WO2011099555A1 - ポリイミドフィルム、およびこれらのポリイミド積層体、ポリイミド金属積層体 - Google Patents
ポリイミドフィルム、およびこれらのポリイミド積層体、ポリイミド金属積層体 Download PDFInfo
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- WO2011099555A1 WO2011099555A1 PCT/JP2011/052856 JP2011052856W WO2011099555A1 WO 2011099555 A1 WO2011099555 A1 WO 2011099555A1 JP 2011052856 W JP2011052856 W JP 2011052856W WO 2011099555 A1 WO2011099555 A1 WO 2011099555A1
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- polyimide
- film
- layer
- polyimide film
- polyamic acid
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- 0 CC1(C=CC(NC(C)=NC(*)=NC(Nc2ccccc2)=C)=CC=C1)N Chemical compound CC1(C=CC(NC(C)=NC(*)=NC(Nc2ccccc2)=C)=CC=C1)N 0.000 description 2
Classifications
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- 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
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- 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
- B32B15/088—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 polyamides
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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
-
- 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
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- 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
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- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- 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
- C08G73/02—Polyamines
- C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
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- 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
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
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- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/128—Adhesives without diluent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- H05K1/0346—Organic insulating material consisting of one material containing N
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- 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
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
-
- 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
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/202—LCD, i.e. liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use 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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31721—Of polyimide
Definitions
- the present invention relates to a polyimide film having improved adhesion to an adhesive.
- the present invention also provides a polyimide film in which a metal layer is laminated on a polyimide film via an adhesive layer, or a metal layer directly by a dry or wet process (without using an adhesive layer).
- D) relates to a polyimide metal laminate formed on the surface.
- Polyimide films are widely used in the fields of electric / electronic devices and semiconductors because they are excellent in heat resistance, chemical resistance, mechanical strength, electrical properties, dimensional stability, and the like.
- a flexible printed wiring board FPC
- a copper-clad laminated board formed by laminating a copper foil on one or both sides of a polyimide film is used.
- the polyimide film generally has a sufficient peel strength even when a metal layer is provided on the polyimide film by dry plating such as metal vapor deposition or sputtering, or when a metal layer is provided on the polyimide film by wet plating such as electroless plating. Large laminates may not be obtained.
- Patent Document 1 describes a polyimide using a triazine-based diamine, and describes an example in which a polyimide solution is applied to a metal foil.
- Patent Document 2 discloses a terminal-modified imide oligomer using a triazine-based diamine
- Patent Document 3 discloses a polymer electrolyte using a triazine-based diamine.
- An object of the present invention is to provide a polyimide film having improved adhesion to an adhesive and / or adhesion to a metal layer.
- the object of one aspect of the present invention is to improve the properties of the polyimide film surface that is not sufficiently large in adhesion to the adhesive or the adhesion to the metal layer, and to improve the adhesion and adhesion to the metal layer. It is to improve.
- a polyimide metal laminate in which a metal foil is laminated on a polyimide film via an adhesive layer or a polyimide metal laminate in which a metal layer is directly laminated on a polyimide film, It is to provide a polyimide film having a high peel strength even after being heated at or after being heated under high temperature and high humidity conditions.
- Another object of the present invention is to provide a laminate of a polyimide film and an adhesive, a polyimide metal laminate obtained by laminating a metal foil via an adhesive layer, or a polyimide metal laminate in which a metal layer is directly laminated. It is to be.
- the present invention relates to the following matters.
- the polyimide layer (a) is obtained from a tetracarboxylic dianhydride component and a diamine component containing a diamine compound represented by the general formula (1).
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents an alkyl group or aryl group having 1 to 12 carbon atoms.
- the polymer solution (a) capable of obtaining the polyimide layer (a) is applied to one or both sides of the self-supporting film of the polyamic acid solution (b) capable of obtaining the polyimide layer (b), and heated. 2.
- polyimide film as described in 2 or 3 above, wherein the polymer solution (a) is a polyamic acid solution (a) from which the polyimide layer (a) can be obtained.
- the polyimide constituting the polyimide layer (b) comprises a tetracarboxylic dianhydride component containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or pyromellitic dianhydride, phenylene 9.
- a polyimide laminate comprising the polyimide film according to any one of 1 to 9 above and an adhesive layer laminated on the surface of the polyimide layer (a) of the polyimide film.
- a polyimide metal laminate wherein a metal layer is laminated in contact with the adhesive layer of the 12 polyimide laminate.
- a polyimide metal laminate comprising the polyimide film according to any one of 1 to 9 above and a metal layer formed by dry or wet plating on the surface of the polyimide layer (a) of the polyimide film. body.
- a method for producing a polyimide film according to any one of 1 to 9 above Using the polyamic acid solution (b) capable of obtaining the polyimide layer (b) to produce a self-supporting film; Coating a polymer solution (a) capable of obtaining the polyimide layer (a) on one or both surfaces of the produced self-supporting film; And a heat treatment step for heating the self-supporting film coated with the polymer solution (a).
- a method for producing a polyimide film according to any one of 1 to 9 above A polyamic acid solution (b) capable of obtaining the polyimide layer (b) and a polymer solution (a) capable of obtaining the polyimide layer (a) are cast on a support to form a multilayer liquid film. Process, And a heat treatment step for heating the multilayer liquid film.
- a polyimide film having improved adhesion with an adhesive or adhesion with a metal layer it is possible to provide a polyimide film having improved adhesion with an adhesive or adhesion with a metal layer.
- a polyimide film whose adhesion to an adhesive is not sufficiently large or a polyimide film whose adhesion to a metal layer is not sufficiently large is used as a base. Even so, it is possible to improve the properties of the surface, so that the adhesion with the adhesive and / or the adhesion (adhesion) with the metal layer is maintained while maintaining the properties of the base polyimide film. It can be improved.
- a laminate of a polyimide film and an adhesive, a polyimide metal laminate obtained by laminating a polyimide film and a metal foil via an adhesive layer, or a metal layer without an adhesive A polyimide metal laminate formed and laminated directly on the surface of the polyimide film can be provided.
- the polyimide film disclosed in the present application is made of a polyimide having at least a surface obtained from a tetracarboxylic dianhydride component and a diamine component containing a diamine compound represented by the following general formula (1). Is formed.
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents an alkyl group or aryl group having 1 to 12 carbon atoms.
- the present invention is roughly divided into the following first to third aspects.
- the polyimide film has at least a polyimide layer (b) and a polyimide layer (a) laminated in contact with the polyimide layer (b), wherein the polyimide layer (a) Is a polyimide obtained from a tetracarboxylic dianhydride component and a diamine component containing the diamine compound represented by the general formula (1).
- the tetracarboxylic dianhydride component may be abbreviated as a tetracarboxylic acid component or an acid component.
- a polyimide film is a polyimide film used for the use laminated
- the polyimide film is used for forming a metal layer by plating on the film surface without using an adhesive layer, and is represented by the tetracarboxylic dianhydride component and the general formula (1). It is formed with a single layer of polyimide obtained by reacting with a diamine component containing 10 to 100 mol% of the diamine compound to be obtained, and preferably in the heat treatment step under the condition that the maximum heating temperature is 450 ° C. or higher. It is a film.
- a 1st aspect has a polyimide layer (b) and the polyimide layer (a) laminated
- the polyimide layer (a) refers to a portion of the polyimide layer (a) among a plurality of layers forming the polyimide film.
- a polyimide layer (b) means the part of a polyimide layer (b) among the several layers which form the polyimide film. The same applies to the following embodiments.
- the polyimide film in the present invention may contain other layers in addition to the polyimide layer (a) and the polyimide layer (b). In this case, a multilayer polyimide film is obtained.
- a polyimide film consists only of the form by which the polyimide layer (a) was laminated
- a polyimide film consists only of the form by which the polyimide layer (a) was laminated
- laminated in contact means a state in which the polyimide layer (a) is laminated in contact with the surface of the polyimide layer (b).
- the contact portion (boundary region) between the laminated polyimide layer (a) and the polyimide layer (b) is a polyamic acid solution (a) that forms each polyimide layer, and It may be chemically modified by (b) to form an intermediate layer (including a gradient layer whose composition changes continuously). A form in which this intermediate layer is formed is also included in the present invention.
- the polyimide layer (a) is a polyimide obtained from a tetracarboxylic dianhydride component and a diamine component containing a diamine compound represented by the general formula (1).
- the polyimide layer (b) has the same or different composition as the polyimide layer (a). In the following description, the composition of the polyimide layer (b) is different from the composition of the polyimide layer (a).
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents an alkyl group or aryl group having 1 to 12 carbon atoms.
- the polyimide layer (a) is excellent in adhesion with the adhesive layer and / or adhesion with a metal layer (wet plating or dry plating method) as described later.
- the polyimide layer (a) may be formed on one side of the polyimide film or on both sides.
- the polyimide film may have a further different polyimide layer, it usually has only a polyimide layer (b) and a polyimide layer (a) (one side or both sides).
- the polyimide film of this embodiment maintains the excellent properties such as the mechanical properties and heat resistance of the polyimide layer (b), while the polyimide layer (a) has surface properties (adhesiveness with adhesive, metal layer and This is advantageous in that the adhesiveness and the like can be improved.
- the polyimide layer (a) is also advantageous in that it has excellent alkali resistance.
- the thickness of the polyimide layer (a) can be arbitrarily changed, as one of the features of this embodiment, the film is obtained while utilizing the characteristics of the polyimide layer (b) without largely changing the characteristics of the polyimide layer (b). It is also possible to modify the surface.
- the thickness of the polyimide layer (a) is preferably such that the characteristics of the polyimide layer (b) do not change significantly, for example, preferably 1 ⁇ m or less and 0.05 to 1 ⁇ m.
- the thickness of the polyimide film is not particularly limited, but is 5 to 120 ⁇ m, preferably 6 to 75 ⁇ m, and more preferably 7 to 60 ⁇ m.
- the method for producing the polyimide film of the first aspect is not particularly limited as long as the polyimide layer (a) and the polyimide layer (b) are formed so as to be in direct contact with each other.
- a polyimide layer (a) precursor solution (polyamic acid) and a polyimide layer (b) precursor solution (polyamic acid) are cast on a support by coextrusion.
- a method of forming a multilayer liquid film, heating and drying to obtain a self-supporting film, and then heating to obtain polyimide can also be employed.
- the method of casting on a support is not limited to coextrusion.
- the form which forms this multilayer liquid film is applicable also to the method of chemically imidating mentioned later.
- a polyimide solution ( a) refers to a solution in which polyimide (a) is dissolved in an organic solvent.
- the polyimide (b) which comprises a polyimide layer (b) is soluble in an organic solvent, in order to form a polyimide layer (b), it is a polyimide instead of the said polyimide layer (b) precursor solution.
- a solution (b) (which means a solution in which polyimide (b) is dissolved in an organic solvent) can be used.
- the material for forming the polyimide layer (a) is a polyimide layer (a) precursor solution
- the material for forming the polyimide layer (b) can be a polyimide solution (b).
- the material which forms a polyimide layer (a) can be a polyimide solution (a)
- the material which forms a polyimide layer (b) can be used as a polyimide layer (b) precursor solution.
- the polyimide layer (a) and the polyimide layer (b) will be described together with a method of applying a solution for giving the polyimide layer (a) to the surface of the self-supporting film.
- the polyimide film of the first aspect of the present invention is Casting a polyamic acid solution (b) (polyamic acid + solvent) capable of obtaining a polyimide layer (b) on a support, heating and drying it to obtain a self-supporting film; Applying a polymer solution (a) capable of obtaining a polyimide layer (a) on one or both sides of the obtained self-supporting film; And a heat treatment step of heating the self-supporting film coated with the polymer solution (a). Therefore, the polyimide film of the first aspect of the present invention is preferably a polyimide film obtained by the above production method.
- the polymer solution refers to a polyamic acid solution, a polyimide solution, or a mixture of a polyamic acid solution and a polyimide solution.
- a polyamic acid solution (a) is preferably used as the polymer solution (a) used for coating.
- a polyamic acid solution (a) is preferably used.
- polyimide (a) constituting the polyimide layer (a) is soluble in an organic solvent, polyimide is used.
- a solution (a) or a mixed solution of the polyimide solution (a) and the polyamic acid solution (a) can also be used.
- the polyimide layer (b) of the polyimide film of the present invention is obtained by thermal imidization and / or chemical imidization, and when at least one of the tetracarboxylic acid component and the diamine component contains a plurality of compounds, it is random. It may be copolymerized, may be block copolymerized, or may have a structure of a combination thereof.
- the polyimide layer (a) of the polyimide film of the present invention may be randomly copolymerized or block copolymerized, Or you may have the structure of these combination.
- Polyamic acid solution capable of obtaining a polyimide layer (b) (polyamic acid solution composition in which an imidization catalyst, a dehydrating agent, a release aid, inorganic fine particles and the like are selected and added to the polyamic acid solution as necessary
- a polymer solution (a) such as a polyamic acid solution (a) on one or both sides of the self-supporting film. Coating, then thermally dehydrating and cyclizing, removing the solvent to obtain a polyimide film (thermal imidization method).
- a polyamic acid solution to which a polyimide layer (b) can be obtained, to which an imidation catalyst, a cyclization catalyst and a dehydrating agent are added (a polyamic acid solution composition in which inorganic fine particles are selected and added as necessary) And a polyamic acid on one or both sides of the self-supporting film, and a step of heating and drying to obtain a self-supporting film.
- a method chemical imidation method for chemically imidizing having a step of applying a polymer solution (a) such as the solution (a) and then obtaining a polyimide film by heating and removing the solvent and imidizing the solution. Can be mentioned.
- the tetracarboxylic acid component preferably contains at least s-BPDA and / or PMDA.
- s-BPDA is preferably 50 mol% or more, more preferably 70 mol% or more, Especially preferably, it contains 75 mol% or more.
- the polyimide film obtained by this is excellent in mechanical properties and the like.
- One benzene nucleus diamine such as paraphenylenediamine (1,4-diaminobenzene; PPD), 1,3-diaminobenzene, 2,4-toluenediamine, 2,5-toluenediamine, 2,6-toluenediamine, etc.
- Diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4 ' -Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4 ' -Diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4'-diaminodip
- the benzene core of three diamines 4) 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino Phenoxy) phenyl] ketone, bis [4- (4-a
- the diamine component used in the polyimide layer (b) is preferably a diamine compound selected from PPD and diaminodiphenyl ethers, more preferably one kind selected from PPD, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether.
- the polyimide film obtained by this is excellent in mechanical properties and the like.
- the polyimide layer (b) is preferably a polyimide produced from s-BPDA and PPD or optionally PPD and diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether.
- the PPD / diaminodiphenyl ether (molar ratio) is preferably 100/0 to 85/15.
- PMDA aromatic tetracarboxylic dianhydride which is a combination of s-BPDA and PMDA, PPD, tolidine (ortho form, meta form), 4,4′-diaminodiphenyl ether, 3,4′-diamino
- polyimides made from aromatic diamines such as diaminodiphenyl ethers such as diphenyl ether.
- PPD or an aromatic diamine in which PPD / diaminodiphenyl ethers are 90/10 to 10/90 is preferable.
- s-BPDA / PMDA is preferably 0/100 to 90/10.
- diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether.
- the diaminodiphenyl ethers / PPD is preferably 90/10 to 10/90.
- tetracarboxylic acid component and diamine component used for polyimide layer (a) As the tetracarboxylic acid component used in the polyimide layer (a), the above-described tetracarboxylic acid component used in the polyimide layer (b) is used, and preferable ones are also the same.
- the diamine compound is contained in an amount of 10 to 100 mol%, more preferably 15 to 100 mol%, and still more preferably 25 to 100 mol%.
- the content of the diamine compound represented by the general formula (1) in the diamine component is preferably 10 to 50 mol% in the polyimide layer (a). More preferably, it is in the range of 15 to 40 mol%, particularly preferably in the range of 17 to 30 mol%.
- the 5% weight loss temperature is an index indicating the heat resistance and thermal stability of the film, and is preferably higher.
- the diamine component used for the polyimide layer (a) in addition to the diamine of the general formula (1), the diamine component used for the polyimide layer (b) can be used, and preferably a diamine component selected from PPD and diaminodiphenyl ethers. More preferably, a diamine component containing at least one selected from PPD, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether can be used.
- the polyimide film obtained by this is excellent in mechanical characteristics or thermal characteristics.
- the polyimide layer (a) includes, among others, a tetracarboxylic acid component containing s-BPDA and / or PMDA, a diamine represented by the general formula (1), a diamine represented by the general formula (1), PPD and 4 Polyimide obtained from a polyamic acid produced from a diamine component containing diaminodiphenyl ethers such as 4,4'-diaminodiphenyl ether and 3,4'-diaminodiphenyl ether is preferred.
- the polyimide of the present invention is excellent in that it does not contain at least one proton conductive functional group selected from the group consisting of —SO 3 H, —COOH and —PO 3 H 2 as shown in Patent Document 3. It is preferable since it has heat resistance (the same applies to other embodiments).
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms)
- R 2 represents an alkyl group or an aryl group having 1 to 12 carbon atoms (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms)
- R 1 and R 2 may be different or the same. May be.
- alkyl group or aryl group having 1 to 12 carbon atoms of R 1 and R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, phenyl, benzyl, naphthyl, methylphenyl, and biphenyl.
- aminoanilino group connected to the two NH groups of triazine is 4-aminoanilino or 3-aminoanilino, which may be the same or different, but 4-aminoanilino is preferred.
- diamine compound represented by the general formula (1) examples include 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine and 2,4-bis (3-aminoanilino).
- the polyamic acid solution (b) for providing the polyimide layer (b), and the polyamic acid solution (a) or the polyimide solution (a) as a polymer solution for providing the polyimide layer (a) are an acid component, a diamine component, Can be obtained by polymerizing in an organic polar solvent with substantially equimolar or a slight excess of either component.
- Organic polar solvents for producing polyamic acid solutions and polyimide solutions include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N— Examples thereof include amides such as diethylformamide and hexamethylsulfuramide, sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, and sulfones such as dimethylsulfone and diethylsulfone. These solvents may be used alone or in combination.
- the concentration of all monomers in the organic polar solvent (solid content concentration of the polyamic acid solution) is It may be appropriately selected depending on the purpose of use and the purpose of production.
- the polyamic acid solution (b) has a total monomer concentration in the organic polar solvent of preferably 5 to 40% by mass, more preferably 6 to 35% by mass, particularly preferably 10 to 30%. It is preferable that it is mass%.
- the polyamic acid solution (a) and the polyimide solution (a) can be appropriately determined within a range where a polymerization reaction is possible and easy to handle.
- the solid content concentration of the polymer solution (a) used for coating is preferably 1 to 15% by mass, more preferably 2 to 8% by mass, so that this concentration is obtained during polymerization.
- the monomer concentration at the time of polymerization may be determined, or polymerization may be carried out at a high concentration and diluted to form a coating solution.
- the concentration of all monomers in the organic polar solvent is preferably higher than that of the coating system.
- it is best to form a film such as a method of curing after coating to obtain a multilayer film, or a method of casting on a support to form a multilayer liquid film and then curing. A process can be selected.
- a method for forming the polyimide layer three or more kinds of monomer components (acid component and diamine component) may be mixed and copolymerized, or a plurality of polymer solutions may be prepared and mixed.
- Preparing a plurality of polymer solutions and mixing them includes, for example, a polymer solution (dope solution) obtained from a first acid component and a first diamine component, a second acid component, and a second diamine.
- the polymer solution (dope solution) obtained from the components is mixed.
- the polymerization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component is carried out by, for example, substantially equimolar or either of them.
- the polyamic acid solution is prepared by mixing the components (acid component or diamine component) in a slight excess and reacting at a reaction temperature of 100 ° C. or lower, preferably 80 ° C. or lower for about 0.2 to 60 hours. Can be obtained.
- the polymerization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component is carried out by, for example, substantially equimolar or each component (acid component, or
- the polyimide solution can be obtained by a known method, for example, at a reaction temperature of 140 ° C. or higher, preferably 160 ° C. or higher (preferably 250 ° C. or lower, more preferably 230 ° C. or lower).
- the reaction can be carried out by reacting for 1 to 60 hours to obtain a polyimide solution.
- the solution viscosity is the purpose of use (coating, casting, etc.) and the purpose of production. It may be appropriately selected depending on the situation. Considering the workability of handling this polyamic acid solution, the rotational viscosity of the polyamic acid solution measured at 30 ° C. is about 0.1 to 5000 poise, particularly 0.5 to 2000 poise, more preferably 1 to 2000 poise. The degree is preferred. Therefore, it is desirable to carry out the polymerization reaction to such an extent that the produced polyamic acid exhibits the above viscosity.
- an imidization catalyst, an organic phosphorus-containing compound, inorganic fine particles, and the like may be added to the polyamic acid solution as necessary. If it is chemical imidation, you may add a cyclization catalyst, a dehydrating agent, inorganic fine particles, etc. to a polyamic acid solution as needed. If necessary, inorganic fine particles and the like may be added to the polyimide solution.
- the imidization catalyst examples include a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of the nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic heterocyclic compound.
- Cyclic compounds such as 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methylbenzimidazole, etc.
- Benzimidazoles such as alkylimidazole and N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n- Substituted pyridines such as propylpyridine It can be used to apply.
- the amount of the imidization catalyst used is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 time equivalent to the amic acid unit of the polyamic acid.
- organic phosphorus-containing compounds examples include monocaproyl phosphate, monooctyl phosphate, monolauryl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, triethylene glycol monotridecyl Monophosphate of ether, monophosphate of tetraethylene glycol monolauryl ether, monophosphate of diethylene glycol monostearyl ether, dicaproyl phosphate, dioctyl phosphate, dicapryl phosphate, dilauryl phosphate, dimyristyl phosphate, Dicetyl phosphate, distearyl phosphate, diethylene phosphate of tetraethylene glycol mononeopentyl ether, trie Diphosphate of glycol mono tridecyl ether, diphosphate of tetraethyleneglycol monolauryl ether, and phosphoric acid esters such as diphosphate esters of diethylene glycol monostearyl
- amine ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine Etc.
- Cyclization catalysts include aliphatic tertiary amines such as trimethylamine and triethylenediamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as isoquinoline, pyridine, ⁇ -picoline and ⁇ -picoline. Etc.
- dehydrating agent examples include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride.
- Inorganic fine particles include fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, fine particle silicon nitride powder, and titanium nitride powder.
- Inorganic nitride powder such as silicon carbide powder, inorganic carbide powder such as silicon carbide powder, and inorganic salt powder such as particulate calcium carbonate powder, calcium sulfate powder, and barium sulfate powder.
- These inorganic fine particles may be used in combination of two or more. In order to uniformly disperse these inorganic fine particles, a means known per se can be applied.
- the self-supporting film of the polyamic acid solution (b) is applied to the support by casting the polyamic acid solution (b) on the support to the extent that it becomes self-supporting (meaning the stage before the normal curing process), for example, support It is manufactured by heating to such an extent that it can be peeled off from the body.
- the solid content concentration of the polyamic acid solution (b) is not particularly limited as long as it is in a viscosity range suitable for production, but is usually preferably 5 to 40% by mass, more preferably 6 to 35% by mass, particularly preferably. Is 10 to 30% by mass.
- the heating temperature and heating time at the time of preparing the self-supporting film can be appropriately determined.
- the heating may be performed at a temperature of 100 to 180 ° C. for about 1 to 60 minutes.
- the support is not particularly limited as long as it can cast a polyamic acid solution, but a smooth substrate is preferably used.
- a metal drum or belt such as stainless steel is used.
- the self-supporting film is not particularly limited as long as the solvent is removed and / or imidized to such an extent that it can be peeled off from the support, but in thermal imidization, the loss on heating is 20 to 50 mass. %, And when the weight loss on heating is in the range of 20 to 50% by mass and the imidization ratio is in the range of 7 to 55%, the mechanical properties of the self-supporting film are sufficient. In addition, if the heat loss and imidization rate of the self-supporting film are within the above ranges, it becomes easy to apply the coating solution uniformly and cleanly on the surface of the self-supporting film, and foams into the polyimide film obtained after imidization. , Cracks, crazes, cracks, cracks and the like are not observed, which is preferable.
- the loss on heating of the self-supporting film is a value obtained by the following formula from the mass W1 of the self-supporting film and the mass W2 of the film after curing.
- Heat loss (mass%) ⁇ (W1-W2) / W1 ⁇ ⁇ 100
- the imidation ratio of a partially imidized self-supporting film is determined by measuring the IR spectrum of the self-supporting film and its fully cured product (polyimide film) by the ATR method, and measuring the peak area or height of the vibration band. It can be calculated using the ratio.
- the vibration band peak a symmetric stretching vibration band of an imidecarbonyl group, a benzene ring skeleton stretching vibration band, or the like is used.
- the FT-IR spectrum of the self-supporting film and its full-cure film (polyimide film) is obtained by using a FT / IR6100 manufactured by JASCO Corporation with a Ge crystal and a multiple reflection ATR method with an incident angle of 45 °.
- Imidation rate (%) ⁇ (X1 / X2) / (Y1 / Y2) ⁇ ⁇ 100 (1)
- X1 peak height of 1775 cm ⁇ 1 of the self-supporting film
- X2 peak height of 1515 cm ⁇ 1 of the self-supporting film
- Y1 peak height of 1775 cm ⁇ 1 of the full cure film
- Y2 The peak height of 1515 cm ⁇ 1 of the full cure film.
- polymer solution (a) (polyamic acid solution (a) or polyimide solution (a)) is applied to one side or both sides of the self-supporting film obtained as described above.
- the polymer solution (a) may contain other additive components in addition to the polymer component as long as the properties of the present invention are not impaired.
- a surface treatment agent such as a silane coupling agent and a titanium coupling agent, silicone , Fluorine-based, and hydrocarbon-based surfactants can be included.
- those surfactants are preferably those that decompose and volatilize during the heat treatment step for imidization.
- the rotational viscosity of the polymer solution (a) may be any viscosity that can be applied to a self-supporting film, and is 0.5 to 50000 centipoise (mPa ⁇ s). Preferably there is.
- the solid concentration of the polymer solution (a) is preferably 1 to 15% by mass, more preferably 2 to 8% by mass. In the polymerization, the monomer concentration may be adjusted so that the concentration becomes this level, and the reaction may be performed, or a polymerization solution having a high solid content concentration may be appropriately diluted.
- the concentration of all monomers in the organic polar solvent is preferably higher than that of the coating system.
- the coating amount of the polymer solution (a) can be appropriately determined. In particular, it is preferable to determine the thickness of the polyimide layer (a).
- the polymer solution (a) can be applied to a self-supporting film by a known method, for example, gravure coating method, spin coating method, silk screen method, dip coating method, spray coating method, bar coating method, knife coating.
- a known method for example, gravure coating method, spin coating method, silk screen method, dip coating method, spray coating method, bar coating method, knife coating.
- known coating methods such as a method, a roll coating method, a blade coating method, and a die coating method.
- the self-supporting film coated with the polymer solution (a) is heat-treated to obtain a polyimide film.
- the maximum heating temperature in the heat treatment step is preferably 350 ° C. or higher, preferably 370 ° C. or higher, more preferably 450 ° C. or higher, further preferably 470 ° C. or higher, particularly preferably 490 ° C. Heat to the above.
- the upper limit of the heating temperature may be a temperature at which the properties of the polyimide film do not deteriorate, preferably 600 ° C. or less, more preferably 590 ° C. or less, further preferably 550 ° C. or less, further preferably 540 ° C. or less, and further preferably 530 ° C. Hereinafter, it is most preferably 520 ° C. or less.
- the heat treatment it is appropriate to first gradually perform imidization of the polymer and evaporation / removal of the solvent at a temperature of about 100 ° C. to 400 ° C. for about 0.05 to 5 hours, particularly 0.1 to 3 hours. .
- the heat treatment is performed stepwise at a relatively low temperature of about 100 ° C. to about 170 ° C. for about 0.5-30 minutes, and then at a temperature above 170 ° C. and below 220 ° C.
- the secondary heat treatment is preferably performed for 0.5 to 30 minutes, and then the third heat treatment is performed at a high temperature exceeding 220 ° C. and less than 350 ° C. for about 0.5 to 30 minutes.
- the fourth high-temperature heat treatment is preferably performed at a high temperature of 350 ° C. or higher. Also, this heating process can be performed sequentially or continuously.
- the heat treatment step may be performed on the support, or may be performed by peeling off the support.
- the film Heat treatment may be performed by fixing both end edges in the width direction and expanding or contracting in the width direction or the length direction as necessary.
- the obtained polyimide film of the present invention may be further subjected to a sandblast treatment, a corona treatment, a plasma treatment, an etching treatment or the like on the surface coated with the polymer solution (a).
- the surface of the polyimide film on which the polymer solution (a) is applied is excellent in adhesiveness with the adhesive. Therefore, an adhesive layer can be provided directly on the surface of the polyimide film polymer solution (a) applied side, which is excellent in the initial peel strength between the polyimide film and the adhesive layer, and excellent in peel strength even after high-temperature treatment.
- a polyimide laminate having an effect of reducing or improving strength can be obtained.
- the present invention provides a polyimide film having a polyimide layer (a) constituting a surface layer on at least one side and a polyimide layer (b) serving as a base layer, and an adhesive layer laminated in contact with the polyimide layer (a).
- a polyimide laminate comprising:
- the adhesive to be laminated is not particularly limited as long as it is a heat-resistant adhesive such as polyimide, epoxy, acrylic, polyamide, or urethane used in the electric / electronic field.
- a heat-resistant adhesive such as polyimide, epoxy, acrylic, polyamide, or urethane used in the electric / electronic field.
- polyimide adhesive And heat-resistant adhesives such as epoxy-modified polyimide adhesives, phenol-modified epoxy resin adhesives, epoxy-modified acrylic resin adhesives, and epoxy-modified polyamide adhesives.
- the adhesive can be provided by any method that is practiced in the electronic field itself.
- the adhesive solution may be applied and dried on the application side surface of the polymer solution (a) of the polyimide film, A separately formed film adhesive may be bonded.
- the polyimide laminate further laminates other substrates such as glass substrates, ceramics such as silicon wafers, metal foils, resin films, carbon fibers, glass fibers, resin fibers and other woven fabrics and nonwoven fabrics through an adhesive layer. be able to.
- Another base material can be directly laminated
- the other substrate is preferably a metal foil
- the metal foil include a single metal or an alloy such as copper, aluminum, gold, silver, nickel, and stainless steel, but preferably rolled copper.
- the foil include copper foil such as foil and electrolytic copper foil.
- the thickness of the metal foil is not particularly limited, but is preferably 0.1 ⁇ m to 10 mm, particularly 7 to 60 ⁇ m.
- a metal foil with a carrier provided with a metal or resin carrier can be used in order to improve the handleability.
- the present invention further includes a polyimide film having the polyimide layer (a) and the polyimide layer (b), an adhesive layer laminated on the surface of the polyimide layer (a), and the adhesive layer.
- a laminated body having another laminated base material particularly preferably a polyimide metal laminated body in which a metal foil is laminated as the other base material.
- Examples of the pressing device or heating / pressing device used when laminating include a pair of crimping metal rolls (the crimping part may be made of metal or ceramic sprayed metal), a double belt press and a hot press.
- the crimping part may be made of metal or ceramic sprayed metal
- a double belt press and a hot press.
- those capable of thermocompression bonding and cooling under pressure are preferred, and among them, a hydraulic double belt press is particularly preferred.
- the surface on the application side of the polymer solution (a) of the polyimide film has good adhesion and adhesion, and in addition to the above, a photosensitive material, a thermocompression bonding material, and the like can be directly laminated.
- the polyimide film of this embodiment is also excellent in adhesion with the metal layer. Therefore, a metal layer can be formed directly on the surface of the polyimide film polymer solution (a) on the application side (that is, by plating without using an adhesive layer), and the initial peeling of the polyimide film and the metal layer can be performed. It is possible to obtain a polyimide metal laminate that is excellent in strength, excellent in peel strength even after high-temperature treatment, and has a small decrease in peel strength, or excellent in peel strength after the high-temperature treatment is greater than that in the initial stage.
- heating is performed so that the maximum heating temperature is preferably 450 ° C. or higher, more preferably 470 ° C. or higher.
- This polyimide metal laminate preferably has excellent adhesion that does not decrease the peel strength not only in the initial stage but also after heat treatment at 150 ° C. or after heat treatment at 121 ° C., 0.2 MPa, 100% RH. .
- the present invention further provides a polyimide metal laminate having a polyimide film having a polyimide layer (a) and a polyimide layer (b), and a metal layer laminated on the surface of the polyimide layer (a).
- the metal layer can be formed on the surface of the polyimide layer (a) by plating.
- the plating method include a metalizing method, which is a dry plating method, and a wet plating method.
- the metallizing method here is a method in which a metal layer is provided by a vapor deposition method, unlike a wet plating method or lamination of a metal foil, and a known method such as vacuum evaporation, sputtering, ion plating, electron beam or the like is used. Can be used.
- Metals used in the metalizing process include metals such as copper, nickel, chromium, manganese, aluminum, iron, molybdenum, cobalt, tungsten, vanadium, titanium, tantalum, alloys thereof, oxides of these metals, and the like. Although the metal carbide of these can be used, it is not limited to these materials.
- the thickness of the metal layer formed by the metalizing method can be appropriately selected according to the purpose of use, and is preferably in the range of 1 to 1000 nm, more preferably 5 to 500 nm because it is suitable for practical use.
- the number of metal layers formed by the metalizing method can be appropriately selected according to the purpose of use, and may be one layer, two layers, or three or more layers.
- the first layer (layer directly in contact with the polyimide film) is made of nickel, chromium, manganese, aluminum, iron, molybdenum, cobalt, tungsten, vanadium, titanium, tantalum, etc. by metalizing method
- the second layer is copper or copper alloys, oxides of these metals, carbides of these metals, etc. It is preferable to form by.
- a metal layer such as copper of about 1 to 40 ⁇ m can be provided on the second layer by wet plating.
- the wet plating method is used as a method for forming a metal layer on the polyimide film of this embodiment, a known plating method can be used, and examples thereof include electrolytic plating and electroless plating, and these can be combined. .
- the metal used in the wet plating method is not limited as long as it is a metal that can be wet plated.
- the thickness of the metal layer formed by the wet plating method can be appropriately selected according to the purpose of use, and is preferably in the range of 0.1 to 50 ⁇ m, more preferably 1 to 30 ⁇ m because it is suitable for practical use.
- the number of metal layers formed by the wet plating method can be appropriately selected according to the purpose of use, and may be one layer, two layers, or three or more layers.
- wet plating method a known wet plating process can be used.
- an elf seed process manufactured by EBARA Eugelite Co., Ltd. or a catalyst bond process which is a surface treatment process of Nikko Metal Co., Ltd. is applied.
- Conventionally known methods such as a method of performing electroless copper plating after the treatment.
- the Elf Seed Process (Hagiwara Eugilite Co., Ltd.) is a process that modifies the polyimide film surface, applies a catalyst, reduces the electroless nickel plating, and then activates the electroless nickel plating film.
- a conductive metal layer can be obtained by electrolytic copper plating.
- the catalyst bond process (Nikko Metals Co., Ltd.) is a pretreatment process for plating. By pretreatment, it improves the adsorptivity of palladium, which is a wet plating catalyst, and provides catalyst after the process, by electroless and electrolytic copper plating. A conductive metal layer can be obtained.
- polyimide film As described above, the polyimide film, the polyimide metal laminate (the laminate in which the film and the metal layer are laminated via the adhesive layer, the laminate in which the metal layer is directly formed on the film) shown as the first aspect
- polyimide laminates include printed wiring boards, flexible printed circuit boards, TAB tapes, COF tapes or metal wirings, metal wirings, cover substrates such as chip members such as IC chips, liquid crystal displays, It can be used as a material for electronic components such as organic electroluminescence displays, electronic paper, base substrates such as solar cells, and electronic devices.
- the linear expansion coefficient of the polyimide film may be appropriately selected according to the purpose of use.
- the linear expansion coefficient of the polyimide film Is preferably close to the linear expansion coefficient of a chip member such as a metal wiring or an IC chip.
- both MD and TD are preferably 40 ppm / ° C. or less, more preferably 0 to 30 ppm / ° C., further preferably 5 to 25 ppm / ° C., and 8 to 20 ppm / ° C. It is particularly preferred.
- the linear expansion coefficient of the polyimide film is preferably close to the linear expansion coefficient of glass or silicon.
- a polyimide film having a linear expansion coefficient of 0 to 10 ppm / ° C. can also be obtained.
- the disclosure items of the polyimide film, polyimide laminate, and polyimide metal laminate of the first aspect are summarized as follows. 1.
- the polymer solution (a) capable of obtaining the polyimide layer (a) is applied to one side or both sides of the self-supporting film of the polyamic acid solution (b) capable of obtaining the polyimide layer (b), and heated. It is a polyimide film obtained,
- the polyimide layer (a) is a polyimide film which is a polyimide obtained from a tetracarboxylic dianhydride component and a diamine component containing a diamine compound represented by the formula (1).
- R 1 represents a hydrogen atom or an alkyl or aryl group having 1 to 12 carbon atoms (eg 1 to 10), and R 2 has 1 to 12 carbon atoms (eg 1 to 10 carbon atoms)). Represents an alkyl group or an aryl group.
- the diamine compound represented by the formula (1) is 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine.
- the polyimide film as described. 3.
- the polyimide film according to 1 or 2 wherein the polyimide layer (a) contains 10 to 100 mol% of the diamine compound represented by the formula (1) in the diamine component. 4).
- the polyimide film according to 1 or 2 wherein the polyimide layer (a) contains 25 to 100 mol% of the diamine compound represented by the formula (1) in the diamine component. 5. 5. The polyimide film according to any one of 1 to 4 above, wherein the maximum heating temperature is 350 ° C. or higher. 6). 5. The polyimide film according to any one of 1 to 4 above, wherein the polyimide film has a maximum heating temperature of 450 ° C. or higher. 7). 7. The polyimide film according to any one of 1 to 6, wherein the polyimide layer (a) further contains phenylenediamine and / or diaminodiphenyl ether as a diamine component. 8).
- the polyimide layer (b) comprises a tetracarboxylic dianhydride component containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or pyromellitic dianhydride, phenylenediamine and / or diamino.
- the polyimide film as described in any one of 1 to 9 above, wherein the polymer solution (a) from which the polyimide layer (a) can be obtained is a polyamic acid solution (a) from which the polyimide layer (a) can be obtained.
- 11. 11 A polyimide laminate, wherein an adhesive layer is directly laminated on the coated surface of the polyimide film described in any one of 1 to 10 above.
- 12 A polyimide metal laminate, wherein a metal layer is laminated on the coated surface of the polyimide film according to any one of 1 to 10 above through an adhesive layer.
- 13. 11 A polyimide metal laminate comprising a metal layer formed by dry or wet plating on the surface of the polyimide layer (a) of the polyimide film according to any one of 1 to 10 above.
- a 2nd aspect is a polyimide film used for an adhesive layer and direct lamination
- the present invention relates to a polyimide film obtained by reacting a diamine component containing 5 to 100 mol%, more preferably 10 to 100 mol%, more preferably.
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents an alkyl group or aryl group having 1 to 12 carbon atoms.
- the polyimide film of this aspect corresponds to a film composed entirely of a single layer of the material constituting the polyimide layer (a) described in the first aspect (Part 1). Unless otherwise specified in this part, the description in Part 1 is referred to unless there is a contradiction.
- the polyimide film of this embodiment is obtained by thermal imidization and / or chemical imidization, and when it contains a plurality of tetracarboxylic acid components and diamine components, it is block copolymerized even if it is randomly copolymerized. Or they may be used in combination.
- the thickness of the polyimide film is not particularly limited, but is 5 to 120 ⁇ m, preferably 6 to 75 ⁇ m, and more preferably 7 to 60 ⁇ m.
- a cyclization catalyst and a dehydrating agent are added to the polyamic acid solution, and the polyamic acid solution composition added by selecting inorganic fine particles and the like as necessary is cast on a support in a film form.
- the heating temperature in the heat treatment step is set to 350 ° C. or higher, more preferably 450 ° C. or higher, so that the peel strength after the heat treatment is excellent.
- the heating when heating at the maximum heating temperature, the heating may be performed on the support or may be peeled off from the support.
- the polyimide film is preferably produced from polyamic acid.
- ⁇ Tetracarboxylic acid component and diamine component> The tetracarboxylic acid component and diamine component used for the production of the polyimide film of the second aspect will be described.
- the tetracarboxylic acid component used for the polyimide layer (a) (that is, the same tetracarboxylic acid used for the polyimide layer (b)) is used. It can. Preferred ones are the same as those described for the polyimide layer (a).
- the diamine component used for the polyimide layer (a) in Part 1 can be used. Preferred ones are the same as those described for the polyimide layer (a).
- diamine component other diamine components can be used in addition to the diamine of the general formula (1).
- examples of the diamine to be used in combination can use the diamine component used for the polyimide layer (b) of the first embodiment, similarly to the polyimide layer (a) of the first embodiment, preferably from PPD and diaminodiphenyl ethers. More preferably, a diamine component containing at least one selected from PPD, 4,4′-diaminodiphenyl ether and 3,4′-diaminodiphenyl ether can be used.
- the polyimide film obtained by this is excellent in mechanical characteristics or thermal characteristics.
- the polyimide layer (a) includes, among others, an acid component containing s-BPDA and PMDA, a diamine represented by the general formula (1), a diamine represented by the general formula (1), PPD and 4,4′- A polyimide obtained from a polyamic acid produced from diaminodiphenyl ethers such as diaminodiphenyl ether and 3,4'-diaminodiphenyl ether is preferred.
- the polyimide of the present invention is excellent in that it does not contain at least one proton conductive functional group selected from the group consisting of —SO 3 H, —COOH and —PO 3 H 2 as shown in Patent Document 3. It is preferable because it has heat resistance.
- the diamine compound represented by the general formula (1) contained in the diamine component is in the range of 10 to 50 mol%, more preferably in the range of 15 to 40 mol%, The range of 17 to 30 mol% is particularly preferable.
- a polyamic acid (polyimide precursor) can be obtained by reacting a tetracarboxylic acid component and a diamine component by a known method using the above-mentioned components, for example, by reacting an approximately equimolar amount in an organic solvent.
- a polyamic acid solution (a part thereof may be imidized as long as a uniform solution state is maintained) can be obtained.
- it combines the two or more polyamic acid is excessive advance either component, after combining the respective polyamic acid solution may be mixed under reaction conditions.
- the polyamic acid solution thus obtained can be used for the production of a self-supporting film as it is or after removing or adding a solvent if necessary.
- the resulting polyimide When the resulting polyimide is soluble in an organic solvent, it can be obtained by reacting the tetracarboxylic acid component and the diamine component by a known method using each of the above components.
- the polyimide solution can be obtained by reacting in the solution.
- it is acceptable to two or more polyimide is excessive advance either component, after combining each polyimide solution may be mixed under reaction conditions.
- organic solvent for the polyamic acid solution or the polyimide solution a known solvent can be used.
- a known solvent for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide Etc.
- These organic solvents may be used alone or in combination of two or more.
- the concentration of all monomers in the organic polar solvent may be appropriately selected according to the purpose of use and the purpose of production, for example, the concentration of all monomers in the organic polar solvent. Is preferably 10% by mass to 30% by mass, more preferably 15% by mass to 27% by mass, and particularly preferably 18% by mass to 26% by mass.
- the polymerization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component is, for example, substantially equimolar or either component (acid component or diamine component).
- the reaction is carried out at a reaction temperature of 100 ° C. or lower, preferably 80 ° C. or lower, for about 0.2 to 60 hours to obtain a polyamic acid solution.
- the polymerization reaction of the aromatic tetracarboxylic acid component and the aromatic diamine component is, for example, substantially equimolar or either component (acid component or diamine component).
- the polyimide solution can be obtained by a known method by mixing in a slight excess.
- the reaction temperature is 140 ° C. or higher, preferably 160 ° C. or higher (preferably 250 ° C. or lower, more preferably 230 ° C. or lower) for about 1 to 60 hours.
- a polyimide solution can be obtained by reacting.
- an imidization catalyst, an organic phosphorus-containing compound, inorganic fine particles, and the like may be added to the polyamic acid solution as necessary. If it is chemical imidation, you may add a cyclization catalyst, a dehydrating agent, inorganic fine particles, etc. to a polyamic acid solution as needed. An organic phosphorus-containing compound, inorganic fine particles, and the like may be added to the polyimide solution.
- the imidization catalyst the organic phosphorus-containing compound, the cyclization catalyst, the dehydrating agent, and the inorganic fine particles, those described in Part 1 can be used.
- polyimide fine particles that are insoluble in an organic solvent can be used instead of the inorganic fine particles.
- the self-supporting film of the polyamic acid solution should be peel-coated from the support to the extent that it becomes self-supporting by applying the polyamic acid solution onto the support (meaning the stage before the normal curing process), for example. It is manufactured by heating to the extent that it can be.
- the solid content concentration of the polyamic acid solution used in the present invention is not particularly limited as long as it is in a viscosity range suitable for production, but is usually preferably 10% by mass to 30% by mass, and preferably 15% by mass to 27% by mass. More preferably, 18% by mass to 26% by mass is more preferable.
- ⁇ Heat treatment (imidization) step> the self-supporting film is heat-treated to obtain a polyimide film.
- heating is performed so that the maximum heating temperature is preferably 350 ° C. or higher, more preferably 450 ° C. or higher, and further preferably 470 ° C. or higher.
- the upper limit of the heating temperature may be a temperature at which the characteristics of the polyimide film do not deteriorate, and is preferably 600 ° C. or lower, more preferably 550 ° C. or lower, further preferably 530 ° C. or lower, and particularly preferably 520 ° C. or lower.
- the heat treatment it is appropriate to first gradually perform imidization of the polymer and evaporation / removal of the solvent at a temperature of about 100 ° C. to less than 350 ° C. for about 0.05 to 5 hours, particularly 0.1 to 3 hours. is there.
- the heat treatment is performed stepwise at a relatively low temperature of about 100 ° C. to about 170 ° C. for about 0.5-30 minutes, and then at a temperature above 170 ° C. and below 220 ° C.
- the second heat treatment is preferably performed for 0.5 to 30 minutes, and then the third heat treatment is preferably performed at a high temperature exceeding 220 ° C. and less than 350 ° C. for about 0.5 to 30 minutes.
- pin tenters, clips, frames, etc. at least the edges in the direction perpendicular to the longitudinal direction of the long self-supporting film, that is, the width direction of the film May be fixed, and heat treatment may be performed by expanding and contracting in the width direction or the length direction as necessary.
- the polyimide film of the present invention obtained as described above may be further subjected to sandblasting, corona treatment, plasma treatment, etching treatment and the like.
- the polyimide film of the present invention when the diamine concentration of the general formula (1) in the total diamine component is high (for example, 30% by mass or more), the polyimide film of the present invention obtained has a good polyimide film appearance. Therefore, it is preferable that the polyimide film is thicker (for example, 25 ⁇ m or more) than when it is thin.
- the tetracarboxylic acid component is PMDA and the diamine concentration of the general formula (1) in all the diamine components is high (for example, 80% by mass or more), in order to obtain a polyimide film having a good appearance of the film
- the maximum heating temperature in the heat treatment (imidization) step is preferably low (for example, 300 to 400 ° C.).
- ⁇ Polyimide film laminate> The surface of the polyimide film is excellent in adhesiveness with the adhesive. Therefore, similar to the polyimide film of the first aspect (described in Part 1), the polyimide film of the second aspect is used to laminate the polyimide laminate having the adhesive layer laminated thereon and the other substrate. The body can be manufactured.
- the present invention provides a polyimide laminate having the polyimide film described in the second aspect and an adhesive layer laminated in contact with the polyimide film.
- the present invention provides a laminate comprising the polyimide film described in the second aspect, an adhesive layer laminated in contact with the polyimide film, and another base material laminated via the adhesive layer.
- a polyimide metal laminate in which metal foil is laminated as another substrate is provided.
- the linear expansion coefficient of the polyimide film of the second aspect is also as described in the first aspect.
- the disclosure items of the second aspect are summarized as follows. 1. It is a polyimide film used for direct lamination with the adhesive layer,
- the polyimide constituting this polyimide film comprises a tetracarboxylic dianhydride component and a diamine compound represented by the general formula (1) in excess of 0 to 100 mol%, preferably 5 to 100 mol%, more preferably 10 to A polyimide film obtained by reacting a diamine component containing 100 mol%.
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents an alkyl group or aryl group having 1 to 12 carbon atoms.
- a polyimide laminate comprising the polyimide film as described in any one of 1 to 6 above and an adhesive layer laminated in direct contact with the polyimide film. 8). 7. A laminate comprising the polyimide film according to any one of 1 to 6 above, an adhesive layer laminated in direct contact with the polyimide film, and another base material laminated via the adhesive layer. Particularly preferably, a polyimide metal laminate in which metal foil is laminated as another substrate.
- a third aspect of the present invention will be described.
- a 3rd aspect is related with the polyimide film used in order to form a metal layer by plating on the film surface.
- the polyimide film of the first aspect is suitable for forming a metal layer by dry or wet plating, but the polyimide film according to the third aspect is also suitable for this application.
- the polyimide film according to the third aspect is a film formed in multiple layers like the polyimide film described in the first aspect. Moreover, the polyimide film by the 3rd aspect is a film formed by a single layer similarly to the polyimide film demonstrated by the 2nd aspect.
- the polyimide relates to a polyimide film obtained by reacting a tetracarboxylic dianhydride component with a diamine component containing 10 to 100 mol% of the diamine compound represented by the general formula (1).
- the polyimide film is preferably obtained by heat treatment in a heat treatment step under conditions where the maximum heating temperature is 450 ° C. or higher.
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents an alkyl group or aryl group having 1 to 12 carbon atoms.
- the metal layer is provided by plating, not only in the initial stage, but also after the heat treatment at 150 ° C. or the heat treatment at 121 ° C., 0.2 MPa, 100% RH. It is possible to provide a polyimide film having excellent adhesion that does not decrease in strength.
- a metal layer was provided by plating having excellent adhesion that does not decrease the peel strength.
- a polyimide metal laminate can be provided.
- the polyimide film is a film formed of a single polyimide layer
- the production of the polyimide raw material and the self-supporting film is the same as described in the second embodiment. Therefore, only the heat treatment process will be described.
- the obtained self-supporting film is heated in the heat treatment step so that the maximum heating temperature is preferably 450 ° C. or higher, more preferably 470 ° C. or higher to obtain a polyimide film.
- the upper limit of the heating temperature may be a temperature at which the characteristics of the polyimide film do not deteriorate, and is preferably 600 ° C. or lower, more preferably 550 ° C. or lower, further preferably 530 ° C. or lower, and particularly preferably 520 ° C. or lower. Just do it.
- the heat treatment can be performed in multiple stages. First, at a temperature of about 100 ° C. to 400 ° C., the imidization of the polymer and the evaporation / removal of the solvent are performed in about 0.05 to 5 hours, particularly 0.1 to 3 hours. It is appropriate to carry out gradually.
- the heat treatment is performed stepwise at a relatively low temperature of about 100 ° C. to about 170 ° C. for about 0.5-30 minutes, and then at a temperature above 170 ° C. and below 220 ° C. Secondary heat treatment for 0.5 to 30 minutes, followed by tertiary heat treatment at a high temperature of more than 220 ° C. and less than 450 ° C. for about 0.5 to 30 minutes, and 450 ° C. to 550 ° C., preferably It is necessary to perform high-temperature heat treatment at a maximum heating temperature of 470 to 530 ° C., more preferably 480 to 520 ° C. Also, this heating process can be performed sequentially or continuously.
- pin tenters, clips, frames, etc. at least the edges in the direction perpendicular to the longitudinal direction of the long self-supporting film, that is, the width direction of the film May be fixed, and heat treatment may be performed by expanding and contracting in the width direction or the length direction as necessary.
- the thickness of the polyimide film of the present invention is not particularly limited, but is about 3 to 250 ⁇ m, preferably about 4 to 150 ⁇ m, more preferably about 5 to 125 ⁇ m, and still more preferably about 5 to 100 ⁇ m.
- the polyimide film of the present invention may be further subjected to sandblast treatment, corona treatment, plasma treatment, etching treatment and the like.
- the polyimide film of this embodiment is excellent in adhesion to the metal layer, and a polyimide metal laminate can be produced by forming a metal layer on the surface.
- the surface to be plated may be either the A surface or the B surface.
- Examples of methods for forming a metal layer by plating include metallizing methods and wet plating methods, which are dry plating methods.
- the wet plating method and metallizing method are described in detail in Part 1 ⁇ Polyimide metal laminate (metal layer direct formation)>, and are carried out according to the method described therein (preferable conditions and materials are the same). be able to.
- the polyimide film and the polyimide metal laminate thus obtained are printed wiring boards, flexible printed boards, TAB tapes, COF tapes or metal wirings, and cover substrates such as metal wirings and chip members such as IC chips. It can be used as a material for electronic parts and electronic devices such as base materials such as materials, liquid crystal displays, organic electroluminescence displays, electronic paper, and solar cells.
- the linear expansion coefficient of the polyimide film may be appropriately selected according to the purpose of use.
- insulating substrate materials such as FPC, TAB, COF or metal wiring substrate, metal wiring, chip members such as IC chips, etc.
- the linear expansion coefficient of a polyimide film is preferably close to the linear expansion coefficient of a chip member such as a metal wiring or an IC chip, specifically, MD and TD. Both are preferably 40 ppm / ° C. or less, more preferably 0 to 30 ppm / ° C., further preferably 5 to 25 ppm / ° C., and particularly preferably 8 to 20 ppm / ° C.
- the disclosure items of the third aspect are summarized as follows. 1. It is a polyimide film used to form a metal layer by plating on the polyimide surface, The polyimide constituting this polyimide is obtained by reacting a tetracarboxylic dianhydride component with a diamine component containing 10 to 100 mol% of the diamine compound represented by the general formula (1). A polyimide film obtained by heat treatment under conditions where the heating temperature is 450 ° C. or higher.
- R 1 represents a hydrogen atom or an alkyl group or aryl group having 1 to 12 carbon atoms
- R 2 represents an alkyl group or aryl group having 1 to 12 carbon atoms.
- the tetracarboxylic dianhydride component is a tetracarboxylic dianhydride component containing 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and / or pyromellitic dianhydride.
- the polyimide film as described in any one of 1 to 3 above. 5.
- the polyimide film as described in any one of 1 to 4 above, wherein the plating is dry or wet plating. 6). 6.
- a polyimide metal laminate comprising the polyimide film as described in any one of 1 to 5 above and a metal layer formed by plating.
- the physical properties of the polyimide film were evaluated according to the following methods.
- a) The peel strength is a peel strength at 90 ° peel, and was measured at a peel rate of 50 mm / min in an environment of a temperature of 23 ° C. and a humidity of 50%.
- the surface of the polyimide film the surface on the air side when the polyamic acid solution was cast on the support was the A surface, and the surface on the support side was the B surface.
- the peeling mode between the polyimide and the adherend was observed and displayed in the table with the following contents 1) to 4).
- peel strength of the polyimide laminate A was measured and used as the initial peel strength A. Further, the polyimide laminate A was treated in a hot air dryer at 150 ° C. for 24 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength A.
- the polyimide metal laminate was treated in a hot air dryer at 150 ° C. for 24 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength A2.
- the polyimide metal laminate was treated in a hot air dryer at 150 ° C. for 168 hours, and then the peel strength was measured to obtain a post-heat-resistant peel strength A3.
- the polyimide metal laminate was treated in an environment of 121 ° C., 100% RH, 0.2 MPa for 24 hours using a pressure cooker test apparatus, and then the peel strength was measured to obtain a cooker peel strength A4.
- the polyimide metal laminate was treated for 96 hours in an environment of 121 ° C., 100% RH, 0.2 MPa using a pressure cooker test apparatus, and then the peel strength was measured to obtain a cooker peel strength A5.
- Example Part I (Example corresponding to Part 1) >>
- Preparation of polyamic acid solution and coating solution> (Preparation of polyamic acid solution IA) A predetermined amount of N, N-dimethylacetamide (DMAc) and paraphenylenediamine (PPD) as a diamine component are added to a polymerization tank, and then stirred at 40 ° C., and 3,3 ′, 4,4′-as an acid component. Biphenyltetracarboxylic dianhydride (s-BPDA) and PPD are added stepwise to approximately equimolar and reacted to obtain a polyamic acid polymerization solution (polyimide precursor solution) having a solid concentration of 18% by mass. It was.
- DMAc N, N-dimethylacetamide
- PPD paraphenylenediamine
- monostearyl phosphate triethanolamine salt is added to the polyamic acid polymerization solution at a ratio of 0.25 parts by mass with respect to 100 parts by mass of the polyamic acid, and mixed uniformly to obtain a polyamic acid solution IA. Obtained.
- the rotational viscosity at 30 ° C. of the polyamic acid solution IA was 180 Pa ⁇ s.
- a polyamic acid polymerization solution ID (polyimide precursor solution) was obtained in the same manner as in the preparation of the polyamic acid solution IC except that the amount of ATDA was 50 mol% in all diamine components.
- a polyamic acid polymerization solution IE (polyimide precursor solution) was obtained in the same manner as in the preparation of the polyamic acid solution IC except that the amount of ATDA was 30 mol% in all diamine components.
- a polyamic acid polymerization solution IF (polyimide precursor solution) was obtained in the same manner as in the preparation of the polyamic acid solution IC except that the amount of ATDA was 19 mol% in all diamine components.
- a predetermined amount of N, N-dimethylacetamide (DMAc), paraphenylenediamine (PPD), 2,4-bis (4-aminoanilino) -6-anilino-1,3,5-triazine (ATDA) is added to the polymerization tank. It was. In all diamine components, the amount of ATDA was 80 mol% and the amount of PPD was 20 mol%.
- s-BPDA 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
- PMDA pyromellitic dianhydride
- the polyimide obtained from the polyamic acid solution IF has a high 5% weight loss temperature.
- Example A1 The polyamic acid solution composition IA was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, then peeled off from the glass plate, and the loss of heating was 36.8% by mass. A support film was obtained.
- the coating liquid I-1 was applied to the side A of this self-supporting film using a bar coater No. 3 (coating amount: 6 g / m 2 ), fixing the four sides with a pin tenter, and using an oven, heat imide stepwise from 150 ° C. for 50 seconds, 210 ° C. for 50 seconds, and 370 ° C. for 50 seconds.
- a bar coater No. 3 coating amount: 6 g / m 2
- PI-A1 polyimide laminate A in which a coverlay was laminated on the A surface (coated surface) was obtained by the method described in the section of the evaluation method.
- the peel strength of the polyimide laminate A (PI-A1) was measured, and the results are shown in Table A1.
- the peel strength was also obtained by laminating a coverlay on the evaluation surface (surface coated with the coating solution) by the method described in the evaluation method section in the following examples.
- the peel strength was measured using the polyimide laminate A.
- Table A Table A1 and Table A2
- the name of the polyimide laminate A obtained by laminating the coverlay is the same as the name of the polyimide film (PI-A1 etc.) and is represented as polyimide laminate A (PI-A1) etc.
- Example A2 A polyimide film (PI-A2) was obtained in the same manner as in Example A1, except that side B of the self-supporting film obtained in the same manner as in Example A1 was selected.
- Example A3 The coating liquid I-1 was applied to the surface A of the self-supporting film obtained in the same manner as in Example A1 with a bar coater No. 3 (coating amount: 6 g / m 2 ), heat imidization in steps of 150 ° C. for 50 seconds, 210 ° C. for 50 seconds, 370 ° C. for 50 seconds, 490 ° C. for 50 seconds, and polyimide film (PI -A3) was obtained.
- Example A4 A polyimide film (PI-A4) was obtained in the same manner as in Example A3, except that side B was selected as the coating surface for the coating solution.
- Example A5 A coating liquid I-2 was applied to the surface A of a self-supporting film obtained in the same manner as in Example A1. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A5).
- Example A6 A polyimide film (PI-A6) was obtained in the same manner as in Example A5, except that side B was selected as the coating surface for the coating liquid.
- Example A7 A coating liquid I-2 was applied to the surface A of a self-supporting film obtained in the same manner as in Example A1. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 490 ° C. over about 18 minutes to obtain a polyimide film (PI-A7).
- Example A8 A polyimide film (PI-A8) was obtained in the same manner as in Example A7, except that side B was selected as the coating surface for the coating solution.
- Example A9 A coating liquid I-3 was applied to the surface A of a self-supporting film obtained in the same manner as in Example A1. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A9).
- Example A10 A polyimide film (PI-A10) was obtained in the same manner as in Example A9, except that side B was selected as the coating surface for the coating liquid.
- Example A11 A coating liquid I-3 was applied to the surface A of a self-supporting film obtained in the same manner as in Example A1. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 490 ° C. over about 18 minutes to obtain a polyimide film (PI-A11).
- Example A12 A polyimide film (PI-A12) was obtained in the same manner as in Example A11, except that side B was selected as the coating surface for the coating liquid.
- Example A13 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-4 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized by heating from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A13).
- Example A14 A polyimide film (PI-A14) was obtained in the same manner as in Example A13, except that side B was selected as the coating surface for the coating liquid.
- Example A15 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-4 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 490 ° C. over about 18 minutes to obtain a polyimide film (PI-A15).
- Example A16 A polyimide film (PI-A16) was obtained in the same manner as in Example A15, except that side B was selected as the coating surface for the coating liquid.
- Example A17 Polyamic acid solution IA (without 1,2-dimethylimidazole addition) was cast on a glass plate as a thin film, heated at 138 ° C for 60 seconds using a hot plate, then peeled off from the glass plate and self-supported A characteristic film was obtained.
- the coating liquid I-4 was applied to the side A of this self-supporting film using a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A17).
- Example A18 A polyimide film (PI-A18) was obtained in the same manner as in Example A17, except that side B was selected as the coating surface for the coating liquid.
- Example A19 A coating liquid I-4 was applied to the surface A of a self-supporting film obtained in the same manner as in Example A17. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 490 ° C. over about 18 minutes to obtain a polyimide film (PI-A19).
- Example A20 A polyimide film (PI-A20) was obtained in the same manner as in Example A19, except that side B was selected as the coating surface for the coating liquid.
- Example A21 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-5 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A21).
- Example A22 A polyimide film (PI-A22) was obtained in the same manner as in Example A21, except that side B was selected as the coating surface for the coating liquid.
- Example A23 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-5 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized by heating from 150 ° C. to 490 ° C. over about 18 minutes to obtain a polyimide film (PI-A23).
- Example A24 A polyimide film (PI-A24) was obtained in the same manner as in Example A23, except that side B was selected as the coating surface for the coating liquid.
- Example A25 On the A side of the self-supporting film obtained in the same manner as in Example A17, the coating liquid I-5 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A25).
- Example A26 A polyimide film (PI-A26) was obtained in the same manner as in Example A25, except that side B was selected as the coating surface for the coating liquid.
- Example A27 On the A side of the self-supporting film obtained in the same manner as in Example A17, the coating liquid I-5 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ), the four sides were fixed with a pin tenter, and were continuously heated and imidized from 150 ° C. to 490 ° C. over about 18 minutes using an oven to obtain a polyimide film (PI -A27) was obtained.
- PI -A27 polyimide film
- Example A28 A polyimide film (PI-A28) was obtained in the same manner as in Example A27, except that side B was selected as the coating surface for the coating liquid.
- Example A29 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-6 was applied to the bar coater no. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A29).
- Example A30 A polyimide film (PI-A30) was obtained in the same manner as in Example A29, except that side B was selected as the coating surface for the coating liquid.
- Example A31 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-6 was applied to the bar coater no. 3 (coating amount: 6 g / m 2 ), the four sides were fixed with a pin tenter, and were continuously heated and imidized from 150 ° C. to 490 ° C. over about 18 minutes using an oven to obtain a polyimide film (PI -A31) was obtained.
- Example A32 A polyimide film (PI-A32) was obtained in the same manner as in Example A31 except that surface B was selected as the coating surface for the coating liquid.
- Example A33 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-7 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A33).
- Example A34 A polyimide film (PI-A34) was obtained in the same manner as in Example A33, except that the B surface of the self-supporting film obtained in the same manner as in Example A1 was selected as the coating surface of the coating liquid.
- Example A35 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-7 was applied with a bar coater No. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 490 ° C. over about 18 minutes to obtain a polyimide film (PI-A35).
- Example A36 A polyimide film (PI-A36) was obtained in the same manner as in Example A35, except that side B was selected as the coating surface for the coating liquid.
- Example A37 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-8 was applied with a bar coater no. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 370 ° C. over about 11 minutes to obtain a polyimide film (PI-A37).
- Example A38 A polyimide film (PI-A38) was obtained in the same manner as in Example A37, except that side B was selected as the coating surface for the coating liquid.
- Example A39 On the A side of the self-supporting film obtained in the same manner as in Example A1, the coating liquid I-8 was applied with a bar coater no. 3 (coating amount: 6 g / m 2 ) and continuously imidized from 150 ° C. to 490 ° C. over about 18 minutes to obtain a polyimide film (PI-A39).
- Example A40 A polyimide film (PI-A40) was obtained in the same manner as in Example A39, except that side B was selected as the coating surface for the coating liquid.
- Example A1 In the same manner as in Example A27, a self-supporting film having a loss on heating of 35.6% by mass was obtained. Fix the four sides with a pin tenter without applying the polymer solution to the self-supporting film, and use the oven to continuously heat imidize it from 150 ° C to 490 ° C over about 18 minutes to obtain a polyimide film (PI-A41) Got. The peel strength was measured from the polyimide laminate A (PI-A41) obtained by laminating the coverlay on the A surface.
- Example A2 In the same manner as in Example A27, a self-supporting film having a loss on heating of 35.6% by mass was obtained. Fix the four sides with a pin tenter without applying the polymer solution to the self-supporting film, and use the oven to continuously heat imidize from 150 ° C to 490 ° C over about 18 minutes to obtain a polyimide film (PI-A42) Got. The peel strength was measured from the polyimide laminate A (PI-A42) obtained by laminating the coverlay on the B surface.
- Examples A2 to A4 and A25 to A28 the initial peel strength of the polyimide laminate A is excellent.
- Examples A1 to A4 are superior in heat-resistant peel strength to Examples A25 to A28. This is considered to be the influence of the content of the diamine represented by the general formula (1).
- Examples A3 and A4 are superior in heat-resistant peel strength to Examples A1 and A2. This is considered to be the effect of the maximum heating temperature of the film.
- the peel strength after heat resistance of the A and B surfaces of the film tends to be slightly higher on the B surface.
- the heat-resistant peel strength of the polyimide laminate A is superior to when not using it.
- the ratio of the peel strength after heat resistance to the initial peel strength is 50 to 70 mol% of ATDA in the diamine component, about 0.45 to 3.1, especially large.
- the heat-resistant peel strength tends to be superior as compared with the case of applying to the same surface and curing at 370 ° C.
- Example Part II (Example corresponding to Part 2) >>
- a monostearyl phosphate triethanolamine salt is added to the polyamic acid polymerization solution II-A at a ratio of 0.25 parts by mass with respect to 100 parts by mass of the polyamic acid, and mixed uniformly. II-A was obtained.
- the rotational viscosity of Polyamic Acid Solution II-A at 30 ° C. was 170 Pa ⁇ s.
- a polyamic acid polymerization solution II-B (polyimide precursor solution) having a solid content concentration of 18% by mass was obtained.
- a monostearyl phosphate triethanolamine salt was added to the polyamic acid polymerization solution II-B at a ratio of 0.25 parts by mass with respect to 100 parts by mass of the polyamic acid, and mixed uniformly. II-B was obtained.
- the rotational viscosity of Polyamic Acid Solution II-B at 30 ° C. was 150 Pa ⁇ s.
- a polyamic acid solution II-C was obtained in the same manner as in the preparation of the polyamic acid solution II-B, except that the amount of ATDA was 19 mol% in all diamine components.
- the rotational viscosity of Polyamic Acid Solution II-C at 30 ° C. was 170 Pa ⁇ s.
- a polyamic acid solution II-D was obtained in the same manner as in the preparation of the polyamic acid solution II-B, except that the amount of ATDA in the total diamine component was 10 mol%.
- the rotational viscosity of Polyamic Acid Solution II-D at 30 ° C. was 110 Pa ⁇ s.
- a polyamic acid solution II-E was obtained in the same manner as in the preparation of the polyamic acid solution II-B except that the amount of ATDA in the total diamine component was 6.2 mol%.
- the rotational viscosity of Polyamic Acid Solution II-E at 30 ° C. was 150 Pa ⁇ s.
- a monostearyl phosphate triethanolamine salt was added to the polyamic acid polymerization solution II-F at a ratio of 0.25 parts by mass with respect to 100 parts by mass of the polyamic acid, and mixed uniformly. II-F was obtained.
- the rotational viscosity of Polyamic Acid Solution II-F at 30 ° C. was 190 Pa ⁇ s.
- the reaction was carried out stepwise to obtain a polyamic acid polymerization solution II-H (polyimide precursor solution) having a solid concentration of 18% by mass.
- a polyamic acid polymerization solution II-H polyimide precursor solution
- the amount of s-BPDA was 80 mol% in the total acid dianhydride component.
- a monostearyl phosphate triethanolamine salt was added to the polyamic acid polymerization solution II-H at a ratio of 0.25 parts by mass with respect to 100 parts by mass of the polyamic acid, and mixed uniformly. II-H was obtained.
- the rotational viscosity of Polyamic Acid Solution II-H at 30 ° C. was 120 Pa ⁇ s.
- Example B1 The polyamic acid solution II-A was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, peeled off from the glass plate, and self-supporting with a loss on heating of 33.6% by mass. A film was obtained.
- a polyimide film (PI-B1) was obtained. Obtained.
- a polyimide laminate A (PI-B1) in which a coverlay was laminated on the A surface was obtained by the method described in the evaluation method section.
- the peel strength of the polyimide laminate A (PI-B1) was measured, and the results are shown in Table B.
- the description is omitted, but unless otherwise specified, the four sides of the self-supporting film are fixed with a pin tenter and subjected to heat treatment using an oven.
- the polyimide laminate A obtained by laminating a coverlay on the evaluation surface was peeled off in the following examples by the method described in the section of the evaluation method. The strength was measured. The results of each example are shown in Table B.
- the name of the polyimide laminate A obtained by laminating the coverlay is the same as the name of the polyimide film (PI-B1 etc.) and is represented as polyimide laminate A (PI-B1) etc.
- Table B shows the heat loss of the self-supporting film, the average film thickness of the obtained polyimide film, the laminated surface of the polyimide film with the adhesive layer, and other conditions and results.
- Example B2 A polyimide film (PI-B2) was obtained in the same manner as in Example B1, except that the B side of the self-supporting film obtained in the same manner as in Example B1 was turned up.
- Example B3 A self-supporting film obtained in the same manner as in Example B1, with the A side facing up, was continuously heated and imidized from 150 ° C. to 490 ° C. in about 18 minutes to obtain a polyimide film (PI-B3).
- Example B4 A polyimide film (PI-B4) was obtained in the same manner as in Example B3, except that the B side of the self-supporting film obtained in the same manner as in Example B1 was turned up.
- Example B5 The polyamic acid solution II-B was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, and then peeled from the glass plate to obtain a self-supporting film. With the A-side of this self-supporting film as the top, it was continuously heated and imidized from 150 ° C. to 370 ° C. in about 11 minutes to obtain a polyimide film (PI-B5).
- PI-B5 polyimide film
- Example B7 A side surface of the self-supporting film obtained in the same manner as in Example B5 was faced up and continuously heated and imidized from 150 ° C. to 490 ° C. in about 18 minutes to obtain a polyimide film (PI-B7).
- Example B8 A polyimide film (PI-B8) was obtained in the same manner as in Example B7, except that the B side of the self-supporting film obtained in the same manner as in Example B5 was turned up.
- Example B9 The polyamic acid solution II-C was cast into a thin film on a glass plate, heated at 138 ° C. for 210 seconds using a hot plate, and then peeled from the glass plate to obtain a self-supporting film. With the A side of this self-supporting film as the top, it was continuously heated and imidized from 150 ° C. to 370 ° C. in about 11 minutes to obtain a polyimide film (PI-B9).
- PI-B9 polyimide film
- Example B10 A polyimide film (PI-B10) was obtained in the same manner as in Example B9, except that the B side of the self-supporting film obtained in the same manner as in Example B9 was turned up.
- Example B11 With the A side of the self-supporting film obtained in the same manner as in Example B9 facing upward, it was continuously heated and imidized from 150 ° C. to 490 ° C. in about 18 minutes to obtain a polyimide film (PI-B11).
- Example B12 A polyimide film (PI-B12) was obtained in the same manner as in Example B11 except that the B-side of the self-supporting film obtained in the same manner as in Example B9 was faced up.
- Example B13 The polyamic acid solution II-C was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, and then peeled off from the glass plate to obtain a self-supporting film. With the B surface of this self-supporting film facing upward, it was continuously heated and imidized from 150 ° C. to 370 ° C. in about 11 minutes to obtain a polyimide film (PI-B13). A coverlay was laminated on the A side (as shown in Table B) of this polyimide film (PI-B13) to obtain a polyimide laminate A (PI-B13).
- Example B14 A coverlay was laminated on the B side of a polyimide film (PI-B14. The same film as PI-B13) to obtain a polyimide laminate A (PI-B14).
- Example B15 A self-supporting film was obtained in the same manner as in Example B13. With the B surface of this self-supporting film as the top, it was continuously heated and imidized from 150 ° C. to 490 ° C. in about 18 minutes to obtain a polyimide film (PI-B15). A coverlay was laminated on the A side (as shown in Table B) of this polyimide film (PI-B15) to obtain a polyimide laminate A (PI-B15).
- Example B16 A coverlay was laminated on the B side of a polyimide film (PI-B16. The same film as PI-B15) to obtain a polyimide laminate A (PI-B16).
- Example B17 The polyamic acid solution II-D was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, and then peeled from the glass plate to obtain a self-supporting film. With the A-side of this self-supporting film facing upward, it was continuously imidized by heating from 150 ° C. to 370 ° C. in about 11 minutes to obtain a polyimide film (PI-B17).
- Example B18 A polyimide film (PI-B18) was obtained in the same manner as in Example B17, except that the B side of the self-supporting film obtained in the same manner as in Example B17 was turned up.
- Example B19 With the A side of the self-supporting film obtained in the same manner as in Example B17 facing upward, it was continuously imidized from 150 ° C. to 490 ° C. in about 18 minutes to obtain a polyimide film (PI-B19).
- Example B20 A polyimide film (PI-B20) was obtained in the same manner as in Example B19 except that the B-side of the self-supporting film obtained in the same manner as in Example B17 was faced up.
- Example B21 The polyamic acid solution II-F was cast into a thin film on a glass plate, heated at 138 ° C. for 160 seconds using a hot plate, and then peeled off from the glass plate to obtain a self-supporting film. With the A-side of this self-supporting film as the top, it was continuously heated and imidized from 150 ° C. to 370 ° C. in about 11 minutes to obtain a polyimide film (PI-B21).
- Example B22 A polyimide film (PI-B22) was obtained in the same manner as in Example B21 except that the B side of the self-supporting film obtained in the same manner as in Example B21 was the top.
- Example B25 Polyamic acid solution II-G was cast into a thin film on a glass plate, heated at 138 ° C. for 160 seconds using a hot plate, and then peeled from the glass plate to obtain a self-supporting film. With the A-side of this self-supporting film facing upward, it was continuously heated and imidized from 150 ° C. to 370 ° C. in about 11 minutes to obtain a polyimide film (PI-B25).
- Example B26 A polyimide film (PI-B26) was obtained in the same manner as in Example B25 except that the B-side of the self-supporting film obtained in the same manner as in Example B23 was faced up.
- Example B29 The polyamic acid solution II-H was cast into a thin film on a glass plate, heated at 138 ° C. for 210 seconds using a hot plate, and then peeled from the glass plate to obtain a self-supporting film. With the A-side of this self-supporting film facing upward, it was continuously imidized by heating from 150 ° C. to 370 ° C. in about 11 minutes to obtain a polyimide film (PI-B29).
- Example B30 A polyimide film (PI-B30) was obtained in the same manner as in Example B29, except that the B side of the self-supporting film obtained in the same manner as in Example B27 was turned up.
- Example B31 With the A side of the self-supporting film obtained in the same manner as in Example B27 facing upward, it was continuously heated and imidized from 150 ° C. to 490 ° C. in about 18 minutes to obtain a polyimide film (PI-B31).
- Example B32 A polyimide film (PI-B32) was obtained in the same manner as in Example B31 except that the B-side of the self-supporting film obtained in the same manner as in Example B27 was faced up.
- Example B33 The polyamic acid solution composition II-E was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, then peeled off from the glass plate, and the loss of heating was 35.6% by mass. A support film was obtained.
- Example B34 A coverlay was laminated on the B surface of a polyimide film (PI-B34, the same as PI-B33) to obtain a polyimide laminate A (PI-B34).
- Example B35 With the B side of the self-supporting film obtained in the same manner as in Comparative Example B1 facing up, 150 ° C, 210 ° C, 370 ° C, and 490 ° C were heated and imidized stepwise for 50 seconds each to obtain a polyimide film ( PI-B35) was obtained. A coverlay was laminated on side A (as described in Table B) of the polyimide film (PI-B35) to obtain a polyimide laminate A (PI-B35).
- Example B36 A coverlay was laminated on the B surface of a polyimide film (PI-B36, the same as PI-B35) to obtain a polyimide laminate A (PI-B36).
- Example B37 Polyamic acid solution II-C was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, and then peeled from the glass plate to obtain a self-supporting film. The heat loss of the self-supporting film was 36.1% by mass. With the A-side of this self-supporting film facing upward, it was continuously heated and imidized from 150 ° C. to 510 ° C. in about 18 minutes to obtain a polyimide film (PI-B37) having an average film thickness of 12.5 ⁇ m. A coverlay was laminated on the A surface of the polyimide film (PI-B37) to obtain a polyimide laminate A (PI-B37).
- the initial A was 0.18 kN / m, and the A after heat resistance was 0.38 kN / m. Further, regarding the peel strength mode of the polyimide laminate A (PI-B37), the initial A was “3”, and the A after heat resistance was “3”.
- Example B38 A coverlay was laminated on the B side of a polyimide film (PI-B38, the same film as PI-B37) to obtain a polyimide laminate A (PI-B38).
- the initial A was 0.24 kN / m
- the A after heat resistance was 0.50 kN / m.
- the peel strength mode of the polyimide laminate A (PI-B38) was “3”, and the A after heat resistance was “4”.
- Comparative Example B2 to Comparative Example B4 A polyimide film and a polyimide laminate A were obtained in the same manner as in Comparative Example B1, except that the maximum heating temperature and the coverlay laminate surface were changed as shown in Table B.
- Example B 1) When Examples B13 and B14 are compared with Examples B15 and B16, the heat-resistant peel strength is excellent. This is considered to be the effect of the maximum heating temperature of the film. 2) In Examples B1 to B36, the initial peel strength of the polyimide laminate B is superior to that of the comparative polyimide film cured at the same temperature and laminated with the adhesive on the same surface. This is considered to be the influence of the content of the diamine represented by the general formula (1). 3) In Examples B1 to B36, the heat resistant peel strength of the polyimide laminate B is superior to that of the comparative polyimide film cured at the same temperature and laminated with an adhesive on the same surface. This is considered to be the influence of the content of the diamine represented by the general formula (1).
- the peel strength after heat resistance / initial peel strength is as large as about 0.26 to 3.1. This is considered to be the influence of the content of the diamine represented by the general formula (1).
- the peel strength after heat resistance / initial peel strength was as large as about 0.57 to 1.06.
- all the peeling modes are cohesive failure of the adhesive, and it is considered that the adhesive has a numerical value or higher.
- Example Part III (Examples corresponding to Parts 1 and 3) >>
- a polymerization solution (polyimide precursor solution) of polyamic acid having a partial concentration of 18% by mass was obtained. Then, monostearyl phosphate triethanolamine salt was added to the polyamic acid polymerization solution at a ratio of 0.25 parts by mass with respect to 100 parts by mass of the polyamic acid, and mixed uniformly, and the polyamic acid solution III-A was added. Obtained.
- the rotational viscosity of Polyamic Acid Solution III-A at 30 ° C. was 170 Pa ⁇ s.
- monostearyl phosphate triethanolamine salt is added to the polyamic acid polymerization solution at a ratio of 0.25 parts by mass with respect to 100 parts by mass of the polyamic acid, and mixed uniformly, and the polyamic acid solution III-B is added. Obtained.
- the rotational viscosity of Polyamic Acid Solution III-B at 30 ° C. was 104 Pa ⁇ s.
- coating solution III-2 (Preparation of coating solution III-2)
- DMAc was added to dilute until the total solid content concentration became 2.5 wt% to obtain a coating solution III-2.
- the viscosity of the coating liquid III-2 was 9.95 mPa ⁇ s.
- Example C1 The polyamic acid solution III-B is continuously cast from the slit of the T-die mold, extruded onto a smooth belt-like metal support in a drying furnace to form a thin film, heated at 145 ° C. for a predetermined time, and then supported. The film was peeled from the body to obtain a self-supporting film.
- the heat loss of the obtained self-supporting film was 39.1% by mass, and the imidization ratio of the self-supporting film was 10.4% on the A side and 16.7% on the B side.
- the coating liquid III-1 was applied to the A side of the self-supporting film using a die coater (coating amount: 6 g / m 2 ), and a drying oven at 40 ° C. I passed through.
- PI-C1 polyimide film
- PI-C1 polyimide metal laminate
- the laminated surface of the metal layer is a surface to which a coating liquid is applied.
- the peel strength was measured using the polyimide metal laminate obtained by the wet plating method or the dry plating method described in the section of the evaluation method.
- the results of each example are shown in Table C (Table C1 and Table C2).
- the name of the polyimide metal laminate obtained by laminating the coverlay is the same as the name of the polyimide film (PI-C1 etc.) and is expressed as polyimide metal laminate (PI-C1) etc.
- Table C shows the coating liquid, the coated surface (laminated surface of the metal layer), the average film thickness of the obtained polyimide film, other conditions and results.
- Example C2 A long polyimide film (PI-C2) was produced in the same manner as in Example C1, except that the coating liquid III-2 was applied to the A side of the self-supporting film using a die coater.
- Example C3 In the same manner as in Example C1, except that the coating liquid III-3 was applied to the A side of the self-supporting film using a die coater, the film was heated under the condition that the maximum heating temperature was 100 ° C. to 480 ° C. By imidization, a long polyimide film (PI-C3) was produced.
- PI-C3 polyimide film
- Example C4 In the same manner as in Example C1, except that the coating liquid III-4 was applied to the A side of the self-supporting film using a die coater, the film was heated under the conditions where the maximum heating temperature was 100 ° C. to 480 ° C. By imidization, a long polyimide film (PI-C4) was produced.
- PI-C4 polyimide film
- Example C5 The polyamic acid solution III-B is continuously cast from the slit of the T-die mold, extruded onto a smooth belt-like metal support in a drying furnace to form a thin film, heated at 145 ° C. for a predetermined time, and then supported. The film was peeled from the body to obtain a self-supporting film.
- the heat loss of the obtained self-supporting film was 39.6% by mass, and the imidization ratio of the self-supporting film was 9.9% on the A side and 17.2% on the B side.
- the coating liquid III-1 was applied to the B surface of the self-supporting film using a die coater (application amount: 6 g / m 2 ), and a drying oven at 40 ° C. I passed through.
- Example C6 A long polyimide film (PI-C6) was produced in the same manner as in Example C5 except that the coating liquid III-2 was applied to the B surface of the self-supporting film using a die coater.
- Example C7 A long polyimide film (PI-C7) was produced in the same manner as in Example C5 except that the coating liquid III-3 was applied to the B surface of the self-supporting film using a die coater.
- Example C8 A long polyimide film (PI-C8) was produced in the same manner as in Example C5 except that the coating liquid III-4 was applied to the B surface of the self-supporting film using a die coater.
- Example C1 Except that the coating solution was not applied to the self-supporting film, the film was heated and imidized in the same manner as in Example C6 under the condition that the maximum heating temperature was from 490 ° C to 490 ° C. A film (PI-C9) was produced.
- PI-C9 polyimide film
- a metal was laminated on the B surface by a wet plating method to obtain a polyimide metal laminate (PI-C9).
- the polyamic acid solution III-A was cast into a thin film on a glass plate, heated at 138 ° C. for 60 seconds using a hot plate, and then peeled off from the glass plate to obtain a self-supporting film.
- the self-supporting film is face-up A, the four sides are fixed with a pin tenter, and heated and imidized continuously from 150 ° C. to 490 ° C. in about 18 minutes using an oven to obtain a polyimide film (PI-C10). Obtained.
- PI-C10 polyimide metal laminate
- Table C1 The peel strength of the polyimide metal laminate (PI-C10) was measured, and the results are shown in Table C1.
- Example C9 to 16 Using the polyimide films PI-C1 to C8 obtained in Examples C1 to 8, a metal was laminated on the coated surface by the dry plating method described in the section of the evaluation method, and a polyimide metal laminate (PI-C11 to 18). ) The results are shown in Table C2.
- Comparative Example C2 Using the polyimide film PI-C9 obtained in Comparative Example C1, a metal was laminated on the A side or the B side by the dry plating method described in the section of the evaluation method to obtain a polyimide metal laminate. The results are shown in Table C2.
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Abstract
Description
前記ポリイミド層(a)が、テトラカルボン酸二無水物成分と、一般式(1)で示されるジアミン化合物を含むジアミン成分とから得られることを特徴とするポリイミドフィルム。
前記ポリイミド層(b)を得ることができるポリアミック酸溶液(b)を用いて、自己支持性フィルムを製造する工程と、
製造された自己支持性フィルムの片面または両面に、前記ポリイミド層(a)を得ることができるポリマー溶液(a)を塗工する工程と、
ポリマー溶液(a)が塗布された自己支持性フィルムを加熱する加熱処理工程と
を有することを特徴とするポリイミドフィルムの製造方法。
前記ポリイミド層(b)を得ることができるポリアミック酸溶液(b)と、前記ポリイミド層(a)を得ることができるポリマー溶液(a)とを支持体上に流延し多層液膜を形成する工程と、
前記多層液膜を加熱する加熱処理工程と
を有することを特徴とするポリイミドフィルムの製造方法。
本発明の第1の態様を説明する。第1の態様は、ポリイミド層(b)と、前記ポリイミド層(b)に接して積層されたポリイミド層(a)とを少なくとも有する。ここで、ポリイミド層(a)とは、ポリイミドフィルムを形成している複数の層のうちポリイミド層(a)の部分をいう。また、ポリイミド層(b)とは、ポリイミドフィルムを形成している複数の層のうちポリイミド層(b)の部分をいう。以下の実施形態においても同様である。
ポリイミド層(b)を得ることができるポリアミック酸溶液(b)(ポリアミック酸+溶媒)を支持体上に流延し、これを加熱乾燥して自己支持性フィルムを得る工程と、
得られた自己支持性フィルムの片面または両面に、ポリイミド層(a)を得ることができるポリマー溶液(a)を塗工する工程と、
ポリマー溶液(a)が塗布された自己支持性フィルムを加熱する加熱処理工程と
を有する製造方法により得られる。従って、本発明の第1の態様のポリイミドフィルムは、好ましくは上記製造方法によって得られるポリイミドフィルムである。ここで、ポリマー溶液とは、ポリアミック酸溶液、ポリイミド溶液、またはポリアミック酸溶液とポリイミド溶液の混合物などをいう。
(1)ポリイミド層(b)を得ることができるポリアミック酸溶液(ポリアミック酸溶液に必要に応じてイミド化触媒、脱水剤、離型助剤、無機微粒子などを選択して加えたポリアミック酸溶液組成物を含む)を支持体上に流延し、加熱乾燥して自己支持性フィルムを得る工程と、この自己支持性フィルムの片面または両面にポリアミック酸溶液(a)などのポリマー溶液(a)を塗布し、次いで、熱的に脱水環化、脱溶媒させてポリイミドフィルムを得る工程を有する方法(熱的にイミド化する熱イミド化法)、
(2)ポリイミド層(b)を得ることができる、イミド化触媒、環化触媒および脱水剤を加えたポリアミック酸溶液(さらに必要に応じて無機微粒子などを選択して加えたポリアミック酸溶液組成物を含む)を支持体上に流延し、化学的に脱水環化させて、必要に応じて加熱乾燥して自己支持性フィルムを得る工程と、この自己支持性フィルムの片面または両面にポリアミック酸溶液(a)などのポリマー溶液(a)を塗布し、次いで、これを加熱脱溶媒、イミド化することによりポリイミドフィルムを得る工程を有する方法(化学的にイミド化する化学イミド化法)、が挙げられる。
ポリイミド層(b)に用いられるテトラカルボン酸二無水物の具体例としては、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)およびピロメリット酸二無水物(PMDA)が挙げられ、その他に、2,3,3’,4’-ビフェニルテトラカルボン酸二無水物(a-BPDA)、オキシジフタル酸二無水物、ジフェニルスルホン-3,4,3’,4’-テトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)スルフィド二無水物、2,2-ビス(3,4-ジカルボキシフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン二無水物、2,3,3’,4’-ベンゾフェノンテトラカルボン酸二無水物、3,3’,4,4’-ベンゾフェノンテトラカルボン酸二無水物、ビス(3,4-ジカルボキシフェニル)メタン二無水物、2,2-ビス(3,4-ジカルボキシフェニル)プロパン二無水物、p-フェニレンビス(トリメリット酸モノエステル酸無水物)、p-ビフェニレンビス(トリメリット酸モノエステル酸無水物)、m-ターフェニル-3,4,3’,4’-テトラカルボン酸二無水物、p-ターフェニル-3,4,3’,4’-テトラカルボン酸二無水物、1,3-ビス(3,4-ジカルボキシフェノキシ)ベンゼン二無水物、1,4-ビス(3,4-ジカルボキシフェノキシ)ベンゼン二無水物、1,4-ビス(3,4-ジカルボキシフェノキシ)ビフェニル二無水物、2,2-ビス〔(3,4-ジカルボキシフェノキシ)フェニル〕プロパン二無水物、2,3,6,7-ナフタレンテトラカルボン酸二無水物、1,4,5,8-ナフタレンテトラカルボン酸二無水物、4,4’-(2,2-ヘキサフルオロイソプロピリデン)ジフタル酸二無水物などを挙げることができる。これらは単独でも、2種以上を混合して用いることもできる。用いるテトラカルボン酸二無水物は、所望の特性などに応じて適宜選択することができる。
1)パラフェニレンジアミン(1,4-ジアミノベンゼン;PPD)、1,3-ジアミノベンゼン、2,4-トルエンジアミン、2,5-トルエンジアミン、2,6-トルエンジアミンなどのベンゼン核1つのジアミン、
2)4,4’-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、3,4’-ジアミノジフェニルエーテルなどのジアミノジフェニルエーテル類、4,4’-ジアミノジフェニルメタン、3,3’-ジメチル-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’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、3,3’-ジメチル-4,4’-ジアミノジフェニルメタン、3,3’-ジカルボキシ-4,4’-ジアミノジフェニルメタン、3,3’,5,5’-テトラメチル-4,4’-ジアミノジフェニルメタン、ビス(4-アミノフェニル)スルフィド、4,4’-ジアミノベンズアニリド、3,3’-ジクロロベンジジン、3,3’-ジメチルベンジジン、2,2’-ジメチルベンジジン、3,3’-ジメトキシベンジジン、2,2’-ジメトキシベンジジン、3,3’-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、4,4’-ジアミノジフェニルエーテル、3,3’-ジアミノジフェニルスルフィド、3,4’-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スルフィド、3,3’-ジアミノジフェニルスルホン、3,4’-ジアミノジフェニルスルホン、4,4’-ジアミノジフェニルスルホン、3,3’-ジアミノベンゾフェノン、3,3’-ジアミノ-4,4’-ジクロロベンゾフェノン、3,3’-ジアミノ-4,4’-ジメトキシベンゾフェノン、3,3’-ジアミノジフェニルメタン、3,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルメタン、2,2-ビス(3-アミノフェニル)プロパン、2,2-ビス(4-アミノフェニル)プロパン、2,2-ビス(3-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス(4-アミノフェニル)-1,1,1,3,3,3-ヘキサフルオロプロパン、3,3’-ジアミノジフェニルスルホキシド、3,4’-ジアミノジフェニルスルホキシド、4,4’-ジアミノジフェニルスルホキシドなどのベンゼン核2つのジアミン、
3)1,3-ビス(3-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェニル)ベンゼン、1,4-ビス(3-アミノフェニル)ベンゼン、1,4-ビス(4-アミノフェニル)ベンゼン、1,3-ビス(4-アミノフェノキシ)ベンゼン、1,4-ビス(3-アミノフェノキシ)ベンゼン、1,4-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)-4-トリフルオロメチルベンゼン、3,3’-ジアミノ-4-(4-フェニル)フェノキシベンゾフェノン、3,3’-ジアミノ-4,4’-ジ(4-フェニルフェノキシ)ベンゾフェノン、1,3-ビス(3-アミノフェニルスルフィド)ベンゼン、1,3-ビス(4-アミノフェニルスルフィド)ベンゼン、1,4-ビス(4-アミノフェニルスルフィド)ベンゼン、1,3-ビス(3-アミノフェニルスルホン)ベンゼン、1,3-ビス(4-アミノフェニルスルホン)ベンゼン、1,4-ビス(4-アミノフェニルスルホン)ベンゼン、1,3-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(3-アミノフェニル)イソプロピル〕ベンゼン、1,4-ビス〔2-(4-アミノフェニル)イソプロピル〕ベンゼンなどのベンゼン核3つのジアミン、
4)3,3’-ビス(3-アミノフェノキシ)ビフェニル、3,3’-ビス(4-アミノフェノキシ)ビフェニル、4,4’-ビス(3-アミノフェノキシ)ビフェニル、4,4’-ビス(4-アミノフェノキシ)ビフェニル、ビス〔3-(3-アミノフェノキシ)フェニル〕エーテル、ビス〔3-(4-アミノフェノキシ)フェニル〕エーテル、ビス〔4-(3-アミノフェノキシ)フェニル〕エーテル、ビス〔4-(4-アミノフェノキシ)フェニル〕エーテル、ビス〔3-(3-アミノフェノキシ)フェニル〕ケトン、ビス〔3-(4-アミノフェノキシ)フェニル〕ケトン、ビス〔4-(3-アミノフェノキシ)フェニル〕ケトン、ビス〔4-(4-アミノフェノキシ)フェニル〕ケトン、ビス〔3-(3-アミノフェノキシ)フェニル〕スルフィド、ビス〔3-(4-アミノフェノキシ)フェニル〕スルフィド、ビス〔4-(3-アミノフェノキシ)フェニル〕スルフィド、ビス〔4-(4-アミノフェノキシ)フェニル〕スルフィド、ビス〔3-(3-アミノフェノキシ)フェニル〕スルホン、ビス〔3-(4-アミノフェノキシ)フェニル〕スルホン、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、ビス〔3-(3-アミノフェノキシ)フェニル〕メタン、ビス〔3-(4-アミノフェノキシ)フェニル〕メタン、ビス〔4-(3-アミノフェノキシ)フェニル〕メタン、ビス〔4-(4-アミノフェノキシ)フェニル〕メタン、2,2-ビス〔3-(3-アミノフェノキシ)フェニル〕プロパン、2,2-ビス〔3-(4-アミノフェノキシ)フェニル〕プロパン、2,2-ビス〔4-(3-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〕プロパン、2,2-ビス〔3-(3-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス〔3-(4-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス〔4-(3-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパン、2,2-ビス〔4-(4-アミノフェノキシ)フェニル〕-1,1,1,3,3,3-ヘキサフルオロプロパンなどのベンゼン核4つのジアミン、
などを挙げることができる。これらは単独でも、2種以上を混合して用いることもできる。用いるジアミンは、所望の特性などに応じて適宜選択することができる。
ポリイミド層(a)に用いられるテトラカルボン酸成分は、ポリイミド層(b)に用いられる上述のテトラカルボン酸成分が用いられ、好ましいものも同じである。
R1は水素原子または炭素数1~12(好ましくは炭素数1~10、さらに好ましくは炭素数1~6)のアルキル基またはアリール基を示し、
R2は炭素数1~12(好ましくは炭素数1~10、さらに好ましくは炭素数1~6)のアルキル基またはアリール基を示し、R1とR2は異なっていても良く、同じであっても良い。
ポリイミド層(b)を与えるためのポリアミック酸溶液(b)、およびポリイミド層(a)を与えるためのポリマー溶液としてのポリアミック酸溶液(a)またはポリイミド溶液(a)は、酸成分とジアミン成分とを、実質的に等モル或いはどちらかの成分を少し過剰にして、有機極性溶媒中で重合することにより得られる。
ポリアミック酸溶液(b)の自己支持性フィルムは、ポリアミック酸溶液(b)を支持体上に流延塗布し、自己支持性となる程度(通常のキュア工程前の段階を意味する)、例えば支持体上より剥離することができる程度にまで加熱して製造される。ポリアミック酸溶液(b)の固形分濃度は、製造に適した粘度範囲となる濃度であれば特に限定されないが、通常、好ましくは5~40質量%、さらに好ましくは6~35質量%、特に好ましくは10~30質量%である。
但し、
X1:自己支持性フィルムの1775cm-1のピーク高さ、
X2:自己支持性フィルムの1515cm-1のピーク高さ、
Y1:フルキュアフィルムの1775cm-1のピーク高さ、
Y2:フルキュアフィルムの1515cm-1のピーク高さ、とする。
次に、上述のようにして得られた自己支持性フィルムの片面または両面にポリマー溶液(a)(ポリアミック酸溶液(a)またはポリイミド溶液(a))を塗工する。
次いで、ポリマー溶液(a)の溶液を塗布した自己支持性フィルムを加熱処理してポリイミドフィルムを得る。接着性に優れるフィルムを得るためには、加熱処理工程における最高加熱温度が好ましくは350℃以上、好ましくは370℃以上、より好ましくは450℃以上、さらに好ましくは470℃以上、特に好ましくは490℃以上となるように加熱する。加熱温度の上限はポリイミドフィルムの特性が低下しない温度であれば良く、好ましくは600℃以下、より好ましくは590℃以下、さらに好ましくは550℃以下、さらに好ましくは540℃以下、さらに好ましくは530℃以下、最も好ましくは520℃以下である。
本態様のポリイミドフィルムは、金属層との密着性にも優れている。そのため、ポリイミドフィルムのポリマー溶液(a)の塗布側の面に、金属層を直接(即ち、接着剤層を介することなく、めっきにより)形成することができ、ポリイミドフィルムと金属層の初期の剥離強度に優れ、高温処理後でも剥離強度に優れ、剥離強度の低下が小さい、または、高温処理後の剥離強度が初期のそれよりも大きい剥離強度に優れたポリイミド金属積層体を得ることができる。
1. ポリイミド層(b)を得ることができるポリアミック酸溶液(b)の自己支持性フィルムの片面又は両面に、ポリイミド層(a)を得ることができるポリマー溶液(a)を塗工し、加熱して得られるポリイミドフィルムであり、
ポリイミド層(a)は、テトラカルボン酸二無水物成分と、式(1)で示すジアミン化合物を含むジアミン成分とから得られるポリイミドであるポリイミドフィルム。
2. 式(1)で示すジアミン化合物は、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジンである上記1.記載のポリイミドフィルム。
3. ポリイミド層(a)は、ジアミン成分中、式(1)で示すジアミン化合物を10~100モル%含む上記1又は2に記載のポリイミドフィルム。
4. ポリイミド層(a)は、ジアミン成分中、式(1)で示すジアミン化合物を25~100モル%含む上記1又は2に記載のポリイミドフィルム。
5. ポリイミドフィルムは、最高加熱温度が350℃以上である上記1~4のいずれか1項に記載のポリイミドフィルム。
6. ポリイミドフィルムは、最高加熱温度が450℃以上である上記1~4のいずれか1項に記載のポリイミドフィルム。
7. ポリイミド層(a)は、ジアミン成分としてさらにフェニレンジアミン及び/又はジアミノジフェニルエーテルを含む上記1~6のいずれか1項に記載のポリイミドフィルム。
8. ポリイミドフィルムは、ポリアミック酸溶液(a)を塗工して得られるポリイミド層(a)表面に直接接着層を積層する用途に用いる上記1~7のいずれか1項に記載のポリイミドフィルム。
9. ポリイミド層(b)は、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物及び/又はピロメリット酸二無水物を含むテトラカルボン酸二無水物成分と、フェニレンジアミン及び/又はジアミノジフェニルエーテルを含むジアミン成分とから得られるポリイミドである上記1~8のいずれか1項に記載のポリイミドフィルム。
10. ポリイミド層(a)を得ることができるポリマー溶液(a)は、ポリイミド層(a)を得ることができるポリアミック酸溶液(a)である上記1~9のいずれか1項に記載のポリイミドフィルム。
11. 上記1~10のいずれか1項に記載のポリイミドフィルムの塗工表面に、直接接着剤層を積層したことを特徴とするポリイミド積層体。
12. 上記1~10のいずれか1項に記載のポリイミドフィルムの塗工表面に、接着層を介して金属層を積層したことを特徴とするポリイミド金属積層体。
13. 上記1~10のいずれか1項に記載のポリイミドフィルムの前記ポリイミド層(a)の表面に、乾式または湿式めっきにより形成された金属層を有するポリイミド金属積層体。
本発明の第2の態様を説明する。第2の態様は、接着剤層と直接積層用に用いるポリイミドフィルムであり、ポリイミドは、テトラカルボン酸二無水物成分と、一般式(1)で示されるジアミン化合物を、0を超え100モル%、好ましくは5~100モル%、さらに好ましくは10~100モル%含むジアミン成分とを反応させて得られることを特徴とするポリイミドフィルムに関する。
(1)ポリアミック酸溶液、またはポリアミック酸溶液に必要に応じてイミド化触媒、脱水剤、離型助剤、無機微粒子などを選択して加えたポリアミック酸溶液組成物をフィルム状に支持体上に流延し、加熱乾燥して自己支持性フィルムを得た後、加熱により脱水環化、脱溶媒することによりポリイミドフィルムを得る方法;
(2)ポリアミック酸溶液に環化触媒および脱水剤を加え、さらに必要に応じて無機微粒子などを選択して加えたポリアミック酸溶液組成物をフィルム状に支持体上に流延し、化学的に脱水環化させて、必要に応じて加熱乾燥して自己支持性フィルムを得た後、これを加熱により脱溶媒、イミド化することによりポリイミドフィルムを得る方法;
(3)ポリイミドが有機溶媒に可溶の場合、離型助剤、無機微粒子などを選択して加えたポリイミド溶液組成物をフィルム状に支持体上に流延し、加熱乾燥などにより一部または全部の溶媒を除去した後、最高加熱温度に加熱することによりポリイミドフィルムを得る方法;
(4)ポリイミドが有機溶媒に可溶の場合、離型助剤、無機微粒子などを選択して加えたポリイミド溶液組成物をフィルム状に支持体上に流延し、加熱により溶媒を除去しながら最高加熱温度に加熱することによりポリイミドフィルムを得る方法、
が挙げられる。
第2の態様のポリイミドフィルムの製造に用いられるテトラカルボン酸成分およびジアミン成分について説明する。
ポリアミック酸(ポリイミド前駆体)は、前記各成分を使用し、テトラカルボン酸成分とジアミン成分とを公知の方法で反応させて得ることができ、例えば略等モル量を、有機溶媒中で反応させてポリアミック酸の溶液(均一な溶液状態が保たれていれば一部がイミド化されていてもよい)を得ることができる。また、予めどちらかの成分が過剰である2種類以上のポリアミック酸を合成しておき、各ポリアミック酸溶液を一緒にした後、反応条件下で混合してもよい。このようにして得られたポリアミック酸溶液はそのまま、あるいは必要であれば溶媒を除去または加えて、自己支持性フィルムの製造に使用することができる。
ポリアミック酸溶液の自己支持性フィルムは、ポリアミック酸溶液を支持体上に流延塗布し、自己支持性となる程度(通常のキュア工程前の段階を意味する)、例えば支持体上より剥離することができる程度にまで加熱して製造される。
次いで、自己支持性フィルムを加熱処理してポリイミドフィルムを得る。加熱処理工程において、最高加熱温度が、好ましくは350℃以上、より好ましくは450℃以上、さらに好ましくは470℃以上となるように加熱する。加熱温度の上限はポリイミドフィルムの特性が低下しない温度であれば良く、好ましくは600℃以下、より好ましくは550℃以下、さらに好ましくは530℃以下、特に好ましくは520℃以下である。
ポリイミドフィルムの表面は、接着剤との接着性に優れている。従って、第1の態様のポリイミドフィルム(パート1で説明)と同様に、第2の態様のポリイミドフィルムを使用して、接着剤層を積層したポリイミド積層体およびさらに他の基材を積層した積層体を製造することができる。
1. 接着剤層と直接積層用に用いるポリイミドフィルムであり、
このポリイミドフィルムを構成するポリイミドが、テトラカルボン酸二無水物成分と、一般式(1)で示されるジアミン化合物を、0を超え100モル%、好ましくは5~100モル%、さらに好ましくは10~100モル%含むジアミン成分とを反応させて得られることを特徴とするポリイミドフィルム。
2. 一般式(1)で示されるジアミン化合物が、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジンであることを特徴とする上記1に記載のポリイミドフィルム。
3. 最高加熱温度が350℃以上である加熱工程を経て製造されたことを特徴とする上記1または2に記載のポリイミドフィルム。
4. 最高加熱温度が450℃以上である加熱工程を経て製造されたことを特徴とする上記1または2に記載のポリイミドフィルム。
5. 前記ジアミン成分が、さらにフェニレンジアミンまたはジアミノジフェニルエーテルを含むことを特徴とする上記1~4のいずれかに記載のポリイミドフィルム。
6. 前記テトラカルボン酸二無水物成分が、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物および/またはピロメリット酸二無水物を含むことを特徴とする上記1~5のいずれかに記載のポリイミドフィルム。
7. 上記1~6のいずれかに記載のポリイミドフィルムと、このポリイミドフィルムに直接接して積層されている接着剤層とを有するポリイミド積層体。
8. 上記1~6のいずれかに記載のポリイミドフィルムと、このポリイミドフィルムに直接接して積層されている接着剤層と、この接着剤層を介して積層された他の基材を有する積層体。特に好ましくは他の基材として金属箔が積層されたポリイミド金属積層体。
本発明の第3の態様を説明する。第3の態様は、フィルム表面にめっきにより金属層を形成するために用いられるポリイミドフィルムに関する。第1の態様のポリイミドフィルムが、乾式または湿式めっきによる金属層の形成用に適していることは述べたとおりであるが、第3の態様によるポリイミドフィルムもこの用途に適している。
第3の態様においては、得られた自己支持性フィルムを、加熱処理工程において、最高加熱温度が、好ましくは450℃以上、より好ましくは470℃以上となるように加熱してポリイミドフィルムを得る。加熱温度の上限はポリイミドフィルムの特性が低下しない温度であれば良く、好ましくは600℃以下、より好ましくは550℃以下、さらに好ましくは530℃以下、特に好ましくは520℃以下である。
ればよい。
本態様のポリイミドフィルムは、金属層との密着性に優れており、表面に金属層を形成してポリイミド金属積層体を製造することができる。本態様のポリイミドフィルムを使用する場合、めっきを施す面は、A面、またはB面のどちらであっても良い。
1. ポリイミド表面にめっきにより金属層を形成するために用いるポリイミドフィルムであり、
このポリイミドを構成するポリイミドが、テトラカルボン酸二無水物成分と、一般式(1)で示されるジアミン化合物を10~100モル%含むジアミン成分とを反応させて得られ、加熱処理工程において、最高加熱温度が450℃以上となる条件で加熱処理して得られたことを特徴とするポリイミドフィルム。
2. 一般式(1)で示すジアミン化合物が、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジンであることを特徴とする上記1に記載のポリイミドフィルム。
3. 前記ポリイミドが、ジアミン成分としてさらにフェニレンジアミン又はジアミノジフェニルエーテルを含むことを特徴とする上記1または2に記載のポリイミドフィルム。
4. 前記テトラカルボン酸二無水物成分が、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物および/またはピロメリット酸二無水物を含むテトラカルボン酸二無水物成分であることを特徴とする上記1~3のいずれかに記載のポリイミドフィルム。
5. めっきは、乾式または湿式めっきであることを特徴とする上記1~4のいずれかに記載のポリイミドフィルム。
6. 上記1~5のいずれかに記載のポリイミドフィルムと、めっきにより形成された金属層とを有することを特徴とするポリイミド金属積層体。
ポリイミドフィルムの物性の評価は以下の方法に従って行った。
a)剥離強度は、90°ピールでの剥離強度であり、温度23℃、湿度50%の環境下で、50mm/分の剥離速度で測定した。
b)ポリイミドフィルムの表面は、ポリアミック酸溶液を支持体上にキャスティングしたときの空気側の面をA面とし、支持体側の面をB面とした。
c)表中のポリイミド積層体及びポリイミド金属積層体の剥離強度の欄において、ポリイミドと被着材との剥離モードを観察し、表中に以下の1)から4)の内容で表示した。剥離モードが良いか否かについては、「2)>1)>4)>3)」の順とした。
1)ポリイミド/接着剤の界面剥離(接着剤が白濁)と接着剤の凝集破壊の混合。
2)接着剤の凝集破壊。
3)ポリイミド/接着剤の界面剥離。
4)ポリイミド/接着剤の界面剥離で接着剤が白濁。
・ポリイミド積層体Aの作製:
ポリイミドフィルムの接着性を評価する面(実施例パートIにおいては、ポリアミック酸溶液の塗布面)に、株式会社有沢製作所製カバーレイCVA0525KAを180℃、3MPaで30分プレスして貼り合わせてポリイミド積層体Aを得た。
ポリイミド積層体Aの剥離強度を測定し、初期剥離強度Aとした。また、ポリイミド積層体Aを、150℃の熱風乾燥機中で24時間処理し、その後剥離強度を測定し、耐熱後剥離強度Aとした。
・ポリイミド金属積層体の作製:
ポリイミドフィルム表面に、湿式めっきプロセス(荏原ユージライト株式会社製エルフシードプロセス)により、無電解ニッケルめっき層、電解銅めっき層の順に形成し、さらに65℃で30分間熱処理して、銅厚み10μmのポリイミド金属積層体を得た。
ポリイミド金属積層体の剥離強度を測定し、初期剥離強度A1とした。
・ポリイミド金属積層体の作製:
ポリイミドフィルムの塗工面に、常法のスパッタ法によって1層目の厚み25nmのNi/Cr(質量比:8/2)層と、さらに1層の上に2層目の厚み400nmの銅層を形成し、銅層の上に厚み20μmの銅めっき層を形成して、ポリイミド金属積層体を得た。
乾式めっき法により作成したポリイミド金属積層体の剥離強度の測定は、前で述べた湿式めっき法により得られたポリイミド金属積層体の剥離強度の測定と同様の方法で剥離強度を測定した。
(ポリアミック酸溶液I-Aの調製)
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、ジアミン成分としてパラフェニレンジアミン(PPD)を加えた後、40℃で撹拌しながら、酸成分として3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)をPPDと略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液(ポリイミド前駆体溶液)を得た。そして、このポリアミック酸重合溶液に、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液I-Aを得た。ポリアミック酸溶液I-Aの30℃における回転粘度は180Pa・sであった。
ポリアミック酸溶液I-Aに、さらにアミド酸単位に対して0.05当量のイミド化触媒として1,2-ジメチルイミダゾールを添加し、ポリアミック酸溶液組成物I-Aを得た。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、ジアミン成分として2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液I-B(ポリイミド前駆体溶液)を得た。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、パラフェニレンジアミン(PPD)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。全ジアミン成分中、ATDAの量を70モル%とした。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液I-C(ポリイミド前駆体溶液)を得た。
全ジアミン成分中、ATDAの量を50モル%とした以外は、ポリアミック酸溶液I-Cの調製と同様にし、ポリアミック酸の重合溶液I-D(ポリイミド前駆体溶液)を得た。ポリアミック酸溶液I-DにDMAcを加え、固形分濃度を5質量%としたポリアミック酸の溶液(ポリイミド前駆体溶液)を塗工液I-3とした。
全ジアミン成分中、ATDAの量を30モル%とした以外は、ポリアミック酸溶液I-Cの調製と同様にし、ポリアミック酸の重合溶液I-E(ポリイミド前駆体溶液)を得た。ポリアミック酸溶液I-EにDMAcを加え、固形分濃度を5質量%としたポリアミック酸の溶液(ポリイミド前駆体溶液)を塗工液I-4とした。
全ジアミン成分中、ATDAの量を19モル%とした以外は、ポリアミック酸溶液I-Cの調製と同様にし、ポリアミック酸の重合溶液I-F(ポリイミド前駆体溶液)を得た。ポリアミック酸溶液I-FにDMAcを加え、固形分濃度を5質量%としたポリアミック酸の溶液(ポリイミド前駆体溶液)を塗工液I-5とした。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。その後、40℃で撹拌しながら、酸成分としてピロメリット酸二無水物(PMDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液I-G(ポリイミド前駆体溶液)を得た。ポリアミック酸溶液I-GにDMAcを加え、固形分濃度を5質量%としたポリアミック酸の溶液(ポリイミド前駆体溶液)を塗工液I-6とした。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、パラフェニレンジアミン(PPD)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。全ジアミン成分中、ATDAの量を80モル%、PPDの量を20モル%とした。その後、40℃で撹拌しながら、ピロメリット酸二無水物(PMDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液I-H(ポリイミド前駆体溶液)を得た。ポリアミック酸溶液I-HにDMAcを加え、固形分濃度を5質量%としたポリアミック酸の溶液(ポリイミド前駆体溶液)を塗工液I-7とした。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、ジアミン成分として4,4’-ジアミノジフェニルエーテル(DADE)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。全ジアミン成分中、ATDAの量を80モル%、DADEの量を20モル%とした。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)、ピロメリット酸二無水物(PMDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液I-I(ポリイミド前駆体溶液)を得た。全酸二無水物成分中、s-BPDAの量を80モル%、PMDAの量を20モル%とした。ポリアミック酸溶液I-IにDMAcを加え、固形分濃度を5質量%としたポリアミック酸の溶液(ポリイミド前駆体溶液)を塗工液I-8とした。
(i) ポリアミック酸溶液I-Bの自己支持性フィルムを得た後、150℃から約11分かけて370℃まで加熱処理する条件で、厚み35μmのポリイミドフィルムを作成し、TGAにより空気中、5%重量減少温度を測定した。
(測定結果) ポリアミック酸溶液I-Bより得られるポリイミド:455℃。
(測定結果) ポリアミック酸溶液I-Fより得られるポリイミド:562℃。
ポリアミック酸溶液組成物I-Aをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して、加熱減量が36.8質量%の自己支持性フィルムを得た。
実施例A1と同様にして得た自己支持性フィルムのB面を選択した以外は実施例A1と同様にしてポリイミドフィルム(PI-A2)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に塗工液I-1をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃で50秒、210℃で50秒、370℃で50秒、490℃で50秒と段階的に加熱イミド化して、ポリイミドフィルム(PI-A3)を得た。
塗工液の塗布面にB面を選択した以外は実施例A3と同様にして、ポリイミドフィルム(PI-A4)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-2をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A5)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A5と同様にして、ポリイミドフィルム(PI-A6)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-2をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A7)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A7と同様にして、ポリイミドフィルム(PI-A8)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-3をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A9)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A9と同様にして、ポリイミドフィルム(PI-A10)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-3をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A11)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A11と同様にして、ポリイミドフィルム(PI-A12)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-4をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A13)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A13と同様にして、ポリイミドフィルム(PI-A14)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-4をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A15)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A15と同様にして、ポリイミドフィルム(PI-A16)を得た。
ポリアミック酸溶液I-A(1,2-ジメチルイミダゾール添加なし)をガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面に塗工液I-4をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A17)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A17と同様にして、ポリイミドフィルム(PI-A18)を得た。
実施例A17と同様にして得た自己支持性フィルムのA面に、塗工液I-4をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A19)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A19と同様にして、ポリイミドフィルム(PI-A20)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-5をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A21)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A21と同様にして、ポリイミドフィルム(PI-A22)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-5をバーコーターNo.3で塗布し(塗布量:6g/m2)150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A23)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A23と同様にして、ポリイミドフィルム(PI-A24)を得た。
実施例A17と同様にして得た自己支持性フィルムのA面に、塗工液I-5をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A25)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A25と同様にして、ポリイミドフィルム(PI-A26)を得た。
実施例A17と同様にして得た自己支持性フィルムのA面に、塗工液I-5をバーコーターNo.3で塗布し(塗布量:6g/m2)、四辺をピンテンターで固定して、オーブンを用いて、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A27)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A27と同様にして、ポリイミドフィルム(PI-A28)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-6をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A29)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A29と同様にして、ポリイミドフィルム(PI-A30)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-6をバーコーターNo.3で塗布し(塗布量:6g/m2)、四辺をピンテンターで固定して、オーブンを用いて、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A31)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A31と同様にして、ポリイミドフィルム(PI-A32)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-7をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A33)を得た。
実施例A1と同様にして得た自己支持性フィルムのB面を、塗工液の塗布面に選択した以外は、実施例A33と同様にして、ポリイミドフィルム(PI-A34)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-7をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A35)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A35と同様にして、ポリイミドフィルム(PI-A36)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-8をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から370℃まで約11分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A37)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A37と同様にして、ポリイミドフィルム(PI-A38)を得た。
実施例A1と同様にして得た自己支持性フィルムのA面に、塗工液I-8をバーコーターNo.3で塗布し(塗布量:6g/m2)、150℃から490℃まで約18分かけて連続的に加熱イミド化して、ポリイミドフィルム(PI-A39)を得た。
塗工液の塗布面にB面を選択した以外は、実施例A39と同様にして、ポリイミドフィルム(PI-A40)を得た。
実施例A27と同様にして加熱減量が35.6質量%の自己支持性フィルムを得た。自己支持性フィルムにポリマー溶液を塗布することなく四辺をピンテンターで固定して、オーブンを用いて、150℃から490℃まで約18分かけて連続的に加熱イミド化してポリイミドフィルム(PI-A41)を得た。A面にカバーレイを積層して得られたポリイミド積層体A(PI-A41)から剥離強度を測定した。
実施例A27と同様にして加熱減量が35.6質量%の自己支持性フィルムを得た。自己支持性フィルムにポリマー溶液を塗布することなく四辺をピンテンターで固定して、オーブンを用いて、150℃から490℃まで約18分かけて連続的に加熱イミド化してポリイミドフィルム(PI-A42)を得た。B面にカバーレイを積層して得られたポリイミド積層体A(PI-A42)から剥離強度を測定した。
1)実施例A2~A4,A25~A28では全てポリイミド積層体Aの初期剥離強度が優れる。
2)実施例A1~A4は、実施例A25~A28と比べ、耐熱剥離強度が優れる。これは一般式(1)で示されるジアミンの含有量の影響と考える。
3)実施例A3とA4は、実施例A1とA2に比べ、耐熱剥離強度が優れる。これはフィルムの最高加熱温度の影響であると考える。
4)実施例A1~A4ではフィルムのA面とB面の耐熱後の剥離強度は、B面の方が少し高い傾向を示す。
5)ATDAを使用した場合は、使用していない場合に比べてポリイミド積層体Aの耐熱剥離強度が優れる。
6)初期の剥離強度に対する耐熱後の剥離強度の比(耐熱後の剥離強度/初期の剥離強度)がジアミン成分中のATDAの量が50-70モル%の場合には、約0.45~3.1と特に大きい。
7)490℃でキュアを行った場合には、それぞれ、同一の面に塗布を行い、370℃でキュアを行った場合と比べ、耐熱剥離強度が優れる傾向を示す。
8)実施例A29~A40(テトラカルボン酸成分がPMDA)では、耐熱後の剥離強度/初期の剥離強度が約1.9~5.1と極めて大きく、耐熱後に剥離強度が大きく増加する。また、剥離モードも接着剤の凝集破壊であり、数値以上の接着性を有していると考えられる。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液II-A(ポリイミド前駆体溶液)を得た。そして、このポリアミック酸の重合溶液II-Aに、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液II-Aを得た。ポリアミック酸溶液II-Aの30℃における回転粘度は170Pa・sであった。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、パラフェニレンジアミン(PPD)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。全ジアミン成分中、ATDAの量を30モル%とした。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)、を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液II-B(ポリイミド前駆体溶液)を得た。そして、このポリアミック酸の重合溶液II-Bに、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液II-Bを得た。ポリアミック酸溶液II-Bの30℃における回転粘度は150Pa・sであった。
全ジアミン成分中、ATDAの量を19モル%とした以外は、ポリアミック酸溶液II-Bの調製と同様にし、ポリアミック酸溶液II-Cを得た。ポリアミック酸溶液II-Cの30℃における回転粘度は170Pa・sであった。
全ジアミン成分中、ATDAの量を10モル%とした以外は、ポリアミック酸溶液II-Bの調製と同様にし、ポリアミック酸溶液II-Dを得た。ポリアミック酸溶液II-Dの30℃における回転粘度は110Pa・sであった。
全ジアミン成分中、ATDAの量を6.2モル%とした以外は、ポリアミック酸溶液II-Bの調製と同様にし、ポリアミック酸溶液II-Eを得た。ポリアミック酸溶液II-Eの30℃における回転粘度は150Pa・sであった。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。その後、40℃で撹拌しながら、ピロメリット酸二無水物(PMDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液II-F(ポリイミド前駆体溶液)を得た。そして、このポリアミック酸の重合溶液II-Fに、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液II-Fを得た。ポリアミック酸溶液II-Fの30℃における回転粘度は190Pa・sであった。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、パラフェニレンジアミン(PPD)2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。全ジアミン成分中、ATDAの量を80モル%とした。その後、40℃で撹拌しながら、ピロメリット酸二無水物(PMDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液II-G(ポリイミド前駆体溶液)を得た。そして、このポリアミック酸の重合溶液II-Gに、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液II-Gを得た。ポリアミック酸溶液II-Gの30℃における回転粘度は90Pa・sであった。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、4,4’-ジアミノジフェニルエーテル(DADE)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。全ジアミン成分中、ATDAの量を80モル%とした。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)、ピロメリット酸二無水物(PMDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液II-H(ポリイミド前駆体溶液)を得た。このとき、全酸二無水物成分中、s-BPDAの量を80モル%とした。そして、このポリアミック酸の重合溶液II-Hに、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液II-Hを得た。ポリアミック酸溶液II-Hの30℃における回転粘度は120Pa・sであった。
ポリアミック酸溶液II-Aをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して、加熱減量が33.6質量%の自己支持性フィルムを得た。
実施例B1と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B1と同様にして、ポリイミドフィルム(PI-B2)を得た。
実施例B1と同様にして得た自己支持性フィルムのA面を上とし、150℃から490℃まで約18分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B3)を得た。
実施例B1と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B3と同様にして、ポリイミドフィルム(PI-B4)を得た。
ポリアミック酸溶液II-Bをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面を上として、150℃から370℃まで約11分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B5)を得た。
実施例B5と同様にして得た自己支持性フィルムのA面を上とし、150℃から490℃まで約18分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B7)を得た。
実施例B5と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B7と同様にして、ポリイミドフィルム(PI-B8)を得た。
ポリアミック酸溶液II-Cをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で210秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面を上として、150℃から370℃まで約11分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B9)を得た。
実施例B9と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B9と同様にして、ポリイミドフィルム(PI-B10)を得た。
実施例B9と同様にして得た自己支持性フィルムのA面を上とし、150℃から490℃まで約18分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B11)を得た。
実施例B9と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B11と同様にして、ポリイミドフィルム(PI-B12)を得た。
ポリアミック酸溶液II-Cをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのB面を上とし、150℃から370℃まで約11分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B13)を得た。このポリイミドフィルム(PI-B13)のA面(表Bに示すとおり)にカバーレイを積層してポリイミド積層体A(PI-B13)を得た。
ポリイミドフィルム(PI-B14。PI-B13と同じフィルム)のB面にカバーレイを積層して、ポリイミド積層体A(PI-B14)を得た。
実施例B13と同様にして自己支持性フィルムを得た。この自己支持性フィルムのB面を上とし、150℃から490℃まで約18分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B15)を得た。このポリイミドフィルム(PI-B15)のA面(表Bに示すとおり)にカバーレイを積層して、ポリイミド積層体A(PI-B15)を得た。
ポリイミドフィルム(PI-B16。PI-B15と同じフィルム)のB面にカバーレイを積層して、ポリイミド積層体A(PI-B16)を得た。
ポリアミック酸溶液II-Dをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面を上とし、150℃から370℃まで約11分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B17)を得た。
実施例B17と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B17と同様にして、ポリイミドフィルム(PI-B18)を得た。
実施例B17と同様にして得た自己支持性フィルムのA面を上とし、150℃から490℃まで約18分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B19)を得た。
実施例B17と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B19と同様にして、ポリイミドフィルム(PI-B20)を得た。
ポリアミック酸溶液II-Fをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で160秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面を上とし、150℃から370℃まで約11分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B21)を得た。
実施例B21と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B21と同様にして、ポリイミドフィルム(PI-B22)を得た。
ポリアミック酸溶液II-Gをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で160秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面を上とし、150℃から370℃まで約11分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B25)を得た。
実施例B23と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B25と同様にして、ポリイミドフィルム(PI-B26)を得た。
ポリアミック酸溶液II-Hをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で210秒加熱した後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面を上とし、150℃から370℃まで約11分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B29)を得た。
実施例B27と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B29と同様にして、ポリイミドフィルム(PI-B30)を得た。
実施例B27と同様にして得た自己支持性フィルムのA面を上とし、150℃から490℃まで約18分で連続的に加熱イミド化して、ポリイミドフィルム(PI-B31)を得た。
実施例B27と同様にして得た自己支持性フィルムのB面を上とした以外は実施例B31と同様にして、ポリイミドフィルム(PI-B32)を得た。
ポリアミック酸溶液組成物II-Eをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して、加熱減量が35.6質量%の自己支持性フィルムを得た。
ポリイミドフィルム(PI-B34。PI-B33と同じもの)のB面にカバーレイを積層して、ポリイミド積層体A(PI-B34)を得た。
比較例B1と同様にして得た自己支持性フィルムのB面を上とし、150℃、210℃、370℃、490℃までそれぞれの温度で50秒ずつ段階的に加熱イミド化して、ポリイミドフィルム(PI-B35)を得た。ポリイミドフィルム(PI-B35)のA面(表B記載のとおり)にカバーレイを積層して、ポリイミド積層体A(PI-B35)を得た。
ポリイミドフィルム(PI-B36。PI-B35と同じもの)のB面にカバーレイを積層して、ポリイミド積層体A(PI-B36)を得た。
ポリアミック酸溶液II-Cをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱した後、ガラス板から剥離して自己支持性フィルムを得た。自己支持性フィルムの加熱減量は、36.1質量%であった。この自己支持性フィルムのA面を上とし、150℃から510℃まで約18分で連続的に加熱イミド化して、平均膜厚が12.5μmのポリイミドフィルム(PI-B37)を得た。
このポリイミドフィルム(PI-B37)のA面にカバーレイを積層してポリイミド積層体A(PI-B37)を得た。ポリイミド積層体A(PI-B37)の剥離強度は、初期Aが0.18kN/mであり、耐熱後Aが0.38kN/mであった。また、ポリイミド積層体A(PI-B37)の剥離強度モードは、初期Aが「3」であり、耐熱後Aが「3」であった。
ポリイミドフィルム(PI-B38。PI-B37と同じフィルム)のB面にカバーレイを積層して、ポリイミド積層体A(PI-B38)を得た。ポリイミド積層体A(PI-B38)の剥離強度は、初期Aが0.24kN/mであり、耐熱後Aが0.50kN/mであった。また、ポリイミド積層体A(PI-B38)の剥離強度モードは、初期Aが「3」であり、耐熱後Aが「4」であった。
ジアミン成分について、ATDAを使用せず、PPDを100モル%とした以外は、実施例B13と同様な方法でポリイミドフィルム(PI-B37)を得たその後、ポリイミドフィルム(PI-B37)のA面にカバーレイを積層して、ポリイミド積層体A(PI-B37)を得た。
最高加熱温度およびカバーレイの積層面を表Bに示すように変更した以外は、比較例B1と同様な方法でポリイミドフィルムとポリイミド積層体Aを得た。
1)実施例B13及びB14と、実施例B15及びB16とを比較すると、耐熱剥離強度が優れる。これはフィルムの最高加熱温度の影響と考える。
2)実施例B1~B36では、ポリイミド積層体Bの初期剥離強度が、同一温度でキュアし、同一面に接着剤を積層させた比較例のポリイミドフィルムのそれよりも優れる。これは一般式(1)で示されるジアミンの含有量の影響と考える。
3)実施例B1~B36では、全てポリイミド積層体Bの耐熱剥離強度が、同一温度でキュアし、同一面に接着剤を積層させた比較例のポリイミドフィルムのそれよりも優れる。これは一般式(1)で示されるジアミンの含有量の影響と考える。
4)実施例B1~B20では、耐熱後の剥離強度/初期の剥離強度が約0.26~3.1と大きい。これは一般式(1)で示されるジアミンの含有量の影響と考える。
5)PMDAを酸成分として加えた実施例B21~B32では、耐熱後の剥離強度/初期の剥離強度が約0.57~1.06と大きい。また、剥離モードが全て接着剤の凝集破壊であり、数値以上の接着性を有していると考えられる。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、パラフェニレンジアミン(PPD)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。全ジアミン成分中、ATDAの量を19モル%とした。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液(ポリイミド前駆体溶液)を得た。そして、このポリアミック酸重合溶液に、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液III-Aを得た。ポリアミック酸溶液III-Aの30℃における回転粘度は170Pa・sであった。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、パラフェニレンジアミン(PPD)を加えた。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液(ポリイミド前駆体溶液)を得た。そして、このポリアミック酸重合溶液に、ポリアミック酸100質量部に対して0.25質量部の割合でモノステアリルリン酸エステルトリエタノールアミン塩を添加し、均一に混合し、ポリアミック酸溶液III-Bを得た。ポリアミック酸溶液III-Bの30℃における回転粘度は104Pa・sであった。
重合槽に所定量のN,N-ジメチルアセトアミド(DMAc)、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジン(ATDA)を加えた。その後、40℃で撹拌しながら、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(s-BPDA)を全ジアミン成分と略等モルまで段階的に添加して反応させ、固形分濃度が18質量%であるポリアミック酸の重合溶液(ポリイミド前駆体溶液)を得た。ポリアミック酸溶液III-Cの30℃における回転粘度は107Pa・sであった。
ポリアミック酸溶液III-CにDMAcを固形分濃度が2.5wt%となるまで加えて希釈し、塗工液III-1とした。塗工液III-1の粘度は10.2mPa・sであった。
ポリアミック酸溶液III-Cとポリアミック酸溶液III-Bとを、モル比でポリアミック酸溶液III-Cの固形分/ポリアミック酸溶液III-Bの固形分=70/30となるように混合し、その後、全固形分濃度が2.5wt%となるまでDMAcを加えて希釈し、塗工液III-2とした。塗工液III-2の粘度は9.95mPa・sであった。
ポリアミック酸溶液III-Cとポリアミック酸溶液III-Bとを、モル比でポリアミック酸溶液III-Cの固形分/ポリアミック酸溶液III-Bの固形分=37/67となるように混合し、その後、全固形分濃度が2.5wt%となるまでDMAcを加えて希釈し、塗工液III-3とした。塗工液III-3の粘度は10.9mPa・sであった。
ポリアミック酸溶液III-Cとポリアミック酸溶液III-Bとを、モル比でポリアミック酸溶液III-Cの固形分/ポリアミック酸溶液III-Bの固形分=13/87となるように混合し、全固形分濃度が2.5wt%となるまでDMAcを加えて希釈し、塗工液III-4とした。塗工液III-4の粘度は11.0mPa・sであった。
ポリアミック酸溶液III-BをTダイ金型のスリットから連続的にキャスティングし、乾燥炉中の平滑なベルト状の金属支持体上に押出して薄膜を形成し、145℃で所定時間加熱後、支持体から剥離して自己支持性フィルムを得た。得られた自己支持性フィルムの加熱減量は39.1質量%で、自己支持性フィルムのイミド化率はA面側が10.4%、B面側が16.7%であった。
自己支持性フィルムのA面にダイコーターを用いて塗工液III-2を塗布した以外は実施例C1と同様にして、長尺状ポリイミドフィルム(PI-C2)を製造した。
自己支持性フィルムのA面にダイコーターを用いて塗工液III-3を塗布した以外は実施例C1と同様にして、100℃から最高加熱温度が480℃となる条件で当該フィルムを加熱、イミド化して、長尺状ポリイミドフィルム(PI-C3)を製造した。
自己支持性フィルムのA面にダイコーターを用いて塗工液III-4を塗布した以外は実施例C1と同様にして、100℃から最高加熱温度が480℃となる条件で当該フィルムを加熱、イミド化して、長尺状ポリイミドフィルム(PI-C4)を製造した。
ポリアミック酸溶液III-BをTダイ金型のスリットから連続的にキャスティングし、乾燥炉中の平滑なベルト状の金属支持体上に押出して薄膜を形成し、145℃で所定時間加熱後、支持体から剥離して自己支持性フィルムを得た。得られた自己支持性フィルムの加熱減量は39.6質量%で、自己支持性フィルムのイミド化率はA面側が9.9%、B面側が17.2%であった。
自己支持性フィルムのB面にダイコーターを用いて塗工液III-2を塗布した以外は実施例C5と同様にして、長尺状ポリイミドフィルム(PI-C6)を製造した。
自己支持性フィルムのB面にダイコーターを用いて塗工液III-3を塗布した以外は実施例C5と同様にして、長尺状ポリイミドフィルム(PI-C7)を製造した。
自己支持性フィルムのB面にダイコーターを用いて塗工液III-4を塗布した以外は実施例C5と同様にして、長尺状ポリイミドフィルム(PI-C8)を製造した。
自己支持性フィルムに塗工液の塗布を行わなかった以外は実施例C6と同様にして、100℃から最高加熱温度が490℃となる条件で当該フィルムを加熱、イミド化して、長尺状ポリイミドフィルム(PI-C9)を製造した。
ポリアミック酸溶液III-Aをガラス板上に薄膜状にキャストし、ホットプレートを用いて138℃で60秒加熱後、ガラス板から剥離して、自己支持性フィルムを得た。この自己支持性フィルムのA面を上とし、四辺をピンテンターで固定し、オーブンを用いて、150℃から490℃まで約18分で連続的に加熱イミド化して、ポリイミドフィルム(PI-C10)を得た。
実施例C1~8で得たポリイミドフィルムPI-C1~C8を用いて、評価方法の項で説明した乾式めっき法により、塗工面に金属を積層して、ポリイミド金属積層体(PI-C11~18)を得た。結果を表C2に示す。
比較例C1で得たポリイミドフィルムPI-C9を用いて、評価方法の項で説明した乾式めっき法により、A面、またはB面に金属を積層して、ポリイミド金属積層体を得た。結果を表C2に示す。
1)実施例C1~C16では、全てポリイミド金属積層体の剥離強度がA1~A5の全ての剥離試験において、比較例のどの値よりも優れる。これは一般式(1)で示されるジアミンの含有量の影響と考える。
Claims (19)
- 前記ポリイミド層(b)を得ることができるポリアミック酸溶液(b)の自己支持性フィルムの片面または両面に、前記ポリイミド層(a)を得ることができるポリマー溶液(a)を塗工し、加熱して得られることを特徴とする請求項1記載のポリイミドフィルム。
- 前記ポリイミド層(b)を得ることができるポリアミック酸溶液(b)の液膜と、前記ポリイミド層(a)を得ることができるポリマー溶液(a)の液膜とが積層された多層液膜を加熱して得られることを特徴とする請求項1記載のポリイミドフィルム。
- 前記ポリマー溶液(a)が、前記ポリイミド層(a)を得ることができるポリアミック酸溶液(a)であることを特徴とする請求項2または3に記載のポリイミドフィルム。
- 一般式(1)で示すジアミン化合物が、2,4-ビス(4-アミノアニリノ)-6-アニリノ-1,3,5-トリアジンであることを特徴とする請求項1~4のいずれか1項に記載のポリイミドフィルム。
- 前記ジアミン成分が、一般式(1)で示すジアミン化合物を10~100モル%の範囲で含むことを特徴とする請求項1~5のいずれか1項に記載のポリイミドフィルム。
- 前記ジアミン成分が、一般式(1)で示すジアミン化合物を25~100モル%の範囲で含むことを特徴とする請求項1~5のいずれか1項に記載のポリイミドフィルム。
- 前記ジアミン成分が、さらにフェニレンジアミンまたはジアミノジフェニルエーテルを含むことを特徴とする請求項1~7のいずれか1項に記載のポリイミドフィルム。
- 前記ポリイミド層(b)を構成するポリイミドが、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物および/またはピロメリット酸二無水物を含むテトラカルボン酸二無水物成分と、フェニレンジアミンおよび/またはジアミノジフェニルエーテルを含むジアミン成分とから得られることを特徴とする請求項1~8のいずれか1項に記載のポリイミドフィルム。
- 前記ポリイミド層(a)の表面に直接接着剤層が積層される用途における請求項1~9のいずれか1項に記載のポリイミドフィルムの使用。
- 前記ポリイミド層(a)の表面に乾式または湿式めっきにより金属層が形成される用途における請求項1~9のいずれか1項に記載のポリイミドフィルムの使用。
- 請求項1~9のいずれか1項に記載のポリイミドフィルムと、このポリイミドフィルムの前記ポリイミド層(a)の表面に積層されている接着剤層とを有することを特徴とするポリイミド積層体。
- 請求項12のポリイミド積層体の前記接着剤層に接して金属層が積層されていることを特徴とするポリイミド金属積層体。
- 請求項1~9のいずれか1項に記載のポリイミドフィルムと、このポリイミドフィルムの前記ポリイミド層(a)の表面に乾式または湿式めっきにより形成された金属層とを有することを特徴とするポリイミド金属積層体。
- 請求項1~9のいずれか1項に記載のポリイミドフィルムの製造方法であって、
前記ポリイミド層(b)を得ることができるポリアミック酸溶液(b)を用いて、自己支持性フィルムを製造する工程と、
製造された自己支持性フィルムの片面または両面に、前記ポリイミド層(a)を得ることができるポリマー溶液(a)を塗工する工程と、
ポリマー溶液(a)が塗布された自己支持性フィルムを加熱する加熱処理工程と
を有することを特徴とするポリイミドフィルムの製造方法。 - 請求項1~9のいずれか1項に記載のポリイミドフィルムの製造方法であって、
前記ポリイミド層(b)を得ることができるポリアミック酸溶液(b)と、前記ポリイミド層(a)を得ることができるポリマー溶液(a)とを支持体上に流延し多層液膜を形成する工程と、
前記多層液膜を加熱する加熱処理工程と
を有することを特徴とするポリイミドフィルムの製造方法。 - 前記加熱処理工程において、最高加熱温度が350℃以上となる条件で前記自己支持性フィルムが加熱されることを特徴とする請求項15または16記載の製造方法。
- 前記加熱処理工程において、最高加熱温度が450℃以上となる条件で前記自己支持性フィルムが加熱されることを特徴とする請求項15または16記載の製造方法。
- 前記加熱処理工程において、最高加熱温度が470℃以上となる条件で前記自己支持性フィルムが加熱されることを特徴とする請求項15または16記載の製造方法。
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US13/577,900 US20120308816A1 (en) | 2010-02-10 | 2011-02-10 | Polyimide film, polyimide laminate comprising same, and polyimide/metal laminate comprising same |
EP11742298.0A EP2535367A4 (en) | 2010-02-10 | 2011-02-10 | Polyimide film, polyimide laminate comprising same, and polyimide/metal laminate comprising same |
KR1020177030530A KR101886988B1 (ko) | 2010-02-10 | 2011-02-10 | 폴리이미드 필름, 이를 포함하는 폴리이미드 적층체, 및 이를 포함하는 폴리이미드/금속 적층체 |
KR1020177030529A KR101876698B1 (ko) | 2010-02-10 | 2011-02-10 | 폴리이미드 필름, 이를 포함하는 폴리이미드 적층체, 및 이를 포함하는 폴리이미드/금속 적층체 |
KR1020177030528A KR101884585B1 (ko) | 2010-02-10 | 2011-02-10 | 폴리이미드 필름, 이를 포함하는 폴리이미드 적층체, 및 이를 포함하는 폴리이미드/금속 적층체 |
JP2011553885A JP5533890B2 (ja) | 2010-02-10 | 2011-02-10 | ポリイミドフィルム、およびこれらのポリイミド積層体、ポリイミド金属積層体 |
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS488272B1 (ja) * | 1969-08-01 | 1973-03-13 | ||
US3803075A (en) | 1969-08-01 | 1974-04-09 | Ciba Geigy Corp | Soluble polyimides from 2,6-diamino-s-triazines and dianhydrides |
JPS523388B1 (ja) * | 1970-07-31 | 1977-01-27 | ||
JP2005154643A (ja) * | 2003-11-27 | 2005-06-16 | Tamura Kaken Co Ltd | 活性エネルギー線硬化型アルカリ可溶性イミド樹脂、活性エネルギー線硬化型アルカリ可溶性イミド樹脂組成物、ソルダーレジスト用組成物、プリント配線板および感光性ドライフィルム |
JP2006307112A (ja) * | 2005-05-02 | 2006-11-09 | Nippon Futsuso Kogyo Kk | 含フッ素ポリイミド樹脂、その製造方法、プライマーおよび樹脂被覆方法 |
JP2009087763A (ja) | 2007-09-28 | 2009-04-23 | Kaneka Corp | 高分子電解質及びこれを用いた燃料電池用電解質膜 |
JP2009154541A (ja) * | 2009-02-13 | 2009-07-16 | Ube Ind Ltd | 多層ポリイミドフィルムおよび積層体 |
JP2009263570A (ja) | 2008-04-28 | 2009-11-12 | Japan Aerospace Exploration Agency | 末端変性イミドオリゴマーおよびワニス並びにその高弾性率硬化物 |
JP2009280694A (ja) * | 2008-05-22 | 2009-12-03 | Ube Ind Ltd | 表面処理ポリイミドフィルムの製法 |
JP2010031102A (ja) | 2008-07-28 | 2010-02-12 | Iwate Univ | ポリイミドおよびその製造法 |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US36723A (en) * | 1862-10-21 | Improved fruit basket and crate | ||
US3666723A (en) * | 1969-08-01 | 1972-05-30 | Ciba Geigy Corp | Polyimides from 2,6-diamino-s-triazines and dianhydrides |
US3729448A (en) * | 1969-10-31 | 1973-04-24 | R Seltzer | Polyimides from 2,6-diamino-s-triazines and dianhydrides |
BE758261A (fr) * | 1969-10-31 | 1971-04-30 | Geigy Ag J R | Diamino-s-triazines |
US5538789A (en) * | 1990-02-09 | 1996-07-23 | Toranaga Technologies, Inc. | Composite substrates for preparation of printed circuits |
EP0474054B1 (en) * | 1990-08-27 | 1995-12-06 | E.I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
AU703967B2 (en) * | 1994-10-10 | 1999-04-01 | Ciba Specialty Chemicals Holding Inc. | Bisresorcinyltriazines |
US6355357B1 (en) * | 1998-12-21 | 2002-03-12 | Sony Chemicals Corp. | Flexible printed board, polyamic acid and polyamic acid varnish containing same |
JP3287348B2 (ja) * | 1999-12-17 | 2002-06-04 | ソニーケミカル株式会社 | ポリアミック酸ワニス組成物及びフレキシブルプリント基板 |
US6541122B2 (en) * | 2000-03-28 | 2003-04-01 | Ube Industries, Ltd. | Roll of metal film/aromatic polyimide film composite web |
KR100957480B1 (ko) * | 2001-06-04 | 2010-05-14 | 우베 고산 가부시키가이샤 | 금속 코팅된 방향족 폴리이미드 필름의 제조 방법 |
US20030012927A1 (en) * | 2001-06-04 | 2003-01-16 | Ube Industries, Ltd. | Process for preparing metal-coated aromatic polyimide film |
KR100543093B1 (ko) * | 2003-04-09 | 2006-01-20 | 제일모직주식회사 | 트리아진기를 포함한 디아민 화합물, 그로부터 제조된폴리아믹산 및 액정 배향막 |
US8043697B2 (en) * | 2005-04-19 | 2011-10-25 | Ube Industries, Ltd. | Polyimide film-laminated body |
JP2008188954A (ja) * | 2007-02-07 | 2008-08-21 | Kaneka Corp | 片面金属張積層板用基材及び片面金属張積層板の製造方法 |
JP2009148896A (ja) | 2007-11-30 | 2009-07-09 | Toyobo Co Ltd | 積層ポリイミドフィルム及びその製造方法 |
JP5002557B2 (ja) * | 2008-08-05 | 2012-08-15 | 株式会社環境総合テクノス | 型枠構造、型枠構造の構築方法、鉄筋コンクリート造壁体の構築方法 |
JP5564684B2 (ja) * | 2009-07-14 | 2014-07-30 | 国立大学法人岩手大学 | 芳香族ジアミン及びその製造方法並びに樹脂 |
KR101453462B1 (ko) * | 2013-05-16 | 2014-10-23 | 앱클론(주) | Her2에 특이적으로 결합하는 항체 |
-
2011
- 2011-02-10 CN CN201410311889.5A patent/CN104119533B/zh active Active
- 2011-02-10 CN CN201180017864.9A patent/CN102834432B/zh active Active
- 2011-02-10 CN CN201410311957.8A patent/CN104118167A/zh active Pending
- 2011-02-10 EP EP11742298.0A patent/EP2535367A4/en not_active Withdrawn
- 2011-02-10 US US13/577,900 patent/US20120308816A1/en not_active Abandoned
- 2011-02-10 CN CN201410312981.3A patent/CN104118168A/zh active Pending
- 2011-02-10 KR KR1020177030530A patent/KR101886988B1/ko active IP Right Grant
- 2011-02-10 KR KR1020177030528A patent/KR101884585B1/ko active IP Right Grant
- 2011-02-10 TW TW100104436A patent/TWI560212B/zh active
- 2011-02-10 TW TW104126187A patent/TWI560215B/zh active
- 2011-02-10 TW TW104126186A patent/TWI560214B/zh active
- 2011-02-10 KR KR1020177030529A patent/KR101876698B1/ko active IP Right Grant
- 2011-02-10 KR KR1020127023209A patent/KR101791716B1/ko active IP Right Grant
- 2011-02-10 WO PCT/JP2011/052856 patent/WO2011099555A1/ja active Application Filing
- 2011-02-10 TW TW104126185A patent/TWI560213B/zh active
- 2011-02-10 JP JP2011553885A patent/JP5533890B2/ja active Active
-
2014
- 2014-01-21 JP JP2014008448A patent/JP5598619B2/ja active Active
- 2014-01-21 JP JP2014008447A patent/JP5637325B2/ja active Active
- 2014-01-21 JP JP2014008446A patent/JP5886883B2/ja active Active
- 2014-10-15 JP JP2014210450A patent/JP5880658B2/ja active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS488272B1 (ja) * | 1969-08-01 | 1973-03-13 | ||
US3803075A (en) | 1969-08-01 | 1974-04-09 | Ciba Geigy Corp | Soluble polyimides from 2,6-diamino-s-triazines and dianhydrides |
JPS523388B1 (ja) * | 1970-07-31 | 1977-01-27 | ||
JP2005154643A (ja) * | 2003-11-27 | 2005-06-16 | Tamura Kaken Co Ltd | 活性エネルギー線硬化型アルカリ可溶性イミド樹脂、活性エネルギー線硬化型アルカリ可溶性イミド樹脂組成物、ソルダーレジスト用組成物、プリント配線板および感光性ドライフィルム |
JP2006307112A (ja) * | 2005-05-02 | 2006-11-09 | Nippon Futsuso Kogyo Kk | 含フッ素ポリイミド樹脂、その製造方法、プライマーおよび樹脂被覆方法 |
JP2009087763A (ja) | 2007-09-28 | 2009-04-23 | Kaneka Corp | 高分子電解質及びこれを用いた燃料電池用電解質膜 |
JP2009263570A (ja) | 2008-04-28 | 2009-11-12 | Japan Aerospace Exploration Agency | 末端変性イミドオリゴマーおよびワニス並びにその高弾性率硬化物 |
JP2009280694A (ja) * | 2008-05-22 | 2009-12-03 | Ube Ind Ltd | 表面処理ポリイミドフィルムの製法 |
JP2010031102A (ja) | 2008-07-28 | 2010-02-12 | Iwate Univ | ポリイミドおよびその製造法 |
JP2009154541A (ja) * | 2009-02-13 | 2009-07-16 | Ube Ind Ltd | 多層ポリイミドフィルムおよび積層体 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2535367A4 * |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011257731A (ja) * | 2010-05-10 | 2011-12-22 | Jnc Corp | ジアミン、液晶配向剤および液晶表示素子 |
KR101514221B1 (ko) * | 2011-12-07 | 2015-04-23 | 에스케이이노베이션 주식회사 | 다층 폴리이미드 구조의 연성금속적층판 제조방법 |
CN103144404A (zh) * | 2011-12-07 | 2013-06-12 | Sk新技术株式会社 | 多层聚酰亚胺柔性金属包覆层压板的制造方法 |
US20130149515A1 (en) * | 2011-12-07 | 2013-06-13 | Sk Innovation Co., Ltd. | Manufacturing method of multilayer polyimide flexible metal-clad laminate |
JP2018088555A (ja) * | 2012-04-27 | 2018-06-07 | キヤノン株式会社 | 電子部品、電子モジュールおよびこれらの製造方法 |
US9556312B2 (en) | 2012-05-14 | 2017-01-31 | National University Corporation Iwate University | Polyimide precursor, polyimide, polyimide film, polyimide metal laminate, and polyimide solution |
WO2013172331A1 (ja) * | 2012-05-14 | 2013-11-21 | 国立大学法人岩手大学 | ポリイミド前駆体、ポリイミド、ポリイミドフィルム、ポリイミド金属積層体およびポリイミド溶液 |
KR102049473B1 (ko) | 2012-05-14 | 2019-11-27 | 내셔널 유니버시티 코포레이션 이와테 유니버시티 | 폴리이미드 전구체, 폴리이미드, 폴리이미드 필름, 폴리이미드 금속 적층체 및 폴리이미드 용액 |
KR20150013297A (ko) | 2012-05-14 | 2015-02-04 | 내셔널 유니버시티 코포레이션 이와테 유니버시티 | 폴리이미드 전구체, 폴리이미드, 폴리이미드 필름, 폴리이미드 금속 적층체 및 폴리이미드 용액 |
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JP2014072198A (ja) * | 2012-09-27 | 2014-04-21 | Seiren Co Ltd | 金属パターンが形成されたポリイミド樹脂基材の製造方法 |
CN103872256A (zh) * | 2012-12-18 | 2014-06-18 | 财团法人工业技术研究院 | 有机发光二极管 |
KR20150112345A (ko) * | 2014-03-27 | 2015-10-07 | 에스케이씨코오롱피아이 주식회사 | 다층 폴리이미드 필름의 제조방법 |
KR101665060B1 (ko) * | 2014-03-27 | 2016-10-11 | 에스케이씨코오롱피아이 주식회사 | 다층 폴리이미드 필름의 제조방법 |
JP2014169463A (ja) * | 2014-06-27 | 2014-09-18 | Nissan Chem Ind Ltd | トリアジン環含有重合体 |
JP2018044135A (ja) * | 2016-09-16 | 2018-03-22 | 出光興産株式会社 | 自立フィルム、電子デバイス、発光デバイス及び光学デバイス |
JP2019156921A (ja) * | 2018-03-09 | 2019-09-19 | 国立大学法人岩手大学 | ポリイミド、ポリイミドフィルム、ポリイミド金属積層体及び、ポリアミド酸 |
JP7101352B2 (ja) | 2018-03-09 | 2022-07-15 | 国立大学法人岩手大学 | ポリイミド、ポリイミドフィルム、ポリイミド金属積層体及び、ポリアミド酸 |
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