JP2005144908A - Polyimide metal laminated plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide metal laminated plate in which a wiring dislocation and an edge short circuit after the mounting of chips, and faults such as the sinking of metal wiring in a polyimide layer and the peeling of the wiring from the polyimide layer are prevented. <P>SOLUTION: The polyimide metal laminated plate is composed of the polyimide layers and a metal layer. In the laminated plate, at least one polyimide (PI) layer having a modulus of elasticity in a temperature area of at least 350°C of 1-30 GPa exists in the polyimide layers. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyimide metal laminate widely used for flexible wiring boards and the like.

  In recent years, with the downsizing and portability of electronic devices, the use of polyimide metal laminates capable of high-density mounting of components and elements as circuit board materials is increasing. In order to cope with further downsizing and higher density, a method of mounting components and elements called COF (chip on film) directly on a circuit board has become mainstream. Conventionally, as a base material for COF, a polyimide layer is mainly obtained by casting or laminating a polyimide metal laminated plate (see Patent Document 1) obtained by sputtering metal on a polyimide resin film, or rolled copper foil or electrolytic copper foil. There is something that forms.

  Polyimide metal laminates that form a polyimide layer on rolled or electrolytic copper foil generally have a thermoplastic polyimide layer formed between the metal foil layer and the polyimide layer in order to increase the adhesion between the metal foil layer and the polyimide layer. Is.

  By the way, as for chip mounting, there are methods of mounting at low temperatures such as ACF (Anisotropic Conductive Film), NCP (Non Conductive Paste) and ultrasonic bonding, and mounting at high temperatures such as Au-Au bonding and Au-Sn bonding. From the viewpoint of the mounting method using the TAB line and the connection reliability between the chip and the wiring, Au-Au bonding and Au-Sn bonding are still widely used.

When chip mounting is performed on these metal laminates by Au—Sn bonding, there are cases where defects such as wiring and chip bumps sink into polyimide or wiring is shifted. Excessive sinking of the wiring causes a problem that an underfill does not enter and an edge short occurs because the gap between the chip and the polyimide layer becomes narrow. In addition, with respect to the wiring displacement, there was a problem that it contacted the adjacent copper wiring and caused a short circuit. In order to prevent these problems from occurring, it has been desired to have a wiring displacement and a small sinking amount.
JP 2003-188495 A

  The object of the present invention is a polyimide metal laminate that does not suffer from problems such as wiring misalignment, edge shorting, metal wiring sinking into the polyimide layer after wiring, and peeling of the wiring from the polyimide layer. Is to provide. Furthermore, it is to provide a polyimide metal foil laminate that can be filled with underfill without causing any wiring misalignment even during chip mounting by Au-Au bonding or Au-Sn bonding.

  As a result of investigations, the present inventors have studied that a polyimide metal laminate obtained by allowing a polyimide (PI) layer having an elastic modulus of 1 GPa or more and 30 GPa or less in a high temperature range of 350 ° C. or more to exist in the polyimide layer. The present inventors have found that a board can solve the above-mentioned problems and have reached the present invention.

That is, the present invention relates to the following.
(1) A polyimide metal laminate comprising a polyimide layer and a metal layer, wherein at least one polyimide (PI) layer having a modulus of elasticity of 1 GPa or more and 30 GPa or less in a temperature region of 350 ° C. or higher is in the polyimide layer A polyimide metal laminate, characterized by being present in
(2) A polyimide (PI) layer having a modulus of elasticity of 1 GPa or more and 30 GPa or less in a temperature range of 350 ° C. or higher is synthesized from diamine and tetracarboxylic dianhydride. Mol% or more is one or more selected from o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine, and 90 mol% or more of the total tetracarboxylic dianhydride component is pyromellitic dianhydride, One or more compounds selected from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (1) The polyimide metal laminate as described. (3) The polyimide metal laminate according to (1) or (2), wherein the polyimide layer in contact with the metal is thermoplastic polyimide (TPI).
(4) The polyimide according to (3), wherein the glass transition point (Tg) of the thermoplastic polyimide (TPI) is 250 ° C. or more and 375 ° C. or less, and the elastic modulus at the glass transition point or more is 10 MPa or more and 1 GPa or less. Metal laminate.

  The polyimide metal laminate provided by the present invention has a phenomenon in which wiring displacement, edge short, metal wiring sinks into the polyimide layer, such as Au-Au bonding or Au-Sn bonding, and wiring is polyimide. Underfill filling is possible without causing problems such as peeling from the layer.

  Hereinafter, the present invention will be described in detail.

  As an example of the specific configuration of the polyimide metal laminate of the present invention, a dry film-forming method or the like may be applied to one or both sides of a polyimide (PI) film layer having an elastic modulus of 1 GPa or more and 30 GPa or less in a high temperature range of 350 ° C. or higher. A polyimide metal laminate (A) obtained by directly forming a metal layer by plating, a thermoplastic polyimide (TPI) layer is formed on one or both sides of the polyimide (PI) film layer, and the metal foil layer is heated. Polyimide metal laminate (B) obtained by pressure bonding, polyimide metal laminate (C) obtained by forming a thermoplastic polyimide (TPI) layer on the metal foil layer, and thermocompression bonding the polyimide (PI) film layer, Furthermore, the polyimide (PI) is obtained by applying, drying and curing the surface of the thermoplastic polyimide (TPI) layer formed on the metal foil layer. Polyimide-metal laminate (D), and the like.

  In the polyimide metal laminate (A), the dry film forming method and the plating method are performed on the surface of the polyimide (PI) film layer by resistance heating vapor deposition, ion plating vapor deposition, sputtering vapor deposition, electroless plating method in an electrolytic solution, or the like. A method of forming a layer is preferable, and a method of thickening the formed metal layer by an electrolytic plating method or the like is more preferable. The material of the metal layer to be formed by the dry film formation method or plating method is selected from the group consisting of metals such as Cu, Fe, Ni, Mo, Ta, Ti, V, Cr, Co, or alloys thereof. At least one kind of metal is preferable, and oxides or the like thereof may be laminated.

  In the polyimide metal laminate (B), (C), (D), the metal foil in contact with the thermoplastic polyimide layer is selected from the group consisting of Cu, Fe, Ni, Co, Cr, Zn, Al and alloys thereof. At least one kind of metal is preferable, and more preferable examples include copper and copper alloys, iron alloys such as stainless steel, nickel and nickel alloys (including 42 alloys), aluminum and aluminum alloys, and the like. More preferred are copper and copper alloys.

  The thickness of the metal layer formed by the polyimide metal laminate of the present invention is not limited as long as it can be used in a tape shape, but preferably 2 to 150 μm.

  The metal laminate of the present invention is characterized in that at least one of the polyimide layers includes a polyimide (PI) layer having an elastic modulus of 1 GPa or more and 30 GPa or less in a high temperature range of 350 ° C. or more, preferably 1 GPa or more and 10 GPa or less. The polyimide (PI) layer. By using at least one polyimide (PI) layer for the polyimide layer of the polyimide metal laminate, there is a problem that the metal wiring sinks into the polyimide layer during chip mounting, wiring misalignment, edge shorting, and wiring from the polyimide layer. It is preferable that problems such as peeling do not occur.

  The elastic modulus is measured at a temperature lower than the decomposition temperature of polyimide, specifically in the range of 350 ° C. to 500 ° C., and is conventionally used such as TMA (Thermomechanical Analysys) and viscoelasticity measuring machine. In the present invention, any apparatus having at least one elastic modulus in the above range can be applied in the present measurement temperature range.

  As the polyimide (PI) in the polyimide metal laminate of the present invention, 70 mol% or more of the total diamine component as a raw material is at least one or two selected from o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine. It is preferable to be a diamine of at least species, more preferably 80 mol% or more, and still more preferably 90% mol or more of these diamines. Further, 90 mol% or more of the total tetracarboxylic dianhydride component is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4. It is preferably at least one or two or more tetracarboxylic dianhydrides selected from '-benzophenone tetracarboxylic dianhydride, more preferably 95 mol% or more, still more preferably 97 mol% or more. It consists of a dianhydride.

  The polyimide (PI) layer thickness preferably has a thickness of 50% or more of the total polyimide layer thickness in the polyimide metal laminate of the present invention, more preferably 60% or more, and even more preferably 70% or more. Specifically, it can be about 3 to 200 μm, preferably 7 to 150 μm, and more preferably about 10 to 50 μm. In the polyimide (PI), the linear expansion coefficient is preferably 5 to 40 ppm / ° C, and more preferably 10 to 30 ppm / ° C.

  In the polyimide metal laminates (A), (B), and (C), the polyimide (PI) layer is previously formed into a single-layer film state, and polyimide (PI) and / or polyimide (PI) precursor. It is possible to apply a varnish containing a polyimide (PI) film by coating, drying and imidizing on the surface of the support.

  When the varnish contains an organic solvent and the polyimide (PI) precursor is a polyamic acid, it is also preferable to contain a ring-closing catalyst and a dehydrating agent. A method of forming a film, running with a rotating roll, stretching and forming is also preferable.

  Commercially available polyimide (PI) films can also be used. For example, Upilex (registered trademark) S, Upilex (registered trademark) SGA, Upilex (registered trademark) SN (manufactured by Ube Industries, Ltd., trade name) ) And the like. Further, the surface of the polyimide (PI) film may be subjected to plasma treatment, corona discharge treatment or the like.

  In the polyimide metal laminate (D), the polyimide (PI) varnish is applied, dried and imidized on the surface of the thermoplastic polyimide (TPI) layer applied, dried and imidized on the surface of the metal foil layer, and then the polyimide ( PI) layer is formed, and a thermoplastic polyimide (TPIL) having an elastic modulus of 500 MPa or less in a high temperature region of Tg or higher is formed on the surface of the polyimide (PI) layer, and the polyimide (PI) film It is also preferable to perform thermocompression bonding.

  In the polyimide metal laminate (B), (C), (D), as the thermoplastic polyimide (TPI) in contact with the metal layer, the glass transition point (Tg) is preferably 250 ° C. or higher and 375 ° C. or lower. More preferably, it is 250 degreeC or more and 350 degrees C or less. When it exceeds 350 ° C., when it is a metal laminate, the adhesive strength with the metal foil is less likely to be exhibited, and therefore it is preferably 260 ° C. or higher and 340 ° C. or lower.

  Furthermore, it is preferable that the elastic modulus in a high temperature region of Tg or more is 10 MPa or more and 1 GPa or less, and when the elastic modulus is less than 10 MPa, the thermoplastic polyimide is deformed at the time of chip bonding, and the metal wiring easily sinks into the polyimide layer. Therefore, there is a possibility that the thermoplastic polyimide and the chip come into contact with each other, and that the metal wiring is likely to be peeled off from the polyimide layer. In addition, when the elastic modulus is 1 GPa or more, the metal foil and the adhesive strength may be difficult to express. Therefore, the elastic modulus is preferably within the above range, and for future fine wiring applications, in order to improve the peel strength and solder heat resistance, which are indicators of adhesion to the metal foil, from the viewpoint of reliability, The rate range is preferably 40 MPa to 1 GPa, more preferably 100 MPa to 1 GPa, and still more preferably 100 MPa to 700 MPa. The elastic modulus and Tg are preferably measured with a viscoelasticity measuring instrument in the range of 150 ° C. or higher and 500 ° C. or lower. The elastic modulus (storage elastic modulus E) of a single-layer thermoplastic polyimide (TPI) sample is preferably measured. ') And the peak temperature of the loss elastic modulus (E' ') that becomes Tg are preferably obtained as the elastic modulus and Tg.

  Examples of usable thermoplastic polyimide (TPI) include, but are not limited to, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB), 4,4-bis ( 3-aminophenoxy) biphenyl (hereinafter abbreviated as m-BP), 3,3′-diaminobenzophenone (hereinafter abbreviated as DABP), p-phenylenediamine (pPD), 4,4′-diaminodiphenyl ether (ODA) Those using at least one diamine selected from the above are preferred.

  The acid dianhydride is not particularly limited, and a known acid dianhydride can be used, but 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA), pyro It is preferable to use merit acid dianhydride (PMDA) or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA).

  The thermoplastic polyimide (TPI) layer is usually about 0.1 to 20 μm, preferably 0.2 to 10 μm, more preferably 0.3 to 5 μm, and more preferably about 0.4 to 3 μm.

  In the present invention, for the varnish containing polyamic acid which is a precursor of polyimide and / or the varnish containing polyimide, the reaction molar ratio of the diamine component and tetracarboxylic dianhydride is usually in the range of 0.75 to 1.25, Preferably, when the diamine component is 1, the tetracarboxylic dianhydride is in the range of 0.8 to 1.0.

  Furthermore, varnish formed by mixing two or more varnishes, varnish formed by blending bismaleimide compound, polyimide (PI), thermoplastic polyimide (TPI), thermoplastic polyimide (TPIL) formed by coating, drying and imidization ), Polyimide (PI) layer, thermoplastic polyimide (TPI) layer, thermoplastic polyimide (TPIL) layer is also included in the range of polyimide used in the polyimide metal laminate of the present invention, and is heat resistant. In order to improve foaming resistance and the like, it is effective to add the bismaleimide compound.

  As a method of applying a varnish containing polyamic acid, which is a polyimide precursor, or a varnish containing polyimide, a known method such as a die coater, comma coater, roll coater, gravure coater, curtain coater, spray coater, etc. can be adopted. . It is appropriately used depending on the thickness to be applied, the viscosity of the varnish, and the like.

  For the method of thermocompression bonding the thermoplastic polyimide (TPI) layer and the thermoplastic polyimide (TPIL) layer to the polyimide (PI) film layer and the metal foil layer, thermoplastic polyimide (TPI) and thermoplastic polyimide (TPIL) A representative example is a hot press method and / or a heat laminating method that can be pressurized while maintaining the glass transition temperature or higher. Although there is no restriction | limiting in particular as a laminating method, The method of pinching and sticking between a roll and a roll is preferable.

  This polyimide metal-clad laminate is further heated and held at 150 to 500 ° C. after lamination or while laminating, so that a thermoplastic polyimide (TPI) layer, a thermoplastic polyimide (TPIL) layer, and a polyimide (PI) A polyimide metal laminate having excellent adhesion to the film layer and the metal foil layer is obtained. As a heating device, a normal heating furnace, an autoclave, or the like can be used. As a heating atmosphere, air, inert gas (nitrogen, argon), or the like can be used. As a heating method, either a method of continuously heating or a method of leaving a polyimide metal laminate sheet in a heating furnace while being wound around a core is preferable. As the heating method, a conductive heating method, a radiant heating method, a combination method thereof, and the like are preferable. The heating time is preferably in the time range of 0.05 to 5000 minutes.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the elastic modulus and glass transition point (Tg) of the thermoplastic film shown in the Examples, wiring sinking amount measurement / wiring peeling at the time of chip mounting, peel strength, and void were measured by the following methods.
(1) Thermoplastic polyimide elastic modulus and glass transition point (Tg)
Rheometrics RSAII is used to measure the elastic modulus (storage elastic modulus E ') of a single-layer thermoplastic polyimide sample in nitrogen at 1Hz at 3 ° C / min from 25 ° C to 500 ° C in tension mode. At the same time, the peak of loss elastic modulus (E ″) was determined as Tg.
(2) Wiring subsidence measurement / wiring separation After mounting the chip at the circuit processing / chip mounting manufacturer, the sample is encapsulated with resin and polished, and the bump and wiring joint cross section is observed with a metal microscope made by Nippon Optical Co., Ltd. Was done. The difference between the metal wiring and the polyimide layer interface between the chip mounting location and the non-mounting location was measured and used as the amount of wiring sinking. It is determined that the wiring sink amount is preferably 5 μm or less. Further, it was confirmed whether or not the metal wiring was peeled off from the thermoplastic polyimide layer.
(3) Peel strength (kN / m)
A conductor with a length of 50 mm and a width of 2 mm is formed by etching a metal foil. According to the method specified in JIS C-6471, the metal conductor side is peeled from the polyimide layer from the end of the short side, and the stress is measured. To do. The peeling angle was 90 ° and the peeling speed was 50 mm / min. It is judged that the peel strength is preferably 0.60 kN / m or more.
(4) Void From the polyimide surface of the polyimide metal laminate, the interface between the copper foil layer and the polyimide layer was observed 500 to 1500 times with an optical microscope to confirm the occurrence of voids.

Abbreviations for the solvents, acid dianhydrides, and diamines used in the examples are as follows.
DMAc: N, N-dimethylacetamide pPD: p-phenylenediamine ODA: 4,4′-diaminodiphenyl ether APB: 1,3-bis (3-aminophenoxy) benzene m-BP: 4,4′-bis (3- Aminophenoxy) biphenyl BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride PMDA: pyromellitic dianhydride APB-BMI: 1,3-bis (3-maleidophenoxy) benzene

Synthesis example 1
<Synthesis of polyimide (PI) resin precursor (PI-varnish)>
To a container equipped with a stirrer and a nitrogen introduction tube, 196.1 g of DMAc was added as a solvent, and 15.0 g of pPD was added thereto, and the mixture was stirred at room temperature until dissolved. Thereafter, 43.6 g of BTDA is added so that the acid anhydride has a ratio of 0.975 with respect to the diamine component, stirring is performed at 60 ° C., and a polyamic acid solution having a polyamic acid content of 23% by weight, PI-1 varnish was obtained as shown in Table 1.

Synthesis Examples 2-7
Polyimide (PI) and thermoplastic polyimide (TPI) as in Synthesis Example 1 except that the types and ratios of diamine, acid anhydride, polyamic acid content, and APB-BMI addition rate were changed as shown in Table 1. ), A varnish for thermoplastic polyimide (TPIL) (Table 1) was obtained. APB-BMI was added to the polyamic acid so that the content of 10% by weight of the polyamic acid was obtained after obtaining the polyamic acid solution, and the mixture was added by stirring at room temperature. About the polyimide varnish synthesize | combined in the synthesis examples 1-7, Tg and the elasticity modulus were measured (Table 1). Tg was not confirmed in PI-1 and PI-2 varnishes in Synthesis Examples 1 and 2.

  About each polyimide (PI) varnish, it apply | coated on the glass substrate so that the thickness after film-forming might be 25 micrometers and 38 micrometers, and 7 degreeC / min from 50 degreeC to 270 degreeC in inert oven of nitrogen atmosphere After heating at 430.degree. C., heat treatment was further performed at 430.degree. C. for 2 minutes to form a film and peeled from the glass substrate to obtain each polyimide (PI) film.

Example 1
Using commercially available copper foil (Furukawa Circuit Foil Co., Ltd., trade name: F0-WS (thickness 9 μm)), the thickness after drying the TPI-1 varnish of Synthesis Example 4 on a polyimide laminate surface with a roll coater is 1 μm. After being applied, and dried at 100 ° C. for 2 minutes, a thermoplastic polyimide (TPI-1) layer is formed, and the PI-1 varnish of Synthesis Example 1 is formed on the surface of the thermoplastic polyimide (TPI-1) layer. Was applied with a comma coater so that the thickness after drying was 9 μm, and then dried at 115 ° C. for 2 minutes to form a polyimide (PI-1) layer. Furthermore, after applying the TPIL varnish of Synthesis Example 7 on the surface of the polyimide (PI-1) layer with a roll coater so that the thickness after drying becomes 2 μm, it is dried at 100 ° C. for 2 minutes to obtain a thermoplastic polyimide ( TPIL) layer was formed. After that, it was cured and dried at 180 ° C. for 1.6 minutes, and further cured and imidized at 380 ° C. for 2 minutes and further at 430 ° C. for 2 minutes in a nitrogen atmosphere, and the surface of the polyimide layer that did not contact the metal layer was thermoplastic polyimide. A polyimide metal laminate as a (TPIL) layer was obtained. Thereafter, the surface of the polyimide (PI-1) film having a thickness of 25 μm and the surface of the thermoplastic polyimide (TPIL) layer of the polyimide metal laminate were prepared at 260 ° C. and a pressure of 1.5 MPa using a roll laminator. Then, annealing was performed in a batch type autoclave at 350 ° C. for 4 hours in a nitrogen atmosphere, and a flexible metal laminate was obtained as shown in FIG.

About the obtained flexible metal laminated board, the amount of wiring subsidence, wiring peeling, peel strength, warpage, and void at the time of chip mounting were measured and confirmed.
Result is,
Chip mounting result: Wiring sinking 0.5 μm, no wiring peeling Peel strength: 0.65 kN / m
Void: None (Table 2).

Examples-2, 3
Examples-2 and 3 are the same as Example-1 except that the varnish for forming the thermoplastic polyimide (TPI) layer, the polyimide (PI) layer, and the polyimide (PI) film layer was changed as shown in FIG. Each flexible metal laminate was obtained as shown in FIG.

Example-4
Using a 38 μm-thick polyimide (PI-1) film prepared in advance, the TPI-2 varnish of Synthesis Example 5 was applied to the polyimide laminate surface with a roll coater so that the thickness after drying was 1 μm. After drying at 180 ° C. for 2 minutes, it is cured at 180 ° C. for 1.6 minutes and further cured and imidized at 380 ° C. for 2 minutes, further at 430 ° C. for 2 minutes in a nitrogen atmosphere, and the polyimide laminate surface is thermoplastic. The insulating film which is a polyimide (TPI-2) layer was obtained. Thereafter, the surface of the thermoplastic polyimide (TPI-2) layer and a commercially available copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., trade name: F0-WS (thickness 9 μm)) were pressed at 350 ° C. under a pressure of 1 Then, thermocompression bonding was performed under the condition of 0.5 MPa, and then annealing was performed in a batch-type autoclave at a temperature of 350 ° C. for 4 hours in a nitrogen atmosphere to obtain a flexible metal laminate as shown in FIG.

Example-5
Example 5 was carried out in the same manner as in Example 4 except that the varnish for forming the polyimide (PI) film layer was changed as shown in FIG. 1, and a flexible metal laminate was obtained as shown in FIG.
With respect to the flexible metal laminates obtained in Examples-1, 2, 3, 4, and 5, the amount of wiring subsidence, wiring peeling, peel strength, and void when mounted on the chip were measured and confirmed. The results are shown in Table 2.

Comparative example 1, 2
Comparative Example-1, 2 as in Example-1, except that the varnish for forming the thermoplastic polyimide (TPI) layer, the polyimide (PI) layer, and the polyimide (PI) film layer was changed as shown in FIG. Each flexible metal laminate was obtained as shown in FIG.

Comparative Example-3, 4
A flexible metal laminate is produced in the same manner as in Example-4 except that the varnish for forming the thermoplastic polyimide (TPI) layer and the polyimide (PI) film layer is changed as shown in FIG. Was obtained as shown in FIG.

  The flexible metal laminates obtained in Comparative Examples-1, 2, 3, and 4 were measured and confirmed for the amount of wiring sinking, wiring peeling, peel strength, and void when the chip was mounted. The results are shown in Table 2.

  A polyimide wiring laminate is obtained that does not cause problems such as wiring displacement, edge shorting, metal wiring sinking into the polyimide layer after chip mounting on the polyimide metal stack, and problems such as wiring peeling off from the polyimide layer. Widely applied to substrates.

The structure of the polyimide metal laminated board manufactured in Examples 1-5 and Comparative Examples 1-4 is shown.

Claims (4)

A polyimide metal laminate comprising a polyimide layer and a metal layer, wherein at least one or more polyimide (PI) layers having an elastic modulus of 1 GPa or more and 30 GPa or less in a temperature region of 350 ° C. or more are present in the polyimide layer. A polyimide metal laminate characterized by that. A polyimide (PI) layer having a modulus of elasticity of 1 GPa or more and 30 GPa or less in a temperature range of 350 ° C. or higher is synthesized from diamine and tetracarboxylic dianhydride, and is 70 mol% or more of the total diamine component as a raw material. Is one or more selected from o-phenylenediamine, p-phenylenediamine, and m-phenylenediamine, and 90 mol% or more of the total tetracarboxylic dianhydride component is pyromellitic dianhydride, 3, 3 2. The polyimide according to claim 1, which is one or more compounds selected from ', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-benzophenonetetracarboxylic dianhydride. Metal laminate. The polyimide metal laminate according to claim 1, wherein the polyimide layer in contact with the metal is thermoplastic polyimide (TPI). 4. The polyimide metal laminate according to claim 3, wherein the glass transition point (Tg) of the thermoplastic polyimide (TPI) is 250 ° C. or more and 375 ° C. or less, and the elastic modulus at the glass transition point or more is 10 MPa or more and 1 GPa or less. Board.

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