TWI461119B - Multilayer fluorine resin film and printed wiring board - Google Patents

Description

Multilayer fluororesin film and printed wiring board

The present invention relates to a multilayer fluororesin film used for a flexible printed wiring board or the like which is used for miniaturization and weight reduction of an electronic device, and a copper-clad multilayer fluororesin film in which a copper foil of a metal foil is laminated. A copper foil is a printed wiring board formed by removing a part of a circuit pattern, and a multilayer printed wiring board formed by laminating these.

In general, in the signal transmission in the high-frequency region, the transmission speed is required to be improved and the noise is reduced. In the flexible printed wiring board, the substrate material, the wiring technology, and the circuit form are also discussed.

Conventionally, an electrically insulating layer of a flexible printed wiring board comprising a laminate of a conductor layer and an electrical insulator layer is a polyimide resin having excellent heat resistance. The following three methods can be applied to the production method of the laminate comprising the polyimide layer and the conductor layer.

(1) a method of bonding a polyimide film to a copper foil through an adhesive layer,

(2) a method of forming a metal layer on a polyimide film by vapor deposition and/or metal plating,

(3) A method in which a polyimide film precursor is applied to a metal foil, and then a polyimide resin is formed from the precursor by heat treatment or the like to form a polyimide film on the metal foil (see Patent) Document 1).

However, in such a method, the adhesion between the polyimide layer and the conductor layer is insufficient, which may cause malfunction of the circuit. Further, since the transmission loss is large when it is configured as a printed wiring board, it is not suitable as a high-frequency component.

A method of improving the adhesion between the conductor layer and the electrical insulator layer by forming irregularities of about 3 μm on the surface of the conductor layer on the side contacting the electrical insulator layer has been disclosed (see Patent Document 2). However, in such a method, due to the surface effect of the high-frequency region, the signal arrival time varies on the surface having the unevenness and the non-roughened surface, so it is necessary to reduce the unevenness as much as possible.

A polyimine which lowers the dielectric constant by dispersing inorganic fine particles such as cerium oxide in polyimine is disclosed. However, in such a method, since it is difficult to microdisperse the inorganic fine particles to the polyimide at the nanometer level, the problem of surface smoothness or transparency of the polyimide film is impaired. When the surface smoothness is impaired, when the polyimide film is used for the substrate of the printed substrate, the adhesion to the copper foil constituting the metal layer is deteriorated, and the quality of the printed substrate is lowered.

It has been disclosed that a specific structure of a dielectric constant is lowered by using an aromatic diamine compound in which two diphenyl ethers having a tertiary butyl group having a small fraction of a side chain in a side chain are bonded to each other to form a dielectric constant. Polyimine (see Patent Document 3). However, in such a method, since it is necessary to use a specific structure of the aromatic diamine compound, the versatility of the polyimine which has various structures can be used.

After the aromatic dianhydride and the aromatic diamine are reacted to obtain a polylysine in a solution state, the polyamic acid is rapidly heated to volatilize the residual solvent and the generated condensation water, thereby obtaining uniform foaming. Polyimine foam (see Patent Document 4). However, in such a method, not only is it difficult to form polylysine into a film form, but it is a foam, which may impair surface smoothness or transparency, and has a problem that mechanical strength is lowered due to bubbles.

In general, it is known that when a fluorine atom is introduced into a molecule of a polyimide, the dielectric constant can be lowered. For example, a polyimine-metal composite film having a metal layer formed on the surface of a fluorinated polyimide film has been disclosed (see Patent Document 5). In addition, a multilayer wiring board in which at least one type selected from the group consisting of a base material, an adhesive layer, and a surface protective layer is used is disclosed (see Patent Document 6). However, in such a method, as the content of fluorine atoms in the molecule introduced into the polyimine is increased, the tensile modulus and the tensile strain at break of the film composed of the polyimide are lowered. And the problem of reduced mechanical strength.

A laminate in which a fluororesin having a minimum dielectric constant in a plastic is laminated with a metal plate has been disclosed (see Patent Document 7). However, in such a method, when the fluororesin film is perforated at a high speed, it is rubbed off from the metal plate with the blade edge, resulting in a problem of a decrease in yield. Further, the tensile strength and elongation of the mechanical properties of the fluororesin film are the same as those of the polyolefin at room temperature, and the coefficient of linear expansion is 60 ppm/° C. to 160 ppm/° C. for example, when the coefficient of linear expansion is 16 ppm/° C. When the copper foil is laminated, the deviation of the linear expansion coefficient of each other is large, there is a concern of peeling during use, or there is a concern that warpage may occur.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-001510

[Patent Document 2] Japanese Laid-Open Patent Publication No. 05-055746

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-323061

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2004-342541

[Patent Document 5] Japanese Patent No. 2866155

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2001-308542

[Patent Document 7] Japanese Laid-Open Patent Publication No. 2002-125297

An object of the present invention is to use a polyimine resin which is less deformed and has good heat resistance as a core material under high temperature treatment of a substrate suitable as an electronic component, and to provide a fluororesin on the surface, thereby providing a At the same time, the low linear expansion coefficient of the polyimine resin (as a multilayer fluororesin film having a linear expansion coefficient equivalent to that of the copper foil), high mechanical properties, and a low dielectric constant of the fluororesin, A multilayer fluororesin film having a low water absorption rate (reducing the high water absorption of polyimine), a copper-clad multilayer fluororesin film, a printed wiring board, and a multilayer printed wiring board.

The present inventors have intensively studied and found that a fluororesin layer laminated on a double-sided fluororesin film of a polyimide film is used for a copper clad laminate, a printed wiring board, and an FPC, TAB tape, When the COF is wound with a film or the like, a product which does not cause peeling or the like at a high temperature and high humidity and which has excellent electrical characteristics can be obtained, and thus the present invention has been completed.

That is, the first invention of the present application is constituted by the following constitution.

A multilayer fluororesin film which is a multilayer fluororesin film composed of (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer, which is sequentially laminated, wherein the multilayer fluororesin film The linear expansion coefficient is 10 ppm/° C. to 30 ppm/° C., and the thickness ratio of the (A) layer is 60% to 90% of the entire (A) layer/multilayer fluororesin film, and the (A) layer is made of tetrafluoroethylene. A perfluoroalkyl vinyl ether copolymer (PFA), a tetrafluoroethylene ‧ hexafluoropropylene copolymer (FEP), a tetrafluoroethylene ‧ hexafluoropropylene ‧ perfluoroalkyl vinyl ether copolymer (EPE) Thermoplastic fluororesin layer.

2. The multilayer fluororesin film of 1, wherein the (A) layer is a functional group-containing thermoplastic fluororesin layer.

3. A multilayer fluororesin film according to 1. or 2. wherein the (B) layer is a polybenzonitrile benzoate The polyimine layer of the azole component has a linear expansion coefficient of -10 ppm / ° C ~ 10 ppm / ° C.

4. The multilayer fluororesin film according to any one of items 1 to 3, wherein the (A) layer has a thickness of from 1.0 μm to 50 μm, and the (B) layer has a thickness of from 1.0 μm to 38 μm.

5. The multilayer fluororesin film according to any one of 1. to 4, wherein the storage elastic modulus of the (A) layer at room temperature: storage elasticity of the E' (A) and (B) layers at room temperature Modulus: E'(B) ratio {E'(A)/E'(B)} is 2.0%~20%.

A copper-clad-layered fluororesin film in which a copper foil is laminated on at least one side of a multilayer fluororesin film according to any one of 1. to 5.

A printed wiring board comprising a part of a copper foil of a copper-clad multilayer fluororesin film of 6. removed to form a circuit pattern.

A multilayer printed wiring board comprising a multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board according to any one of 1. to 7.

Further, the second invention of the present application is constituted by the following constitution.

A multilayer fluororesin film which is formed by laminating a (C) copper layer on a (B) surface of a copper clad laminate (CCL) of a (B) polyimine resin layer without an adhesive. A) a fluororesin film formed of a fluororesin layer in which the linear expansion coefficient of the (A) layer (B) layered layer in the multilayer fluororesin film is 10 ppm/° C. to 30 ppm/° C., and the thickness of the (A) layer The ratio of {(A) layer / (A) layer (B) layered layer body is 60% to 90%, and the layer (A) is composed of tetrafluoroethylene ‧ perfluoroalkyl vinyl ether copolymer (PFA), four A thermoplastic fluororesin layer formed of any one of vinyl fluoride, hexafluoropropylene copolymer (FEP), tetrafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether copolymer (EPE).

10. The multilayer fluororesin film according to item 9, wherein the (A) layer is a functional group-containing thermoplastic fluororesin layer.

11. A multilayer fluororesin film according to 9. or 10. wherein the layer (B) is polybenzonitrile benzo The polyimine layer of the azole component has a linear expansion coefficient of -10 ppm / ° C ~ 10 ppm / ° C.

The multilayer fluororesin film according to any one of items 9 to 11, wherein the (A) layer has a thickness of from 1.0 μm to 50 μm, and the (B) layer has a thickness of from 1.0 μm to 38 μm.

13. The multilayer fluororesin film according to any one of items 9 to 12, wherein (A) layer has a storage elastic modulus at room temperature: storage elasticity of E' (A) and (B) layers at room temperature Modulus: E'(B) ratio {E'(A)/E'(B)} is 2.0%~20%.

A copper-clad-layered fluororesin film which is laminated with a copper foil on the (A) side of the multilayer fluororesin film according to any one of 9. to 13.

A printed wiring board comprising a multilayer fluororesin film according to any one of 9. to 14. and a copper layer of a copper-clad multilayer fluororesin film removed to form a circuit pattern.

A multilayer printed wiring board comprising a multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board as disclosed in any one of 9. to 15.

The multilayer fluororesin film composed of the (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer of the first invention of the present application can simultaneously achieve polyimine The low linear expansion coefficient of the resin (as a multilayer fluororesin film, which has the same linear expansion coefficient as that of the copper foil), high mechanical properties, low dielectric constant with low fluororesin, and low water absorption (reduced poly A multilayer film of high water absorption of ruthenium.

In the second invention of the present application, the (C) copper layer is formed on the (B) side of the copper clad laminate (CCL) of the (B) polyimine resin layer without an adhesive, and further laminated (A) a fluororesin film obtained by laminating a fluororesin layer, wherein the multilayer fluororesin film has a multilayer fluororesin film having a linear expansion coefficient of (A) layer (B) of 10 ppm/° C. to 30 ppm/° C. At the same time, the low linear expansion coefficient of the polyimine resin (as a multilayer fluororesin film having a linear expansion coefficient equivalent to that of the copper foil), high mechanical properties, and a low dielectric constant of the fluororesin, A multilayer film having a low water absorption rate (reducing the high water absorption of polyimine).

The multilayer fluororesin film of the present invention has good adhesion to a copper foil, has a small deviation from a linear expansion coefficient of 16 ppm/° C. of the copper foil, and has a low water absorption rate, and is hardly obtained even in an environment of high temperature and high humidity. Warpage or distortion occurs, and as a result, the quality of the printed wiring board and the like, and the yield at the time of production can also be improved.

The copper-clad multilayer fluororesin film using the multilayer fluororesin film of the present invention, the printed wiring board, and the multilayer printed wiring board, that is, the use as an electronic component exposed to high temperature, can also be made to be less prone to warpage during manufacture. It is highly meaningful in the industry, or the manufacture of high-quality electronic parts that do not cause the peeling of the multilayer fluororesin film and the copper foil, and the improvement of the yield.

Form of implementing the invention

The invention is described in detail below.

The (A) fluororesin layer used in the present invention is a fluororesin film obtained by a method of forming a film by casting a film of a fluororesin melt, or by coating the fluororesin melt on a polysiloxane. The layer formed of the amine resin layer (film) is preferably in the form of a fluororesin film in view of handleability, productivity, and the like.

The fluororesin can be appropriately selected and used from the conventionally known thermoplastic fluororesin used in general molding.

Examples of the thermoplastic fluororesin include polymers or copolymers of unsaturated fluorinated hydrocarbons, unsaturated fluorochlorinated hydrocarbons, ether-containing unsaturated hydrocarbons, or copolymerization of such unsaturated fluorinated hydrocarbons with ethylene. Things and so on. Specific examples are polymers or copolymers selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene fluoride and vinyl fluoride, or such monomers and A copolymer of ethylene or the like.

More specific examples of the thermoplastic fluororesin include tetrafluoroethylene ‧ perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene ‧ hexafluoropropylene copolymer (FEP), tetrafluoroethylene ‧ hexafluoropropylene ‧ perfluoroalkane Ethylene vinyl ether copolymer (EPE), tetrafluoroethylene/ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene, ethylene copolymer (ECTFE), etc. .

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

The fluororesin is particularly preferably a thermoplastic fluororesin containing a functional group. When a thermoplastic fluororesin containing no functional group is used, in order to obtain an adhesive property that can withstand practical requirements, the polyimide film must be subjected to calender treatment, corona treatment, plasma treatment, ion gun treatment, etching treatment, and the like. Surface treatment has doubts that lead to increased costs.

The functional group-containing thermoplastic fluororesin, for example, contains a compound selected from the group consisting of a carboxylic acid group or a derivative thereof, a hydroxyl group, a nitrile group, a cyanate group, an amine methyl oxy group, a phosphinomethoxy group, a halogen phosphine oxy group, a sulfonic acid group. A thermoplastic fluororesin (functional group-containing fluororesin) having a functional group or a sulfonium halide group. The functional group-containing fluororesin is generally used in a thermoplastic fluororesin which is generally used in the above-mentioned molding, and which does not significantly impair the properties. When the functional group-containing fluororesin is obtained, for example, the thermoplastic fluororesin shown in the above examples used in general molding can be synthesized in advance, and then introduced by addition or substitution of these functional groups, or in the foregoing exemplification In the synthesis of the thermoplastic fluororesin, a monomer having such a functional group is copolymerized to obtain a monomer.

Specific examples of the aforementioned functional groups are -COOH, -CH2COOH, -COOCH3, -CONH2, -OH, -CH2OH, -CN, -CH2O(CO)NH2, -CH2OCN, -CH2OP(O)(OH)2, - CH2OP(O)C12, -SO2F, etc. These functional groups are preferably introduced into the fluororesin by copolymerizing a fluorine-containing monomer having a functional group at the time of production of the fluororesin.

The monomer having such a functional group is preferably copolymerized in an amount of from 0.5 to 10% by weight based on the functional group-containing fluororesin, more preferably from 1 to 5% by weight. The distribution of the functional group-containing monomer in the functional group-containing fluororesin may be uniform or non-uniform. When the content ratio of the functional group-containing monomer in the functional group-containing fluororesin is too low, it is less effective as a compatibilizing agent, and on the other hand, when the content ratio is too high, due to the functional group-containing fluorine The strong interaction of the resins may cause a reaction similar to the crosslinking reaction, which increases the viscosity and makes it difficult to melt-form. Further, when the content ratio of the functional group-containing monomer is too high, the heat resistance of the functional group-containing fluororesin tends to be deteriorated.

The viscosity or molecular weight of the functional group-containing fluororesin is not particularly limited, and may be preferably within a range not exceeding the viscosity or molecular weight of the thermoplastic fluororesin for general molding of the functional group-containing fluororesin. Degree.

The fluororesin preferably contains 0.1 to 2% by mass of an antistatic agent which imparts antistatic properties. The antistatic agent is preferably a surfactant such as a nonionic surfactant, an anionic surfactant, a cationic surfactant, or a zwitterionic surfactant.

The fluororesin preferably further contains an inorganic filler which can lower the dielectric constant or dielectric tangent. The inorganic fillers are, for example, cerium oxide, 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, aluminum hydroxide, basic magnesium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, calcium citrate, Montestone, bentonite, activated clay, sea Asphalt, filamentous aragonite, sericite, glass fiber, glass beads, cerium oxide ball, carbon black, graphite, carbon fiber, carbon sphere, wood powder, zinc borate, and the like.

The inorganic filler may be used singly or in combination of two or more. The content of the inorganic filler is preferably from 1 to 100% by mass based on the fluororesin. Further, when the inorganic filler is porous, the dielectric constant or dielectric tangent can be further lowered, which is more preferable.

The thickness of the fluororesin is preferably from 1.0 μm to 50 μm, more preferably from 1.0 μm to 38 μm, still more preferably from 1.0 μm to 25 μm. If the film thickness is thicker than 50 μm, it is less preferable for the purpose of lightening the electronic parts. On the other hand, when the film thickness is thinner than 1.0 μm, the effect of surface modification such as improvement in electrical characteristics by fluororesin, reduction in water absorbability, and improvement in adhesion is small, which is not preferable.

The storage elastic modulus of the fluororesin: E' (A) is not particularly limited and is known. When a fluororesin having the above composition is used, a value of 0.3 GPa to 1.0 GPa can be generally used.

Further, the linear expansion coefficient of the fluororesin is not particularly limited, and it is generally known that a fluororesin having the above composition can be used in a value of from 50 ppm/°C to 150 ppm/°C.

Further, from the viewpoint of high frequency correspondence, the dielectric constant of the film and the dielectric tangent are preferably small. The dielectric constant and dielectric tangent of the fluororesin layer are not particularly limited, and it is known that a fluororesin having the above composition can be used in a relatively low value. Specifically, the dielectric constant of 1 MHz is 2.0 to 2.2, and the dielectric tangent of 1 MHz is 3.0 × 10 ^-4 to 5.0 × 10 ^-4 .

On the surface of the fluororesin, treatment with a coupling agent (amino decane, epoxy decane, etc.), sand blasting, calendering, corona treatment, plasma treatment, ion gun treatment, etching may be applied as necessary. Processing and so on.

The (B) polyimine resin layer used in the present invention is, for example, an aromatic tetracarboxylic acid (an acid anhydride, an acid and a guanamine-bonded derivative collectively referred to as the same, the same below) and an aromatic diamine. A method for forming a film by performing a solution casting, drying, and heat treatment (yttrium imidization) of a polyglycine solution obtained by reacting an amine (an amine and a guanamine-bonded derivative, the same as the following) The obtained polyimide film or the layer formed by applying the polyamic acid solution to the fluororesin layer (film) and drying and heat-treating (yttrium) to treat or produce In view of the above, it is preferably a form of a polyimide film.

The following mainly describes the polyimide film.

The polyimine is not particularly limited, and a preferred example is a combination of the following aromatic diamines and aromatic tetracarboxylic acids (anhydrides).

A. An aromatic tetracarboxylic acid having a pyrophoric acid residue and having a benzoic acid A combination of aromatic diamines of the azole structure.

B. Combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.

C. Combination of an aromatic diamine having a diphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyromellitic acid residue.

Among the best ones, A. has benzo A polyimide film of an aromatic diamine residue of an azole structure.

Benzene The structure of the aromatic diamine of the azole structure is not particularly limited, and specifically, the following are shown. These diamines are preferably 70 mol% or more, and more preferably 80 mol% or more of all diamines.

[Chemical Formula 1] 5-amino-2-(p-aminophenyl)benzo Azole

[Chemical Formula 2] 6-Amino-2-(p-aminophenyl)benzo Azole

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

[Chemical Formula 4] 6-Amino-2-(m-aminophenyl)benzo Azole

[Chemical Formula 5] 2,2'-p-benzoquinone (5-aminobenzobenzene) Oxazole

[Chemical Formula 6] 2,2'-p-benzoquinone (6-aminobenzobenzene) Oxazole

[Chemical Formula 7] 1-(5-Aminobenzobenzene Azole)-4-(6-aminobenzone) Azole

[Chemical formula 8] 2,6-(4,4'-diaminodiphenyl)benzene [1,2-d:5,4-d'] double Azole

[Chemical formula 9] 2,6-(4,4'-diaminodiphenyl)benzene [1,2-d:4,5-d'] double Azole

[Chemical Formula 10] 2,6-(3,4'-diaminodiphenyl)benzene [1,2-d:5,4-d'] Azole

[Chemical formula 11] 2,6-(3,4'-diaminodiphenyl)benzene [1,2-d:4,5-d'] double Azole

[Chemical Formula 12] 2,6-(3,3'-diaminodiphenyl)benzene [1,2-d:5,4-d'] Azole

[Chemical formula 13] 2,6-(3,3'-diaminodiphenyl)benzene [1,2-d:4,5-d'] double Azole

Among them, from the viewpoint of ease of synthesis, an amino group (aminophenyl) benzo is preferred. Each isomer of azole, especially 5-amino-2-(p-aminophenyl)benzo Oxazole. Among them, the so-called "isomers" are amine (aminophenyl) benzo Each of the isomers is determined by the coordination position of the two amine groups of the azole (for example, each of the compounds described in "Chemical Formula 1" to "Chemical Formula 4"). These diamines may be used alone or in combination of two or more.

In addition, if it is 30 mol% or less of all the diamines, one type or two or more types of diamines exemplified below may be used. Such diamines are, for example, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(3-aminophenoxy)phenyl]one, bis[4-(3) -aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfonic acid, 2,2-bis[4-(3-aminophenoxy)benzene Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine , p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4' -diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylarylene, 3,4'-diaminodiphenylarylene , 4,4'-diaminodiphenylarylene, 3,3'-diaminodiphenyl sulfonic acid, 3,4'-diaminodiphenyl sulfonic acid, 4,4'-diamine Diphenyl sulfonic acid, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 3,3' -diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(4-aminophenoxy)phenyl Methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1 , 2-bis[4-(4-aminophenoxy)phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-double [ 4-(4-Aminophenoxy)phenyl]propane, 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-amine Phenyloxy)phenyl]propane, 1,1-bis[4-(4-aminophenoxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy) Phenyl]butane, 1,4-bis[4-(4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl] Alkane, 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-aminophenoxy)-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-hexafluoropropane, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy) Benzo, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]one, bis[4-(4-aminobenzene) Oxy)phenyl]sulfide , bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]sulfonic acid, bis[4-(3-aminobenzene) Oxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzylidene]benzene, 1,3-bis[4-(3-aminophenoxy)benzylidene]benzene, 1,4-bis[4-(3-aminophenoxy)benzylidene]benzene, 4, 4'-bis[(3-aminophenoxy)benzylidene]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-double [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]arene, 4 , 4'-bis[3-(4-aminophenoxy)benzylidene]diphenyl ether, 4,4'-bis[3-(3-aminophenoxy)benzylidene] Diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl ketone, 4,4'-bis[4-( 4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfonic acid, double [4-{4 -(4-Aminophenoxy)phenoxy}phenyl]sulfonic acid, 1,4-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzoate Benzene, 1,3-bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amine 5--6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-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'-diphenoxy Diphenyl ketone, 4,4'-diamino-5,5'-diphenoxydiphenyl ketone, 3,4'-diamino-4,5'-diphenoxydiphenyl ketone , 3,3'-diamino-4-phenoxydiphenyl ketone, 4,4'-diamino-5-phenoxydiphenyl ketone, 3,4'-diamino-4- Phenoxydiphenyl ketone, 3,4'-diamino-5'-phenoxydiphenyl ketone, 3,3'-diamino-4,4'-dibisphenoxydiphenyl Ketone, 4,4'-diamino-5,5'-dibisphenoxydiphenyl ketone, 3,4'-diamino-4,5'-dibisphenoxydiphenyl ketone, 3,3'-diamino-4-bisphenoxydiphenyl ketone 4,4'-Diamino-5-bisphenoxydiphenyl ketone, 3,4'-diamino-4-bisphenoxydiphenyl ketone, 3,4'-diamino-5 '-Bisphenoxydiphenyl ketone, 1,3-bis(3-amino-4-phenoxybenzylidene)benzene, 1,4-bis(3-amino-4-phenoxy) Benzomethane)benzene, 1,3-bis(4-amino-5-phenoxybenzylidene)benzene, 1,4-bis(4-amino-5-phenoxybenzylidene) Benzene, 1,3-bis(3-amino-4-bisphenoxybenzhydryl)benzene, 1,4-bis(3-amino-4-bisphenoxybenzhydryl)benzene , 1,3-bis(4-amino-5-bisphenoxybenzhydryl)benzene, 1,4-bis(4-amino-5-bisphenoxybenzhydryl)benzene, 2 , 6-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, and a part or all of hydrogen atoms on the aromatic ring of the above aromatic diamine a halogen atom or alkoxy group having a carbon number of 1 to 3 or an alkoxy group, a cyano group, or a part or all of a hydrogen atom of an alkyl group or an alkoxy group substituted by a halogen atom; An aromatic diamine or the like substituted with an oxy group.

The molecular structure of the aromatic tetracarboxylic anhydride is not particularly limited, and specifically, the following are shown. These acid anhydrides are preferably 70 mol% or more, and more preferably 80 mol% or more of all the acid anhydrides.

[Chemical Formula 14] pyrethic acid dianhydride

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

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

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

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

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

These tetracarboxylic dianhydrides may be used singly or in combination of two or more.

In addition, if it is 30 mol% or less of all tetracarboxylic dianhydrides, it is also possible to use one or more types of non-aromatic tetracarboxylic dianhydrides exemplified below. Such tetracarboxylic anhydrides, for example, butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride , cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3,5, 6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-en-3-(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane- 3-(1,2),5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3-(1,2),5,6-tetracarboxylic acid Anhydride, 1-ethylcyclohexane-1-(1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1-(2,3), 3,4-tetracarboxylate Acid 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[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3 , 5,6-tetracarboxylic dianhydride, and the like.

The solvent used in the reaction (polymerization) of the aromatic tetracarboxylic acid and the aromatic diamine to obtain a polyamic acid is any one of a monomer capable of dissolving a raw material and a produced polyamine. It is not particularly limited, and is preferably a polar organic solvent such as N-methyl-2-pyrrolidone, N-ethinyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethyl Mercaptoamine, N,N-dimethylacetamide, dimethyl hydrazine, hexamethylphosphoniumamine, ethyl cellosolve acetate, diethylene glycol dimethyl ether, cyclobutyl hydrazine, Halogenated phenols and the like. These solvents may be used singly or in combination. The amount of the solvent may be any amount as long as the amount of the monomer of the raw material can be sufficiently dissolved. The specific amount is usually 5 to 40% by weight, preferably 10 to 30% by weight based on the weight of the solution of the monomer.

The conditions for the polymerization reaction of polylysine (hereinafter also referred to simply as "polymerization reaction") can be carried out using conventionally known conditions, and specific examples are in an organic solvent at a temperature ranging from 0 to 80 ° C. Stir and/or mix for 10 minutes to 30 hours. It is also possible to divide the polymerization reaction or increase or decrease the temperature as necessary. In this case, the order of addition of the two monomers is not particularly limited, but it is preferred to add the aromatic tetracarboxylic acid to the solution of the aromatic diamine. The viscosity of the polyaminic acid solution prepared by the polymerization reaction is preferably from 10 to 2000 Pa‧s in terms of the stability of liquid transport from the viewpoint of the Brookfield viscometer (25 ° C). Especially good is 100~1000Pa‧s.

The vacuum defoaming in the polymerization reaction is effective for producing a good polyamic acid solution. Further, a small amount of terminal blocking agent may be added to the aromatic diamine before the polymerization to control the polymerization. The terminal blocking agent is, for example, a compound having a carbon-carbon double bond such as maleic anhydride. The amount of the maleic anhydride to be used is preferably from 0.001 to 1.0 mol per 1 mol of the aromatic diamine.

In order to form a polyimide film from a polyamic acid solution prepared by a polymerization reaction, for example, a green film is obtained by applying a polyaminic acid solution onto a support and drying it ( A self-supporting precursor film), followed by heat treatment of the green sheets to carry out the oxime imidization reaction. The application of the polyaminic acid solution to the support includes a solution cast film from a discharge port having a slit, and extrusion by an extruder, but the present invention is not limited thereto, and the conventional use can be suitably used. Know the coating method of the solution.

The conditions for obtaining the green sheet by drying the polylysine coated on the support are not particularly limited, and the temperature is, for example, 70 to 150 ° C, and the drying time is, for example, 5 to 180 minutes. A drying device that achieves such conditions can also be used in the past, such as hot air, hot nitrogen, far infrared rays, high frequency induction heating, and the like. Next, in order to obtain the intended polyimide film from the obtained embryo sheet, a ruthenium imidization reaction is carried out, and in the specific method, a conventionally known oxime imidization reaction can be used. For example, there is a method in which a polyaminic acid solution containing no ring-closing catalyst and a dehydrating agent is used, and if necessary, a stretching treatment is carried out, followed by heat treatment to carry out a hydrazine imidization reaction (so-called thermal ring closure method). The heating temperature at this time is, for example, 100 to 500 ° C. From the viewpoint of film properties, it is particularly preferable to carry out the treatment at 150 to 250 ° C for 3 to 20 minutes, and then at 350 to 500 ° C for 3 to 20 minutes. The 2-stage heat treatment of the treatment.

Other examples of the ruthenium iodization reaction include, for example, a chemical ring closure in which a ring-closing catalyst and a dehydrating agent are previously contained in a polyaminic acid solution, and the ruthenium imidization reaction is carried out by the action of the above-mentioned ring-closing catalyst and a dehydrating agent. law. In this method, after the polyproline solution is applied to the support, a part of the oxime imidization reaction is carried out to form a film having self-supporting properties, and then the ruthenium iodization is completely performed by heating. In this case, a part of the conditions of the ruthenium imidization reaction is preferably carried out at 100 to 200 ° C for 3 to 20 minutes, and the conditions of the ruthenium imidization reaction are completely carried out, preferably at 200 to 400 ° C. Heat treatment for 3 to 20 minutes.

The thickness of the polyimide film forming the polyimine resin layer is preferably 1.0 μm to 38 μm, more preferably 1.0 μm to 25 μm, still more preferably 1.0 μm to 12.5 μm. When the film thickness is thicker than 38 μm, it is less preferable for the purpose of lightening the electronic component. Further, the ratio of the polyimine to the entire laminate is high, which adversely affects the water absorption or the physical properties of the electrical properties, and thus is not preferable. On the other hand, when the film thickness is thinner than 1.0 μm, it is easily broken during transportation and wrinkles are easily formed, so that it is difficult to form a film.

The storage elastic modulus of the polyimine film forming the polyimine resin layer: E' (B) is not particularly limited, but is preferably 6.0 GPa or more, particularly preferably 7.0 GPa or more, and more preferably 8.0 GPa or more. . When the tensile breaking strength is smaller than 6.0 GPa, there may be a concern that the polyimide film does not have the effect of reinforcing the fluororesin layer.

Further, the linear expansion coefficient of the polyimide film forming the polyimine resin layer is preferably -10 ppm/° C. to 10 ppm/° C., particularly preferably −7.5 ppm/° C. to 7.5 ppm/° C., more preferably -5ppm/°C~5ppm/°C. When the coefficient of linear expansion exceeds this range, there is a concern that strain or wrinkles may occur under high temperature exposure such as solder bonding.

In the polyimine film forming the polyimine resin layer, a coupling agent (amine decane, epoxy decane, etc.), sand blasting, calendering, corona treatment, plasma treatment, ion can be performed as necessary. Gun processing, etching treatment, etc.

The method for producing a copper-clad laminate (CCL) in which the (C) copper layer is formed on the (B) polyimine resin layer without the adhesive of the second invention of the present application is not particularly limited, and for example, the following means .

‧ A method of forming a copper layer on a polyimide film by vacuum coating techniques such as vapor deposition, sputtering, or ion deposition.

‧ A method of forming a copper layer on a polyimide film by wet plating such as electroless plating or electroplating.

‧ A method in which a polyaminic acid solution is applied onto a copper foil and dried and heat-treated (醯iminated).

The (C) copper layer can be formed on the (B) polyimine resin layer without using an adhesive by using these means alone or in combination.

The linear expansion coefficient of the multilayer fluororesin film of the present invention is preferably from 10 ppm/°C to 30 ppm/°C, more preferably from 10 ppm/°C to 28 ppm/°C, still more preferably from 10 ppm/°C to 25 ppm/°C. When the coefficient of linear expansion exceeds this range, when the layer is laminated with a copper foil having a linear expansion coefficient of 16 ppm/° C., the deviation between the linear expansion coefficients of the two increases, and there is a fear that peeling or warpage tends to occur during use.

In order to set the linear expansion coefficient of the multilayer fluororesin film to be in the range of 10 ppm/° C. to 30 ppm/° C., the thickness ratio of the (A) layer of the multilayer fluororesin film is 60% of the {(A) layer/multilayer fluororesin film}. 90%, and (A) layer storage elastic modulus at room temperature: E' (A) and (B) layer storage elastic modulus at room temperature: E' (B) ratio {E' (A ) / E ' ( B ) } is preferably 2.0% to 20%, particularly preferably a thickness ratio of 65% to 90% and a storage elastic modulus ratio of 2.5% to 15%, more preferably a thickness ratio of 65% to 85%. And the storage elastic modulus ratio is 3.0% to 10%.

When the thickness ratio or the storage elastic modulus ratio exceeds this range, the multilayer fluororesin film of the target linear expansion coefficient cannot be obtained.

The thickness of the copper foil used in the present invention is preferably 1.0 μm to 25 μm, more preferably 1.0 μm to 12.5 μm, still more preferably 1.0 μm to 10 μm.

The copper foil lamination method of the copper-clad multilayer fluororesin film used in the present invention is not particularly limited, and for example, the following means are available.

‧ A method in which a multilayer fluororesin film is bonded to a copper foil and then welded by hot molding.

‧ A method of forming a copper layer on a multilayer fluororesin film by a vacuum coating technique such as vapor deposition, sputtering, or ion deposition.

‧ A method of forming a copper layer on a multilayer fluororesin film by a wet plating method such as electroless plating or electrolytic plating.

The copper foil can be laminated on at least one side of the multilayer fluororesin film by the use of these means alone or in combination (in the second invention of the present application, the (A) plane of the multilayer fluororesin film).

The multilayer fluororesin film or the copper-clad multilayer fluororesin film of the present invention can be applied to, for example, a conductive copper foil layer by a general method or a thick film metal layer which is plated after being formed thereon as necessary. After drying on the side, the wiring circuit pattern is formed by the steps of exposure, development, etching, and photoresist stripping, and then solder resist coating, plasticizing, and electroless tin plating are performed as necessary to obtain flexibility. A printed wiring board, a multilayer printed wiring board in which these layers are multilayered, or a printed wiring board on which a semiconductor wafer is directly mounted. The method of fabricating, multilayering, and mounting the semiconductor wafer is not particularly limited, and can be appropriately selected and implemented from a generally known method.

In the copper foil layer used in the present invention, a coating film of an inorganic substance such as a metal monomer or a metal oxide can be formed on the surface of the thick film metal layer side which is plated after it is necessary to be formed thereon. In addition, the copper foil layer or the surface of the thick film metal layer plated after being formed thereon may be treated with a coupling agent (amine decane, epoxy decane, etc.), sand blasting, calendering, and electricity. Halo treatment, plasma treatment, ion gun treatment, etching treatment, and the like.

Example

The present invention will be more specifically described below by showing examples and comparative examples, but the present invention is not limited to the following examples. The evaluation methods of the physical properties in the following examples are as follows.

1. Reduction viscosity (ηsp/C)

Dissolved in N-methyl-2-pyrrolidone (or N,N-dimethylacetone) at 30 ° C in a manner such that the polymer concentration becomes 0.2 g/dl by means of an Ubroad-type viscometer The solution of the amine) was measured.

2. Thickness

The film to be measured was measured using a micrometer (Millitron 1245D, manufactured by Feinpruf Co., Ltd.).

3. Storage elastic modulus

The film of the measurement object was subjected to viscoelasticity measurement (DMA) under the following conditions, and the value of the storage elastic modulus at 25 ° C: E' was determined.

Device name: Rheogel-E4000 made by UBM

Casting: stretching casting

Sample length: 14mm

Sample width: 5mm

Frequency: 10Hz

Temperature rise start temperature: 0 ° C

Heating rate: 5 ° C / min

Ambient gas: nitrogen

4. Linear expansion coefficient (CTE)

The film of the measurement target was measured for the expansion ratio in the MD direction and the TD direction under the following conditions, and the expansion ratio/temperature was measured at intervals of 10 to 100 ° C at 100 to 100 ° C and 100 to 110 ° C, and the measurement was carried out until 400 ° C. The average value of the total measured values from 100 ° C to 350 ° C was calculated as CTE (average value).

Device Name: TMA4000S made by MAC Science

Sample length: 10mm

Sample width: 2mm

Initial load: 34.5g/mm ²

Heating start temperature: 25 ° C

Temperature rise temperature: 400 ° C

Heating rate: 5 ° C / min

Ambient gas: argon

5. Melting point

The film to be measured was subjected to differential scanning calorimetry (DSC) under the following conditions, and the melting point (Tm) was determined in accordance with JIS K 7121.

Device Name: DSC3100S made by MAC Science

Heating pot: aluminum pot (non-hermetic type)

Sample quality: 4mg

Heating start temperature: 30 ° C

Temperature rise temperature: 400 ° C

Heating rate: 20 ° C / min

Ambient gas: argon

6. Dielectric constant, dielectric tangent

The fluororesin film to be measured was cut into a size of 3 mm (thickness) × 200 mm × 120 mm to prepare a test film. The conductive paste was applied to both sides of the test film to perform wiring, and the dielectric constant and dielectric tangent of 1 MHz were measured.

7. Peel strength

The peel strength between the multilayer fluororesin film/copper foil can be determined by performing a 90° peel test under the following conditions.

Device name: Autograph AG-IS manufactured by Shimadzu Corporation

Sample length: 100mm

Sample width: 10mm

Measuring temperature: 25 ° C

Peeling speed: 50mm/min

Ambient gas: atmosphere

"Evaluation of Substrate" heat and humidity resistance

The multilayer fluororesin film and each copper-clad multilayer fluororesin film were treated under JEDEC LEVEL1 conditions (85 ° C / 85% RH - 168 hr + 245 ° C / 3 sec × 3 times), and the peel strength after the test was evaluated. In addition, by the visual inspection after the test, the peeling, swelling, and discoloration were not observed at all, and only a slight detachment, swelling, and discoloration were observed as Δ, and peeling, swelling, and discoloration were observed as ×.

Evaluation of Substrate Heat Resistance

The multilayer fluororesin film and each copper-clad multilayer fluororesin film were placed in a stainless steel mesh cage, heat-treated in the air at 250 ° C to 24 hr, and the peel strength after the test was evaluated. In addition, by the visual inspection after the test, the peeling, swelling, and discoloration were not observed at all, and only a slight detachment, swelling, and discoloration were observed as Δ, and peeling, swelling, and discoloration were observed as ×.

[Manufacturing Example 1]

(Production of Polyimine Film A)

Adding 5-amino-2-(p-aminophenyl)benzene to a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, followed by nitrogen substitution. After 223 parts by mass of azole and 4416 parts by mass of N,N-dimethylacetamide and completely dissolved, Snow-Tex (DMAC-ST30, Nissan Chemical Co., Ltd.) obtained by dispersing colloidal cerium oxide in dimethylacetamide was added. 40.5 parts by mass (containing 8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride were stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown and viscous polyamic acid solution A. . Its reducing concentration was 3.9 dl/g.

The polyamic acid solution A was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate, and dried at 110 ° C for 5 minutes using a knife coater. Thereafter, the polylysine film was taken up without being peeled off from the support. The polyproline membrane is passed through a needle comber having a three-stage heat treatment zone, and heat treatment is performed in the first stage at 150 ° C for 2 minutes, the second stage at 220 ° C for 2 minutes, and the third stage at 475 ° C for 4 minutes. After 20 minutes through the tenter, a two-side smoothing process was carried out through six rolls, and finally cut into a width of 500 mm to obtain a polyimide film A1 to A4.

Table 1 shows the physical property values of the obtained polyimine films A1 to A4.

[Manufacturing Example 2]

(Production of Polyimine Film B)

After substituting nitrogen in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 200 parts by mass of diaminodiphenyl ether and 4170 parts by mass of N-methyl-2-pyrrolidone are added and completely dissolved, and then colloid is added. 40.5 parts by mass of Snow-Tex (DMAC-ST30, manufactured by Nissan Chemical Industries Co., Ltd.) in which cerium oxide is dispersed in dimethylacetamide (containing 8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride The mixture was stirred at a reaction temperature of 25 ° C for 5 hours to obtain a brown and viscous polyamic acid solution B. Its reducing concentration is 3.6 dl/g. The polyamic acid solution B was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a knife coater, and dried at 110 ° C for 5 minutes. Thereafter, the polylysine film was taken up without being peeled off from the support. The polyamic acid film is passed through a needle carding machine having a three-stage heat treatment zone, and heat treatment is performed in the first stage of 150 ° C × 2 minutes, the second stage of 220 ° C × 2 minutes, and the third stage of 400 ° C × 4 minutes. A two-side smoothing process was carried out through 6 rolls after passing through the tenter, and finally cut into a width of 500 mm to obtain a polyimide film B.

Table 1 shows the physical property values of the obtained polyimide film B.

[Manufacturing Example 3]

(Production of Polyimine Film C)

After a nitrogen gas substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 108 parts by mass of phenylenediamine and 4010 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal cerium oxide was dispersed. 40.5 parts by mass of Snow-Tex (DMAC-ST30, manufactured by Nissan Chemical Industries Co., Ltd.) made of dimethylacetamide (containing 8.1 parts by mass of cerium oxide) and 292.5 parts by mass of diphenyltetracarboxylic dianhydride. The mixture was stirred at a reaction temperature of 25 ° C for 12 hours to obtain a brown and viscous polyamic acid solution C. Its reducing concentration is 4.3 dl/g.

The polyamic acid solution C was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a knife coater, and dried at 110 ° C for 5 minutes. Thereafter, the polylysine film was taken up without being peeled off from the support. The polyamic acid film is passed through a needle carding machine having a three-stage heat treatment zone, and heat treatment is performed in the first stage of 150 ° C × 2 minutes, the second stage of 220 ° C × 2 minutes, and the third stage of 460 ° C × 4 minutes. A two-side smoothing process was carried out by passing six rolls after 20 minutes through a tenter, and finally cut into 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.

[Manufacturing Example 4]

(Production of fluororesin film)

A fluororesin film was produced by a generally known method using a commercially available fluororesin.

Table 2 and Table 3 show the types and physical properties of the obtained fluororesin film.

In the figure, PAF is tetrafluoroethylene. Perfluoroalkyl vinyl ether copolymer, FEP is tetrafluoroethylene ‧ hexafluoropropylene copolymer, EPE is tetrafluoroethylene ‧ hexafluoropropylene ‧ perfluoroalkyl vinyl ether copolymer, ETFE It is a tetrafluoroethylene ‧ ethylene copolymer.

[Manufacturing Example 5]

(production of polyimine film a)

Adding 5-amino-2-(p-aminophenyl)benzene to a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, followed by nitrogen substitution. After 223 parts by mass of azole and 4416 parts by mass of N,N-dimethylacetamide and completely dissolved, Snow-Tex (DMAC-ST30, Nissan Chemical Co., Ltd.) obtained by dispersing colloidal cerium oxide in dimethylacetamide was added. 40.5 parts by mass (containing 8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride were stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown and viscous polyamic acid solution A. . Its reducing concentration was 3.9 dl/g.

The polyamic acid solution A was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate, and dried at 110 ° C for 5 minutes using a knife coater. Thereafter, the polylysine film was taken up without being peeled off from the support. The polyproline membrane is passed through a needle comber having a three-stage heat treatment zone, and heat treatment is performed in the first stage at 150 ° C for 2 minutes, the second stage at 220 ° C for 2 minutes, and the third stage at 475 ° C for 4 minutes. After 20 minutes through the tenter, a double-sided smoothing process was carried out by 6 rolls, and finally cut into a width of 500 mm to obtain a polyimide film a1 to a4.

Table 11 shows the physical property values of the obtained polyimine films a1 to a4.

Then, sputtering and plating are performed.

The polyimide film a1 to a4 were cut into an A4 size, and sandwiched between a stainless steel frame having an opening and fixed. The frame is fixed to the substrate holder in the sputtering apparatus. The substrate holder is fixed in such a manner that the substrate holder is adhered to the polyimide film. Therefore, the temperature of the polyimide film can be set by circulating the refrigerant in the substrate holder. The plasma treatment of the surface of the polyimide film is then carried out. The plasma treatment conditions were as follows: under the conditions of argon gas, frequency 13.56 MHz, output of 200 W, and gas pressure of 1 × 10 ^-3 Torr, the temperature at the time of the treatment was 2 ° C, and the treatment time was 2 minutes. Then, using a nickel-chromium (chromium 10% by mass) alloy target at a frequency of 13.56 MHz, an output of 450 W, and a pressure of 3 × 10 ^-3 Torr, DC magnetron sputtering was used in an argon atmosphere. A nickel-chromium alloy film (bottom layer) having a thickness of 7 nm was formed at a rate of 1 nm/second, and then a refrigerant having a temperature of 2 ° C was controlled in the inner surface of the sputtering surface of the substrate so that the temperature of the substrate was set to 2 ° C. Circulation. Then, sputtering was performed in a state of being in contact with the SUS plate of the substrate holder to form a copper film having a thickness of 0.25 μm, and polyimine films a1 to a4 having the underlying metal thin film formed on one side thereof were obtained. Among them, the thickness of the copper and NiCr layers can be confirmed by a fluorescent X-ray method. The obtained polyimide film a1 to a4 on which the underlying metal thin film was formed on one side was fixed in a plastic frame, and a copper sulfate plating bath was used to form a copper layer having a thickness of 9 μm. The plating conditions were immersed in a plating solution (copper sulfate 80 g/l, sulfuric acid 210 g/l, HCl, a small amount of a gloss agent), and a current of 1.5 Adm ² was passed. Subsequently, it was subjected to heat treatment drying at 120 ° C for 10 minutes to obtain copper-clad laminates (CCL) a1 to a4 of a polyimide film having a copper layer formed on one side.

[Manufacturing Example 6]

(Production of polyimine film b)

After substituting nitrogen in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 200 parts by mass of diaminodiphenyl ether and 4170 parts by mass of N-methyl-2-pyrrolidone are added and completely dissolved, and then colloid is added. 40.5 parts by mass of Snow-Tex (DMAC-ST30, manufactured by Nissan Chemical Industries Co., Ltd.) in which cerium oxide is dispersed in dimethylacetamide (containing 8.1 parts by mass of cerium oxide) and 217 parts by mass of pyromellitic dianhydride The mixture was stirred at a reaction temperature of 25 ° C for 5 hours to obtain a brown and viscous polyamic acid solution B. Its reducing concentration is 3.6 dl/g. The polyamic acid solution B was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a knife coater, and dried at 110 ° C for 5 minutes. Thereafter, the polylysine film was taken up without being peeled off from the support. The polyamic acid film is passed through a needle carding machine having a three-stage heat treatment zone, and heat treatment is performed in the first stage of 150 ° C × 2 minutes, the second stage of 220 ° C × 2 minutes, and the third stage of 400 ° C × 4 minutes. A two-side smoothing process was carried out by passing six rollers after 20 minutes through a tenter, and finally cut into a width of 500 mm to prepare a polyimide film b.

Table 11 shows the physical property values of the obtained polyimide film b.

Then, sputtering and plating were carried out in the same manner as in Production Example 5 to obtain a copper clad laminate (CCL) b.

[Manufacturing Example 7]

(Production of polyimine film c)

After a nitrogen gas substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 108 parts by mass of phenylenediamine and 4010 parts by mass of N-methyl-2-pyrrolidone were added and completely dissolved, and then colloidal cerium oxide was dispersed. 40.5 parts by mass of Snow-Tex (DMAC-ST30, manufactured by Nissan Chemical Industries Co., Ltd.) made of dimethylacetamide (containing 8.1 parts by mass of cerium oxide) and 292.5 parts by mass of diphenyltetracarboxylic dianhydride. The mixture was stirred at a reaction temperature of 25 ° C for 12 hours to obtain a brown and viscous polyamic acid solution C. Its reducing concentration is 4.3 dl/g.

The polyamic acid solution C was applied to a lubricant-free surface of a film A-4100 (manufactured by Toyobo Co., Ltd.) made of polyethylene terephthalate using a knife coater, and dried at 110 ° C for 5 minutes. Thereafter, the polylysine film was taken up without being peeled off from the support. The polyamic acid film is passed through a needle carding machine having a three-stage heat treatment zone, and heat treatment is performed in the first stage of 150 ° C × 2 minutes, the second stage of 220 ° C × 2 minutes, and the third stage of 460 ° C × 4 minutes. A two-side smoothing process was carried out by passing six rolls after 20 minutes through a tenter, and finally cut into 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.

Then, sputtering and plating were carried out in the same manner as in Production Example 5 to obtain a copper clad laminate (CCL) c.

[Manufacturing Example 8]

(Production of fluororesin film)

A fluororesin film was produced by a generally known method using a commercially available fluororesin. Tables 12 and 13 show the types and physical properties of the obtained fluororesin film.

[Example 1]

The functional group-containing fluororesin film D1 (Fluon PFA, grade, manufactured by Asahi Glass Co., Ltd.) was placed on both sides of a polyimide film A1 cut to a size of 150 mm × 150 mm, and 330 ° C above the melting point of the fluororesin film. A heat-press molding was carried out at 5 MPa for 30 minutes to prepare a multi-layer fluororesin film.

On the other hand, a functional group-containing fluororesin film D1, a copper foil having a thickness of 9 μm (manufactured by UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) was placed on both sides of a polyimide film A1 cut to a size of 150 mm × 150 mm. On the other hand, heat-pressure-molding was performed at 330 ° C and 5 MPa which is more than the melting point of the fluororesin film for 30 minutes to obtain a double-sided copper-clad multilayer fluororesin film.

Table 4 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film. 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 the film quality are the evaluation results of the double-sided copper-clad multilayer fluororesin film.

[Examples 2, 3]

A laminate was produced and evaluated in the same manner as in Example 1 except that the polyimide film A2 and A3 were used instead of the polyimide film A1.

Table 4 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

[Example 4]

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

[Examples 5 and 6]

A laminate was produced and evaluated in the same manner as in Example 4 except that the polyimide film A2 and A3 were used instead of the polyimide film A1.

Table 5 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

[Embodiment 7]

A laminate was produced and evaluated in the same manner as in Example 6 except that the functional group-containing fluororesin film D3 (Fluon PFA 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 double-sided copper-clad multilayer fluororesin film.

[Examples 8 to 11]

The polyimine film A2 cut into a size of 150 mm × 150 mm was placed in a plasma processor manufactured by Nissin Electronics Co., Ltd., and after vacuum evacuation, oxygen gas was introduced and the discharge was excited to perform plasma treatment. The treatment conditions were a vacuum of 3 × 10 Pa, a gas flow rate of 1.5 SLM, and a discharge power of 12 kW.

A fluororesin film E (Fluon PFA, manufactured by Asahi Glass Co., Ltd.), F (manufactured by Neoflon PFA, manufactured by Daikin Industries Co., Ltd.), G (manufactured by Neoflon FEP, Daikin Industries Co., Ltd.), and H (EPE, manufactured by Daikin Industries, Ltd.) They are respectively disposed on both sides of the obtained plasma-treated polyimide film A2, and subjected to heat and pressure molding at 330 ° C and 5 MPa above the melting point of the fluororesin film to prepare a multi-layer fluororesin. membrane.

On the other hand, a fluororesin film E to H having no functional group and a copper foil having a thickness of 9 μm are disposed on both sides of the plasma-treated polyimide film A2, and 330 or more of the melting point of the fluororesin film. The double-sided copper-clad multilayer fluororesin film was obtained by heating and press molding at ° C and 5 MPa for 30 minutes.

Table 6 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

[Comparative Example 1]

A laminate was produced and evaluated in the same manner as in Example 2 except that the polyimide film B was replaced with the polyimide film B.

Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

When the linear expansion coefficient of the polyimide film is too large, the linear expansion coefficient of the obtained multilayer fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased, so the adhesion after the reliability test and The membrane quality is reduced.

[Comparative Examples 2, 3]

In addition to the functional group-containing fluororesin film 1 (Fluon LM-ETFE AH2000, manufactured by Asahi Glass Co., Ltd.), J (Neoflon EFEP RP5000, manufactured by Daikin Industries Co., Ltd.), and the functional group-containing fluororesin film D1, In the same manner as in Example 2, a laminate was produced and evaluated.

Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the adhesion and film quality after the reliability test are lowered.

[Comparative Examples 4 and 5]

In addition to the functional group-free fluororesin film K (Fluon ETFE, manufactured by Asahi Glass Co., Ltd.), L (Neoflon ETFE, manufactured by Daikin Industries Co., Ltd.), and the functional group-free fluororesin film E, The same method is used to make a laminate and evaluate it.

Table 7 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the adhesion and film quality after the reliability test are lowered.

[Comparative Example 6]

A laminate was produced and evaluated in the same manner as in Example 1 except that the polyimide film A4 was used instead of the polyimide film A1. Table 8 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced.

[Comparative Example 7]

A laminate was produced and evaluated in the same manner as in Comparative Example 6, except that the functional group-containing fluororesin film D2 (Fluon PFA grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film D1.

Table 8 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced.

[Comparative Examples 8 to 10]

A laminate was produced in the same manner as in Examples 4 to 6 except that the functional group-containing fluororesin film D4 (Fluon PFA, grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film D2. Evaluation.

Table 8 shows the evaluation results of the obtained multilayer fluororesin film and double-sided copper-clad multilayer fluororesin film.

When the thickness ratio of the fluororesin is too large, the linear fluororesin of the obtained multilayer fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased, so that the adhesion after the reliability test and the film quality are lowered.

[Examples 12 to 13, Comparative Examples 11 to 12]

(Evaluation of warpage of copper-clad multilayer fluororesin film)

The functional group-containing fluororesin film D3 was placed on both sides of a polyimide film A1 to A4 cut to a size of 150 mm × 150 mm, and heated at 330 ° C and 5 MPa above the melting point of the fluororesin film for 30 minutes. Pressurized to form a multi-layer fluororesin film.

Further, the functional group-containing fluororesin film D3 and a copper foil having a thickness of 9 μm (manufactured by UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) were placed on both sides of a polyimide film A1 to A4 cut to a size of 150 mm × 150 mm. On the other hand, heat-pressure-molding was performed at 330 ° C and 5 MPa which is more than the melting point of the fluororesin film for 30 minutes to obtain a double-sided copper-clad multilayer fluororesin film.

Then, the functional group-containing fluororesin film D3 was placed on one side of a polyimide film A1 to A4 cut to a size of 150 mm × 150 mm, and the functional group-containing fluororesin film D3 was sequentially laminated to a thickness of 9 μm. The copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) was placed on the other surface, and heat-pressed and formed at 330 ° C and 5 MPa above the melting point of the fluororesin film to obtain a single-sided copper-clad multilayer fluororesin. membrane.

The appearance inspection of the obtained single-sided and double-sided copper-clad multilayer fluororesin film was evaluated as ○ without warpage, Δ with warpage, and × when curled into a roll. The evaluation results are shown in Table 9.

When the linear expansion coefficient of the multilayer fluororesin film is larger than the linear expansion coefficient of the copper foil, in the asymmetric configuration of the single-sided copper-clad multilayer fluororesin film, the multilayer fluororesin film is warped to the inside.

[Examples 14 to 15, Comparative Example 13]

(Evaluation of warpage of copper-clad multilayer fluororesin film)

The functional group-containing fluororesin film D2 was placed on both sides of a polyimide film A2 to A4 cut to a size of 150 mm × 150 mm, and heated at 330 ° C and 5 MPa above the melting point of the fluororesin film for 30 minutes. Pressurized to form a multi-layer fluororesin film.

Further, a functional group-containing fluororesin film D2, a copper foil having a thickness of 9 μm (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) was placed on both sides of a polyimide film A2 to A4 cut to a size of 150 mm × 150 mm. On the other hand, heat-pressure-molding was performed at 330 ° C and 5 MPa which is more than the melting point of the fluororesin film for 30 minutes to obtain a double-sided copper-clad multilayer fluororesin film.

Then, the functional group-containing fluororesin film D2 was placed on one side of a polyimide film A2 to A4 cut to a size of 150 mm × 150 mm, and the functional group-containing fluororesin film D3 was sequentially laminated to a thickness of 9 μm. The copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) was placed on the other surface, and subjected to heat and pressure molding at 330 ° C and 5 MPa of the fluororesin film at a temperature of 30 MPa or more to obtain a single-sided copper-clad 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, in the asymmetric configuration of the single-sided copper-clad multilayer fluororesin film, the copper foil is warped to the inside.

[Application Example 1]

The functional group-containing fluororesin film D1 was placed on one surface of a polyimide film A2 cut into a size of 150 mm × 150 mm, and the functional group-containing fluororesin film D1 and the copper foil having a thickness of 9 μm were sequentially disposed. On the other hand, heat-pressure-molding was performed at 330 ° C and 5 MPa which is more than the melting point of the fluororesin film for 30 minutes to obtain a single-sided copper-clad multilayer fluororesin film.

On the other hand, using the double-sided copper-clad polyimide laminate obtained in Example 2, a photoresist (FR-200, manufactured by Shipley Co., Ltd.) was applied to one surface and dried, and then a glass mask was used. The film was exposed to light and then developed with a 1.2 mass% aqueous KOH solution. Subsequently, it was etched at a spray pressure of ² kgf/cm ² at 40 ° C and a copper chloride etching machine containing HCl and hydrogen peroxide to form a test pattern, and then washed and annealed at 125 ° C for 1 hour. A single-sided copper-clad multilayer fluororesin film (printed wiring board) having a single-sided pattern was obtained.

The pattern forming surface of the single-sided copper-clad multilayer fluororesin film (printed wiring board) having a single-sided pattern is opposed to the fluororesin surface of the single-sided copper-clad multilayer fluororesin film, and is 330 ° C above the melting point of the fluororesin film. The multilayer pressure-sensitive wiring board shown in Fig. 1 was obtained by heat-press molding at 30 MPa for 30 minutes. In the multilayer printed wiring board produced, since the copper wiring is covered with a fluororesin having a low dielectric constant, it is extremely useful as a member for high frequency.

[Example 16]

The functional group-containing fluororesin film d1 (Fluon PFA grade, manufactured by Asahi Glass Co., Ltd.) was placed on one surface of a polyimide film a1 cut to a size of 150 mm × 150 mm, and 330 ° C above the melting point of the fluororesin film. The layer (A) layer (B) layered body was obtained by heat-press molding at 30 MPa for 30 minutes.

Table 14 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B) obtained.

On the other hand, a functional group-containing fluororesin film d1 and a copper foil (manufactured by UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 9 μm were placed in a copper clad laminate (CCL) a1 cut to a size of 150 mm × 150 mm. The polyimine film a1 surface was subjected to heat and pressure molding at 330 ° C and 5 MPa of the fluororesin film at a temperature of 30 MPa or more to obtain a copper-clad multilayer fluororesin film.

Table 14 shows the evaluation results of the moisture resistance test and the heat resistance test of the obtained copper-clad multilayer fluororesin film.

[Examples 17, 18]

The polyimine film a1, a3 was used instead of the polyimine film a1, and the copper clad laminate (CCL) a2, a3 was used instead of the copper clad laminate (CCL) a1, and the others were the same as in the embodiment 16. The method is to make a laminate and evaluate it.

Table 14 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

[Embodiment 19]

A laminate was produced and evaluated in the same manner as in Example 16 except that the functional group-containing fluororesin film d2 (Fluon PFA grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d1.

Table 15 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

[Examples 20, 21]

The polyimine film a1, a3 was used instead of the polyimide film a1, and the copper clad laminate (CCL) a2, a3 was used instead of the copper clad laminate (CCL) a1, and the others were the same as in the example 19 The method is to make a laminate and evaluate it.

Table 15 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

[Example 22]

A laminate was produced and evaluated in the same manner as in Example 21 except that the functional group-containing fluororesin film d3 (Fluon PFA, grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d2.

Table 15 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

[Examples 23 to 26]

The polyimine film a2 cut into a size of 150 mm × 150 mm was placed in a plasma processor manufactured by Nissin Electronics Co., Ltd., and after vacuum evacuation, oxygen gas was introduced and the discharge was excited to perform plasma treatment. The treatment conditions were a vacuum of 3 × 10 Pa, a gas flow rate of 1.5 SLM, and a discharge power of 12 kW.

A functional group-free fluororesin film e (Fluon PFA, manufactured by Asahi Glass Co., Ltd.), f (manufactured by Neoflon PFA, manufactured by Daikin Industries Co., Ltd.), g (manufactured by Neoflon FEP, Daikin Industries Co., Ltd.), and h (EPE, manufactured by Daikin Industries, Ltd.) Each of the prepared plasma-treated polyimide film a2 was placed on one surface of the urethane-treated film at a temperature of 330 ° C or 5 MPa above the melting point of the fluororesin film for 30 minutes to obtain (A). Layer (B) layered body.

Table 16 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B).

On the other hand, the copper clad laminate (CCL) a2 was placed in a plasma processor manufactured by Nissin Electronics Co., Ltd., and after vacuum evacuation, oxygen gas was introduced and the discharge was excited to perform plasma treatment. The treatment conditions were a vacuum of 3 × 10 Pa, a gas flow rate of 1.5 SLM, and a discharge power of 12 kW.

A copper foil having no functional group-containing fluororesin film e~h and a thickness of 9 μm is disposed on the surface of the obtained polyimide-coated copper clad laminate (CCL) a2 on the polyimide film A2. The fluororesin film was subjected to heat and pressure molding at 330 ° C or 5 MPa above the melting point of the fluororesin film to obtain a copper-clad multilayer fluororesin film.

Table 16 shows the evaluation results of the obtained moist heat resistance test and heat resistance test.

[Comparative Example 14]

The polyimine film b was replaced with the polyimide film a1, and the copper clad laminate (CCL) b was used instead of the copper clad laminate (CCL) a1, and the same procedure as in Example 17 was carried out. The laminate is evaluated and evaluated.

Table 17 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

When the linear expansion coefficient of the polyimide film is too large, the linear expansion coefficient of the obtained multilayer fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased, so the adhesion after the reliability test and The membrane quality is reduced.

[Comparative Examples 15, 16]

In addition to the functional group-containing fluororesin film i (Fluon LM-ETFE AH2000, manufactured by Asahi Glass Co., Ltd.), j (Neoflon EFEP RP5000, manufactured by Daikin Industries Co., Ltd.), and the functional group-containing fluororesin film d1, The laminate was produced in the same manner as in Example 17 and evaluated.

Table 17 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the adhesion and film quality after the reliability test are lowered.

[Comparative Examples 17, 18]

In addition to the functional group-free fluororesin film k (Fluon ETFE, manufactured by Asahi Glass Co., Ltd.), 1 (Neoflon ETFE, manufactured by Daikin Industries Co., Ltd.), and the functional group-free fluororesin film e, The same method is used to make a laminate and evaluate it.

Table 17 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

Since ETFE is inferior in heat resistance, moist heat resistance, and electrical properties as compared with a perfluoro resin such as PFA, FEP, or EPE, the adhesion and film quality after the reliability test are lowered.

[Comparative Example 19]

A polyimide laminate film a4 was used instead of the polyimide film a1, and a copper clad laminate (CCL) a4 was used instead of the copper clad laminate (CCL) a1, and the same procedure as in Example 16 was carried out. The laminate is evaluated and evaluated.

Table 18 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced.

[Comparative Example 20]

A laminate was produced and evaluated in the same manner as in Comparative Example 19 except that the functional group-containing fluororesin film d2 (Fluon PFA grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d1.

Table 18 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

When the thickness ratio of the fluororesin is too small, although the linear expansion coefficient of the obtained multilayer fluororesin film is small, since the contribution of the low moisture absorption rate of the fluororesin is small, the adhesion after the reliability test is small. And the membrane quality is reduced.

[Comparative Examples 21 to 23]

A laminate was produced in the same manner as in Examples 19 to 21 except that the functional group-containing fluororesin film d4 (Fluon PFA grade, manufactured by Asahi Glass Co., Ltd.) was used instead of the functional group-containing fluororesin film d2. Evaluation.

Table 18 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and coefficient of linear expansion of the layered layer (A) layer (B), and the moisture resistance test and heat resistance test of the copper-clad multilayer fluororesin film. Evaluation results.

When the thickness ratio of the fluororesin is too large, the linear fluororesin of the obtained multilayer fluororesin film is also large, and the deviation from the linear expansion coefficient of the copper foil is increased, so that the adhesion after the reliability test and the film quality are lowered.

[Examples 27 to 28, Comparative Examples 24 to 25]

(Evaluation of warpage of copper-clad multilayer fluororesin film)

The functional group-containing fluororesin film d3 was placed on one surface of a polyimide film a1 to a4 cut to a size of 150 mm × 150 mm, and heated at 330 ° C and 5 MPa above the melting point of the fluororesin film for 30 minutes. The layered body of (A) layer (B) was obtained by press molding. Table 19 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B) obtained. Further, the functional group-containing fluororesin film d3 and a copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 9 μm were placed in a copper clad laminate (CCL) a1 to a4 cut to a size of 150 mm × 150 mm. On the surface of the polyimide film a1 to a4, heat-and-pressure molding was carried out for 30 minutes at 330 ° C and 5 MPa which is equal to or higher than the melting point of the fluororesin film to obtain a double-sided copper-clad multilayer fluororesin film.

The appearance inspection of the obtained copper-clad multilayer fluororesin film was evaluated as ○ without warpage and × with warpage. The evaluation results are shown in Table 19.

[Examples 29 to 30, Comparative Example 26]

(Evaluation of warpage of copper-clad multilayer fluororesin film)

The functional group-containing fluororesin film d2 was placed on one surface of a polyimide film a2 to a4 cut to a size of 150 mm × 150 mm, and heated at 330 ° C and 5 MPa above the melting point of the fluororesin film for 30 minutes. The layered body of (A) layer (B) was obtained by press molding. Table 20 shows the results of evaluation of the thickness ratio, storage elastic modulus ratio, and linear expansion coefficient of the layered layer (A) layer (B) obtained.

Further, a functional group-containing fluororesin film d2 and a copper foil (UWZ, manufactured by Furukawa Circuit Foil Co., Ltd.) having a thickness of 9 μm were placed in a copper clad laminate (CCL) a2 to a4 cut to a size of 150 mm × 150 mm. The surface of the polyimine film a2 to a4 was subjected to heat and pressure molding at 330 ° C and 5 MPa of the melting point of the fluororesin film for 30 minutes to obtain a double-sided copper-clad multilayer fluororesin film. The evaluation results of the obtained copper-clad multilayer fluororesin film are shown in Table 20.

[Application Example 2]

The functional group-containing fluororesin film d1 was placed on the surface of the polyimide film a2 of a copper-clad laminate (CCL) a2 cut to a size of 150 mm × 150 mm, at 330 ° C and 5 MPa above the melting point of the fluororesin film. A heat-press molding was carried out for 30 minutes to prepare a multi-layer fluororesin film.

On the other hand, using a copper-clad polyimide laminate obtained in Example 17, a photoresist (FR-200, manufactured by Shipley Co., Ltd.) was applied onto a copper foil surface, dried, and then densified with a glass mask. Exposure was carried out, followed by development with a 1.2% by mass aqueous KOH solution. Subsequently, it was etched at a spray pressure of ² kgf/cm ² at 40 ° C and a copper chloride etching machine containing HCl and hydrogen peroxide to form a test pattern, and then washed and annealed at 125 ° C for 1 hour. A copper-clad multilayer fluororesin film (printed wiring board) with a pattern was obtained.

The pattern forming surface of the copper-clad multilayer fluororesin film (printed wiring board) with the pattern is opposed to the fluororesin surface of the multilayer fluororesin film, and is heated at 330 ° C and 5 MPa above the melting point of the fluororesin film for 30 minutes. The multilayer printed wiring board shown in Fig. 2 was obtained by press molding. In the multilayer printed wiring board produced, since the copper wiring is covered with a fluororesin having a low dielectric constant, it is extremely useful as a member for high frequency.

[Industrial availability]

A multilayer fluororesin film composed of a layer (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer of the first invention of the present application, wherein the layer of the fluororesin film a multilayer fluororesin film having a coefficient of expansion of 10 ppm/° C. to 30 ppm/° C., and a copper-clad multilayer fluororesin film having a copper foil laminated on at least one side of the multilayer fluororesin film and removing a part of the copper foil to form a circuit pattern And the printed wiring board of the composition, and the second invention of the present application (B) formed of the (C) copper layer on the copper-clad laminate (CCL) of the (B) polyimide resin layer without an adhesive. Further, a multilayer fluororesin film having a layer (A) of a fluororesin layer in which a linear expansion coefficient of the layered layer (A) layer (B) in the multilayer fluororesin film is 10 ppm/° C. to 30 ppm/° C. a multilayer fluororesin film, and a copper-clad multilayer fluororesin film in which a copper foil is laminated on the (A) surface of the multilayer fluororesin film, and a printed wiring board in which the copper foil is partially removed to form a circuit pattern, even in In the high-temperature and high-humidity treatment, it can also withstand the quality of the printed wiring board, etc., which is followed by the multilayer fluororesin film and the copper foil. Also enhance yield during production, and enables the manufacture of high-quality electronic components, and therefore the industry is the most meaningful.

(Figure 1)

1. . . Copper foil

2. . . Fluororesin film

3. . . Polyimine film

(Fig. 2)

1. . . Copper layer

2. . . Fluororesin film

3. . . Polyimine film

Fig. 1 is a schematic view showing an example of a multilayer printed wiring according to a first invention of the present application.

Fig. 2 is a schematic view showing an example of a multilayer printed wiring of a second invention of the present application.

Claims (14)

A multilayer fluororesin film which is a multilayer fluororesin film composed of (A) fluororesin layer/(B) polyimine resin layer/(A) fluororesin layer, wherein the layer of the fluororesin film is sequentially laminated The coefficient of expansion is 10 ppm/°C to 30 ppm/°C, and the thickness ratio of the (A) layer is 60% to 90% of the total (A) layer/multilayer fluororesin film, and the layer (A) is made of tetrafluoroethylene. Perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene. Hexafluoropropylene copolymer (FEP), tetrafluoroethylene. Hexafluoropropylene. A thermoplastic fluororesin layer formed of any one of perfluoroalkyl vinyl ether copolymers (EPE), and the (A) layer is a functional group-containing thermoplastic fluororesin layer. For example, the multi-layer fluororesin film of claim 1 wherein the layer (B) is polybenzonitrile The polyimine layer of the azole component has a linear expansion coefficient of -10 ppm / ° C ~ 10 ppm / ° C. The multilayer fluororesin film according to claim 1 or 2, wherein the (A) layer has a thickness of 1.0 μm to 50 μm, and the (B) layer has a thickness of 1.0 μm to 38 μm. A multilayer fluororesin film according to claim 1 or 2, wherein the storage elastic modulus of the layer (A) at room temperature: storage elastic modulus of the E' (A) and (B) layers at room temperature: The ratio of E'(B) {E'(A)/E'(B)} is 2.0%~20%. A copper-clad multilayer fluororesin film in which a copper foil is laminated on at least one side of a multilayer fluororesin film according to any one of claims 1 to 4. A printed wiring board comprising a part of a copper foil of a copper-clad multilayer fluororesin film of the fifth aspect of the patent application to form a circuit pattern. A multilayer printed wiring board comprising a multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board as disclosed in any one of claims 1 to 6. A multilayer fluororesin film which is formed by forming a (C) copper layer on the (B) side of a copper clad laminate (CCL) of a (B) polyimine resin layer without an adhesive, and further layering (A) a fluororesin film in which the linear expansion coefficient of the (A) layer (B) layered layer in the multilayer fluororesin film is 10 ppm/° C. to 30 ppm/° C., and the thickness ratio of the (A) layer {(A) layer / (A) layer (B) laminated layer body} is 60% to 90%, and the (A) layer is made of tetrafluoroethylene. Perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene. Hexafluoropropylene copolymer (FEP), tetrafluoroethylene. Hexafluoropropylene. A thermoplastic fluororesin layer formed of any one of perfluoroalkyl vinyl ether copolymers (EPE), and the (A) layer is a functional group-containing thermoplastic fluororesin layer. A multilayer fluororesin film as claimed in claim 8 wherein the layer (B) is a polybenzonitrile benzoate The polyimine layer of the azole component has a linear expansion coefficient of -10 ppm / ° C ~ 10 ppm / ° C. The multilayer fluororesin film according to claim 8 or 9, wherein the (A) layer has a thickness of 1.0 μm to 50 μm, and the (B) layer has a thickness of 1.0 μm to 38 μm. A multilayer fluororesin film according to claim 8 or 9, wherein the storage elastic modulus of the layer (A) at room temperature: storage elastic modulus of the E' (A) and (B) layers at room temperature: The ratio of E'(B) {E'(A)/E'(B)} is 2.0%~20%. A copper-clad multilayer fluororesin film, which is in the range of The (A) layer of the multilayer fluororesin film of any of the 11 items is laminated with a copper foil. A printed wiring board comprising a multilayer fluororesin film according to any one of claims 8 to 12 and a copper layer of a copper-clad multilayer fluororesin film removed to form a circuit pattern. A multilayer printed wiring board comprising a multilayer fluororesin film, a copper-clad multilayer fluororesin film, and a printed wiring board as disclosed in any one of claims 8 to 13.