Aqueous surface treatment agent and laminate

Abstract

The present invention provides an aqueous surface treatment agent and a laminate which can obtain excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. The aqueous surface treatment agent is used for surface treatment of metal, and the aqueous surface treatment agent comprises: a nitrogen-containing silane coupling agent; and an amide group-containing resin which has an amide group in a side chain.

Description

Technical Field

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

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

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

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

[0005] In view of this, as long as the adhesion between the copper foil and the resin film can be ensured without roughening the surface of the copper foil, the transmission loss caused by the roughening treatment can be reduced, and the manufacturing process can be simplified and the cost can be reduced.

[0006] In view of this, for example, in Patent Document 1, a surface treatment agent for copper is disclosed, which can be treated into a smooth state without roughening the surface of copper such as etching, and can maintain the adhesion between copper and insulating materials such as resin. The surface treatment agent for copper contains a tin compound, a complexing agent, and a water-soluble polymer or a water-dispersible polymer, and the water-soluble polymer or the water-dispersible polymer has at least one functional group selected from the group consisting of an amino group, an epoxy group, a thiol group, a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, an imino group, and a silanol group.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: WO 2010 / 010716 Summary of the Invention

[0010] Problems to be Solved by the Invention

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

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

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

[0014] Means for solving the problem

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

[0016] In one embodiment of the aqueous surface treatment agent according to the present invention, the amide group is -CO-NH2.

[0017] In one embodiment of the aqueous surface treatment agent according to the present invention, the amide group-containing resin is polyacrylamide.

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

[0019] The laminate according to the present invention sequentially has a metal and a film of any one of the above aqueous surface treatment agents.

[0020] In one embodiment of the laminate according to the present invention, the metal is copper or a copper alloy.

[0021] In one embodiment of the laminate according to the present invention, the laminate sequentially has the metal, the film, and a resin film.

[0022] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed circuit board.

[0023] Advantageous effects of the invention

[0024] According to the present invention, it is possible to provide an aqueous surface treatment agent capable of obtaining excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. Further, according to the present invention, it is possible to provide a laminate having a metal and a film of an aqueous surface treatment agent capable of obtaining excellent adhesion to a resin film. Detailed description of the invention

[0025] Hereinafter, embodiments of the present invention will be described. These descriptions are for illustrative purposes of the present invention and do not limit the present invention in any way.

[0026] In the present invention, two or more embodiments can be arbitrarily combined.

[0027] In the present invention, the term "solid component" is a concept including solid components and non-volatile components.

[0028] Unless otherwise noted, the materials, components, compounds, resins, groups, and solvents described in this specification can be used individually or in combination of two or more.

[0029] In this specification, unless otherwise noted, a numerical range is intended to include the upper and lower limits of that range. For example, 1% by mass to 20% by mass means a range of 1% by mass or more and 20% by mass or less.

[0030] In this specification, the nitrogen-containing silane coupling agent and the amide group-containing resin are sometimes referred to as component (A) and component (B), respectively.

[0031] When a certain compound is equivalent to both a nitrogen-containing silane coupling agent and an amide group-containing resin, the compound is not regarded as an amide group-containing resin but as a silane coupling agent.

[0032] In this specification, “-co-” indicates a copolymer including repeating units based on monomers on both sides thereof. For example, acrylamide-co-acrylic acid indicates a copolymer including repeating units based on acrylamide and repeating units based on acrylic acid. In addition, “-co-” indicates that the arrangement of the repeating units in the copolymer is not specified and can be any one of random, alternating, periodic, or block.

[0033] · Aqueous surface treatment agent

[0034] The aqueous surface treatment agent according to the present invention is used for surface treatment of metals. Among them, the aqueous surface treatment agent includes: a nitrogen-containing silane coupling agent; and an amide group-containing resin having an amide group in a side chain.

[0035] Hereinafter, each component of the aqueous surface treatment agent according to the present invention will be illustrated by way of example.

[0036] · Component (A): Nitrogen-containing silane coupling agent

[0037] As component (A), a known nitrogen-containing silane coupling agent can be used.

[0038] As the nitrogen-containing group that component (A) has, for example, the following can be cited: amino group (-NH2), imino group (=NR, -N(R)-), quaternary ammonium group (-N + R3), ureido group (-NHCONH2), isocyanate group (-N=C=O), isocyanurate group, etc. In one embodiment, component (A) has one or more groups 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 groups selected from the group consisting of an amino group and an imino group.

[0039] (A) component may have a nitrogen-containing aromatic ring. (A) component may have, for example: residues such as pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, oxadiazole, isoxazole, thiazole, isothiazole, furan, pyridine, pyridazine, pyrimidine, pyrazine, triazine, tetrazine, azepine, diazepine, triazepine, etc.; residues such as indole, isoindole, indazole, purine, quinoline, isoquinoline, benzotriazole, etc.; residues such as carbazole, acridine, β-carboline, acridone, peridine, phenazine, phenanthridine, phenothiazine, phenoxazine, phenanthroline, etc.; residues such as quinazoline, indolo[2,3-b]quinoline, etc.; residues such as indolo[3,2-c]acridine, etc.

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

[0041] In a preferred embodiment, the component (A) is selected from one or more of the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane.

[0042] The content of the component (A) in the aqueous surface treatment agent can be appropriately adjusted. For example, the content of the component (A) can be set to 80% by mass to 99% by mass relative to the total amount of the solid components in the aqueous surface treatment agent.

[0043] In one embodiment, the total concentration of the component (A) and the component (B) is 100 ppm to 30000 ppm relative to the whole aqueous surface treatment agent.

[0044] In one embodiment, the mass M of the component (A) A relative to the mass M of the component (B) B 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. Further, in 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. Further, in another embodiment, the ratio M A / M B is 3 to 100.

[0045] · Component (B): Amide group-containing resin

[0046] As the component (B), a known amide group-containing resin having an amide group in the side chain can be used. As the component (B), for example, polyamide having an amide group in the side chain, polyacrylamide having an amide group in the side chain, polyacrylamide copolymer having an amide group in the side chain, etc. can be mentioned.

[0047] As the polyacrylamide having an amide group in the side chain, for example, cationic polyacrylamide, nonionic polyacrylamide, etc. can be mentioned.

[0048] As the component (B), for example, the following can be cited: polyacrylamide (product catalog number of Sigma-Aldrich is 535311, hereinafter, the numbers in parentheses in this paragraph represent the product catalog numbers of Sigma-Aldrich), poly(N-isopropylacrylamide), potassium poly(acrylamide-co-acrylic acid) (432776), poly(N-isopropylacrylamide) with carboxylic acid and thiol termini (806366), poly(N-isopropylacrylamide) with N-hydroxysuccinimide ester termini (900188), sodium poly(acrylamide-co-acrylic acid) (511471), poly(N-isopropylacrylamide) with amine termini (724823), poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-acrylonitrile) (191981), poly(N-isopropylacrylamide) with carboxylic acid termini (724807), poly(N-isopropylacrylamide-co-methacrylic acid) (724858), poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (191973), poly(N,N-dimethylacrylamide) with dodecyl trithiocarbonate termini (773638), poly(acrylamide-co-diallyldimethylammonium chloride) (409081), poly(N-isopropylacrylamide) with azide termini (747068), poly(ethylene glycol)-block-poly(N-isopropylacrylamide) (747181), poly(N-(2-hydroxypropyl)methacrylamide) (804746), poly(N-isopropylacrylamide-co-butyl acrylate) (762857), poly[(2-ethylammonium ethyl sulfate dimethacrylate)-co-(1-vinylpyrrolidone)] (190888), etc.

[0049] In addition, as commercially available products of the component (B), in addition to the above, the products with the trade names of "Haricoat G35", "Haricoat G50", "Haricoat G51", "Haricoat GA-1", "Haricoat 1057" manufactured by Harima Chemicals Group, Inc. of Japan can be cited; the product with the Sigma-Aldrich product catalog number of 725668; the products with the trade names of "PAS-2141CL", "PAS-J-81L", "PAS-J-81", "PAS-J-41" manufactured by Nittobo medical Co., Ltd. of Japan, etc.

[0050] The component (B) can also 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 modification of the functional group.

[0051] (B) The component may be water-soluble, or may also be an emulsion or a dispersion.

[0052] In one embodiment, the amide group of the (B) component is -CO-NH2.

[0053] In one embodiment, the (B) component is polyacrylamide. In another embodiment, the (B) component comprises one or more selected from the group consisting of cationic polyacrylamide and nonionic polyacrylamide. In another embodiment, the (B) component is one or more selected from the group consisting of cationic polyacrylamide and nonionic polyacrylamide. In another embodiment, the (B) component comprises one or more selected from the group consisting of products with Sigma-Aldrich catalog numbers 432776, 511471, 409081 and products with trade names "PAS-2141CL", "PAS-J-81L", "PAS-J-81" and "PAS-J-41" manufactured by Nittobo Medical Co., Ltd., Japan. Furthermore, in another embodiment, the (B) component is one or more selected from the group consisting of products with Sigma-Aldrich catalog numbers 432776, 511471, 409081 and products with trade names "PAS-2141CL", "PAS-J-81L", "PAS-J-81" and "PAS-J-41" manufactured by Nittobo Medical Co., Ltd., Japan.

[0054] The content of the (B) component in the aqueous surface treatment agent can be appropriately adjusted. For example, the content of the (B) component can be set to 1% by mass to 20% by mass relative to the total amount of the solid components in the aqueous surface treatment agent.

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

[0056] · Solvent

[0057] In order to adjust the concentration of the solid component and the drying rate, the aqueous surface treatment agent according to the present invention may further contain an organic solvent mixed with water as needed. As the organic solvent mixed with water, for example, the following can be cited: ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N,N'-dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, 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, etc.

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

[0059] The aqueous surface treatment agent of the present embodiment may also contain known acids, bases, surface regulators, and defoamers incorporated in existing aqueous surface treatment agents.

[0060] · Preparation method of aqueous surface treatment agent

[0061] The preparation method of the aqueous surface treatment agent is not particularly limited, and it is only necessary to mix the component (A) and the component (B). In addition to the component (A) and the component (B), other components such as solvents can be mixed in any order.

[0062] · Laminate

[0063] The laminate according to the present invention is a laminate having a film of a metal and an aqueous surface treatment agent in this order. Thus, excellent adhesion between the metal and the resin film via the film of the aqueous surface treatment agent can be obtained.

[0064] · Metal

[0065] The metal is not particularly limited as long as it is a metal that needs to have adhesion to the resin film, etc. Well-known metals can be used. For example, copper, nickel, aluminum, etc. can be cited.

[0066] As copper, for example, rolled copper foil, electrolytic copper foil, etc. can be cited. In addition, copper can also be, for example, a copper alloy with tin, zinc, nickel, arsenic, silicon, titanium, or chromium, etc. In one embodiment, the metal of the laminate is copper or a copper alloy. In another embodiment, the metal of the laminate is one or more selected from the group consisting of rolled copper foil and electrolytic copper foil.

[0067] The metal of the laminate of the present invention can be a roughened metal or an unroughened metal. In the laminate of the present invention, since it contains a film of the aqueous surface treatment agent of the present invention, excellent adhesion to the resin film can be obtained even for an unroughened metal. In one embodiment, the metal of the laminate is an unroughened metal.

[0068] Regarding the surface roughness of one side of the metal, for example, Rz (ten-point mean roughness) is 10 μm or less, 5 μm or less, 3 μm or less, 2 μm or less, 1.5 μm or less, 1.4 μm or less, 1.3 μm or less, 1.2 μm or less, 1.1 μm or less, 1.0 μm or less, 0.9 μm or less, 0.8 μm or less, 0.7 μm or less, 0.6 μm or less, 0.5 μm or less, 0.4 μm or less, 0.3 μm or less, 0.2 μm or less, or 0.1 μm or less. Additionally, regarding the surface roughness of one side of the metal, for example, Rz is 0.1 μm or more. Rz can be measured in accordance with JIS B 0601 (2013) using the commercially available laser microscope OPTELIC SHYBRID manufactured by Lasertec Corporation, Japan.

[0069] The thickness of the metal can be appropriately adjusted, for example, it is 1 μm to 200 μm. In one embodiment, the thickness of the metal is 1 μm or more, 5 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 100 μm or more, or 150 μm or more. In another embodiment, the thickness of the metal is 200 μm or less, 150 μm or less, 100 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less.

[0070] · Film of the aqueous surface treatment agent

[0071] The film of the aqueous surface treatment agent is a film formed using the aqueous surface treatment agent of the present invention.

[0072] In the laminate, the metal and the film of the aqueous surface treatment agent may be arranged in the order of the metal and the aqueous surface treatment agent. They can be arranged such that the metal and the film of the aqueous surface treatment agent are adjacent, that is, laminated in direct contact, or they can be laminated with other layers or films interposed between the metal and the film of the aqueous surface treatment agent.

[0073] The film of the aqueous surface treatment agent only needs to be laminated on at least a part of at least one surface of the metal, and it can also be laminated on the entire one surface or two surfaces (opposite two surfaces) of the metal.

[0074] In one embodiment of the laminate according to the present invention, the laminate sequentially has the metal, the film, and the resin film.

[0075] · Resin film

[0076] As the resin film, there is no particular limitation, and known resin films can be used. As the resin film, for example, there can be mentioned: polyimide film for printed circuit board applications, modified polyimide (MPI) film, polyamide film, polyester film (e.g., polyethylene terephthalate film, poly-1,4-cyclohexanedimethylene terephthalate film, etc.), liquid crystal polymer film, polycarbonate film, cycloolefin polymer film, fluororesin film, etc.

[0077] The thickness of the resin film can be appropriately adjusted, for example, it is 5 μm to 200 μm. In one embodiment, the thickness of the resin film is 5 μm or more, 10 μm or more, 15 μm or more, 20 μm or more, 25 μm or more, 30 μm or more, 35 μm or more, 40 μm or more, 45 μm or more, 50 μm or more, 100 μm or more, or 150 μm or more. In another embodiment, the thickness of the resin film is 200 μm or less, 150 μm or less, 100 μm or less, 50 μm or less, 45 μm or less, 40 μm or less, 35 μm or less, 30 μm or less, 25 μm or less, 20 μm or less, 15 μm or less, or 10 μm or less.

[0078] · Other layers or films

[0079] As the layer or film that can be disposed between the metal and the film of the aqueous surface treatment agent, for example, there can be mentioned the plating layer, chromate film, etc. formed by the surface treatment of the metal.

[0080] As the plating layer, for example, there can be mentioned Ni plating layer, Ni-P plating layer, Ni-Co plating layer, Ni-Mo plating layer, Zn plating layer, Zn-Ni plating layer, Cu-Zn plating layer, Cu-Ni plating layer, Cu-Ni-Co plating layer, etc.

[0081] Regarding the use of the laminate of the present invention, there is no particular limitation. For example, there can be mentioned flexible printed circuit boards, household electrical appliances, information terminals, building materials, etc.

[0082] In one embodiment of the laminate according to the present invention, the laminate is a flexible printed circuit board.

[0083] · Manufacturing method of the laminate

[0084] The manufacturing method of the laminate is not particularly limited as long as it can laminate to successively have the metal and the film of the aqueous surface treatment agent, and known manufacturing methods of flexible printed circuit boards, etc. can be used. As the manufacturing method of the laminate, for example, there can be mentioned a method including the following steps: a step of preparing the metal and the aqueous surface treatment agent; a step of coating the surface treatment agent on at least a part of at least one surface of the metal; a step of heating or drying the coated surface treatment agent to form a film of the surface treatment agent.

[0085] The coating method of the surface treatment agent is not particularly limited, and known coating methods can be used. As the coating method, for example, dipping, bar coating, roll coating, shower coating, spray coating, brush coating, etc. can be cited.

[0086] The heating or drying temperature of the surface treatment agent is not particularly limited, and is, for example, 50°C to 250°C.

[0087] The heating or drying time of the surface treatment agent is not particularly limited, and is, for example, 2 seconds to 1 hour.

[0088] The thickness of the film is not particularly limited and can be adjusted appropriately. The thickness of the film is, for example, 1 nm to 10 μm in terms of dry film thickness.

[0089] As a manufacturing method when the laminate has a structure of metal / water-based surface treatment agent film / resin film, for example, the following method can be cited: after forming a laminate of metal / water-based surface treatment agent film, a resin film is disposed on the film, and then the metal, water-based surface treatment agent film, and resin film are pressed.

[0090] As the temperature during pressing, for example, it is 100°C to 450°C.

[0091] As the pressure during pressing, for example, it is 0.1 MPa to 10 MPa.

[0092] Examples

[0093] Hereinafter, examples are listed to further illustrate the present invention in detail. However, these examples are for the purpose of exemplifying the present invention and do not impose any limitation on the present invention.

[0094] The materials used in the examples are as follows.

[0095] · Component (A)

[0096] A1: 3-aminopropyltrimethoxysilane, trade name "KBM-903"

[0097] A2: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, trade name "KBM-603"

[0098] A3: 3-aminopropyltriethoxysilane, trade name "KBE-903"

[0099] A4: N-(2-aminoethyl)-3-aminopropyltriethoxysilane, trade name "KBE-603"

[0100] A5: N-2-(Aminoethyl)-3-aminopropylmethyldimethoxysilane, trade name "KBM-602"

[0101] A6: N-Phenyl-3-aminopropyltrimethoxysilane, trade name "KBM-573"

[0102] ·Silane coupling agent for comparison

[0103] Silane coupling agent for comparison 1: Vinyltriethoxysilane, trade name "KBE-1003", marked as "CS1" in the table

[0104] Silane coupling agent for comparison 2: 3-Methacryloxypropyltriethoxysilane, trade name "KBE-503", marked as "CS2" in the table

[0105] A1 to A6 and CS1 to CS2 are all manufactured by Shin-Etsu Chemical Co., Ltd. of Japan.

[0106] ·Component (B)

[0107] B1: Nonionic polyacrylamide with an amide group in the side chain, manufactured by Hallstar Kasei Co., Ltd. of Japan, trade name "Haricoat1057"

[0108] B2: Anionic polyacrylamide with an amide group in the side chain, manufactured by Hallstar Kasei Co., Ltd. of Japan, trade name "HaricoatG-50"

[0109] B3: Manufactured by Nittobo Medical Co., Ltd. of Japan, trade name "PAS-2141CL"

[0110] B4: Poly(N-isopropylacrylamide) manufactured by Sigma-Aldrich Corporation of the United States

[0111] ·Amide group-containing resin for comparison

[0112] Manufactured by Toray Industries, Inc. of Japan, trade name "AQ NYLON T-70", which is a nylon with an amide group in the main chain, marked as "CA1" in the table

[0113] The devices and materials used in the examples are as follows.

[0114] Press: Manufactured by Kodaira Seisakusho of Japan, trade name "PYS-10"

[0115] Electrolytic copper foil: An electrolytic copper foil with a thickness of 20 μm treated with chromate. This electrolytic copper foil has not been roughened.

[0116] Load measuring device: Manufactured by MinebeaMitsumi, Inc., Japan, with the product name "LTS-200N-S100"

[0117] Polyimide film: Manufactured by UBE Industries, Ltd., Japan, with the product name "Upirex (registered trademark)-25VT", and a thickness of 25 μm

[0118] Examples 1 to 22 and Comparative Examples 1 to 6

[0119] The aqueous surface treatment agent was prepared by mixing component (A), component (B) and deionized water at the concentrations shown in Table 1.

[0120] · Fabrication of the laminate

[0121] An unroughened electrolytic copper foil was immersed in the aqueous surface treatment agent of Example 1 for 5 seconds and then lifted. Subsequently, the electrolytic copper foil was dried at 120 °C for 30 seconds to form a film of the aqueous surface treatment agent on the surface of the electrolytic copper foil. Then, the intermediate was arranged in a layer structure of electrolytic copper foil / film of the aqueous surface treatment agent / polyimide film on a press. Subsequently, the temperature of the press was raised to 300 °C over 1 hour. While maintaining the state of 300 °C, a pressure of 5.8 MPa was applied to the intermediate from the electrolytic copper foil side and the polyimide film side with the press and maintained for 30 minutes. Then, a laminate having a three-layer structure of electrolytic copper foil / film of the aqueous surface treatment agent / polyimide film was obtained.

[0122] For Examples 2 to 22 and Comparative Examples 1 to 6, the aqueous surface treatment agent was also changed, and thus a laminate having a three-layer structure of electrolytic copper foil / film of the aqueous surface treatment agent / polyimide film was obtained in the same manner as in Example 1.

[0123] · Evaluation of adhesion

[0124] The following peel strength test was performed on the obtained laminate to evaluate the adhesion. The results are shown in Table 1.

[0125] · Peel strength test

[0126] 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 the load measuring device, the front end of the copper foil was clamped with a jig, and a 90° peel test was performed at a peel rate of 50 mm / minute over a length of 50 mm in accordance with JIS C 6481 to measure the peel strength.

[0127] Table 1

[0128]

[0129]

[0130] According to the present invention, it is possible to provide an aqueous surface treatment agent capable of obtaining excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil.

[0131] Industrial applicability

[0132] According to the present invention, it is possible to provide an aqueous surface treatment agent capable of obtaining excellent adhesion between a copper foil and a resin film without roughening the surface of the copper foil. Further, according to the present invention, it is possible to provide a laminate having a film of a metal and an aqueous surface treatment agent capable of obtaining excellent adhesion to a resin film.

Claims

1. A water-based surface treatment agent for metal surface treatment, wherein: The aqueous surface treatment agent comprises: Nitrogen-containing silane coupling agents; and Amide-containing resins, The amide group-containing resin has an amide group on a side chain.

2. The aqueous surface treatment agent according to claim 1, wherein The amide group is -CO-NH2.

3. The aqueous surface treatment agent according to claim 1, wherein The amide-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. A laminate comprising: Metal; and A film of the aqueous surface treatment agent according to any one of claims 1 to 4.

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

7. The laminate according to claim 5, wherein The stacked body has, in order: said metal; The membrane; and Resin film.

8. The laminate according to claim 7, wherein The laminate is a flexible printed circuit board.

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