Aqueous surface treatment agent and laminate

Abstract

The present invention addresses the problem of providing a surface treatment agent which enables the achievement of excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. Disclosed is an aqueous surface treatment agent which is used for a surface treatment of a metal, the agent including a nitrogen-containing silane coupling agent and an epoxy compound. The epoxy compound has two or more epoxy groups in each molecule, and the ratio (Ms / Me) of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound is 3 or more.

Description

Aqueous surface treatment agent and laminate

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

[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 there is an increasing demand for printed wiring boards that can transmit high-frequency signals.

[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.

[0007] International Publication No. 2010 / 010716

[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.

[0011] The aqueous surface treatment agent according to the present invention is an aqueous surface treatment agent used for treating metal surfaces, and comprises a nitrogen-containing silane coupling agent and an epoxy compound, wherein the epoxy compound has two or more epoxy groups per molecule, and the ratio of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound (Ms / Me) is at least 3. This allows excellent adhesion between a copper foil and a 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, the epoxy compound has an epoxy equivalent of 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 to 200.

[0016] The laminate according to the present invention is a laminate having, in this order, a metal and a coating of any one of the aqueous surface treatment agents described above.

[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 includes, in this order: the metal; the coating; and a resin film.

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

[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.

[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] As used herein, ranges of values ​​are intended to include the upper and lower limits of the range unless otherwise specified, e.g., 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] Aqueous surface treatment agent The aqueous surface treatment agent according to the present invention is used for the surface treatment of a metal, and 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 ratio (Ms / Me) of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound is 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 (—NH ２ ), imino group (=NR, -N(R)-), quaternary ammonium group (-N ＋ R ３ ), ureido group (-NHCONH ２ ), an isocyanate group (—N═C═O), an isocyanurate group, etc. In one embodiment, component (A) has one or more groups selected from the group consisting of an amino group, an imino group, a quaternary ammonium group, a ureido 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 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 acrindoline, 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 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-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), all manufactured by Shin-Etsu Chemical Co., Ltd., and VD-5 (containing a triazine ring), all 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 as appropriate, provided that the ratio (Ms / Me) of the mass of component (A) to the mass of component (B), Me, 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 more. A ratio (Ms / Me) of 3 or more 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 more, 4 or more, 5 or more, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, 150 or more, 200 or more, or 300 or more. 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 As component (B), a known epoxy compound having two or more epoxy groups per molecule can be used. Examples of component (B) include aliphatic glycidyl ether type epoxy compounds, aromatic glycidyl ether type epoxy compounds, and alicyclic epoxy compounds.

[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, the 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 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 / eq or less, 550 g / eq or less, 500 g / eq or less, 450 g / eq or less, 400 g / eq or less, 350 g / eq or less, 300 g / eq or less, 250 g / eq or less, 200 g / eq or less, 180 g / eq or less, 150 g / eq or less, or 100 g / eq or less. In yet another embodiment, the epoxy equivalent weight of component (B) is 90 to 180 g / eq.

[0046] The content of component (B) in the aqueous surface treatment agent may be adjusted as appropriate, provided that 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, 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, as necessary, in order 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] - Method for preparing aqueous surface treatment agent The method for preparing the aqueous surface treatment agent is not particularly limited, and it is sufficient that the components (A) and (B) are 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] 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 as appropriate 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] - Film of aqueous surface treatment agent The film of 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. Examples of the resin film include 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 Films 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] - Manufacturing method of laminate The manufacturing method of 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 manufacturing methods for flexible printed wiring boards, etc. Examples of the manufacturing method of 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 side 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 of the surface treatment agent is not particularly limited, and is, for example, from 2 seconds to 1 hour.

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

[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 pressing is, for example, 0.1 to 10 MPa.

[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, 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" Comparative silane coupling agents Comparative silane coupling agent 1: vinyltriethoxysilane, trade name "KBE-1003", indicated as "CS1" in the table. Comparative silane coupling agent 2: 3-methacryloxypropyltriethoxysilane, trade name "KBE-503", indicated as "CS2" in the table. A1 to A6 and CS1 to CS2 are all manufactured by Shin-Etsu Chemical Co., Ltd. Component (B) B1: Sorbitol polyglycidyl ether, epoxy group number 4, epoxy equivalent weight 173 g / equivalent, trade name "Denacol EX-614B" B2: Glycerol polyglycidyl ether, mixture of epoxy groups 2 and 3, epoxy equivalent weight 141 g / equivalent, trade name "Denacol EX-313" B3: Sorbitol polyglycidyl ether, epoxy group number 4, epoxy equivalent weight 191 g / equivalent, trade name "Denacol EX-622" B4: Ethylene glycol diglycidyl ether, epoxy group number 2, epoxy equivalent weight 95 g / equivalent, trade name "Denacol EX-810P" B5: Trimethylolpropane polyglycidyl ether, mixture of epoxy groups 2 and 3, epoxy equivalent weight 130 g / equivalent, trade name "Denacol EX-321L" B6: Polyethylene glycol diglycidyl ether, epoxy group number 2, epoxy equivalent weight 268 g / equivalent, trade name "Denacol EX-830" B7: Polyethylene glycol diglycidyl ether, epoxy group number 2, epoxy equivalent weight 551 g / equivalent, trade name "Denacol EX-861" Comparative epoxy compounds CE1: Phenol (EO) ５Glycidyl ether, epoxy group number 1, epoxy equivalent weight 400 g / equivalent, trade name "Denacol EX-145" CE2: lauryl alcohol (EO) １５ Glycidyl ether, epoxy group number 1, epoxy equivalent weight 971 g / equivalent, trade name "Denacol EX-171" CE3: 3-glycidoxypropyltrimethoxysilane, epoxy group number 1, epoxy equivalent weight 236 g / equivalent, trade name "KBM-403" B1 to B7 and CE1 to 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: Kodaira Seisakusho Co., Ltd., trade name "PYS-10" Electrodeposited copper foil: chromate-treated electrolytic copper foil with a thickness of 20 μm. This electrolytic copper foil was not roughened. Polyimide film: UBE Co., Ltd., trade name "UPILEX (registered trademark)-25VT", thickness 25 μm Load measuring device: MinebeaMitsumi Inc., trade name "LTS-200N-S100"

[0078] Examples 1 to 41 Component (A), component (B), and deionized water were blended 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 in the concentrations shown in Table 2 to prepare aqueous surface treatment agents.

[0080] Preparation of Laminate: 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 press was maintained for 30 minutes. A 45 μm-thick laminate with a three-layer structure of electrolytic copper foil / aqueous surface treatment agent coating / polyimide film was then obtained.

[0081] In Examples 2 to 41 and Comparative Examples 1 to 10, the aqueous surface treatment agent was changed, and similarly to Example 1, a three-layer laminate of electrolytic copper foil / aqueous surface treatment agent film / polyimide film was obtained.

[0082] The obtained laminate was subjected to the following peel strength test to evaluate the adhesion. 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 gripped 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]

[0085]

[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.

[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 the surface treatment of metals, comprising 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 ratio (Ms / Me) of the mass Ms of the nitrogen-containing silane coupling agent to the mass Me of the epoxy compound is 3 or more.

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

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

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

6. A laminate having, in order, a metal and a film of the aqueous surface treatment agent according to any one of claims 1 to 5.

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

8. The laminate according to claim 6, having, in order, the metal, the film, and a resin film.

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

Images