WO2014171345A1 - 金属箔積層体 - Google Patents
金属箔積層体 Download PDFInfo
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- WO2014171345A1 WO2014171345A1 PCT/JP2014/059846 JP2014059846W WO2014171345A1 WO 2014171345 A1 WO2014171345 A1 WO 2014171345A1 JP 2014059846 W JP2014059846 W JP 2014059846W WO 2014171345 A1 WO2014171345 A1 WO 2014171345A1
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- WIPO (PCT)
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- metal foil
- resin
- epoxy resin
- polyimide resin
- mass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4042—Imines; Imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention relates to a metal foil laminate in which a polyimide resin is laminated on at least one surface of a metal foil, and a flexible printed board using the metal foil laminate.
- the present invention relates to a metal foil laminate suitable as a chip on film (hereinafter referred to as COF) substrate on which electronic components such as IC (integrated circuit) or LSL (large scale integrated circuit) are mounted.
- COF chip on film
- polyimide resins are widely used as insulating materials for electric and electronic devices because they are excellent in heat resistance, insulation and chemical resistance.
- it is often used as a raw material for flexible printed wiring boards, and is used as a wiring board material for various electronic devices, mounting substrate materials, for example, device mounting substrates for display devices such as liquid crystal display devices, plasma displays, organic EL displays, and smart devices.
- mounting substrate materials for example, device mounting substrates for display devices such as liquid crystal display devices, plasma displays, organic EL displays, and smart devices.
- a COF substrate is a composite part in which a semiconductor chip such as an IC or LSI is directly mounted on a film-like wiring board.
- a display device such as a larger rigid wiring board, a liquid crystal display device, or an organic EL display is used. Used by connecting to a device mounting board.
- the COF substrate is made from a two-layer metal foil laminate (two-layer flexible metal foil laminate) in which a metal foil such as copper foil is laminated on a heat-resistant resin film such as polyimide.
- a fine pattern is formed on the copper foil surface of the two-layer flexible metal foil laminate by a method such as a photolithography method, and further, plating such as tin and a solder resist are coated on necessary portions.
- the plated COF lead pattern and the connection terminals (bumps) of the chip are connected to ACF / ACP (joining method using anisotropic conductive film / paste), NCF / NCP (non-conductive film).
- Patent Document 1 a laminate type in which a metal foil and a polyimide film are bonded with a thermoplastic polyimide adhesive
- Patent Document 2 a metal foil Cast type casted and laminated with polyimide resin
- Patent Document 3 Metalizing type (manufactured by directly depositing metal such as Cr on the polyimide film by sputtering, etc., and electrolessly and / or electrolytically plating copper)
- Patent Document 3 Metalizing type
- Patent Document 4 and Patent Document 5 disclose a two-layer flexible metal foil laminate in which bump sinking is improved by a casting method, but the problems of folding resistance and spring back are not solved.
- Patent Document 6 the improvement of folding resistance is examined by a laminating method, but the improvement of bump sinking is insufficient.
- Patent Documents 7 and 8 improvement of springback, improvement of adhesiveness, and the like are examined by a metalizing method, but it still has a problem that it is inadequate and folding resistance is inferior.
- a functional group that becomes a crosslinking point is introduced into the side chain in the resin, or a large amount of polyfunctional isocyanate, polyfunctional phenol, phenoxy resin, or the like is used together, and polyimide resin or the like is included in the cross-linked structure with these blends.
- the polymer is physically and / or chemically introduced. Therefore, even though a certain degree of heat resistance can be imparted, it is difficult to impart a mountability of 400 ° C. or more, and mechanical properties such as folding resistance and flex resistance are also lowered. It was difficult to satisfy all of folding resistance, bending resistance, and low springback.
- Patent Document 9 discloses a case where a crosslinkable composition is obtained by blending a large amount of an epoxy resin with a polyamide-imide resin and Patent Document 10 further using a phenoxy resin together.
- a functional group serving as a crosslinking point is introduced into the polyimide resin
- Patent Document 13 Patent Document 14, Patent Document 15, and Patent Document 16
- an epoxy resin serving as an excessive crosslinking agent is used.
- Efficient crosslinking is attempted by blending phenoxy resin.
- it is difficult to obtain a tough molded body with any resin composition and it is difficult to achieve both flexibility, bending resistance, flexibility, and low springback, which are trade-offs with mountability. Was the current situation.
- the object of the present invention is to solve the above-mentioned problems, and is intended to produce a metal foil laminate for a flexible printed circuit board, such as a COF substrate, and a flexible printed wiring board at low cost. That is, regarding a metal foil laminate suitable as a substrate for COF, the substrate film of the chip when bonding the chip and the metal wiring while maintaining the high quality of the warp, dimensional accuracy, adhesion, etc. of the substrate as before. Prevention of sinking into the layer (that is, mountability) and flexback, folding resistance, flexibility, which are in a trade-off relationship with the mountability, and springback that is regarded as a problem when bending and mounting a board Etc. (ie, low springback) at the same time.
- the present inventors have achieved the object of the present invention by forming a crosslinked structure by blending a small amount of an epoxy resin with a polyimide resin that is soluble in solvent and excellent in heat resistance to form a resin composition.
- the epoxy resin used by this invention fulfill
- an epoxy resin is added to a polyimide resin that defines various characteristics, and the reaction conditions described below are employed to form a crosslinked structure only with the functional group at the resin terminal of the polyimide resin.
- the low warpage, dimensional accuracy, adhesiveness, etc. satisfy the mounting properties, the bending resistance, the folding resistance, the flexibility and the low spring back simultaneously while maintaining the conventional characteristics.
- the resin has the inherent bending resistance, folding resistance, flexibility, and low springback by setting the crosslinking point only to the end of the resin that defines the composition, molecular weight, acid value, logarithmic viscosity, etc. It has been possible to find a structure that retains its mechanical properties and withstands mountability.
- the present invention is the following flexible metal foil laminate and flexible printed circuit board.
- a heat resistant resin composition containing a polyimide resin crosslinked with an epoxy resin is a metal foil laminate of a base film and a metal foil laminated on at least one side of the metal foil, and the following (a) and (B) a metal foil laminate, (A) The compounding amount of the epoxy resin when the total amount of the polyimide resin and the epoxy resin is 100% by mass is 0.1% by mass or more and 10% by mass or less; (B) N-methyl-2-pyrrolidone was added to the base film obtained by removing the metal foil from the metal foil laminate so that the concentration of the base film was 0.5% by mass, and at 100 ° C. for 2 hours. The insoluble rate after heat treatment is 40% or more.
- the metal foil laminate according to any one of Items 1 to 5 which is the following (j):
- the polyimide resin is a polyamide-imide resin, and the structural unit of the polyamide-imide resin contains 5 to 99 mol% of the repeating structural unit represented by the formula (1);
- the epoxy resin is a phenol novolac glycidyl ether of the following general formula (2). [N is an integer from 1 to 20] (Section 8) Item 8.
- a flexible printed wiring board comprising the metal foil laminate according to any one of Items 1 to 7.
- the flexible printed wiring board according to Item 8 wherein the value of the folding resistance test based on JIS C 5016 is more than 190 times.
- the flexible printed wiring board obtained from the metal foil laminate of the present invention prevents the chip from sinking into the base film layer when joining the chip and the metal wiring, that is, mountability, bending mounting of the substrate, etc. It is suitable as a chip-on-film (hereinafter referred to as COF) substrate because it reduces the problem of springback and the like, and also has excellent bending resistance, folding resistance, and flexibility (panel assembly). Furthermore, since the resin composition used in the present invention is soluble in an organic solvent, it can be produced at low cost without the need for heat treatment at high temperatures. Naturally, the quality required for the COF substrate such as low warpage, dimensional accuracy, and adhesiveness is maintained at a high level. Therefore, since a high-performance flexible substrate can be manufactured at low cost, there are significant industrial advantages.
- COF chip-on-film
- the metal foil laminate of the present invention is a laminate of the base film and metal foil in which a base film containing a heat resistant resin composition is laminated on at least one side of the metal foil.
- the heat-resistant resin composition is preferably formed by crosslinking only the functional group at the resin terminal of the polyimide resin with an epoxy resin.
- the polyimide resin may be basically any resin as long as it has a thermal expansion coefficient equivalent to that of the metal foil and is excellent in heat resistance, but is preferably a polyimide resin and / or a polyamideimide. It is a resin, more preferably a polyimide resin soluble in an organic solvent and / or a polyamideimide resin soluble in an organic solvent.
- a polyimide resin is obtained by a polycondensation reaction of an acid component and an amine component (or an isocyanate component corresponding thereto).
- a diisocyanate method, an acid chloride method, a low temperature solution polymerization method, a room temperature solution polymerization method and the like are conventionally known. It can manufacture by the method of. Industrially, a diisocyanate method in which the resulting polymerization solution can be used as it is as a varnish for casting described later is preferable.
- “soluble in an organic solvent” means N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolide.
- Single solvent selected from the group consisting of non, tetramethylurea, sulfolane, dimethyl sulfoxide, ⁇ -butyrolactone, cyclohexanone, and cyclopentanone, or a mixed organic containing at least one of these in an amount of 20% by mass or more It means that the resin dissolves in 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more in any one of the solvents.
- the resin is 10% by mass or more, preferably 15% by mass or more, and more preferably 20% by mass or more in N-methyl-2-pyrrolidone (purity 99.9%).
- Whether or not the resin is dissolved is determined by using resin powder that passes 80 mesh in a 200 ml beaker when the resin is solid, and using it as it is when it is liquid.
- the resin powder was added to the aforementioned organic solvent so that the amount was 10, 15, and 20% by mass, and after gently stirring at 25 ° C. for 24 hours, the solution was allowed to stand at 25 ° C. for 24 hours, and was visually gelled. It is determined that the material that was not homogenized, cloudy, or precipitated is dissolved.
- the polyimide resin that can be used in the present invention is not particularly limited, but a polyimide resin having a functional group only at a resin terminal is preferable. If there is a functional group only at the resin terminal of the polyimide resin, the functional group present only at the terminal reacts with the glycidyl group of the epoxy resin. If a functional group is present at a location other than the resin end, a crosslinking reaction with the epoxy resin occurs, and the inherent properties of the resin such as bending resistance, folding resistance, flexibility, and low spring back are lowered, which is not preferable.
- a carboxyl group, an acid anhydride group, an isocyanate group, an amino group, and the like are preferable, and a carboxyl group and an acid anhydride group are particularly preferable.
- the polyimide resin that can be used in the present invention is not particularly limited, but a polyimide resin that is soluble in an organic solvent is preferable.
- the acid component used in the polyimide resin that can be used in the present invention include pyromellitic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 3, 3 ′, 4,4′diphenylsulfonetetracarboxylic acid, 3,3 ′, 4,4′-diphenylethertetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4 Monomers such as 5-tetracarboxylic acid, naphthalene-1,4,5,8-tetracarboxylic acid, monoanhydrides, dianhydrides, and esterified products can be used
- amine component (or the corresponding isocyanate component) used in the polyimide resin that can be used in the present invention include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4- Diaminoxylene, P-xylenediamine, m-xylenediamine, 2,4-diaminodurene, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, benzidine, 3,3′-dihydroxybenzidine, 3,3′-dimethoxybenzidine, 3,3′-dimethyl-4,4′-diaminobiphenyl (o-tolidine), 3,3′-diethyl-4,4′-diaminobiphenyl 2,2′-dimethyl-4,4′-di
- the polyamide-imide resin that can be used in the present invention is not particularly limited, but a polyamide-imide resin that is soluble in an organic solvent is preferable.
- the acid component used in the polyamideimide resin that can be used in the present invention include trimellitic anhydride, diphenyl ether-3,4,4′-tricarboxylic acid anhydride, diphenylsulfone-3,4,4′-tricarboxylic acid anhydride, Monocarboxylic acid monomers such as benzophenone-3,4,4′-tricarboxylic acid anhydride and naphthalene-1,2,5-tricarboxylic acid anhydride can be used alone or as a mixture of two or more.
- dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, diphenylsulfone dicarboxylic acid, benzophenone dicarboxylic acid, biphenyl dicarboxylic acid, and the acid component of the polyimide resin may be used alone or as examples of compounds It can be used as a mixture of two or more. Or it can use combining the compound illustrated by the acid component of the above-mentioned dicarboxylic acid and a polyimide resin.
- amine component or an isocyanate component corresponding thereto
- compounds exemplified in the amine component of a polyimide resin can be used.
- the acid component and amine component shown below can be used as long as the object of the present invention is not impaired.
- ⁇ Copolymerizable acid component examples include aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanoic acid, and monoanhydrides, dianhydrides, and esterified products of aliphatic tricarboxylic acids such as butane-1,2,4-tricarboxylic acid.
- aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanoic acid
- monoanhydrides, dianhydrides, and esterified products of aliphatic tricarboxylic acids such as butane-1,2,4-tricarboxylic acid.
- Alicyclic dicarboxylic acids such as 4,4′-dicarboxylic acid, cyclohexanetricarboxylic acid, dicyclohexyl ether-3,3 ′, 4′-tricarboxylic acid, dicyclohexylsulfone-3,4,4′-tricarboxylic acid, dicyclohexylmethane-3 , 4,4'-tricarboxylic acid and other aliphatic tetracarboxylic acid monoanhydrides, esterified products, cyclopentane-1,2,3 , 4-tetracarboxylic acid and other alicyclic tetracarboxylic acid monoanhydrides, dianhydr
- amine components include trans-1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-diaminocyclohexane (trans / cis mixture), 1,3-diaminocyclohexane, 4,4′-methylenebis ( (Cyclohexylamine) (trans isomer, cis isomer, trans / cis mixture), isophoronediamine, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2.2.1] heptane, , 6-bis (aminomethyl) bicyclo [2.2.1] heptane, 3,8-bis (aminomethyl) tricyclo [5.2.1.0] decane, 1,3-diaminoadamantane, 4,4 ′ -Methylenebis (2-methylcyclohexylamine), 4,
- the polyimide resin that can be used in the present invention is capable of sinking into the base film layer (mountability) when bonding the chip and the metal wiring, and springback, bending resistance, From the balance of flexibility, flexibility, and production cost, an aromatic polyimide resin and / or an aromatic polyamideimide resin that is soluble in an organic solvent is preferable, and more preferably in a structural unit of the polyamideimide resin.
- Polyamideimide resin containing a repeating unit represented by formula (1) preferably 5 mol% or more and 99 mol% or less, more preferably 30 mol% or more and 95 mol% or less, and further preferably 50 mol% or more and 80 mol% or less. Is good. If it is less than 5 mol%, there may be a problem in mountability. If it exceeds 99 mol%, the solubility in an organic solvent becomes poor, so that the processability in a solution may be difficult.
- trimellitic anhydride TMA
- BTDA 4,4′-benzophenonetetracarboxylic dianhydride
- BPDA Biphenyltetracarboxylic dianhydride
- TMA / BTDA / BPDA 80-50 / 5-20
- a polyamideimide resin of / 15 to 45 is preferable.
- o-tolidine diisocyanate is a polyamideimide resin having a composition ratio of all the isocyanate components (or amine components corresponding thereto) of 50 mol% or more.
- these polyamideimide resins can be used by mixing two or more resins polymerized separately.
- a polyimide resin is obtained by a polycondensation reaction of an acid component and an amine component (or an isocyanate component corresponding thereto).
- a diisocyanate method, an acid chloride method, a low temperature solution polymerization method, a room temperature solution polymerization method and the like are conventionally known. It can manufacture by the method of.
- a diisocyanate method is preferred in which a polymer is obtained by a decarboxylation reaction, and the obtained polymerization solution can be used as it is as a varnish for casting described later.
- the polyimide resin used in the present invention can be obtained by heat polycondensation of the above-mentioned acid component and diisocyanate component corresponding to the amine component in an organic solvent at a substantially stoichiometric amount of 100 to 200 ° C. Can do.
- the polymerization solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, sulfolane, dimethylsulfoxide.
- ⁇ -butyrolactone cyclohexanone, cyclopentanone, etc., preferably N-methyl-2-pyrrolidone, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone.
- these solvents can be used as they are as a solution for producing a metal-clad laminate as described later. Some of these can be replaced with hydrocarbon organic solvents such as toluene and xylene, ether organic solvents such as diglyme, triglyme and tetrahydrofuran, and ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone.
- the logarithmic viscosity of the polyimide resin before crosslinking with the epoxy resin of the present invention is 0.40 dl / g or more in N-methyl-2-pyrrolidone (polymer concentration 0.5 g / dl) at 30 ° C.
- 3.50 dl / g or less is good, preferably 0.80 dl / g or more and 3.50 dl / g or less, more preferably 1.00 dl / g or more and 3.50 dl / g or less, and further preferably 1.30 dl / g or more. 3. 50 dl / g or less.
- ⁇ Measurement of logarithmic viscosity> For the measurement of the logarithmic viscosity of the polyimide resin before crosslinking, a powdery polymer sample prepared by reprecipitation and purification of a solution containing the polyimide resin before crosslinking with a large amount of acetone is used. The powder sample is dissolved in N-methyl-2-pyrrolidone so that the polymer concentration is 0.5 g / dl, and the solution viscosity and solvent viscosity of the solution are measured at 30 ° C. with an Ubbelohde type viscosity tube. The logarithmic viscosity value is calculated by the following formula from the result.
- V1 represents a solution viscosity measured with an Ubbelohde type viscosity tube
- V2 represents a solvent viscosity measured with an Ubbelohde type viscosity tube
- V1 and V2 represent a polymer solution and a solvent (N-methyl-2-pyrrolidone).
- V3 is the polymer concentration (g / dl).
- the varnish obtained after polymerization can also be used as a measurement sample.
- the measurement sample solution is adjusted so that the polymer concentration is 0.5 g / dl in terms of solid content from the varnish concentration.
- the logarithmic viscosity of the polyimide resin in the uncrosslinked portion after being crosslinked with the epoxy resin can be measured by using the polyimide resin extract from which the uncrosslinked portion is extracted by measuring the insolubility described below.
- a powdery polymer sample prepared by reprecipitation and purification of the extract with a large amount of acetone is used.
- the polyimide resin in the uncrosslinked portion is a polyimide resin that has not reacted with the epoxy resin, but even if it partially reacts with the epoxy resin, it is completely a network structure. The part which is not (not insolubilized) is also included.
- the logarithmic viscosity of the polyimide resin in the uncrosslinked portion after being cross-linked by the epoxy resin of the present invention is the logarithmic viscosity at 30 ° C. in N-methyl-2-pyrrolidone (polymer concentration 0.5 g / dl). 0.40 dl / g or more and 3.50 dl / g or less is good, preferably 0.80 dl / g or more and 3.50 dl / g or less, more preferably 1.00 dl / g or more and 3.50 dl / g or less, more preferably 1.30 dl / g or more and 3.50 dl / g or less.
- the number average molecular weight of the polyimide resin before crosslinking with the epoxy resin of the present invention preferably has a molecular weight corresponding to 10,000 or more and 200,000 or less, more preferably 21,000 or more and 180,000 or less, and further preferably 47,000 or more and 160000 or less. .
- the number average molecular weight is less than 10,000, mechanical properties such as bending resistance and folding resistance of the metal foil laminate and the flexible printed wiring board may be insufficient. Further, if it exceeds 200,000, the solution viscosity becomes high, so that it may be difficult to form the metal foil laminate. Moreover, there exists a tendency for mounting property (dent of the base film layer in chip
- the column uses shodex AD800P, shodex AD805 / S, shodex AD804 / S, shodex AD803 / S, and shodex AD802 / S in series.
- the molecular weight of the polyimide resin in the uncrosslinked portion after being crosslinked by the epoxy can be measured by using an extract of the polyimide resin from which the uncrosslinked portion is extracted by measuring the insolubility described later.
- a powdery polymer sample prepared by reprecipitation and purification of the extract with a large amount of acetone is used.
- the polyimide resin in the uncrosslinked portion is a polyimide resin that does not react with epoxy, but even if it partially reacts with epoxy, it has a completely network structure. The part which is not (insolubilized) is also included.
- the number average molecular weight of the polyimide resin in the uncrosslinked portion after being crosslinked by the epoxy resin of the present invention is preferably one having a molecular weight corresponding to 10,000 or more and 200,000 or less, more preferably 21,000 or more and 180,000 or less, more preferably 47000 or more and 160000 or less.
- the number average molecular weight is less than 10,000, mechanical properties such as bending resistance and folding resistance of the metal foil laminate and the flexible printed wiring board may be insufficient. Further, if it exceeds 200,000, the solution viscosity becomes high, so that it may be difficult to form the metal foil laminate. Moreover, there exists a tendency for mounting property (dent of the base film layer in chip
- the acid value of the polyimide resin before crosslinking with the epoxy resin of the present invention is preferably 5 eq / ton or more and 1000 eq / ton or less, more preferably 10 eq / ton or more and 600 eq / ton or less, and further preferably 15 eq / ton or more and 300 eq / ton.
- it is particularly preferably 20 eq / ton or more and 160 eq / ton or less. If the acid value is less than 5 eq / ton, the molding process when processing into the metal foil laminate becomes difficult, and the mountability (dent of the base film layer at the chip mounting temperature) tends to deteriorate. If it exceeds 1000 eq / ton, mechanical properties such as bending resistance and folding resistance of the metal foil laminate and flexible printed wiring board may be insufficient.
- 0.1 g of a powdered polymer used for the measurement of logarithmic viscosity was precisely weighed, and a mixed solvent of N-methyl-2-pyrrolidone / dimethylformamide (50/50 volume ratio) was added to 1 dl. Add to make.
- crosslinking with an epoxy can be measured by using the extract of the polyimide resin from which the uncrosslinked part was extracted by the measurement of the insoluble rate mentioned later.
- a powdery polymer sample prepared by reprecipitation and purification of the extract with a large amount of acetone is used.
- the polyimide resin in the uncrosslinked portion is a polyimide resin that does not react with epoxy, but even if it partially reacts with epoxy, it has a completely network structure. The part which is not (insolubilized) is also included.
- the acid value of the polyimide resin in the uncrosslinked portion after being crosslinked by the epoxy resin of the present invention is preferably 5 eq / ton or more and 1000 eq / ton or less, more preferably 10 eq / ton or more and 600 eq / ton or less, and further preferably 15 eq. / Ton to 300 eq / ton, particularly preferably 20 eq / ton to 160 eq / ton. If it is less than 5 eq / ton, the molding process when processing into the metal foil laminate becomes difficult, and the mountability (dent of the base film layer at the chip mounting temperature) tends to deteriorate. If it exceeds 1000 eq / ton, mechanical properties such as bending resistance and folding resistance of the metal foil laminate and flexible printed wiring board may be insufficient.
- ⁇ Heat resistant resin composition> it can be set as the varnish for casting to the below-mentioned metal foil by adding an epoxy resin to the polymerization solution of the polyimide-type resin obtained by the above, reacting and / or mix
- the total amount of the polyimide resin and the epoxy resin in the heat resistant resin composition is 30% by mass or more, preferably 50% by mass or more when the total solid component in the heat resistant resin composition is 100% by mass. More preferably, it is 70 weight or more. If it is less than 30% by mass, the mountability may be deteriorated.
- the crosslinked structure of the present invention is obtained by adding an epoxy resin to a polyimide resin that defines various characteristics, and adopting the reaction conditions described later, so that only the terminal functional group of the polyimide resin is crosslinked. Forming and satisfying simultaneously mountability, bending resistance, folding resistance, flexibility, and low springback.
- Examples of the epoxy resin used in the present invention include bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, o -Cresol novolac type epoxy resin, polyfunctional glycidylamine type epoxy resin, epoxy resin containing dicyclopentadiene skeleton, triglycidyl isocyanurate, bixylenol type epoxy resin, fluorene epoxy resin, epoxy resin containing naphthalene skeleton, triphenylmethane type epoxy Resin, tetraphenylmethane type epoxy resin, biphenyl type epoxy resin, epoxy resin with flexibility such as rubber modification, urethane modification, etc., epoxy resin containing heterocyclic ring Compound having a polyfunctional alicyclic glycidyl group such as epoxy resin.
- glycidyl ethers such as bisphenol S diglycidyl ether, glycidyl ester types such as glycidyl hexahydrophthalate and dimer acid glycidyl esters, glycidyl amines such as triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, and 3,4-epoxycyclohexylmethyl
- Alicyclic or alicyclic epoxies such as carboxylate, epoxidized polybutadiene, and epoxidized soybean oil can be used alone or as a mixture.
- any compound having a functional group capable of reacting with a carboxyl group, amino group or isocyanate group, which is a terminal functional group of a polyimide resin can be used as a crosslinking agent.
- Oxetane group-containing compounds such as type oxetane resins can also be used.
- the oxetane group-containing compound is not particularly limited as long as it has an oxetane ring in the molecule and can be cured.
- 3-ethyl-3-hydroxymethyloxetane, 1,4-bis- ⁇ [(3 -Ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene 3-ethyl 3- (phenoxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3- (2-ethylhexyloxy) Methyl) oxetane, 3-ethyl-3- ⁇ [3- (triethoxyl) propoxy] methyl ⁇ oxetane, 3,3-bis (hydroxymethyl) oxetane, di [1-hydroxymethyl (3-oxetanyl)] methyl ether, 3,3-bis (hydroxymethyl) oxetane,
- These compounds containing an oxetane ring may be used alone or in combination of two or more.
- preferable epoxy resins that can simultaneously satisfy mountability, flex resistance, folding resistance, flexibility, and low springback are bisphenol A type epoxy resins, novolac type epoxy resins, dicyclopentadiene type epoxy resins, many Functional glycidylamine type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins.
- Commercially available products can be used as they are, for example, EPICLON (registered trademark) 840 (bisphenol A type epoxy resin) manufactured by DIC Corporation, JER154JER152, JER157S70 (novolak type epoxy resin) manufactured by Mitsubishi Chemical Corporation, DIC Corporation.
- HP-7200 dicyclopentadiene type epoxy resin manufactured by Mitsubishi Gas Chemical Co., Ltd.
- TETRAD registered trademark
- -X polyfunctional glycidylamine type epoxy resin
- EPICLON registered trademark
- HP-4032 naphthalene type epoxy resin
- YX4000 biphenyl type epoxy resin
- bisphenol A type epoxy resin novolak type epoxy resin, dicyclopentadiene type epoxy resin, and more preferred are phenol novolak glycidyl ether, cresol novolak glycidyl ether, brominated phenol novolak glycidyl ether, brominated cresol novolak glycidyl.
- Novolac type epoxy resins such as ether
- bisphenol A type epoxy resins such as bisphenol A glycidyl ether and brominated bisphenol A diglycidyl ether, and most preferred are phenol novolac glycidyl ethers of the following general formula (2).
- the epoxy equivalent of the epoxy resin used in the present invention is preferably 10 g / eq or more and 1000 g / eq or less, more preferably 50 g / eq or more and 500 g / eq or less, and still more preferably 80 g / eq or more and 200 g / eq or less.
- the epoxy equivalent is usually determined by potentiometric titration with a perchloric acid acetic acid standard solution according to JIS K 7236.
- the amount of the epoxy resin is preferably 0.1% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 10% by mass or less, when the total amount of the polyimide resin and the epoxy resin is 100% by mass. Preferably they are 1 mass% or more and 8 mass% or less, Most preferably, they are 2 mass% or more and 5 mass% or less. If it is less than 0.1% by mass, the mountability (dent of the base film layer at the chip mounting temperature) tends to deteriorate, and if it exceeds 10% by mass, the metal foil laminate and the flex resistance of the flexible printed wiring board, Mechanical properties such as folding resistance may be insufficient.
- a curing accelerator can be used as necessary.
- the curing accelerator is not particularly limited as long as it can accelerate the curing reaction between the carboxyl group, amino group, isocyanate group and the compound containing an oxirane ring (epoxy resin), which is the terminal functional group of the polyimide resin. There is no.
- curing accelerators examples include imidazole derivatives, guanamines such as acetoguanamine, benzoguanamine, diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, urea derivatives, melamine, Polyamines such as basic hydrazides, their organic acid salts and / or epoxy adducts, amine complexes of boron trifluoride, ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6 -Triazine derivatives such as xylyl-S-triazine, trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hex
- a curing accelerator having latent curability is preferable, and examples thereof include organic acid salts of DBU and DBN and / or tetraphenylboroate, and a photocationic polymerization catalyst. You may use these individually or in mixture of 2 or more types.
- the use amount of the curing accelerator a conventionally known appropriate amount is used.
- the amount is 0.1 to 30 parts by mass with respect to 100 parts by mass of the compound (epoxy resin) containing an oxirane ring, but the object of the present invention can be achieved without a catalyst.
- a curing agent can be used as necessary.
- Any conventionally known curing agent for epoxy resins can be used as the curing agent that catalyzes the curing reaction of the epoxy resin.
- amine compounds such as diaminodiphenylmethane, diaminodiphenyl sulfide, diaminobenzophenone, diaminodiphenylsulfone, diethyltriamine, triethylamine, benzyldimethylamine, basic compounds such as triphenylphosphine, 2-alkyl-4-methylimidazole, 2-phenyl
- Examples include imidazole derivatives such as -4-alkylimidazole, acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, boron trifluoride amine complexes such as boron trifluoride triethylamine complex, and dicyandiamide. . You may use these individually
- the compounding amount is a conventionally known appropriate amount. Usually, it is 1 to 20 parts by mass with respect to 100 parts by mass of the compound containing an oxirane ring, but the object of the present invention can be achieved without a curing agent.
- an acid anhydride as a hardening
- the epoxy resin or, if necessary, a catalyst and a curing agent are usually added in a predetermined amount to the obtained resin solution after polymerization and mixed until uniform.
- a predetermined amount of the epoxy resin is added to the resin solution and then heated and stirred at a temperature of 50 ° C. to 200 ° C. for 1 hour to 10 hours.
- the above heat resistance of the present invention is improved for the purpose of improving various properties of the metal foil laminate and the flexible printed wiring board, such as transparency, mechanical properties, electrical properties, slipperiness, and flame retardancy.
- Other resins, organic compounds, and inorganic compounds may be mixed or reacted with the functional resin solution.
- lubricant silicon, talc, silicone, etc.
- adhesion promoter flame retardant (phosphorus, triazine, aluminum hydroxide, etc.), stabilizer (antioxidant, UV absorber, polymerization inhibitor, etc.), plating activity Agents, organic and inorganic fillers (talc, titanium oxide, fluoropolymer fine particles, pigments, dyes, calcium carbide, etc.), silicone compounds, fluorine compounds, isocyanate compounds, blocked isocyanate compounds, acrylic resins, urethane resins, Resins such as polyester resin, polyamide resin, phenol resin, polyimide resin and organic compounds, or these curing agents, inorganic compounds such as silicon oxide, titanium oxide, calcium carbonate, iron oxide and the like within a range not impairing the object of the present invention. Can be used together.
- the metal foil laminate of the present invention is a laminate of a base film containing a heat resistant resin composition and a metal foil. In this invention, it is preferable that it is a flexible metal foil laminated body.
- Metal foil As the metal foil used in the present invention, a copper foil, an aluminum foil, a steel foil, a nickel foil, and the like can be used, and a composite metal foil obtained by combining these can also be used. Copper foil is preferred.
- organic rust prevention treatment (benzothiazole, benzotrizole, imidazole, etc.), inorganic rust prevention treatment (zinc, chromate, zinc alloy, etc.), silane coupling agent treatment (epoxy silane coupling agent, amino Silane coupling agents, mercapto-based silane coupling agents, etc.), surface plating treatment such as overlay plating treatment and burn plating treatment may be applied.
- the surface roughness (Rz) of the surface on which the heat resistant resin composition is laminated is 5.0 ⁇ m or less, preferably 2.0 ⁇ m or less, and most preferably 1.0 ⁇ m or less. If it exceeds 5.0 ⁇ m, the patterning property is inferior, and the haze value of the resin film layer after the copper foil is removed by etching increases, so the visibility may deteriorate. Visibility is a measure of alignment when mounting a semiconductor chip. Usually, the positioning pattern is identified via a base resin film with a CCD camera. If it is too low, mounting becomes difficult. There is.
- the lower limit of the surface roughness is not limited as low as possible, but the object of the present invention can be achieved as long as it is about 0.1 ⁇ m.
- the glossiness is 300 or more, preferably 400 or more, more preferably 600 or more, and particularly preferably 800 or more.
- the glossiness is measured according to JIS Z 8741-1997, and is usually irradiated at an incident angle of 60 °, and the reflected light at 60 ° is measured.
- it is about 800 the object of the present invention can be achieved.
- the gloss level is obtained by irradiating measurement light at a constant incident angle and measuring the intensity of reflected light at a constant angle.
- 20 °, 45 Incident angles and reflection angles such as °, 60 °, 75 °, and 85 ° are defined.
- the base film layer after the copper foil is removed by etching in the flexible printed circuit board reflects the surface state of the copper foil, resulting in less irregular reflection and transparency. If the film layer is excellent and the glossiness is low, the reverse is considered.
- the transparency when the glossiness is used as an index is strictly the amount of scattered light at a certain angle at the incident angle and reflection angle at a certain angle, and the amount of scattered light. It is not practical as an index of transparency of the material film. That is, the alignment on the COF substrate is performed by, for example, irradiating the substrate with visible light of about 400 nm to 800 nm and image processing the identification pattern. However, the alignment is not necessarily an angle of 60 °, but rather vertical. It is close to the angle of incidence and reflection angle. Therefore, the base film layer after the copper foil is removed by etching, reflecting the surface state of the copper foil, for example, the amount of irregular reflection close to the vertical angle is small and the glossiness is not necessarily high and low. May not be correlated. For example, the surface angle is assumed that the incident angle is 5 ° and the irregular reflection is small at the vertical reflection angle, but the incident angle and the reflection angle are large at 60 °, and the former is closer to practical use in the alignment of the COF substrate.
- the metal foil laminate having more excellent visibility when the substrate is irradiated with visible light of about 400 nm to 800 nm vertically.
- it is more preferably 20% or more, more preferably 25% or more, still more preferably 30% in the visible light region of 400 nm to 800 nm. That's it. If it is less than 20%, the visibility is poor. The higher the reflectivity, the better. However, if it is about 80%, the object of the present invention can be achieved.
- the thickness of the metal foil is not particularly limited, but for example, a metal foil of 3 to 50 ⁇ m can be suitably used.
- the metal foil is usually in the form of a ribbon, and its length is not particularly limited.
- the width of the ribbon-like metal foil is not particularly limited, but generally it is preferably about 25 to 300 cm, particularly about 50 to 150 cm.
- electrolytic foil or rolled foil can be used as it is.
- HLS manufactured by Nippon Electrolytic Co., Ltd.
- F0-WS “F0-WS”
- U-WZ manufactured by Furukawa Electric Co., Ltd.
- NA-VLP Furukawa Electric Co., Ltd.
- DFF Mitsui Mining & Smelting Co., Ltd.
- CF-T9D-SVR “ CF-TGD-SV ”, etc.
- the method for producing the metal foil laminate of the present invention is not particularly limited. For example, by applying the casting varnish obtained as described above to one side of the metal foil, initial drying, heat treatment, etc. Can be manufactured.
- the coating method is not particularly limited, and conventionally well-known methods can be applied. Can be applied onto metal foil after adjusting the viscosity of the coating solution with a roll coater, knife coater, doctor blade coater, gravure coater, die coater, multilayer die coater, reverse coater, reverse roll coater, etc.
- the initial drying conditions after coating are not particularly limited, but in general, initial drying is performed at a temperature 70 to 130 ° C. lower than the boiling point (Tb (° C.)) of the solvent used for the varnish for casting.
- Tb boiling point
- the initial drying temperature varies depending on the type of solvent, but is generally about 60 to 150 ° C., preferably about 80 to 120 ° C.
- the time required for the initial drying is generally an effective time for the solvent remaining rate in the coating film to be about 5 to 40% under the above-mentioned temperature conditions, but is generally about 1 to 30 minutes, particularly 2 About 15 minutes. It is preferable to further dry (secondary drying) at a temperature near the boiling point of the solvent or at a temperature equal to or higher than the boiling point.
- the heat treatment conditions are not particularly limited and may be dried at a temperature near or above the boiling point of the solvent, but is generally 120 ° C. to 500 ° C., preferably 200 ° C. to 400 ° C. If it is less than 120 degreeC, drying time will become long and productivity will fall. If it exceeds 500 ° C., the deterioration reaction may proceed depending on the resin composition, and the base film layer may become brittle. Further, the cross-linking point with the epoxy resin is thermally decomposed and oxidized and deteriorates in mountability.
- the time required for the heat treatment may be an effective time that generally eliminates the residual solvent ratio in the coating film under the above temperature conditions, but is generally about several minutes to several tens of hours.
- the initial drying and heat treatment may be performed under an inert gas atmosphere or under reduced pressure.
- the inert gas include nitrogen, carbon dioxide, helium, and argon, but it is preferable to use easily available nitrogen.
- the reaction is preferably performed at a pressure of about 10 ⁇ 5 to 10 3 Pa, preferably about 10 ⁇ 1 to 200 Pa.
- the drying method for both initial drying and secondary drying there are no particular limitations on the drying method for both initial drying and secondary drying, but it can be performed by a conventionally known method such as a roll support method or a floating method.
- the heat treatment may be continuous heat treatment in a heating furnace such as a tenter type, wound in a wound state, and heat treated in a batch type oven. In the case of a batch type, it is preferable to wind up so that an application surface and a non-application surface do not contact.
- the thickness of the heat-resistant resin composition layer of the metal foil laminate (hereinafter also referred to as a base film or a base film layer) can be selected from a wide range, but is generally 3 to 300 ⁇ m after being completely dried.
- the thickness is preferably about 10 to 100 ⁇ m. If the thickness is less than 3 ⁇ m, mechanical properties such as film strength and handling properties are inferior, and in the COF substrate mounting process, the carrier tape transportability and chip mounting properties deteriorate. On the other hand, when the thickness exceeds 300 ⁇ m, characteristics such as flexibility and workability (drying property, coating property) tend to be lowered. In the COF substrate, folding resistance, particularly fine pitch folding resistance and bending resistance deteriorates, and problems such as springback also occur. Moreover, you may surface-treat as needed. For example, surface treatment such as hydrolysis, corona discharge, low temperature plasma, physical roughening, and easy adhesion coating treatment can be performed.
- the base film insoluble rate of the metal foil laminate after initial drying and heat treatment is preferably 40% or more, more preferably 75% or more, still more preferably 80% or more, and most preferably 86% or more.
- the initial drying and heat treatment conditions are defined as described above so that the insoluble rate falls within a predetermined range.
- the logarithmic viscosity and number average molecular weight of the polyimide resin, the compounding amount of the epoxy resin is appropriately determined, and the composition and acid value of the polyimide resin are set within a predetermined range to achieve a suitable insoluble rate. can do.
- the insoluble rate is less than 40%, the mountability is insufficient.
- the upper limit of the insolubility is not particularly limited, but if it is about 90%, the object of the present invention can be sufficiently achieved.
- the N-methyl-2-pyrrolidone solution containing the dissolved portion of the obtained base film layer (sometimes referred to as “polyimide resin extract from which the uncrosslinked portion is extracted”) has the above-mentioned “logarithmic viscosity It can be used for “measurement”, “measurement of average molecular weight”, “measurement of acid value” and the like.
- the insolubility is the dissolution treatment at 100 ° C. for 2 hours only with the portion of the base film layer excluding the metal foil from the metal foil laminate in a 0.5 mass% solution in N-methyl-2-pyrrolidone.
- the insoluble content of the subsequent resin layer is shown by the following formula.
- Insolubility (%) [Mi / Mf] ⁇ 100 (In the formula, Mi represents the weight (g) of the base film layer after the dissolution treatment, and Mf represents the weight (g) of the base film layer before the dissolution treatment.)
- the double-sided metal foil laminate having metal foils on both sides of the present invention is a conventionally known method such as heating lamination of the resin surfaces of the metal foil laminate in which the metal foil is laminated only on one side molded as described above. It can be manufactured by a method such as pasting or pasting together by a conventionally known method through an adhesive layer.
- the laminating method is not particularly limited, and conventionally known methods such as roll laminating, press laminating, and belt press laminating can be adopted.
- the laminating temperature is usually equal to or higher than the Tg of the resin and is 200 ° C. to 500 ° C. It is preferably 250 ° C. to 450 ° C., more preferably 330 ° C. to 400 ° C.
- the laminating time is not particularly limited, but is usually 10 seconds to 10 hours, preferably 1 minute to 1 hour, more preferably 3 minutes to 30 minutes. If it is less than 10 seconds, the adhesiveness is insufficient, and if it exceeds 10 hours, the resin layer is deteriorated and the mechanical properties tend to be lowered. In addition, the cross-linking point is thermally decomposed and thermally deteriorated to deteriorate the mountability.
- the adhesive composition in the case of laminating through the adhesive layer is not particularly limited, and acrylonitrile butadiene rubber (NBR) adhesive, polyamide adhesive, polyester adhesive, polyester urethane adhesive, epoxy resin , Acrylic resin, polyimide resin, polyamideimide resin, polyesterimide resin, and other adhesives can be used, but from the viewpoints of mountability, flex resistance, folding resistance, flexibility, and low springback, etc.
- NBR acrylonitrile butadiene rubber
- a polyimide resin system, a polyamideimide resin system, a polyesterimide resin system, or a resin composition in which an epoxy resin is blended with these resins is preferable.
- the thickness of the adhesive layer is preferably about 1 to 30 ⁇ m.
- the thickness of the adhesive is not particularly limited as long as it does not hinder the performance of the flexible printed circuit board, but if the thickness is too thin, sufficient adhesiveness may not be obtained. If the thickness is too thick, the bending resistance, folding resistance, flexibility, low springback characteristics, and the like may deteriorate.
- a flexible printed wiring board can be produced by a conventionally known process, for example, by a method such as a subtractive method.
- the flexible printed wiring board obtained by the present invention does not deform the substrate film layer even at a chip mounting temperature of 400 ° C. or higher.
- the folding resistance is a value of a folding test based on JIS C 5016 before coating the circuit surface (before coating the circuit surface with a solder resist or a heat resistant film), and is greater than 190 times, preferably 700 times. Above, more preferably 1000 times or more.
- the Gurley type bending resistance which is an index of low spring bag property, is lower than 800 mg, preferably 760 mg or less, more preferably 600 mg or less.
- the heat-resistant film is bonded to the wiring board (base substrate on which the conductor circuit is formed) with an adhesive. A method or a method of applying a liquid coating agent to a wiring board by a screen printing method can be applied.
- polyimide resin-based, polyamide-imide resin-based, polyester-imide resin-based films can be used, but from the viewpoints of mountability, bending resistance, folding resistance, flexibility, and low springback characteristics, etc.
- the film obtained from the polyimide resin of the present invention is preferable.
- Adhesives include acrylonitrile butadiene rubber (NBR) adhesive, polyamide adhesive, polyester adhesive, polyester urethane adhesive, epoxy resin, acrylic resin, polyimide resin, polyamideimide resin, polyesterimide Resin-based adhesives can be used, but polyimide resin-based, polyamide-imide resin-based, or epoxy to these resins from the viewpoint of mountability, flex resistance, folding resistance, flexibility, and low springback characteristics
- NBR acrylonitrile butadiene rubber
- polyamide adhesive polyester adhesive
- polyester urethane adhesive epoxy resin
- acrylic resin polyimide resin
- polyamideimide resin polyamideimide resin
- polyesterimide Resin-based adhesives can be used, but polyimide resin-based, polyamide-imide resin-based, or epoxy to these resins from the viewpoint of mountability, flex resistance, folding resistance, flexibility, and low springback characteristics
- a resin composition containing a resin is preferred.
- liquid coating agent conventionally known epoxy-based or polyimide-based inks can be used, but from the viewpoint of mountability, bending resistance, folding resistance, flexibility, low springback characteristics, etc., preferably polyimide resin Or a polyamideimide resin system, or a resin composition in which an epoxy resin is blended with these resins.
- an adhesive sheet such as an epoxy system or a polyimide system to the wiring board, and in this case also from the viewpoint of mounting properties, bending resistance, folding resistance, flexibility, low springback characteristics, etc.
- an adhesive sheet such as an epoxy system or a polyimide system
- it is a polyimide resin system, a polyamideimide resin system, or a resin composition in which an epoxy resin is blended with these resins.
- Arbitrary patterns can be formed as circuit wiring patterns.
- the flexible printed wiring board of the present invention exhibits a high level of performance even in a circuit provided with a fine wiring pattern. Therefore, the flexible printed wiring board of the present invention is particularly advantageous in a circuit provided with a fine wiring pattern.
- the wiring thickness of the circuit can be 30 ⁇ m or less, the wiring thickness can be 20 ⁇ m or less, and the wiring thickness can be 10 ⁇ m or less. It is.
- the interval between the wirings can be set to 30 ⁇ m or less, can be set to 20 ⁇ m or less, and can be set to 10 ⁇ m or less.
- a fine pattern is formed on a copper foil surface of a two-layer metal foil laminate by a method such as a photolithography method, and further, plating such as tin and a solder resist is coated at a necessary place. it can.
- the semiconductor chip can be mounted by mounting a plated COF lead pattern and chip connection terminals (bumps) by a conventionally known method such as Au-Au bonding or Au-Sn bonding.
- the flexible printed wiring board manufactured in this manner is suitable for a COF substrate, such as a device mounting substrate for a display device such as a liquid crystal display, a plasma display, an organic EL display, a smart phone, a tablet terminal, a digital camera, a portable type. It can be widely used as a substrate material for IC mounting of electronic devices that are becoming smaller, lighter, and thinner, such as relay cables between boards for game machines, operation switch unit boards, and the like.
- V1 represents a solution viscosity measured with an Ubbelohde type viscosity tube
- V2 represents a solvent viscosity measured with an Ubbelohde type viscosity tube
- V1 and V2 represent a polymer solution and a solvent (N-methyl-2-pyrrolidone).
- V3 is the polymer concentration (g / dl).
- ⁇ Measurement of functional group of polyimide resin The measurement of the functional group in the polyimide resin was confirmed by calculating an amine value, an isocyanate value, and an acid value as follows.
- ⁇ Measurement of acid value of polyimide resin> 0.1 g of the powdery polymer used for the measurement of logarithmic viscosity was precisely weighed, and a mixed solvent of N-methyl-2-pyrrolidone / dimethylformamide (50/50 volume ratio) was added to this so that the total was 1 dl. A sample specimen to be titrated was prepared. Subsequently, the solution was titrated with a 1 / 50N potassium hydroxide (ethanol / dimethylformamide solution, volume ratio 50/50) titrant using a potentiometric titrator (AT310, manufactured by Kyoto Electronics Co., Ltd.). The temperature was 25 ° C., and measured according to JIS K2501 (or according to Kyoto Electronics Co., Ltd. Application Note No TII-9800 ver. 01).
- a sample was prepared by dissolving 100 mg of a polyimide resin in 0.6 ml of DMSO-d6. The prepared sample was measured by 1 H-NMR. A sample was prepared by mixing a polyimide resin and DMSO-d6 so that the volume ratio was 1: 1, and measurement was performed by 13 C-NMR.
- ⁇ Measurement of average molecular weight of polyimide resin> The number average molecular weight and polydispersity were measured by the GPC method.
- a sample for measurement was prepared by diluting a resin varnish obtained by polymerization with N-methyl-2-pyrrolidone in which 0.1% by mass of lithium bromide was dissolved to a concentration of 0.5 g / dl.
- N-methyl-2-pyrrolidone in which 0.1% by mass of lithium bromide was dissolved was used as a mobile phase.
- a refractometer manufactured by Showa Denko KK, SE-51 was used. Measurement was performed using a calibration curve prepared from standard polystyrene.
- the folding resistance test which is a measure of the flex resistance and low springback property (repulsive force) of flexible printed wiring boards and metal foil laminates, was prepared as an evaluation sample according to JIS C 5016, with a load of 500 g and a bending diameter of 0. Measured under the condition of .38 mm.
- the test sample (base film) for evaluating the Gurley type bending resistance, insolubility, and mountability was obtained by using the metal foil laminate obtained in each of Examples and Comparative Examples described later at 40 ° C. and 35% cupric chloride.
- the copper foil was removed by etching using the solution.
- ⁇ Gurley type bending resistance (bending repulsive force): index of flexibility and low springback> Film (base film) produced by etching and removing the metal layer of the metal foil laminate obtained in each of Examples and Comparative Examples as an index of the bending resistance and low springback property of the metal foil laminate and flexible printed wiring board ) was measured by the Gurley method under the following conditions. Using a Gurley Bending Softness Tester manufactured by Toyo Seisakusho Co., Ltd., the measured value is the scale when the film test piece is attached to the chuck of the movable arm, rotated left and right at 2 rpm, and the lower end of the film test piece is separated from the pendulum. I read it.
- Measuring device Gurley Stiffness Tester (Garle Stiffness Tester) manufactured by Toyo Manufacturing Co., Ltd. Sample size: 25.4 mm (width) x 88.9 mm (length) x 20 ⁇ m (thickness) Arm rotation speed: 2 rpm
- Insolubility (%) [Mi / Mf] ⁇ 100 (In the formula, Mi represents the weight (g) of insoluble matter, and Mf represents the weight (g) of the resin film.)
- ⁇ Mountability Index of sinkability of IC chip bump>
- An IC chip was disposed on the base film, and a thermocompression bonding test was performed under the following conditions using a flip chip bonder (M95 manufactured by HISOL).
- the substrate film after the test was observed with an SEM, the amount of deformation due to the sinking of the chip bumps was measured, 5 ⁇ m or more was evaluated as x, 2 ⁇ m or less was evaluated as ⁇ , and 1 ⁇ m or less was evaluated as ⁇ .
- Bonding head tool temperature 400 ° C
- Stage temperature 100 ° C Pressure: 20 mgf / ⁇ m 2
- Example 1 In a reaction vessel, 211.3 g (1.10 mol) of trimellitic anhydride, 132.1 g (0.50 mol) of o-tolidine diisocyanate, 125.3 g of 4,4′-diphenylmethane diisocyanate (0.50) in a nitrogen stream. Mol), 0.6 g of potassium fluoride, and 2500 g of N-methyl-2-pyrrolidone (purity 99.9%) were added, the temperature was raised to 100 ° C., and the reaction was allowed to proceed for 5 hours. Next, the mixture was reacted at 130 ° C.
- polyamideimide composition A The obtained polyamideimide resin (referred to as polyamideimide composition A) was dissolved in a polymerization solvent, and the resin properties of logarithmic viscosity, acid value, and number average molecular weight were as shown in Table 1. Thereafter, 24 g of phenol novolac type epoxy resin (JER154 manufactured by Mitsubishi Chemical Corporation) (6% by mass with respect to the total solid content) was blended to prepare a varnish for casting. Then obtained.
- phenol novolac type epoxy resin JER154 manufactured by Mitsubishi Chemical Corporation
- Metal foil laminates are manufactured using cast varnish, flexible printed wiring board for folding resistance evaluation, and insolubility, Gurley type bending resistance (indicator of low springback), and each base for mounting evaluation A material film was prepared and each characteristic was evaluated. The results are shown in Table 1.
- Example 2 Only trimellitic anhydride, which is the acid component of Example 1, was changed to 1.02 mol, and the viscosity was adjusted appropriately so as to have the logarithmic viscosity and molecular weight shown in Table 1, to prepare a polyamideimide resin varnish. All the polyamideimide resin varnishes obtained in Example 2 were dissolved in a solvent, and the resin properties of the obtained resin varnish were as shown in Table 1. Thereafter, 12 g of phenol novolac type epoxy resin (JER154 manufactured by Mitsubishi Chemical Corporation) (3 mass% based on the total solid content) was blended to prepare a varnish for casting.
- phenol novolac type epoxy resin JER154 manufactured by Mitsubishi Chemical Corporation
- polyamideimide composition B The obtained polyamideimide resin (referred to as polyamideimide composition B) was dissolved in a solvent, and the resin properties of logarithmic viscosity, acid value, and number average molecular weight were as shown in Table 1. Thereafter, 12 g of phenol novolac type epoxy resin (JER154 manufactured by Mitsubishi Chemical Corporation) (3 mass% based on the total solid content) was blended to prepare a varnish for casting.
- phenol novolac type epoxy resin JER154 manufactured by Mitsubishi Chemical Corporation
- Examples 4, 5, 6, 7, 8, 9, 10 and Comparative Examples 2, 3, 4, 5 Only the total molar amount of all the acid components was changed as shown in Table 1 while maintaining the molar ratio between the components of the total acid component of Example 3, and appropriately adjusted so that the logarithmic viscosity and molecular weight of Table 1 were obtained.
- the polyamide imide resin varnish was prepared.
- Examples 4, 5, 6, 7, 8, 9, 10 Polyamideimide resins obtained in Comparative Examples 2, 3, 4, 5 were all dissolved in a solvent, and the resin properties were as shown in Table 1. It was. Then, the kind of epoxy resin was made to be the same as that of Example 3, and only the blending amount was changed to the contents of Table 1, and a varnish for casting was produced.
- polyimide resin polyimide composition A
- resin properties of logarithmic viscosity, acid value, and number average molecular weight were as shown in Table 1. Thereafter, 5 g of phenol novolac type epoxy resin (JER154 manufactured by Mitsubishi Chemical Corporation) (1% by mass with respect to the total solid content) was blended to prepare a varnish for casting.
- Example 12 Only the total molar amount of all the acid components was changed as shown in Table 1 while maintaining the molar ratio between the components of the total acid component of Example 11, and appropriately adjusted to have a logarithmic viscosity and molecular weight.
- a polyimide resin varnish was prepared.
- the polyimide resins obtained in Example 12 and Comparative Examples 6, 7, and 8 were all dissolved in the solvent, and the resin properties were as shown in Table 1.
- the kind of epoxy resin was made into the same as that of Example 11, the compounding quantity was changed into the content of Table 1, and the varnish for casting was produced.
- Example 11 a metal foil laminate was produced, and a flexible printed wiring board for evaluating folding resistance, insolubility, Gurley type bending resistance (an index of low springback property), and mounting property evaluation Each base film was prepared and each characteristic was evaluated. The characteristic evaluation results are shown in Table 1.
- the epoxy compounding amount (% by mass) represents the compounding amount (% by mass) of the epoxy resin when the total amount of the polyimide resin and the epoxy resin is 100% by mass.
- Polyamideimide A, polyamideimide B, polyamideimide C, and polyimide A were all soluble in N-methyl-2-pyrrolidone (purity 99.9%) by 10% by mass or more.
- the polyamideimide A, polyamideimide B, and polyimide A of Examples 1 to 12 and Comparative Examples 1 to 8 are apparent from the production method, but the acid value, amine value, isocyanate value, and NMR measurement Thus, all the resins had a carboxyl group, an amino group, and an isocyanate group only at the terminal.
- Polyamideimide C of Comparative Example 9 had a carboxyl group in addition to the terminal as measured by the same analytical method.
- the metal foil laminate of the present invention and the flexible printed wiring board obtained from the metal foil laminate, sinking into the base film layer of the chip when bonding the semiconductor chip and the metal wiring (mountability), bending mounting of the substrate, etc.
- flexible printed wiring boards that are directly mounted with electronic components such as ICs and LSIs in applications such as liquid crystal display devices, smart phones, and tablet terminals, which are becoming smaller, lighter, and thinner, especially as a chip-on-film substrate. Can be used widely.
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Abstract
Description
即ち、COF用基板として好適な金属箔積層体に関し、基板の反りや寸法精度、接着性等の特性は従来通り高い品質を維持したまま、チップと金属配線を接合する際のチップの基材フィルム層への沈み込みの防止(すなわち実装性) と、その実装性とトレードオフの関係にある耐屈曲性、耐折性、柔軟性、及び基板の折り曲げ実装時等に問題視されているスプリングバック等の低減(すなわち低スプリングバック)を両立させ同時に実現することである。
エポキシ樹脂により架橋されてなるポリイミド系樹脂を含む耐熱性樹脂組成物が金属箔の少なくとも片面に積層された基材フィルムと金属箔との金属箔積層体であり、かつ、以下の(a)及び(b)であることを特徴とする金属箔積層体;
(a)ポリイミド系樹脂とエポキシ樹脂の総量を100質量%としたときのエポキシ樹脂の配合量が0.1質量%以上10質量%以下であること;
(b)金属箔積層体から金属箔を取り除いて得られる基材フィルムに、基材フィルムの濃度が0.5質量%となるようにN-メチル-2-ピロリドンを加え、100℃で2時間加熱処理した後の不溶率が40%以上であること。
(項2)
さらに、以下の(c)及び/又は(d)であることを特徴とする項1に記載の金属箔積層体;
(c)架橋前のポリイミド系樹脂の対数粘度が、N-メチル-2-ピロリドン中(ポリマー濃度0.5g/dl)、30℃での測定条件下で、0.40dl/g以上3.50dl/g以下であること;
(d)エポキシ樹脂により架橋された後の未架橋部分のポリイミド系樹脂の対数粘度が、N-メチル-2-ピロリドン中(ポリマー濃度0.5g/dl)、30℃での測定条件下で、0.40dl/g以上3.50dl/g以下であること。
(項3)
さらに、以下の(e)及び/又は(f)であることを特徴とする項1又は項2のいずれかに記載の金属箔積層体;
(e)架橋前のポリイミド系樹脂の数平均分子量が10000以上200000以下であること。
(f)エポキシ樹脂により架橋された後の未架橋部分のポリイミド系樹脂の数平均分子量が10000以上200000以下であること。
(項4)
さらに、以下の(g)及び/又は(h)であることを特徴とする項1~3のいずれかのいずれかに記載の金属箔積層体;
(g)架橋前のポリイミド系樹脂の酸価が5eq/ton以上1000eq/ton以下であること;
(h)エポキシ樹脂により架橋された後の未架橋部分のポリイミド系樹脂の酸価が5eq/ton以上1000eq/ton以下であること。
(項5)
さらに、以下の(i)であることを特徴とする項1~4のいずれかに記載の金属箔積層体;
(i)耐熱性樹脂組成物中の全固形成分を100質量%としたときに、ポリイミド系樹脂及びエポキシ樹脂の合計の配合量が30質量%以上であること。
(項6)
さらに、以下の(j)であることを特徴とする項1~5のいずれかに記載の金属箔積層体;
(j)ポリイミド系樹脂がポリアミドイミド樹脂であり、ポリアミドイミド樹脂の構造単位中に、式(1)で示される繰り返し構造単位が5モル%以上99モル%以下含まれること;
(項7)
さらに、以下の(k)であることを特徴とする項1~6のいずれかに記載の金属箔積層体;
(k)エポキシ樹脂が下記一般式(2)のフェノールノボラックグリシジルエーテルであること。
〔nは、1から20の整数〕
(項8)
項1~7のいずれかに記載の金属箔積層体を含有するフレキシブルプリント配線板。
(項9)
JIS C 5016に基づく耐折性試験の値が、190回超である項8に記載のフレキシブルプリント配線板。
(項10)
ガーレ式剛軟度が、800mg未満である項8または項9に記載のフレキシブルプリント配線板。
本発明の金属箔積層体は、金属箔の少なくとも片面に耐熱性樹脂組成物を含有する基材フィルムが積層された該基材フィルムと金属箔との積層体である。耐熱性樹脂組成物は、ポリイミド系樹脂の樹脂末端の官能基のみがエポキシ樹脂により架橋されてなることが好ましい。
ポリイミド系樹脂の樹脂末端の官能基としては、カルボキシル基、酸無水物基、イソシアネート基、アミノ基等が好ましく、カルボキシル基、酸無水物基が特に好ましい。
本発明で使用できるポリイミド樹脂は、特に限定されないが、有機溶剤に可溶なポリイミド樹脂が好ましい。本発明で使用できるポリイミド樹脂に用いる酸成分としては、ピロメリット酸、3,3’,4,4’-ベンゾフェノンテトラカルボン酸、3,3’,4,4’-ビフェニルテトラカルボン酸、3,3’ ,4,4’ジフェニルスルホンテトラカルボン酸、3,3’ ,4,4’-ジフェニルエーテルテトラカルボン酸、ナフタレン-2,3,6,7-テトラカルボン酸、ナフタレン-1,2,4,5-テトラカルボン酸、ナフタレン-1,4,5,8-テトラカルボン酸などの一無水物、二無水物、エステル化物などのモノマーを単独、或いは2種以上の混合物として使用できる。
本発明で使用できるポリイミド樹脂に用いるアミン成分(或いはそれに対応するイソシアネート成分)としては、p-フェニレンジアミン、m-フェニレンジアミン、2,4-ジアミノトルエン、2,5-ジアミノトルエン、2,4-ジアミノキシレン、P-キシレンジアミン、m-キシレンジアミン、2,4-ジアミノデュレン、1,4-ナフタレンジアミン、1,5-ナフタレンジアミン、2,6-ナフタレンジアミン、2,7-ナフタレンジアミン、ベンジジン、3,3’-ジヒドロキシベンジジン、3,3’-ジメトキシベンジジン、3,3’-ジメチル-4,4’-ジアミノビフェニル(o-トリジン)、3,3’-ジエチル-4,4’-ジアミノビフェニル、2,2’-ジメチル-4,4’-ジアミノビフェニル、2,2’-ジエチル-4,4’-ジアミノビフェニル、3,3’-ジメトキシ-4,4’-ジアミノビフェニル、3,3’-ジエトキシ-4,4’-ジアミノビフェニル、2,2’-ビス(トリフルオロメチル)ベンジジン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルエーテル、3,4’-ジアミノジフェニルエーテル、2,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルエーテル、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノジフェニルスルホン、4,4’-ジアミノベンゾフェノン、3,3’-ジアミノベンゾフェノン、4、4’-ジアミノジフェニルスルフィド、3、3’-ジアミノジフェニルスルフィド、4、4’-ジアミノジフェニルプロパン、3、3’-ジアミノジフェニルプロパン、4,4’-メチレンビス(2-メチルアニリン)、4,4’-メチレンビス(2-エチルアニリン)、4,4’-メチレンビス(2,6-ジメチルアニリン)、4,4’-メチレンビス(2,6-ジエチルアニリン)、4,4’-ジアミノベンズアニリド、1,4-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,3-ビス(3-アミノフェノキシ)ベンゼン、ジアミノターフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス(4-(3-アミノフェノキシ)フェニル)スルホン、ビス(4-(4-アミノフェノキシ)フェニル)スルホン、2,2-ビス(4-(4-アミノフェノキシ)フェニル)プロパン、2,2-ビス(4-(4-アミノフェノキシ)フェニル)ヘキサフルオロプロパン、2,2-ビス(4-アミノフェニル)ヘキサフルオロプロパンなどのモノマーを単独、或いは2種以上の混合物として使用できる。
本発明で使用できるポリアミドイミド樹脂は、特に限定されないが、有機溶剤に可溶なポリアミドイミド樹脂が好ましい。本発明で使用できるポリアミドイミド樹脂に用いる酸成分としては、トリメリット酸無水物、ジフェニルエーテル-3,4,4’-トリカルボン酸無水物、ジフェニルスルホン-3,4,4’-トリカルボン酸無水物、ベンゾフェノン-3,4,4’-トリカルボン酸無水物、ナフタレン-1,2,5-トリカルボン酸無水物などのトリカルボン酸無水物類のモノマーが単独或いは2種以上の混合物として使用できる。
本発明で使用できるポリアミドイミド樹脂に用いるアミン成分(或いはそれに対応するイソシアネート成分)としては、ポリイミド樹脂のアミン成分で例示の化合物が使用できる。
酸成分としては、アジピン酸、アゼライン酸、セバシン酸、ドデカン酸等の脂肪族ジカルボン酸類、ブタン-1,2,4-トリカルボン酸等の脂肪族トリカルボン酸の一無水物、二無水物、エステル化物、ブタン-1,2,3,4-テトラカルボン酸、シクロペンタン-1,2、3,4-テトラカルボン酸等の脂肪族テトラカルボン酸の一無水物、二無水物、エステル化物、 シクロヘキサン-4,4’-ジカルボン酸等の脂環族ジカルボン酸類、シクロヘキサントリカルボン酸、ジシクロヘキシルエーテル-3,3’,4’-トリカルボン酸、ジシクロヘキシルスルホン-3,4,4’-トリカルボン酸、ジシクロヘキシルメタン-3,4,4’-トリカルボン酸等の脂肪族テトラカルボン酸の一無水物、エステル化物、シクロペンタン-1,2、3,4-テトラカルボン酸等の脂環族テトラカルボン酸一無水物、二無水物、エステル化物、などが、単独、若しくは、混合物として使用できる。また、ポリイミド樹脂の酸成分として例示の酸成分を単独、若しくは、混合物として使用できる。
アミン成分としては、トランス-1,4-ジアミノシクロヘキサン、シス-1,4-ジアミノシクロヘキサン、1,4-ジアミノシクロヘキサン(トランス/シス混合物)、1,3-ジアミノシクロヘキサン、4,4’-メチレンビス(シクロヘキシルアミン) (トランス体、シス体、トランス/シス混合物)、イソホロンジアミン、1,4-シクロヘキサンビス(メチルアミン)、2,5-ビス(アミノメチル)ビシクロ〔2.2.1〕ヘプタン、2,6-ビス(アミノメチル)ビシクロ〔2.2.1〕ヘプタン、3,8-ビス(アミノメチル)トリシクロ〔5.2.1.0〕デカン、1,3-ジアミノアダマンタン、4,4’-メチレンビス(2-メチルシクロヘキシルアミン)、4,4’-メチレンビス(2-エチルシクロヘキシルアミン)、4,4’-メチレンビス(2,6-ジメチルシクロヘキシルアミン)、4,4’-メチレンビス(2,6-ジエチルシクロヘキシルアミン)、2,2-ビス{4-(4-アミノシクロヘキシルエーテル)シクロヘキシル}プロパン、2,2-ビス{4-(4-アミノシクロヘキシルエーテル)シクロヘキシル}ヘキサフルオロプロパン、などの脂環族ジアミン類、テトラメチレンジアミン、ヘキサメチレンジアミンなどの脂肪族ジアミン、或いはこれらに対応するジイソシアネートを単独あるいは2種以上の混合物として用いても良い。
ポリイミド系樹脂は、酸成分とアミン成分(或いは、これに対応するイソシアネート成分)の重縮合反応により得られ、例えば、ジイソシアネート法、酸クロリド法、低温溶液重合法、室温溶液重合法など、従来公知の方法で製造できる。好ましくは、脱炭酸反応によりポリマーが得られ、得られた重合溶液が、そのまま、後述のキャスト用ワニスとして用いることのできる、ジイソシアネート法が好ましい。
本発明のエポキシ樹脂による架橋前のポリイミド系樹脂の対数粘度は、N-メチル-2-ピロリドン中(ポリマー濃度0.5g/dl)、30℃での対数粘度にして、0.40dl/g以上3.50dl/g以下が良く、好ましくは0.80dl/g以上3.50dl/g以下、より好ましくは、1.00dl/g以上3.50dl/g以下、さらに好ましくは1.30dl/g以上3.50dl/g以下である。対数粘度が0.40dl/g未満では、金属箔積層体、フレキシブルプリント配線板の耐屈曲性、耐折性等の機械的特性が不十分となる。また、3.50dl/g超では溶液粘度が高くなる為、金属箔積層体へ加工する際の成形加工が困難となることがある。また、実装性(チップ実装温度での基材フィルム層の凹み)が悪化する傾向にある。
架橋前のポリイミド系樹脂の対数粘度の測定は、架橋前のポリイミド系樹脂を含む溶液を大量のアセトンで、再沈殿、精製して作製した粉末状のポリマーサンプルを用いる。粉末状サンプルをポリマー濃度が0.5g/dlとなるようにN-メチル-2-ピロリドンに溶解し、その溶液の溶液粘度及び溶媒粘度を30℃で、ウベローデ型の粘度管により測定する。対数粘度値は、その結果より、下記の式で計算する。
対数粘度(dl/g)=[ln(V1/V2)]/V3
{上記式中、V1はウベローデ型粘度管により測定した溶液粘度を示し、V2はウベローデ型粘度管により測定した溶媒粘度を示すが、V1及びV2はポリマー溶液及び溶媒(N-メチル-2-ピロリドン)が粘度管のキャピラリーを通過する時間から求める。また、V3は、ポリマー濃度(g/dl)である。}
或いは、重合後の得られたワニスを測定サンプルとして用いることもできる。この場合は、ワニス濃度より固形分換算し、ポリマー濃度が0.5g/dlとなるように測定サンプル溶液を調整する。
また、エポキシ樹脂により架橋された後の未架橋部分のポリイミド系樹脂の対数粘度は、後述の不溶率の測定で、未架橋部分が抽出されたポリイミド系樹脂の抽出液を用いることで測定できる。好ましくは、抽出液を大量のアセトンで再沈殿、精製して作製した粉末状のポリマーサンプルを用いる。
ここで、未架橋部分のポリイミド系樹脂とは、本願の場合、その多くはエポキシ樹脂と反応していないポリイミド系樹脂であるが、一部、エポキシ樹脂と反応していても、完全にネットワーク構造となっていない(不溶化していない)部分も含まれる。
本発明のエポキシ樹脂による架橋前のポリイミド系樹脂の数平均分子量は、10000以上200000以下に相当する分子量を有するものが好ましく、より好ましくは21000以上180000以下、さらに好ましくは、47000以上160000以下である。数平均分子量が10000未満では、金属箔積層体、フレキシブルプリント配線板の耐屈曲性、耐折性等の機械的特性が不十分となることがある。また、200000超では溶液粘度が高くなる為、金属箔積層体へ加工する際の成形加工が困難となることがある。また、実装性(チップ実装温度での基材フィルム層の凹み)が悪化する傾向にある。
分子量の測定は、GPC法により標準物質から作成した検量線を用いて以下の条件で測定する。
移動相:臭化リチウムを0.1質量%溶解したN-メチル-2-ピロリドン
ディテクター:屈折率計(昭和電工(株)製、SE-51)
標準物質:以下の分子量の標準ポリスチレン
(1)6770000
(2)2870000
(3)1260000
(4) 355000
(5) 102000
(6) 43900
(7) 9500
(8) 5400
(9) 2800
また、カラムは、shodex AD800P、shodex AD805/S、shodex AD804/S、shodex AD803/S、shodex AD802/S、を直列に接続し使用する。
また、エポキシにより架橋された後の未架橋部分のポリイミド系樹脂の分子量は、後述の不溶率の測定で、未架橋部分が抽出されたポリイミド系樹脂の抽出液を用いることで測定できる。好ましくは、抽出液を大量のアセトンで再沈殿、精製して作製した粉末状のポリマーサンプルを用いる。ここで、未架橋部分のポリイミド系樹脂とは、本願の場合、その多くはエポキシと反応していないポリイミド系樹脂であるが、一部、エポキシと反応していても、完全にネットワーク構造となっていない(不溶化していない)部分も含まれる。
本発明のエポキシ樹脂による架橋前のポリイミド系樹脂の酸価は、5eq/ton以上1000eq/ton以下が好ましく、より好ましくは10eq/ton以上600eq/ton以下、さらに好ましくは15eq/ton以上300eq/ton以下、特に好ましくは20eq/ton以上160eq/ton以下である。酸価が5eq/ton未満では、金属箔積層体へ加工する際の成形加工が困難となり、また、実装性(チップ実装温度での基材フィルム層の凹み)が悪化する傾向にある。1000eq/ton超では、金属箔積層体、フレキシブルプリント配線板の耐屈曲性、耐折性等の機械的特性が不十分となることがある。
酸価の測定は、JIS K2501に準じ、1/50N 塩酸(エタノール/ジメチルホルムアミド溶液、容量比=50/50)滴定液で、電位差滴定装置(京都電子(株)製、AT310)を用い、25℃で滴定する。検体となるサンプルは、対数粘度の測定で用いた粉末状のポリマー0.1gを精秤し、これに、N-メチル-2-ピロリドン/ジメチルホルムアミド(50/50容量比)の混合溶媒を1dlとなるよう加え、作製する。
また、エポキシにより架橋された後の未架橋部分のポリイミド系樹脂の酸価は、後述の不溶率の測定で、未架橋部分が抽出されたポリイミド系樹脂の抽出液を用いることで測定できる。好ましくは、抽出液を大量のアセトンで再沈殿、精製して作製した粉末状のポリマーサンプルを用いる。
ここで、未架橋部分のポリイミド系樹脂とは、本願の場合、その多くはエポキシと反応していないポリイミド系樹脂であるが、一部、エポキシと反応していても、完全にネットワーク構造となっていない(不溶化していない)部分も含まれる。
本発明では、上述により得られたポリイミド系樹脂の重合溶液にエポキシ樹脂を加え、反応および/または配合し、耐熱性樹脂組成物とすることで、後述の金属箔へのキャスト用ワニスにできる。従って、使用する好ましい溶媒は、前述の重合溶媒と同様である。
耐熱性樹脂組成物中のポリイミド系樹脂とエポキシ樹脂の合計の配合量は、耐熱性樹脂組成物中の全固形成分を100質量%としたときに、30質量%以上、好ましくは50質量%以上、さらに好ましくは、70重量以上である。30質量%より少ないと、実装性が悪化することがある。
それぞれ市販のものがそのまま使用でき、例えば、DIC(株)製EPICLON(登録商標)840(ビスフェノールA型エポキシ樹脂)、三菱化学(株)製JER154JER152、JER157S70(ノボラック型エポキシ樹脂)、DIC(株)製HP-7200(ジシクロペンタジエン型エポキシ樹脂)、三菱ガス化学(株)製TETRAD(登録商標)-X、TETRAD(登録商標)-C(多官能グリシジルアミン型エポキシ樹脂)、DIC(株)製EPICLON(登録商標)HP-4032(ナフタレン型エポキシ樹脂)、三菱化学(株)製YX4000(ビフェニル型エポキシ樹脂)等がある。より好ましくは、ビスフェノールA型エポキシ樹脂、ノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂であり、さらに好ましくは、フェノールノボラックグリシジルエーテル、クレゾールノボラックグリシジルエーテル、臭素化フェノールノボラックグリシジルエーテル、臭素化クレゾールノボラックグリシジルエーテルなどのノボラック型エポキシ樹脂、及びビスフェノールAグリシジルエーテル、ブロム化ビスフェノールAジグリシジルエーテルなどのビスフェノールA型エポキシ樹脂であり、最も好ましいのは下記一般式(2)のフェノールノボラックグリシジルエーテルである。
上述のようにして作製された耐熱性樹脂組成物からなるキャスト用ワニスを用いて金属箔と積層することにより金属箔積層体とすることができる。すなわち、本発明の金属箔積層体は、耐熱性樹脂組成物を含有する基材フィルムと金属箔との積層体である。本発明では、フレキシブル金属箔積層体であることが好ましい。
本発明に用いる金属箔としては、銅箔、アルミニウム箔、スチール箔、及びニッケル箔などを使用することができ、これらを複合した複合金属箔などについても用いることができる。好ましくは銅箔である。
本発明において、初期乾燥、熱処理後の金属箔積層体の基材フィルム不溶率は40%以上が好ましく、より好ましくは75%以上、さらに好ましくは80%以上、最も好ましくは86%以上である。逆に言えば、不溶率を所定の範囲に収まるよう、初期乾燥、熱処理条件を上述のように規定している。すなわち、上述のとおり、ポリイミド系樹脂の対数粘度や数平均分子量、エポキシ樹脂の配合量を適切に定め、さらにポリイミド系樹脂の組成や酸価を所定の範囲とすることで好適な不溶率を達成することができる。不溶率が40%未満では、実装性が不十分である。不溶率の上限は特にないが、90%程度であれば本発明の目的を十分達成できる。
なお、得られる基材フィルム層の溶解部分を含むN-メチル-2-ピロリドン溶液(「未架橋部分が抽出されたポリイミド系樹脂の抽出液」ということがある)は、前述の「対数粘度の測定」、「平均分子量の測定」、及び「酸価の測定」などに供することができる。
尚、不溶率とは、金属箔積層体から金属箔を除いた部分の基材フィルム層のみをN-メチル-2-ピロリドン中0.5質量%濃度の溶液で100℃、2時間溶解処理した後の樹脂層の不溶分を示し、下式で示されるものである。
不溶率(%)=[Mi/Mf]×100
(式中、Miは溶解処理後の基材フィルム層の重量(g)を示し、Mfは溶解処理前の基材フィルム層の重量(g)を示す。)
本発明で得られるフレキシブルプリント配線板は、400℃以上ものチップ実装温度でも基材フィルム層の変形は生じない。耐折性は、回路表面を被覆する前(ソルダーレジストや耐熱性フィルムで回路表面を被覆する前)のJIS C 5016に基づく耐折性試験の値で、190回より大きく、好ましくは、700回以上、より好ましくは1000回以上である。また、低スプリンングバッグ性の指標となるガーレ式剛軟度(或いは曲げ反発力)は、800mgより低く、好ましくは760mg以下、より好ましくは600mg以下である。
導体回路のソルダーレジスト、或いは、汚れやキズなどから保護する目的で回路表面を被覆する場合は、耐熱性フィルムを接着剤を介して、配線板(導体回路が形成されたベース基板)に貼り合わせる方法、或いは、液状の被覆剤をスクリーン印刷法で配線板に塗布する方法などが適用できる。
このようにして製造されるフレキシブルプリント配線板は、COF基板に好適であり、液晶ディスプレイ、プラズマディスプレイ、有機ELディスプレイなどの表示装置用デバイス実装基板や、スマートホン、タブレット端末、デジタルカメラ、携帯型ゲーム機などの基板間中継ケーブル、操作スイッチ部基板等、小型化、軽量化、軽薄化が進む電子機器のIC実装用基板材料等に幅広く使用できる。
また、官能基がポリマー末端であることは、分子量と官能基当量、NMRからの官能基定量結果から、確認できた。
ポリイミド系樹脂を含む溶液を大量のアセトンで、再沈殿、精製して作製した粉末状のポリマーサンプルを用いた。粉末状サンプルをポリマー濃度が0.5g/dlとなるようにN-メチル-2-ピロリドンに溶解し、その溶液の溶液粘度及び溶媒粘度を30℃で、ウベローデ型の粘度管により測定した。対数粘度値は、その結果より、下記の式で計算した。
対数粘度(dl/g)=[ln(V1/V2)]/V3
{上記式中、V1はウベローデ型粘度管により測定した溶液粘度を示し、V2はウベローデ型粘度管により測定した溶媒粘度を示すが、V1及びV2はポリマー溶液及び溶媒(N-メチル-2-ピロリドン)が粘度管のキャピラリーを通過する時間から求める。また、V3は、ポリマー濃度(g/dl)である。}
ポリイミド系樹脂中の官能基の測定は、以下のようにアミン価、イソシアネート価、酸価を算出することで確認した。
対数粘度の測定で用いた粉末状のポリマー0.1gを精秤し、これに、N-メチルー2-ピロリドン/ジメチルホルムアミド(50/50容量比)の混合溶媒を全体で1dlとなるよう加え、滴定するサンプル検体を作製した。次いで、1/50N 水酸化カリウム(エタノール/ジメチルホルムアミド溶液、容量比=50/50)滴定液で、電位差滴定装置(京都電子(株)製、AT310)を用いて滴定した。温度は25℃とし、JIS K2501に準じ、(或いは、京都電子(株)Application Note No TII-9800 ver.01に準じ、)測定した。
酸価の測定と同様にし、滴定するサンプル検体を作製し、
JIS K 7301に準じ(或いは、京都電子(株)Application Note No TII-98003に準じ)、ジ-n-ブチルアミンを1/50N塩酸(エタノール/ジメチルホルムアミド溶液、容量比=50/50)滴定液で、電位差滴定装置(京都電子(株)製、AT310)を用いて逆滴定した。
酸価の測定と同様にし、滴定するサンプル検体を作製し、1/50N 塩酸(エタノール/ジメチルホルムアミド溶液、容量比=50/50)滴定液で、電位差滴定装置(京都電子(株)製、AT310)を用いて滴定した。測定は、京都電子(株)Application Note TII-97003に準じた。
ポリイミド系樹脂100mgをDMSO-d6 0.6mlに溶解し、試料を調整した。調整した試料を1H-NMRにて測定した。また、ポリイミド系樹脂とDMSO-d6を体積比が1:1となるように混合して試料を調整し、13C-NMRにて測定した。
数平均分子量、及び多分散度の測定は、GPC法により測定した。測定の為のサンプルは、重合により得られた樹脂ワニスを臭化リチウムを0.1質量%溶解したN-メチル-2-ピロリドンで0.5g/dlの濃度に希釈し、調整した。移動相としては、臭化リチウムを0.1質量%溶解したN-メチル-2-ピロリドンを、ディテクターは、屈折率計(昭和電工(株)製、SE-51)を用い、以下の分子量の標準ポリスチレンから作製した検量線を用いて測定した。
(1)6770000
(2)2870000
(3)1260000
(4) 355000
(5) 102000
(6) 43900
(7) 9500
(8) 5400
(9) 2800
また、カラムは、shodex AD800P、shodex AD805/S、shodex AD804/S、shodex AD803/S、shodex AD802/S、を直列に接続し使用した。
後述の各実施例、比較例で得られた樹脂溶液を厚さ12μmの電解銅箔(福田金属箔粉工業(株)製CF-T9D-SVR、表面粗度Rz1.1μm)に乾燥後の厚みが30μmになるようにナイフコーターで塗布した。次いで、50℃~100℃の温度下、透明でタックフリーな状態になるまで乾燥後、ステンレス製の枠に上下面、左右面の端を固定し、真空下、200℃60分、220℃60分、260℃10時間、320℃10分の条件で加熱処理した。
フレキシブルプリント配線版や金属箔積層体の耐屈曲性、低スプリングバック性(反撥力)の尺度となる耐折性試験は、JIS C 5016により、評価用サンプルを作製し、荷重500g、屈曲径0.38mmの条件で測定した。
ガーレ式剛軟度、不溶率、実装性評価用のテストサンプル(基材フィルム)は、後述の各実施例、比較例で得られた金属箔積層体を40℃、35%の塩化第二銅溶液を用いて、銅箔をエッチング除去し作製した。
金属箔積層体、フレキシブルプリント配線板の剛軟度、低スプリングバック性の指標として、各実施例、比較例で得られた金属箔積層体の金属層をエッチング除去し作製したフィルム(基材フィルム)をガーレ法により以下の条件で測定した。(株)東洋製作所製ガーレ剛軟度試験機を用い、測定値は、フィルム試験片を可動アームのチャックに取り付け、2rpmで左右に回転させ、フィルム試験片下端が振子から離れた時の目盛りを読み取った。
測定装置;(株)東洋製作所製ガーレ剛難度試験機(ガーレステフネステスタ)
サンプルサイズ;25.4mm(巾)×88.9mm(長さ)×20μm(厚み)
アーム回転速度;2rpm
基材フィルムをN-メチル-2-ピロリドンに溶解させ、基材フィルム層の0.5質量%N-メチル-2-ピロリドン溶液を得た。溶液の調製は100ml三角フラスコを用いて行った。
次いで、この溶液を、100℃で2時間加熱処理(100℃のオイルバスに溶液の入った三角フラスコを漬け静置する)し、室温まで冷却後、三角フラスコ中の不溶分を100mlのN-メチル-2-ピロリドンで洗い流しながら、不溶分をガラスフィルター(3G-2番)で濾別した。
その後、ガラスフィルターごと200℃で20時間真空乾燥し、その重量を測定し、その値からあらかじめ測定しておいたガラスフィルターの重量を差引き、不溶分の重量を測定した。このようにして求めた不溶分の重量(Mi)と樹脂フィルムの重量(Mf)より、下記式により計算した。
不溶率(%)=[Mi/Mf]×100
(式中、Miは不溶分の重量(g)を示し、Mfは樹脂フィルムの重量(g)を示す。)
基材フィルムにICチップを配設し、フリップチップボンダー(HISOL社製M95)で、以下条件で熱圧着試験を実施した。試験後の基材フィルムをSEM観察し、チップバンプの沈み込みによる変形量を測定、5μm以上を×、2μm以下を○、1μm以下を◎とした。
ボンディングヘッドツール温度;400℃
ステージ温度;100℃
圧力;20mgf/μm2
溶液粘度の測定は、東洋計器(株)製B型粘度計でNo6ロータ、10rpmの条件で測定した。
反応容器に、窒素気流下、無水トリメリット酸211.3g(1.10モル)、o-トリジンジイソシアネート132.1g(0.50モル)、4,4’ -ジフェニルメタンジイソシアネート125.3g(0.50モル)、フッ化カリウム0.6g、及びN-メチル-2-ピロリドン(純度99.9%)2500gを加え、100℃まで昇温し、そのまま5時間反応させた。次いで、130℃で3時間反応させ、溶液粘度が400dPa・sになるよう、N-メチル-2-ピロリドンを加え濃度を調整、室温まで冷却した。得られたポリアミドイミド樹脂(ポリアミドイミド組成Aとする)は、重合溶媒に溶解しており、対数粘度、酸価、数平均分子量の各樹脂特性は表1の通りであった。
その後、フェノールノボラック型エポキシ樹脂(三菱化学(株)製JER154)24g(全固形分に対し6質量%)を配合し、キャスト用ワニスを作製した。次いで、得られた。
キャスト用ワニスを用いて金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。結果を表1に示す。
実施例1の酸成分である無水トリメリット酸のみ1.02モルに変更し、表1の対数粘度、分子量になるよう、適宜調整し、ポリアミドイミド樹脂ワニスを作製した。実施例2、で得られたポリアミドイミド樹脂ワニスはいずれも溶媒に溶解しており、得られた樹脂ワニスの樹脂特性は表1の通りであった。
その後、フェノールノボラック型エポキシ樹脂(三菱化学(株)製JER154)12g(全固形分に対し3質量%)を配合し、キャスト用ワニスを作製した。次いで、得られたキャスト用ワニスを用いて金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。特性評価結果を表1に示す。
実施例1の酸成分である無水トリメリット酸のみ1.15モルに変更し、表1の対数粘度、分子量になるよう、適宜調整し、ポリアミドイミド樹脂ワニスを作製した。比較例1で得られたポリアミドイミド樹脂ワニスはいずれも溶媒に溶解しており、得られた樹脂ワニスの樹脂特性を表1の通りであった。
その後、フェノールノボラック型エポキシ樹脂(三菱化学(株)製JER154)4g(全固形分に対し1質量%)を配合しキャスト用ワニスを作製した。次いで、得られたキャスト用ワニスを用いて金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。特性評価結果を表1に示す。
反応容器に、窒素気流下、無水トリメリット酸161.4g(0.84モル)、3,3’ ,4,4’ -ベンゾフェノンテトラカルボン酸二無水物50.8g(0.16モル)、3,3’ ,4,4’-ビフェニルテトラカルボン酸二無水物15.5g(0.05モル)、o-トリジンジイソシアネート264.3g(1.00モル)、フッ化カリウム0.6g、及びN-メチル-2-ピロリドン(純度99.9%)2230gを加え、100℃まで昇温しそのまま6時間反応させた。次いで、130℃で4時間反応させ、溶液粘度が300dPa・sになるよう、N-メチル-2-ピロリドンを加え濃度を調整、室温まで冷却した。得られたポリアミドイミド樹脂(ポリアミドイミド組成Bとする)は溶媒に溶解しており、の対数粘度、酸価、数平均分子量の各樹脂特性は表1の通りであった。
その後、フェノールノボラック型エポキシ樹脂(三菱化学(株)製JER154)12g(全固形分に対し3質量%)を配合し、キャスト用ワニスを作製した。次いで、得られたキャスト用ワニスを用いて金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。結果を表1に示す。
実施例3の全酸成分の各構成要素間のモル比率を維持したまま全酸成分の合計のモル量のみ表1に記載のように変更し、表1の対数粘度、分子量になるよう、適宜調整し、ポリアミドイミド樹脂ワニスを作製した。実施例4、5、6、7、8、9、10比較例2、3、4、5で得られたポリアミドイミド樹脂はいずれも溶媒に溶解しており、樹脂特性は表1の通りであった。
その後、エポキシ樹脂の種類は実施例3と同様にし、配合量のみ表1の内容に変え、キャスト用ワニスを作製した。次いで、得られたキャスト用ワニスを用いて金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。特性評価結果を表1に示す。
反応容器に、窒素気流下、3,3’ ,4,4’-ビフェニルテトラカルボン酸二無水物150.1g(0.51モル%)、3,3’ ,4,4’-ジフェニルスルホンテトラカルボン酸二無水物182.6g(0.51モル%)、o-トリジンジイソシアネート264.3g(1.00モル%)、フッ化カリウム0.6g、及びN-メチル-2-ピロリドン(純度99.9%)2890gを加え、100℃まで昇温し、そのまま6時間反応させた。次いで、130℃で2時間反応させ、溶液粘度が400dPa・sになるよう、N-メチル-2-ピロリドンを加え濃度を調整、室温まで冷却した。得られたポリイミド樹脂(ポリイミド組成Aとする)は溶媒に溶解しており、の対数粘度、酸価、数平均分子量の各樹脂特性は表1の通りであった。
その後、フェノールノボラック型エポキシ樹脂(三菱化学(株)製JER154)5g(全固形分に対し1質量%)を配合し、キャスト用ワニスを作製した。次いで、得られたキャスト用ワニスを用いて金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。結果を表1に示す。
実施例11の全酸成分の各構成要素間のモル比率を維持したまま全酸成分の合計のモル量のみ表1に記載のように変更し、対数粘度、分子量になるよう、適宜調整し、ポリイミド樹脂ワニスを作製した。実施例12、比較例6、7、8で得られたポリイミド樹脂はいずれも溶媒に溶解しており、樹脂特性は表1の通りであった。
その後、エポキシ樹脂の種類は実施例11と同様にし、配合量を表1の内容に変え、キャスト用ワニスを作製した。次いで実施例11と同様にして、金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。特性評価結果を表1に示す。
全酸成分を無水トリメリット酸(0.99モル)およびトリメリット酸(0.11モル)とし、その他は、実施例1同様にし、ポリアミドイミド樹脂ワニスを作製した。ポリアミドイミド樹脂は溶媒に溶解しており、樹脂特性は表1の通りであった。
その後、その後、フェノールノボラック型エポキシ樹脂(三菱化学(株)製JER154)4g(全固形分に対し1質量%)を配合しキャスト用ワニスを作製した。次いで実施例1と同様にして、金属箔積層体を製造し、耐折性評価用のフレキシブルプリント配線板、及び不溶率、ガーレ式剛軟度(低スプリングバック性の指標)、実装性評価用の各基材フィルムを作製、各特性を評価した。特性評価結果を表1に示す。
また、実施例1~12、比較例1~8のポリアミドイミドA、ポリアミドイミドB、及びポリイミドAは、その製造方法から明らかではあるが、酸価、アミン価、イソシアネート価、及び、NMRの測定により、いずれの樹脂も末端にのみカルボキシル基、アミノ基、イソシアネート基を有していた。比較例9のポリアミドイミドCは、同様な分析手法で測定したところ、末端以外にも、カルボキシル基を有していた。
Claims (10)
- エポキシ樹脂により架橋されてなるポリイミド系樹脂を含む耐熱性樹脂組成物が金属箔の少なくとも片面に積層された基材フィルムと金属箔との金属箔積層体であり、かつ、以下の(a)及び(b)であることを特徴とする金属箔積層体;
(a)ポリイミド系樹脂とエポキシ樹脂の総量を100質量%としたときのエポキシ樹脂の配合量が0.1質量%以上10質量%以下であること;
(b)金属箔積層体から金属箔を取り除いて得られる基材フィルムに、基材フィルムの濃度が0.5質量%となるようにN-メチル-2-ピロリドンを加え、100℃で2時間加熱処理した後の不溶率が40%以上であること。 - さらに、以下の(c)及び/又は(d)であることを特徴とする請求項1に記載の金属箔積層体;
(c)架橋前のポリイミド系樹脂の対数粘度が、N-メチル-2-ピロリドン中(ポリマー濃度0.5g/dl)、30℃での測定条件下で、0.40dl/g以上3.50dl/g以下であること;
(d)エポキシ樹脂により架橋された後の未架橋部分のポリイミド系樹脂の対数粘度が、N-メチル-2-ピロリドン中(ポリマー濃度0.5g/dl)、30℃での測定条件下で、0.40dl/g以上3.50dl/g以下であること。 - さらに、以下の(e)及び/又は(f)であることを特徴とする請求項1又は請求項2のいずれかに記載の金属箔積層体;
(e)架橋前のポリイミド系樹脂の数平均分子量が10000以上200000以下であること。
(f)エポキシ樹脂により架橋された後の未架橋部分のポリイミド系樹脂の数平均分子量が10000以上200000以下であること。 - さらに、以下の(g)及び/又は(h)であることを特徴とする請求項1~3のいずれかのいずれかに記載の金属箔積層体;
(g)架橋前のポリイミド系樹脂の酸価が5eq/ton以上1000eq/ton以下であること;
(h)エポキシ樹脂により架橋された後の未架橋部分のポリイミド系樹脂の酸価が5eq/ton以上1000eq/ton以下であること。 - さらに、以下の(i)であることを特徴とする請求項1~4のいずれかに記載の金属箔積層体;
(i)耐熱性樹脂組成物中の全固形成分を100質量%としたときに、ポリイミド系樹脂及びエポキシ樹脂の合計の配合量が30質量%以上であること。 - 請求項1~7のいずれかに記載の金属箔積層体を含有するフレキシブルプリント配線板。
- JIS C 5016に基づく耐折性試験の値が、190回超である請求項8に記載のフレキシブルプリント配線板。
- ガーレ式剛軟度が、800mg未満である請求項8または請求項9に記載のフレキシブルプリント配線板。
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Cited By (4)
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WO2016121392A1 (ja) * | 2015-01-30 | 2016-08-04 | パナソニックIpマネジメント株式会社 | 両面金属張積層板及びその製造方法 |
JP2018076541A (ja) * | 2013-04-16 | 2018-05-17 | 東洋紡株式会社 | 金属箔積層体 |
WO2021044793A1 (ja) * | 2019-09-03 | 2021-03-11 | 昭和電工株式会社 | 複合積層体及び金属-樹脂接合体 |
WO2022202628A1 (ja) * | 2021-03-23 | 2022-09-29 | ユニチカ株式会社 | ポリアミドイミド |
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TWI696680B (zh) * | 2015-03-30 | 2020-06-21 | 日商荒川化學工業股份有限公司 | 聚醯亞胺系黏著劑、薄膜狀黏著材料、黏著層、黏著薄片、覆銅積層板及印刷線路板、以及多層線路板及其製造方法 |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11240107A (ja) * | 1998-12-04 | 1999-09-07 | Toyobo Co Ltd | 金属箔積層体 |
JP2001203467A (ja) * | 2000-12-07 | 2001-07-27 | Nippon Steel Chem Co Ltd | プリント基板用耐熱性接着剤フィルム及びその製造方法 |
JP2007091799A (ja) * | 2005-09-27 | 2007-04-12 | Kaneka Corp | 熱硬化性樹脂組成物、及びその利用 |
JP2009147289A (ja) * | 2007-11-19 | 2009-07-02 | Hitachi Chem Co Ltd | 封止用フィルム |
JP2009270054A (ja) * | 2008-05-09 | 2009-11-19 | Hitachi Chem Co Ltd | 絶縁樹脂組成物、及び支持体付絶縁フィルム |
JP2011184508A (ja) * | 2010-03-05 | 2011-09-22 | Nippon Steel Chem Co Ltd | ポリイミド樹脂硬化膜及び光学補償部材 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03131630A (ja) * | 1989-10-17 | 1991-06-05 | Toyobo Co Ltd | 耐熱性成形物 |
JP4131339B2 (ja) * | 1997-03-04 | 2008-08-13 | 東洋紡績株式会社 | 積層体 |
JP4032449B2 (ja) * | 1997-03-25 | 2008-01-16 | 東洋紡績株式会社 | 絶縁電線 |
JP4432145B2 (ja) | 1999-03-26 | 2010-03-17 | 東レ株式会社 | フレキシブル印刷回路基板用接着剤組成物及びそれを用いたカバーレイフィルム及びフレキシブル印刷回路基板 |
JP4560697B2 (ja) * | 1999-08-04 | 2010-10-13 | 東洋紡績株式会社 | フレキシブル金属積層体及びその製造方法 |
JP4032831B2 (ja) | 2001-06-04 | 2008-01-16 | 宇部興産株式会社 | 放電処理ポリイミドフィルム、放電処理方法、金属薄膜付きポリイミドフィルムおよびその製造方法 |
JP4022851B2 (ja) * | 2001-11-01 | 2007-12-19 | 荒川化学工業株式会社 | 金属付きポリイミドフィルムの製造方法および当該製造方法により得られる金属付きポリイミドフィルム |
KR100605517B1 (ko) * | 2001-11-01 | 2006-07-31 | 아라까와 가가꾸 고교 가부시끼가이샤 | 폴리이미드-금속 적층체 및 폴리아미드이미드-금속 적층체 |
TWI320046B (en) * | 2002-02-26 | 2010-02-01 | Polyamide-imide resin, flexible metal-clad laminate and flexible print substrate | |
US20050119381A1 (en) * | 2002-03-08 | 2005-06-02 | Shigeru Tanaka | Thermosetting resin composition and laminates and circuit board substrates made by using the same |
JP2006021455A (ja) | 2004-07-09 | 2006-01-26 | Mitsui Chemicals Inc | ポリイミド金属積層体 |
JP4640409B2 (ja) * | 2003-09-01 | 2011-03-02 | 東洋紡績株式会社 | 金属張積層体 |
JP5251897B2 (ja) | 2003-09-01 | 2013-07-31 | 東洋紡株式会社 | ポリアミドイミド樹脂を用いたフィルム、フレキシブル金属張積層体及びフレキシブルプリント基板 |
JP2005306956A (ja) | 2004-04-20 | 2005-11-04 | Kaneka Corp | ポリイミド組成物及びそれを用いた耐熱性樹脂組成物 |
JP4564336B2 (ja) | 2004-11-04 | 2010-10-20 | 新日鐵化学株式会社 | Cof用銅張積層板及びcof用キャリアテープ |
WO2006098409A1 (ja) * | 2005-03-17 | 2006-09-21 | Hitachi Chemical Company, Ltd. | 樹脂組成物及びそれを含む被膜形成材料 |
JP4986256B2 (ja) | 2005-12-21 | 2012-07-25 | 味の素株式会社 | 変性ポリイミド樹脂を含有するプリプレグ |
JP2008248114A (ja) | 2007-03-30 | 2008-10-16 | Shin Etsu Chem Co Ltd | 接着剤組成物 |
JP5292793B2 (ja) | 2007-12-14 | 2013-09-18 | 東レ株式会社 | 半導体用接着シート、それを用いた半導体装置および半導体装置の製造方法 |
JP5594144B2 (ja) * | 2008-11-10 | 2014-09-24 | 味の素株式会社 | プリント配線板用樹脂組成物 |
JP2012006200A (ja) | 2010-06-23 | 2012-01-12 | Asahi Kasei E-Materials Corp | ポリイミド金属積層体、及びそれを用いたプリント配線板 |
WO2012057171A1 (ja) * | 2010-10-29 | 2012-05-03 | エア・ウォーター株式会社 | 樹脂組成物、それを用いたプリプレグ及び積層板 |
JP2012186307A (ja) | 2011-03-04 | 2012-09-27 | Sumitomo Metal Mining Co Ltd | 2層フレキシブル基板とその製造方法、並びに2層フレキシブル基板を基材とした2層フレキシブルプリント配線板と、その製造方法 |
JP2012219107A (ja) * | 2011-04-04 | 2012-11-12 | Hitachi Chemical Co Ltd | ポリアミドイミド樹脂組成物、その製造法、それを用いた硬化性樹脂組成物及び塗料 |
JP5910236B2 (ja) * | 2011-04-12 | 2016-04-27 | 東洋紡株式会社 | ポリアミドイミドフィルムの製造方法 |
JP5891644B2 (ja) | 2011-08-05 | 2016-03-23 | 日立化成株式会社 | 接着フィルム、該接着フィルムを用いた多層プリント配線板、及び該多層プリント配線板の製造方法 |
WO2014171345A1 (ja) * | 2013-04-16 | 2014-10-23 | 東洋紡株式会社 | 金属箔積層体 |
-
2014
- 2014-04-03 WO PCT/JP2014/059846 patent/WO2014171345A1/ja active Application Filing
- 2014-04-03 JP JP2014530984A patent/JP6287840B2/ja active Active
- 2014-04-03 KR KR1020157016792A patent/KR102001282B1/ko active IP Right Grant
- 2014-04-03 CN CN201480020543.8A patent/CN105102221B/zh active Active
- 2014-04-14 TW TW103113587A patent/TWI602691B/zh active
-
2018
- 2018-02-07 JP JP2018020064A patent/JP2018076541A/ja active Pending
-
2019
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11240107A (ja) * | 1998-12-04 | 1999-09-07 | Toyobo Co Ltd | 金属箔積層体 |
JP2001203467A (ja) * | 2000-12-07 | 2001-07-27 | Nippon Steel Chem Co Ltd | プリント基板用耐熱性接着剤フィルム及びその製造方法 |
JP2007091799A (ja) * | 2005-09-27 | 2007-04-12 | Kaneka Corp | 熱硬化性樹脂組成物、及びその利用 |
JP2009147289A (ja) * | 2007-11-19 | 2009-07-02 | Hitachi Chem Co Ltd | 封止用フィルム |
JP2009270054A (ja) * | 2008-05-09 | 2009-11-19 | Hitachi Chem Co Ltd | 絶縁樹脂組成物、及び支持体付絶縁フィルム |
JP2011184508A (ja) * | 2010-03-05 | 2011-09-22 | Nippon Steel Chem Co Ltd | ポリイミド樹脂硬化膜及び光学補償部材 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018076541A (ja) * | 2013-04-16 | 2018-05-17 | 東洋紡株式会社 | 金属箔積層体 |
WO2016121392A1 (ja) * | 2015-01-30 | 2016-08-04 | パナソニックIpマネジメント株式会社 | 両面金属張積層板及びその製造方法 |
JP2016141015A (ja) * | 2015-01-30 | 2016-08-08 | パナソニックIpマネジメント株式会社 | 両面金属張積層板及びその製造方法 |
WO2021044793A1 (ja) * | 2019-09-03 | 2021-03-11 | 昭和電工株式会社 | 複合積層体及び金属-樹脂接合体 |
JP6919076B1 (ja) * | 2019-09-03 | 2021-08-11 | 昭和電工株式会社 | 複合積層体及び金属−樹脂接合体 |
WO2022202628A1 (ja) * | 2021-03-23 | 2022-09-29 | ユニチカ株式会社 | ポリアミドイミド |
Also Published As
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JPWO2014171345A1 (ja) | 2017-02-23 |
JP2018076541A (ja) | 2018-05-17 |
JP2019178342A (ja) | 2019-10-17 |
TWI602691B (zh) | 2017-10-21 |
TW201504037A (zh) | 2015-02-01 |
JP6287840B2 (ja) | 2018-03-07 |
CN105102221B (zh) | 2017-06-06 |
CN105102221A (zh) | 2015-11-25 |
KR102001282B1 (ko) | 2019-07-17 |
KR20150143407A (ko) | 2015-12-23 |
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