Metal-resin laminate and method for manufacturing a metal-resin laminate

Abstract

Provided is a metal-resin layered body that is obtained by layering a metal material and a thermosetting resin, wherein the shear bond strength between the metal material and the thermosetting resin is 10 MPa or greater.

Description

Technical Field

[0001] The present invention relates to a metal resin laminate formed by laminating a metal material and a thermosetting resin, and more particularly to a metal resin laminate in which a thermosetting resin is firmly bonded to the surface of a metal material.

Background Art

[0002] Techniques for integrating a metal material and a resin are required in a wide range of fields such as aircraft, automobiles, household electrical appliances, and industrial equipment, and metal resin laminates formed by laminating a metal material and a thermosetting resin have been studied.

[0003] For example, in Patent Document 1, as a composite of a metal alloy and a molded product of a thermosetting resin composition, as the metal alloy, one having a predetermined roughness and ultrafine irregularities on its surface and a surface layer made of a thin layer of a metal oxide or a metal phosphate is used, and the thermosetting resin composition is cured in a state of penetrating into the ultrafine irregularities on the surface of the metal alloy, whereby a composite in which the metal alloy and the molded product are joined without an adhesive intervening therebetween is described.

Prior Art Documents

Patent Documents

[0004]

Patent Document Ⅰ

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, when the present inventor examined the technique of Patent Document 1, it was found that there is still room for improvement in the joining of the metal alloy and the molded product of the thermosetting resin composition. In particular, when the present inventor conducted further studies, it became clear that the presence of the thin layer of a metal oxide or a metal phosphate existing between the metal alloy and the molded product of the thermosetting resin composition is one of the causes of the decrease in the bonding strength.

[0006] The present invention has been made in view of such a situation, and an object thereof is to provide a metal resin laminate in which a thermosetting resin is firmly bonded to the surface of a metal material, and a method for manufacturing a metal resin laminate capable of efficiently manufacturing such a metal resin laminate.

Means for Solving the Problems

[0007] Conventionally, for the adhesion between a metal and a resin, it has been considered that a relatively thick oxide layer is required on the metal surface. On the other hand, when the present inventor conducted studies to achieve the above object, in a metal resin laminate formed by laminating a metal material and a thermosetting resin, it was found that peeling occurs between such a relatively thick oxide layer and the metal material, and that a high adhesive force is achieved when such a relatively thick oxide layer is not present, leading to the completion of the present invention.

[0008] That is, according to the present invention, there is provided a metal resin laminate formed by laminating a metal material and a thermosetting resin, wherein the shear adhesive force between the metal material and the thermosetting resin is 10 MPa or more.

[0009] In the metal resin laminate of the present invention, it is preferable that the metal material and the thermosetting resin are laminated directly or through an oxide layer. In the metal resin laminate of the present invention, it is preferable that the metal material contains at least one metal selected from the group consisting of copper, nickel, aluminum, chromium, and iron. In the metal resin laminate of the present invention, it is preferable that the metal material is copper or a copper alloy. In the metal resin laminate of the present invention, it is preferable that the thermosetting resin is a polymer obtained by bulk polymerization of a polymerizable composition containing a norbornene-based monomer. The metal resin laminate of the present invention may further have a layer different from the layer composed of the metal material and the thermosetting resin.

[0010] Furthermore, according to the present invention, a method for producing a metal-resin laminate comprising a metal material and a thermosetting resin laminate is provided, A first step involves preparing a metallic material having an oxide layer with a thickness of 2 nm or more on its surface and a centerline average surface roughness Ra of 1.5 nm or more. A second step involves contacting the metal material prepared in the first step with an acid, A method for manufacturing a metal-resin laminate is provided, comprising a third step of contacting a thermosetting resin material with the surface of the metal material that has been contacted with an acid in the second step, and curing it.

[0011] In the method for manufacturing a metal-resin laminate of the present invention, it is preferable that the first step includes a step of obtaining a metal material having an oxide layer of 2 nm or more thickness on its surface and a center-line average surface roughness Ra of 1.5 nm or more by oxidizing the metal material in air or in liquid. In the method for manufacturing a metal-resin laminate of the present invention, it is preferable that the metal material includes at least one metal selected from the group consisting of copper, nickel, aluminum, chromium, and iron. In the method for manufacturing a metal-resin laminate of the present invention, it is preferable that the metal material is copper or a copper alloy. In the method for producing a metal-resin laminate of the present invention, it is preferable that the thermosetting resin material is a polymerizable composition containing a norbornene monomer. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a metal-resin laminate in which a thermosetting resin is firmly bonded to the surface of a metal material, and a method for efficiently producing such a metal-resin laminate. [Modes for carrying out the invention]

[0013] <Metal-resin laminate> The metal-resin laminate of the present invention is a metal-resin laminate formed by laminating a metal material and a thermosetting resin, wherein the shear adhesive force between the metal material and the thermosetting resin is 10 MPa or more.

[0014] In the metal-resin laminate of the present invention, it is preferable that the metal material and the thermosetting resin are laminated substantially without an oxide layer in between, that is, laminated by direct bonding. However, an oxide layer may be interposed between the metal material and the thermosetting resin in part or all of the space. Specifically, the thickness of the oxide layer produced by spontaneous oxidation varies depending on the type of metal material and is not particularly limited, but is usually up to about 30 nm. Therefore, the thickness of the oxide layer is preferably less than 30 nm, and depending on the type of metal material, preferably less than 5 nm, and more preferably less than 2 nm. The thickness of the oxide layer can be measured by a method using an X-ray photoelectron spectrometer, as described later.

[0015] The metal material is not particularly limited, and various metal materials such as iron, copper, nickel, gold, silver, platinum, palladium, cobalt, zinc, lead, tin, titanium, chromium, aluminum, magnesium, manganese, and alloys thereof can be used. However, it is preferable that it contains at least one metal selected from the group consisting of copper, nickel, aluminum, chromium, and iron. Among these, copper, copper alloys, aluminum, or iron alloys (stainless steel) are more preferable, copper or copper alloys are even more preferable, and copper is particularly preferable. As for copper, high-purity copper such as tough pitch copper or oxygen-free copper (for example, purity of 95% by mass or higher, preferably 99% by mass or higher, and more preferably 99.9% by mass or higher) is particularly preferred. Examples of copper alloys include brass, phosphor bronze, silver alloy, and aluminum bronze. All copper alloys are covered, including pure copper alloys such as C1020 and C1100 specified in the Japanese Industrial Standards (JIS H 3000 series), brass alloys of the C2600 series, copper white alloys of the C5600 series, and other iron-based copper alloys used for connectors.

[0016] Furthermore, while the shape of the metal material is not particularly limited, a plate-like or thin-film shape is preferred because it allows for good formation of a laminate with the thermosetting resin. In the case of a plate-like or thin-film shape, its thickness is preferably 0.001 to 100 mm, more preferably 0.1 to 50 mm, and particularly preferably 0.5 to 40 mm.

[0017] The metal material may be metal foil, or it may be a substrate such as a circuit board for manufacturing printed circuit boards, or terminal electrodes of various electronic components. In particular, by using the metal material as terminal electrodes of various electronic components and laminating a thermosetting resin on top of it, the thermosetting resin can be used as a sealing material.

[0018] Thermosetting resins are not particularly limited, but examples include norbornene-based resins, unsaturated polyester resins, acrylic resins, vinyl ester resins, alkyd resins, amino resins, epoxy resins, urethane resins, phenolic resins, and silicone resins. Among these, norbornene-based resins and epoxy resins are preferred from the viewpoint of being able to further increase the bonding strength to metal materials, and norbornene-based resins are preferred.

[0019] As a norbornene-based resin, a polymerizable composition containing a norbornene monomer can be suitably used as a thermosetting resin material for forming a norbornene-based resin (thermosetting resin). By bulk polymerization of such a polymerizable composition containing a norbornene monomer, a norbornene-based resin (thermosetting resin) as a cured product can be suitably obtained.

[0020] The norbornene monomer can be any compound having a norbornene ring structure and is not particularly limited, but examples include dicyclic monomers such as norbornene and norbornadiene; tricyclic monomers such as dicyclopentadiene; tetracyclic monomers such as tetracyclododecene; pentacyclic monomers such as tricyclopentadiene; heptacyclic monomers such as tetracyclopentadiene; and derivatives thereof having an alkenyl group with 2 to 10 carbon atoms, an alkynyl group with 2 to 10 carbon atoms, an alkylidene group with 1 to 10 carbon atoms, an epoxy group, or a (meth)acrylic group. The norbornene monomer can be used alone or in combination of two or more. From the viewpoint of further enhancing the effects of the present invention, the tricyclic monomer is preferred, and dicyclopentadiene is particularly preferred. The norbornene monomer used preferably contains 50% by mass or more of the tricyclic monomer, and among them dicyclopentadiene.

[0021] The content of norbornene monomer in the polymerizable composition used in the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and may be 100% by mass, based on 100% by mass of the total polymerizable monomer contained in the polymerizable composition. By setting the content of norbornene monomer within the above range, the bonding strength to metal materials can be further increased.

[0022] Furthermore, in the present invention, monocyclic cycloolefins may be used as polymerizable monomers to be contained in the polymerizable composition.

[0023] Monocyclic cycloolefins are not particularly limited, but include cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, cyclopentadiene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, and derivatives thereof having a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C1-C10 alkylidene group, an epoxy group, or a (meth)acrylic group. Monocyclic cycloolefins can be used individually or in combination of two or more.

[0024] Furthermore, the polymerizable composition used in the present invention may contain other polymerizable monomers that can polymerize with norbornene monomers and monocyclic cycloolefins. Examples of such other polymerizable monomers include other cycloolefin monomers and (meth)acrylate monomers such as phenoxyethylene glycol (meth)acrylate. (Meth)acrylate monomers can function as adhesion aids between metal materials and norbornene resins. In this specification, (meth)acrylate means methacrylate or acrylate.

[0025] The content of polymerizable monomers other than norbornene monomers in the polymerizable composition used in the present invention is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, out of 100% by mass of the total polymerizable monomers contained in the polymerizable composition, and may be 0% by mass.

[0026] In the polymerizable composition used in the present invention, the total content of polymerizable monomers is preferably 10 to 95% by mass, more preferably 15 to 93% by mass, and even more preferably 20 to 90% by mass, of 100% by mass of the total polymerizable composition.

[0027] Furthermore, the polymerizable composition used in the present invention preferably contains a metathesis polymerization catalyst as a polymerization catalyst. The metathesis polymerization catalyst is not particularly limited as long as it can perform ring-opening polymerization of norbornene monomers, and known catalysts can be used.

[0028] The metathesis polymerization catalyst used in the present invention is a complex formed by bonding a transition metal atom as the central atom with multiple ions, atoms, polyatomic ions, and / or compounds. As the transition metal atom, atoms from groups 5, 6, and 8 (long-period periodic table, the same applies hereinafter) are used. The atoms of each group are not particularly limited, but as a group 5 atom, for example, tantalum is used; as a group 6 atom, for example, molybdenum and tungsten are used; and as a group 8 atom, for example, ruthenium and osmium are used. Among these transition metal atoms, ruthenium and osmium from group 8 are preferred. That is, as the metathesis polymerization catalyst used in the present invention, a complex with ruthenium or osmium as the central atom is preferred, and a complex with ruthenium as the central atom is more preferred. As a complex with ruthenium as the central atom, a ruthenium carbene complex formed by coordinating a carbene compound to ruthenium is preferred. Here, "carbene compound" is a general term for compounds containing a methylene free radical, and refers to compounds with a divalent carbon atom (carbene carbon) that is uncharged, represented as (>C:). Ruthenium carbene complexes exhibit excellent catalytic activity during bulk ring-opening polymerization, resulting in polymers with less odor from unreacted monomers, leading to high productivity and the acquisition of high-quality polymers. Furthermore, they are relatively stable to oxygen and moisture in the air and are not easily deactivated, so they can be used in the atmosphere. Metathesis polymerization catalysts may be used individually or in combination of multiple types.

[0029] Examples of ruthenium carbene complexes include those represented by the following general formula (1) or general formula (2). [ka]

[0030] In the above general formulas (1) and (2), R 1 and R 2Each of these is independently a hydrogen atom; a halogen atom; or a C1-C20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; and these groups may have substituents or may be bonded to each other to form a ring. 1 and R 2 Examples of groups that bond to each other to form a ring include indenylidene groups, such as phenylindenylidene groups, which may have substituents.

[0031] Specific examples of C1-C20 organic groups that may contain halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or silicon atoms include C1-C20 alkyl groups, C2-C20 alkenyl groups, C2-C20 alkynyl groups, C6-C20 aryl groups, C1-C20 alkoxy groups, C2-C20 alkenyloxy groups, C2-C20 alkynyloxy groups, C6-C20 aryloxy groups, and C1-C8 Examples of C1-C20 organic groups include alkylthio groups, carbonyloxy groups, alkoxycarbonyl groups with 1 to 20 carbon atoms, alkylsulfonyl groups with 1 to 20 carbon atoms, alkylsulfonyl groups with 1 to 20 carbon atoms, alkylsulfonic acid groups with 1 to 20 carbon atoms, arylsulfonic acid groups with 6 to 20 carbon atoms, phosphonic acid groups, arylphosphonic acid groups with 6 to 20 carbon atoms, alkylammonium groups with 1 to 20 carbon atoms, and arylammonium groups with 6 to 20 carbon atoms. These C1-C20 organic groups, which may contain halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or silicon atoms, may have substituents. Examples of substituents include C1-C10 alkyl groups, C1-C10 alkoxy groups, and C6-C10 aryl groups.

[0032] X 1 and X 2 Each of these independently represents an arbitrary anionic ligand. An anionic ligand is a ligand that has a negative charge when separated from the central metal atom, and examples include halogen atoms, diketonate groups, substituted cyclopentadienyl groups, alkoxy groups, aryloxy groups, and carboxyl groups.

[0033] L 1 and L 2 represent a heteroatom-containing carbene compound or a neutral electron-donating compound other than a heteroatom-containing carbene compound. The heteroatom-containing carbene compound and the neutral electron-donating compound other than the heteroatom-containing carbene compound are compounds that have a neutral charge when separated from the central metal. From the viewpoint of improving catalytic activity, a heteroatom-containing carbene compound is preferred. The heteroatom means an atom of Group 15 and Group 16 of the periodic table, and specific examples thereof include a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, an arsenic atom, and a selenium atom, etc. Among these, from the viewpoint of obtaining a stable carbene compound, a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom are preferred, and a nitrogen atom is more preferred.

[0034] As the heteroatom-containing carbene compound, a compound represented by the following general formula (3) or (4) is preferred, and from the viewpoint of improving catalytic activity, a compound represented by the following general formula (3) is more preferred.

Chemical formula

[0035] In the above general formulas (3) and (4), R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom. Specific examples of the organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom or a silicon atom are the same as those in the above general formulas (1) and (2). Also, R 3 , R 4 , R 5 and R 6 may be bonded to each other in any combination to form a ring.

[0036] Furthermore, since the effects of the present invention become even more pronounced, R 5 and R 6 It is preferable that R is a hydrogen atom. 3 and R 4 The aryl group may have substituents, a phenyl group having an alkyl group with 1 to 10 carbon atoms as a substituent is more preferred, and a mesityl group is even more preferred.

[0037] Examples of the neutral electron-donating compounds include oxygen atoms, water, carbonyls, ethers, nitriles, esters, phosphines, phosphinites, phosphites, sulfoxides, thioethers, amides, imines, aromatics, cyclic diolefins, olefins, isocyanides, and thiocyanates.

[0038] In the above general formulas (1) and (2), R 1 , R 2 , X 1 , X 2 , L 1 and L 2 These elements may be used individually and / or combined with each other in any combination to form polydentate chelate ligands.

[0039] Furthermore, among the compounds represented by the above general formula (1) or (2), the ruthenium carbene complex used in the present invention is preferably the compound represented by the above general formula (1) in that the effects of the present invention are more pronounced, and more preferably the compound represented by the following general formula (5) or general formula (6).

[0040] The general formula (5) is shown below. [ka]

[0041] In the above general formula (5), Z is an oxygen atom, a sulfur atom, a selenium atom, NR 12 PR 12 Or AsR 12 And R 12Z is a hydrogen atom; a halogen atom; or an organic group having 1 to 20 carbon atoms which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; however, an oxygen atom is preferred for Z because the effects of the present invention become even more pronounced.

[0042] Note, R 1 , R 2 , X 1 and L 1 The same applies as in the cases of general formulas (1) and (2) above, and each may form a polydentate chelate ligand individually and / or by combining with each other in any combination, but X 1 and L 1 It does not form a polydentate chelate ligand, and R 1 and R 2 It is preferable that these groups are bonded to each other to form a ring, more preferably they are indenylidene groups which may have substituents, and even more preferably they are phenylindenylidene groups. Furthermore, specific examples of organic groups having 1 to 20 carbon atoms that may contain halogen atoms, oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, or silicon atoms are the same as in the cases of general formulas (1) and (2) above.

[0043] In the above general formula (5), R 7 and R 8 Each of these groups is independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, or a C6-C20 heteroaryl group. These groups may have substituents or may be bonded to each other to form a ring. Examples of substituents include a C1-C10 alkyl group, a C1-C10 alkoxy group, or a C6-C10 aryl group. When a ring is formed, it may be an aromatic ring, an alicyclic ring, or a heterocyclic ring. However, it is preferable to form an aromatic ring, more preferably an aromatic ring with C6-C20 atoms, and even more preferably an aromatic ring with C6-C10 atoms.

[0044] In the above general formula (5), R 9 , R 10 and R 11Each of these is independently a hydrogen atom; a halogen atom; or a C1-C20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; these groups may have substituents and may be bonded to each other to form a ring. Specific examples of C1-C20 organic groups which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom are the same as in the cases of general formulas (1) and (2) above.

[0045] R 9 , R 10 and R 11 It is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0046] Specific examples of compounds represented by the above general formula (5) and methods for producing them include, for example, those described in International Publication No. 03 / 062253 (Japanese Patent Publication No. 2005-515260).

[0047] The general formula (6) is shown below. [ka]

[0048] In the above general formula (6), m is 0 or 1. m is preferably 1, in which case Q is an oxygen atom, a nitrogen atom, a sulfur atom, a methylene group, an ethylene group, or a carbonyl group, and is preferably a methylene group.

[0049] In the above general formula (6), [ka] The bond is either a single bond or a double bond, preferably a single bond.

[0050] R 1 , X 1 , X 2 and L 1The same applies as in the cases of general formulas (1) and (2) above, and each may form a polydentate chelate ligand individually and / or by combining with each other in any combination, but X 1 , X 2 and L 1 It does not form a polydentate chelate ligand, and R 1 It is preferable that it is a hydrogen atom.

[0051] R 13 ~R 21 This is a hydrogen atom; a halogen atom; or a C1-C20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom; these groups may have substituents and may be bonded to each other to form a ring. Specific examples of a C1-C20 organic group which may contain a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, or a silicon atom are the same as in the cases of general formulas (1) and (2) above.

[0052] R 13 R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. 14 ~R 17 is preferably a hydrogen atom, and R 18 ~R 21 This is preferably a hydrogen atom or a halogen atom.

[0053] Specific examples of compounds represented by the above general formula (6) and methods for producing them include, for example, those described in International Publication No. 11 / 079799 (Japanese Patent Publication No. 2013-516392).

[0054] The amount of metathesis polymerization catalyst is preferably 0.005 mmol or more, more preferably 0.01 to 50 mmol, and even more preferably 0.015 to 20 mmol, based on 1 mole of the total amount of polymerizable monomer used in the reaction.

[0055] Furthermore, the polymerizable composition used in the present invention may optionally contain radical generators, diisocyanate compounds, polyfunctional (meth)acrylate compounds, coupling agents, and other optional components.

[0056] Radical generators generate radicals upon heating, thereby inducing crosslinking reactions in norbornene-based resins formed by bulk polymerization. The sites where radical generators induce crosslinking reactions are mainly carbon-carbon double bonds contained in norbornene-based resins, but crosslinking may also occur at saturated bond sites. Examples of radical generators include organic peroxides, diazo compounds, and nonpolar radical generators.

[0057] The amount of radical generator in the polymerizable composition used in the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer used in the reaction.

[0058] Examples of diisocyanate compounds include 4,4'-methylenediphenyl diisocyanate (MDI), toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylenediisocyanate, 4-isopropyl-1,3-phenylenediisocyanate, 4-chlor-1,3-phenylenediisocyanate, 4-butoxy-1,3-phenylenediisocyanate, 2,4-diisocyanate diphenyl ether, 1,4-phenylenediisocyanate, tolylenediisocyanate, xylylenediisocyanate (XDI), 1,5-naphthalenediisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, and 4,4'-diisocyanate diphenyl ether. Examples include aromatic diisocyanate compounds such as oenzyl; aliphatic diisocyanate compounds such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; alicyclic diisocyanate compounds such as 4-cyclohexylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, and hydrogenated XDI; and polyurethane prepolymers obtained by reacting these diisocyanate compounds with low molecular weight polyols or polyamines such that the terminal ends are isocyanates. Furthermore, conventionally used and known polyfunctional isocyanate groups obtained by using these compounds as isocyanurates, biuret forms, adduct forms, or polymeric forms can be used without particular limitation. Examples of such compounds include 2,4-toluylene diisocyanate dimers, triphenylmethane triisocyanate, tris-(p-isocyanatephenyl)thiophosphite, polyfunctional aromatic isocyanate compounds, polyfunctional aromatic aliphatic isocyanate compounds, polyfunctional aliphatic isocyanate compounds, fatty acid-modified polyfunctional aliphatic isocyanate compounds, polyfunctional blocked polyfunctional aliphatic isocyanate compounds, polyfunctional blocked polyfunctional aliphatic isocyanate compounds, and polyisocyanate prepolymers.Among these, aromatic diisocyanate compounds, aliphatic diisocyanate compounds, and alicyclic diisocyanate compounds, which are polyfunctional non-blocking isocyanate compounds, are preferably used due to their excellent availability and ease of handling. These compounds can be used individually or in combination of two or more.

[0059] Polyfunctional blocked isocyanate compounds are those in which at least two isocyanate groups in the molecule are reacted with an active hydrogen-containing compound to make them inert at room temperature. These isocyanate compounds generally have a structure in which the isocyanate groups are masked by blocking agents such as alcohols, phenols, ε-caprolactam, oximes, and active methylene compounds. Polyfunctional blocked isocyanate compounds generally do not react at room temperature and therefore have excellent storage stability, but the isocyanate groups can be regenerated by heating to 140-200°C, allowing them to exhibit excellent reactivity.

[0060] The diisocyanate compounds may be used individually or in combination of two or more. The amount of diisocyanate compound in the polymerizable composition used in the present invention is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer used in the reaction.

[0061] Furthermore, from the viewpoint of further improving the bonding strength to metallic materials, polyfunctional (meth)acrylate compounds may be used. It is presumed that by using a polyfunctional (meth)acrylate compound together with a diisocyanate compound, the active hydrogen-reactive groups of the diisocyanate compound form chemical bonds with the hydroxyl groups present in the polyfunctional (meth)acrylate compound, thereby further increasing the bonding strength to metallic materials. Preferred examples of polyfunctional (meth)acrylate compounds include ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and neopentyl glycol dimethacrylate.

[0062] The polyfunctional (meth)acrylate compounds may be used individually or in combination of two or more. The amount of polyfunctional (meth)acrylate compound in the polymerizable composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass, based on 100 parts by mass of the total amount of polymerizable monomer used in the reaction.

[0063] While there are no particular limitations on the coupling agent, a silane coupling agent having at least one hydrocarbon group with a norbornene structure (norbornene skeleton) is preferred from the viewpoint of improving the adhesion between the metal material and the norbornene-based resin. Specific examples of such silane coupling agents include bicycloheptenyltrimethoxysilane, bicycloheptenyltriethoxysilane, bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, and bicycloheptenylhexyltriethoxysilane, but preferably bicycloheptenylethyltrimethoxysilane, bicycloheptenylethyltriethoxysilane, bicycloheptenylhexyltrimethoxysilane, and bicycloheptenylhexyltriethoxysilane, more preferably bicycloheptenylethyltrimethoxysilane and bicycloheptenylethyltriethoxysilane, and even more preferably bicycloheptenylethyltrimethoxysilane.

[0064] The content of the silane coupling agent having at least one hydrocarbon group having a norbornene structure in the polymerizable composition used in the present invention is preferably 0.1 to 5% by mass, more preferably 0.3 to 2% by mass, and even more preferably 0.5 to 1% by mass.

[0065] Furthermore, the polymerizable composition may also contain coupling agents other than silane coupling agents, such as silane coupling agents that do not have hydrocarbon groups having a norbornene structure, thiol coupling agents, aluminate coupling agents, titanate coupling agents, fatty acid esters, etc.

[0066] Other optional ingredients include surfactants, activity regulators, elastomers, antioxidants (anti-aging agents), colorants, light stabilizers, and flame retardants.

[0067] The activator is a compound that acts as a co-catalyst for the metathesis polymerization catalyst described above, thereby improving the polymerization activity of the catalyst. Examples of activators include alkylaluminum halides such as ethylaluminum dichloride and diethylaluminum chloride; alkoxyalkylaluminum halides obtained by substituting some of the alkyl groups of these alkylaluminum halides with alkoxy groups; and organotin compounds. The amount of activator used is not particularly limited, but is preferably 0.1 to 100 moles, and more preferably 1 to 10 moles, per mole of the total metathesis polymerization catalyst used in the polymerizable composition.

[0068] The activity regulator is used to prevent polymerization from starting prematurely when a polymerizable composition is prepared by mixing two or more reaction stocks, as described later, and then injected into a mold to initiate polymerization.

[0069] When using a transition metal compound from Group 5 or Group 6 of the periodic table as a metathesis polymerization catalyst, suitable activity regulators include compounds that reduce the metathesis polymerization catalyst, such as alcohols, haloalcohols, esters, ethers, and nitriles. Among these, alcohols and haloalcohols are preferred, with haloalcohols being more preferred.

[0070] Specific examples of alcohols include n-propanol, n-butanol, n-hexanol, 2-butanol, isobutyl alcohol, isopropyl alcohol, and t-butyl alcohol. Specific examples of haloalcohols include 1,3-dichloro-2-propanol, 2-chloroethanol, and 1-chlorobutanol.

[0071] Lewis base compounds are particularly suitable as activity regulators when using ruthenium carbene complexes as metathesis polymerization catalysts. Examples of Lewis base compounds include those containing phosphorus atoms, such as tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, triphenylphosphine, and n-butylphosphine; and those containing nitrogen atoms, such as n-butylamine, pyridine, 4-vinylpyridine, acetonitrile, ethylenediamine, N-benzylidenemethylamine, pyrazine, piperidine, and imidazole. Furthermore, norbornene substituted with alkenyl groups, such as vinylnorbornene, propenylnorbornene, and isopropenylnorbornene, are polymerizable monomers and also act as activity regulators. The amount of these activity regulators used should be appropriately adjusted depending on the compound being used.

[0072] Examples of elastomers include natural rubber, polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-diene polymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and their hydrides. The viscosity can be adjusted by dissolving the elastomer in the polymerizable composition. Furthermore, the impact resistance of the norbornene-based resin formed by the bulk polymerization of the composition can be improved by adding the elastomer. The amount of elastomer used is preferably 0.5 to 20 parts by mass, more preferably 2 to 10 parts by mass, per 100 parts by mass of the total amount of polymerizable monomer in the polymerizable composition.

[0073] Examples of antioxidants (anti-aging agents) include various antioxidants for plastics and rubbers, such as phenolic, phosphorus-based, and amine-based antioxidants. As a dispersant, anionic surfactants, cationic surfactants, and nonionic surfactants can be used as desired, but nonionic surfactants are preferred.

[0074] Dyes and pigments are used as coloring agents. There are many types of dyes, and any known ones can be selected as appropriate. Examples of pigments include carbon black, graphite, lead yellow, iron oxide yellow, titanium dioxide, zinc oxide, trilead tetroxide, red lead, chromium oxide, Prussian blue, and titanium black.

[0075] Examples of light stabilizers include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxanilide-based UV absorbers, hindered amine-based UV absorbers, and benzoate-based UV absorbers.

[0076] Examples of flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, halogen-based flame retardants, and metal hydroxide-based flame retardants such as aluminum hydroxide or magnesium hydroxide.

[0077] Furthermore, the polymerizable composition used in the present invention may contain a filler as an optional component. Various fillers can be used and are not particularly limited, but it is preferable to use an inorganic filler consisting of a fibrous filler with an aspect ratio of 5 to 100 or a particulate filler with an aspect ratio of 1 to 2. The aspect ratio of the filler refers to the ratio of the average major axis diameter of the filler to the 50% volume cumulative diameter. Here, the average major axis diameter is the number-average major axis diameter calculated as the arithmetic mean of the major axis diameters of 100 randomly selected fillers using optical microscope images. The 50% volume cumulative diameter is a value obtained by measuring the particle size distribution using X-ray transmission. Furthermore, it is preferable that the surface of the filler is hydrophobic. In the metal-resin laminate of the present invention, it is preferable that the thermosetting resin does not contain a filler from the viewpoint of increasing the adhesive strength with the metal material, and therefore, it is preferable to use a polymerizable composition that does not contain a filler as used in the present invention.

[0078] When a filler is included in the polymerizable composition used in the present invention, the amount of the filler is preferably 5 to 55 parts by mass, and more preferably 10 to 45 parts by mass, based on 100 parts by mass of the total amount of norbornene monomer and metathesis polymerization catalyst.

[0079] The polymerizable composition used in the present invention is prepared by appropriately mixing the above components according to known methods. The polymerizable composition used in the present invention may also be prepared by preparing two or more pre-compound solutions and mixing the two or more pre-compound solutions using a mixing device or the like immediately before bulk polymerization to obtain a norbornene-based resin. The pre-compound solutions are prepared by dividing the above components into two or more solutions so that bulk polymerization does not occur with just one solution, but when all solutions are mixed, a polymerizable composition containing each component in a predetermined proportion (total content of each component: 100% by mass) is obtained. Two combinations of such two or more reaction stock solutions are given below, (a) and (b), depending on the type of metathesis polymerization catalyst used.

[0080] (a): As the metathesis polymerization catalyst, one can be used that does not have polymerization reaction activity on its own but exhibits polymerization reaction activity when used in combination with an activator. In this case, a polymerizable composition can be obtained by mixing a pre-compound solution (Solution A) containing a polymerizable monomer containing a norbornene monomer and an activator, and a pre-compound solution (Solution B) containing a polymerizable monomer containing a norbornene monomer and a metathesis polymerization catalyst. Furthermore, a pre-compound solution (Solution C) containing a polymerizable monomer containing a norbornene monomer, but not containing either a metathesis polymerization catalyst or an activator, may also be used in combination.

[0081] (b): When a metathesis polymerization catalyst that has polymerization reaction activity on its own is used, a polymerizable composition can be obtained by mixing a pre-compound solution (i) containing a polymerizable monomer including a norbornene monomer with a pre-compound solution (ii) containing a metathesis polymerization catalyst. In this case, the pre-compound solution (ii) is usually a solution in which the metathesis polymerization catalyst is dissolved or dispersed in a small amount of inert solvent. Examples of such solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and trimethylbenzene; ketones such as methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2-pentanone; cyclic ethers such as tetrahydrofuran; and diethyl ether, dichloromethane, dimethyl sulfoxide, and ethyl acetate.

[0082] Any optional components such as radical generators, diisocyanate compounds, and polyfunctional (meth)acrylate compounds may be included in any of the aforementioned pre-compound solutions, or added in the form of a mixture other than the aforementioned pre-compound solutions.

[0083] Mixing equipment used for mixing the above-mentioned pre-mixed liquids includes, for example, impact mixing equipment commonly used in reaction injection molding, as well as low-pressure mixers such as dynamic mixers and static mixers.

[0084] Furthermore, the metal-resin laminate of the present invention has a shear adhesive force of 10 MPa or more between the metal material and the thermosetting resin. According to the present invention, by having a shear adhesive force of 10 MPa or more between the metal material and the thermosetting resin, the thermosetting resin can be firmly bonded to the surface of the metal material. There are no particular limitations on the method for achieving a shear adhesive force of 10 MPa or more between the metal material and the thermosetting resin, but examples include a method for manufacturing a metal-resin laminate using the method for manufacturing a metal-resin laminate of the present invention, which will be described later.

[0085] In the metal-resin laminate of the present invention, the shear adhesive strength between the metal material and the thermosetting resin may be 10 MPa or more, but is preferably 20 MPa or more, and more preferably 30 MPa or more. The upper limit of the shear adhesive strength is not particularly limited, but is usually 35 MPa or less.

[0086] In this invention, the shear adhesion strength between a metal material and a thermosetting resin can be measured in accordance with SEMI G69-0996. Specifically, for a metal-resin laminate (a metal-resin laminate in which a thermosetting resin is laminated on a portion of the surface of a metal material) formed by laminating a metal material and a thermosetting resin, the shear strength can be measured using a bonding strength evaluation device (bond tester) (SS30WD, manufactured by Nishishin Shoji Co., Ltd.) under the conditions of a shear rate (speed at which shear is applied by moving the shear tool toward the thermosetting resin) of 0.12 mm / min and a distance of 50 μm between the metal material surface and the tip of the shear tool. In this case, such measurements should be performed on five samples, and the average value should be taken as the shear adhesion strength. In particular, the shear adhesion strength measured by this measurement method indicates the adhesion strength when a shear force is applied, and is the adhesion strength required in applications where a shear force is applied, such as in sealing agent applications, and is different from the bonding strength measured by tensile testing. For example, as described in Patent Document 1 (Japanese Patent Publication No. 2010-274600) above, even when the joint strength measured by tensile testing is relatively high, the shear adhesive strength is not necessarily sufficient in practice.

[0087] Furthermore, the metal-resin laminate of the present invention may have another layer (additional layer) in addition to the metal material and the thermosetting resin layer described above. For example, the metal-resin laminate of the present invention may comprise the metal material, the thermosetting resin layer described above, and the additional layer in this order. Examples of such an additional layer include various substrates such as metal, glass, and plastic. The shape of the substrate is not particularly limited and includes films, sheets, plates, panels, trays, rods, boxes, housings, etc.

[0088] Examples of metals include iron and steel, stainless steel, aluminum, copper, nickel, chromium, and their alloys. It can also be applied to composite materials having a metal plating layer on the surface, in which case the plating substrate is not particularly limited as long as plating is possible, and may be various materials such as metal, glass, and plastic.

[0089] Examples of glass include alkali glass, alkali-free glass, and quartz glass. Examples of plastics include polyolefin resins such as polyethylene and polypropylene; polyamide resins such as nylon; aromatic polyester resins such as polyethylene terephthalate (PET); acrylic resins such as polyacrylonitrile (PAN); and polyvinyl resins such as vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PVDC), and polyvinyl chloride (PVC).

[0090] Furthermore, such additional layers may, for example, contain the filler described above, and may be used to laminate onto the metal material described above in a state of being laminated with the layer made of the thermosetting resin described above (for example, a support).

[0091] <Method for manufacturing metal-resin laminates> The metal-resin laminate of the present invention can be manufactured, for example, by the following method for manufacturing the metal-resin laminate of the present invention. In other words, the method for manufacturing a metal-resin laminate of the present invention is A method for producing a metal-resin laminate comprising a metal material and a thermosetting resin, A first step involves preparing a metallic material having an oxide layer with a thickness of 2 nm or more on its surface and a centerline average surface roughness Ra of 1.5 nm or more. A second step involves contacting the metal material prepared in the first step with an acid, The process further comprises a third step in which a thermosetting resin material is brought into contact with the surface of the metal material that has been brought into contact with the acid in the second step, and then cured.

[0092] (1st step) The first step of the manufacturing method of the present invention is to prepare a metallic material having an oxide layer with a thickness of 2 nm or more on its surface and a centerline average surface roughness Ra of 1.5 nm or more.

[0093] There are no particular limitations on the method for obtaining a metallic material having an oxide layer of 2 nm or more thickness on its surface and a center-line average surface roughness Ra of 1.5 nm or more (hereinafter, as appropriate, referred to as "oxide layer-forming metallic material"). However, a preferred method is to oxidize an untreated metallic material that does not have such an oxide layer and center-line average surface roughness Ra in air or in a liquid. Alternatively, any commercially available metallic material may be used as is, as long as it has an oxide layer of 2 nm or more thickness on its surface and a center-line average surface roughness Ra of 1.5 nm or more.

[0094] Methods for oxidizing an untreated metal material in air include heating the untreated metal material in air to achieve the above-mentioned range for the thickness of the oxide layer and the average centerline surface roughness Ra, and are not particularly limited. Examples include heating the untreated metal material in air using a heating means such as an oven or hot plate, or using the heating caused by laser irradiation when cutting the untreated metal material with a laser.

[0095] The heating temperature in the air oxidation method is not particularly limited, but is preferably 80 to 300°C, more preferably 100 to 250°C, and even more preferably 150 to 200°C. The heating time is preferably 10 seconds to 3 hours, more preferably 30 seconds to 1 hour, and even more preferably 60 seconds to 1 hour. In the method utilizing heating by laser irradiation, the temperature of the metal material after the temperature rise due to laser irradiation should be within the above range, and the laser irradiation time should also be within the above range.

[0096] Alternatively, while not particularly limited, a method for oxidizing an untreated metal material in a solution is to bring the untreated metal material into contact with a treatment solution containing an oxidizing agent. Examples of methods for bringing an untreated metal material into contact with a treatment solution containing an oxidizing agent include immersing the untreated metal material in a treatment solution containing an oxidizing agent, or applying a treatment solution containing an oxidizing agent to the surface of the untreated metal material.

[0097] The oxidizing agent is not particularly limited, but for example, sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate, etc. can be used, and these can be used in aqueous solution. In addition, various additives (for example, phosphates such as trisodium phosphate dodecahydrate) and surface-active molecules may be added to the treatment solution containing the oxidizing agent. Examples of surface-active molecules include porphyrin, macro-ring porphyrin, expanded porphyrin, ring-contracted porphyrin, linear porphyrin polymer, porphyrin sandwich coordination complex, porphyrin sequence, silane, tetraorgano-silane, aminoethyl-aminopropyl-trimethoxysilane, (3-aminopropyl)trimethoxysilane, (1-[3-(trimethoxysilyl)propyl]urea)((l-[3-(Trimethoxysilyl)propyl]urea)), (3-aminopropyl)triethoxysilane, ((3-glycidyloxypropyl)trimethoxy Examples include silane, (3-chloropropyl)trimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane, dimethyldichlorosilane, 3-(trimethoxysilyl)propyl methacrylate, ethyltriacetoxysilane, triethoxy(isobutyl)silane, triethoxy(octyl)silane, tris(2-methoxyethoxy)(vinyl)silane, chlorotrimethylsilane, methyltrichlorosilane, silicon tetrachloride, tetraethoxysilane, phenyltrimethoxysilane, chlorotriethoxysilane, ethylene-trimethoxysilane, amines, and sugars.

[0098] The treatment conditions in the liquid oxidation method are not particularly limited, but the temperature of the treatment solution containing the oxidizing agent is preferably 40 to 95°C, more preferably 45 to 80°C, and the reaction time is preferably 0.5 to 30 minutes, more preferably 1 to 10 minutes.

[0099] In the first step, the thickness of the oxide layer formed on the surface of the oxide layer-forming metal material may be 2 nm or more, but from the viewpoint of making the bond between the metal material and the thermosetting resin in the resulting metal-resin laminate stronger, it is preferably 10 nm or more, more preferably 20 nm or more, particularly preferably 30 nm or more, even more preferably 40 nm or more, and even more preferably 50 nm or more, with an upper limit of usually 300 nm. In addition, the centerline average surface roughness Ra of the oxide layer-forming metal material prepared in the first step may be 1.5 nm or more, but from the viewpoint of making the bond between the metal material and the thermosetting resin in the resulting metal-resin laminate stronger, it is preferably 2.5 nm or more, more preferably 5 nm or more, preferably 30 nm or less, and even more preferably 20 nm or less. In addition, the oxide layer-forming metal material prepared in the first step may have a center-line average surface roughness Ra within the above range, but from the viewpoint of making the bond between the metal material and the thermosetting resin in the resulting metal-resin laminate stronger, it is preferable that the ten-point average surface roughness Rz be 2 nm or more, more preferably 40 nm or more, particularly preferably 50 nm or more, preferably 150 nm or less, and more preferably 100 nm or less.

[0100] As a method for measuring the thickness of the oxide layer, an X-ray photoelectron spectrometer (for example, product name "JPS-9200S," manufactured by JEOL Ltd.) is used to analyze carbon atoms (C), oxygen atoms (O), and metal atoms (copper atoms (Cu) if the metal material is copper). The depth of the oxygen atoms is determined as the distance (nm) in terms of SiO2, and this can be measured as the thickness of the oxide layer.

[0101] Furthermore, the centerline-average surface roughness Ra and the ten-point-average surface roughness Rz of oxide-forming metal materials can be measured by using a scanning probe microscope (for example, product name "SPM9700," manufactured by Shimadzu Corporation) in contact mode and observing the surface of the oxide-forming metal material in a scanning area of ​​1 μm square.

[0102] Furthermore, in the first step, when obtaining an oxide layer-forming metal material by oxidizing an untreated metal material in air or in liquid, the untreated metal material may be degreased before performing the air or liquid oxidation. Examples of degreasing methods include alkaline degreasing, solvent degreasing, emulsion degreasing, electrolytic degreasing, or mechanical degreasing, but alkaline degreasing using sodium hydroxide, potassium hydroxide, etc., and solvent degreasing using acetone, etc., are preferred.

[0103] Furthermore, since the untreated metal material used in the first step usually has an oxide layer formed by spontaneous oxidation, when obtaining an oxide layer-forming metal material by oxidizing the untreated metal material in the first step using air oxidation or liquid oxidation, it is also possible to remove the oxide layer formed by spontaneous oxidation beforehand, and then use the untreated metal material from which the oxide layer formed by spontaneous oxidation has been removed to obtain an oxide layer-forming metal material by oxidizing it in air or liquid. For example, one method for removing the oxide layer formed by spontaneous oxidation is to contact the surface of the untreated metal material with an acid such as sulfuric acid, hydrochloric acid, and nitric acid, and it is preferable to wash the untreated metal material in an aqueous solution containing an acid such as sulfuric acid, hydrochloric acid, and nitric acid (acid washing). In addition, after such acid washing, a degreasing treatment may be performed as needed, and the above-mentioned method is an example of a degreasing treatment.

[0104] (2nd process) The second step of the manufacturing method of the present invention is to contact the oxide layer-forming metal material prepared in the first step described above with an acid. In the second step, by contacting the oxide layer-forming metal material with an acid, the oxide layer formed on the surface of the oxide layer-forming metal material is removed, thereby treating the surface of the metal material.

[0105] In particular, the oxide layer-forming metal material prepared in the first step has an oxide layer with a thickness of 2 nm or more on its surface and a center-line average surface roughness Ra of 1.5 nm or more. According to the inventors' knowledge, when the oxide layer is removed from such an oxide layer-forming metal material having an oxide layer and a center-line average surface roughness Ra, the exposed metal material surface has a surface condition suitable for bonding with a thermosetting resin (appropriately roughened).

[0106] More specifically, according to the second step, the centerline average surface roughness Ra of the metal material after acid treatment (metal material from which the oxide layer has been removed) can be roughened to preferably 5 nm or more, more preferably 5 to 100 nm, even more preferably 5 to 50 nm, even more preferably 5 to 30 nm, and particularly preferably 8 to 27 nm. Then, according to the manufacturing method of the present invention, by laminating a thermosetting resin onto a metal material having such a surface state, a metal-resin laminate can be obtained in which the thermosetting resin is firmly bonded to the surface of the metal material. In the second step, the centerline average surface roughness Ra of the metal material after acid treatment is sufficient to be within the above range, but the ten-point average surface roughness Rz is preferably 20 nm or more, more preferably 30 to 300 nm, even more preferably 40 to 200 nm, and even more preferably 55 to 180 nm.

[0107] In the second step, the method for contacting the oxide layer-forming metal material with an acid is not particularly limited, as long as it can remove the oxide layer formed on the surface of the oxide layer-forming metal material. However, a preferred method is to wash the oxide layer-forming metal material in an aqueous solution containing an acid (acid washing). Examples of acids include sulfuric acid, hydrochloric acid, and nitric acid.

[0108] The concentration of the acid in the aqueous solution containing the acid used for acid cleaning is not particularly limited, but should be such that the oxide layer can be removed without corroding the metal material. Preferably, it is 5 to 30% by mass, more preferably 5 to 10% by mass. The temperature of the aqueous solution containing the acid when performing acid cleaning is preferably 0 to 60°C, more preferably 20 to 40°C, and the acid cleaning time is preferably 1 to 10 minutes, more preferably 1 to 5 minutes.

[0109] Furthermore, when contacting the oxide layer-forming metal material with acid in the second step, the oxide layer-forming metal material may be degreased before contacting it with acid. Examples of degreasing methods include alkaline degreasing, solvent degreasing, emulsion degreasing, electrolytic degreasing, or mechanical degreasing, but alkaline degreasing using sodium hydroxide, potassium hydroxide, etc., and solvent degreasing using acetone, etc., are preferred.

[0110] (3rd step) The third step of the manufacturing method of the present invention is to bring a thermosetting resin material into contact with the surface of a metal material that has been brought into contact with an acid in the second step described above, and to cure it. In the third step, the thermosetting resin material (a resin material before curing for forming a thermosetting resin) is brought into contact with the surface of a metal material (hereinafter, as appropriate, referred to as the "acid-treated metal material") obtained in the second step, which has had its surface exposed by contact with an acid, and is cured to obtain a metal-resin laminate formed by laminating a metal material and a thermosetting resin (a cured product of the thermosetting resin material).

[0111] While there are no particular limitations on the method of curing a thermosetting resin material by bringing it into contact with the surface of an acid-treated metal material, from the viewpoint of productivity, a preferred method is to place the acid-treated metal material in a mold having a desired shape, and then inject the thermosetting resin material into the mold containing the acid-treated metal material and cure it.

[0112] For example, when the thermosetting resin in a metal-resin laminate, which is formed by laminating a metal material and a thermosetting resin, is composed of a norbornene-based resin, the polymerizable composition containing the norbornene-based monomer described above is injected into a mold in which the metal material has been placed after acid treatment, and cured by bulk polymerization on the surface of the metal material after acid treatment, thereby obtaining a metal-resin laminate formed by laminating a metal material and a norbornene-based resin. In this case, unlike the technique described in Patent Document 1, the injection of the polymerizable composition into the mold can be easily performed at room temperature and atmospheric pressure. In this case, the polymerizable composition containing the norbornene-based monomer may be divided into two or more pre-mixing liquids, and the two or more pre-mixing liquids may be introduced separately into a collision mixing device, instantaneously mixed with a mixing head, and injected into the mold in which the metal material has been placed after acid treatment. Furthermore, heating may be performed as necessary when carrying out bulk polymerization.

[0113] Alternatively, when the thermosetting resin in a metal-resin laminate, which is formed by laminating a metal material and a thermosetting resin, is made of epoxy resin, a raw material liquid for forming the epoxy resin (if it consists of two or more raw material liquids, a mixture thereof) is poured into a mold in which the metal material has been placed after acid treatment, and cured by heating as necessary, thereby obtaining a metal-resin laminate formed by laminating a metal material and an epoxy resin.

[0114] In the third step, it is preferable to use a metal material after acid treatment in which an oxide layer is not substantially formed on its surface, but it may also be a metal material in which an oxide layer is formed on part or all of its surface. That is, by using a metal material after acid treatment in which an oxide layer is not substantially formed on its surface, the metal material and the thermosetting resin can be laminated substantially without an oxide layer in between, i.e., laminated by direct bonding. Furthermore, if a metal material after acid treatment in which an oxide layer is formed on part or all of its surface is used, an oxide layer (which varies depending on the type of metal material, but is preferably an oxide layer with a thickness of less than 30 nm) can be interposed between part or all of the metal material and the thermosetting resin.

[0115] Furthermore, the lamination of the additional layer can be carried out by, for example, using a method in which a thermosetting resin material is brought into contact with the surface of an acid-treated metal material and cured, by placing the acid-treated metal material in a mold having a desired shape, injecting the thermosetting resin material into the mold containing the acid-treated metal material, and curing it. In this case, following the injection of the thermosetting resin material, the adherend as described above is placed on the acid-treated metal material via the thermosetting resin material, and then the thermosetting resin material is cured. Alternatively, the thermosetting resin material can be injected to obtain a semi-cured state (so-called B-stage), and then the adherend as described above is placed on the acid-treated metal material via the semi-cured thermosetting resin material, and the material is fully cured.

[0116] The metal-resin laminate obtained in this manner has a thermosetting resin firmly bonded to the surface of a metal material. More specifically, it has high bonding strength when shear force is applied, and therefore can be suitably applied to a wide range of applications where integration of metal material and resin is required. In particular, because the bond between the metal material and the thermosetting resin is strong, the metal-resin laminate of the present invention can achieve high reliability when used in various applications. [Examples]

[0117] The present invention will be described below based on examples, but the present invention is not limited in any way by these examples. Unless otherwise specified, "parts" and "%" are based on mass.

[0118] <Centerline mean surface roughness Ra, ten-point mean surface roughness Rz> Copper plates with a copper oxide layer (oxide layer-forming metal material) and copper plates after sulfuric acid washing (acid-treated metal material) were observed and measured using a scanning probe microscope (product name "SPM9700", manufactured by Shimadzu Corporation) in contact mode, with a scanning area of ​​1 μm square.

[0119] <Thickness of the copper oxide layer (oxide layer)> For copper plates having a copper oxide layer (oxide layer-forming metal material) and copper plates after sulfuric acid washing (acid-treated metal material), carbon atoms (C), oxygen atoms (O), and copper atoms (Cu) were analyzed using an X-ray photoelectron spectrometer (product name "JPS-9200S", manufactured by JEOL Ltd.). The depth of the oxygen atoms was determined as the distance (nm) in terms of SiO2, and this was defined as the thickness of the copper oxide layer (oxide layer).

[0120] <Shear bonding strength between copper plate (metal material) and thermosetting resin> The shear bonding strength between copper plates (metal material) and thermosetting resin was measured in accordance with SEMI G69-0996. Specifically, for metal-resin laminate samples, the bond strength evaluation device (bond tester) (SS30WD, manufactured by Nishishin Shoji Co., Ltd.) was used to measure the shear rate (speed at which the shear tool is moved toward the thermosetting resin to apply shear) at 0.12 mm / min and the distance between the metal material surface and the tip of the shear tool was 50 μm. This measurement was performed on five samples, and the average value was defined as the shear bonding strength.

[0121] <Example 1> A 1mm thick, 10mm square copper plate (product name "C1100", manufactured by Mitsubishi Materials Corporation) was degreased with acetone by immersion in acetone for 1 minute at room temperature. Afterward, it was washed with deionized water and dried under vacuum for 1 minute. Next, the degreased copper plate was placed on a hot plate at 190°C and heated in air for 1 minute to oxidize it, forming a copper oxide layer on the surface. This resulted in a copper plate with a copper oxide layer (oxide layer-forming metal material). The obtained copper plate with a copper oxide layer (oxide layer-forming metal material) was then measured according to the above method, including the centerline average surface roughness Ra, the ten-point average surface roughness Rz, and the thickness of the copper oxide layer. The measurement results are shown in Table 1.

[0122] Next, the copper plate having the obtained copper oxide layer (oxide layer forming metal material) was degreased with acetone by immersing it in acetone for 1 minute at room temperature, washed with deionized water, and dried under vacuum for 1 minute. Then, the copper plate having the copper oxide layer that had been degreased with acetone was degreased with alkali by immersing it in a 1% Shikaclean LX-IIII aqueous solution (1% alkaline aqueous solution) at room temperature for 5 minutes, washed with deionized water, and dried under vacuum for 1 minute.

[0123] Next, a copper plate having an alkali-degreased copper oxide layer (oxide layer-forming metal material) was immersed in a 10% sulfuric acid aqueous solution for 5 minutes to remove the copper oxide layer, followed by washing with deionized water and drying under vacuum for 1 minute to obtain a sulfuric acid-washed copper plate (acid-treated metal material). The obtained sulfuric acid-washed copper plate (acid-treated metal material) was measured according to the above method for the centerline average surface roughness Ra, the ten-point average surface roughness Rz, and the thickness of the copper oxide layer (oxide layer). The measurement results are shown in Table 1.

[0124] Then, a pudding cup-shaped mold with a base diameter of 3.53 mm, a top diameter of 3.00 mm, and a height of 3.00 mm was placed on the copper plate (metal material after acid treatment) obtained above after sulfuric acid washing, and a monomer solution consisting of 95.3 parts RIM monomer (manufactured by Nippon Zeon Co., Ltd.), 2.2 parts dicyclopentadiene monoepoxide (DCPME), 1.7 parts bicycloheptenylethyltrimethoxysilane, and 0.8 parts phenoxyethylene glycol methacrylate was added, along with 0.0 parts of the ruthenium catalyst (Zhan1N) shown in formula (7) below. A polymerizable composition was prepared by dissolving 3 parts of 0.3 parts of 2,6-di-t-butyl-p-cresol (BHT, an antioxidant), and 30 parts of triphenylphosphine in 30 parts of cyclopentanone to form a metathesis polymerization catalyst. This catalyst was mixed at room temperature in a monomer solution:catalyst solution ratio of 100:3.5. The polymerizable composition was introduced into a mold at room temperature and pressure, left to stand at room temperature for 30 minutes, and then heated in an oven at 200°C for 1 hour to obtain a metal-resin laminate of a copper plate (metal material) and norbornene-based resin, which had a pudding cup-shaped layer made of norbornene-based resin. The shear adhesion strength between the copper plate (metal material) and the thermosetting resin (norbornene-based resin) was then measured using the obtained metal-resin laminate according to the method described above. The measurement results are shown in Table 1. The composition of the above RIM monomer consists of approximately 90 parts of dicyclopentadiene and approximately 10 parts of tricyclopentadiene. [ka] (In the formula, Mes represents the mesityl group.)

[0125] <Example 2> Except for changing the heating time in air to 5 minutes using a hot plate heated to 190°C, a copper plate with a copper oxide layer (oxide layer forming metal material), a copper plate after sulfuric acid washing (acid-treated metal material), and a metal-resin laminate were obtained in the same manner as in Example 1 and evaluated in the same way. The results are shown in Table 1.

[0126] <Example 3> Except for changing the heating time in air to 60 minutes using a hot plate heated to 190°C, a copper plate with a copper oxide layer (oxide layer forming metal material), a copper plate after sulfuric acid washing (acid-treated metal material), and a metal-resin laminate were obtained in the same manner as in Example 1 and evaluated in the same way. The results are shown in Table 1.

[0127] <Example 4> Except for using epoxy resin as the thermosetting resin material, copper plates having a copper oxide layer (oxide layer forming metal material), copper plates after sulfuric acid washing (acid-treated metal material), and metal-resin laminates were obtained in the same manner as in Example 3 and evaluated in the same way. The results are shown in Table 1. In Example 4, the epoxy resin used was product name "jER828" (manufactured by Mitsubishi Chemical Corporation) as the main component and "LV11" (manufactured by Mitsubishi Chemical Corporation) as the curing agent. A polymerizable composition was prepared by mixing the main component and curing agent in a mass ratio of 100:33 at room temperature. This composition was injected into a mold at room temperature and atmospheric pressure, left to stand at room temperature for 24 hours, and then heated in an oven at 80°C for 3 hours to obtain a metal-resin laminate.

[0128] <Comparative Example 1> Using the same copper plate as in Example 1, acetone degreasing and alkaline cleaning were performed in the same manner as in Example 1, except that heating in air using a hot plate at a temperature of 190°C and sulfuric acid cleaning were not performed. Using the copper plate in its state with a native oxide layer formed, a metal-resin laminate was obtained by laminating it with a norbornene-based resin, and the evaluation was performed in the same manner. The results are shown in Table 1.

[0129] <Comparative Example 2> Using the same copper plate as in Example 1, a copper plate after sulfuric acid washing (acid-treated metal material) and a metal-resin laminate were obtained in the same manner as in Example 1, except that heating in air was not performed using a hot plate heated to 190°C. The results are shown in Table 1.

[0130] <Comparative Example 3> A copper plate having a copper oxide layer (oxide layer forming metal material) was obtained in the same manner as in Example 1. After acetone degreasing and alkaline cleaning in the same manner as in Example 1, the copper plate, with the copper oxide layer still formed, was used without sulfuric acid cleaning and laminated with a norbornene-based resin in the same manner as in Example 1 to obtain a metal-resin laminate, which was evaluated in the same manner. The results are shown in Table 1.

[0131] <Comparative Example 4> Except for changing the heating time in air to 5 minutes using a hot plate heated to 190°C, a copper plate having a copper oxide layer (oxide layer forming metal material) was obtained in the same manner as in Comparative Example 3. After acetone degreasing and alkaline cleaning, the copper plate, with the copper oxide layer still formed, was used without sulfuric acid cleaning and laminated with norbornene-based resin to obtain a metal-resin laminate, which was evaluated in the same manner. The results are shown in Table 1.

[0132] <Comparative Example 5> Except for changing the heating time in air to 60 minutes using a hot plate heated to 190°C, a copper plate having a copper oxide layer (oxide layer forming metal material) was obtained in the same manner as in Comparative Example 3. After acetone degreasing and alkaline cleaning, the copper plate, with the copper oxide layer still formed, was used without sulfuric acid cleaning and laminated with norbornene-based resin to obtain a metal-resin laminate, which was evaluated in the same manner. The results are shown in Table 1.

[0133] <Comparative Example 6> Except for using epoxy resin as the thermosetting resin material, a copper plate having a copper oxide layer (oxide layer forming metal material) was obtained in the same manner as in Comparative Example 5. After acetone degreasing and alkaline cleaning, the copper oxide layer was used in its formed state without sulfuric acid cleaning, and a metal-resin laminate was obtained by laminating it with epoxy resin in the same manner as in Example 4, and evaluated in the same manner. The results are shown in Table 1.

[0134] [Table 1]

[0135] As shown in Table 1, according to the present invention, a metal-resin laminate was obtained in which the shear adhesive force between the metal material and the thermosetting resin was 10 MPa or more, and the thermosetting resin was firmly bonded to the surface of the metal material (Examples 1-4). In particular, by comparing the results of Example 3 and Comparative Example 5 with those of Example 4 and Comparative Example 6, it can be said that when norbornene-based resin is used as the thermosetting resin, the improvement in shear adhesion strength is greater compared to when epoxy resin is used.

Claims

1. A metal-resin laminate formed by laminating a metal material and a thermosetting resin, The thermosetting resin is a polymer obtained by bulk polymerization of a polymerizable composition containing norbornene monomers. A metal-resin laminate having a shear adhesion strength of 10 MPa or more, as measured in accordance with SEMI G69-0996, between the metal material and the thermosetting resin.

2. The metal-resin laminate according to claim 1, wherein the metal material and the thermosetting resin are bonded directly or laminated via an oxide layer.

3. The metal-resin laminate according to claim 1 or 2, wherein the metal material comprises at least one metal selected from the group consisting of copper, nickel, aluminum, chromium, and iron.

4. The metal-resin laminate according to claim 3, wherein the metal material is copper or a copper alloy.

5. The metal-resin laminate according to claim 1 or 2, further comprising a layer other than the layer made of the metal material and the thermosetting resin.

6. A method for producing a metal-resin laminate comprising a metal material and a thermosetting resin, A first step is to prepare a metallic material having an oxide layer with a thickness of 2 nm or more on its surface and a centerline average surface roughness Ra of 1.5 nm or more. A second step involves contacting the metal material prepared in the first step with an acid, A method for manufacturing a metal-resin laminate, comprising: a third step of contacting a thermosetting resin material with the surface of the metal material that has been contacted with an acid in the second step, and curing it.

7. The method for producing a metal-resin laminate according to claim 6, wherein the first step is to obtain a metal material having an oxide layer of 2 nm or more thickness on its surface and a center-line average surface roughness Ra of 1.5 nm or more by oxidizing the metal material in air or in liquid.

8. The method for manufacturing a metal-resin laminate according to claim 6 or 7, wherein the metal material comprises at least one metal selected from the group consisting of copper, nickel, aluminum, chromium, and iron.

9. The method for manufacturing a metal-resin laminate according to claim 8, wherein the metal material is copper or a copper alloy.

10. The method for producing a metal resin laminate according to claim 6 or 7, wherein the thermosetting resin material is a polymerizable composition containing a norbornene monomer.

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