Aqueous surface treatment agent and laminate

Abstract

To provide a surface treatment agent which can obtain excellent adhesion between a copper foil and a resin film, without coarsening the surface of the copper foil.SOLUTION: An aqueous surface treatment agent used in surface treatment of metal contains a nitrogen-containing silane coupling agent, and an epoxy compound, wherein the epoxy compound has two or more epoxy groups in one molecule, and a ratio (Ms / Me) of a mass Ms of the nitrogen-containing silane coupling agent to a mass Me of the epoxy compound is 3 or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aqueous surface treatment agent and a laminate. [Background technology]

[0002] Currently, devices that use high-frequency radio waves are being developed in preparation for the widespread adoption of fifth-generation mobile communication systems, and demand for printed circuit boards that can transmit high-frequency signals is increasing.

[0003] Copper foils such as rolled copper foils and electrolytic copper foils are used as materials for such printed wiring boards. Conventionally, copper foils have been used after their surfaces have been roughened to improve adhesion with resin films.

[0004] However, when the surface of the copper foil is roughened, there is a problem that the electrical signal is attenuated during the transmission of high frequency signals, resulting in an increased transmission loss.

[0005] On the other hand, 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 due to the roughening treatment can be reduced, and the manufacturing process can be simplified and costs can be reduced.

[0006] In contrast to this, for example, Patent Document 1 discloses a copper surface treatment agent that can treat the copper surface to a smooth state without roughening treatment such as etching and that can maintain adhesion between 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 or water-dispersible polymer, and the water-soluble or 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 phosphate group, an imino group, and a silanol group. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2010 / 010716 Summary of the Invention [Problem to be solved by the invention]

[0008] However, it was found that there is room for further improvement in the adhesion between the copper foil and the resin film.

[0009] Therefore, an object of the present invention is to provide a surface treatment agent that can provide excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil.

[0010] Another object of the present invention is to provide a laminate having a metal and a coating of an aqueous surface treatment agent, which can provide excellent adhesion to a resin film. [Means for solving the problem]

[0011] The aqueous surface treatment agent according to the present invention is an aqueous surface treatment agent used for metal surface treatment, a nitrogen-containing silane coupling agent; an epoxy compound, the epoxy compound has two or more epoxy groups in one molecule, The aqueous surface treatment agent has a ratio (Ms / Me) of the mass of the nitrogen-containing silane coupling agent Ms to the mass of the epoxy compound Me of at least 3. This allows for excellent adhesion between the copper foil and the resin film to be obtained without roughening the surface of the copper foil.

[0012] In one embodiment of the aqueous surface treatment agent according to the present invention, when The amount is 90 to 180 g / equivalent.

[0013] In one embodiment of the aqueous surface treatment agent according to the present invention, the epoxy compound is an aliphatic glycidyl ether type epoxy compound.

[0014] In one embodiment of the aqueous surface treatment agent according to the present invention, the nitrogen-containing silane coupling agent has one or more groups selected from the group consisting of an amino group and an imino group.

[0015] In one embodiment of the aqueous surface treatment agent according to the present invention, the ratio (Ms / Me) is 3-200.

[0016] The laminate according to the present invention comprises, in order: Metal and A film of any one of the aqueous surface treatment agents described above; The laminate has the following structure.

[0017] In one embodiment of the laminate according to the present invention, the metal is copper or a copper alloy.

[0018] In one embodiment of the laminate according to the present invention, the laminate comprises, in order: The metal; The coating; A resin film; It has.

[0019] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed wiring board. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a surface treatment agent that can provide excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil, and also to provide a laminate having a metal and a coating of the aqueous surface treatment agent that can provide excellent adhesion to a resin film. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, embodiments of the present invention will be described. These descriptions are for the purpose of illustrating the present invention and are not intended to limit the present invention in any way.

[0022] In the present invention, two or more embodiments can be combined in any manner.

[0023] In the present invention, the term "solid content" is a concept that encompasses solid content and non-volatile content.

[0024] Unless otherwise specified, the materials, components, compounds, resins, groups, and solvents described herein may be used alone or in combination of two or more.

[0025] In this specification, unless otherwise specified, numerical ranges are intended to include the upper and lower limits of the range. For example, 90 to 180 g / equivalent means a range of 90 g / equivalent to 180 g / equivalent.

[0026] In this specification, the nitrogen-containing silane coupling agent and the epoxy compound may be referred to as component (A) and component (B), respectively.

[0027] Water-based surface treatment agent The aqueous surface treatment agent according to the present invention is used for surface treatment of a metal, a nitrogen-containing silane coupling agent; an epoxy compound, the epoxy compound has two or more epoxy groups in one molecule, The aqueous surface treatment agent has a ratio (Ms / Me) of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound of 3 or more.

[0028] Each component of the aqueous surface treatment agent according to the present invention will be illustrated below.

[0029] Component (A): Nitrogen-containing silane coupling agent As the component (A), a known nitrogen-containing silane coupling agent can be used.

[0030] Examples of the nitrogen-containing group contained in component (A) include an amino group (-NH2), an imino group (=NR, -N(R)-), a quaternary ammonium group (-N +Examples of such groups include an amino group, an imino group, a quaternary ammonium group, a ureido group, an isocyanate group, and an isocyanurate group. In one embodiment, component (A) has one or more groups selected from the group consisting of an amino group and an imino group.

[0031] Component (A) may have a nitrogen-containing aromatic ring. Component (A) may have, for example, a residue of pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furazan, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, azepine, diazepine, triazepine, etc.; a residue of indole, isoindole, indazole, purine, quinoline, isoquinoline, benzotriazole, etc.; a residue of carbazole, acridine, β-carboline, acridone, perimidine, phenazine, phenanthridine, phenothiazine, phenoxazine, phenanthroline, etc.; a residue of quindoline, quinindoline, etc.; or a residue of acrylindoline, etc.

[0032] The component (A) may have a nitrogen-containing aromatic ring in addition to a group other than a nitrogen-containing aromatic ring.

[0033] Examples of 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-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, and N-2-(aminoethyl)-8-aminooctyl Examples of suitable silanes include trimethoxysilane, N-2-(aminoethyl)-1-aminomethyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-isocyanatepropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine, and N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine. Other examples include X-12-1290 (containing an isocyanurate group), X-12-1214A (containing a benzotriazole group), and X-12-1172ES (containing an imino group) manufactured by Shin-Etsu Chemical Co., Ltd., and VD-5 (containing a triazine ring) manufactured by Shikoku Chemical Industry Co., Ltd.

[0034] 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.

[0035] The content of component (A) in the aqueous surface treatment agent may be adjusted appropriately so long as the ratio (Ms / Me) of the mass of component (A) to the mass of component (B) is 3 or greater. For example, the content of component (A) may be 75.0 to 99.5 mass% relative to the total solid content of the aqueous surface treatment agent. In one embodiment, the content of component (A) is 75.0 mass% or greater, 80.0 mass% or greater, 85.0 mass% or greater, 90.0 mass% or greater, 95.0 mass% or greater, or 98.0 mass% or greater relative to the total solid content of the aqueous surface treatment agent. In another embodiment, the content of component (A) is 99.5 mass% or less, 98.0 mass% or less, 95.0 mass% or less, 90.0 mass% or less, 85.0 mass% or less, or 80.0 mass% or less relative to the total solid content of the aqueous surface treatment agent.

[0036] In one embodiment, the total concentration of components (A) and (B) relative to the entire aqueous surface treatment agent is 100 to 30,000 ppm. In another embodiment, the total concentration of components (A) and (B) relative to the entire aqueous surface treatment agent is 100 ppm or more, 500 ppm or more, 1,000 ppm or more, 5,000 ppm or more, 10,000 ppm or more, 15,000 ppm or more, 20,000 ppm or more, or 25,000 ppm or more. In yet another embodiment, the total concentration of components (A) and (B) relative to the entire aqueous surface treatment agent is 30,000 ppm or less, 25,000 ppm or less, 20,000 ppm or less, 15,000 ppm or less, 10,000 ppm or less, 5,000 ppm or less, 1,000 ppm or less, or 500 ppm or less.

[0037] In the aqueous surface treatment agent of the present invention, the ratio (Ms / Me) of the mass of component (A) Ms to the mass of component (B) Me is 3 or greater. A ratio (Ms / Me) of 3 or greater enhances adhesion between the metal and the resin film via the coating 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 yet another embodiment, the ratio (Ms / Me) is 3-200.

[0038] Component (B): Epoxy compound Component (B) can be a known epoxy compound having two or more epoxy groups in one molecule, such as an aliphatic glycidyl ether epoxy compound, an aromatic glycidyl ether epoxy compound, or an alicyclic epoxy compound.

[0039] In this specification, an aliphatic glycidyl ether type epoxy compound refers to an aliphatic compound having two or more glycidyl ether groups. In this specification, an aromatic glycidyl ether type 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.

[0040] In one embodiment of the aqueous surface treatment agent according to the present invention, the epoxy compound is an aliphatic glycidyl ether type epoxy compound.

[0041] The number of epoxy groups per molecule of component (B) is two or more, for example, 2, 3, 4, or 5.

[0042] Examples of 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, phthalic acid diglycidyl ester, polypropylene glycol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane diglycidyl ether, dicyclopentadiene diepoxide, and bicyclononadiene diepoxide, all of which have two epoxy groups; glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, and diglycerol triglycidyl ether, all of which have three epoxy groups; and sorbitol tetraglycidyl ether and polyglycerol polyglycidyl ether, all of which have four epoxy groups. Other examples include Denacol EX-991L, EX-521, and EX-1610 manufactured by Nagase ChemteX Corporation.

[0043] 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.

[0044] 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 more, 200 or more, 250 or more, 300 or more, 350 or more, 400 or more, 450 or more, 500 or more, 550 or more, 600 or more, 650 or more, or 700 or more. 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.

[0045] The epoxy equivalent of component (B) can be, for example, 90 to 600 g / equivalent. In one embodiment, the epoxy equivalent of component (B) is 90 g / equivalent or more, 100 g / equivalent or more, 150 g / equivalent or more, 200 g / equivalent or more, 250 g / equivalent or more, 300 g / equivalent or more, 350 g / equivalent or more, 400 g / equivalent or more, 450 g / equivalent or more, 500 g / equivalent or more, or 550 g / equivalent or more. 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 to 180 g / equivalent.

[0046] The content of component (B) in the aqueous surface treatment agent may be adjusted appropriately so 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) may be 0.5 to 25.0 mass% relative to the total solid content of the aqueous surface treatment agent. In one embodiment, the content of component (B) is 0.5 mass% or greater, 1.0 mass% or greater, 5.0 mass% or greater, 10.0 mass% or greater, 15.0 mass% or greater, or 20.0 mass% or greater relative to the total solid content of the aqueous surface treatment agent. In another embodiment, the content of component (B) is 25.0 mass% or less, 20.0 mass% or less, 15.0 mass% or less, 10.0 mass% or less, 10.0 mass% or less, or 5.0 mass% or less relative to the total solid content of the aqueous surface treatment agent.

[0047] The aqueous surface treatment agent according to the present invention may contain, in addition to the components (A) and (B), components used in known surface treatment agents, such as solvents such as water, alcohol, and acetone; water-soluble polymers and water-dispersible polymers described in Patent Document 1; resins; pH adjusters; rust inhibitors; acids; bases; surface conditioners; antifoaming agents; condensates of the components (A) themselves; and condensates of the component (A) with other components.

[0048] ·solvent The aqueous surface treatment agent according to the present invention may further contain a water-miscible organic solvent, if necessary, to adjust the solid content concentration or drying speed. Examples of the water-miscible organic solvent 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, isopropyl alcohol 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.

[0049] As the water, known water can be used, for example, distilled water, purified water, deionized water, tap water, etc.

[0050] Preparation method of aqueous surface treatment agent The method for preparing the aqueous surface treatment agent is not particularly limited, and the components (A) and (B) may be mixed so that the mass ratio (Ms / Me) of the components (A) and (B) is at least 3. In addition to the components (A) and (B), other components such as a solvent may be mixed in any order.

[0051] Laminates The laminate according to the present invention is a laminate having, in order, a metal and a coating of an aqueous surface treatment agent, thereby achieving excellent adhesion between the metal and the resin film via the coating of the aqueous surface treatment agent.

[0052] ·metal The metal is not particularly limited as long as it is a metal that is required to have adhesion to the resin film, and known metals can be used, such as copper, nickel, and aluminum.

[0053] Examples of copper include rolled copper foil and electrolytic copper foil. Copper may also be a copper alloy with, for example, 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 one or more selected from the group consisting of rolled copper foil and electrolytic copper foil.

[0054] The metal of the laminate of the present invention may be a roughened metal or a non-roughened metal. Since the laminate of the present invention contains a coating of the aqueous surface treatment agent of the present invention, even a non-roughened metal can have excellent adhesion to a resin film. In one embodiment, the metal of the laminate is a non-roughened metal.

[0055] The surface roughness of one side of the metal is, 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 one side of the metal is, for example, Rz of 0.1 μm or more. Rz can be measured in accordance with JIS B 0601 (2013) using a commercially available laser microscope, OPTELICS HYBRID, manufactured by Lasertec Corporation.

[0056] The thickness of the metal may be adjusted appropriately and is, for example, 1 to 200 μm. In one embodiment, the thickness of the metal is 1 μm or more, 5 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 100 μm or more, or 150 μm or more. 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.

[0057] -Water-based surface treatment film The film of the aqueous surface treatment agent is a film formed using the aqueous surface treatment agent of the present invention.

[0058] In the laminate, the metal and the film of the aqueous surface treatment agent may be arranged in this order, and the metal and the film of the aqueous surface treatment agent may be laminated adjacent to each other, i.e., in direct contact with each other, or the metal and the film of the aqueous surface treatment agent may be laminated with another layer or film interposed between them.

[0059] The coating of the aqueous surface treatment agent may be laminated on at least a portion of at least one surface of the metal, and may be laminated on the entirety of one or both surfaces (both opposing surfaces) of the metal.

[0060] In one embodiment of the laminate according to the present invention, the laminate has, in order, the metal, the coating, and a resin film.

[0061] Resin film The resin film is not particularly limited, and known resin films can be used, such as polyimide films, modified polyimide (MPI) films, polyamide films, polyester films (e.g., polyethylene terephthalate films, poly-1,4-cyclohexanedimethylene terephthalate films, etc.), liquid crystal polymer films, polycarbonate films, cycloolefin polymer films, and fluororesin films, which are used for printed wiring boards.

[0062] The thickness of the resin film may be adjusted appropriately and is, for example, 5 to 200 μm. In one embodiment, the thickness of the resin film is 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, 45 μm or more, 50 μm or more, 100 μm or more, or 150 μm or more. 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.

[0063] Other layers or coatings Examples of layers or films that may be disposed between the metal and the film of the aqueous surface treatment agent include plating and chromate films formed by surface treatment of the metal.

[0064] Examples of plating 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.

[0065] The uses of the laminate of the present invention are not particularly limited, and examples thereof include flexible printed wiring boards, home appliances, information terminals, and building materials.

[0066] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed wiring board.

[0067] ·Laminate manufacturing method The method for producing the laminate is not particularly limited as long as it can laminate the metal and the aqueous surface treatment agent in order to form a film of the aqueous surface treatment agent, and known methods for producing flexible printed wiring boards can be used. Examples of the method for producing the laminate include a method including a step of preparing a metal and an aqueous surface treatment agent, a step of applying the surface treatment agent to at least a portion of at least one surface of the metal, and a step of heating or drying the applied surface treatment agent to form a film of the surface treatment agent.

[0068] The method for applying the surface treatment agent is not particularly limited, and any known application method can be used, such as immersion, bar coating, roll coating, shower coating, spraying, or brush coating.

[0069] The heating or drying temperature of the surface treatment agent is not particularly limited, and is, for example, 50 to 250°C.

[0070] The heating or drying time for the surface treatment agent is not particularly limited, and is, for example, 2 seconds to 1 hour.

[0071] The thickness of the coating is not particularly limited and may be adjusted as appropriate, and is, for example, 1 nm to 10 μm in dry thickness.

[0072] When the laminate has a configuration of metal / aqueous surface treatment agent film / resin film, a manufacturing method can be exemplified by a method in which a laminate of metal / aqueous surface treatment agent film is formed, a resin film is placed on the film, and then the metal, the aqueous surface treatment agent film, and the resin film are pressure-bonded together.

[0073] The temperature for pressure bonding is, for example, 100 to 450°C.

[0074] The pressure to be applied when pressure bonding is, for example, 0.1 to 10 MPa. [Example]

[0075] The present invention will be described in more detail below by way of examples, but these examples are intended to illustrate the present invention and are not intended to limit the present invention in any way.

[0076] The materials used in the examples are as follows: Component (A) A1: 3-aminopropyltrimethoxysilane, product name "KBM-903" A2: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, product name "KBM-603" A3: 3-aminopropyltriethoxysilane, product name "KBE-903" A4: N-(2-aminoethyl)-3-aminopropyltriethoxysilane, product name "KBE-603" A5: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, product name "KBM-602" A6: N-phenyl-3-aminopropyltrimethoxysilane, product name "KBM-573" Comparative silane coupling agent Comparative silane coupling agent 1: Vinyltriethoxysilane, product name "KBE-1003", indicated as "CS1" in the table Comparative silane coupling agent 2: 3-methacryloxypropyltriethoxysilane, product name "KBE-503" (referred to as "CS2" in the table) A1 to A6 and CS1 to CS2 are all manufactured by Shin-Etsu Chemical Co., Ltd. ·(B) Component B1: Sorbitol polyglycidyl ether, epoxy group number 4, epoxy equivalent weight 173 g / equivalent, product name "Denacol EX-614B" B2: Glycerol polyglycidyl ether, mixture of epoxy groups 2 and 3, epoxy equivalent weight 141 g / equivalent, product name "Denacol EX-313" B3: Sorbitol polyglycidyl ether, epoxy group number 4, epoxy equivalent weight 191 g / equivalent, product name "Denacol EX-622" B4: Ethylene glycol diglycidyl ether, epoxy group number 2, epoxy equivalent weight 95g / equivalent, product name "Denacol EX-810P" B5: Trimethylolpropane polyglycidyl ether, mixture of epoxy groups 2 and 3, epoxy equivalent weight 130 g / equivalent, product name "Denacol EX-321L" B6: Polyethylene glycol diglycidyl ether, epoxy group number 2, epoxy equivalent weight 268 g / equivalent, product name "Denacol EX-830" B7: Polyethylene glycol diglycidyl ether, epoxy group number 2, epoxy equivalent weight 551 g / equivalent, product name "Denacol EX-861" Comparative epoxy compounds CE1: Phenol (EO) 5 glycidyl ether, epoxy group number 1, epoxy equivalent weight 400g / equivalent, product name "Denacol EX-145" CE2: Lauryl alcohol (EO) 15 Glycidyl ether, epoxy group number 1, epoxy equivalent weight 971g / equivalent, product name "Denacol EX-171" CE3: 3-glycidoxypropyltrimethoxysilane, epoxy group number 1, epoxy when Amount: 236g / equivalent, product name: “KBM-403” B1 to B7 and CE1 and CE2 are all manufactured by Nagase ChemteX Corporation, and CE3 is manufactured by Shin-Etsu Chemical Co., Ltd.

[0077] The devices and materials used in the examples are as follows: Press machine: Product name "PYS-10" manufactured by Kodaira Manufacturing Co., Ltd. Electrolytic copper foil: chromate-treated electrolytic copper foil with a thickness of 20 μm. This electrolytic copper foil is not roughened. Polyimide film: UBE Corporation's product name "UPILEX (registered trademark)-25VT", thickness 25 μm Load measuring device: MinebeaMitsumi product name "LTS-200N-S100"

[0078] Examples 1 to 41 Component (A), component (B), and deionized water were mixed to give the concentrations shown in Table 1 to prepare aqueous surface treatment agents.

[0079] Comparative Examples 1 to 10 Component (A), component (B), and deionized water were blended at the concentrations shown in Table 2 to prepare an aqueous surface treatment agent.

[0080] -Laminate fabrication An unroughened electrolytic copper foil was immersed in the aqueous surface treatment agent of Example 1 for 5 seconds and then removed. The electrolytic copper foil was then dried at 120°C for 30 seconds to form a coating of the aqueous surface treatment agent on the surface of the electrolytic copper foil. An intermediate was then placed in a press with a layer structure of electrolytic copper foil / aqueous surface treatment agent coating / polyimide film. The press was then heated to 300°C over 1 hour. While maintaining the temperature at 300°C, a pressure of 5.8 MPa was applied to the intermediate from the electrolytic copper foil side and the polyimide film side in the press, and the intermediate was held for 30 minutes. A 45 μm-thick laminate was then obtained with a three-layer structure of electrolytic copper foil / aqueous surface treatment agent coating / polyimide film.

[0081] For Examples 2 to 41 and Comparative Examples 1 to 10, laminates each having a three-layer structure of electrolytic copper foil / aqueous surface treatment agent film / polyimide film were obtained in the same manner as in Example 1, except that the aqueous surface treatment agent was changed.

[0082] Adhesion evaluation The obtained laminate was subjected to the following peel strength test to evaluate adhesion, and the results are shown in Tables 1 and 2.

[0083] Peel strength test A 10 mm wide x 60 mm long cut was made in the copper foil from the copper foil side of the laminate. Using a load measuring device, the tip of the copper foil was held with a gripper, and a 90° peel test was performed over a length of 50 mm at a peel rate of 50 mm / min in accordance with JIS C 6481 to measure the peel strength.

[0084] [Table 1]

[0085] [Table 2]

[0086] According to the present invention, it is possible to provide a surface treatment agent that can obtain excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. [Industrial Applicability]

[0087] According to the present invention, it is possible to provide a surface treatment agent that can provide excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil, and also to provide a laminate having a metal and a coating of the aqueous surface treatment agent that can provide excellent adhesion to a resin film.

Claims

1. An aqueous surface treatment agent used for metal surface treatment, a nitrogen-containing silane coupling agent; an epoxy compound, the epoxy compound has two or more epoxy groups in one molecule, The aqueous surface treatment agent has a ratio (Ms / Me) of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound of 3 or more.

2. 2. The aqueous surface treatment agent according to claim 1, wherein the epoxy equivalent of the epoxy compound is 90 to 180 g / equivalent.

3. 2. The aqueous surface treatment agent according to claim 1, wherein the epoxy compound is an aliphatic glycidyl ether type epoxy compound.

4. 2. The aqueous surface treatment agent according to claim 1, wherein the nitrogen-containing silane coupling agent has at least one group selected from the group consisting of an amino group and an imino group.

5. 2. The aqueous surface treatment agent according to claim 1, wherein the ratio (Ms / Me) is 3 to 200.

6. In order, Metal and A film of the aqueous surface treatment agent according to any one of claims 1 to 5; A laminate having

7. The laminate of claim 6 , wherein the metal is copper or a copper alloy.

8. In order, The metal; The coating; A resin film; The laminate of claim 6, having

9. The laminate according to claim 8 , which is a flexible printed wiring board.

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