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 Art

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

[0003] Copper foils such as rolled copper foil and electrolytic copper foil are used as materials for such printed wiring boards. Conventionally, copper foil has been used after roughening the surface of the copper foil in order 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 manufacturing process can be simplified and the cost can be reduced.

[0006] On the other hand, for example, in Patent Document 1, a copper surface treatment agent that can treat the surface of copper in a smooth state without roughening treatment such as etching and can maintain the adhesion between copper and an insulating material such as resin is disclosed. The copper surface treatment agent 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.

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 that can obtain excellent adhesion with 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 amide group-containing resin, and the amide group-containing resin is an aqueous surface treatment agent having an amide group in its side chain. Thereby, excellent adhesion between the copper foil and the resin film can 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-NH2.

[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 selected from the group consisting of an amino group and an imino group.

[0015] The laminate according to the present invention is, in order, a metal, a film of any of the above aqueous surface treatment agents, and is a laminate having the same.

[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 sequentially includes, the metal, the film, a resin film, and has the same.

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

Advantages of the Invention

[0019] 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 that exhibit excellent adhesion to a resin film.

Embodiments for Carrying Out the Invention

[0020] 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.

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

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

[0023] 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.

[0024] In this specification, unless otherwise specified, a numerical range is 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 certain compound meets both the nitrogen-containing silane coupling agent and the amide group-containing resin, the compound is treated as a silane coupling agent rather than an amide group-containing resin.

[0027] In this specification, “-co-” represents a copolymer containing repeating units based on the monomers on both sides thereof. For example, acrylamide-co-acrylic acid represents a copolymer containing a repeating unit based on acrylamide and a repeating unit based on acrylic acid. Also, “-co-” means that there is no specification for the sequence of the repeating units in the copolymer, and it may be random, alternating, periodic, or block.

[0028] · Aqueous surface treatment agent The aqueous surface treatment agent according to the present invention is an aqueous surface treatment agent used for surface treatment of metals, comprising a nitrogen-containing silane coupling agent, and an amide group-containing resin, and the amide group-containing resin is an aqueous surface treatment agent having an amide group in its side chain.

[0029] Hereinafter, each component of the aqueous surface treatment agent according to the present invention will be exemplified and described.

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

[0031] Examples of the nitrogen-containing group in component (A) include an amino group (-NH2), an imino group (=NR, -N(R)-), a quaternary ammonium group (-N + R3), a ureido group (-NHCONH2), an isocyanate group (-N=C=O), an 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, an isocyanurate group, and a benzotriazole group. In another embodiment, component (A) has one or more selected from the group consisting of an amino group and an imino group.

[0032] Component (A) may have an aromatic ring containing nitrogen. Component (A) includes, for example, residues such as pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furazan, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, azepine, diazepine, triazepine; residues such as indole, isoindole, indazole, purine, quinoline, isoquinoline, benzotriazole; residues such as carbazole, acridine, β-carboline, acridone, perimidine, phenazine, phenanthridine, phenothiazine, phenoxazine, phenanthroline; residues such as kindrin, quinindrin; residues such as acrindrin.

[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 and the like. 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. and the like can be mentioned.

[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] The content of component (A) in the aqueous surface treatment agent may be adjusted as appropriate. For example, the content of component (A) can be 80 to 99% by mass based on the total solid content of the aqueous surface treatment agent.

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

[0037] In one embodiment, the mass M of component (B) B to the mass M of component (A) A of the ratio (M A / M B ) is 3 or more. 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. In yet another embodiment, the ratio M 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. In yet another embodiment, the ratio M A / M B is 3 to 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. Examples of component (B) include polyamide having an amide group in the side chain, polyacrylamide having an amide group in the side chain, and polyacrylamide copolymer having an amide group in the side chain.

[0039] Examples of polyacrylamide having an amide group in the side chain include cationic polyacrylamide and nonionic polyacrylamide.

[0040] (B) components include, for example, polyacrylamide (Sigma-Aldrich catalog number: 535311, hereinafter, the numbers in parentheses in this paragraph represent Sigma-Aldrich catalog numbers), poly(N-isopropylacrylamide), potassium poly(acrylamide-co-acrylic acid) (432776), poly(N-isopropylacrylamide) carboxylic acid-thiol terminal (806366), poly(N-isopropylacrylamide) N-hydroxysuccinimide ester terminal (900188), sodium poly(acrylamide-co-acrylic acid) (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 terminal (773638), poly(acrylamide-co-diallyldimethylammonium chloride) (409081), poly(N-isopropylacrylamide) azide terminal (747068), poly(ethylene glycol)-block-poly(N-isopropylacrylamide) (747181), poly(N-(2-hydroxypropyl)methacrylamide) (804746), poly(N-isopropylacrylamide-co-butyl acrylate) (762857), poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] (190888), and the like.

[0041] In addition, as commercially available products of component (B), in addition to those described above, there are product names manufactured by Harima Chemicals, Inc., "Haricot G35", "Haricot G50", "Haricot G51", "Haricot GA-1", "Haricot 1057"; Sigma-Aldrich catalog numbers: 725668; product names manufactured by Nittobo Medical Co., Ltd., "PAS-2141CL", "PAS-J-81L", "PAS-J-81", "PAS-J-41", and the like.

[0042] Component (B) may be an amide-modified resin obtained by using a resin having a functional group other than an amide group in the side chain as a starting material and introducing an amide group by modifying the functional group.

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

[0044] In one embodiment, the amide group of component (B) is -CO-NH2.

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

[0046] The content of component (B) in the aqueous surface treatment agent may be adjusted as appropriate. For example, the content of component (B) can be 1 to 20% by mass based on the total solid content of the aqueous surface treatment agent.

[0047] In addition to components (A) and (B), the aqueous surface treatment agent according to the present invention may contain 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, condensates of component (A) with each other, condensates of component (A) with other components, etc. described in Patent Document 1.

[0048] · Solvent In order to adjust the solid content concentration and drying rate, the aqueous surface treatment agent according to the present invention may further contain an organic solvent miscible with water as needed. 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.

[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 this 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 preparation method of the aqueous surface treatment agent is not particularly limited, and components (A) and (B) may be mixed. In addition to components (A) and (B), other components such as solvents may be mixed in any order.

[0052] ·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.

[0053] ·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, etc. can be mentioned.

[0054] Examples of copper include rolled copper foil, electrolytic copper foil, etc. Further, copper may be a copper alloy with, for example, 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.

[0055] 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.

[0056] The surface roughness of one side of the metal is, for example, Rz (ten-point mean 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. Also, 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 can 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.

[0058] · 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.

[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 adjacent to each other, that is, directly in contact with each other and laminated, or may be laminated via another layer or film between the metal and the film of the aqueous surface treatment agent.

[0060] The film of the aqueous surface treatment agent may 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.

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

[0062] · 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.

[0063] The thickness of the resin film can 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.

[0064] · Other layer or film 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.

[0065] Examples of the plating include 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.

[0066] The use of the laminate of the present invention is not particularly limited, and examples thereof include flexible printed wiring boards, household electrical appliances, information terminals, building materials, and the like.

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

[0068] · Manufacturing method of the laminate The manufacturing method of 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 in order, and a known manufacturing method of a flexible printed wiring board or the like can be used. Examples of the manufacturing method of the laminate include a method including a step of preparing a metal and an aqueous surface treatment agent, a step of applying the surface treatment agent to at least a 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.

[0069] The application method of the surface treatment agent is not particularly limited, and known application methods can be used. Examples of the application method include dipping, bar coating, roll coating, shower coating, spraying, brushing, etc.

[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 of the surface treatment agent is not particularly limited, and is, for example, 2 seconds to 1 hour.

[0072] 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.

[0073] As a manufacturing method in the case where 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 pressing the metal, the film of aqueous surface treatment agent, and the resin film is mentioned.

[0074] The temperature in the case of pressing is, for example, 100 to 450°C.

[0075] The pressure in the case of pressing is, for example, 0.1 to 10 MPa.

Examples

[0076] 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.

[0077] 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: Nonionic polyacrylamide having an amide group in the side chain, trade name "Haricot 1057" manufactured by Harima Kasei Co., Ltd. B2: Anionic polyacrylamide having an amide group in the side chain, trade name "Haricot G-50" manufactured by Harima Kasei Co., Ltd. B3: Product named "PAS-2141CL" manufactured by Nitto Boseki Medical Co., Ltd. B4: Poly(N-isopropylacrylamide) manufactured by Sigma-Aldrich Co., LLC · Comparative amide group-containing resin Product named "AQ Nylon T-70" manufactured by Toray Industries, Inc., nylon having an amide group in the main chain, denoted as "CA1" in the table

[0078] The equipment and materials used in the examples are as follows. Press: Product named "PYS-10" manufactured by Kodaira Seisakusho 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 instrument: Product named "LTS-200N-S100" manufactured by Minebea Mitsumi Inc. Polyimide film: Product name "Upilex (registered trademark)-25VT" manufactured by UBE Industries, Ltd., thickness 25 μm

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

[0080] · Preparation of laminate An 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 a press machine with a 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 a press machine and held for 30 minutes. Next, a laminate having a three-layer structure of electrolytic copper foil / aqueous surface treatment agent film / polyimide film was obtained.

[0081] For Examples 2 to 22 and Comparative Examples 1 to 6 as well, a laminate having 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 by changing the aqueous surface treatment agent.

[0082] · Evaluation of adhesion For the obtained laminate, the following peel strength test was performed to evaluate the adhesion. The results are shown in accordance with Table 1.

[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 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 capable of obtaining 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 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 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 amide group-containing resin, wherein the amide group-containing resin has an amide group in the side chain, the aqueous surface treatment agent.

2. The amide group is -CO-NH ２ The aqueous surface treatment agent according to claim 1, wherein it is as such.

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

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. In order, a metal, a film of the aqueous surface treatment agent according to any one of Claims 1 to 4, a laminate having the same.

6. The laminate according to Claim 5, wherein the metal is copper or a copper alloy.

7. In order, the metal, the film, a resin film, a laminate having the same according to Claim 5.

8. The laminate according to Claim 7, wherein the laminate is a flexible printed wiring board.

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