JP2009269372A - Polyimide laminated board pasted with metal and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated board pasted with metal in which camber or distortion of a base material hardly occurs when manufactured and peeling of a metal foil from a base material film does not occur when used as a printed wiring board under high temperature and high humidity environment and to provide the printed wiring board obtained by machining the laminated board pasted with metal. <P>SOLUTION: On at least one surface of a polyimide film, the metal foil is laminated via a thermoplastic resin layer to form a polyimide laminated board pasted with metal. The thermoplastic resin layer contains a fluororesin and a liquid crystal high molecule of a thermotropic type, content of the fluororesin in the thermoplastic resin layer is 20 to 80 mass% and content of the liquid crystal high molecule of the thermotropic type is 20 to 80 mass%. Further the polyimide laminated board pasted with metal and the printed wiring board using the polyimide laminated board pasted with metal are also constituted. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a metal-clad laminate obtained by laminating a metal foil on a polyimide film used for electronic devices, flexible printed wiring boards, and the like that are reduced in size and weight, and a printed wiring board obtained by processing the metal-clad laminate. .
More specifically, TAB (Tape Automated Bonding), COF (Chip on Film), PGA (Pin Grid Array), BGA (Ball Grid Array), CSP (Chip Scale Package), LOC (Lead on Chip) in semiconductor packaging and the like. The present invention relates to a metal-bonded polyimide laminate used for the flexible printed circuit board used for tapes and the like.

  In recent years, electronic devices have been improved in functionality, performance, and size, and there is a demand for downsizing and weight reduction of electronic components used therewith. For this reason, multilayer printed wiring boards, semiconductor element packaging methods, and wiring materials or wiring components for mounting them have been required to have higher density, higher functionality, and higher performance. Therefore, it can be suitably used as a high density mounting material such as a semiconductor package, COL (Chip on Lead) and LOC package, MCM (Multi Chip Module), or an FPC (Flexible Print Circuit) material such as a multilayer flexible printed wiring board. A material excellent in heat resistance, electrical reliability, adhesiveness, and insulation is required.

When a metal layer such as a metal foil is laminated via an adhesive resin layer to form an insulating layer in a printed wiring board, a so-called prepreg in which a glass fiber cloth is impregnated with an uncured epoxy resin is used as an insulating layer It has been. Further, an aramid fiber cloth is used instead of the glass fiber cloth. However, these prepregs have a thick cloth and cannot meet the demand for lightening in recent years. In addition, when an epoxy resin is used as an insulating layer, there are problems such as non-uniformity of the insulating layer due to non-uniform flow, resin contamination, and the like, and further, a lack of reliability of insulation due to a large dielectric loss tangent.
In an attempt to solve the above problem, an adhesive resin film in which a resin made of a silicone copolymer polyimide resin having a thickness of 50 μm and an epoxy resin is provided on a temporary support has been proposed (see Patent Document 1). Although this method is also excellent in permeability between circuits (conductors), the above-mentioned problems cannot be solved completely, and an insulating layer such as a high-frequency circuit board that requires strict guarantee of characteristic impedance There are challenges in forming.
It has also been proposed to use a thermoplastic polyimide resin (see, for example, Patent Documents 2 and 3), and an adhesive resin layer made of thermoplastic polyimide and a thermosetting resin is provided on at least one surface of the polyimide film. A film has also been proposed (see Patent Document 4).
JP 2003-089784 A JP 2000-143981 A JP 2003-306649 A JP 2003-011308 A

  However, it has not been sufficient yet, such as warping and distortion easily due to differences in physical properties in the film when making electronic parts, and the substrate film and the metal foil are easily peeled off under solder reflow and other severe conditions. In particular, a polyimide benzoxazole film is attracting attention among non-thermoplastic polyimide films having excellent dimensional stability at high temperatures, but an adhesive resin layer utilizing the characteristics has not been obtained.

  The present invention is a metal-laminated laminate in which warpage and distortion of the base material are unlikely to occur during production, and there is no peeling between the base film and the metal foil even when used as a printed wiring board in a high-temperature and high-humidity environment. And it aims at providing a printed wiring board.

As a result of intensive studies, the present inventors have used a specific resin as an adhesive resin layer and peeled off at high temperatures and high humidity when used in metal-laminated polyimide laminates, FPC, TAB tape, COF tape film, etc. The present invention has been completed by finding that an excellent high-quality uniform product can be obtained.
That is, this invention consists of the following structures.
1. In a metal-bonded polyimide laminate in which a metal foil is laminated on at least one surface of a polyimide film via a thermoplastic resin layer, the thermoplastic resin layer contains a fluororesin and a thermotropic liquid crystal polymer, A metal-bonded polyimide laminate having a fluororesin content of 20 to 80% by mass and a thermotropic liquid crystal polymer content of 20 to 80% by mass in the plastic resin layer.
2. 1. The thermotropic liquid crystal polymer is a wholly aromatic polyester. Metal-laminated polyimide laminate.
3. 1. The thermoplastic fluororesin, wherein the fluororesin is a thermoplastic fluororesin obtained by copolymerization using a fluorine-containing ethylenic monomer having at least a hydroxyl group and an ethylenic monomer having no hydroxyl group. Or 2. Metal-laminated polyimide laminate.
4). The ethylenic monomer having no hydroxyl group of the fluororesin is one or more selected from tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ether. ~ 3. A metal-laminated polyimide laminate.
5. 1. The polyimide film is a polyimide film having a polyimide benzoxazole component and has a linear expansion coefficient of −10 ppm / ° C. to 10 ppm / ° C. ~ 4. A metal-laminated polyimide laminate.
6). 1. The metal foil is a copper foil. ~ 5. A metal-laminated polyimide laminate.
7). 1 above. ~ 6. A printed wiring board comprising a circuit pattern formed by removing a part of the metal foil of any of the metal-bonded polyimide laminates.

In the metal-bonded polyimide laminate of the present invention, when the thermoplastic resin layer contains a fluororesin and a thermotropic liquid crystal polymer, the fluororesin and the thermotropic liquid crystal polymer have a sea-island type phase separation structure. By virtue of the adhesive effect of the sea component fluororesin and the reinforcing effect of the fluororesin by the thermotropic liquid crystal polymer of the island component, an excellent effect that combines moldability, adhesiveness, and heat resistance is exhibited.
Since the metal-bonded polyimide laminate of the present invention has the above-mentioned specific thermoplastic resin layer, the polyimide film has excellent adhesion to metal foil even in high-temperature and high-humidity processing, and is dimensionally stable in a high-temperature and high-humidity environment. Since it is excellent in properties and hardly warps or distorts, the quality of printed wiring boards and the yield during production are improved.

The present invention is described in detail below.
The polyimide film mainly composed of a non-thermoplastic polyimide used as a base material in the present invention is, for example, an aromatic tetracarboxylic acid (an anhydride, an acid, and an amide bond derivative are collectively referred to as a class) and an aromatic. Obtained by a method in which a polyamic acid solution obtained by reacting diamines (generically referred to as amines and amide-bonded derivatives hereinafter) is cast, dried, and heat-treated (imidized) to form a film. It is a polyimide film. Here, the non-thermoplastic polyimide is (1) a high concentration of imide units in repeating units in the polymer chain, and (2) a rigid molecular chain in which planar aromatic imide groups are arranged linearly or planarly. Means that the molecule does not show a clear melting point and glass transition temperature because the molecules are in a strong association state.
Although the said polyimide film is not specifically limited, The combination of the following aromatic diamine and aromatic tetracarboxylic acid (anhydride) is mentioned as a preferable example.
A. Combination with aromatic tetracarboxylic acid having pyromellitic acid residue and aromatic diamine having benzoxazole structure.
B. A combination of an aromatic diamine having a phenylenediamine skeleton and an aromatic tetracarboxylic acid having a biphenyltetracarboxylic acid skeleton.
C. A combination of an aromatic diamine having a diphenyl ether skeleton and an aromatic tetracarboxylic acid having a pyromellitic acid residue.
In particular, A. A polyimide film having an aromatic diamine residue having a benzoxazole structure is preferred.

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

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

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

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

These tetracarboxylic dianhydrides may be used alone or in combination of two or more.
Furthermore, as long as it is 30 mol% or less of the total tetracarboxylic dianhydrides, one or more of the non-aromatic tetracarboxylic dianhydrides exemplified below may be used in combination. Examples of such tetracarboxylic acid anhydrides include butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, and cyclobutanetetracarboxylic acid. Acid dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3 5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3 -(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride 1-ethylcyclohexane -(1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane- 1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] Heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1 -(2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane -2,3,5,6-tetracarboxylic dianhydride, bisic [2.2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride An anhydride etc. are mentioned.

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

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

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

  The conditions for drying the polyamic acid coated on the support to obtain a green sheet are not particularly limited, and examples include a temperature of 70 to 150 ° C. and a drying time of 5 to 180 minutes. A conventionally known drying apparatus that satisfies such conditions can be applied, and examples thereof include hot air, hot nitrogen, far infrared rays, and high frequency induction heating. Next, in order to obtain a target polyimide film from the obtained green sheet, an imidization reaction is performed. As a specific method thereof, a conventionally known imidization reaction can be appropriately used. For example, there may be mentioned a method (so-called thermal ring closure method) in which an imidization reaction proceeds by subjecting to a heat treatment after performing a stretching treatment as necessary using a polyamic acid solution not containing a ring closure catalyst or a dehydrating agent. The heating temperature in this case is exemplified by 100 to 500 ° C., and from the viewpoint of film physical properties, more preferably, a two-stage heat treatment in which treatment is performed at 350 to 500 ° C. for 3 to 20 minutes after treatment at 150 to 250 ° C. for 3 to 20 minutes. Is mentioned.

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

The thickness of the polyimide film is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 50 μm, and still more preferably 1 to 25 μm for the purpose of reducing the weight of electronic components. is there. Further, the thickness unevenness of these films is also preferably 20% or less, and the use of these films can greatly contribute to lightness, smallness and thinness of electronic components.
It is preferable for the above-described reason that the polyimide film has a linear expansion coefficient (CTE) of −10 to 10 ppm / ° C. for the reason described above, more preferably −5 to 10 ppm / ° C., and still more preferably, -5 to 5 ppm / ° C.

The fluororesin used for the thermoplastic resin layer in the present invention is preferably thermoplastic, more preferably a thermoplastic fluororesin having a hydroxyl group, specifically a fluorine-containing ethylenic monomer having a hydroxyl group and What was manufactured by copolymerizing with the fluorine-containing ethylenic monomer which does not have a hydroxyl group can be illustrated.
As the fluorine-containing ethylenic monomer having a hydroxyl group,
^{_{CX 2 = CX 1 -R f -CH}} 2 OH
Can be mentioned. In the formula, X and X ¹ are the same or different, both are hydrogen atoms or fluorine atoms, R _f is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms, fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, carbon number The fluorine-containing alkylene group containing a 1-40 ether bond or the fluorine-containing oxyalkylene group containing a C1-C40 ether bond is represented.

As the fluorine-containing ethylenic monomer having a hydroxyl group, more specifically,
^{_{CF 2 = CF-R f 1}} -CH 2 OH
Can be mentioned. In the formula, R _f ¹ is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms or —OR _f ² , where R _f ² is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms or 1 to 1 carbon atoms. It is a divalent fluorine-containing alkylene group containing 40 ether bonds.
Also,
^{_{CF 2 = CFCF 2 -OR f 3}} -CH 2 OH
Can be mentioned. Wherein, -R _f ³ represents a divalent fluorine-containing alkylene group containing an ether bond of the divalent fluorine-containing alkylene group or 1 to 39 carbon atoms to 39 carbon atoms.
Also,
^{_{CH 2 = CFCF 2 -R f 4}} -CH 2 OH
Can be mentioned. Wherein, -R _f ⁴ is a divalent fluorine-containing alkylene group or -OR _f ⁵ (R _f ⁵ is a divalent fluorine-containing alkylene group or from 1 to the number of carbon atoms of 1 to 39 carbon atoms, of 1 to 39 carbon atoms A divalent fluorine-containing alkylene group containing 39 ether bonds).
Also,
^{_{CH 2 = CH-R f 6}} -CH 2 OH
Can be mentioned. Wherein, R _f ⁶ is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms.
On the other hand, examples of the fluorine-containing monomer not containing a hydroxyl group include tetrafluoroethylene, perfluoroalkyl vinyl ether, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and the like, preferably tetrafluoroethylene and A copolymer of perfluoroalkyl vinyl ether and a copolymer of tetrafluoroethylene and hexafluoropropylene.

  The content rate of the fluororesin in the thermoplastic resin layer in the present invention is 20 to 80% by mass, preferably 30 to 70% by mass, and more preferably 40 to 60% by mass. When the content of the fluororesin is less than 20% by mass, it is not preferable for reasons such as difficulty in melt molding and a decrease in adhesiveness. On the other hand, if the content of the fluororesin exceeds 80% by mass, the reinforcing effect of the thermotropic liquid crystal polymer is not sufficient, and the heat resistance is inferior.

Examples of the thermotropic liquid crystal polymer used in the thermoplastic resin layer in the present invention include a liquid crystal polyester resin, a liquid crystal polyamide resin, and a liquid crystal polyester amide resin, and a liquid crystal polyester resin is particularly preferable. Here, the thermotropic type liquid crystal polymer is a liquid crystal (dissolved in the three-dimensional position, although some order is maintained in the particle direction in the intermediate state between the crystal and the liquid by heating and melting. It means a polymer that becomes a state. The liquid crystal polyester resin may be a polyester resin having a mesogen group (group having liquid crystal forming ability) such as a p-substituted aromatic ring, a linear biphenyl group, and a substituted naphthyl group as a structural unit. Specifically, p-hydroxybenzoic acid monomer, p-hydroxybenzoic acid and diol (aromatic diol such as dihydroxybiphenyl, C _2-6 alkanediol such as ethylene glycol), aromatic dicarboxylic acid ( Examples thereof include a copolymer with at least one monomer selected from terephthalic acid and the like and aromatic hydroxycarboxylic acid (such as oxynaphthoic acid). More specifically, poly p-hydroxybenzoic acid, a copolymer of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and terephthalic acid Examples thereof include a copolymer, a copolymer of p-hydroxybenzoic acid units and ethylene terephthalate units, and a copolymer of p-hydroxybenzoic acid and 2-oxy-6-naphthoic acid.
Thermotropic liquid crystal polymers have high mechanical properties because they maintain some order in the particle direction due to heat and pressure, but can take a three-dimensional positional order. Nevertheless, it has excellent melt fluidity.

The content of the thermotropic liquid crystal polymer in the thermoplastic resin layer in the present invention is 20 to 80% by mass, preferably 30 to 70% by mass, and more preferably 40 to 60% by mass. When the content of the thermotropic liquid crystal polymer exceeds 80% by mass, it is not preferable for reasons such as difficulty in melt molding and a decrease in adhesiveness. Further, if the content of the thermotropic liquid crystal polymer is less than 20% by mass, the reinforcing effect is not sufficient and the heat resistance is inferior.

The formulation of the thermotropic liquid crystal polymer fluororesin can melt the fluororesin and mix the liquid crystal polymer, and is not particularly limited, but a predetermined amount of liquid crystal is added to the fluororesin pellets and powder. A method of mixing polymers and mixing them using a twin-screw or single-screw extruder, or a method of preparing a high-concentration filler masterbatch in advance and mixing them during molding can be used.
As the thermoplastic resin containing the fluororesin and the thermotropic liquid crystal polymer used in the present invention, a film forming method used for the production of a synthetic resin film can be applied and used. For example, it can be produced by a T-die molding method, an inflation molding method, an inside mandrel method, a vacuum foamer molding method, or the like.

In the present invention, the thermoplastic resin layer contains a fluororesin and a thermotropic liquid crystal polymer, so that the fluororesin and the thermotropic liquid crystal polymer have a sea-island type phase separation structure, and a sea component fluororesin. Contributes to adhesiveness, and the thermotropic liquid crystal polymer of the island component has a mechanism that reinforces the fluororesin, so that it exhibits an excellent effect that combines moldability, adhesiveness, and heat resistance.
In the thermoplastic resin layer of the present invention, other thermoplastic resins, thermosetting resins, dispersants, stabilizers, in addition to the fluororesin and thermotropic liquid crystal polymer, within a range not inhibiting the effects of the present invention. Etc. can be contained.

The metal foil used in the present invention is not particularly limited as long as it is a conductive metal foil, but silver, copper, gold, platinum, rhodium, nickel, aluminum, iron, chromium, zinc, tin, brass , White bronze, bronze, monel, molybdenum, tungsten, tin lead solder, tin copper solder, tin silver solder, etc., alone or their alloys are used, but using copper in the balance between performance and economy This is a preferred embodiment. When the metal foil layer is used for a circuit (conductive), the thickness of the metal layer is preferably 1 to 175 μm, more preferably 3 to 50 μm. When using the polyimide film which bonded the metal foil layer as a heat sink, the thickness of a metal layer becomes like this. Preferably it is 50-3000 micrometers.
In the metal-clad polyimide laminate of the present invention, a metal-clad polyimide laminate having an effective relative dielectric constant of 2.2 to 2.8 is more preferable.

The metal lamination method of the metal-bonded polyimide laminate used in the present invention is not particularly limited, and the following means are exemplified.
-Means for bonding with polyimide film / thermoplastic resin laminate and metal foil and then welding by hot pressing.
A means for forming a metal layer on a polyimide film / thermoplastic resin laminate using a vacuum coating technique such as vapor deposition, sputtering, or ion plating.
A means for forming a metal layer on a polyimide film / thermoplastic resin laminate by a wet plating method such as electroless plating or electroplating.
The metal layer can be laminated on at least one surface of the polyimide film / thermoplastic resin laminate by alone or in combination.

  The metal-bonded polyimide laminate of the present invention is coated with a photoresist on the side of a conductive metal foil layer or a post-added thick film metal layer formed on the conductive metal foil layer, if necessary, and then exposed to light. , Development, etching, photoresist stripping process, wiring circuit pattern is formed, solder resist coating is applied, plastic and electroless tin plating is performed as necessary, flexible printed wiring board, multilayer printed wiring board in which they are multilayered In addition, a printed wiring board having a semiconductor chip directly mounted thereon can be obtained. There are no particular limitations on the method for creating these circuits, making them multi-layered, and mounting a semiconductor chip, and the methods may be appropriately selected from known methods.

  On the surface of the metal (foil) layer used in the present invention or, if necessary, the thick film metal layer attached later, an inorganic coating such as a single metal or a metal oxide may be formed. Good. In addition, the surface of the metal foil layer or the post-attached thick film metal layer formed on the metal foil layer, if necessary, is treated with a coupling agent (aminosilane, epoxysilane, etc.), sand plast treatment, rolling treatment, corona treatment, You may use for a plasma process, an ion gun process, an etching process, etc. Similarly, the surface of the polyimide film may be subjected to honing treatment, corona treatment, plasma treatment, ion gun treatment, etching treatment, and the like.

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

1. Reduced viscosity of polyamic acid (ηsp / C)
A solution dissolved in N-methyl-2-pyrrolidone (or N, N-dimethylacetamide) so that the polymer concentration was 0.2 g / dl was measured at 30 ° C. with an Ubbelohde type viscosity tube.

2. The thickness of the polyimide film The polyimide film to be measured was measured using a micrometer (Minetron 1245D, manufactured by Fine Reef).

3. Thickness unevenness of polyimide film About the polyimide film to be measured, in the width direction (TD direction), the entire width is measured at intervals of 1 cm in the width direction, and the average thickness, the maximum thickness, and the minimum thickness between them are calculated. Used to calculate. Moreover, about the longitudinal direction (MD direction), it measured for 5 m at intervals of 5 cm in the longitudinal direction, and average thickness, maximum thickness, and minimum thickness in the meantime were taken out and calculated using the following formula.
Thickness unevenness (%) = ((maximum thickness−minimum thickness) / average thickness) × 100

4). Tensile elastic modulus, tensile break strength, and tensile break elongation of polyimide film The polyimide film to be measured is subjected to a tensile fracture test under the following conditions, and the tensile modulus, tensile break strength, and tensile break elongation are measured in the MD direction. It was measured.
Device name: Autograph made by Shimadzu Corporation
Sample length: 100mm
Sample width: 10mm
Drawing speed: 50mm / min
Distance between chucks: 40 mm

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

6). The thermoplastic resin to be measured was subjected to differential scanning calorimetry (DSC) under the following conditions, and the melting point (Tm) was determined according to JIS K7121.
Device name: DSC3100S manufactured by MAC Science
Bread: Aluminum bread (non-airtight type)
Sample mass: 4mg
Temperature rising start temperature: 30 ° C
Temperature rise end temperature: 400 ° C
Temperature increase rate: 20 ° C / min
Atmosphere: Argon

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

<< Evaluation of Substrate >> Moisture and Heat Resistance Each metal-bonded polyimide laminate made of polyimide film, thermoplastic resin, and metal foil is placed in a stainless mesh cage and then used with a PCT device (PC242-III, manufactured by Hirayama Seisakusho). A pressure heat treatment was performed for 96 hours in a saturated vapor pressure of 2 ° C. and the peel strength after the test was evaluated. In addition, in the appearance inspection after the test, the case where peeling, blistering, and discoloration were not observed was indicated as “◯”, the case where slight peeling, blistering, and discoloration were observed as Δ, and the case where peeling, blistering, and discoloration were observed as “X”.

<< Evaluation of Substrate >> Heat Resistance Each of the metal-laminated polyimide laminates made of polyimide film, thermoplastic resin, and metal foil is placed in a stainless steel mesh bag and subjected to heat treatment at 400 ° C. for 1 hour in an N ₂ atmosphere. The peel strength was evaluated. In addition, in the appearance inspection after the test, the case where peeling, blistering, and discoloration were not observed was indicated as “◯”, the case where slight peeling, blistering, and discoloration were observed as Δ, and the case where peeling, blistering, and discoloration were observed as “X”.

<< Evaluation of Substrate >> Migration Resistance Voltage (DC60V) is applied to a polyimide film with a comb-shaped pattern made of a polyimide film, thermoplastic resin, and metal foil having a 40 μm pitch comb-shaped pattern. Place in an RH constant temperature and humidity chamber (FX412P type, manufactured by ETAC) and measure the insulation resistance value every 5 minutes under voltage load, and measure the time until the resistance value between lines reaches 100 MΩ or less. Evaluation was made with ○ for time or more, Δ for 500 hours or more and less than 1000 hours, and × for less than 500 hours.

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

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

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

[Production Example 4]
(Creation of thermoplastic resin film A)
40 parts by mass of a liquid crystal polymer (Sumikasuper E101, manufactured by Sumitomo Chemical Co., Ltd.) that is polyparahydroxybenzoic acid, a fluororesin that is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (neoflon PFA RAP, manufactured by Daikin Industries, Ltd.) ) 60 parts by mass were blended and melt kneaded using a twin screw extruder (KZW20-25G). The obtained kneaded raw material was formed into a film having a thickness of 15 μm with a film forming machine in which a 600 mm T-die was attached to the tip of a 40 mm diameter extruder.
Table 2 shows the physical property values of the obtained resin film A.

[Production Example 5]
(Creation of thermoplastic resin film B)
Liquid crystal polymer that is a copolymer of 4,4-dihydroxybiphenol, terephthalic acid, and parahydroxybenzoic acid instead of the liquid crystal polymer that is polyparahydroxybenzoic acid (Sumika Super E101, manufactured by Sumitomo Chemical Co., Ltd.) A thermoplastic resin film B was obtained in the same manner as in Production Example 4 except that (Sumika Super S1000, manufactured by Sumitomo Chemical Co., Ltd.) was used.
Table 2 shows the physical property values of the obtained resin film B.

[Production Example 6]
(Creation of thermoplastic resin film C)
Instead of the liquid crystal polymer that is polyparahydroxybenzoic acid (Sumikasuper E101, manufactured by Sumitomo Chemical Co., Ltd.), the liquid crystal polymer that is a copolymer of 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid (Vectra A950) A thermoplastic resin film C was obtained in the same manner as in Production Example 4, except that Polyplastics) was used.
Table 2 shows the physical property values of the obtained resin film C.

[Production Example 7]
(Creation of thermoplastic resin film D)
Instead of the liquid crystal polymer that is polyparahydroxybenzoic acid (Sumika Super E101, manufactured by Sumitomo Chemical Co., Ltd.), the liquid crystal polymer that is a copolymer of ethylene glycol, terephthalic acid, and parahydroxybenzoic acid (Novacurate, A thermoplastic resin film D was obtained in the same manner as in Production Example 4 except that Mitsubishi Engineering Plastics) was used.
Table 2 shows the physical property values of the obtained resin film D.

[Production Example 8]
(Creation of thermoplastic resin film E)
Instead of fluororesin (neoflon PFA RAP, manufactured by Daikin Industries), which is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, fluororesin (neoflon FEP, Daikin, which is a copolymer of tetrafluoroethylene and hexafluoropropylene) A thermoplastic resin film E was obtained in the same manner as in Production Example 4 except that Kogyo Kogyo Co., Ltd. was used.
Table 2 shows the physical property values of the obtained resin film E.

[Production Example 9]
(Creation of thermoplastic resin film F)
Instead of fluororesin (neoflon PFA RAP, manufactured by Daikin Industries), which is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, fluororesin (neoflon ETFE, Daikin Industries, Ltd.) that is a copolymer of tetrafluoroethylene and ethylene A thermoplastic resin film F was obtained in the same manner as in Production Example 4 except for using
Table 2 shows the physical property values of the obtained resin film F.

[Production Example 10]
(Creation of thermoplastic resin film G)
A thermoplastic resin film G was obtained in the same manner as in Production Example 4 except that a liquid crystal polymer (Sumikasuper E101, manufactured by Sumitomo Chemical Co., Ltd.), which is polyparahydroxybenzoic acid, was not blended.
Table 3 shows the physical property values of the obtained resin film G.

[Production Example 11]
(Creation of thermoplastic resin film H)
20 parts by mass of a liquid crystal polymer (Sumikasuper E101, manufactured by Sumitomo Chemical Co., Ltd.) which is polyparahydroxybenzoic acid, a fluororesin (neoflon PFA RAP, manufactured by Daikin Industries, Ltd.) which is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether ) A thermoplastic resin film H was obtained in the same manner as in Production Example 4 except that 80 parts by mass was blended.
Table 3 shows the physical property values of the obtained resin film H.

[Production Example 12]
(Creation of thermoplastic resin film I)
80 parts by mass of a liquid crystal polymer (Sumikasuper E101, manufactured by Sumitomo Chemical Co., Ltd.) that is polyparahydroxybenzoic acid, a fluororesin that is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (neoflon PFA RAP, manufactured by Daikin Industries, Ltd.) ) A thermoplastic resin film I was obtained in the same manner as in Production Example 4 except that 20 parts by mass was blended.
Table 3 shows the physical property values of the obtained resin film I.

[Production Example 13]
(Creation of thermoplastic resin film J)
A resin film J was obtained in the same manner as in Production Example 4 except that a fluororesin (neoflon PFA RAP, manufactured by Daikin Industries), which is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, was not blended. It was impossible to produce a high-quality film.

[Production Example 14]
(Creation of thermoplastic resin film K)
Instead of using a liquid crystalline polymer that is polyparahydroxybenzoic acid (Sumika Super E101, manufactured by Sumitomo Chemical Co., Ltd.), a PET resin (manufactured by Toyobo Co., Ltd.) that is a copolymer of ethylene glycol and terephthalic acid is used. Resin film K was obtained in the same manner as in Production Example 4.
Table 3 shows the physical property values of the obtained resin film K.

[Production Example 15]
(Creation of thermoplastic resin film L)
After purging the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 368.4 g (1.0 mol) of 4,4′-bis (3-aminophenoxy) biphenyl and 59.24 g of phthalic anhydride (0.4 mol), pyromellitic anhydride 174.5 g (0.8 mol) and m-cresol 2,172 g were charged, heated to 200 ° C. with stirring, and kept at 200 ° C. for 6 hours. Next, toluene was charged into the reaction solution, the precipitate was filtered off, washed several times with toluene, and then dried at 250 ° C. for 6 hours in a nitrogen atmosphere to obtain 510 g of polyimide powder. The polyimide powder was kneaded and melted at 380 to 410 ° C. using a twin screw extruder, extruded and granulated into pellets. The obtained pellets were supplied to a single screw extruder (molding temperature 420 ° C.) having a diameter of 50 mm, passed through a 10 μm leaf disk type filter attached to the front part of the T die, and extruded from a 1100 mm wide T die to be a thermoplastic resin. Film L was obtained.
Table 4 shows the physical property values of the obtained resin film L.

[Production Example 16]
(Creation of thermoplastic resin film M)
After replacing the inside of the reaction vessel equipped with a nitrogen introduction tube, a thermometer, and a stirring rod with nitrogen, 192 g of trimellitic anhydride, 211 g of o-tolidine diisocyanate (80 mol%), 35 g of 2,4-tolylene diisocyanate, 1 g of ethylenediamine was charged, and N-methyl-2-pyrrolidone was further charged so that the polymer concentration was 40%. After making it react at 120 degreeC for about 1 hour, it was made to react, further stirring at 180 degreeC for 5 hours. Next, heating was stopped, and while cooling, N-methyl-2-pyrrolidone was further added and diluted to obtain a polyamideimide solution having a solid concentration of 20%.
This polyamideimide solution was coated on a non-lubricant surface of a polyethylene terephthalate film (A-4100, manufactured by Toyobo Co., Ltd.) using a comma coater, dried at 120 ° C. for 3 minutes, and then peeled off from the support. Pass through a pin tenter with two heat treatment zones, heat treatment at 320 ° C. for 2 minutes for the first stage, 320 ° C. for 2 minutes for the second stage, 320 ° C. for 2 minutes for the third stage, slit to 500 mm width, and thermoplastic resin film M was obtained.
Table 4 shows the physical property values of the obtained resin film M.
In addition, the content rate in a table | surface represents the mass% in the thermoplastic resin film of a liquid crystal polymer.

[Example 1]
A thermoplastic resin film A and an electrolytic copper foil having a thickness of 18 μm (CF-T9, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.) are arranged in this order on one surface of a polyimide film A cut out to a size of 150 mm × 150 mm. Metal-bonded polyimide laminate in which copper foil is laminated to a polyimide film through thermoplastic resin film A (thermoplastic resin layer) by performing heat and pressure molding at 330 ° C. and 5 MPa, which is higher than the melting point of film A, for 30 minutes. 1 was obtained.
Using the obtained metal-bonded polyimide laminate, a photoresist (FR-200, manufactured by Shipley Co., Ltd.) was applied and dried, and then contacted and exposed with a glass photomask, and further developed with a 1.2 mass% KOH aqueous solution. Next, etching is performed with a cupric chloride etching line containing HCl and hydrogen peroxide at a spray pressure of 40 ° C. and 2 kgf / cm ² , and a “comb pattern” as shown in FIG. 1 is necessary for the evaluation test. The conductor width and conductor spacing were 40 μm / 40 μm, and the number of patterns was 20 test patterns on one side, followed by cleaning and annealing at 125 ° C. for 1 hour.
Table 5 shows the evaluation results of the resulting metal-attached polyimide laminate 1 and the comb-patterned metal-attached polyimide laminate 1.

[Examples 2-3]
A laminate was prepared and evaluated in the same manner as in Example 1 except that polyimide films B and C were used instead of polyimide film A.
Table 5 shows the evaluation results of the obtained metal-attached polyimide laminates 2 to 3 and the comb-patterned metal-attached polyimide laminates 2 to 3.

[Examples 4 to 6]
A laminate was prepared and evaluated in the same manner as in Example 1 except that the thermoplastic resin films B to D were used instead of the thermoplastic resin film A.
Table 5 shows the evaluation results of the obtained metal-attached polyimide laminates 4 to 6 and the comb-patterned metal-attached polyimide laminates 4 to 6.
[Examples 7 and 8]
A laminate was prepared and evaluated in the same manner as in Example 1 except that the thermoplastic resin films E and F were used instead of the thermoplastic resin film A.
Table 6 shows the evaluation results of the obtained metal-attached polyimide laminates 7 and 8 and the comb-patterned metal-attached polyimide laminates 7 and 8.

[Examples 9 and 10]
A laminate was prepared and evaluated in the same manner as in Example 1 except that the thermoplastic resin films H and I were used instead of the thermoplastic resin film A.
Table 6 shows the evaluation results of the obtained metal-attached polyimide laminates 9 and 10 and the comb-patterned metal-attached polyimide laminates 9 and 10.
Example 11
Example 1 was used except that an aluminum foil (purity 99.3%, manufactured by Toyo Aluminum Co., Ltd.) having a thickness of 10 μm was used instead of an electrolytic copper foil (CF-T9, manufactured by Fukuda Metal Foil Powder Co., Ltd.) having a thickness of 18 μm. A laminate was prepared by the method of and evaluated.
Table 6 shows the evaluation results of the obtained metal-attached polyimide laminate 11 and the comb-patterned metal-attached polyimide laminate 11.

[Comparative Example 1]
A laminate was prepared and evaluated in the same manner as in Example 1 except that the thermoplastic resin film G was used instead of the thermoplastic resin film A.
Table 7 shows the evaluation results of the obtained metal-attached polyimide laminate 12 and the comb-patterned metal-attached polyimide laminate 12.

[Comparative Example 2]
A laminate was prepared and evaluated in the same manner as in Example 1 except that the thermoplastic resin film K was used instead of the thermoplastic resin film A.
Table 7 shows the evaluation results of the obtained metal-attached polyimide laminate 13 and the comb-patterned metal-attached polyimide laminate 13.

[Comparative Example 3]
The same method as in Example 1 except that the thermoplastic resin film L is used instead of the thermoplastic resin film A, and the heat-pressure molding is performed at 390 ° C. and 10 MPa, which is equal to or higher than the melting point of the thermoplastic resin film, for 15 minutes. A laminate was prepared and evaluated.
Table 7 shows the evaluation results of the obtained metal-attached polyimide laminate 14 and the comb-patterned metal-attached polyimide laminate 14.

[Comparative Example 4]
The same as Example 1 except that the thermoplastic resin film M is used instead of the thermoplastic resin film A, and the heat-pressure molding is performed at 330 ° C. and 10 MPa that is equal to or higher than the glass transition temperature of the thermoplastic resin film for 15 minutes. A laminate was prepared by the method of and evaluated.
Table 7 shows the evaluation results of the obtained metal-attached polyimide laminate 15 and the comb-patterned metal-attached polyimide laminate 15.

  The metal-bonded polyimide laminate of the present invention is less likely to be warped or distorted during production and can be stably manufactured. The obtained metal-bonded laminate and a printed wiring board using the metal-bonded laminate are Since the peeling of the metal foil can be suppressed as much as possible even in a humid environment, it can be used in the field of electronic components exposed to harsh environments such as high temperature and high humidity.

It is the schematic which shows an example of a comb-shaped pattern.

Claims (7)

  In a metal-bonded polyimide laminate in which a metal foil is laminated on at least one surface of a polyimide film via a thermoplastic resin layer, the thermoplastic resin layer contains a fluororesin and a thermotropic liquid crystal polymer, A metal-bonded polyimide laminate having a fluororesin content of 20 to 80% by mass and a thermotropic liquid crystal polymer content of 20 to 80% by mass in the plastic resin layer.   The metal-coated polyimide laminate according to claim 1, wherein the thermotropic liquid crystal polymer is a wholly aromatic polyester.   The metal bonding according to claim 1 or 2, wherein the fluororesin is a thermoplastic fluororesin obtained by copolymerization using a fluorine-containing ethylenic monomer having at least a hydroxyl group and an ethylenic monomer not having a hydroxyl group. Polyimide laminate.   The ethylenic monomer having no hydroxyl group of the fluororesin is one or more selected from tetrafluoroethylene, hexafluoropropylene, and perfluoroalkyl vinyl ethers. The metal-bonded polyimide laminate described.   The metal-coated polyimide laminate according to any one of claims 1 to 4, wherein the polyimide film is a polyimide film having a polyimide benzoxazole component and has a linear expansion coefficient of -10 ppm / ° C to 10 ppm / ° C.   The metal-bonded polyimide laminate according to any one of claims 1 to 5, wherein the metal foil is a copper foil.   A printed wiring board comprising a circuit pattern formed by partially removing the metal foil of the metal-bonded polyimide laminate according to claim 1.

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