JP2006257285A - Resin composition and laminated metal plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in adhesive strength to a surface of contact of a laminated metal plate, further excellent in adhesion at a low temperature and soldering heat resistance as well, and also to provide a resin laminated metal plate using the resin. <P>SOLUTION: The resin composition is characterized by incorporating a polyimide resin composition, which is obtained from a diamine component and an acid dianhydride component containing the compound of formula (1), or its precursor with the bismaleimide compound of formula (2) (where m is an integer of 0-6). The laminated metal plate has at least one layer consisting of the above resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel resin composition used for a resin layer of a metal laminate and the like and a metal laminate having at least one resin layer made of the resin composition.

  Polyimide is excellent in heat resistance, chemical resistance, mechanical strength, electrical characteristics, etc., so it is widely applied not only in the aerospace field where heat resistance is required, but also as a heat resistant adhesive used in electronic fields. Yes. In recent years, polyimide heat-resistant adhesives have been required to have low-temperature adhesive properties in addition to heat resistance in processing.

As a resin having sufficient heat resistance and low-temperature adhesiveness, a resin composed of a polyamic acid and / or polyimide and a specific bismaleimide compound as disclosed in Patent Document 1 has been developed. Although the resin composition disclosed in the publication certainly has low-temperature adhesiveness and good heat resistance, further enhancement and stability of peel strength is desired.
Japanese Patent Laid-Open No. 2004-209962

  An object of the present invention is to provide a resin composition excellent in the adhesive strength of the adhesive surface of a resin metal laminate and having low temperature adhesion and solder heat resistance, and a metal resin laminate using the resin. .

  As a result of the study, the resin composition obtained by blending a bismaleimide compound having a specific skeleton with a polyimide and / or polyimide precursor produced using a specific acid dianhydride and a diamine component, The inventors have found that the above problems can be solved and completed the present invention.

  That is, the present invention provides the following general formula (1)

A polyimide resin composition obtained from an acid dianhydride component containing a compound represented by formula (II) and a diamine component, or a precursor thereof, the following general formula (2)

(Wherein m represents an integer of 0 to 6), and a bismaleimide compound, preferably a bismaleimide represented by the general formula (2). Provided is a resin composition in which 1 to 80% by weight of a compound is added to a resin composition, and a laminate comprising a metal layer and a resin layer, the metal laminate having at least one layer of the resin composition To do.

  The resin composition of the present invention uses a specific acid dianhydride represented by the general formula (1) as a raw material, so that when used for a metal laminate, the resin composition is chelated on a metal surface substrate and has an adhesive strength on an adhesive surface. It was excellent and it became possible to provide low-temperature adhesiveness and solder heat resistance by blending a bismaleimide compound represented by the general formula (2).

  Hereinafter, the present invention will be described in detail. The resin composition of the present invention has the following general formula (1)

A polyimide resin composition obtained from an acid dianhydride component containing a compound represented by formula (II) and a diamine component, or a precursor thereof, the following general formula (2)

(Wherein m represents an integer of 0 to 6) and a resin composition characterized by comprising a bismaleimide compound, and having at least one layer of the resin composition The present invention relates to a metal laminated plate composed of a metal layer and a resin layer.

  The acid dianhydride represented by the general formula (1) is a compound called diphenyl sulfone tetracarboxylic dianhydride, and is not particularly limited as long as it is represented by the above structural formula. Even things can be used.

  The ratio of the acid dianhydride represented by the general formula (1) to the entire acid dianhydride is not particularly limited, but is preferably 10% to 100%, more preferably 25% or more, more preferably 50% or more. More preferably, it is 70% or more. There is no restriction | limiting in particular as acid dianhydrides other than the acid dianhydride represented by General formula (1) in the whole acid dianhydride, For example, pyromellitic dianhydride, 3-fluoro pyromellitic dianhydride 3,6-difluoropyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 '', 4,4 ''-terphenyltetracarboxylic acid Dianhydride, 3,3 ′ ″, 4,4 ′ ″-quaterphenyltetracarboxylic dianhydride, 3,3 ″ ″, 4,4 ″ ″-kinkphenyltetracarboxylic dianhydride Anhydride, 2,2 ', 3,3'-biphenyl Tracarboxylic dianhydride, methylene-4,4′-diphthalic dianhydride, 1,1-ethynylidene-4,4′-diphthalic dianhydride, 2,2-propylidene-4,4′-diphthalic acid Dianhydride, 1,2-ethylene-4,4′-diphthalic dianhydride, 1,3-trimethylene-4,4′-diphthalic dianhydride, 1,4-tetramethylene-4,4′- Diphthalic dianhydride, 1,5-pentamethylene-4,4′-diphthalic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3 -Hexafluoropropane dianhydride, difluoromethylene-4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride 1,1,2,2,3,3-hexafluoro-1,3-trimethyle -4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4′-diphthalic dianhydride, oxy-4,4′-diphthalic acid Dianhydride, thio-4,4′-diphthalic dianhydride, sulfonyl-4,4′-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3 , 3-tetramethylsiloxane dianhydride, 1,3-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenyl) benzene dianhydride, 1, 3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-di Ruboxyphenoxy) benzene dianhydride, 1,3-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-di Carboxyphenyl) -2-propyl] benzene dianhydride, bis [3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4- (3,4-dicarboxyphenoxy) phenyl] methane anhydride 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride,

2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride, 1,3-bis (3,4 Dicarboxyphenoxy) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Anhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1 2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3 ′, 4,4′-bicyclohexyltetracarboxylic dianhydride, carbonyl -4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4 , 4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethynylidene-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene -4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis (cyclohexane -1,2- Carboxylic acid) dianhydride, oxy-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride Sulfonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 5, 5′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-difluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2, 2 ′, 5,5 ′, 6,6′-hexafluoro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis (trifluoromethyl) -3,3 ′ , 4,4'-biphenyltetracarboxylic acid 5,5′-bis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 6,6′-bis (trifluoromethyl) -3,3 ′, 4 , 4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 5,5′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-tetrakis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 5,5 ', 6,6'-tetrakis (trifluoromethyl) -3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) -3,3 ′, 4,4′-biphenyl Tetracarboxylic dianhydride, 3,3′-difluoroo -4,4'-diphthalic dianhydride, 5,5'-difluorooxy-4,4'-diphthalic dianhydride, 6,6'-difluorooxy-4,4'-diphthalic dianhydride 3,3 ′, 5,5 ′, 6,6′-hexafluorooxy-4,4′-diphthalic dianhydride,

3,3′-bis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 6, 6'-bis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride, 3,3 ', 5,5'-tetrakis (trifluoromethyl) oxy-4,4'-diphthalic dianhydride 3,3 ′, 6,6′-tetrakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 5,5 ′, 6,6′-tetrakis (trifluoromethyl) oxy-4, 4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) oxy-4,4′-diphthalic dianhydride, 3,3′-difluorosulfonyl -4,4'-diphthalic dianhydride, 5,5'-di Fluorosulfonyl-4,4′-diphthalic dianhydride, 6,6′-difluorosulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexa Fluorosulfonyl-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) sulfonyl -4,4'-diphthalic dianhydride, 6,6'-bis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 3,3 ', 5,5'-tetrakis (trifluoro Methyl) sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 6,6′-tetrakis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 5,5 ′, 6 , 6'-tetrakis (trifluorome L) Sulfonyl-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) sulfonyl-4,4′-diphthalic dianhydride, 3 3,3'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic acid Anhydride, 6,6′-difluoro-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexafluoro-2, 2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3′-bis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 5,5′-bis (trifluoromethyl) -2,2- Perfluoropropylidene-4,4′-diphthalic dianhydride, 6,6′-difluoro-2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 3,3 ′, 5, 5'-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic dianhydride, 3,3 ', 6,6'-tetrakis (trifluoromethyl) -2,2 -Perfluoropropylidene-4,4'-diphthalic dianhydride, 5,5 ', 6,6'-tetrakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4'-diphthalic acid Dianhydride, 3,3 ′, 5,5 ′, 6,6′-hexakis (trifluoromethyl) -2,2-perfluoropropylidene-4,4′-diphthalic dianhydride, 9-phenyl- 9- (trifluoromethyl) key Ntene-2,3,6,7-tetracarboxylic dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride, bicyclo [2,2, 2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 9,9-bis [4- (3,4-dicarboxy) phenyl] fluorene dianhydride, 9,9- And bis [4- (2,3-dicarboxy) phenyl] fluorene dianhydride. These can be used in combination with an acid dianhydride represented by the general formula (1).

  There is no particular limitation on the above-mentioned polyamic acid composed of acid dianhydride or diamine which is a raw material for polyimide resin, and examples include m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p. -Aminobenzylamine, bis (3-aminophenyl) sulfide, (3-aminophenyl) (4-aminophenyl) sulfide, bis (4-aminophenyl) sulfide, bis (3-aminophenyl) sulfoxide, (3-amino Phenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4aminophenyl) sulfone, 3,3′-diaminobenzophenone, 3,4 '-Diaminobenzophenone, 4,4 -Diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1 , 1-bis [4- (4-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (4-aminophenoxy) phenyl ] Ethane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bi [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] butane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1, 1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,3 -Bis (3-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4'-bis (4-aminophenoxy) benzene,

4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-amino Phenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfoxide, bis [ 4- (aminophenoxy) phenyl] sulfoxide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] Ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis [4- (3 Aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 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} phenyl] sulfone, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1 3-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,3-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (4- (2-aminophenoxy) phenoxy) Benzene, 1,3-bis (2- (2-aminophenoxy) phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,3-bis (2- (4-amino) Phenoxy) phenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,4-bis (3- (2-Aminophenoxy) phenoxy) benzene, 1,4-bis (4- (2-aminophenoxy) phenoxy) benzene, 1,4-bis (2- (2-amido) Phenoxy) phenoxy) benzene, 1,4-bis (2- (3-aminophenoxy) phenoxy) benzene, 1,4-bis (2- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (3- (2-aminophenoxy) phenoxy) benzene, 1,2- Bis (4- (4-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (3-aminophenoxy) phenoxy) benzene, 1,2-bis (4- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (2-aminophenoxy) phenoxy) benzene, 1,2-bis (2- (3-aminophenoxy) phenoxy) benzene , 1,2-bis (2- (4-aminophenoxy) phenoxy) benzene, 1,3-bis (3- (3-aminophenoxy) phenoxy) -2-methylbenzene, 1,3-bis (3- (4-Aminophenoxy) phenoxy) -4-methylbenzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2-ethylbenzene, 1,3-bis (3- (2-aminophenoxy) phenoxy ) -5-sec-butylbenzene, 1,3-bis (4- (3-aminophenoxy) phenoxy) -2,5-dimethylbenzene, 1,3-bis (4- (2-amino-6-methylphenoxy) ) Phenoxy) benzene, 1,3-bis (2- (2-amino-6-ethylphenoxy) phenoxy) benzene, 1,3-bis (2- (3-aminophenoxy) -4-methyl Phenoxy) benzene, 1,3-bis (2- (4-aminophenoxy) -4-tert-butyl phenoxy) benzene,

1,4-bis (3- (3-aminophenoxy) phenoxy) -2,5-di-tert-butylbenzene, 1,4-bis (3- (4-aminophenoxy) phenoxy) -2,3-dimethyl Benzene, 1,4-bis (3- (2-amino-3-propylphenoxy) phenoxy) benzene, 1,2-bis (3- (3-aminophenoxy) phenoxy) -4-methylbenzene, 1,2- Bis (3- (4-aminophenoxy) phenoxy) -3-n-butylbenzene, 1,2-bis (3- (2-amino-3-propylphenoxy) phenoxy) benzenebis (3-aminopropyl) tetramethyl Aromatic diamines such as disiloxane, bis (10-aminodecamethylene) tetramethyldisiloxane, bis (3-aminophenoxymethyl) tetramethyldisiloxane And the like. These may be used alone or in combination of two or more.

  In the bismaleimide compound represented by the general formula (2), m represents an integer of 0-6, more preferably 0-4, and still more preferably 1-2. The position of the ether bond between the aromatic rings is not particularly limited, and any of them can be used, but is preferably bonded at the meta position. Preferable specific examples include 1,3-bis (3-maleimidophenoxy) benzene and the like, but are not limited thereto, and these can be used alone or in combination of two or more.

  These bismaleimide compounds can be produced by condensing and dehydrating a corresponding diamine compound and maleic anhydride, for example, by the method described in JP-A-4-99764.

  In the case of producing the metal laminate of the present invention, the blending ratio of the bismaleimide compound to the polyimide is not particularly limited, but preferably 1 to the total weight of the polyamic acid which is the polyimide precursor. 80% by weight, more preferably 1-50% by weight. If the blending amount of the bismaleimide compound is less than 1% by weight, the effect of improving the soldering heat resistance which is the object of the present invention may not be seen so much. If it exceeds 80% by weight, the adhesive strength of the metal foil is lowered. Tend to.

  Examples of the blending method of the bismaleimide compound into the polyamic acid include, for example, (a) a method of adding a bismaleimide compound to the resin precursor solution, and (b) during polymerization of the resin precursor solution, for example, a diamine compound or Examples include a method of adding tetracarboxylic dianhydride or in the middle of polymerization, (c) a method of mixing the resin precursor powder and a bismaleimide compound with solids, and the like. It is not limited. Further, after the resin precursor is dehydrated and imidized in advance to form a solution, a bismaleimide compound may be blended.

  When using the resin composition of this invention for a metal laminated board, what consists of the resin composition of this invention is used for any resin layer which forms a metal laminated board. In addition to the resin composition, the resin composition for metal laminates, for example, polyimide, polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyethersulfone, polyetherketone, An appropriate amount of ether ether ketone, polyphenyl sulfide, modified polyphenylene oxide group, polyamide imide, polyether imide, epoxy resin or the like can be blended. Although the metal laminated board of this invention has the resin layer and metal layer which consist of a resin composition mentioned above as an essential component, it is more preferable to use this resin layer for the contact bonding layer which touches a metal. However, an adhesive layer and / or a non-adhesive layer made of another resin composition as an intermediate layer between the adhesive layer and the metal layer, and / or on the side of the adhesive layer that does not contact the metal layer. Further, one or more metal layers may be present. That is, a plurality of resin layers and metal layers containing the resin may be present in any combination. Moreover, you may have the resin layer formed by mix | blending the said compound with multiple layers. Further, a plurality of metal layers may be present.

  As a method for forming the resin layer, there are methods such as processing and laminating into a film shape, coating and drying in a varnish shape, and laminating, but the method is not limited thereto. As an example of the resin film, a commercially available non-thermoplastic polyimide film can also be used. For example, Upilex (registered trademark) S, Upilex (registered trademark) SGA, Upilex (registered trademark) SN (trade name), Kapton (registered trademark) H, Kapton (registered trademark) V, Kapton (registered) Trademark) EN (made by Toray DuPont Co., Ltd., trade name), Apical (registered trademark) AH, Apical (registered trademark) NPI, Apical (registered trademark) NPP, Apical (registered trademark) HP (manufactured by Kaneka Chemical Co., Ltd.) , Product name) and the like. The surface of each resin layer may be subjected to plasma treatment, corona discharge treatment, or the like. The thickness of each resin layer is not particularly limited depending on the purpose, but is preferably in the range of 0.1 to 300 μm, more preferably 0.2 to 100 μm, and still more preferably 0.3 to 50 μm.

  As the type of the metal layer, all known metals and alloys can be applied. Further, as a method for forming the metal layer, there are methods such as laminating, sputtering, or plating a metal foil, but the method is not limited to these methods. For example, rolled copper foil, electrolytic copper foil, copper alloy foil, and stainless steel foil are preferable from the viewpoints of cost, thermal conductivity, rigidity, and the like. Moreover, although there is no restriction | limiting in the thickness of a metal layer, 1-150 micrometers can be utilized preferably. More preferably, it is 2 to 25 μm.

  In order to produce the metal laminate of the present invention, for example, a non-thermoplastic polyimide film is coated with a varnish containing a polyamic acid which is a polyimide precursor made of the resin composition of the present invention, dried and cured, and then a resin layer. And a method of manufacturing by heat-pressing the corresponding surface of the metal foil on the surface of the resin layer. The thickness of the resin composition after application to the non-thermoplastic polyimide film is preferably in the range of 0.1 to 100 μm, more preferably in the range of 0.2 to 20 μm, and further preferably in the range of 0.3 to 5 μm. More preferably, it is the range of 0.4-3 micrometers.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, the metal laminated board in an Example was measured with the following method.

90 ° peel adhesion strength: Measured according to IPC-TM-650 method, 2, 4, 9.
Solder heat resistance test: IPC-TM-650 No. The test was conducted in accordance with 2.4.13, and the test was performed at a soldering temperature of 340 ° C. to confirm whether blistering occurred. Furthermore, the sample used was 85 ° C., 85% relative humidity, and conditioned for 50 hours.

Abbreviations of solvents, diamines, acid dianhydrides, and bismaleimides used in the examples are as follows.
DMAc: N, N-dimethylacetamide APBR: 1,3-bis (4-aminophenoxy) benzene APB: 1,3-bis (3-aminophenoxy) benzene DSDA: diphenylsulfone tetracarboxylic dianhydride BTDA: 3, 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride APB-BMI: 1,3-bis (3-maleidophenoxy) benzene

Example 1
To a container equipped with a stirrer and a nitrogen introduction tube, 80.00 g of DMAc was added as a solvent, and 12.00 g of APBR was added thereto, followed by stirring at room temperature until dissolved. Thereafter, 14.34 g of DSDA was added to the diamine component so that the acid anhydride had a molar ratio of 0.975, and the mixture was stirred at 60 ° C. to obtain a polyamic acid solution having a polyamic acid content of 20% by weight. It was. A stirred bismaleimide compound-containing polyamic acid solution was obtained at room temperature until APB-BMI was added and dissolved so that the weight ratio of APB-BMI in the solid content of the resulting varnish polyamic acid solution was 20%. The obtained polyamic acid solution was applied to both sides of a commercially available polyimide resin film (trade name: Kapton (registered trademark) 80EN, manufactured by Toray DuPont Co., Ltd.) with a roll coater so that the thickness after drying was 3 μm. Then, drying was performed by heating from 50 ° C. to 240 ° C. at a temperature rising rate of 7 ° C./min in an air float type drying furnace to obtain an insulating film whose both surfaces are thermoplastic resin layers. After that, a metal foil and an insulating film were laminated to a commercially available electrolytic copper foil (F1-WS 12 μm manufactured by Furukawa Circuit Foil Co., Ltd.) at 240 ° C. and a pressure of 1.5 MPa using a roll laminator, and then a batch type autoclave was used. Annealing was performed in a nitrogen atmosphere at a temperature of 280 ° C. for 4 hours to obtain a resin metal laminate having a width of 500 mm and a length of 1000 m. The 90 ° peel adhesion strength of the obtained resin metal laminate was an average of 1.3 kN / m and a minimum value of 1.1 kN / m at 50 measurement points. Further, the solder heat resistance temperature was 340 ° C., and no swelling occurred.

Comparative Examples 1, 2, 3
Comparative Examples 1, 2 and 3 were carried out in the same manner as in Example 1 except that the APB-BMI content relative to the solid content of diamine, acid anhydride and polyamic acid was changed as shown in Table 1. Are shown in Table 1.

  It is a resin made from a specific acid dianhydride and a specific bismaleimide compound, and has excellent low-temperature adhesion, adhesion strength to metal, and solder heat resistance, and is widely applied to flexible wiring boards and the like.

Claims (3)

The following general formula (1)

A polyimide resin composition obtained from an acid dianhydride component containing a compound represented by formula (II) and a diamine component, or a precursor thereof, the following general formula (2)

A resin composition comprising a bismaleimide compound represented by the formula (wherein m represents an integer of 0 to 6). The resin composition according to claim 1, wherein the bismaleimide compound represented by the general formula (2) is added to the resin composition in an amount of 1 to 80% by weight. A metal laminate comprising a metal layer and a resin layer, wherein the metal laminate comprises at least one resin layer obtained from the resin composition according to claim 1 or 2.