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 amide group-containing resin, wherein the amide group-containing resin has an amide group at its side chain.SELECTED DRAWING: None

Description

[Technical Field]

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

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

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

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

[0005] On the other hand, if the adhesion between the copper foil and the resin film can be ensured without roughening the surface of the copper foil, the transmission loss due to the roughening treatment can be reduced, and the manufacturing process can be simplified and costs can be reduced.

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

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

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

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

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

[0011] The aqueous surface treatment agent according to the present invention is an aqueous surface treatment agent used for metal surface treatment, a nitrogen-containing silane coupling agent; an amide group-containing resin, The amide group-containing resin is an aqueous surface treatment agent having an amide group in the side chain, which allows excellent adhesion between the copper foil and the resin film to be obtained without roughening the surface of the copper foil.

[0012] In one embodiment of the aqueous surface treatment agent according to the present invention, the amide group is —CO—NH 2 .

[0013] In one embodiment of the aqueous surface treatment agent according to the present invention, the amide group-containing resin is polyacrylamide.

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

[0016] In one embodiment of the laminate according to the present invention, the metal is copper or a copper alloy.

[0017] In one embodiment of the laminate according to the present invention, the laminate comprises, in order: The metal; The coating; A resin film; It has.

[0018] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed wiring board. [Effects of the Invention]

[0019] According to the present invention, it is possible to provide a surface treatment agent that can provide excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil, and also to provide a laminate having a metal and a coating of the aqueous surface treatment agent that can provide excellent adhesion to a resin film. DETAILED DESCRIPTION OF THE INVENTION

[0020] 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.

[0021] In the present invention, two or more embodiments can be combined in any manner.

[0022] In the present invention, the term "solid content" is a concept that encompasses solid content and non-volatile content.

[0023] Unless otherwise specified, the materials, components, compounds, resins, groups, and solvents described herein may be used alone or in combination of two or more.

[0024] In this specification, unless otherwise specified, numerical ranges are intended to include the upper and lower limits of the range. For example, 1 to 20% by mass means a range of 1% by mass or more and 20% by mass or less.

[0025] In this specification, the nitrogen-containing silane coupling agent and the amide group-containing resin may be referred to as component (A) and component (B), respectively.

[0026] When a compound corresponds to both a nitrogen-containing silane coupling agent and an amide group-containing resin, the compound is treated as a silane coupling agent, not as an amide group-containing resin.

[0027] In this specification, "-co-" indicates a copolymer containing repeating units based on the monomers on both sides. For example, acrylamide-co-acrylic acid indicates a copolymer containing repeating units based on acrylamide and repeating units based on acrylic acid. Furthermore, "-co-" does not specify the arrangement of the repeating units in the copolymer, and means that it may be random, alternating, periodic, or block.

[0028] Water-based surface treatment agent The aqueous surface treatment agent according to the present invention is an aqueous surface treatment agent used for metal surface treatment, a nitrogen-containing silane coupling agent; an amide group-containing resin, The amide group-containing resin is an aqueous surface treatment agent having an amide group on the side chain.

[0029] Each component of the aqueous surface treatment agent according to the present invention will be illustrated below.

[0030] Component (A): Nitrogen-containing silane coupling agent As the component (A), a known nitrogen-containing silane coupling agent can be used.

[0031] Examples of the nitrogen-containing group contained in component (A) include an amino group (-NH2), an imino group (=NR, -N(R)-), a quaternary ammonium group (-N + Examples of such groups include an amino group, an imino group, a quaternary ammonium group, an ureido group, an isocyanate group, an isocyanurate group, and a benzotriazole group. In another embodiment, component (A) has one or more groups selected from the group consisting of an amino group and an imino group.

[0032] Component (A) may have a nitrogen-containing aromatic ring. Component (A) may have, for example, a residue of pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furazan, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, azepine, diazepine, triazepine, etc.; a residue of indole, isoindole, indazole, purine, quinoline, isoquinoline, benzotriazole, etc.; a residue of carbazole, acridine, β-carboline, acridone, perimidine, phenazine, phenanthridine, phenothiazine, phenoxazine, phenanthroline, etc.; a residue of quindoline, quinindoline, etc.; or a residue of acrylindoline, etc.

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

[0034] In a preferred embodiment, component (A) is one or more selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

[0035] The content of component (A) in the aqueous surface treatment agent may be adjusted as appropriate, for example, the content of component (A) may be 80 to 99 mass % relative to the total amount of solids in the aqueous surface treatment agent.

[0036] In one embodiment, the total concentration of the component (A) and the component (B) relative to the entire aqueous surface treatment agent is 100 to 30,000 ppm.

[0037] In one embodiment, the mass M of component (B) B Mass M of component (A) A The ratio (M A / M B ) is greater than or equal to 3. In another embodiment, the ratio M A / M B 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. A / M B 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. A / M B is between 3 and 100.

[0038] Component (B): Amide group-containing resin As component (B), a known amide group-containing resin having an amide group in the side chain can be used, such as a polyamide having an amide group in the side chain, a polyacrylamide having an amide group in the side chain, or a polyacrylamide copolymer having an amide group in the side chain.

[0039] Examples of polyacrylamides having amide groups in the side chains include cationic polyacrylamides and nonionic polyacrylamides.

[0040] Examples of component (B) include polyacrylamide (Sigma-Aldrich catalog number: 535311; hereinafter, the numbers in parentheses in this paragraph represent Sigma-Aldrich catalog numbers), poly(N-isopropylacrylamide), poly(acrylamide-co-acrylic acid) potassium salt (432776), poly(N-isopropylacrylamide) carboxylic acid-thiol terminal (806366), poly(N-isopropylacrylamide) N-hydroxysuccinimide ester terminal (900188), poly(acrylamide-co-acrylic acid) sodium salt (511471), poly(N-isopropylacrylamide) amine terminal (724823), poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) (191981), poly(N-isopropylacrylamide) carboxylic acid terminal (724807), poly (N-isopropylacrylamide-co-methacrylic acid) (724858), poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (191973), poly(N,N-dimethylacrylamide) dodecyltrithiocarbonate terminated (773638), poly(acrylamide-co-diallyldimethylammonium chloride) (409081), poly(N-isopropylacrylamide) azide terminated (747068), Examples include poly(ethylene glycol)-block-poly(N-isopropylacrylamide) (747181), poly(N-(2-hydroxypropyl)methacrylamide) (804746), poly(N-isopropylacrylamide-co-butylacrylate) (762857), and poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] (190888).

[0041] In addition to the above, commercially available products of component (B) include those manufactured by Harima Chemicals Co., Ltd. under the trade names "Haricoat G35," "Haricoat G50," "Haricoat G51," "Haricoat GA-1," and "Haricoat 1057"; Sigma-Aldrich catalog number: 725668; and those manufactured by Nittobo Medical Co., Ltd. under the trade names "PAS-2141CL," "PAS-J-81L," "PAS-J-81," and "PAS-J-41."

[0042] The component (B) may be an amide-modified resin obtained by starting from a resin having a functional group other than an amide group in the side chain and modifying the functional group to introduce an amide group.

[0043] The form of component (B) may be water-soluble, or may be an emulsion or dispersion.

[0044] In one embodiment, the amide group of component (B) is —CO—NH 2 .

[0045] In one embodiment, component (B) is polyacrylamide. In another embodiment, component (B) comprises one or more selected from the group consisting of cationic polyacrylamides and nonionic polyacrylamides. In another embodiment, component (B) comprises one or more selected from the group consisting of cationic polyacrylamides and nonionic polyacrylamides. In yet another embodiment, component (B) comprises one or more selected from the group consisting of Sigma-Aldrich catalog numbers 432776, 511471, and 409081 and Nittobo Corporation trade names "PAS-2141CL," "PAS-J-81L," "PAS-J-81," and "PAS-J-41." In yet another embodiment, component (B) is one or more selected from the group consisting of Sigma-Aldrich catalog numbers 432776, 511471, and 409081 and Nittobo Corporation trade names "PAS-2141CL," "PAS-J-81L," "PAS-J-81," and "PAS-J-41."

[0046] The content of component (B) in the aqueous surface treatment agent may be adjusted as appropriate, for example, the content of component (B) may be 1 to 20 mass % relative to the total amount of solids in 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; condensates of the components (A) themselves; and condensates of the component (A) with other components.

[0048] ·solvent The aqueous surface treatment agent according to the present invention may further contain a water-miscible organic solvent, if necessary, to adjust the solid content concentration or drying speed. Examples of the water-miscible organic solvent include ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, isopropyl alcohol and 1-methoxy-2-propanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; and pyrrolidone solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone.

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

[0050] The aqueous surface treatment agent of the present embodiment may contain known acids, bases, surface conditioners, and antifoaming agents that are blended in conventional aqueous surface treatment agents.

[0051] Preparation method of aqueous surface treatment agent The method for preparing the aqueous surface treatment agent is not particularly limited, and it is sufficient to mix the components (A) and (B). In addition to the components (A) and (B), other components such as a solvent may also be mixed in any order.

[0052] Laminates The laminate according to the present invention is a laminate having, in order, a metal and a coating of an aqueous surface treatment agent, thereby achieving excellent adhesion between the metal and the resin film via the coating of the aqueous surface treatment agent.

[0053] ·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.

[0054] 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.

[0055] 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.

[0056] 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 B0601 (2013) using a commercially available laser microscope, OPTELICS HYBRID, manufactured by Lasertec Corporation.

[0057] The thickness of the metal may be adjusted appropriately and is, for example, 1 to 200 μm. In one embodiment, the thickness of the metal is 1 μm or more, 5 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 100 μm or more, or 150 μm or more. In another embodiment, the thickness of the metal is 200 μm or less, 150 μm or less, 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less.

[0058] -Water-based surface treatment film The film of the aqueous surface treatment agent is a film formed using the aqueous surface treatment agent of the present invention.

[0059] 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.

[0060] 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.

[0061] In one embodiment of the laminate according to the present invention, the laminate has, in order, the metal, the coating, and a resin film.

[0062] Resin film The resin film is not particularly limited, and known resin films can be used, such as polyimide films, modified polyimide (MPI) films, polyamide films, polyester films (e.g., polyethylene terephthalate films, poly-1,4-cyclohexanedimethylene terephthalate films, etc.), liquid crystal polymer films, polycarbonate films, cycloolefin polymer films, and fluororesin films, which are used for printed wiring boards.

[0063] 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.

[0064] Other layers or coatings Examples of layers or films that may be disposed between the metal and the film of the aqueous surface treatment agent include plating and chromate films formed by surface treatment of the metal.

[0065] 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.

[0066] 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.

[0067] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed wiring board.

[0068] ·Laminate manufacturing method The method for producing the laminate is not particularly limited as long as it can laminate the metal and the aqueous surface treatment agent in order to form a film of the aqueous surface treatment agent, and known methods for producing flexible printed wiring boards can be used. Examples of the method for producing the laminate include a method including a step of preparing a metal and an aqueous surface treatment agent, a step of applying the surface treatment agent to at least a portion of at least one surface of the metal, and a step of heating or drying the applied surface treatment agent to form a film of the surface treatment agent.

[0069] 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.

[0070] The heating or drying temperature of the surface treatment agent is not particularly limited, and is, for example, 50 to 250°C.

[0071] The heating or drying time for the surface treatment agent is not particularly limited, and is, for example, 2 seconds to 1 hour.

[0072] The thickness of the coating is not particularly limited and may be adjusted as appropriate, and is, for example, 1 nm to 10 μm in dry thickness.

[0073] 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.

[0074] The temperature for pressure bonding is, for example, 100 to 450°C.

[0075] The pressure to be applied when pressure bonding is, for example, 0.1 to 10 MPa. [Example]

[0076] 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.

[0077] The materials used in the examples are as follows: Component (A) A1: 3-aminopropyltrimethoxysilane, product name "KBM-903" A2: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, product name "KBM-603" A3: 3-aminopropyltriethoxysilane, product name "KBE-903" A4: N-(2-aminoethyl)-3-aminopropyltriethoxysilane, product name "KBE-603" A5: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, product name "KBM-602" A6: N-phenyl-3-aminopropyltrimethoxysilane, product name "KBM-573" Comparison silane coupling agent Comparative silane coupling agent 1: Vinyltriethoxysilane, product name "KBE-1003", indicated as "CS1" in the table Comparative silane coupling agent 2: 3-methacryloxypropyltriethoxysilane, 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. ·(B) Component B1: Nonionic polyacrylamide having amide groups in the side chains, trade name "Haricoat 1057" manufactured by Harima Chemicals Co., Ltd. B2: Anionic polyacrylamide having amide groups in the side chains, trade name "Haricoat G-50" manufactured by Harima Chemicals Co., Ltd. B3: Product name "PAS-2141CL" manufactured by Nittobo Medical Co., Ltd. B4: Poly(N-isopropylacrylamide) from Sigma-Aldrich ·Comparative amide group-containing resin Toray Industries, Inc.'s product name "AQ Nylon T-70," a nylon with an amide group on the main chain, is shown as "CA1" in the table.

[0078] The devices and materials used in the examples are as follows: Press machine: Product name "PYS-10" manufactured by Kodaira Manufacturing Co., Ltd. Electrolytic copper foil: chromate-treated electrolytic copper foil with a thickness of 20 μm. This electrolytic copper foil is not roughened. Load measuring device: MinebeaMitsumi product name "LTS-200N-S100" Polyimide film: UBE Corporation's product name "UPILEX (registered trademark)-25VT", thickness 25 μm

[0079] Examples 1 to 22 and Comparative Examples 1 to 6 Component (A), component (B), and deionized water were mixed to give the concentrations shown in Table 1 to prepare aqueous surface treatment agents.

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

[0081] In Examples 2 to 22 and Comparative Examples 1 to 6, laminates each having a three-layer structure of electrolytic copper foil / aqueous surface treatment agent film / polyimide film were obtained in the same manner as in Example 1, except that the aqueous surface treatment agent was changed.

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

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

[0084] [Table 1]

[0085] 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]

[0086] According to the present invention, it is possible to provide a surface treatment agent that can provide excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil, and also to provide a laminate having a metal and a coating of the aqueous surface treatment agent that can provide excellent adhesion to a resin film.

Claims

1. An aqueous surface treatment agent used for metal surface treatment, a nitrogen-containing silane coupling agent; an amide group-containing resin, The amide group-containing resin has an amide group in a side chain, The aqueous surface treatment agent has a ratio (MA / MB) of the mass of the nitrogen-containing silane coupling agent MA to the mass of the amide group-containing resin MA of 3 to 100.

2. The amide group is —CO—NH ２ The aqueous surface treatment agent according to claim 1,

3. 2. The aqueous surface treatment agent according to claim 1, wherein the amide group-containing resin is polyacrylamide.

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

5. The aqueous surface treatment agent according to claim 1, which is an aqueous surface treatment agent used for direct surface treatment of the metal.

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

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

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

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

10. A laminate as described in claim 6, wherein the metal and the coating are in direct contact.

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