TWI248869B - Metallic laminate - Google Patents

Abstract

This invention provides a polyimide metallic laminate which contains heat resistance resin with excellent adhesion at low temperature, and the laminate is hard to expand as applied in free lead weld, or in Au-Sn junction installed in COF, or in Au-Au junction, and is further excellent in heat resistance in weld. The objective metallic laminate and resin composition thereof are characterized in that resin composition laminate is formed from bismaleimide compound in accordance with formula (I), which the laminate is supported on at least one side of metallic foil. Wherein polyamic acid and/or polyimide is represented as formula (I), (wherein m is an integer and is greater than zero; X are respectively independent and the same or different and are O, SO2, S, CO, CH2, C(CH3)2, C(CF3)2, or direct bond; furthermore, R1 are the same or different and are hydrogen atoms, halogen atoms or hydrocarbon radicals, the substituting site of benzoic ring of R1 is respectively independent.)

Description

1248869 发明Invention Description: [Technical Field] The present invention relates to a metal laminate and a polyimide laminate which are superior in low-temperature adhesion and superior in solder heat resistance. A resin composition for the body. [Prior Art] Polyimide is superior in heat resistance, chemical resistance, mechanical strength, electrical properties, etc., and therefore, it is used not only in the aerospace field where heat resistance is required, but also as a flexible A heat-resistant adhesive used in a representative electronic field such as a printed circuit board or a semiconductor package. In recent years, in the case of a polyimide-based heat-resistant adhesive, the so-called low-temperature adhesion property required for the processing is increased by heat resistance. For example, Patent Document 1 discloses a resin composition formed of a polyimine resin having a siloxane unit, an epoxy resin, or a phosphate-based plasticizer. However, in this case, since any component of the polyimide resin, the epoxy resin, and the plasticizer contains an aliphatic unit, there is a problem that the thermal decomposition temperature is low from the viewpoint of heat resistance. On the other hand, as a material having sufficient adhesive strength and heat resistance, it is disclosed in Patent Document 2, and/or Patent Document 3, and Patent Document 4, etc., to disclose specific polyamine and bismalelate. The development of the resin composed of the imine compound is not necessarily sufficient from the viewpoint of the temperature of 300 ° C or higher and the viewpoint of low-temperature adhesion. Further, 1248869 is disclosed in the patent publication. Limit its use to the manufacture of films. On the other hand, from the viewpoint of environmental protection in recent years, in the case of electronic component packaging, lead-free soldering is formed, so that the package of the components of the wafer is still in the process of disassembling the so-called repair wafer or member, in terms of solder heat resistance. It is preferred to be a polytheneimide metal laminate. Further, in terms of the use of the so-called rigid or flexible multilayer substrate, it has been insufficiently credible to criticize the solder heat resistance temperature required in the past, and it is desired to have higher heat resistance. In the case where the metal laminated body is a flexible circuit board assembly module (hereinafter referred to as COF), an internal pin bonding or flip chip bonding machine is used, and an An-300 ° C or higher temperature is used for An- Au bonding, or Au-Sn bonding, bonding of wafers to metal wiring. Therefore, even in the case of using C Ο F, a substrate superior in solder heat resistance is desired. At present, the COF substrate is mainly a non-thermoplastic polyimide, and is a polyimide-based metal laminate obtained by a metal sputtering method on a polyimide film (see Patent Document 5). However, in the case of the sputtering method, the yield is likely to be deteriorated due to pinholes of the metal layer, and it is preferable to use a polyimide-based metal laminate having no pinholes. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 1 0-2 1 2468. Patent Document 2: Japanese Laid-Open Patent Publication No. Hei 01-289862. Patent Document 3: Japanese Patent Laid-Open No. Hei 6- 1 45 63 8. Patent Document 4: Japanese Laid-Open Patent Publication No. Hei 6-129639. Patent Document 5: Japanese Laid-Open Patent Publication No. Hei 07-070762. [Disclosure] 1248869 [Problems to be Solved by the Invention] An object of the present invention is to provide a resin composition for a polyimide composition having excellent low-temperature adhesion. Furthermore, it is to provide a polyimide metal laminate which is superior in solder heat resistance without pinholes, and an Au-Sn joint or Au-Au joint for use in a COF package. Polyimide metal laminate which is not easy to swell and which is superior in solder heat resistance. [Means for Solving the Problem] As a polyimine metal laminate having no pinholes, the inventors of the present invention have a flexible circuit board in which a rolled copper foil or an electrolytic copper foil is laminated with polyimide. In the case of using polyimine as an adhesive, it will be found that the polypyridamine used has problems such as foaming, and the result of reviewing the events is to cooperate with the polymerization. a specific bis-maleic anhydride imide in aminic acid and/or polyimine, which is found to be superior in low-temperature adhesion or superior in solder heat resistance, thereby solving the above problems. And the present invention has been completed. That is, the present invention is as described below. (1) A metal laminate which is laminated on at least one side of a metal foil by a resin composition formed by a bismaleimide compound of the formula, characterized in that the polyamic acid is laminated And/or the general formula (1) of polyimine is 1248869

(where m ' represents an integer above 〇; χ is independently the same or different, and is represented as 0, so2, s, CO, ch2, c(ch3) 2, C(CF3) 2 or Direct bond; further, R1 represents the same or different hydrogen atom, halogen atom, hydrocarbon group, and the substituent positions of the benzene ring are independent of each other). (2) The metal laminate according to (1), wherein the metal laminate system has a polyimine layer formed on one or both sides of one or more layers of the polyimide film, and the polyimine is formed The layer has a structure in which a single layer or a double layer of the metal is laminated. _ (3) The metal laminate according to (1), which has a repeating unit structure represented by the formula, wherein the poly-proline and/or the polyimine have a general formula (2) and a general formula (3), respectively.

1248869

(wherein η represents an integer of 0 or more; γ is independently the same or different, and is represented by 〇, so2, s, co, ch2, c(ch3)2, C(CF3) 2 or directly Bonding; further, A is a tetravalent organic group; R2 is the same or different, and is represented by a hydrogen atom, a halogen atom, or a hydrocarbon group, and the substituent positions of the benzene ring are independently of each other. ). (4) A metal laminate according to (3), wherein A represents a tetravalent organic group, and the general formula (4) is

XX : ΧΜΧ (where Ζ is 0, S02, S, C0, CH2, C(CH3) 2, C (cf3) 2 or a direct bond). (5) A resin composition for a polyimine metal laminate, which is formed by blending a bis-maleic anhydride imide compound represented by the formula ψ m, characterized in that the poly-proline and/or the poly The general formula (i) of quinone imine is 0 R1

R1 . , R1

R1 m R1V^yR1 0 JJ v / X R1 R1 0 0 R1 , R1 •10- (1 ) 1248869 (where m is an integer greater than 0; X is independent of each other, and is represented as 〇, S02, S, CO, ch2, c(ch3)2 or a direct bond; further, R1 is the same or different, a sub, a halogen atom, a hydrocarbon group, and the substitution of each benzene ring is independent of each other). [Embodiment] Hereinafter, the present invention will be described in detail. The present invention relates to a metal laminate characterized in that at least one side of a metal foil is laminated with a resin composition formed by a bismaleic acid compound of the formula, which is characterized by a proline and/or a poly The general formula (1) of the quinone imine is the same, and the hydrogen primary position of C(CF3)2 is represented by: in the anhydride:

(wherein m is an integer of 0 or more; X is respectively the same or different, and is represented by 〇, S02, S, CO, CH2, C (C(CF3) 2 or a direct bond; R1 represents a hydrogen atom, a halogen atom or a hydrocarbon group of the phase, and is independent of each other at the phenyl position. In the general formula (1), m is an integer representing 〇 or more, and is more than 6, more 0 to 4. In addition, the X series are independent and different, and represent 0, S02, S, C0, CH2, C(CH3)2, 2 or a direct bond, preferably 〇, c(ch3) 2, the direct standing can be phase ch3) 2, the same or different ring replacement is preferably 0 to, but also the phase c (CF3) bond. 1248869

Rl is the same or different, and is represented by a hydrogen atom, a halogen atom, or a hydrocarbon group, and the substituent positions of the respective benzene rings are independent of each other. Preferably, the substituent position of the benzene ring is a compound bonded at a meta or ortho position. The polyamic acid and/or the polyimine of the present invention are not particularly limited, but preferably have a repetitive structure represented by the formula, and the general formula (2) and the general formula (3) are

(wherein η represents an integer of 0 or more; and Y is independently the same or different, and is represented as 0, S02, S, C0, CH2, C(CH3)2, C(CF3) 2 or directly Bonding; further, A is a tetravalent organic group; R2 is the same or different, and is represented by a hydrogen atom, a halogen atom, or a hydrocarbon group, and the substituent positions of the benzene ring are independently of each other. ). Preferably, they have general formula (5) and general formula (6) -12- 1248869

(wherein, 1 is an integer of 1 to 7; R2 is the same or different, and is represented by a hydrogen atom, a halogen atom, or a hydrocarbon group, and the substituent positions of the respective benzene rings are independent of each other. From a hydrogen atom and a nitrogen atom, bonded to the same benzene ring, or two different heteroatoms, which are at the meta or ortho position for at least one benzene ring. The repeat unit structure represented by the organic group) preferably has the general formula (7) and the general formula (8), respectively.

-13- 1248869 (wherein the lanthanide represents an integer from 1 to 7, selected from an oxygen atom and a nitrogen atom and bonded to the same or a different benzene ring of the two heteroatoms, for at least one benzene ring In the case of a meta or a neighbor, and the A system represents a tetravalent organic group, the repeat unit structure is preferably the general formula (9) and the general formula (10).

The weight expressed (wherein, 彳 and A represent the same complex unit structure as described above. In the general formulae (2) to (3), n represents an integer of 〇 or more, preferably 0 to 6, More preferably, it is 0 to 4. In the general formulae (5) to (1〇), "is an integer from i to 7, preferably from i to 5, more preferably from 1 to 3. Further, the γ-system is independently And may be the same, or different, and expressed as 〇, S, S'C〇, CH2'C(CH3)2, c(CF3)2 or a direct bond, preferably Ο, CO, C (CH3 2. Direct bonding. In the general formulae (2) to (6), 'R2 is formed to be the same or different, and is represented by a hydrogen atom, a halogen atom, a hydrocarbon group, and each of the benzene rings. - 1248869 The substituent positions are independently of each other, and preferably the substituent of the benzene ring is a compound which is bonded in the meta or ortho position. It is represented by A in the general formulas (2) to (10). The tetravalent organic group is not particularly limited, but examples thereof include an aliphatic group selected from a carbon number of 2 to 27, a cycloaliphatic group, a monocyclic aromatic group, and a condensed polycyclic ring. Bottom aromatic a group, a tetravalent organic group formed of a non-condensed polycyclic aromatic group in which an aromatic group is directly or in a crosslinked phase, preferably a general formula (4).

(wherein Z is 0, S02, S, C0, CH2, C(CH3)2, C(cf3) 2 or a direct bond) is expressed by the above formula. In the general formulae (1) to (3), (5), and (6), as the halogen atom represented by R1 and R2, for example, a chlorine atom or a fluorine atom, as a hydrocarbon group, for example, a methyl group or a lower alkyl group such as an ethyl group, a lower alkyl group such as a vinyl group or an allyl group, an aralkyl group such as a benzyl group or a phenethyl group, an aryl group such as a phenyl group or a naphthyl group, or a methoxy group. An alkoxy group such as an ethoxy group or an alkyl halide such as a trifluoromethyl group. As the bis-maleic anhydride imide compound represented by the general formula (1), for example, 1,3-bis(3-maleic anhydride acetal phenoxy)benzene, bis(3-(3-ma) Anhydride acetal phenoxy)phenyl)ether, 1,3-bis(3-(3-maleic anhydride)-phenoxy)benzene, bis(3-(3-(3-ma) Anthraquinone-15- 1248869 (oxy)phenyl)phenyl)phenyl)ether, L3•bis(3-(3_(3_maleic anhydride) phenoxy)phenoxy)phenoxy Benzene, N, N, -p-phenylene bismaleimide, N,N,-m-phenylene bismaleimide, bis(4-maleic anhydride) Methyl, N,N,-4,4,-diphenyl ether bismaleic acid field imine, ^. ^,-Diphenyl ether dimaleic anhydride imide, ^^,-3,3'-phenyl ketone bismaleimide, 2,2-bis(4-(4-maleic anhydride) Iminophenoxy)phenyl)propane, 4,4,-bis(4-(3-maleic anhydride)-phenyl)propane, 4,4,-bis(3-maleic anhydride) Aminophenoxy)diphenyl, 2,2-bis(4-(3-maleic anhydride)-phenyl)-;[,;[,13,3,3-hexafluoropropane, double ( 4-(3-maleic anhydride acetaminophen) phenyl) ketone, bis(4-(3-maleic anhydride) phenyl) sulfide, bis(4 _(3 _ Malay) Anhydride acetal phenoxy)phenyl) hydrazine, however, is not limited only by this. The bis-maleic anhydride imide compound can be condensed by a method described in, for example, Japanese Patent Application Laid-Open No. Hei No. Hei. And dehydration reaction to manufacture. Further, in the case of producing the metal laminate of the present invention, the compounding ratio of the polyimine of the bismaleimine imide compound is not particularly limited, and as a precursor of the polyimine, polyamine The total weight of the acid is preferably from 1 to 70% by weight, more preferably from 0.1 to 50% by weight. When the compounding amount of the bismaleimine sub-imine compound is less than 0.1% by weight, the effect of improving the solder heat resistance which is the object of the present invention cannot be seen, and when it exceeds 70% by weight, the decrease occurs. The tendency of the subsequent strength of the metal foil. -16- 1248869 A method for blending polyamic acid as a bismaleimide compound, (A) a method of adding a bismaleuric acid imide compound to a polyaminic acid solution, (B) In the polymerization of polylysine, for example, when a diamine compound or a tetracarboxylic dianhydride is charged, or a method of adding in a polymerization process, (C) a powder of polylysine and a double horse The acid anhydride imide compound is mixed with each solid, and the like, but is not limited thereto. Further, the poly-proline is preliminarily dehydrated and imidized to form a polyimine solution, and then a bismaleimide imide compound may be blended.

The polyamic acid represented by the general formula (2) is such that the general formula (11) is H

(wherein, η, Y, and R22 represent the same meanings as defined above) and the general formula (1 2 ) is

(wherein, the oxime is the same as defined above) is represented by a tetracarboxylic dianhydride reaction, and the resin composition formed of polyglycolic acid is imidized by dehydration. The resin composition is also the object of the present invention. -17- 1248869 Specific examples of the aromatic diamine compound represented by the general formula (9) include, for example, bis(3-(3·aminophenoxy)phenyl)ether, ι,3-bis (3_ (3-aminophenoxy)phenyl)benzene, bisaminophenoxy)phenyl)phenyl)ether, 1,3-bis(3-(3-(3-aminophenoxy)phenyl)benzene Base) benzene, hydrazine-phenylenediamine, P-phenylenediamine, phenylenediamine, 4,4, diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3, _Diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3,-diaminodiphenyl ether, 3,4,-diaminodiphenyl ether, 4,4'-diamino group Benzophenone, 3,4,diaminobenzophenone, bisaminophenyl), bis(4-(3-aminophenoxy)phenyl) maple, bis(3-aminophenyl) Sulfide, bis(4-aminophenyl) sulfide, 1,3-bis(4-(4-(aminophenoxy)-α,α-dimethylbenzyl)benzene, 4,4 , bis(3-aminophenoxy)diphenyl, 2,2-bis(4-aminophenoxyphenyl)propane, 1,3-bis(1-(4-(4-aminophenoxy) Phenyl)-1-methylethyl)benzene, 1,4-bis(1-(4-(4-amino) Phenoxy)phenyl)-1-methylethyl)benzene, 1,4-bis(1-(4-(3-aminophenoxy)phenyl)-1-methylethyl)benzene, 2.2 - bis(3-(3-aminophenoxy)phenyl)-1,1,1,3,3,3-hexafluoropropane, 2.2-bis(3-(4-aminophenoxy)phenyl) -1,1,1,3,3,3-hexafluoropropane, but is not limited thereto. In the formula of the general formula (12), A represents a tetravalent organic group, specifically, for example, To represent an aliphatic group selected from a carbon number of 2 to 27, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed one in which the aromatic groups are linked to each other directly or by crosslinking. The tetravalent organic group of the group of the cyclic aromatic group. Further, it is not particularly limited to the tetracarboxylic acid-18-1248869 dianhydride represented by the general formula 2), which can be obtained by using a conventional tetracarboxylic dianhydride. Polyimine with various glass transition temperatures. Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-diamine phthalic anhydride, oxy-4,4'-dicarboxylic acid dianhydride, and 2,2. - bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, ethylene glycol bis(triphenylhexacarboxylic acid) dianhydride, 2,2 bis (3,4-dibromobenzidine) -1,1,1,3,3,3-hexafluoropropane dianhydride, preferably, for example, 2,2',3,35-benzophenone tetracarboxylic dianhydride, 3,3',4 , 4'-benzophenone tetracarboxylic dianhydride, 1,2-bis(3,4-dicarboxybiphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxybiphenyl)benzene Anhydride, 1,4-bis(3,4-dicarboxybiphenyl)phthalic anhydride, 2,2'-bis((3,4-dicarboxy)phenyl)diphenyl ketone dianhydride, 2,3' - bis((3,4-dicarboxy)phenyl)diphenyl ketone dianhydride, 2,4'-bis((3,4-dicarboxy)phenyl)diphenyl ketone dianhydride, 3,3' - bis((3,4-dicarboxy)phenyl)diphenyl ketone dianhydride, 3,4'-bis((3,4-dicarboxy)phenyl)diphenyl ketone dianhydride, 4,4' - bis((3,4-dicarboxy)phenyl)diphenyl ketone dianhydride. These are used singly or in combination of two or more. As a method for producing the polyglycolic acid of the present invention, a method comprising the all-known known polylysine can be applied. Among them, those which react in an organic solvent are preferred. As the solvent used in the reaction, for example, N,N-dimethylanisamine, N,N-dimethylacetamidoamine, N-methyl, 2-pyrrolidone, 1, 2 - Dimethoxyethane and the like. The concentration of the reaction raw material in the reaction is usually 2 to 50% by weight, preferably 10 to 50% by weight, and the reaction temperature is usually 60 ° C or lower, preferably 50 ° C or lower. The reaction pressure system is not particularly limited and can be sufficiently carried out under normal pressure. Further, the reaction time varies depending on the kind of the reaction raw material, the type of the solvent, 1248869, and the reaction temperature. It is generally sufficient for 0.5 to 24 hours. By such a recondensation reaction, polylysine represented by the general formula (2) can be produced. The polyimine which is represented by the general formula (3) is obtained by heating the polylysine to 100 ° C to 400 ° C to carry out hydrazine imidization or by using hydrazine imidization such as acetic anhydride. The chemical oxime imidization is carried out to obtain a polyimine having a repeating unit structure corresponding to poly-proline. Further, the polyimine of the present invention can be obtained by carrying out the reaction at 130 ° C to 25 ° C while simultaneously carrying out the production of polyaminic acid and the heat oximation reaction. That is, the diamine component and the dianhydride component are suspended or dissolved in an organic solvent, and the reaction is carried out under heating at 130 ° C to 250 ° C to simultaneously produce polyglycine and dehydrazide imidization. Thus, the polyimine of the present invention can be obtained. The resin composition for the polyimine metal laminate of the present invention may be blended in an appropriate amount with other resins as described below, without impairing the object of the present invention, namely, polyethylene, polypropylene, Polycarbonate, polyarylate compound, polyamine, poly milling, polyether maple, polyether ketone, polydiether ketone, polyphenyl sulfide, deformed polyphenylene ether, polyamine-imine, poly Amine, epoxy resin, etc. The film may be produced from the resin composition of the polyimine metal laminate of the present invention, and the method is not particularly limited. For example, (A) coating the polyaminic acid solution to the substrate (glass plate, metal plate) Or a heat-resistant resin film), followed by heating and imidization; (B) coating the polyimide solution onto the substrate (glass plate, metal plate, or with resistance to -20- 1248869 Thermal resin film) After heating, the method of heating. Further, it may have an adhesive tape composed of an adhesive layer formed of the above resin composition and a heat-resistant film. The insulating tape is formed by a single-sided tape in which only the adhesive layer is formed on one surface of the heat-resistant film, or a double-sided tape in which the adhesive layer is formed on both surfaces of the heat-resistant film, or It is made up of other arbitrary layers. According to the resin composition for a polyimine metal laminate of the present invention, in order to produce an adhesive tape, the solution containing the resin composition is applied to one side or both sides of the heat-resistant film, and the most It is good to carry out the dryer. In this case, the thickness after coating is 0.5 to 100 / / m, preferably 1 to 3 0 / / m / m, as a heat-resistant film, such as polyimine, polyphenylene sulfide, polyether, polyether A film of a heat-resistant resin such as a ketone, a polydiether ketone or a terephthalic acid-ethylene glycol polycondensate, a composite heat-resistant film such as an epoxy resin-glass fiber or an epoxy resin-polyimine-glass fiber. In particular, it is preferred from the viewpoint of heat resistance or dimensional stability. The thickness of the film heat-resistant film formed of the polyimide resin is preferably from 5 to 130 #m, more preferably from 12.5 to 75/m. The metal laminate of the present invention is a resin group or a product layer which can be blended on at least one side of a metal foil with the above-described bismaleuric acid imide compound. An example of the specific production method is, for example, a non-thermoplastic polyimide film coated with a thermoplastic polyimine compound which has been compounded with a bis-maleic anhydride imide compound represented by the general formula (1), or a varnish comprising a polyamic acid precursor of the thermoplastic polyimide, which is dried and hardened to form a thermoplastic polyimide layer on the surface of the thermoplastic layer 1248869 A method of manufacturing a surface of a metal by hot pressing. The metal laminate of the present invention is a component which forms a subsequent layer and a metal foil formed of the above resin composition. An adhesive layer formed of another resin composition or a non-adhesive layer may be present in a single layer or a plurality of layers as an intermediate layer between the adhesive layer and the metal case. Further, in the metal laminate of the present invention, it is preferable to incorporate a resin composition formed of a bis-maleic anhydride imide compound represented by the general formula (1) in any of the layers. It is a resin layer formed by multi-layering the above compound. In the case of producing the metal laminated body of the present invention, it is preferable that the solution containing the above resin composition is coated on a metal foil and dried. At this time, the thickness after coating is preferably in the range of 0.5 to 100 / / m. When 0 · 5 // m or less, there is a case where sufficient adhesion cannot be obtained. If it exceeds 100//m, there is a case where the adhesion cannot be greatly improved. The metal foil sheet may be applied to a conventional metal foil or alloy foil. However, from the viewpoints of cost surface, thermal conductivity, rigidity, and the like, a rolled copper foil, an electroplated copper foil, a copper alloy foil, or the like may be used. Stainless steel foil is preferred. Further, the thickness of the metal foil is not limited as long as it is in the form of a belt, but it is preferably used in the range of 2 to 150. More preferably, it is 2 to 10 5 // In the metal laminate of the present invention, it is preferred to form a polyimine layer on one side or both sides of one or more layers of the polyimide film. The amine layer is a structure having a single-sided or double-sided metal laminate, and the polyimine layer contains the bismaleic anhydride imidized-22-1248869 compound represented by the general formula (1). Resin composition. As the polyimide film, preferably a non-thermoplastic polyimide film, a composition comprising a specific diamine and a specific tetracarboxylic dianhydride can be used. As a specific diamine, for example, quinone-phenylenediamine, P-phenylenedi-phenylenediamine, 4,4, diaminophenyl ether, 3,4'-diaminophenyl ether, 3,3, phenylene ether, etc. . These systems may be used alone or in combination of two or more. Specific tetracarboxylic dianhydrides are, for example, pyromellitic dianhydride, 3,3', diamine biphenyl anhydride, and 2,2',3,3'-benzidine. These types can be used alone or in combination of two or more types. Further, as the non-thermoplastic polyimide film, a commercially available thermosensitive polyimide film can also be used. For example, Ubex (trade name) (trademark) S, Ubex (trade name) (registered trademark) SGA, Rex (trade name) (registered trademark) SN (Ube Industries Co., Ltd. limited manufacturing , trade name), Ke Pudong (trade name; Kapton) (registered trademark) Ke Pudong (trade name; Kapton) (registered trademark) V, Ke Pudong (name; Kapton) (registered trademark) EN (Dongli· DuPont Co., Ltd., trade name), Abikar (trade name) (registered trademark) AH, Carl (trade name) (registered trademark) NPI, Abikar (trade name) trademark) HP (Zhongyuan Chemical Industry Co., Ltd. Manufacturing, commercial products, etc. The surface of non-thermoplastic polyimides can also be subjected to plasma treatment, electro-electric treatment, etc. The thickness of the non-thermoplastic polyimide layer is not particularly limited depending on the purpose. In the range of 2 50 μm. In addition, the commercially available non-thermoplastic polyimide film does not contain the amine, diamine 4,4,- or make it non-registered. Secretary Abi (note) Halo release, layer -23- 1248869 The side of the thermoplastic polyimide layer may also be laminated with a non-thermoplastic polyimide which is different in its structure. Further, in the present invention, in a polyimide film, an adhesive tape or a metal laminate On the adhesive layer, a release protective film, a carrier film, and a carrier metal foil may be provided. As the carrier film, for example, polyethylene, terephthalic acid-ethylene glycol polycondensate, polypropylene, etc. may be used as the carrier metal. a foil, such as a rolled copper foil, an electroplated copper foil, a copper alloy foil, a stainless steel foil, etc. The thickness is 1 to 200 / / m, preferably 10 to 1 / zm. In addition, between the layer and the adhesive layer The 90° peeling strength is preferably in the range of 0.01 to 10 kN/m. The polyimine metal laminate provided by the present invention has a remarkable superior solder heat resistance effect. The conventional bismaleic anhydride is used. The imide resin is known as a heat resistant resin, which means its thermal decomposition temperature, and has no direct correlation with solder heat resistance. Specifically, it also has a double maleic anhydride shrinkage in the prior art. Tree obtained from imine and diamine The 5% weight reduction temperature is about 40 ° C before and after. On the other hand, even if the polyimide is a thermoplastic polyimide, it has a high heat resistance before and after 500 ° C. However, The metal laminate of the thermoplastic polyimide used in the past has a solder heat resistance of at most 260 ° C or less, which causes a high temperature tendency which cannot be sufficiently adapted to the recent use temperature. Here, attempts have been made to use a glass transition temperature. High-temperature thermoplastic polyimides are used as countermeasures. However, the formation temperature between the metal foils is high, and it cannot be found that they have sufficient bonding strength in the conventional process; in addition, the occurrence of thermoplastic polyimides cannot be achieved. The unevenness of the surface of the metal foil is completely embedded, which is called a defect of the void. Here, in the present invention, by mixing bismaleimide imide to polyimine, it is possible to easily carry out lamination with a metal and reduce formation by lowering the glass transition temperature. The solder heat resistance can be raised to a level higher than the conventional temperature. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. Further, the physical properties of the polyimine in the examples were determined by the following methods. Glass transition temperature (Tg): measured by differential scanning calorimeter (DSC3110, manufactured by Mike Technology Co., Ltd.) and temperature rise conditions at 10 ° C / min. In addition, regarding the Tg obtained by the DSC method, the peak of the loss elastic modulus (E" obtained by the solid viscoelastic device RSAII (manufactured by ARES) and the temperature rising condition at 1 Hz and 5t: /min is used. 90° peeling strength: measured according to IPC-TM-65 0method, 2, 4, 9. In addition, the welding heat resistance test in the example is IPC-TM-65 0 (The institute for Interconnecying and Packaging Electronic According to C ircuits, the welding temperature is set to 2 4 0 °C, 2 60 °C, 2 80 °C, 300 °C, 320 °C, 340 °C) No. 2.4.13 The maximum temperature at which the discoloration at the interface between the metal and the polyimide is not swelled or set is the heat resistance temperature of the solder. Further, the sample is 85 ° C, the relative humidity is 85%, and the state has been adjusted for 50 hours. Example 1] -25- 1248869 In a vessel equipped with a stirrer and a nitrogen introduction tube, 12.00 g, l, 3 - bis (1,3-(3-aminophenoxy)phenyl)benzene was inserted ( 3-maleic anhydride imide phenoxy)benzene 1.94 g, and N,N-dimethylacetamide 4 8 · 70 g, in nitrogen Under the atmosphere, stir at 50 ° C for 1 hour. After that, reduce the system temperature to room temperature, and pay attention to 3,3,,4,4,-benzophenone tetrahydro acid anhydride 1 1 · 9 0 g The temperature of the solution is increased, added in portions, and heated again to 5 ° C for 4 hours. A portion of the obtained polyamic acid solution containing the solution of the bismaleimide compound is poured and poured. After the glass substrate is heated, the film is heated at 50 ° C to 270 ° C to obtain a film having a thickness of 20 / / m. The glass transition temperature (Tg) of the obtained polyimide film is 1 〇. 6. (In addition, a part of the obtained polyamic acid solution containing the solution of the bis-maleic anhydride imide compound was poured into a copper box (SLP-35, manufactured by Nippon Electrolysis Co., Ltd., thickness 35//). m) a metal laminate obtained by heating 5 to 270 ° C at a heating rate of 7 ° C to obtain a polyimide thickness of 12 μm. In order to evaluate low-temperature adhesion, the metal laminate is Copper foil (SLP-35, thickness 35 // m made by Sakamoto Electrolysis Co., Ltd.) using a pulse splicer (Gail Co., Ltd. (transliteration) Ltd., TC-1320UD), to 1 9 0 ° C, 3 Μ P a heated pressure tank 2 by a copper seconds. Using the obtained test pieces, the basis of IPC-TM-65 0method, 2,4,9 for 90. In the peeling test, the result was 1·6 kN/m 0 [Examples 2 to 4] The same as Example 1 except that the type and amount of the diamine compound or the bis-maleic anhydride imide compound were changed. Polymerization, coordination, evaluation -26-1248869. The results are disclosed in Table 1. 1,3-bis(3-(3-aminophenoxy)phenyl)benzene, I,3-bis(3-(3-(3-aminophenoxy)phenyl)phenyl group used herein Benzene and 1,3-bis(3-(3-malehydride)-phenyl)benzene were identified by 1H-NMR and FD-mass spectrometry. 1,3-bis(3-(3-aminophenoxy)phenyl)benzene: W-NMR (CD3 S0CD3 ) δ : 5.24 (s, 4H ), 6 · 1 2 - 6 · 1 6 (ddd5 2Η, J = 7.83, 2.43, 0·82Ηζ), 6.23 (t, 2Η, J=2.30Hz) 5 6.33 - 6.37 (ddd, 2Η5 J = 7.83, 2.43, 0.82Hz), 6.61 ( t5 2Η, J = 2 · 43Ηζ), 6·67 ( t,1H, J = 2·43Ηζ), 6.71 - 6.80( m,6H), 6.99( t,2H, J= 7.83Hz ), 7.35 ( t,2H,J = 7.83Hz ), 7.38 (t, 1H, J = 7.83Hz) FD-mass spectrometer 476 (M + );

1,3-bis(3-(3-(3-carbophenoxy)phenyl)phenyl)benzene: j-NMR (CD3SOCD3) (5 ·· 5.21(s,4H) , 6.12 — 6.16 ( ddd , 2H, J = 7.83, 2.16, 0·8 1Ηζ), 6.21 ( t, 8H, J = 2.16Hz), 6·31—6·36 (ddd, 2H, 7·83, 2.16, 0·81Ηζ), 6.6 7 - 6 · 8 2 ( m,1 3 H ), 6.98(t,8H,J=8.1〇Hz), 7.31 - 7.42(m,5H), FD_ mass spectrometer 6 6 0 ( M + ); 3-bis(3-(3-maleic anhydride) phenyloxy)phenyl)benzene: 1h_Nmr

(CDC13) 5 : 6.72( t,3H,J= 2·3 0Ηζ),6·79 — 6 8 3 ( dd,6H J = 7.8 3, 2.4 3 Hz ) 5 7.0 5 - 7.0 8( m5 5H)5 7.12 - 7.16( m, 5H) 7.34 - 7.51 (m, 5H), FD - mass spectrometer 636 (M + ). [Example 5] In a container equipped with a stirrer and a nitrogen gas introduction tube, 85 g of methyl vinylamine was added as a solvent, and this was added. 69.16 g of bis(l -27- 1248869 oxy)benzene was stirred at room temperature until dissolved. Thereafter, 3,3',4,4'-benzophenone tetracarboxylic acid dioxan 75.8^ was added at 60. (: stirring was carried out to obtain a polyaminic acid solution. The content of polyglycine was 15% by weight. 48.3 g of 1,3-bis(3-maleic anhydride acetal) benzene was added to the solution. The obtained partial enamel paint was 500 00g, and it was stirred at room temperature for 2 hours. The commercially available polyimine resin film (manufactured by Toray DuPont Co., Ltd.) was used. Trade name: Kepdong (trade name; Kapton) (registered trademark) 1 5 0EN ), the bismaleuric acid imide compound obtained by the above method contains a part of poly-proline, which is coated by a roller to form a dried film. Coating was performed at a thickness of 2 μm, and was carried out at 1 15 °C for 2 minutes, at 150 °C for 2 minutes, at 180 °C for 2 minutes, at 240 °C for 2 minutes, at 265 °C. After drying for 2 minutes and drying in an air floating type to obtain an insulating film having a thermoplastic polyimide film layer on one side, it is commercially available as an electrolytic copper foil (manufactured by Furukawa Foil Co., Ltd.). On F0-WS9//m), the metal foil is posted at 240 ° C and a pressure of 1.5 MPa by laminating the rolls. And an insulating film, and then annealed by a pressure cooker at a temperature of 280 ° C for 4 hours under a nitrogen atmosphere to obtain a polyimine metal laminate. The obtained polyimine metal laminate The heat resistance temperature of the soldering was 32 (TC. Further, the interface between the copper foil and the polyimide was observed in a cross section of 1250, and the surface of the copper box was removed by etching, and no void was observed. [Example 6 to Example 1] 3) The same polymerization, blending, and evaluation as in Example 5 were carried out except that the type and amount of the diamine, the acid dianhydride, and the bismaleimide imide were changed. -28- 1248869 The results are disclosed in the table. 2. Further, no void was observed at the interface between the copper foil and the polyimide reaction from all the samples. [Example 1 4] In a container equipped with a stirrer and a nitrogen introduction tube, it was added to form polylysine. The N,N-dimethylacetamino group having a content of 15% by weight is used as a solvent, and p-phenylenediamine and 3,45-oxydiphenylamine are added in a ratio of 30 mol% and 70 mol%. Stir at room temperature until dissolved. After that, The molar amount of the total diamine was set to 1, and the amount of 0.98 5 molar parts of 3,3',4,4'-benzophenone tetracarboxylic dianhydride was added, and the mixture was stirred at 60 ° C to obtain polylysine. Solution: In order to add 1,3-bis(3-maleic anhydride acetal) benzene to polyglycine for 40% by weight, it was added to the obtained enamel paint, and stirred at room temperature for 2 hours. The bi-maleic anhydride imide compound obtained by the extraction contains a poly-proline solution, which is cast on a glass substrate and heated at 50 ° C to 270 ° C at a heating rate of 7 t / min. A film having a thickness of 20/im was obtained. The glass transition temperature (Tg) of the obtained polyimide film was 220 ° C. 6 Further, a commercially available polyimide film (manufactured by Toray DuPont Co., Ltd. 5 trade name · Ke Pudong (product) was used. Kapton (registered trademark) 150EN), the obtained bis-maleic anhydride imide compound, containing a part of polylysine by means of an applicator to form a dried thickness of 2 / / m Coating was carried out at a heating rate of 7 ° C / min, and heated from 50 ° C to 270 ° C to obtain an insulating film having a single-sided thermoplastic polyimide film layer. Thereafter, it was superposed on a commercially available electrolytic copper foil (F0-WS 9 μm manufactured by Furukawa Circuit Foil Co., Ltd.), and dried at 130 ° C for about one hour, and then the temperature was 300 °. (:, -29- 1248869 Pressure 2.5Mpa, stamping for 4 hours to post metal foil and insulating film, to obtain a polythene imide metal laminate. No gap was observed between the copper foil and the polyimide. The result of the peeling test was 0.85 kN/m. [Example 1 5 and Example 16] The examples and the amounts of the diamine, the acid dianhydride, and the bismaleic acid imide were changed. The same polymerization, blending, and evaluation were carried out in the same manner. The results are shown in Table 3. Further, voids were not observed in the interface between the copper foil and the polyimide reaction in all the samples. [Comparative Example 1] The same polymerization, blending, and evaluation were carried out in the same manner as in Example 1 except for the bismaleimine imide compound. The results are shown in Table 1 ^ The peeling strength is OkN/m, but not at all. Comparative Example 2] In a vessel equipped with a stirrer and a nitrogen introduction tube, N,N-dimethylacetamidoamine 8 5 5 g was added as a solvent, and 1,3-double was added thereto. 3-amine phenoxy)benzene 69.1 6g, stirred at room temperature until dissolved Then, 3,3',4,4'-benzophenonetetracarboxylic dianhydride 75.842 was added, and stirred at 60 ° C to obtain a polyaminic acid solution. The content of polyglycine was 1 5 % by weight. The commercially available polyimine resin film (manufactured by Toray Dupont Co., Ltd., trade name: Kapton (trade name; Kapton) (registered trademark) 1 50 ΕΝ), One part of the amine acid solution was coated by a roller to form a dried thickness of 2 // m, and the drying was carried out at 1 15 ° C for 2 minutes, at 150 ° C for 2 minutes, at 180 °. C was subjected to 2 minutes, at 24 0 -30 to 1248869 ° C for 2 minutes, at 265 ° C for 2 minutes, and dried by an air floating type drying oven to obtain a single-sided thermoplastic polyimide film layer. Insulating film. Thereafter, on the same commercially available electrolytic copper foil as in Example 5, the metal foil and the insulating film were laminated at 240 ° C and a pressure of 1.5 MPa by lamination. , by means of a batch pressure cooker, annealing at a temperature of 280 ° C for 4 hours under a nitrogen atmosphere to obtain a polyfluorene An amine metal laminate. The obtained heat-resistant temperature of the polyimide laminate is 260 ° C. In addition, it is observed that the interface between the copper foil and the polyimide is present in the number / / m to several tens / / [Vacuum of a degree of m. [Comparative Example 3 to Comparative Example 5] The same polymerization, blending, and evaluation were carried out as in Example 14, 4, and 5, except that the bis-maleic anhydride imide compound was not blended. One item is disclosed in Table 3. The peeling strength was 〇kN/m and was not followed at all, and the evaluation of the void could not be performed. -31- 1248869 [Table 1] Diamine compound *1) Acid dianhydride *2) Double horse Acid anhydride imide compound *3) Tg DSC method peeling strength unit mol mol wt% °C kN/m Example 1 APB 0.0410 BTDA 0.0369 ΑΡΒ-ΒΜΙ 40 106 1.6 Example 2 APB5 0.0329 BTDA 0.03112 ΑΡΒ-ΒΜΙ 20 116 2.4 Example 3 APB5 0.0329 BTDA 0.0313 ΑΡΒ-ΒΜΙ 15 125 1.6 Example 4 APB7 0.0200 BTDA 0.0190 ΑΡΒ-ΒΜΙ 10 115 2.2 Comparative Example 1 APB 0.0410 BTDA 0.0369 — 195 0 [Table 2] Diamine compound *1) Acid dianhydride Material*2) bismaleic anhydride imide Material *3) Solder heat resistance mol mol wt% °c Example 5 APB 0.2366 BTDA 0.2354 ΑΡΒ-ΒΜΙ 25 320 Example 6 APB 0.2366 BPDA 0.2354 ΑΡΒ-ΒΜΙ 20 300 Example 7 DAPB 0.2366 BTDA 0.2354 ΑΡΒ-ΒΜΙ 40 350 Implementation Example 8 m-BP 0.2366 PDMA 0.2354 ΑΡΒ-ΒΜΙ 40 350 Example 9 APB5 0.2366 BTDA 0.2354 ΑΡΒ-ΒΜΙ 20 320 Example 10 ODA 0.2366 BTDA 0.2354 ΑΡΒ-ΒΜΙ 40 360 Example 11 APB 0.2366 BTDA 0.2354 ΒΜΙ-ΜΡ 25 350 Implementation Example 12 APB 0.2366 BTDA 0.2354 BMI-S 25 350 Example 13 DABP 0.2366 ODPA 0.2354 BMI-S 10 320 Comparative Example 2 APB 0.2366 BTDA 0.2354 A 260 -32- 1248869 [Table 3] Diamine compound * 1) Acid dianhydride *2) Bismaleimide imide compound*3) Tg solid viscoelastic method peeling strength mol mol wt wt% °C kN/m Example 14 3,4,-ODA (70 mol%) 0.0150 PPD (30 mol % ) 0.0064 BTDA 0.0211 ΑΡΒ-ΒΜΙ 40 220 0.85 Comparative Example 3 Same as above - 290 0 Example 15 ODA (70 mol%) 0.0150 m-BP (30 mol%) 0.0064 PMDA 0.0211 ΑΡΒ-ΒΜΙ 40 260 0.7 Comparative Example 4 Same as above 340 0 Example 16 ODA (70 mol%) 0.0150 PPD (30 mol%) 0.0064 PMDA (50 mol %) 0.0105 BPDA (50 mol %) 0.0105 ΑΡΒ-ΒΜΙ 40 242 0.6 Comparative Example 5 Same as above - 320 0 Note *1) APB : 1,3-bis(3-aminophenoxy)benzene APB5 : 1,3-bis(3-(aminophenoxy)phenyl)benzene APB7 : 1,3-bis(3- (3- (3) -aminophenoxy)phenyl)phenyl)benzene DABP : 3,3'-diaminobenzophenone m-BP : 4,4'-(3-aminophenoxy)diphenyl ODA: 4 , 4'-oxydiphenylamine (4,4'-diaminodiphenyl ether) 3,4'-ODA: 3,4'-oxydiphenylamine (3,4·diaminodiphenyl ether) PPD : p-benzene Diamine-33- 1248869 Note*2) BTDA: 3,3,,4,4,-benzophenone tetracarboxylic dianhydride BPDA: 3,3',4,4,-diamine phthalic anhydride ODPA: 3 , 3',4,4'-diphenyl ether tetraresic acid dianhydride PMDA: pyromellitic dianhydride injection *3) ΑΡΒ-ΒΜΙ: 1,3 - bis (3 -maleic anhydride acetal phenoxy Benzene APB5-BMI: 1,3 -bis(3-(3-maleic anhydride acetaminophen) phenoxy)benzene BMI-MP: N,N,-m-benzoicin anhydride imide BMI-S: bis(4-maleic anhydride acetimidate phenyl)methyl [invention [Effects] The resin composition of the present invention is excellent in low-temperature adhesion due to the Tg-reducing effect, and is preferably a heat-resistant adhesive which can be used in the field of electronics. In addition, according to the present invention, even if a higher processing temperature is not used, a laminate having a higher bonding strength without residual voids at the interface between the metal and the polyimide can be obtained, and further, a polyimine metal can be provided. The laminated board is superior in terms of the LS I wafer or component packaging procedure which is extremely harsh in temperature conditions, and the difficulty in generating expansion in soldering heat resistance in such maintenance procedures. [Simple description of the diagram] Μ 〇 j\\\ -34-

Claims (1)

1248869 Ail ¢.: Picking up, patent application scope: a 5th 92 1 1 7653 "Metal laminate" patent case (revised on December 10, 1993) 1. A metal laminate, at least in the metal foil On one side, a resin composition formed by the bismaleimine imide compound in the formula is laminated, wherein the general formula (1) of the polyamic acid and/or polyimine is (wherein m is an integer from 0 to 6; X is independently the same or different, and is represented by Ο, S02, S, CO, CH2, C(CH3) 2, C (CF3): or Is a direct bond; further, R1 represents the same or a different hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, or a halogenated alkyl group, and The substituent positions of the benzene ring are independent of each other). 2. The metal laminate according to claim 1, wherein the metal laminate system forms a polyimide layer on one or both sides of the layer of the polyimide film, and the polyazide layer is formed. The amine layer has a structure in which a single layer or a double layer of the metal is laminated. 3. The metal laminate according to claim 1, which has a repeating unit structure as shown in the formula, wherein the poly-proline and/or the polyimine are respectively 1248869 having the general formula (2) and/or Formula (3) 〇 Q 刚”I Luzhou H〇-ff \-n-0 0 Η (wherein η represents an integer of 0 to 6; the oxime systems are independently the same or different, and are represented as 0, S〇2, S, C0, ch2, c (CH3) 2, C (CF3) 2 Or a direct bond; in addition, A is a tetravalent organic group; R2 is the same or different, and is represented by a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, or an aryl group. An alkoxy group or a halogenated alkyl group which is independently of each other in the substituent positions of the benzene ring. 4. A metal laminate according to item 3 of the patent application, wherein A represents a tetravalent organic group, and the general formula (4) is (where Ζ is 0, S〇2, S, CO, CH2, C(CH3) 2, C(CF3) 2 or 1248869 is a direct bond). 5 a resin composition for a polyimine metal laminate, which is formed by a bis-maleic anhydride imide compound represented by a formula in the formula, characterized in that the polyamic acid and/or polyfluorene The general formula of imine (1) is (wherein m is an integer from 0 to 6; X is independently the same or different, and is represented by 〇, S02, S, CO, CH2, C(CH3)2, C(CF3)2 or a direct bond; further, R1 is the same or different, and is represented by a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxy group, or a halogenated alkyl group. The substituent positions of the respective benzene rings are independently of each other).