TW201032680A - Multilayer fluorine resin film and printed wiring board - Google Patents

Abstract

An object of the present invention is to provide a laminate with high thermal dimension stability which uses a polyimide film as substrate. Provided are a multilayer fluorine resin film formed by laminating fluorine resin layer/polyimide resin layer/fluorine resin layer in sequence; a multilayer fluorine resin film with a linear expansion coefficient of 10 ppm/DEG C to 30 ppm/DEG C; a copper-clad multilayer fluorine resin film which laminates a copper foil onto at least one surface of the multilayer fluorine resin film; and a printed wiring board formed by removing part of the copper foil from the copper-clad multilayer fluorine resin film.

Description

[Technical Field] The present invention relates to a multilayer fluororesin film used for a flexible printed wiring board or the like which is used for miniaturization and weight reduction of electronic equipment and parts, and copper of a metal foil. A copper-clad multilayer fluororesin film in which a foil is laminated, a printed wiring board in which a part of the copper foil is removed to form a circuit pattern, and a multilayer printed wiring board in which these layers are laminated. ^ [Prior Art] In general, in the high-frequency area signal transmission, the transmission speed is required to be improved and the noise is reduced. In the flexible printed wiring board, the substrate material, wiring technology, and circuit form are also discussed. . In the case of the electrically insulating layer of the flexible printed wiring board comprising the laminate of the conductor layer and the electrical insulator layer, a polyimide resin having excellent heat resistance is used. The following three methods can be applied to the production method of the laminate comprising the polyimide layer and the conductor layer. © (1) a method of forming a polyimide film with a copper foil through an adhesive layer, and (2) a method of forming a metal layer on a polyimide film by vapor deposition and/or metal plating, (3) A method in which a polyimide resin precursor is applied to a metal foil, and then a polyimide resin is formed from the precursor by heat treatment or the like to form a polyimide film on the metal foil (refer to a patent) Document 1). However, in such a method, the adhesion between the polyimide layer and the conductor layer is insufficient, and the malfunction of the circuit may be caused. In addition, since the transmission loss is large when the printed wiring board is formed in 201032680, it is not suitable as a high-frequency component. It has been disclosed that the adhesion between the conductor layer and the electrical insulator layer is improved by forming an unevenness of about 3/im on the surface of the conductor layer on the side contacting the electrical insulator layer (see Patent Document 2). However, in this method, due to the surface effect in the high-frequency region, the signal arrival time varies on the surface having the unevenness and the non-roughened surface, so it is necessary to reduce the unevenness as much as possible. A polyimine which lowers the dielectric constant by dispersing inorganic fine particles such as cerium oxide in polyimine is disclosed. However, in such a method, since it is difficult to microdisperse the inorganic fine particles to the polyimide at the nanometer level, the surface smoothness or transparency of the polyimide film is impaired. When the surface smoothness is impaired, when the polyimide film is used for the substrate of the printed substrate, the adhesion to the copper foil constituting the metal layer is deteriorated, and the quality of the printed substrate is lowered. φ has disclosed a specific structure for lowering the dielectric constant by using an aromatic diamine compound in which two diphenyl ether structures having a tertiary butyl group having a small partial polarization in a side chain are bonded to each other by a linking group. Polyimine (see Patent Document 3). However, in such a method, since it is necessary to use a specific structure of an aromatic diamine compound, there is a lack of versatility applicable to polyimine having various structures. After the aromatic dianhydride and the aromatic diamine are reacted to obtain a polylysine in a solution state, the polyamic acid is rapidly heated to volatilize the residual solvent and the condensed water produced in 201032680, thereby obtaining a uniform emission. A foamed polyimine foam (see Patent Document 4). However, in such a method, it is difficult to form the polyamic acid into a film shape, and it is a foam, which may impair the surface smoothness or transparency, and has a problem that the mechanical strength is lowered due to the presence of air bubbles. In general, it is known that when a fluorine atom is introduced into a molecule of a polyimide, the dielectric constant can be lowered. For example, a polyimine-metal composite film having a metal layer formed on the surface of a fluorinated polyimide film has been disclosed (see Patent Document 5). In addition, a multilayer wiring board in which at least one type selected from the group consisting of a substrate, an adhesive layer, and a surface protective layer is used is disclosed (refer to Patent Document 6). In the general method, as the content of fluorine atoms in the molecule introduced into the polyimine is increased, the tensile modulus and the tensile strain at break of the film composed of the polyimide are lowered, and the mechanical strength is lowered. Reduce the problem. A laminate in which a fluororesin having a minimum dielectric constant in a plastic is laminated with a metal plate has been disclosed (see Patent Document 7). However, in such a method, when the fluororesin film is perforated at a high speed, it is rubbed off from the metal plate with the blade edge, resulting in a problem of a decrease in yield. Further, the tensile strength and elongation of the mechanical properties of the fluororesin film are the same as those of the polyolefin at room temperature and the coefficient of linear expansion is 60 ppm/° C. to 160 ppm/° C. for example, when the coefficient of linear expansion is 16 ppm/ When the copper foil of °C is laminated, the deviation of the linear expansion coefficient of each other is large, there is a concern of peeling during use, or there is a concern that warpage may occur. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open No. Hei. No. JP-A-2002-342541 (Patent Document 5) Japanese Patent Laid-Open No. Hei. No. 2001-308542 (Patent Document 7) SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The object of the present invention is to use a polyimide resin which is suitable for use as a substrate for an electronic component and which has less deformation and heat resistance as a core material. 'And fluororesin is disposed on the surface, thereby providing a low linear expansion coefficient (as a multilayer fluororesin film having a linear expansion coefficient equivalent to that of the copper foil) which can simultaneously achieve the characteristics of the polyimide resin (higher) Mechanical properties, multi-layer fluororesin film with low dielectric constant, low water absorption (lower absorbing rate of polyimine), copper-clad multilayer fluororesin film, printed wiring board, and multi-layer printing Wire board. The present inventors have intensively studied and found that a fluororesin layer laminated on a double-sided fluororesin film of a polyimide film is used for a copper clad laminate and a printed wiring board. In the case of FPC, TAB tape, COF tape film, etc., it is possible to obtain a product which does not cause peeling or the like at high temperature and high humidity, and which has excellent electrical characteristics, and thus completed the present invention. 201032680 That is, the first invention of the present application is constituted by the following constitution. 1. A multilayer fluororesin film which is a multilayer fluororesin film composed of (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer, which is sequentially laminated, wherein the multilayer fluororesin film The linear expansion coefficient is 10 ppm/° C. to 30 ppm/° C., and the thickness ratio of the (A) layer is 60% to 90% of the entire (A) layer/multilayer fluororesin film, and the (A) layer is composed of four. Any of fluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene hexafluoropropylene copolymer (FEP), tetrafluoroethylene hexafluoropropylene·perfluoroalkyl vinyl ether copolymer (EPE) The resulting thermoplastic fluororesin layer. 2. A multilayer fluororesin film according to 1. wherein the (A) layer is a functional group-containing thermoplastic fluororesin layer. 3. A multilayer fluororesin film according to 1. or 2. wherein the layer (B) is a polyimine layer having a polybenzonitrile benzoxazole component, and the coefficient of linear expansion is -l〇PPm/°C. 10ppm"C. 4. The multilayer fluororesin film of any one of 1. to 3. wherein the (A) layer has a thickness of 1.0/zm to 50/m and the (B) layer has a thickness of 5. The multilayer fluororesin film according to any one of the above, wherein (A) layer has a storage elastic modulus at room temperature: E' (A) and (B) layer storage elastic modulus at room temperature: E' (B) ratio {E, (A) / E' (B)} is 2.0% to 20% ° 6. A copper-clad multilayer fluororesin film, which is in any one of 1. to 5_ A copper foil is laminated on at least one side of the multilayer fluororesin film. 7. A printed wiring board comprising a part of a copper-clad multilayer fluororesin film t of 6. removed to form a circuit pattern. A multilayer printed wiring board comprising a multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board as disclosed in any one of 1 to 7. Further, the second invention of the present application is constituted by the following constitution. A multilayer fluororesin film which is formed by laminating a (C) copper layer on a (B) surface of a copper clad laminate (CCL) of a (B) polyimine resin layer without an adhesive. A) a fluororesin film formed of a fluororesin layer in which the linear expansion coefficient of the (A) layer (B) laminate in the multilayer fluororesin film is 10 〇 ppm / ❹ ° C to 30 ppm / ° C, ( A) The thickness ratio of the layer is 60% to 90% of {(A) layer / (A) layer (B) layered layer}, and the layer (A) is composed of tetrafluoroethylene perfluoroalkyl vinyl ether copolymer A thermoplastic fluororesin layer formed of (PFA), a tetrafluoroethylene-hexafluoropropylene copolymer (FEP), or a tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE). 10. The multilayer fluororesin film according to item 9, wherein the (A) layer is a functional group-containing thermoplastic fluororesin layer. Φ 11. A multilayer fluororesin film according to 9. or 10. wherein the (B) layer is a polyimine layer having a polyimine benzoxazole component and has a coefficient of linear expansion of -10 〇 PPm / . . The multilayer fluororesin film according to any one of the items 9 to 11. wherein the (A) layer has a thickness of 1.0/zm to 50 μm, and the (B) layer has a thickness of 1. Mm~38ym. 13. The multilayer fluororesin film according to any one of items 9 to 12, wherein (A) layer has a storage elastic modulus at room temperature: storage elasticity of E' (A) and (B) layers at room temperature Modulus: E, (B) ratio {E, (A) / E' (B)} is 2.0% ~ 20%. A copper-clad-layered fluororesin film which is laminated with a copper foil on the (A) side of the multilayer fluororesin film according to any one of items 9. to 13. A printed wiring board comprising a plurality of layers of a fluororesin film according to any one of 9. to 14. and a copper layer of a copper-clad multilayer fluororesin film removed to form a circuit pattern. A multilayer printed wiring board comprising a multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board according to any one of ninth to fifteenth.效果 Effect of the Invention The multilayer fluororesin film composed of the sequential laminated layer (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer of the first invention of the present application can be simultaneously achieved. Polyetherimide resin has a low linear expansion coefficient (as a multilayer fluororesin film, which has the same linear expansion coefficient as copper foil), high mechanical properties, low dielectric constant and low water absorption with fluororesin Multilayer film with a rate (reducing the high water absorption of polyimine).第二 In the second invention of the present application, the (C) copper layer is formed on the (B) side of the copper clad laminate (CCL) of the (B) polyimine resin layer without an adhesive, and further laminated ( A) a fluororesin film formed of a fluororesin layer, wherein the (A) layer (B) layered layer of the multilayer fluororesin film has a linear expansion coefficient of 10 ppm/° C. to 30 ppm/° C. The film is a low linear expansion coefficient (as a multilayer fluororesin film which has the same linear expansion coefficient as that of the copper foil), high mechanical properties, and low characteristics of the fluororesin, which can simultaneously achieve the characteristics of the polyimide resin. A multilayer film having a dielectric constant and a low water absorption (reducing the high water absorption of polyimine). 201032680 The multilayer fluororesin film of the present invention has good adhesion to copper foil, has a small deviation from the linear expansion coefficient of copper foil of 16 ppm/°C, and has low water absorption rate, even in an environment of high temperature and high humidity. There is almost no warpage or distortion, and as a result, the quality of the printed wiring board and the like, and the yield at the time of production can be improved. The copper-clad multilayer fluororesin film, the printed wiring board, and the multilayer printed wiring board using the multilayer fluororesin film of the present invention can be used as an electronic component exposed to high temperature, and the substrate can be prevented from being warped at the time of manufacture. The manufacture of high-quality electronic parts that do not cause the peeling of the multilayer fluororesin film and the copper foil, and the improvement of the yield, are highly meaningful in the industry. [Embodiment] Mode for Carrying Out the Invention The present invention will be described in detail below. The (A) fluororesin layer used in the present invention is a fluororesin film obtained by a method of forming a film by solution casting a fluororesin melt, or e is applied to the fluororesin melt to a polyfluorene. The layer formed of the imide resin layer (film) is preferably in the form of a fluororesin film in view of handleability, productivity, and the like. The fluororesin can be appropriately selected from the conventionally known thermoplastic fluororesins used in general molding. Examples of the thermoplastic fluororesin include a polymer or copolymer of an unsaturated fluorinated hydrocarbon, an unsaturated fluorochlorinated hydrocarbon, an ether group-containing unsaturated hydrocarbon, or the like, or copolymerization of such an unsaturated fluorinated hydrocarbon with ethylene. Things and so on. Specific examples are polymers or copolymers selected from the group consisting of -10 201032680 tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride and vinyl fluoride, or A copolymer of a monomer and ethylene, and the like. More specific examples of the thermoplastic fluororesin include tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene, hexafluoropropylene copolymer (FEP), tetrafluoroethylene hexafluoropropylene perfluoroalkane. Ethylene vinyl ether copolymer (EPE), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene/ethylene copolymer (ECTFE), etc. . Among them, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), a tetrafluoroethylene/hexafluoropropylene copolymer, which is preferably a perfluoro copolymer, is preferred from the viewpoints of heat resistance, flame retardancy, and electrical properties. (FEP), tetrafluoroethylene·hexafluoropropylene·perfluoroalkyl vinyl ether copolymer (EPE). As the fluororesin, it is particularly preferred to use a functional group-containing thermoplastic fluororesin. When a thermoplastic fluororesin containing no functional group is used, in order to obtain an adhesive which can withstand practical requirements, the polyimide film must be subjected to calendering, corona treatment, plasma treatment, ion gun treatment, etching. Treatment and other surface treatments have doubts that lead to cost increases. The functional group-containing thermoplastic fluororesin, for example, contains a compound selected from the group consisting of a carboxylic acid group or a derivative thereof, a hydroxyl group, a nitrile group, a cyanate group, an amine methyl oxy group, a phosphinomethoxy group, a halogen phosphine oxy group, a sulfonic acid group. A thermoplastic fluororesin (functional group-containing fluororesin) having a functional group or a sulfonium halide group. The functional group-containing fluororesin is generally used in a range in which the above-mentioned functional group -11-201032680 is contained in the thermoplastic fluororesin which is generally used in the above-mentioned molding. When the functional group-containing fluororesin is obtained, for example, the thermoplastic fluororesin shown in the above examples used in general molding can be synthesized in advance, and then introduced by addition or substitution of these functional groups, or in the foregoing exemplification In the synthesis of the thermoplastic fluororesin, a monomer having such a functional group is copolymerized to obtain a monomer. Specific examples of the aforementioned functional groups are -COOH, -CH2COOH, -COOCH3, -CONH2, -OH, -CH20H, -CN, -CH20(C0)NH2, win-CH20CN, -CH20P(0)(0H)2. -CH20P(0)C12, -S02F, etc. The functional group is preferably introduced into the fluororesin by copolymerizing a fluorine-containing monomer having a functional group in the production of a fluororesin. The monomer having such a functional group is preferably The amount of 0.5 to 10% by weight is copolymerized to the functional group-containing fluororesin, more preferably 1 to 5% by weight. The distribution of the functional group-containing monomer in the functional group-containing fluororesin may be uniform or non-uniform. When the content ratio of the functional group-containing monomer in the functional group-containing fluororesin is too low, it is less effective as a compatibilizing agent, and on the other hand, when the proportion of the cerium is too high, due to the functional group The strong interaction of the fluororesins may cause a reaction similar to the crosslinking reaction, which causes an increase in viscosity and is difficult to melt-form. Further, when the content ratio of the functional group-containing monomer is too high, the heat resistance of the functional group-containing fluororesin tends to be deteriorated. The viscosity or molecular weight of the functional group-containing fluororesin is not particularly limited, and may be preferably within a range not exceeding the viscosity or molecular weight of the thermoplastic fluororesin for general molding of the functional group-containing fluororesin. Degree. -12- 201032680 The fluororesin preferably further contains an antistatic agent imparting antistatic properties of ι. 2 to 2% by mass. The antistatic agent is preferably a surfactant such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a zwitterionic surfactant. The fluororesin preferably further contains an inorganic ruthenium material which lowers the dielectric constant or dielectric tangent. The inorganic cerium filling materials are, for example, cerium oxide, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, oxidized calcium, magnesium oxide, iron oxide, tin oxide, cerium oxide, hydrogen peroxide. Calcium, magnesium oxyhydroxide, aluminum hydroxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium citrate, Montestone, bentonite, Activated clay, sepiolite, filamentous aluminite, sericite, glass fiber, glass beads, cerium oxide ball, carbon black, graphite, carbon fiber, carbon sphere, wood powder, zinc borate, and the like. The inorganic ruthenium filler may be used alone or in combination of two or more. The content of the non-machined ruthenium is preferably from 1 to 100% by mass based on the fluororesin. Further, when the inorganic ruthenium is porous, the dielectric constant or dielectric tangent can be further lowered, so that it is more preferable. The thickness of the fluororesin is preferably 1.0 #m to 50/zm, more preferably 1.0 #m to 38/zm, still more preferably 1.0#m to 25/zm. If the film thickness is thicker than 50/zm, it is not good for the purpose of lightening the electronic parts. On the other hand, when the film thickness is thinner than 1.0/zm, the effect of surface modification such as improvement in electrical characteristics, decrease in water absorbability, and improvement in adhesion of the fluororesin is small, so that it is less preferable. -13- 201032680 The storage elastic modulus of the fluororesin: E' (A) is not particularly limited, and is known. When a fluororesin having the above composition is used, generally 0.3 GPa to 1.0 gPa can be used. Further, the linear expansion coefficient of the fluororesin is not particularly limited, and it is known that a fluororesin having the above composition can be used in an amount of from 50 ppm/°C to 150 ppm/°C. Further, from the viewpoint of high frequency correspondence, the dielectric constant of the film and the dielectric tangent are preferably small. The dielectric constant and dielectric tangent of the fluororesin layer are not particularly limited, and it is generally known that a fluororesin having the above composition can be used. Specifically, the dielectric constant of 1 MHz is 2.0 to 2.2, and the dielectric tangent of 1 MHz is 3.0x10-4 to 5.0x10·4. On the surface of the fluororesin, treatment according to a coupling agent (amino decane, epoxy decane, etc.), sand blasting, calendering, corona treatment, plasma treatment, ion gun treatment, etching may be applied as necessary. Processing and so on. The (B) polyimine resin layer used in the present invention is, for example, an aromatic φ scented tetracarboxylic acid (generally referred to as an acid anhydride, an acid and a guanamine-bonded derivative, the same hereinafter) and an aromatic A polyamine acid solution obtained by reacting a diamine (generally referred to as an amine and a guanamine-bonded derivative, the same applies hereinafter), and performing solution casting, drying, and heat treatment (醯imination) to form a film. The polyimine film obtained by the method, or the layer formed by applying the polyamic acid solution to the fluororesin layer (film), drying, heat treatment (醯imination), etc., is treated or In view of productivity, etc., it is preferably a form of a polyimide film. The following mainly describes the polyimide film. The above polyimine is not particularly limited, and a preferred example is a combination of the following aromatic diamines and aromatic tetracarboxylic acids (anhydrides). A. Combination of an aromatic tetracarboxylic acid having a pyrophoric acid residue and an aromatic diamine having a benzoxazole structure. B. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton. C. Combination of an aromatic diamine having a diphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyrophoric acid residue. Among them, a special polyimine film having an aromatic diamine residue having a benzoxazole structure is A. The structure of the above aromatic diamine having a benzoxazole structure is not particularly limited, and specifically, the following are shown. These diamines are preferably 70 mol% or more, and more preferably 80 mol% or more of all diamines. [Chemical Formula 1] 5-amino-2-(p-aminophenyl)benzoxazole

6-Amino-2-(p-aminophenyl)benzoxazole

[Chemical Formula 3] 5-amino-2-(m-aminophenyl)benzoxazole

-15- 201032680 [Chemical Formula 4] 6-Amino-2-(m-aminophenyl)benzoxazole

[Chemical Formula 5] 2,2'-p-benzoic bis(5-aminobenzoxazole)

[Chemical Formula 6] 2,2'-p-benzoic bis(6-aminobenzoxazole)

[Chemical Formula 7] 1-(5-Aminobenzoxazole)-4-(6-Aminobenzoxazole)benzene

:5,4-d,]bis [Chemical Formula 8] 2,6-(4,4'-Diaminodiphenyl)benzene [1,2-d

Dfazole

2,6-(4,4'-Diaminodiphenyl)benzene [l,2-d oxazole: 4,5-d'] bis -16 - 201032680

2,6-(3,4'-Diaminodiphenyl)benzene [1,2-d: 5,4-d'] Bis-Pfazole h2n

Ο [Chemical Formula 1 1] 2,6-(3,4'-Diaminodiphenyl)benzene [l,2-d : 4,5-d']

2,6-(3,3'-Diaminodiphenyl)benzene [l,2-d: 5,4-d'] double n-oxazole

2,6-(3,3'-Diaminodiphenyl)benzene [l,2-d: 4,5-d'] Difexazole

Among them, from the viewpoint of ease of synthesis, it is preferred that each isomer of an amine group (aminophenyl)-17-201032680 benzoxazole, particularly preferably 5-amino-2-(p-aminobenzene) Benzobenzoxazole. Here, the "isomers" are the respective isomers depending on the coordination positions of the two amine groups of the amine group (aminophenyl) benzoxazole (for example, the above "Chemical Formula 1"~ Each compound described in "Chemical Formula 4"). These diamines may be used alone or in combination of two or more. In addition, if it is 30 mol% or less of all the diamines, one type or two or more types of diamines exemplified below may be used. Such diamines are, for example, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]one, bis[4-(3) -aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfonic acid, 2,2-bis[4-(3-aminophenoxy)benzene Propane, 2.2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, pair Phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-di Aminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylarylene, 3,4'-diaminodiphenyl arsenide, 4 , 4'-diaminodiphenyl argon, 3,3,-diaminodiphenyl sulfonic acid, 3,4,-diaminodiphenyl sulfonic acid, 4,4'-diamino Diphenylsulfonic acid, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,3'- Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl] Methane, 1,1 - bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4 -(4-Aminophenoxy)phenyl]propane, 1,2-bis[4-(4-aminophenoxy)phenyl]propane, 1.3-bis[4-(4-aminophenoxyl) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy-18-201032680)phenyl]propane, 1,1-bis[4-(4-aminophenoxy) Phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, M-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-aminophenoxy)phenyl]butane, 2-[4 -(4-Aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3-methylphenyl]propane, 2,2-bis[4-(4-amine Phenoxy)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3, 5· dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4 -aminophenoxy)phenyl] ❹ -1,1,1,3,3,3-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3-double ( 3-aminophenoxy)benzene, 1,4-bis(4-amine Phenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]one, bis[4-(4-amine Phenyloxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]sulfonic acid, double [4-(3-Aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy) Benzomethylene]benzene, 1,3-bis[4-(3-aminophenoxy)benzylidene]benzene, 1,4-0 bis[4-(3-aminophenoxy) Benzomethylene]benzene, 4,4'-bis[(3-aminophenoxy)benzylidene]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl Propane, 1,3-bis[4-(3-aminophenoxy)phenyl]propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis[3-(3- Aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-double [ 4-(3-Aminophenoxy)phenyl]ethane, 1,2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4-(3-aminobenzene) Oxyphenyl) benzylidene, 4,4'-bis[3-(4-aminophenoxy)benzylidene]diphenyl ether, 4,4'-bis[3-(3-amine base Oxy) benzhydryl diphenyl ether, -19- 201032680 4,4'-bis[4-(4-amino, α-dimethylbenzyl)phenoxy]diphenyl ketone, 4,4'-bis[4-(4-Amino- ο:,α-dimethylbenzyl)phenoxy]diphenyl sulfonic acid, bis[4-(4-(4-aminobenzene) Oxy)phenoxy}phenyl]sulfonic acid, 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3 _bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethyl) Phenyloxy)-cx,q:-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-α,α-dimethylbenzene Methyl]benzene, 1,3-bis[4-(4-amino-6-methylphenoxy)-α,α-dimethylbenzyl]benzene, 〇1,3-bis[4- (4-Amino-6-cyanophenoxy) 1, £^-dimethylbenzyl]benzene, 3,3'-diamino-4,4'-diphenoxydiphenyl ketone, 4,4'-Diamino-5,5'-diphenoxydiphenyl ketone, 3,4'-diamino-4,5'-diphenoxydiphenyl ketone, 3,3' -diamino-4-phenoxydiphenyl ketone, 4,4'-diamino-5-phenoxydiphenyl ketone, 3,4'-diamino-4-benzene Diphenyl ketone, 3,4'-diamino-5'-phenoxydiphenyl ketone, 3,3'-diamino-4,4'-dibisphenoxydiphenyl ketone, 4,4'-Diamino-5,5'-dibisphenoxydiphenyl ketone, 3,4'-diamino-4,5'-φ dibisphenoxydiphenyl ketone, 3 , 3'-Diamino-4-bisphenoxydiphenyl ketone, 4,4'-diamino-5-bisphenoxydiphenyl ketone, 3,4'-diamino-4- Diphenoxy. Diphenyl ketone, 3,4'-diamino-5'-bisphenoxydiphenyl ketone, 1,3-bis(3-amino-4-phenoxybenzidine) Benzene, 1,4-bis(3-amino-4-phenoxybenzylidene)benzene, 1,3-bis(4-amino-5-phenoxybenzylidene)benzene, 1,4-bis(4-amino-5-phenoxybenzylidene)benzene, 1,3-bis(3-amino-4-bisphenoxybenzhydryl)benzene, 1,4 - bis(3-amino-4-bisphenoxybenzhydryl)benzene, 1,3-bis(4-amino-5-bisphenoxybenzhydryl)benzene, 1,4-double (4-Amino-5-bisphenyl-20-201032680 oxybenzylidene)benzene, 2,6-bis[4-(4-amino-indole, fluorene:-dimethylbenzyl)benzene Oxybenzonitrile, and a part of the aromatic ring of the above aromatic diamine a carbon number of 1 or more of a hydrogen atom of a part or all of a hydrogen atom through a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group, a cyano group, or an alkyl group or an alkoxy group; An aromatic diamine or the like substituted with a halogenated alkyl group or an alkoxy group. The molecular structure of the aromatic tetracarboxylic anhydride is not particularly limited, and the carbonyl has the following ones. These acid anhydrides are preferably 70 mol% or more, and more preferably 80 mol% or more of all the acid anhydrides. [Chemical Formula 14] pyrethic acid dianhydride

[Chemical Formula 15] 3,3',4,4'-biphenyltetracarboxylic anhydride

[Chemical Formula 16] 4,4'-oxydiphthalic anhydride

-21- 201032680 [Chemical Formula 17] 3,3',4,4'-diphenyl ketone tetracarboxylic anhydride

[Chemical Formula 18] 3,3',4,4'-diphenylsulfonic acid tetracarboxylic anhydride

[Chemical Formula 19] 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propionic anhydride

These tetracarboxylic dianhydrides may be used singly or in combination of two or more. In addition, if it is 30 mol% or less of all tetracarboxylic dianhydrides, one type or two or more types of non-aromatic tetracarboxylic dianhydrides exemplified below may be used. Such tetracarboxylic anhydrides, for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride , cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3,5, 6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-en-3-(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane- 3-(1,2),5,6-tetracarboxylic dianhydride, 1--22- 201032680 methyl-3-ethylcyclohex-1-ene-3-(1,2),5,6 - Tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3),3, 4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3), 3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane-^(2,3), 3,4-tetracarboxylic dianhydride, hydrazine, 3·dipropylcyclohexane-1-(2,3), 3-(2,3)-tetracarboxylic dianhydride, dicyclohexyl-3, 4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene -2,3,5,6-tetracarboxylic dianhydride or the like. ◎ A solvent used in the reaction (polymerization) of the aromatic tetracarboxylic acid and the aromatic diamine to obtain a polyamic acid, as long as it is a monomer capable of dissolving a raw material and a produced polyamine Further, it is not particularly limited, and is preferably a polar organic solvent such as fluorene-methyl-2-pyrrolidone, fluorenyl-acetamido-2-pyrrolidone, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-II. Ethylformamide, hydrazine, hydrazine-dimethylacetamide, dimethyl hydrazine, hexamethylphosphoniumamine, ethyl cellosolve acetate, diethylene glycol dimethyl ether, cyclobutyl hydrazine , halogenated phenols, etc. These solubilizing agents can be used singly or in combination. The amount of the solvent used may be such that the amount of the monomer of the raw material can be sufficiently dissolved. The specific amount is usually from 5 to 40% by weight, preferably from 1 to 30% by weight, based on the weight of the solution of the monomer to be dissolved. For the conditions for the polymerization of polylysine (hereinafter also referred to simply as "polymerization"), conventionally known conditions can be used, and specific examples are in the organic solvent at a temperature range of 〇~80 °C. Stir continuously and/or mix for 1 〜 to 30 hours. It is also possible to divide the polymerization reaction or increase or decrease the temperature as necessary. In this case, the order of addition of the two monomers is not particularly limited, but it is preferred to add the aromatic -23-201032680 tetracarboxylic acid to the solution of the aromatic diamine. The viscosity of the polyaminic acid solution prepared by the polymerization reaction is preferably 10 to 2000 Pa from the viewpoint of stability of liquid transport from the viewpoint of the Brookfield viscometer (25 ° C). s, especially good for 100~1000Pa. s. Those who perform vacuum defoaming in the polymerization reaction are effective for producing a good polyamic acid solution. Further, a small amount of a terminal blocking agent may be added to the aromatic diamine to control the polymerization before the polymerization. The terminal blocking agent, for example, a compound having a carbon-carbon double bond such as maleic anhydride. The amount of the dianic anhydride used is preferably from 0.001 to 1.0 mol per 1 mol of the aromatic diamine. In order to form a polyimide film from a polyamic acid solution prepared by a polymerization reaction, for example, a green film is obtained by applying a polyaminic acid solution onto a support and drying it ( A self-supporting precursor film), followed by heat treatment of the green sheets to carry out a hydrazine imidization reaction. The application of the polyaminic acid solution to the support includes a casting solution of a solution from a slit having a slit, and extrusion by an extruder, but is not limited thereto, and may be appropriately used. The coating means of the known solution. The conditions for obtaining the green sheet by drying the polylysine coated on the support are not particularly limited, and the temperature is, for example, 70 to 1501, and the drying time is, for example, 5 to 180 minutes. A drying device that achieves such conditions can also be used in the past, such as hot air, hot nitrogen, far infrared rays, high frequency induction heating, and the like. Next, in order to obtain a polyimine film of interest from the obtained green sheet, a ruthenium imidization reaction is carried out, and the specific method can be carried out by using a conventionally known ruthenium iodide reaction -24-201032680. For example, there is a method in which a polyamido acid solution containing no ring-closing catalyst and a dehydrating agent is used, and if necessary, a stretching treatment is carried out, followed by heat treatment to carry out a hydrazine imidization reaction (so-called heat-closed ring method). The heating temperature at this time is, for example, 100 to 5 001: from the viewpoint of film physical properties, it is preferably carried out at 150 to 250 ° C for 3 to 20 minutes, and then at 350 to 500 ° C. 2-stage heat treatment of ~20 minutes of treatment. Examples of other oxime imidization reactions include, for example, a chemical in which a ring-closing catalyst φ and a dehydrating agent are contained in a polyaminic acid solution, and the ruthenium imidization reaction is carried out by the action of the above-mentioned ring-closing catalyst and a dehydrating agent. Closed loop method. In this method, after the polyproline solution is applied to the support, a part of the ruthenium imidization reaction is carried out to form a self-supporting film, and the ruthenium imidization is completely carried out by heating. In this case, a part of the conditions of the ruthenium imidization reaction is preferably carried out at 100 to 200 ° C for 3 to 20 minutes, and the conditions of the ruthenium imidization reaction are completely carried out, preferably at 200 to 400 ° C. Heat treatment is carried out for 3 to 20 minutes. The thickness of the polyimine film forming the polyimine resin layer is preferably 1.0/zm to 38/zm, more preferably 1.00 to 25; t/m, more preferably 1.0 to 12.5. Em. When the film thickness is thicker than 38; am, it is less preferable for the purpose of lightening the electronic parts. Further, the ratio of the polyimine to the entire laminate is high, which adversely affects the water absorption or the physical properties of the electrical properties, and is therefore inferior. On the other hand, when the film thickness is thinner than l.〇//m, it is easily broken during transportation, and it is easy to form a fold, which makes it difficult to form a film. The storage elastic modulus of the polyimine film forming the polyimine resin layer is -25, and the number of E' (B) is not particularly limited, and is preferably 6. OGPa or more, and particularly preferably 7.0 GPa or more. Good for 8.0GPa or above. When the tensile breaking strength is smaller than 6.0 GPa, there may be a concern that the polyimide film does not have the effect of reinforcing the fluororesin layer. Further, the linear expansion coefficient of the polyimine film forming the polyimine resin layer is preferably -10 ppm / ° C to 10 ppm / ° C, particularly preferably - 7.5 ppm / ° C ~ 7.5 ppm / ° C More preferably -5 ppm / ° C ~ 5 ppm / ° C. When the coefficient of linear expansion exceeds this range, there is a concern that strain or wrinkles may occur under high temperature exposure such as solder bonding. In the polyimine film forming the polyimine resin layer, a coupling agent (amine decane, epoxy decane, etc.), sandblasting, calendering, corona treatment, plasma treatment, ionization may be performed as necessary. Gun processing, etching treatment, etc. The second invention of the present application is a method for producing a copper-clad laminate (CCL) in which the (C) copper layer is formed on the (B) polyimine resin layer without the adhesive, and φ is not particularly limited, and for example, the following means. A copper layer is formed on the polyimide film by a vacuum coating technique such as vapor deposition, sputtering, or ion shovel. • A method of forming a copper layer into a polyimide film by wet plating such as electroless plating or electroplating. • A method in which a polyaminic acid solution is applied to a copper foil and dried and heat treated (醢iminated). By using these means singly or in combination, the (C) copper layer can be formed on the (B) polyimine resin layer without the adhesive -26-201032680. The linear expansion coefficient of the multilayer fluororesin film of the present invention is preferably from 10 ppm/°C to 30 ppm/°C, more preferably from 10 ppm/°C to 28 ppm/°C, still more preferably from 10 ppm/°C to 25 ppmrc. When the coefficient of linear expansion exceeds this range, when the layer is laminated with a copper foil having a linear expansion coefficient of 16 ppm/°C, the linear expansion coefficients of the two are increased, and there is a fear that peeling or warpage is likely to occur during use. In order to set the linear expansion coefficient of the multilayer fluororesin film to be in the range of 10 ppm/° C. to 30 ppm/° C., the thickness ratio of the (A) layer of the multilayer fluororesin film is 60 for the {(A) layer/multilayer fluororesin film}. %~90%, and storage elastic modulus of layer (A) at room temperature: storage elastic modulus of E'(A) and (B) layers at room temperature: ratio of E'(B){E' (A)/E'(B)} is preferably 2.0% to 20%, particularly preferably a thickness ratio of 65% to 90% and a storage elastic modulus ratio of 2.5% to 15%, more preferably a thickness ratio of 65%- 85% and the storage elastic modulus ratio is 3.0% to 10%. When the thickness ratio or the storage elastic modulus ratio exceeds this range, the multilayer fluororesin film of the target linear expansion coefficient cannot be obtained. The thickness of the copper foil used in the present invention is preferably 1.0//m to 25/zm, more preferably 1.0/zm to 12.5/zm, still more preferably 1.0/zm to 10/m. The copper foil lamination method of the copper-clad multilayer fluororesin film used in the present invention is not particularly limited, and for example, the following means are available. • A method in which a multilayer fluororesin film is bonded to a copper foil and then welded by hot molding. • A method of forming a copper layer on a multilayer fluororesin film using a vacuum coating technique such as vapor deposition, sputtering, or ion deposition. -27- 201032680 • A method of forming a copper layer on a multilayer fluororesin film by wet plating such as electroless plating or electrolytic plating. The copper foil can be laminated on at least one side of the multilayer fluororesin film by the use of these means alone or in combination (the (A) side of the multi-layer fluororesin film in the second invention of the present application). The multilayer fluororesin film or the copper-clad multilayer fluororesin film of the present invention can be applied to, for example, a conductive copper foil layer by a general method or a thick film metal layer which is plated after being formed thereon as necessary. After the side is dried and dried, the wiring circuit pattern is formed by the steps of exposure, development, etching, and photoresist stripping, and then solder resist coating, plasticizing, and electroless tin plating are performed as necessary to obtain a flexible A printed wiring board, a multilayer printed wiring board in which these layers are multilayered, or a printed wiring board on which a semiconductor wafer is directly mounted. The method of manufacturing, multilayering, and mounting the semiconductor wafer of these circuits is not particularly limited, and can be appropriately selected and implemented in a generally known manner. Q The copper foil layer used in the present invention may be a coating film of an inorganic substance such as a metal monomer or a metal oxide on the surface of the thick film metal layer which is formed after being formed thereon. In addition, the copper foil layer or the surface of the thick film metal layer on the furnace after it is necessary to be formed thereon may be treated with a coupling agent (amine decane, epoxy decane, etc.), sandblasted, calendered, and electrically. Halo treatment, plasma treatment, ion gun treatment, etching treatment, and the like. EXAMPLES Hereinafter, the present invention will be described more specifically by showing examples and comparative examples, -28-201032680, but the present invention is not limited to the following examples. The evaluation methods of the physical properties in the following examples are as follows. 1. Reduced viscosity (77 sp/C) dissolved in N-methyl-2-rrolane by means of an Ubbel-type viscometer 'at a concentration of 0.2 g/dl at 3 °C A solution of the ketone (or N,N-dimethylacetamide) was measured. 2. Thickness The film of the measurement target was measured using a micrometer (manufactured by Feinpruf, Inc., Millitron 1245D). 3. Storage elastic modulus The viscoelasticity measurement (DMA) of the film to be measured was determined by the following conditions. . Storage elastic modulus: E'. Device name: Rheogel-E4000 manufactured by UBM Co., Ltd. Casting: Tensile castings Sample length: 14mm © Sample width: 5mm Frequency: 10Hz Temperature rise temperature: 0°C Temperature increase rate: 5°C /min Ambient gas: Nitrogen 4·Line Expansion coefficient (CTE) The film of the measurement target was measured for the expansion ratio in the MD direction and the TD direction under the following conditions, and was 90 to 100. (:, 100~11 (TC-like every 1 (TC interval -29- 201032680 fixed expansion rate / temperature, carry out this measurement to 400 ° C, and calculate the total measurement from 100 ° C to 3 50 ° C The average 値 of 値 is taken as CTE (average 値).

Device name: TMA4000S manufactured by MAC Science Co., Ltd. Sample length: 10 mm Sample width. 2 mm Initial load: 34.5 g/mm2 Temperature rise temperature: 25t

Temperature rise end temperature: 400 ° C 升温 Temperature increase rate: 5 ° C / min Ambient gas: Helium gas 5. Melting point The film to be measured is subjected to differential scanning calorimetry (DSC) under the following conditions, and the melting point is determined according to JIS Κ 7121. (Tin). Device name: DSC3100S heating pot made by MAC Science: Aluminum pan (non-hermetic type) φ Sample quality: 4mg Temperature rise temperature: 30°C Temperature rise temperature: 400°C Temperature increase rate: 20°C /min Ambient gas: Argon Gas 6. Dielectric constant, dielectric tangent The fluororesin film of the measurement object was cut into a size of 3 mm (thickness) x 200 mm x 120 mm to prepare a test film. The conductive paste was applied to both sides of the test film -30-201032680 for wiring, and the dielectric constant and dielectric tangent of 1 MHz were measured. 7. Peel strength The peel strength between the multilayer fluororesin film/copper foil can be determined by performing a 90 peel test under the following conditions. Device name: Autograph AG-IS manufactured by Shimadzu Corporation. Sample length: 100mm Sample width: l〇mm Measurement temperature: 25°C Peeling speed: 50mm/min Ambient gas: Atmosphere "Evaluation of substrate" Moisture resistance for multilayer fluororesin film Each of the copper-clad multilayer fluororesin films was treated under JEDEC LEVEL1 conditions (85. / 85% RH-168hr + 245 t: /3secx 3 times), and the peel strength after the test was evaluated. In addition, by the visual inspection after the test, it was found that no peeling, swelling, or discoloration was observed at all. Only Q was observed, and some peeling, swelling, and discoloration were observed as Δ, and peeling, swelling, and discoloration were observed as X. . "Evaluation of Substrate" Heat resistance for a multilayer fluororesin film and each copper-clad multilayer fluororesin film' is placed in a stainless steel mesh cage, heat-treated in the atmosphere at 250 ° C - 24 hr, and the evaluation test Peel strength after. In addition, 'by the visual inspection after the test, no peeling, swelling, or discoloration was observed at all." Only a few peeling, swelling, and discoloration were observed as △, and peeling, swelling, and swelling were observed. Is X. [Production Example 1] (Production of Polyimine Film A) After a nitrogen gas substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 5-amino-2-(p-aminophenyl)benzene was added. And 223 parts by mass of carbazole, 4416 parts by mass of hydrazine, hydrazine dimethyl acetamide, and completely dissolved, and then added Snow-Tex (DMAC-ST30, which is obtained by dispersing colloidal cerium oxide in dimethyl acetamide. 40.5 parts by mass (containing 8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride were stirred at a reaction temperature of 25 t for 24 hours to obtain a brown and viscous polylysine. Solution A. Its reducing concentration was 3.9 dl/g. The polyamidic acid solution A was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate, and dried at 110 ° C using a doctor blade coater. After a minute, the polylysine film was taken up without being peeled off from the support. The poly-proline membrane was passed through a needle carding machine with a 3-stage hot zone, and the first section was heat treated at 150 °C for 2 minutes, the second stage at 220 °C for 2 minutes, and the third for 475 °C for 4 minutes. In the 20 minutes after passing the tenter, a double-sided smoothing process was carried out through 6 rolls, and finally cut into a width of 500 mm to obtain a polyimide film A1 to A4. Table 1 shows the physical properties of the obtained polyimine film A 1 to A4. [Production Example 2] (Preparation of Polyimine Film B) 200 parts by mass of diaminodiphenyl ether was added to a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar in a nitrogen-substituted period of -32 to 201032680. 4,170 parts by mass of N-methyl-2-pyrrolidone and completely dissolved, and then added to the Snow-Tex (DMAC-ST30, manufactured by Nissan Chemical Industries Co., Ltd.) which has colloidal cerium oxide dispersed in dimethylacetamide. Parts (containing 8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride were stirred at a reaction temperature of 25 ° C for 5 hours to obtain a brown and viscous polyamic acid solution B. It has a reducing concentration of 3.6 dl/g. The polyamic acid solution B was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a knife coater at 110 ° C. After drying for 5 minutes, the polylysine film was taken up without being peeled off from the support. The polyproline membrane is passed through a needle comber having a three-stage heat treatment zone, and heat treatment is performed in the first stage of 150 ° C for 2 minutes, the second stage of 220 ° C for 2 minutes, and the third stage of 400 ° C for 4 minutes. 20 minutes after the tenter, a double-sided smoothing process was carried out by 6 rolls, and finally cut into a width of 500 mm to prepare a polyimide film B. Table 1 shows the physical properties of the obtained polyimide film B.制造 [Production Example 3] (Production of Polyimine Film C) After a nitrogen gas substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 108 parts by mass of phenylenediamine and N-methyl-2- are added. After 4010 parts by mass of pyrrolidone and completely dissolved, 40.5 parts by mass of Snow-Tex (DMAC-ST30, manufactured by Nissan Chemical Industries Co., Ltd.) obtained by dispersing colloidal cerium oxide in dimethylacetamide (containing cerium oxide 8.1 mass) Part by weight, 292.5 parts by mass of diphenyltetracarboxylic dianhydride, stirred at a reaction temperature of 25 t for 12 hours '-33- 201032680 to obtain a brown and viscous polyamine solution C. The reduction concentration was 4.3 dl/g. The polyamine acid solution C was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a doctor blade coater. On the other hand, after drying for 1 minute at 1 i (rc), the polyamic acid film was taken up without peeling from the support. The polyamic acid film was passed through a needle carding machine having a 3-stage heat treatment zone. Perform the first paragraph 150 °c x 2 minutes, the second paragraph 220. (: x 2 minutes, the third stage 46CTC x 4 minutes heat treatment '20 minutes after passing the tenter, through two rollers for double-sided smoothing process 'final The cut ruthenium was 500 mm wide to obtain a polyimide film C having a thickness of 25/zm. Table 1 shows the physical properties of the obtained polyimide film C. Project unit manufacturing example 1 Manufacturing Example 1 Manufacturing Example 1 Production Example 1 Production Example 2 Production Example 3 Polyimine film _ A1 A2 A3 Α4 BC Thickness μπι 3.0 5.0 10 25 5.0 5.0 Linear expansion coefficient ppm/°C 0.50 1.1 1.5 1.8 20 20 Storage elastic modulus GPa 9.0 9.0 9.0 9.0 5.0 8.5 Melting point °C Pick i〇L Pick 4rrt. Μ /frrt. Tear no /fnr Μ [Production Example 4] (Production of fluororesin film) Use A commercially available fluororesin is produced by a generally known method. Table 2 and Table 3 show the types and physical properties of the obtained fluororesin film. In the figure, the PAF is tetragas and benzene. Efficient ether copolymer 'FEP is tetrafluoroethylene. Hexafluoropropylene copolymer' EPE is tetrafluoroethylene. Hexafluoropropylene. Perfluoroalkyl vinyl ether copolymer, ETFE is tetrafluoroethylene. -34- 201032680 Table 2 Project unit Manufacturing example 4 Manufacturing example 4 Manufacturing example 4 Manufacturing example 4 Manufacturing example 4 Production example 4 Polyimine film - D1 D2 D3 D4 EF Composition - PFA PFA PFA PFA PFA PFA Dielectric constant - 2.1 2.1 2.1 2.1 2.1 2.1 Dielectric tangent xlO·4 3.0 3.0 3.0 3.0 3.0 3.0 Thickness βχη 10 12.5 25 50 12.5 12.5 Functional groups are available in Μ 线 Linear expansion coefficient ppm/°C 180 180 180 180 150 150 Storage flexibility Modulus GPa 0.55 0.55 0.55 0.55 0.50 0.50 Melting point °C 300 300 300 300 300 300 Table 3 Project unit Manufacturing example 4 Manufacturing example 4 Manufacturing example 4 Manufacturing example 4 Manufacturing example 4 Manufacturing example 4 Polyimine film G Η IJ κ L Composition of FEP EPE ETFE ETFE ETFE ETFE dielectric constant 2.1 2.1 2.7 2.7 2.7 2.7 Dielectric tangent xlO^ 5.0 5.0 50 50 50 50 Thickness βχη 12.5 12.5 12.5 12.5 12.5 12.5 No yfrrr functional group yfrrr No linear expansion coefficient ppm/°C 80 90 130 130 100 100 Storage elastic mold Number GPa 0.45 0.40 0.75 0.85 0.80 0.85 Melting point °c 260 290 240 200 250 250

[Production Example 5] (Production of Polyimine Film a) -35- 201032680 After nitrogen substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 5-amino-2-(p-amino group) was added. 223 parts by mass of phenyl)benzoxazole, 4416 parts by mass of N,N-dimethylacetamide and completely dissolved, and then added 311 (^- by dispersing colloidal cerium oxide in dimethylacetamide) 16\(〇]^八(:-3丁30, manufactured by Nissan Chemical Industries Co., Ltd.) 40.5 parts by mass (containing 8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride at a reaction temperature of 25 °C After stirring for 24 hours, a brown and viscous polyamine liquid acid solution A was obtained, which had a reducing concentration of 3.9 dl/g. 涂布 The polyphthalic acid solution A was coated on polyterephthalic acid using a knife coater. On the lubricant-free surface of the film A-4100 (manufactured by Toyobo Co., Ltd.) made of ethylenediester, the polyamic acid film was taken up without being peeled off from the support after drying at 11 (TC for 5 minutes). The polyproline membrane was passed through a needle comber having a three-stage heat treatment zone, and the first stage was 150 ° C x 2 minutes, the second stage was 220 ° C x 2 minutes, and the third stage was 475 ° C x 4 minutes. In the heat treatment of the clock, the double-side smoothing process was carried out through 6 rolls after passing the tenter, and finally the cutting Q was 500 mm wide to obtain a polyimide film a1 to a4. Table 1 1 shows the system The physical properties of the polyimine film a1 to a4 are obtained. Next, sputtering and electroplating are performed. The polyimine film a1 to a4 is cut into an A4 size, and is placed in a stainless steel frame having an opening and fixed. The frame holder is fixed to the substrate holder in the sputtering apparatus so as to fix the substrate holder to the polyimide film. Therefore, the refrigerant is circulated in the substrate holder. The temperature of the polyimide film can be set. Then the plasma of the surface of the polyimide film is treated at -36-201032680. The plasma treatment conditions are in argon, frequency 13.56 MHz, output 200W, pressure lxl (T3Torr). The condition, the temperature at the time of treatment is 2 ° C. The treatment time is 2 minutes. Then, under the conditions of a frequency of 13.56 MHz, an output of 450 W, and a pressure of 3 x 10 _ 3 T rr, a nickel-chromium (chromium is 1 〇 mass %) alloy target is used. Thickness 7 at a rate of 1 nm/sec by DC magnetron sputtering in an argon atmosphere a nickel-chromium alloy film (bottom layer) of nm, and then a refrigerant whose temperature is controlled at 2 ° C flows through the inner surface of the sputtering surface of the substrate so that the temperature of the substrate is 2 ° C. SUS plate contact of the substrate holder

In the G state, sputtering was carried out to form a copper film having a thickness of 0.25 /zm, and a polyimide film a~a4 having a single-layer metal film formed on one side was obtained. The thickness of the 'copper and NiCr layer' can be confirmed by the fluorescent X-ray method. The obtained polyimine film a~a4 having the underlying metal film formed on one side was fixed in a plastic frame, and a copper sulfate plating bath was used to form a copper layer having a thickness of 9/zm. The electroplating conditions were immersed in a plating solution (copper sulfate 80 g/l, sulfuric acid 210 g/l, HC1, a small amount of a gloss agent), and a current of 1.5 Adm2 was passed. Subsequently, heat treatment was carried out at 120 ° C for 10 φ minutes to obtain a copper clad laminate (CCL) al~a4 having a copper layer-formed polyimine film formed on one side. [Production Example 6] (Production of Polyimine Film b) After a nitrogen gas substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 200 parts by mass of diaminodiphenyl ether and N-methyl group were added. After 2-170 parts by mass of -2-pyrrolidone and completely dissolved, Snow-Tex (DMAC-ST30, manufactured by Chemical Industry Co., Ltd.), which is obtained by dispersing colloidal cerium oxide in dimethylacetamide, is added. Parts by mass (8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride were stirred at a reaction temperature of 25 ° C for 5 hours to obtain a brown and viscous polyamic acid solution B. It has a reducing concentration of 3.6 dl/g. The polyamic acid solution B was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a knife coater at 110 ° C. After drying for 5 minutes, the polylysine film was taken up without being peeled off from the support. The polyproline membrane is passed through a needle comber having a 3-stage heat treatment zone, and heat treatment is performed in the first stage at 150 ° C for 2 minutes, the second stage at 220 ° C for 2 minutes, and the third stage at 400 ° C for 4 minutes. A two-side smoothing process was carried out by passing six rollers after 20 minutes through a tenter, and finally cut into a width of 500 mm to prepare a polyimide film b. Table 11 shows the physical properties of the obtained polyimide film b. Then, sputtering and plating were carried out in the same manner as in Production Example 5 to obtain a copper clad laminate (CCL) b. [Production Example 7] 〇 (Production of Polyimine Film C) After the nitrogen gas was substituted in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 108 parts by mass of phenylenediamine and N-methyl-2- were added. After 4010 parts by mass of pyrrolidone and completely dissolved, 40.5 parts by mass of Snow-Tex (DMAC-ST30, manufactured by Nissan Chemical Industries Co., Ltd.) obtained by dispersing colloidal cerium oxide in dimethylacetamide (containing cerium oxide 8.1 mass) And 25.2 parts by mass of diphenyltetracarboxylic dianhydride were stirred at a reaction temperature of 25 ° C for 12 hours to obtain a brown and viscous polyamine solution C. Its reducing concentration is 4.3 dl/g. -38- 201032680 The polyamic acid solution c was applied to the lubricant-free surface of film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a doctor blade coater at 1 i. After drying for 5 minutes at rc, the poly-proline film was taken up without being peeled off from the support. The poly-proline film was passed through a needle carding machine having a 3-stage heat treatment zone to carry out the first stage 150. °c X2 minutes, 2nd stage 220 tx2 minutes, 3rd stage 460°Cx4 minutes heat treatment, 20 minutes after passing the tenter, through 6 rollers for double-sided smoothing process, finally cutting I is 5000 mm wide Further, a polyimide film c having a thickness of 25 #m was obtained. Table 11 shows the physical properties of the obtained polyimide film c. Then, sputtering and plating were carried out in the same manner as in Production Example 5. A copper-clad laminate (CCL) c was obtained. [Production Example 8] (Production of a fluororesin film) A fluororesin film was produced by a generally known method using a commercially available fluororesin. Table 12 and Table 13 are used. The type of the fluororesin film produced and the properties thereof were shown. [Example 1] A functional group-containing fluororesin film D1 (Fluon PFA followed by grade, Asahi Glass) (manufactured by the company), placed on both sides of a polyimide film A1 cut to a size of 150 mm x 150 mm, and subjected to heat and pressure molding at 30 ° C and 5 MPa of the melting point of the fluororesin film for 30 minutes. On the other hand, a functional group-containing fluororesin film D1 and a copper box (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 9/m were sequentially placed in a size of 150 mm x 150 mm for cutting -39-201032680. On the polyimine film, a double-sided copper-clad multilayer fluororesin film was obtained by heat-press molding at 330 ° C and 5 MPa above the melting point of the resin film to obtain a double-sided copper-clad multilayer fluororesin film. The evaluation results of the multilayer fluororesin film and the double-sided copper-clad multilayer gas-resin film. The following 'thickness ratio, storage elastic modulus ratio, and linear expansion coefficient are the evaluation results of the multilayer fluororesin film, which is a double-sided copper-clad multilayer fluororesin film. [Equation 2, 3] A laminate was produced and evaluated in the same manner as in Example 1 except that the polyimide film A2 and A3 were used instead of the polyimide film A1. Table 4 shows the obtained multilayer fluororesin film, double-sided coating Evaluation results of copper multilayer fluororesin film [Table 4] Project unit Example 1 Example 2 Example 3 Polyimine film A1 A2 A3 Fluoro resin film-D1 D1 D1 Thickness ratio % 87 80 67 Storage elastic modulus Specific ratio 6.1 6.1 6.1 Linear expansion coefficient ppm/. 28 25 15 Initial peel strength N/cm 13 1 13 13 Membrane quality 〇〇〇 Wet heat test Peeling strength N/cm 10 10 10 Film quality 〇〇〇 heat resistance test peel strength N/cm 5 8 10 Membrane - Δ 〇〇 -40 - 201032680 [Example 4] In place of the functional group-containing fluororesin film D1 (Fiuon PFA, grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film D1. In the same manner as in Example 1, a laminate was produced and evaluated. Table 5 shows the evaluation results of the multilayer fluororesin film and the double-sided copper-clad multilayer fluororesin film which were produced. [Examples 5 and 6] φ A laminate was produced and evaluated in the same manner as in Example 4 except that the polyimide film A2 and A3 were used instead of the polyimide film A1. Table 5 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. [Example 7] A fluororesin film D3 (Fluon PFA, grade, manufactured by Asahi Glass Co., Ltd.) containing a functional group was used instead of the functional group-containing fluororesin film D2, and the same procedure as in Example 6 was carried out. The laminate is evaluated and evaluated. Table 5 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. -41 - 201032680 [Table 5] Project unit Example 4 Example 5 Example 6 Example 7 Polyimine film-A1 Α2 A3 A3 Fluororesin film - D2 D2 D2 D3 Thickness ratio % 89 83 71 83 Storage elastic mold Number ratio % 6.1 6.1 6.1 6.1 Line expansion drive number ppm/°C 30 25 20 25 Initial peel strength N/cm 15 15 15 18 Membrane - 〇〇〇〇Damp heat resistance test peel strength N/cm 13 13 13 15 Test film quality 〇〇〇〇 heat resistance test peel strength N/cm 8 10 13 13 membranous - Δ 〇〇〇

[Example 8 to 1 1J

The polyimine film A2 cut into a size of I50 mm x 150 mm was placed in a plasma processor manufactured by Hi-Tech Co., Ltd., and after vacuum evacuation, oxygen gas was introduced and the discharge was excited to perform plasma treatment. The treatment conditions were a vacuum of 3 x l 〇 Pa, a gas flow rate of 1.5 SLM, and a discharge power of 12 kW. A functional group-free fluororesin film E (Fluon PFA, manufactured by Asahi Glass Co., Ltd.), F (Neoflon PFA, manufactured by Daikin Industries Co., Ltd.), and G (Neoflon FEP,

Manufactured by Daikin Industries Co., Ltd., H (EPE, manufactured by Daikin Industries Co., Ltd.) on both sides of the obtained plasma-treated polyimide film A2, at a temperature of 30 ° C above the melting point of the fluororesin film, A heat-press molding was carried out at 5 MPa for 30 minutes to prepare a multi-layer fluororesin film. On the other hand, the fluororesin film E~H containing no functional group and the copper foil having a thickness of 9 -42 to 201032680 are disposed on both sides of the plasma-treated polyimide film A2 in the form of fluorine. The resin film was subjected to heat and pressure molding at 30 ° C and 5 MPa above the melting point of the resin film for 30 minutes to obtain a double-sided copper-clad multilayer fluororesin film. Table 6 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. [Table 6] Project unit Example 8 Example 9 Example 10 Example 11 Polyamide film - A2 A2 A2 A2 _lip film - EFG Η Thickness ratio % 83 83 83 83 Storage elastic modulus ratio % 5.6 5.6 5.0 4.4 Linear expansion coefficient ppm/°C 23 23 10 10 Peel strength N/cm 10 10 10 13 Initial film quality — 〇〇〇〇Damp heat resistance test Peel strength N/cm 8 8 8 10 Film quality 〇〇〇〇 heat resistance test Peel strength N /cm 8 8 8 8 Membrane - 〇〇〇〇 [Comparative Example 1] A laminate was produced in the same manner as in Example 2 except that the polyimine film B was used instead of the polyimide film A1. to evaluate. Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. •43- 201032680 When the linear expansion coefficient of the polyimide film is too large, the linear expansion coefficient of the obtained multilayer fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased', so after the reliability test The adhesion and membranous quality are reduced. [Comparative Examples 2, 3]

In addition to the functional group-containing fluororesin film I (Fluon LM-ETFE AH2000 'made by Asahi Glass Co., Ltd.), J (Neoflon EFEP RP5000, manufactured by Daikin Industries Co., Ltd.), and the functional group-containing fluororesin film D1, The laminate was produced in the same manner as in Example 2 and evaluated. ❹ Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the adhesion after the reliability test and the film quality are lowered. [Comparative Examples 4 and 5] In place of the functional group-free fluororesin film K (Fluon ETFE, manufactured by Asahi Glass Co., Ltd.) and L (Neoflon ETFE, manufactured by Daikin Industries Co., Ltd.), a fluororesin film containing no functional group was used. A laminate was produced and evaluated in the same manner as in Example 8 except for E. Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the adhesion after the reliability test and the film quality are lowered. -44- 201032680 [Table 7]

Project unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Polyimine film _ B A2 A2 A2 Α2 Fluororesin film _ D2 IJKL Thickness ratio % 83 83 83 83 83 Storage elastic modulus ratio % 11 8.3 9.4 8.9 9.4 Line expansion number ppm/°C 70 25 25 23 23 Initial peel strength N/cm 15 13 13 10 10 Membrane _ 〇〇〇〇〇 Moisture resistance test Peel strength N/cm 10 0 0 0 0 Membrane _ 〇 XXXX Heat test peel strength N/cm 3 5 5 3 3 Membrane — XXXXX

[Comparative Example 6] A laminate was produced and evaluated in the same manner as in Example 1 except that the polyimide film A4 was used instead of the polyimide film Ai. Table 8 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced. [Comparative Example 7] In addition to the functional group-containing fluororesin film D2 (Fluon PFA followed by -45-201032680, grade, manufactured by Asahi Glass Co., Ltd.), the functional group-containing fluororesin film D1 was used instead of Comparative Example 6. The same method is used to make a laminate and evaluate it. Table 8 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced. [Comparative Examples 8 to 10] In addition to the functional group-containing fluororesin film D4 (Fluon PFA, grade, manufactured by Asahi Glass Co., Ltd.), the functional group-containing fluororesin film D2 was replaced, and the others were the same as in Examples 4 to 6. The method is to make a laminate and evaluate it. Table 8 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. When the thickness ratio of the fluororesin is too large, the Q-ray expansion coefficient of the obtained fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased, so the adhesion after the reliability test and the film quality are lowered. -46 - 201032680 [Table 8]

Project unit Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Polyimine film A4 A4 A1 A2 A3 雠 Film _ D1 D2 D4 D4 D4 Thickness ratio % 44 50 97 95 91 Storage elastic modulus ratio % 6.1 6.1 6.1 6.1 6.1 Thread expansion number ppm/°C 5.0 5.0 100 80 60 Initial peel strength N/cm 13 15 18 18 18 Membrane enthalpy heat and humidity test Peel strength N/cm 5 5 13 13 13 Membrane XX 〇〇〇 heat resistance test peel strength N/cm 8 10 5 5 5 membranous _ 〇〇 XXX

[Examples 12 to 13 and Comparative Examples 1 to 12] (Evaluation of warpage of copper-clad multilayer fluororesin film) © The functional group-containing fluororesin film D3 was placed in a size of 150 mm x 150 mm. On both sides of the amine films A1 to A4, heat-press molding was carried out at 330 ° C and 5 MPa which is equal to or higher than the melting point of the fluororesin film to form a multi-layer fluororesin film. Further, the functional group-containing fluororesin film D3 and the copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 9 gm were placed on both sides of the polyimide film A1 to A4 cut to a size of 150 mm x 150 mm. The film was heat-pressed at - 30 ° C and 5 MPa above the melting point of the fluororesin film for 30 minutes to form a double-sided copper-clad multilayer fluororesin film. Then, the functional group-containing fluororesin film D3 is disposed on one side of the polyimide film A1 to A4 cut to a size of 150 mm x 150 mm, and the functional group-containing fluororesin film D3, thickness 9# is sequentially applied. The copper foil of m (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) was placed on the other surface, and heat-pressed and formed at 30 ° C and 5 MP a above the melting point of the fluororesin film to obtain a single-sided coating. Copper multilayer fluororesin film. ^ By subjecting the obtained single-sided and double-sided copper-clad multilayer fluororesin film to external inspection, the warp-free person is evaluated as 〇, the warp is △, and the curled into a roll is X. The evaluation results are shown in Table 9. When the linear expansion coefficient of the multilayer fluororesin film is larger than the linear expansion coefficient of the copper foil, in the asymmetric configuration of the single-sided copper-clad multilayer fluororesin film, the multilayer fluororesin film is warped to the inside. [Table 9] Project unit Comparative Example 11 Comparative Example 12 Example 12 Example 13 Polyimine film _ A1 A2 A3 A4 Fluororesin film-D3 D3 D3 D3 Thickness ratio % 94 91 83 67 Age elastic modulus ratio % 6.1 6.1 6.1 6.1 Line Expansion Number ppm/°C 80 60 25 15 Warpage (double-sided warp (single-sided copper) — XX 〇〇-48- 201032680 [Examples 14 to 15, Comparative Example 13] (Evaluation of warpage of copper-clad multilayer fluororesin film) The functional group-containing fluororesin film D2 was placed on both sides of a polyimide film A2 to A4 cut to a size of 150 mm x 150 mm, in a fluororesin The film was subjected to heat and pressure molding at 30 ° C and 5 MPa above the film melting point for 30 minutes to prepare a multi-layer fluororesin film. Further, a functional group-containing fluororesin film D2 and a copper foil having a thickness of 9 #m were sequentially ( UWZ and Furukawa Circuit Foil Co., Ltd. are placed on both sides of a polyimide film A2 to A4 cut to a size of 150 mm x 150 mm, and heated at 330 ° C and 5 MPa above the melting point of the fluororesin film for 30 minutes. Press-forming to produce a double-sided copper-clad multilayer fluororesin film. Then, the functional group-containing fluororesin film D2 is disposed. The fluororesin film D3 containing a functional group and the copper foil of a thickness of 9/zm (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) were sequentially cut into a single surface of a polyacrylamide film A2 to A4 having a size of 150 mm x 150 mm. On the other side, a single-sided copper-clad multilayer fluororesin film was obtained by heat-press molding for 30 minutes at 330 ° C and 5 MPa above the melting point of the fluororesin film. Table 10 shows the obtained single-sided fluororesin film. And the evaluation result of the double-sided copper-clad multi-layer fluororesin film. When the linear expansion coefficient of the multi-layer fluororesin film is smaller than the linear expansion coefficient of the copper foil, in an asymmetric configuration such as a single-sided copper-clad multi-layer fluororesin film, The copper box is warped to the inside. -49- 201032680 [Table 10] Project unit Example 14 Example 15 Comparative Example 13 Polyimine film-A2 A3 A4 fluororesin film _ D2 D2 D2 Thickness ratio % 83 71 50 Storage Elastic modulus ratio % 6.1 6.1 6.1 Linear expansion coefficient ppm/°C 25 20 5 Warpage (double-sided copper) _ 〇〇〇 warp (single-sided copper) — 〇〇Δ

[Application Example 1] The functional group-containing fluororesin film D1 was placed on one side of a polyimide film A2 cut to a size of 150 mm x 150 mm, and the functional group-containing fluororesin film D1 was sequentially applied. 9; um copper foil was placed on the other side, and subjected to heat and pressure molding at 330 ° C and 5 MPa above the melting point of the fluororesin film to obtain a single-sided copper-clad multilayer fluororesin film. On the other hand, using the double-sided copper-clad polyimide laminate obtained in Example 2, a photoresist (FR-200, manufactured by Shipley Co., Ltd.) was applied to one side and dried, and then a glass mask was used. The adhesion exposure was carried out, followed by development with a 1.2 mass% aqueous KOH solution. Next, a copper chloride etching machine containing HCl and hydrogen peroxide is used at 40. (3, 2kgf/cm2 of the ejection pressure is etched to form a test pattern, and then washed and subjected to an annealing treatment at 125° for 1 hour to obtain a single-sided copper-clad multilayer fluororesin film having a single-sided pattern. (Printed wiring board) -50- 201032680 The pattern forming surface of the single-sided copper-clad multilayer fluororesin film (printed wiring board) with one side of the pattern and the fluororesin surface of the single-sided copper-clad multilayer fluororesin film face each other The multilayer printed wiring board shown in Fig. 1 was obtained by heat-press molding at 30 ° C and 5 MPa above the melting point of the fluororesin film to obtain a multilayer printed wiring board as shown in Fig. 1. Since it is covered with a fluororesin having a low dielectric constant, it is extremely useful as a member for high frequency. [Table 11] Project unit weave example 5 Manufacturing example 5 Manufacturing example 5 Manufacturing example 5 Manufacturing example ό Manufacturing example 7 Membrane a a2 a3 a4 bc Thickness μτα 3.0 5.0 10 25 5.0 5.0 Linear expansion coefficient ppm/. 0.5 1.1 1.5 1.8 20 20 Storage elastic modulus GPa 9.0 9.0 9.0 9.0 5.0 8.5 Melting point °c No fnrr m Jnr. No [Table 12] Project unit manufacturing example 8 Manufacturing 8 Weaving Example 8 Manufacturing Example 8 Manufacturing Example 8 Manufacturing Example 8 Poly film d2 d3 d4 ef Composition PFA PFA PFA PFA PFA PFA Dielectric constant 2.1 2.1 2.1 11 2.1 2.1 Dielectric tangent xlOJ 3.0 3.0 3.0 3.0 3.0 3.0 Thickness βΐη 20 25 50 100 25 25 Functional group with or without wireless expansion _ppmppm/°C 180 180 180 180 150 150 Storage elasticity view GPa 0.55 0.55 0.55 0.55 0.50 0.50 Melting point °c 300 300 300 300 300 300 -51- 201032680 [Table 13 】 Project unit manufacturing example 8 Manufacturing example 8 Manufacturing example 8 Manufacturing example 8 Manufacturing example 8 Manufacturing example 8 Polyimine film-ghijk 1 Composition_ FEP EPE ETFE ETFE ETFE ETFE Dielectric constant _ 2.1 2.1 2.7 2.7 2.7 2.7 Dielectric tangent ΧΙΟ*4 5.0 5.0 50 50 50 50 Thickness βχα 25 25 25 25 25 25 Functional group __ Nothing to have wireless expansion frequency ppm/°C 80 90 130 130 100 100 Storage elastic modulus GPa 0.45 0.40 0.75 0.85 0.80 0.85 Melting point °c 260 290 240 200 250 250 [Example 16] A functional group-containing fluororesin film dl (Fluon PFA, grade, manufactured by Asahi Glass Co., Ltd.) was placed in a polyimide film having a size of 150 mm x 150 mm. On one side, above the melting point of the fluororesin film is 330 ° C, 5MPa at 30 minutes into the heated pressure molding line G, yielding (A) laminate layer (B) layer. Table 14 shows the results of evaluation of the thickness ratio, the storage elastic modulus ratio, and the linear expansion coefficient of the layered layer (A) layer (B). On the other hand, a functional group-containing fluororesin film dl and a copper foil having a thickness of 9 cm (manufactured by UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) were placed on a copper-clad laminate (CCL) al of a size of 150 mm x 150 mm. The aminated surface of the imide film was subjected to heat and pressure molding at 30 ° C and 5 MPa of the fluororesin film at a temperature of 30 MPa or more to obtain a copper-clad multilayer fluororesin film. -52- 201032680 Table 14 shows the evaluation results of the moisture resistance test and the heat resistance test of the obtained copper-clad multilayer fluororesin film. [Examples 17, 18] In place of the polyimine film a1 instead of the polyimine film a1, a copper clad laminate (CCL) a2, a3 was used instead of the copper clad laminate (CCL) & In the same manner as in Example 16, a laminate was produced and evaluated. Table 14 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results. [Table 14] Project unit Example 16 Example 17 Example 18 Poly film _ al a2 a3 Fluororesin film _ dl dl dl Thickness ratio % 87 80 67 Storage elastic modulus ratio % 6.1 6.1 6.1 Linear expansion coefficient ppm/°C 28 25 15 Initial peel strength N/cm 13 13 13 Membrane....... 〇〇〇Damp heat resistance peel strength N/cm 10 10 10 Membrane __ 〇〇〇 Heat resistance test Peel strength N/cm 5 8 10 Membrane-Δ 〇〇-53- 201032680 [Example 19] In addition to the functional group-containing fluororesin film d2 (Fluon PFA followed by grade, manufactured by Asahi Glass Co., Ltd.), the functional group-containing fluororesin film dl was replaced with The laminate was produced in the same manner as in Example 16 and evaluated. Table 15 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results. [Examples 20, 21] ❹ In addition to the polyimine film a2, a3 instead of the polyimide film a1, a copper clad laminate (CCL) a2, a3 was used instead of the copper clad laminate (CCL) al Further, a laminate was produced and evaluated in the same manner as in Example 19. Table 15 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.实施 [Example 22] The same procedure as in Example 21 was carried out except that the functional group-containing fluororesin film d3 (Flu〇n PFA followed by grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d2. To make a laminate and evaluate it. Table 15 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results. -54- 201032680 [Table 15] Project unit Example 19 Example 20 Example 21 Example 22 Polyimine film a a2 a3 a3 Fluororesin film _ d2 d2 d2 d3 Thickness ratio % 89 83 71 83 Storage elastic modulus Specific ratio 6.1 6.1 6.1 6.1 Linear expansion coefficient ppm/°C 30 25 20 25 Initial peel strength N/cm 15 15 15 18 Membrane _ 〇〇〇〇 Moisture resistance test Peel strength N/cm 13 13 13 15 Membrane _ 〇〇〇 〇Heat resistance test Peeling strength N/cm 8 10 13 13 Membrane _ Δ 〇〇〇 [Example 2 3 to 2 6 ] The polyimine film a2 set to a size of 150 mm x 150 mm was set at ® Electronics Co., Ltd. The plasma processor is subjected to vacuum evacuation, and then oxygen is introduced and the discharge is excited to perform plasma treatment. The treatment conditions were a vacuum of 3 x 10 Pa, a gas flow rate of i.5 SLM, and a discharge power of 12 kW. A fluororesin film e (Fluon PFA, manufactured by Asahi Glass Co., Ltd.), f (Neofl〇n PFA, manufactured by Daikin Industries Co., Ltd.), g (Neoflon FEP, manufactured by Daikin Industries, Ltd.), and h (EPE, Daikin Industries, Inc.) The system is disposed on one side of the obtained plasma-treated polyimine film a2, and is heated and pressurized for 30 minutes at 33 (TC, 5 MPa) above the fluorine tree 3 - 201032680 Forming, and (A) layer (B) layered body is produced. Table 16 shows the thickness ratio, storage elastic modulus ratio, and linear expansion of the (A) layer (B) laminated body obtained. On the other hand, the copper clad laminate (CCL) a2 is placed in a plasma processor manufactured by Nissho Electronics Co., Ltd., and after vacuum evacuation, oxygen is introduced and the discharge is excited to perform plasma treatment. The vacuum degree is 3xlOPa, the gas flow rate is 1.5 SLM, and the discharge power is 12 kW. The fluororesin film e~h containing no functional group and the copper foil 厚度 having a thickness of 9/m are sequentially disposed in the prepared plasma-treated coating. The surface of the polyimine film a2 of the copper laminate (CCL) a2 is carried out at 3 30 ° C and 5 MPa above the melting point of the fluororesin film. The copper-clad multilayer fluororesin film was obtained by heating and press molding for 0 minutes. Table 16 shows the evaluation results of the obtained moist heat resistance test and heat resistance test. [Table 16] Item Unit Example 23 Example 24 Example 25 Example 26 Poly Brewing Film — a2 a2 a2 a2 mmmm — efgh Thickness ratio % 83 83 83 83 Storage elastic modulus ratio % 5.6 5.6 5.0 4.4 Linear expansion coefficient ppm/°C 23 23 10 10 Initial peel strength N/cm 10 10 10 13 Membrane - 〇〇〇〇Damp heat resistance peel strength N/cm 8 8 8 10 Membrane - 〇〇〇〇 heat resistance test Peel strength N/cm 8 8 8 8 Membrane - 〇〇〇〇-56- 201032680 [ Comparative Example 1 4] In addition to using the polyimine film b to replace the polyimide film a1, a copper clad laminate (CCL) b was used instead of the copper clad laminate (Ccl) al, and the other example 17 The same method was used to make a laminate and evaluated. The surface enthalpy shows the thickness ratio of the layer (A) layer (B), the storage elastic modulus ratio, and the coefficient of linear expansion, and copper coating. Multi-layer fluororesin film resistance to heat and humidity test, heat resistance The evaluation result of the test. ^ When the linear expansion coefficient of the polyimide film is too large, the linear expansion coefficient of the obtained multilayer fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased, so reliability Continuation and film quality reduction after the test [Comparative Examples 15 and 16] In addition to the functional group-containing fluororesin film i (Fluon LM-ETFE AH2000, manufactured by Asahi Glass Co., Ltd.), j (Neoflon EFEP RP5000, manufactured by Daikin Industries Co., Ltd.) A laminate was produced and evaluated in the same manner as in Example 17 except that the functional group-containing fluororesin film dl was replaced. 17 Table 17 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the (A) layer (B) laminated body, and the moisture resistance test and heat resistance of the copper-clad multilayer fluororesin film. The evaluation results of the test. Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the adhesion after the reliability test and the film quality are lowered. [Comparative Examples 17 and 18] In place of the functional group-free fluororesin, a functional group-free fluororesin film k (Fluon ETFE, manufactured by Asahi Nippon-57-201032680, manufactured by UNeoflon ETFE, Daikin Industries Co., Ltd.) was used. A laminate was produced and evaluated in the same manner as in Example 23 except for the film e. Table 17 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results. Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the susceptibility and film quality after the reliability test are lowered. [Table 17] Item_Unit Comparative Example 14 Comparative Example 15 Comparative Example 16 Comparative Example 17 Comparative Example 18 Polyimine film _ b a2 a2 a2 a2 Fluororesin film _ _ d2 ijk 1 Thickness ratio % 83 83 83 83 83 Storage Elastic modulus ratio % 11 8.3 9.4 8.9 9.4 Line expansion hall number ppm/°C 70 25 25 23 23 Initial peel strength N/cm 15 13 13 10 10 Membrane quality 〇〇〇〇〇 Wet heat test Stripping Stuffed N/cm 10 0 0 0 0 Membrane _ 〇XXXX Heat resistance test Peel strength N/cm 3 5 5 3 3 Membrane-XXXX x - -58- 201032680 [Comparative Example 19] In addition to the use of polyimine film a4 instead of polyimine film Al, a laminate was produced and evaluated in the same manner as in Example 16 except that a copper clad laminate (CCL) a4 was used instead of the copper clad laminate (CCL) al. Table 18 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results. When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced. [Comparative Example 20] The same procedure as in Comparative Example 19 was carried out except that the functional group-containing fluororesin film d2 (Fluon PFA grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d1. The laminate is evaluated and evaluated. Table 18 shows the results of evaluation of the thickness ratio of the (A) layer (B) layered body, the storage modulus of the storage modulus, and the coefficient of linear expansion, and the moisture resistance test of the copper-clad multilayer fluororesin film. Evaluation results of the heat resistance test. When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced. [Comparative Examples 21 to 23] In addition to the functional group-containing fluororesin film d4 (Fluon PFA, grade, manufactured by Asahi Glass Co., Ltd.), the functional group-containing fluororesin film d2 was used instead of -59-201032680. The same method as ~21 is used to make a laminate and evaluate it. Table 18 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results. When the thickness ratio of the fluororesin is too large, the linear fluororesin of the obtained fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased, so that the adhesion after the reliability test and the film quality are lowered. [Table 18]

Project unit ratio KM 19 Comparative Example 20 Comparative Example 21 Comparative Example 22 Comparative Example 23 Polyfluorene film _ a4 a4 al a2 a3 Fluororesin film d2 d4 d4 d4 Thickness ratio % 44 50 97 95 91 Storage elastic modulus ratio % 6.1 6.1 6.1 6.1 6.1 Thread expansion number ppm/°C 5.0 5.0 100 80 60 Initial peel strength N/cm 13 15 18 18 18 Membrane enthalpy heat and humidity test Peel strength N/cm 5 5 13 13 13 Membrane XX 〇 〇〇 heat resistance test stripping brewing N/cm 8 10 5 5 5 membranous _ 〇〇 XXX

[Examples 27 to 28, Comparative Examples 24 to 25] (Evaluation of warpage of copper-clad multilayer fluororesin film) -60-201032680 The functional group-containing fluororesin film d3 was placed in a size of 150 mm x 150 mm. One side of the imine film a~a4 was subjected to heat and pressure molding at 30 ° C and 5 MPa of the melting point of the fluororesin film for 30 minutes to obtain a layered layer of the layer (A). Table 19 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layer (A) layered body obtained. Further, the functional group-containing fluororesin film d3 and the copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 9/zm were placed in a copper-clad laminate (CCL) al~a4 cut to a size of 150 mm x 150 mm. On the surface of the polyimine film a1 to 4, heat-and-pressure molding was carried out for 30 minutes at a temperature of 30 ° C and 5 MPa above the melting point of the fluororesin film to obtain a double-sided copper-clad multilayer fluororesin film. By visually inspecting the obtained copper-clad multilayer fluororesin film, the warp-free person was evaluated as 〇, and the warped person was evaluated as X. The evaluation results are shown in Table 19. [Table 19] Project unit Comparative Example 24 Comparative Example 25 Example 27 Example 28 Polyamine film __ al a2 a3 a4 Fluororesin film _ d3 d3 d3 d3 Thickness ratio % 94 91 83 67 Storage elastic modulus ratio % 6.1 6.1 6.1 6.1 Linear expansion coefficient ppm/°C 80 60 n% r· ZD 15 Warping _ XX 〇〇

[Examples 29 to 30, Comparative Example 26] (Evaluation of warpage of copper-clad multilayer fluororesin film) -61 - 201032680 The functional group-containing fluororesin film d2 was placed in a size of 150 mm x 150 mm. On one surface of the amine films a2 to a4, heat-pressure-molding was carried out at 330 ° C and 5 MPa which is equal to or higher than the melting point of the fluororesin film to obtain a (A) layer (B) layered body. Table 20 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layer (A) layered body obtained. Further, a functional group-containing fluororesin film d2 and a copper foil having a thickness of 9 cm (manufactured by UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) were placed in a polylayer of a copper-clad laminate (CCL) a2 to a4 cut to a size of 150 mm x 150 mm. The surface of the imine film a2 to a4 was subjected to heat and pressure molding at 30,000 t and 5 MPa which are equal to or higher than the melting point of the fluororesin film to obtain a double-sided copper-clad multilayer fluororesin film. The evaluation results of the obtained copper-clad multilayer fluororesin film are shown in Table 20. [Table 2 0]

Project unit Injury J 29 Example 30 Comparative Example 26 Polyimine film — a2 a3 a4 facial grease film d2 d2 d2 Thickness ratio % 83 71 50 Storage elastic modulus ratio % 6.1 6.1 6.1 Linear expansion coefficient ppm/. . 25 20 5 Warping — 〇 〇 X

[Application Example 2] The functional group-containing fluororesin film dl was placed on a polyimide film A2 surface of a copper clad laminate (CCL) a2 cut to a size of 150 mm x 150 mm - 62 - 201032680 on the fluororesin film The laminate was subjected to heat and pressure molding at 330 ° C and 5 MPa above the melting point for 30 minutes to prepare a multi-layer fluororesin film. On the other hand, using the copper-clad polyimide laminate obtained in Example 17, a photoresist (FR-200, manufactured by Shipley Co., Ltd.) was applied to the surface of the copper foil.

After drying, the film was subjected to a close exposure with a glass mask, and then developed with a 1.2 mass% KOH aqueous solution. Subsequently, etching was carried out at a spray pressure of 2 kgf/cm 2 at 40 ° C and a copper chloride etching machine containing hydrogen fluoride and hydrogen peroxide to form a test pattern A, followed by washing and annealing at 125 ° C for 1 hour. The copper-clad multilayer fluororesin film (printed wiring board) with a pattern is prepared. The pattern forming surface of the copper-clad multilayer fluororesin film (printed wiring board) with the pattern is opposed to the fluororesin surface of the multilayer fluororesin film, and is carried out at 30,000 ° C and 5 MPa above the melting point of the fluororesin film. The multilayer printed wiring board shown in Fig. 2 was obtained by heat and pressure molding for 30 minutes. In the multilayer printed wiring board produced, since the copper wiring is covered with a fluororesin having a low dielectric constant, it is extremely useful as a member for high frequency. Q [Industrial Applicability] The multilayer fluororesin film composed of the sequential laminated layer (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer of the first invention of the present application a multilayer fluororesin film having a linear expansion coefficient of 10 ppm/° C. to 30 ppm/° C. of the multilayer fluororesin film, and a copper-clad multilayer fluororesin film having a copper foil laminated on at least one side of the multilayer fluororesin film And a printed wiring board in which the copper foil is partially removed to form a circuit pattern, and the second invention of the present application forms a (C) copper layer on the (B) polyimine resin layer without an adhesive. Copper-clad-63- 201032680 (B) side of the laminate (CCL), further laminated with a multilayer fluororesin film of (A) fluororesin layer, wherein (A) layer (B) of the multilayer fluororesin film a multilayer fluororesin film having a linear expansion coefficient of 10 ppm/° C. to 30 ppm/° C. and a copper-clad multilayer fluororesin film having a copper foil laminated on the (A) surface of the multilayer fluororesin film and The copper foil is partially printed to form a circuit pattern to form a printed wiring board, and can withstand high temperature and high humidity processing. In addition to the fluororesin film and the copper foil, the quality of the printed wiring board, etc., and the yield at the time of production can be improved, and the manufacture of high-quality electronic components can be realized. Therefore, it is highly meaningful in the industry. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an example of a multilayer printed wiring of the first invention of the present application. Fig. 2 is a schematic view showing an example of the multilayer printed wiring of the second invention of the present application. [Main component symbol description] (Fig. 1) 1 Copper foil 2 Fluororesin film 3 Polyimide film (Fig. 2) 1 Copper layer 2 Fluororesin film 3 Polyimide film -64-

Claims (1)

201032680 VII. Patent application scope: 1. A multi-layer fluororesin film which is a multi-layer fluororesin film composed of (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer. Wherein the multilayer fluororesin film has a coefficient of linear expansion of from 10 〇 PPm / ° C to 30 ppm / ° C ' (A) thickness ratio of the layer {total (A) layer / multilayer fluororesin film} is 60% to 90%' And the (A) layer is composed of tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene·hexafluoropropylene copolymer (FEP), tetrafluoroethylene·hexafluoropropylene·perfluoroalkyl A thermoplastic fluoroquinone resin layer formed by any one of vinyl ether copolymers (EPE). 2. The multilayer fluororesin film according to claim 1, wherein the (A) layer is a functional group-containing thermoplastic fluororesin layer. 3. The multilayer fluororesin film according to claim 1 or 2, wherein the layer (B) is a polyimine layer having a polybenzonitrile benzoxazole component, and the coefficient of linear expansion is -10??111 /°〇~10?卩111/° (3. 4. The multilayer fluororesin film according to any one of claims 1 to 3, wherein the thickness of the (A) layer is 1.Oym~50"111 The (B) layer has a thickness of 1.0 μm to 38 μm. 5. The multilayer fluororesin film according to any one of claims 1 to 4, wherein (A) layer is stored at room temperature Elastic modulus: E' (A) and (B) layer storage elastic modulus at room temperature: E' (B) ratio {E' (A) / E' (B)} is 2.0 % ~ 2 0 6. A copper-clad multilayer fluororesin film which is laminated with at least one side of a multilayer fluororesin film according to any one of claims 1 to 5. -65- 201032680 7. a printed wiring board which is formed by removing a part of a copper foil of a copper-clad multilayer fluororesin film of claim 6 to form a circuit pattern. 8. A multilayer printed wiring board which is patented as claimed In items 1 to 7 of the scope A multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board are laminated to form a multilayer fluororesin film which is formed by forming a (C) copper layer without an adhesive. Β) a (poly) surface of a copper-clad laminate (CCL) of a polyimide film, a multilayer fluororesin film formed by laminating a fluororesin layer, wherein the multilayer fluororesin film The (Α) layer (Β) layered layer has a linear expansion coefficient of 10 ppm/°C to 30 ppm/°C, and the thickness ratio of the (Α) layer is _ {(A) layer/(A) layer (Β) layered layer body} 60% ~ 90%, and the (A) layer is composed of tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene hexafluoropropylene copolymer (FEP), tetrafluoroethylene hexafluoro A thermoplastic fluororesin layer formed by any one of a propylene-perfluoroalkyl vinyl ether copolymer (EPE). Q 10. A multilayer fluororesin film according to claim 9 wherein the (A) layer contains a functional group. A thermoplastic fluororesin layer. 11. A multilayer fluororesin film according to claim 9 or 10 wherein the (B) layer is a polyimine having a polybenzonitrile benzoxazole component. 'And the coefficient of linear expansion is -1 〇?? melon / ° (: ~ 1 (^? 111 / ° (: 12. 12. The multi-layer fluororesin film of any one of claims 9 to 11, wherein A) The thickness of the layer is 1. 〇Mm~5〇Mm, and the thickness of the (B) layer is -66 - .201032680. The multilayer fluororesin film according to any one of claims 9 to 12, wherein A) Storage elastic modulus at room temperature: E, (A) and (B) Storage elastic modulus at room temperature: E' (B) ratio (A) / E' (B)} It is 2.0%~20%. A copper-clad multilayer fluororesin film which is laminated with a copper foil on the (A) side of the multilayer fluororesin film according to any one of claims 9 to 13. A printed wiring board which removes a part of a copper layer of a multilayer fluororesin film and a copper-clad multilayer fluororesin film according to any one of claims 9 to 14 to form a circuit pattern. Composition. A multilayer printed wiring board comprising a multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board as disclosed in any one of claims 9 to 15. -67-