HK1103380A

HK1103380A - Heat-resistant resin laminated film, multilayer film with metal layer including same, and semiconductor device

Info

Publication number: HK1103380A
Application number: HK07107601.9A
Authority: HK
Inventors: 渡边拓生; 松本悠
Original assignee: 东丽株式会社
Priority date: 2004-03-04
Filing date: 2005-03-01
Publication date: 2007-12-21

Description

Heat-resistant resin laminated film, metal-layer-coated laminated film containing same, and semiconductor device

Technical Field

The present invention relates to a heat-resistant resin laminated film, a metal layer-clad laminated film including the same, and a semiconductor device. More specifically, the present invention relates to a method for producing a metal-clad laminate film used for a flexible printed circuit board (FPC) widely used in the field of electronic industry, and relates to a metal-clad laminate film used for Tape Automated Bonding (TAB), a Chip On Film (COF), and the like as a method for mounting a semiconductor Integrated Circuit (IC), a semiconductor device using the same, and a method for producing a metal-clad laminate film.

Background

In recent years, the size and weight of electronic devices have been increasingly reduced. With the progress of higher density and higher performance of semiconductor integrated circuits, miniaturization and higher performance of wiring patterns of FPCs have been required.

Conventionally, TAB is used in a mounting system of a semiconductor integrated circuit, and as a substrate for FPC used for TAB, a "three-layer laminate" product in which a copper foil is bonded to a flexible heat-resistant insulating film such as a polyimide film through an adhesive layer such as an epoxy resin is used.

Since the inner leads for mounting an IC in TAB are of a fine lead structure, a 40 μm pitch has become a technical limit for miniaturization due to a decrease in strength with a decrease in the width of the leads or a decrease in the thickness of the copper foil, and instead, a COF method in which inner leads are formed on a heat-resistant insulating film and mounted by a Flip Chip (FC) technique has become widespread. Although the copper wiring of the fine lead line structure is directly bonded to the IC in TAB, since the copper wiring on the heat-resistant insulating film is bonded to the IC in COF, heat at the time of bonding is applied to the heat-resistant insulating film.

Conventionally, adhesives of "three-layer type laminate" products used for TAB or general FPC are epoxy resin, phenol resin, acrylonitrile resin, butadiene resin, etc., and their heat resistance is inferior to polyimide used as a heat-resistant insulating film, so that the excellent properties of polyimide film cannot be sufficiently exhibited. In particular, in the case of IC bonding by COF, a tin-plated wiring is often bonded to a gold bump of the IC (group bonding under gold-tin eutectic), and heat and pressure applied during bonding are directly applied to the adhesive layer. Typically, heat at 300-400 ℃ is applied to apply pressure to press into the IC, and in order to uniformly bond the wires to the gold bumps, a pressure of 0.2-0.3N is applied to each bump. When the FPC board using the resin as the adhesive layer is soldered under such conditions, the adhesive layer is thermally decomposed, and the wiring is seriously trapped in the adhesive layer, which causes a problem such as disconnection. Further, since the resin contains impurity ions, there is also a problem that insulation reliability is lowered, and therefore, the resin is not suitable as a COF material.

Currently, as FPC substrates for COF, a "two-layer type" in which an adhesive is not used, and a "two-layer type" in which a conductive metal layer is formed on a heat-resistant insulating film such as a polyimide film by a method such as vacuum deposition, sputtering, ion plating, or plating, and a "two-layer type" in which a heat-resistant insulating layer is formed by applying a resin on a copper foil are widely used.

The "two-layer type plated product" has a problem that the adhesion property to a metal layer is poor although the kind of a base material and the thickness of the metal layer can be freely changed because the metal layer such as copper is directly formed on a heat-resistant insulating film as a base material. Further, there is a problem that pinholes and the like are easily generated, and it is difficult to improve productivity, which results in high cost. Although the "two-layer type cast" product has good adhesion performance with a metal layer, it is formed by coating a heat-resistant resin layer on a copper foil, and there is a quality problem that when the copper foil is thinned, wrinkles or creases are generated on the copper foil due to volume shrinkage or thermal shrinkage at the time of drying and curing, and particularly when the thickness of the copper foil is 12 μm or less, the workability is further deteriorated and the productivity is lowered.

In recent years, the use of a polyimide-based resin as an adhesive layer in a "three-layer laminate" has been studied. The "three-layer laminate" is produced by bonding a commercially available copper foil to a film base material such as polyimide through an adhesive layer, and is advantageous in terms of cost.

Conventionally, a substrate for FPC called "two-layer-like" has been proposed which is obtained by laminating a polyimide resin having a rigid structure as a core part and an aromatic polyimide multilayer film having a thermoplastic polyimide resin laminated on the surface thereof by thermocompression bonding a metal foil such as a copper foil (see, for example, patent documents 1 and 2). These FPC boards have high adhesion to metal foil, but they are required to be used as a double-sided copper-clad product. In a product having copper coated on one side, there is a problem that a substrate is seriously warped in a state where a copper layer is etched, that is, in a state where a wiring pattern is formed. In addition, even in a product with both sides coated with copper, if there is a difference in film thickness between the thermoplastic polyimide resin layers formed on both sides of the polyimide resin layer of the core portion, warpage is caused.

In addition, there has been proposed a substrate for FPC in which a metal layer is laminated on one surface of a polyimide film through a thermoplastic polyimide resin layer, and a heat-resistant polyimide layer is provided on the other surface of the polyimide film (see, for example, patent documents 3 and 4). With such a configuration, although the substrate warpage after copper layer etching can be suppressed, there is a problem in terms of productivity such as increase in the number of steps.

Patent document 1: japanese patent laid-open publication No. Hei 9-99518 (pages 2-7)

Patent document 2: japanese patent laid-open publication No. 2002-114848 (pages 6-8)

Patent document 3: japanese patent laid-open publication No. Hei 9-148695 (pages 2-7)

Patent document 4: japanese patent laid-open No. 2000-96010 (pages 3-7)

Disclosure of the invention

In view of the above circumstances, an object of the present invention is to provide a heat-resistant resin laminated film in which a heat-resistant resin layer is laminated on a heat-resistant insulating film such as a polyimide film, which is free from warpage, and a metal-clad laminated film in which a heat-resistant insulating film and a metal foil are laminated via a heat-resistant resin layer, which is free from warpage in a state in which a copper layer is etched, that is, in a state in which a wiring pattern is formed, and a highly reliable semiconductor device using the same.

That is, the present invention provides a heat-resistant resin laminated film in which a heat-resistant resin layer having a linear expansion coefficient K of the heat-resistant resin layer is laminated on at least one surface of a heat-resistant insulating film_A(ppm/. degree. C.) k-10. ltoreq.k_AA heat-resistant resin laminated film having a linear expansion coefficient of not more than k +20(k is a linear expansion coefficient of the heat-resistant insulating film), and a metal-clad laminated film in which a metal foil is laminated on the heat-resistant resin layer side of the heat-resistant resin laminated film. Further, the present invention provides a heat-resistant resin laminated film in which a heat-resistant resin layer is laminated on at least one surface of a heat-resistant insulating film, wherein the heat-resistant resin layer is composed of 2 or more heat-resistant resin layers, and at least 1 of the heat-resistant resin layers has a coefficient of linear expansion k_A(ppm/. degree. C.) k-10. ltoreq.k_AA heat-resistant resin laminate film according to claim 1, wherein k +20(k is a coefficient of linear expansion of the heat-resistant insulating film) is not more than k. Further, the present invention provides a metal-clad laminate film in which a metal foil is laminated on the heat-resistant resin layer side of the heat-resistant resin laminate film of the present invention. Further, the present invention provides a semiconductor device comprising the metal layer-clad laminate film of the present invention. Further, the present invention provides a method for producing a metal-clad laminate film in which a metal foil is laminated on at least one surface of a heat-resistant insulating film via a heat-resistant resin layer, the method comprising laminating a metal foil having a linear expansion coefficient k_A(ppm/. degree. C.) k-10. ltoreq.k_AA step of laminating at least one heat-resistant resin layer of the heat-resistant resin layers having k +20(k is a coefficient of linear expansion of the heat-resistant insulating film) or less, and a step of laminating the metal foil/heat-resistant resin laminate with at least 1 heat-resistant resin layer as requiredAnd a step of bonding and thermocompression bonding the heat-resistant insulating film of the heat-resistant resin layer. Further, the present invention provides a method for producing a metal-clad laminate film in which a metal foil is laminated on at least one surface of a heat-resistant insulating film through a heat-resistant resin layer, the method comprising laminating a metal-clad laminate film containing a linear expansion coefficient k on the heat-resistant insulating film_A(ppm/. degree. C.) k-10. ltoreq.k_AA step of laminating at least one heat-resistant resin layer of the heat-resistant resin layers in the range of k +20(k is the linear expansion coefficient of the heat-resistant insulating film), and a step of laminating the heat-resistant insulating film/heat-resistant resin laminate with a metal foil laminated with at least 1 heat-resistant resin layer as required and thermocompression bonding.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, an FPC board can be obtained which is free from warpage in a heat-resistant resin laminated film obtained by laminating a heat-resistant resin layer on a heat-resistant insulating film such as a polyimide film, and which is free from warpage in a case where a wiring pattern is formed in a state in which a copper layer is etched in a metal-clad laminated film obtained by laminating a metal foil on a heat-resistant insulating film such as a polyimide film via a heat-resistant resin layer to form an FPC board. Further, a highly reliable semiconductor device can be provided by using the metal layer-clad laminate film of the present invention.

Brief description of the drawings

Fig. 1 is a schematic view showing one embodiment of a printed circuit board according to the present invention.

Fig. 2 is a schematic view showing one embodiment of the printed circuit board of the present invention.

Fig. 3 is a schematic view showing one embodiment of the printed circuit board of the present invention.

Fig. 4 is a schematic view showing one embodiment of a roll laminator usable in the present invention.

Fig. 5 is a schematic view showing another embodiment of a roll laminator which can be used in the present invention.

Best mode for carrying out the invention

The heat-resistant resin laminated film of the present invention is a film in which a heat-resistant resin layer having a linear expansion coefficient k is laminated on at least one surface of a heat-resistant insulating film_A(ppm/. degree. C.) k-10. ltoreq.k_AK +20(k is a linear expansion coefficient of the heat-resistant insulating film). The heat-resistant resin layer may have 2 or more layers, and in this case, at least 1 layer of the heat-resistant resin layer satisfies the linear expansion coefficient k_A(ppm/. degree. C.) k-10. ltoreq.k_AA resin layer of k +20 or less. In this specification, the linear expansion coefficient k is defined as_A(ppm/. degree. C.) k-10. ltoreq.k_AThe heat-resistant resin layer having k +20(k is a linear expansion coefficient of the heat-resistant insulating film) or less is referred to as a "heat-resistant resin layer A".

By matching the linear expansion coefficient of the heat-resistant resin layer a with that of a heat-resistant insulating film such as a polyimide film, warpage of the heat-resistant resin laminated film can be suppressed. Coefficient of linear expansion k of the heat-resistant resin layer A_A(ppm/. degree. C.) at k-10 or more, preferably at k-7 or more, more preferably at k-5 or more; and k +20 or less, preferably k +15 or less, and more preferably k +10 or less (k is a linear expansion coefficient of the heat-resistant insulating film). Coefficient of linear expansion k_AWhen k-10 or less is reached, the heat-resistant insulating film in the heat-resistant resin laminated film is recessed to cause warpage, and when k +20 or more is reached, the heat-resistant resin layer a is recessed to cause warpage.

Further, in the case of using as a laminate film for a metal-clad layer for an FPC board, since dimensional stability is required to be good, a heat-resistant insulating film having a low linear expansion coefficient is used, and the linear expansion coefficient (k) is 5 to 25 ppm/DEG C, preferably 10 to 20 ppm/DEG C. Therefore, the coefficient of linear expansion k of the heat-resistant resin layer A at this time_AIs 5 to 30 ppm/DEG C, preferably 8 to 25 ppm/DEG C, and more preferably 11 to 23 ppm/DEG C.

The linear expansion coefficient includes a thermal expansion coefficient, a humidity expansion coefficient, and the like, and in the present invention, the linear expansion coefficient refers to a thermal expansion coefficient. The linear expansion coefficient can be measured by a measurement method using a thermomechanical analyzer (TMA method), and the linear expansion coefficient can be measured in a temperature range of 30 ℃ to 300 ℃, 50 ℃ to 200 ℃, 100 ℃ to 300 ℃, or the like.

In the present invention, the linear expansion coefficient is an average linear expansion coefficient from a reference temperature to a measurement temperature, and is calculated by the calculation formula (1).

Mean linear expansion coefficient ═ 1/L (L) × [ (L)_t-L₀)/(T_t-T₀)] (1)

In the formula, T₀As reference temperature, T_tFor set temperature, L is the sample length, L_oIs the length of the sample at the reference temperature, L_tIs the length of the sample at the set temperature.

In the present invention, the reference temperature is the linear expansion coefficient k of the heat-resistant resin layer A at room temperature of 25 to 35 ℃ in each temperature range from room temperature to 100 ℃ or 200 ℃ or 300 ℃ or the like_A(ppm/. degree. C.) so that k is not less than k at k-10_APreferably, k +20 (k: linear expansion coefficient of the heat-resistant insulating film). Since the heat-resistant resin laminated film, the process for producing the metal layer-coated laminated film using the heat-resistant resin laminated film, or the use condition of the metal layer-coated laminated film may be subjected to a temperature of about 300 ℃, the coefficient of linear expansion k is within a temperature range of room temperature to 300 ℃_AWithin the above range, the preferred range is particularly preferred.

The heat-resistant resin layer a used in the present invention may be an acrylic resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a polyetherimide resin, a polyethersulfone resin, a polysulfone resin, or the like, and these resins may be used alone or in combination of 2 or more. The polyimide resin is preferably used from the viewpoint of heat resistance, insulation reliability and adhesiveness.

The polyimide resin is a polymer resin in which a polyamic acid or an ester compound thereof as a precursor thereof is heated or a suitable catalyst is used to form an imide ring or other cyclic structure.

The polyimide-based resin used in the heat-resistant resin layer a contains, in the diamine component, preferably 40 to 50 mol%, more preferably 60 mol% or more of aromatic diamine having a structure represented by the general formulae (1) to (3) based on the total diamine component. When the content of the aromatic diamine is less than 40 mol%, the linear expansion coefficient becomes large, and warpage occurs in a heat-resistant resin laminated film or the like.

(in the formula, R¹-R⁸The same or different ones, and selected from hydrogen atom, alkyl group with carbon number of 1-30, alkoxy group with carbon number of 1-30, halogen, hydroxyl group, carboxyl group, sulfo group, nitro group, and cyano group. )

Specific examples of the aromatic diamine include: p-phenylenediamine, m-phenylenediamine, 2, 5-diaminotoluene, 2, 4-diaminotoluene, 3, 5-diaminobenzoic acid, 2, 6-diaminobenzoic acid, 2-methoxy-1, 4-phenylenediamine, 2-hydroxy-1, 4-phenylenediamine, 2-chloro-1, 4-phenylenediamine, 2-nitro-1, 4-phenylenediamine, 2-cyano-1, 4-phenylenediamine, 2, 5-diaminosulfonic acid, 4 ' -diamino-benzanilide, 3 ' -dimethyl-4, 4 ' -diamino-benzanilide, 2, 4 ' -diaminotoluene, 2-chloro-1, 4-phenylenediamine, 2-nitro-1, 4-phenylenediamine, 2-cyano-1, 4-phenylenediamine, 2, 5-diaminobenzene, 2, 4 ' -diamino, 3-methoxy-4, 4 '-diamino-benzanilide, benzidine, 2' -dimethylbenzidine, 3 '-dimethoxybenzidine, 3' -dichlorobenzidine, and the like.

Monocyclic aromatic heterocyclic diamines such as 2, 4-diaminopyridine and 2, 6-diaminopyridine, polycyclic aromatic diamines such as 1, 5-diaminonaphthalene and 2, 7-diaminofluorene, and the like can also be used. Among the above diamines, p-phenylenediamine, 4 '-diamino-benzanilide, and 2, 2' -dimethylbenzidine are preferably used.

In the present invention, the use of a siloxane-based diamine represented by the general formula (4) in combination with the diamine can reduce the water absorption of the resulting polyimide-based resin. However, since the linear expansion coefficient of the siloxane-based diamine increases sharply by adding it, the amount of the siloxane-based diamine added is 0.1 to 10 mol%, preferably 0.5 to 8 mol%, more preferably 1 to 6 mol% of the total diamine component.

(here, n in the general formula (4) represents an integer of 1 to 30. also, R¹¹And R¹²Each of which may be the same or different, represents a lower alkylene group or a phenylene group. R¹³-R¹⁶Each of which may be the same or different, represents a lower alkyl group, a phenyl group or a phenoxy group. )

In this case, the water absorption of the heat-resistant resin layer a is 1.5% or less, preferably 1.3% or less, and more preferably 1.2% or less. When the water absorption rate is 1.5% or more, warpage occurs due to moisture expansion, or insulation reliability is lowered.

The siloxane-based diamine represented by the general formula (4) having a long chain is not preferable because the reactivity is deteriorated, the polymerization degree of the polymer is lowered, and the heat resistance is deteriorated. The number of n in the general formula (4) is in the range of 1 to 30, preferably in the range of 1 to 15, and more preferably in the range of 1 to 5.

Specific examples of the siloxane-based diamine represented by the general formula (4) include: 1, 1, 3, 3-tetramethyl-1, 3-bis (4-aminophenyl) disiloxane, 1, 3, 3-tetraphenoxy-1, 3-bis (4-aminoethyl) disiloxane, 1, 3, 3, 5, 5-hexamethyl-1, 5-bis (4-aminophenyl) trisiloxane, 1, 3, 3-tetraphenyl-1, 3-bis (2-aminoethyl) disiloxane, 1, 3, 3-tetraphenyl-1, 3-bis (3-aminopropyl) disiloxane, 1, 5, 5-tetraphenyl-3, 3-dimethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1, 5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 1, 5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (5-aminopentyl) trisiloxane, 1, 3, 3-tetramethyl-1, 3-bis (2-aminoethyl) disiloxane, 1, 3, 3-tetramethyl-1, 3-bis (3-aminopropyl) disiloxane, 1, 3, 3-tetramethyl-1, 3-bis (4-aminobutyl) disiloxane, 1, 3-dimethyl-1, 3-dimethoxy-1, 3-bis (4-aminobutyl) disiloxane, 1, 5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (2-aminoethyl) trisiloxane, 1, 5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 1, 5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (5-aminopentyl) trisiloxane, 1, 1, 3, 3, 5, 5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1, 3, 3, 5, 5-hexaethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1, 3, 3, 5, 5-hexapropyl-1, 5-bis (3-aminopropyl) trisiloxane and the like. The siloxane-based diamines may be used alone or in combination of 2 or more.

In the present invention, the diamine may be used in combination with an aliphatic diamine, a cyclic hydrocarbon-containing alicyclic diamine, an aromatic diamine other than the above, and specific examples thereof include 1, 3-diaminocyclohexane, 1, 4-diaminocyclohexane, 4 ' -methylenebis (cyclohexylamine), 3 ' -methylenebis (cyclohexylamine), 4 ' -diamino-3, 3 ' -dimethyldicyclohexylmethane, 4 ' -diamino-3, 3 ' -dimethyldicyclohexyl, p-aminobenzylamine, m-aminobenzylamine, 4 ' -diaminodiphenyl ether, 3 ' -diaminodiphenyl ether, 3, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl sulfone, 3 ' -diaminodiphenyl sulfone, and the like, 3, 3 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfide, 3 '-diaminobenzophenone, 3, 4' -diaminobenzophenone, 4 '-diaminobenzophenone, 3' -dimethyl-4, 4 '-diaminodiphenylmethane, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (3-aminophenoxy) phenyl ] propane, bis [4- (4-aminophenoxy) phenyl ] methane, bis [4- (3-aminophenoxy) phenyl ] methane, bis [4- (4-aminophenoxy) phenyl ] ether, bis (4-aminophenoxy) phenyl) ether, bis (4-aminobenzophenone) ether, bis (4-aminophenoxy) phenyl ] propane, bis (4, Bis [4- (3-aminophenoxy) phenyl ] ether, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) fluorene, 9-bis (3-aminophenyl) fluorene, and the like.

In the polyimide-based resin used in the heat-resistant resin layer a, the tetracarboxylic acid component includes pyromellitic dianhydride, 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride, 2, 3, 3 ', 4' -biphenyltetracarboxylic dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic dianhydride, 3, 4, 9, 10-perylenetetracarboxylic dianhydride, 2, 3, 6, 7-naphthalenetetracarboxylic dianhydride, 1, 4, 5, 8-naphthalenetetracarboxylic dianhydride, 1, 2, 5, 6-naphthalenetetracarboxylic dianhydride, 3, 3 ', 4, 4' -p-terphenyltetracarboxylic dianhydride, 3, 3 ', 4, 4' -m-terphenyltetracarboxylic dianhydride, 2, 3, 6, 7-anthracenetetracarboxylic dianhydride, 1, 2, 7, 8-phenanthrenetetracarboxylic dianhydride, which accounts for 40 mol% or more of the total tetracarboxylic acid component, it is preferably 50 mol% or more, and more preferably 60 mol% or more. They may be used alone or in combination of 2 or more. Among the tetracarboxylic acid components, pyromellitic dianhydride and 3, 3 ', 4, 4' -biphenyltetracarboxylic acid dianhydride are particularly preferred.

Further, tetracarboxylic acid components which can be used in combination include: specific examples of alicyclic tetracarboxylic dianhydrides having cyclic hydrocarbons and aromatic tetracarboxylic dianhydrides other than those described above include: 2, 3, 5-tricarboxycyclopentylacetic acid dianhydride, 1, 2, 3, 4-cyclobutanetetracarboxylic acid dianhydride, 1, 2, 3, 4-cyclopentanetetracarboxylic acid dianhydride, 1, 2, 3, 5-cyclopentanetetracarboxylic acid dianhydride, 1, 2, 4, 5-bicyclohexenetetracarboxylic acid dianhydride, 1, 2, 4, 5-cyclohexanetetracarboxylic acid dianhydride, 1, 3, 3a, 4, 5, 9 b-hexahydro-5- (tetrahydro-2, 5-dioxa-3-furanyl) -naphtho [1, 2-C ] furan-1, 3-dione, 3, 3 ', 4, 4' -benzophenonetetracarboxylic acid dianhydride, 2 ', 3, 3' -benzophenonetetracarboxylic acid dianhydride, 2, 3, 3 ', 4' -benzophenonetetracarboxylic acid dianhydride, 3, 3 ', 4, 4 ' -diphenyl ether tetracarboxylic dianhydride, 2, 3, 3 ', 4 ' -diphenyl ether tetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -biphenyl trifluoropropane tetracarboxylic dianhydride, 3, 3 ', 4, 4 ' -diphenyl sulfone tetracarboxylic dianhydride, 4, 4 ' - (hexafluoroisopropylidene) diphthalic anhydride, and the like.

The molecular weight of the polyimide resin used in the present invention can be adjusted by making the tetracarboxylic acid component and the diamine component equimolar or making either one excessive. The polymer chain ends may be capped with an end-capping agent such as an acid component or an amine component by adding an excess of either the tetracarboxylic acid component or the diamine component. The blocking agent for the acid component is preferably a diacid or an anhydride thereof, and the blocking agent for the amine component is preferably a monoamine. In this case, the molar ratio of the acid equivalent of the tetracarboxylic acid component including the end-capping agent of the acid component or the amine component to the amine equivalent of the diamine component is preferably equal.

When the molar ratio is adjusted so that the tetracarboxylic acid component is in excess or the diamine component is in excess, a diacid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, aniline, or an anhydride thereof, or a monoamine may be added as an end-capping agent.

The molar ratio of the tetracarboxylic acid component/diamine component of the polyimide resin in the present invention is usually 100/100, but when the viscosity of the resin solution is too high, it is preferable to adjust the molar balance of the tetracarboxylic acid component/diamine component to a range of 100/100 to 95 or 100 to 95/100 so that the viscosity of the resin solution is within a range in which problems such as coating property do not occur. However, when the molar balance is lost, the molecular weight of the resin is lowered, and the strength of the cured film tends to be lowered, or the adhesion to the metal layer or the heat-resistant insulating film tends to be weakened, so that it is preferable to adjust the molar ratio to a range where the adhesion is not weakened.

In the present invention, a polyamic acid, which is one of precursors of a polyimide-based resin, is synthesized by a known method. For example, the tetracarboxylic acid component and the diamine component may be selectively combined and reacted in a solvent at a molar ratio set forth above at 0 to 80 ℃. In this case, the reaction may be carried out by adding a monoamine, a diacid or an anhydride thereof to the tetracarboxylic dianhydride and the diamine simultaneously for the purpose of capping the polymer chain, or may be carried out after the reaction and polymerization of the tetracarboxylic dianhydride and the diamine.

Examples of the solvent for synthesizing the polyamic acid include amide polar solvents such as N-methyl-2-pyrrolidone, N-dimethylacetamide, and N, N-dimethylformamide, lactone polar solvents such as β -propiolactone, γ -butyrolactone, γ -valerolactone, δ -valerolactone, γ -caprolactone, and ∈ -caprolactone, and methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol, ethyl carbitol, diethylene glycol dimethyl ether, and ethyl lactate. They may be used alone or in combination of 2 or more. The concentration of the polyamic acid is usually preferably 5 to 60% by weight, and more preferably 10 to 40% by weight.

In the present invention, other resins and fillers may be added to the resin used for the heat-resistant resin layer a within a range not impairing the effects of the present invention. Examples of the other resins include heat-resistant polymer resins such as acrylic resins, acrylonitrile resins, butadiene resins, urethane resins, polyester resins, polyamide-imide resins, polyether-imide resins, epoxy resins, phenol resins, polysulfone resins, and polyether sulfone resins. The filler includes fine particles of organic or inorganic structure, filler, and the like. Specific examples of the fine particles and fillers include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, talc, and the like. The total content of these heat-resistant polymer resin and filler is usually 60% or less, preferably 20% or less, and most preferably 0% of the total weight of the heat-resistant resin layer a.

The glass transition temperature of the heat-resistant resin layer A is 250-400 ℃, preferably 260-380 ℃, and more preferably 280-350 ℃. When the glass transition temperature is exceeded, the amount of change in the linear expansion coefficient becomes large, and therefore, when the glass transition temperature is 250 ℃ or less, the linear expansion coefficient from room temperature to 300 ℃ becomes too large. Further, when the glass transition temperature is 400 ℃ or higher, the adhesive properties are deteriorated.

The glass transition temperature of the heat-resistant resin layer a of the present invention can be measured by various measurement methods, for example, a measurement method using a differential scanning calorimetry analyzer (DSC method), a measurement method using a thermomechanical analyzer (TMA method), and a dynamic viscoelasticity measurement method using a dynamic thermomechanical measurement apparatus (DMA method). In the DMA method, the glass transition temperature is represented by the maximum value of tan δ.

Although the thickness of the heat-resistant resin layer A is not particularly limited, it is usually 0.2 to 12 μm, preferably 0.5 to 10 μm, and more preferably 1 to 7 μm.

The heat-resistant insulating film for use in the present invention uses a heat-resistant polymer, for example, an aromatic polyimide-based resin, a polyphenylene sulfide-based resin, an aromatic polyamide-based resin, a polyamide imide-based resin, an aromatic polyester-based resin, and the like, and specific examples thereof include "Kapton" manufactured by Torilo Dupont, "ユ - ピレツクス" manufactured by Yukahixing corporation, "アピカル" manufactured by Kazuo chemical industry, ミクトロン "manufactured by Torilo corporation, and" ベクスタ "manufactured by クラレ (Kabushiki corporation). Among these, the use of an aromatic polyimide resin is particularly preferable. Further, although there is no particular limitation on the glass transition temperature of the heat-resistant insulating film, it is usually 300 ℃ or higher, and preferably 400 ℃ or higher. More preferably, the glass transition temperature is not significantly higher than 500 ℃.

Although the thickness of the heat-resistant insulating film is not particularly limited, it is preferably 3 to 150. mu.m, more preferably 5 to 75 μm, particularly preferably 10 to 50 μm. Below 3 μm the strength as a support is insufficient. On the other hand, if it exceeds 150 μm, the flexibility may be reduced and the article may be difficult to bend.

It is preferable that the heat-resistant insulating film used in the present invention is subjected to a treatment for improving adhesion on one or both surfaces thereof as necessary.

Treatments for improving the adhesion include: a physical method such as a wet blasting method in which fine particles such as glass beads are dispersed in water or the like by sandblasting or the like to form irregularities on the surface of the film, a chemical method such as a permanganic acid solution or an alkali solution to form irregularities on the surface of the film, a discharge treatment such as a normal pressure plasma treatment, a corona discharge treatment, a low temperature plasma treatment, or the like. In the present invention, it is preferable to perform a discharge treatment such as an atmospheric pressure plasma treatment, a corona discharge treatment, or a low temperature plasma treatment to improve the adhesiveness.

The atmospheric plasma treatment is performed in Ar and N₂、He、CO₂And a method of performing discharge treatment in an atmosphere of CO, air, steam, or the like. The process conditions vary depending on the process apparatus, the type of process gas, the flow rate, the frequency of the power supply, and the like, and an appropriate optimum condition can be selected.

The low-temperature plasma treatment may be carried out under reduced pressure, and the method is not particularly limited, and for example, a method of treating a substrate by placing the substrate in an internal electrode type discharge treatment apparatus having a counter electrode composed of a drum-shaped electrode and a plurality of rod-shaped electrodes, applying a high direct current or alternating current voltage between the electrodes in a state where the treatment gas is adjusted to 1 to 1000Pa, preferably 5 to 100Pa, and generating a plasma of the treatment gas by generating a discharge, and the plasma may be applied to the surface of the substrate. The conditions of the low-temperature plasma treatment vary depending on the treatment apparatus, the type of treatment gas, the pressure, the frequency of the power supply, and the like, and an appropriate optimum condition can be selected. The kind of the processing gas is, for example, Ar, N₂、He、CO₂CO, air, water vapor, O₂、CF₄And the like, which may be used alone or in admixture thereof.

Although corona discharge treatment may be used, it is preferable to select a heat-resistant resin layer which is easily bonded to the laminate because the effect of improving the adhesion is inferior to that of low-temperature plasma treatment when corona discharge treatment is used.

The heat-resistant resin laminated film of the present invention is used as a metal layer-covered laminated film for an FPC board (flexible printed wiring board) in which a metal foil is attached to one side of a heat-resistant resin layer. When used for an FPC board, a temperature of about 300 ℃ is applied to a step of laminating a metal foil on the heat-resistant resin laminated film to produce a metal layer-coated laminated film, a soldering step of an IC chip, or the like, and therefore a linear expansion coefficient in a temperature range from room temperature (20 to 35 ℃) to 300 ℃ is important.

The metal layer may be formed by lamination of metal foil, vacuum evaporation, sputtering, ion plating, electroless plating, electrolytic plating, or the like, and these methods may be used alone or in combination of 2 or more. From the viewpoint of productivity and cost, a lamination method of producing a metal-clad laminate film by attaching a metal foil to the heat-resistant resin layer side of a heat-resistant resin laminate film and forming a metal layer by hot pressing is most preferable.

The metal layer used in the present invention is made of a metal foil such as copper foil, aluminum foil, and SUS foil, and usually copper foil is used. The copper foil includes electrolytic copper foil and rolled copper foil, and any of them can be used.

In order to improve the adhesion between a metal foil such as a copper foil and a resin, a roughening treatment may be performed on the adhesion surface side. The copper foil is generally referred to as an S-side and an M-side on both sides, and is generally bonded to the M-side when a resin or the like is bonded. Therefore, the roughening treatment is usually performed on the M-plane side in many cases. In the case where resin or the like is bonded to both surfaces of the copper foil, both the S-surface and the M-surface may be roughened. The roughening treatment is, for example, a step of depositing copper fine particles of 1 to 5 μm on one or both surfaces of a green foil formed by electrolytic plating to form irregularities on the surfaces, by electrodeposition or the like, in the case of a copper foil.

With the miniaturization of the wiring pattern of FPC, it is preferable that the irregularities on the surface of the copper foil be as small as possible regardless of the S-plane or M-plane, and it is preferable to use a copper foil having a smooth surface on both sides without roughening the surface of the copper foil. The surface roughness of the copper foil is such that Ra (center line average roughness) is 0.5 μm or less, preferably 0.4 μm or less, and Rz (ten point average roughness) is 2.0 μm or less, preferably 1.8 μm or less on the S-plane; in addition, Ra of the M-plane is 0.7 μ M or less, preferably 0.5 μ M or less, more preferably 0.4 μ M or less, Rz is 3.0 μ M or less, preferably 2.0 μ M or less, more preferably 1.8 μ M or less.

The thickness of the copper foil is in the range of 1 to 150. mu.m, and can be suitably selected depending on the application. As the wiring pattern of FPC is miniaturized, the film thickness of copper foil is preferably as thin as possible. However, the copper foil is thin and difficult to handle in one piece, and a copper foil having a thickness of 3 μm or 5 μm is used by being handled as a carrier-mounted copper foil attached to a support (carrier) such as a resin or a metal foil having a thickness of about 20 to 50 μm, and then being thermally pressed to the resin or the like and then peeled off from the support. The thickness of the copper foil of the present invention is 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less. The thickness is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more.

In order to prevent discoloration of the copper foil, the surface is preferably subjected to rust-proofing treatment. Rust prevention treatment is generally performed by laminating a thin film layer of nickel, zinc, chromium compound or the like on the surface of a copper foil. Further, it is also preferable to further perform a silane coupling treatment on the surface of the copper foil in order to improve the adhesion to a resin or the like.

The metal layer-coated laminate film of the present invention can be a single-sided metal layer product or a double-sided metal layer product, and can have various configurations such as a layer structure of a heat-resistant resin layer, and various manufacturing methods can be employed by these configurations.

The evaluation of warpage in the present invention is carried out in a state of a heat-resistant resin laminated film in which a metal foil such as a copper foil is laminated and then the metal layer is entirely etched. The measurement may be performed after a heat-resistant resin layer is stacked on the heat-resistant insulating film and subjected to appropriate heat treatment or the like. When the sample is subjected to heat treatment or the like, it is preferably left at room temperature of 20 to 30 ℃ and humidity of 50 to 60% RH for 24 hours or more and then measured. The sample was cut into an arbitrary size of 50mm × 50mm square, and then left on a flat plate, and the warpage height at 4 corners was measured, and the average value was taken as the warpage value.

When the sample had a square shape of 50mm × 50mm, the sample was rolled into a roll when the warp height was 20mm or more, and the warp height could not be measured accurately. The warp height is 4mm or less, preferably 3mm or less, and more preferably 1mm or less.

Fig. 1 shows a1 st embodiment of the metal layer-clad laminate film of the present invention. Fig. 1(a) shows a form of a multilayer film having a metal layer on one surface, and fig. 1(b) shows a form of a multilayer film having a metal layer on both surfaces, which is a laminate formed of a heat-resistant insulating film 2, a heat-resistant resin layer 3, and a metal foil 1. The method for producing the film comprises forming a linear expansion coefficient k on a heat-resistant resin film 2 or a metal foil 1_A(ppm/. degree. C.) k-10. ltoreq.k_AA heat-resistant resin layer 3 having a linear expansion coefficient of not more than k +20(k is a linear expansion coefficient of the heat-resistant insulating film). Next, a metal foil is attached to the obtained heat-resistant insulating film/heat-resistant resin layer laminate so as to face the heat-resistant resin layer, and thermocompression bonding is performed. Alternatively, a heat-resistant insulating film is laminated on the metal foil/heat-resistant resin layer laminate so as to face the heat-resistant resin layer, and the laminate is thermocompression bonded to obtain a metal layer-coated laminate film.

In the method of manufacturing a metal layer-coated laminate film shown in fig. 1, the heat-resistant resin layer 3 of a laminate in which the heat-resistant resin layer 3 is laminated on the heat-resistant insulating film 2 and the metal foil 1, or the heat-resistant resin layer 3 of a laminate in which the heat-resistant resin layer 3 is laminated on the metal foil 1 and the heat-resistant insulating film 2 are opposed to each other and thermocompressed, and a high temperature of 300 ℃ or higher, preferably 350 ℃ or higher, and more preferably 380 ℃ or higher is required for thermocompression bonding. Even when thermocompression bonding is performed at such a high temperature, the adhesive strength after bonding is relatively small.

Fig. 2 shows a2 nd embodiment of the metal layer-clad laminate film of the present invention. FIG. 2(a) is a form of a multilayer film having a metal layer on one surface, FIG. 2(b) is a form of a multilayer film having a metal layer on both surfaces, the heat-resistant resin layer is composed of 2 or more layers, and at least 1 layer is composed of a material having a coefficient of linear expansion k_A(ppm/. degree. C.) k-10. ltoreq.k_AA heat-resistant resin layer A having a linear expansion coefficient of not more than k +20(k is a linear expansion coefficient of the heat-resistant insulating film). The metal layer-clad laminate film in which the heat-resistant resin layer a is laminated by bonding to the metal layer is most preferred because it is less likely to warp after the metal layer is etched. Also, in the metal layer andthe heat-resistant resin layers a may be provided with a thickness within a range in which no warpage occurs, and a heat-resistant resin layer having a composition and physical properties different from those of the heat-resistant resin layers a for the purpose of improving adhesion and the like. The heat-resistant resin layer disposed between the metal layer and the heat-resistant resin layer A has a film thickness of 0.001 to 5 μm, preferably 0.01 to 3 μm, and more preferably 0.1 to 2 μm. As the resin constituting this heat-resistant resin layer, the same resin as that used for the heat-resistant resin layer B described later can be used.

The method for producing the metal layer-coated laminated film shown in fig. 2 includes the following exemplary methods. A plurality of heat-resistant resin layers 4 including at least 1 heat-resistant resin layer a3 were sequentially laminated on the heat-resistant insulating film 2 or the metal foil 1. Next, the metal foil 1 is attached to the obtained heat-resistant insulating film 2/heat-resistant resin layer 4 laminate so as to face the heat-resistant resin layer 4 of the laminate, and thermocompression bonding is performed. Alternatively, a heat-resistant insulating film 2 is laminated on the laminate of the metal foil 1/the heat-resistant resin layer 4 so as to face the heat-resistant resin layer of the laminate, and the laminate is thermocompression bonded to obtain a metal layer-coated laminate film. Further, 1 or more heat-resistant resin layers are formed on the heat-resistant insulating film 2 and the metal foil 1, respectively, and the heat-resistant resin layers of the obtained heat-resistant insulating film/heat-resistant resin layer laminate and the heat-resistant resin layers of the metal foil/heat-resistant resin layer laminate are bonded to each other in an opposed manner and thermocompression bonded to each other, thereby obtaining a metal layer-coated laminate film. In this case, the heat-resistant resin layer a is preferably laminated on the metal foil side.

Fig. 3 shows a3 rd embodiment of the metal layer-clad laminate film of the present invention. Fig. 3(a) shows a form of a multilayer film having a metal layer on one surface, and fig. 3(b) shows a form of a multilayer film having a metal layer on both surfaces. The metal layer-clad laminate film shown in fig. 3 is particularly preferable in the form shown in fig. 2. Laminating a linear expansion coefficient k on the metal layer side_A(ppm/. degree. C.) k-10. ltoreq.k_AA heat-resistant resin layer A having a linear expansion coefficient of k +20 or less (k is a linear expansion coefficient of the heat-resistant insulating film), and a heat-resistant resin layer (referred to as a heat-resistant resin layer B) having a lower glass transition temperature than that of the heat-resistant resin layer A is laminated on the heat-resistant insulating film side.

The method for producing the metal layer-clad laminated film according to embodiment 3 may be the same as the method for producing the metal layer-clad laminated film according to embodiment 2. A particularly preferred production method is a production method including the steps of laminating the heat-resistant resin layer A3 on the metal foil 1, laminating the heat-resistant resin layer B5 on the heat-resistant insulating film 2 to form a laminate of the metal foil/heat-resistant resin layer A3 and a laminate of the heat-resistant insulating film 2/heat-resistant resin layer B5, and laminating and thermocompression-bonding the heat-resistant resin layer A3 and the heat-resistant resin layer B5 in opposition to each other to obtain a metal-clad laminate film. The metal layer-clad laminate film is free from warpage after the metal layer is etched, has high adhesion, and can be thermocompression bonded at a relatively low temperature, which is advantageous in terms of productivity.

The linear expansion coefficient of the heat-resistant resin layer B (1 or 2 or more heat-resistant resin layers other than the heat-resistant resin layer A satisfying the above range of linear expansion coefficient) is not necessarily within the above range of linear expansion coefficient of the heat-resistant resin layer A, and is usually about 30 ppm/DEG C to 500 ppm/DEG C, preferably about 40 ppm/DEG C to 200 ppm/DEG C. The inventors of the present application have first found that if at least 1 of the above-mentioned heat-resistant resin layers a is present, even if at least 1 of the heat-resistant resin layers B having a large coefficient of linear expansion is present, it is possible to suppress warpage of the laminated film and the metal-clad laminated film to a satisfactory degree. Therefore, the heat-resistant resin layer B can be formed of a resin having a higher adhesiveness, and thus the adhesiveness between the multilayer film and the metal layer-coated multilayer film can be improved.

As the heat-resistant resin layer B used in the present invention, a thermoplastic resin and/or a thermosetting resin can be used, and examples thereof include: acrylic resins, acrylonitrile-based resins, butadiene-based resins, urethane-based resins, polyester-based resins, epoxy-based resins, phenol-based resins, polyimide-based resins, polyamide-imide-based resins, polyether-sulfone-based resins, polysulfone-based resins, and the like, and these resins may be used alone or in a mixture of 2 or more. In view of heat resistance, insulation reliability and adhesiveness, it is preferable to use a polyimide resin, an epoxy resin, a phenol resin or a polyamide resin. These resins may be added with fillers such as organic or inorganic fine particles and fillers. Specific examples of the fine particles and fillers include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, talc, and the like.

When the heat-resistant resin layer B of the present invention is a polyimide resin, the glass transition temperature of the heat-resistant resin layer B is preferably from 120 ℃ to 280 ℃, more preferably from 150 ℃ to 250 ℃, and even more preferably from 170 ℃ to 220 ℃. When the glass transition temperature is less than 120 ℃, although the adhesion is good, the moist heat resistance is poor, and when it is more than 280 ℃, the adhesion is poor.

As the polyimide resin used in the heat-resistant resin layer B of the present invention, various diamines and tetracarboxylic dianhydrides can be used as long as the glass transition temperature falls within the above range. The use of the siloxane-based diamine represented by the general formula (4) as the diamine component is preferable because the adjustment of the glass transition temperature of the resulting polyimide-based resin is facilitated, the water absorption rate can be reduced, and the adhesive strength can be increased. The amount of the diamine to be added is 5 to 95 mol%, preferably 10 to 80 mol%, more preferably 15 to 60 mol%, based on the total diamine component.

(here, n in the general formula (4) represents an integer of 1 to 30. also, R¹¹And R¹²Each of which is the same or different, represents a lower alkylene group or a phenylene group. R¹³-R¹⁶Each of which is the same or different, represents a lower alkyl group, a phenyl group or a phenoxy group. )

When the heat-resistant resin layer B of the present invention is a thermosetting resin containing an epoxy compound, the glass transition temperature of the heat-resistant resin layer B is 50 to 250 ℃, preferably 80 to 220 ℃, and more preferably 100-200 ℃. When the glass transition temperature is less than 50 ℃, heat resistance and moist heat resistance are poor, and when the glass transition temperature is more than 250 ℃, adhesiveness is poor.

Examples of the thermosetting resin include resins containing epoxy compounds, cyanate compounds, benzoxazole compounds, bismaleimide compounds, and unsaturated compounds such as ethynyl group-containing compounds, but in the present invention, a resin containing an epoxy compound is preferably used.

Examples of the epoxy compound used in the heat-resistant resin layer B of the present invention include phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, thiodiphenol, epoxy compounds of aralkyl resins formed by a xylylene bond of phenol or naphthol, epoxy compounds of phenol-dicyclopentadiene resins, alicyclic epoxy compounds, heterocyclic epoxy compounds, glycidyl ester type epoxy compounds obtained by reacting polybasic acid such as phthalic acid or dimer acid with epichlorohydrin, diaminodiphenylmethane, diaminodiphenylsulfone, polyamine such as isocyanuric acid, and epichlorohydrin, and glycidyl amine type epoxy compounds obtained by reacting epichlorohydrin, brominated epoxy compounds, and epsilon-caprolactone-modified 3, 4-epoxycyclohexylmethyl-3', cyclohexene oxide-containing epoxy compounds such as 4 ' -epoxycyclohexane carboxylate, trimethylcaprolactone-modified 3, 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexane carboxylate, β -methyl- δ -valerolactone-modified 4-epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexane carboxylate, and the like. Furthermore, polyorganosiloxane having a glycidyl group or a siloxane-modified epoxy compound obtained by reacting the above epoxy compound with an organosiloxane having a carboxyl group can be used, but the present invention is not limited to these. Further, at least one of these epoxy compounds and siloxane-modified epoxy compounds may be used in combination.

The curing agent for the epoxy compound is not particularly limited, and examples thereof include: polyamines such as diethylenetriamine, triethylenetriamine, m-xylylenediamine, diaminodiphenylmethane, polyamides such as dimer acid polyamide, acid anhydrides such as phthalic anhydride, tetrahydromethylphthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, and methylnadic anhydride, 3-aminophenol, resorcinol, catechol, hydroquinone, 1, 2, 3-benzenetriol, 3-hydroxybenzoic acid, 3-cyanophenol, 2, 3-diaminophenol, 2-amino-3-hydroxybenzoic acid, 3-hydroxyphenylacetamide, 3-hydroxyisophthalic acid, 3-hydroxyphenylacetic acid, 3-phenolsulfonic acid, phenol novolak, phenol アラルキル, phenol resins such as bisphenol A and bisphenol F, cresol-type phenol resins, polythiols, and the like, Tertiary amines such as 2-ethyl-4-methylimidazole and tris (dimethylaminomethyl) phenol, and lewis acid complexes such as boron trifluoride-ethylamine complex. Among these, phenol resins are preferably used.

A thermoplastic resin having plasticity in a temperature range of 80 to 200 ℃ may be further added to the heat-resistant resin layer B. Examples of such resins are: polyolefins such as polyethylene, polypropylene and ethylene copolymer resins, styrene resins such as polystyrene and ABS resins, polyvinyl chloride, vinylidene chloride, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyarylate, polyoxybenzoyl, polycarbonate, polyacetal, polyphenylene ether, and the like, and among these, polyamide resins are preferably used in view of their excellent deterioration properties and electrical properties at high temperatures. Various known polyamide-based resins can be used, and particularly, those containing a dicarboxylic acid having 36 carbon atoms (so-called dimer acid) having low water absorption as an essential component are suitable. The dimer acid-containing polyamide resin is obtained by polycondensation of a dimer acid and a diamine by a conventional method, but in this case, a dicarboxylic acid such as adipic acid, azelaic acid, and sebacic acid other than the dimer acid may be contained as a copolymerization component. As the diamine, known diamines such as ethylenediamine, hexamethylenediamine and piperazine can be used, but from the viewpoint of hygroscopicity and solubility, it is preferable to use 2 or more kinds of diamines in combination. The content of the thermoplastic resin is not particularly limited, but is usually 70% or less, preferably 20% or less, based on the weight of the heat-resistant resin layer B.

A curing accelerator may be added to the thermosetting resin constituting the heat-resistant resin layer B. As the curing accelerator, there can be used known curing accelerators such as aromatic polyamines, boron trifluoride amine complexes such as boron trifluoride triethylamine complex, imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole, organic acids such as phthalic anhydride and trimellitic anhydride, dicyandiamide, triphenylphosphine and the like. The content of such a curing accelerator is not particularly limited, but is usually 5% or less, preferably 1% or less, based on the weight of the heat-resistant resin layer B.

The solvent used for mixing and dissolving the above-mentioned compounds may be methyl cellosolve, butyl cellosolve, methyl ethyl ketone, dioxane, acetone, cyclohexanone, cyclopentanone, isobutanol, isopropanol, tetrahydrofuran, dimethyl sulfoxide, γ -butyrolactone, toluene, xylene, chlorobenzene, benzyl alcohol, isophorone, methoxymethyl butanol, ethyl lactate, propylene glycol monomethyl ether and its acetate, N-methyl-2-pyrrolidone, or a solvent containing 1 or more of these.

The film thickness of the heat-resistant resin layer a (the total film thickness when a plurality of heat-resistant resin layers a are present) is 2 times or more, preferably 2.5 times or more, and more preferably 3 times or more, the film thickness of the heat-resistant resin layer B (the total film thickness when a plurality of heat-resistant resin layers B are present). If the film thickness of the heat-resistant resin layer a is 2 times or less the film thickness of the heat-resistant resin layer B, warpage after etching of the metal layer may increase.

The thermocompression bonding in the present invention can be performed by a thermocompressor, a heat roll laminator, or the like. The heat roll laminator can continuously thermally press-bond a long film or metal foil, and is preferably used from the viewpoint of good productivity. Thermocompression bonding using a heat roll laminator as shown in fig. 4, the metal foil 8 and the laminated film 9 in which the heat-resistant resin layer is laminated are passed through 1 pair of heat rolls 6 and 7 to the heating roll portion, and thermocompression bonding is performed. Here, fig. 4(a) shows a method of thermocompression bonding a metal layer-coated laminate film on one side and fig. 4(b) shows a method of thermocompression bonding a metal layer-coated laminate film on both sides using a hot roll laminator. Reference numeral 10 in fig. 4 (and later fig. 5) is an article take-up roll.

Various combinations of metal roll-metal roll, metal roll-rubber roll, rubber roll-rubber roll, and the like can be used for the rolls of the hot roll laminator. In general, in the case of a laminated film having a copper layer on one surface, a combination of a metal roller and a rubber roller is used, and the copper foil is brought into contact with the metal roller and the heat-resistant insulating film is brought into contact with the rubber roller, thereby performing thermocompression bonding. However, when the roll temperature is 200 ℃ or higher, a combination of a metal roll and a metal roll is preferable. In the case of a laminated film having copper layers on both sides, a metal roll-metal roll combination is used.

Conditions such as the roll temperature, the nip pressure, and the transport speed of the heat-roll laminator are appropriately selected depending on the kind, composition, production method, and the like of the heat-resistant resin layer to be used. In general, the roll temperature is preferably set in the range of 50 to 500 ℃ and in the range of 100-450 ℃. The heating of the rolls may be such that only one roll is heatable, but preferably both rolls are heatable. It is more preferred that both rolls are heatable and that both rolls can be individually temperature controlled. The nip pressure of the hot roll laminator is usually set in the range of 0.5 to 200N/mm in line pressure, and preferably set in the range of 2 to 150N/mm. The conveying speed is generally set in the range of 0.1 to 50m/min, preferably in the range of 0.4 to 30 m/min.

When the lamination is carried out at a roll temperature of 300 ℃ or higher, it is preferable to carry out the lamination in a nitrogen atmosphere or in a vacuum in order to prevent oxidation of a metal foil such as a copper foil. As shown in fig. 5, a heat-resistant resin film such as a polyimide film may be thermocompression bonded by sandwiching a heat-resistant resin film such as SUS or aluminum between the surface of the heat roller and the metal foil 8 or the film 9 in which the heat-resistant resin layer is laminated, as a protective film 11. Here, fig. 5(a) shows a method of thermocompression bonding a metal layer-coated laminate film on one side and fig. 5(b) shows a method of thermocompression bonding a metal layer-coated laminate film on both sides using a hot roll laminator. In fig. 5, reference numeral 11 denotes a protective film supply roll, and 12 denotes a protective film take-up roll.

The method for producing the metal layer-clad laminate film shown in fig. 1 will be described below with reference to specific examples.

Taken as the linear expansion coefficient k_A(ppm/. degree. C.) k-10. ltoreq.k_AK +20(k is linear expansion coefficient of the heat-resistant insulating film)) The polyamic acid resin solution of the precursor of the polyimide resin is applied to at least one surface of a heat-resistant insulating film (for example, a polyimide film) in such a range that the film thickness after curing becomes 0.2 to 12 μm, preferably 0.5 to 10 μm, more preferably 1 to 7 μm. The coating method includes: bar coating, roll coating, blade coating, コンマ coating, reverse coating, knife float coating, gravure roll coating, and the like.

The solution coated on the polyimide film as described above is heated continuously or intermittently at a temperature of about 60 to 200 ℃ for 1 to 60 minutes to remove the solvent. Then, heat treatment is carried out for 1-48h at the temperature range of 200-400 ℃, preferably 240-350 ℃ and more preferably 260-320 ℃ to convert the polyamic acid resin of the heat-resistant resin layer into polyimide resin, so as to form the laminated material of the heat-resistant resin layer containing the polyimide film/polyimide resin. The heat treatment of the present invention is also performed in a targeted range which is gradually increased to the above range.

A copper foil was bonded to the heat-resistant resin layer side of the obtained polyimide film/heat-resistant resin layer laminate in an opposed manner, and the laminate was thermally pressed by a hot roll laminator. Thermocompression bonding using a hot roll laminator as shown in fig. 5(a) shows a case of a laminated film having a metal layer on one side, and fig. 5(b) shows a case of a laminated film having a metal layer on both sides), a polyimide film having a thickness of 20 to 500 μm, preferably 30 to 200 μm is used as a protective film, and a laminate of a copper foil and the polyimide film/heat-resistant resin layer a is sandwiched between the protective films. The temperature of the heat roll at this time is, for example, 300 ℃ to 500 ℃ in the constitution shown in FIG. 1, preferably 350 ℃ to 450 ℃ and more preferably 380 ℃ to 420 ℃. The nip pressure is a linear pressure of 2 to 150N/mm, preferably 5 to 100N/mm, and more preferably 10 to 80N/mm.

In the present invention, the obtained copper-clad laminate film may be further subjected to a heat treatment, and the heat treatment method in this case may be any of a batch-type treatment in which a copper-clad laminate film is wound around a roll, a continuous roll-to-roll treatment, and a sheet-by-sheet treatment in which a sheet is cut. The heat treatment is carried out for 1-48h in the temperature ranges of 200-400 ℃, 240-350 ℃ and more preferably 260-320 ℃, and can be gradually increased to the target temperature. In order to prevent oxidation of the copper layer, it is preferable to perform the treatment in vacuum or nitrogen atmosphere.

The following describes a method for producing a metal-clad laminate film shown in fig. 3, with reference to a specific example.

The coating solution was applied and heated in the same manner as above to remove the solvent and dry it. Then, heat treatment is performed to convert the polyamic acid resin of the heat-resistant resin layer into a polyimide resin, thereby forming a laminate of the heat-resistant resin layer including a copper foil and a polyimide resin. The conditions and the like are the same as those in the above-mentioned production method. At this time, the target temperature in the above range may be gradually raised. In order to prevent oxidation of the copper foil, it is preferable to perform heat treatment in vacuum or nitrogen atmosphere.

Then, a polyamic acid resin solution which is a precursor of a polyimide resin having a lower glass transition temperature than that of the heat-resistant resin layer A is applied to at least one surface of the polyimide film to a film thickness of 0.01 to 5 μm, preferably 0.1 to 4 μm, and more preferably 0.5 to 3 μm after curing, and then dried and heat-treated to form a laminate of the heat-resistant resin layer B comprising the polyimide film/the polyimide resin. The coating, drying and heat treatment methods are the same as described above.

The heat-resistant resin layer a and the heat-resistant resin layer B of each laminate were laminated in opposition and thermocompression bonded to obtain a copper-clad laminate film. In the thermal compression bonding using the heat roll laminator, the heat roll temperature at this time is, for example, 200-. Further, the nip pressure is a linear pressure of 2 to 100N/mm, preferably 5 to 80N/mm, and more preferably 10 to 60N/mm.

When the hot roll temperature is 300 ℃ or lower, the thermal compression bonding by the method shown in FIG. 4 can be used without the need of the thermal compression bonding by the protective film as shown in FIG. 5. After thermocompression bonding, the obtained copper-clad laminate film may be further subjected to heat treatment in the same manner as described above.

In the above-mentioned production method, the heat-resistant resin layer a and the heat-resistant resin layer B are preferably produced by a method in which the heat-resistant resin layer a and the heat-resistant resin layer B are not converted into polyimide resins, but are bonded in the state of polyamic acid resins, thermocompression bonded, and then the obtained copper-clad laminate film is subjected to a heat treatment to convert the polyamic acid resins of the heat-resistant resin layer a and the heat-resistant resin layer B into polyimide resins.

The manufacturing method can further reduce the temperature during thermal compression bonding because the thermal compression bonding is carried out in the state of the polyamic acid, and the temperature of the hot roller laminator is 100-260 ℃, preferably 140-240 ℃, and further preferably 160-220 ℃.

By using the metal layer-clad laminate film of the present invention, a wiring pattern can be formed on the metal layer, whereby a flexible printed circuit board (FPC) can be manufactured. The pitch of the wiring pattern is not particularly limited, but is preferably 10 to 150. mu.m, more preferably 15 to 100. mu.m, and still more preferably 20 to 80 μm.

As an example of a method for mounting a semiconductor chip (IC) and manufacturing a semiconductor device, a manufacturing example using a COF method using a flip chip technique will be described.

The metal layer-clad laminate film of the present invention is slit to a target width. Then, a photoresist film is coated on the metal layer, and after a wiring pattern is formed by exposure to a mask, the metal layer is wet-etched to remove the remaining photoresist film, thereby forming a metal wiring pattern. After plating 0.2 to 0.8 μm of tin or gold on the formed metal wiring pattern, a solder resist was applied on the wiring pattern to obtain a COF tape.

The IC with gold bumps formed thereon was flip-chip bonded to the inner leads of the COF tape obtained in the above manner, and the resulting product was encapsulated with a resin to obtain a semiconductor device of the present invention.

As IC mounting methods, there are a metal bonding method in which wiring and bumps of an IC are group-bonded, a wire bonding method in which a bonding portion of an IC is bonded to an inner lead of a COF tape by wire bonding, an ACF method in which bonding is performed by an adhesive film of a conductive filler contained in an adhesive layer, and an NCP method in which bonding is performed by a nonconductive adhesive. Although the ACF and NCP methods can be bonded at a relatively low temperature, a metal bonding method, particularly a gold-tin eutectic bonding method, is generally widely used in terms of connection reliability and the like.

In the case of eutectic gold-tin bonding, a load of 20 to 30g is applied to each 1 bump in order to absorb a variation in height between the bump on the IC side and the wiring on the wiring side. In addition, since a temperature of 280 ℃ or higher is necessary for forming eutectic crystal between gold and tin and bonding with high reliability, the temperature of the bonding surface is generally set to 300-400 ℃.

Examples

The present invention will be described with reference to examples, but the present invention is not limited to these examples. The measurement methods of warpage, glass transition temperature, and water absorption rate are described below.

(1) Evaluation of warpage

After the copper foil was laminated, the entire copper layer was etched with an iron chloride solution. After cutting the sample into 50 mm. times.50 mm, the sample was left standing at 25 ℃ and 50% RH for 24 hours, and then the sample was placed on a flat plate to measure the height of warpage at 4 corners, and the average value was taken as the warpage value.

(2) Determination of adhesion (normality)

The copper-clad laminate film was etched to a width of 2mm with an iron chloride solution, and the metal layer having a width of 2mm was peeled off at a tensile rate of 50mm/min at 90 ℃ using "テンシロン" UTM-4-100 manufactured by TOYO BOLDWIN.

(3) Determination of the coefficient of Linear expansion

A resin solution having a predetermined thickness was applied to the glossy surface of an electrolytic copper foil having a thickness of 18 μm by a bar coater, and then dried at 80 ℃ for 10min and 150 ℃ for 10min, and further heat-treated at 280 ℃ for 1h under a nitrogen atmosphere to heat-cure the same. Then, the electrolytic copper foil was etched on the entire surface thereof with an iron chloride solution to obtain a single film of a heat-resistant resin layer.

Cutting the obtained single film into a shape with a specific widthThe resulting mixture was formed into a cylindrical shape, and measured at a temperature-raising rate of 5 ℃/min in a range of 30 to 300 ℃ with a thermomechanical analyzer SS-6100 (manufactured by セイコ - インスルメンツ Co.). From the obtained measurement structure, the average linear expansion coefficient at 30 to 300 ℃ was calculated by the calculation formula (2). Here, L₃₀Is the length of the sample at 30 ℃, L₃₀₀Is the sample length at 300 ℃.

Average coefficient of linear expansion ═ 1/L₃₀)×[(L₃₀₀-L₃₀)/(300-30)] (2)

(4) Determination of glass transition temperature

A polyamic acid resin solution (PA1-8) was applied to the glossy surface of an electrolytic copper foil 18 μm thick to a predetermined thickness by a bar coater, and then dried at 80 ℃ for 10min and 150 ℃ for 10min, and further heat-treated at 280 ℃ for 1h under a nitrogen atmosphere to heat-cure the copper foil. Then, the electrolytic copper foil was etched on the entire surface thereof with an iron chloride solution to obtain a single film of a heat-resistant resin layer.

A polyamide/epoxy/phenol heat-resistant resin solution (EP1) having a predetermined thickness was applied to the glossy surface of an electrolytic copper foil having a thickness of 18 μm by a bar coater, and then dried at 80 ℃ for 10min and 120 ℃ for 10min, and further heat-treated at 160 ℃ for 1 hour to heat-cure the resin. Then, the electrolytic copper foil was etched on the entire surface thereof with an iron chloride solution to obtain a single film of a heat-resistant resin layer.

About 10mg of the obtained single film of the heat-resistant resin was sealed in an aluminum standard container, and measured by a DSC-50 type differential scanning calorimeter (DSC method) manufactured by Shimadzu corporation, and the glass transition temperature was calculated from the inflection point of the obtained DSC curve. After pre-drying at 80 ℃ for 1h, the temperature was measured at a rate of 20 ℃/min.

(5) Measurement of Water absorption

A polyamide/epoxy/phenol heat-resistant resin solution (EP1) having a predetermined thickness was applied to the glossy surface of an electrolytic copper foil having a thickness of 18 μm by a bar coater, and then dried at 80 ℃ for 10min and 120 ℃ for 10min, and further heat-treated at 160 ℃ for 1 hour to be heat-cured. Then, the electrolytic copper foil was etched on the entire surface thereof with an iron chloride solution to obtain a single film of a heat-resistant resin layer.

About 200mg of the obtained single film of the heat-resistant resin was immersed in water at 30 ℃ for 24 hours and then dried at 80 ℃ for 3 hours. The weight after water immersion and the weight after drying were measured, respectively, and the difference was divided by the weight after drying to calculate the water absorption.

The abbreviations for the carboxylic dianhydride and diamine shown in the following production examples are as follows:

BPDA: 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride

OPDA: 3, 3 ', 4, 4' -diphenyl ether tetracarboxylic dianhydride

And (3) PMDA: pyromellitic dianhydride

SiDA: 1, 1, 3, 3-tetramethyl-1, 3-bis (3-aminopropyl) disiloxane

And (3) DAE: 4, 4' -diaminodiphenyl ether

PDA: p-phenylenediamine

DBAB: 4, 4' -diamino-benzanilides

m-TB: 4, 4' -dimethylbenzidine

NMP: n-methyl-2-pyrrolidone.

Production example 1

In a reaction vessel equipped with a thermometer, an inlet for dry nitrogen, a heating/cooling device using warm water/cooling water, and a stirring device, 12.43g (0.05mol) of SiDA, 50.05g (0.25mol) of DAE, and 75.67g (0.7mol) of PDA were charged together with 2450g of NMP and dissolved, after which 294.2g (1mol) of BPDA was charged and reacted at 70 ℃ for 6 hours to obtain a 15 wt% polyamic acid resin solution (PA 1). The resin imidized from the polyamic acid resin solution (PA1) had a linear expansion coefficient of 20 ppm/deg.C, a water absorption of 1.1% by weight, and a glass transition temperature of 283 ℃.

Production examples 2 to 7

A15 wt% polyamic acid resin solution (PA2-7) was obtained in the same manner as in production example 1, except that the kinds and amounts of the carboxylic dianhydride and the diamine were changed as shown in Table 1. Table 1 shows the linear expansion coefficient, water absorption rate and glass transition temperature of the resin imidized from the polyamic acid resin solution (PA 2-7).

Production example 8

A15 wt% polyamic acid resin solution (PA8) was obtained in the same manner as in production example 1, except that the kinds and amounts of the carboxylic dianhydride and the diamine were changed as shown in Table 1. Table 1 shows the linear expansion coefficient, water absorption rate and glass transition temperature of the resin imidized from the polyamic acid resin solution (PA 8).

Table 1 (mol number in upper row and addition/g in lower row)

		Tetracarboxylic acid component		Diamine component					Solvent DMAc	Coefficient of linear expansion (ppm/. degree.C.)	Water absorption Rate (% by weight)	Glass transition temperature (. degree. C.)
		Tetracarboxylic acid component		Diamine component									BPDA	OPDA	SiDA	DAE	PDA	DABA	m-TB
		Production example 1	PA1	1.00294.20		0.0512.43	0.2550.05	0.7075.67					BPDA	OPDA	SiDA	DAE	PDA	DABA	m-TB		2450	20	1.1	283
Production example 2	PA2	Production example 1	PA1	1.00294.20		0.0512.43	0.2550.05	0.7075.67	1.00294.20			0.4080.08	0.6064.86			2488	20	1.6	295		2450	20	1.1	283
Production example 2	PA2	Production example 3	PA3	1.00294.20		0.0512.43	0.3570.07		1.00294.20			0.4080.08	0.6064.86			2488	20	1.6	295	0.60136.38	2907	18	1.2	304
Production example 4	PA4	Production example 3	PA3	1.00294.20		0.0512.43	0.3570.07		1.00294.20			0.80160.16	0.2021.62			2697	42	1.8	310	0.60136.38	2907	18	1.2	304
Production example 4	PA4	Production example 5	PA5	1.00294.20		0.0512.43	0.75150.15		1.00294.20			0.80160.16	0.2021.62			2697	42	1.8	310	0.2045.46	2846	39	1.1	298
Production example 6	PA6	Production example 5	PA5	1.00294.20		0.0512.43	0.75150.15			1.00310.20	0.1024.85	0.90180.18				2920	68	1.0	254	0.2045.46	2846	39	1.1	298
Production example 6	PA6	Production example 7	PA7	0.70205.90	0.3093.10	0.4099.40	0.60120.12			1.00310.20	0.1024.85	0.90180.18				2920	68	1.0	254		2938	89	0.4	192
Production example 8	PA8	Production example 7	PA7	0.70205.90	0.3093.10	0.4099.40	0.60120.12		1.00294.20			0.2040.04	0.4043.24		0.4084.92	2620	16	1.4	291		2938	89	0.4	192

BPDA: 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride

OPDA: 3, 3 ', 4, 4' -diphenyl ether tetracarboxylic dianhydride

SiDA: 1, 1, 3, 3-tetramethyl-1, 3-bis (3-aminopropyl) disiloxane

And (3) DAE: 4, 4' -diaminodiphenyl ether

PDA: p-phenylenediamine

DABA: 4, 4' -diamino-benzanilides

DMAc: n, N-dimethyl acetamide

m-TB: 2, 2' -dimethylbenzidine

Production example 9

250g (50 wt%) of polyamide resin "マクロメルト" 6030 manufactured by ヘンケル Japan, 105g (21 wt%) of epoxy resin "エピコ - ト" 828 manufactured by oiled シエルエポキシ, 145g (29 wt%) of phenol resin CKM-1636 manufactured by Showa polymer was dissolved in 680g of isopropyl alcohol and 1760g of chlorobenzene to obtain a 17 wt% polyamide/epoxy/phenol heat-resistant resin solution (EP 1). The polyamide/epoxy/phenol heat-resistant resin solution (EP1) obtained by heat-curing at 160 ℃ has a coefficient of linear expansion of 100 ppm/DEG C or more, a water absorption of 1.1% by weight and a glass transition temperature of 62 ℃.

Example 1

The polyamic acid resin solution PA1 was coated on a 25 μm-thick polyimide film (made by Toray DuPont Kapton 100EN, whose constituent component was PMDA/BPDA/DAE/PDA, no significant glass transition point at 500 ℃ or lower) which had been subjected to low-temperature plasma treatment in an Ar atmosphere by a reverse roll coater so that the film thickness after drying was 3 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10 min. The coated product was heat-treated at 290 ℃ for 5min in a nitrogen atmosphere to imidize it and remove the residual solvent, thereby obtaining a polyimide film/heat-resistant resin layer laminate.

The heat-resistant resin layer of the polyimide film/heat-resistant resin layer laminate was bonded to a roughened copper foil (TQ-VLP, manufactured by mitsui metals) having a thickness of 12 μm and having been roughened on the adhesive surface side, and a polyimide film (Kapton 500H manufactured by dony dupont) having a thickness of 125 μm was sandwiched between two rolls and the polyimide film/heat-resistant resin layer laminate and the copper foil as a protective film as shown in fig. 5(a), respectively, and thermocompression bonding was performed at a line pressure of 70N/mm and a speed of 1m/min, thereby obtaining a laminate film having one surface coated with a copper layer. The warpage of the obtained copper layer-coated laminate film was measured to be 0 mm. Further, the adhesive force was 7N/cm.

Examples 2 and 3

A copper layer-coated multilayer film was obtained in the same manner as in example 1, except that the kinds and thicknesses of the polyimide film, the copper foil, and the heat-resistant resin layer were changed as shown in table 2. Table 2 summarizes the results of the warpage evaluation of the obtained copper layer-coated laminate film.

The polyimide film used herein was Kapton 100EN (thickness 25 μm) manufactured by DuPont, Toray corporation and "ユ - ピレツクス" 25S (composition: BPDA/PDA, no significant glass transition point at 500 ℃ C.) (thickness 25 μm) manufactured by Uyu Kyoho. The copper foil was a copper foil TQ-VLP (thickness 12 μm) having one surface roughened, which was produced by Mitsui metal Co., Ltd., an F1-WS copper foil (thickness 12 μm) produced by Guhe サ - キツトフオイル Co., Ltd., and an F0-WS copper foil (thickness 12 μm) produced by Guhe サ - キツトフオイル Co., Ltd., both sides smoothed.

The linear expansion coefficient of Kapton 100EN was 17 ppm/deg.C, and the linear expansion coefficient of "ユ - ピレツクス" 25S was 14 ppm/deg.C.

Comparative examples 1 and 2

TABLE 2

	Polyimide film	Linear expansion coefficient k (ppm/. degree. C.) of polyimide film	Copper foil	Heat-resistant resin layer			Warp (mm)	Adhesion (N/cm)
				Heat-resistant resin layer					Species of	Coefficient of linear expansion kA (ppm/. degree.C.)	Film thickness (mum)
				Example 1	カプトン100EN	17			Species of	Coefficient of linear expansion kA (ppm/. degree.C.)	Film thickness (mum)	TQ-VLP	PA1	20	3	0	7
Example 2	ユ - ピレツクス 25S	14	F1-WS	Example 1	カプトン100EN	17	PA1	20	5	0	7	TQ-VLP	PA1	20	3	0	7
Example 2	ユ - ピレツクス 25S	14	F1-WS	Example 3	カプトン100EN	17	PA1	20	5	0	7	TQ-VLP	PA2	20	2	0	6
Comparative example 1	カプトン100EN	17	TQ-VLP	Example 3	カプトン100EN	17	PA4	42	3	＞20	10	TQ-VLP	PA2	20	2	0	6
Comparative example 1	カプトン100EN	17	TQ-VLP	Comparative example 2	ユ - ピレツクス 25S	14	PA4	42	3	＞20	10	F1-WS	PA6	68	5	＞20	10

Example 4

The polyamic acid resin solution PA1 was coated on a roughened copper foil (TQ-VLP, manufactured by Mitsui metals Co., Ltd.) having a thickness of 12 μm and having been subjected to roughening treatment on the adhesive surface side with a reverse roll coater so that the thickness after drying was 3 μm, and then dried at 80 ℃ for 10min and further at 140 ℃ for 10 min. The coated product was heat-treated at 290 ℃ for 5min in a nitrogen atmosphere to imidize it and remove the residual solvent, thereby obtaining a copper foil/heat-resistant resin layer A laminate.

Similarly, a polyamic acid resin solution PA7 was applied to a 25 μm-thick polyimide film (Kapton 100EN manufactured by DuPont, Toray) subjected to low-temperature plasma treatment in an Ar atmosphere by a reverse roll coater so that the film thickness after drying was 1 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10 min. The coated product was heat-treated at 290 ℃ for 5min in a nitrogen atmosphere to imidize it and remove the residual solvent, thereby obtaining a laminate of a polyimide film/heat-resistant resin layer B.

The heat-resistant resin layer a and the heat-resistant resin layer B of the laminate of the copper foil/heat-resistant resin layer a and the polyimide film/heat-resistant resin layer B prepared above were opposed to each other, and a polyimide film (Kapton 500H manufactured by dongli dupont) having a thickness of 125 μm was sandwiched as a protective film between the two rolls and the laminate of the copper foil/heat-resistant resin layer a and the laminate of the polyimide film/heat-resistant resin layer B, respectively, as shown in fig. 5(a), and thermocompression bonded at a line pressure of 50N/mm and a speed of 2m/min to obtain a laminate film having one surface coated with a copper layer. The warpage of the obtained copper layer-coated laminate film was measured to be 0 mm. The adhesive force was 11N/cm.

Examples 5 to 9

A copper layer-coated multilayer film was obtained in the same manner as in example 4, except that the kinds and thicknesses of the polyimide film, the copper foil, the heat-resistant resin layer a, and the heat-resistant resin layer B were changed as shown in table 3. Table 3 summarizes the results of the warpage evaluation of the obtained copper layer-coated laminate film.

Comparative examples 3 to 5

TABLE 3

	Copper foil	Heat-resistant resin layer A			Polyimide film	Polyimide (PA)Linear expansion coefficient k (ppm/. degree. C.) of imine film	Heat-resistant resin layer B			Warp (mm)	Adhesion (N/cm)
		Heat-resistant resin layer A					Heat-resistant resin layer B					Species of	Coefficient of linear expansion kA (ppm/. degree.C.)	Film thickness (mum)	Species of	Coefficient of linear expansion (ppm/. degree.C.)	Film thickness (mum)
		Example 4	TQ-VLP	PA1			20	3	カプトン100EN			Species of	Coefficient of linear expansion kA (ppm/. degree.C.)	Film thickness (mum)	Species of	Coefficient of linear expansion (ppm/. degree.C.)	Film thickness (mum)	17	PA7	89	1	0	11
Example 5	F1-WS	Example 4	TQ-VLP	PA1	PA1	20	20	3	カプトン100EN	5	ユ-ピレツクス25S	14	PA6	68	2	0	11	17	PA7	89	1	0	11
Example 5	F1-WS	Example 6	TQ-VLP	PA2	PA1	20	20	3	カプトン100EN	5	ユ-ピレツクス25S	14	PA6	68	2	0	11	17	PA6	68	1	0	10
Example 7	TQ-VLP	Example 6	TQ-VLP	PA2	PA2	20	20	3	カプトン100EN	5	ユ-ピレツクス25S	14	PA6	68	3	3	10	17	PA6	68	1	0	10
Example 7	TQ-VLP	Example 8	FO-WS	PA3	PA2	20	18	2	カプトン100EN	5	ユ-ピレツクス25S	14	PA6	68	3	3	10	17	PA6	68	1	0.1	10
Example 9	TQ-VLP	Example 8	FO-WS	PA3	PA3	18	18	2	カプトン100EN	3	カプトン100EN	17	PA7	89	1	0	11	17	PA6	68	1	0.1	10
Example 9	TQ-VLP	Comparative example 3	TQ-VLP	PA4	PA3	18	42	3	カプトン100EN	3	カプトン100EN	17	PA7	89	1	0	11	17	PA7	89	1	＞20	10
Comparative example 4	F1-WS	Comparative example 3	TQ-VLP	PA4	PA5	39	42	3	カプトン100EN	5	カプトン100EN	17	PA6	68	2	＞20	10	17	PA7	89	1	＞20	10
Comparative example 4	F1-WS	Comparative example 5	TQ-VLP	PA6	PA5	39	68	2	ユ-ピレツクス25S	5	カプトン100EN	17	PA6	68	2	＞20	10	14	PA6	68	1	＞20	10

Example 10

The polyamic acid resin solution PA1 was applied to a roughened copper foil (TQ-VLP, manufactured by Mitsui metals Co., Ltd.) having a thickness of 12 μm and having been subjected to roughening treatment on the adhesive surface side, by a reverse roll coater, so that the thickness after drying was 3 μm, and the copper foil/heat-resistant resin layer A was obtained by drying at 80 ℃ for 10min and further at 140 ℃ for 10 min.

Similarly, a polyimide film (Kapton 100EN manufactured by dony dupont) having a thickness of 25 μm and subjected to low-temperature plasma treatment in an Ar atmosphere was coated with the polyamic acid resin solution PA7 by a reverse roll coater so that the film thickness after drying was 1 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10min to obtain a laminate of the polyimide film/heat-resistant resin layer B.

The laminate of the copper foil/heat-resistant resin layer a and the polyimide film/heat-resistant resin layer B was laminated such that the heat-resistant resin layer a and the heat-resistant resin layer B were opposed to each other, and hot-pressed and joined at a line pressure of 10N/mm and a speed of 1m/min in a roll laminator heated to a roll surface temperature of 200 ℃. The warpage of the obtained copper layer-coated laminate film was measured to be 0 mm. Also, the adhesive force was 12N/cm.

Examples 11 to 13

A copper layer-coated multilayer film was obtained in the same manner as in example 10, except that the kinds and thicknesses of the polyimide film, the copper foil, the heat-resistant resin layer a, and the heat-resistant resin layer B were changed as shown in table 4. Table 4 summarizes the results of the warpage evaluation of the obtained copper layer-coated laminate film.

Example 14

Comparative examples 6 to 8

A copper layer-coated multilayer film was obtained in the same manner as in example 4, except that the kinds and thicknesses of the polyimide film, the copper foil, the heat-resistant resin layer a, and the heat-resistant resin layer B were changed as shown in table 4. Table 4 summarizes the results of the warpage evaluation of the obtained copper layer-coated laminate film.

TABLE 4

	Copper foil	Heat-resistant resin layer A			Polyimide film	The linear expansion coefficient k (ppm/. degree.C.) of the polyimide film)	Heat-resistant resin layer B			Warp (mm)	Adhesion (N/cm)
		Heat-resistant resin layer A					Heat-resistant resin layer B					Species of	Coefficient of linear expansion kA (ppm/. degree.C.)	Film thickness (mum)	Species of	Coefficient of linear expansion (ppm/. degree.C.)	Film thickness (mum)
		Example 10	TQ-VLP	PA1			20	3	カプトン100EN			Species of	Coefficient of linear expansion kA (ppm/. degree.C.)	Film thickness (mum)	Species of	Coefficient of linear expansion (ppm/. degree.C.)	Film thickness (mum)	17	PA7	89	1	0	12
Example 11	TQ-VLP	Example 10	TQ-VLP	PA1	PA1	20	20	3	カプトン100EN	3	カプトン100EN	17	PA7	89	3	3	12	17	PA7	89	1	0	12
Example 11	TQ-VLP	Example 12	F1-WS	PA2	PA1	20	20	4	ユ-ピレツクス25S	3	カプトン100EN	17	PA7	89	3	3	12	14	PA7	89	2	0.1	11
Example 13	F0-WS	Example 12	F1-WS	PA2	PA3	18	20	4	ユ-ピレツクス25S	5	カプトン100EN	17	PA7	89	2	0	11	14	PA7	89	2	0.1	11
Example 13	F0-WS	Example 14	TQ-VLP	PA8	PA3	18	16	4	カプトン100EN	5	カプトン100EN	17	PA7	89	2	0	11	17	PA7	89	2	0	11
Comparative example 6	TQ-VLP	Example 14	TQ-VLP	PA8	PA4	42	16	4	カプトン100EN	3	カプトン100EN	17	PA7	89	1	＞20	11	17	PA7	89	2	0	11
Comparative example 6	TQ-VLP	Comparative example 7	TQ-VLP	PA5	PA4	42	39	5	ユ-ピレツクス25S	3	カプトン100EN	17	PA7	89	1	＞20	11	14	PA7	89	2	＞20	11
Comparative example 8	TQ-VLP	Comparative example 7	TQ-VLP	PA5	PA6	68	39	5	ユ-ピレツクス25S	4	カプトン100EN	17	PA7	89	2	＞20	11	14	PA7	89	2	＞20	11

Example 15

The polyamic acid resin solution PA1 was applied to a 25 μm-thick polyimide film (Kapton 100EN manufactured by DuPont, Toray) subjected to low-temperature plasma treatment in an Ar atmosphere by a reverse roll coater so that the film thickness after drying was 3 μm, dried at 80 ℃ for 10min, further dried at 140 ℃ for 10min, and then applied thereon with the polyamic acid resin solution PA6 so that the film thickness after drying was 1 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10 min. The coated product was heat-treated at 290 ℃ for 5min in a nitrogen atmosphere to imidize and remove the residual solvent, thereby obtaining a laminate of a polyimide film/a heat-resistant resin layer A/a heat-resistant resin layer B.

A roughened copper foil (TQ-VLP, manufactured by mitsui metals) having a thickness of 12 μm and having been subjected to roughening treatment on the adhesive surface side was bonded to the heat-resistant resin layer B of the polyimide film/heat-resistant resin layer a/heat-resistant resin layer B laminate thus prepared, and a polyimide film (Kapton 500H manufactured by dony dupont) having a thickness of 125 μm was sandwiched between two rolls as a protective film, the polyimide film/polyimide resin layer laminate and the copper foil, respectively, as shown in fig. 5, and thermocompression bonded at a line pressure of 50N/mm and a speed of 2m/min, thereby obtaining a copper-clad laminate film. The warpage of the obtained copper layer-coated laminate film was measured to be 3 mm. Further, the adhesive force was 10N/cm.

Example 16

The polyamic acid resin solution PA6 was coated on a roughened copper foil (TQ-VLP, manufactured by Mitsui metals Co., Ltd.) having a thickness of 12 μm and subjected to roughening treatment on the adhesive surface side with a reverse roll coater so that the dried film thickness was 0.5 μm, dried at 80 ℃ for 10min, further dried at 140 ℃ for 10min, and then coated thereon with the polyamic acid resin solution PA1 so that the dried film thickness was 3 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10 min. The coated product was heat-treated at 290 ℃ for 5min in a nitrogen atmosphere to imidize and remove the residual solvent, thereby obtaining a laminate of copper foil/heat-resistant resin layer B/heat-resistant resin layer A.

Similarly, a polyamic acid resin solution PA7 was applied to a 25 μm-thick polyimide film (Kapton 100EN manufactured by DuPont, Toray) subjected to low-temperature plasma treatment in an Ar atmosphere by a reverse roll coater so that the film thickness after drying was 1 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10 min. The coated product was heat-treated at 290 ℃ for 5min in a nitrogen atmosphere to imidize and remove the residual solvent, thereby obtaining a laminate of a polyimide film/heat-resistant resin layer B.

The laminate of the copper foil/heat-resistant resin layer B/heat-resistant resin layer a and the heat-resistant resin layer B of the laminate of the polyimide film/heat-resistant resin layer B were opposed to each other, and a polyimide film (Kapton 500H manufactured by dony dupont) having a thickness of 125 μm as a protective film was sandwiched between the two rolls and the laminate of the copper foil/heat-resistant resin layer B/heat-resistant resin layer a and the laminate of the polyimide film/heat-resistant resin layer B, respectively, as shown in fig. 5, and thermocompression-bonded at a line pressure of 50N/mm and a speed of 2m/min to obtain a laminate film one surface of which was coated with a copper layer. The warpage of the obtained copper layer-coated laminate film was measured to be 0.2 mm. Also, the adhesive force was 12N/cm.

Example 17

A roughened copper foil (TQ-VLP, manufactured by Mitsui metals Co., Ltd.) having a thickness of 12 μm and having been subjected to roughening treatment on the adhesive surface side was coated with a polyamic acid resin solution PA7 using a reverse roll coater so that the dried film thickness was 0.3 μm, dried at 80 ℃ for 10min, further dried at 140 ℃ for 10min, and then a polyamide resin solution PA1 was coated thereon so that the dried film thickness was 3 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10min, to obtain a laminate of copper foil/heat-resistant resin layer B/heat-resistant resin layer A.

The laminate of the copper foil/heat-resistant resin layer B/heat-resistant resin layer A and the laminate of the polyimide film/heat-resistant resin layer B, in which the heat-resistant resin layer A and the heat-resistant resin layer B were opposed to each other, was thermally pressure-bonded at a line pressure of 10N/mm and a speed of 1m/min by means of a roll laminator heated to a roll surface temperature of 200 ℃ and then imidized in a stepwise temperature-rising curing system [ (80 ℃, 30min) + (150 ℃, 1h) + (280 ℃, 2h) ] under a nitrogen atmosphere, followed by gradually cooling to room temperature to obtain a laminate film one surface of which was coated with a copper layer. The warpage of the obtained copper layer-coated laminate film was measured to be 0.1 mm. Also, the adhesive force was 14N/cm.

Example 18

The polyamic acid resin solution PA1 was coated on a roughened copper foil (TQ-VLP, manufactured by Mitsui metals Co., Ltd.) having a thickness of 12 μm and subjected to roughening treatment on the adhesive surface side with a reverse roll coater so that the thickness after drying was 5 μm, dried at 80 ℃ for 10min, and further dried at 140 ℃ for 10 min. The coated product was heat-treated at 290 ℃ for 5min in a nitrogen atmosphere to imidize and remove the residual solvent, thereby obtaining a copper foil/heat-resistant resin layer A laminate.

Then, a polyimide film (25S ユ - ピレツクス manufactured by Ushihiki Kaisha, Ltd.) having a thickness of 25 μm and subjected to low-temperature plasma treatment in an Ar atmosphere was coated with a polyamide/epoxy/phenol heat-resistant resin solution (EP1) by a reverse roll coater so that the film thickness after drying was 2 μm, dried at 80 ℃ for 10min, and further dried at 120 ℃ for 10min to obtain a polyimide film/heat-resistant resin layer B laminate.

The laminate of the copper foil/heat-resistant resin layer a and the laminate of the polyimide film/heat-resistant resin layer B, in which the heat-resistant resin layer a and the heat-resistant resin layer B were opposed to each other, was thermally pressed at a linear pressure of 6N/mm and a speed of 1m/min in a roll laminator heated to 140 ℃ at the roll surface temperature, and then the heat-resistant resin layer B was thermally cured in a stepwise temperature-rise curing system [ (80 ℃, 30min) + (120 ℃, 1h) + (160 ℃, 2h) ] under a nitrogen atmosphere, and was gradually cooled to room temperature, thereby obtaining a multilayer film one surface of which was coated with a copper layer. The warpage of the obtained copper layer-coated laminate film was measured to be 0 mm. The adhesive force was 11N/cm.

Example 19

The polyamic acid resin solution PA8 was applied to a roughened copper foil (TQ-VLP, manufactured by Mitsui metals Co., Ltd.) having a thickness of 12 μm and having been subjected to roughening treatment on the adhesive surface side, by a reverse roll coater, so that the thickness after drying was 5 μm, and the copper foil/heat-resistant resin layer A was obtained by drying at 80 ℃ for 10min and further at 140 ℃ for 10 min.

Then, a polyamide/epoxy/phenol heat-resistant resin solution (EP1) was coated on a polyimide film (Kapton 100EN manufactured by DuPont, Toray) having a thickness of 25 μm, which was subjected to low-temperature plasma treatment in an Ar atmosphere, by a reverse roll coater so that the film thickness after drying was 2 μm, dried at 80 ℃ for 10min, and further dried at 120 ℃ for 10min, to obtain a laminate of the polyimide film/heat-resistant resin layer B.

The laminate of the copper foil/heat-resistant resin layer a and the laminate of the polyimide film/heat-resistant resin layer B, in which the heat-resistant resin layer a and the heat-resistant resin layer B were opposed to each other, were thermally pressed at a linear pressure of 6N/mm and a speed of 1m/min in a roll laminator heated to 140 ℃ at the roll surface temperature, and then imidized and heat-cured in a stepwise temperature-rising curing system [ (80 ℃, 30min) + (150 ℃, 1h) + (280 ℃, 1h) ] under a nitrogen atmosphere, and were gradually cooled to room temperature to obtain a copper-clad laminate film. The warpage of the obtained copper layer-coated laminate film was measured to be 0 mm. The adhesive force was 11N/cm.

From the above results, it was found that the heat-resistant resin laminated film of the present invention was not warped regardless of whether the metal layer was in a laminated state or in a state where the metal layer was etched over the entire surface of the metal layer. On the other hand, in the comparative example, although the metal layer was not warped in the laminated state, a large warp occurred in the metal layer in the entire surface etched state, and the metal layer was rolled into a cylinder.

Example 20

On the copper layer of the copper-clad laminate film obtained in example 1, a photoresist film was applied by a reverse roll coater to a film thickness of 4 μm after drying, and then exposed through a mask to form a wiring pattern using an alkali developing solution, followed by wet etching of the copper foil with an aqueous solution of ferric chloride. The remaining photoresist film is removed to form a copper wiring pattern. After electroless plating of 0.4 μm tin on the formed copper wiring pattern, solder resist was applied on the wiring pattern to obtain a COF tape. The resulting COF tape was free from warpage.

The semiconductor chip with gold bumps formed thereon was bonded to the inner leads of the COF tape obtained in the above manner by a flip-chip mounting method, and the resulting chip was encapsulated with a resin to obtain a semiconductor device. Since the COF tape is free from warpage and has few defects such as poor bonding, the semiconductor device exhibits good reliability.

Example 21

The same procedure as in example 20 was repeated, except that the copper clad laminate film obtained in example 6 was used. The COF tape is free from warpage, and a semiconductor device produced therefrom is free from short-circuiting of wiring, and exhibits good reliability.

Example 22

The same procedure as in example 20 was repeated, except that the copper clad laminate film obtained in example 13 was used. The COF tape is free from warpage, and the wiring of a semiconductor device made of the COF tape is free from short-circuiting, and exhibits good reliability.

Claims

1. A heat-resistant resin laminated film comprising a heat-resistant resin layer laminated on at least one surface of a heat-resistant insulating film, wherein the heat-resistant resin layer has a coefficient of linear expansion (k)_A(ppm/. degree. C.) k-10. ltoreq.k_AK +20(k is a linear expansion coefficient of the heat-resistant insulating film).

2. A heat-resistant resin laminated film as claimed in claim 1, which is a heat-resistant resin laminated film comprising a heat-resistant resin layer laminated on at least one surface of a heat-resistant insulating filmThe middle heat-resistant resin layer is composed of more than 2 heat-resistant resin layers, and at least 1 of the heat-resistant resin layers has a linear expansion coefficient k_A(ppm/. degree. C.) k-10. ltoreq.k_AK +20(k is a linear expansion coefficient of the heat-resistant insulating film).

3. The heat-resistant resin laminate film as claimed in claim 1 or 2, wherein the heat-resistant insulating film has a linear expansion coefficient k of 5 to 25ppm/° C_A(ppm/. degree. C.) k-10. ltoreq.k_AThe coefficient of linear expansion of the heat-resistant resin layer in the range of k +20(k is the coefficient of linear expansion of the heat-resistant insulating film) or less is 5 to 30 ppm/DEG C.

4. A heat-resistant resin laminate film as claimed in any one of claims 1 to 3, wherein a coefficient of linear expansion k is formed_A(ppm/. degree. C.) k-10. ltoreq.k_AThe resin of the heat-resistant resin layer in the range of k +20(k is a coefficient of linear expansion of the heat-resistant insulating film) is a polyimide-based resin whose diamine component includes 40 mol% or more of at least one aromatic diamine having a structure represented by any one of the general formulae (1) to (3) in the total diamine component,

in the formula, R¹-R⁸The same or different, selected from hydrogen atom, alkyl group with carbon number of 1-30, alkoxy group with carbon number of 1-30, halogen, hydroxyl, carboxyl, sulfo, nitro and cyano.

5. The heat-resistant resin laminate film according to claim 4, wherein the diamine component of the polyimide-based resin comprises at least one selected from the group consisting of p-phenylenediamine, 4 '-diamino-benzanilide and 2, 2' -dimethylbenzidine in an amount of 40 mol% or more based on the total diamine components.

6. A heat-resistant resin laminated film as claimed in claim 4, wherein the tetracarboxylic acid component of the polyimide-based resin comprises at least 40 mol% of pyromellitic dianhydride and/or biphenyltetracarboxylic dianhydride based on the total tetracarboxylic acid component.

7. A metal-clad laminate film comprising a metal foil laminated on the heat-resistant resin layer side of the heat-resistant resin laminate film according to any one of claims 1 to 6.

8. The metal-clad laminate film according to claim 7, which is a metal-clad laminate film comprising a metal foil laminated on at least one side of a heat-resistant insulating film via a heat-resistant resin layer, wherein the heat-resistant resin layer comprises at least 2 layers, and a coefficient of linear expansion k is laminated on the side contacting the metal layer_A(ppm/. degree. C.) k-10. ltoreq.k_AA heat-resistant resin layer (A) having a linear expansion coefficient of not more than k +20(k is the linear expansion coefficient of the heat-resistant insulating film), and a heat-resistant resin layer (B) having a lower glass transition temperature than that of the heat-resistant resin layer (A) is laminated on the side in contact with the heat-resistant insulating film.

9. The metal-clad laminate film of claim 8 wherein the glass transition temperature of the heat-resistant resin layer A is 250 ℃ to 400 ℃.

10. The metal-layer-clad laminate film according to claim 8 or 9, wherein the film thickness of the heat-resistant resin layer a is 2 times or more the film thickness of the heat-resistant resin layer B.

11. The metal-layer-clad laminate film as claimed in any one of claims 8 to 10, wherein the heat-resistant resin layer B is a polyimide-based resin.

12. The metal-clad laminate film as claimed in claim 11, wherein the glass transition temperature of the heat-resistant resin layer B is 120 ℃ to 280 ℃.

13. The metal-layer-clad laminate film as claimed in any one of claims 8 to 10, wherein the heat-resistant resin layer B is a thermosetting resin containing an epoxy compound.

14. The metal-clad laminate film as claimed in claim 13, wherein the glass transition temperature of the heat-resistant resin layer B is 50 ℃ to 250 ℃.

15. A semiconductor device comprising the metal-clad laminate film according to any one of claims 6 to 14.

16. A method for producing a metal-clad laminate film comprising a metal foil laminated on at least one surface of a heat-resistant insulating film via a heat-resistant resin layer, the method comprising laminating a metal foil having a coefficient of linear expansion k_A(ppm/. degree. C.) k-10. ltoreq.k_AA step of laminating at least 1 heat-resistant resin layer of the heat-resistant resin layers having a linear expansion coefficient of not more than k +20(k is the linear expansion coefficient of the heat-resistant insulating film), and a step of bonding the metal foil/heat-resistant resin layer laminate to the heat-resistant insulating film laminated with at least 1 heat-resistant resin layer as required and thermocompression bonding.

17. A method for producing a metal-clad laminate film comprising a heat-resistant insulating film and a metal foil laminated on at least one side of the heat-resistant insulating film via a heat-resistant resin layer, the method comprising laminating a metal-clad laminate film having a coefficient of linear expansion k on the heat-resistant insulating film_A(ppm/. degree. C.) k-10. ltoreq.k_AA step of laminating at least 1 heat-resistant resin layer of the heat-resistant resin layer having a linear expansion coefficient of not more than k +20(k is the linear expansion coefficient of the heat-resistant insulating film), and a step of bonding the heat-resistant insulating film/heat-resistant resin layer laminate to a metal foil laminated with at least 1 heat-resistant resin layer as required and thermocompression bonding.