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 Art

[0002] Currently, devices using high-frequency radio waves are being developed for the spread of the fifth-generation mobile communication system and the like, and the demand for printed wiring boards compatible with the transmission of high-frequency signals is increasing.

[0003] For such materials of printed wiring boards, copper foils such as rolled copper foil and electrolytic copper foil are used. Conventionally, the surface of the copper foil has been roughened to enhance the adhesion to the resin film.

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

[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 simplification of the manufacturing process and cost reduction are also possible.

[0006]

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, it has been found that there is still 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 obtain 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 film of an aqueous surface treatment agent with excellent adhesion to a resin film.

MEANS FOR SOLVING THE PROBLEMS

[0011] The aqueous surface treatment agent according to the present invention is an aqueous surface treatment agent used for surface treatment of a metal, a nitrogen-containing silane coupling agent, and an epoxy compound, and 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. This aqueous surface treatment agent can obtain excellent adhesion between a copper foil and a resin film 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 equivalent of the epoxy compound 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 selected from the group consisting of amino groups and imino groups.

[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 comprises, in order, a metal, a film of any of the above aqueous surface treatment agents, and is a laminate having

[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 film, a resin film, and 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 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 metal and a film of an aqueous surface treatment agent with excellent adhesion to a resin film.

Modes for Carrying Out the Invention

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

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

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

[0024] The materials, components, compounds, resins, groups, and solvents described in this specification may be used alone or in combination of two or more, unless otherwise specified.

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

[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 An aqueous surface treatment agent used for surface treatment of a metal according to the present invention, A nitrogen-containing silane coupling agent, and An epoxy compound, and contains, The epoxy compound has two or more epoxy groups in one molecule, An aqueous surface treatment agent in which 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] Hereinafter, each component of the aqueous surface treatment agent according to the present invention will be exemplified and described.

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

[0030] Examples of the nitrogen-containing group of component (A) include an amino group (-NH2), an imino group (=NR, -N(R)-), a quaternary ammonium group (-N +Examples include a ureido group (-NHCONH2), an isocyanate group (-N=C=O), and an isocyanurate group. In one embodiment, the component (A) has at least one 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, the component (A) has at least one selected from the group consisting of an amino group and an imino group.

[0031] (A) The component may have an aromatic ring containing nitrogen. The component (A) may have residues such as pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furazan, 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, perimidine, phenazine, phenanthridine, phenothiazine, phenoxazine, phenanthroline, etc.; residues such as kindoline, quinindoline, etc.; and residues such as acrindoline, etc.

[0032] (A) In addition to a group other than an aromatic ring containing nitrogen, the component may have an aromatic ring containing nitrogen.

[0033] (A) components include, for example, 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, 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 (isocyanurate group-containing), X-12-1214A (benzotriazole group-containing), X-12-1172ES (imino group-containing) manufactured by Shin-Etsu Chemical Co., Ltd., VD-5 (triazine ring-containing) manufactured by Shikoku Kasei Kogyo Co., Ltd., etc. are included.

[0034] In a preferred embodiment, the (A) component is at least one 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] In the aqueous surface treatment agent, the content of component (A) only needs to be such that the ratio (Ms / Me) of the mass Ms of component (A) to the mass Me of component (B) is 3 or more, and it can be adjusted as appropriate. For example, the content of component (A) can be 75.0 to 99.5% by mass based on the total amount of the solid content of the aqueous surface treatment agent. In one embodiment, the content of 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 based on the total amount of the solid content of the aqueous surface treatment agent. In another embodiment, the content of 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 based on the total amount of the solid content of the aqueous surface treatment agent.

[0036] In one embodiment, the total concentration of component (A) and component (B) with respect to the entire aqueous surface treatment agent is 100 to 30000 ppm. In another embodiment, the total concentration of component (A) and component (B) with respect to the entire aqueous surface treatment agent is 100 ppm or more, 500 ppm or more, 1000 ppm or more, 5000 ppm or more, 10000 ppm or more, 15000 ppm or more, 20000 ppm or more, or 25000 ppm or more. In yet another embodiment, the total concentration of component (A) and component (B) with respect to the entire aqueous surface treatment agent is 30000 ppm or less, 25000 ppm or less, 20000 ppm or less, 15000 ppm or less, 10000 ppm or less, 5000 ppm or less, 1000 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 Ms of component (A) to the mass Me of component (B) is 3 or more. By the ratio (Ms / Me) being 3 or more, the adhesion between the metal and the resin film through the film of the aqueous surface treatment agent is enhanced. 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 to 200.

[0038] · Component (B): epoxy compound As component (B), a known epoxy compound having two or more epoxy groups in one molecule can be used. Examples of component (B) include aliphatic glycidyl ether type epoxy compounds, aromatic glycidyl ether type epoxy compounds, alicyclic epoxy compounds, and the like.

[0039] In this specification, the aliphatic glycidyl ether type epoxy compound means an aliphatic compound having two or more glycidyl ether groups. In this specification, the aromatic glycidyl ether type epoxy compound means an aromatic compound having two or more glycidyl ether groups. In this specification, the alicyclic epoxy compound means 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 in one molecule of component (B) is two or more, and for example, is 2, 3, 4, or 5.

[0042] (B) component includes, for example, ethylene glycol diglycidyl ether having two epoxy groups, 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, bicyclononadiene diepoxide; glycerol triglycidyl ether having three epoxy groups, trimethylolpropane triglycidyl ether, diglycerol triglycidyl ether; sorbitol tetraglycidyl ether having four epoxy groups, polyglycerol polyglycidyl ether, etc. In addition, for example, Denacol EX - 991L, EX - 521, EX - 1610 manufactured by Nagase ChemteX Corporation, etc. may be mentioned.

[0043] In a preferred embodiment, the (B) component is at least one 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] As the molecular weight of the (B) component, for example, it can be 170 - 750. In one embodiment, the molecular weight of the (B) component 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 (B) component 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] As the epoxy equivalent of component (B), for example, it can be 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 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 of component (B) is 90 to 180 g / equivalent.

[0046] The content of component (B) in the aqueous surface treatment agent may be such that the ratio (Ms / Me) of the mass Ms of component (A) to the mass Me of component (B) is 3 or more, and it may be adjusted as appropriate. For example, the content of component (B) can be 0.5 to 25.0% by mass based on the total solid content of the aqueous surface treatment agent. In one embodiment, the content of component (B) is 0.5% by mass or more, 1.0% by mass or more, 5.0% by mass or more, 10.0% by mass or more, 15.0% by mass or more, or 20.0% by mass or more based on the total solid content of the aqueous surface treatment agent. In another embodiment, the content of component (B) is 25.0% by mass or less, 20.0% by mass or less, 15.0% by mass or less, 10.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less based on 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 components (A) and (B), components used in known surface treatment agents. The aqueous surface treatment agent may contain, for example, solvents such as water, alcohol, and acetone; water-soluble polymers, water-dispersible polymers, resins, pH adjusters, rust inhibitors, acids, bases, surface conditioners, defoamers, condensates of component (A) with each other, condensates of component (A) with other components, etc. described in Patent Document 1.

[0048] · Solvent The aqueous surface treatment agent according to the present invention may further contain an organic solvent miscible with water as needed to adjust the solid content concentration and drying rate. Examples of the organic solvent miscible with water include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, isopropyl alcohol, 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, and the like.

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

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

[0051] · Laminate The laminate according to the present invention is a laminate having, in order, a metal and a film of an aqueous surface treatment agent. Thereby, excellent adhesion between the metal and the resin film through the film of the aqueous surface treatment agent can be obtained.

[0052] · Metal The metal is not particularly limited as long as it is a metal that requires adhesion to the resin film, etc., and known metals can be used. For example, copper, nickel, aluminum, and the like can be mentioned.

[0053] Examples of the copper include rolled copper foil, electrolytic copper foil, etc. Further, the copper may 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. In the laminate of the present invention, since it contains the film of the aqueous surface treatment agent of the present invention, excellent adhesion to the resin film can be obtained even with a non-roughened metal. 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. Further, 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, for example, it is 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 the aqueous surface treatment agent 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 adjacent to each other, that is, directly in contact with each other and laminated, or may be laminated with other layers or films interposed therebetween.

[0059] 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 may be laminated on the whole of one surface or both surfaces (opposite surfaces) of the metal.

[0060] In one embodiment of the laminate according to the present invention, the laminate has, in order, the metal, the film, 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 film, modified polyimide (MPI) film, polyamide film, polyester film (for example, polyethylene terephthalate film, poly-1,4-cyclohexanedimethylene terephthalate film, etc.), liquid crystal polymer film, polycarbonate film, cycloolefin polymer film, fluororesin film, etc., which are used for printed wiring board applications.

[0062] The thickness of the resin film may be adjusted as appropriate. For example, it is 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 the layer or film that may be disposed between the metal and the film of the aqueous surface treatment agent include, for example, plating formed by surface treatment of the metal, chromate film, and the like.

[0064] Examples of the plating include, for example, Ni plating, Ni-P plating, Ni-Co plating, Ni-Mo plating, Zn plating, Zn-Ni plating, Cu-Zn plating, Cu-Ni plating, Cu-Ni-Co plating, and the like.

[0065] The use of the laminate of the present invention is not particularly limited, and examples include, for example, flexible printed wiring boards, household electrical appliances, information terminals, building materials, and the like.

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

[0067] · Method for manufacturing a laminate The method for manufacturing the laminate is not particularly limited as long as it can be laminated to have a metal and a film of an aqueous surface treatment agent, and a known method for manufacturing a flexible printed wiring board or the like can be used. Examples of the method for manufacturing the laminate include, for example, a step of preparing a metal and an aqueous surface treatment agent, a step of applying the surface treatment agent to at least a part 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 a known application method can be used. Examples of the application method include, for example, dipping, bar coating, roll coating, shower coating, spraying, brush coating, and the like.

[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, 2 seconds to 1 hour.

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

[0072] As a manufacturing method when the laminate has a structure of metal / film of aqueous surface treatment agent / resin film, for example, after forming a laminate of metal / film of aqueous surface treatment agent, a resin film is disposed on the film, and then, a method of crimping the metal, the film of aqueous surface treatment agent, and the resin film can be mentioned.

[0073] The temperature in the case of crimping is, for example, 100 to 450°C.

[0074] The pressure in the case of crimping is, for example, 0.1 to 10 MPa.

Examples

[0075] Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for the purpose of exemplifying the present invention and do not 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 agent Comparative silane coupling agent 1: vinyltriethoxysilane, trade name "KBE-1003", denoted as "CS1" in the table Comparative silane coupling agent 2: 3-methacryloxypropyltriethoxysilane, trade name "KBE-503", denoted 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, number of epoxy groups 4, epoxy equivalent 173 g / equivalent, trade name "Denacol EX-614B" B2: glycerol polyglycidyl ether, a mixture of 2 and 3 epoxy groups, epoxy equivalent 141 g / equivalent, trade name "Denacol EX-313" B3: sorbitol polyglycidyl ether, number of epoxy groups 4, epoxy equivalent 191 g / equivalent, trade name "Denacol EX-622" B4: ethylene glycol diglycidyl ether, number of epoxy groups 2, epoxy equivalent 95 g / equivalent, trade name "Denacol EX-810P" B5: trimethylolpropane polyglycidyl ether, a mixture of 2 and 3 epoxy groups, epoxy equivalent 130 g / equivalent, trade name "Denacol EX-321L" B6: polyethylene glycol diglycidyl ether, number of epoxy groups 2, epoxy equivalent 268 g / equivalent, trade name "Denacol EX-830" B7: polyethylene glycol diglycidyl ether, number of epoxy groups 2, epoxy equivalent 551 g / equivalent, trade name "Denacol EX-861" · Comparative epoxy compound CE1: phenol (EO)5 glycidyl ether, number of epoxy groups 1, epoxy equivalent 400 g / equivalent, trade name "Denacol EX-145" CE2: lauryl alcohol (EO) 15 glycidyl ether, number of epoxy groups 1, epoxy equivalent 971 g / equivalent, trade name "Denacol EX-171" CE3: 3-glycidoxypropyltrimethoxysilane, number of epoxy groups 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 equipment and materials used in the examples are as follows. Press: The product name is "PYS-10" manufactured by Kodaira Seisakusho Co., Ltd. Electrolytic copper foil: An electrolytic copper foil with a thickness of 20 μm that has been chromate-treated. This electrolytic copper foil has not been roughened. Polyimide film: The product name is "Upilex (registered trademark)-25VT" manufactured by UBE Industries, Ltd., with a thickness of 25 μm Load measuring instrument: The product name is "LTS-200N-S100" manufactured by Minebea Mitsumi Inc.

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

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

[0080] · Preparation of laminate The electrolytic copper foil without roughening treatment was immersed in the aqueous surface treatment agent of Example 1 for 5 seconds and then pulled up. Next, 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 placed in the press machine with the layer structure of electrolytic copper foil / aqueous surface treatment agent film / polyimide film. Next, the temperature of the press machine was raised to 300 °C over 1 hour. While maintaining 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 machine and held for 30 minutes. Next, a laminate with a three-layer structure of electrolytic copper foil / aqueous surface treatment agent film / polyimide film and a thickness of 45 μm was obtained.

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

[0082] ·Evaluation of adhesion For the obtained laminate, the following peel strength test was carried out to evaluate the adhesion. The results are shown together in Tables 1 and 2.

[0083] ·Peel strength test 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 instrument, the tip of the copper foil was gripped with a gripping tool, and a 90° peel test was carried out 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 obtain 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 metal with excellent adhesion to a resin film and a film of an aqueous surface treatment agent.

Claims

1. An aqueous surface treatment agent used for 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. In sequence, a metal; and a film of the aqueous surface treatment agent according to any one of Claims 1 to 5, to form a laminate.

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

8. In sequence, the metal; the film; and a resin film, to form the laminate according to Claim 6.

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

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