TW200825128A - 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

200825128 IX. Description of the Invention [Technical Field] The present invention relates to a surface treatment method for a polyimide resin layer and a method for producing a metallized laminate comprising a polyimide layer on a metal foil layer, and more specifically A method for surface treatment of a polyimide film layer for a printed wiring board and a method for producing a metal-clad laminate.

[Prior Art] The electronic circuit of an electronic device is a printed wiring board processed by a laminate circuit formed of an insulating material and a conductive material. The printed wiring board is such that the surface of the insulating substrate (and the inside) is formed of a conductive material based on an electrically conductive material, and is classified into a plate-shaped rigid printed wiring board according to the type of insulating resin used for the substrate, and is flexible. Flexible printed wiring board. The flexible printed wiring board is characterized by its flexibility, and is therefore suitable for use in connection with a movable portion that can be repeatedly bent. Further, since the flexible printed wiring board can be housed in the electronic device in a bent state, it can be used as a space saving wiring material. In the flexible substrate for the material of the flexible printed wiring board, the insulating resin of the substrate is mostly made of polyimide and polyimide resin, but is used in an overwhelming manner to have a heat-resistant polyimide resin. More layers. Further, in general, copper foil is used as a conductive material for electrical conductivity. The flexible substrate is structurally distinguishable into a three-layer flexible substrate and a two-layer flexible substrate. The three-layer flexible substrate is a base film layer (main layer of an insulating resin layer), an adhesive layer, and a copper foil obtained by bonding a base film such as polyimide or an adhesive such as an epoxy resin or an acrylic resin to a copper foil. Layer 3 layered laminate -5 - 200825128 * . Further, the two-layer flexible substrate is a special method, and a laminate of a base film layer and a copper foil layer is used without using an adhesive. The two-layer flexible substrate does not contain heat resistance such as epoxy resin or acrylic resin. Low adhesive layer, so high reliability can make the entire circuit thin, so it can increase its usage. - On the other hand, when the thermal expansion coefficient of the base film layer of the flexible substrate is low, curling can be prevented, but the polyimide resin having a low thermal expansion coefficient is inferior in the adhesiveness, so that no adhesive is used. When a polyimide resin is used, it is necessary to provide a polyimide resin layer which is excellent in adhesion to the adhesive layer on the back surface side. Further, a flexible substrate having a copper foil layer on both sides is known, and a method for producing the same is as follows: a method of manufacturing a single-sided flexible substrate having a copper foil layer on one side, and then laminating two single-sided flexible substrates; or A method of laminating copper foil on a single-sided flexible substrate or the like. In this case, it is preferable to use a flexible substrate which does not contain an adhesive layer or which imparts an adhesive layer. In recent years, with the demand for high performance and high performance of electronic devices, it is expected that printed wiring boards for circuit board materials used in electronic devices can be made high in density. In order to increase the density of the printed wiring board, the shunting circuit wiring width and the * pitch are required, that is, the pitch is required to be refined. In order to increase the density of the printed wiring board and to refine the V-direction, it is preferable to use a copper foil having a low surface roughness. However, the fixing effect of the copper foil having a low surface roughness, that is, the ability to invade the surface of the copper foil of the insulating resin layer is low, and the mechanical strength is not obtained, so there is a problem that the adhesion force to the insulating resin is poor. Therefore, it is a problem to increase the adhesion of the copper foil and the insulating resin having a low surface roughness. Polyethylenimine resins are generally known to have poor adhesion. Further, in order to prevent curling of the base film layer of the laminate used in the printed wiring board, it is preferable that -6 - 200825128

In order to use a polyimide resin layer having a low coefficient of thermal expansion, there is an inverse relationship between low thermal expansion and adhesion. Therefore, in order to improve the adhesion strength, there have been reports of surface modification techniques for various polyimide films. An example of this is a surface modification method using plasma treatment, but it requires a high-priced device and has a problem of an increase in running cost. For the surface modification method of the polyimide-treated polyimide film, for example, Japanese Laid-Open Patent Publication No. Hei 5-2222, No. Hei. No. Hei 8-1-2779, No. Hei. Specific examples disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2006-7518. However, in the current state of the art, it is impossible to obtain an adhesive force for a copper foil and a polyimide film layer having a low surface roughness. Further, the surface modification method using wet etching which is advantageous in terms of cost is attracting attention, but generally, the surface modification method which is dry etching like plasma treatment is still insufficient in adhesion, and there is an improvement demand. A surface modification method of such a wet etching is disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. There has been disclosed a method of thermally compressing a polyimine and a metal treated with a polar solvent containing an aliphatic primary amine. However, this method requires a polyimide layer of a polyimide, so that the insulating resin layer is thick. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

It is an object of the present invention to modify the surface of a polyimide resin layer to improve adhesion. Further, the surface of the polyimide film layer having a low expansion property suitable for the base film layer is modified to improve the adhesion, and the adhesive polyimide layer or the adhesive for imparting the adhesive layer may be omitted. Floor. Another object of the invention is to provide a method for producing a metal clad laminate which can ensure sufficient adhesion strength even when the distance between the corresponding printed substrates is fine, and which can be made extremely thinner than the insulating resin layer. Further, the object is to improve the subsequent method of thermocompression bonding after laminating the polyimine resin layer. Another object is to provide a method of manufacturing a double-sided metal clad laminate. Means for Solving the Problem In order to achieve the above object, the present inventors have found that after the wet etching method is appropriately modified, the polyimide layer of the polyimide resin layer using the method can provide little change in the thickness of the polyimide layer. Further, the present invention can be completed by improving a polyimide resin layer having excellent adhesion to the bonding strength of the metal foil. The present invention relates to a method for forming a modified layer on a surface of a polyimide resin layer, characterized in that a) a layer on the surface side of a polyimide resin layer is treated with an aqueous alkaline solution to form an alkali treatment layer. And, b) the step of impregnating the alkali treatment layer with a polar solvent solution containing an amine compound and drying to form an amine group-containing compound layer. 200825128 Further, the present invention relates to a method for forming a modified layer on a surface of a polyimide resin layer, which comprises a) treating a layer on the surface side of a polyimide resin layer with an alkaline aqueous solution to form an alkali treatment. a step of layering, and b) a step of impregnating the alkali treatment layer with a polar solvent solution containing an amine compound, drying to form an amine group-containing compound layer, and c) subjecting the amine group-containing compound layer to a quinone imidization treatment to form The step of upgrading the quinone imidization layer. Further, the present invention relates to a method for producing a metal-clad laminate, characterized in that 'there is a step I' and a step of forming a modified layer on the surface of the polyimide layer to form a modified layer on the surface of the modified layer. In the method for producing a metallized laminate according to the step of the metal layer, the step I) is provided with a) a step of treating the layer on the surface side of the polyimide resin layer with an aqueous alkaline solution to form an alkali treatment layer, and b) The treatment layer is impregnated with a polar solvent solution containing an amine compound and then dried to form a layer containing an amine group compound. Further, the present invention relates to a method for producing a metal-clad laminate, which comprises the steps of: "providing a" a layer on the surface side of the polyimide resin layer treated with an aqueous alkaline solution to form an inspection layer, and b) The alkali treatment layer is subjected to a step of impregnating a polar solvent solution containing an amine compound and then drying to form an amine group-containing compound layer and a step of recombining the metal foil on the surface of the amine group-containing compound layer. Further, the present invention relates to a method for producing a metal-clad laminate, which comprises the steps of: a) treating a layer on the surface side of a polyimide resin layer with an aqueous alkaline solution to form an alkali treatment layer, and b) The alkali treatment layer is impregnated with a layer of a metal thin film on the surface of the amine group-containing compound layer by impregnating a polar solvent solution containing an amine compound and then drying to form an amine group-containing compound layer and e.

Further, the present invention relates to a method for producing a metal-clad laminate, which comprises the steps of: a) treating a layer on the surface side of a polyimide resin layer with an aqueous alkaline solution to form an inspection layer, and b) The step of impregnating the polar solvent solution containing the amine compound and then drying to form the amine group-containing compound layer, and c) the step of subjecting the amine group-containing compound layer to the quinone imidization to form the modified ruthenium imidization layer And d) a step of recombining the metal foil on the surface of the modified yttrium imidization layer. Further, the present invention relates to a method for producing a metal-clad laminate, which comprises the steps of: a) treating a layer on the surface side of the polyimide resin layer with an aqueous alkaline solution to form an alkali treatment layer, and b) a step of immersing the alkali solvent-containing layer in a polar solvent solution containing an amine compound to form an amine group-containing compound layer, and c) subjecting the amine group-containing compound layer to oxime imidization to form a modified yttrium imidization layer, And e) forming a metal thin film layer on the surface of the modified yttrium imide layer. Further, the present invention relates to a method for bonding a polyimide layer of a polyimide, which is characterized in that a method of superposing a layer of a polyimide layer on a layer of a first polyimide film and a layer of a second polyimide film is carried out. Provided with A) a layer of the first polyimine resin, a) a step of treating the layer on the surface side of the layer of the polyimide resin layer (P 1 ) with an aqueous alkaline solution to form an alkali treatment layer, B) The dimeric quinone imide resin layer is subjected to a step of forming a layer of the alkali treatment layer on the surface side of the polyethylenimine resin layer (P2) with an alkaline aqueous solution at -10 to 200825128, and b) making the test treatment a step of impregnating a polar solvent solution containing an amine compound to form an amine group-containing compound layer, and C) superposing an amine compound treatment layer of the second polyimine resin layer (P2) on the first polyimine The step of reheating the alkali treatment layer of the resin layer (P1). Further, the present invention relates to a method for producing a double-sided metal-clad laminate, which is characterized in that a single-sided metal-clad laminate having a metal foil on one side of two polyimide-imide resin layers is superposed, and a polyimide resin is laminated. In the method for manufacturing a double-sided metal-clad laminate having a metal foil on both sides of the layer, A) is provided for the first single-sided metallized laminate, and a) the polyimide resin layer (P 1 ) is treated with an alkaline aqueous solution. a layer on the surface side to form an alkali treatment layer, B) a second single-sided metallization laminate, a) treating a layer on the surface side of the polyimide layer (P2) with an aqueous alkaline solution to form a base Steps of treating the layer 'and b) the step of impregnating the alkali treatment layer with a polar solvent solution containing the amine compound and drying to form an amine group-containing compound layer, and C) the second single-sided metallized laminate of the polyimide The layer of the amine group-containing compound of the resin layer (P2) is superposed on the alkali-treated layer of the polyimide layer of the first single-sided metallized laminate (P1) and then thermocompression-bonded. The thickness of the alkali-treated layer formed in the above step (a) is preferably from 〇.005 to 3.0/zm. Further, the polyimine resin layer may be a layer of a laminate formed of a surface of a laminate, or a layer of a polyimide resin layer which forms a surface layer of a polyimide film. -11 - 200825128 The amino group compound used in the above step (b) is preferably an aromatic amine having a primary or secondary amine group, an aliphatic amine having at least 3 functional groups of a primary amino group, and an amine. A selected one of a decane coupling agent, a diamine siloxane, and a polyimine precursor resin, wherein the poly phthalimide precursor resin is polyamic acid. A decane coupling agent having an amine group such as 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethyl Oxydecane, N 2 -(aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylene)propane At least one selected from the group consisting of a base amine and N-phenyl-3-aminopropyltrimethoxydecane. The diamino sulfoxane is, for example, a diamine siloxane oxide represented by the following general formula (1). 【化1】

R3 Rg H2N—Ar2—HSi-O-^Si—Ar7 mR6

Wherein Ar2 and Ai*7 are a divalent hydrocarbon group, and R3 to R6 are a hydrocarbon group having a carbon number of 1 to 6, and m is a number from 1 to 20. The metal used for the thermal compression bonding performed in the above step d) or d 2) is preferably a copper foil, a copper alloy foil or a stainless steel foil. The invention will be described in detail below. The polyimine resin layer used in the present invention is not particularly limited, and may be a film (sheet) formed of a polyimide resin, or may be laminated on a substrate such as a copper foil, a glass plate, or a resin film. Polyimine resin layer in the state. • 12- 200825128 The substrate refers to a sheet-like resin or a metal foil in which a polyimide resin layer is laminated. However, at least one side of the polyimide layer is present as a surface layer. Further, the polyimide layer has a thickness of from 3 to 100 / / m, preferably from 3 to 50 / m. After the surface treatment of the above polyimide film layer, at least a two-layered article having the original polyimide film layer (unmodified polyimine resin layer) and the modified layer can be formed.

The polyimine resin forming the polyimine resin layer comprises a polyimine resin, and a polyamidimide, a polybenzimidazole, a polyimine, a polyether quinone, a polyoxyalkylene. A heat-resistant resin having a quinone imine group in a structure such as quinone. Further, a commercially available polyimine resin or a polyimide film can be used. In the polyimine resin layer, the method of the present invention is applied to a polyimide resin layer having low adhesion and low thermal expansion. Specifically, the coefficient of thermal linear expansion is lxl〇_6~30xl〇6 (1/K), preferably 1χ1 (Γ6~25χ 10_6 (1/Κ), more preferably 15χ10·6 to 25xl0·6 (1 /Κ) The effect of the low thermal expansion polyimine resin layer is large, and it can be applied to the polyimine resin layer exceeding the above coefficient of thermal expansion to improve adhesion. Polyimine resin layer is used. The polyimine resin is preferably a polyimine resin having a structural unit represented by the general formula (2).

Wherein, An is a tetravalent aromatic compound represented by formula (3) or formula (4),

Ar3 is a divalent aromatic group 'R! represented by formula (5) or formula (6) independently of a monovalent hydrocarbon group or alkoxy group having 1 to 6 carbon atoms, and X and Y are independently a single bond-13- 200825128 or a valence of 2 to 15 carbon atoms, 〇, s, c〇, s〇, s〇2 or CONH selected in the binary group, ^ is independently an integer from 〇 to 4, q is a structure The existence of the unit is 1 to 1 莫 of Moerby. [化3]

The above structural unit may be present in a separate polymer or in the structural unit of the copolymer. Copolymers having a complex number of structural units may exist in blocks or in a random form. Among the polyimine resins having such a structural unit, a suitable polyimine resin is a non-thermoplastic polyimide resin. Since the polyimine resin is generally obtained by reacting a diamine with an acid diol, a specific example of the polyimide resin can be understood from the description of the diamine and the acid dianhydride. In the above general formula (1), Ar3 may be a residue of a diamine, and An may be a residue of an acid dianhydride. Therefore, the polyimine resin is preferably described by a diamine and an acid dianhydride. However, it is not limited to the polyimine resin obtained by the method. The diamine is preferably, for example, 4,4'-diaminodiphenyl ether, 2'-methoxy-4,4f-diaminophenylaniline, 1,4-bis(4-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-dimethyl-4,4' -diaminobiphenyl, 3,3, dihydroxy-4,4, diamine-14-200825128 bisbiphenyl, 4,4'-diaminobenzidine anilide, and the like.

Further preferred are, for example, 2,2-bis-[4-(3-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy)phenyl]pyrene, bis[4- (3-Aminophenoxy)phenyl]indole, bis[4-(4-aminophenoxy)]biphenyl, bis[4-(3-aminophenoxy)biphenyl, bis[1] -(4-Aminophenoxy.)]biphenyl, bis[1-(3-aminophenoxy)]biphenyl, bis[4-(4-aminophenoxy)phenyl]methane, Bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)benzene Ether, bis[4-(4-aminophenoxy)]benzophenone, bis[4-(3-aminophenoxy)]benzophenone, bis[4,4'-( 4-aminophenoxy)]phenylaniline, bis[4,4'-(3-aminophenoxy)]phenylanilide, 9,9-bis[4-(4-aminophenoxy) Phenyl]anthracene, 9,9-bis[4-(3-aminophenoxy)phenyl]anthracene, and the like. Other diamines such as 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-aminophenoxy)phenyl] Hexafluoropropane, 4,4'-extended methyldimethylaniline, 4,4'-extended methyldi-2,6-dimethylaniline, 4,4, methyl-2,6-diethylaniline , 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4,diaminodiphenylethane, 3,3,diaminodiphenyl Ethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diamine Diphenyl sulfide, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl fluorene, 4,4'-[]amino phenyl acid, 3,3· _>Amino-Phenyl, 3,4'- _Aminodiphenyl ether, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4 ·-Diaminobiphenyl, 3,3-dimethoxybenzidine, 4,4"-diamino-indole-triplet-15- 200825128 Benzene, 3,3"-diamino-p-terphenyl , m-phenylenediamine, p-phenylenediamine, 2,6-diaminopyridine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4- Aminophenoxy Benzene, 4,4'-[ 1,4-phenylphenylbis(1-methylethylidene)]diphenylamine, 4,4'-[1,3-phenylene bis(1-methyl Ethyl)]diphenylamine, bis(P-aminocyclohexyl)methane, bis(p-/3-amino-t-butylphenyl)ether, bis(P-/3-methyl-5-amine Pentyl) benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-di Amino naphthalene, 2,6-diaminonaphthalene, 2,4-bis(/3-amino-t-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. The acid dianhydride is preferably, for example, pyromellitic anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride. Further preferably, 2, 2', 3, 3·-, 2, 3, 3, 4, or 3, 3f, 4, 4f-benzophenone tetracarboxylic dianhydride, 2, 3', 3,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3,biphenyltetracarboxylic dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic dianhydride, Bis(2,3-dicarboxyphenyl)ether dianhydride or the like. Further preferably, 3, 3", 4, 4"-, 2, 3, 3", 4"- or 2, 2", 3, 3"-p-triphenyltetracarboxylic dianhydride, 2, 2-bis(2,3- or 3,4-dicarboxyphenyl)-propane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)methane dianhydride, bis(2,3- or 3,4-dicarboxyphenyl)ruthenic anhydride, 1,1-bis(2,3- or 3,4-dicarboxyphenyl)ethane dianhydride, etc. Other acid dianhydrides such as 1, 2, 7 , 8-, 1, 2, 6, 7 or 1,2,9,10-phenanthrene-tetracarboxylic dianhydride, 2,3,6,7-nonanedicarboxylic dianhydride, 2,2-dual ( 3,4-Dicarboxyphenyl-16- 200825128 L tetrafluoropropane dianhydride, 2,3,5,6-cyclohexane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride _, i , 2,5,6-naphthalenetetracarboxylic dianhydride, I'M-naphthalene tetraphthalic acid dianhydride, 4,8-monomethyl hexahydronaphthalene tetracarboxylic dianhydride, 2,6· or 2,7- Dichloronaphthalene-l54,5,8•tetracarboxylic dianhydride, 2,3,6,7·(or,4,5,8·) tetrachlorona-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-茈_four Carboxylic dianhydride

Fire 兀 1,2,3 5 4 tetradecanoic acid anhydride, 卩比晓 _ 2,3,5,6 ·tetrahydro acid dianhydride, decyl 2,3,4,5-tetracarboxylic acid Anhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4-bis(2,3-carboxyloxy)diphenylmethane dianhydride, and the like. One of the amines and the acid dianhydride used may be used alone or in combination of two or more. Further, the above diamine or acid dianhydride may be used in the above general formula (1), and the other amine or acid dianhydride is used at a rate of 90 mol%. Hereinafter, it is preferably 50 mol% or less. Further, the type of diamine and acid anhydride, and the molar ratio of each of two or more kinds of diamines or acid dianhydrides can be used to control thermal expansion property, adhesion, and glass transition point (Tg). The method for producing the polyimide layer of the polyimide resin is not particularly limited. For example, a solution of a polyamidite resin precursor of a polyimide resin precursor may be applied to a substrate, and dried and imidized on the substrate. A method of forming a polyimide layer of a polyimide resin. The method of applying the polyaminic acid resin solution to the substrate is not particularly limited, and it can be applied by a coater such as a carding machine, a die, a blade, or a slit. Further, the method of drying and hydrazine imidization is not particularly limited, and for example, heat treatment at a temperature of 80 to 400 ° C for 1 to 60 minutes may be employed. When this heat treatment is performed, the polyglycine can be dehydrated and closed, and a layer of -17-200825128 polyimine resin can be formed on the substrate. Further, the polyimine resin layer on which the polyimide film layer is formed on the substrate can be directly used or used after peeling.

The polyimide layer may be formed of a single layer or a plurality of layers. When the polyimine resin layer is a plurality of layers, it may be formed by coating another polyimide resin layer on a polyimide film formed of different constituent components. When the polyimine resin layer is formed of three or more layers, the same composition of the polyimide resin can be used twice or more. The preferred layer in the industry is constructed as a simple two or single layer, particularly preferably a single layer. Further, the polyimide layer has a thickness of from 3 to 100 / zm, preferably from 3 to 50 / / m, more preferably from 5 to 30 / zm. In the method for forming a modified layer on the surface of the polyimine resin layer of the present invention, a) a step of treating the layer on the surface side of the polyimide film layer with an aqueous alkaline solution to form an alkali treatment layer (step a) And b) the step of impregnating the test layer with a polar solvent solution containing an amine compound and drying to form an amine group-containing compound layer (step b). Further, if necessary, c) a step (c) of subjecting the amine group-containing compound layer to oxime imidization to form a modified ruthenium imidization layer. The method for producing a metal-clad laminate according to the present invention comprises the steps of forming a modified layer on the surface of the polyimide layer (step I)), and forming a metal layer on the surface of the modified layer. (Step II)). Wherein step I) is provided with the above steps a and b. Step c can be provided if necessary. Step II) A step of preparing (d) a metal foil to be superposed on the surface of the amine-containing compound layer or the modified yttrium imidization layer (both layers may be referred to as a modified layer) and then thermocompression bonding (step d), Or e) a step of forming a metal thin film layer on the surface of the amine group-containing compound layer or the modified oxime imidization layer (step e). Step 18 - 200825128 Although step d is a step of recombining the metal foil on the surface of the amine-containing compound layer or the modified yttrium imidization layer, but in order to distinguish the thermal compression of the amine-containing compound layer, And the thermal compression of the modified yttrium imide layer, the former is referred to as step d 1, and the latter is referred to as step d2. Similarly, step e is a step of forming a metal thin film layer on the surface of the amine group-containing compound layer or the modified oxime imidization layer, but in order to distinguish it from the amine group-containing compound layer or the modified yttrium imidization layer, The former is referred to as step e 1, and the latter is referred to as step e 2 . In the method for attaching the polyimide film of the present invention and the method for producing a double-sided metal-clad laminate, in addition to the above steps a and b, the second polyimide layer (P2) is further included. The amine compound layer is superposed on the alkali treatment layer of the first polyimide layer (P1) and then thermocompression-bonded (step C). Steps a and b can be performed in the same manner in any case. The other steps c to e are also the same. Next, a method of forming a modified layer on the surface of the polyimide resin layer will be described by the steps a, b, and c. In the step a, the surface side of the polyimide resin layer is treated with an aqueous alkaline solution to form an alkali treatment layer. The alkaline aqueous solution to be used is preferably 0.5 to 50% by weight, a liquid temperature of 5 to 80° (aqueous sodium hydroxide or potassium hydroxide), and is suitable for dipping, spraying or brush coating. For example, when the impregnation method is used, the effective treatment time is from 1 sec to 60 minutes, preferably from 1 to 30 wt%, and the aqueous solution having a liquid temperature of 25 to 60 ° C is treated for 30 seconds to 10 minutes. The processing conditions of the polyimine resin layer are appropriately changed. Generally, when the concentration of the alkaline aqueous solution is light, the surface treatment time of the polyimide resin layer needs to be strengthened. When the liquid temperature of the alkaline aqueous solution is high, the temperature is shortened. Processing time - 19 - 200825128

between. When the aqueous solution is treated with an alkaline aqueous solution, the surface of the polyimide resin layer is impregnated with an aqueous alkaline solution, and the polyimide layer is subjected to alkali treatment. It is inferred that the alkali treatment reaction is mainly the hydrolysis of the quinone bond. The alkali treatment layer formed by the alkali treatment has a thickness of from 1/200 to 1/2, preferably from 1/100 to 1/5, of the thickness of the polyimide layer. The other viewpoint is preferably from 0.005 to 3.0/m, more preferably from 〇_〇5 to 2.0//m, still more preferably from 0.1 to 2.0/m. Further, other points are preferably 〇·005 to 0.1 /z m, and more preferably 0.01 to 0.1 // m, more preferably 〇.〇5 to 0.1#m (for example, when step e is provided). When the thickness of the treatment layer is outside the above range, it is difficult to find sufficient adhesion strength between the polyimide layer and the metal layer. When the polyimide resin layer is a polyimide film, it can be simultaneously modified on both sides. In the alkali-treated layer formed by the alkali treatment, a salt derived from an alkali metal of an alkaline aqueous solution and a carboxyl group at the terminal of the polyimide resin is formed, and therefore it is preferably washed with an acidic aqueous solution. The acidic aqueous solution used may be any aqueous solution exhibiting acidity. Particularly preferred are aqueous hydrochloric acid and aqueous sulfuric acid. Further, the concentration may be from 5 to 50% by weight, preferably from 5 to 5% by weight. The pH is preferably 2 or less. Thereafter, it may be washed with water and then dried to be supplied to step b. Step b is a step of impregnating the alkali treatment layer with a polar solvent solution containing an amine compound to form an aromatic amine group-containing compound layer. The amine-based compound is preferably an 'aromatic amine-based compound' aliphatic amino group-based compound, a sand-based coupling agent having an amine group, a diamine-based oxirane, and a polyimine precursor resin. The aromatic amino group-containing compound may be an aromatic amine having a first- or second-order amine group, and particularly preferably an aromatic amine having a 1-stage amine-substituted aryl group ring. Number of amine groups -20- 200825128

It is from 1 to 5, preferably from 1 to 3, more preferably 2. The aromatic amine-based compound has a molecular weight of 90 to 1 Torr, preferably 1 Torr to 6 Torr, more preferably n Torr to 50,000. Further, the aromatic aromatic compound is, for example, a compound having at least 1, preferably from 10 to 10, more preferably 1 to 4 aromatic rings, and the aromatic ring may be substituted or unsubstituted with a substituent other than the amine group. . The substituent other than the amine group is preferably a functional group having a condensation polymerization with a terminal carboxyl group which is present in the alkali-treated layer, for example, a carboxyl group, a sulfur group or the like. The aromatic ring is a condensed ring such as a benzene ring or a naphthalene ring. a compound having a plurality of aromatic rings such as a biphenyl ring or the like or other Ar-X-Ar, Ar-Y-Ar-X-Ar-Y-Ar (wherein Ar is an aromatic ring such as a benzene ring, X And Y is independently a compound in which a divalent group such as co, o, s, so, so2, CONH, or CnH^ is substituted with an amine group. Substituents other than the amine group are, for example, a branched or linear alkyl group having 1 to 18 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), and an aromatic group having 6 to 13 carbon atoms (e.g., benzene). a group), an aralkyl group having 7 to 12 carbon atoms (e.g., benzyl group), and the like. Further, a hydroxyl group can be used as a substituent of the aromatic ring. A compound of an aromatic ring such as an aminophenol is substituted with a hydroxy group. Further, a condensed ring system having 1 to 20 carbon atoms can be used as the aromatic amine-containing compound of the present invention. The condensed ring to which the present invention is applied is, for example, diaminonaphthalene. Specific examples of the aromatic amino group-based compound are shown below, but are not limited to this example. Further, one or more aromatic amine-based compounds can be used. Aniline, toluidine, aminonaphthalene, aminobiphenyl, 2,2-bis-[4-(4-aminophenoxy)phenyl]propane, 2,2-bis-[4-(3-amine Phenyloxy)phenyl]propane, bis-[4-(4-aminophenoxy)phenyl]anthracene, bis-[4-(3-aminophenoxy)phenyl]indole, double [4-(4-Aminophenoxy)-21 - 200825128

Biphenyl, bis-[4-(3-aminophenoxy)biphenyl, bis-[1-(4-aminophenoxy)]biphenyl, bis-[1-(3-aminobenzene) Oxy))biphenyl, bis-[4-(4-aminophenoxy)phenyl]methane, bis-[4-(3-aminophenoxy)phenyl]methane, bis-[4- (4-Aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, bis-[4-(4-aminophenoxy)]diphenyl Methyl ketone, bis-[4-(3-aminophenoxy)]benzophenone, bis-[4,4'-(4-aminophenoxy)]phenylanilide, bis-[4, 4f-(3-Aminophenoxy)]phenylanilide, 9,9-bis-[4-(4-aminophenoxy)phenyl]anthracene, 9,9-bis-[4- (3 -aminophenoxy)phenyl]anthracene, 2,2-bis-[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis-[4-(3-amine Benzophenoxy)phenyl]hexafluoropropane, 4,41-methyldi-indole-toluidine, 4,4, methyldi-2,6-dimethylaniline, 4,4'-stretch Methyl-2,6-diethylaniline, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4,diaminodiphenylethane , 3,3, diamine Phenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'- Diaminodiphenyl sulfide, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl ether, 3, 3-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, benzidine, 3,3'-diaminobiphenyl, 3,3f-dimethyl-4,4'- Diaminobiphenyl, 3,3'-dimethoxybenzidine, 4,4,diamino-P-terphenyl, 3,3"·diamino-P-terphenyl, m-phenylene Diamine, p-phenylenediamine, 2,6-diamino P, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminobenzene) Oxy)benzene, 4,4 into [1,4-phenylphenylbis(1-methylethylidene)]diphenylamine, 4,4(-[1,3-phenylenebis(1-methyl) Ethylene)]diphenylamine, bis(p-aminocyclo-22-200825128 hexyl)methyl, bis(P-/3-amino-t-butylphenyl) ether, double (p-no-A) Benzyl-6-aminopentyl)benzene, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, 1,5-diamino group Naphthalene, 2,6-diaminonaphthalene, 2,4-bis(/3-amino-t-butyl)toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine , p-xylene-2,5-diamine, m-xylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5·2 Amino-1,3,4-oxadiazole, piperazine and the like.

The aliphatic Fee-based compound may be an aliphatic amine having a functional group of at least 3 primary amine groups. The aliphatic amine-based compound is preferably, for example, only composed of a carbon atom, a hydrogen atom and a nitrogen atom, and specifically, for example, tris(2-aminoethyl)amine. When the polyimine resin layer is followed by the metal layer, when an aliphatic amine having no more than three amine groups is used, it is difficult to find sufficient adhesion strength between the polyimide layer and the metal layer. Sandyard coupling agent with amine group such as '3-aminopropyltriethoxy sand pot, 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyl Trimethoxy decane, N-2-(aminoethyl)-3.aminopropylmethyldimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethyl At least one selected from the group consisting of butylene)propylamine and N-phenylaminopropyltrimethoxyxine. Particularly preferred is 3-aminopropyldiethoxylate, 3-aminopropyldimethoxydecane. The diaminocarboxane to be used is preferably a diamine oxirane represented by the above general formula (1). Specific examples are preferably as shown below. Diamine oxirane -23- 200825128 [Chemical 4]

Ch3 H3C H2N^H2C)^Si^〇H^Si-fCH2)-NH2 CH3 h3c 3 CH3 h3c H2N X H2C)^4—〇H^i"fCH2)>NH2 ch3 H3C 4

2 Η

In the above formula, the average m number is from 1 to 20, preferably from 5 to 15. When it exceeds this range, the adhesion to the copper foil is lowered. The polyimine precursor resin is preferably a polyimine precursor resin having a structural unit represented by the general formula (7). In the general formula (7), Ar4 is a divalent aromatic group 'Ar5 represented by the formula (8) or the formula (9), which is a tetravalent aromatic group represented by the formula (10) or the formula (11), and h is independently The monovalent carbonized amino group having 1 to 6 carbon atoms or the electrophilic group 'v and w' is a divalent hydrocarbon group having 1 or 15 fluorene number. 0, S, CO, S〇2 or the 2 valence group selected in CONH, m is independently an integer from 0 to 4, and the presence of the p-series structural unit is from 0.1 to 1.0. -24- 200825128 【化5】

【化6】

The above structural unit may be present in a separate polymer, and the structural unit is present. Copolymers with a complex number of structural units exist, or exist randomly. In the above general formula (7), Ar4 may be referred to as a residue of a diamine called an acid dianhydride, and thus may be a diamine or an acid dianhydride. However, it is not limited to the polydiamine diamine obtained by the method, such as 4,4, diaminodiphenyl ether, 2,-methoxybenzidine, 1,4-bis(4-aminophenoxy) Benzene, L3 phenoxy)benzene, 2,2^bis[4-(4-aminophenoxy)-2,2'-dimethyl-4,4f-diaminobiphenyl, 3,3' - Dihydroxy-4 benzene, 4,4'-diaminophenyl anilide. Others are the diamines listed above. 11): with the copolymer =, can block the I group, Ar5 can be; better preferred: the precursor resin base-4,4f-diamine-bis(4-amino:) propane, 4'- Diamine-based manimine resin -25-

200825128 Acid dianhydride such as pyromellitic anhydride, 3,3,2,4,4,1-biphenyltetramine, 3,3,4,4,-diphenylphosphonium tetracarboxylic dianhydride, 4,4' An oxydiamine which is exemplified by the above polyimine resin. As the diamine and the acid dianhydride, one type or two or more types of ruthenium I may be used, and diamines and acid dianhydrides other than the above may be used. Polyimine precursors, selected from the group of diamines and acid dianhydrides, and the use of two or more kinds; the molar ratio of each of the acid dianhydrides, such as diamines and acids in an organic solvent, for example, at a temperature of 20 The dianhydride is obtained by reaction. It is preferably carried out under conditions in which the diamine is in an excess amount or under the conditions of the polyimine precursor resin. That is, the diamine and the acid dianhydride are used in an amount of more than 1.0, more preferably from 1.001 to 1, more preferably from 1.1 to 5.0, still more preferably from 1.5 to 3.0, in terms of the diamine/acid dianhydride (mol ratio). Further, the molecular weight is such that the above molar ratio is nearly 1 〇, and the oligomer having a smaller molecular weight can be obtained when the specific enthalpy is increased. However, when the 2.0 is written, the unreacted diamine remains, so that the surface treatment effect can be improved by drying or by removing the yttrium at the end of the polyamidene resin in the alkali treatment layer. The polyimine precursor resin may be an oligomer having a weight average molecular weight of 2,000, preferably 2,000 to 10,00, more preferably 30,000. The use of such a low molecular weight polyimine precursor shirt facilitates the impregnation of the alkali treatment layer with the polyimide precursor resin and the treatment of the dentin base to the modified quinone imidization layer. Further, the thickness of the entire amine resin layer in the state before and after the surface treatment of the polyanthracene deer (before step a and after step c) can be made almost unchanged. Citrate dianhydride: anhydride. Further, the oxime resin may be: a diamine or a dianhydride to 60 ° C: the end is preferably 〜. 0 is preferably 1 plus, because the ratio = exceeds ί, the reaction is 5 00 to g 6,000 In the case of the oxime resin, all of the resin layers are condensed into the yttrium--26-200825128. These amine-based compounds may be used alone or in combination, and an aromatic amine-based compound, an aliphatic amine-based compound, an amine-based decane coupling agent, or an amine group may be used. Two or more selected from the group consisting of diamine siloxanes and polyimine precursor resins

These amine compounds can be used as a solution for a polar solvent. The polar solvent may be one which can dissolve the amine compound, and is not particularly limited. For example, it can be used as an aromatic amine-based compound, an aliphatic amine-based compound, a decane coupling agent having an amine group, a diamine sulfoxane and a polyimide solvent, such as water or methanol, ethanol, or propanol. An alcohol such as butanol, or a ketone such as acetone, dimethyl ketone or methyl ethyl ketone or an ether such as tetrahydrofuran, or N-methylpyrrolidone, dimethylacetamide or dimethylformamide. Grade 3 amines, dimethyl alum, etc. A polar solvent suitable for diamine sulfoxane, such as an alcoholic solvent such as methanol, ethanol, propanol or isopropanol, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, hydrazine, hydrazine diethylamine, N,N-dimethylmethoxyacetamide 'dimethyl Amidoxime solvent such as hydrazine or N-methyl-2-pyrrolidone, ether solvent such as tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether or dioxane, acetone, MEK, 2 a ketone solvent such as pentanone, 3-pentanone or r-butyrolactone, or an aromatic hydrocarbon-based solvent such as toluene or xylene. The solvent may be used singly or in combination of several kinds, and water may be mixed. Methanol is preferred. The concentration of the solution containing the polar solvent of the amine compound is preferably such that the concentration of the amine compound is 0.0001 to 1 M (0.0001 to 1 mol/L), preferably 〇· 〇0 0 1 to 0.1 Μ, more preferably 0.0. 0 0 5 to 0 · 1 Μ, especially preferably 0.000 5 to 〇·〇1Μ. The solution concentration of -27-200825128 containing a polar solvent of a polyimine precursor resin may be such that the diamine component is in the above range. Further, in another aspect, the solution concentration of the polar solvent containing the amine compound, particularly the concentration of the broth coupling agent or the diamine-based cerium oxide solution, may be 0.1 to 5 wt%, preferably 0.5 to 1 wt% of the mercapto compound. When the concentration is high, since the alkali-treated layer is prevented from being impregnated with the amine-based compound solution, the amount adhering to the modified layer is too large, so that it is not desirable to have a high concentration.

The impregnation method may be a method of bringing a solution containing a polar solvent containing an amine compound into contact with an alkali treatment layer, and is not particularly limited, and a known method can be used. For example, a dipping method, a spray method, a brush coating method, a printing method, or the like can be used. The temperature may be from 〇 to 100 ° C, preferably from 10 to 401: normal temperature. Further, when the impregnation method is used, the impregnation time may be from 30 seconds to 1 hour, preferably from 1 to 15 minutes. Dry after impregnation. The drying method is not particularly limited, and natural drying, air gun drying, oven drying, and the like can be used. The drying conditions may vary depending on the type of polar solvent, and may be from 5 seconds to 60 minutes at 10 to 150 ° C, preferably from 10 seconds to 30 minutes at 25 to 150 ° C, more preferably from 30 to 120 °. C for 1 minute to 1 minute. The post-impregnation drying treatment allows a solution containing a polar solvent of an amine compound to be impregnated into the interior by an alkali treatment layer to form an amine group-containing compound layer. The thickness of the impregnation thickness, i.e., the thickness of the amine-containing compound layer, may be from 1/10 to 1.5 times the thickness of the alkali-treated layer, preferably from 1/2 to 1.2 times, more preferably from 〇.8 to ι·2 times. The polyimine resin layer obtained by drying is a surface-treated polyimide film having a surface-modified surface having an improved adhesion layer. -28- 200825128 The surface-treated polyimide film layer obtained by modifying the surface of the polyimide resin layer in steps a and b can have excellent adhesion, and therefore is suitable for metal foil, resin film, and other polymerization. Uses such as quinone imine resin layer. Further, after the amide-imidization treatment of the amine-containing compound, the ruthenium imidization layer can be formed by imidization, since the modified ruthenium imidization layer also has excellent adhesion, so it is suitable for the subsequent metal foil, Uses such as resin film and other polyimide resin layers.

In the method of forming a modified layer on the surface of the polyimine resin layer of the present invention, it is preferred to have step c in addition to steps a and b. In the step c, the above-mentioned amine group-containing compound layer is subjected to oxime imidization treatment to form a modified oxime imidization layer. The ruthenium imidization method may be a chemical hydrazine imidization by heating ruthenium or a catalyst, and is not particularly limited. For example, when heating oxime imidization, it may be 1 to 40 (TC, preferably The total ruthenium imidization is carried out at 150 to 400 ° C, and the chemical hydrazine imidization of the catalyst can be combined with the ruthenium imidation. In the ruthenium imidization treatment, it is inferred that the main component is an amine compound and a polyfluorene. The imide resin layer, in particular, the quinone imidization reaction which is present at the terminal carboxyl group of the alkali-treated layer. Therefore, the poly-imine resin having a low molecular weight and increasing the terminal carboxyl group in the step a can be used in the step c to lower the molecular weight. The lower end is imidized and stabilized, so it is presumed that the adhesion of the polyimine resin layer can be improved. In the method of forming the modified layer on the surface of the polyimine resin layer of the present invention, the alkali of the step a The thickness of the treatment layer is preferably from 0.005 to 3.0 / / m. The amine compound used in the step b may be an aromatic amine having a amine group of a grade 1 or a grade 2. The layer of the polyimide resin layer may be formed into a layer. Surface layer of compound -29- 200825128 Polyimine resin layer Or a polyimine resin layer forming a surface layer of a polyimide film. The method for producing a metallized laminate of the present invention is described in the method for producing a metallized laminate. The step of modifying the layer) and the step of providing a metal layer on the modified layer formed in the step I). Step a and step b, or step a, step b, and step c in the step ί) may be carried out by a method of forming a modified layer on the surface of the JL-polyimine resin layer. In the method of manufacturing a metal clad laminate, step c is preferably provided in addition to steps a and b. The surface treated polyimine resin layer obtained by the method is then subjected to step II). Step Π) is a step of providing a metal layer on the modified layer formed in the step I). The method of providing the metal layer may be a method of superposing a metal foil on the surface of the reforming layer and then thermocompression bonding (step d), or a method of forming a metal thin film layer (step e). The modified layer formed in the step I) may be the modified layer obtained in the step b or the modified layer obtained in the step c. Therefore, in step II), the step d and the step e may be carried out for any of the modified layers. Metals constituting the metal layer are, for example, iron, nickel, bismuth, aluminum, zinc, indium, aluminum, gold, tin, chromium, stainless steel, giant, titanium, copper, lead, magnesium, manganese and alloy foils thereof. Among them, copper, copper alloy or stainless steel is preferred. The metal layer may have a thickness of from 0.001 to 50 #m, preferably from 0.1 to 30/m. The thermal compression bonding method of the step d is not particularly limited, and a known known method can be employed. The method of attaching the metal foil is, for example, a general hydraulic press, a vacuum type hydraulic press, a pressurized pot pressurizing vacuum press machine, a continuous heat laminator or the like. In the method of attaching a metal foil, it is preferable to use a vacuum hydraulic press and a continuous thermal laminator from the viewpoint of obtaining sufficient pressure to easily remove residual volatile components -30-200825128 and preventing oxidation of the metal foil. Further, in the case of thermocompression bonding, it is preferred to heat the alloy foil at 150 to 45 ° C, more preferably 150 to 400 ° C, particularly preferably 150 to 380 ° C. Another point of view may be the temperature above the glass transition temperature of the polyimide or imidization layer. Further, the pressing pressure varies depending on the type of press machine to be used, but it is preferably from 1 to 50 MPa.

Metal foil such as iron foil, nickel foil, tantalum foil, aluminum foil, zinc foil, indium foil, silver foil, gold foil, tin foil, zirconium foil, stainless steel foil, group foil, titanium foil, copper foil, lead foil, magnesium foil, manganese foil And its alloy foil. Among them, copper foil or stainless steel foil is preferred. The copper foil is a copper foil or a copper alloy containing copper as a main component, and is preferably a copper foil having a copper content of 90% by mass or more, particularly preferably 95% by mass or more. A metal containing a copper foil such as chromium, chromium, nickel, ruthenium, zinc, ruthenium or the like. Further, it may be an alloy foil containing two or more kinds of these metals. In addition, the material of the stainless steel is not limited, and it is preferably stainless steel such as SUS 3 04. The surface of the metal foil laminated polyimide layer may be subjected to a decane coupling agent treatment. The decane coupling agent is preferably a decane coupling agent having a functional group such as an amine group or a fluorenyl group, more preferably a decane coupling agent having an amine group. Specifically, for example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N - (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyltriethoxydecane, N-(2-amine Ethyl ethyl)-3-aminopropylmethyldimethoxydecane, and the like. Among them, preferred is 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, n-(2-aminoethyl)-3-amino-31 - 200825128 propyltrimethoxy Baseline, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-triethoxydecyl-N-(1,3-dimethylbutylene) At least one selected from the group consisting of propylamine and N-phenyl-3-aminopropyltrimethoxydecane. Particularly preferred is 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane.

The decane coupling agent can be used in the form of a solution of a polar solvent. Suitable polar solvents such as water or polar organic solvents containing water. The polar organic solvent may be a polar liquid having an affinity for water, and is not particularly limited. Such polar organic solvents are, for example, methanol, ethanol, propanol, isopropanol, acetone, tetrahydrofuran dimethylformamide, dimethylacetamide or the like. The decane coupling agent solution may be a solution having a concentration of 0.01 to 5% by mass, preferably 0.1 to 2.0% by mass, more preferably 0.5 to 1.0% by weight. The method for treating the decane coupling agent may be a method of contacting a polar solvent solution containing a decane coupling agent, and is not particularly limited, and a known method can be employed. For example, a dipping method, a spray method, a brush coating method, a printing method, or the like is used. The temperature may be from 0 to 100 ° C, preferably from 10 to 40 ° C. Further, when the impregnation method is used, the effective immersion time is from 1 sec to 1 hour, preferably from 30 to 15 minutes. Dry after treatment. The drying method is not particularly limited and can be naturally dried, air-dried or oven-dried. The drying conditions may vary depending on the type of the polar solvent, and may be from 5 to 60 minutes at 10 to 150 ° C, preferably from 1 to 30 minutes at 25 to 150 ° C, more preferably from 30 to 120. 1 minute to 10 minutes at °C. The copper foil is used as a metal foil, for example, when used in a flexible substrate. The thickness of the copper foil used for this purpose is preferably from 3 to 50 // m, more preferably from 5 to 30 - 32 to 200825128 // m 'but the copper-clad laminate used for the purpose of fine pitching is required, Further, a thin copper foil is preferred, and in this case, it is preferably 5 to 20 // m. Further, in the present invention, even if a copper foil having a small surface roughness is used, excellent adhesion can be obtained for the resin layer. Therefore, it is particularly preferable to use a copper foil having a small surface roughness. The thickness of the surface of the copper foil is preferably from 10 points and the average thickness is from 0.1 to 3 // m. In particular, the copper foil used for the purpose of refining the pitch is preferably a surface roughness of 0.1 to 1.0 m m at an average of ten points.

For example, stainless steel is used as a metal foil for use in a suspension mounted on a hard disk drive (hereinafter referred to as an HDD suspension). The stainless steel foil used for this purpose may have a thickness of 10 to 100 / / m, preferably 15 to 7 〇 / / m, more preferably 15 to 50 / / m. The laminate obtained by the method for producing a metal-clad laminate according to the present invention is a laminate having a metal foil on one side or both sides of a polyimine resin layer. The laminate having a metal foil on one side may be obtained by laminating a metal foil to a surface-treated polyimide film obtained by the surface treatment method of the present invention. When the surface treatment polyimine resin layer is laminated on a substrate such as glass or a resin film, the laminate may be peeled off from the substrate if necessary. Surface Treatment Polyimine Resin When a metal foil such as a copper foil is laminated, a double-sided metal-clad laminate can be formed on the polyimide foil side layer alloy foil. Further, the metal clad laminate having a metal foil on both sides may be obtained by subjecting both surfaces of the surface-treated polyimide film to a surface treatment by a method other than the above, and then laminating the metal foil on the both sides. In addition, after the single-sided metal-clad laminate having the metal foil on one side is manufactured, at least one single-sided metal-clad laminate is subjected to surface treatment of the above-mentioned polyimine resin layer, and then double-joined and heat-bonded with two single-sided metal pastes. Laminate layer of polyimine-33-

200825128 It is worth it. In the method for producing a metallized laminate of the present invention, the thickness of the step J1 layer is preferably 〇 至 〇 5 to 3.0 // m. Further, the compound of the step b is preferably an aliphatic amine having a functional group of at least three of the amine groups having an amine group of a first or a second amine group, preferably a decane coupling agent having an amine group. Further, the diamine oxime is preferably a polyimide precursor resin. Next, the method of manufacturing the gold paste provided in the step e in the step II) will be explained. Steps a and b can be performed as described above. In the method for producing the metal-clad laminate, in addition to the step a, it is preferred to have the step c. Therefore, when step c is provided, the resulting metal ruthenium layer on the surface of the modified yttrium imide layer can be prepared (e2). In the method for producing the metal clad laminate, the degree of the step a is preferably from 0.005 to 3.0/zm. Further, in step b, preferred is an aromatic amine having a grade 1 or 2 amine group. Further, an aliphatic amine having three functional groups of a 1-amino group is preferred. In addition, an amine-based decane coupling agent. Further, a diamine oxirane is preferred. Anthraquinone precursor resin. In the method of forming the metal thin film layer in the step e, a vacuum deposition method, a sputtering method, an electron beam evaporation method, or the like is not particularly used, and a sputtering method is particularly preferable. This sputtering method can be classified into various methods such as DC sputtering I, DC magnetron sputtering, RF magnetron sputtering, and EC sputtering sputtering, and can be suitably employed without particular limitation. The amine amine used in the base of polya. Also with. In addition, the preferred hospital is better. Steps e and b of the laminate are further carried out in step c. Step e (the alkali-based compound of the step-alkali treatment layer has at least preferably another polycondensation limit, such as ion plating, RF sputtering In the formation condition of the metal thin film layer of the sputtering method -34-200825128, for example, when argon gas is used as the sputtering gas, the pressure is preferably lxl 〇_2 to IPa, more preferably 5x10- 2 to SxlOipa, preferably a sputtering power density of 1 to loowcm-2, more preferably 1 to 50 WcnT2.

When a metal thin film is formed, copper is preferably used as the thin film layer. In this case, in order to further improve the adhesion, a copper thin film layer may be provided on the surface of the polyimide film layer after the underlying metal thin film layer is provided. The underlying metal film layer is, for example, nickel, chromium or a combination thereof. When the underlying metal thin film layer is provided, the thickness thereof is 1/2 or less of the thickness of the copper thin film layer, preferably 1/5 or less, and the thickness may be 1 to 50 nm. The underlying metal thin film layer is also preferably formed by sputtering. The copper used may be alloy copper containing some 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. Metals which may contain copper such as chromium, zirconium, nickel, ruthenium, zinc, ruthenium and the like. Further, the thickness of the copper thin film layer formed by the step e (step el or step e2) of the copper alloy film containing two or more of these metals may be 0.001 to 1. 〇 / / m, preferably 0.01 to 〇 5. //m, more preferably 〇·〇5 to 0.5/zm, particularly preferably 0.1 to 〇.5/zm. When the copper film layer is thicker, a thick film can be formed by electroless plating or electrolytic plating. Next, a method of attaching the polyimine resin layer of the present invention will be explained. The method of superposing the polyimine resin layer of the first polyimine resin layer (P1) and the second polyimide film layer (P2) and then the polyimide layer of the polyimide layer is provided with the following steps A) , :B) and C). -35- 200825128 A) Step a on the first polyimine resin layer (ρι). B) performing step a and step b on the second polyimine resin layer (p2), and superposing the amine-containing compound layer of the second polyimine resin layer (p2) on the first polyimide resin The layer (ρι) is modified, and the step d3 is reheated. Step a and step b can be carried out in the same manner as step a and step b above. Step d3 can be carried out in the same manner as in the above step d. Preparing two polyimine resin layers, modifying the surface and then adhering to each other, 'the first polyimine resin layer is called a polyimide layer (pi), and the second polyimide layer is It is called a polyimide resin layer (P2). The polyimine resin layer (P 1 ) and the polyimide resin layer (P2) may be the same or different. That is, the type of the polyimine resin, the laminated structure of the polyimide film layer, the presence or absence of the substrate, etc. may be the same or different. The production of the polyimine resin layer (P1) or the polyimide resin layer (P2) is simple and simple, but it may be composed of a plurality of layers. When it is composed of a plurality of layers, the adhesion depends on the polyimide layer of the surface layer of the polyimide layer, so that the improvement of the adhesion or the description of the surface treatment can be understood by mainly explaining the polyimide layer of the surface layer. That is, the first polyimine resin layer (P 1 ) is subjected to the step a, the second polyimide resin layer (P2) is subjected to the steps a and b, and then the step d3 is carried out. If necessary, the washing step and the cutting step may be performed before and after the steps. In the step d3, the treatment layer of the amine compound of the polyimine resin layer (P2) is superposed on the alkali treatment layer of the polyimide layer (P1) (-36-200825128), the alkali treatment layer and the amine compound The processing level is called the surface treatment level) and is reheated. The surface treatment layer can be double-sided or single-sided. When the surface is double-sided, it can laminate more than 3 layers. The thermocompression bonding method is not particularly limited, and the step d described in the above-described method for producing a metal clad laminate can be employed. The thermocompression bonding can be carried out under the temperature conditions for producing the hydrazine imidation, and the thermocompression can form the modified amine-containing compound layer of the second polyamidimide resin layer (P2) which completes steps a and b. Amination of the layer, and further enhance the adhesion. When both the polyimide resin layer (P1) and the polyimide resin layer (P2) have no metal foil, a layer of the polyimide layer (P1) and the layer of the polyimide layer (P2) can be obtained. Compound. When any one or more of the polyimine resin layer (?1) and the polyimine resin layer (P2) have a substrate such as a film, a polyimide layer having a substrate on one or both sides can be obtained ( P1) and a laminate of the polyimide resin layer (P2). The substrate can be peeled off if necessary. When the physical properties of the polyimide layer (P 1 ) and the polyimide resin layer (P2) are different, they may each have good physical properties. Further, when a layer of 1 or more of the polyimine resin layer (P 1 ) and the polyimine resin layer (P2) is a plurality of layers, a laminate of 3 or more layers can be formed. Further, the laminate for use in a printed wiring board can be obtained by one-side or double-sided thermocompression bonding of a laminate having a laminate of a polyimide layer on the surface. Any one of the polyimine resin layer (P1) and the polyimine resin layer (P2) has a metal foil on one side of the polyimide layer, and the other side does not have a metal foil. Single-sided metal laminates are available. At this time, the physical properties of the polyimine resin layer (P 1 ) and the polyimide resin layer (P2) are not -37-200825128 at the same time, and each has good physical properties. In addition, the metal foil is thermocompression bonded to the layer of the polyacrylamide resin of the single-sided metal laminate, and the double-sided metal laminate can be obtained. When the polyimine resin layer (P1) and the polyimide component resin layer (P2) have a metal foil on one side of the polyimide film, the double-sided metallized laminate can be obtained by thermocompression bonding. At this time, the physical properties of the polyimine resin layer (P 1 ) and the polyimine resin layer (P2) are not the same, and each of them has good physical properties. Next, a method of manufacturing the double-sided metal clad laminate of the present invention will be described in detail. The double-sided metal-clad laminate having a metal foil on one side of the polyimide layer is laminated, and a double-sided metal-clad laminate having a metal foil on both sides of the polyimide film can be obtained. A) Step a is performed on the surface side layer of the first single-sided metal-clad laminate of the polyimide layer (P 1 ). B) Performing steps a and b on the second single-sided metallized laminate. C) alkali treatment of the amine-based compound treatment layer of the second single-sided metal-clad laminate of the polyimine resin layer (P2) on the first single-sided metal-clad laminate (P1) Step 'reheat press-bonding step d3 ° wherein step a, step b and step d3 can be carried out as described above. Further, A) performing a step a on the first single-sided metal-clad laminate, B) performing steps a and b on the second single-sided metal-clad laminate, and C) performing the first single-sided metallized laminate and the second When step d3 of the single-side metal-clad laminate is hot-pressed, except that the prepared polyimide resin layer is a layer of a single-sided metallized layer of a metal foil of -38-200825128 metal foil on one side. Other steps, such as step A), step B) and step C), or step a, step b and step d3, which are described in the following method of the polyimine resin layer of the present invention, are carried out, such as iron foil, nickel Foil, enamel foil, aluminum foil, zinc foil, indium foil, silver foil, gold foil, tin foil, zirconium foil, stainless steel foil, giant foil, titanium foil, copper foil, lead foil, magnesium foil, manganese foil and alloy foil thereof. Among them, copper foil, copper alloy or stainless steel foil is preferred. The copper foil is used as a metal foil, for example, when used in a flexible substrate. The thickness of the copper foil used for the purpose is preferably from 3 to 50 // m, more preferably from 5 to 30 // m, but when used for a double-sided metal-clad laminate requiring a fine pitch, It is preferably a thin copper foil (including a copper alloy foil), and preferably 5 to 20/m at this time. The stainless steel foil is used as a metal foil, for example, when it is used for a suspension mounted on a hard disk drive (hereinafter referred to as an HDD suspension). The thickness of the stainless steel foil used for this purpose is preferably from 10 to 100 / / m, more preferably from 15 to 70 / / m, particularly preferably from 15 to 5 M. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to the examples. Further, the present invention is specifically noted, and various measurements and evaluations are as follows. [Measurement of the strength of the joint] -39- 200825128 The method of measuring the strength of the joint is to use an electronic tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) to measure a sample of a short booklet having a width of 10 mm at room temperature, 1 0 0°, 1 Omm. Tear strength is reassessed. Then, the criterion for judging the strength is that it is qualified when the strength is 〇.4 kN/m or more, and is not acceptable when it is less than 44 kN/m. Further, when the strength is 〇.4 kN/m or more and less than 66 kN/m, it is regarded as good, and when it is 0.6 kN/m or more, it is considered to be excellent. [Measurement of glass transition temperature] Using a viscoelastic analyzer (RSA-II manufactured by Ray-European Co., Ltd.), a 1 Hz vibration frequency was given to a sample having a width of 10 mm, and the temperature was raised from room temperature to 400 ° C at a rate of 10 ° C / minute. Then, the loss angle (Tan 5) is greatly sought. [Measurement coefficient of thermal expansion coefficient] Using a thermomechanical analyzer (manufactured by Seiko Co., Ltd.), the temperature was raised to 250 ° C, and the temperature was maintained for 10 minutes, and then cooled at a rate of 5 ° C /min. '24 (TC The average linear thermal expansion coefficient (CTE) to l〇〇°C. [Measurement of the thickness of the modified layer] The sample profile was observed by a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation) to confirm the thickness of the modified layer. The code used is the compound shown below. BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane 11 八 3:4,4,-(3,3,-dihydroxy) Diaminobiphenyl-40- 200825128 ΤΑΡΜ: Tris(4-aminophenyl)methanol TAEA: tris(2-aminoethyl)amine DAPE: 3,4,-diaminodiphenyl ether APES: 3 -Aminopropyl ethoxy decane ASD : 4,4, diaminobiphenyl sulfide DABA: 4,4 丨-diaminophenyl anilide EDA · · Ethyl diamine ETA : ethanolamine PSX-Me : The diamine-based oxazepine represented by the following formula (12) (wherein the average m number is from 1 to 20, and the average molecular weight is 740) PSX-Ph: the diamine-based oxime oxygen represented by the following formula (13) (in the formula, the total of j and η 2 to 20, and j and η are both 1 or more 'average sub-quantity is 1,3 20 ) 【化7】 ^N- ch3 ch3 H^-eCHg^peS iO^-S l-tCH2-^-NH2 (1 2) ch3 ch3 (4. ch3

(13) In order to measure the adhesion strength of the commercially available polyimide resin layer, the following three kinds of polyimide films having a thickness of 25.0 m were prepared. 1) Kapton EN: manufactured by DuPont 100mmxl00mmx25/zm, linear thermal expansion coefficient 16x1 0·6/Κ 2) Epika: 钟 xxx〇〇mmx25 -41 - 200825128

// m, line thermal expansion coefficient 1 6 x 1 0 ·6 / K 3) Yupili 25S: 1 〇〇mmxl〇〇mmx25 /zm manufactured by Ube Industries, Ltd., linear thermal expansion coefficient 12χ10·6/Κ [Embodiment] EXAMPLES Hereinafter, the present invention will be specifically described based on the examples, but the present invention is not limited to the examples. Reference Example 1 Stirring of 2,2,-dimethyl-4,4'-diaminobiphenyl 31.8 g and 1,3-bis (4-) in 425-dimethylacetamide 425 g at a temperature Aminophenoxy)benzene 4.9 g for 30 minutes. Next, 28.6 g of pyromellitic dianhydride and 9·6 g of biphenyl-3,4,3,4'-tetracarboxylic dianhydride were added, and the mixture was stirred at room temperature for 3 hours under nitrogen to obtain a solution viscosity of 28, 000 poise of polyamine resin solution. The polyamic acid resin solution was applied onto a stainless steel substrate, dried at 130 ° C for 5 minutes, and then heated to 3 60 ° C for 15 minutes to complete lamination of the stainless steel substrate after the imidization. Polyamide film 1. The polyimine film 1 was peeled off from a stainless steel substrate, and as a result, the film 1 had a coefficient of thermal expansion of 21 x 1 (Γ6/Κ, and the thickness of the polyimide layer was 25/m. Reference Example 2 Stirring at a temperature of N, N -4,V-diamino-2,2'-dimethylbiphenyl, 14.9 g of dimethylacetamide, and 4,4, diaminodiphenyl ether, 6.01 g -42 - 200825128, 30 minutes Next, 21.4 g of pyromellitic dianhydride was added, and after stirring at room temperature for 3 hours under nitrogen, a polyiminoimine resin solution having a solution viscosity of 1 2,000 poise was obtained. The polyimine resin solution was applied to a stainless steel base. After drying at 130 ° C for 5 minutes, the temperature was raised to 370 ° C in 15 minutes, and the polyimide film 2 laminated on the stainless steel substrate was obtained after the imidization. The stainless steel substrate was peeled off. The polyimide film 2 was obtained, and as a result, the film 2 had a coefficient of thermal expansion of 24 χ1 (Γ6/Κ, and the thickness of the polyimide layer was 25/m).

Reference Example 3 A solution of 2,2-bis[4-(4-aminophenoxy)phenyl]propane oxime.41 g (0.001 mol) was dissolved in 50 ml of diethylene glycol dimethyl ether, and diethyl 2 After dissolving a solution of 0.16 g (0.005 mol) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride in 50 ml of alcohol dimethyl ether, the mixture was stirred for 2 hours to obtain a polyimine-containing precursor. A solution of a resin (weight average molecular weight 4,300). Next, 900 ml of methanol was added to the solution, and 0.101 g (0.001 mol) of triethylamine was further added. After stirring for 30 minutes, a polyamidene precursor resin solution A (hereinafter also referred to as a solution of the precursor A) was obtained. The weight average molecular weight of the polyimine precursor resin contained in the polyimine precursor resin solution is based on HLC-8220GPC manufactured by Dongsuo Co., Ltd., and is connected to TSK-GEL SUPER manufactured by Dongsuo Co., Ltd. HM_M column measurement. The gauge line for obtaining the weight average molecular weight is made of polystyrene as a standard material. The developing solvent used was a solution in which lithium bromide and phosphoric acid were mixed in N,N-dimethylacetamide to a ratio of 0.03 mol/liter. -43- 200825128 Reference Example 4 5 g of 3-aminopropyltrimethoxydecane, 500 g of methanol and 2.5 g of water were mixed, and the mixture was stirred for 2 hours to adjust to a decane coupling agent solution. The stainless steel foil 1 (SU S3 04 HT A, manufactured by Nippon Steel Corporation, thickness 20 0 / m, surface roughness on the resin layer side: ten-point average roughness Rz0.8 # m) was immersed in In the decane coupling agent solution (liquid temperature of about 20 ° C), after 30 seconds, it was taken out to the atmosphere to drip excess liquid. Subsequently, it was blown dry with compressed air for about 15 minutes, and then heat-treated at 1 1 〇 °C for 30 minutes to obtain a stainless steel tank 2 treated with a decane coupling agent. Example 1 A polyimide film (Kapton EN) was immersed in a 5N potassium hydroxide aqueous solution at 50 ° C for 5 minutes, and then the impregnated polyimide film was sufficiently washed with ion-exchanged water, and then immersed in After 1 wt% aqueous hydrochloric acid solution (25 ° C) for 30 seconds, it was sufficiently washed with ion-exchanged water and then blown dry with compressed air to obtain a surface-treated polyimine film a 1 . The alkali-treated layer on one side of the surface-treated polyimide film a1 was 0.70 // m. The film was immersed in a methanol solution (25t:) of BAPP at a concentration of 0.0005 M for 30 seconds, and then blown dry with compressed air to obtain a surface-treated polyimine film bl. The film was heat-treated at 300 ° C for 3 minutes to obtain a surface-treated polyimine film c 1 . At this time, the modified yttrium imide layer on one side of the surface-treated polyimide film c 1 was 0.65 / m. Copper foil 1 (surface roughness: Rz = 0.8// m, thickness: 18// m) 挟-44- 200825128 After holding the film on both sides, use a high-performance high-temperature vacuum press at 370 ° C, 20 MPa, The hot press was carried out under the conditions of 1 minute to obtain a double-sided copper laminate p. The adhesive strength of the polyimide film to the copper foil was 1.0 kN/m. Example 2

The surface treated polyimine film was prepared in the same manner as in Example 1 except that it was immersed in a methanol solution of 0.001 M DAPE in methanol (25 ° C) for 5 minutes instead of immersing 0.0005 M of BAPP in the methanol solution of Example 1 for 30 seconds. A2, b2, C2 and double-sided copper clad laminate f2. The thickness of the modified yttrium imide layer on the surface of the surface treated polyimine film c2 was 〇.52//m. Example 3 A surface-treated polyimine film a3, b3 and c3 were prepared in the same manner as in Example 1 except that the methanol solution of Example 5 immersed in 0.0005 M of BAPP was changed to 30 minutes. After holding the polyimide film c3 with copper foil 2 (surface roughness: Rz = 1.5 / m, thickness: 18 / / m), it was subjected to hot pressing under the same conditions as in Example 1 to obtain a double-sided copper layer. Plywood f 3. Example 4 A surface treatment polypethane was prepared in the same manner as in Example 1 except that it was immersed in a methanol solution of 0.001 M HAB in methanol (25 ° C) for 5 minutes instead of immersing 0.0005 M of BAPP in the methanol solution of Example 1 for 30 seconds. Imine films a4, b4, c4 and double-sided copper laminate p4. -45- 200825128 Example 5 Surface preparation was carried out in the same manner as in Example 1 except that immersion was carried out in a methanol solution of 0.001 M TAPM in methanol (25 ° C) for immersing in a methanol solution of 0.0005 M of BAPP in Example 1 for 30 seconds. The polyimide film a5, b5, c5 and the double-sided copper laminate p5 were treated. Example 6. Surface treatment polymerization was carried out in the same manner as in Example 1 except that immersion in a methanol solution of 0.001 M TAEA in methanol (25 ° C) for 1 minute instead of 0.000 5 M BAPP in Example 1 was carried out for 30 seconds. Bismuth imide film a6, b6, c6 and double-sided copper clad laminate f6. Example 7 except that a polyimine film (Uppie 25S) was immersed in a 5N aqueous potassium hydroxide solution (50 ° C) for 30 minutes, and the substituted polyimine film was immersed in 5 N potassium hydroxide. The surface treated polyimine film a7, b7, c7 and the double-sided copper clad laminate f7 were prepared in the same manner as in Example 1 except that the aqueous solution (50 ° C) was used for 5 minutes. The alkali treatment layer thickness on one side of the surface-treated polyimide film a7 was 0.56. Example 8 A non-polyimine film was immersed in a 5 N potassium hydroxide aqueous solution, except that a polyimide film (film 1 of Reference Example 1) was immersed in a 5 N aqueous potassium hydroxide solution (50 ° C) for 5 minutes. 5 minutes in (50 ° C), other • 46- 200825128 The same as Example 1 was used to prepare a surface-treated polyimine film-coated copper laminate f8. The surface treated polyimine thin alkali treated layer had a thickness of 0.22. A8' b8, c8 and double film on one side

Example 9 except that a polyimide film (refer to Example 2%% of Example 2, thin crucible 2) was immersed in a 5 Torr aqueous potassium hydroxide solution (50 ° C) for 5 minutes ^ ^ CXT ^ ^ ^ , Substituting the polyimide film in a 5 N aqueous solution of potassium hydroxide (5 minutes in 5 Torr, other surface treatment of the surface treated polyimine limbs a9, b9, c9 and double-sided copper layer Plywood f9. The thickness of the alkali treated layer on one side of the surface treated polyacid W makeup thin a9 was 0.30.

Example 1 〇 In addition to the surface treatment of the polyimine plate Π0. 1 taking the film instead of copper, 1 other, the same as the embodiment 8 made of alum, bl〇, cio and double-sided metallized layer Example 1 1 except that the stainless steel foil 2 was used instead of the copper foil 1 for the surface treatment of the polyimide film All, bii, ply π 1. Others are the same as the embodiment 8 c 1 1 and the double-sided metallized layer embodiment 1 2 except that the stainless steel foil 1 is used to take the sina-like copper poise 1 , and the same as the embodiment 9 -47-200825128 as the surface treatment polyfluorene Imine film a 〖2, bl2, cl2 and double-sided metal-clad laminate Π 2. Example 13 A surface-treated polyimide film al3, bl3, cl3 and a double-sided metal clad laminate 3 were produced in the same manner as in Example 9 except that the copper foil 1 was replaced with a stainless steel foil 2. Comparative Example 1 After holding a polyimide film (Kapton EN) in a copper foil 1, it was subjected to hot pressurization at a temperature of 3 70 ° C, 20 MPa, and 1 minute using a high-performance high-temperature vacuum presser to obtain a double-sided surface. Copper laminated board. The strength of the polyimide film and the copper foil is 〇.lkN/m. Comparative Example 2 A polyimide film (Kapton EN) was immersed in a 5N potassium hydroxide aqueous solution (5 (TC) for 5 minutes, and then the impregnated polyimine film was sufficiently washed with ion-exchanged water, and then impregnated. After drying in an Iwt% aqueous hydrochloric acid solution (251) for 5 minutes, it was sufficiently washed with ion-exchanged water and then blown dry with compressed air to obtain a surface-treated polyimine film. After holding the film with copper foil 1, the same example The conditions of 1 were subjected to hot pressurization to obtain a double-sided copper-clad laminate. Comparative Example 3 A polyimide film (Kapton EN) was immersed in a 5N potassium hydroxide-48-200825128 aqueous solution (50 ° C) 5 After a minute, the impregnated polyimide film was sufficiently washed with ion-exchanged water and immersed in a 1 wt% aqueous hydrochloric acid solution (25 ° C) for 5 minutes. Thereafter, it was sufficiently washed with ion-exchanged water and then blown dry with compressed air. After the film was heat-treated at 300 ° C for 3 minutes, a polyimide film was surface-treated. After the film was held by copper foil 1, the film was thermally pressed under the same conditions as in Example 1 to obtain a double-sided copper-clad laminate. Comparative Example 4 A polyimide film (Kapton EN) was immersed in a BAPP of 0.0005M. After 5 minutes in a methanol solution (25 ° C), it was dried by compressed air and then heat treated at 300 ° C for 3 minutes to obtain a surface-treated polyimine film. After the polyimide film was held by copper foil 1, The film was heat-pressed under the same conditions as in Example 1 to obtain a double-sided copper-clad laminate. Comparative Example 5 A polyimide film (Kapton EN) was immersed in a methanol solution (25 ° C) of 0.0005 Torr. After 5 minutes, the surface treated polyimine film was blown dry with compressed air. After the polyimide film was held by copper foil i, it was subjected to hot pressing under the same conditions as in Example 1 to obtain a double-sided copper layer. The above conditions and results are shown in Table 1. The strength was then the adhesion strength between the polyimide film and the copper foil. Further, the heat treatment of Examples 1 to 13 and Comparative Examples 3 to 4 was 3 minutes at 300 °C. Comparative Examples 1 to 2 and 5 were not subjected to heat treatment. Further, the metal layer was formed by thermocompression. -49- 200825128 [Table 1] Polyimine film alkali treatment layer thickness (//m) Amino compound metal Fan Bond Strength (kN/m) Example 1 Kapton EN 0.70 BAPP Copper Foil 1 1.0 Example 2 Kapton EN 0.7 0 DAPE Copper foil 1 0.9 Example 3 Kapton EN 0.70 BAPP Copper foil 2 0.6 Example 4 Kapton EN 0.70 HAB Copper foil 1 0.7 Example 5 Kapton EN 0.70 TAPM Copper foil 1 0.6 Example 6 EN 0.70 TAEA Copper foil 1 0.8 Example 7 Yupili 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 11 Film 1 0.22 BAPP Stainless Steel Foil 2 1.2 Example 12 Film 2 0.30 BAPP Stainless Steel Foil 1 0.9 Example 13 Film 2 0.30 BAPP Stainless Steel Foil 2 1.0 Comparative Example 1 Kapton EN - Copper Foil 1 0.1 Comparison Example 2 Kapton EN 0.70 • Copper foil 1 0.1 Comparative Example 3 Kapton EN 0.70 • Copper foil 1 0.1 Comparative Example 4 Kapton EN BAPP Copper foil 1 0.1 Comparative Example 5 Kapton EN - BAPP Copper Box 1 0.1

Example 1 4 After immersing a polyimide film (Kapton®) in a 5N potassium hydroxide aqueous solution (50 ° C) for 5 minutes, the polyimine film was washed with ion-exchanged water and thoroughly washed with water. The mixture was further immersed in an aqueous solution of 1 wt% hydrochloric acid (25 ° C) for 5 minutes, and then sufficiently washed with ion-exchanged water and then blown with compressed air to obtain a surface-treated polyimine film a 4 . The film was immersed in a 0.5 wt% aqueous solution of APES for 30 seconds, and then blown dry with compressed air to obtain a surface-treated polyimine film bl4 of -50 - 200825128. The film was dried by heating at 1 1 ° C for 30 minutes, then held in a copper foil 1 and then hot-added using a high-performance high-temperature vacuum press at 370 ° C, 20 Μ P a for 1 minute. Pressed, double-sided copper laminate d 1 4. The adhesive strength of the polyimide film to the copper foil was 0.4 kN/m. Comparative Example 6 A polyimide film (Kapton EN) was immersed in a 0.5 wt% aqueous solution of APES for 30 seconds, and then blown dry with compressed air. 10t: Heating and drying for 30 minutes. In the same manner as in Example 1, a double-sided copper-clad laminate was produced from the polyimide film, but the treatment layer was not solidified. The above conditions and results are shown in Table 2. [Table 2] Polyimine film alkali treatment layer thickness (//m) Amine compound metal foil adhesion strength (kN/m) Example Η Kapton EN 0.70 APES copper foil 1 0.4 Comparative Example 6 Kapton EN - APES copper foil 1 cannot be followed by Example 1. 5 The polyimide film (Kapton EN) was immersed in a 5N potassium hydroxide aqueous solution (50 ° C) for 5 minutes, and then washed thoroughly with ion-exchanged water. The polyimine film after the staining is further immersed in a 1 wt% aqueous hydrochloric acid solution (25 ° C) for 5 minutes, and then fully washed with ion-exchanged water, and then blown dry with compressed air to obtain a surface-treated polyimine film. Al 5. The film was immersed in a polyfluorene imide resin solution A (25 ° C) of Example 3, 200825128, and air-dried to obtain a surface-treated polyimine film bl5. The film was treated for 3 minutes to obtain a surface-treated polyimine thin. After the film was held by the copper foil 1, high-performance ϊ was used. The heat-added laminate Π5 was heat-treated at 3 70 t:, 20 MPa, and 1 minute. The polyimide film and the copper foil were strongly adhered to Example 1 6 except that the polyimine film (Uppie 25 S) was immersed in an aqueous potassium oxide solution (50 ° C) for 30 minutes, replacing the thin stain in 5N. The surface-treated polyimine film al6, bl6, and C16 plywood 6 were prepared in an aqueous potassium hydroxide solution for 5 minutes. Example 1 7 In addition to using a polyimine film (Epicazone) in an aqueous solution of sodium oxide (50 ° C) for 1 〇 minutes, instead of using a thin stain in a 5N aqueous potassium hydroxide solution (50 ° C) Example 15 Preparation of a surface treated polyimide film al 7 double-sided copper laminate Π 7. The modified layer thickness on the surface treated polyimine thin was 0.73/m. Example 1 After 8 hours, the film was compressed by 3 〇〇 heating film c 1 5 〇 warm vacuum press machine to obtain a double-sided copper-plated degree of 1.lkN/m stained with 5N hydroquinone film. Example 1 5 and double-sided copper paste stained with 1N hydrogen: bismuth imide film immersion, outside the clock, other with the same, bl7, cl 7 and film al7 single side -52- 200825128 except for the polyimide film (reference The film n of Example 1 was immersed in SN & ammonia S ft f solution #5 〇C ) Φ 5 minutes Μ The substituted polyimine film was immersed in 5 Torr of potassium hydroxide solution (5 (TC ) for 5 minutes) Further, as in Example 15, a surface-treated polyimide film aU, bl8, el8 and a double-sided copper-clad laminate fl8 were produced. Example 1 9 except that a polyimide film (film 2 of Reference Example 2) was impregnated into 5N. The surface treated polyimine was prepared in the same manner as in Example 15 except that the polyimide film was immersed in a 5N potassium hydroxide aqueous solution (50 ° C) for 5 minutes in an aqueous ammonia solution (50 ° C). Films al9, bi9, el9 and double-sided copper clad laminates 9. Comparative Example 7 Immersion of polyimine film (Kapton EN) in polyimide precursor resin After 5 minutes in the liquid A (25 ° C), it was blown dry with compressed air, and then heat-treated at 300 ° C for 3 minutes to obtain a surface-treated polyimine film. After holding the film with copper foil 1, the same example The conditions of 15 were hot pressed to obtain a double-sided copper-clad laminate. Comparative Example 8 A polyimide film (Kapton EN) was immersed in a polyimide solution A (25 ° C). After 5 minutes, it was blown dry with compressed air to obtain a surface-treated polyimine film. After holding the film with copper foil 1, it was heat-pressed under the conditions of Example 15 of the actual-53-200825128 to obtain a double-sided copper paste. The laminate has a bonding strength of (KlkN/m) between the polyimide film and the copper foil. The results are shown in Table 3. The above conditions and results show that the bonding strength of the polyimide film and the copper foil is as shown in Table 3. The heat treatments of Examples 5 to 19 and Comparative Example 7 were 3 hours at 300 ° C, and the heat treatment was not carried out in Comparative Example 8. The formation of the metal layer was also thermocompression bonding. [Table 3] Polyimine Film alkali treatment layer thickness (//m) Amine compound metal foil adhesion strength (kN/m) Example 15 Kapton EN 0.70 Precursor A Copper Box 1 —\ _ 1.1 Example 16 Yupili 25S 0.56 Precursor A Copper foil 1 0.9 Example Π Epika NPI 0.73 Precursor A Copper foil 1 0.9 Example 18 Film 1 0.22 Precursor A Copper foil 1 1.2 Example 19 Film 2 0.30 Precursor A Copper foil 1 1.2 Comparative Example 7 Kapton EN - Precursor A Copper foil 1 0.2 Comparative Example 8 Kapton EN - Precursor A Copper box 1 0.1 Example 2 0 Polyimine The film (Kapton EN) was immersed in a 5N aqueous potassium hydroxide solution (50 ° C) for 5 minutes, and then the polyimide film was washed with ion-exchanged water and then immersed in a 1 wt% hydrochloric acid aqueous solution. The surface treatment of the polyimide film a20 was carried out for 5 minutes in (25 ° C) and then thoroughly washed with ion-exchanged water and then blown dry with compressed air. The film was immersed in a 0.5 wt% solution of PSX-Ph in methanol (25 ° C) for 30 seconds, and then blown dry with compressed air to obtain a surface-treated polyimine film b20. The film was dried by heating at 1 1 ° C for 30 minutes, then held in a copper foil 1 and heated at -37-200825128 using a high-performance high-temperature vacuum press at 37 (TC, 20 MPa, 1 minute). A double-sided copper-clad laminate d20 was obtained. The adhesive strength of the polyimide film and the copper foil was 〇.4 kN/m. Example 2 1

The same as Example 20 except that it was immersed in a methanol solution (25 ° C) of 0.5 wt% of PSX-Me for 30 seconds, instead of immersing in a methanol solution of 0.5 wt% of PX-Ph in Example 20 for 30 seconds. A surface-treated polyimide film a21, b21 and a double-sided copper-clad laminate d21 were produced. Comparative Example 9 A polyimide film (Kapton EN) was immersed in a 5 wt% solution of PSX-Ph in methanol (25 ° C) for 30 seconds, then blown dry with compressed air, and then 1 1 〇 ° C heat treatment for 30 minutes. In the same manner as in Example 1, a double-sided copper-clad laminate was produced from the polyimide film, but the treatment layer was not solidified. The above conditions and results are shown in Table 4. In all other cases, the heat treatment was 30 minutes at 1 10 °C. In addition, the formation method of the metal layer is all thermocompression bonding. [Table 4] Polyimine film alkali treatment layer thickness (/zm) Amino compound metal foil adhesion strength (kN/m) Example 20 Kapton EN 0.70 PSX-Ph Copper foil 1 0.4 Example 21 Kapton EN 0.70 PSX-Me Copper foil 1 0.4 Comparative Example 9 Kapton EN - PSX-Ph Copper foil 1 Cannot be followed by Example 22 -55- 200825128 5 Immersion of polyimide film (Kapton®) at 〇 °C After 5 minutes in a 5N aqueous potassium hydroxide solution, the impregnated polyimine film was sufficiently washed with ion-exchanged water and immersed in a 1 wt% aqueous hydrochloric acid solution (25 ° C) for 5 minutes. The water was sufficiently washed with water and then blown dry with compressed air to obtain a surface treated polyimine film a22. The surface-treated film was immersed in a 0.5 wt% aqueous solution of APES for 30 seconds, and then blown dry with compressed air to obtain a surface-treated polyimine film b22. After heat treatment at 110 ° C for 30 minutes, the film was placed in a RF magnetron sputtering apparatus (ANELVA; SPF-3 3 2HS) as a metal material film, and the pressure in the tank was reduced to 3 x 1 (T4Pa). Thereafter, argon gas was introduced to bring the degree of vacuum to 2 乂 10 Torr & and the plasma was used to generate plasma. The plasma was made of nickel: chromium metal [ratio 8:2, 99.9 wt%, hereinafter referred to as nickel chrome The heat-resistant metal (first sputtered layer 1a) was formed into a film of polyimide film at a film thickness of 30 nm. After forming a nickel-chromium heat-resistant metal, copper (99.99 wt%) was sputtered on the nickel in the same environment. The second sputtered layer lb is obtained on the chrome heat resistant metal to have a film thickness of 〇2/m, and the copper sputter film (second sputtered layer lb) is used as an electrode to form a thickness in the electrolytic plating bath. // m copper plating layer (plating layer 1 c ). The electrolytic plating bath used is copper sulfate bath (copper sulfate 1〇〇g/L, sulfuric acid 220 g/L, chlorine 40 mg/L, anode is phosphorus-containing copper) ), a plating film is formed at a current density of 2.0 A/dm 2 . After plating, it is sufficiently washed with distilled water and then dried to obtain a polyimide film/nickel-chromium heat-resistant metal 1 a/copper sputter layer lb/electrolytic copper layer 1 c The metal-clad laminate e22 was formed. The adhesion strength of the polyimide film to copper was 0.4 kN/m. -56- 200825128 Example 2 3

5 After immersing the polyimide film (film 2 of Reference Example 2) in a 5N potassium hydroxide aqueous solution at 30 ° C for 30 seconds, the impregnated polyimine film was sufficiently washed with ion-exchanged water, and then Immersed in 1 wt. /. The aqueous hydrochloric acid solution (25C) was washed with ion-exchanged water for 5 minutes, and then washed with compressed air to obtain a surface-treated polyimine film a23. The thickness of the alkali treatment layer on one side of the surface treated film a2 3 was 002 / / m. The film was immersed in a methanol solution (25 ° C) of 0.0001 M concentration for 5 minutes, and then blown dry with compressed air to obtain a surface-treated polyimine film b23. After heat-treating the film at 300 °C for 3 minutes, a polyimide film c23 was surface-treated. At this time, the modified yttrium imide layer on one side of the surface-treated polyimide film c23 is about 〇.〇2//m. The film was placed in a RF magnetron sputtering apparatus (ANELVA; SPF-332HS) by a metal material film formation method, and the pressure in the tank was reduced to 3×1 (T4Pa, and then argon gas was introduced to make the degree of vacuum ZxlO^Pa. The plasma is generated by the RF power source, and the plasma is made of nickel: chromium metal [ratio 8 : 2, 99.9 wt%, hereinafter referred to as nickel-chromium heat-resistant metal (first sputter layer 2a)]. Film formation on a polyimide film. After forming a nickel-chromium heat-resistant metal, copper (99·99 wt%) is sputtered on the nichrome layer in the same environment to have a film thickness of 〇·2 # m, The second sputter layer 2b is obtained. Next, the sputter film (second sputter layer 2b) is used as an electrode, and a copper plating layer having a thickness of 8 // m is formed in the electrolytic plating bath (electroplating layer 2 〇. Electrolysis used) The electroplating bath is a copper sulfate bath (copper sulfate 10〇g/L, sulfuric acid 220g/L, chlorine 40mg/L, anode is phosphorus-containing copper), and is formed into a plating film with a current density of 2.0A/dm2-57-200825128. After thoroughly washing with distilled water and drying, a metal-clad laminate g23 composed of a polyimide film/nickel-chromium heat-resistant metal 2a/copper sputter layer 2b/electrolytic copper layer 2c is obtained. Polyimide film and the adhesive strength of copper 0 · 9 kN / square Example 2 4 m

Surface treatment of the same treatment as in Example 23 was carried out except that it was immersed in a methanol solution (25 ° C) of 0.001 M HAB for 5 minutes instead of the methanol solution of BAPP immersed in 0.0001 M in Example 23 for 5 minutes. Imine films a24, b24, c24 and metal-clad laminate g24. Example 2 5 In place of 5 minutes of immersion in 0 000 1 M of BAPP in a methanol solution (25 ° C) immersed in ASD of 〇·〇〇1 5 for 5 minutes. Further, in the same manner as in Example 23, the surface-treated polyimide film a25, b25, C25 and the metal-clad laminate g25 were produced. Example 2 6 was prepared in the same manner as in Example 23 except that it was immersed in a methanol solution of DABA in a concentration of 0.001 M (25 ° C) for 5 minutes instead of immersing in a methanol solution of BAPP of 0.000 1 M in Example 23 for 5 minutes. The polyimide film a26, b26, c26 and the metal-clad laminate g26 were surface-treated. Comparative Example 1 0 -58- 200825128 A polyimide film (Kapton®) was prepared, which was placed in a RF magnetron sputtering apparatus as a metal material film forming method, and the inside of the tank was decompressed to 3xl (T4Pa). After that, argon gas is introduced to make the degree of vacuum Sxli^Pa, and then the plasma is generated by the RF power source. The plasma is made of nickel: chromium metal [ratio 8:2, 99.9 wt%, hereinafter referred to as nickel-chromium heat-resistant metal (The first sputter layer 6a) was formed into a polyimide film by a film thickness of 30 nm. After forming a nickel-chromium heat-resistant metal, copper (99.99 wt%) was sputtered on the nichrome alloy under the same environment. The film thickness was 0.2/m, and the second sputter layer 6b was obtained. Next, the sputter film (second sputter layer 6b) was used as an electrode to form a copper plating layer having a thickness of 8 // m in the electrolytic plating bath. Layer (electroplated layer 6c). The electrolytic plating bath used is a copper sulfate bath (copper sulfate 100g/L, sulfuric acid 220g/L, chlorine 40mg/L, anode is phosphorus-containing copper), and forms electricity at a current density of 2.0A/dm2. Coating. After plating, it is fully washed with distilled water and dried. It is composed of polyimide film/nickel-chromium heat-resistant metal 6a/copper sputter layer 6b/electrolytic copper layer 6c. Metal-bonded laminate. The adhesion strength of the polyimide film to the copper foil is less than lk·lkN/m. Comparative Example 1 1 The polyimide film (Kapton EN) was immersed in 5N at 5 °C. After 5 minutes in an aqueous potassium hydroxide solution, the impregnated polyimine film was sufficiently washed with ion-exchanged water, and further immersed in a 1 wt% aqueous hydrochloric acid solution (25 ° C) for 5 minutes, and then sufficiently washed with ion-exchanged water, and then washed again. Drying with compressed air. The polyimide film can be formed into a RF magnetron sputtering device as a metal material, and the pressure in the tank is reduced to 3x1 0_4Pa, and then argon gas is introduced to make the vacuum -59-200825128 degrees. After 2x1 (Γ1 Pa, the plasma is used to generate plasma. The plasma is made of nickel: chromium alloy layer [ratio 8: 2, 99.9 wt%, hereinafter referred to as nichrome layer (first sputter layer 7a) The film thickness of the film was formed on the polyimide film by a film thickness of 30 nm. After the nickel-chromium heat resistant alloy layer was formed, copper (99.99 wt%) was sputtered on the layer of the ferronickel layer in the same environment to make the film thickness 0.2 / m, the second sputter layer 7b is obtained. Next, the sputter film (second sputter layer 7b) is used as an electrode for electrolytic plating. A copper plating layer (plating layer 7c) having a thickness of 8 // m is formed. The electrolytic plating bath used is a copper sulfate bath (copper sulfate 100 g/L, sulfuric acid 220 g/L, chlorine 40 mg/L, anode is phosphorus-containing copper). A plating film is formed at a current density of 2.0 A/dm 2 . After plating, it is sufficiently washed with distilled water and dried to obtain a polyimide film/nickel-chromium layer 7a/copper sputter layer 7b/electrolytic copper layer 7c. Metal laminated board. The adhesive strength of the polyimide film to the copper foil is 0·lkN/m. Comparative Example 1 2 The acrylonitrile thin 0 (Kapton E N ) was immersed in 〇. 5 w t % of the APES aqueous solution for 30 seconds, and then blown dry with compressed air, and then! 1〇t: Heat treatment for 30 minutes. The polyimide film was placed in a RF magnetron sputtering apparatus as a metal material to form a metal thin film. The pressure in the tank placed in the sample was reduced to 3xl (T4Pa was introduced and argon gas was introduced to make the degree of vacuum 2x lO^Pa, and then the plasma was generated by RF power. The plasma was made of nickel: chrome alloy layer [ratio 8: 2 ' 99.9 wt%, hereinafter referred to as a nichrome layer (first sputter layer 8a), has a film thickness of 3 Onm formed on a polyimide-thin-60-200825128 film. After forming a nichrome layer In the same environment, copper (99.99 wt%) was sputtered on the nichrome layer to a film thickness of 0.2 μm to obtain a second sputter layer 8b. Next, the sputter film (second sputter layer 8b) was used. As an electrode, a copper plating layer (plating layer 8 c ) having a thickness of 8 // m is formed in the electrolytic plating bath. The electrolytic plating bath used is a copper sulfate bath (copper sulfate l〇〇g/L, sulfuric acid 220 g/L). , chlorine 40mg / L, anode is phosphorus-containing copper), forming a plating film with a current density of 2.0A / dm2. After plating, it is fully washed with distilled water and dried to obtain a polyimide film/nickel-chromium alloy layer 8a/copper. a metallized laminate of the sputtered layer 8b/electrolytic copper layer 8c. The bonding strength between the polyimide film and the copper foil is less than 1 kN/m. The results are shown in Table 5. Further, the heat treatment of Example 22 and Comparative Example 12 was carried out at 11 ° C for 30 minutes, the examples 23 to 26 were 300 for 3 minutes, and the comparative examples 1 to 1 were not subjected to heat treatment. The metal layer was formed by sputtering + electroplating. [Table 5] Thickness of alkali treated layer of polyimine film ((iv) Amine compound adhesion strength (kN/m) Example 22 Kapton EN 0.70 APES 0.4 Example 23 Film 2 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 Kapton EN • <0.1 Comparative Example 11 Kapton EN 0.70 0.1 Comparative Example 12 Kapton EN • APES <0.1 - 61 - 200825128 Example 27 The polyimine film (Kapton®) was immersed in a 5N potassium hydroxide aqueous solution at 5 ° C for 5 minutes, The ion-exchanged water was sufficiently washed with the impregnated polyimide film, and then immersed in a 1 wt% aqueous hydrochloric acid solution (25 ° C) for 5 minutes, and then fully washed with ion-exchanged water, and then dried by compression to obtain a surface treatment. Polyimine film a27. Part of the polyimide film a27 is used in the following example The modified layer of the polyimide film a27 was immersed in a methanol solution (25 ° C) of BAPP at a concentration of 0.0005 M for 30 seconds, and then blown dry with compressed air to form an amine compound on the surface of the polyimide film. Layer of polyimide film b27. After the surface treatment surface of the polyimine film a27 and the polyimide film b27 was superposed, it was subjected to hot pressurization at 400 ° C, 20 MPa, and 1 minute using a high-performance high-temperature vacuum press. As a result, the bonding strength between the two polyimide films a2 7 and b27 was 1.2 kN/m. Example 2 8 In addition to the modified layer of the polyimide film a2 7 immersed in a methanol solution (25 ° C) of 〇.〇〇1 μ of D 5 for 5 minutes, the immersion in Example 27 was carried out in 〇·〇 The polyimine film b28 at the surface of the polyimide film formed on the surface of the polyimide film was mixed with the mixture obtained in Example 27, and the polycondensation of the polyimide film obtained in Example 27 was carried out. After the surface treatment surface of the quinone imine film a27 and the polyimide film b28, it was subjected to hot pressurization in the same manner as in Example 27. Knot -62- 200825128 The bonding strength between the polyimine films a27 and b28 is l.〇kN/m. Example 29 A polyimide film was prepared in the same manner as in Example 2 except that the modified layer of the polyimine film a27 obtained in Example 27 was immersed in a 0.0005 M solution of BAPP in methanol from 30 seconds to 5 minutes. The surface forms a polyimide film b29 of an amine compound treatment layer. After the surface of the obtained polyimine film a27 and the polyimide film b2 9 was superposed, the pressure was applied in the same manner as in Example 27. As a result, the adhesion strength between the polyimide films a27 and b29 was 〇.9 kN/m. Example 3 0 After immersing a polyimide film (Epika NPI) in a 1N aqueous sodium hydroxide solution (50 ° C) for 1 minute, the impregnated polyimide film was sufficiently washed with ion-exchanged water. The mixture was further immersed in a 1 wt% aqueous hydrochloric acid solution (25 ° C) for 5 minutes, and then sufficiently washed with ion-exchanged water, and then blown dry with compressed air to obtain a surface-treated polyimine film a30. A part of the polyimide film a3 was used in the following examples. The modified layer of the polyimide film a30 was immersed in a methanol solution (25 ° C) of BAPP at a concentration of 0.0005 M for 20 seconds, and then blown dry with compressed air to form an amine-based compound treatment layer on the surface of the polyimide film. Polyimine film b30. After the surface treatment surface of the polyimine film a3 and the polyimide film b30 was superposed, hot pressing was carried out in the same manner as in Example 27. As a result, the adhesion strength between the polyimide film a30-63-200825128 and b30 was i.lkN/m. Example 3 1 In addition to immersing in a 5N potassium hydroxide aqueous solution (5 (TC) for 30 minutes with a polyimide film (Uppie 25S), the substituted polyimine film was stained in a 5N potassium hydroxide aqueous solution 5 Minutes, other polyimine film a3 1 which was formed into a modified layer on the surface of the polyimide film by the same example, and a polyimide film was formed on the thin surface of the polyimide film using the polyimine film a31. The polyimine film b3 1 of the layer was superposed on the surface of the polyimine film a31 and the polyimide film b31, and then subjected to thermal pressurization in the same manner as in Example 27. As a result, between the polyimide film a and b31 The strength was then I.lkN/m. Example 3 2 After the surface treatment surface of the polyimine film a27 obtained in Example 27 and the polyimide film b30 obtained in Example 30 was superposed, the heat treatment was carried out in the same manner as in Example 27. As a result, the adhesion between the polyimide film a27 and b30 was 1.0 kN/m. Example 3 3 5 0 ° C, the polyimide film (film 1 of Reference Example 1) was impregnated with 5 N potassium hydroxide. After 5 minutes in an aqueous solution, the impregnated polyimide film was sufficiently washed with ion-exchanged water and immersed in 1 wt% salt. 5 minutes in aqueous solution at 5 ° C), then fully washed with ion-exchanged water, and then immersed in hydrogen peroxide at 27 〇 film. 31 cases are stronger than water (shrink-64 - 200825128 air-dried, surface-treated polypethane Imine film a3 3. A part of the polyimide film a33 is used in the following example: The modified layer of the polyimide film a3 3 is immersed in a methanol solution (20 ° C) of EDA having a concentration adjusted to 0.00 1 M 5 After a minute, it is blown dry with compressed air to obtain a polyimide film b33 on the surface of the polyimide film layer to form an amine compound treatment layer. The surface of the polyimide film a3 3 and the polyimide film b33 are superposed. Thereafter, thermal compression was carried out in the same manner as in Example 27. As a result, the bonding strength between the polyimide film a3 3 and b33 was 0.6 kN/m. Example 3 4 Except that the polyethylene film was impregnated with 0.001 Å of ETA. The methanol solution (20 ° C) was substituted for 5 minutes in a methanol solution (20 ° C) immersed in o.ooiM EDA, and the same as in Example 3 3 to form an amine on the surface of the polyimide resin layer. The polyamidimide film b34 of the base compound-treated layer is superposed on the polyimide film obtained in Example 33. After a33 and the surface treated surface of the polyimide film b34, it was subjected to hot pressurization in the same manner as in Example 27. As a result, the bonding strength between the polyimide film a33 and b34 was 〇.4 kN/m. Example 3 5 50 °C The polyimine film (film 2 of Reference Example 2) was immersed in a 5N potassium hydroxide aqueous solution for 5 minutes, and then the impregnated polyimine film was sufficiently washed with ion-exchanged water, and then immersed in a 1 wt% hydrochloric acid aqueous solution. Medium 5-65-200825128 minutes, then fully washed with ion-exchanged water, and then blown dry with compressed air to obtain a surface treated polyimine film a3 5 . The surface-treated side of the polyimine film a35 and the polyimide film b33 obtained in Example 33 was subjected to thermal pressurization in the same manner as in Example 27. As a result, the bonding strength between the polyimide films a35 and b33 was 〇.7 kN/m. Example 3 6

The surface of the polyimine film a3 5 obtained in Example 35 and the surface treated surface of the polyimide film b34 obtained in Example 34 were subjected to hot pressurization in the same manner as in Example 27. As a result, the adhesion strength between the polyimide film a3 5 and b33 was 0.4 kN/m. Comparative Example 1 3 Two polyimide films (Kapton EN) were prepared, and after superposition, they were subjected to hot pressurization in the same manner as in Example 27. As a result, each of the polyimide films was easily peeled off. Comparative Example 14 Two polyimide films (Epika NPI) were prepared, and after superposition, they were subjected to hot pressurization in the same manner as in Example 27. As a result, each of the polyimide films was easily peeled off. Comparative Example 15 After the polyimine film (Kapton EN) and the polyimide film (Epika®) were superposed, thermal compression was carried out in the same manner as in Example 27. As a result, each of the polyimide films was easily peeled off. -66 - 200825128 Comparative Example 1 6 Two polyimide films (film i of Reference Example 1) were prepared, and after each polyimine resin layer was superposed, hot pressing was carried out in the same manner as in Example 27. Results Each polyimine film was easily peeled off. Comparative Example 1 7 Two polyimide film a2 7 obtained in Example 27 were prepared, and the surface treatment layer of each polyimide film was superposed and then subjected to hot pressing in the same manner as in Example 27. As a result, the adhesion strength between the polyimide films was 〇.lkN/m. Comparative Example 18 Two polyethyleneimine films a33 obtained in Example 33 were prepared, and the surface-treated layers of the respective polyimide pigments were superposed, and then hot-pressed in the same manner as in Example 27. As a result, the bonding strength between the layers of the polyimide resin did not reach 〇 · j kN/m. Comparative Example 1 9 Preparation Example 3 3 The obtained polyimide film 3, and the obtained polyimide film a3 5 obtained in Example 35, after superposing the surface modification layer of each polyimide resin layer Example 2 7 was subjected to hot pressurization. As a result, the adhesion strength between the layers of the polyimide film was less than lk.lkN/m. The above conditions and results are shown in Tables 6 and 7. The subsequent method of the two polyimine resin layers is thermocompression bonding. -67- 200825128 [Table 6]

Polyimine film thickness (//m) Amine compound strength (kN/m) Example 27 Kapton EN 0.70 Meaning 1.2 Kapton EN 0.70 BAPP Example 28 Kapton EN 0.70 • 1.0 Kapton EN 0.70 DAPE Example 29 Kapton EN 0.70 0.9 Kapton EN 0.70 BAPP Example 30 Epica NPI 0.73 • 1.1 Epica NPI 0.73 BAPP Example 31 Yupili 25S 0.56 雠1·1 Yupili 25S 0.56 BAPP Example 32 Kapton EN 0.70 - 1.0 Epika MPI 0.73 BAPP Example 33 Film 1 0.22 . 0.6 Film 1 0.22 EDA Example 34 Film 1 0.22 - 0.4 Film 1 0.22 ETA Example 35 Film 2 0.30 0.7 Film 1 0.22 EDA Example 36 Film 2 0.30 - 0.4 Film 1 0.22 ETA Film 2 0.30 - -68- 200825128 [Table 7] Polyimine film alkali treatment layer thickness (//m) Amine compound adhesion strength (kN/m ) Comparative Example 13 Kapton EN 0.0 Kapton EN - • Comparative Example 14 Epica NPI - Detected 0.0 Epica NPI _ Comparative Example 15 Kapton EN - - 0.0 Epika EN - Sun Comparative Example 16 Film 1 - 雠· 0.0 Thin Film 1 - Comparative Example 17 Kapton EN 0.70 0.1 Kapton EN 0.70 - Comparative Example 18 Film 1 0.22 • <0.1 Film 1 0.22 • Comparative Example 19 Film 1 0.22 • <0.1 Film 2 0.30 -

Industrial Applicability The present invention can easily improve the adhesion of the polyimide layer by a surface treatment. Further, even if it is suitable for forming a low-thickness copper foil having a fine pitch, the adhesion can be improved, so that the copper-clad laminate used for the high-density printed wiring board can be manufactured at low cost. In addition, it can be used for the use of HDD suspensions, so the industrial price is high. -69-

Claims (1)

200825128 X. Patent Application No. 1 · A method for forming a modified layer on the surface of a polyimide resin layer, characterized in that a) a layer on the surface side of the polyimide resin layer is treated with an alkaline aqueous solution to form The step of treating the treatment layer, and b) the step of immersing the alkali treatment layer with a polar solvent solution containing an amine compound to form an amine group-containing compound layer. 2. The method of forming a modified layer according to claim 1, wherein a) a step of treating a layer on the surface side of the polyimide film layer with an aqueous alkaline solution to form an inspection layer, and b) the test The treatment layer is impregnated with a polar solvent solution containing an amine compound and then dried to form an amine group-containing compound layer, and c) is subjected to oxime imidization of the amine group-containing compound layer to form a modified yttrium imide layer. step. 3. The method of forming a modified layer according to claim 1 or 2, wherein the alkali-treated layer has a thickness in the range of 0.005 to 3.0/m. 4. The method of forming a modified layer according to claim 1 or 2, wherein the amine compound is an aromatic amine having a grade 1 or 2 amine group. 5. The method of forming a modified layer according to claim 1 or 2, wherein the amine compound is an aliphatic amine having a functional group of at least 3 primary amine groups. 6. The method of forming a modified layer according to claim 1 or 2, wherein the amine compound is a polyimine precursor resin. 7. The method of forming a reforming layer according to claim 1 or 2 wherein the polyimine resin layer is a layer of a polyimide resin layer forming a surface layer of the laminate. -70-200825128 8 - The method of forming a reforming layer according to claim 1 or 2 wherein the polyimine resin layer is a polyimide film forming a surface layer of a polyimide film. 9. A method of manufacturing a metal-clad laminate, comprising: a step of forming a modified layer on a surface of a polyimide resin layer, and II) a step of forming a metal layer on a surface of the modified layer In the method of manufacturing a metal-clad laminate, a) treating the layer on the surface side of the polyimide layer with an aqueous alkaline solution to form an alkali treatment layer, and b) impregnating the alkali treatment layer with a solution of a polar solvent containing an amine compound to form an amine-containing compound layer The steps. The manufacturing method of the metal-clad laminate according to claim 9, wherein the step I) except the step of treating the layer on the surface side of the polyimide resin layer with an aqueous alkaline solution to form an alkali-treated layer, And b) the alkali treatment layer is impregnated with a polar solvent solution containing an amine compound and then dried to form an amine group-containing compound layer, and c) is subjected to oxime imidization of the amine group-containing compound layer to form a modified ruthenium The step of imidizing the layer. 1 1 The method for producing a metallized laminate according to claim 9 or 2, wherein the step II) is constituted by the step of re-compression bonding the heavy alloy on the surface of the modified layer. 1 2 . The method of manufacturing a metallized laminate of the metallized laminate of the ninth or the ninth aspect of the invention is in the form of a step of forming a gold thin film layer on the surface of the modified layer. . The method of manufacturing a metallized laminate according to any one of claims 9 to 12, wherein the thickness of the treatment layer is 〇.〇〇5 to 3.0 // m. The method for producing a metal-clad laminate according to any one of claims 9 to 12, wherein the amine-based compound is a perfantamine having a grade 1 or 2 fee group. The method for producing a metallized laminate according to any one of claims 9 to 12, wherein the amine compound is an aliphatic amine having a functional group of at least three grade 1 Fee groups. The method of producing a metallized laminate according to any one of claims 9 to 12 wherein the amine compound is a polyimide precursor resin. The method for producing a metallized laminate according to any one of claims 9 to 12, wherein the amine compound is a decane coupling agent having an amine group. 1 8 · A method for producing a metallized laminate according to item 7 of the patent application 'The decane coupling agent having an amine group is 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxy Baseline, n-2-(aminoethyl)-3-aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyl-methoxysilane At least 1 selected from the group consisting of ruthenium, 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine and N-phenyl-3-aminopropyltrimethoxydecane Kind. The method for producing a metallized laminate according to any one of claims 9 to 12, wherein the amine compound is a diamine siloxane. 20. The method for producing a metal-clad laminate according to the ninth application, wherein the diamine-based oxime is a diamine-based oxirane oligomer represented by the following general formula (1). 1] R5 H2N—Ar2H-?i-Ο Cut i-Ar7 — NH2 (1) R4 r6 where Ar2 and Ar7 are divalent hydrocarbon groups, and R3 to R6 are carbon number 1 to 6 carbon atoms, m is 1 to 20 number. 2 1 . The method for producing a metal clad laminate according to claim 1 wherein the metal foil is a copper foil, a copper alloy foil or a stainless steel foil. An adhesive method of a polyimine resin layer, characterized in that a layer of a polyimine resin layer of a first polyimide layer (P1) and a second layer of a polyimide resin layer (P2) is laminated In the method of the polyimine resin layer, A) is provided for the first polyimine resin layer (P 1 ) a) treating the surface side layer of the polyimide resin layer with an alkaline aqueous solution to form an alkali treatment a step of layer, B) performing a second polyimide layer (P2), a) treating a layer on the surface side of the polyimide layer with an aqueous alkaline solution to form an alkali treatment layer, and b) treating the alkali a step of immersing a polar solvent solution containing an amine compound in a layer to form an amine group-containing compound layer, and C) superposing an amine group-containing compound layer of the second polyimide layer (P2) on the surface of the layer-73-200825128 A step of reheating the alkali treatment layer of the polyimide layer (pi). 23. The method according to claim 22, wherein at least one of the first polyimine resin layer (P1) and the second polyimide layer (P2) is poly A polyimide-based resin layer of a single-sided metal-clad laminate having a metal foil on one side of the bismuth imide resin layer. A method for producing a double-sided metal-clad laminate, characterized in that a polyimine resin layer obtained by laminating a single-sided metal-clad laminate having a metal foil on one side of two polyimide-imide resin layers is superposed In the method for manufacturing a double-sided metal-clad laminate having a metal foil on both sides, A) is provided for the first single-sided metallized laminate, and a) the polyimide resin layer (P 1 ) is treated with an alkaline aqueous solution. a layer on the surface side to form an alkali treatment layer, B) a second single-sided metallization laminate, a) treating a layer on the surface side of the polyimide layer (P2) with an aqueous alkaline solution to form a base a step of treating the layer, and b) the step of impregnating the alkali-treated layer with a polar solvent solution containing the amine-based compound to form an amine-containing compound layer, and C) the second single-sided metal-clad laminate of the polyimide resin The amine-based compound treatment layer of the layer (P2) is superposed on the alkali-treated layer of the first single-sided metal-clad laminate of the polyimide layer (P1), and then thermocompression-bonded. -74 - 200825128 VII. Designated representative map: (1) The representative representative of the case is: No (2), the representative symbol of the representative figure is a simple description. · No. 8. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: Chemical 1 [Chemical 1] R3 R5 H2N_Ar2-f-Si~〇-i^"Si-Ar7-ΝΗ〗 (工) Heart R6