Water-based surface treatment agents and laminates

Abstract

This invention provides a surface treatment agent that can achieve excellent adhesion between copper foil and resin film without roughening the surface of copper foil. An aqueous surface treatment agent for surface treatment of metals comprises a nitrogen-containing silane coupling agent and an epoxy compound, wherein the epoxy compound has two or more epoxy groups in one molecule, and the mass ratio (Ms / Me) of the nitrogen-containing silane coupling agent to the mass ratio (Ms / Me) of the epoxy compound is 3 or more.

Description

Technical Field

[0001] The present invention relates to a water-based surface treatment agent and a laminate. Prior Art

[0002] Currently, with the widespread adoption of fifth-generation mobile communication systems, devices utilizing high-frequency radio waves are being developed, leading to an increasing demand for printed wiring boards capable of transmitting high-frequency signals.

[0003] Such printed wiring boards are made of copper foils such as rolled copper foil and electrolytic copper foil. Conventionally, copper foils have been roughened to improve adhesion to resin films.

[0004] However, roughening the surface of copper foil can lead to signal attenuation and increased transmission losses during high-frequency signal transmission.

[0005] In contrast, if the adhesion between the copper foil and the resin film can be ensured without roughening the surface of the copper foil, the transmission loss caused by the roughening treatment can be reduced, and the manufacturing steps can be simplified and the cost can be reduced.

[0006] In contrast, for example, Patent Document 1 discloses a copper surface treatment agent that can be used to smooth the copper surface without roughening the copper surface by etching or other means and that can maintain adhesion between the copper and an insulating material such as a resin. The copper surface treatment agent contains a tin compound, a complexing agent, and a water-soluble polymer or a water-dispersible polymer, wherein the water-soluble polymer or the water-dispersible polymer has at least one functional group selected from the group consisting of an amino group, an epoxy group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, an imine group, and a silanol group. [Prior art literature] [Patent Document]

[0007] [Patent Document 1] International Publication No. 2010 / 010716 Summary of the Invention

[0008] [Problems to be solved by the invention]

[0009] However, it was found that there is room for further improvement in the adhesion between the copper foil and the resin film.

[0010] Therefore, an object of the present invention is to provide a surface treatment agent that can achieve excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil.

[0011] Another object of the present invention is to provide a laminate having a metal film and a film of a water-based surface treatment agent that can achieve excellent adhesion with a resin film. [Methods to solve the problem]

[0012] The aqueous surface treatment agent of the present invention is an aqueous surface treatment agent for metal surface treatment, and the aqueous surface treatment agent comprises Nitrogen-containing silane coupling agent, and Epoxides, The epoxy compound has two or more epoxy groups in one molecule. The ratio of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound (Ms / Me) is greater than or equal to 3. This allows excellent adhesion between the copper foil and the resin film to be achieved without roughening the surface of the copper foil.

[0013] In one embodiment of the water-based surface treatment agent of the present invention, the epoxy equivalent of the epoxy compound is 90 g / equivalent to 180 g / equivalent.

[0014] In one embodiment of the aqueous surface treatment agent of the present invention, the epoxy compound is an aliphatic glycidyl ether type epoxy compound.

[0015] In one embodiment of the water-based surface treatment agent of the present invention, the nitrogen-containing silane coupling agent has one or more selected from the group consisting of an amine group and an imine group.

[0016] In one embodiment of the aqueous surface treatment agent of the present invention, the ratio (Ms / Me) is 3 to 200.

[0017] The layered product of the present invention is a layered product having Metal, and A film of any of the above-mentioned aqueous surface treatment agents.

[0018] In one embodiment of the laminate of the present invention, the metal is copper or a copper alloy.

[0019] In one embodiment of the laminate of the present invention, the laminate has The metal, The membrane, and Resin film.

[0020] In one embodiment of the laminated body of the present invention, the laminated body is a flexible printed wiring board. [Effects of the Invention]

[0021] The present invention provides a surface treatment agent capable of achieving excellent adhesion between copper foil and a resin film without roughening the copper foil surface. Furthermore, the present invention provides a laminate comprising a metal capable of achieving excellent adhesion to a resin film and a film comprising a water-based surface treatment agent. Simple diagram description

[0022] none Implementation Method

[0023] The following describes embodiments of the present invention. These descriptions are for the purpose of illustrating the present invention and do not limit the present invention in any way.

[0024] In the present invention, two or more embodiments can be arbitrarily combined.

[0025] In the present invention, the term "solid content" is a concept that includes solid content and non-volatile content.

[0026] Unless otherwise specified, the materials, components, compounds, resins, bases, and solvents described in this specification may be used alone or in combination of two or more.

[0027] In this specification, unless otherwise specified, numerical ranges are intended to include both the upper and lower limits of the range. For example, 90 g / equivalent to 180 g / equivalent refers to a range of 90 g / equivalent or more and 180 g / equivalent or less.

[0028] In this specification, the nitrogen-containing silane coupling agent and the epoxy compound may be referred to as component (A) and component (B), respectively.

[0029] Water-based surface treatment agent A water-based surface treatment agent is a water-based surface treatment agent used in the surface treatment of metals of the present invention, comprising Nitrogen-containing silane coupling agent, and Epoxides, The epoxy compound has two or more epoxy groups in one molecule. The ratio of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound (Ms / Me) is 3 or more.

[0030] Hereinafter, each component of the aqueous surface treatment agent of the present invention will be described with examples.

[0031] Component (A): Nitrogen-containing silane coupling agent As the component (A), a known silane coupling agent containing nitrogen can be used.

[0032] Examples of nitrogen-containing groups contained in component (A) include an amine group (-NH₂), an imine group (=NR, -N(R)-), a quaternary ammonium group (-N+R₃), a urea group (-NHCONH₂), an isocyanate group (-N=C=O), and an isocyanurate group. In one embodiment, component (A) has one or more groups selected from the group consisting of an amine group, an imine group, a quaternary ammonium group, a urea group, an isocyanate group, and an isocyanurate group. In another embodiment, component (A) has one or more groups selected from the group consisting of an amine group and an imine group.

[0033] Component (A) may have an aromatic ring containing nitrogen. Component (A) may have, for example, residues of pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furazine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, azobenzene, diazonone, or triazonone; residues of indole, isoindole, indazole, purine, quinoline, isoquinoline, or benzotriazole; residues of carbazole, acridine, β-carboline, acridone, phenazine, phenanthroline, phenanthroline, phenathiazine, phenoxazine, or phenanthroline; residues of quinoline, quinindoline, or azaindoline.

[0034] The component (A) may have an aromatic ring containing nitrogen in addition to a group other than the aromatic ring containing nitrogen.

[0035] Examples of the component (A) include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, and the like. Other examples include X-12-1290 (containing an isocyanurate group), X-12-1214A (containing a benzotriazole group), and X-12-1172ES (containing an imine group) manufactured by Shin-Etsu Chemical Co., Ltd., and VD-5 (containing a triazine ring) manufactured by Shikoku Chemicals Co., Ltd.

[0036] In a preferred embodiment, component (A) is one or more selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

[0037] The content of component (A) in the aqueous surface treatment agent can be adjusted as appropriate, as long as the ratio (Ms / Me) of the mass of component (A) Ms to the mass of component (B) Me is 3 or greater. For example, the content of component (A) can be 75.0% to 99.5% by mass relative to the total solids content of the aqueous surface treatment agent. In one embodiment, the content of component (A) is 75.0% by mass or greater, 80.0% by mass or greater, 85.0% by mass or greater, 90.0% by mass or greater, 95.0% by mass or greater, or 98.0% by mass or greater, relative to the total solids content of the aqueous surface treatment agent. In another embodiment, the content of component (A) is 99.5% or less, 98.0% or less, 95.0% or less, 90.0% or less, 85.0% or less, or 80.0% or less, relative to the total solids content of the aqueous surface treatment agent.

[0038] In one embodiment, the total concentration of components (A) and (B) relative to the total aqueous surface treatment agent is 100 ppm to 30,000 ppm. In another embodiment, the total concentration of components (A) and (B) relative to the total aqueous surface treatment agent is 100 ppm or higher, 500 ppm or higher, 1,000 ppm or higher, 5,000 ppm or higher, 10,000 ppm or higher, 15,000 ppm or higher, 20,000 ppm or higher, or 25,000 ppm or higher. In yet another embodiment, the total concentration of components (A) and (B) relative to the total aqueous surface treatment agent is 30,000 ppm or lower, 25,000 ppm or lower, 20,000 ppm or lower, 15,000 ppm or lower, 10,000 ppm or lower, 5,000 ppm or lower, 1,000 ppm or lower, or 500 ppm or lower.

[0039] In the aqueous surface treatment agent of the present invention, the ratio (Ms / Me) of the mass Ms of component (A) to the mass Me of component (B) is 3 or greater. A ratio (Ms / Me) of 3 or greater improves the adhesion between the metal and resin films of the film of the aqueous surface treatment agent. In one embodiment, the ratio (Ms / Me) is 3 or greater, 4 or greater, 5 or greater, 10 or greater, 20 or greater, 30 or greater, 40 or greater, 50 or greater, 60 or greater, 70 or greater, 80 or greater, 90 or greater, 100 or greater, 150 or greater, 200 or greater, or 300 or greater. In another embodiment, the ratio (Ms / Me) is 500 or less, 400 or less, 300 or less, 200 or less, 150 or less, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, 40 or less, 30 or less, 20 or less, 10 or less, or 5 or less. In another embodiment, the ratio (Ms / Me) is 3-200.

[0040] Component (B): Epoxy compound As component (B), a known epoxy compound having two or more epoxy groups in one molecule can be used. Examples of component (B) include aliphatic glycidyl ether epoxy compounds, aromatic glycidyl ether epoxy compounds, and alicyclic epoxy compounds.

[0041] In this specification, an aliphatic glycidyl ether epoxy compound refers to an aliphatic compound having two or more glycidyl ether groups. In this specification, an aromatic glycidyl ether epoxy compound refers to an aromatic compound having two or more glycidyl ether groups. In this specification, an alicyclic epoxy compound refers to an alicyclic compound having two or more epoxy groups.

[0042] In one embodiment of the aqueous surface treatment agent of the present invention, the epoxy compound is an aliphatic glycidyl ether type epoxy compound.

[0043] One molecule of the component (B) has two or more epoxy groups, for example, two, three, four, or five.

[0044] Examples of the component (B) include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, resorcinol glycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, diglycidyl phthalate, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane diglycidyl ether, dicyclopentadiene diepoxide, and bicyclononadiene diepoxide; glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and diglycerol triglycidyl ether having three epoxy groups; and sorbitol tetraglycidyl ether and polyglycerol polyglycidyl ether having four epoxy groups. Other examples include Denacol EX-991L, Denacol EX-521, and Denacol EX-1610 manufactured by Nagase Chemtex.

[0045] In a preferred embodiment, component (B) is one or more selected from the group consisting of sorbitol tetraglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, ethylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether.

[0046] The molecular weight of component (B) can be, for example, 170 to 750. In one embodiment, the molecular weight of component (B) is 170 or greater, 200 or greater, 250 or greater, 300 or greater, 350 or greater, 400 or greater, 450 or greater, 500 or greater, 550 or greater, 600 or greater, 650 or greater, or 700 or greater. In another embodiment, the molecular weight of component (B) is 750 or less, 700 or less, 650 or less, 600 or less, 550 or less, 500 or less, 450 or less, 400 or less, 350 or less, 300 or less, 250 or less, or 200 or less.

[0047] The epoxy equivalent of component (B) can be, for example, 90 g / equivalent to 600 g / equivalent. In one embodiment, the epoxy equivalent of component (B) is 90 g / equivalent or greater, 100 g / equivalent or greater, 150 g / equivalent or greater, 200 g / equivalent or greater, 250 g / equivalent or greater, 300 g / equivalent or greater, 350 g / equivalent or greater, 400 g / equivalent or greater, 450 g / equivalent or greater, 500 g / equivalent or greater, or 550 g / equivalent or greater. In another embodiment, the epoxy equivalent weight of component (B) is 600 g / equivalent or less, 550 g / equivalent or less, 500 g / equivalent or less, 450 g / equivalent or less, 400 g / equivalent or less, 350 g / equivalent or less, 300 g / equivalent or less, 250 g / equivalent or less, 200 g / equivalent or less, 180 g / equivalent or less, 150 g / equivalent or less, or 100 g / equivalent or less. In yet another embodiment, the epoxy equivalent weight of component (B) is 90 g / equivalent to 180 g / equivalent.

[0048] The content of component (B) in the aqueous surface treatment agent can be adjusted as appropriate, as long as the ratio (Ms / Me) of the mass of component (A) Ms to the mass of component (B) Me is 3 or greater. For example, the content of component (B) can be 0.5% to 25.0% by mass relative to the total solids content of the aqueous surface treatment agent. In one embodiment, the content of component (B) is 0.5% by mass or greater, 1.0% by mass or greater, 5.0% by mass or greater, 10.0% by mass or greater, 15.0% by mass or greater, or 20.0% by mass or greater, relative to the total solids content of the aqueous surface treatment agent. In another embodiment, the content of component (B) is 25.0% by mass or less, 20.0% by mass or less, 15.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less, relative to the total solids content of the aqueous surface treatment agent.

[0049] The aqueous surface treatment agent of the present invention may contain, in addition to components (A) and (B), components used in known surface treatment agents. For example, the aqueous surface treatment agent may contain a solvent such as water, alcohol, or acetone; a water-soluble polymer, a water-dispersible polymer, a resin, a pH adjuster, a rust inhibitor, an acid, an alkali, a surface conditioner, a defoaming agent, condensates of components (A) and condensates of component (A) with other components, and the like.

[0050] ·Solvent To adjust the solid content concentration or drying rate, the aqueous surface treatment agent of the present invention may further contain an organic solvent miscible with water, as needed. Examples of organic solvent miscible with water include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, isopropanol, and 1-methoxy-2-propanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone.

[0051] As water, known water can be used, and examples thereof include distilled water, purified water, deionized water, and tap water.

[0052] Preparation method of water-based surface treatment agent The preparation method of the water-based surface treatment agent is not particularly limited, as long as the mass ratio (Ms / Me) of component (A) to component (B) is 3 or greater. In addition to components (A) and (B), other components such as a solvent may be mixed in any order.

[0053] ·Laminated body The laminate of the present invention is a laminate having a metal and a film of a water-based surface treatment agent in this order. This allows for excellent adhesion between the metal and the resin film through the film of the water-based surface treatment agent.

[0054] ·Metal The metal is not particularly limited as long as it requires adhesion to the resin film, and a known metal can be used. Examples thereof include copper, nickel, and aluminum.

[0055] Examples of copper include rolled copper foil and electrolytic copper foil. Furthermore, copper may be alloyed with tin, zinc, nickel, arsenic, silicon, titanium, or chromium. In one embodiment, the metal of the laminate is copper or a copper alloy. In another embodiment, the metal of the laminate is at least one selected from the group consisting of rolled copper foil and electrolytic copper foil.

[0056] The metal in the laminate of the present invention may be either roughened or unroughened. The laminate of the present invention includes a film of the aqueous surface treatment agent of the present invention, and thus, even unroughened metal can achieve excellent adhesion to the resin film. In one embodiment, the metal in the laminate is unroughened metal.

[0057] The surface roughness of a single metal surface can be, for example, Rz (ten-point average roughness) of 10 μm or less, 5 μm or less, 3 μm or less, 2 μm or less, 1.5 μm or less, 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, 1.0 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, or 0.1 μm or less. Furthermore, the surface roughness of a single metal surface can be, for example, Rz of 0.1 μm or greater. Rz can be measured in accordance with Japanese Industrial Standards (JIS) B 0601 (2013) using a commercially available laser microscope, OPTELICS HYBRID, manufactured by Lasertec.

[0058] The thickness of the metal can be adjusted appropriately, for example, from 1 μm to 200 μm. In one embodiment, the thickness of the metal is 1 μm or greater, 5 μm or greater, 10 μm or greater, 20 μm or greater, 30 μm or greater, 40 μm or greater, 50 μm or greater, 100 μm or greater, or 150 μm or greater. In another embodiment, the thickness of the metal is 200 μm or less, 150 μm or less, 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less.

[0059] ·Water-based surface treatment agent film The film of the aqueous surface treatment agent is a film formed using the aqueous surface treatment agent of the present invention.

[0060] In the laminate, the metal and the film of the water-based surface treatment agent need only be arranged in sequence. The metal and the film of the water-based surface treatment agent may be stacked adjacent to each other, i.e., in direct contact, or may be stacked with another layer or film interposed between them.

[0061] The film of the water-based surface treatment agent only needs to be deposited on at least a portion of at least one side of the metal, and may also be deposited on all of one side or both sides (opposite sides) of the metal.

[0062] In one embodiment of the laminate of the present invention, the laminate includes the metal, the film, and a resin film in this order.

[0063] Resin film The resin film is not particularly limited, and known resin films can be used. Examples of the resin film include polyimide films, modified polyimide (MPI) films, polyamide films, polyester films (such as polyethylene terephthalate films and poly(1,4-cyclohexanedimethylene terephthalate) films) used for printed wiring boards, liquid crystal polymer films, polycarbonate films, cycloolefin polymer films, and fluororesin films.

[0064] The thickness of the resin film can be adjusted appropriately, for example, within a range of 5 μm to 200 μm. In one embodiment, the thickness of the resin film is 5 μm or greater, 10 μm or greater, 15 μm or greater, 20 μm or greater, 25 μm or greater, 30 μm or greater, 35 μm or greater, 40 μm or greater, 45 μm or greater, 50 μm or greater, 100 μm or greater, or 150 μm or greater. In another embodiment, the thickness of the resin film is 200 μm or less, 150 μm or less, 100 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, or 10 μm or less.

[0065] Other layers or membranes Examples of the layer or film that can be disposed between the metal and the film of the aqueous surface treatment agent include a plating layer formed by surface treatment of the metal and a chromate film.

[0066] Examples of the plating layer include Ni plating, Ni—P plating, Ni—Co plating, Ni—Mo plating, Zn plating, Zn—Ni plating, Cu—Zn plating, Cu—Ni plating, and Cu—Ni—Co plating.

[0067] The application of the laminate of the present invention is not particularly limited, and examples thereof include flexible printed wiring boards, home appliances, information terminals, and building materials.

[0068] In one embodiment of the laminated body of the present invention, the laminated body is a flexible printed wiring board.

[0069] ·Method for manufacturing a laminate The method for producing the laminate is not particularly limited as long as a film having a metal and an aqueous surface treatment agent can be laminated in this order, and known methods for producing flexible printed wiring boards can be used. Examples of methods for producing the laminate include the following steps: preparing a metal and an aqueous surface treatment agent; applying the surface treatment agent to at least a portion of at least one side of the metal; and heating or drying the applied surface treatment agent to form a film of the surface treatment agent.

[0070] The method for applying the surface treatment agent is not particularly limited, and a known coating method can be used. Examples of the coating method include dipping, rod coating, roller coating, shower coating, spraying, and brushing.

[0071] The heating or drying temperature of the surface treatment agent is not particularly limited, and is, for example, 50°C to 250°C.

[0072] The heating or drying time of the surface treatment agent is not particularly limited, and is, for example, 2 seconds to 1 hour.

[0073] The thickness of the film is not particularly limited and can be adjusted appropriately. The thickness of the film is, for example, 1 nm to 10 μm in terms of dry film thickness.

[0074] As a manufacturing method for a laminate having a structure of metal / aqueous surface treatment agent film / resin film, for example, the following method can be cited: after forming a laminate of metal / aqueous surface treatment agent film, a resin film is arranged on the film, and then the metal, the aqueous surface treatment agent film, and the resin film are press-bonded.

[0075] The temperature during compression bonding is, for example, 100° C. to 450° C.

[0076] The pressure during compression bonding is, for example, 0.1 MPa to 10 MPa. [Example]

[0077] Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are for the purpose of illustrating the present invention and do not limit the present invention in any way.

[0078] The materials used in the examples are shown below. ·(A)Ingredients A1: 3-Aminopropyltrimethoxysilane, trade name "KBM-903" A2: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, trade name "KBM-603" A3: 3-Aminopropyltriethoxysilane, trade name "KBE-903" A4: N-(2-aminoethyl)-3-aminopropyltriethoxysilane, trade name "KBE-603" A5: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, trade name "KBM-602" A6: N-phenyl-3-aminopropyltrimethoxysilane, trade name "KBM-573" Comparison of silane coupling agents Comparative Silane Coupling Agent 1: Vinyltriethoxysilane, trade name "KBE-1003", represented as "CS1" in the table Comparative Silane Coupling Agent 2: 3-Methacryloyloxypropyltriethoxysilane, trade name "KBE-503", represented as "CS2" in the table A1~A6 and CS1~CS2 are all manufactured by Shin-Etsu Chemical Co., Ltd. (B) ingredient B1: Sorbitol polyglycidyl ether, 4 epoxy groups, epoxy equivalent weight 173 g / equivalent, trade name "Denacol EX-614B" B2: Glycerol polyglycidyl ether, a mixture of 2 and 3 epoxy groups, epoxy equivalent weight 141 g / equivalent, trade name "Denacol EX-313" B3: Sorbitol polyglycidyl ether, 4 epoxy groups, epoxy equivalent weight 191 g / equivalent, trade name "Denacol EX-622" B4: Ethylene glycol diglycidyl ether, 2 epoxy groups, epoxy equivalent weight 95 g / equivalent, trade name "Denacol EX-810P" B5: Trimethylolpropane polyglycidyl ether, a mixture of 2 and 3 epoxy groups, epoxy equivalent weight 130 g / equivalent, trade name "Denacol EX-321L" B6: Polyethylene glycol diglycidyl ether, 2 epoxy groups, epoxy equivalent weight 268 g / equivalent, trade name "Denacol EX-830" B7: Polyethylene glycol diglycidyl ether, 2 epoxy groups, epoxy equivalent weight 551 g / equivalent, trade name "Denacol EX-861" Comparison of epoxy compounds CE1: Phenol (EO) 5-glycidyl ether, 1 epoxy group, epoxy equivalent weight 400 g / equivalent, trade name "Denacol EX-145" CE2: Lauryl alcohol (EO) 15-glycidyl ether, 1 epoxy group, epoxy equivalent weight 971 g / equivalent, trade name "Denacol EX-171" CE3: 3-Glycidyloxypropyltrimethoxysilane, 1 epoxy group, epoxy equivalent weight 236 g / equivalent, trade name "KBM-403" B1~B7 and CE1~CE2 are all manufactured by Nagase Chemtex Co., Ltd., and CE3 is manufactured by Shin-Etsu Chemical Co., Ltd.

[0079] The devices and materials used in the examples are shown below. Press: Kodaira Manufacturing Co., Ltd., trade name "PYS-10" Electrolytic copper foil: 20 μm thick electrolytic copper foil treated with chromate. This electrolytic copper foil is not roughened. Polyimide film: UBE's trade name "upilex (registered trademark)-25VT", thickness 25 μm Load tester: MinebeaMitsumi, trade name "LTS-200N-S100"

[0080] Example 1 to Example 41 Component (A), component (B) and deionized water were mixed to achieve the concentrations shown in Table 1 to prepare a water-based surface treatment agent.

[0081] Comparative Examples 1 to 10 Component (A), component (B), and deionized water were mixed at the concentrations shown in Table 2 to prepare a water-based surface treatment agent.

[0082] ·Production of laminated bodies An unroughened electrolytic copper foil was immersed in the aqueous surface treatment agent of Example 1 for 5 seconds and then pulled. The foil was then dried at 120°C for 30 seconds to form a film of the aqueous surface treatment agent on the surface of the foil. An intermediate product with a layered structure of electrolytic copper foil / aqueous surface treatment film / polyimide film was then formed on a press. The press temperature was then raised to 300°C over 1 hour. While maintaining the temperature at 300°C, a pressure of 5.8 MPa was applied to the intermediate product from both the electrolytic copper foil and polyimide film sides using the press for 30 minutes. This resulted in a 45 μm thick laminate with a three-layer structure of electrolytic copper foil / aqueous surface treatment film / polyimide film.

[0083] For Examples 2 to 41 and Comparative Examples 1 to 10, the aqueous surface treatment agent was also changed, and a three-layer laminate having an electrolytic copper foil / aqueous surface treatment agent film / polyimide film structure was obtained in the same manner as in Example 1.

[0084] Evaluation of adhesion The obtained laminate was subjected to the following peel strength test to evaluate the adhesiveness. The results are shown in Tables 1 and 2.

[0085] Peel strength test A 10 mm wide x 60 mm long cut was made on the copper foil side of the laminate. Using a load tester, grip the tip of the copper foil with a clamp and perform a 90° peel test over a 50 mm length at a peel rate of 50 mm / min in accordance with JIS C 6481 to measure the peel strength.

[0086] [Table 1] [Table 1] Nitrogen-containing silane coupling agent Epoxides Mass ratio (Ms / Me) Total solid content concentration (A+B) (ppm) Peel strength (N / cm) type Solid content concentration (ppm) type Number of epoxy groups Epoxy equivalent (g / equivalent) Solid content concentration (ppm) Example 1 A1 9900 B1 4 173 100 99 10000 7.15 2 A1 9000 B1 4 173 1000 9 10000 8.72 3 A1 8000 B1 4 173 2000 4 10000 7.69 4 A1 1600 B1 4 173 400 4 2000 15.67 5 A1 80 B1 4 173 20 4 100 8.97 6 A1 9900 <h2 style=";text-align:left;direction:ltr">B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2、3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 99<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.94<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.39<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2、3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.36<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2、3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.53<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.16<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 11<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8.36<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 12<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10.21<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 13<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.23<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 14<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 15<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.97<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 16<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.08<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 17<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.10<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 18<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 11.26<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 19<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10.04<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A5<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8.21<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 21<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A5<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.66<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 22<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A5<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.65<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 23<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A6<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.58<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 24<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A6<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8.36<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 25<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A6<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.62<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 26<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 191<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7.99<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 27<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 191<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.36<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 28<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 80<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 191<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 20<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 100<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 9.58 29 A1 8000 B4 2 95 2000 4 10000 7.78 30 A1 1600 B4 2 95 400 4 2000 12.36 31 A1 80 B4 2 95 20 4 100 11.89 32 A1 8000 B5 2、3 130 2000 4 10000 8.50 33 A1 1600 B5 2、3 130 400 4 2000 9.89 34 A1 80 B5 2、3 130 20 4 100 9.36 35 A1 1600 B6 2 268 400 4 2000 5.88 36 A1 1600 B7 2 551 400 4 2000 5.37 37 A1 24000 B1 4 173 6000 4 30000 7.23 38 A1 2000 B1 4 173 50 40 2050 9.02 39 A1 9950 B1 4 173 50 199 10000 8.61 40 A1 7500 B1 4 173 2500 3 10000 9.00 41 A1 1500 B1 4 173 500 3 2000 9.00

[0087] [Table 2] [Table 2] Silane coupling agent Epoxides Mass ratio (Ms / Me) Total solid content concentration (A+B) (ppm) Peel strength (N / cm) type Solid content concentration (ppm) type Number of epoxy groups Epoxy equivalent (g / equivalent) Solid content concentration (ppm) Comparative Example 1 A1 10000 - - - - - 10000 3.40 2 A2 10000 - <h2 style=";text-align:left;direction:ltr">-<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 3.69<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> -<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 0<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 0.50<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 173<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 3000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 3.22<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 5<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> B2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2,3<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 141<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 3000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 10,000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 3.76<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 6<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CE1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2.30<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 7<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> A2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1600<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> CE2<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 971<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 400<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 4<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 2000<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 1.85<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr"> 8<h2 style=";text-align:left;direction:ltr"> A2 1600 CE3 1 236 400 4 2000 3.61 9 CS1 1900 B1 4 173 100 19 2000 2.30 10 CS2 1900 B1 4 173 100 19 2000 1.85

[0088] According to the present invention, a surface treatment agent can be provided that can achieve excellent adhesion between copper foil and a resin film without roughening the surface of the copper foil. [Industrial Applicability]

[0089] The present invention provides a surface treatment agent capable of achieving excellent adhesion between copper foil and a resin film without roughening the copper foil surface. Furthermore, the present invention provides a laminate comprising a metal capable of achieving excellent adhesion to a resin film and a film comprising a water-based surface treatment agent.

[0090] none

Claims

1. An aqueous surface treatment agent for surface treatment of metals, the aqueous surface treatment agent comprising a nitrogen-containing silane coupling agent and an epoxy compound, wherein the epoxy compound has two or more epoxy groups in one molecule, the mass ratio (Ms / Me) of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound is 3 or more, and the epoxy equivalent of the epoxy compound is 90 g / equivalent to 180 g / equivalent.

2. The water-based surface treatment agent as described in claim 1, wherein, The epoxy compound is an aliphatic glycidyl ether type epoxy compound.

3. The water-based surface treatment agent as described in claim 1, wherein, The nitrogen-containing silane coupling agent has one or more members selected from the group consisting of amine and imine groups.

4. The water-based surface treatment agent as described in claim 1, wherein, The ratio (Ms / Me) is 3 to 200.

5. A laminate comprising, in sequence, a metal and a film of an aqueous surface treatment agent as claimed in any one of claims 1 to 4.

6. The laminate as described in claim 5, wherein, The metal is copper or a copper alloy.

7. The laminate as claimed in claim 5, comprising the metal, the film, and the resin film in sequence.

8. The laminate as described in claim 7, wherein, The stacked body is a flexible printed wiring board.