JP2003231208A - Metal laminated body with thermoplastic polyimide resin layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal laminated body with both low temperature adhesive properties and soldering heat resistance and being suitable for a base material forming a part of a semiconductor package and the like. <P>SOLUTION: The metal laminated body of the present invention has a metal layer and a thermoplastic polyimide resin layer. The thermoplastic polyimide resin layer comprises a thermoplastic polyimide resin formed of diamine ingredients and acid anhydride ingredients. In this polyimide, as the diamine ingredients, a mole 1,3-bis(3-(3-aminophenoxy)phenoxy)benzene, b mole specified diaminosiloxane compound and c mole other diamine are used and as the acid anhydride ingredients, d mole specified aromatic dicarboxylic acid dianhydride of a specified formula such as 3,3',4,4'-benzophenone tetracaboxylic acid dianhydride and e mole other acid dianhydride are used and they are bonded together by ratios of 0.5≤(a+b)/(a+b+c)≤1.0, 0<a/(a+b)<1.0, 0<d/(d+e)≤1.0 and 0.9≤(d+e)/(a+b+c)<1.0. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a metal laminate having a metal layer and a layer made of a thermoplastic polyimide resin having both low temperature adhesiveness and heat resistance.

[0002]

2. Description of the Related Art Conventionally, since thermoplastic polyimide resins have excellent heat resistance, chemical resistance, mechanical strength, and electrical characteristics, they have been used in the field of electronic materials typified by flexible printed boards and semiconductor packages. It is widely used as a heat-resistant adhesive. As excellent in both heat resistance and adhesiveness, U.S. Pat.
The polyimide adhesive disclosed in Japanese Patent Publication No. 1-143477 is known. However, although these have excellent heat resistance and adhesiveness, there is a problem that it is necessary to set the bonding temperature to a high temperature in order to obtain a good bonded state.

Also, in recent years, as the functionality of semiconductor packages has increased, the amount of heat generated by semiconductor elements has increased. In order to release the thermal energy generated by this heat generation to the outside of the package, it is necessary to attach a heat sink to the lower side of the semiconductor element. Conventionally, a double-sided adhesive tape has been used to bond the heat sink to the lead frame, but for the purpose of cost reduction and improvement of wire bonding reliability, a base material in which the heat sink is pre-coated with an adhesive has been developed. . However, in this case, since the adhesive is applied to the entire heat sink, there is a portion that comes into contact with the mold resin when assembled as a semiconductor package, and if the package is passed through the reflow process for mounting, the adhesive / There is a problem that interface peeling occurs at the interface of the mold resin and the reliability of the semiconductor package is reduced.

[0004]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a metal composed of a thermoplastic polyimide resin having excellent low temperature adhesiveness, suppressing the occurrence of interfacial peeling at the adhesive / mold resin interface, and having excellent heat resistance. It is to provide a laminated body. In the present invention, the low adhesion temperature is 100 ° C to
It refers to a temperature range of 300 ° C, more preferably 100 ° C to 250 ° C.

[0005]

A metal laminate having a thermoplastic polyimide resin layer of the present invention is a metal laminate having a metal layer and a thermoplastic polyimide resin layer, and the thermoplastic polyimide resin layer is a diamine component. And a thermoplastic polyimide resin formed from an acid dianhydride component, wherein the thermoplastic polyimide resin is a diamine represented by the following formula (1);

[0006]

[Chemical 4]

Diaminosiloxane compound represented by the general formula (2); b mol

[0008]

[Chemical 5]

(In the formula (2), R ₁ and R ₂ have a divalent carbon number of 1 to 1).
4 is an aliphatic group or an aromatic group, R _{3 to} R ₆ are monovalent aliphatic groups or aromatic groups, and m is an integer of 1 to 20. ) And another diamine compound; a diamine component consisting of c moles, and an acid dianhydride represented by the general formula (3); d moles

[0010]

[Chemical 6]

Represents ) And other acid dianhydrides;
formed with an acid dianhydride component consisting of e moles,
The diamine component and the acid dianhydride component are 0.5 ≦ (a + b) / (a + b + c) ≦ 1.0, 0 <a / (a + b) <1.0, 0 <d / (d + e) ≦ 1.0, and 0.9 ≦ (d + e) The feature is that they are bonded at a ratio of /(a+b+c)<1.0.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Next, the metal laminate of the present invention will be specifically described. The metal laminate of the present invention has a metal layer and a thermoplastic polyimide resin layer. Here, the thermoplastic polyimide resin layer forming the metal laminate is formed of a specific thermoplastic polyimide resin formed of a diamine component and an acid dianhydride component.

The diamine component used in the preparation of the thermoplastic polyimide resin in the present invention is represented by the above formula (1).
1,3-bis (3- (3-aminophenoxy) phenoxy) benzene, a diaminosiloxane compound represented by the general formula (2), and other diamine components. Examples of the diaminosiloxane compound represented by the general formula (2) used for preparing the thermoplastic polyimide resin in the present invention include, for example, ω and ω ′.
-Bis (2-aminoethyl) polydimethylsiloxane, ω,
ω'-bis (3-aminopropyl) polydimethylsiloxane, ω, ω'-bis (4-aminobutyl) polydimethylsiloxane, ω, ω'-bis (4-aminophenyl) polydimethylsiloxane, and ω, ω'-bis (3-aminopropyl) polydiphenylsiloxane and the like can be mentioned.

Other diamine compounds which can be used in combination with the diaminosiloxane compound represented by the general formula (2) include, for example, 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-aminophenyl) (4-aminophenyl) sulfoxide, bis (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, bis (4-amino Phenyl) 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 ' -Diaminodiphenyl 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-bis (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-hexafluoropro Bread, 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-aminophenoxy) phenyl) ketone, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3- (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) diphenyl sulfone, 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-aminophenoxy) 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-aminophenoxy) 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-amino Phenoxy) 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) )-Four-
Methylphenoxy) benzene, 1,3-bis (2- (4-aminophenoxy) -4-tert-butylphenoxy) benzene, 1,4-bis (3- (3-aminophenoxy) phenoxy) -2,5- Di-tert-
Butylbenzene, 1,4-bis (3- (4-aminophenoxy) phenoxy) -2,3-dimethylbenzene, 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 and 1,2-bis (3- (2-amino-
Examples include 3-propylphenoxy) phenoxy) benzene and the like.

A thermoplastic polyimide resin is obtained by the reaction of the above diamine component and the following acid dianhydride.
Examples of the acid dianhydride represented by the general formula (3) used in the present invention include, for example, 2,2 ′, 3,3′-benzophenonetetracarboxylic acid dianhydride and 3,3 ′, 4,4 ′. -Benzophenone tetracarboxylic acid dianhydride, 1,2-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,3-bis (3,4-dicarboxybenzoyl) benzene dianhydride, 1,4 -Bis (3,4-dicarboxybenzoyl) benzene dianhydride, 2,2'-bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, 2,3 '
-Bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, 2,4'-bis ((3,4-dicarboxy) phenoxy)
Benzophenone dianhydride, 3,3'-bis ((3,4-dicarboxy) phenoxy) benzophenone dianhydride, 3,4'-bis
((3,4-dicarboxy) phenoxy) benzophenone dianhydride, and 4,4'-bis ((3,4-dicarboxy) phenoxy)
Examples thereof include benzophenone dianhydride.

Other acid dianhydrides which can be used in combination with the acid dianhydride represented by the general formula (3) include, for example, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride and 3,6-
Difluoropyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ', 4,4' -Biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -terphenyltetracarboxylic dianhydride, 3,3 "', 4,4"'-quaterphenyltetracarboxylic dianhydride, 3,3 "", 4,4 ""-Kink phenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride 1,1-ethynylidene-4,4'-diphthalic dianhydride, 2,2-propylidene-4,4'-diphthalic 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 acid dianhydride, 1,
1,2,2-Tetrafluoro-1,2-ethylene-4,4'-diphthalic dianhydride, 1,1,2,2,3,3-hexafluoro-1,3-trimethylene-4,4 '-Diphthalic acid dianhydride, 1,1,2,2,3,3,4,4-octafluoro-1,4-tetramethylene-4,4'-diphthalic acid dianhydride, 1,1,2 , 2,3,3,4,4,5,5-Decafluoro-1,5-pentamethylene-4,4'-diphthalic acid 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-dicarboxyphenoxy) benzene dianhydride, 1,3 -Bis (2-
(3,4-Dicarboxyphenyl) -2-propyl) benzene dianhydride, 1,4-bis (2- (3,4-dicarboxyphenyl)
-2- (Propyl) benzene dianhydride, bis (3- (3,4-dicarboxyphenoxy) phenyl) methane dianhydride, bis (4
-(3,4-Dicarboxyphenoxy) phenyl) methane dianhydride, 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, ethylene glycol bistrimellitic dianhydride, 1,3-Propanediol bistrimellitic dianhydride, 1,4-butanediol bistrimellitic dianhydride, 1,5-pentanediol bistrimellitic dianhydride, 1,6-hexanediol bistrimellitic dianhydride Anhydride, 1,8-octanediol bistrimellitic dianhydride, 1,10-decanediol bistrimellitic dianhydride, 1,16-hexadecanediol bistrimellitic dianhydride, 2,2-bis (4- Hydroxyphenyl) propanedibenzoate-3,3 ', 4,4'-tetracarboxylic 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 dianhydride, 3,4,9,10-perylenetetra Carboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic acid 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-dicarboxylic 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'-biphenyltetra Carboxylic dianhydride, 2,2'-bis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 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'-biphenyltetracarboxylic dianhydride, 3,3'-difluorooxy-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 acid dianhydride, 6,6'-bis (trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 3,3 ', 5,5'-Tetrakis (trifluoromethyl) oxy-4 , 4'-Diphthalic acid dianhydride, 3,3 ', 6,6'-Tetrakis (trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 5,5', 6,6'-Tetrakis (Trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride, 3,3 ', 5,5', 6,6'-hexakis (trifluoromethyl) oxy-4,4'-diphthalic acid dianhydride Substance, 3,3'-difluorosulfonyl-4,4'-diphthalic dianhydride, 5,5'-difluorosulfonyl-4,4'-diphthalic dianhydride, 6,6'-
Difluorosulfonyl-4,4'-diphthalic acid dianhydride, 3,
3 ', 5,5', 6,6'-Hexafluorosulfonyl-4,4'-diphthalic acid dianhydride, 3,3'-bis (trifluoromethyl) sulfonyl-4,4'-diphthalic acid dianhydride 5,5'-bis (trifluoromethyl) sulfonyl-4,4'-diphthalic acid dianhydride,
6,6'-bis (trifluoromethyl) sulfonyl-4,4'-diphthalic acid dianhydride, 3,3 ', 5,5'-tetrakis (trifluoromethyl) sulfonyl-4,4'-diphthalic acid dianhydride Anhydrous, 3,
3 ', 6,6'-Tetrakis (trifluoromethyl) sulfonyl
-4,4'-diphthalic dianhydride, 5,5 ', 6,6'-tetrakis (trifluoromethyl) sulfonyl-4,4'-diphthalic dianhydride, 3,3', 5,5 ' , 6,6'-Hexakis (trifluoromethyl) sulfonyl-4,4'-diphthalic acid dianhydride, 3,3'-Difluoro-2,2-perfluoropropylidene-4,4'-diphthalic acid dianhydride 5,5'-difluoro-2,2-perfluoropropylidene-4,4'-diphthalic acid dianhydride, 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- -Fluoropropylidene-4,4'-diphthalic dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-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,
Examples include 9,9-bis (4- (3,4-dicarboxy) phenyl) fluorene dianhydride, and 9,9-bis (4- (2,3-dicarboxy) phenyl) fluorene dianhydride. To be

In the thermoplastic polyimide resin constituting the metal laminate of the present invention, the molar ratio of each of the diamine component and the acid dianhydride component is such that the compound represented by the above formula (1) which is an essential component of the diamine and the general The compound represented by the formula (2) is bonded at a molar ratio satisfying the relations of 0.5 ≦ (a + b) / (a + b + c) ≦ 1.0 and 0 <a / (a + b) <1.0. The compound represented by the general formula (3), which is a component, is bonded in a molar ratio satisfying the relationship of 0 <d / (d + e) ≦ 1.0. If the bonding molar ratio of each of the above components is not within the above range, the glass transition temperature is high and low-temperature adhesiveness is not exhibited, or the solder heat resistance is significantly inferior.

When (d + e) / (a + b + c) is less than 0.9, when the adhesive is formed into a film, the molecular weight is low, and the strength required for practical use cannot be obtained, and (d + e) / ( a + b +
If c) is 1.0 or more, the solder heat resistance of the metal laminate is significantly poor, and therefore it is necessary to satisfy the relationship of 0.9 ≦ (d + e) / (a + b + c) <1.0.

The thermoplastic polyimide resin as described above is
Generally, it has a glass transition point, and the glass transition temperature measured with the thermoplastic polyimide resin in the form of a film.
(Tg) is usually 30 to 300 ° C., preferably 30 to 20
Within the range of 0 ° C. For the production of the thermoplastic polyimide resin that constitutes the metal laminate of the present invention, any method capable of producing polyimide, including known methods, can be applied. Above all, it is preferable to carry out the reaction in an organic solvent. As the solvent used in such a reaction, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, N- Cyclohexyl-2-pyrrolidone, 1,
3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl)
Ether, 1,2-bis (2-methoxyethoxy) ethane, bis
(2- (methoxyethoxy) ethyl) ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine,
Picoline, dimethyl sulfoxide, dimethyl sulfone,
Examples thereof include tetramethylurea, hexamethylphosphoramide, cyclohexanone, cyclopentanone, phenol, cresol, chlorophenol, anisole, benzene, toluene, and xylene. These may be used alone or in combination of two or more.

The concentration of the reaction raw material in this reaction is usually 2 to 50% by weight, preferably 5 to 30% by weight, and the reaction temperature is usually 60 ° C. or lower, preferably 50 ° C.
It is the following. The reaction pressure is not particularly limited, and it can be carried out at normal pressure. The reaction time varies depending on the type of reaction raw material, the type of solvent and the reaction temperature, but is usually 0.5 to 24.
Time is enough. By such a polycondensation reaction, a polyamic acid that is a precursor of the thermoplastic polyimide resin forming the metal laminate of the present invention is produced. A polyimide having a repeating unit structure corresponding to the polyamic acid is obtained by heating the polyamic acid to 100 to 400 ° C. for imidization or chemically imidizing with an imidizing agent such as acetic anhydride. To be

The above reaction temperature is set to 130 ° C. to 250 ° C.
By setting the temperature in the range of 0 ° C., the generation of the polyamic acid and the thermal imidization reaction proceed at the same time, and the thermoplastic polyimide resin forming the metal laminate of the present invention can be obtained in a single step. That is, the diamine component and the acid dianhydride component are suspended or dissolved in an organic solvent,
By carrying out the reaction under heating at 0 ° C. to simultaneously generate the polyamic acid and the dehydration imidization, the thermoplastic polyimide resin constituting the metal laminate of the present invention can be obtained.

The thermoplastic polyimide resin constituting the metal laminate of the present invention includes other resins such as polyethylene, polypropylene, polycarbonate, polyarylate, polyamide, polysulfone, polyether sulfone, etc. within a range not impairing the object of the present invention. It is also possible to blend an appropriate amount of polyether ketone, polyether ether ketone, polyphenyl sulfide, modified polyphenylene oxide, polyamide imide, polyether imide, bismaleimide, epoxy resin or the like.

The metal laminate of the present invention contains the adhesive layer made of the above-mentioned thermoplastic polyimide resin and the metal foil as essential components, and as an intermediate layer between the adhesive layer and the metal foil,
An adhesive layer or a non-adhesive layer made of another resin composition may be present. To produce the metal laminate of the present invention, a solution containing the above-mentioned thermoplastic polyimide resin,
Alternatively, a solution containing the precursor polyamic acid may be applied to the metal foil and dried. At that time, the thickness after coating is preferably a dry thickness in the range of 0.5 to 100 μm. If it is less than 0.5 μm, sufficient adhesive force may not be obtained, and if it exceeds 100 μm, significant improvement in adhesiveness cannot be expected.

The thickness of the metal foil constituting the metal laminate of the present invention is 3 μm to 200 μm, but if it finally functions as a heat sink, the thickness is preferably 50 μm or more. If it is less than 50 μm, a sufficient heat radiation effect cannot be obtained. The upper limit of the thickness of the metal foil is 20 considering that the above-mentioned thermoplastic polyimide resin is continuously applied.
The limit is 0 μm. If the thickness exceeds 200 μm, the workability of transporting the laminate is deteriorated. As the type of metal foil, all known metal foils and alloy foils can be applied, but rolled copper foils, electrolytic copper foils, copper alloy foils, and stainless steel foils are cost-friendly, thermal conductive, and rigid. It is suitable.

The metal laminate of the present invention is prepared by dissolving the above-mentioned acid amide in a good solvent such as N-methyl-2-pyrrolidone on the surface of the metal foil and applying the solution, followed by heating. To form a thermoplastic polyimide resin, or by directly applying the thermoplastic polyimide resin to the surface of the metal foil. In the present invention, a peelable protective film may be provided on the adhesive layer of the metal laminate. Examples of the protective film include polyethylene, polyethylene terephthalate, polypropylene and the like, and the thickness is 1 to 200 μm, preferably 10
˜100 μm. The 90 ° peeling adhesive strength between the protective film and the adhesive layer is preferably in the range of 0.01 to 10 g / cm.

[0026]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0027]

Example 1 In a container equipped with a stirrer and a nitrogen introducing tube,
4.7652 g (0.0100 mol) of 1,3-bis (3- (3-aminophenoxy) phenoxy) benzene and a diaminosiloxane compound (Toray Dow Corning Silicone BY16-871EG) 2.4850 g (0 0.0100 mol)
And 31.5781 g of N-methyl-2-pyrrolidone were inserted, and the mixture was stirred at 40 ° C. for 30 minutes in a nitrogen atmosphere.

After that, the temperature in the system is set to 10 ° C. or lower,
3 ', 4,4'-benzophenone tetracarboxylic acid dianhydride 6.
2833 g (0.0195 mol) was added in portions while paying attention to the rise of the solution temperature, and the temperature was kept at 10 ° C or lower for 3 hours.
Stir at room temperature for 3 hours. After dissolving the obtained polyamic acid in N-methyl-2-pyrrolidone at a concentration of 0.5 g / dl, the logarithmic viscosity was measured at 35 ° C.
It was dl / g.

A portion of this polyamic acid was taken and cast on a copper foil (Nippon Denshoku Co., Ltd., SLP-18, thickness 18 μm) and then heated from 50 ° C. to 270 ° C. at a heating rate of 7 ° C./min. Thus, a metal laminate having a polyimide thickness of 6 μm was obtained. The glass transition temperature (Tg) of the polyimide film obtained by etching the copper foil portion of the thus obtained metal laminate with a ferric chloride solution is measured by a thermomechanical analyzer (TMA4000 manufactured by Mac Science Co., Ltd.) As a result, 122 ℃
Met.

Further, in order to evaluate the low-temperature adhesiveness, a part of the obtained polyamic acid was used as a copper foil (manufactured by Nippon Denshoku Co., Ltd.,
SLP-35, thickness 35μm) and cast from 50 ℃ to 2
Polyimide thickness 6 by heating to 70 ° C at a heating rate of 7 ° C / min
A metal laminate having a thickness of μm was obtained. This metal laminate was applied to a copper foil (SLP-35, thickness 35 μm, manufactured by Nippon Electrolysis Co., Ltd.) using a pulse bonder (TC-1320UD, manufactured by Kell Co., Ltd.).
It was thermocompression bonded at 0 ° C. and 30 kg / cm ² for 8 seconds. Using the obtained test piece, a 90 ° peel test was conducted according to IPC-TM-650 method, 2, 4, 9 and found to be 1.52 kg / cm.
Met.

Further, in order to evaluate the solder heat resistance,
Part of the obtained polyamic acid was cast on a copper foil (manufactured by Nippon Denshoku Co., Ltd., SLP-105WB, 105 μm thick), and 50
A metal laminate having a polyimide thickness of 6 μm was obtained by heating from 0 ° C. to 270 ° C. at a heating rate of 7 ° C./min. Subsequently, a 25 mm square and 10 mm thick mold resin (CEL9200-ME1 manufactured by Hitachi Chemical Co., Ltd.) was press-molded (molding conditions: 160 ° C., 75 kg / cm ² , 5) on the thermoplastic polyimide resin.
Min), annealing (annealing conditions: under air, 175 ° C., 5
Time) to produce 10 test pieces.

This test piece was left in an atmosphere of 85 ° C./85% RH for 48 hours, then immersed in a solder bath at 260 ° C. for 30 seconds, and then the metal foil portion was etched. 10
For each of the test pieces, it was visually observed whether or not peeling occurred at the adhesive / mold resin interface. As a result, no peeling occurred at all of the 10 test pieces.

[0033]

[Examples 2 to 4 and Comparative Examples 1 to 3] Polyamic acid was polymerized in the same manner as in Example 1 with the types and ratios of the diamine component and the acid dianhydride component shown in Table 1, and the same evaluation was performed. . The results are also shown in Table 1.

[0034]

[Table 1]

[0035]

As is clear from the results shown in Table 1, the specific diamine component and the specific acid dianhydride were mixed in the range of 0.5 ≦ (a +
b) / (a + b + c) ≦ 1.0, 0 <a / (a + b) <1.0, 0 <d / (d + e) ≦
1.0, 0.9 ≦ (d + e) / (a + b + c) <1.0, a metal laminate of the present invention in which a layer made of a thermoplastic polyimide resin obtained by reacting is laminated on a metal foil layer has low-temperature adhesiveness and soldering. It also has heat resistance and is suitable as a base material forming a part of a semiconductor package or the like.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F100 AB01A AB17 AK49B BA02                       BA07 GB41 JA05B JB16B                       JJ03 JL11 YY00A YY00B                 4J043 PA04 QB15 QB26 RA34 SA06                       SA85 SB02 TA22 UA121                       UA122 UA161 UB121 UB122                       ZA02 ZA12 ZB11 ZB50 ZB58

Claims (3)

[Claims] 1. A metal laminate having a metal layer and a thermoplastic polyimide resin layer, wherein the thermoplastic polyimide resin layer comprises:
It is composed of a thermoplastic polyimide resin formed from a diamine component and an acid dianhydride component, and the thermoplastic polyimide resin is a diamine represented by the following formula (1); A diaminosiloxane compound represented by the following general formula (2): b mol (In the formula (2), R ₁ and R ₂ represent a divalent aliphatic group or aromatic group having 1 to 4 carbon atoms, R _{3 to} R ₆ represent a monovalent aliphatic group or aromatic group, m Represents an integer of 1 to 20), and another diamine compound; a diamine component consisting of c moles, an acid dianhydride represented by the following general formula (3); Represents ) And another acid dianhydride; an acid dianhydride component consisting of e moles, wherein the diamine component and the acid dianhydride component are 0.5 ≦ (a + b) / (a + b + c) ≦ 1.0 , 0 <a / (a + b) <1.0, 0 <d / (d + e) ≦ 1.0, and 0.9 ≦ (d + e) / (a + b + c) <1.0. 2. The metal laminate according to claim 1, wherein the glass transition temperature of the thermoplastic polyimide resin is in the range of 30 ° C. to 200 ° C. 3. The thermoplastic polyimide resin layer has a thickness in the range of 0.5 to 100 μm, and the metal layer has a thickness of 3.
It is in the range of ~ 200 μm.
The metal laminate described.