CN109575283A - Polyimide film, metal-clad and circuit substrate - Google Patents

Polyimide film, metal-clad and circuit substrate Download PDF

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Publication number
CN109575283A
CN109575283A CN201811133042.7A CN201811133042A CN109575283A CN 109575283 A CN109575283 A CN 109575283A CN 201811133042 A CN201811133042 A CN 201811133042A CN 109575283 A CN109575283 A CN 109575283A
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layer
polyimide film
polyimide
thermal expansion
expansion coefficient
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CN201811133042.7A
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CN109575283B (en
Inventor
橘髙直树
菊池伊织
西山哲平
平石克文
安藤敏男
樱井慎郎
樱井慎一郎
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • 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
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H05K1/0277—Bendability or stretchability details
    • H05K1/028—Bending or folding regions of flexible printed circuits
    • 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
    • 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
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The present invention provides a kind of warpage and is inhibited and the metal-clad and circuit substrate for realizing high dimensionally stable precision there is no the anisotropic polyimide film of length direction and the thermal expansion coefficient in width direction and using the polyimide film.The polyimide film, the polyimide layer including single-layer or multi-layer, and meet: (a) thickness is in 3 μm or more and 50 μm or less of range；(b) thermal expansion coefficient is 10ppm/K or less；(c) it is stood in the mode that the convex surface of the central portion of the polyimide film of the 50mm square after 23 DEG C, 50% relative humidity of humidity 20 hours is contacted on flat face, and when the average value of the float-amount of quadrangle is set as average amount of warpage, average amount of warpage is 10mm or less；(d) difference of the thermal expansion coefficient (CTE-MD) in the direction length (MD) and the thermal expansion coefficient (CTE-TD) in the direction width (TD) is ± 3ppm/K or less.

Description

Polyimide film, metal-clad and circuit substrate
Technical field
The present invention relates to a kind of polyimide film, metal-clad and circuit substrates.
Background technique
Polyimide film heat resistance, chemical-resistant, electrical insulating property, in terms of have excellent characteristic, Therefore various fields are widely used in.Especially with excellent heat resistance, there is this characteristic of high rigidity, and be used as flexible printing cloth The base material film of line plate (Flexible Printed Circuits, FPC) etc..
In recent years, with miniaturization, lightweight, the development of space saving of electronic equipment, to thin and light amount, with flexible Even if still there is the FPC of excellent durability to need to increase for property, alternating bending.Still may be used even if FPC is interior in a limited space Realize three-dimensional and highdensity installation, therefore, purposes be just expanded to for example hard disk drive (Hard Disk Drive, HDD), the moving part of the electronic equipments such as digital versatile disc (Digital Versatile Disc, DVD), smart phone Wiring or the parts such as cable (cable), connector (connector).
FPC is to manufacture in the following manner: metal foil (usually copper foil) being laminated on polyimide film or passes through Sputtering is deposited to form metal layer, carries out wiring processing to thus resulting laminated body.
For example, in the process of photoetching (photolithography) process or installation FPC that are carried out to copper-clad laminated board In, engaged, cut off on the basis of the alignment mark (alignment mark) being set in copper-clad laminated board, exposed, The various processing such as etching.Machining accuracy in these processes becomes in terms of the reliability for maintaining the electronic equipment equipped with FPC It is important.However, copper-clad laminated board has the structure that the different layers of copper of thermal expansion coefficient and resin layer are laminated, therefore, by Stress is generated in interlayer in layers of copper and the difference of the thermal expansion coefficient of resin layer.Part or all of the stress is in etch copper Layer be released from the case where wiring processing, thus occurs flexible, and becomes and makes the changed master of the size of wiring pattern Want reason.Therefore, change in size finally occurs in the stage of FPC, become between causing wiring or wiring with the connection of terminal not Good reason, so that the reliability of circuit substrate or yield be made to reduce.Therefore, in the polyimide film as circuit base material And in copper-clad laminated board, dimensional stability is very important characteristic.
The polyimides that a kind of surface planar orientation degree at the table back side of polyimide film is controlled is proposed in patent document 1 Film.However, the dimensional accuracy of the polyimide film in patent document 1 and insufficient, there are the following problems: in metal-clad Or when high temperature process in the manufacture of circuit substrate, it is easy to happen the change in size caused by thermally expanding.
A kind of polyamides by using on main chain with diamino-diphenyl ethers and phenylenediamine is proposed in patent document 2 Imines and the polyimide film for reducing the film roll after high-temperature process bent (film curl), but dimensional accuracy and insufficient.
Present inventor obtains following opinion: postponing (retardation) in the face by controlling polyimide film And the polyimide film of excellent in dimensional stability is obtained, to carry out patent application (Japan Patent Patent 2016- in advance 089514)。
Existing technical literature
Patent document
1 Japanese Patent Laid-Open 2014-201632 bulletin of patent document
2 International Publication WO2016/11490 handbook of patent document
Summary of the invention
Problem to be solved by the invention
It is inhibited the purpose of the present invention is to provide a kind of warpage and the thermal expansion system in length direction and width direction The small polyimide film of several anisotropy and using the polyimide film realize high dimensionally stable precision cover gold Belong to plywood and circuit substrate.
Technical means to solve problem
Present inventor makes great efforts research, as a result, it has been found that, by control the thickness of polyimide film, thermal expansion coefficient and Birefringence in face (Δ n), can to solve the problem, so as to complete the present invention.
That is, polyimide film of the invention includes the polyimide layer of single-layer or multi-layer, and the spy of the polyimide film Sign is to meet following conditions (a)~condition (d):
(a) thickness is in 3 μm or more and 50 μm or less of range；
(b) thermal expansion coefficient is 10ppm/K or less；
(c) with the convex of the central portion of the polyimide film of the 50mm square after 23 DEG C, 50% relative humidity of humidity 20 hours Face contact is stood in the mode on flat face, and when the average value of the float-amount of quadrangle is set as average amount of warpage, is averagely stuck up Song amount is 10mm or less；
(d) thermal expansion coefficient (thermal expansion coefficient-longitudinal direction in the direction length (longitudinal (Machine Direction, MD)) (Coefficient of Thermal Expansion-Machine Direction, CTE-MD)) it is (lateral with width (Transverse Direction, TD)) direction thermal expansion coefficient (thermal expansion coefficient-transverse direction (Coefficient of Thermal Expansion-Transverse Direction, CTE-TD)) difference be ± 3ppm/K or less.
Polyimide film of the invention can also be in addition to the condition of (a)~(d), and then to meet:
(e) (Δ n) is 2 × 10 to birefringence in face-3Below.
Polyimide film of the invention can also be that the polyimide layer is multilayer, and minimum including thermal expansion coefficient 1st polyimide layer of single layer and be laminated in the 1st polyimide layer unilateral single-layer or multi-layer the 2nd polyimides Layer.It can also be that the thermal expansion coefficient (CTE1) of the 1st polyimide layer and the heat of the 2nd polyimide layer are swollen in the situation Swollen coefficient (CTE2) meets following numerical expressions (1):
1ppm/K < (CTE2-CTE1)≤10ppm/K (1)
Here, the CTE1 is the average value in the direction MD of the 1st polyimide layer and the thermal expansion coefficient in the direction TD, The CTE2 is the average value in the direction MD of the 2nd polyimide layer and the thermal expansion coefficient in the direction TD.
Polyimide film of the invention can also be that the 2nd polyimide layer is single layer.
Polyimide film of the invention can also be that the 1st polyimide layer includes residual comprising tetrabasic carboxylic acid residue and diamines The polyimides of base, and relative to all diamines residue contained by the polyimides, containing 20 moles of % or more by following Diamines residue derived from diamine compound represented by general formula (A1).
[changing 1]
In the general formula (A1), concatenating group X0Indicate that singly-bound, Y independently indicate the carbon that can replace through halogen atom or phenyl The monovalent hydrocarbon of number 1~3 or the alkoxy or alkenyl of carbon number 1~3, n1Indicating 0~2 integer, p and q independently indicate 0~ 4 integer.
Polyimide film of the invention can also be that at least one layer of the 2nd polyimide layer includes residual comprising tetrabasic carboxylic acid The polyimides of base and diamines residue.Can also be in the situation, relative to all diamines residue contained by the polyimides, The diamines residue by derived from the diamine compound represented by the general formula (A1) containing 20 moles of % or more.
Metal-clad of the invention includes: insulating layer；And the metal at least one face of the insulating layer Layer, and the insulating layer includes any one of described polyimide film.
Circuit substrate of the invention is to carry out circuit fabrication to the metal layer in the metal-clad to form.
The effect of invention
Polyimide film of the invention is that warpage is inhibited and uses the anisotropy of low heat expansion polyimides small Film, therefore using the polyimide film metal-clad and circuit substrate in, it can be achieved that high dimensionally stable precision. In addition, polyimide film of the invention and can reduce change in size when processing, therefore can also be suitable for since operability is excellent Ground is used to form metal-clad and circuit substrate using the polyimide film.
Specific embodiment
Next, embodiments of the present invention will be described.
[polyimide film]
The polyimide film of one embodiment of the present invention be include single-layer or multi-layer polyimide layer polyimides Film, and meet following conditions (a)~condition (d).
(a) thickness is in the range of 3 μm~50 μm.
In order to control thermal expansion coefficient, the thickness of the polyimide film of present embodiment in the range of 3 μm~50 μm, it is excellent In the range of selecting 3 μm~30 μm, it is 10 μm~28 μm more preferable in the range of, it is 15 μm~25 μm particularly preferred in the range of be advisable. If less than 3 μm, there is the decline due to electrical insulating property or the decline of operability in the thickness of the polyimide film of present embodiment And the processing of manufacturing process the case where becoming difficult, if having birefringence in face, (control of Δ n) becomes tired more than 50 μm Difficulty, and generate the increased tendency of thermal expansion coefficient.
(b) thermal expansion coefficient is 10ppm/K or less.
In order to reduce change in size, the thermal expansion coefficient of the polyimide film of present embodiment is with 10ppm/K model below It encloses, preferably 7ppm/K range below is advisable.If thermal expansion coefficient is more than 10ppm/K, manufacture with polyimides of the invention When film is the metal-clad or circuit substrate of substrate, change in size is not reduced, and the position for generating electronic component sometimes is inclined The problems such as shifting.
(c) with the convex of the central portion of the polyimide film of the 50mm square after 23 DEG C, 50% relative humidity of humidity 20 hours Face (here, so-called " convex surface " refers on the whole the face of curved peripheral side in gently curved polyimide film segment) connects When touching and stood in the mode on flat face, and the average value of the float-amount of quadrangle being set as average amount of warpage, average amount of warpage For 10mm or less.
It is used as the metal-clad and circuit substrate of substrate in order to promote manufacture for the polyimide film of present embodiment When operability and prevent processing when float caused by electronic component positional shift, the polyimide film of present embodiment Average amount of warpage be advisable with 10mm range below, preferably 5mm range below.
(d) thermal expansion coefficient (CTE-TD) of the thermal expansion coefficient (CTE-MD) in the direction length (MD) and the direction width (TD) Difference be ± 3ppm/K or less.
It is used as the metal-clad and circuit substrate of substrate in order to reduce manufacture for the polyimide film of present embodiment When with processing when change in size, the CTE-MD and CTE-TD of the polyimide film of present embodiment difference with ± 3ppm/K or less Range, preferably ± 1ppm/K range below is advisable.
In addition, the polyimide film of one embodiment of the present invention be preferably with the condition except (a)~(d) with Outside, and then meet following conditions (e) and be advisable.
(e) (Δ n) is 2 × 10 to birefringence in face-3Below.
(Δ n) is with 2 × 10 for birefringence in the face of the polyimide film of present embodiment-3Below, preferably 0.8 × 10-3With Under, more preferable 0.6 × 10-3It is advisable below.
In addition, the polyimide film of one embodiment of the present invention is preferably to include the polyamides of multilayer polyimide layer Imines film is advisable.
In the case where the polyimide film of one embodiment of the present invention includes multilayer polyimide layer, polyimide layer The 1st polyimide layer including the minimum single layer of thermal expansion coefficient and the unilateral single layer for being laminated in the 1st polyimide layer Or the 2nd polyimide layer of multilayer, and
The thermal expansion coefficient (CTE1) of 1st polyimide layer and the thermal expansion coefficient (CTE2) of the 2nd polyimide layer To be advisable in the range of following numerical expressions (1):
1ppm/K < (CTE2-CTE1)≤10ppm/K (1)
By changing thermal expansion coefficient on the thickness direction of polyimide film, and prevent the delay of thickness direction (ROL) reduction, and average amount of warpage can be reduced.The difference (CTE2-CTE1) of CTE1 and CTE2 preferably 2ppm/K or more and In the range of 10ppm/K or less, in the range of more preferable 2ppm/K or more and 7ppm/K or less.Here, CTE1 is the described 1st poly- The average value of the thermal expansion coefficient in the direction the MD and direction TD of imide layer, CTE2 are the direction MD of the 2nd polyimide layer And the average value of the thermal expansion coefficient in the direction TD.
The form > of < polyimide film
If form has no spy as described above, the polyimide film of present embodiment meets condition (a) to condition (d) It does not limit, can be the film (piece) comprising insulating resin, can also be to be laminated in copper foil, glass plate, polyimides mesentery, polyamide-based State on the substrates such as the resin sheets such as film, polyester mesentery.
< filler >
The polyimide film of present embodiment can also optionally contain inorganic filler.As inorganic filler, specifically, example It can such as enumerate: silica, aluminium oxide, magnesia, beryllium oxide, boron nitride, aluminium nitride, silicon nitride, aluminum fluoride, calcirm-fluoride. These can be used a kind of or are used in mixed way two or more.
< polyimides >
It includes the polyimide layer of polyimides that the polyimide film of present embodiment, which has resin component, and including single layer Or multilayer.It here, also may include that the 1st of the minimum single layer of thermal expansion coefficient is poly- in the case where polyimide layer includes multilayer Imide layer and unilateral the 2nd polyimide layer including single-layer or multi-layer for being laminated in the 1st polyimide layer.In addition, In this specification, in the case where not distinguishing " the 1st polyimide layer " and " the 2nd polyimide layer ", it is only denoted as " polyimides Layer ".
The polyimides for constituting polyimide layer is that tetracarboxylic dianhydride will be made to be subject to the resulting polyamic acid of diamine reactant Imidizate and winner.Therefore, in the polyimide film of present embodiment, constitute polyimide layer polyimides include by Tetrabasic carboxylic acid residue and the diamines residue as derived from diamines derived from tetracarboxylic dianhydride.In addition, in the present invention, so-called tetrabasic carboxylic acid Residue indicates that the tetravalence base as derived from tetracarboxylic dianhydride, so-called diamines residue indicate the divalent as derived from diamine compound Base.
Hereinafter, understanding the specific of polyimides used in present embodiment by being illustrated to acid anhydrides with diamines Example.
Tetrabasic carboxylic acid residue contained by polyimides is for example preferably enumerated: by 3,3', 4,4'- biphenyltetracarboxylic dianhydride (3,3', 4,4'-biphenyl tetracarboxylic dianhydride, BPDA), 2,2', 3,3'- biphenyltetracarboxyacid acids two Tetrabasic carboxylic acid residue derived from acid anhydride etc..Among described, especially the tetrabasic carboxylic acid residue as derived from BPDA (is also referred to as BPDA below Residue) order structure easy to form, and (the variable quantity of Δ n), therefore especially of birefringence in the face under hot environment can be reduced It is preferred that.Another in addition, though BPDA residue can assign the self-supporting of the gel mould of the polyamic acid as polyimide precursor Aspect has the tendency that increasing the CTE after imidizate.From the point of view of this viewpoint, BPDA residue is relative to contained by polyimides All tetrabasic carboxylic acid residues, in the range of preferably 20 moles of %~70 mole %, more preferable 20 moles of %~60 mole % It is advisable in range.
Tetrabasic carboxylic acid residue other than the BPDA residue contained by polyimides is preferably enumerated: by Pyromellitic Acid two Tetrabasic carboxylic acid residue derived from acid anhydride (pyromellitic dianhydride, PMDA) (also referred to as PMDA residue below).PMDA Residue relative to all tetrabasic carboxylic acids residue contained by polyimides, in the range of preferably 0 mole of %~60 mole %, more preferably It is advisable in the range of 0 mole of %~50 mole %.PMDA residue is any, but to play control thermal expansion coefficient and control glass Change the residue of the effect of transition temperature.
Other tetrabasic carboxylic acid residues can for example enumerate the tetrabasic carboxylic acid residue as derived from aromatic tetracarboxylic dianhydride below: 3, 3', 4,4'- diphenyl sulfone tetracarboxylic dianhydride, 4,4'- oxygen double phthalic anhydrides, 2,3', 3,4'- biphenyltetracarboxylic dianhydride, 2, 2', 3,3'- benzophenone tetracarboxylic dianhydride, 2,3,3', 4'- benzophenone tetracarboxylic dianhydride or 3,3', 4,4'- benzophenone four Carboxylic acid dianhydride, 2,3', 3,4'- diphenyl ether tetracarboxylic dianhydride, bis- (2,3- dicarboxyphenyi) ether dianhydrides, 3,3 ", 4,4 "-to three Biphenyltetracarboxylic dianhydride, 2,3,3 ", 4 "-para-terpheny tetracarboxylic dianhydrides or 2,2 ", 3,3 "-para-terpheny tetracarboxylic dianhydrides, 2, Bis- (2,3- the dicarboxyphenyi)-propane dianhydrides of 2- or bis- (3,4- the dicarboxyphenyi)-propane dianhydrides of 2,2-, bis- (2,3- dicarboxyls Phenyl) methane dianhydride or bis- (3,4- dicarboxyphenyi) methane dianhydrides, bis- (2,3- dicarboxyphenyi) sulfone dianhydrides or bis- (3,4- bis- Carboxyl phenyl) sulfone dianhydride, bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of 1,1- or bis- (3,4- dicarboxyphenyi) ethane two of 1,1- Acid anhydride, 1,2,7,8- phenanthrene-tetracarboxylic dianhydride, 1,2,6,7- phenanthrene-tetracarboxylic dianhydride or 1,2,9,10- phenanthrene-tetracarboxylic dianhydride, 2,3,6, Bis- (3,4- dicarboxyphenyi) the tetrafluoropropane dianhydrides of 7- anthracene tetracarboxylic dianhydride, 2,2-, 2,3,5,6- hexamethylene dianhydride, 1,2,5,6- Naphthalene tetracarboxylic acid dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride, dimethyl -1,2,3,5,6 4,8-, 7- hexahydro naphthalene -1,2,5,6- tetracarboxylic dianhydride, 2,6- dichloronaphtalene -1,4,5,8- tetracarboxylic dianhydride or dichloronaphtalene -1,4,5 2,7-, 8- tetracarboxylic dianhydride, 2,3,6,7- Tetrachloronaphthalene -1,4,5,8- tetracarboxylic dianhydride or 1,4,5,8- Tetrachloronaphthalene -2,3,6,7- tetrabasic carboxylic acid Dianhydride, 2,3,8,9-- tetracarboxylic dianhydride, 3,4,9,10-- tetracarboxylic dianhydride, 4,5,10,11-- tetracarboxylic dianhydride or 5, 6,11,12-- tetracarboxylic dianhydride, pentamethylene -1,2,3,4- tetracarboxylic dianhydride, pyrazine -2,3,5,6- tetracarboxylic dianhydride, pyrroles Alkane -2,3,4,5- tetracarboxylic dianhydride, thiophene -2,3,4,5- tetracarboxylic dianhydride, bis- (2,3- di carboxyl phenyloxy) diphenyl of 4,4'- Methane dianhydride etc..
In tetrabasic carboxylic acid residue contained by polyimides, by 2,3', 3,4'- diphenyl ether tetracarboxylic dianhydrides, 3,3', 4,4'- The tetrabasic carboxylic acid of diphenyl sulfone tetracarboxylic dianhydride, the double phthalic anhydrides of 4,4'- oxygen and 2,3', 3,4'- biphenyltetracaboxylic dianhydride Tetrabasic carboxylic acid residue derived from dianhydride relative to all tetrabasic carboxylic acids residue contained by polyimides, with preferably 20 moles of % or less, More preferable 15 moles of % or less are advisable.Relative to all tetrabasic carboxylic acids residue contained by polyimides, if these tetrabasic carboxylic acid residues are super 20 moles of % are crossed, then the orientation decline of molecule, (control of Δ n) becomes difficult birefringence in face.
In the polyimide film of present embodiment, diamines residue contained by polyimides is for example preferably enumerated by following Diamines residue derived from diamine compound represented by general formula (A1) (hereinafter sometimes referred to as " A1 residue ").
[changing 1]
In the formula (A1), concatenating group X0Indicate that singly-bound or-COO-, Y independently indicate to take through halogen atom or phenyl The perfluoroalkyl or alkenyl of the monovalent hydrocarbon of the carbon number 1~3 in generation or the alkoxy of carbon number 1~3 or carbon number 1~3, n1Indicate 0 ~2 integer, p and q independently indicate 0~4 integer.Here, so-called " independently " refers in the formula (A1), Duo Gequ Can be identical for base Y, integer p, integer q, it can also be different.
A1 residue order structure easy to form and the orientation for promoting direction in the face of strand, therefore can inhibit two-fold in face Penetrate rate (Δ n).From the point of view of this viewpoint, A1 residue rubs relative to all diamines residue contained by polyimides with preferably 20 It is advisable in the range of your % or more, more preferable 50 moles of % or more and then preferably 70 moles of %~99 mole %.
In addition, A1 residue for example preferably enumerates diamines residue represented by the following general formula (1).
[changing 2]
In the general formula (1), R1、R2Independently indicate the carbon number 1~3 that can replace through halogen atom or phenyl alkyl or The alkoxy of carbon number 1~3 or the alkenyl of carbon number 2~3.
The order structure easy to form of diamines residue represented by general formula (1) is particularly advantageous and inhibits under hot environment Birefringence (the variable quantity of Δ n) in face.From the point of view of this viewpoint, diamines residue represented by general formula (1) is relative to polyamides Asia All diamines residues contained by amine, with preferably 20 moles of % or more, more preferable 50 moles of % or more, and then preferably 60 moles of %~ It is advisable in the range of 90 moles of %.
The preferred concrete example of diamines residue represented by general formula (1) can be enumerated two as derived from diamine compound below Amine residue: 2,2'- dimethyl -4,4'- benzidines (2,2'-dimethyl-4,4'-diaminobiphenyl, m-TB), 2,2'- diethyl -4,4'- benzidines (2,2'-diethyl-4,4'-diaminobiphenyl, m-EB), 2,2'- diethyl Oxygroup -4,4'- benzidine (2,2'-diethoxy-4,4'-diaminobiphenyl, m-EOB), 2,2'- dipropoxy - 4,4'- benzidines (2,2'-dipropoxy-4,4'-diaminobiphenyl, m-POB), 2,2'- n-propyl -4,4'- Benzidine (2,2'-n-propyl-4,4'-diaminobiphenyl, m-NPB), 2,2'- divinyl -4,4'- diamino Base biphenyl (2,2'-divinyl-4,4'-diaminobiphenyl, VAB), 4,4'- benzidine, diamino -2 4,4'-, Bis- (trifluoromethyl) biphenyl of 2'- (4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, TFMB) etc..This In a little diamine compounds, especially 2,2'- dimethyl -4,4'- benzidine (m-TB) order structure easy to form can reduce Birefringence in face under hot environment (variable quantity of Δ n), therefore particularly preferably.
Diamines residue other than diamines residue represented by general formula (1) is preferably enumerated by p-phenylenediamine (p- Phenylenediamine, p-PDA), diamines residue derived from m-phenylene diamine (MPD) (m-phenylenediamine, m-PDA) etc., More preferably it is advisable with the diamines residue as derived from p-PDA (also referred to as PDA residue below).PDA residue is relative to polyamides All diamines residues contained by imines, in the range of preferably 0 mole of %~80 mole %, more preferable 0 mole of %~50 rub It is advisable in the range of your %.PDA residue is any, but to play control thermal expansion coefficient and controlling the work of glass transition temperature Residue.
In addition, about " diamine compound ", the hydrogen atom in two amino of end can be substituted, example in this specification It such as can be-NR3R4(here, R3、R4Independently indicate the arbitrary substituent groups such as alkyl).
In addition, in order to promote elongation and the bending resistance etc. in the case where polyimide film is made, preferably polyamides Imines includes selected from least one of group by composed by the diamines residue represented by the following general formula (2)~general formula (4) two Amine residue.
[changing 3]
In the formula (2), R5And R6Separately indicate can taking through halogen atom for halogen atom or carbon number 1~4 The alkyl or alkoxy or alkenyl in generation, X are independently indicated selected from-O- ,-S- ,-CH2-、-CH(CH3)-、-C(CH3)2-、- CO-、-COO-、-SO2, bilvalent radical in-NH- or-NHCO-, m and n independently indicate 0~4 integer.
[changing 4]
In the formula (3), R5、R6And R7Separately indicate halogen atom or carbon number 1~4 can be through halogen atom Substituted alkyl or alkoxy or alkenyl, X are independently indicated selected from-O- ,-S- ,-CH2-、-CH(CH3)-、-C(CH3)2-、- CO-、-COO-、-SO2, bilvalent radical in-NH- or-NHCO-, m, n and o independently indicate 0~4 integer.
[changing 5]
In the formula (4), R5、R6、R7And R8Separately indicate halogen atom or carbon number 1~4 can be through halogen The alkyl or alkoxy or alkenyl that atom replaces, X1And X2It separately indicates singly-bound, be selected from-O- ,-S- ,-CH2-、-CH (CH3)-、-C(CH3)2-、-CO-、-COO-、-SO2, bilvalent radical in-NH- or-NHCO-, but by X1And X2The two is singly-bound Except situation, m, n, o and p independently indicate 0~4 integer.
In addition, so-called " independently ", refers in the formula (2) to one of formula (4) or formula (2) is into formula (4), Multiple concatenating group X, concatenating group X1, concatenating group X2, multiple substituent Rs5, substituent R6, substituent R7, substituent R8And then integer M, Integer n, integer o, integer p can be identical, can also be different.
Diamines residue represented by general formula (2)~general formula (4), can be to polyimides due to the position with bendability Film assigns flexibility.Here, diamines residue represented by general formula (3) and general formula (4) is since phenyl ring is 3 or 4, in order to The terminal groups for being bonded to phenyl ring, are preferably set as to the position (para) by the increase for inhibiting thermal expansion coefficient (CTE).In addition, from From the viewpoint of assigning flexibility to polyimide film and inhibit the increase of thermal expansion coefficient (CTE), general formula (2)~general formula (4) the diamines residue represented by is relative to all diamines residue contained by polyimides, with preferably 10 moles of %~40 mole % In the range of, be advisable in the range of more preferable 10 moles of %~30 mole %.If diamines represented by general formula (2)~general formula (4) The reduction that the elongation in the case where film reduces, and generates bending resistance etc. is then made in less than 10 moles % of residue.Another party Face, if more than 40 moles %, the orientation of molecule is reduced, and low CTEization becomes difficult.
In general formula (2), preferably more than one of m and n are 0, in addition, base R5And base R6Preference can enumerate: carbon The alkoxy or alkenyl of the alkyl or carbon number 1~3 that can replace through halogen atom of number 1~4.In addition, in general formula (2), connection The preference of base X can be enumerated :-O- ,-S- ,-CH2-、-CH(CH3)-、-SO2Or-CO-.Diamines residue represented by general formula (2) Preferred concrete example can enumerate the diamines residue as derived from diamine compound below: 4,4'- diamino-diphenyl ether (4, 4'-diamino diphenyl ether, 4,4'-DAPE), 3,3'- diamino-diphenyl ether, 3,4'- diamino-diphenyl ether, 4,4'- diaminodiphenyl-methane, 3,3'- diaminodiphenyl-methane, 3,4'- diaminodiphenyl-methane, 4,4'- diamino Diphenyl propane, 3,3'- diamino-diphenyl propane, 3,4'- diamino-diphenyl propane, 4,4'- diamino diphenyl sulfide, 3,3'- diamino diphenyl sulfide, 3,4'- diamino diphenyl sulfide, 4,4'- diamino diphenyl sulfone, 3,3'- diamino two Phenylsulfone, 4,4'- diaminobenzophenone, 3,4'- diaminobenzophenone, 3,3'- diaminobenzophenone etc..
In general formula (3), preferably more than one of m, n and o are 0, in addition, base R5, base R6And base R7Preference can It enumerates: the alkoxy or alkenyl of the alkyl or carbon number 1~3 that can replace through halogen atom of carbon number 1~4.In addition, general formula (3) In, the preference of concatenating group X can be enumerated :-O- ,-S- ,-CH2-、-CH(CH3)-、-SO2Or-CO-.Two represented by general formula (3) The preferred concrete example of amine residue can enumerate the diamines residue as derived from diamine compound below: bis- (the 4- aminobenzene oxygen of 1,3- Base) benzene (1,3-bis (4-aminophenoxy) benzene, TPE-R), bis- (4- amino-benzene oxygen) benzene (Isosorbide-5-Nitrae-bis (4- of Isosorbide-5-Nitrae- Aminophenoxy) benzene, TPE-Q), bis- (4- amino-benzene oxygen) -2,5- di-t-butyl benzene (bis (4- Aminophenoxy) -2,5-di-tert-butyl benzene, DTBAB), bis- (4- amino-benzene oxygen) benzophenone of 4,4- (4,4-bis (4-aminophenoxy) benzophenone, BAPK), 1,3- bis- [2- (4- aminophenyl) -2- propyl] benzene, 1, Bis- [2- (4- aminophenyl) -2- propyl] benzene of 4- etc..
In general formula (4), preferably more than one of m, n, o and p are 0, in addition, base R5, base R6, base R7And base R8's Preference can be enumerated: the alkoxy or alkenyl of the alkyl or carbon number 1~3 that can replace through halogen atom of carbon number 1~4.In addition, In general formula (4), concatenating group X1And concatenating group X2Preference can enumerate: singly-bound ,-O- ,-S- ,-CH2-、-CH(CH3)-、-SO2- Or-CO-.Wherein, from the viewpoint of assigning crooked position, by concatenating group X1And concatenating group X2Except the case where the two is singly-bound. The preferred concrete example of diamines residue represented by general formula (4) can enumerate the diamines residue as derived from diamine compound below: 4,4'- bis- (4- amino-benzene oxygen) biphenyl (4,4'-bis (4-aminophenoxy) biphenyl, BAPB), the bis- [4- of 2,2'- (4- amino-benzene oxygen) phenyl] propane (BAPP), bis- [4- (4- amino-benzene oxygen) phenyl] ether (2,2'-bis [4- (4- of 2,2'- Aminophenoxy) phenyl] ether, BAPE), bis- [4- (4- amino-benzene oxygen) phenyl] sulfones etc..
Other diamines residues can for example enumerate the diamines residue as derived from aromatic diamine compound below: 2,2- Double-[4- (3- amino-benzene oxygen) phenyl] propane, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones, bis- [4- (3- amino-benzene oxygens)] Biphenyl, bis- [1- (3- amino-benzene oxygen)] biphenyl, bis- [4- (3- amino-benzene oxygen) phenyl] methane, bis- [4- (3- aminobenzene oxygen Base) phenyl] ether, bis- [4- (3- amino-benzene oxygen)] benzophenone, 9,9- bis- [4- (3- amino-benzene oxygen) phenyl] fluorenes, 2,2- Double-[4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2- be bis--[4- (3- amino-benzene oxygen) phenyl] hexafluoropropane, 3,3'- Dimethyl -4,4'- benzidine, two-ortho-aminotoluene of 4,4'- methylene, two -2,6- dimethylaniline of 4,4'- methylene, 4, 4'- methylene -2,6- diethylaniline, 3,3'- diamino-diphenyl ethane, 3,3'- benzidine, 3,3'- dimethoxy Benzidine, 3,3 "-diamino-para-terpheny, 4,4'- [1,4- phenylene is bis- (1- methyl ethylidene)] dianil, 4,4'- [1, 3- phenylene is bis- (1- methyl ethylidene)] dianil, bis(p-aminocyclohexyl)methane, bis- (to beta-amino-tert-butyl-phenyls) Ether, bis- (to Beta-methyl-δ-Aminopentyl) benzene, to bis- (2- methyl -4- Aminopentyl) benzene, to bis- (1,1- dimethyl -5- amino Amyl) benzene, 1,5- diaminonaphthalene, 2,6- diaminonaphthalene, bis- (beta-amino-tert-butyl) toluene of 2,4-, 2,4 di amino toluene, Dimethylbenzene -2,5- diamines, paraxylene -2,5- diamines, m-xylene diamine, p dimethylamine, 2,6- diamino-pyridine, 2,5- bis- Aminopyridine, 2,5- diaminostilbene, 3,4- oxadiazoles, piperazine etc..
In polyimides, by selecting the type of the tetrabasic carboxylic acid residue and diamines residue or using two or more four Respective molar ratio in the case where carboxylic acid residues or diamines residue can control thermal expansion coefficient, storage coefficient of elasticity, stretch bullet Property coefficient etc..In addition, can exist in the form of block with the structural unit of multiple polyimides, it can also nothing Rule ground exist, from inhibition face in birefringence (from the viewpoint of the deviation of Δ n), preferably randomly exist.
The manufacturing method > of < polyimide film
The form of the manufacturing method of the polyimide film of present embodiment is for instance that [1] is coated with polyamides in supporting base material The solution of amino acid and after being dried is subject to imidizate and the method that manufactures polyimide film；[2] it is coated in supporting base material The solution of polyamic acid and after being dried, the gel mould of polyamic acid is removed from supporting base material, is subject to imidizate and makes The method for making polyimide film.In addition, the polyimide film in present embodiment is that the polyamides comprising multilayer polyimide layer is sub- In the case where amine film, the form of manufacturing method can for example be enumerated: [3] repeat multiple polyamic acid in supporting base material After the coating and drying of solution, the method (casting method) of imidizate is carried out；[4] by multilayer extrusion simultaneously by polyamic acid It is coated with the state that multilayer formation is folded with after drying, carries out method (multilayer extrusion method) of imidizate etc..
[1] method for example may include process 1a~process 1c below:
(1a) is coated with the solution of polyamic acid in supporting base material, and is subject to dry process；
(1b) is heat-treated and imidizate polyamic acid in supporting base material, and the work of polyimide layer is consequently formed Sequence；And
(1c) separates supporting base material with polyimide layer, thus to obtain the process of polyimide film.
[2] method for example may include process 2a~process 2c below:
(2a) is coated with the solution of polyamic acid in supporting base material, and is subject to dry process；
(2b) is by the process of supporting base material and the gel UF membrane of polyamic acid；And
(2c) is heat-treated and imidizate the gel mould of polyamic acid, thus to obtain the process of polyimide film.
[3] method is to repeat multiple process 1a or process 2a in [1] method or [2] method, is being propped up The laminate structure that polyamic acid is formed on support group material can be implemented in the same manner as [1] method or [2] method in addition to this.
[4] method is to pass through multilayer extrusion in the process 1a of [1] method or the process 2a of [2] method It is coated with the laminate structure of polyamic acid simultaneously and is dried, it in addition to this, can be same as [1] method or [2] method Implement on ground.
The polyimide film manufactured in the present invention is preferably the imidizate that polyamic acid is completed in supporting base material.By In carrying out imidizate in the state that the resin layer of polyamic acid is fixed in supporting base material, therefore it can inhibit imidizate The telescopic variation of polyimide layer in the process, and maintain the thickness or dimensional accuracy of polyimide film.
In addition, (the Δ n): by the polyamic acid in supporting base material of birefringence in control plane can also be carried out by the following method The gel mould uniaxial extension or twin shaft of polyamic acid are extended, simultaneously or successively carry out imidizate by gel UF membrane.This When, in order to more closely highly control Δ n, preferably appropriate adjustment extend operation and heating rate when imidizate, The conditions such as the completion temperature of imidizate, weight bearing.
The synthesis > of < polyimides
In general, polyimides can be manufactured in the following manner: react tetracarboxylic dianhydride in a solvent with diamine compound, Heating closed loop is carried out after generating polyamic acid.For example, being dissolved in tetracarboxylic dianhydride and diamine compound with substantially equimolar In solvent, in the range of 0 DEG C~100 DEG C at a temperature of stir 30 minutes~24 hours and carry out polymerization reaction, thus obtain Obtain the polyamic acid of the precursor as polyimides.When reaction, with precursor generated become in organic solvent 5 weight %~ Mode in the range of 30 weight %, in the range of preferably 10 weight of weight %~20 % dissolves reacted constituent.Polymerization reaction Used in organic solvent can for example enumerate: n,N-Dimethylformamide (N, N-dimethyl formamide, DMF), N, N- dimethyl acetamide (N, N-dimethyl acetamide, DMAc), N, N- diethyl acetamide, N- methyl -2- pyrrolidines Ketone (N-methyl-2-pyrrolidone, NMP), 2- butanone, dimethyl sulfoxide (dimethyl sulfoxide, DMSO), six Methyl phosphamide, N- methyl caprolactam, dimethyl suflfate, cyclohexanone, dioxanes, tetrahydrofuran, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), cresols etc..It can also be used by these solvents and with two or more, into And can also and the aromatic hydrocarbon as dimethylbenzene, toluene.In addition, there is no particular restriction for the usage amount of this organic solvent, The concentration for being preferably adjusted to the polyamic acid solution obtained by polymerization reaction becomes 5 weight of weight %~30 % or so Such usage amount and use.
Synthesized polyamic acid is frequently advantageous that in the form of reaction dissolvent solution and uses, and can optionally carry out dense Contract, dilute or be replaced into other organic solvents.In addition, polyamic acid usual solvents solubility is excellent, therefore it is advantageously used. In the range of the viscosity of the solution of polyamic acid is preferably 500cps~100,000cps.If deviateing the range, painting is utilized It is bad that uneven thickness, striped etc. are easy to produce when cloth machine etc. carries out coat operations, in film.Polyamic acid is set to be subject to imidizate There is no particular restriction for method, such as is suitable for spending 1 under the conditions of using the temperature in the solvent in the range of 80 DEG C~400 DEG C Hour~carry out within 24 hours heating such heat treatment.
< metal-clad >
There is no particular restriction for the material of metal layer in the metal-clad of present embodiment, such as can enumerate: copper, no Become rusty steel, iron, nickel, beryllium, aluminium, zinc, indium, silver, gold, tin, zirconium, tantalum, titanium, lead, magnesium, manganese and their alloy etc..Wherein, especially excellent Select copper or copper alloy.
The thickness of metal layer is not particularly limited, such as in the case where using copper foil as metal layer, with preferably 35 μm Below, it is advisable in the range of more preferably 5 μm~25 μm.From the viewpoint of production stability and operability, preferably by copper The lower limit value of the thickness of foil is set as 5 μm.
It can also in order to improve the cementability of polyimide film and metal layer about the metal-clad of present embodiment The modifying process such as corona treatment are for example implemented to the surface of polyimide film.In addition, in polyimide film and metal layer For example thermoplastic polyimide layer can also be laminated for the layer of contact.The metal-clad of present embodiment can cover metal for single side Plywood can also be two-sided metal-clad.
About the metal-clad of present embodiment, for example, also be ready for comprising present embodiment polyimide film and The resin film of composition, and after forming seed layer (seed layer) to its splash-proofing sputtering metal, such as layers of copper is formed by copper facing.
In addition, the metal-clad of present embodiment can also be prepared in the following manner: preparing to include present embodiment Polyimide film and the resin film that constitutes, and using the methods of thermo-compression bonding to its laminated metal foil.
< circuit substrate >
The metal-clad of present embodiment mainly as the materials of the circuit substrates such as FPC and it is useful.That is, using common The metal layer of the copper-clad laminated board of present embodiment is processed into pattern-like and forms wiring layer by method, thus can be manufactured as this The circuit substrates such as the FPC of an embodiment of invention.
[embodiment]
Embodiment described below carries out more specific description to feature of the invention.But the scope of the present invention is not limited to Embodiment.In addition, as long as no special instructions, then various measurements, evaluation are to utilize following methods in embodiment below.
[measurement of thermal expansion coefficient (CTE)]
Using thermomechanical analyzer (trade name of Brooker (Bruker) company manufacture: 4000SA), to 3mm × 20mm's The polyimide film one side of size applies the weight bearing of 5.0g, so that it is warming up to 250 DEG C from 30 DEG C with certain heating rate on one side, And then keep at said temperatures after ten minutes, it is cooling with 5 DEG C/min of speed, it is swollen to find out 250 DEG C to 100 DEG C of evenly heat Swollen coefficient (thermal expansion coefficient).In addition, so-called CTE-MD, is the thermal expansion coefficient in the direction length (MD), so-called CTE-TD, for width Spend the thermal expansion coefficient in the direction (TD).
[measurement for postponing (RO) in face]
Use the birefringence meter (trade name of photonic crystal lattice (Photonic-Lattice) company manufacture: wide scope (wide Range) birefringent evaluation system WPA-100 measures region: MD:200mm × TD:150mm), find out side in the face of given sample To delay.In addition, incidence angle is 0 °, measurement wavelength is 543nm.
[preparation for postponing the sample for evaluation of (RO) in face]
The end of left and right two (left (Left) and right (Right)) in the direction TD in polyimide film and central portion (Center), sample L (left side), sample R (right side) and sample C are prepared with A4 size (TD:210mm × MD:297mm) cutting respectively (central portion).
[in face birefringence (evaluation of Δ n)]
For each of sample L, sample R and sample C, postpone (RO) in aspect of measure respectively.By the measured value of each sample Maximum value " in face birefringence (Δ n) " is set as divided by the resulting value of thickness of sample for evaluation.
[delay (ROL) of thickness direction and the measurement of birefringence (Δ nz)]
For polyimide film by cutting off the sample (thickness: 0.5 μm) prepared using the film of ultrathin sectioning, Using microscope-type birefringence meter, (trade name of photonic crystal lattice (Photonic-Lattice) company manufacture: microscope is installed It is with birefringent distribution view camera PI- miniature (micro)) measure the delay (ROL) of thickness direction.In addition, incidence angle is 0 °, measurement wavelength is 520nm.
In addition, the value of ROL is set as " birefringence (Δ divided by thickness (0.5 μm) resulting value of film cutting sample nz)”。
[measurement of warpage]
About the warpage of polyimide film, to the polyimide film of the size of 50mm × 50mm under 23 DEG C, humidity 50% After damping 20 hours, the mode being contacted on flat face with the convex surface of the central portion of sample is stood, measure the quadrangle of sample from Its average value is set as average amount of warpage by the distance that standing face is floated.
Contracted notation used in Examples and Comparative Examples indicates compound below.
M-TB:2,2'- dimethyl -4,4'- benzidine
DAPE:4,4'- diamino-diphenyl ether
PMDA: pyromellitic acid anhydride
BPDA:3,3', 4,4'- biphenyltetracarboxylic dianhydride
DMAc:N, N- dimethyl acetamide
(synthesis example 1)
Under nitrogen flowing, it is thrown in such a way that solid component concentration becomes 15 weight % into the detachable flask of 300ml The DAPE (0.0127 mole), the m-TB (0.0721 mole) of 15.333g and the DMAc of 212.5g for entering 2.550g, are stirred at room temperature It mixes and is dissolved.Then, after the PMDA (0.0620 mole) of BPDA (0.0207 mole) and 13.532g for adding 6.0847g, Continue stirring at room temperature 3 hours and carry out polymerization reaction, prepares polyamic acid solution a.
Then, it in the supporting base material of stainless steel, is equably coated in such a way that the thickness after solidifying becomes about 25 μm After polyamic acid solution a, the heat drying at 130 DEG C.In turn, DEG C interim heat treatment of progress from 130 DEG C to 360, is completed Imidizate prepares resin film 1 (CTE:7.6ppm/k).
(synthesis example 2)
Under nitrogen flowing, it is thrown in such a way that solid component concentration becomes 15 weight % into the detachable flask of 300ml The DAPE (0.0059 mole), the m-TB (0.0787 mole) of 16.740g and the DMAc of 212.5g for entering 1.188g, are stirred at room temperature It mixes and is dissolved.Then, after the PMDA (0.0618 mole) of BPDA (0.0206 mole) and 13.502g for adding 6.071g, Continue stirring at room temperature 3 hours and carry out polymerization reaction, prepares polyamic acid solution b.
Then, it in the supporting base material of stainless steel, is equably coated in such a way that the thickness after solidifying becomes about 25 μm After polyamic acid solution b, the heat drying at 130 DEG C.In turn, DEG C interim heat treatment of progress from 130 DEG C to 360, is completed Imidizate prepares resin film 2 (CTE:3.9ppm/k).
(synthesis example 3)
Under nitrogen flowing, it is thrown in such a way that solid component concentration becomes 15 weight % into the detachable flask of 300ml The DAPE (0.0043 mole), the m-TB (0.0817 mole) of 17.381g and the DMAc of 212.5g for entering 0.862g, are stirred at room temperature It mixes and is dissolved.Then, after the PMDA (0.0712 mole) of BPDA (0.0126 mole) and 15.554g for adding 3.703g, Continue stirring at room temperature 3 hours and carry out polymerization reaction, prepares polyamic acid solution c.
Then, it in the supporting base material of stainless steel, is equably coated in such a way that the thickness after solidifying becomes about 25 μm After polyamic acid solution c, the heat drying at 130 DEG C.In turn, DEG C interim heat treatment of progress from 130 DEG C to 360, is completed Imidizate prepares resin film 3 (CTE:1.3ppm/k).
(production example 1)
On 18 μm of thickness of copper foil, the polyamic acid solution prepared in synthesis example 1 is coated with equably with 180 μm of thickness After a, the heat drying at 130 DEG C and solvent is removed.Then, from 160 DEG C to 360 DEG C with about 15 DEG C/min of heating rate Be heat-treated and imidizate, prepare be formed on copper foil 25 μm of thickness polyimide layer supporting base material 1.
[embodiment 1]
On the face of the polyimide layer side of supporting base material 1, in such a way that the thickness after solidifying becomes about 25 μm equably After the polyamic acid solution b prepared in coating synthesis example 2, the heat drying at 130 DEG C.Then, DEG C progress from 130 DEG C to 360 Imidizate is completed in interim heat treatment, after being cooled to room temperature, is removed from supporting base material 1, is thus prepared polyimide film 1.
The evaluation result of polyimide film 1 is as follows.It, will be in addition, in the polyimide film before being removed from supporting base material The face of supporting base material contact is set as the face A, another surface is set as the face B.
CTE:3.9ppm/K
CTE-MD:3.8ppm/K
CTE-TD:4.0ppm/K
Postpone (RO): 18nm in face
Birefringence (Δ n): 0.72 × 10 in face-3
Average amount of warpage: 1.0mm
The delay (ROL) in place of 4 μm away from the face A in the depth direction: 70nm
The delay (ROL) in place of 20 μm away from the face B in the depth direction: 69nm
The birefringence (Δ nz) in place of 4 μm away from the face A in the depth direction: 140 × 10-3
The birefringence (Δ nz) in place of 20 μm away from the face B in the depth direction: 138 × 10-3
[embodiment 2]
On the face of the polyimide layer side of supporting base material 1, become uniform in a manner of about 12.5 μm by the thickness after solidifying After the polyamic acid solution c prepared in ground coating synthesis example 3, the heat drying at 130 DEG C.On it with the thickness after solidifying at It is that about 12.5 μm of mode is equably coated with the polyamic acid solution a prepared in synthesis example 1, and at 130 DEG C after heat drying, DEG C interim heat treatment of progress, completes imidizate from 130 DEG C to 360, after being cooled to room temperature, removes from supporting base material 1, by This prepares polyimide film 2.
The evaluation result of polyimide film 2 is as follows.
The CTE:1.5ppm/K (surface side A) and 8.2ppm/K (surface side B) of each layer
CTE-MD:6.6ppm/K
CTE-TD:6.1ppm/K
Postpone (RO): 11nm in face
Birefringence (Δ n): 0.44 × 10 in face-3
Average amount of warpage: 1.2mm
The CTE difference (CTE2-CTE1) of 1st polyimide layer (surface side A) and the 2nd polyimide layer (surface side B): 6.7ppm/K
[embodiment 3]
On the face of the polyimide layer side of supporting base material 1, in such a way that the thickness after solidifying becomes about 16 μm equably After the polyamic acid solution c prepared in coating synthesis example 3, the heat drying at 130 DEG C.Become on it with the thickness after solidifying About 9 μm of mode is equably coated with the polyamic acid solution b prepared in synthesis example 2, and at 130 DEG C after heat drying, from 130 DEG C interim heat treatment is carried out to 360 DEG C, complete imidizate, after being cooled to room temperature, remove from supporting base material 1, thus make Standby polyimide film 3.
The evaluation result of polyimide film 3 is as follows.
The CTE:2.5ppm/K (surface side A) and 5.1ppm/K (surface side B) of each layer
CTE-MD:4.0ppm/K
CTE-TD:4.3ppm/K
Postpone (RO): 3.0nm in face
Birefringence (Δ n): 0.12 × 10 in face-3
Average amount of warpage: 0.7mm
The CTE difference (CTE2-CTE1) of 1st polyimide layer (surface side A) and the 2nd polyimide layer (surface side B): 2.6ppm/K
It is installed respectively in the sputter cathode (cathode) of roll-to-roll (roll to roll) sputtering equipment for by substrate - 20 weight % evanohm target of nickel and copper target of metal layer film forming.To progress vacuum row in the device for being provided with polyimide film 3 After gas, argon gas is imported, and the pressure in device is remained into 1.3Pa, prepare the polyimide film 1 of subsidiary copper film layer.Substrate The film thickness of metal layer (- 20 weight % evanohm of nickel) is 20nm, and the film thickness of copper film layer is 200nm.
Using the polyimide film 1 of subsidiary copper film layer, conductor electricity is formed by half addition (semi-additive) method Road floor, prepares circuit substrate.
[embodiment 4]
Using branch manifold (multi-manifold) formula of the wide 200mm of lip it is three-layer co-extruded go out three layers of die head (die), with from leaning on The polyamic acid that the side of nearly supporting base material 1, which is risen, becomes the polyamic acid solution c prepared in synthesis example 3, prepares in synthesis example 2 is molten The mode of the double-layer structure of the sequence of liquid b is squeezed out and is cast on the face for the polyimide resin layer side for being coated on supporting base material 1.So Afterwards, 130 DEG C to 360 DEG C at a temperature of carry out interim heat treatment, imidizate is completed, after being cooled to room temperature, from support Substrate 1 is removed, and polyimide film 4 is thus prepared.
The evaluation result of polyimide film 4 is as follows.
The CTE:2.3ppm/K (surface side A) and 5.3ppm/K (surface side B) of each layer
CTE-MD:4.2ppm/K
CTE-TD:4.5ppm/K
Postpone (RO): 5nm in face
Birefringence (Δ n): 0.20 × 10 in face-3
Average amount of warpage: 1.3mm
The CTE difference of 1st polyimide layer (surface side A, thickness: 16 μm) and the 2nd polyimide layer (surface side B, thickness: 9 μm) (CTE2-CTE1): 3.0ppm/K
(reference example 1)
On the face through demoulding processing of supporting base material 2 (stainless steel, thickness: 16 μm), become with the thickness after solidifying After about 35 μm of mode is equably coated with the polyamic acid solution b prepared in synthesis example 2, the heat drying at 130 DEG C.Then, DEG C interim heat treatment of progress, completes imidizate from 130 DEG C to 380, after being cooled to room temperature, removes from supporting base material 2, by This prepares polyimide film 5.
The evaluation result of polyimide film 5 is as follows.
CTE-MD:3.9ppm/K
CTE-TD:3.8ppm/K
Postpone (RO): 18nm in face
Birefringence (Δ n): 0.51 × 10 in face-3
Average amount of warpage: 11.3mm
(reference example 2)
In supporting base material 2, equably it is coated with obtained in synthesis example 1 in such a way that the thickness after solidifying becomes about 16 μm Polyamic acid solution a after, the heat drying at 130 DEG C.On it in such a way that the thickness after solidifying becomes about 9 μm equably It is coated with polyamic acid solution b obtained in synthesis example 2, and at 130 DEG C after heat drying, DEG C progress rank from 130 DEG C to 360 The heat treatment of section property, completes imidizate, after being cooled to room temperature, removes from supporting base material 2, thus prepares polyimide film 6.
The evaluation result of polyimide film 6 is as follows.
CTE-MD:13.5ppm/K
CTE-TD:14.6ppm/K
Postpone (RO): 19.4nm in face
Birefringence (Δ n): 0.78 × 10 in face-3
Average amount of warpage: 13.0mm
[embodiment 5]
In supporting base material 2, equably it is coated in such a way that the thickness after solidifying becomes about 18 μm and is prepared in synthesis example 2 Polyamic acid solution b and heat drying.Synthesis example 3 is equably coated in such a way that the thickness after solidifying becomes about 20 μm on it The polyamic acid solution c of middle preparation after heat drying, is heat-treated, and imidizate is completed, after being cooled to room temperature, from support Substrate 2 is removed, and polyimide film 7 is thus prepared.
The evaluation result of polyimide film 7 is as follows.
The CTE:2.6ppm/K (surface side A) and 7.8ppm/K (surface side B) of each layer
CTE-MD:5.3ppm/K
CTE-TD:5.5ppm/K
Birefringence (Δ n): 1.4 × 10 in face-3
Average amount of warpage: 8.0mm
The CTE difference of 1st polyimide layer (surface side A, thickness: 18 μm) and the 2nd polyimide layer (surface side B, thickness: 20 μm) (CTE2-CTE1): 5.2ppm/K
It confirms 1~embodiment of embodiment 5 and 1~reference example of reference example 2 is that polyamic acid solution is coated on branch support group Dry and imidizate polyimide film is completed on material and in supporting base material, and in any polyimide film, CTE is each Good to the same sex, birefringence is also low in face, therefore, excellent in dimensional stability.
If being compared to the embodiment 1 and reference example 1 that polyimide layer is single layer, accurately controlled in embodiment 1 The thickness of polyimide film processed and the birefringence (Δ nz) of thickness direction, thus average amount of warpage can be suppressed to 10mm with Under.It is single layer and polyimide film with a thickness of in 35 μm of reference examples 1 below in polyimide layer, result is average warpage Amount is more than 10mm, and in embodiment 5, by the way that polyimide layer is set as two layers, average amount of warpage can be suppressed to 10mm with Under.
In addition, if being compared to the 2~embodiment of embodiment 5 and reference example 2 that polyimide layer is multilayer, embodiment In 2~embodiment 4, the layer being directly laminated in supporting base material is set as to the 1st polyimide layer of low heat expansion, its heat is swollen Swollen coefficient (CTE) is designed the CTE less than the 2nd polyimide layer in the range of meeting numerical expression (1), thus can inhibit towards the face A The warpage of side, and the average amount of warpage of polyimide film is suppressed to 10mm or less.On the other hand, in reference example 2, by two stratas CTE big polyimide layer is configured at the surface side A in imide layer, and therefore, result is that average amount of warpage is more than 10mm.It is to this Only, in the case where forming multilayer polyimide layer in supporting base material, the birefringence (Δ of thickness direction is not accounted for Nz the control of the CTE of each interlayer), therefore, the Δ nz for being directly laminated in the surface side A of the polyimide layer in supporting base material become It is low, there is the increased tendency of CTE compared with the surface side B, as reference example 2, is easy to happen the warpage towards the surface side A.In contrast, really Recognize, as shown in 2~embodiment of embodiment 5, it is contemplated that the birefringence (Δ nz) of thickness direction will be directly laminated in Layer in supporting base material is set as the 1st polyimide layer, its CTE is designed to be less than other polyimide layers for being laminated, and (the 2nd is poly- Imide layer) CTE, thus can manufacture the multilayer polyimide film that warpage is inhibited.
More than, embodiments of the present invention are described in detail with the purpose of illustration, but the present invention is not by described Embodiment restricts.

Claims (8)

1. a kind of polyimide film, the polyimide layer including single-layer or multi-layer, the polyimide film are characterized in that meeting Following condition a~condition d:
Condition a: thickness is in 3 μm or more and 50 μm or less of range；
Condition b: thermal expansion coefficient is 10ppm/K or less；
Condition c: with the convex surface of the central portion of the polyimide film of the 50mm square after 23 DEG C, 50% relative humidity of humidity 20 hours The mode being contacted on flat face is stood, and when the average value of the float-amount of quadrangle is set as average amount of warpage, average warpage Amount is 10mm or less；
Condition d: the difference of the thermal expansion coefficient of the thermal expansion coefficient and width direction of length direction is ± 3ppm/K or less.
2. polyimide film according to claim 1, wherein in addition to the condition a~condition d, and then meet:
Condition e: birefringence is 2 × 10 in face-3Below.
3. polyimide film according to claim 1, wherein the polyimide layer is multilayer, and is including thermal expansion The 2nd for counting the 1st polyimide layer of minimum single layer and being laminated in the unilateral single-layer or multi-layer of the 1st polyimide layer is poly- Imide layer,
The thermal expansion coefficient CTE1 of the 1st polyimide layer and thermal expansion coefficient CTE2 of the 2nd polyimide layer meets following Numerical expression (1):
1ppm/K < (CTE2-CTE1)≤10ppm/K (1)
Wherein, CTE1 is the average value of the longitudinal direction of the 1st polyimide layer and the thermal expansion coefficient of transverse direction, CTE2 For the average value of the thermal expansion coefficient of the longitudinal direction and transverse direction of the 2nd polyimide layer.
4. polyimide film according to claim 3, wherein the 2nd polyimide layer is single layer.
5. polyimide film according to claim 3 or 4, wherein the 1st polyimide layer includes residual comprising tetrabasic carboxylic acid The polyimides of base and diamines residue, and relative to all diamines residue contained by the polyimides, containing 20 moles of % with On the diamines residue by derived from the diamine compound represented by the following general formula (A1),
In formula (A1), concatenating group X0Indicate that singly-bound, Y independently indicate the one of the carbon number 1~3 that can replace through halogen atom or phenyl The alkoxy or alkenyl of valency alkyl or carbon number 1~3, n1Indicate that 0~2 integer, p and q independently indicate 0~4 integer.
6. polyimide film according to claim 3 or 4, wherein at least one layer of the 2nd polyimide layer includes packet The polyimides of residue containing tetrabasic carboxylic acid and diamines residue, and relative to all diamines residue contained by the polyimides, contain The diamines residue by derived from the diamine compound represented by the general formula (A1) of 20 moles of % or more.
7. a kind of metal-clad, comprising: insulating layer；And the metal layer at least one face of the insulating layer, In, the insulating layer includes polyimide film according to any one of claim 1 to 6.
8. a kind of circuit substrate is to carry out circuit to the metal layer in metal-clad according to claim 7 to add Work forms.
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