Multi-layered polyimide film, metal-clad laminate, and method for producing multi-layered polyimide film

A multi-layered polyimide film comprising:

• a non-thermoplastic polyimide layer, and
• an adhesive layer that is disposed on at least one surface of the non-thermoplastic polyimide layer and contains polyimide,
• wherein:
• a dielectric loss tangent of the non-thermoplastic polyimide layer at a frequency of 10 GHz, a temperature of 23° C., and a relative humidity of 50% is 0.0030 or less,
• the adhesive layer has no melting peak or has a melting heat of 1.0 J/g or less at a melting peak in a temperature range of 100° C. or higher and 420° C. or lower, and
• the polyimide contained in the adhesive layer has one or more tetracarboxylic dianhydride residues selected from the group consisting of a pyromellitic dianhydride residue and a 3,3′,4,4′-biphenyltetracarboxylic dianhydride residue, and one or more diamine residues selected from the group consisting of a 1,3-bis(4-aminophenoxy) benzene residue and a 4,4′-diamino-2,2′-dimethylbiphenyl residue,
• a non-thermoplastic polyimide in the non-thermoplastic polyimide layer comprises diamine residues comprising a p-phenylenediamine residue and a 1,3-bis(4-aminophenoxy) benzene residue,
• a content ratio of the p-phenylenediamine residue to the total amount of the diamine residues constituting the non-thermoplastic polyimide is 60 mol % or more and 95 mol % or less,
• a content ratio of the 1,3-bis(4-aminophenoxy) benzene residue to the total amount of the diamine residues constituting the non-thermoplastic polyimide is 5 mol % or more and 40 mol % or less
• wherein the non-thermoplastic polyimide in the non-thermoplastic polyimide layer comprises dianhydride residues comprising a 3,3′,4,4′-biphenyltetracarboxylic dianhydride residue, a 4,4′-oxydiphthalic anhydride residue, and a pyromellitic dianhydride residue, wherein:
• a content ratio of the 3,3′,4,4′-biphenyltetracarboxylic dianhydride residue to the total amount of the dianhydride residues constituting the non-thermoplastic polyimide is 50 mol % or more and 70 mol % or less,
• a content ratio of the 4,4′-oxydiphthalic anhydride residue to the total amount of the dianhydride residues constituting the non-thermoplastic polyimide is 20 mol % or more and 40 mol % or less, and
• a content ratio of the pyromellitic dianhydride residue to the total amount of the dianhydride residues constituting the non-thermoplastic polyimide is 2 mol % or more and 8 mol % or less.