerization by heating in the presence of a catalyst similar to the vinyl ester resin.
  • the one or more layers constituting the film may contain, as an optional component, a film forming agent, a tackifier, or both.
  • Other optional components that can be used in the film include, for example, colorants such as fillers, pigments and dyes, heat stabilizers, UV absorbers, and antioxidants.
  • the film forming agent By using the film forming agent, it is possible to improve the film forming property at the time of manufacturing the film and the shape retention after manufacturing.
  • the film forming agent include chlorinated polyolefins such as polyethylene, polypropylene, polyvinyl chloride, chlorinated polyethylene and chlorinated polypropylene, polystyrene copolymers such as thermoplastic polyurethane, polystyrene, polystyrene-maleic anhydride copolymer, and thermoplastic polyesters. Examples thereof include polyethylene polymers such as polyethylene, thermoplastic polyamides and hydroxyethyl cellulose, polyvinyl acetal, and polyvinyl butyral.
  • the film can be reliably fixed to the metal substrate, whereby the resin coating layer can be formed at a desired position with high accuracy.
  • the tackifier include rosin-based resins such as disproportionate rosin ester, polymerized rosin ester, and hydrogenated rosin ester, terpene-based resin, terpene phenol resin, aromatic-modified terpene resin, hydrogenated terpene resin, and aliphatic-based resin.
  • C5 series petroleum resin
  • aromatic (C9) petroleum resin aromatic (C9) petroleum resin
  • aliphatic-arosin (C5-C9 series) petroleum resin hydrogenated petroleum resin
  • kumaron inden resin phenolic resin
  • styrene resin examples include xylene-based resins.
  • the film can be produced, for example, by the following procedure.
  • Reactant 2 obtained by reacting a thermoplastic epoxy resin produced by a double addition reaction of a bifunctional epoxy resin and a bifunctional phenol compound with maleic anhydride in a maleic anhydride-modified polyolefin skeleton, or (3) A film precursor composition 1 containing a mixture of a thermoplastic epoxy resin and a polyolefin, and if necessary, a solvent and an optional component is prepared.
  • the reactants 1, the reactants 2, and the mixture of the thermoplastic epoxy resin and the polyolefin are the same as described for the modified polyolefin layer.
  • the film precursor composition 1 is applied, sprayed, or extruded and laminated on a release film or release paper having a release coating such as a silicone type so as to form a film having a thickness of 1 ⁇ m to 10 mm after drying. ..
  • the coating can be performed using a bar coater, a roll coater, or the like.
  • the spraying can be performed using a spray coater or the like.
  • Extrusion stacking can be performed using a single-screw or twin-screw extruder.
  • the film can be formed on the release film or the release paper by leaving it in an environment of room temperature to 40 ° C. to volatilize the solvent.
  • the release film or the release paper may be used for handling the film as a carrier (support) of the film, or the film may be peeled off from the release film or the release paper to obtain a self-standing film.
  • the modified polyolefin layer of the film is completely filled with a component (for example, a bifunctional epoxy resin, a bifunctional phenol compound, a maleic anhydride-modified polyolefin, etc.) which is a constituent unit of the reactant 1, the reactant 2, or the thermoplastic epoxy resin. It may be contained in a state of reacting to, or a part of them may be contained in an unreacted state. In the latter case, when the metal base material or the resin member and the film (resin coating layer) are bonded, the unreacted component may be further reacted. With the reaction of the unreacted components, the bonding strength between the film (resin coating layer) and the metal base material or the resin member may be increased.
  • a component for example, a bifunctional epoxy resin, a bifunctional phenol compound, a maleic anhydride-modified polyolefin, etc.
  • a film composed of a plurality of layers including a modified polyolefin layer and a layer other than the modified polyolefin layer can be produced, for example, by the following procedure.
  • a film precursor composition 2 containing the components is prepared.
  • the resin composition containing the thermoplastic epoxy resin and the composition containing the monomer of the thermoplastic epoxy resin are the same as those described for the thermoplastic epoxy resin layer.
  • the resin composition containing the curable resin is the same as that described for the curable resin layer.
  • the film precursor composition 2 is applied, sprayed, or extruded and laminated on a release film or release paper having a release coating such as a silicone type so as to form a film having a thickness of 1 ⁇ m to 10 mm after drying. ..
  • the thermoplastic epoxy is left to stand in an environment of room temperature to 40 ° C. to volatilize the solvent, heat it to proceed with the double addition reaction or the curing reaction, or irradiate it with visible light or ultraviolet rays to proceed with the curing reaction.
  • a resin layer or a curable resin layer is formed on a release film or a release paper.
  • the modified polyolefin layer By forming the modified polyolefin layer on these layers by the above procedure, a film composed of a plurality of layers including the modified polyolefin layer and a layer other than the modified polyolefin layer can be obtained.
  • the order of forming the modified polyolefin layer and the layer other than the modified polyolefin layer may be changed. That is, the thermoplastic epoxy resin layer or the curable resin layer may be formed on the modified polyolefin layer formed in advance by the above-mentioned procedure.
  • thermoplastic epoxy resin layer or the curable resin layer of the film is in a state in which the constituent units of these resins (for example, a bifunctional epoxy resin, a bifunctional phenol compound, a polyol, an isocyanate compound, etc.) are completely reacted. It may be contained in, and a part thereof may be contained in an unreacted state. In the latter case, the unreacted components may be further reacted when the metal substrate and the film are bonded. With the reaction of this unreacted component, it may be possible to increase the bonding strength between the film and the metal substrate.
  • a bifunctional epoxy resin, a bifunctional phenol compound, a polyol, an isocyanate compound, etc. may be contained in, and a part thereof may be contained in an unreacted state. In the latter case, the unreacted components may be further reacted when the metal substrate and the film are bonded. With the reaction of this unreacted component, it may be possible to increase the bonding strength between the film and the metal substrate.
  • the thickness of the film depends on the type of resin of the resin member and the bonding area, but is preferably 1 ⁇ m to 10 mm, more preferably 2 ⁇ m or more, from the viewpoint of obtaining excellent bonding properties with the metal substrate and the resin member. It is 8 mm, more preferably 3 ⁇ m to 5 mm. Specifically, when the carbon fiber reinforced resin member (CFRP member) or the glass fiber reinforced resin member (GFRP member) is bonded to the metal base material, the thickness of the film is preferably 0.1 to 10 mm, which is more preferable. Is 0.2 to 8 mm, more preferably 0.5 to 5 mm. When the film has multiple layers, the thickness of the film is the total thickness of each layer.
  • the planar shape of the film can be appropriately set according to the bonding location between the metal base material and the resin member and the desired bonding strength.
  • the planar shape of the film can be, for example, a geometric shape such as a square, a rectangle, a triangle, a circle, or an ellipse.
  • the planar shape of the film can also be grid-like, comb-like, or the like so that a single continuous film provides multiple joints.
  • the resin coating layer of the present disclosure is derived from a film.
  • the film When arranging the film on the surface of the metal substrate, it is preferable to heat the film, and it is more preferable to heat and pressurize the film.
  • the heating can be 50 ° C to 180 ° C.
  • the pressurization can be 0.01 MPa to 50 MPa.
  • the modified polyolefin layer is exposed, in other words, the layer other than the modified polyolefin layer has or has a surface treatment. It is laminated so as to be in contact with a non-metal substrate or a functional group-containing layer.
  • the resin coating layer is formed on the surface of the metal base material with excellent bondability, and exhibits excellent bondability with the resin member.
  • the metal base material is provided with excellent adhesiveness (bondability via the resin coating layer) to the resin member containing polyolefin. Therefore, it can be said that the resin coating layer is a primer layer arranged on the joint surface of the metal base material.
  • the primer layer is interposed between the metal base material and the resin member when the metal member and the resin member are joined, and the adhesiveness of the metal base material to the resin member (via the resin coating layer). It means that it is a layer that improves bondability).
  • the surface of the metal base material is protected by the resin coating layer, it is possible to suppress deterioration such as adhesion of dirt to the surface of the metal base material and oxidation. Therefore, it is possible to obtain a metal member capable of maintaining excellent adhesiveness to the resin member even when stored for a long period of several months.
  • the metal type of the metal base material is not particularly limited, and examples thereof include aluminum, iron, titanium, magnesium, stainless steel, and copper. Of these, aluminum is particularly preferably used from the viewpoint of light weight and ease of processing.
  • the metal base material may be an extruded material, a die-cast material, a forged material, a cast material, or the like.
  • the metal base material has at least a surface treatment on the surface to be joined with the resin member.
  • the surface-treated portion (surface-treated portion) of the metal substrate is regarded as a part of the metal substrate.
  • Examples of the surface treatment include cleaning / degreasing treatment with a solvent, blast treatment, polishing treatment, plasma treatment, laser treatment, etching treatment, and chemical conversion treatment, which are surface treatments that generate hydroxyl groups on the surface of a metal substrate. It is preferable to have. These surface treatments may be performed with only one type or two or more types. As a specific method for these surface treatments, known methods can be used.
  • the surface treatment is to remove contaminants on the surface of the metal base material and / or to form fine irregularities on the surface of the metal base material to roughen the surface for the purpose of anchoring effect.
  • the bondability between the surface of the metal substrate and the film can be improved, and as a result, the adhesiveness between the metal substrate and the resin member to be bonded (bondability via the film) is improved. You can also do it.
  • the surface treatment at least one selected from the group consisting of blast treatment, polishing treatment, etching treatment and chemical conversion treatment is preferable.
  • cleaning / degreasing treatment examples include degreasing the surface of a metal substrate with an organic solvent such as acetone or toluene.
  • the cleaning / degreasing treatment is preferably performed before other surface treatments.
  • blast processing examples include shot blasting and sand blasting.
  • polishing treatment examples include buffing using a polishing cloth, roll polishing using polishing paper (sandpaper), and electrolytic polishing.
  • Plasma treatment uses a high-voltage power supply to inject a plasma beam emitted from a rod called an electrode onto the surface of a material to first clean the foreign matter or oil film on the surface and then put energy into the gas according to the material. This is a method of exciting surface molecules.
  • the plasma treatment include atmospheric pressure plasma treatment capable of imparting a hydroxyl group or other polar groups to the surface.
  • Laser treatment is a technique for rapidly heating and cooling only the surface layer by laser irradiation to improve the surface properties of a material, and is an effective method for roughening the surface.
  • a known laser treatment technique can be used as the laser treatment.
  • etching treatment examples include a chemical etching treatment such as an alkali method, a phosphoric acid-sulfuric acid method, a fluoride method, a chromic acid-sulfuric acid method, and a salt iron method, and an electrochemical etching treatment such as an electrolytic etching method. ..
  • the etching treatment is preferably an alkaline method using a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution as an etching solution, and a caustic soda method using a sodium hydroxide aqueous solution is more preferable.
  • the alkaline method can be carried out, for example, by immersing the metal substrate in an aqueous solution of sodium hydroxide or potassium hydroxide having a concentration of 3 to 20% by mass at 20 to 70 ° C. for 1 to 15 minutes.
  • a chelating agent, an oxidizing agent, a phosphate or the like may be added to the etching solution. After soaking, it is preferable to neutralize (de-smut) with a 5 to 20% by mass nitric acid aqueous solution, wash with water, and dry.
  • the chemical conversion treatment mainly forms a chemical conversion film as a surface treatment portion on the surface of a metal base material.
  • Examples of the chemical conversion treatment include boehmite treatment and zirconium treatment.
  • the chemical conversion treatment is preferably boehmite treatment.
  • a boehmite film is formed on the surface of the metal base material by treating the metal base material with hot water.
  • Ammonia, triethanolamine or the like may be added to water as a reaction accelerator.
  • a zirconium compound film is formed on the surface of the metal base material by immersing the metal base material in a zirconium salt-containing liquid such as zirconium phosphate.
  • the metal substrate is immersed in a chemical agent for zirconium treatment (for example, "Pearl Coat 3762” manufactured by Nihon Parkerizing Co., Ltd., "Pearl Coat 3796", etc.) at 45 to 70 ° C. for 0.5 to 3 minutes. It is preferable to do this.
  • the zirconium treatment is preferably performed after the etching treatment by the caustic soda method.
  • the metal base material is aluminum, it is preferable that the metal base material is subjected to at least one surface treatment selected from etching treatment and boehmite treatment.
  • One or more functional group-containing layers may be provided on the surface of the metal substrate in contact with the film.
  • the functional group of the functional group-containing layer reacts with the hydroxyl group on the surface of the metal substrate and the functional group of the resin constituting the film to form a chemical bond, thereby adhering the surface of the metal substrate to the film.
  • the property can be improved, and as a result, the adhesiveness (bonding property via a film) between the metal base material and the resin member to be bonded can also be improved.
  • the functional group-containing layer is preferably formed by treating the surface of the metal base material with at least one selected from the group consisting of the following (1') to (7').
  • seed and silane coupling agent having an amino group (3') Glycidyl compound, amino compound, isocyanate compound, compound having (meth) acryloyl group and glycidyl group, and compound having (meth) acryloyl group and amino group.
  • a combination of at least one selected from the group consisting of a compound having an acryloyl group, an amino compound and a thiol compound and a silane coupling agent having a glycidyl group (6') isocyanate compound (7') thiol compound isocyanate compound.
  • the functional group-containing layer preferably contains the functional group introduced by the above treatment, and specifically, preferably contains at least one functional group selected from the group consisting of the following (1) to (7).
  • At least one functional group derived from the silane coupling agent and selected from the group consisting of a glycidyl group, an amino group, a (meth) acryloyl group and a mercapto group (2) An amino group derived from the silane coupling agent.
  • a glycidyl compound, an amino compound, an isocyanate compound, a (meth) acryloyl group and a glycidyl group are added to a mercapto group derived from a silane coupling agent.
  • a glycidyl group derived from a silane coupling agent is reacted with at least one selected from the group consisting of a compound having an amino group and a (meth) acryloyl group, an amino compound, and a thiol compound.
  • the above-mentioned surface treatment portion can be provided on the surface of the metal base material.
  • Anchor effect due to fine irregularities on the surface treatment part and chemical bonds formed by the functional groups of the functional group-containing layer reacting with the hydroxyl groups on the surface of the metal substrate and the functional groups of the resin constituting the film. Due to the synergistic effect, the adhesiveness between the surface of the metal base material and the film and the adhesiveness between the metal base material and the resin member to be bonded (bondability via the film) can be further improved.
  • the method for forming the functional group-containing layer using a silane coupling agent, an isocyanate compound, a thiol compound, or the like is not particularly limited, and examples thereof include a spray coating method and a dipping method.
  • the metal substrate is immersed in a solution of a silane coupling agent having a concentration of 5 to 50% by mass at room temperature to 100 ° C. for 1 minute to 5 days, and then immersed at room temperature to 100 ° C. for 1 minute to 5 hours.
  • a functional group-containing layer can be formed by drying.
  • silane coupling agent for example, a known one used for surface treatment of glass fiber or the like can be used.
  • a silanol group produced by hydrolyzing a silane coupling agent or a silanol group of an oligomer product formed by condensing a silanol group reacts with a hydroxyl group existing on the surface of a metal substrate to bond to form a film.
  • a functional group based on the structure of the silane coupling agent that can be chemically bonded to the functional group of the constituent resin can be imparted (introduced) to the metal substrate.
  • the silane coupling agent is not particularly limited, and for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane.
  • the isocyanate compound is based on the structure of the isocyanate compound which can be chemically bonded to the functional group of the resin constituting the film by reacting and bonding the isocyanato group in the isocyanate compound with the hydroxyl group existing on the surface of the metal substrate.
  • a functional group can be imparted (introduced) to a metal substrate.
  • the isocyanate compound is not particularly limited, and is, for example, a polyfunctional isocyanate such as diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI); and 2-isosia.
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • TDI tolylene diisocyanate
  • IPDI isophorone diisocyanate
  • 2-isosia for example, “Karenzu MOI (registered trademark)” manufactured by Showa Denko Co., Ltd.
  • 2-isocyanatoethyl acrylate for example, "Karenzu AOI (registered trademark)” manufactured by Showa Denko Co., Ltd. "," AOI-VM (registered).
  • Examples thereof include isocyanate compounds having a radically reactive group such as ”)”) and 1,1- (bisacryloyloxyethyl) ethyl isocyanate (for example, "Karenzu BEI (registered trademark)” manufactured by Showa Denko Co., Ltd.).
  • the thiol compound is based on the structure of the thiol compound which can be chemically bonded to the functional group of the resin constituting the film by reacting and bonding the mercapto group in the thiol compound with the hydroxyl group existing on the surface of the metal substrate.
  • a functional group can be imparted (introduced) to a metal substrate.
  • the thiol compound is not particularly limited, and is, for example, pentaerythritol tetrakis (3-mercaptopropionate) (for example, "QX40” manufactured by Mitsubishi Chemical Co., Ltd., “QE-340M” manufactured by Toray Fine Chemical Co., Ltd.). , Ether-based first-class thiol (for example, “Cup Cure 3-800” manufactured by Cognis), 1,4-bis (3-mercaptobutyryloxy) butane (for example, "Karensu MT (registered) manufactured by Showa Denko KK).
  • pentaerythritol tetrakis (3-mercaptopropionate) for example, "QX40” manufactured by Mitsubishi Chemical Co., Ltd., "QE-340M” manufactured by Toray Fine Chemical Co., Ltd.
  • Ether-based first-class thiol for example, "Cup Cure 3-800” manufactured by Cognis
  • Metal member-resin member joint By joining the resin member on the resin coating layer of the metal member, it is possible to manufacture a metal member-resin member joint body in which the metal member and the resin member are joined with high bonding strength.
  • the resin member contains polyolefin.
  • the polyolefin is not particularly limited, and examples thereof include polyethylene and polypropylene.
  • Polypropylene is generally a highly rigid homopolymer obtained by polymerizing only propylene, a highly transparent and flexible random polymer copolymerized with a small amount of ethylene, and a rubber component (EPR) uniformly and finely dispersed in the homopolymer or random polymer. It is classified as a block copolymer with high impact resistance.
  • Polypropylene may contain homopolymers, random polymers, or block copolymers, or mixtures thereof.
  • Polypropylene may be a high-strength type containing talc, glass fiber, or carbon fiber. Examples of the talc-containing polypropylene include TRC104N, which is a trade name manufactured by SunAllomer Ltd.
  • glass fiber-containing polypropylene examples include product name PP-GF40-01 F02 manufactured by Daicel FineChem Co., Ltd.
  • carbon fiber-containing polypropylene examples include product name PP-CF40-01 F008 manufactured by Daicel FineChem Co., Ltd.
  • Glass fiber-containing polypropylene is a type of glass fiber reinforced resin (GFRP), and carbon fiber-containing polypropylene is a type of carbon fiber reinforced resin (CFRP).
  • the resin containing reinforcing fibers such as glass fiber and carbon fiber may be in the form of a molded body such as a sheet molding compound (SMC) or a bulk molding compound (BMC).
  • SMC is a sheet-shaped molded body obtained by impregnating reinforcing fibers such as glass fiber and carbon fiber with a resin composition in which polypropylene, a low shrinkage agent, a filler and the like are mixed.
  • a metal member-resin member joint is manufactured by separately manufacturing a metal member and a resin member and joining (adhering) them.
  • the joining can be performed by at least one method selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a heat pressing method.
  • FIG. 1 which is an explanatory view of this embodiment, the film 4 and the metal base material 2 are prepared (upper stage), and the film 4 is placed on the surface of at least a part of the metal base material 2 so that the modified polyolefin layer is exposed.
  • a metal member 1 in which a resin coating layer (derived from film 4) is laminated is formed on the metal base material 2 (middle stage), and is placed on the resin coating layer (derived from film 4) of the metal member 1.
  • the metal member-resin member joint 10 is manufactured (lower stage). According to this embodiment, since a device such as an injection molding machine is not required for manufacturing the metal member-resin member joint, the degree of freedom in the dimensions and shape of the metal member or the resin member is high, and the shape is large or complicated. A metal member-resin member joint can be easily manufactured.
  • a metal member-resin member joint is manufactured by joining (adhering) the metal member and the resin member at the same time as molding the resin member. Specifically, the joining is performed simultaneously with the molding of the resin member on the resin coating layer of the metal member by an injection molding method, a transfer molding method, a press molding method, a filament winding molding method, or a hand lay-up molding method. ..
  • FIG. 2 which is an explanatory view of this embodiment, the film 4 and the metal base material 2 are prepared (upper stage), and the film 4 is placed on the surface of at least a part of the metal base material 2 so that the modified polyolefin layer is exposed.
  • a metal member 1 in which a resin coating layer (derived from film 4) is laminated is formed on the metal base material 2 (middle stage), and is placed on the resin coating layer (derived from film 4) of the metal member 1.
  • the metal member-resin member joint 10 is manufactured (lower stage). According to this embodiment, since it is not necessary to separately mold the resin member, it is possible to reduce the manufacturing process of the metal member-resin member joint.
  • the method for manufacturing the metal member-resin member joint of the second embodiment is to prepare the above film, to sandwich the film between the metal base material and the resin member so that the modified polyolefin layer comes into contact with the resin member. It includes joining a metal base material and a resin member via a film. The joining can be performed by at least one method selected from the group consisting of an ultrasonic welding method, a vibration welding method, an electromagnetic induction method, a high frequency method, a laser method, and a heat pressing method.
  • an ultrasonic welding method a vibration welding method
  • an electromagnetic induction method a high frequency method
  • a laser method and a heat pressing method.
  • the film 4 is arranged between the metal base material 2 and the resin member 6 (upper stage), and the film 4 is made of a metal base so that the modified polyolefin layer comes into contact with the resin member 6.
  • the metal member-resin member joint 10 is manufactured by sandwiching the material 2 and the resin member 6 and joining the metal base material 2 and the resin member 6 via the film 4 (lower stage). In the second embodiment, it can be considered that the production of the metal member and the production of the metal member-resin member joint are performed at the same time.
  • the film is arranged so as to be in contact with the surface-treated portion or the functional group-containing layer of the metal substrate. According to the second embodiment, the number of manufacturing steps of the metal member-resin member joint can be further reduced.
  • FIG. 4 shows a schematic cross-sectional view of the metal member-resin member joint of one embodiment.
  • the metal base material 2 having the surface treatment portion 2a and the resin member 6 are joined via the film 4 (resin coating layer).
  • the film 4 has a multilayer structure having a modified polyolefin layer 4a, a thermoplastic epoxy resin layer 4b and / or a curable resin layer 4c, so that the modified polyolefin layer 4a is in contact with the resin member 6. Is located in.
  • FIG. 5 shows a schematic cross-sectional view of a metal member-resin member joint of another embodiment.
  • the functional group-containing layer 3 is arranged between the film 4 and the metal base material 2, and the film 4 is laminated on the functional group-containing layer 3.
  • the metal member-resin member joint may have an adhesive layer arranged between the film (resin coating layer) and the resin member.
  • FIG. 6 shows a schematic cross-sectional view of the metal member-resin member joint of this embodiment.
  • the metal member-resin member joint 10 has an adhesive layer 5 arranged between the film 4 (resin coating layer) and the resin member 6.
  • the metal base material and the resin member can be bonded with higher bonding strength by using the adhesive layer.
  • the adhesive for the adhesive layer is appropriately selected depending on the type of resin of the resin member, and for example, known adhesives such as epoxy resin-based, urethane resin-based, and vinyl ester resin-based adhesives can be used.
  • the metal member-resin member bonded body is thermally deformed due to the difference in the coefficient of thermal expansion between the metal base material and the resin member in the process of cooling to room temperature after joining (bonding). May be done. From the viewpoint of suppressing and alleviating such thermal deformation, it is desirable that the total thickness of the film (resin coating layer) and the adhesive layer be 4 ⁇ m or more.
  • the above-mentioned total thickness should be determined in consideration of physical properties such as the elongation rate of the film (resin coating layer) and the adhesive layer in the temperature change at the time of joining (the temperature change from the heating temperature at the time of joining to room temperature cooling). Is preferable.
  • the preferable upper limit of the total thickness of the film (resin coating layer) and the adhesive layer is 10 mm.
  • the layer involved in the joining between the metal member and the resin member is referred to as a joining layer, and the thickness thereof is referred to as the thickness of the joining layer.
  • the metal member-resin member joint has an adhesive layer
  • both the film (resin coating layer) and the adhesive layer are the bonding layers
  • the total thickness of the film (resin coating layer) and the adhesive layer is the bonding layer. Is the thickness of.
  • the film (resin coating layer) is the joint layer, and the thickness thereof is the thickness of the joint layer.
  • the method and film for manufacturing a metal member-resin member joint of the present disclosure include, for example, a door side panel, a bonnet roof, a tailgate, a steering hanger, an A pillar, a B pillar, a C pillar, a D pillar, a crash box, and a power control unit.
  • Automotive parts such as housings, electric compressor members (inner wall, suction port, exhaust control valve (ECV) insertion, mount boss, etc.), lithium-ion battery (LIB) spacers, battery cases, LED headlamps, etc. , And can be used in the manufacture of electrical and electronic products such as smartphones, laptops, tablet computers, smart watches, large LCD TVs (LCD-TVs), and outdoor LED lighting.
  • the composition of the aluminum alloy is Si: 0.45% by mass, Fe: 0.21% by mass, Cu: 0.05% by mass, Mg: 0.75% by mass, Cr: 0.05% by mass, and the balance is Al and It was an unavoidable impurity.
  • the tensile strength of the aluminum plate was 240 MPa, and its Young's modulus was 68 GPa.
  • the aluminum plate was immersed in a sodium hydroxide aqueous solution having a concentration of 5% by mass for 1.5 minutes, neutralized with a nitric acid aqueous solution having a concentration of 5% by mass, washed with water, and dried to perform an etching treatment.
  • the etched aluminum plate was boiled in pure water for 10 minutes and then baked at 250 ° C. for 10 minutes to perform boehmite treatment to form a boehmite film on the surface of the aluminum plate.
  • the aluminum plate after the boehmite treatment was prepared by dissolving 2 g of 3-aminopropyltrimethoxysilane (“KBM-903” manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) in 1000 g of industrial ethanol in a silane cup at 70 ° C. After immersing in the ring agent-containing solution for 20 minutes, the aluminum plate was taken out and dried to form a functional group-containing layer on the surface of the boehmite film. In this way, an aluminum substrate having an amino group-containing layer on the etching treatment and the boehmite film was prepared.
  • KBM-903 3-aminopropyltrimethoxysilane manufactured by Shinetsu Silicone Co., Ltd .
  • a silane coupling agent 1000 g of industrial ethanol in a silane cup at 70 ° C.
  • ⁇ Manufacturing example 4 Copper base material> As a metal base material, a copper plate having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.5 mm was degreased with acetone.
  • the degreased copper plate was prepared with a silane cup at 70 ° C. in which 0.5 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shinetsu Silicone Co., Ltd .; a silane coupling agent) was dissolved in 100 g of industrial ethanol. After immersing in the ring agent-containing solution for 5 minutes, the copper plate was taken out and dried, and a functional group derived from the silane coupling agent was introduced on the surface of the degreased copper plate.
  • KBM-503 manufactured by Shinetsu Silicone Co., Ltd .
  • a silane coupling agent a silane coupling agent
  • 1,4-bis (3-mercaptobutyryloxy) butane (Carens MT (registered trademark) BD1 manufactured by Showa Denko KK), which is a bifunctional thiol compound: 0.6 g, 2,4,6-tris (dimethyl).
  • Aminomethyl) phenol (DMP-30): 0.05 g was immersed in a solution dissolved in 150 g of toluene at 70 ° C. for 10 minutes, then pulled up and dried. In this way, a copper base material having two functional group-containing layers (methacryloyl group-containing layer and mercapto group-containing layer) was prepared on the degreased surface.
  • Iron base material> As a metal base material, an iron plate having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.5 mm was sanded using # 100 sandpaper to form fine irregularities on the surface of the iron plate. In this way, an iron substrate having a sanded surface was produced.
  • Magnesium base material> As a metal base material, a magnesium plate having a thickness of 18 mm ⁇ 45 mm and a thickness of 1.5 mm was sanded using # 100 sandpaper to form fine irregularities on the surface of the magnesium plate. Next, the same operation as in Production Example 4 was carried out to form a functional group-containing layer on the surface of the magnesium plate after the sanding treatment. In this way, a magnesium base material having two functional group-containing layers (methacryloyl group-containing layer and mercapto group-containing layer) was prepared on the sanding treatment.
  • ⁇ Manufacturing example 7 SUS base material> As a metal base material, a martensitic stainless steel (SUS403) steel sheet with a thickness of 18 mm ⁇ 45 mm and a thickness of 1.5 mm is sanded using # 100 sandpaper to form fine irregularities on the surface of the stainless steel sheet. did. Next, the same operation as in Production Example 3 was performed to form a functional group-containing layer on the surface of the stainless steel sheet after the sanding treatment. In this way, a SUS substrate having an amino group-containing layer on the sanding treatment was produced.
  • SUS403 martensitic stainless steel
  • Table 2 shows the details of the metal base material and the functional group-containing layer of Production Examples 3 to 7.
  • Example 1 Preparation of film A> A xylene solution of modified PP-1 is applied on a release film so that the thickness after drying is 30 ⁇ m, and the solvent is volatilized by leaving it in the air at room temperature for 30 minutes to volatilize the solvent on the release film. Film A was produced.
  • thermoplastic epoxy resin composition A xylene solution of a thermoplastic epoxy resin composition is applied onto a release film so that the thickness after drying is 30 ⁇ m, and the solvent is volatilized by leaving it in the air at room temperature for 30 minutes to volatilize the release film.
  • a thermoplastic epoxy resin layer was formed on the film.
  • a xylene solution of modified PP-2 was applied to the surface of the thermoplastic epoxy resin layer so that the thickness after drying was 30 ⁇ m.
  • the solvent was volatilized by leaving the coating film in the air at room temperature for 30 minutes and then held at 150 ° C. for 30 minutes to prepare a film B having a modified polyolefin layer and a thermoplastic epoxy resin layer.
  • Example 3 Metal member-resin member joint> In a drying oven at a temperature of 120 ° C., a film A from which the release film was peeled off was pressure-bonded onto a functional group-containing layer of an aluminum base material to prepare a metal member having a resin coating layer derived from the film A.
  • the metal member and the resin member A are overlapped with each other so that the resin coating layer of the metal member and the resin member A are in contact with each other and the joint portion has a length of 5 mm and a width of 10 mm.
  • Ultrasonic welding was performed using an ultrasonic welding machine SONOPET-JII430T-M (28.5 KHz) manufactured by Seidensha Electronics Co., Ltd. As a result, a test piece for tensile test (metal member-resin member joint) conforming to ISO19095 was produced.
  • Example 4 Injection molding joining> Polypropylene resin (PP resin) containing glass fibers (PP resin) (Daicel FineChem Co., Ltd.) on a resin coating layer of a metal member produced in the same procedure as in Example 3 except that the aluminum base material of Example 3 was changed to an iron base material.
  • PP-GF40-01 F02 manufactured by Injection Molding Machine (SE100V manufactured by Sumitomo Heavy Industries, Ltd .; Cylinder temperature 200 ° C, Tool temperature 30 ° C, Injection speed 50 mm / sec, Peak / Holding pressure 195/175 [MPa / MPa] ]
  • the resin member was joined to the metal member while being molded by injection molding.
  • test piece for tensile test (PP resin, 10 mm ⁇ 45 mm ⁇ 3 mm, joint length 5 mm) (metal member-resin member joint) conforming to ISO19095 was produced.
  • the joint strength of the test piece was measured by the same method as in Example 3. The measurement results are shown in Table 3.
  • Example 5 Sandwich joining> A film A from which the release film has been peeled off is sandwiched between the aluminum base material and the resin member A so that the film A comes into contact with the functional group-containing layer of the aluminum base material, and the joint portion has a length of 5 mm and a width of 10 mm.
  • ultrasonic welding was performed using an ultrasonic welding machine SONOPET-JII430T-M (28.5 KHz) manufactured by Seidensha Electronics Co., Ltd.
  • SONOPET-JII430T-M 28.5 KHz
  • Example 6 Metal member-resin member joining> In a drying furnace at a temperature of 120 ° C., the film B from which the release film was peeled off was pressure-bonded onto the functional group-containing layer of the copper substrate so that the modified polyolefin layer was exposed, and the resin coating layer derived from the film B was pressed. A metal member having the above was produced.
  • the metal member and the resin member A are overlapped with each other so that the resin coating layer of the metal member and the resin member A are in contact with each other and the joint portion has a length of 5 mm and a width of 10 mm.
  • Ultrasonic welding was performed using an ultrasonic welding machine SONOPET-JII430T-M (28.5 KHz) manufactured by Seidensha Electronics Co., Ltd.
  • SONOPET-JII430T-M 28.5 KHz
  • a test piece for tensile test (metal member-resin member joint) conforming to ISO19095 was produced.
  • the joint strength of the test piece was measured by the same method as in Example 3. The measurement results are shown in Table 3.
  • Example 7 Injection molding joining> Polypropylene resin (PP resin) containing carbon fibers (PP resin) (Daicel FineChem Co., Ltd.) on a resin coating layer of a metal member produced in the same procedure as in Example 6 except that the copper base material of Example 6 was changed to a SUS base material.
  • PP-CF40-01 F008 manufactured by injection molding machine (SE100V manufactured by Sumitomo Heavy Industries, Ltd .; cylinder temperature 200 ° C, tool temperature 30 ° C, injection speed 50 mm / sec, peak / holding pressure 195/175 [MPa / MPa] ]), The resin member was joined to the metal member while being molded by injection molding.
  • test piece for tensile test (PP resin, 10 mm ⁇ 45 mm ⁇ 3 mm, joint length 5 mm) (metal member-resin member joint) conforming to ISO19095 was produced.
  • the joint strength of the test piece was measured by the same method as in Example 3. The measurement results are shown in Table 3.
  • Example 8 Sandwich joining> The release film is formed so that the modified polyolefin layer of the film B comes into contact with the resin member A and the thermoplastic epoxy resin layer comes into contact with the functional group-containing layer of the magnesium base material between the magnesium base material and the resin member A.
  • the ultrasonic welding machine SONOPET- Ultrasonic welding was performed using JII430TM (28.5 KHz).
  • JII430TM 28.5 KHz
  • a test piece for tensile test metal member-resin member joint
  • the joint strength of the test piece was measured by the same method as in Example 3. The measurement results are shown in Table 3.
  • Metal member-resin member joint A test piece for a tensile test (metal member-resin member joint) was produced by the same procedure as in Example 3 except that the film C was used instead of the film A. The joint strength of the test piece was measured by the same method as in Example 3. The measurement results are shown in Table 3.
  • the present invention can be used for manufacturing a metal member-resin member joint.
  • Metal member 2 Metal base material 2a: Surface treatment part 3: Functional group-containing layer 4: Film (resin coating layer) 4a: Modified polyolefin layer 4b: Thermoplastic epoxy resin layer 4c: Curable resin layer 5: Adhesive layer 6: Resin member 10: Metal member-resin member bonded body

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PCT/JP2021/041191 2020-12-17 2021-11-09 金属部材－樹脂部材接合体の製造方法及びフィルム Ceased WO2022130833A1 (ja)

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CN202180084575.4A CN116635219A (zh) 2020-12-17 2021-11-09 金属构件-树脂构件接合体的制造方法及膜
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