JP2007130773A - Metal layer applied laminated film, wiring board using the film and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metal layer applied laminated film which prevents the disconnection caused by the sinking of wiring in a resin at the time of mounting of IC and enhanced in the adhesive strength of a heat-resistant resin layer, the metal foil and a heat-resistant insulating film, a wiring board using it and a semiconductor device enhanced in reliability. <P>SOLUTION: In the metal layer applied laminated film constituted so that the metal layer is provided on at least one side of the heat-resistant insulating film through the heat-resistant resin layer containing a polyimide resin, the heat-resistant resin layer is constituted of at least two layers, that is, the heat-resistant resin layer (A) on the contact side with the metal layer and the heat-resistant resin layer (B) on the contact side with the heat-resistant insulating film. The elastic modulus of the heat-resistant resin layer (A) at 300°C is 50 MPa or above and the heat-resistant resin layer (B) contains a polyimide resin having at least one kind of a functional group, which is selected from an hydroxy group, an amino group, a carboxyl group and a cyano group, in its side chain. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminated film with a metal layer. More particularly, the present invention relates to a laminated film with a metal layer for a flexible printed circuit board (FPC) widely used in the electronics industry and a method for manufacturing the same, and a tape automated method for mounting a semiconductor integrated circuit (IC). The present invention relates to a laminated film with a metal layer used for bonding (TAB), chip-on-film (COF) and the like, a semiconductor device using the same, and a method for producing the laminated film with a metal layer.

  In recent years, progress in downsizing and weight reduction of electronic devices has been accelerated. In semiconductor integrated circuits, high density and high performance have been advanced, and accordingly, FPCs are required to have finer and higher performance wiring patterns. COF systems capable of realizing pitches of 40 μm or less have become widespread. There is one. In the COF method, since the inner leads and the IC are directly formed on the heat-resistant insulating film, heat at the time of IC mounting is also applied to the heat-resistant insulating film. For this reason, in a “three-layer laminate” product in which a copper foil is bonded to a heat-resistant insulating film, which is a conventional FPC substrate, via an adhesive layer such as an epoxy resin, the wiring is placed in the adhesive layer during IC mounting. There are problems such as large sinking and disconnection. In addition, there is a problem in heat resistance such as decomposition of the adhesive layer itself.

  Therefore, as a FPC board for COF, “two-layer type” that does not use an adhesive is widely used, but “two-layer cast” in which a resin is coated on copper foil to form a heat-resistant insulating layer. Products are formed by coating a copper foil with a heat-resistant resin layer, so when the copper foil becomes thin, wrinkles and undulations enter the copper foil due to volume shrinkage and heat shrinkage during drying and curing, especially the thickness of the copper foil When the thickness is 12 μm or less, the operability is further deteriorated. In addition, in a “two-layer plating” product in which a conductive metal layer is formed on a heat-resistant insulating film such as a polyimide film by vacuum deposition, sputtering, ion plating, plating, or the like, the heat-resistant insulating film that is the base material Since a metal layer such as copper is directly formed thereon, there is a problem that the adhesiveness with the metal layer is low.

  On the other hand, as a "three-layer laminate" product, a metal foil such as copper foil is thermocompression bonded to an all-aromatic polyimide multilayer film in which a polyimide resin having a rigid structure is used as a core and a thermoplastic polyimide resin is laminated on the surface. A laminated FPC board has been proposed (see, for example, Patent Document 1). Since the adhesive layer is a polyimide resin, the adhesive layer is not decomposed by the heat at the time of IC mounting, but because it is a thermoplastic polyimide having a glass transition temperature, the wiring is large in the adhesive layer at the time of IC mounting. Problems remain, such as sinking and disconnection.

  There has been proposed an FPC board in which a thermoplastic polyimide using a diamine having a hydroxyl group or a carboxyl group as a diamine component is used as an adhesive layer (see, for example, Patent Document 2), but an adhesive made of a thermoplastic polyimide under a metal layer. Since there is an agent layer, there is a problem that the wiring is greatly submerged in the adhesive layer when the IC is mounted and the wire is disconnected.

In order to suppress the sinking of wiring during IC mounting, two adhesive layers are provided, an adhesive layer having an elastic modulus of 10 to 2000 MPa at 300 ° C. on the metal layer side, and a heat resistant insulating film side such as a polyimide film. A laminated film with a metal layer in which an adhesive layer having an elastic modulus at 300 ° C. of 0.1 to 100 MPa is proposed (see, for example, Patent Document 3). If the temperature of the bonding interface at the time of IC mounting is about 300 ° C., the sinking of the wiring into the adhesive layer has been improved. However, when the IC is mounted at 360 ° C., the adhesive layer is greatly deformed, such as undulation. Sinking occurs, causing problems such as disconnection. In order to obtain IC mounting productivity and reliability after bonding, it is necessary to mount at as high a temperature as possible. Metal that does not sink or break into the adhesive layer of wiring when mounted at 360 ° C There is a need for laminated films with layers.
JP-A-9-99518 (pages 2-7) JP 2002-363284 A (page 4-13) JP 2005-125688 A (pages 17-31)

  In view of such a situation, the object of the present invention is to prevent the wiring from sinking into the resin during IC mounting and disconnection, and furthermore, a metal layer having a high adhesive force between the heat-resistant resin layer, the metal foil, and the heat-resistant insulating film A laminated film, a wiring board using the laminated film, and a highly reliable semiconductor device.

  In order to solve the above problems, the present invention has the following configuration. That is, the present invention is a laminated film with a metal layer having a metal layer on at least one surface of a heat-resistant insulating film via a heat-resistant resin layer containing a polyimide resin, and the heat-resistant resin layer is at least a metal layer The heat-resistant resin layer (A) and the heat-resistant resin layer (B) on the side in contact with the heat-resistant insulating film are composed of two or more heat-resistant resin layers. ) At 300 ° C. and the heat-resistant resin layer (B) has at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group in the side chain. It is a laminated | multilayer film with a metal layer characterized by containing.

  According to the present invention, when the IC is mounted, the wiring does not sink into the resin and is not disconnected, and further, the laminated film with the metal layer having a high adhesive force between the heat resistant resin layer, the metal foil, and the heat resistant insulating film, and A wiring board using this can be obtained. Moreover, a highly reliable semiconductor device can be obtained by using the laminated film with a metal layer of the present invention.

  The laminated film with a metal layer of the present invention has a metal layer on at least one surface of a heat-resistant insulating film via a heat-resistant resin layer containing a polyimide resin.

  The polyimide resin refers to a polymer resin in which an imide ring or other cyclic structure is formed, and can be obtained from the precursor polyamic acid or its ester compound by heating or an appropriate catalyst. The polyimide resin of the present invention is preferably derived from at least a tetracarboxylic dianhydride component and a diamine component.

  In the present invention, the heat-resistant resin layer includes at least two heat-resistant resins including a heat-resistant resin layer (A) on the side in contact with the metal layer and a heat-resistant resin layer (B) on the side in contact with the heat-resistant insulating film. The heat resistant resin layer (A) and the heat resistant resin layer (B) may be the same or different in composition and / or characteristics. Further, between the heat-resistant resin layer (A) and the heat-resistant resin layer (B), the heat-resistant resin layer (A) and the heat-resistant resin layer (B) have the same or different composition and / or characteristics 1 There may be more than one heat-resistant resin layer. From the viewpoint of productivity and the like, the heat-resistant resin layer is more preferably two layers of a heat-resistant resin layer (A) and a heat-resistant resin layer (B).

  Next, the heat resistant resin layer (A) will be described. In the present invention, the elastic modulus at 300 ° C. of the heat resistant resin layer (A) is 50 MPa or more, and more preferably 100 MPa or more. By configuring the laminated film with a metal layer of the present invention as described above, the wiring does not sink into the resin even when the IC is mounted at a high temperature.

  Examples of the elastic modulus measurement method include a dynamic viscoelasticity measurement method (DMA method) and a wave propagation method. The measurement by the DMA method gives a sinusoidal deformation to the sample at a constant frequency, and can be performed in various measurement modes such as pulling, pushing, and twisting, and storage modulus, loss modulus, loss modulus / storage modulus. The tan δ expressed as a rate can be measured. In the present invention, the storage elastic modulus measured by the DMA method under conditions of a tensile mode, a frequency of 1 Hz, and a heating rate of 5 ° C./min is expressed as an elastic modulus.

  Furthermore, the glass transition temperature of the heat resistant resin layer (A) is preferably 250 ° C. or higher, and more preferably 280 ° C. or higher. If the glass transition temperature is 250 ° C. or higher, the bonding resistance during IC mounting will be better. Further, the linear expansion coefficient of the heat resistant resin layer (A) is preferably 5 to 25 ppm / ° C, and more preferably 10 to 18 ppm / ° C. When the linear expansion coefficient is 5 to 25 ppm / ° C., warpage in the state of the wiring substrate in which the wiring pattern is formed on the metal layer of the laminated film with the metal layer and in the state of the heat resistant resin laminated film in which the metal layer is completely removed Becomes smaller.

  Examples of the method for measuring the glass transition temperature of the heat-resistant resin layer include a measuring method using a differential scanning calorimeter (DSC method), a measuring method using a thermomechanical analyzer (TMA method), and a dynamic thermomechanical measurement. Examples thereof include a dynamic viscoelasticity measurement method (DMA method) using an apparatus. In the DMA method, the maximum value of tan δ is expressed as the glass transition temperature. In the present invention, a value measured by the DMA method under the conditions of a tensile mode, a frequency of 1 Hz, and a heating rate of 5 ° C./min is defined as a glass transition temperature.

The linear expansion coefficient includes a thermal expansion coefficient and a humidity expansion coefficient, and the linear expansion coefficient in the present invention refers to a thermal expansion coefficient. The linear expansion coefficient can be measured by a measurement method using a thermomechanical analyzer (TMA method), and linear expansion in all temperature ranges such as 30 ° C to 300 ° C, 50 ° C to 200 ° C, and 100 ° C to 300 ° C. The coefficient can be measured. The linear expansion coefficient in the present invention is an average linear expansion coefficient from the reference temperature to the measurement temperature, and is calculated from the calculation formula (1).
Average linear expansion coefficient = (1 / L) × [(Lt−L0) / (Tt−T0)] (1)
Here, T0: reference temperature, Tt: set temperature, L: sample length, L0: sample length at reference temperature, and Lt: sample length at set temperature.

  The linear expansion coefficient in the present invention is an average linear expansion coefficient from 30 ° C. to 300 ° C., and refers to a value measured by the TMA method under a temperature rising rate of 5 ° C./min.

  The linear expansion coefficient of the heat-resistant resin layer (A) of the present invention is preferably −5 to +5 ppm / ° C., preferably −2 to +2 ppm / ° C. with respect to the linear expansion coefficient of the heat-resistant insulating film. . By being in this range, the warp in the state of the heat resistant resin laminated film in which the metal layer of the laminated film with the metal layer is entirely removed is reduced. Since the linear expansion coefficient of the heat-resistant insulating film contributes to the dimensional change rate of the wiring board, it is preferably 5 to 27 ppm / ° C, more preferably 8 to 21 ppm / ° C.

  The measurement of the warpage is, for example, by cutting a laminated film with a metal layer and a heat-resistant resin laminated film from which the metal layer has been completely removed into a shape of 50 × 50 mm, placing this on a flat table, and The warp height can be measured and evaluated by the average value. In this evaluation method, the warp is preferably 5 mm or less, more preferably 2 mm or less.

  For the heat-resistant resin layer (A) of the present invention, polyimide resins having the following tetracarboxylic dianhydride residues and diamine residues are preferably used. The tetracarboxylic dianhydride residue includes at least one tetracarboxylic dianhydride selected from 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride, diamine The residue is preferably composed of at least one diamine selected from p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, and 3,4′-diaminodiphenyl ether. For the purpose of improving adhesiveness, a siloxane-based diamine residue represented by the general formula (3) may be copolymerized with the diamine residue. In this case, the content of the siloxane diamine residue represented by the general formula (3) is preferably 0.1 to 10 mol%, more preferably 0.5 to 7 mol%, based on the total diamine residues.

In formula, n shows the range of 1-30. R ² and R ³ may be the same or different and each represents a lower alkylene group having 1 to 30 carbon atoms or a phenylene group. R ^{4 to} R ⁷ may be the same or different and each represents a lower alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group.

  Specific examples of the siloxane diamine represented by the general formula (3) include 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3 -Tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1, 3,3-tetraphenyl-1,3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1, 5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis ( 4-aminobutyl) trisiloxane, 1 1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) ) Disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (4-aminobutyl) ) Disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5 -Bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5- Tetramethyl-3,3-dimethoxy-1,5 Bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5- Hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane, and the like, It is not limited to these. The siloxane diamines may be used alone or in combination of two or more.

  Next, the heat resistant resin layer (B) will be described. The heat resistant resin layer (B) contains a polyimide resin having at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group in the side chain. Such a polyimide resin has at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group on an acid dianhydride residue and / or a diamine residue which is a component of the polyimide resin. It has a polyimide resin. By using such a polyimide-based resin, a laminated film with a metal layer that does not cause sinking or disconnection of wiring into the resin even when bonded at an interface temperature of 360 ° C. during IC mounting is obtained, and bonding resistance is improved. .

  In the present invention, the diamine residue has a diamine having at least one functional group selected from one or more hydroxyl groups, carboxyl groups and cyano groups in the molecule and / or three or more amino groups in the molecule. A polyimide resin having a compound residue is preferred. Further, these residues are preferably 2 to 40 mol%, more preferably 4 to 25 mol%, based on all diamine residues. When the content of these residues is 2 mol% or more, the effect of improving the bonding resistance of the laminated film with a metal layer is larger, and when it is 40 mol% or less, the adhesiveness is good.

  Here, the adhesiveness of the laminated film with the metal layer can be measured by peeling off the metal layer. Examples of the method for measuring the adhesive force include a method in which a pattern having a line width of 2 mm is formed on a metal layer, and this is measured by pulling it up at a speed of 50 mm / min in a 90 ° direction. In the present invention, the peeling interface at the time of peeling is any of cohesive failure in the metal layer-heat resistant resin layer, the heat resistant insulating film-heat resistant resin layer, the heat resistant resin-heat resistant resin layer, or the heat resistant resin layer. It may become serious, or they may be combined and peeled off. At any peeling interface, the adhesive strength is preferably 8 N / cm or more, more preferably 10 N / cm or more.

  Examples of the diamine having at least one functional group selected from one or more hydroxyl groups, carboxyl groups, and cyano groups in the molecule and / or compounds having three or more amino groups in the molecule include those represented by the general formula (1) or A compound represented by the general formula (2) is preferable. Furthermore, the compound represented by General formula (2) is especially preferable from an adhesive point.

In the formula, each R ¹ may be the same or different and is selected from OH, COOH, NH ₂ and CN. m is an integer of 1 to 4, and k and l are integers of 0 to 4. However, k + l ≧ 1. X represents a single bond, O, CO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ or C (CF ₃ ) ₂ .

  Specific examples of the compound represented by the general formula (1) or the general formula (2) include 2,5-diaminophenol, 3,5-diaminophenol, 2,4-diaminophenol, 4,4′-dihydroxy- 3,3'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 4,4'-dihydroxy-3,3'-diaminodiphenyl ether, 3,3'-dihydroxy-4,4'- Diaminodiphenyl ether, 4,4'-dihydroxy-3,3'-diaminodiphenyldi (trifluoromethyl) methane, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4 '-Diaminodiphenylsulfone, 3,3'-dihydroxy-4,4'-diaminodiphenylmethylene, 3,3'-diaminobenzene Player's side, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,4-and di-aminobenzonitrile and the like. The above diamines may be used alone or in combination of two or more.

  In addition to this, melamine, 3,6-diaminonaphthalen-1-ol, 3,5,7-triaminonaphthalen-1-ol, 4,7-diaminonaphthalene-2, as long as the properties such as adhesiveness are not impaired. -Ol, 4,6-diaminonaphthalen-2-ol, 4,6,7-triaminonaphthalen-2-ol, 3,7-diaminoanthracen-2-ol, 3,6-diaminoanthracen-2-ol, Uses 3,6,7-triaminoanthracen-2-ol, naphthalene-1,3,6-triamine, naphthalene-1,3,5,7-tetraamine, anthracene-2,3,6,7-tetraamine, etc. You may do it.

  In the present invention, the diamine residue of the polyimide resin having at least one functional group selected from a hydroxyl group, amino group, carboxyl group, and cyano group in the side chain is represented by the general formula (3). It is preferable that 1 or more types of the residue of siloxane type diamine represented by these are copolymerized. As for content of the residue of the siloxane type diamine represented by General formula (3), 2-60 mol% is preferable in all the diamine residues, More preferably, it is 5-40 mol%. When the content of the diamine residue is 2 mol% or more, the effect of improving the adhesive strength is large, and when it is less than 60 mol%, the bonding resistance is good.

In formula, n shows the range of 1-30. R ² and R ³ may be the same or different and each represents a lower alkylene group having 1 to 30 carbon atoms or a phenylene group. R ^{4 to} R ⁷ may be the same or different and each represents a lower alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group.

  In addition to the diamine, an aliphatic diamine, an alicyclic diamine containing a cyclic hydrocarbon, an aromatic diamine containing an aromatic ring or an aromatic heterocyclic ring, or the like can be used in combination.

  Specific examples of the aliphatic diamine include 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, Examples include 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, and the like.

  Specific examples of alicyclic diamines containing cyclic hydrocarbons include 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), and 3,3′-methylenebis (cyclohexylamine). 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl and the like.

  Specific examples of the aromatic diamine containing an aromatic ring or an aromatic heterocyclic ring include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 2,4-diaminopyridine, 2,6-diaminopyridine, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 3,5-diaminobenzyl arylate, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 2,5-diaminotoluene, o-tolidine 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-bis (4-amino Phenoxy) biphenyl, diaminobenzanilide, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-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- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, etc. It is done. These diamines may be used alone or in combination of two or more.

  As the acid dianhydride component in the present invention, an alicyclic tetracarboxylic dianhydride containing a cyclic hydrocarbon, an aromatic tetracarboxylic dianhydride containing an aromatic ring or an aromatic heterocyclic ring, and the like can be used. .

  Specific examples of the alicyclic tetracarboxylic dianhydride containing a cyclic hydrocarbon include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexene tetracarboxylic dianhydride 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-C] furan-1,3-dione, but is not limited thereto.

  Specific examples of the aromatic tetracarboxylic dianhydride include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic acid Dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3 3,3 ', 4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-biphenyltrifluoropropanetetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid Acid dianhydride 3,4,9,10-peri Tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetra Carboxylic dianhydride, 3,3 ″, 4,4 ″ -paraterphenyl tetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -metaterphenyl tetracarboxylic dianhydride, 2,3, 6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, and the like. It is not limited to.

  The above tetracarboxylic dianhydrides can be used alone or in admixture of two or more. In view of heat resistance, it is preferable to use an aromatic tetracarboxylic dianhydride.

  The molecular weight of the polyimide resin used in the heat resistant resin layer (A) or (B) of the present invention is adjusted by making the acid dianhydride component or the diamine component equimolar, or by making either excessive. It can be carried out. Either the acid component or the diamine component may be excessive, and the polymer chain ends may be sealed with an end-capping agent such as an acid component or an amine component. A dicarboxylic acid or an anhydride thereof is preferably used as the terminal blocking agent for the acid component, and a monoamine is preferably used as the terminal blocking agent for the amine component. At this time, it is preferable that the acid equivalent of the acid component including the end-capping agent of the acid component or the amine component and the amine equivalent of the diamine component are equimolar.

  When the molar ratio is adjusted so that the acid dianhydride component is excessive or the diamine component is excessive, dicarboxylic acid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, aniline or its anhydride, monoamine is terminated. It may be added as a sealant.

  In the present invention, the molar ratio of the acid dianhydride component / diamine component of the polyimide resin is usually 100/100, but when the viscosity of the resin solution becomes too high, 100/100 to 95, or 100 to 95 / It is preferable to adjust by adjusting the molar balance of the acid dianhydride component / diamine component within the range of 100 so that the viscosity of the resin solution does not cause problems in coating properties and the like. However, if the molar balance is lost, the molecular weight of the resin decreases, the strength of the cured film decreases, and the adhesive strength with the metal layer and the heat-resistant insulating film tends to decrease, so the adhesive strength does not weaken. It is preferable to adjust the molar ratio within the range.

  In the present invention, polyamic acid, which is one of polyimide resin precursors, is synthesized by a known method. For example, it can synthesize | combine by selectively combining a tetracarboxylic dianhydride component and a diamine component, and making it react at 0-80 degreeC in a solvent by the said predetermined molar ratio. At this time, the monoamine, dicarboxylic acid or anhydride thereof for sealing the polymer chain end may be charged and reacted simultaneously with tetracarboxylic dianhydride or diamine, and tetracarboxylic dianhydride or diamine may be reacted. You may make it react and add after polymerizing and you may make it react.

  Examples of the solvent for polyamic acid synthesis include amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, β-propiolactone, γ-butyrolactone, Lactone polar solvents such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and others, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, methyl carbitol, ethyl carbitol And tall, diethylene glycol dimethyl ether (diglyme), and ethyl lactate. These may be used alone or in combination of two or more. As a density | concentration of a polyamic acid, 5 to 60 weight% is preferable normally, More preferably, it is 10 to 40 weight%.

  In the present invention, an organic solvent-soluble polyimide is also synthesized by a known method. For example, after synthesizing the polyamic acid by the above method, the polyamic acid can be converted to polyimide by reacting in a solvent at 140 to 240 ° C. as it is. At this time, you may remove the produced | generated water by adding nonpolar solvents, such as toluene and xylene, and making it azeotrope at 140-240 degreeC. After completion of the synthesis, a polyimide resin can be obtained by adding the reaction solution to water, methanol or the like while stirring and reprecipitation. Although the said solvent can be used as a solvent, Amide type | system | group polar solvents, such as N-methyl-2- pyrrolidone, N, N- dimethylacetamide, N, N- dimethylformamide, are preferable. The resulting polyimide resin is β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, A soluble polyimide resin solution is obtained by dissolving in methyl carbitol, ethyl carbitol, diethylene glycol dimethyl ether (diglyme), ethyl lactate or the like. As a density | concentration of a polyimide, 5 to 60 weight% is preferable normally, More preferably, it is 10 to 40 weight%.

  In the present invention, the heat resistant resin used in the heat resistant resin layer may contain other resins and fillers as long as the effects of the present invention are not impaired. Other resins include heat-resistant polymer resins such as acrylic resins, acrylonitrile resins, butadiene resins, urethane resins, polyester resins, polyamide resins, polyamideimide resins, epoxy resins, and phenol resins. Can be mentioned. Examples of the filler include organic or inorganic fine particles, fillers, and the like. Specific examples of the fine particles and filler include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, talc, mica, mica and the like.

  The heat-resistant insulating film used in the present invention needs to be an insulating film. As the level of heat resistance, the melting point is 280 ° C. or higher, preferably 300 ° C. or higher, more preferably 350 ° C. or higher, or the maximum allowable temperature for continuous use for a long time specified by JIS C4003 is 121 ° C. or higher, preferably What is necessary is just to satisfy the conditions at 150 degreeC or more, More preferably, the thing in 200 degreeC or more. If the value falls below the lower limit of the numerical range, the long-term heat-resistant reliability is inferior, which is not preferable.

  The material for the heat-resistant insulating film in the present invention is not particularly limited as long as the above-described conditions are satisfied, but a heat-resistant polymer is preferably used. Specifically, for example, aromatic polyimide resins, polyphenylene sulfide resins, aromatic polyamide resins, polyamideimide resins, aromatic polyester resins, and the like, Toray Dupont Co., Ltd. ) "Kapton" (registered trademark), Ube Industries, Ltd. "Upilex" (registered trademark), Kaneka Corporation "Apical" (registered trademark), Toray Industries, Inc. "Mikutron" (registered) Trademark), “Kexar” (registered trademark) manufactured by Kuraray Co., Ltd., and the like. Among these, aromatic polyimide resin “Kapton” (registered trademark) manufactured by Toray DuPont Co., Ltd., “Upilex” (registered trademark) manufactured by Ube Industries, Ltd., “Apical” manufactured by Kaneka Chemical Industry Co., Ltd. "(Registered trademark)" is particularly preferably used.

  Although the thickness of a heat resistant insulating film is not specifically limited, Preferably it is 3-150 micrometers, More preferably, it is 5-75 micrometers, Most preferably, it is 10-50 micrometers. If it is 3 μm or more, the support is sufficiently strong, and if it is less than 150 μm, it is flexible and can be easily bent.

  One side or both sides of the heat-resistant insulating film used in the present invention is preferably subjected to adhesion improving treatment according to the purpose.

  Adhesion improvement treatment includes a process of physically forming irregularities on the surface of the film by wet blasting or the like in which a liquid in which fine particles such as glass beads are dispersed in sandblast or water is sprayed on the film at high speed, a permanganic acid solution or There are discharge treatments such as treatment for forming irregularities on the film surface chemically with an alkaline solution, atmospheric pressure plasma treatment, corona discharge treatment, and low-temperature plasma treatment. In the present invention, it is preferable to perform the adhesion improving treatment by performing a discharge treatment such as a normal pressure plasma treatment, a corona discharge treatment, and a low temperature plasma treatment.

The atmospheric pressure plasma treatment is a method of performing a discharge treatment in an atmosphere of Ar, N ₂ , He, CO ₂ , CO, air, water vapor, or the like. The processing conditions vary depending on the processing apparatus, the type of processing gas, the flow rate, the frequency of the power source, etc., but the optimum conditions can be selected as appropriate.

The low-temperature plasma treatment can be performed under reduced pressure, and the method is not particularly limited. For example, the treatment is performed in an internal electrode type discharge treatment apparatus having a counter electrode composed of a drum electrode and a plurality of rod electrodes. A substrate is set, and the process gas is adjusted to 1 to 1000 Pa, preferably 5 to 100 Pa, and a discharge is performed by applying a DC or AC high voltage between the electrodes to generate plasma of the process gas, For example, a method of treating the surface of the substrate by exposing it to plasma is preferably used. The conditions for the low-temperature plasma processing vary depending on the processing apparatus, the type of processing gas, the pressure, the frequency of the power source, etc., but the optimum conditions can be selected as appropriate. As the type of processing gas, for example, Ar, N ₂ , He, CO ₂ , CO, air, water vapor, O ₂ , CF _{4 and the} like can be used alone or in combination.

  Corona discharge treatment can also be used, but when corona discharge treatment is used, the effect of improving adhesiveness may be small compared to low-temperature plasma treatment, so select a heat-resistant resin layer that is easy to adhere It is preferable.

  The metal layer of the present invention is formed from a metal foil such as a copper foil, an aluminum foil, or a SUS foil, and a copper foil is usually used. Copper foil includes electrolytic copper foil and rolled copper foil, and either can be used.

  A metal foil such as a copper foil may be subjected to a roughening treatment on the bonding surface side in order to improve adhesion with a resin or the like. Both surfaces of the copper foil are generally referred to as a glossy surface (S surface) and a mat surface (M surface), respectively. When a resin or the like is bonded, it is usually bonded to the M surface side. Therefore, the roughening treatment is usually performed on the M surface side in many cases. When a resin or the like is adhered to both surfaces of the copper foil, both the S surface and the M surface may be roughened. For example, in the case of copper foil, the roughening treatment is a step of forming irregularities on the surface by depositing 1-5 μm copper fine particles on one or both sides of the original foil formed by electrolytic plating by electrodeposition or the like. .

  As the FPC wiring pattern is miniaturized, the unevenness of the copper foil surface is preferably as small as possible not only on the S surface but also on the M surface. Copper foil is more preferable. As for the roughness of the copper foil surface, Ra (center line average roughness) on the S surface 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 It is 1.8 μm or less. Further, Ra is 0.7 μm or less on the M-plane, preferably 0.5 μm or less, more preferably 0.4 μm or less, and Rz is 3.0 μm or less, preferably 2.0 μm or less, more preferably 1.8 μm or less. It is.

  The film thickness of the copper foil is in the range of 1 to 150 μm, and can be used as appropriate according to the application. However, as the FPC wiring pattern is miniaturized, it is preferable that the film thickness of the copper foil is thinner. . However, as the copper foil becomes thinner, it becomes difficult to handle alone, and a copper foil having a thickness of 3 μm or 5 μm is handled as a copper foil with a carrier attached to a support (carrier) such as a resin or metal foil having a thickness of about 20 to 50 μm. The support is peeled off after being heat-pressed on a resin or the like. The thickness of the copper foil in the present invention is 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less.

  The copper foil may have a rust-proof surface for preventing discoloration and the like. Rust prevention treatment is generally performed by laminating a thin film layer of nickel, zinc, chromium compound or the like on the copper foil surface. Further, the surface of the copper foil may be further subjected to a silane coupling treatment in order to improve the adhesion with a resin or the like.

  The laminated film with a metal layer of the present invention comprises (1) a polyimide resin having at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group on a side chain on at least one side of a heat-resistant insulating film. A step of coating a heat-resistant resin contained therein to form a laminate of a heat-resistant insulating film / heat-resistant resin layer (B); (2) a heat-resistant resin having an elastic modulus at 300 ° C. of 50 MPa or more on a metal foil; Coating the metal foil / heat-resistant resin layer (A) to form a laminate, (3) the laminate obtained in the step (1), and the laminate obtained in the step (2). It can be obtained by a process of laminating the respective heat-resistant resin layers relative to each other, thermocompression bonding, and laminating.

  In this invention, the laminated film with a metal layer obtained at the process of (3) can further be heat-processed. By performing the heat treatment, the adhesive force at the adhesive interface can be further improved, and the residual stress generated at the adhesive interface can be reduced. Conditions such as the temperature of the heat treatment and the treatment time can be appropriately selected depending on the kind and / or composition of the heat-resistant resin layer, but it is preferable to treat in a nitrogen atmosphere for the purpose of preventing oxidation of the metal layer.

  In the present invention, the polyamic acid solution is applied to a metal foil or a heat-resistant insulating film in the steps (1) and (2), dried and then heat-treated to imidize, or an already imidized polyimide solution to a metal foil or It is applied to a heat-resistant insulating film, dried, and a heat-resistant resin layer made of a polyimide resin is laminated. In step (3), the heat-resistant resin layers are opposed to each other, laminated by thermocompression bonding, with a metal layer. A laminated film can be produced. Before heat-pressing in the step (3), each heat-resistant resin layer surface may be subjected to a surface treatment such as plasma treatment. Moreover, after thermocompression bonding, heat treatment may be performed at 200 to 400 ° C., preferably 250 to 350 ° C. as necessary, and it is preferable to raise the temperature stepwise to the target temperature.

  As a method for producing a laminated film with a metal layer of the present invention, a polyamic acid solution is applied to a metal foil or a heat-resistant insulating film and dried in the steps (1) and (2), and a heat-resistant resin layer is laminated on each. Before completely imidating the heat-resistant resin layer, the heat-resistant resin layers are bonded to each other in the step (3) and bonded together by thermocompression bonding, followed by heat treatment to remove the residual solvent contained in the heat-resistant resin layer. A method of producing a laminated film with a metal layer by removing and completely converting the polyamic acid into polyimide is more preferable. The heat treatment conditions are appropriately selected depending on the composition of the heat-resistant resin layer and the like, but are preferably 200 to 400 ° C., preferably 250 to 350 ° C., and the temperature is preferably raised stepwise to the target temperature.

  An example of the manufacturing method of the laminated | multilayer film with a metal layer of this invention is shown concretely.

  A polyamic acid resin solution, which is a precursor of a polyimide resin having an elastic modulus at 300 ° C. of 50 MPa or more, which becomes the heat resistant resin layer (A), is formed on at least one surface of the copper foil, and the film thickness after curing is 0.3 to It coats so that it may become 12 micrometers, and forms the laminated body of copper foil / polyamic-acid resin layer (A '). Examples of the coating method include a bar coater, roll coater, knife coater, comma coater, reverse coater, doctor blade float coater, and gravure coater. Drying during coating is continuous or intermittent at a temperature of 60 to 200 ° C. For 20 seconds to 60 minutes.

  Next, a polyamic acid resin solution that is a precursor of a polyimide resin having at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group in the side chain, which becomes the heat resistant resin layer (B). The polyimide film / polyamic acid resin layer (B ′) laminate is formed on at least one side of the polyimide film so that the film thickness after drying is 0.1 to 5 μm. As a coating method, the same method as the case where it coats on copper foil is mentioned. At this time, it is more preferable that the polyimide film film surface is plasma-treated for improving adhesiveness.

  The obtained copper foil / polyamic acid resin layer (A ′) laminate and the heat-resistant insulating film / polyamic acid resin layer (B ′) laminate were subjected to removal of adsorbed moisture, and then the polyamic acid resin layer (A ′). ) And the polyamic acid resin layer (B ′) are made to face each other and bonded by heating with a heated roll laminator.

  The roll of the heating roll laminator can be used in various combinations such as a metal roll-metal roll, a metal roll-rubber roll, and a rubber roll-rubber roll. Roll temperature is 100-240 degreeC, Preferably it is 120-200 degreeC. The roll may be heated only by one of the rolls, but preferably can be heated by both rolls. More preferably, both rolls can be heated, and the temperature can be controlled independently. The linear pressure when the roll is nipped is 1 to 80 N / mm, preferably 5 to 50 N / mm.

  The laminated film with a copper layer obtained by thermocompression bonding is further subjected to heat treatment at a temperature range of 200 to 400 ° C., preferably 220 to 350 ° C. for 1 to 48 hours, thereby removing the residual solvent in the heat resistant resin layer. Simultaneously with the removal, the polyamic acid resin is converted into a polyimide resin and is bonded more firmly. The heat treatment is preferably performed stepwise up to the target temperature in the above range, and is preferably performed in a vacuum or in a nitrogen atmosphere in order to prevent oxidation of the copper foil.

  In the heat treatment of the present invention, it is preferable to heat-treat the laminated film with copper foil in a roll manner, but the heat treatment may be continuously carried out in a roll-to-roll manner. Moreover, you may heat-process with a sheet | seat as a cut sheet.

  By the said manufacturing method, the copper film can obtain the laminated | multilayer film with a metal layer which adhere | attached the polyimide film with the two heat resistant resin layers of a heat resistant resin layer (A) and a heat resistant resin layer (B).

  In the present invention, the film thickness of the heat resistant resin layer (A) is 2 times or more, preferably 2.5 times or more, more preferably 3 times or more of the film thickness of the heat resistant resin layer (B). Moreover, it is 120 times or less, More preferably, it is 50 times or less, Furthermore, it is 20 times or less. When the film thickness of the heat resistant resin layer (A) is more than twice the film thickness of the heat resistant resin layer (B), the bonding resistance is improved.

  The film thickness of the entire heat resistant resin layer is 0.4 to 20 μm, preferably 1.5 to 14 μm. When the film thickness is 0.4 μm or more, the adhesion between the metal layer and the heat-resistant insulating film is good, and when it is 20 μm or less, the heat-resistant resin laminated film after the wiring pattern processing of the metal layer is warped. Hateful. At this time, the film thickness of the heat resistant resin layer (A) is 0.3 to 15 μm, preferably 1 to 10 μm, and the film thickness of the heat resistant resin layer (B) is 0.1 to 5 μm, preferably 0.5. ˜4 μm.

  By using the laminated film with a metal layer of the present invention to form a wiring pattern on the metal layer, the wiring board of the present invention used for a flexible printed circuit board (FPC board), a wiring board for COF, etc. can be produced. it can. The pitch of the wiring pattern is not particularly limited, but is preferably in the range of 10 to 150 μm, more preferably 15 to 100 μm, and still more preferably 20 to 80 μm.

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

  The laminated film with copper foil of the present invention is slit to a desired width. Next, after applying a photoresist film on the copper foil and forming a wiring pattern by mask exposure, the copper foil is wet-etched, and the remaining photoresist film is removed to form a copper wiring pattern. After 0.2 to 0.8 μm of tin is plated on the formed copper wiring pattern, a solder resist is applied on the wiring pattern to obtain a COF wiring board.

  The semiconductor device of the present invention can be obtained by bonding an IC having gold bumps formed on the inner leads of the COF wiring board obtained by the above method by flip chip mounting and sealing with resin.

  Here, as a mounting method of the IC, a metal bonding method in which wiring and IC bumps are gang-bonded, a wire bonding method in which the bonding portion of the IC and the inner lead of the COF tape are bonded by wire bonding, and conductive in the adhesive layer. There are an ACF method in which an adhesive film containing a filler is interposed and an NCP method in which bonding is performed using a non-conductive adhesive. ACF and NCP methods can be bonded at a relatively low temperature, but metal bonding methods, particularly gold-tin eutectic bonding methods are generally widely used from the viewpoint of connection reliability.

  In the bonding by the gold-tin eutectic, a load of 10 to 30 g is applied per bump in order to absorb the height variation between the bump on the IC side and the wiring on the wiring side. Also, in order for gold and tin to form a eutectic and to bond with high reliability, a temperature of 280 ° C. or higher is required at the bonding interface, so that the temperature of the bonding interface is generally 300 to 400 ° C. In addition, the tool temperature of the bonder is set to 380 to 500 ° C. A bonding time of 2 to 4 seconds is required for bonding at a bonding interface temperature of 300 ° C. with high reliability, but a bonding time of about 0.5 to 2 seconds is sufficient at a bonding interface temperature of 360 ° C. . Bonding at a bonding interface temperature of 360 ° C. is effective because it is necessary to shorten the bonding time in order to increase productivity. The laminated film with a metal layer of the present invention can be particularly suitably used for joining at such a high temperature.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Prior to describing the examples, methods for measuring adhesive strength, warpage, bonding resistance, elastic modulus, glass transition temperature, and linear expansion coefficient will be described.

(1) Adhesive strength A laminated film with copper foil was etched to a width of 2 mm with a ferric chloride solution, and the copper foil having a width of 2 mm was pulled with TOYO BOLDWIN "TENSIRON" UTM-4-100 at a pulling speed of 50 mm / min. Measured at 90 ° peel.

(2) Warpage The copper foil of the laminated film with copper foil was entirely etched with a ferric chloride solution. After cutting the sample into 50 mm × 50 mm, the sample was left for 24 hours under the condition of 25 ° C. and 50% RH, and then left on a flat plate, and the height of the four corners was measured. Value.

(3) Bonding resistance After applying a positive resist 300RH manufactured by Tokyo Ohka Co., Ltd. on the copper foil surface of the laminated film with copper foil so that the film thickness after drying becomes 4 μm, 60 μm P (wiring width: 30 μm / space: 30 μm) was exposed through a mask on which a bonding pattern was formed, and a bonding wiring pattern was formed on the resist film using a developer PMER P-1S manufactured by Tokyo Ohka Co., Ltd. Using this as a mask, the copper foil was etched with a ferric chloride solution and the resist film was removed with an alkaline aqueous solution to form a copper wiring pattern with a wiring width of 30 μm and a number of wirings of 400 bonding portions.

  Bonding uses flip chip bonder FC2000 manufactured by Toray Engineering Co., Ltd., stage temperature 80 ° C, load 80N, indentation time 3 seconds, tool temperature 380 ° C (bonding interface temperature: 300 ° C), stage temperature 80 ° C, load 80N, indentation With copper foil with a wiring pattern formed by aligning IC chips with 400 pins of gold bumps of height 15μm and 40 × 40μm □ under two conditions of time 1 second and tool temperature 450 ° C (bonding interface temperature: 360 ° C) Bonded to the laminated film. After removing the IC chip, the shape of the wiring at the junction was observed and evaluated using SEM.

(4) Elastic modulus, glass transition temperature After applying the polyamic acid resin solution to the glossy surface of an electrolytic copper foil having a thickness of 18 μm with a bar coater so as to have a predetermined thickness, it is 10 minutes at 80 ° C. and 10 minutes at 150 ° C. It was dried and further heat-cured by heating at 280 ° C. for 1 hour under a nitrogen atmosphere. Next, the entire surface of the electrolytic copper foil was etched with a ferric chloride solution to obtain a single film of a heat resistant resin layer.

This was cut into a predetermined shape, and using a DMS6100 manufactured by Seiko Instruments Inc., elastic modulus, glass transition temperature (tan δ) at a temperature range of room temperature to 350 ° C., vibration frequency of 1 Hz, heating rate of 5 ° C./min. Was measured.
(5) Linear expansion coefficient After applying the polyamic acid resin solution to the glossy surface of the electrolytic copper foil having a thickness of 18 μm with a bar coater so as to have a predetermined thickness, it is dried at 80 ° C. for 10 minutes and at 150 ° C. for 10 minutes, Furthermore, heat treatment was performed by heating at 280 ° C. for 1 hour in a nitrogen atmosphere. Next, the entire surface of the electrolytic copper foil was etched with a ferric chloride solution to obtain a single film of a heat resistant resin layer.

The obtained single membrane is cut into a shape having a specific width, and is formed into a cylindrical shape, and a temperature range of 30 to 300 ° C. using a thermomechanical analyzer SS-6100 (manufactured by Seiko Instruments Inc.). The measurement was performed at a temperature elevation rate of 5 ° C./min. The temperature was raised to 300 ° C., cooled to 30 ° C. or lower, and then again raised to 300 ° C. From the measurement result obtained for the second time, the average of 30 to 300 ° C. was calculated using the calculation formula (2). The linear expansion coefficient was calculated. Here, L30 is the sample length at 30 ° C., and L300 is the sample length at 300 ° C.
Average linear expansion coefficient = (1 / L30) × [(L300−L30) / (300−30)] (2)
The names of the abbreviations of acid dianhydride and diamine shown in the following production examples are as follows.
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride ODPA: 3,3', 4,4'-biphenyl ether tetracarboxylic dianhydride SiDA: 1,1,3,3-tetra Methyl-1,3-bis (3-aminopropyl) disiloxane DAE: 4,4′-diaminodiphenyl ether PDA: p-phenylenediamine APB: 1,3-bis (3-aminophenoxy) benzene BAHF: 4,4 ′ -Dihydroxy-3,3'-diaminodiphenyl (trifluoromethyl) methane ADPE: 4,4'-dihydroxy-3,3'-diaminodiphenyl ether DAB: 3,3'-diaminobenzidine MBAA: 3,3'-dicarboxy -4,4'-diaminodiphenylmethane DABZ: 3,5-diaminobenzoic acid DABN: 3,4-diaminobenzonitrile NM : N- methyl-2-pyrrolidone.

Production Example 1
In a reaction kettle equipped with a thermometer, a dry nitrogen inlet, a heating / cooling device with hot water / cooling water, and a stirring device, 50.1 g (0.25 mol) of DAE and 81.1 g (0.75 mol) of PDA were added. After charging and dissolving together with 2394 g of NMP, 291.3 g (0.99 mol) of BPDA was added and reacted at 50 ° C. for 6 hours to obtain a 15 wt% polyamic acid resin solution (PA1). The resin obtained by imidizing the polyamic acid resin solution (PA1) had an elastic modulus at 300 ° C. of 920 MPa, a glass transition temperature of 312 ° C., and a linear expansion coefficient of 14 ppm / ° C.

Production Examples 2-3
The same operation as in Production Example 1 was carried out except that the types and amounts of acid dianhydride and diamine were changed as shown in Table 1 to obtain a 15 wt% polyamic acid resin solution (PA2-3). Table 1 shows the elastic modulus, glass transition temperature, and linear expansion coefficient of a resin obtained by imidizing the polyamic acid resin solution (PA2 to 3) at 300 ° C.

Production Examples 4-17
The same operation as in Production Example 1 was carried out except that the types and amounts of acid dianhydride and diamine were changed as shown in Table 2 to obtain 15 wt% polyamic acid resin solutions (PB1 to 14).

Example 1
The polyamic acid resin solution PA1 was applied to an electrolytic copper foil having a thickness of 18 μm (TQ-VLP manufactured by Mitsui Kinzoku Co., Ltd.) with a reverse coater so that the film thickness after drying was 6 μm, and 1 minute at 80 ° C. Further, it was dried at 150 ° C. for 10 minutes to obtain a copper foil / polyamic acid resin layer laminate.

  Similarly, the polyamic acid resin solution PB1 is applied to a 38 μm-thick polyimide film (“Kapton” 150EN manufactured by Toray DuPont Co., Ltd.) that has been previously subjected to low-temperature plasma treatment in an argon atmosphere, and the film thickness after drying is 2 μm. Then, it was coated with a reverse coater and dried at 80 ° C. for 1 minute and further at 150 ° C. for 10 minutes to obtain a polyimide film / polyamic acid resin layer laminate.

  A roll laminator heated at a surface temperature of 180 ° C. so that the polyamic acid resin layers of the copper foil / polyamic acid resin layer laminate and the polyimide film / polyamic acid resin layer laminate produced above face each other. After bonding at a speed of 0.5 m / min, heating step cure [(80 ° C., 30 minutes) + (150 ° C., 1 hour) + (230 ° C., 3 hours)] + (320 ° C.) in a nitrogen atmosphere 2 hours)], and gradually cooled to room temperature to obtain a laminated film with a single-sided copper foil. Table 3 summarizes the evaluation results on the bonding resistance, warpage, and adhesive strength of the obtained laminated film with single-sided copper foil.

Examples 2-13
Except having changed the kind of polyimide film, copper foil, heat-resistant resin layer, and film thickness as shown in Table 3, the same operation as in Example 1 was performed to obtain a laminated film with a single-sided copper foil. Table 3 summarizes the evaluation results on the bonding resistance, warpage, and adhesive strength of the obtained laminated film with single-sided copper foil.

  The polyimide films used here are “Kapton” 100EN, “Kapton” 150EN manufactured by Toray DuPont Co., Ltd., “Upilex” 25S manufactured by Ube Industries, Ltd., and “Apical” 25 NPI manufactured by Kaneka Co., Ltd. . The copper foil is TQ-VLP, NA-VLP, NS-VLP manufactured by Mitsui Kinzoku Co., Ltd.

Comparative Examples 1-3
Except having changed the kind of polyimide film, copper foil, heat-resistant resin layer, and film thickness as shown in Table 3, the same operation as in Example 1 was performed to obtain a laminated film with a single-sided copper foil. Table 3 summarizes the evaluation results on the bonding resistance, warpage, and adhesive strength of the obtained laminated film with single-sided copper foil.

Comparative Example 4
Polyamide acid resin solution PB2 is dried on a 25 μm thick polyimide film (“Kapton” 100EN manufactured by Toray DuPont Co., Ltd.) that has been subjected to low-temperature plasma treatment in an argon atmosphere in advance so that the film thickness after drying becomes 3 μm. And then dried at 80 ° C. for 1 minute and further at 150 ° C. for 10 minutes to obtain a polyimide film / polyamic acid resin layer laminate.

  A 12 μm thick electrolytic copper foil (NA-VLP manufactured by Mitsui Kinzoku Co., Ltd.) is bonded to the polyamic acid resin layer side of the polyimide film / polyamic acid resin layer laminate produced above, and the surface temperature of the roll is 180 ° C. After laminating with a heated roll laminator at a linear pressure of 8 N / mm and a speed of 0.5 m / min, heating step cure [(80 ° C., 30 minutes) + (150 ° C., 1 hour) + (230 ° C.) under a nitrogen atmosphere 3 hours)] + (320 ° C., 2 hours)] and gradually cooled to room temperature to obtain a laminated film with a single-sided copper foil. Table 3 summarizes the evaluation results on the bonding resistance, warpage, and adhesive strength of the obtained laminated film with single-sided copper foil.

Comparative Examples 5-8
A laminated film with a single-sided copper foil was obtained in the same manner as in Comparative Example 4 except that the types and thicknesses of the polyimide film, copper foil and heat-resistant resin layer were changed as shown in Table 3. Table 3 summarizes the evaluation results on the bonding resistance, warpage, and adhesive strength of the obtained laminated film with single-sided copper foil.

Comparative Example 9
The polyamic acid resin solution PA1 was applied to an electrolytic copper foil having a thickness of 18 μm (TQ-VLP manufactured by Mitsui Kinzoku Co., Ltd.) with a reverse coater so that the film thickness after drying was 4 μm, and 1 minute at 80 ° C. Further, it was dried at 150 ° C. for 10 minutes to obtain a copper foil / polyamic acid resin layer laminate.

  A 25 μm-thick polyimide film (“Apical” manufactured by 25NPI Kaneka Corporation) that has been subjected to low-temperature plasma treatment in an argon atmosphere is attached to the polyamic acid resin layer side of the copper foil / polyamic acid resin layer laminate produced above. In addition, after laminating with a roll laminator heated to a roll surface temperature of 180 ° C. at a linear pressure of 8 N / mm and a speed of 0.5 m / min, heating step cure in a nitrogen atmosphere [(80 ° C., 30 minutes) + (150 [deg.] C., 1 hour) + (230 [deg.] C., 3 hours)] + (320 [deg.] C., 2 hours)] and gradually cooled to room temperature to obtain a laminated film with a single-sided copper foil. When the obtained laminated film with a single-sided copper foil was observed with an optical microscope from the polyimide film side, many voids having a size of about 20 to 200 μmφ were observed at the interface between the heat-resistant resin layer and the polyimide film. Table 3 summarizes the evaluation results for bonding resistance, warpage, and adhesive strength.

Comparative Example 10
A laminated film with a single-sided copper foil was obtained in the same manner as in Comparative Example 9 except that the types and thicknesses of the polyimide film, copper foil and heat-resistant resin layer were changed as shown in Table 3. When the obtained laminated film with a single-sided copper foil was observed with an optical microscope from the polyimide film side, many voids having a size of about 20 to 200 μmφ were observed at the interface between the heat-resistant resin layer and the polyimide film. Table 3 summarizes the evaluation results for bonding resistance, warpage, and adhesive strength.

  From the above results, the product of the present invention has good bonding resistance in IC mounting under a tool temperature of 450 ° C. (bonding interface temperature of 360 ° C.). Moreover, there was almost no curvature and a high adhesive force was obtained. On the other hand, in the comparative example, the heat resistance resin layer was deformed in the IC mounting, and the wiring was sunk, resulting in poor bonding resistance. In Comparative Examples 9 and 10, the bonding resistance was good, but there were many voids that were unbonded portions at the bonding interface, and only a low bonding force was obtained.

Example 14
A photoresist film was applied on the copper foil of the laminated film with copper foil obtained in Example 2 so that the film thickness after drying with a reverse coater was 4 μm, and 40 μm P (wiring width: 20 μm / space: 20 μm). After exposing through the mask in which the bonding pattern of this was formed and forming a wiring pattern with an alkali developing solution, the copper foil was wet-etched with the ferric chloride aqueous solution. The remaining photoresist film was removed to form a copper wiring pattern. After electroless plating of 0.4 μm of tin on the formed copper wiring pattern, a solder resist was applied on the wiring pattern to obtain a wiring board for COF. There was no warping of the obtained COF wiring board.

  A semiconductor chip on which gold bumps were formed was joined to the inner lead of the COF wiring board obtained by the above method by flip chip mounting and sealed with resin to obtain a semiconductor device. The semiconductor device obtained by the above method did not short-circuit the wiring, and high reliability was obtained.

Claims (9)

A laminated film with a metal layer having a metal layer on at least one side of a heat-resistant insulating film with a heat-resistant resin layer containing a polyimide resin, wherein the heat-resistant resin layer is at least on the side in contact with the metal layer The heat-resistant resin layer (A) is composed of two or more heat-resistant resin layers including the heat-resistant resin layer (B) on the side in contact with the heat-resistant insulating film. The elastic modulus is 50 MPa or more, and the heat-resistant resin layer (B) contains a polyimide resin having at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group in the side chain. A laminated film with a metal layer. The laminated layer with a metal layer according to claim 1, wherein the glass transition temperature of the heat resistant resin layer (A) is 250 ° C or higher, and the average linear expansion coefficient at 30 to 300 ° C is 5 to 25 ppm / ° C. the film. A polyimide resin having at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group and a cyano group in the side chain has at least an acid dianhydride residue and a diamine residue. Characterized in that it contains a residue of a diamine having at least one functional group selected from one or more hydroxyl groups, carboxyl groups and cyano groups in the molecule and / or a compound having three or more amino groups in the molecule. The laminated film with a metal layer according to claim 1. A polyimide resin having at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group in the side chain has at least one selected from one or more hydroxyl groups, carboxyl groups, and cyano groups in the molecule. The laminated film with a metal layer according to claim 3, wherein the diamine and / or the residue of the compound having 3 or more amino groups in the molecule is contained in an amount of 2 to 40 mol% in the total diamine residues. A diamine having at least one functional group selected from one or more hydroxyl groups, carboxyl groups and cyano groups in the molecule and / or a compound having three or more amino groups in the molecule is represented by the general formula (1) or It is at least 1 sort (s) represented by Formula (2), The laminated | multilayer film with a metal layer of Claim 3 characterized by the above-mentioned.

(In the formula, each R ¹ may be the same or different and is selected from OH, COOH, NH ₂ and CN. M is an integer of 1 to 4, k and l are integers of 0 to 4. However, k + 1 ≧ 1 X represents a single bond, O, CO, SO ₂ , CH ₂ , C (CH ₃ ) ₂ or C (CF ₃ ) ₂ A polyimide resin having at least one functional group selected from a hydroxyl group, an amino group, a carboxyl group, and a cyano group in the side chain has at least an acid dianhydride residue and a diamine residue. The metal-layered laminated film according to claim 3, wherein the residue of the siloxane-based diamine represented by (2) is contained in an amount of 2 to 60 mol% in all diamine residues.

(In the formula, n represents a range of 1 to 30. Moreover, R ² and R ³ may be the same or different and each represents a lower alkylene group or a phenylene group. R ^{4 to} R ⁷ are the same or And may be different and represents a lower alkyl group, a phenyl group or a phenoxy group.) A method for producing a laminated film with a metal layer in which a metal layer is laminated on at least one side of a heat-resistant insulating film via a heat-resistant resin layer, wherein (1) at least one side of the heat-resistant insulating film has a hydroxyl group on a side chain, A heat resistant resin containing a polyimide resin having at least one functional group selected from an amino group, a carboxyl group, and a cyano group is applied to form a laminate of a heat resistant insulating film / heat resistant resin layer (B). (2) A step of applying a heat-resistant resin having an elastic modulus at 300 ° C. of 50 MPa or more on a metal foil to form a metal foil / heat-resistant resin layer (A) laminate, (3) ( 2. The metal according to claim 1, further comprising the steps of laminating the laminate obtained in the step 1) and the respective heat-resistant resin layers of the laminate obtained in the step (2), and laminating them by thermocompression bonding. Multilayer fill with layers The method of production. The wiring board formed by pattern-forming the metal layer of the laminated | multilayer film with a metal layer in any one of Claims 1-6. A semiconductor device using the wiring board according to claim 8.