JP2008188893A - Laminate film with metal layer, and flexible circuit board and semiconductor device using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate film with a metal layer which comprises a heat-resistant resin layer and a metal layer, causes less camber and is high-quality with fewer appearance defects, e.g. tack marks and abnormal protrusions. <P>SOLUTION: The laminate film with a metal layer has a metal layer 1 on one side of a laminate of two or more heat-resistant-resin layer 2 and 3. The outermost heat-resistant resin layer A with no contact with the metal layer contains a heat-resistant resin and a filler, and the filler has a median diameter of 0.1-7 μm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  In recent years, progress in downsizing and weight reduction of electronic devices has been accelerated. Also in semiconductor integrated circuits, higher density and higher performance are progressing, and accordingly, miniaturization and higher performance of wiring patterns are also required for FPC.

  As the substrate for FPC, a laminated film with a single-sided metal layer in which a metal layer such as copper foil is laminated on one side, and a laminated substrate with a double-sided metal layer in which metal layers are laminated on both sides are used. In a laminated substrate with a double-sided metal layer, since it generally has a symmetric configuration with respect to the thickness direction, even when the metal layer is entirely removed, the substrate is less likely to warp, but in a laminated film with a single-sided metal layer, Since the structure is asymmetric with respect to the thickness direction, the substrate is likely to warp, particularly when the entire metal layer is removed.

  In recent years, as a substrate for FPC, due to demands for high heat resistance and dimensional stability, a “two-layer product” such as a cast type in which a polyimide resin is coated and laminated on a copper foil or a laminate type using a polyimide-based adhesive is used. Is often used. In these “two-layer products” laminated films with a single-sided metal layer, there is a problem that warpage is further increased.

  In order to reduce warpage, a cast-type laminated film with a single-sided metal layer (for example, a patent) in which three layers of polyimide layers are coated and laminated on a copper foil in the order of high thermal expansion polyimide, low thermal expansion polyimide, and high thermal expansion polyimide. Reference 1), a laminate-type laminated film with a single-sided metal layer, in which a metal foil is laminated on one side of a polyimide film via a thermoplastic polyimide, and a polyimide layer is laminated on the other side to prevent warping (For example, refer to Patent Documents 2 and 3).

Although it is possible to improve the warp by using these methods, in the manufacturing process, after applying and laminating a polyamic acid resin solution, which is a precursor of polyimide, and then thermocompression bonding and / or imidization of the metal foil In order to prevent the warpage in the heat treatment step, the polyimide layer laminated for the purpose of preventing warpage remains tacky marks that are considered to have been peeled off after heat sealing (tacking), resulting in a problem of appearance defects.
JP-A-1-245586 (page 2-9) JP-A-9-148695 (page 2-6) JP 2005-186274 A (page 3-12)

  In view of such circumstances, the object of the present invention is to provide a high-quality metal layer with a small warp and less appearance defects such as tack marks and abnormal protrusions in a laminated film with a metal layer having a metal layer on one side of a heat-resistant resin layer. It is to provide a laminated film, and to provide a flexible circuit board and a semiconductor device using the laminated film.

  That is, the present invention is a laminated film with a metal layer having a metal layer on one side of two or more heat resistant resin layers, and the outermost heat resistant resin layer A on the side not in contact with the metal layer is at least heat resistant. A laminated film with a metal layer, comprising a resin and a filler, wherein the filler has a median diameter of 0.1 to 7 μm.

  According to the present invention, in a laminated film with a metal layer having a metal layer on one side of a heat-resistant resin layer, a high-quality laminated film with a metal layer having a small warp and less appearance defects such as tack marks and abnormal protrusions is obtained. Can do. Furthermore, by using the laminated film with a metal layer of the present invention, it is possible to provide a high-quality flexible circuit board and a semiconductor device with few appearance defects.

  The laminated film with a metal layer of the present invention is obtained by laminating a metal layer on one side of two or more heat resistant resin layers, and the outermost heat resistant resin layer A on the side not in contact with the metal layer is at least heat resistant. And a filler having a median diameter of 0.1 to 7 μm. With such a configuration, it is possible to obtain a high-quality laminated film with a metal layer that is less warped and has few appearance defects such as tack marks and abnormal protrusions generated in the production process of the laminated film with a metal layer, particularly a heat treatment step.

  The tack mark refers to a mark in which a heat resistant resin layer or the like is attached to the surface of the metal layer or the heat resistant resin layer. For example, when heat-treated in a state where the laminated film with the metal layer is wound, the outermost heat-resistant resin layer not in contact with the metal layer is partially weakly bonded to the inner or outer peripheral metal layer surface, When the laminated film with the metal layer is unwound, the heat resistant resin that is weakly adhered to the surface of the metal layer partially remains. Further, the abnormal protrusion refers to a protrusion having a size of 50 μmφ or more. For example, it is formed by aggregation of fillers.

  In the present invention, it has been found that the generation of tack marks can be suppressed by adding a filler to the outermost heat-resistant resin layer A that is not in contact with the metal layer among the two or more heat-resistant resin layers. It was. The lower limit of the particle diameter (median diameter) of the filler is 0.1 μm, preferably 1.5 μm or more. Moreover, an upper limit is 7 micrometers, Preferably it is 3 micrometers or less. If the median diameter of the filler is less than 0.1 μm, it becomes difficult to disperse the filler in the heat-resistant resin, and a special dispersion step is required, resulting in poor productivity. Moreover, stability after dispersion | distribution worsens and many abnormal protrusions by aggregation of a filler generate | occur | produce. On the other hand, if the median diameter of the filler exceeds 7 μm, the filler in the heat-resistant resin solution easily settles, resulting in poor coating properties and a large number of abnormal protrusions. In the present invention, by setting the median diameter of the filler to 0.1 μm to 7 μm, a laminated film with a metal layer with few appearance defects such as tack marks and abnormal protrusions can be produced with high productivity.

  In the present invention, the median diameter of the filler contained in the heat resistant resin layer A is obtained by cutting the heat resistant resin layer A into an ultrathin film and directly observing the particle diameter at a magnification of 100,000 to 200,000 times by TEM. (Observation with a transmission electron microscope by ultra-thin film section method). The obtained TEM photograph is analyzed using image analysis software to determine the particle size distribution, and the particle diameter (median diameter) at which the relative particle amount distribution is 50% is calculated. The filler has a spherical shape, a needle shape, a plate shape, or the like. Here, the analysis is performed assuming a spherical shape.

  Moreover, the median diameter of a filler can also be measured in the state of the resin solution which forms the heat resistant resin layer A. In this case, a laser diffraction / scattering method is used in which a particle group is irradiated with laser light, a particle size distribution is obtained by calculation from an intensity distribution pattern of diffraction / scattered light emitted therefrom, and a median diameter is calculated. In this invention, the filler containing resin solution to measure is diluted and adjusted so that it may become a density | concentration of 0.01 to 10 weight%, and it measures on a volume basis using a laser diffraction type particle size distribution measuring apparatus.

  Examples of the filler that can be used in the present invention include organic or inorganic fine particles. Specific examples thereof include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica, and talc. These can be used, and these can be used alone or in combination of two or more.

  In the present invention, the filler content in the heat-resistant resin layer A is preferably 0.1% by weight or more, and more preferably 0.6% by weight or more. Moreover, 10 weight% or less is preferable and 7 weight% or less is more preferable. When the content of the filler is in the above range, the occurrence of tack marks and abnormal protrusions on the surface of the heat resistant resin layer is further suppressed, and a laminated film with a metal layer having excellent appearance quality can be obtained.

  The heat resistant resin layer constituting the laminated film with a metal layer of the present invention includes an acrylic resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a polyetherimide resin, a polyethersulfone resin, and a polysulfone resin. Etc. can be used alone or in combination of two or more. In the present invention, a polyimide resin is preferably used from the viewpoint of heat resistance, insulation reliability, and adhesiveness.

  As a metal layer used for the laminated film with a metal layer of the present invention, a metal foil such as a copper foil, an aluminum foil, and a SUS foil can be exemplified, and a copper foil is usually used. Copper foil includes electrolytic copper foil and rolled copper foil, and either can be used. The film thickness of the copper foil is 1 to 50 μm, preferably 3 to 20 μm. The surface of the copper foil may be rust-prevented to prevent discoloration or 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. Moreover, in order to improve adhesiveness with a heat resistant resin layer etc., the adhesion surface side may be roughened, and silane coupling treatment may be applied.

  The laminated film with a metal layer of the present invention is a production method in which a heat resistant resin layer is directly applied to a metal foil such as a copper foil and laminated, or a metal such as a copper foil via a heat resistant resin layer. It can be obtained by a production method in which a foil is laminated by thermocompression bonding.

  First, as a first embodiment, a laminated film with a metal layer obtained by directly coating and laminating a heat resistant resin layer on a metal foil will be described with reference to FIG. Usually, a heat resistant resin layer B2 having a linear expansion coefficient kB of 20 ppm / ° C. or less, preferably 5 to 18 ppm / ° C. is laminated on a metal foil 1 such as a copper foil. When the linear expansion coefficient kB is in the above range, the difference in the linear expansion coefficient from the metal layer is small, so that the warp of the laminated film with the metal layer can be reduced, which is preferable. However, when a heat-resistant resin having a linear expansion coefficient of 20 ppm / ° C. or less is applied and dried to laminate the heat-resistant resin layer B, a gradient tends to occur in the linear expansion coefficient in the film thickness direction in the heat-resistant resin layer B. There is a tendency that the coefficient of linear expansion is relatively large at a portion close to the metal foil side. For this reason, warp is likely to occur in the film after removing the copper foil or the circuit board on which the copper wiring pattern is formed. The warpage is suppressed by laminating a heat resistant resin layer A3 having a linear expansion coefficient kA larger than the linear expansion coefficient kB of the heat resistant resin layer B on the surface opposite to the surface on which the metal layer is laminated. Can do. As a manufacturing method of the said laminated film with a metal layer, the manufacturing method which coats and laminates the heat resistant resin layer B and the heat resistant resin layer A in order on metal foil is preferable.

  The linear expansion coefficient kA of the heat resistant resin layer A is preferably larger than kB, preferably 20 ppm / ° C. or more, 100 ppm / ° C. or less, more preferably 70 ppm / ° C. or less. If it is this range, the curvature of the laminated film with a metal layer and the laminated film after metal layer removal can be made smaller.

  The linear expansion coefficient includes a thermal expansion coefficient and a humidity expansion coefficient, and the linear expansion coefficient in the present invention is a thermal expansion coefficient. The linear expansion coefficient can be measured by a measurement method (TMA method) using a thermomechanical analyzer.

  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. In the present invention, the linear expansion coefficient up to 200 ° C. is measured with a reference temperature of 30 ° C.

  The glass transition temperature of the heat resistant resin layer A is 200 ° C. or higher, preferably 300 ° C. or higher. If it is this range, the prevention effect of a tack trace can be made higher.

  The glass transition temperature of the heat-resistant resin layer in the present invention refers to that measured by a measuring method using a differential scanning calorimeter (DSC method) at a temperature rising rate of 20 ° C./min.

  The heat resistant resin layer A includes at least a heat resistant resin and a filler. Examples of the heat resistant resin include a polyimide resin, a polyphenylene sulfide resin, a polyamide resin, a polyamideimide resin, a polyester resin, an epoxy resin, A mixture of resins selected from two or more of these can be used, and polyimide resins are particularly preferred from the viewpoint of heat resistance. As the polyimide resin, those capable of obtaining the linear expansion coefficient and the glass transition temperature are preferable. Specifically, pyromellitic dianhydride, aromatic tetracarboxylic dianhydride selected from at least one selected from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, p-phenylenediamine, A polyimide resin synthesized from an aromatic diamine selected from at least one of 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, and 2,2′-dimethylbenzidine can be preferably used, and more preferably, It is a polyimide resin synthesized from merit acid dianhydride and 4,4′-diaminodiphenyl ether.

  The heat resistant resin layer B is preferably a heat resistant resin made of a polyimide resin, a polyphenylene sulfide resin, a polyamide resin, a polyamideimide resin, a polyester resin, or the like, and particularly preferably a polyimide resin. Examples of the polyimide resin include pyromellitic dianhydride, aromatic tetracarboxylic dianhydride selected from at least one selected from 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, p-phenylenediamine, An aromatic polyimide resin synthesized from an aromatic diamine selected from at least one of 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, and 2,2′-dimethylbenzidine is preferable.

  Furthermore, for the purpose of improving the adhesion between the metal layer and the heat resistant resin layer B, a heat resistant resin layer may be further provided between the metal layer and the heat resistant resin layer B.

  Next, as a 2nd aspect, the laminated film with a metal layer obtained by heat-pressing a metal layer to a heat resistant resin film through a heat resistant resin layer is demonstrated using FIG. The heat resistant resin film has a self-holding property, and usually a heat resistant insulating film is preferably used. A heat-resistant resin layer C4 having adhesiveness is laminated on the heat-resistant resin layer B (heat-resistant resin film) 2, and a metal layer such as a copper foil is thermocompression bonded via the heat-resistant resin layer C. Since the heat resistant resin layer C functions as an adhesive layer, adhesion to the metal layer and the heat resistant resin layer B is required.

  Examples of the heat resistant resin layer A used in the second aspect include those described in the first aspect.

  The heat-resistant insulating film used as the heat-resistant resin layer B in the second embodiment is made of an aromatic polyimide resin, a polyphenylene sulfide resin, an aromatic polyamide resin, a polyamideimide resin, an aromatic polyester resin, or the like. A heat-resistant insulating film is mentioned, and a polyimide film made of an aromatic polyimide resin is particularly preferable. Specific products of polyimide film include “Kapton” (registered trademark) manufactured by Toray DuPont Co., Ltd., “Upilex” (registered trademark) manufactured by Ube Industries, Ltd., and “Apical” (registered trademark) manufactured by Kaneka Corporation. ) And the like.

  Although the thickness of a heat resistant insulating film is not specifically limited, From a viewpoint of the intensity | strength as a support body, Preferably it is 3 micrometers or more, More preferably, it is 5 micrometers or more, More preferably, it is 10 micrometers or more. Further, from the viewpoint of flexibility, it is preferably 150 μm or less, more preferably 75 μm or less, and further preferably 50 μm or less.

  The linear expansion coefficient kB at 30 to 200 ° C. of the heat resistant insulating film is preferably 20 ppm / ° C. or less, more preferably 5 to 18 ppm / ° C. As a polyimide film having such a linear expansion coefficient, at least one tetracarboxylic dianhydride selected from pyromellitic dianhydride and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, A polyimide film made of a polyimide resin obtained from a diamine selected from at least one of p-phenylenediamine and 4,4′-diaminodiphenyl ether is preferable. Examples of such polyimide films include “Kapton” (registered trademark) EN type, “Upilex” (registered trademark) S type, and “Apical” (registered trademark) NPI type. “Kapton” (registered trademark) EN type is particularly preferably used from the viewpoint of adhesiveness, dimensional stability and the like.

  One side or both sides of the heat-resistant insulating film may be subjected to adhesion improving treatment according to the purpose. As the adhesion improving treatment, a discharge treatment such as a normal pressure plasma treatment, a corona discharge treatment, a low temperature plasma treatment or the like is preferable.

  For the heat-resistant resin layer C, a heat-resistant resin having thermosetting and / or thermoplasticity can be used, and it is particularly preferable to use a heat-resistant resin having thermoplasticity. As the heat resistant resin, an acrylic resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a polyetherimide resin, a polyethersulfone resin, a polysulfone resin, or the like can be used alone or in combination. In the present invention, a polyimide resin is preferably used from the viewpoint of heat resistance, insulation reliability, and adhesiveness.

  The composition of the polyimide resin used for the heat resistant resin layer C can be arbitrarily selected as long as it satisfies properties such as adhesiveness. The polyimide resin is a polymer resin in which an imide ring or other cyclic structure is formed by heating a precursor polyamic acid or an ester compound thereof or by an appropriate catalyst. The polyimide resin can be polymerized from tetracarboxylic dianhydride and diamine.

  Examples of the tetracarboxylic dianhydride that can be preferably used in the present invention include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-. Biphenyltetracarboxylic dianhydride, 2,2 ′, 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"- Paraterphenyl tetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -metaterphenyl tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2, 7,8-phenanthrenetetracarboxylic dianhydride, , 3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl Trifluoropropanetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfonetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2 , 3,4-siku Butanetetracarboxylic 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 and the like may be mentioned, and these may be used alone or in combination of two or more.

  Examples of the diamine that can be preferably used in the present invention include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 2-methoxy-1,4-phenylenediamine, 4,4′-diaminobenzanilide, 3,4′-diaminobenzanilide, 3,3′-diaminobenzanilide, 3,3′-dimethyl-4,4′- Diaminobenzanilide, benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethylmethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine, 1,5-diamino Naphthalene, 2,7-diaminofluorene, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 3,3'-methylenebis (cyclohexylamine), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'- Dimethyldicyclohexyl, p-aminobenzylamine, m-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3, 3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4, 4'-diaminobenzophenone, 3,3'-dimethyl -4,4'-diaminodiphenylmethane, 4,4'-bis (4-aminophenoxy) biphenyl, 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, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3- Aminophenyl) fluorene and the like. These may be used alone or in combination of two or more.

  In this invention, high adhesion | attachment with a metal layer and / or a heat resistant insulating film can be obtained by using together with the said diamine and using the siloxane type diamine represented by General formula (1). The content of the siloxane-based diamine is 0.1 mol% or more, preferably 0.5 mol% or more, more preferably 1 mol% or more, preferably 80 mol% or less, more preferably 60 mol%, based on the total diamine component. The mol% or less, more preferably 50 mol% or less. By containing the siloxane-based diamine in the above range, high adhesive strength can be obtained, and the glass transition temperature of the polyimide resin becomes a preferable range.

However, n of General formula (1) shows the integer of 1-30. R ¹ and R ² may be the same or different and each represents an alkylene group having 1 to 30 carbon atoms or a phenylene group. R ^{3 to} R ⁶ may be the same or different and each represents an alkyl group having 1 to 30 carbon atoms, a phenyl group, or a phenoxy group.

  When the long-chain siloxane diamine represented by the general formula (1) is used, the reactivity becomes poor, and the polymerization degree of the polymer tends to be low. For this reason, from the viewpoint that the degree of polymerization of the polymer is within an appropriate range and a resin layer having high heat resistance can be obtained, n in the general formula (1) is preferably 15 or less, and more preferably 5 or less.

  Specific examples of the siloxane diamine represented by the general formula (1) 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- Examples include hexaethyl-1,5-bis (3-aminopropyl) trisiloxane and 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane. The siloxane diamine may be used alone or in combination of two or more.

  The glass transition temperature of the heat resistant resin layer C is 150 ° C. or higher, preferably 200 ° C. or higher, more preferably 240 ° C. or higher, preferably 380 ° C. or lower, more preferably 320 ° C. or lower, more preferably 280 ° C. or lower. . When the glass transition temperature of the heat-resistant resin layer C is in the above range, the production efficiency in the thermocompression bonding process is good, and the adhesion to the metal layer and / or the heat-resistant resin layer A is good.

  In the present invention, the heat resistant resin layer C 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, mica and talc.

  Next, the manufacturing method of the polyimide resin composition preferably used for the heat resistant resin layer in this invention is demonstrated.

  The polyimide resin or the polyamic acid resin that is a precursor thereof can be synthesized by a known method. For example, it can synthesize | combine by selectively combining tetracarboxylic dianhydride and diamine, stirring at 0-80 degreeC in a solvent for 1 to 100 hours, and making it react. It is preferable to synthesize at a molar ratio of excess acid or excess diamine so that the viscosity characteristics of the resin composition and the properties such as adhesion of the resulting laminated film with a metal layer become desired characteristics. In order to seal the end of the polymer chain, dicarboxylic acid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, aniline or its anhydride, and monoamine are charged simultaneously with tetracarboxylic dianhydride and diamine. Alternatively, tetracarboxylic dianhydride and diamine may be reacted and added after polymerization to 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%.

  When obtaining a polyimide resin, the polyamic acid resin solution synthesize | combined above is raised to the temperature of 120-300 degreeC, is stirred for 1 to 100 hours, and is converted into a polyimide. Also, at room temperature to 200 ° C., an imidation catalyst such as acetic anhydride, trifluoroacetic anhydride, p-hydroxyphenylacetic acid, pyridine, picoline, imidazole, quinoline, triethylamine or the like is added alone or in combination of two or more, and polyimide Can also be converted. The content of the imidization catalyst is preferably 1% by weight or more, and more preferably 3% by weight or more based on the polyamic acid resin in the polyamic acid resin composition. Moreover, 20 weight% or less is preferable and 10 weight% or less is more preferable. If content of an imidation catalyst is the said range, imidation temperature can be made low and the storage stability of a polyamic-acid resin composition is also good.

  In the present invention, the imidation catalyst is added to the polyamic acid resin solution to form a heat-resistant resin precursor layer, and then converted to polyimide simultaneously with drying of the solvent to form a heat-resistant resin layer. Alternatively, the heat resistant resin layer may be formed using an organic solvent-soluble polyimide resin.

  Next, a method for producing a laminated film with a metal layer in which the heat resistant resin layer B and the heat resistant resin layer A are coated and laminated in this order on the metal layer will be described with specific examples.

  A polyamic acid resin composition, which is a precursor of a polyimide resin having a linear expansion coefficient kB of 20 ppm / ° C. or less on one side of a roll-shaped copper foil, has a film thickness after drying / curing of 5 to 100 μm, preferably 7 to A polyamic acid resin composition which is a polyimide resin precursor having a linear expansion coefficient kA larger than the linear expansion coefficient kB of the heat resistant resin layer B, which is continuously applied and dried so as to have a thickness of 50 μm. Is dried and cured so that the thickness after drying and curing is 0.1 to 20 μm, preferably 0.5 to 10 μm, and the laminate is wound up.

  The ratio of the film thickness of the heat-resistant resin layer B and the heat-resistant resin layer A is appropriately determined within the range in which the laminated film with the metal layer and the laminated film after removing the metal layer do not warp depending on the composition and physical properties of the polyimide resin. You can choose.

  Examples of the coating method include a bar coater, a roll coater, a knife coater, a comma coater, a reverse coater, a doctor blade float coater, a gravure coater, and a slit coater. Drying is performed continuously at a temperature of about 60 to 200 ° C. The solvent of the polyamic acid resin composition coated on the copper foil is removed intermittently by heating for 1 to 60 minutes.

  Next, the obtained laminate is re-rolled with a gap that does not wind in the heat treatment step, and heat-treated at a temperature range of 250 to 500 ° C, preferably 300 to 400 ° C for 1 to 48 hours. The polyamic acid resin of the conductive resin layer is converted into a polyimide resin to obtain a laminated film with copper foil. The heat treatment step in the present invention may be raised stepwise up to the target temperature in the above range.

  When the heat-resistant resin layer A does not contain a filler, the heat-resistant resin layer B adheres weakly to the adjacent copper foil surface in the heat treatment step. And / or the trace (tack trace) which the heat-resistant resin layer etc. adhered on the surface of the heat-resistant resin layer A remains, resulting in poor appearance. In the present invention, since the heat-resistant resin layer A contains a filler, the above-mentioned tack marks are less likely to remain, and since the median diameter of the filler is in an appropriate range, there are few abnormal protrusions, A high-quality laminated film with a metal layer with few appearance defects can be obtained.

  Next, a metal in which a heat-resistant resin layer C and a heat-resistant resin layer A are respectively laminated on both surfaces of a heat-resistant resin layer B made of a polyimide film, and a metal layer is laminated on the heat-resistant resin layer C by thermocompression bonding. A method for producing a laminated film with a layer will be described with specific examples.

  As a heat resistant resin layer A, one side of a roll-shaped heat resistant insulating film (for example, polyimide film) having a linear expansion coefficient kB of 20 ppm / ° C. or less, which has been subjected to adhesion improvement treatment such as low temperature plasma treatment in advance, is made of polyimide resin. A polyamic acid resin as a precursor and a composition containing a filler are continuously applied and dried so that the film thickness after drying and curing is 0.2 to 20 μm, and further, a heat resistant insulating film On the other side, a polyamic acid resin composition, which is a precursor of an adhesive thermoplastic polyimide resin, as a heat-resistant resin layer C, has a thickness after drying and curing of 0.2 to 20 μm. The heat resistant resin laminated film is wound up by applying and drying continuously.

  Examples of the coating method include a bar coater, a roll coater, a knife coater, a comma coater, a reverse coater, a doctor blade float coater, a gravure coater, and a slit coater, and drying is performed continuously at a temperature of about 60 to 240 ° C. Heat intermittently for 1-60 minutes to remove the solvent.

  Next, a metal foil such as a copper foil is bonded to the heat-resistant resin layer C, and heat-pressed using a hot press, a heated roll laminator, or the like to produce a laminated film with a metal layer. In the present invention, a heated roll laminator (FIG. 3) capable of continuously heat-pressing a metal foil can be preferably used from the viewpoint of productivity.

  When the heat-resistant resin layer A and / or C is heat-pressed with a metal foil in the state of a polyamic acid resin, if the temperature of the laminator heating rolls 11 and 12 is too high, foaming occurs in water generated by imidization. Therefore, the temperature of the heating rolls 11 and 12 is 100-230 degreeC, Preferably it is 150-200 degreeC. The nip pressure of the heating rolls 11 and 12 is 1 to 70 N / mm, preferably 3 to 30 N / mm, as a linear pressure. The copper foil is unwound 13 and the heat-resistant resin laminated film is unwound from the unwinding 14, and is heat-pressed by the heating rolls 11 and 12, and the resulting laminated film with a metal layer is wound up by the winding 15. .

  Next, the obtained laminated film with a metal layer is heat-treated to convert the polyamic acid resin into an imide. As the heat treatment method at this time, any one of a batch method treatment in which a laminated film with a metal layer is wound, a continuous treatment in a roll-to-roll method, and a single wafer treatment in a cut sheet may be used. The heat treatment may be performed in a temperature range of 200 to 450 ° C., preferably 260 to 380 ° C. for 1 to 48 hours, and stepwise up to the target temperature. Moreover, in order to prevent oxidation of a metal layer, it is preferable to process in a vacuum or nitrogen atmosphere.

  When heat-resistant resin layer A and / or C heat-presses metal foil in the state of a polyimide resin, the temperature of the heating rolls 11 and 12 of a laminator is 250-450 degreeC, Preferably it is 300-400 degreeC. The nip pressure of the heating rolls 11 and 12 is 1 to 150 N / mm, preferably 5 to 90 N / mm, as a linear pressure. For the purpose of preventing oxidation of metal foil such as copper foil, as shown in FIG. 4 or FIG. 5, heat resistant film such as polyimide film is protected between the metal foil and / or heat resistant insulating film and the heating roll. It is preferable to heat-press by interposing as a film.

  If the heat-resistant resin layer A does not contain a filler, the heat-resistant resin layer A weakly adheres to the roll surface of the heated laminator and the protective film in the heat-bonding step using a heated roll laminator or the like, and in the heat treatment step Since the heat-resistant resin layer B is weakly bonded to the adjacent metal foil surface, the metal foil surface and / or the heat-resistant resin layer A surface is left with traces (tack marks) attached to the heat-resistant resin layer and the like, resulting in poor appearance. It becomes. In the present invention, since the heat-resistant resin layer A contains a filler, the above-described tack marks are less likely to remain, and since the filler particle diameter is in an appropriate range, there are few abnormal protrusions, A high-quality laminated film with a metal layer with few appearance defects can be obtained.

  A flexible printed circuit board (FPC) can be manufactured by forming a wiring pattern in a metal layer using the laminated film with a metal layer of the present invention. 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 a semiconductor chip (IC), a manufacturing example by a COF method using a flip chip technique will be described.

  The laminated film with a metal layer of the present invention is slit to a desired width. Next, a photoresist film was applied on the metal layer, and a wiring pattern was formed by mask exposure. Then, the metal layer was wet-etched, and the remaining photoresist film was removed to form a metal wiring pattern. After tin or gold is plated to 0.2 to 0.8 μm on the formed metal wiring pattern, a solder resist is applied on the wiring pattern to obtain a COF tape.

  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 tape obtained by the above method by flip chip mounting and sealing with resin.

  IC mounting methods include metal bonding method for gang bonding wiring and IC bumps, wire bonding method for bonding IC bonding parts and COF tape inner leads by wire bonding, and conductive filler in the adhesive layer. There are an ACF method in which bonding is performed with an adhesive film 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 20 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. In addition, since a temperature of 280 ° C. or higher is necessary for gold and tin to form a eutectic and to bond with high reliability, the temperature of the bonding surface is generally set to be 300 to 400 ° C. .

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. A method for measuring linear expansion coefficient, glass transition temperature, filler particle diameter (median diameter), and a method for evaluating warpage and poor appearance will be described.

(1) Measurement of linear expansion coefficient The resin solution obtained in each production example was applied to a glossy surface of an electrolytic copper foil having a thickness of 18 μm with a bar coater so as to have a predetermined thickness, and then at 80 ° C. for 10 minutes, 150 The film was dried at 10 ° C. for 10 minutes, and further heat-treated at 280 ° C. for 1 hour in a nitrogen atmosphere to be cured. 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 polyimide film or the single film obtained above is cut into a specific width shape, made into a cylindrical shape, and using a thermomechanical analyzer SS-6100 (manufactured by Seiko Instruments Inc.), The measurement was performed at a temperature range of 30 to 200 ° C. and a temperature rising rate of 5 ° C./min. From the obtained measurement results, an average linear expansion coefficient of 30 to 200 ° C. was calculated using the calculation formula (2). Here, L30 is the sample length at 30 ° C., and L200 is the sample length at 200 ° C.
Average linear expansion coefficient = (1 / L30) × [(L200−L30) / (200−30)] (2)
(2) Measurement of glass transition temperature The resin solution obtained in each production example was applied to a glossy surface of an electrolytic copper foil having a thickness of 18 μm with a bar coater so as to have a predetermined thickness, then at 80 ° C. for 10 minutes, 150 The film was dried at 10 ° C. for 10 minutes, and further heat-treated at 280 ° C. for 1 hour in a nitrogen atmosphere to be thermally cured. 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.

  About 10 mg of a single film of the obtained heat-resistant resin is packed in an aluminum standard container and measured using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation) (DSC method). The glass transition temperature was calculated from the inflection point. After preliminary drying at 80 ° C. × 1 hour, the measurement was performed at a heating rate of 20 ° C./min.

(3) Measurement of particle diameter (median diameter) of filler The resin solution containing filler obtained in each production example was diluted with NMP so that the filler concentration was 0.1% by weight, and laser diffraction particle size distribution measurement was performed. Using a device SALD-2000J (manufactured by Shimadzu Corporation), the particle size distribution was measured on a volume basis at 25 ° C. to determine the median diameter of the filler.

(4) Evaluation of curvature After cutting the laminated film with the copper layer obtained in each Example and the laminated film obtained by etching the copper layer of the laminated film with the copper layer into 50 mm × 50 mm, conditions of 25 ° C. and 50% RH After being left for 24 hours, it was allowed to stand on a flat plate, the height of the four corners was measured, and the average value was taken as the value of the warp. Here, in the laminated film with a copper layer, the warp to the copper layer side is a + warp, and in the laminated film obtained by etching the copper layer, the warp to the side on which the copper layer is provided is a + warp.

(5) Evaluation of poor appearance (tack marks) The film with a copper layer obtained in each example was cut into 200 mm × 1000 mm □, and the number of tack marks on the copper layer surface and the polyimide layer surface was counted by visual observation.

(6) Evaluation of poor appearance (abnormal protrusions) The film with a copper layer obtained in each example was cut into 100 mm × 100 mm □, and the number of abnormal protrusions having a size of 50 μmφ or more on the surface of the polyimide layer was determined by Nikon Corporation. Counting was performed at a magnification of 100 times using an optical microscope XD-10.

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 PMDA: pyromellitic dianhydride SiDA: 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) ) Disiloxane DAE: 4,4′-diaminodiphenyl ether PDA: p-phenylenediamine 2-MI: 2-methylimidazole NMP: 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 60 ° C. for 6 hours to obtain a 15 wt% polyamic acid resin solution (PA1). The linear expansion coefficient of the resin obtained by imidizing the polyamic acid resin solution (PA1) was 16 ppm / ° C., and the glass transition temperature was 315 ° 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 12 wt% polyamic acid resin solution (PA2-3). Table 1 shows the linear expansion coefficient and glass transition temperature of the resin obtained by imidizing the polyamic acid resin solution (PA2 to 3).

Production Example 4
Charge 1,000 g of the polyamic acid resin solution (PA2) obtained in Production Example 2 with 1.21 g of talc SG-95 (manufactured by Nippon Talc Co., Ltd.) and 8.87 g of NMP, and stir at room temperature for 2 hours. A solution (PA2-1) was obtained. The particle diameter (median diameter) of the filler in the resin solution with filler (PA2-1) was 2.46 μm.

Production Examples 5 to 16
Except having changed the polyamic acid resin solution, the kind of filler, and the charged amount as shown in Table 3, the same operation as in Production Example 4 was performed to obtain a resin solution with filler (PA2-2 to 12, PA1-1). Table 3 shows the particle diameter (median diameter) of the filler in the resin solution containing the filler.

  Table 2 summarizes the filler types and average particle diameters (catalog values) used here.

Example 1
Polyamide acid resin solution PA1 is coated with a comma coater on a roughened surface of roll-shaped electrolytic copper foil UCLP-SE (manufactured by Nippon Electrolytic Co., Ltd.) so that the thickness after drying and curing is 22 μm. Then, it was dried at 80 ° C. for 2 minutes and further at 150 ° C. for 10 minutes, and a polyamic acid resin layer to be the heat resistant resin layer B was laminated. Furthermore, the polyamic acid resin solution PA2-1 is coated thereon with a reverse coater so that the thickness after drying and curing becomes 3 μm, and dried at 80 ° C. for 2 minutes, and further at 150 ° C. for 5 minutes, and heat resistant resin The polyamic acid resin layer to be layer A was laminated, and the obtained laminate was wound up.

  Next, the laminate is wound around a 6-inch diameter SUS core with the copper foil facing outward, and heated step cure [(80 ° C., 30 minutes) + (150 ° C., 1 hour) + (350 ° C.) under a nitrogen atmosphere] 2 hours)], the heat resistant resin layer was imidized to obtain a laminated film with a copper layer.

  The warp of the obtained laminated film with a copper layer and the laminated film after removing the copper layer was 0 mm, and there were no appearance defects such as tack marks and abnormal protrusions on the laminated film with a copper layer.

Examples 2-12
Except having changed the film thickness of the heat resistant resin layer B, the kind of the heat resistant resin layer A, and the film thickness as shown in Table 4, the same operation as in Example 1 was performed to obtain a laminated film with a copper layer.

  Table 4 summarizes the evaluation results of the appearance defects such as warpage of the obtained laminated film with a copper layer and warpage of the laminated film after removing the copper layer, tack marks and abnormal protrusions of the laminated film with a copper layer.

Comparative Example 1
Polyamide acid resin solution PA1 is coated with a comma coater on a roughened surface of roll-shaped electrolytic copper foil UCLP-SE (manufactured by Nippon Electrolytic Co., Ltd.) so that the thickness after drying and curing is 25 μm. Then, it was dried at 80 ° C. for 2 minutes and further at 150 ° C. for 10 minutes, a polyamic acid resin layer to be the heat-resistant resin layer B was laminated, and the obtained laminate was wound up.

  Next, the laminate is wound around a 6-inch diameter SUS core with the copper foil facing outward, and heated step cure [(80 ° C., 30 minutes) + (150 ° C., 1 hour) + (350 ° C.) under a nitrogen atmosphere] 2 hours)], the heat resistant resin layer was imidized to obtain a laminated film with a copper layer.

  The warp of the obtained laminated film with a copper layer was 3 mm, and the warp of the laminated film after removing the copper layer was 9 mm. Regarding the appearance defect of the laminated film with a copper layer, there were 0 abnormal protrusions, but 23 tack marks.

Comparative Examples 2-4
Except having changed the film thickness of the heat resistant resin layer B, the kind of the heat resistant resin layer A, and the film thickness as shown in Table 4, the same operation as in Example 1 was performed to obtain a laminated film with a copper layer.

  Table 4 summarizes the evaluation results of warpage and appearance defects of the obtained laminated film with a copper layer and the laminated film after removing the copper layer.

Example 13
The polyamic acid resin solution PA2-1 was dried on a roll-shaped polyimide film ("Kapton" (registered trademark) 80EN Toray DuPont Co., Ltd.) having a thickness of 20 μm that had been subjected to low-temperature plasma treatment in advance in an argon atmosphere. The polyamic acid resin layer used as the heat resistant resin layer A was laminated | stacked by applying with a reverse coater so that the thickness after hardening might be set to 2 micrometers, and drying for 2 minutes at 80 degreeC, and also for 5 minutes at 150 degreeC.

  Next, on the opposite surface of the polyimide film, the polyamic acid resin solution PA3 was applied with a reverse coater so that the thickness after drying and curing was 2 μm, dried at 80 ° C. for 2 minutes, and further dried at 150 ° C. for 5 minutes, A polyamic acid resin layer to be the heat resistant resin layer C was laminated.

  The heat-resistant resin layer C (polyamic acid resin layer) of the laminate is laminated with a roughened surface of 12 μm thick electrolytic copper foil UCLP-SE (manufactured by Nihon Denki Co., Ltd.), and the roll surface temperature is set to 180 ° C. With a heated roll laminator (FIG. 3), thermocompression bonding was performed at a linear pressure of 50 N / mm and a speed of 1 m / min, and the resulting laminate was wound up.

  Next, the laminate is wound around a 6-inch diameter SUS core with the copper foil facing outward, and heated step cure [(80 ° C., 30 minutes) + (150 ° C., 1 hour) + (280 ° C.) under a nitrogen atmosphere. 2 hours)], the heat resistant resin layer was imidized to obtain a laminated film with a copper layer.

  The warp of the obtained laminated film with a copper layer and the laminated film after removing the copper layer was 0 mm, and there were no appearance defects such as tack marks and abnormal protrusions on the laminated film with a copper layer.

Examples 14-24
Except having changed the kind of polyimide film and the kind of heat resistant resin layer A as shown in Table 5, the same operation as Example 13 was performed and the laminated film with a copper layer was obtained.

  Table 5 summarizes the evaluation results of the appearance defects such as warpage of the obtained laminated film with a copper layer, and warpage of the laminated film after removing the copper layer, tack marks and abnormal protrusions of the laminated film with a copper layer.

Comparative Example 5
The polyamic acid resin solution PA3 is dried and cured on a roll-shaped polyimide film ("Kapton" (registered trademark) 80EN Toray DuPont Co., Ltd.) having a thickness of 20 μm that has been previously subjected to low-temperature plasma treatment in an argon atmosphere. The film was coated with a reverse coater so as to have a thickness of 2 μm, dried at 80 ° C. for 2 minutes, and further dried at 150 ° C. for 5 minutes, and a polyamic acid resin layer to be the heat resistant resin layer C was laminated.

  The heat-resistant resin layer C (polyamic acid resin layer) of the laminate is laminated with a roughened surface of 12 μm thick electrolytic copper foil UCLP-SE (manufactured by Nihon Denki Co., Ltd.), and the roll surface temperature is set to 180 ° C. With a heated roll laminator (FIG. 3), thermocompression bonding was performed at a linear pressure of 50 N / mm and a speed of 1 m / min, and the resulting laminate was wound up.

  Next, the laminate is wound around a 6-inch diameter SUS core with the copper foil facing outward, and heated step cure [(80 ° C., 30 minutes) + (150 ° C., 1 hour) + (280 ° C.) under a nitrogen atmosphere. 2 hours)], the heat resistant resin layer was imidized to obtain a laminated film with a copper layer.

  The resulting laminated film with a copper layer had 0 appearance defects such as tack marks and abnormal protrusions, but the warped of the laminated film with the copper layer was 1 mm, and the warped of the laminated film after removing the copper layer was 9 mm. there were.

Comparative Example 6
A laminated film with a copper layer was obtained in the same manner as in Comparative Example 5 except that the polyimide film was changed to “Kapton” (registered trademark) 50EN.

  Table 5 summarizes the evaluation results of the appearance defects such as warpage of the obtained laminated film with a copper layer, and warpage of the laminated film after removing the copper layer, tack marks and abnormal protrusions of the laminated film with a copper layer.

Comparative Examples 7-9
Except having changed the kind of polyimide film and the kind of heat resistant resin layer A as shown in Table 5, the same operation as Example 13 was performed and the laminated film with a copper layer was obtained.

  Table 5 summarizes the evaluation results of warpage and appearance defects of the obtained laminated film with a copper layer and the laminated film after removing the copper layer.

Example 25
2-MI was added as an imidization catalyst so as to be 7% by weight with respect to the solid content of the polyamic acid resin in the polyamic acid resin solution PA2-1, stirred at room temperature for 2 hours, and then rolled in advance in an argon atmosphere. Apply a reverse coater to a 20 μm thick polyimide film (“Kapton” (registered trademark) 80EN manufactured by Toray DuPont Co., Ltd.) that has been subjected to low temperature plasma treatment at 2 μm after drying and curing. Then, it was dried at 80 ° C. for 2 minutes and further at 200 ° C. for 5 minutes, and the heat resistant resin layer A was laminated.

  Next, 2-MI was added so that it might become 7 weight% with respect to the polyamic-acid resin solid content of the polyamic-acid resin solution PA3, and it stirred at room temperature for 2 hours, Then, after drying and hardening on the other surface of a polyimide film The film was coated with a reverse coater so as to have a thickness of 2 μm, dried at 80 ° C. for 2 minutes and further at 200 ° C. for 5 minutes, and the heat-resistant resin layer C was laminated to obtain a laminated film.

  A roll laminator in which a rough surface of a 12 μm thick electrolytic copper foil UCLP-SE (manufactured by Nihon Electrolysis Co., Ltd.) is bonded to the heat resistant resin layer C of the laminated film and the surface temperature of the roll is heated to 360 ° C., As shown in FIG. 4, a 125 μm-thick polyimide film (“Kapton” (registered trademark) 500H manufactured by Toray DuPont Co., Ltd.) is interposed between both rolls, copper foil, and laminated film as a protective film, and a linear pressure of 50 N / Mm, thermocompression-bonded at a speed of 1 m / min, to obtain a laminated film with a copper layer.

  The warp of the obtained laminated film with a copper layer and the laminated film after removing the copper layer was 0 mm, and there were no appearance defects such as tack marks and abnormal protrusions on the laminated film with a copper layer.

Examples 26-27
Except having changed the kind of polyimide film and the kind of heat-resistant resin layer A as shown in Table 6, the same operation as Example 25 was performed and the laminated film with a copper layer was obtained.

  Table 6 summarizes the evaluation results of the appearance defects such as warpage of the obtained laminated film with a copper layer, and warpage of the laminated film after removing the copper layer, tack marks, abnormal protrusions, etc. of the laminated film with a copper layer.

Comparative Example 10
2-MI was added as an imidization catalyst so as to be 7% by weight with respect to the solid content of the polyamic acid resin in the polyamic acid resin solution PA3, and the mixture was stirred at room temperature for 2 hours. A 20 μm-thick polyimide film (“Kapton” (registered trademark) 80EN manufactured by Toray DuPont Co., Ltd.), which has been plasma-treated, is applied with a reverse coater so that the thickness after drying and curing becomes 2 μm. Drying was carried out at 2 ° C. for 2 minutes and further at 200 ° C. for 5 minutes, and the heat-resistant resin layer C was laminated to obtain a laminated film.

  A roll laminator in which the roughened surface of a 12 μm thick electrolytic copper foil UCLP-SE (manufactured by Nihon Electrolysis Co., Ltd.) is bonded to the heat resistant resin layer C of the laminated film, and the roll surface temperature is heated to 360 ° C., As shown in FIG. 4, a 125 μm-thick polyimide film (“Kapton” (registered trademark) 500H manufactured by Toray DuPont Co., Ltd.) is interposed between both rolls, copper foil and laminated film as a protective film, and a linear pressure of 50 N / Mm, thermocompression bonding at a speed of 1 m / min, to obtain a laminated film with a copper layer.

  The resulting laminated film with a copper layer had 0 appearance defects such as tack marks and abnormal protrusions, but the warped of the laminated film with the copper layer was 1 mm, and the warped of the laminated film after removing the copper layer was 9 mm. there were.

Comparative Example 11
A laminated film with a copper layer was obtained in the same manner as in Comparative Example 10 except that the polyimide film was changed to “Kapton” (registered trademark) 50EN.

  Table 6 summarizes the evaluation results of the appearance defects such as warpage of the obtained laminated film with a copper layer, and warpage of the laminated film after removing the copper layer, tack marks, abnormal protrusions, etc. of the laminated film with a copper layer.

Comparative Examples 12-14
Except having changed the kind of polyimide film and the kind of heat resistant resin layer A as shown in Table 6, the same operation as Example 25 was performed and the laminated film with a copper layer was obtained.

  Table 6 summarizes the evaluation results of warpage and appearance defects of the obtained laminated film with a copper layer and the laminated film after removing the copper layer. In addition, many tack marks were generated on the protective film.

  As described above, in the examples of the present invention, the warpage of the laminated film with the copper layer and the laminated film after the removal of the copper layer is very small. Almost no poor appearance occurred. On the other hand, in the comparative example, a large warp occurred in the laminated film with the copper layer and the laminated film after removing the copper layer, and even if no warp occurred, Comparative Examples 2-4, 7-9, As in 12 to 14, many appearance defects such as tack marks occurred.

Example 28
A photoresist film was applied on the copper layer of the laminated film with a copper layer obtained in Example 2 so that the film thickness after drying with a reverse coater was 4 μm, dried, mask-exposed, and a wiring pattern with an alkali developer. After forming the copper foil, the copper foil was wet-etched with a 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 COF tape. The obtained COF tape was not warped.

  A semiconductor chip on which gold bumps were formed was joined to the inner lead of the COF tape obtained by the above method by flip chip mounting, and sealed with a resin to obtain a semiconductor device. Since there is no warp in the COF tape, there are few defects due to poor bonding and the semiconductor device showed good reliability.

Example 29
The same operation as in Example 28 was performed except that the laminated film with a copper layer obtained in Example 16 was used. There was no warping in the COF tape, and the semiconductor device produced from this time did not short-circuit the wiring and showed good reliability.

Example 30
The same operation as in Example 28 was performed except that the laminated film with a copper layer obtained in Example 26 was used. There was no warping in the COF tape, and the semiconductor device produced from this time did not short-circuit the wiring and showed good reliability.

Schematic which showed the one aspect | mode of the laminated | multilayer film with a metal layer of this invention Schematic which showed the other aspect of the laminated | multilayer film with a metal layer of this invention Schematic showing one embodiment of a roll laminator that can be used in the present invention Schematic showing another embodiment of a roll laminator that can be used in the present invention Schematic showing another embodiment of a roll laminator that can be used in the present invention

Explanation of symbols

1 Metal layer 2 Heat resistant resin layer B
3 Heat resistant resin layer A
4 Heat-resistant resin layer C
11 Laminate roll (top)
12 Laminate roll (bottom)
13 Metal foil unwinding 14 Heat resistant resin laminated film unwinding 15 Product winding 16 Protective film unwinding 17 Protective film winding

Claims (11)

A laminated film with a metal layer having a metal layer on one side of two or more heat-resistant resin layers, and the outermost heat-resistant resin layer A on the side not in contact with the metal layer contains at least a heat-resistant resin and a filler And the median diameter of the said filler is 0.1-7 micrometers, The laminated | multilayer film with a metal layer characterized by the above-mentioned. The laminated film with a metal layer according to claim 1, wherein the filler content in the heat-resistant resin layer A is 0.1 to 10% by weight. 3. The laminated film with a metal layer according to claim 1, wherein all of the heat resistant resin layers are polyimide resin layers. It is a laminated film with a metal layer having two heat resistant resin layers, and the linear expansion coefficient kB at 30 to 200 ° C. of the heat resistant resin layer B on the metal layer side is 20 ppm / ° C. or less. The linear expansion coefficient kA is larger than kB, The laminated film with a metal layer according to any one of claims 1 to 3. The method for producing a laminated film with a metal layer according to claim 4, wherein the heat-resistant resin layer B and the heat-resistant resin layer A are coated and laminated on the metal layer in this order. A heat-resistant resin layer C having a metal layer having three heat-resistant resin layers, the heat-resistant resin layer C having adhesiveness from the metal layer side, and having a linear expansion coefficient kB at 30 to 200 ° C. of 20 ppm / ° C. or less The laminated film with a metal layer according to any one of claims 1 to 3, wherein the resin layer B and the heat resistant resin layer A are laminated in this order, and the linear expansion coefficient kA of the heat resistant resin layer A is larger than kB. The laminated film with a metal layer according to claim 6, wherein the heat-resistant resin layer C is a thermoplastic polyimide layer, and the heat-resistant resin layer B is a polyimide film. The heat-resistant resin layer A is formed from a resin composition containing at least a heat-resistant resin, a filler, and an imidization catalyst, The laminated film with a metal layer according to claim 6 or 7. A heat-resistant resin layer C and a heat-resistant resin layer A are laminated on both sides of a heat-resistant resin layer B made of a polyimide film, respectively, and a metal foil is laminated on the heat-resistant resin layer C by thermocompression bonding. The manufacturing method of the laminated | multilayer film with a metal layer of Claim 6 to do. The flexible circuit board which gave the wiring pattern process to the metal layer of the laminated film with a metal layer in any one of Claims 1-9. A semiconductor device using the flexible circuit board according to claim 10.

Images