JP5625906B2 - Multilayer fluororesin film and printed wiring board - Google Patents

Description

  The present invention relates to a multilayer fluororesin film used for an electronic device, a flexible printed circuit board that is reduced in size and weight, a copper-coated multilayer fluororesin film laminated with a copper foil that is a metal foil, and a copper foil. The present invention relates to a printed wiring board formed by removing a part thereof to form a circuit pattern, and a multilayer printed wiring board formed by laminating them.

In general, improvement in transmission speed and reduction in noise are demanded in signal transmission in a high-frequency region, and studies on substrate materials, wiring technology, circuit form, etc. are also being advanced for flexible printed wiring boards.
Conventionally, a polyimide resin excellent in heat resistance is used as an electrical insulator layer in a flexible printed wiring board composed of a laminate having a conductor layer and an electrical insulator layer. The following three methods are used as a manufacturing method of the laminated body which consists of a polyimide resin layer and a conductor layer.
(1) A method of bonding a polyimide film and a copper foil through an adhesive layer,
(2) A method of forming a metal layer on a polyimide resin film by a method such as vapor deposition and / or metal plating,
(3) A method of coating a metal foil with a polyimide resin precursor, then forming a polyimide resin from the precursor by heat treatment or the like, and forming a polyimide resin layer on the metal foil (see Patent Document 1).
However, in such a method, the adhesiveness between the polyimide resin layer and the conductor layer is not sufficient, which may cause malfunction of the circuit. Further, since a propagation loss when a printed wiring board is large, it is not suitable as a high-frequency member.

It is disclosed that adhesion between the conductor layer and the electrical insulator layer is improved by forming irregularities of about 3 μm on the surface of the conductor layer on the side in contact with the electrical insulator layer (see Patent Document 2). ). However, in such a method, due to the skin effect in the high frequency region, the signal arrival time is shifted between the uneven surface and the non-roughened surface, so that the uneven surface needs to be made as low profile as possible.

A polyimide whose dielectric constant is reduced by dispersing inorganic fine particles such as silica in polyimide is disclosed. However, in such a method, since it is difficult to finely disperse inorganic fine particles in polyimide at a nano level, there is a problem that the surface smoothness and transparency of the polyimide film are impaired. When the surface smoothness is impaired, when a polyimide film is used as the base material of the printed board, the adhesion to the copper foil constituting the metal layer is inferior, and the quality of the printed board is lowered.

A polyimide having a specific structure having a reduced dielectric constant is disclosed by using an aromatic diamine compound in which two diphenyl ether structures having a t-butyl group having a low polarizability in the side chain are connected to each other by a linking group. (See Patent Document 3). However, in such a method, since it is necessary to use an aromatic diamine compound having a specific structure, it lacks versatility that it can be applied to polyimides having various structures.
After reacting an aromatic dianhydride and an aromatic diamine to obtain a polyamic acid in a solution state, the polyamic acid is rapidly heated to volatilize residual solvent and generated condensed water, thereby uniformly foaming. A polyimide foam is disclosed (see Patent Document 4). However, in such a method, it is difficult to form the polyamic acid into a film, and since it is a foam, the surface smoothness and transparency are impaired, and since it has bubbles, the mechanical strength is low. There is a problem of lowering.

  In general, it is known that when a fluorine atom is introduced into a polyimide molecule, the dielectric constant decreases. For example, a polyimide-metal composite film having a metal layer formed on the surface of a fluorinated polyimide film is disclosed (see Patent Document 5). Also disclosed is a multilayer wiring board using a fluorinated polyimide film as at least one selected from the group consisting of a base material, an adhesive layer and a surface protective film (see Patent Document 6). However, in such a method, as the content of fluorine atoms introduced into the polyimide molecule increases, the tensile modulus and tensile fracture strain of the polyimide film decrease, and the mechanical strength decreases. There's a problem.

  A laminate in which a fluororesin film having the smallest dielectric constant among plastics and a metal plate are laminated is disclosed (see Patent Document 7). However, such a method has a problem that the fluororesin film is peeled off from the metal plate by rubbing against the blade at the time of punching at a high speed, resulting in a decrease in yield. Further, the tensile strength and elongation, which are mechanical properties of the fluororesin film, are equivalent to polyolefin at room temperature, and the linear expansion coefficient is 60 ppm / ° C. to 160 ppm / ° C., for example, the linear expansion coefficient is 16 ppm / ° C. When laminated with a copper foil, there was a large difference between the linear expansion coefficients of each other, and there was a risk of peeling during use or warping.

JP 2004-001510 A JP 05-055546 A JP 2001-323061 A Japanese Patent Laid-Open No. 2004-325441 Japanese Patent No. 2866155 JP 2001-308542 A JP 2002-125297 A

  The present invention has a feature of polyimide resin by using a polyimide resin having a core that is less deformed and having excellent heat resistance even when subjected to high temperature treatment, which is suitable as a base material for electronic components, and arranging a fluororesin on the surface. A certain low linear expansion coefficient (linear expansion coefficient equivalent to copper foil as a multilayer fluororesin film), high mechanical properties, low dielectric constant and low water absorption (reducing the high water absorption of polyimide), which are the characteristics of fluororesin An object is to provide a compatible multilayer fluororesin film, a copper-clad multilayer fluororesin film, a printed wiring board, a multilayer printed wiring board, and the like.

As a result of intensive studies, the present inventors have found that a multilayer fluororesin film in which a fluororesin layer is laminated on both sides of a polyimide film is used for a copper-clad laminate, a printed wiring board, an FPC, a TAB tape, a COF tape film, and the like. The present invention was completed by finding that a product that does not peel off at high temperature and high humidity and has excellent electrical characteristics can be obtained.
That is, the first invention of the present application has the following configuration.
1. (A) Fluororesin layer / (B) Polyimide resin layer / (A) Fluororesin layer is a multilayer fluorinated resin film laminated in this order, and the linear expansion coefficient of the multilayer fluorinated resin film is 10 ppm / ° C. to 30 ppm / C, the thickness ratio of the (A) layer {total (A) layer / multilayer fluororesin film} is 60% to 90%, and the (A) layer is co-polymerized with tetrafluoroethylene / perfluoroalkyl vinyl ether. It is a thermoplastic fluororesin layer made of polymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), or tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer (EPE). A multilayer fluororesin film.
2. (A) The layer is a layer of a functional group-containing thermoplastic fluororesin. Multilayer fluororesin film.
3. (B) The layer is a polyimide layer having a polyimide benzoxazole component, and the linear expansion coefficient is −10 ppm / ° C. to 10 ppm / ° C. Or 2. Multilayer fluororesin film.
4). (A) The thickness of the layer is 1.0 μm to 50 μm, and (B) the thickness of the layer is 1.0 μm to 38 μm. ~ 3. Any multilayer fluororesin film.
5. (A) Storage elastic modulus at room temperature of layer: E ′ (A) and storage elastic modulus at room temperature of layer (B): ratio of E ′ (B) {E ′ (A) / E ′ (B)} Is 2.0% to 20%. ~ 4. 5. Any multilayer fluororesin film 1. ~ 5. A copper-coated multilayer fluororesin film in which a copper foil is laminated on at least one surface of any multilayer fluororesin film.
7). 6). A printed wiring board formed by removing a part of the copper foil of the copper-coated multilayer fluororesin film to form a circuit pattern.
8). 1. ~ 7. A multilayer printed wiring board formed by laminating any one of the multilayer fluorine resin films, the copper-coated multilayer fluorine resin film, and the printed wiring board.
The second invention of the present application has the following configuration.
9. (B) A multilayer fluororesin film in which (A) a fluororesin layer is further laminated on the (B) surface of a copper-clad laminate (CCL) in which a copper layer is formed without using an adhesive on the polyimide resin layer (C) The linear expansion coefficient of the (A) layer (B) layer laminate in the multilayer fluororesin film is 10 ppm / ° C. to 30 ppm / ° C., and (A) layer thickness ratio {(A) layer / (A) layer (B) layer laminate} is 60% to 90%, and the (A) layer is a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), a tetrafluoroethylene / hexafluoropropylene copolymer. A multilayer fluororesin film which is a thermoplastic fluororesin layer made of any one of a polymer (FEP) and a tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer (EPE). Film.
10. (A) The layer is a layer of a functional group-containing thermoplastic fluororesin. Multilayer fluororesin film.
11. (B) The layer is a polyimide layer having a polyimide benzoxazole component, and the linear expansion coefficient is −10 ppm / ° C. to 10 ppm / ° C. Or 10. Multilayer fluororesin film.
12 (A) The thickness of the layer is 1.0 μm to 50 μm, and the (B) layer is 1.0 μm to 38 μm. ~ 11. Any multilayer fluororesin film.
13. (A) Storage elastic modulus at room temperature of layer: E ′ (A) and storage elastic modulus at room temperature of layer (B): ratio of E ′ (B) {E ′ (A) / E ′ (B)} Is 2.0% to 20%. -12. A copper-laminated multilayer fluororesin film in which a copper foil is laminated on the (A) surface of any multilayer fluororesin film 14.9-13.
A printed wiring board formed by removing a part of the copper layer of the multilayer fluororesin film of any one of 15.9 to 14 and the copper-clad multilayer fluororesin film to form a circuit pattern.
The multilayer printed wiring board formed by laminating | stacking the multilayer fluorine resin film in any one of 16.9-15, a copper adhesion multilayer fluorine resin film, and a printed wiring board.

The multilayer fluororesin film in which the (A) fluororesin layer / (B) polyimide resin layer / (A) fluororesin layer of the first invention of the present application is laminated in this order has a low linear expansion coefficient ( As a multilayer fluororesin film, it is possible to achieve both the linear expansion coefficient equivalent to copper foil), high mechanical properties, low dielectric constant and low water absorption (reducing the high water absorption of polyimide), which are the characteristics of fluororesin. It is a multilayer film.
The (A) fluororesin layer is further laminated on the (B) surface of the copper-clad laminate (CCL) in which the (C) copper layer is formed on the (B) polyimide resin layer of the second invention of the present application without using an adhesive. A multilayer fluororesin film having a linear expansion coefficient of 10 ppm / ° C. to 30 ppm / ° C. of the (A) layer (B) layer laminate in the multilayer fluororesin film is a polyimide resin Features low linear expansion coefficient (linear expansion coefficient equivalent to copper foil as a multilayer fluororesin film), high mechanical properties, low dielectric constant and low water absorption (features high water absorption of polyimide) ).
The multilayer fluororesin film of the present invention is excellent in adhesion to copper foil, and has a small deviation from the linear expansion coefficient of copper foil of 16 ppm / ° C. and low water absorption rate. Even underneath, warping and distortion hardly occur, and as a result, the quality of the obtained printed wiring board and the production yield are improved.
The copper-coated multilayer fluororesin film, the printed wiring board, and the multilayer printed wiring board using the multilayer fluororesin film of the present invention are used as electronic parts exposed to high temperatures, and warp or strain of the base material during the production thereof. The production of high-quality electronic components without yielding of the multilayer fluororesin film and the copper foil and the improvement of the yield can be realized, which is extremely meaningful in the industry.

It is the schematic which shows an example of the multilayer printed wiring of 1st invention of this application. It is the schematic which shows an example of the multilayer printed wiring of 2nd invention of this application.

The present invention is described in detail below.
The (A) fluororesin layer used in the present invention is formed by applying a fluororesin film obtained by casting a fluororesin melt into a film, or applying the fluororesin melt to a polyimide resin layer (film). In view of handling and productivity, the form of a fluororesin film is preferable.
The fluororesin can be appropriately selected from conventionally known thermoplastic fluororesins used for general molding.
Examples of thermoplastic fluororesins include polymers or copolymers such as unsaturated fluorinated hydrocarbons, unsaturated fluorinated chlorinated hydrocarbons, ether group-containing unsaturated hydrocarbons, or these unsaturated fluorinated hydrocarbons. Examples include ethylene copolymers. Specific examples include polymers or copolymers of monomers selected from tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether), vinylidene fluoride and vinyl fluoride, or these monomers and Examples include ethylene copolymers.
More specific examples of thermoplastic fluororesin include tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / hexafluoropropylene / per Fluoroalkyl vinyl ether copolymer (EPE), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE) ) And the like.

Among these, from the viewpoints of heat resistance, flame retardancy, and electrical properties, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (PFA), which is a copolymer of perfluorine ( FEP) and tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer (EPE) are preferred.

The fluororesin is more preferably a functional group-containing thermoplastic fluororesin. When a thermoplastic fluororesin that does not contain a functional group is used, it is necessary to subject the polyimide film to surface treatment such as honing treatment, corona treatment, plasma treatment, ion gun treatment, and etching treatment in order to obtain adhesiveness that can withstand practical use. Therefore, the cost may increase.
The thermoplastic fluororesin containing a functional group includes a carboxylic acid group or a derivative group thereof, a hydroxyl group, a nitrile group, a cyanato group, a carbamoyloxy group, a phosphonooxy group, a halophosphonooxy group, a sulfonic acid group or a derivative group thereof, and a sulfo group. Mention may be made of thermoplastic fluororesins (functional group-containing fluororesins) containing functional groups selected from halide groups. Thus, as the functional group-containing fluororesin, a thermoplastic fluororesin usually used in the general molding is used in which the functional group is contained within a range that does not significantly impair the properties. In order to obtain such a functional group-containing fluororesin, for example, a thermoplastic fluororesin as shown in the above example used for general molding is synthesized and then introduced by adding or substituting these functional groups. Alternatively, it can be obtained by copolymerizing monomers having these functional groups during the synthesis of the thermoplastic fluororesin exemplified above.

Specific examples of the functional group include -COOH, -CH2COOH, -COOCH3, -CONH2, -OH, -CH2OH, -CN, -CH2O (CO) NH2, -CH2OCN, -CH2OP (O) (OH) 2,- Groups such as CH2OP (O) Cl2 and -SO2F can be exemplified. These functional groups are preferably introduced into the fluororesin by copolymerizing a fluorine-containing monomer having a functional group during the production of the fluororesin.

These monomers containing functional groups are preferably copolymerized in the functional group-containing fluororesin in an amount of 0.5 to 10% by weight, more preferably 1 to 5% by weight. Distribution of the functional group-containing monomer in the functional group-containing fluororesin may be uniform or non-uniform. If the content ratio of the functional group-containing monomer in the functional group-containing fluororesin is too small, the effect as a compatibilizer is small, while if the content ratio increases, the functional group-containing fluororesin resembles a cross-linking reaction due to strong interaction between the functional group-containing fluororesins. Reactions can occur and the viscosity can suddenly increase, making melt molding difficult. Moreover, when the content rate of a functional group containing monomer increases, there exists a tendency for the heat resistance of a functional group containing fluororesin to worsen.
There is no particular limitation on the viscosity or molecular weight of the functional group-containing fluororesin, but it is within the range not exceeding the viscosity or molecular weight of the thermoplastic fluororesin for general molding blended with these functional group-containing fluororesins, preferably the same. Good level.
The fluororesin preferably contains 0.1 to 2% by mass of an antistatic agent that imparts antistatic properties. As the antistatic agent, surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants are preferable.

The fluororesin preferably contains an inorganic filler that lowers the dielectric constant and dielectric loss tangent. Inorganic fillers include silica, clay, talc, calcium carbonate, mica, diatomaceous earth, alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium hydroxide, magnesium hydroxide, water Aluminum oxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, calcium silicate, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass Examples include beads, silica-based balloons, carbon black, graphite, carbon fibers, carbon balloons, wood powder, and zinc borate.
The inorganic filler may be used alone or in combination of two or more. As for content of an inorganic filler, 1-100 mass% is preferable with respect to a fluororesin. Further, it is preferable that these inorganic fillers are porous because the dielectric constant and dielectric loss tangent are further reduced.

The thickness of the fluororesin layer is preferably 1.0 μm to 50 μm, more preferably 1.0 μm to 38 μm, and still more preferably 1.0 μm to 25 μm. Thicknesses greater than 50 μm are not preferred for the purpose of reducing the weight of electronic components. On the other hand, a film thickness of less than 1.0 μm is not preferable because surface modification effects such as improvement of electrical characteristics, reduction of water absorption, and improvement of adhesiveness due to the fluororesin are reduced.
The storage elastic modulus: E ′ (A) of the fluororesin layer is not particularly limited, and it is known that a value of 0.3 GPa to 1.0 GPa is generally used when the fluororesin having the above composition is used.
Moreover, the linear expansion coefficient of the said fluororesin layer is not specifically limited, If it uses the fluororesin of the said composition, generally taking the value of 50 ppm / degrees C-150 ppm / degrees C is known.
Furthermore, it is preferable that the dielectric constant and dielectric loss tangent of the film are small from the viewpoint of high frequency response. The dielectric constant and dielectric loss tangent of the fluororesin layer are not particularly limited, and it is known that generally low values are obtained when the fluororesin having the composition is used. Specifically, the dielectric constant at 1 MHz is 2.0 to 2.2, and the dielectric loss tangent at 1 MHz is 3.0 × 10 ^{−4 to} 5.0 × 10 ⁻⁴ .
The surface of the fluororesin layer is subjected to a treatment with a coupling agent (aminosilane, epoxysilane, etc.), a sand plast treatment, a rolling treatment, a corona treatment, a plasma treatment, an ion gun treatment, an etching treatment as necessary. Also good.

The (B) polyimide resin layer used in the present invention is composed of, for example, aromatic tetracarboxylic acids (anhydrides, acids, and amide bond derivatives are collectively referred to as classes below) and aromatic diamines (amines and amide bonds). A polyimide film obtained by a method of casting, drying, heat treatment (imidization) to form a film, and the polyamic acid solution. Is a layer formed by applying to a fluororesin layer (film), drying, and heat-treating (imidizing), and the form of polyimide film is preferable from the viewpoint of handling and productivity.
Hereinafter, the polyimide film will be mainly described in detail.
Although the said polyimide is not specifically limited, The combination of the following aromatic diamine and aromatic tetracarboxylic acid (anhydride) is mentioned as a preferable example.
A. Combination with aromatic tetracarboxylic acid having pyromellitic acid residue and aromatic diamine having benzoxazole structure.
B. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
C. A combination of an aromatic diamine having a diphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyromellitic acid residue.
In particular, A. A polyimide film having an aromatic diamine residue having a benzoxazole structure is preferred.

  The molecular structure of the aromatic diamines having the benzoxazole structure is not particularly limited, and specific examples include the following. These diamines are preferably 70 mol% or more, more preferably 80 mol% or more of the total diamine.

  Among these, from the viewpoint of easy synthesis, each isomer of amino (aminophenyl) benzoxazole is preferable, and 5-amino-2- (p-aminophenyl) benzoxazole is more preferable. Here, “each isomer” refers to each isomer in which two amino groups of amino (aminophenyl) benzoxazole are determined according to the coordination position (eg, the above “formula 1” to “formula 4”). Each compound described in the above. These diamines may be used alone or in combination of two or more.

  Furthermore, as long as it is 30 mol% or less of the total diamine, one or more of the diamines exemplified below may be used in combination. Examples of such diamines include 4,4′-bis (3-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, and bis [4- (3-aminophenoxy) phenyl]. Sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3′-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-dia Nodiphenyl sulfide, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4 , 4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 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-amino) Phenoxy) phenyl] ethane, 1,1-bis [4- 4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-aminophenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, , 4-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-a Minophenoxy) -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] -1,1,1,3,3,3-hexa Fluoropropane, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4 -Aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-amino) Enoxy) phenyl] sulfoxide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1, 3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] Benzene, 4,4′-bis [(3-aminophenoxy) benzoyl] 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-bis [4- (3-aminophenoxy) phenyl] ethane, 1 , 2-bis [4- (3-aminophenoxy) phenyl] ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-Amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, bis [4- {4- (4-aminophenoxy) phenoxy} fe Sulfone, 1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethyl Benzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluoro) Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4 -Amino-6-cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-dipheno Cibenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamino-5-phenoxybenzophenone, 3,4'-diamino- 4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3,4′-diamino-4,5′-dibiphenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 4,4′-diamino-5-biphenoxybenzophenone, 3,4′-diamino-4 -Biphenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone 1,3-bis (3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) Benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-bi) Phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- ( 4-amino-α, α-dimethylbenzyl) phenoxy] benzonitrile and some or all of the hydrogen atoms on the aromatic ring of the aromatic diamine are halogen atoms, An alkyl group having 1 to 3 carbon atoms, an alkoxyl group, a cyano group, or an alkyl group or an alkoxyl group having 1 to 3 carbon atoms in which some or all of the hydrogen atoms of the alkyl group or alkoxyl group are substituted with halogen atoms. Examples thereof include substituted aromatic diamines.

  The molecular structure of the aromatic tetracarboxylic acid anhydrides is not particularly limited, and specific examples include the following. These acid anhydrides are preferably 70 mol% or more, more preferably 80 mol% or more of the total acid anhydride.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
Furthermore, as long as it is 30 mol% or less of the total tetracarboxylic dianhydrides, one or more of the non-aromatic tetracarboxylic dianhydrides exemplified below may be used in combination. Examples of such tetracarboxylic acid anhydrides include butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutanetetracarboxylic acid. Acid 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-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3 -(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride 1-ethylcyclohexane -(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-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, bisic [2.2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride An anhydride etc. are mentioned.

  The solvent used when reacting (polymerizing) the aromatic tetracarboxylic acid and the aromatic diamine to obtain a polyamic acid is particularly suitable as long as it can dissolve both the raw material monomer and the produced polyamic acid. Although not limited, polar organic solvents are preferred, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, dimethyl Examples thereof include sulfoxide, hexamethylphosphoric amide, ethyl cellosolve acetate, diethylene glycol dimethyl ether, sulfolane, and halogenated phenols. These solvents can be used alone or in combination. The amount of the solvent used may be an amount sufficient to dissolve the monomer as a raw material. As a specific amount used, the weight of the monomer in the solution in which the monomer is dissolved is usually 5 to 40% by weight, The amount is preferably 10 to 30% by weight.

  Conventionally known conditions may be applied for the polymerization reaction for obtaining the polyamic acid (hereinafter also simply referred to as “polymerization reaction”). As a specific example, in a temperature range of 0 to 80 ° C., 10 Stirring and / or mixing continuously for minutes to 30 hours. If necessary, the polymerization reaction may be divided or the temperature may be increased or decreased. In this case, the order of adding both monomers is not particularly limited, but it is preferable to add aromatic tetracarboxylic acid anhydrides to the solution of aromatic diamines. The viscosity of the polyamic acid solution obtained by the polymerization reaction is measured with a Brookfield viscometer (25 ° C.), and is preferably 10 to 2000 Pa · s, more preferably 100 to 1000 Pa · s, from the viewpoint of the stability of liquid feeding. It is.

Vacuum defoaming during the polymerization reaction is effective for producing a good quality polyamic acid solution. Moreover, you may perform superposition | polymerization by adding a small amount of terminal blockers to aromatic diamines before a polymerization reaction. Examples of the end capping agent include compounds having a carbon-carbon double bond such as maleic anhydride. The amount of maleic anhydride used is preferably 0.001 to 1.0 mol per mol of aromatic diamine.
In order to form a polyimide film from the polyamic acid solution obtained by the polymerization reaction, a green film (a self-supporting precursor film is obtained by applying the polyamic acid solution on a support and drying, then, Examples of the method of imidization reaction by subjecting the green film to heat treatment include, but are not limited to, application of the polyamic acid solution to the support, including casting from a slit-attached base and extrusion by an extruder. A conventionally known solution coating means can be appropriately used.

  The conditions for drying the polyamic acid coated on the support to obtain a green sheet are not particularly limited, and examples include a temperature of 70 to 150 ° C. and a drying time of 5 to 180 minutes. A conventionally known drying apparatus that satisfies such conditions can be applied, and examples thereof include hot air, hot nitrogen, far infrared rays, and high frequency induction heating. Next, in order to obtain a target polyimide film from the obtained green sheet, an imidization reaction is performed. As a specific method thereof, a conventionally known imidation reaction can be appropriately used. For example, there may be mentioned a method (so-called thermal ring closure method) in which an imidization reaction proceeds by subjecting it to a heat treatment after performing a stretching treatment as necessary using a polyamic acid solution containing no ring closure catalyst or a dehydrating agent. The heating temperature in this case is exemplified by 100 to 500 ° C. From the viewpoint of film physical properties, more preferably, a two-stage heat treatment in which the treatment is performed at 150 to 250 ° C. for 3 to 20 minutes and then treatment at 350 to 500 ° C. for 3 to 20 minutes. Is mentioned.

  Another example of the imidization reaction is a chemical ring closure method in which a polyamic acid solution contains a ring closure catalyst and a dehydrating agent, and the imidization reaction is performed by the action of the ring closing catalyst and the dehydrating agent. In this method, after the polyamic acid solution is applied to the support, the imidization reaction is partially advanced to form a film having self-supporting property, and then imidization can be performed completely by heating. In this case, the condition for partially proceeding with the imidization reaction is preferably a heat treatment for 3 to 20 minutes at 100 to 200 ° C., and the condition for allowing the imidization reaction to be completely performed is preferably 200 to 400 ° C. For 3 to 20 minutes.

As for the thickness of the polyimide film which forms the said polyimide resin layer, 1.0 micrometer-38 micrometers are preferable, More preferably, they are 1.0 micrometer-25 micrometers, More preferably, they are 1.0 micrometer-12.5 micrometers. A film thickness greater than 38 μm is not preferred for the purpose of reducing the weight of electronic components. Moreover, since the ratio of the polyimide with respect to the whole laminated body becomes high and exerts a bad influence on physical properties, such as a water absorption rate and an electrical property, it is unpreferable. On the other hand, if the film thickness is less than 1.0 μm, film formation is very difficult because the film is easily broken during conveyance and easily wrinkled.
The storage elastic modulus: E ′ (B) of the polyimide film forming the polyimide resin layer is not particularly limited, but is preferably 6.0 GPa or more, more preferably 7.0 GPa or more, and even more preferably 8.0 GPa or more. . If the tensile strength at break is less than 6 GPa, the effect of reinforcing the fluororesin layer by the polyimide film may not be obtained.
The linear expansion coefficient of the polyimide film forming the polyimide resin layer is preferably −10 ppm / ° C. to 10 ppm / ° C., more preferably −7.5 ppm / ° C. to 7.5 ppm / ° C., more preferably − 5 ppm / ° C to 5 ppm / ° C. If the linear expansion coefficient exceeds this range, distortion and wrinkles may occur during high temperature exposure such as soldering.
For the polyimide film forming the polyimide resin layer, treatment with a coupling agent (aminosilane, epoxysilane, etc.), sandplast treatment, rolling treatment, corona treatment, plasma treatment, ion gun treatment, etching treatment, etc. You may use for.

The method for producing a copper-clad laminate (CCL) in which (C) a copper layer is formed on the polyimide resin layer (B) used in the second invention of the present application is not particularly limited, and the following means are exemplified. The
A means for forming a copper layer on a polyimide film using vacuum coating techniques such as vapor deposition, sputtering, and ion plating.
A means for forming a copper layer on a polyimide film by a wet plating method such as electroless plating or electroplating.
-Means for applying a polyamic acid solution to a copper foil, drying and heat-treating (imidization).
By combining these means alone or in combination, the copper layer (C) can be formed on the (B) polyimide resin layer without using an adhesive.

In the present invention, the linear expansion coefficient of the multilayer fluororesin film is preferably 10 ppm / ° C. to 30 ppm / ° C., more preferably 10 ppm / ° C. to 28 ppm / ° C., and further preferably 10 ppm / ° C. to 25 ppm / ° C. When the coefficient of linear expansion exceeds this range, when laminated with a copper foil having a coefficient of linear expansion of 16 ppm / ° C, the difference between the coefficients of linear expansion is large, and there is a risk of peeling during use or warping. There is a fear.
In order to make the linear expansion coefficient of the multilayer fluororesin film within the range of 10 ppm / ° C. to 30 ppm / ° C., the thickness ratio of the (A) layer in the multilayer fluororesin film {total (A) layer / multilayer fluororesin film} Is 60% to 90%, and the storage elastic modulus of the layer (A) at room temperature: E ′ (A) and the storage elastic modulus of the layer (B) at room temperature: E ′ (B) ratio {E ′ (A) / E ′ (B)} is preferably 2.0% to 20%, more preferably a thickness ratio of 65% to 90% and a storage modulus ratio of 2.5% to 15%. More preferably, the thickness ratio is 65% to 85%, and the storage modulus ratio is 3.0% to 10%.
When the thickness ratio or the storage elastic modulus ratio exceeds this range, a multilayer fluororesin film having a target linear expansion coefficient cannot be obtained.

The thickness of the copper foil used in the present invention is preferably 1.0 μm to 25 μm, more preferably 1.0 μm to 12.5 μm, and still more preferably 1.0 μm to 10 μm.
The copper foil lamination method for the copper-clad multilayer fluororesin film used in the present invention is not particularly limited, and the following means are exemplified.
-Means for welding by hot pressing after laminating the multilayer fluororesin film and copper foil.
-Means for forming a copper layer on a multilayer fluororesin film using vacuum coating techniques such as vapor deposition, sputtering, and ion plating.
A means for forming a copper layer on a multilayer fluororesin film by a wet plating method such as electroless plating or electroplating.
A copper foil can be laminated on at least one side of the multilayer fluororesin film (on the (A) side of the multilayer fluororesin film in the second invention of the present application) by combining these means alone or in combination.

  The multilayer fluororesin film or copper-laminated multilayer fluororesin film of the present invention can be obtained by applying a photoresist on the side of a conductive copper foil layer or a post-added thick film metal layer formed on the conductive copper foil layer, if necessary. After applying and drying, a wiring circuit pattern is formed by the steps of exposure, development, etching, and photoresist peeling, and further, solder resist coating, plastic and electroless tin plating are performed as necessary, flexible printed wiring boards, and multilayered A multi-layer printed wiring board or a printed wiring board on which a semiconductor chip is directly mounted is obtained. There are no particular limitations on the method for creating these circuits, making them multi-layered, and mounting a semiconductor chip, and the methods may be appropriately selected from known methods.

  An inorganic coating such as a single metal or a metal oxide may be formed on the surface of the copper foil layer used in the present invention or, if necessary, the post-attached thick film metal layer. In addition, the surface of the copper foil layer or a post-added thick film metal layer formed on the copper foil layer, if necessary, is treated with a coupling agent (aminosilane, epoxysilane, etc.), sandplast treatment, rolling treatment, corona treatment, You may use for a plasma process, an ion gun process, an etching process, etc.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated more concretely, this invention is not limited by a following example. In addition, the evaluation method of the physical property in the following examples is as follows.

1. Reduced viscosity (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube.
2. Thickness The film to be measured was measured using a micrometer (Minetron 1245D, manufactured by Finelfu).

3. About the film | membrane of storage elastic modulus measurement object, viscoelasticity measurement (DMA) was performed on the following conditions, and the value of storage elastic modulus: E 'in 25 degreeC was calculated | required.
Device name: Rheogel-E4000 manufactured by UBM
Jig: Stretch jig
Sample length: 14mm
Sample width: 5 mm
Frequency: 10Hz
Temperature rise start temperature: 0 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Nitrogen

4). Linear expansion coefficient (CTE)
For the film to be measured, the stretch rate in the MD direction and the TD direction is measured under the following conditions, and the stretch rate / temperature at intervals of 90 to 100 ° C., 100 to 110 ° C.,. Was performed up to 400 ° C, and the average value of all measured values from 100 ° C to 350 ° C was calculated as CTE (average value).
Device name: TMA4000S manufactured by MAC Science
Sample length: 10mm
Sample width: 2mm
Initial load: 34.5 g / mm ²
Temperature rise start temperature: 25 ° C
Temperature rise end temperature: 400 ° C
Temperature increase rate: 5 ° C / min
Atmosphere: Argon

5. The film to be measured was subjected to differential scanning calorimetry (DSC) under the following conditions, and the melting point (Tm) was determined according to JIS K7121.
Device name: DSC3100S manufactured by MAC Science
Bread: Aluminum bread (non-airtight type)
Sample mass: 4mg
Temperature rising start temperature: 30 ° C
Temperature rise end temperature: 400 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Argon A fluororesin film to be measured for dielectric constant and dielectric loss tangent was cut into a size of 3 mm (thickness) × 200 mm × 120 mm to prepare a test film. Conductive paste was applied to both sides of the test film and wired, and the dielectric constant and dielectric loss tangent at 1 MHz were measured.

7). Peel strength The peel strength between the multilayer fluororesin film / copper foil was determined by conducting a 90 ° peel test under the following conditions.
Device name: Autograph AG-IS, manufactured by Shimadzu Corporation
Sample length: 100mm
Sample width: 10mm
Measurement temperature: 25 ° C
Peeling speed: 50mm / min
Atmosphere: Atmosphere

<< Evaluation of Substrate >> Moist Heat Resistance Multilayer Fluoropolymer Films and Copper-Coated Multilayer Fluoropolymer Films are Treated under JEDEC LEVEL1 Conditions (85 ° C / 85% RH-168hr + 245 ° C / 3sec × 3 times), and peeling after test The strength was evaluated. In addition, in the appearance inspection after the test, the case where peeling, blistering, or discoloration was not observed was indicated as “◯”, the case where peeling, blistering, or discoloration was slightly observed was indicated as Δ, and the case where peeling, blistering, or discoloration was observed was indicated as “X”.
<< Evaluation of Substrate >> Heat Resistance The multilayer fluororesin film and each copper-laminated multilayer fluororesin film were placed in a stainless mesh cage and subjected to heat treatment at 250 ° C. for 24 hours in the atmosphere to evaluate the peel strength after the test. In addition, in the appearance inspection after the test, the case where peeling, blistering, or discoloration was not observed was indicated as “◯”, the case where peeling, blistering, or discoloration was slightly observed was indicated as Δ, and the case where peeling, blistering, or discoloration was observed was indicated as “X”.

[Production Example 1]
(Preparation of polyimide film A)
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole and 4416 parts by mass of N, N-dimethylacetamide were added. 40.5 parts by mass of Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) (containing 8.1 parts by mass of silica), pyromellitic acid, which is prepared by completely dissolving the colloidal silica in dimethylacetamide. When 217 parts by mass of dianhydride was added and stirred for 24 hours at a reaction temperature of 25 ° C., a brown and viscous polyamic acid solution A was obtained. This reduced viscosity was 3.9 dl / g.
This polyamic acid solution A was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage 150 ° C. × 2 minutes, the second stage 220 ° C. × 2 minutes, the third stage 475 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-sided free process, and finally slit to 500 mm width to obtain polyimide films A1 to A4.
Table 1 shows the physical property values of the obtained polyimide films A1 to A4.

[Production Example 2]
(Preparation of polyimide film B)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 200 parts by mass of diaminodiphenyl ether and 4170 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica was added. 40.5 parts by mass of Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) dispersed in dimethylacetamide (containing 8.1 parts by mass of silica), 217 parts by mass of pyromellitic dianhydride were added, and 25 ° C. When the mixture was stirred at the reaction temperature of 5 hours, a brown viscous polyamic acid solution B was obtained. This reduced viscosity was 3.6 dl / g. This polyamic acid solution B was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage is 150 ° C. × 2 minutes, the second stage is 220 ° C. × 2 minutes, the third stage is 400 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-side free process, and finally slit to 500 mm width to obtain polyimide film B.
Table 1 shows the physical property values of the obtained polyimide film B.

[Production Example 3]
(Preparation of polyimide film C)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, 108 parts by mass of phenylenediamine and 4010 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica was added. Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) 40.5 parts by mass (including 8.1 parts by mass of silica) dispersed in dimethylacetamide and 292.5 parts by mass of diphenyltetracarboxylic dianhydride In addition, when the mixture was stirred at a reaction temperature of 25 ° C. for 12 hours, a brown viscous polyamic acid solution C was obtained. This reduced viscosity was 4.3 dl / g.
This polyamic acid solution C was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage is 150 ° C. × 2 minutes, the second stage is 220 ° C. × 2 minutes, the third stage is 460 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-side free process, and finally slit to a width of 500 mm to obtain a polyimide film C having a thickness of 25 μm.
Table 1 shows the physical property values of the obtained polyimide film C.

[Production Example 4]
(Create fluororesin film)
Using a commercially available fluororesin, a fluororesin film was prepared by a conventionally known method.
The types and physical properties of the obtained fluororesin film are shown in Tables 2 and 3.
In the figure, PAF is a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, FEP is a tetrafluoroethylene / hexafluoropropylene copolymer, EPE is a tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, ETFE represents a tetrafluoroethylene / ethylene copolymer.

[Production Example 5]
(Preparation of polyimide film a)
The inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, and then 223 parts by mass of 5-amino-2- (p-aminophenyl) benzoxazole and 4416 parts by mass of N, N-dimethylacetamide were added. 40.5 parts by mass of Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) (containing 8.1 parts by mass of silica), pyromellitic acid, which is prepared by completely dissolving the colloidal silica in dimethylacetamide. When 217 parts by mass of dianhydride was added and stirred for 24 hours at a reaction temperature of 25 ° C., a brown and viscous polyamic acid solution A was obtained. This reduced viscosity was 3.9 dl / g.
This polyamic acid solution A was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage 150 ° C. × 2 minutes, the second stage 220 ° C. × 2 minutes, the third stage 475 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-side free process, and finally slit to 500 mm width to obtain polyimide films a1 to a4.
Table 11 shows the physical properties of the obtained polyimide films a1 to a4.
Next, sputtering and plating were performed.
The polyimide films a1 to a4 were cut to A4 size and fixed by being sandwiched between stainless steel frames having openings. This frame was fixed to a substrate holder in the sputtering apparatus. The substrate holder and the polyimide film are fixed in close contact. For this reason, the temperature of a polyimide film can be set by flowing a refrigerant in a substrate holder. Next, plasma treatment of the polyimide film surface was performed. The plasma treatment conditions were as follows: argon gas, frequency 13.56 MHz, output 200 W, gas pressure 1 × 10 ⁻³ Torr, treatment temperature 2 ° C., treatment time 2 minutes. Next, a frequency of 13.56 MHz, an output of 450 W, a gas pressure of 3 × 10 ⁻³ Torr, a nickel-chromium (chromium 10 mass%) alloy target, and a DC magnetron sputtering method in an argon atmosphere, 1 nm / second. A nickel-chromium alloy film (underlayer) having a thickness of 7 nm is formed at a rate of 2 mm, and then, the refrigerant whose temperature is controlled to 2 ° C. on the back surface of the sputtered surface of the substrate is set so that the substrate temperature is set to 2 ° C. Washed away. Next, sputtering was performed in contact with the SUS plate of the substrate holder to form a copper thin film having a thickness of 0.25 μm, thereby obtaining single-side underlying metal thin film-forming polyimide films a1 to a4. Here, the thickness of the copper and NiCr layers was confirmed by a fluorescent X-ray method. The obtained single-sided underlying metal thin film forming polyimide films a1 to a4 were fixed to a plastic frame, and a copper layer having a thickness of 9 μm was formed using a copper sulfate plating bath. The electrolytic plating conditions were immersion in an electrolytic plating solution (copper sulfate 80 g / l, sulfuric acid 210 g / l, HCl, a small amount of brightener), and electricity was passed through 1.5 Adm ² . Then, it heat-dried at 120 degreeC for 10 minute (s), and obtained copper bonding laminated board (CCL) a1-a4 which is a polyimide film which formed the copper layer in the single side | surface.

[Production Example 6]
(Preparation of polyimide film b)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was purged with nitrogen, 200 parts by mass of diaminodiphenyl ether and 4170 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica was added. 40.5 parts by mass of Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) dispersed in dimethylacetamide (containing 8.1 parts by mass of silica), 217 parts by mass of pyromellitic dianhydride were added, and 25 ° C. When the mixture was stirred at the reaction temperature of 5 hours, a brown viscous polyamic acid solution B was obtained. This reduced viscosity was 3.6 dl / g. This polyamic acid solution B was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage is 150 ° C. × 2 minutes, the second stage is 220 ° C. × 2 minutes, the third stage is 400 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-side free process, and finally slit to 500 mm width to obtain a polyimide film b.
Table 11 shows the physical property values of the obtained polyimide film b.
Next, sputtering and plating were performed in the same manner as in Production Example 5 to obtain a copper-clad laminate (CCL) b.

[Production Example 7]
(Preparation of polyimide film c)
After the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod was replaced with nitrogen, 108 parts by mass of phenylenediamine and 4010 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal silica was added. Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) 40.5 parts by mass (including 8.1 parts by mass of silica) dispersed in dimethylacetamide and 292.5 parts by mass of diphenyltetracarboxylic dianhydride In addition, when the mixture was stirred at a reaction temperature of 25 ° C. for 12 hours, a brown viscous polyamic acid solution C was obtained. This reduced viscosity was 4.3 dl / g.
This polyamic acid solution C was coated on a non-lubricant surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 110 ° C. for 5 minutes, and then not peeled off from the support. The polyamic acid film was wound up. The polyamic acid film is passed through a pin tenter having three heat treatment zones, the first stage is 150 ° C. × 2 minutes, the second stage is 220 ° C. × 2 minutes, the third stage is 460 ° C. × 4 minutes, and 20 minutes after passing through the tenter. Six rolls were passed to give a double-side free process, and finally slit to a width of 500 mm to obtain a polyimide film c having a thickness of 25 μm. Table 11 shows the physical property values of the obtained polyimide film c.
Next, sputtering and plating were performed in the same manner as in Production Example 5 to obtain a copper-clad laminate (CCL) c.

[Production Example 8]
(Create fluororesin film)
Using a commercially available fluororesin, a fluororesin film was prepared by a conventionally known method. Tables 12 and 13 show the types and physical properties of the obtained fluororesin films.

[Example 1]
A functional group-containing fluororesin film D1 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) is arranged on both sides of the polyimide film A1 cut out to a size of 150 mm × 150 mm, and 30 at 330 ° C. and 5 MPa which is equal to or higher than the melting point of the fluororesin film. Heat-press molding was performed for a minute to obtain a multilayer fluororesin film.
On the other hand, a functional group-containing fluororesin film D1 and a 9 μm-thick copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) are arranged in this order on both sides of a polyimide film A1 cut out to a size of 150 mm × 150 mm. The film was heated and pressed at 330 ° C. and 5 MPa for 30 minutes to obtain a double-sided copper-laminated multilayer fluororesin film.
The evaluation results of the obtained multilayer fluororesin film and double-sided copper-laminated multilayer fluororesin film are shown in Table 4. Hereinafter, the thickness ratio, the storage elastic modulus ratio, and the linear expansion coefficient are the evaluation results of the multilayer fluororesin film, and the peel strength and quality are the evaluation results of the double-sided copper-bonded multilayer fluororesin film.

[Examples 2 and 3]
A laminate was prepared and evaluated in the same manner as in Example 1 except that polyimide films A2 and A3 were used instead of polyimide film A1.
The evaluation results of the obtained multilayer fluororesin film and double-sided copper-laminated multilayer fluororesin film are shown in Table 4.

Example 4
A laminate was prepared and evaluated in the same manner as in Example 1 except that a functional group-containing fluororesin film D2 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film D1.
Table 5 shows the evaluation results of the obtained multilayer fluororesin film and the double-sided copper-laminated multilayer fluororesin film.

[Examples 5 and 6]
A laminate was prepared and evaluated in the same manner as in Example 4 except that polyimide films A2 and A3 were used instead of polyimide film A1.
Table 5 shows the evaluation results of the obtained multilayer fluororesin film and the double-sided copper-laminated multilayer fluororesin film.

Example 7
A laminate was prepared and evaluated in the same manner as in Example 6 except that a functional group-containing fluororesin film D3 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film D2.
Table 5 shows the evaluation results of the obtained multilayer fluororesin film and the double-sided copper-laminated multilayer fluororesin film.

[Examples 8 to 11]
The polyimide film A2 cut out to a size of 150 mm × 150 mm was set in a Nikketsu plasma treatment machine and evacuated to a vacuum. Then, oxygen gas was introduced to cause discharge, and plasma treatment was performed. The processing conditions are a degree of vacuum of 3 × 10 Pa, a gas flow rate of 1.5 SLM, and a discharge power of 12 KW.
Functional group-free fluororesin film E (Fluon PFA, manufactured by Asahi Glass Co., Ltd.), F (neoflon PFA, manufactured by Daikin Industries, Ltd.), G (neoflon FEP, manufactured by Daikin Industries), on both surfaces of the obtained plasma-treated polyimide film A2. H (EPE, manufactured by Daikin Industries, Ltd.) was placed, and heat-pressure molding was performed at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, for 30 minutes to obtain a multilayer fluororesin film.
On the other hand, functional group-free fluororesin films E to H and a copper foil having a thickness of 9 μm are arranged in this order on both surfaces of the plasma-treated polyimide film A2, and heated for 30 minutes at 330 ° C. and 5 MPa which is higher than the melting point of the fluororesin film. It pressure-molded and obtained the double-sided copper adhesion multilayer fluororesin film.
The evaluation results of the obtained multilayer fluororesin film and double-sided copper-laminated multilayer fluororesin film are shown in Table 6.

[Comparative Example 1]
A laminate was prepared and evaluated in the same manner as in Example 2 except that polyimide film B was used instead of polyimide film A1.
Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-laminated multilayer fluororesin film.
When the linear expansion coefficient of the polyimide film is large, the linear expansion coefficient of the obtained multi-layer fluororesin is also large, and the deviation from the linear expansion coefficient of the copper foil is large, so that the adhesion and quality after the reliability test are lowered.

[Comparative Examples 2 and 3]
Example 2 except that functional group-containing fluororesin film I (Fluon LM-ETFE AH2000, manufactured by Asahi Glass Co., Ltd.) and J (neoflon EFEP RP5000, manufactured by Daikin Industries, Ltd.) are used instead of functional group-containing fluororesin film D1. A laminate was prepared and evaluated in the same manner.
Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-laminated multilayer fluororesin film.
Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with perfluorinated resins such as PFA, FEP, and EPE, the adhesiveness and quality after the reliability test are lowered.

[Comparative Examples 4 and 5]
A functional group-free fluororesin film K (Fluon ETFE, manufactured by Asahi Glass Co., Ltd.) and L (neoflon ETFE, manufactured by Daikin Industries) are used in place of the functional group-free fluororesin film E in the same manner as in Example 8. A laminate was prepared by the method and evaluated.
Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-laminated multilayer fluororesin film.
Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with perfluorinated resins such as PFA, FEP, and EPE, the adhesiveness and quality after the reliability test are lowered.

[Comparative Example 6]
A laminate was prepared and evaluated in the same manner as in Example 1 except that polyimide film A4 was used instead of polyimide film A1.
Table 8 shows the evaluation results of the obtained multilayer fluororesin film and the double-sided copper-laminated multilayer fluororesin film.
If the thickness ratio of the fluororesin is too small, the linear expansion coefficient of the resulting multi-layer fluororesin will be small, but the contribution of low moisture absorption, which is a feature of the fluororesin, will be small. Decreased.

[Comparative Example 7]
A laminate was prepared and evaluated in the same manner as in Comparative Example 6 except that a functional group-containing fluororesin film D2 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film D1.
Table 8 shows the evaluation results of the obtained multilayer fluororesin film and the double-sided copper-laminated multilayer fluororesin film.
If the thickness ratio of the fluororesin is too small, the linear expansion coefficient of the resulting multi-layer fluororesin will be small, but the contribution of low moisture absorption, which is a feature of the fluororesin, will be small. Decreased.

[Comparative Examples 8 to 10]
A laminate is prepared and evaluated in the same manner as in Examples 4 to 6 except that a functional group-containing fluororesin film D4 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) is used instead of the functional group-containing fluororesin film D2. did.
Table 8 shows the evaluation results of the obtained multilayer fluororesin film and the double-sided copper-laminated multilayer fluororesin film.
If the thickness ratio of the fluororesin is too large, the linear expansion coefficient of the resulting multi-layer fluororesin also increases, and the deviation from the linear expansion coefficient of the copper foil increases, resulting in decreased adhesion and quality after the reliability test. .

[Examples 12 to 13, Comparative Examples 11 to 12]
(Evaluation of warping of copper-coated multilayer fluororesin film)
A functional group-containing fluororesin film D3 is arranged on both surfaces of polyimide films A1 to A4 cut out to a size of 150 mm × 150 mm, and heat-press molding is performed at 330 ° C. and 5 MPa, which is equal to or higher than the melting point of the fluororesin film, A multilayer fluororesin film was obtained.
In addition, a functional group-containing fluororesin film D3 and a 9 μm-thick copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) are arranged in this order on both surfaces of polyimide films A1 to A4 cut out to a size of 150 mm × 150 mm. Heat-press molding was performed for 30 minutes at 330 ° C. and 5 MPa, which is higher than the melting point, to obtain a double-sided copper-laminated multilayer fluororesin film.
Furthermore, functional group-containing fluororesin film D3 is provided on one side of polyimide films A1 to A4 cut out to a size of 150 mm × 150 mm, functional group-containing fluororesin film D3 is provided on the other side, and a 9 μm thick copper foil (UWZ, Furukawa Circuit Foil). Were made in this order, and heat-pressure molding was performed at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, for 30 minutes to obtain a single-sided copper-laminated multilayer fluororesin film.
By visual inspection of the obtained single-sided and double-sided copper-laminated multilayer fluororesin film, the case without warp was evaluated as ◯, the case with warp Δ, and the case wrapped in a roll shape was evaluated as ×. Table 9 shows the evaluation results.
When the linear expansion coefficient of the multilayer fluororesin film is larger than the linear expansion coefficient of the copper foil, the multilayer fluororesin film is warped inward in an asymmetric configuration such as a single-sided copper-laminated multilayer fluororesin film.

[Examples 14 to 15, Comparative Example 13]
(Evaluation of warping of copper-coated multilayer fluororesin film)
A functional group-containing fluororesin film D2 is arranged on both surfaces of polyimide films A2 to A4 cut out to a size of 150 mm × 150 mm, and heat-pressure molding is performed at 330 ° C. and 5 MPa, which is equal to or higher than the melting point of the fluororesin film, A multilayer fluororesin film was obtained.
In addition, a functional group-containing fluororesin film D2 and a 9 μm thick copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) are arranged in this order on both surfaces of the polyimide films A2 to A4 cut out to a size of 150 mm × 150 mm. Heat-press molding was performed for 30 minutes at 330 ° C. and 5 MPa, which is higher than the melting point, to obtain a double-sided copper-laminated multilayer fluororesin film.
Furthermore, functional group-containing fluororesin film D2 is provided on one side of polyimide films A2 to A4 cut out to a size of 150 mm × 150 mm, functional group-containing fluororesin film D3 is provided on the other side, and a 9 μm-thick copper foil (UWZ, Furukawa Circuit Foil) Were made in this order, and heat-pressure molding was performed at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, for 30 minutes to obtain a single-sided copper-laminated multilayer fluororesin film.
Table 10 shows the evaluation results of the obtained single-sided and double-sided copper-clad multilayer fluororesin film.
When the linear expansion coefficient of the multilayer fluororesin film is smaller than the linear expansion coefficient of the copper foil, the copper foil is warped inward in an asymmetric configuration such as a single-sided copper-laminated multilayer fluororesin film.

[Application Example 1]
A functional group-containing fluororesin film D1 is placed on one side of a polyimide film A2 cut into a size of 150 mm × 150 mm, a functional group-containing fluororesin film D1 and a copper foil with a thickness of 9 μm are arranged in this order on the other side. Heat-press molding was performed for 30 minutes at 330 ° C. and 5 MPa, which is higher than the melting point, to obtain a single-sided copper-laminated multilayer fluororesin film.
On the other hand, the double-sided copper-clad polyimide laminate obtained in Example 2 was used, and a photoresist (FR-200, manufactured by Shipley Co., Ltd.) was applied and dried on one side, followed by close exposure with a glass photomask, and further 1.2 mass. Development was performed with a% KOH aqueous solution. Next, using a cupric chloride etching line containing HCl and hydrogen peroxide, etching is performed at a spray pressure of 40 ° C. and 2 kgf / cm ² to form a test pattern, followed by cleaning, and annealing at 125 ° C. for 1 hour. Processing was performed to obtain a single-sided copper-coated multilayer fluororesin film (printed wiring board) with a single-sided pattern.
The pattern-forming surface of the single-sided copper-clad multilayer fluororesin film (printed wiring board) with a single-sided pattern faces the fluororesin surface of the single-sided copper-clad multilayer fluororesin film, at 330 ° C and 5 MPa, which is above the melting point of the fluororesin film Heat-press molding was performed for 30 minutes to obtain a multilayer printed wiring board as shown in FIG. The obtained multilayer printed wiring board is very useful as a high-frequency member because the copper wiring is covered with a fluororesin having a low dielectric constant.

Example 16
A functional group-containing fluororesin film d1 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) is arranged on one side of a polyimide film a1 cut out to a size of 150 mm × 150 mm, and is 30 ° C. and 5 MPa at 330 ° C., which is equal to or higher than the melting point of the fluororesin film. Heat-press molding was performed for a minute, and the (A) layer (B) layer laminated body was obtained.
Table 14 shows the evaluation results of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the obtained (A) layer (B) layer laminate.
On the other hand, a functional group-containing fluororesin film d1 and a 9 μm-thick copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) are arranged in this order on the surface of the polyimide film a1 of a copper-clad laminate (CCL) a1 cut into a size of 150 mm × 150 mm. Then, heat-press molding was performed for 30 minutes at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, to obtain a copper-bonded multilayer fluororesin film.
Table 14 shows the evaluation results of the heat and moisture resistance test and heat resistance test of the obtained copper-clad multilayer fluororesin film.

[Examples 17 and 18]
A laminate in the same manner as in Example 16 except that polyimide films a2 and a3 are used instead of polyimide film a1 and copper-clad laminates (CCL) a2 and a3 are used instead of copper-clad laminate (CCL) a1. Was created and evaluated.
Table 14 shows the evaluation results of the thickness ratio, the storage elastic modulus ratio, the linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.

Example 19
A laminate was prepared and evaluated in the same manner as in Example 16 except that a functional group-containing fluororesin film d2 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d1.
Table 15 shows the evaluation results of the thickness ratio, the storage elastic modulus ratio, the linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.

[Examples 20 and 21]
A laminate in the same manner as in Example 19 except that polyimide films a2 and a3 are used instead of polyimide film a1 and copper-clad laminates (CCL) a2 and a3 are used instead of copper-clad laminate (CCL) a1. Was created and evaluated.
Table 15 shows the evaluation results of the thickness ratio, the storage elastic modulus ratio, the linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.

[Example 22]
A laminate was prepared and evaluated in the same manner as in Example 21, except that a functional group-containing fluororesin film d3 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d2.
Table 15 shows the evaluation results of the thickness ratio, the storage elastic modulus ratio, the linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.

[Examples 23 to 26]
The polyimide film a2 cut out to a size of 150 mm × 150 mm was set in a Nikketsu plasma treatment machine and evacuated to a vacuum. Then, oxygen gas was introduced to cause discharge, and plasma treatment was performed. The processing conditions are a degree of vacuum of 3 × 10 Pa, a gas flow rate of 1.5 SLM, and a discharge power of 12 KW.
Functional group-free fluorine resin film e (Fluon PFA, manufactured by Asahi Glass Co., Ltd.), f (neoflon PFA, manufactured by Daikin Industries, Ltd.), g (neoflon FEP, manufactured by Daikin Industries Co., Ltd.), h (EPE, manufactured by Daikin Industries, Ltd.), respectively, and heat-pressure molding was performed at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, for 30 minutes to obtain a (A) layer (B) layer laminate. .
Table 16 shows the evaluation results of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the obtained (A) layer (B) layer laminate.
On the other hand, the copper-clad laminate (CCL) a2 was set in a Nikketsu plasma treatment machine and evacuated to a vacuum. Then, oxygen gas was introduced to cause discharge, and plasma treatment was performed. The processing conditions are a degree of vacuum of 3 × 10 Pa, a gas flow rate of 1.5 SLM, and a discharge power of 12 KW.
A functional group-free fluororesin film eh and a 9 μm-thick copper foil are arranged in this order on the surface of the polyimide film a2 of the obtained plasma-treated copper-clad laminate (CCL) a2, and 330 above the melting point of the fluororesin film. Heat-press molding was performed at 5 ° C. for 30 minutes at a temperature of 5 ° C. to obtain a copper-bonded multilayer fluororesin film.
Table 16 shows the evaluation results of the heat and moisture resistance test and heat resistance test of the obtained copper-clad multilayer fluororesin film.

[Comparative Example 14]
A laminate is prepared in the same manner as in Example 17 except that polyimide film b is used instead of polyimide film a1, and copper-clad laminate (CCL) b is used instead of copper-clad laminate (CCL) a1. evaluated.
Table 17 shows the evaluation results of the thickness ratio, the storage elastic modulus ratio, the linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.
When the linear expansion coefficient of the polyimide film is large, the linear expansion coefficient of the obtained multi-layer fluororesin is also large, and the deviation from the linear expansion coefficient of the copper foil is large, so that the adhesion and quality after the reliability test are lowered.

[Comparative Examples 15 and 16]
Example 17 is used except that a functional group-containing fluororesin film i (Fluon LM-ETFE AH2000, manufactured by Asahi Glass Co., Ltd.) and j (neoflon EFEP RP5000, manufactured by Daikin Industries, Ltd.) are used instead of the functional group-containing fluororesin film d1. A laminate was prepared and evaluated in the same manner.
Table 17 shows the evaluation results of the thickness ratio, the storage elastic modulus ratio, the linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.
Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with perfluorinated resins such as PFA, FEP, and EPE, the adhesiveness and quality after the reliability test are lowered.

[Comparative Examples 17 and 18]
A functional group-free fluororesin film k (Fluon ETFE, manufactured by Asahi Glass Co., Ltd.) and l (neoflon ETFE, manufactured by Daikin Industries, Ltd.) are used in place of the functional group-free fluororesin film e. A laminate was prepared by the method and evaluated.
Table 17 shows the evaluation results of the thickness ratio, the storage elastic modulus ratio, the linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.
Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with perfluorinated resins such as PFA, FEP, and EPE, the adhesiveness and quality after the reliability test are lowered.

[Comparative Example 19]
A laminate is created in the same manner as in Example 16 except that polyimide film a4 is used instead of polyimide film a1, and copper-clad laminate (CCL) a4 is used instead of copper-clad laminate (CCL) a1. evaluated.
Table 18 shows the evaluation results of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.
If the thickness ratio of the fluororesin is too small, the linear expansion coefficient of the resulting multi-layer fluororesin will be small, but the contribution of low moisture absorption, which is a feature of the fluororesin, will be small. Decreased.

[Comparative Example 20]
A laminate was prepared and evaluated in the same manner as in Comparative Example 19 except that a functional group-containing fluororesin film d2 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d1.
Table 18 shows the evaluation results of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.
If the thickness ratio of the fluororesin is too small, the linear expansion coefficient of the resulting multi-layer fluororesin will be small, but the contribution of low moisture absorption, which is a feature of the fluororesin, will be small. Decreased.

[Comparative Examples 21 to 23]
A laminate is prepared and evaluated in the same manner as in Examples 19 to 21, except that a functional group-containing fluororesin film d4 (Fluon PFA adhesive grade, manufactured by Asahi Glass Co., Ltd.) is used instead of the functional group-containing fluororesin film d2. did.
Table 18 shows the evaluation results of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the obtained (A) layer (B) layer laminate, the wet heat resistance test and the heat resistance test of the copper-coated multilayer fluororesin film. Show.
If the thickness ratio of the fluororesin is too large, the linear expansion coefficient of the resulting multi-layer fluororesin also increases, and the deviation from the linear expansion coefficient of the copper foil increases, resulting in decreased adhesion and quality after the reliability test. .

[Examples 27 to 28, Comparative Examples 24 to 25]
(Evaluation of warping of copper-coated multilayer fluororesin film)
A functional group-containing fluororesin film d3 is arranged on one side of polyimide films a1 to a4 cut out to a size of 150 mm × 150 mm, and heat-press molding is performed at 330 ° C. and 5 MPa, which is equal to or higher than the melting point of the fluororesin film, (A) Layer (B) A layered product was obtained. Table 19 shows the evaluation results of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the obtained (A) layer (B) layer laminate. Moreover, the functional group containing fluororesin film d3 and the 9-micrometer-thick copper foil on the polyimide film a1-a4 surface of the copper-clad laminate (CCL) a1-a4 cut into a size of 150 mm × 150 mm (UWZ, manufactured by Furukawa Circuit Foil) Were arranged in this order, and heat-press molding was performed at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, for 30 minutes to obtain a copper-clad multilayer fluororesin film.
By visual inspection of the obtained copper-clad multilayer fluororesin film, those without warping were evaluated as “good” and those with warping ×. The evaluation results are shown in Table 19.

[Examples 29 to 30, Comparative Example 26]
(Evaluation of warping of copper-coated multilayer fluororesin film)
A functional group-containing fluororesin film d2 is arranged on one side of polyimide films a2 to a4 cut out to a size of 150 mm × 150 mm, and heat-pressure molding is performed at 330 ° C. and 5 MPa, which is equal to or higher than the melting point of the fluororesin film, (A) Layer (B) A layered product was obtained. Table 20 shows the evaluation results of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the obtained (A) layer (B) layer laminate.
Moreover, the functional group containing fluororesin film d2 and the 9-micrometer-thick copper foil on the polyimide film a2-a4 surface of the copper-clad laminate (CCL) a2-a4 cut into a size of 150 mm × 150 mm (UWZ, manufactured by Furukawa Circuit Foil) Were arranged in this order, and heat-press molding was performed at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, for 30 minutes to obtain a copper-clad multilayer fluororesin film. Table 20 shows the evaluation results of the obtained copper-clad multilayer fluororesin film.

[Application 2]
A functional group-containing fluororesin film d1 is placed on the surface of the polyimide film a2 of a copper-clad laminate (CCL) a2 cut into a size of 150 mm × 150 mm, and heated at 330 ° C. and 5 MPa, which is higher than the melting point of the fluororesin film, for 30 minutes. Pressure molding was performed to obtain a multilayer fluororesin film.
On the other hand, using the copper-clad multilayer fluororesin film obtained in Example 17, a photoresist (FR-200, manufactured by Shipley Co., Ltd.) was applied to the copper foil surface, dried, and then closely exposed with a glass photomask. Development was performed with a 2% by weight aqueous KOH solution. Next, using a cupric chloride etching line containing HCl and hydrogen peroxide, etching is performed at a spray pressure of 40 ° C. and 2 kgf / cm ² to form a test pattern, followed by cleaning, and annealing at 125 ° C. for 1 hour. Processing was performed to obtain a patterned copper-coated multilayer fluororesin film (printed wiring board).
The pattern formation surface of the patterned copper-coated multilayer fluororesin film (printed wiring board) and the fluororesin surface of the multilayer fluororesin film face each other, and heat-press for 30 minutes at 330 ° C and 5 MPa above the melting point of the fluororesin film. Molding was performed to obtain a multilayer printed wiring board as shown in FIG. The obtained multilayer printed wiring board is very useful as a high-frequency member because the copper wiring is covered with a fluororesin having a low dielectric constant.

  A multi-layer fluororesin film in which the fluororesin layer / polyimide resin layer / fluororesin layer of the first invention of the present application are laminated in this order, and a multi-layer fluororesin film having a linear expansion coefficient of 10 ppm / ° C. to 30 ppm / ° C., Copper-coated multi-layer fluororesin film in which copper foil is laminated on at least one surface of the multi-layer fluororesin film, a printed wiring board in which this copper foil is partially removed to form a circuit pattern, and (B) polyimide resin of the second invention of the present application (C) A multilayer fluororesin film in which (A) a fluororesin layer is further laminated on the (B) surface of a copper-clad laminate (CCL) in which a copper layer is formed without using an adhesive, A multilayer fluororesin film in which the linear expansion coefficient of the (A) layer (B) layered product in the multilayer fluororesin film is 10 ppm / ° C to 30 ppm / ° C, and the multilayer fluororesin film The copper-coated multilayer fluororesin film in which copper foil is laminated on the (A) surface of the film and the printed wiring board having a circuit pattern obtained by removing a part of this copper foil are multilayer fluororesin film even in high-temperature and high-humidity processing. It can withstand adhesion between copper foil and copper foil, improves the quality of the obtained printed wiring board and the like, improves the production yield, and realizes the production of high-quality electronic components.

(Figure 1)
1 Copper foil 2 Fluororesin film 3 Polyimide film (Figure 2)
1 Copper layer 2 Fluororesin film 3 Polyimide film

Claims (13)

(A) Fluororesin layer / (B) Polyimide resin layer / (A) Fluororesin layer is a multilayer fluorinated resin film laminated in this order, and the linear expansion coefficient of the multilayer fluorinated resin film is 10 ppm / ° C. to 30 ppm / C, the thickness ratio of the (A) layer {total (A) layer / multilayer fluororesin film} is 60% to 90%, and the (A) layer is co-polymerized with tetrafluoroethylene / perfluoroalkyl vinyl ether. It is a thermoplastic fluororesin layer made of polymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), or tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer (EPE). Ah it is, and (B) layer is a layer of polyimide having a polyimide benzoxazole component, and ( Storage modulus at room temperature of layer A): E ′ (A) and storage modulus at room temperature of layer (B): ratio of E ′ (B) {E ′ (A) / E ′ (B)} A multilayer fluororesin film that is 2.0% to 20% . The multilayer fluororesin film according to claim 1, wherein the layer (A) is a functional group-containing thermoplastic fluororesin layer. (A) The thickness of a layer is 1.0 micrometer-50 micrometers, and the thickness of (B) layer is 1.0 micrometer-38 micrometers, The multilayer fluororesin film in any one of Claims 1-2 . Copper-clad multilayer fluororesin film on at least one surface a copper foil is laminated multilayer fluororesin film according to any one of claims 1-3. The printed wiring board formed by removing a part of copper foil of the copper adhesion multilayer fluororesin film of Claim 4 , and forming a circuit pattern. A multilayer printed wiring board formed by laminating the multilayer fluororesin film according to any one of claims 1 to 5 , a copper-laminated multilayer fluororesin film, and a printed wiring board. (B) A multilayer fluororesin film in which (A) a fluororesin layer is further laminated on the (B) surface of a copper-clad laminate (CCL) in which a copper layer is formed without using an adhesive on the polyimide resin layer (C) The linear expansion coefficient of the (A) layer (B) layer laminate in the multilayer fluororesin film is 10 ppm / ° C. to 30 ppm / ° C., and (A) layer thickness ratio {(A) layer / (A) layer (B) layer laminate} is 60% to 90%, and the (A) layer is a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), a tetrafluoroethylene / hexafluoropropylene copolymer. polymer (FEP), a layer der thermoplastic fluororesin comprising any one of tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE) is, and (B) layer is , A polyimide layer having a polyimide benzoxazole component, and (A) layer storage modulus at room temperature: E ′ (A) and (B) layer storage modulus at room temperature: E ′ (B) A multilayer fluororesin film having a ratio {E ′ (A) / E ′ (B)} of 2.0% to 20% . The multilayer fluororesin film according to claim 7 , wherein the layer (A) is a layer of a functional group-containing thermoplastic fluororesin. The multilayer fluororesin film according to claim 7 or 8 , wherein the layer (B) is a polyimide layer having a polyimide benzoxazole component, and has a linear expansion coefficient of -10 ppm / ° C to 10 ppm / ° C. The multilayer fluororesin film according to any one of claims 7 to 9 , wherein (A) the layer has a thickness of 1.0 to 50 µm, and (B) the layer has a thickness of 1.0 to 38 µm. A copper-clad multilayer fluororesin film in which a copper foil is laminated on the (A) surface of the multilayer fluororesin film according to claim 7 . The printed wiring board formed by removing a part of copper layer of the multilayer fluororesin film in any one of Claims 7-11 , and a copper adhesion multilayer fluororesin film, and forming a circuit pattern. The multilayer printed wiring board formed by laminating | stacking the multilayer fluorine resin film in any one of Claims 7-12 , a copper adhesion multilayer fluorine resin film, and a printed wiring board.