Aqueous surface treatment agent and laminate

Abstract

The present invention provides an aqueous surface treatment agent and a laminate which can obtain excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. The aqueous surface treatment agent is used for surface treatment of metal, and the aqueous surface treatment agent comprises: a nitrogen-containing silane coupling agent; and an epoxy compound having two or more epoxy groups in one molecule, the ratio (Ms / Me) of the mass (Ms) of the nitrogen-containing silane coupling agent to the mass (Me) of the epoxy compound being 3 or more.

Description

Technical Field

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

[0002] At present, for the popularization of the fifth-generation mobile communication system and the like, devices using high-frequency radio waves have been developed, and the demand for printed circuit boards corresponding to the transmission of high-frequency signals is increasing.

[0003] As materials for such printed circuit boards, copper foils such as rolled copper foil and electrolytic copper foil are used. Conventionally, in order to improve the adhesion to the resin film, the copper foil is used after the surface of the copper foil is roughened.

[0004] However, if the surface of the copper foil is roughened, there is a problem that the electric signal attenuates and the transmission loss increases during the transmission of high-frequency signals.

[0005] In view of this, 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 also the manufacturing process can be simplified and the cost can be reduced.

[0006] In view of this, for example, in Patent Document 1, a surface treatment agent for copper is disclosed, which can be treated into a smooth state without roughening the surface of copper such as etching, and can maintain the adhesion between copper and insulating materials such as resin. The surface treatment agent for copper contains a tin compound, a complexing agent, and a water-soluble polymer or a water-dispersible polymer, and 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 imino group, and a silanol group.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: International Publication No. 2010 / 010716 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] However, it is known that there is room for further improvement in the adhesion between the copper foil and the resin film.

[0012] Therefore, an object of the present invention is to provide an aqueous surface treatment agent that can obtain excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil.

[0013] Another object of the present invention is to provide a laminate having a film of a metal and an aqueous surface treatment agent that can obtain excellent adhesion to a resin film.

[0014] Means for Solving the Problem

[0015] The aqueous surface treatment agent according to the present invention is used for surface treatment of metals, wherein the aqueous surface treatment agent contains: a nitrogen-containing silane coupling agent; and an epoxy compound having 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. Thus, excellent adhesion between the copper foil and the resin film can be obtained without roughening the surface of the copper foil.

[0016] In one embodiment of the aqueous surface treatment agent according to the present invention, the epoxy equivalent of the epoxy compound is 90 g / equivalent to 180 g / equivalent.

[0017] 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.

[0018] In one embodiment of the aqueous surface treatment agent according to the present invention, the nitrogen-containing silane coupling agent has one or more selected from the group consisting of an amino group and an imino group.

[0019] In one embodiment of the aqueous surface treatment agent according to the present invention, the ratio (Ms / Me) is 3 to 200.

[0020] The laminate according to the present invention sequentially has: a metal; and a film of any one of the above aqueous surface treatment agents.

[0021] In one embodiment of the laminate according to the present invention, the metal is copper or a copper alloy.

[0022] In one embodiment of the laminate according to the present invention, the laminate sequentially has: the metal; the film; and a resin film.

[0023] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed circuit board.

[0024] Advantages of the Invention

[0025] According to the present invention, it is possible to provide an aqueous surface treatment agent capable of obtaining excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. In addition, according to the present invention, it is possible to provide a laminate of a metal and a film of an aqueous surface treatment agent having excellent adhesion to a resin film. Detailed Embodiments

[0026] Hereinafter, embodiments of the present invention will be described. These descriptions are for illustrative purposes of the present invention and do not limit the present invention in any way.

[0027] In the present invention, two or more embodiments can be arbitrarily combined.

[0028] In the present invention, the term "solid component" is a concept that includes solid components and non-volatile components.

[0029] Unless otherwise noted, the materials, components, compounds, resins, groups, and solvents described in this specification can be used alone or in combination of two or more.

[0030] In this specification, unless otherwise noted, a numerical range is intended to include the upper and lower limits of the range. For example, 90 g / equivalent to 180 g / equivalent means a range of 90 g / equivalent or more and 180 g / equivalent or less.

[0031] In this specification, the nitrogen-containing silane coupling agent and the epoxy compound are sometimes referred to as component (A) and component (B), respectively.

[0032] · Aqueous surface treatment agent

[0033] The aqueous surface treatment agent according to the present invention is used for surface treatment of metals. Among them, the aqueous surface treatment agent contains: a nitrogen-containing silane coupling agent; and an epoxy compound having 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.

[0034] Hereinafter, each component of the aqueous surface treatment agent according to the present invention will be exemplified.

[0035] · Component (A): Nitrogen-containing silane coupling agent

[0036] As component (A), a known nitrogen-containing silane coupling agent can be used.

[0037] As the nitrogen-containing group of component (A), for example, the following can be cited: amino group (-NH2), imino group (=NR, -N(R)-), quaternary ammonium group (-N + R3), ureido group (-NHCONH2), isocyanate group (-N=C=O), isocyanurate group, etc. In one embodiment, component (A) has one or more 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 selected from the group consisting of an amino group and an imino group.

[0038] The (A) component may have a nitrogen-containing aromatic ring. For example, the (A) component may have residues such as pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furan, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, azepine, diazepine, triazepine, etc.; residues such as indole, isoindole, indazole, purine, quinoline, isoquinoline, benzotriazole, etc.; residues such as carbazole, acridine, β-carboline, acridone, peridine, phenazine, phenanthridine, phenothiazine, phenoxazine, o-phenanthroline, etc.; residues such as quinazoline, indolo[2,3-b]quinoline, etc.; residues such as indolo[3,2-c]acridine, etc.

[0039] In addition to the groups other than the nitrogen-containing aromatic ring, the (A) component may also have a nitrogen-containing aromatic ring.

[0040] Examples of the (A) component include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(1,3-dimethyl-butyl)aminopropyltriethoxysilane (3-(triethoxysilyl)-N-(1,3-Dimethyl-butylidene)propylamine), N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, N-2-(aminoethyl)-1-aminomethyltrimethoxysilane, 3-ureidopropyltrialkoxysilane, 3-ureidopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, tris(-trimethoxysilylpropyl)isocyanurate, 3-isocyanatopropyltriethoxysilane, [3-(6-aminohexylamino)propyl]trimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, bis[3-(triethoxysilyl)propyl]amine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, etc. In addition, for example, X-12-1290 (containing isocyanurate group), X-12-1214A (containing benzotriazole group), X-12-1172ES (containing imino group) manufactured by Shin-Etsu Chemical Co., Ltd. of Japan, VD-5 (containing triazine ring) manufactured by Shikoku Kasei Kogyo Co., Ltd. of Japan, etc. can be cited.

[0041] In a preferred embodiment, the component (A) is selected from one or more of 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.

[0042] The content of the component (A) in the aqueous surface treatment agent can be appropriately adjusted as long as the ratio (Ms / Me) of the mass (Ms) of the component (A) to the mass (Me) of the component (B) is 3 or more. For example, the content of the component (A) can be set to 75.0% by mass to 99.5% by mass relative to the total amount of the solid components of the aqueous surface treatment agent. In one embodiment, the content of the component (A) is 75.0% by mass or more, 80.0% by mass or more, 85.0% by mass or more, 90.0% by mass or more, 95.0% by mass or more, or 98.0% by mass or more relative to the total amount of the solid components of the aqueous surface treatment agent. In another embodiment, the content of the component (A) is 99.5% by mass or less, 98.0% by mass or less, 95.0% by mass or less, 90.0% by mass or less, 85.0% by mass or less, or 80.0% by mass or less relative to the total amount of the solid components of the aqueous surface treatment agent.

[0043] In one embodiment, the total concentration of the component (A) and the component (B) is 100 ppm to 30,000 ppm relative to the whole aqueous surface treatment agent. In another embodiment, the total concentration of the component (A) and the component (B) is 100 ppm or more, 500 ppm or more, 1000 ppm or more, 5000 ppm or more, 10,000 ppm or more, 15,000 ppm or more, 20,000 ppm or more, or 25,000 ppm or more relative to the whole aqueous surface treatment agent. Further, in another embodiment, the total concentration of the component (A) and the component (B) 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, 5000 ppm or less, 1000 ppm or less, or 500 ppm or less relative to the whole aqueous surface treatment agent.

[0044] 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 more. By making the ratio (Ms / Me) 3 or more, the adhesion between the metal and the resin film through the film of the aqueous surface treatment agent is improved. 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. Further, in another embodiment, the ratio (Ms / Me) is 3 to 200.

[0045] · Component (B): Epoxy compound

[0046] As component (B), a known epoxy compound having two or more epoxy groups in one molecule can be used. As component (B), for example, an aliphatic glycidyl ether type epoxy compound, an aromatic glycidyl ether type epoxy compound, an alicyclic epoxy compound, etc. can be cited.

[0047] In this specification, an aliphatic glycidyl ether type epoxy compound means an aliphatic compound having two or more glycidyl ether groups. In this specification, an aromatic glycidyl ether type epoxy compound means an aromatic compound having two or more glycidyl ether groups. In this specification, an alicyclic epoxy compound means an alicyclic compound having two or more epoxy groups.

[0048] 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.

[0049] The number of epoxy groups in one molecule of component (B) is two or more, for example, 2, 3, 4, or 5.

[0050] As the component (B), for example, the following can be cited: 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, tetrahydroindene diepoxide (Bicyclononadiene diepoxide); glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether having three epoxy groups; sorbitol tetraglycidyl ether, polyglycerol polyglycidyl ether having four epoxy groups, etc. In addition, for example, EX - 991L, EX - 521, EX - 1610, etc. manufactured by Nagase ChemteX Corporation, Japan can be cited.

[0051] 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.

[0052] As the molecular weight of the component (B), for example, it can be 170 to 750. In one embodiment, the molecular weight of the 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 the 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.

[0053] The epoxy equivalent of component (B), for example, can be from 90 g / equivalent 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 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. Further, in another embodiment, the epoxy equivalent of component (B) is from 90 g / equivalent to 180 g / equivalent.

[0054] The content of component (B) in the aqueous surface treatment agent can be appropriately adjusted as long as the ratio (Ms / Me) of the mass (Ms) of component (A) to the mass (Me) of component (B) is 3 or more. For example, the content of component (B) relative to the total amount of the solid components of the aqueous surface treatment agent can be set to 0.5 mass% to 25.0 mass%. In one embodiment, relative to the total amount of the solid components of the aqueous surface treatment agent, the content of component (B) is 0.5 mass% or more, 1.0 mass% or more, 5.0 mass% or more, 10.0 mass% or more, 15.0 mass% or more, or 20.0 mass% or more. In another embodiment, relative to the total amount of the solid components of the aqueous surface treatment agent, 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.

[0055] In addition to components (A) and (B), the aqueous surface treatment agent according to the present invention may further contain components used in known surface treatment agents. The aqueous surface treatment agent can, for example, contain: solvents such as water, alcohols, and acetone; water-soluble polymers, water-dispersible polymers, resins, pH adjusters, rust inhibitors, acids, bases, surface modifiers, defoamers, condensates of component (A) with each other, condensates of component (A) with other components, etc. described in Patent Document 1.

[0056] · Solvent

[0057] In order to adjust the concentration of the solid component and the drying rate, the aqueous surface treatment agent according to the present invention may further contain an organic solvent mixed with water as needed. As the organic solvent mixed with water, for example, the following can be cited: 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; pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone, etc.

[0058] As water, well-known water can be used. For example, distilled water, purified water, deionized water, tap water, etc. can be cited.

[0059] · Preparation method of the aqueous surface treatment agent

[0060] The preparation method of the aqueous surface treatment agent is not particularly limited as long as it is mixed in such a way that the mass ratio (Ms / Me) of component (A) and component (B) is 3 or more. In addition to component (A) and component (B), other components such as solvents can be mixed in any order.

[0061] · Laminate

[0062] The laminate according to the present invention is a laminate having a metal and a film of the aqueous surface treatment agent in sequence. Thereby, excellent adhesion between the metal and the resin film via the film of the aqueous surface treatment agent can be obtained.

[0063] · Metal

[0064] The metal is not particularly limited as long as it is a metal that needs to have adhesion to the resin film, etc. Well-known metals can be used. For example, copper, nickel, aluminum, etc. can be cited.

[0065] As copper, for example, rolled copper foil, electrolytic copper foil, etc. can be cited. In addition, copper can also be, for example, a copper alloy with tin, zinc, nickel, arsenic, silicon, titanium, or chromium, etc. 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.

[0066] The metal of the laminate of the present invention can be a roughened metal or an unroughened metal. In the laminate of the present invention, due to the film of the aqueous surface treatment agent of the present invention, excellent adhesion to the resin film can be obtained even for an unroughened metal. In one embodiment, the metal of the laminate is an unroughened metal.

[0067] Regarding the surface roughness of one side of the metal, for example, Rz (ten-point mean roughness) is 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. Additionally, regarding the surface roughness of one side of the metal, for example, Rz is 0.1 μm or more. Rz can be measured in accordance with JIS B 0601 (2013) using a commercially available laser microscope OPTELICSHYBRID manufactured by Lasertec Corporation, Japan.

[0068] The thickness of the metal can be appropriately adjusted, for example, it is 1 μm 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.

[0069] · Film of the aqueous surface treatment agent

[0070] The film of the aqueous surface treatment agent is a film formed using the aqueous surface treatment agent of the present invention.

[0071] In the laminate, the metal and the film of the aqueous surface treatment agent may be arranged in the order of the metal and the film of the aqueous surface treatment agent. They can be arranged such that the metal and the film of the aqueous surface treatment agent are adjacent, that is, laminated in direct contact, or they can be laminated with other layers or films interposed between the metal and the film of the aqueous surface treatment agent.

[0072] The film of the aqueous surface treatment agent only needs to be laminated on at least a part of at least one surface of the metal, and it can also be laminated on the whole of one surface or two surfaces (opposite two surfaces) of the metal.

[0073] In one embodiment of the laminate according to the present invention, the laminate sequentially has the metal, the film, and the resin film.

[0074] · Resin film

[0075] As the resin film, there is no particular limitation, and known resin films can be used. As the resin film, for example, there can be mentioned: polyimide films for printed circuit board applications, 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, fluororesin films, etc.

[0076] The thickness of the resin film can be appropriately adjusted, for example, it is 5 μm 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.

[0077] · Other layers or films

[0078] As the layer or film that can be disposed between the metal and the film of the aqueous surface treatment agent, for example, there can be mentioned a plating layer, a chromate film, etc. formed by surface treatment of the metal.

[0079] As the plating layer, for example, there can be mentioned Ni plating layer, Ni-P plating layer, Ni-Co plating layer, Ni-Mo plating layer, Zn plating layer, Zn-Ni plating layer, Cu-Zn plating layer, Cu-Ni plating layer, Cu-Ni-Co plating layer, etc.

[0080] Regarding the use of the laminate of the present invention, there is no particular limitation. For example, there can be mentioned flexible printed circuit boards, household electrical appliances, information terminals, building materials, etc.

[0081] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed circuit board.

[0082] · Manufacturing method of the laminate

[0083] The manufacturing method of the laminate is not particularly limited as long as it can laminate to successively have a film of a metal and an aqueous surface treatment agent, and known manufacturing methods of flexible printed circuit boards, etc. can be used. As the manufacturing method of the laminate, for example, there can be mentioned a method including the following steps: a step of preparing a metal and an aqueous surface treatment agent; a step of coating the surface treatment agent on at least a part of at least one surface of the metal; a step of heating or drying the coated surface treatment agent to form a film of the surface treatment agent.

[0084] The coating method of the surface treatment agent is not particularly limited, and known coating methods can be used. As the coating method, for example, dipping, bar coating, roll coating, shower coating, spray coating, brush coating, etc. can be cited.

[0085] The heating or drying temperature of the surface treatment agent is not particularly limited, and is, for example, 50°C to 250°C.

[0086] The heating or drying time of the surface treatment agent is not particularly limited, and is, for example, 2 seconds to 1 hour.

[0087] 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.

[0088] As a manufacturing method when the laminate has a structure of metal / water-based surface treatment agent film / resin film, for example, the following method can be cited: After forming a laminate of metal / water-based surface treatment agent film, a resin film is disposed on the film, and then the metal, the water-based surface treatment agent film, and the resin film are pressed together.

[0089] As the temperature during pressing, for example, it is 100°C to 450°C.

[0090] As the pressure during pressing, for example, it is 0.1 MPa to 10 MPa.

[0091] Examples

[0092] Hereinafter, examples are listed to further illustrate the present invention in detail. However, these examples are for the purpose of exemplifying the present invention and do not impose any limitations on the present invention.

[0093] The materials used in the examples are as follows.

[0094] · Component (A)

[0095] A1: 3-aminopropyltrimethoxysilane, trade name "KBM-903"

[0096] A2: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, trade name "KBM-603"

[0097] A3: 3-aminopropyltriethoxysilane, trade name "KBE-903"

[0098] A4: N-(2-aminoethyl)-3-aminopropyltriethoxysilane, trade name "KBE-603"

[0099] A5: N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, trade name "KBM-602"

[0100] A6: N-Phenyl-3-aminopropyltrimethoxysilane, trade name "KBM-573"

[0101] · Silane coupling agent for comparison

[0102] Silane coupling agent for comparison 1: Vinyltriethoxysilane, trade name "KBE-1003", marked as "CS1" in the table

[0103] Silane coupling agent for comparison 2: 3-Methacryloxypropyltriethoxysilane, trade name "KBE-503", marked as "CS2" in the table

[0104] A1 to A6 and CS1 to CS2 are all manufactured by Shin-Etsu Chemical Co., Ltd. of Japan.

[0105] · Component (B)

[0106] B1: Sorbitol polyglycidyl ether, number of epoxy groups is 4, epoxy equivalent is 173 g / equivalent, trade name "DENACOL EX-614B"

[0107] B2: Glycerol polyglycidyl ether, a mixture of 2 and 3 epoxy groups, epoxy equivalent is 141 g / equivalent, trade name "DENACOL EX-313"

[0108] B3: Sorbitol polyglycidyl ether, number of epoxy groups is 4, epoxy equivalent is 191 g / equivalent, trade name "DENACOL EX-622"

[0109] B4: Ethylene glycol diglycidyl ether, number of epoxy groups is 2, epoxy equivalent is 95 g / equivalent, trade name "DENACOL EX-810P"

[0110] B5: Trimethylolpropane polyglycidyl ether, a mixture of 2 and 3 epoxy groups, epoxy equivalent is 130 g / equivalent, trade name "DENACOL EX-321L"

[0111] B6: Polyethylene glycol diglycidyl ether, number of epoxy groups is 2, epoxy equivalent is 268 g / equivalent, trade name "DENACOL EX-830"

[0112] B7: Polyethylene glycol diglycidyl ether, number of epoxy groups is 2, epoxy equivalent is 551 g / equivalent, trade name "DENACOL EX-861"

[0113] · Epoxy compound for comparison

[0114] CE1: Phenyl (EO)5 glycidyl ether, with 1 epoxy group, epoxy equivalent of 400 g / equivalent, trade name “DENACOL EX-145”

[0115] CE2: Lauryl alcohol (EO)15 glycidyl ether, with 1 epoxy group, epoxy equivalent of 971 g / equivalent, trade name “DENACOL EX-171”

[0116] CE3: 3-Glycidoxypropyltrimethoxysilane, with 1 epoxy group, epoxy equivalent of 236 g / equivalent, trade name “KBM-403”

[0117] B1 to B7 and CE1 to CE2 are all manufactured by Nagase ChemteX Corporation, Japan, and CE3 is manufactured by Shin-Etsu Chemical Co., Ltd., Japan.

[0118] The devices and materials used in the examples are as follows.

[0119] Press: Manufactured by Kodaira Seisakusho, Japan, trade name “PYS-10”

[0120] Electrolytic copper foil: An electrolytic copper foil with a thickness of 20 μm treated with chromate. This electrolytic copper foil has not been roughened.

[0121] Polyimide film: Manufactured by UBE Industries, Ltd., Japan, trade name “Upirex (registered trademark)-25VT”, thickness of 25 μm

[0122] Load cell: Manufactured by Minebea Mitsumi Inc., Japan, trade name “LTS-200N-S100”

[0123] Examples 1 to 41

[0124] The aqueous surface treatment agent was prepared by mixing component (A), component (B) and deionized water at the concentrations shown in Table 1.

[0125] Comparative Examples 1 to 10

[0126] The aqueous surface treatment agent was prepared by mixing component (A), component (B) and deionized water at the concentrations shown in Table 2.

[0127] · Fabrication of the laminate

[0128] An unroughened electrolytic copper foil was dipped in the aqueous surface treatment agent of Example 1 for 5 seconds and then lifted. Subsequently, the electrolytic copper foil was dried at 120 °C for 30 seconds to form a film of the aqueous surface treatment agent on the surface of the electrolytic copper foil. Next, an intermediate was arranged in a layer structure of electrolytic copper foil / film of aqueous surface treatment agent / polyimide film on a press. Subsequently, the press was heated to 300 °C over the course of 1 hour. While maintaining the state of 300 °C, a pressure of 5.8 MPa was applied to the intermediate from the electrolytic copper foil side and the polyimide film side with the press and held for 30 minutes. Subsequently, a laminate having a three-layer structure of electrolytic copper foil / film of aqueous surface treatment agent / polyimide film and a thickness of 45 μm was obtained.

[0129] For Examples 2 to 41 and Comparative Examples 1 to 10, an aqueous surface treatment agent was also used, and thus a laminate having a three-layer structure of electrolytic copper foil / film of aqueous surface treatment agent / polyimide film was obtained in the same manner as in Example 1.

[0130] ·Evaluation of adhesion

[0131] The following peel strength test was performed on the obtained laminate and the adhesion was evaluated. The results are shown in Tables 1 and 2.

[0132] ·Peel strength test

[0133] From the copper foil side of the laminate, a cut with a width of 10 mm × a length of 60 mm was made in the copper foil. Using a load measuring device, the front end of the copper foil was clamped with a jig, and a 90° peel test was performed at a peel speed of 50 mm / minute over a length of 50 mm in accordance with JIS C 6481, and the peel strength was measured.

[0134] Table 1

[0135]

[0136]

[0137]

[0138] Table 2

[0139]

[0140] According to the present invention, it is possible to provide an aqueous surface treatment agent capable of obtaining excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil.

[0141] Industrial applicability

[0142] According to the present invention, it is possible to provide an aqueous surface treatment agent capable of obtaining excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. Further, according to the present invention, it is possible to provide a laminate having a film of a metal and an aqueous surface treatment agent capable of obtaining excellent adhesion to a resin film.

Claims

1. A water-based surface treatment agent for metal surface treatment, wherein: The aqueous surface treatment agent comprises: Nitrogen-containing silane coupling agent; as well as Epoxides, The epoxy compound has two or more epoxy groups in one molecule. 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 compound has an epoxy equivalent of 90 g / equivalent 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 an amino group and an imino group.

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

6. A laminate comprising: 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, wherein: The stacked body has, in order: said metal; The membrane; and Resin film.

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

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