WO2008004520A1 - Method of modifying surface of polyimide resin layer and process for producing metal-clad laminate - Google Patents

Abstract

A method of polyimide resin layer surface treatment which enables printed wiring boards to retain an adhesion strength sufficient for pitch reduction and can conform to extreme thickness reduction in insulating resin layers; and a process for producing a metal-clad laminate. The method of treating a surface of a polyamide resin layer comprises a step in which the surface of the polyimide resin layer is modified with an aqueous alkali solution and a step in which a polar solution containing an amino compound such as an aromatic amino compound or diaminosiloxane is applied to the modified surface of the polyimide resin layer and is dried to form a layer treated with the amino compound. The method may further include a step in which the amino-compound-treated layer on the polyimide resin layer is imidized. A metal foil is thermally press-bonded to or a metal is vapor-deposited on the surface-treated polyimide resin layer to obtain a metal-clad laminate. Two such surface-treated polyimide resin layers are thermally press-bonded to obtain a polyimide resin laminate.

Description

 Specification

 Method for surface modification of polyimide resin layer and method for manufacturing metal-clad laminate

 TECHNICAL FIELD [0001] The present invention relates to a surface treatment method for a polyimide resin layer and a method for producing a metal-clad laminate in which a polyimide resin layer is laminated on a metal foil, and more specifically, a polyimide suitable for a printed wiring board. The present invention relates to a surface treatment method for a resin layer and a method for producing a metal-clad laminate.

 Background art

 In an electronic circuit of an electronic device, a printed wiring board obtained by processing a laminated board including an insulating material and a conductive material is used. A printed wiring board is formed by forming a conductive pattern based on electrical design on the surface (and inside) of an insulating substrate with a conductive material. Depending on the type of insulating resin used as a base material, a plate-shaped rigid printed wiring board is used. Broadly divided into flexible boards and flexible printed wiring boards. A flexible printed wiring board is characterized by its flexibility, and it is an essential part for connection in movable parts that constantly bend. In addition, the flexible printed wiring board can be stored in a state of being bent in an electronic device, and thus is used as a space-saving wiring material. The flexible substrate used as the material for flexible printed wiring boards is mostly made of polyimide ester polyimide resin as the insulating resin used as the base material, but the amount of heat-resistant polyimide resin is overwhelming. Many. On the other hand, copper foil is generally used as the conductive material from the viewpoint of conductivity.

[0003] Flexible substrates include a three-layer flexible substrate and a two-layer flexible substrate because of their structure. A three-layer flexible board is made by bonding a base film such as polyimide and copper foil together with an adhesive such as epoxy resin or acrylic resin, and then base film layer (main layer of insulating resin layer), adhesive layer, copper foil It is a laminate composed of three layers. On the other hand, the two-layer flexible board is a laminated board composed of two layers, a base film layer and a copper foil layer, using a special method and without using an adhesive. Since the two-layer flexible substrate does not include an adhesive layer with low heat resistance such as epoxy resin or acrylic resin, it is possible to reduce the thickness of the entire circuit with high reliability, and the amount of use is increasing. On the other hand, from another viewpoint, the base film layer of the flexible substrate has a low thermal expansion coefficient to prevent curling. Although a polyimide resin having a low coefficient of thermal expansion is inferior in adhesiveness, a polyimide resin layer with good adhesion should be attached to the adhesive surface when all of the polyimide resin is used without using an adhesive. It was necessary to provide as an adhesion-imparting layer on the side. A flexible substrate having a copper foil layer on both sides is also known. After producing a single-sided flexible substrate having a copper foil layer on one side, a method of laminating two single-sided flexible substrates on each other, or a single-sided substrate. A method of laminating a copper foil on a flexible substrate is known. Also in this case, a flexible substrate that does not include an adhesive layer or an adhesion-imparting layer is desired!

 [0004] In recent years, demands for higher performance and higher functionality in electronic devices are increasing, and accordingly, higher density of printed wiring boards, which are circuit board materials used in electronic devices, is desired. In order to increase the density of the printed wiring board, it is necessary to reduce the width and interval of the circuit wiring, that is, to increase the fine pitch. In order to increase the density and fine pitch of a printed wiring board, it has been desired to use a copper foil having a low surface roughness. However, a copper foil with a low surface roughness has a small anchoring effect, that is, a bite into the unevenness of the copper foil surface of the insulating resin layer, so that no mechanical adhesive strength can be obtained. There was a problem that the adhesive strength was lowered. Therefore, increasing the adhesive strength between the copper foil with low surface roughness and the insulating resin is an issue.

 [0005] Polyimide resin is generally known to have poor adhesion. In addition, the base film layer of the laminate used for printed wiring boards is preferably a polyimide resin layer with a low coefficient of thermal expansion to prevent curling. Have conflicting relationships. Therefore, various surface modification techniques for polyimide films have been reported to improve the adhesive strength. One example is a surface modification method by plasma treatment, but there is a problem that an expensive apparatus is required and the running cost is increased. Examples of surface modification methods for polyimide films by plasma treatment include, for example, JP-A-5-222219, JP-A-8-12779, JP-A-11-209488, JP-A-2004-51712, Specific examples are disclosed in Japanese Patent Publication No. 2006-7518. However, with these conventional techniques, it is currently impossible to obtain a satisfactory adhesive strength between the copper foil having a low surface roughness and the polyimide resin layer.

[0006] Further, a surface modification method by wet etching that is advantageous in terms of cost is also attracting attention. In general, the adhesiveness is not sufficient as compared with the surface modification method by dry etching such as plasma treatment, and thus further improvement in this point has been required. As such a surface modification method by wet etching, for example, JP-A-11-49880 can be mentioned. According to this, a method of thermocompression bonding between a polyimide treated in a polar solvent containing an aliphatic primary amine and a metal via a polyimide adhesive is disclosed. However, this method has a problem that it is necessary to provide a polyimide adhesive layer, and the insulating resin layer becomes thick.

 [0007] Patent Document 1: JP-A-5-222219

 Patent Document 2: JP-A-8-12779

 Patent Document 3: Japanese Patent Laid-Open No. 11-209488

 Patent Document 4: Japanese Patent Laid-Open No. 2004-51712

 Patent Document 5: Japanese Patent Laid-Open No. 2006-7518

 Patent Document 6: Japanese Patent Laid-Open No. 11-49880

 Disclosure of the invention

 Problems to be solved by the invention

[0008] An object of the present invention is to improve the adhesion by modifying the surface of a polyimide resin layer. In addition, the surface of a low thermal expansion polyimide resin layer suitable as a base film layer is modified to improve adhesion, and the adhesive polyimide resin layer or adhesive layer that becomes an adhesion-imparting layer can be omitted. For the purpose. Another object is to provide a method for producing a copper clad laminate having an ultra-thin adhesive layer, and to ensure sufficient adhesion strength to meet the fine pitch of printed circuit boards, while also ensuring that the insulating The object is to provide a method of manufacturing a copper clad laminate that can cope with thinning. Another object of the present invention is to improve an adhesion method in which polyimide resin layer surfaces are superposed and thermocompression bonded. Another object is to provide a method for producing a double-sided metal-clad laminate.

 Means for solving the problem

[0009] In order to achieve the above object, the present inventors have studied, and as a result of appropriately improving the wet etching method, the polyimide resin layer using the wet etching method has the same thickness as the polyimide resin layer. Excellent adhesive polyimide with high adhesive strength to metal foil that can hardly be changed The present inventors have found that a resin layer can be provided and have completed the present invention.

[0010] The present invention includes: a) a step of forming a surface layer of a polyimide resin layer with an alkaline aqueous solution to form an alkali treatment layer; and b) a polar solvent solution containing an amino compound on the surface of the alkali treatment layer. And a method of forming a modified layer on the surface of the polyimide resin layer, comprising: impregnation and drying to form an amino compound-containing layer.

[0011] In addition, the present invention provides: a) a step of treating the surface side of the polyimide resin layer with an alkaline aqueous solution to form an alkali treated layer; and b) a polar solvent containing an amino compound on the surface of the alkali treated layer. A surface of a polyimide resin layer comprising: a step of impregnating a solution and drying to form an amino compound-containing layer; and c) a step of imidizing the amino compound-containing layer to form a modified imidized layer. The present invention relates to a method for forming a modified layer.

[0012] The present invention also provides a metal-clad laminate comprising: I) a step of forming a modified layer on the surface of the polyimide resin layer; and ii) a step of forming a metal layer on the surface of the modified layer. In the manufacturing method of step I),

 a) a step of forming an alkali-treated layer by treating the surface side of the polyimide resin layer with an alkaline aqueous solution; and b) impregnating and drying a polar solvent solution containing an amino compound on the surface of the alkali-treated layer to contain an amino compound. And a step of forming a layer. The present invention relates to a method for manufacturing a metal-clad laminate.

 [0013] In addition, the present invention includes: a) a step of treating the surface side of the polyimide resin layer with an alkaline aqueous solution to form an alkali treated layer; and b) a polar solvent containing an amino compound on the surface of the alkali treated layer. The present invention relates to a method for producing a metal-clad laminate comprising a step of impregnating a solution and drying to form an amino compound-containing layer, and d) a step of overlaying a metal foil on the surface of the amino compound-containing layer and thermocompression bonding.

 [0014] Further, the present invention provides: a) a step of forming a surface of the polyimide resin layer with an alkaline aqueous solution to form an alkali treated layer; and b) a polar solvent containing an amino compound on the surface of the alkali treated layer. The present invention relates to a method for producing a metal-clad laminate comprising a step of impregnating a solution and drying to form an amino compound-containing layer, and e) a step of forming a metal thin film layer on the surface of the amino compound-containing layer.

[0015] Further, the present invention provides: a) a layer on the surface side of the polyimide resin layer treated with an alkaline aqueous solution; A step of forming a potassium treatment layer, b) impregnating a polar solvent solution containing an amino compound on the surface of the alkali treatment layer and drying to form an amino compound-containing layer, and C) imidizing the amino compound-containing layer. Forming a modified imidized layer, and d) overlaying a metal foil on the surface of the modified imidized layer and thermocompression bonding,

[0016] Further, the present invention includes: a) a step of forming a surface of the polyimide resin layer with an alkali aqueous solution to form an alkali treated layer; and b) a polar solvent containing an amino compound on the surface of the alkali treated layer. Impregnating the solution and drying to form an amino compound-containing layer; c) imidizing the amino compound-containing layer to form a modified imidized layer; and e) a surface of the modified imidized layer. And a method of forming a metal thin film layer.

 [0017] Further, the present invention relates to a method for bonding a polyimide resin layer by superimposing a first polyimide resin layer surface and a second polyimide resin layer surface,

 A) For the first polyimide resin layer surface, a) a step of forming an alkali-treated layer by treating the surface side of the polyimide resin layer (P1) with an aqueous alkaline solution,

 B) Regarding the second polyimide resin layer, a) a step of forming an alkali treatment layer by treating the surface side of the polyimide resin layer (P2) with an alkaline aqueous solution, b) amino acid combination with the alkali treatment layer surface Impregnating a polar solvent solution containing a product and drying to form an amino compound-containing layer;

C) The step of superimposing the amino compound treatment layer surface of the second polyimide resin layer (P2) on the alkali treatment layer surface of the first polyimide resin layer (P1) and thermocompression bonding,

 It is related with the adhesion method of the polyimide resin layer characterized by having.

[0018] Further, according to the present invention, a double-sided metal-clad laminate having metal foils on both sides of a polyimide resin layer by laminating and bonding two single-sided metal-clad laminates having a metal foil on one side of a polyimide resin layer. In the manufacturing method of

 A) For the first single-sided metal-clad laminate, a) a step of treating the surface side of the polyimide resin layer (P1) with an aqueous alkali solution to form an alkali treatment layer;

B) For the second single-sided metal-clad laminate, a) a step of treating the surface side of the polyimide resin layer (P2) with an aqueous alkali solution to form an alkali treatment layer; b) A step of impregnating and drying a polar solvent solution containing a compound to form an amino compound-containing layer When,

 C) Overlay the surface of the polyimide resin layer (P1) of the first single-sided metal-clad laminate with the alkali-treated layer side of the polyimide resin layer (P2) of the second single-sided metal-clad laminate, and thermocompression bond A process for producing a double-sided metal-clad laminate, characterized by comprising:

[0019] The thickness of the alkali treatment layer formed in the step a) is preferably in the range of 0.005 to 3.0 μm. Further, the polyimide resin layer can be a polyimide resin layer that forms the surface layer of the laminate, or can be a polyimide resin layer that forms the surface layer of the polyimide resin film.

 [0020] The amino compound used in the above step b) includes an aromatic amine having a primary or secondary amino group, an aliphatic amine having at least three primary amino groups as functional groups, amino Advantageously, silane coupling agents having groups, diaminosiloxanes and polyimide precursors are also selected. Here, the polyimide precursor resin is polyamic acid.

 [0021] Examples of the silane coupling agent having an amino group include 3aminopropyltriethoxysilane, 3aminopropyltrimethoxysilane, N—2- (aminoethynole) 3aminopropyltrimethoxysilane, N-2- ( Aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N— (1,3 dimethylbutylidene) propylamine, and N-phenyl 3-aminopropyltrimethoxysilane force selected at least 1 There are seeds.

 As the diaminosiloxane, there is a diaminosiloxane oligomer represented by the following general formula (1).

Here, Ar and Ar represent a divalent hydrocarbon group, R to R are hydrocarbon groups having 1 to 6 carbon atoms.

 2 7 3 6

 M represents a number from 1 to 20.

[0023] The metal foil used in the thermocompression bonding performed in the above step d) or d2) includes a copper foil and a copper alloy. Foil or stainless steel foil is preferred.

Hereinafter, the present invention will be described in detail.

 [0025] The polyimide resin layer used in the present invention is not particularly limited, and may be a film (sheet) having a high polyimide resin capacity. The polyimide resin layer may be stacked on a substrate such as a copper foil, a glass plate, or a resin film. It may be a polyimide resin layer in a layered state. In addition, the base material here means a sheet-like resin or metal foil on which a polyimide resin layer is laminated. However, at least one side of the polyimide resin layer exists as a surface layer. The polyimide resin layer has a thickness of 3 to: LOO / z m, preferably 3 to 50 / ζ πι. By performing surface treatment, the polyimide resin layer has at least two layers of an initial polyimide resin layer (unmodified polyimide resin layer) and a modified layer.

 [0026] The polyimide resin that forms the polyimide resin layer includes imide groups in the structure of polyamide imide, polybenzimidazole, polyimide ester, polyether imide, polysiloxane imide, etc., including so-called polyimide resin. There is a heat-resistant rosin. Commercially available polyimide resin or polyimide film can also be used suitably.

[0027] Among the polyimide resin layers, the method of the present invention is suitable for a polyimide resin layer having low adhesion and low thermal expansion. Specifically, linear thermal expansion coefficient of ^{1 X 10 "6 ~30 Χ 10} _ 6 (1 / Κ), preferably ^{1 X 10- 6 ~25 X 10"} 6 (1 / Κ), more preferably 15 X When applied to a low thermal expansion polyimide resin layer of 10 " ⁶ to 25 X 10" ⁶ (1 / Κ), a great effect is obtained. However, it can be applied to a polyimide resin layer having a thermal coefficient of thermal expansion exceeding the above, and the adhesion is improved.

 [0028] The polyimide resin used in the polyimide resin layer is preferably a polyimide resin having a structural unit represented by the general formula (2).

However, Ar shows the tetravalent aromatic group represented by Formula (3) or Formula (4), Ar is Formula (5) or Formula (6) R is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms or

 1

 An alkoxy group, X and Y independently represent a single bond or a divalent hydrocarbon group having 1 to 15 carbon atoms, a divalent group selected from 0, S, CO, SO, SO or CONH, and n represents Independently of 0-4

 2

 Q represents an integer, q represents the molar ratio of the constituent units, and ranges from 0.1 to 1.0.

[0030] The structural unit may exist in a homopolymer or as a structural unit of a copolymer. In the case of a copolymer having a plurality of structural units, it may be present as a block or randomly. Among polyimide resins having such a structural unit, a polyimide resin that can be suitably used is a non-thermoplastic polyimide resin.

 [0031] Since polyimide resin is generally produced by reacting diamine and acid dianhydride, a specific example of polyimide resin can be understood by explaining diamine and acid dianhydride. In the above general formula (1), Ar can be referred to as a residue of diamine, and Ar is a residue of acid dianhydride.

 3 1

 Therefore, a preferable polyimide resin is explained by diamine and acid dianhydride. However, it is not limited to the polyimide resin obtained by this method.

Examples of the diamine include 4,4, -diaminodiphenyl ether, 2, -methoxy-4,4, -diaminobenzaldehyde, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis. (4-aminophenoxy) benzene, 2,2, -bis [4- (4-aminophenoxy) phenol] propane, 2,2, -dimethyl-4,4, -diaminobiphenyl, 3,3, -dihydroxy -4,4, -Diaminobiphenyl, 4,4, -Diaminobe Preferable examples include nusa-lid.

 2,2-bis- [4- (3-aminophenoxy) phenol] propane, bis [4- (4-aminophenoxy) phenol] sulfone, bis [4- (3-aminophenoxy) phenol ] Sulfone, bis [4- (4-aminophenoxy)] biphenyl, bis [4- (3-aminophenoxy) biphenyl, bis [1- (4-aminophenoxy)] biphenyl, bis [1- (3 -Aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) phenol] methane, bis [4- (3-aminophenoxy) phenol] methane, bis [4- (4-aminophenoxy) phenol ] Ether, Bis [4- (3-Aminophenoxy) phenol] Ether, Bis [4- (4-Aminophenoxy)] Benzophenone, Bis [4- (3-Aminophenoxy)] Benzophenone, Bis [4,4 (4-Aminophenoxy)] benzaldehyde, bis [4,4 (3-aminophenoxy)] benzaldehyde, 9,9- The [4- (4-aminophenoxy) Hue - le] fluorene, 9, 9-bis [4- (3-aminophenoxy) Hue - le] fluorene, and the like preferably.

Other diamines include 2,2-bis- [4- (4-aminophenoxy) phenol] hexafluoropropane, 2,2-bis- [4- (3-aminophenoxy) phenol] hexafluor Lopropane, 4,4'-methylenedi-0-toluidine, 4,4'-methylenedi-2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 4,4, -diaminodiphenylpropane, 3,3, -diaminodiphenylpropane, 4,4, -diaminodiphenylethane, 3,3, -diaminodiphenylethane, 4,4, -diaminodiphenylmethane, 3,3, -diaminodiphenylmethane, 4, 4, -diaminodiphenylsulfide, 3,3, -diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether, 3,3-diaminodiphenyl Diether, 3,4'-diaminodiphenyl Ether, benzidine, 3,3 - diamino Biff enyl, 3,3, - dimethicone Le - _{4, 4,} - Jiaminobifue - le, 3,3, - dimethoxy benzidine, 4,4 '- Jiamino - p-Terufue - Le 3,3 "-damino-p-terfel, m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-Aminophenoxy) Benzene, 4,4 [1,4-Phenylenebis (1-methylethylidene)] bisaline, 4,4 '-[1,3-Phenylenebis (1-methylenoethylidene)] bisa -Phosphorus, bis (p-aminocyclohexyl) methan, bis (p-β-amino-1-butylphenol) ether, bis (p-β-methyl-δ-aminopentyl) benzene, ρ-bis ( 2-Methyl-4-amino-pentyl) benzene, ρ-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-di Mino naphthalene, 2,4-bis ( β-Amino-1-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine and the like.

 [0034] Examples of acid dianhydrides include pyromellitic anhydride, 3,3,, 4,4, -biphenyltetracarboxylic dianhydride, 3,3, 4,4, _diphenylsulfone. Preferred examples include tetracarboxylic dianhydride and 4,4, -oxydiphthalic anhydride.

 In addition, 2,2 ', 3,3'-, 2,3,3', 4'- or 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3', 3,4, -biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3', 3,4'_diphenyl ether tetracarboxylic acid Preferred examples include dianhydrides and bis (2,3-dicarboxyphenyl) ether dianhydrides. Also, 3,3 ", 4,4"-, 2,3,3 ", 4"-or 2,2 ", 3,3" -p-terphenyl tetracarboxylic dianhydride, 2,2- Bis (2,3- or 3,4-dicarboxyphenol) -propane dianhydride, bis (2,3- or 3.4-dicarboxyphenyl) methane dianhydride, bis (2,3- or 3 1,4-dicarboxyphenyl) sulfone dianhydride, 1,1_bis (2,3- or 3,4-dicarboxyphenyl) ethane anhydride and the like are preferable.

[0035] Other acid dianhydrides include 1,2,7,8-, 1,2,6,7- or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3, 6,7-anthracenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,6- or 2,7-dichloro Naphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7- (or 1,4,5,8-) tetrachloronaphthalene-1,4,5,8- (or 2,3,6,7-) tetracarboxylic dianhydride, 2,3,8,9-, 3,4,9,10-, 4,5, 10,11- or 5,6,11, 12 -Perylene-tetracarboxylic dianhydride, Clopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride Thiophene-2,3,4,5-tetracarboxylic acid dihydrate, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride, etc. It is.

Each of diamine and acid dianhydride may be used alone or in combination of two or more. In addition, other diamines and acid dianhydrides not included in the general formula (1) can be used together with the above diamines or acid dianhydrides. In this case, other diamines or acid dianhydrides may be used. the proportion is 90 mol% or less, preferably be 50 mol _^0/0 or less. By selecting the types of diamine and acid dianhydride, and the molar ratios when using two or more kinds of diamine or acid dianhydride, thermal expansion, adhesion, glass transition point (Tg), etc. Can be controlled.

 [0037] The method for producing the polyimide resin layer is not particularly limited. For example, a polyamide acid resin solution, which is a precursor of polyimide resin, is applied on a substrate, dried, imidized, and then applied onto the substrate. There is a method of forming a polyimide resin layer. The method for applying the polyamic acid rosin solution onto the substrate is not particularly limited, and it can be applied with a coater such as a comma, die, knife, or lip.

 [0038] Further, the drying and imidization methods are not particularly limited, and for example, a heat treatment is preferably employed when heating is performed at a temperature of 80 to 400 ° C for 1 to 60 minutes. By performing such heat treatment, dehydration and ring closure of the polyamic acid proceeds, so that a polyimide resin layer can be formed on the substrate. The polyimide resin layer in which the polyimide resin layer is formed on the substrate may be used as it is or may be used after peeling off.

 [0039] The polyimide resin layer may be formed of only a single layer or may be composed of a plurality of layers. In the case where a plurality of polyimide resin layers are used, other polyimide resins can be sequentially formed on a polyimide resin layer composed of different constituent components. When the polyimide resin layer has three or more layers, the same composition polyimide resin may be used twice or more. Simple layer structure Two layers or single layers, in particular single layers, can be obtained industrially advantageously. Also, the thickness of the polyimide layer is 3 to: LOO / z m preferably 【3 to 50! More preferably, it should be in the range of 5-30 m.

[0040] In the method of forming the modified layer on the surface of the polyimide resin layer of the present invention, a) a step of forming an alkali-treated layer by treating the surface side of the polyimide resin layer with an alkaline aqueous solution (step a) And b) impregnating and drying a polar solvent solution containing an amino compound on the surface of the alkali-treated layer. Forming a compound-containing layer (step b). Further, if necessary, c) a step (X @ c) of forming a modified imidized layer by imidizing the amino compound-containing layer is provided.

 [0041] In the method for producing a metal-clad laminate of the present invention, a step of forming a modified layer on the surface of the polyimide resin layer (step 1)) and a step of forming a metal layer on the surface of the modified layer (step 1) Step iii)). Here, the step I) includes the step a and the step b. Further, if necessary, step c is provided. In step II), d) a step of overlaying metal foil on the surface of the amino compound-containing layer or modified imido layer (both are called modified layers) and thermocompression bonding (step d), or e) containing the amino compound Forming a metal thin film layer on the surface of the layer or the modified imido layer (step e). Step d is a step in which a metal foil is superposed on the surface of the amino compound-containing layer or the modified imido layer and thermocompression bonded. When distinguishing the case of pressing, the former is called process dl and the latter is called process d2. Similarly, step e is a step of forming a metal thin film layer on the surface of the amino compound-containing layer or the modified imidized layer. When distinguishing between cases, the former is referred to as step el and the latter as step e2.

 [0042] In the method for adhering a polyimide resin layer and the method for producing a double-sided metal-clad laminate of the present invention, in addition to the above steps a and b, the surface of the first polyimide resin layer (P1) is treated with an alkali. A step (Step C) in which the surface of the second polyimide resin layer (P2) is laminated and thermocompression bonded.

 [0043] Steps a and b can be carried out in the same manner in any case. The same applies to the other processes c to e. Therefore, the process a, the process b, and the process c will be described as a representative method for forming a modified layer on the surface of the polyimide resin layer.

[0044] In step a, a layer on the surface side of the polyimide resin layer is treated with an alkaline aqueous solution to form an alkali-treated layer. As the alkaline aqueous solution, it is preferable to use an alkaline aqueous solution of sodium hydroxide or potassium hydroxide of 0.5 to 50 wt% and a liquid temperature of 5 to 80 ° C. A dipping method, spray method or brush coating is preferred. Etc. can be applied. For example, when the immersion method is applied, it is effective to treat for 10 seconds to 60 minutes. Preferably, the treatment is performed for 30 seconds to 10 minutes with an alkaline aqueous solution of 1 to 30 wt% and a liquid temperature of 25 to 60 ° C. Depending on the structure of the polyimide resin layer, the processing conditions can be changed as appropriate. Of alkaline aqueous solution When the concentration is low, the surface treatment time of the polyimide resin layer becomes long. In addition, the processing time is shortened when the temperature of the alkaline aqueous solution increases. When treated with an alkaline aqueous solution, the alkaline aqueous solution penetrates from the surface side of the polyimide resin layer, and the polyimide resin layer is alkali-treated. This alkali treatment reaction is considered to be mainly hydrolysis of imide bonds. The thickness of the alkali-treated layer formed by the alkali treatment should be in the range of 1/200 to 1/2, preferably 1/100 to 1/5 of the polyimide resin layer thickness. From another point of view, 0.005 to 3. O ^ m, preferably 0.05 to 2. O ^ m, more preferably 0.1 to 2. O / zm force is good. Furthermore, the viewpoint power of additional U is 0.005 to 0.1! ^ Preferably [0.001 to 0.1! ^, More preferably [0.05 to 0.1 m force ^ (eg, process When attached to e). When the thickness of the alkali-treated layer is outside the above range, sufficient adhesion strength between the polyimide resin layer and the metal layer is hardly exhibited. If the polyimide resin layer is a polyimide resin film, both sides may be modified at the same time.

 [0045] In the alkali-treated layer formed by the alkali treatment, a salt of an alkali metal and a carboxyl group at the end of the polyimide resin may be formed due to the alkaline aqueous solution. It is preferable to wash. Any aqueous acid solution can be used as long as it is acidic. In particular, an aqueous hydrochloric acid solution or an aqueous sulfuric acid solution is preferable. In addition, the concentration may be in the range of 0.5 to 50 wt%, but preferably in the range of 0.5 to 5 wt%. More preferably, the pH is 2 or less. Then, after washing with water, dry and use for step b.

 [0046] In step b, the surface of the alkali-treated layer is impregnated with a polar solvent solution containing an amino compound and dried to form an aromatic amino compound-containing layer. Preferred examples of the amino compound include an aromatic amino compound, an aliphatic amino compound, a silane coupling agent having an amino group, diaminosiloxane, and a polyimide precursor resin.

[0047] The aromatic amino compound is preferably an aromatic amine having a primary or secondary amino group, and in particular, an aromatic amine having a primary amino group substituted with an aromatic ring. Good. The number of amino groups is 1-5, preferably 1-3, more preferably 2. The molecular weight of the aromatic amino compound is 90 to L000, preferably 100 to 600, and more preferably 110 to 500. Examples of the aromatic amino compound include compounds having at least 1, preferably 1 to 10, and preferably 1 to 4 aromatic rings. The aromatic ring is other than an amino group. It may or may not be substituted with the above substituent. As the substituent other than the amino group, those having a terminal carboxyl group present in the alkali-treated layer and a functional group capable of condensation polymerization such as a hydroxyl group and a mercapto group are preferable. Aromatic rings include condensed rings such as a benzene ring and a naphthalene ring. Compounds having a plurality of aromatic rings include Ar-X-Ar, Ar-Y-Ar-X-Ar-Y-Ar (where Ar is an aromatic group such as a benzene ring) in addition to biphenyl rings. Amino group, X and Y are independently divalent groups such as CO, 0, S, SO, SO, CONH, CH)

 2 n 2n

 There are compounds that have been replaced. Examples of the substituent other than the amino group include branched or straight chain alkyl groups having 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, etc.), aromatic groups having 6 to 13 carbon atoms ( For example, phenyl), an aralkyl group having 7 to 12 carbon atoms (for example, benzyl) and the like. Hydroxyl groups can also be used as aromatic ring substituents. An example of a compound in which an aromatic ring is substituted with a hydroxyl group is aminophenol. Furthermore, a condensed ring system having 10 to 20 carbon atoms can also be used as the aromatic amine group-containing compound of the present invention. One example of a fused ring system that can be used in the present invention is diaminonaphthalene.

 [0048] Specific examples of aromatic amino compounds are shown below, but are not limited to these! /. One or more aromatic amino compounds can be used.

[0049] Arin, toluidine, aminominophthalene, aminobiphenyl, 2,2-bis- [4- (4-aminophenoxy) phenol] propane, 2,2-bis- [4- (3- Aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy)] biphenyl Bis [4- (3-aminophenoxy) biphenyl, bis [1- (4-aminophenoxy)] biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) phenol ] Methane, bis [4- (3-aminophenoxy) phenol] methane, bis [4- (4-aminophenoxy) phenol] ether, bis [4- (3-aminophenoxy) phenol] ether, Bis [4- (4-aminophenoxy)] benzophenone, Bis [4- (3-aminophenoxy)] ben Phenone, bis [4,4 (4-aminophenoxy)] benzaldehyde, bis [4,4 (3-aminophenoxy)] benzaldehyde, 9,9-bis [4- (4-aminophenoxy) phenol- L] fluorene, 9,9-bis [4- (3-aminophenoxy) phenol] fluorene, 2,2-bis- [4- (4-aminophenoxy) phenol] hexafluoropropane, 2, 2-bis- [4- (3-aminophenoxy) phenol] hexafluoropropane, 4,4, -methylenedi-0-toluidine, 4,4, -methyl Range-2,6-Xylidine, 4,4, -Methylene-2,6-Dethylaniline, 4,4, -Diaminodiphenylpropane, 3,3, -Diaminodiphenylpropane, 4,4, -Diaminodiphenylethane, 3,3, -diaminodiphenylethane, 4,4, -diaminodiphenylmethane, 3,3, -diaminodiphenylmethane, 4,4, -diaminodiphenylsulfide, 3,3, -diaminodiphenylsulfide, 4, 4, -diaminodiphenyl sulfone, 3,3, -diaminodiphenyl sulfone, 4,4, -diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, benzi Gin, 3,3, -diaminobiphenyl, 3,3, -dimethyl-4,4, -diaminobiphenyl, 3,3, -dimethoxybenzidine, 4,4 'diamino-p-terphenyl, 3 , 3 'diamino-p-terfell, m-hue-rangeamamine P-Phenylenediamine, 2,6-Diaminopyridine, 1,4-Bis (4-aminophenoxy) benzene, 1,3-Bis (4-aminophenoxy) benzene, 4,4 and [1,4-Phenolenebis (1-Methylethylidene)] bisaline, 4,4 [1,3-Phenylenebis (1-methylethylidene)] bisaline, bis (p-aminocyclohexyl) methane, bis (p- -amino- 1-butylphenol) ether, bis (p-β-methyl-δ-aminopentyl) benzene, ρ-bis (2-methyl-4-aminopentyl) benzene, ρ-bis (1,1-dimethyl-5-aminopentyl) ) Benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (j8-amino-1-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5- Diamine, p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2, Examples include 5-diaminopyridine, 2,5-diamino-1,3,4-oxadiazole, piperazine and the like.

[0050] The aliphatic amino compound is preferably an aliphatic amine having at least three primary amino groups as functional groups. Such aliphatic amino compounds are preferably composed only of carbon atoms, hydrogen atoms and nitrogen atoms, and specific examples include tris (2-aminoethyl) amine. When bonding the polyimide resin layer to the metal layer

When an aliphatic amine having no three or more primary amino groups is used, sufficient adhesion strength between the polyimide resin layer and the metal layer is hardly exhibited.

[0051] Examples of the silane coupling agent having an amino group include 3aminopropyltriethoxysilane, 3aminopropyltrimethoxysilane, N-2- (aminoethyl) 3aminopropyltrimethoxysilane, N-2- ( Aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N— (1,3 dimethylbutylidene) propylamine and N-phenol- It should be at least one selected for the ability of 3-aminopropyltrimethoxysilane. In particular, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane are preferred.

 As the diaminosiloxane, diaminosiloxane represented by the above general formula (1) is preferably used. Specific examples include diaminosiloxanes represented by the following formula.

 [0053]

CH ₃ H ₃ C

In the above formula, the average m number is in the range of 1 to 20, preferably in the range of 5 to 15. If it exceeds this range, the adhesiveness with the copper foil is lowered.

 As the polyimide precursor resin, a polyimide precursor resin having a structural unit represented by the general formula (7) is preferable. In the general formula (7), Ar is a divalent compound represented by the formula (8) or the formula (9).

 Four

 Represents an aromatic group, Ar represents a tetravalent aromatic group represented by formula (10) or formula (11), and R represents

 5 2 independently represents a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, V and W are independently a single bond or a divalent hydrocarbon group having 1 to 15 carbon atoms, 0, S, CO, From SO or CONH

 2

M represents independently an integer of 0 to 4, and p represents the mole of the structural unit. Indicates a range of 0.1 to 1.0,

 [0055]

[0057] The structural unit may be present in the homopolymer or as a structural unit of the copolymer. In the case of a copolymer having a plurality of structural units, it may be present as a block or randomly.

 [0058] In the general formula (7), Ar can be a residue of diamine, and Ar is an acid dianhydride.

 4 5

 Therefore, a preferable polyimide resin is explained by diamine and acid dianhydride. However, it is not limited to the polyimide precursor resin obtained by this method.

[0059] Examples of diamine include 4,4, -diaminodiphenyl ether, 2, -methoxy-4,4, -diaminobenzalide, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis. (4-Aminophenoxy) benzene, 2,2 bis [4- (4-Aminophenoxy) phenol] propane, 2,2 Dimethinole-4,4, -Diaminobiphenyl, 3,3, -Dihydroxy-4,4 , -Diaminobiphenyl, 4,4, -Diaminobenza-lide and the like. In addition, the diamines mentioned in the description of the polyimide resin can be mentioned. [0060] Examples of acid dianhydrides include pyromellitic anhydride, 3,3,, 4,4, -biphenyltetracarboxylic dianhydride, 3,3, 4,4, _diphenylsulfone. Examples thereof include tetracarboxylic dianhydride and 4,4, -oxydiphthalic anhydride. In addition, the acid dianhydrides mentioned in the description of the polyimide resin can be used.

 [0061] Each of diamine and acid dianhydride may be used alone or in combination of two or more. In addition, diamine and acid dianhydride other than those described above can be used in combination. The polyimide precursor resin is selected from the types of diamine and acid dianhydride, and when two or more diamines or acid dianhydrides are used, the molar ratio of each is selected. Can be obtained by reaction in an organic solvent, for example, at a temperature of 20-60 ° C. Advantageously, diamine is used under an excess condition relative to the acid dianhydride or under a condition in which the end of the polyimide precursor resin is an amino group. That is, the ratio of the amount of diamine and acid dianhydride used should be more than 1.0 as diamine Z acid dianhydride (molar ratio), preferably 1.001 to 10.0, more preferably 1.1 to 5.0. Particularly preferably, it is 1.5 to 3.0.

 [0062] Since the molecular weight increases as it approaches the molar specific force, an oligomer with a low molecular weight can be obtained by increasing this ratio. In addition, when the molar ratio exceeds 2.0, unreacted diamine remains, which is removed during drying or imidization, and is also removed from the carboxyl group at the end of the polyimide resin present in the alkali-treated layer. Reacts to enhance the surface treatment effect.

 [0063] The polyimide precursor resin may be an oligomer having a weight average molecular weight of 500 to 20,000, preferably 2,000 to 10,000, more preferably 3,000 to 6,000. By applying such a low molecular weight type polyimide precursor resin, it is possible to facilitate the impregnation of the polyimide precursor resin into the alkali-treated layer and change most of the alkali-treated layer into a modified imidized layer. it can. Furthermore, the thickness of the entire polyimide resin layer can be made almost unchanged before and after the surface treatment of the polyimide resin layer (before step a and after step c).

[0064] In addition to the use of one or more of these amino compounds, an aromatic amino compound, an aliphatic amino compound, a silane coupling agent having an amino group, diaminosiloxane, and a polyimide precursor resin are selected. Two or more types can be used. [0065] These amino compounds are used as a solution in a polar solvent. The polar solvent is not particularly limited as long as it dissolves the amino compound. For example, polar solvents suitable for aromatic amino compounds, aliphatic amino compounds, silane coupling agents having amino groups, diaminosiloxanes and polyimide precursor resins include water or methanol, ethanol, propanol, butanol. Alcohols such as acetone, ketones such as acetone, dimethyl ketone and methyl ethyl ketone, ethers such as tetrahydrofuran, tertiary amines such as N-methylpyrrolidone, dimethylacetamide and dimethylformamide, dimethylsulfoxide, etc. To mention. Polar solvents suitable for diaminosiloxane include alcohol solvents such as methanol, ethanol, propanol, isopropanol, N, N dimethylformamide, N, N decylformamide, N, N dimethylacetamide, N, Amide solvents such as N jetylacetamide, N, N jetylacetamide, N, N dimethylmethoxyacetamide, dimethyl sulfoxide, N-methyl 2-pyrrolidone, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol jetyl ether, dioxane And ether solvents such as solvents, ketone solvents such as acetone, MEK, 2-pentanone, 3-pentanone, and 7-pentalatataton, and aromatic hydrocarbon solvents such as toluene and xylene. These may be used alone or as a mixture of several kinds. They may be mixed with water. Preferably, it is methanol.

 [0066] The concentration of the polar solvent solution containing these amino compounds is 0.0001 to 1M (0.0001 to 1 monolayer / L), preferably 0.0015 to 0.1M, as the concentration of the amino compound. More preferably, it is in the range of 0.005 to 0.1 mm, more preferably in the range of 0.0005 to 0.01 M. The concentration of the polar solvent solution containing the polyimide precursor resin is preferably in the above range as a concentration in terms of diamine component. From another point of view, the concentration of the polar solvent solution containing the amino compound, particularly the concentration of the silane coupling agent or diaminosiloxane solution is 0.1 to 5 wt%, preferably 0.5 to Lwt%. It is good.

 [0067] When the concentration of the amino compound is high, the amino compound solution is not only impregnated into the alkali-treated layer, but the amount adhering to the surface of the modified layer is increased, so that a high concentration is not desirable.

[0068] The impregnation method is not particularly limited as long as it can be brought into contact with a solution of a polar solvent containing an amino compound on the surface of the alkali treatment layer, and a known method can be used. Example For example, an immersion method, a spray method, a brush coating method, a printing method, or the like can be used. Temperature is

The room temperature may be 0 to 100 ° C, preferably 10 to 40 ° C. In the case of applying the dipping method, the impregnation time is effectively 30 seconds to 1 hour, preferably 1 to 15 minutes.

 [0069] After impregnation, dry. The drying method is not particularly limited, and natural drying, spray drying with an air gun, drying with an oven, or the like can be used. The drying conditions depend on the type of polar solvent, but are 10 to 150 ° C for 5 seconds to 60 minutes, preferably 25 to 150 ° C for 10 seconds to 30 minutes, more preferably 30 to 120 ° C, 1 Min to 10 min.

 [0070] In this impregnation / drying treatment, a solution of a polar solvent containing an amino compound penetrates into the alkali treatment layer surface force to form an amino compound-containing layer. The permeation thickness, that is, the thickness of the amino compound-containing layer should be 1/10 to 1.5 times, preferably 1/2 to 1.2 times, more preferably 0.8 to 1.2 times the thickness of the alkali treatment layer. Good. The polyimide resin layer obtained by drying becomes a surface-treated polyimide resin layer having a modified layer whose surface is modified and adhesion is improved.

 [0071] Since the surface-treated polyimide resin layer in which the surface of the polyimide resin layer is modified in step a and step b has excellent adhesion, it is used for adhesion to metal foil, resin film, other polyimide resin layers, etc. Suitable for. In addition, the amino compound-containing layer is imidized by imidization to form a modified imidized layer. This modified imidized layer is also excellent in adhesiveness, and thus has a metal foil, a resin film, and the like. Suitable for bonding with polyimide resin layer.

 [0072] In the method for forming a modified layer on the surface of the polyimide resin layer of the present invention, it is preferable to include step c in addition to step a and step b.

[0073] In step c, the amino compound-containing layer is imidized to form a modified imidized layer. The imidization can be performed either by imidization by heating or by chemical imidization using a catalyst, and is not limited. For example, when imidization by heating is performed, 100 to 400 ° C, preferably In the case where imidization is not sufficient to perform complete imidization at a temperature of 150 to 400 ° C, a chemical imidization with a catalyst may be used in combination. In this imidization treatment, it is considered that the reaction in which the amino compound reacts with the terminal carboxyl group present in the polyimide resin layer, particularly the alkali treatment layer, causes imidization. Therefore, polyimide resin having a low molecular weight and increased terminal carboxyl groups in step a is added to step c. In this state, the terminal is imidized and stabilized in a low molecular weight state, and as a result, the adhesion of the polyimide resin layer is considered to be improved.

 [0074] In the method for forming a modified layer on the surface of the polyimide resin layer of the present invention, the thickness of the alkali-treated layer in step a is preferably in the range of 0.005-3. O / zm. . The amino compound used in step b is preferably an aromatic amine having a primary or secondary amino group. The polyimide resin layer may be a polyimide resin layer that forms the surface layer of the laminate, or it may be a polyimide or resin layer that forms the surface layer of the polyimide resin film. Good.

 [0075] Next, the method for producing the metal-clad laminate of the present invention will be described in detail. The method for producing a metal-clad laminate includes a step I) of forming a modified layer and a step of providing a metal layer on the modified layer formed in step I).

 [0076] Step a and step b or step a, step b and step c in step I) can be performed in the same manner as in the method for forming a modified layer on the surface of the polyimide resin layer. In the method for producing a metal-clad laminate, it is preferable to include step c in addition to step a and step b. The surface-treated polyimide resin layer obtained by this method is subjected to step II).

 [0077] Step i) is a step of providing a metal layer on the modified layer formed in step I). As a method for providing the metal layer, there is a method in which a metal foil is superposed on the surface of the modified layer and thermocompression bonded (step d), or a method of forming a metal thin film layer (step e). The modified layer formed in step I) has the force of the modified layer obtained in step b and the modified layer obtained in step c. The same can be done for the modified layer. Examples of the metal constituting the metal layer include iron, nickel, beryllium, aluminum, zinc, indium, silver, gold, tin, zirconium, stainless steel, tantalum, titanium, copper, lead, magnesium, manganese, and alloy foils thereof. Among these, copper, copper alloy, or stainless steel is suitable. The thickness of the metal layer is in the range of 0.001 to 50111, preferably 0.1 to 30 / ζ πι.

[0078] In step d, the method of thermocompression bonding is not particularly limited, and a known method can be adopted as appropriate. Examples of the method of laminating the metal foil include a normal hide mouth press, a vacuum type hide mouth press, an autoclave pressurizing vacuum press, and a continuous thermal laminator. Among the methods of laminating metal foils, sufficient press pressure can be obtained and the remaining It is preferable to use a vacuum-hide-mouth press and a continuous thermal laminator from the viewpoint that the volatile components can be easily removed, and further, the oxidation of the metal foil can be prevented.

[0079] In thermocompression bonding, it is preferable to press the metal foil while heating in the range of 150 to 450 ° C. More preferably, it is in the range of 150 to 400 ° C. More preferably, it is within the range of 150 to 380 ° C. From another point of view, the temperature is preferably equal to or higher than the glass transition temperature of the polyimide resin layer or the modified imidized layer. As for the press pressure, a force that depends on the type of press equipment used is usually about 1-50 MPa.

[0080] As metal foil, iron foil, nickel foil, beryllium foil, aluminum foil, zinc foil, indium foil, silver foil, gold foil, tin foil, zirconium foil, stainless steel foil, tantalum foil, titanium foil, copper foil, lead Examples of the foil include magnesium foil, manganese foil, and alloy foils thereof. Among these, copper foil (including copper alloy foil) or stainless steel foil is suitable. The copper foil here means copper or a copper alloy foil containing copper as a main component. Preferred is a copper foil having a copper content of 90% by mass or more, particularly preferably 95% by mass or more. Examples of the metal contained in the copper foil include chromium, zirconium, nickel, silicon, zinc, and beryllium. An alloy foil containing two or more of these metals may also be used. The material of the stainless steel foil is not limited, but a stainless steel foil such as SUS304 is preferable.

[0081] The metal foil may be treated with a silane coupling agent on the surface on which the polyimide resin layer is laminated. As the silane coupling agent, a silane coupling agent having a functional group such as an amino group or a mercapto group is preferred, and a silane coupling agent having an amino group is more preferred. Specific examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) − Examples include 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3-aminominomethyldimethoxysilane. Among these, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminominotrimethoxysilane, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, and N-phenyl-3-aminopropyltrimethoxysilane must also be selected. Is good. In particular, 3-aminopropyltriethoxysilane, 3-amino Nopropyltrimethoxysilane is preferred.

[0082] The silane coupling agent is used as a solution in a polar solvent. As the polar solvent, water or a polar organic solvent containing water is suitable. The polar organic solvent is not particularly limited as long as it is a polar liquid having an affinity for water. Examples of such polar organic solvents include methanol, ethanol, propanol, isopropanol, acetone, tetrahydrofuran, dimethylformamide, dimethylacetamide, and the like. Silane coupling agent solution ί Also, 0.01 to 5 weight _^0/0, preferably ί or 0.1 to 2.0 wt _^0/0, more preferably ί or 0.5 to 1.0 wt% concentration solution of Good.

 The silane coupling agent treatment is not particularly limited as long as it is a method in which a solution of a polar solvent containing a silane coupling agent comes into contact with the silane coupling agent, and a known method can be used. For example, an immersion method, a spray method, a brush coating method or a printing method can be used. The temperature may be 0 to: LOO ° C, preferably 10 to 40 ° C. In the case of applying the immersion method, it is effective to treat the immersion time for 10 seconds to 1 hour, preferably 30 seconds to 15 minutes. Dry after treatment. The drying method is not particularly limited, and natural drying, spray drying with an air gun, oven drying, or the like can be used. The drying conditions depend on the type of polar solvent, but are 10 to 150 ° C for 5 seconds to 60 minutes, preferably 25 to 150 ° C for 10 seconds to 30 minutes, more preferably 30 to 120 ° C. 1 to 10 minutes.

 [0084] As an example in which the metal foil is a copper foil, there is a case where it is used for a flexible substrate. The preferred thickness of the copper foil when used in this application is in the range of 3-50 / ζ πι, more preferably in the range of 5-30 μm. Thin copper foil is preferably used for the laminate, and in this case, a range of 5 to 20 m is suitable. In addition, the present invention is particularly suitable when a copper foil having a low surface roughness is used because excellent adhesion to the resin layer can be obtained even if a copper foil having a low surface roughness is used. The preferred surface roughness of the copper foil is 10-point average roughness in the range of 0.1 to 3 / ζ πι. In particular, for copper foils used in applications where fine pitch is required, a 10-point average roughness of 0.1 to 1.0 m is suitable for the surface roughness.

[0085] An example in which the metal foil is a stainless steel foil is a case where the metal foil is used for a suspension (hereinafter referred to as HDD suspension) mounted on a hard disk drive. This application The preferred thickness of the stainless steel foil when used as 10 is: the range of LOO m is more preferable, the range of 15 to 70 μm is more preferable, and the range of 15 to 50 μm is more preferable.

[0086] The laminate obtained by the method for producing a metal-clad laminate of the present invention is a laminate having a metal foil on one or both sides of a polyimide resin layer. A laminate having a metal foil on one side is obtained by laminating a metal foil on a surface-treated polyimide resin layer obtained by the surface treatment method of the present invention. When the surface-treated polyimide resin layer is laminated on a substrate such as glass or a resin film, it is made a laminate and then peeled off from the substrate if necessary. When the surface-treated polyimide resin layer is laminated on a metal foil such as a copper foil, a double-sided metal-clad laminate can be obtained by laminating the metal foil on the polyimide resin layer side. In addition to the above method, the metal-clad laminate having metal foil on both sides is obtained by laminating metal foil on both surfaces of the surface-treated polyimide resin layer. It is possible. Furthermore, after manufacturing a single-sided metal-clad laminate having a metal foil on one side, surface treatment of the polyimide resin layer was performed on at least one single-sided metal-clad laminate, and then two single-sided metal-clad laminates It can also be produced by a method in which the polyimide layers are stacked and thermocompression bonded.

 [0087] In the method for producing a metal-clad laminate of the present invention, the thickness of the alkali-treated layer in step a is preferably in the range of 0.005 to 3.0 m. The amino compound used in step b is preferably an aromatic amine having a primary or secondary amino group. An aliphatic amine having at least three primary amino groups as functional groups is preferred. A silane coupling agent having an amino group is preferred. Further, diaminosiloxane is preferred. Moreover, a polyimide precursor resin is preferable.

 [0088] Next, a method for producing a metal-clad laminate including step e in step II) will be described. Step a and step b are carried out as described above, and then attached to step e. In this method for producing a metal-clad laminate, it is preferable to include step c in addition to step a and step b. That is, when the step c is provided, a step e (step) of forming a metal thin film layer on the surface of the modified imido layer in the step c is provided.

 [0089] In this method for producing a metal-clad laminate, the thickness of the alkali-treated layer in step a is 0.

A range of 005-3.0 m is preferred. In addition, the amino compound used in step b and Therefore, an aromatic amine having a primary or secondary amino group is preferable. An aliphatic amine having at least three primary amino groups as functional groups is preferred. A silane coupling agent having an amino group is preferred. Further, diaminosiloxane is preferred. A polyimide precursor resin is preferred.

[0090] In the step e, the method for forming the metal thin film layer is not particularly limited. For example, a vacuum evaporation method, a sputtering method, an electron beam evaporation method, an ion plating method and the like can be used. Is preferred. This sputtering method includes various methods such as DC sputtering, RF sputtering, DC magnetron sputtering, RF magnetron sputtering, EC sputtering, and laser beam sputtering, but is not particularly limited and can be appropriately employed. The conditions for forming the metal thin film layer by Supattari ring method, for example, argon gas was used as Supattaga scan, the pressure is preferably 1 X 10_ ² ~: LPa, more preferably an 5 X 10 ^_2 ~5 X 10- is Yo, how to do, the sputtering power density is preferably L～100Wcm ^_2, more preferably l~50Wc m_ ² conditions.

 [0091] The metal thin film is preferably formed using copper as the thin film layer. Under the present circumstances, the base metal thin film layer which improves adhesiveness more may be provided in a surface treatment polyimide resin layer, and a copper thin film layer may be provided on it. Examples of the base metal thin film layer include nickel, chromium, and an alloy layer thereof. When the base metal thin film layer is provided, the thickness thereof is 1/2 or less, preferably 1/5 or less of the thickness of the copper thin film layer, and is preferably about 1 to 50 nm. It is preferable to form the underlying metal thin film layer by sputtering.

 [0092] Copper to be used may be alloy copper partially containing other metals. The copper or copper alloy formed by the sputtering method preferably has a copper content of 90% by mass or more, particularly preferably 95% by mass or more. Examples of the metal that copper can contain include chromium, zirconium, nickel, silicon, zinc, and beryllium. Also, it may be a copper alloy thin film containing two or more of these metals.

 [0093] The thickness of the copper thin film layer formed in step e (step el or step e2) is 0.001 to 1.

The range is preferably in the range of O 2 / zm, preferably 0.01 to 0. 0, more preferably 0.05 to 0.5 m, and still more preferably 0.1 to 0.5 / zm. When the copper thin film layer is further thickened, it may be thickened by electroless plating or electrolytic plating. Next, a method for bonding the polyimide resin layer of the present invention will be described.

 It is a method of bonding the polyimide resin layer by superimposing the polyimide resin layer surface of the first polyimide resin layer (P1) and the second polyimide resin layer (P2), and the following steps A), B) and C).

 A) The first polyimide resin layer (P1) is subjected to step a.

 B) The second polyimide resin layer (P2) is subjected to steps a and b.

 C) Superimposing the modified polyimide resin layer (P1) on the modified layer surface of the first polyimide resin layer (P2) with the amino compound-containing layer surface of the second polyimide resin layer (P2) and subjecting it to thermocompression bonding d3.

 Here, step a and step b can be performed in the same manner as step a and step b described above. Step d3 can be performed in the same manner as step d above.

 [0095] Two polyimide resin layers are prepared, their surfaces are modified, and then bonded to each other. The first polyimide resin layer is referred to as a polyimide resin layer (P1), and the second polyimide resin layer is referred to as a polyimide resin layer (P2). The polyimide resin layer (P1) and the polyimide resin layer (P2) may be the same or different. That is, it may be the same or different in the type of polyimide resin, the laminated structure of the polyimide resin layer, the presence or absence of a substrate, and the like. The polyimide resin layer (P1) or the polyimide resin layer (P2) is simple to produce as a single layer, but may be composed of a plurality of layers. In the case of a plurality of layers, the adhesiveness is determined by the polyimide resin layer of the surface layer. Therefore, the explanation relating to the improvement of the adhesiveness or the surface treatment is understood as mainly the description of the polyimide resin layer of the surface layer.

 [0096] The first polyimide resin layer (P1) is subjected to Step a, and the second polyimide resin layer (P1) is subjected to Step a and Step b. Then, it attaches | subjects to process d3. If necessary, a washing process, a cutting process, and the like can be added before and after these processes.

 [0097] In step d3, the amino compound treatment layer surface of the polyimide resin layer (P2) is superimposed on the alkali treatment layer surface of the polyimide resin layer (P1) (the alkali treatment layer surface and the amino compound treatment layer surface are referred to as the surface treatment layer surface). Combine and thermocompression bond. The surface treatment layer surface may be double-sided or single-sided. If the surface treatment layer surface is a double-sided surface, it can be laminated in three or more layers.

[0098] The method for thermocompression bonding is not particularly limited, and a method similar to step d described in the method for producing a metal-clad laminate may be employed. Thermocompression bonding force Then, by this thermocompression bonding, the amino compound-containing layer forms a modified imidized layer for the second polyimide resin layer (P2) subjected to steps a and b. Thereby, the adhesive strength is further improved.

 [0099] When both the polyimide resin layer (P1) and the polyimide resin layer (P2) do not have a metal foil, a laminate of the polyimide resin layer (P1) and the polyimide resin layer (P2) is obtained. . When one or more of the polyimide resin layer (P1) and the polyimide resin layer (P2) has a substrate such as a film, the polyimide resin layer (P1) and the polyimide having the substrate on one side or both sides A laminate of the resin layer (P2) is obtained. This substrate can be peeled off if necessary. When the properties of the polyimide resin layer (P1) and the polyimide resin layer (P2) are different, it is possible to have the good physical properties of each. Furthermore, if necessary, one or more layers of the polyimide resin layer (P1) and the polyimide resin layer (P2) can be multilayered to form a laminate of three or more layers. A laminate suitable for a printed wiring board can be obtained by thermocompression bonding a metal foil to one or both sides of a laminate having a polyimide resin layer on the surface.

 [0100] When one of the polyimide resin layer (P1) and the polyimide resin layer (P2) has a metal foil on one side of the polyimide resin layer, and the other does not have a metal foil, A single-sided metal-clad laminate can be obtained by this hot pressing. Also in this case, when the physical properties of the polyimide resin layer (P1) and the polyimide resin layer (P2) are different, it is possible to have good physical properties of each. Furthermore, a double-sided metal-clad laminate can be obtained by heat-bonding a metal foil to the polyimide resin layer surface of the single-sided metal-clad laminate.

 [0101] When the polyimide resin layer (P1) and the polyimide resin layer (P2) have a metal foil on one side of the polyimide resin layer, a double-sided metal-clad laminate can be obtained by thermocompression bonding. Also in this case, when the physical properties of the polyimide resin layer (P1) and the polyimide resin layer (P2) are different, they can have good physical properties.

 [0102] Next, the method for producing the double-sided metal-clad laminate of the present invention will be described in detail.

Two-sided metal-clad laminates with metal foil on one side of the polyimide resin layer are laminated and bonded together to produce a double-sided metal-clad laminate with metal foils on both sides of the polyimide resin layer. A) For the first single-sided metal-clad laminate, the layer on the surface side of the polyimide resin layer (P1) is subjected to step a. B) The second single-sided metal-clad laminate is attached to step a and step b.

 C) Laminate the polyimide resin layer (P2) of the second single-sided metal-clad laminate with the alkali-treated layer side of the polyimide resin layer (P1) of the first single-sided metal-clad laminate, and thermocompression bond To process step d3.

 Here, step a, step b, and step d3 can be performed as described above.

 [0103] Here, A) Step a performed on the first single-sided metal-clad laminate, B) Steps a and b performed on the second single-sided metal-clad laminate, and C) First Step d3 is a step of thermocompression bonding the single-sided metal-clad laminate and the second single-sided metal-clad laminate. D3 is a polyimide resin layer of a single-sided metal-clad laminate with a metal foil on one side. Except for step A), step B) and step C), or step a, step b and step d3 described in the method for adhering a polyimide resin layer of the present invention, Can do.

 [0104] As metal foil, iron foil, nickel foil, beryllium foil, aluminum foil, zinc foil, indium foil, silver foil, gold foil, tin foil, zirconium foil, stainless steel foil, tantalum foil, titanium foil, copper foil, lead Examples of the foil include magnesium foil, manganese foil, and alloy foils thereof. Of these, copper foil, copper alloy, or stainless steel foil is suitable. As an example in which the metal foil is a copper foil, there is a case where the metal foil is used for a flexible substrate.

 [0105] The preferred thickness of the copper foil when used for this purpose is in the range of 3 to 50 m, more preferably in the range of 5 to 30 μm, but it is used in applications where fine pitch is required. Thin copper foil (including copper alloy foil) is preferably used for the double-sided copper clad laminate, and in this case, a range of 5 to 20 m is suitable.

 [0106] An example in which the metal foil is stainless steel foil is used for a suspension (hereinafter referred to as HDD suspension) mounted on a hard disk drive. The preferred thickness of the stainless steel foil when used for this purpose is in the range of 10 to: LOO m, more preferably in the range of 15 to 70 μm, and even more preferably in the range of 15 to 50 μm. BEST MODE FOR CARRYING OUT THE INVENTION

[0107] Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to these examples. In the examples of the present invention, various measurements and evaluations are as follows unless otherwise specified. [0108] [Measurement of adhesive strength]

 The adhesive strength was measured by measuring a 180 mm, 10 mm peel strength at room temperature for a sample cut into a strip shape having a width of 10 mm using a Tensilon tester (manufactured by Toyo Seiki Seisakusho). As a criterion for determining the adhesive strength, a case where the adhesive strength was 0.4 kN / m or more was accepted, and a case where it was less than 0.4 kN / m was rejected. Also, the case where the adhesive strength is 0.4 kN / m or more and less than 0.6 kN / m is good, and the case where the adhesive strength is 0.6 kN / m or more is good.

 [0109] [Measurement of glass transition temperature]

 Using a viscoelasticity analyzer (RSA—Π, manufactured by Rheometric Science Effy Co., Ltd.), using a sample with a width of 10 mm, applying 1 Hz vibration, from room temperature to 400 ° C 1

It was determined from the maximum loss tangent (Tan δ) when the temperature was raised at a rate of 0 ° CZ.

[0110] [Measurement of linear thermal expansion coefficient]

 Using a thermomechanical analyzer (Seiko Instruments Inc.), raise the temperature to 250 ° C, hold it at that temperature for 10 minutes, then cool it at a rate of 5 ° CZ.

The average coefficient of linear thermal expansion (CTE) up to 0 ° C was determined.

[0111] [Measurement of modified layer thickness]

 The cross section of the sample was observed using a scanning transmission electron microscope (manufactured by Hitachi, Ltd.) to confirm the thickness of the modified layer.

[0112] The abbreviations used in the examples represent the following compounds.

 BAPP: 2, 2—Bis [4— (4-Aminophenoxy) phenol] propane

 ΗΑΒ: 4,4 '-(3,3'-dihydroxy) diaminobiphenyl

 ΤΑΡΜ: Tris (4-aminophenol) methanol

 ΤΑΕΑ: Tris (2-aminoethinole) amine

 DAPE: 3,4'-diaminodiphenyl ether

 APES: 3-Aminopropylethoxysilane

 ASD: 4,4'-diaminobiphenylsulfide

 DABA: 4,4'—Gaminobensanilide

EDA: Ethylenediamine ETA: ethanolamine

 PSX-Me: diaminosiloxane represented by the following formula (12) (however, the average m-number is in the range of 1-20 and the average molecular weight is 740)

 PSX-Ph: diaminosiloxane represented by the following formula (13) (however, the total number of j and n is in the range of 2 to 20, j and n are both 1 or more, and the average molecular weight is 1, 320.)

H 2 N -f-C II H _2- ) _f ~ H ₂ (1 2)

[0114] In measuring the adhesive strength of a commercially available polyimide resin layer, the following three types of polyimide films having a thickness of 25 µm were prepared.

 1) Kapton EN: Toray 'DuPont, 100mm X 100mm X 25m, coefficient of linear thermal expansion 16 X I

2) Avical NPI: 100 mm X 100 mm X 25 m, Kaneka Chemical Co., Ltd., linear thermal expansion coefficient 16 X 10— ⁶ / K

 3) Upilex 25S: Ube Industries 100mm X 100mm X 25 μm, linear thermal expansion coefficient 12 X Example

 [0115] Hereinafter, the present invention will be specifically described based on examples, but the present invention is of course not limited thereto.

[0116] Reference Example 1

To 425 g of N, N-dimethylacetamide, stir 31.8 g of 2,2 ′ dimethyl-4,4′-diaminobiphenyl and 4.9 g of 1,3 bis (4 aminophenoxy) benzene at room temperature for 30 minutes. It was. After that, 28.6 g of pyromellitic dianhydride and 9.6 g of bifury 3,4,3 ', 4'-te Tracarboxylic dianhydride was added, and the mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere to obtain a polyamic acid resin solution having a solution viscosity of 28,000 boise. This polyamic acid resin solution was applied to a stainless steel substrate, dried at 130 ° C for 5 minutes, heated to 360 ° C over 15 minutes to complete imidization, and laminated on the stainless steel substrate. A polyimide film 1 was obtained. This polyimide film 1 was peeled off from the stainless steel substrate. The obtained film 1 had a coefficient of thermal expansion of 21 X 10 −6 / K, and the polyimide layer had a thickness of 25 μm.

[0117] Reference Example 2

To 200 g of N, N-dimethylacetamide, 14.9 g of 4,4'-diamino-1,2'-dimethylbiphenyl and 6. Olg of 4,4'-diaminodiphenyl ether are stirred at room temperature for 30 minutes. did. Thereafter, 21.4 g of pyromellitic dianhydride was added and stirred at room temperature for 3 hours under a nitrogen atmosphere to obtain a polyamic acid resin solution having a solution viscosity of 12,000 boise. This polyamic acid resin solution is applied to a stainless steel substrate, dried at 130 ° C for 5 minutes, and heated to 360 ° C over 15 minutes to complete imidization. Thus, polyimide film 2 laminated on the stainless steel substrate was obtained. The polyimide film 2 was peeled off with a stainless steel substrate. Linear thermal expansion coefficient of the resulting films 2 is a 24 X 10- ⁶ / K, a thickness of the polyimide layer was 25 m.

[0118] Reference Example 3

 0.41 g (0. OOlmol) of 2,2-bis [4- (4-aminophenoxy) phenol] propane dissolved in 50 ml of diethylene glycol dimethyl ether and 0.161 g (0.005 mol) of 3 , 3 ', 4,4'-Benzophenone tetracarboxylic dianhydride dissolved in 50 ml of diethylene glycol dimethyl ether was mixed and stirred for 2 hours to obtain polyimide precursor resin (weight average A solution containing molecular weight 4,300) was obtained. After adding 900 ml of methanol to this solution, add 0.101 g of triethylamine (0.OOlmol) and stir for 30 minutes to obtain polyimide precursor resin solution A (hereinafter, solution of precursor A). Both were produced.

[0119] The weight-average molecular weight of the polyimide precursor resin contained in the polyimide precursor resin solution is HLC-8220GPC manufactured by Tosoh Corporation, and TSK-GEL SUPER HM-M manufactured by Tosoh Corporation is 4 Measurements were made using this connected column. A calibration curve for determining the weight average molecular weight was prepared using polystyrene as a standard substance. Unfolding As a medium, a solution in which lithium bromide and phosphoric acid were mixed with Ν, Ν-dimethylacetamide so as to be 0.03 mol / L each was used.

[0120] Reference Example 4

 A silane coupling agent solution was prepared by mixing 5 g of 3-aminopropyltrimethoxysilane, 500 g of methanol and 2.5 g of water and stirring for 2 hours. Stainless steel foil 1 (Shin Nippon Steel Co., Ltd. SUS304 H-TA, thickness 20 μm, surface roughness on the resin layer side: 10-point average roughness RzO. 8 m) previously washed with water is a silane coupling agent solution. After dipping in (liquid temperature of about 20 ° C) for 30 seconds, the liquid was once pulled up into the atmosphere and the excess liquid was dropped. Then, it was dried by blowing compressed air for about 15 seconds. Thereafter, a heat treatment was performed at 110 ° C. for 30 minutes to obtain a silane coupling agent-treated stainless steel foil 2.

[0121] Example 1

 After immersing the polyimide film (Kapton EN) in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, thoroughly wash the immersed polyimide film with ion-exchanged water, and lwt% hydrochloric acid solution (25 ° C) After being soaked for 30 seconds, the surface-treated polyimide film al was obtained by thoroughly washing with ion-exchanged water, spraying with compressed air and drying. The thickness of the alkali-treated layer on one side of this surface-treated polyimide film al was 0.70 m. The film was immersed in a methanol solution (25 ° C) of 0.005 M concentration of BAPP for 30 seconds, and then dried by blowing compressed air to obtain a surface-treated polyimide film bl. This film was heat-treated at 300 ° C. for 3 minutes to produce a surface-treated polyimide film cl. At this time, the thickness of the modified imidized layer on one side of the surface-treated polyimide film cl was 0.65 μm. Copper foil 1 (surface roughness: Rz = 0.8 / ζ πι, thickness) Sas: 18 / zm) and hot-pressed with a high-performance high-temperature vacuum press at 370 ° C, 20MPa for 1 minute to produce a double-sided copper-clad laminate fl. The bond strength between the polyimide film and copper foil was 1. OkNZm.

[0122] Example 2

The same procedure as in Example 1 was performed except that a 0.005 M DAPE methanol solution (25 ° C) was immersed for 5 minutes in place of the 0.005 M BAPP methanol solution in Example 1. Surface-treated polyimide films a2, b2 and c2 and double-sided copper-clad laminate f2 . The thickness of the modified imido layer on one side of the surface-treated polyimide film c2 is 0.52 / zm.

[0123] Example 3

 Surface-treated polyimide films a3, b3, and c3 were prepared in the same manner as in Example 1 except that the immersion was performed in a methanol solution of 0.0005M BAPP in Example 1 for 5 minutes instead of 30 seconds. The polyimide film c3 was sandwiched between copper foils 2 (surface roughness: Rz = 1.5 m, thickness: 18 m) and hot pressed under the same conditions as in Example 1 to produce a double-sided copper clad laminate f3 .

[0124] Example 4

 In the same manner as in Example 1, except that a 0.005 M BAPP methanol solution in Example 1 was immersed for 30 seconds in place of a 0.001 M HAB methanol solution (25 ° C) in 5 minutes, Surface-treated polyimide films a4, b4 and c4 and double-sided copper-clad laminate f4 were prepared.

[0125] Example 5

 In the same manner as in Example 1, except that the 0.005M BAPP methanol solution in Example 1 was immersed for 30 seconds in a methanol solution of 0.001M TAPM (25 ° C) for 30 seconds, Surface-treated polyimide films a5, b5 and c5 and double-sided copper-clad laminate f5 were prepared.

[0126] Example 6

 In the same manner as in Example 1, except that 0.005 M TAEA methanol solution (25 ° C) was immersed for 1 minute instead of 30 seconds immersion in 0.005 M BAPP methanol solution in Example 1, the surface Treated polyimide films a6, b6 and c6 and double-sided copper-clad laminate 16 were produced.

[0127] Example 7

 Instead of immersing the polyimide film in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, in 5N potassium hydroxide aqueous solution (50 ° C), polyimide film (Iupilex 25S) in 30 minutes Surface-treated polyimide films a7, b7 and c7 and double-sided copper-clad laminate 17 were produced in the same manner as in Example 1 except that the immersion was performed. The thickness of the alkali-treated layer on one side of the surface-treated polyimide film a7 was 0.56.

[0128] Example 8

Instead of immersing the polyimide film in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes In a 5N aqueous potassium hydroxide solution (50 ° C), a polyimide film (the film of Reference Example 1)

Surface-treated polyimide films a8, b8 and c8 and double-sided copper clad laminate f8 were prepared in the same manner as in Example 1 except that 1) was immersed for 5 minutes. The thickness of the alkali-treated layer on one side of the surface-treated polyimide film a8 was 0.22.

 [0129] Example 9

 In the 5N aqueous solution of potassium hydroxide and potassium hydroxide, the polyimide film is immersed in a 5N aqueous potassium hydroxide solution (50 ° C) instead of being immersed in 50 ° C for 5 minutes.

Surface-treated polyimide films a9, b9 and c9 and double-sided copper clad laminate f9 were prepared in the same manner as in Example 1 except that 2) was immersed for 5 minutes. The thickness of the alkali-treated layer on one side of the surface-treated polyimide film a9 was 0.30.

 [0130] Example 10

 Surface-treated polyimide films alO, blO and clO and double-sided metal-clad laminate flO were produced in the same manner as in Example 8 except that stainless steel foil 1 was used instead of copper foil 1.

[0131] Example 11

 Surface-treated polyimide films al 1, bl 1 and cl 1 and double-sided metal-clad laminate fl 1 were prepared in the same manner as in Example 8 except that stainless steel foil 2 was used instead of copper foil 1.

[0132] Example 12

 Surface-treated polyimide films al2, bl2, and cl2 and double-sided metal-clad laminate fl2 were prepared in the same manner as in Example 9 except that stainless steel foil 1 was used instead of copper foil 1.

[0133] Example 13

 Surface-treated polyimide films al3, bl3 and cl3 and double-sided metal-clad laminate fl3 were prepared in the same manner as in Example 9 except that stainless steel foil 2 was used instead of copper foil 1.

[0134] Comparative Example 1

 A polyimide film (Kapton EN) was sandwiched between copper foils 1 and heat-pressed with a high-performance high-temperature vacuum press at 370 ° C, 20 MPa for 1 minute to produce a double-sided copper-clad laminate. The adhesive strength between the polyimide film and the copper foil was 0. lkNZm.

[0135] Comparative Example 2

Polyimide film (Kapton EN) in 5N potassium hydroxide aqueous solution (50 ° C) for 5 minutes After soaking, thoroughly rinse the polyimide film soaked in ion-exchanged water, soak in lwt% aqueous hydrochloric acid solution (25 ° C) for 5 minutes, thoroughly rinsed with ion-exchanged water, blow with compressed air and dry. A surface-treated polyimide film was produced. This film was sandwiched between copper foils 1 and hot pressed under the same conditions as in Example 1 to produce a double-sided copper-clad laminate.

[0136] Comparative Example 3

 After immersing the polyimide film (Kapton EN) in 5N aqueous potassium hydroxide (50 ° C) for 5 minutes, the immersed polyimide film is thoroughly washed with ion-exchanged water, and lwt% hydrochloric acid solution (25 ° C ) Was immersed in water for 5 minutes, washed thoroughly with ion-exchanged water, and dried by blowing compressed air. The film was heat-treated at 300 ° C for 3 minutes to produce a surface-treated polyimide film. This film was sandwiched between copper foils 1 and hot pressed under the same conditions as in Example 1 to produce a double-sided copper-clad laminate.

[0137] Comparative Example 4

 After immersing the polyimide film (Kapton EN) in 0.005M BAPP methanol solution (25 ° C) for 5 minutes, blown with compressed air, dried, and heat-treated at 300 ° C for 3 minutes for surface treatment. A polyimide film was prepared. This polyimide film was sandwiched between copper foils 1 and hot pressed under the same conditions as in Example 1 to produce a double-sided copper-clad laminate.

[0138] Comparative Example 5

 A polyimide film (Kapton EN) was immersed in a 0.005M BAPP methanol solution (25 ° C) for 5 minutes, and then dried by blowing compressed air to produce a surface-treated polyimide film. This polyimide film was sandwiched between copper foils 1 and hot pressed under the same conditions as in Example 1 to produce a double-sided copper-clad laminate.

 [0139] The above conditions and results are summarized in Table 1. The adhesive strength indicates the adhesive strength between the polyimide film and the copper foil. The heat treatment of Examples 1 to 13 and Comparative Examples 3 to 4 is 300 ° C. for 3 minutes, and Comparative Examples 1 to 2 and 5 are not heat-treated. The metal layer is formed by thermocompression bonding in all examples.

[0140] [Table 1] Alkali treatment layer Adhesive strength e. Reimito Film Amino Compound Metal Foil

 Thickness (m) (k / m) Example 1 Cuff. f> EN 0. 70 BAPP Copper foil 1 1.0 Example 2 Cuff. Ton EN 0. 70 DAPE Copper foil 1 0.9 Example 3 Cuff. F> EN 0. 70 BAPP Copper foil 2 0.6 Example 4 cuff 'thigh 0. 70 HAB Copper foil 1 0. 7 Example 5 Cuff. Ton EN 0. 70 TAPM Copper foil 1 0. 6 Example 6 Katon EN 0. 70 TAEA Copper foil 1 0. 8 Example 7 Upilex 25S 0.56 BAPP Copper foil 1 1. 0 Example 8 Film 1 0. 22 BAPP copper foil 1 1.2 Example 9 film 2 0. 30 BAPP copper foil 1 1. 0 Example 10 film 1 0.22 BAPP stainless steel foil 1 0. 9 Example 1 1 film 1 0. 22 BAPP Stainless Foil 2 1.2 Example 12 Film 2 0. 30 BAPP Stainless Foil 1 0.9 Example 13 Film 2 0. 30 BAPP Stainless Foil 2 1.0 Comparative Example 1 Cuff. YJ ― 1 Copper foil 1 0.1 Comparative example 2 Cuff. F EN 0. 70 ― Copper foil 1 0. 1 Comparative example 3 Cuff. Ton EN 0. 70 ― Copper foil 1 0. 1 Comparative example 4 F> EN ― BAPP Copper foil 1 0. 1 Comparative example 5 Power, ton EN ― BAPP Copper foil 1 0. 1 Example 14

After immersing the polyimide film (Kapton EN) in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, thoroughly wash the immersed polyimide film with ion-exchanged water and add lwt% hydrochloric acid solution (25 ° C After being immersed in C) for 5 minutes, it was thoroughly washed with ion-exchanged water, sprayed with compressed air and dried to obtain a surface-treated polyimide film al4. This film was immersed in a 0.5 wt% AP ES aqueous solution for 30 seconds, and then dried by blowing compressed air to obtain a surface-treated polyimide film bl4. This film was heat-dried at 110 ° C for 30 minutes, then sandwiched between copper foils 1, and then hot-pressed at 370 ° C, 20 MPa for 1 minute with a high-performance high-temperature vacuum press machine. Was made. The adhesive strength between the polyimide film and the copper foil was 0.4 kNZm.

[0142] Comparative Example 6

 A polyimide film (Kapton EN) was immersed in a 0.5 wt% APES aqueous solution for 30 seconds, dried by blowing compressed air, and dried by heating at 110 ° C for 30 minutes. A double-sided copper-clad laminate was produced from this polyimide film in the same manner as in Example 1, but the treated layer was consolidated and could not be bonded. The above conditions and results are summarized in Table 2.

[0143] [Table 2]

[0144] Example 15

 After immersing the polyimide film (Kapton EN) in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, thoroughly wash the immersed polyimide film with ion-exchanged water, and lwt% hydrochloric acid solution (25 ° C) After being soaked for 5 minutes, the surface-treated polyimide film al5 was obtained by thoroughly washing with ion-exchanged water, spraying with compressed air and drying. This film was immersed in the polyimide precursor resin solution A (25 ° C) of Reference Example 5 for 5 minutes, and then dried by blowing compressed air to obtain a surface-treated polyimide film bl5. The film was heat-treated at 300 ° C for 3 minutes to produce a surface-treated polyimide film cl5.

 This film was sandwiched between copper foils 1 and heat-pressed with a high-performance high-temperature vacuum press at 370 ° C, 20 MPa for 1 minute to produce a double-sided copper clad laminate fl5. The bond strength between the polyimide film and copper foil was 1. lkNZm.

[0145] Example 16

In 5N potassium hydroxide aqueous solution, polyimide film is immersed in 5N potassium hydroxide aqueous solution (50 ° C) instead of 5 minutes immersion at 50 ° C in polyimide film (Upilex 25S) A surface-treated polyimide film al6, bl6 and cl6 and a double-sided copper-clad laminate fl6 were prepared in the same manner as in Example 15 except that the film was immersed for 30 minutes.

[0146] Example 17

 In a 5N aqueous solution of potassium hydroxide and potassium hydroxide, instead of immersing the polyimide film at 50 ° C for 5 minutes, in a 1N aqueous sodium hydroxide solution (50 ° C), the polyimide film (Abical NPI) is 10 A surface-treated polyimide film al7, bl7 and cl7 and a double-sided copper-clad laminate fl7 were produced in the same manner as in Example 15 except that the immersion was carried out. The thickness of the modified layer on one side of the surface-treated polyimide film al7 was 0.73 / zm.

[0147] Example 18

 Instead of immersing the polyimide film in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, in the 5N sodium hydroxide aqueous solution (50 ° C), the polyimide film (film of Reference Example 1) Surface-treated polyimide films al8, bl8 and cl8 and double-sided copper clad laminate fl8 were prepared in the same manner as in Example 15 except that 1) was immersed for 5 minutes.

[0148] Example 19

 Instead of immersing the polyimide film in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, in the 5N sodium hydroxide aqueous solution (50 ° C), the polyimide film (film of Reference Example 2) Surface-treated polyimide films al9, bl9 and cl9 and double-sided copper clad laminate fl9 were prepared in the same manner as in Example 15 except that 2) was immersed for 5 minutes.

[0149] Comparative Example 7

 After immersing the polyimide film (Kapton EN) in polyimide precursor resin solution A (25 ° C) for 5 minutes, it is dried by spraying with compressed air, and heat treatment is performed at 300 ° C for 3 minutes. A imide film was prepared. This film was sandwiched between copper foils 1 and hot pressed under the same conditions as in Example 15 to produce a double-sided copper-clad laminate.

[0150] Comparative Example 8

After immersing the polyimide film (Kapton EN) in the polyimide precursor resin solution A (25 ° C) for 5 minutes, a surface-treated polyimide film was produced by blowing compressed air and drying. This film was sandwiched between copper foils 1 and hot pressed under the same conditions as in Example 15 to produce a double-sided copper-clad laminate. The adhesive strength between the polyimide film and the copper foil was 0. lkNZm. Result The results are shown in Table 3.

 [0151] The above conditions and results, and the adhesive strength between the polyimide film and the copper foil are summarized in Table 3.

 The heat treatment of Examples 15 to 19 and Comparative Example 7 is 300 ° C. for 3 minutes, and Comparative Example 8 is not subjected to heat treatment. The metal layer is formed by thermocompression bonding in all examples.

[0152] [Table 3]

[0153] Example 20

 After immersing the polyimide film (Kapton EN) in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, thoroughly wash the immersed polyimide film with ion-exchanged water, and then add lwt% hydrochloric acid solution (25 ° C After immersing in C) for 5 minutes, the surface-treated polyimide film a20 was obtained by thoroughly washing with ion-exchanged water, spraying with compressed air, and drying. This film was immersed in a 0.5 wt% PS X-Ph methanol solution (25 ° C.) for 30 seconds, and then dried by blowing compressed air to obtain a surface-treated polyimide film b20.

 This film is heat-dried at 110 ° C for 30 minutes, then sandwiched between copper foils 1, and then hot-pressed at 370 ° C, 20MPa for 1 minute with a high-performance high-temperature vacuum press. Plate d 20 was produced. The adhesive strength between the polyimide film and the copper foil was 0.4 kNZm.

[0154] Example 21

Instead of dipping in 0.5 wt% PSX-Ph methanol solution in Example 20 for 30 seconds Surface treated polyimide films a21 and b21 and double-sided copper-clad laminate d21 were prepared in the same manner as Example 20 except that it was immersed in a methanol solution (25 ° C) of 0.5 wt% PSX-Me for 30 seconds. did.

[0155] Comparative Example 9

 The polyimide film (Kapton EN) was dipped in 0.5 wt% PSX-Ph methanol solution (25 ° C) for 30 seconds, dried by blowing compressed air, and heated and dried at 110 ° C for 30 minutes. A double-sided copper-clad laminate was produced from this polyimide film in the same manner as in Example 1, but the treated layer was fixed and could not be bonded.

 [0156] Table 4 summarizes the above conditions and results. In all examples, the heat treatment is 110 ° C for 30 minutes. The metal layer is formed by thermocompression bonding in all examples.

 [0157] [Table 4]

[0158] Example 22

After immersing the polyimide film (Kapton EN) in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, thoroughly wash the immersed polyimide film with ion-exchanged water, and lwt% hydrochloric acid solution (25 ° C) After being soaked for 5 minutes, it was thoroughly washed with ion exchange water, sprayed with compressed air and dried to obtain a surface-treated polyimide film a22. This surface-treated film was immersed in a 0.5 wt% APES aqueous solution for 30 seconds and then dried by blowing compressed air to obtain a surface-treated polyimide film b22. After heat-treating this film at 110 ° C for 30 minutes, it was set in an RF magnetron sputtering device (ANEL VA; SPF-332HS) so that a metal raw material was formed on this film, and the inside of the tank was 3 X 10 After reducing the pressure to ^_4 Pa, argon gas was introduced and the degree of vacuum was set to 2 ^× 10 ^_1 Pa, and plasma was generated by an RF power source. In this plasma Neckel: Chrome alloy layer [ratio 8: 2, 99.9 wt%, hereinafter, a nichrome layer (first sputtering layer la)] was formed on a polyimide film so as to have a film thickness of 30 nm. After forming the nichrome layer, 0.2 m of copper (99.99 wt%) was further formed on the -chrome layer by sputtering in the same atmosphere to obtain a second sputtering layer lb.

Next, a copper plating layer (plating layer lc) having a thickness of 8 μm was formed in an electrolytic plating bath using the copper sputtered film (second sputtering layer lb) as an electrode. As an electrolytic bath, use a copper sulfate bath (copper sulfate 100 g / L, sulfuric acid 220 g / L, chlorine 40 mg / L, anode is phosphorus-containing copper), and a plating film with a current density of 2. OA / dm ² Formed. After plating, it was washed with sufficient distilled water and dried. In this way, a metal-clad laminate e22 composed of a polyimide film, a chrome layer, a laZ copper sputter layer, a lbZ electrolytic plating copper layer, lc, was obtained. The adhesive strength between the polyimide film and copper was 0.4 kNZm.

Example 23

After immersing the polyimide film (film 2 of Reference Example 2) in 5N potassium hydroxide aqueous solution at 50 ° C for 30 seconds, the immersed polyimide film was washed thoroughly with ion-exchanged water, and lw t% hydrochloric acid aqueous solution ( After immersing in 25 ° C. for 5 minutes, the surface-treated polyimide film a23 was obtained by thoroughly washing with ion-exchanged water and spraying and drying with compressed air. The thickness of the alkali-treated layer on one side of this surface-treated film a23 was 0.02 m. This film was immersed in a methanol solution (25 ° C) of B0001 having a concentration of 0.0001 M for 5 minutes, and then dried by blowing compressed air to obtain a surface-treated polyimide film b23. This film was heat-treated at 300 ° C for 3 minutes to produce a surface-treated polyimide film c23. At this time, the thickness of the modified imidized layer on one surface of the surface-treated polyimide film c23 was about 0.02 μm. Set the RF magnetron sputtering device (ANELVA; SPF-332HS) so that the metal raw material is deposited on this film, depressurize the tank to 3 X 10 ^_4 Pa, and then introduce argon gas to reduce the degree of vacuum. Plasma was generated by RF power supply at 2 X ^10_1 Pa. With this plasma, a nickel: chromium alloy layer [ratio 8: 2, 99.9 wt%, hereinafter referred to as a nichrome layer (first sputtering layer 2a)] was formed on a polyimide film so as to have a film thickness of 30 nm. After forming the nichrome layer, in the same atmosphere, 0.2 μm of copper (99.99 wt%) was further formed on the -chrome layer by sputtering to obtain a second sputtering layer 2b. Next, a copper plating layer (plating layer 2c) having a thickness of 8 IX m was formed in an electrolytic plating bath using the sputtered film (second sputtering layer 2b) as an electrode. As an electrolytic bath, use a copper sulfate bath (copper sulfate 100 g / L, sulfuric acid 220 g / L, chlorine 40 mg / L, anode is phosphorous copper), plating at current density 2. OA / dm ² A film was formed. After plating, it was washed with enough distilled water and dried. In this way, a metal-clad laminate g23 composed of the polyimide film chromium layer 2aZ copper sputtered layer 2bZ electrolytic plated copper layer 2c was obtained. The bond strength between the polyimide film and copper was 0.9 kNZm.

[0160] Example 24

 In the same manner as in Example 23 except that the sample was immersed in a methanol solution of 0.001M HAB (25 ° C) for 5 minutes instead of being immersed in a methanol solution of 0.0001M BAPP in Example 23 for 5 minutes. Processed polyimide films a24 b24 and c24 and metal-clad laminate g24

[0161] Example 25

 In the same manner as in Example 23 except that the sample was immersed in a methanol solution of 0.001M ASD (25 ° C) for 5 minutes instead of being immersed in a methanol solution of 0.0001M BAPP in Example 23 for 5 minutes. Processed polyimide films a25 b25 and c25 and metal-clad laminate g25

[0162] Example 26

 Instead of immersing in 0.001 M BAPP methanol solution in Example 23 for 5 minutes instead of immersing in 0.001 M DABA methanol solution (25 ° C) for 5 minutes, the same procedure as in Example 23 was performed. Surface-treated polyimide films a26 b26 and c26 and metal-clad laminate g26 were produced.

[0163] Comparative Example 10

Prepare a polyimide film (Kapton EN), set it in the RF magnetron sputtering device so that the metal material is deposited on this film, depressurize the tank to 3 X 10 ^_4 Pa, then introduce argon gas and vacuum The temperature was set to 2 X 10 ^_1 Pa, and plasma was generated with an RF power source. With this plasma, a nickel: chromium alloy layer [ratio 8: 2 99.9 wt%, hereinafter, a nichrome layer (first sputtering layer 6a)] was deposited on the polyimide film to a film thickness of 30. - After forming the ROM layer, in the same atmosphere, copper (99.99 wt%) was further formed on the -chrome layer by sputtering to form a 0.2 / zm second sputtering layer 6b.

Next, a copper plating layer (plating layer 6c) having a thickness of 8 / zm was formed in an electrolytic plating bath using the sputtered film (second sputtering layer 6b) as an electrode. As an electrolytic bath, use a copper sulfate bath (copper sulfate 100 g / L, sulfuric acid 220 g / L, chlorine 40 mg / L, anode is phosphorous copper), plating at current density 2. OA / dm ² A film was formed. After plating, it was washed with enough distilled water and dried. In this manner, a metal-clad laminate composed of a polyimide film, a chromium layer, 6aZ copper sputtered layer, 6bZ electrolytically plated copper layer, 6c was obtained. The adhesion strength between the polyimide film and the copper foil was less than 0.1 lkNZm.

[0164] Comparative Example 11

After immersing the polyimide film (Kapton EN) in 5N aqueous potassium hydroxide solution at 50 ° C for 5 minutes, thoroughly wash the immersed polyimide film with ion-exchanged water, and add lwt% hydrochloric acid solution (25 ° C). After soaking for 5 minutes, it was thoroughly washed with ion-exchanged water and dried by blowing compressed air. Set it in an RF magnetron sputtering device so that a metal raw material is deposited on this polyimide film, depressurize the tank to 3 X 10 ^_4 Pa, and then introduce argon gas to a vacuum of 2 X 10 ^{_ 1} Pa. And plasma was generated by the RF power supply. Using this plasma, a nickel: chromium alloy layer [ratio 8: 299.99 wt%, hereinafter, a nichrome layer (first sputtering layer 7a)] was formed on a polyimide film to a film thickness of 30. After forming the nichrome layer, a second sputtering layer 7b was obtained by depositing 0.2 μm of copper (99.99 wt%) on the -chrome layer by sputtering in the same atmosphere.

Next, a copper plating layer (plating layer 7c) having a thickness of 8 / zm was formed in an electrolytic plating bath using the sputtered film (second sputtering layer 7b) as an electrode. As an electrolytic bath, use a copper sulfate bath (copper sulfate 100 g / L, sulfuric acid 220 g / L, chlorine 40 mg / L, anode is phosphorous copper), plating at current density 2. OA / dm ² A film was formed. After plating, it was washed with enough distilled water and dried. In this way, a metal-clad laminate composed of a polyimide film, a chromium layer, 7aZ, a copper sputtered layer, 7bZ, an electrolytically plated copper layer, 7c was obtained. The adhesion strength between the polyimide film and the copper foil was 0. lkNZm.

[0165] Comparative Example 12 The polyimide film (Kapton EN) was immersed in a 0.5 wt% APES aqueous solution for 30 seconds, dried by blowing compressed air, and heat-treated at 110 ° C for 30 minutes. A metal thin film was formed by setting in an RF magnetron sputtering apparatus so that a metal raw material was formed on this polyimide film. The chamber in which the sample was set was depressurized to 3 × 10 ^_4 Pa, and then argon gas was introduced to make the degree of vacuum 2 ^× 10 ^_1 Pa, and plasma was generated by the RF power supply. With this plasma, a nickel: chromium alloy layer [ratio 8: 299.99 wt%, hereinafter, a nichrome layer (first sputtered layer 8a)] was formed on a polyimide film to a film thickness of 30. After forming the nichrome layer, 0.2 μm of copper (99.99 wt%) was further formed on the -chrome layer by sputtering in the same atmosphere to obtain a second sputtering layer 8b.

Next, a copper plating layer (plating layer 8c) having a thickness of 8 / zm was formed in an electrolytic plating bath using the sputtered film (second sputtering layer 8b) as an electrode. As an electrolytic bath, use a copper sulfate bath (copper sulfate 100 g / L, sulfuric acid 220 g / L, chlorine 40 mg / L, anode is phosphorous copper), plating at current density 2. OA / dm ² A film was formed. After plating, it was washed with enough distilled water and dried. In this way, a metal-clad laminate composed of a polyimide film chromium layer 8aZ copper sputtered layer 8bZ electrolytic plated copper layer 8c was obtained. The adhesion strength between the polyimide film and the copper foil was less than 0.1 lkNZm.

[0166] The above conditions and results are summarized in Table 5. In addition, the heat treatment is performed at 110 ° C. for 30 minutes in Example 22 and Comparative Example 12, Example 23 26 is at 300 ° C. for 3 minutes, and Comparative Example 10 11 is not subjected to calo heat treatment. The metal layer is formed by sputtering + plating in all examples.

[0167] [Table 5]

Alkali treatment layer Adhesive strength

 Home Reimito Film Amino Compound

 Thickness (/ x m) (k N / m)

 Example 22 Power foot EN 0. 70 APES 0.4

 Example 23 Film 0.02 BAPP 0.9

 Example 24 Film 2 0.02 HAB 0.7

 Example 25 Film 2 0.02 ASD 0.6

 Example 26 Film 2 0.02 DABA 0.6

 Comparative Example 10 Force, ton EN

 Comparative Example 1 1 cuff. f> EN 0. 70 ― 0. 1

 Comparative Example 12 cuff. T EN EN APES KU 0. 1

[0168] Example 27

 After immersing the polyimide film (Kapton EN) in 5N aqueous solution of potassium hydroxide at 50 ° C for 5 minutes, thoroughly wash the immersed polyimide film with ion-exchanged water, and add 1wt% hydrochloric acid aqueous solution (25 After immersing in (C) for 5 minutes, it was thoroughly washed with ion exchange water, sprayed with compressed air and dried to obtain surface-treated polyimide film a27. Part of the polyimide film a27 was used in the following example.

 [0169] The modified layer surface of the polyimide film a27 was immersed in a methanol solution (25 ° C) of 0.005M concentration of BAPP for 30 seconds, and then dried by blowing compressed air to the surface of the polyimide film. A polyimide film b27 was obtained.

 Surface treatment surfaces of polyimide film a27 and polyimide film b27 were superposed, and heat-pressed with a high-performance high-temperature vacuum press at 400 ° C, 20 MPa for 1 minute. The adhesion strength between the two polyimide films a27 and b27 was 1.2 kNZm.

 [0170] Example 28

Instead of immersing the modified layer surface of the polyimide film a27 obtained in Example 27 in 0.005M BAPP methanol solution for 30 seconds, immersing in 0.001M DAPE methanol solution (25 ° C) for 5 minutes. A polyimide film b28 having an amino compound treatment layer formed on the polyimide film surface was obtained in the same manner as in Example 27 except that. The surface of the polyimide film a27 and the polyimide film b28 were superposed and heat-pressed in the same manner as in Example 27. The adhesive strength between the polyimide films a28 and b28 was 1. OkNZm.

[0171] Example 29

 A polyimide film was obtained in the same manner as in Example 27 except that the modified layer surface of the polyimide film a27 obtained in Example 27 was immersed in 0.005M BAPP methanol solution for 5 minutes instead of 30 seconds. A polyimide film b29 having an amino compound treatment layer formed on the surface was obtained. The surface of the polyimide film a27 and the polyimide film b29 were superposed and heat-pressed in the same manner as in Example 27. The adhesive strength between the polyimide films a27 and b29 was 0.9 kNZm.

[0172] Example 30

 After immersing the polyimide film (Abical NPI) in 1N sodium hydroxide aqueous solution (50 ° C) for 10 minutes, the immersed polyimide film is thoroughly washed with ion-exchanged water, and lwt% hydrochloric acid aqueous solution (25 ° C) After being soaked for 5 minutes, it was thoroughly washed with ion-exchanged water, sprayed with compressed air and dried to obtain a surface-treated polyimide film a30. A part of the polyimide film a30 was used in the following example.

 [0173] The surface of the modified layer of the polyimide film a30 was immersed in a methanol solution (25 ° C) of 0.005 M concentration of BAPP for 20 seconds, and then dried by spraying compressed air to the polyimide film surface. A polyimide film b30 was obtained.

 The polyimide film a30 and the surface treatment surface of the polyimide film b30 were superposed and hot pressed in the same manner as in Example 27. The adhesive strength between the polyimide films a30 and b30 was 1. lkNZm.

 [0174] Example 31

Instead of immersing the polyimide film in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, in 5N potassium hydroxide aqueous solution (50 ° C), polyimide film (Iupilex 25S) in 30 minutes A polyimide film a31 having a modified layer formed on the polyimide film surface was obtained in the same manner as in Example 27 except that the immersion was performed. Further, using a polyimide film a31, in the same manner as in Example 27, a polyimide film in which an amino compound treatment layer was formed on the polyimide film surface was used. Rum b31 was obtained.

 The polyimide film a31 and the surface-treated surface of the polyimide film b31 were superposed and hot pressed in the same manner as in Example 27. The adhesive strength between the polyimide films a31 and b31 was 1. lkNZm.

[0175] Example 32

 The polyimide film a27 obtained in Example 27 and the surface-treated surface of the polyimide film b30 obtained in Example 30 were superposed and subjected to hot pressing in the same manner as in Example 27. The adhesion strength between the polyimide films a27 and b30 was 1. OkNZm.

[0176] Example 33

 After immersing the polyimide film (film 1 of Reference Example 1) in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, the immersed polyimide film was washed thoroughly with ion-exchanged water, and then lwt% hydrochloric acid aqueous solution (25 After immersing in (C) for 5 minutes, it was thoroughly washed with ion exchange water, sprayed with compressed air and dried to obtain surface-treated polyimide film a33. Part of the polyimide film a33 was used in the following example.

 [0177] The modified layer surface of the polyimide film a33 was immersed in a methanol solution (20 ° C) adjusted to 0.001M EDA concentration for 5 minutes, and then dried by spraying with compressed air. A polyimide film b33 having an amino compound treatment layer formed on the surface was prepared.

 The polyimide film a33 and the surface-treated surface of the polyimide film b33 were superposed and hot pressed in the same manner as in Example 27. The adhesive strength between the polyimide films a33 and b33 was 0.6 kNZm.

 [0178] Example 34

 Except for immersing the polyimide film a33 in 0.001M EDA methanol solution (20 ° C) for 5 minutes instead of immersing it in 0.001M ETA methanol solution (20 ° C) for 5 minutes. In the same manner as in Example 33, a polyimide film b34 having an amino compound treatment layer formed on the surface of the polyimide resin layer was produced.

The polyimide film a33 obtained in Example 33 and the surface-treated surface of the polyimide film b34 were superposed and hot pressed in the same manner as in Example 27. The adhesive strength between the polyimide films a33 and b33 was 0.4 kNZm. [0179] Example 35

 After immersing the polyimide film (film 2 of Reference Example 2) in 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, the immersed polyimide film was washed thoroughly with ion-exchanged water, and lwt% hydrochloric acid aqueous solution (25 After immersing in (C) for 5 minutes, it was thoroughly washed with ion exchange water, sprayed with compressed air and dried to obtain surface-treated polyimide film a35.

 The polyimide film a35 and the surface-treated surface of the polyimide film b33 obtained in Example 33 were overlapped, and heat pressing was performed in the same manner as in Example 27. The adhesive strength between the polyimide films a35 and b33 was 0.7 kNZm.

[0180] Example 36

 The polyimide film a35 obtained in Example 35 and the surface-treated surface of the polyimide film b34 obtained in Example 34 were superposed and subjected to hot pressing in the same manner as in Example 27. The adhesive strength between the polyimide films a35 and b33 was 0.4 kNZm.

[0181] Comparative Example 13

 Two polyimide films (Kapton EN) were prepared, superposed, and hot pressed in the same manner as in Example 27. Each polyimide film peeled easily.

[0182] Comparative Example 14

 Two polyimide films (Abical NPI) were prepared, which were superposed and hot pressed in the same manner as in Example 27. Each polyimide film peeled easily.

[0183] Comparative Example 15

 A polyimide film (Kapton EN) and a polyimide film (Abical NPI) were superposed and hot pressed in the same manner as in Example 27. Each polyimide film peeled easily.

[0184] Comparative Example 16

 Two polyimide films (Film 1 of Reference Example 1) were prepared, and the polyimide resin layer surfaces were superposed, and hot pressing was performed in the same manner as in Example 27. Each polyimide resin layer easily peeled off.

[0185] Comparative Example 17

Two polyimide films a27 obtained in Example 27 were prepared, and the surface treatment layer surfaces of the respective polyimide films were superposed and hot-pressed in the same manner as in Example 27. Polyimide film The adhesion strength between the rums was 0. lkNZm.

[0186] Comparative Example 18

 Two polyimide films a33 obtained in Example 33 were prepared, and the surface treatment layer surface of each polyimide resin was superposed, and hot pressing was performed in the same manner as in Example 27. The adhesion strength between the polyimide resin layers was less than 0.1 lkNZm.

[0187] Comparative Example 19

 Prepare the polyimide film a33 obtained in Example 33 and the polyimide film a35 obtained in Example 35, superimpose the surface modification layer surfaces of the respective polyimide resins, and perform hot pressing in the same manner as in Example 27. It was. The adhesion strength between the polyimide resin layers was less than 0.1 lkNZm.

 [0188] The above conditions and results are summarized in Table 6 and Table 7. The bonding method of the two polyimide resin layers is thermocompression bonding in all examples!

[0189] [Table 6]

Alkali treatment layer

 Ho. Liimito 'Film Amino Compound

 Thickness (Π1) (k N / m) Cuff 'ton EN 0. 70 ― Example 27 1.2 Cuff. Ton EN 0. 70 BAPP Ton EN 0. 70 ― Example 28 1.0 Cuff. EN 0. 70 DAPE cuff '0. 70 ― Example 29 0. 9 Cuff. h> EN 0. 70 BAPP Avical NPI 0. 73 ― Example 30 1.1 Apical NPI 0. 73 BAPP Upilex 25S 0. 56 ―

Example 31 1.1

Upilex 25S 0. 56 BAPP cuff. EN 0.70 ― Example 32 1. 0 Capital NPI 0. 73 BAPP film 1 0.22 ― Example 33 0.6 Film 1 0.22 EDA film 1 0.22 ― Example 34 0.4 Film 1 0. 22 ETA film 2 0. 30 ― Example 35 0.7 Film 1 0.22 EDA film 2 0. 30 ― Example 36 Film 1 0.22 ETA 0.4 Film 2 0. 30 ― 7] Alkali treatment layer

 Ho. Liimide film Ami / Compound

 Thickness (m) (k N / m)

 Cuff. T EN ― One

 Comparative Example 13 0. 0

 Cuff. T EN

 Avical NPI

 Comparative Example 14 0. 0

 Abical PI

 Cuff 'b> EN ― ―

 Comparative Example 15 0. 0

 Abical PI

 Film 1

 Comparative Example 16 0. 0

 Film 1 ― ―

 Cuff. T EN 0. 70

 Comparative Example 17 0. 1

 Cuff. T EN 0. 70 ―

 Film 1 0.22 ―

 Comparative Example 18

 Film 1 0.22 ―

 Film 1 0.22 ―

 Comparative Example 19

 Film 2 0. 30-Industrial applicability

 According to the present invention, the adhesion of the polyimide resin layer can be dramatically improved by a simple surface treatment. Adhesion can be improved even with a low-roughness copper foil suitable for fine pitch formation, which makes it possible to manufacture copper-clad laminates used for high-density printed wiring boards at low cost. It can also be used for HDD suspension applications, so its industrial value is high.

Claims

The scope of the claims  [1] a) a step of forming a surface of the polyimide resin layer with an aqueous alkali solution to form an alkali-treated layer; and b) impregnating and drying a polar solvent solution containing an amino compound on the surface of the alkali-treated layer. And forming a modified layer on the surface of the polyimide resin layer, comprising the step of forming an amino compound-containing layer.  [2] a) a step of forming a surface of the polyimide resin layer with an alkaline aqueous solution to form an alkali-treated layer; and b) impregnating and drying a polar solvent solution containing an amino compound on the surface of the alkali-treated layer. In addition to the step of forming the amino compound-containing layer, the modified layer according to claim 1, further comprising: c) imidizing the amino compound-containing layer to form a modified imidized layer. How to form.  [3] The method for forming a modified layer according to claim 1 or 2, wherein the thickness of the alkali-treated layer is in the range of 0.005 to 3.0 m.  4. The method for forming a modified layer according to claim 1 or 2, wherein the amino compound is an aromatic amine having a primary or secondary amino group. 5. The method for forming a modified layer according to claim 1 or 2, wherein the amino compound is an aliphatic amine having at least three primary amino groups as functional groups. 6. The method for forming a modified layer according to claim 1 or 2, wherein the amino compound is a polyimide precursor resin.  7. The method for forming a modified layer according to claim 1 or 2, wherein the polyimide resin layer is a polyimide resin layer that forms a surface layer of the laminate. 8. The method for forming a modified layer according to claim 1 or 2, wherein the polyimide resin layer is a polyimide resin layer that forms a surface layer of a polyimide resin film. [9] In a method for producing a metal-clad laminate comprising: I) a step of forming a modified layer on the surface of the polyimide resin layer; and II) a step of forming a metal layer on the surface of the modified layer.  Process I) a) a step of forming an alkali-treated layer by treating the surface side of the polyimide resin layer with an alkaline aqueous solution; and b) impregnating and drying a polar solvent solution containing an amino compound on the surface of the alkali-treated layer to contain an amino compound. A metal-clad laminate comprising a step of forming a layer. Manufacturing method.  [10] Process I)  a) a step of forming an alkali-treated layer by treating the surface side of the polyimide resin layer with an alkaline aqueous solution; and b) impregnating and drying a polar solvent solution containing an amino compound on the surface of the alkali-treated layer to contain an amino compound. 10. The method for producing a metal-clad laminate according to claim 9, further comprising: c) a step of imidizing the amino compound-containing layer to form a modified imidized layer in addition to the step of forming a layer. [11] Step II)  The method for producing a metal-clad laminate according to claim 9 or 10, wherein d) a process force for superimposing metal foil on the surface of the modified layer and thermocompression bonding is also provided.  [12] Step II)  11. The method for producing a metal-clad laminate according to claim 9 or 10, comprising a step of forming a metal thin film layer on the surface of the modified layer.  [13] The method for producing a metal-clad laminate according to any one of [9] to [12], wherein the thickness of the alkali-treated layer is in the range of 0.005 to 3.0 m.  14. The method for producing a metal-clad laminate according to any one of claims 9 to 12, wherein the amino compound is an aromatic amine having a primary or secondary amino group.  15. The method for producing a metal-clad laminate according to any one of claims 9 to 12, wherein the amino compound is an aliphatic amine having at least three primary amino groups as functional groups.  16. The method for producing a metal-clad laminate according to any one of claims 9 to 12, wherein the amino compound is a polyimide precursor resin.  [17] The method for producing a metal-clad laminate according to any one of [9] to [12], wherein the amino compound is a silane coupling agent having an amino group. [18] Silane coupling agent with amino group 3 Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, N— 2— (aminoethyl) 3 Aminopropyltrimethoxysilane, N-2- ( Aminoethyl) 3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl N- (1,3 dimethylbutylidene) propylamine, and N-ferro-3 triaminosilane are also at least one selected. As stated in claim 17 The manufacturing method of the metal-clad laminated board of mounting.  [19] The method for producing a metal-clad laminate according to any one of [9] to [12], wherein the amino compound strength is diaminosiloxane.  20. The method for producing a metal-clad laminate according to claim 19, wherein the diaminosiloxane is a diaminosiloxane oligomer represented by the following general formula (1).

Here, Ar and Ar represent a divalent hydrocarbon group, R to R are hydrocarbon groups having 1 to 6 carbon atoms.  2 7 3 6  M represents a number from 1 to 20. 21. The method for producing a metal-clad laminate according to claim 11, wherein the metal foil is a copper foil, a copper alloy foil or a stainless steel foil.  [22] In the method of bonding the polyimide resin layer by overlapping the polyimide resin layer surface of the first polyimide resin layer (P1) and the second polyimide resin layer (P2),  A) For the first polyimide resin layer (P1), a) a step of treating the surface side of the polyimide resin layer with an alkaline aqueous solution to form an alkali treatment layer;  B) For the second polyimide resin layer (P2): a) a step of treating the surface side of the polyimide resin layer with an alkaline aqueous solution to form an alkali treatment layer; b) amino acid combination with the alkali treatment layer surface Impregnating a polar solvent solution containing a product and drying to form an amino compound-containing layer; C) a step of superimposing an amino compound-containing layer surface of the second polyimide resin layer (P2) on the surface of the alkali treatment layer of the first polyimide resin layer (P1) and thermocompression bonding. Adhesion method of the resin layer.  [23] A polyimide resin layer of a single-sided metal-clad laminate in which at least one of the first polyimide resin layer (P1) and the second polyimide resin layer (P2) has a metal foil on one side of the polyimide resin layer The method for adhering a polyimide resin layer according to claim 22. [24] A method for producing a double-sided metal-clad laminate having a metal foil on both sides of a polyimide resin layer by laminating and bonding two single-sided metal-clad laminates having a metal foil on one side of a polyimide resin layer Leave  A) For the first single-sided metal-clad laminate, a) a step of treating the surface side of the polyimide resin layer (P1) with an aqueous alkali solution to form an alkali treatment layer;  B) For the second single-sided metal-clad laminate, a) a step of treating the surface side of the polyimide resin layer (P2) with an aqueous alkali solution to form an alkali treatment layer; b) Impregnating with a polar solvent solution containing a compound and drying to form an amino compound-containing layer;  C) Overlay the surface of the polyimide resin layer (P1) of the first single-sided metal-clad laminate with the alkali-treated layer of the polyimide resin layer (P2) of the second single-sided metal-clad laminate. The manufacturing method of the double-sided metal-clad laminated board characterized by having the process to carry out.