WO2011078259A1 - Flexible circuit board and structure of bend section of flexible circuit board - Google Patents
Flexible circuit board and structure of bend section of flexible circuit board Download PDFInfo
- Publication number
- WO2011078259A1 WO2011078259A1 PCT/JP2010/073198 JP2010073198W WO2011078259A1 WO 2011078259 A1 WO2011078259 A1 WO 2011078259A1 JP 2010073198 W JP2010073198 W JP 2010073198W WO 2011078259 A1 WO2011078259 A1 WO 2011078259A1
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- WO
- WIPO (PCT)
- Prior art keywords
- circuit board
- flexible circuit
- metal foil
- wiring
- foil
- Prior art date
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Images
Classifications
-
- 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
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- 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
- H05K1/0393—Flexible materials
-
- 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
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
Definitions
- the present invention relates to a flexible circuit board that is used with a bent portion in any one of them, and a bent portion structure of the flexible circuit board. More specifically, the invention has durability against bending and is flexible. The present invention relates to an excellent flexible circuit board and a bent portion structure of the flexible circuit board.
- a flexible circuit board (flexible printed circuit board) having a resin layer and a wiring made of metal foil can be used by being bent, a movable part in a hard disk, a hinge part of a mobile phone, Widely used in various electronic and electrical devices such as sliding slides, printer heads, optical pickups, and notebook PCs.
- the flexible circuit board can be folded and stored in a limited space or used in various movements of electronic devices. Corresponding flexibility is required. Therefore, it is necessary to improve the mechanical characteristics such as the strength of the flexible circuit board so that it can cope with the bending with a smaller radius of curvature at the bent portion and the operation in which the bending is frequently repeated. It has become.
- the flexible circuit board (see Patent Document 1) wired so as to be inclined with respect to the rotation axis, or in the rotation direction of the hinge portion.
- a method has been proposed in which a spiral portion formed by spiraling one or more turns is formed and the change in the diameter of the spiral portion due to the opening / closing operation is reduced to reduce damage by increasing the number of turns (see Patent Document 2). .
- any of these methods restricts the design of the flexible circuit board.
- the strength (I) of the (200) plane determined by X-ray diffraction (X-ray diffraction in the thickness direction of the copper foil) of the rolled copper foil was determined by X-ray diffraction of fine powder copper (200 ) It has been reported that when I / I 0 > 20 with respect to the surface strength (I 0 ), the film has excellent flexibility (see Patent Documents 3 and 4). That is, the flexibility of the copper foil improves as the cube orientation, which is the recrystallized texture of copper, develops. Therefore, a flexible circuit board in which the degree of development of the cube texture is defined by the parameter (I / I 0 ) A copper foil suitable as a wiring material is known.
- a rolled copper alloy foil containing elements such as Fe, Ni, Al, Ag, etc. in a concentration in the range of solid solution in copper, and obtained by annealing and recrystallization under predetermined conditions is shear along the sliding surface. It has been reported that the deformation is facilitated and the flexibility is excellent (see Patent Document 5).
- a copper foil containing impurities such as oxygen and silver may be used for a flexible circuit board that requires a high bending property, and its purity is about 99% to 99.9% by mass. Copper foil. In the present invention, purity is expressed as mass concentration unless otherwise specified. Further, at the test level, there are examples in which tough pitch copper having a purity of about 99.5% and oxygen-free copper containing no oxide, which are widely used as cable conductors, are used (see Patent Documents 3 and 4). Impurities of tough pitch copper include several hundred ppm of oxygen (mostly included as copper oxide), silver, iron, sulfur, phosphorus, and the like.
- Oxygen-free copper is usually copper having a purity of about 99.96 to 99.995%, and has been greatly reduced in oxygen to 10 ppm or less.
- Patent Documents 3 and 4 described above it is reported that the bending fatigue characteristics of a copper foil made of oxygen-free copper is superior to that of a tough pitch copper foil and depends on the presence or absence of copper oxide.
- impurities such as silver, phosphorus, and sulfur.
- the present inventors have no restrictions on the design of the flexible circuit board, and the flexible circuit board has durability against repeated bending and bending with a small radius of curvature.
- the present inventors found that a substrate was obtained and completed the present invention.
- an object of the present invention is to provide a flexible circuit board having excellent durability, and in particular, repeated bending with a small radius of curvature, such as a hinge part or a slide sliding part of a mobile phone or a small electronic device. It is to provide a flexible circuit board that exhibits durability even under severe use conditions such as, and has excellent flexibility.
- Another object of the present invention is to provide durability and resistance to harsh conditions such as hinge portions or slide sliding portions of mobile phones, small electronic devices, etc., particularly in repeated bending portions having a small curvature radius.
- An object of the present invention is to provide an excellent flexible circuit board bent portion structure.
- a flexible circuit board including a resin layer and a wiring formed from a metal foil, and having a bent portion at least at one place of the wiring,
- the metal foil is made of a metal having a face-centered cubic structure, and the basic crystal axis ⁇ 100> of the unit cell of the face-centered cubic structure is 2 in the thickness direction of the metal foil and a certain direction existing in the foil surface.
- the preferential orientation regions having an azimuth difference of 10 ° or less occupy 50% or more in area ratio, and the normal direction with respect to the cross section P of the wiring cut from the ridge line in the bent portion in the thickness direction of the metal foil
- a flexible circuit board, wherein the breaking elongation of the metal foil is 3.5% or more and 20% or less.
- the metal foil is a copper foil having a purity of 99.999% by mass or more.
- a bent portion structure of a flexible circuit board that includes a resin layer and a wiring formed from a metal foil, and is used with a bent portion in at least one portion of the wiring,
- the metal foil is made of a metal having a face-centered cubic structure, and the basic crystal axis ⁇ 100> of the unit cell of the face-centered cubic structure is 2 in the thickness direction of the metal foil and a certain direction existing in the foil surface.
- the preferential orientation region having an azimuth difference of 10 ° or less occupies 50% or more in area ratio Bending part structure of flexible circuit board, wherein elongation at break of metal foil is 3.5% or more and 20% or less.
- the metal foil constituting the wiring at the bent portion when the flexible circuit board is bent hardly causes metal fatigue and has excellent durability against stress and strain. Therefore, it is possible to provide a flexible circuit board having excellent flexibility with sufficient strength to withstand repeated bending and bending with a small radius of curvature without any restrictions on the design of the flexible circuit board. This makes it possible to realize highly durable electronic devices such as thin mobile phones, thin displays, hard disks, printers, and DVD devices.
- FIG. 1 is a diagram illustrating a relationship between a crystal zone axis in a cubic crystal structure and a plane obtained by rotating around the crystal zone axis.
- FIG. 2 is a stereo triangle of (100) standard projection.
- FIG. 3 is an explanatory cross-sectional view showing a state in which the flexible circuit board is bent.
- FIG. 4 is an explanatory plan view showing the relationship between the wiring in the flexible circuit board and the crystal axis of the metal foil, (a) and (b) show the flexible circuit board according to the present invention, and (c) ) And (d) show a prior art flexible circuit board.
- FIG. 5 is a perspective explanatory view of a single-sided copper-clad laminate.
- FIG. 5 is a perspective explanatory view of a single-sided copper-clad laminate.
- FIG. 6 is an explanatory plan view showing a state in which a test flexible circuit board is obtained from a single-sided copper-clad laminate in the embodiment of the present invention.
- FIG. 7 is an explanatory diagram of an MIT flex test apparatus.
- FIG. 8A is an explanatory view of an IPC bending test apparatus, and
- FIG. 8B is an X-X ′ sectional view of a test flexible circuit board used in the IPC bending test.
- the wiring provided in the flexible circuit board of the present invention is formed of a metal foil made of a metal having a face-centered cubic crystal structure.
- a metal having a face-centered cubic crystal structure for example, copper, aluminum, nickel, silver, rhodium, palladium, platinum, gold and the like are known. Copper, aluminum, and nickel are preferable because of their utility as copper, and copper foils that are mainly used as wiring for flexible circuit boards are the most common.
- the present invention provides a flexible circuit board excellent in bending durability and flexibility, and in particular, provides a flexible circuit board having excellent fatigue characteristics in a high strain region where the radius of curvature is 2 mm or less.
- one of i) the metal foil is highly oriented and ii) the elongation at break in the principal stress direction of the metal foil is large at the bent portion.
- it does not become a flexible circuit board that is resistant to fatigue failure during high bending as in the present invention. That is, by satisfying both i) and ii) at the same time, a flexible circuit board that is resistant to fatigue failure during high bending can be obtained.
- the basic crystal axis ⁇ 100> of the unit cell of the face-centered cubic structure is respectively in relation to two orthogonal axes of the thickness direction of the metal foil and a certain direction existing in the foil surface.
- the preferred orientation region within an orientation difference of 10 ° or more occupies 50% or more in area ratio
- the elongation at break of the metal foil in the normal direction relative to the cross section P of the wiring cut in the thickness direction of the metal foil from the ridgeline at the bent portion Needs to be 3.5% or more and 20% or less.
- the metal foil is a polycrystalline body as found in general electrolytic foils and rolled foils, a high breaking elongation can be obtained, but a flexible circuit having high fatigue characteristics against the high strain fatigue required in the present invention. It is not a substrate.
- a flexible circuit board having the characteristics required by the present invention cannot be obtained.
- the breaking elongation of the metal foil in the flexible circuit board which requires particularly high bending characteristics, is an important factor. This is the first time revealed.
- the metal foil may be a rolled foil or an electrolytic foil, but is preferably a rolled foil in order to obtain high orientation.
- a metal foil having a highly oriented cubic texture with ⁇ 100> main orientations in the rolling direction and the normal direction of the foil surface is produced by devising rolling conditions and heat treatment conditions. can do.
- the feature of the mechanical characteristics of the metal foil having a strong cubic orientation is not limited to the use of the flexible circuit board, and is that the elongation at break is anisotropic.
- the elongation at break takes a very small value when pulled in the ⁇ 100> direction.
- the basic crystal axis ⁇ 100> of the unit cell of the face-centered cubic structure is the thickness direction of the metal foil (the normal direction of the foil surface) and one direction existing in the foil surface (one of which is the rolling direction).
- the breaking elongation in the principal stress direction at the bent portion does not reach 3.5%.
- the term “elongation at break” used herein refers to a specimen having a width of 5 to 15 mm, which is sufficiently larger than the thickness of the metal foil, and is 10 to the length. This refers to the elongation to break when a tensile test is performed at a strain rate of% / min.
- the elongation after breaking of the metal foil is determined by the measurement method shown in the following examples, and the value after the flexible circuit board is obtained by laminating with the resin layer.
- the recrystallized texture has a ⁇ 100> orientation in the rolling direction, that is, the longitudinal direction of the metal foil.
- the longitudinal direction of the circuit and the longitudinal direction of the copper foil coincide with each other from the viewpoint of increasing the yield. Therefore, in the normal usage mode in which the longitudinal direction of the circuit is bent, the main stress direction coincides with the ⁇ 100> direction, so that the conventional rolled copper foil cannot obtain high fatigue characteristics against repeated bending.
- the present invention aims to increase the purity of the metal foil used.
- a copper foil intentionally or inevitably contains impurities such as oxygen and silver is used. This is for the purpose of facilitating shear deformation along the slip surface and suppressing an increase in electrical resistance, as described in Patent Document 5, for example.
- these impurity elements reduce the stacking fault energy.
- the present inventors paid attention to this point. That is, when the stacking fault energy is decreased, dislocations are easily expanded and cross slipping is unlikely to occur, and particularly when stretched in the ⁇ 100> direction, elongation is difficult to occur.
- a metal foil preferably a copper foil having a predetermined preferred orientation as described below and preferably having a purity of 99.999% or more is used, whereby the ⁇ 100> direction is used.
- the elongation at break can be increased to 3.5% or more, and as a result, the fatigue characteristics are increased when repeated strain is applied in a high strain region.
- the higher purity of the metal foil is desirable, it is most preferable to use 99.999% to 99.9999% from the viewpoint of manufacturing cost.
- an oxygen-free copper foil having a low oxygen concentration has a face-centered cubic shape depending on rolling and heat treatment conditions in a narrow condition, as shown in the following examples.
- the three-dimensional crystal orientation of the metal foil is defined with respect to the sample coordinate system of the metal foil constituting the circuit, and the degree of integration of the texture is in the following range. That is, a region in which one of the basic crystal axes ⁇ 100> of the face-centered cubic structure, for example, the [001] axis is within 10 ° in orientation difference with respect to the thickness direction of the metal foil (the normal direction of the foil surface) is an area.
- the foil plane which has a preferential orientation that accounts for 50% or more, preferably 75% or more, more preferably 98% or more, and is in a direction parallel to the surface of the metal foil
- another basic crystal An axis having a preferential orientation such that a region within 10 ° from the [100] axis occupies an azimuth difference accounts for 50% or more, desirably 85% or more, and more desirably 99% or more is used.
- it is sufficient that at least the bent portion has the above-mentioned texture integration degree, but preferably all the metal foils laminated on the resin layer have the above-mentioned integration degree.
- a so-called single crystal-like metal foil is preferable without being restricted in wiring design.
- the metal foil used in the present invention has a main orientation of ⁇ 100> in the thickness direction of the metal foil, It can be said that the foil plane has a main orientation of ⁇ 100>.
- indices that indicate the priority of texture orientation that is, the degree of orientation or accumulation
- An index based on simple data can be used.
- the metal foil is a copper foil
- the intensity (I) from (002) perpendicular to the above-mentioned zone axis determined by X-ray diffraction here, according to a general notation method in X-ray diffraction, (200) plane
- the wiring having a predetermined pattern is formed from a copper foil having I / I 0 ⁇ 25 with respect to the strength (I 0 ) of the (200) plane obtained by X-ray diffraction of fine powder copper.
- the I / I 0 is preferably in the range of 33 to 150, more preferably in the range of 50 to 150.
- the parameter I / I 0 represents the degree of orientation of the zone axes of (100) and (110), that is, the common axis [001], and is an objective index indicating the degree of development of the cube texture. is there.
- the metal foil is a rolled copper foil, it is strongly processed at a rolling rate of a certain level or higher, and then recrystallized by applying heat, so that the rolled foil surface is rolled into the (001) main orientation and foil plane.
- a recrystallized cube orientation with the direction as the (100) principal orientation develops.
- the bending fatigue life of the copper foil is improved as the cubic orientation, which is the recrystallized texture of copper, develops.
- a recrystallized texture of the copper foil may be obtained.
- the intermediate annealing conditions and the cold rolling process rate are targeted.
- a rolled copper foil having a large texture of crystal grains and I / I 0 ⁇ 25 can be obtained.
- the copper foil is subjected to heating conditions such that a temperature of 300 to 360 ° C. is loaded for an accumulated time of 5 minutes or more.
- a recrystallized texture of copper foil may be obtained.
- the texture can be specified using the area ratio of the preferentially oriented region that falls within 10 ° with respect to the main orientation of the texture. That is, as to what crystal orientation the predetermined surface of the metal foil has, for example, X-ray diffraction method such as EBSP (Electron Back Scattering Pattern) method, ECP (Electron Channeling Pattern) method or X-ray method such as micro Laue method It can be confirmed by a line diffraction method or the like.
- EBSP Electro Back Scattering Pattern
- ECP Electrode
- X-ray method such as micro Laue method
- the EBSP method analyzes a crystal from a diffraction image called a pseudo Kikuchi line that is diffracted from each crystal plane generated when a focused electron beam is irradiated on the surface of a sample to be measured.
- This is a method of measuring the crystal orientation distribution of the measurement object from the position information of the above, and it is possible to analyze the crystal orientation of the texture in the microscopic region as compared with the X-ray diffraction method.
- An orientation mapping image can be obtained by highlighting the distribution of regions (crystal grains) having substantially the same plane orientation. It is also possible to define the orientation including the orientation plane having an orientation within a predetermined angle with respect to a specific plane orientation, and to extract the existence ratio of each plane orientation by the area ratio. In the EBSP method, in order to obtain an area ratio of a region within a specific angle from a specific orientation, in order to obtain an area ratio at least in a region larger than the circuit bent region in the flexible circuit board of the present invention.
- the difference in structure between the present invention and the inventions described in Patent Documents 3 and 4 is that the orientation definition of the inventions of these Patent Documents is only the normal direction of the foil measured by X-ray.
- the present invention is defined in three dimensions.
- the main strain, the main stress direction that is, the ⁇ 100> integration degree in the foil surface, particularly when bent is important.
- the size of recrystallized grains, that is, crystal grains having a cubic orientation is preferably 25 ⁇ m or more on average.
- the metal foil forming the flexible circuit board is preferably a rolled copper foil having a thickness of 5 to 18 ⁇ m, preferably a thickness of 9 to 12 ⁇ m. It is preferable to use a rolled copper foil.
- the rolled copper foil is thicker than 18 ⁇ m, it becomes difficult to obtain a flexible circuit board having excellent fatigue characteristics in a high strain region where the radius of curvature is 2 mm or less.
- the thickness is less than 5 ⁇ m, handling in laminating the metal foil and the resin layer is difficult, and it is difficult to form a homogeneous flexible circuit board.
- the present invention provides a second method for improving the breaking elongation of a face-centered cubic metal foil close to a highly oriented single crystal.
- the wiring configuration of the flexible circuit board is devised so that the ⁇ 100> direction having a small elongation at break does not become the principal stress direction.
- a metal foil having a highly oriented cubic texture having a ⁇ 100> main orientation in both the rolling direction and the foil surface normal direction is produced. can do.
- the direction of cutting the circuit as wiring is shifted by a predetermined angle from the rolling direction, that is, the ⁇ 100> direction, and the circuit is pulled diagonally, so that flexibility is large in elongation at break in the main stress direction when bent.
- a circuit board can be obtained.
- the cross section P needs to have a main orientation on any plane included in the range of (20 1 0) to (1 20 0) with [001] as the zone axis.
- the relationship between the zone axis and the plane orientation is shown in FIG. (20 1 0) and (1 20 0) have a relationship with [001] as a common axis, that is, a zone axis, from (100) to (110) with [001] as the axis [from (100) (010)] in the plane of rotation. That is, when this is shown on the reverse pole figure with respect to the normal direction of the cross section P, the surfaces of (001), (20 1 0), and (110) are as shown in FIG.
- the metal of the metal foil in the present invention has a face-centered cubic structure.
- the crystal axes of the unit cell are [100], [010], and [001].
- ⁇ 100> preferred orientation in the thickness direction of the metal foil (the direction perpendicular to the surface of the metal foil).
- this axis is expressed as [001], that is, the foil plane orientation is (001), but it is equivalent even if these axes are interchanged due to the symmetry of the face-centered cubic structure, and these are of course included in the present invention. It is.
- the main orientation in the foil plane is in the main strain direction of the bent portion, that is, in the normal direction of the cross section of the wiring cut from the ridge line in the bent portion in the thickness direction (with respect to the perpendicular to the wiring cross section P), It is necessary to have an angle of 2.9 ° to 87.1 ° [(20 1 0) to (1 20 0)], preferably 5.7 ° to 84.3 ° [(10 1 0) ⁇ (1 10 0)], more preferably 11.4 ° to 78.6 ° [(510) to (150)], and more preferably 26.6 ° to 63.4 ° [(210) to It is desirable that the angle is (120)], most preferably 30 ° or 60 ° [(40 23 0) or (23 40 0)].
- [] represents the plane orientation of the cross section P corresponding to each angle. From the symmetry of the crystal, it can also be described that the normal to the wiring cross section P has an angle of 2.9 to 45 ° with the basic crystal axis ⁇ 100> in the metal foil plane.
- the cross section P of the wiring when it is cut in the thickness direction from the ridgeline at the bent portion is, for example, as shown in FIG. 3, when the flexible circuit board is bent in a U shape, a ridgeline L is formed on the outside thereof.
- the ridge line L is an apex formed when the cross section of the flexible circuit board is viewed along the bending direction (thick arrow in FIG. 3) in a state where the flexible circuit board is bent. It is a connected line.
- the case where the ridgeline L moves a flexible circuit board, such as sliding bending mentioned later, for example is also included.
- 3 shows a state in which the resin layer 1 is on the outside and the wiring 2 is bent inward (the side on which a circle having a radius of curvature is inscribed is inward), but the wiring 2 is bent outward. Of course, it may be.
- the metal foil when subjected to a forced displacement with a certain curvature, is mainly subjected to tensile or compressive stress.
- Which part of the flexible circuit board that is bent is subjected to tension or compression depends on the configuration of the metal foil and the resin, but is bent from the neutral axis (or neutral surface) of tension and compression.
- the outermost part which is the outermost part, is severe due to the destruction of the metal, and the tensile stress in the normal direction of the cross section of the wiring when cut in the thickness direction from the ridgeline at the bent part becomes the main stress. That is, the main stress direction of the wiring in the bent portion is the direction indicated by the arrow 21 in FIG. 3, and is typically the normal direction to the wiring cross section P cut from the ridge line of the bent portion in the thickness direction of the metal foil. And the direction perpendicular to the [001] axis oriented in the thickness direction of the metal foil.
- the stress strain characteristic when the metal foil is simply pulled in the main stress direction indicated by the arrow 21 in FIG. 3 is an important characteristic.
- the metal foil having a face-centered cubic crystal structure is bent so that a ridge line perpendicular to the [100] axis is formed.
- the cross section of the wiring cut in the thickness direction of the flexible circuit board from the ridge line at the bent portion becomes the (100) plane, but the cross section P of the wiring when cut in the thickness direction from the ridge line at the bent portion is As shown in FIG.
- the cross section P of the wiring when it is cut in the thickness direction from the ridgeline at the bent portion is preferentially oriented with a main orientation in a specific orientation between (20 1 0) and (1 20 0). Therefore, the reason why the elongation at break is improved is that when a tensile stress is applied in the normal direction of the cross section P, that is, the principal stress direction, the metal having a face-centered cubic structure has eight ⁇ 111 ⁇ , Since the main slip surface having the largest Schmid factor is four, the shear slip is good and local work hardening is less likely to occur.
- the longitudinal direction of the metal foil corresponds to the rolling direction, and as shown in FIGS.
- the most desirable orientation is 30 ° or 60 ° with respect to the main strain direction of the bent portion, that is, the normal direction of the cross section of the wiring when cut from the ridge line in the bent portion in the thickness direction. This is because the direction of stress coincides with the stable orientation of tension.
- at least the cross section P of the wiring when cut in the thickness direction from the ridgeline at the bent portion is between (20 1 0) and (1 20 0) with [001] as the crystal axis. It suffices to have the preferential orientation with the main orientation in the specific orientation.
- the second policy in the present invention is that the metal foil has a face-centered cubic structure, the thickness direction of the metal foil has a main orientation of ⁇ 100>, and the foil surface of the metal foil has ⁇ 100>. And the normal direction of the cross section P of the wiring when cut in the thickness direction from the ridge line at the bent portion is the main direction in a specific direction between (20 1 0) and (1 20 0). A wiring that has a preferential orientation is provided.
- the normal direction of the cross section P is preferably preferentially oriented with a main orientation in a specific orientation between (10 1 0) and (1 10 0), and more preferably (510 ) To (110) having a main orientation in a specific orientation, and more preferably having a main orientation in a specific orientation between (210) and (110).
- the preferred orientation is centered in the vicinity of (40 23 ⁇ ⁇ 0).
- the main direction of the cross section P of the wiring when cut in the thickness direction from the ridge line at can be described as a specific direction between (1 20 0) and (110), preferably (120) to (110) It can also be described that it is preferable to preferentially align with a main direction in a specific direction between them, and most preferably to preferentially align with a main direction in the vicinity of (23 40 0).
- the thickness direction of the metal foil has a main orientation of ⁇ 100>
- the foil surface of the metal foil has a main orientation of ⁇ 100>
- the wiring when cut from the ridgeline at the bent portion in the thickness direction The fact that the cross section P has a main orientation in a specific orientation between (20 1 0) and (1 20 0) is reversed on the stereo triangle of the (100) standard projection shown in FIG.
- the cross-sectional orientation of the wiring when cut in the thickness direction from the ridgeline at the bent portion is either on a line segment connected by a point representing (20 1 0) and a point representing (110)
- the flexible circuit board in the second measure is formed by forming a wiring from a 3 (2) axis-oriented material in which the thickness direction of the metal foil is the [001] axis, and cutting the ridge line at the bent portion in the thickness direction.
- the cross-sectional normal of the wiring at that time has an angle in the range of 2.9 ° to 87.1 ° with the [100] axis in the foil plane.
- the breaking elongation of the metal foil in the principal stress direction at the bent portion can be 3.5% or more, and the repeated strain such that the curvature radius is 2 mm or less, Alternatively, metal fatigue is less likely to occur due to stress, and a flexible circuit board with high flexibility can be obtained. Further, in the present invention, a flexible circuit board excellent in metal fatigue characteristics and bendability can be obtained more reliably by combining the first policy and the second policy described above, and the main stress direction can be obtained.
- the breaking elongation of the metal foil can be 3.5% or more, preferably 4% or more, more preferably 9% or more.
- the basic crystal axis ⁇ 100> of the unit cell of the face-centered cubic structure is in the thickness direction of the metal foil (the normal direction of the foil surface) and in one direction (in the direction of the foil surface)
- Rolling that can be taken within the scope of the present invention, in which the preferential orientation region with an orientation difference of 10 ° or less is 50% in area ratio and the thickness is 18 ⁇ m with respect to two orthogonal axes (one is the rolling direction)
- the upper limit of the foil can be defined as 20% or less, but the basic crystal axis ⁇ 100> of the copper unit cell is two orthogonal directions of the thickness direction of the copper foil and one direction existing in the foil plane.
- the preferential orientation regions each having an orientation difference within 10 ° with respect to the axis occupy 95% or more in area ratio and the thickness is 12 ⁇ m or less
- the upper limit of elongation at break is 15% or less. .
- the type of resin forming the resin layer is not particularly limited, and examples thereof include those used in ordinary flexible circuit boards, such as polyimide and polyamide. , Polyester, liquid crystal polymer, polyphenylene sulfide, polyether ether ketone and the like. Of these, polyimide and liquid crystal polymer are preferred because they exhibit good flexibility when used as a circuit board and are excellent in heat resistance.
- the thickness of the resin layer can be appropriately set in accordance with the use, shape, etc. of the flexible circuit board, but is preferably in the range of 5 to 75 ⁇ m from the viewpoint of flexibility, and in the range of 9 to 50 ⁇ m. Is more preferable, and the range of 10 to 30 ⁇ m is most preferable. If the thickness of the resin layer is less than 5 ⁇ m, the insulation reliability may decrease. On the other hand, if it exceeds 75 ⁇ m, the thickness of the entire circuit board may be too thick when mounted on a small device, etc. A decline in sex is also possible.
- a cover material made of a coverlay film or the like may be used on a wiring formed from a metal foil.
- a polyimide having a tensile elastic modulus at 25 ° C. of 4 to 6 GPa and a thickness of 14 to 17 ⁇ m is used as a resin layer, and a thermosetting resin having a thickness of 8 to 17 ⁇ m is used.
- a cover layer film having a cover layer film having a tensile elastic modulus of 2 to 4 GPa of the entire adhesive layer and the polyimide layer, and a cover material having two layers of an adhesive layer and a polyimide layer having a thickness of 7 to 13 ⁇ m A polyimide having a tensile elastic modulus at 25 ° C. of 6 to 8 GPa and a thickness of 12 to 15 ⁇ m is used as a resin layer, an adhesive layer made of a thermosetting resin having a thickness of 8 to 17 ⁇ m, and a polyimide layer having a thickness of 7 to 13 ⁇ m.
- a cover lay film having a tensile elastic modulus of 2 to 4 GPa for the entire adhesive layer and polyimide layer is used as a cover material.
- the metal foil may be thermally laminated by applying or interposing a thermoplastic polyimide to the polyimide film (so-called laminating). Law).
- a thermoplastic polyimide film used in the laminating method include “Kapton” (Toray DuPont Co., Ltd.), “Apical” (Kanebuchi Chemical Industry Co., Ltd.), “Upilex” (Ube Industries Co., Ltd.), and the like.
- a thermoplastic polyimide resin exhibiting thermoplasticity is preferably interposed.
- a polyimide precursor solution also referred to as a polyamic acid solution
- a polyamic acid solution may be applied to the metal foil, and then dried and cured to obtain a laminate (so-called “so-called”). Cast method).
- the resin layer may be formed by laminating a plurality of resins.
- two or more kinds of polyimides having different linear expansion coefficients may be laminated, and in that case, heat resistance and flexibility are ensured.
- the tensile elastic modulus of the resin layer is preferably 4 to 10 GPa, preferably 5 to 8 GPa, including the case of being composed of a single polyimide and the case of being composed of a plurality of polyimides.
- the linear expansion coefficient of the resin layer is preferably in the range of 10 to 30 ppm / ° C.
- the linear expansion coefficient of the entire resin layer may be in this range.
- a low linear expansion polyimide layer having a linear expansion coefficient of 25 ppm / ° C. or less, preferably 5 to 20 ppm / ° C., and a linear expansion coefficient of 26 ppm / ° C. or more, preferably 30 to It is a resin layer comprising a high linear expansion polyimide layer at 80 ppm / ° C., and can be adjusted to 10 to 30 ppm / ° C.
- the low linear expansion polyimide layer is the main resin layer of the resin layer, and the high linear expansion polyimide layer is preferably provided so as to be in contact with the metal foil.
- the linear expansion coefficient was determined by using a polyimide whose imidization reaction was sufficiently completed as a sample, raising the temperature to 250 ° C. using a thermomechanical analyzer (TMA), cooling at a rate of 10 ° C./min, and 240 to 100 ° C. It can obtain
- TMA thermomechanical analyzer
- the flexible circuit board according to the present invention includes a resin layer and a wiring formed from a metal foil, and is used with a bent portion in one of them.
- it is widely used in various electronic and electrical devices such as movable parts in hard disks, hinges and slides of mobile phones, printer heads, optical pickups, movable parts of notebook PCs, etc., and the circuit board itself Is bent, twisted, or deformed according to the operation of the mounted device, and a bent portion is formed in either of them.
- the flexible circuit board of the present invention since the flexible circuit board of the present invention has a bent portion structure with excellent bending durability, it is frequently bent with repeated operations such as sliding bending, bending bending, hinge bending, and sliding bending.
- the radius of curvature is 0.38 to 2.0 mm in bending behavior, 1.25 to 2.0 mm in sliding bending, and 3. 0 to 5.0 mm, suitable for severe use conditions such as 0.3 to 2.0 mm for slide bending, and for slide applications where bending performance is severe with a narrow gap of 0.3 to 1 mm Especially effective.
- a rolled metal exhibiting a cubic texture in which the [001] axis is finally oriented in the normal direction to the foil surface (perpendicular to the surface of the metal foil) Obtain a composite in which the foil and the resin layer are bonded to each other with the foil surface of the metal foil, and design the principal stress direction of the bending, that is, the normal direction of the cross section of the wiring when cutting from the ridgeline at the bent portion in the thickness direction.
- the foil may have a purity of 99.999% or higher, or iii) the methods i) and ii) may be adopted at the same time.
- the metal foil does not necessarily have to exhibit a cubic texture from the beginning, and the cubic texture may be formed by heat treatment.
- a manufacturing process of a flexible circuit board, specifically a resin A cubic texture may be formed by heat treatment in the layer formation process. That is, by heat treatment, one of the basic crystal axes ⁇ 100> of the unit cell is given priority in the thickness direction of the metal foil so that the area within 10 ° from the ⁇ 100> axis occupies an area ratio of 50% or more.
- another one of the basic crystal axes ⁇ 100> is preferentially oriented in the horizontal direction with respect to the surface of the metal foil so that the area within 10 ° from the ⁇ 100> axis occupies an area ratio of 50% or more.
- the recrystallized texture of the rolled copper foil usually has a rolling plane orientation of ⁇ 100 ⁇ and a rolling direction of ⁇ 100>. Therefore, the (001) main direction is formed as the rolling surface direction.
- the elongation at break can be secured to 3.5% or more regardless of the orientation of the circuit formed and wired, and the flexible application range is wide. Circuit board can be formed.
- the width, shape, pattern, etc. of the wiring are not particularly limited, and may be appropriately designed according to the use of the flexible circuit board, the mounted electronic device, etc. Even if the second measure is adopted, it is necessary to dare to wire in an oblique direction with respect to the rotation axis of the hinge portion, for example, in order to reduce the bending stress on the wiring. Therefore, wiring along the direction orthogonal to the ridgeline in the bent portion, that is, wiring with the minimum necessary minimum distance is possible.
- FIGS. 4A and 4B show a flexible circuit board used for, for example, a hinge part of a cellular phone, which is an example having a resin layer 1, a wiring 2 formed from a metal foil, and a connector terminal 3. is there.
- FIG. 4A and 4B show the position of the ridge line L in the bent portion near the center, and this ridge line L is (with respect to the [100] axis direction of the metal foil forming the wiring 2 ( 90 + ⁇ ) °.
- FIG. 4A is an example in which the wiring is formed obliquely in the vicinity of the ridge line L in the middle of the connector terminals 3 at both ends.
- FIG. Wiring is also possible.
- the slide sliding bend in which the ridge line L in the bent portion moves as in a slide type mobile phone may be the direction of the thick arrow).
- the flexible circuit board in this invention is equipped with the wiring which consists of metal foil in at least one surface of a resin layer, you may make it equip both surfaces of a resin layer with metal foil as needed.
- the metal foil constituting the wiring in the bent portion when the flexible circuit board is bent is highly oriented and has a large elongation at break in the main stress and main strain directions.
- the metal foil even when repeated bending with a small bending radius and high bending is performed, local stress concentration caused by crystal anisotropy hardly occurs and dislocation accumulation hardly occurs. Due to these effects, metal fatigue is less likely to occur, it has excellent durability against stress and strain, and there is no restriction on the design of the flexible circuit board, and even against repeated bending and bending with a small radius of curvature. It is possible to provide a flexible circuit board that has sufficient strength and can be bent.
- Copper foil A and copper foil H are commercially available rolled copper foils
- copper foil B is a commercially available electrolytic copper foil produced in a copper sulfate bath. These are all copper foils that are commercially available as high-bending products, and the purity is 99.9%, which is high as a commercial product.
- Copper foils C to G are processed by the present inventors, and are obtained by casting and solidifying a copper material having a predetermined purity in a graphite mold and rolling it to a predetermined thickness. The thickness of the casting ingot is 10 mm, and after dropping to 1 mm by cold rolling, for copper foil C, copper foil D, and copper foil E, after carrying out intermediate annealing at 300 ° C.
- Process condition A the copper foil F was cold-rolled to 9 micrometers (process condition B), without performing intermediate annealing. Further, the copper foil G was subjected to an intermediate annealing temperature of 800 ° C. and cold-rolled to 9 ⁇ m (process condition C).
- Example 1 The polyamic acid solution a prepared above is applied to seven types of copper foils from copper foil A to copper foil G, dried (after curing, a 2 ⁇ m-thick thermoplastic polyimide film is formed), and then polyamic acid b is applied thereon. And dried (after forming a low thermal expansion coefficient polyimide with a film thickness of 9 ⁇ m), and further coated with polyamic acid a and dried (after curing, formed with a polyimide film with a film thickness of 2 ⁇ m), 300 ⁇ A polyimide layer having a three-layer structure was formed through a heating condition in which a temperature of 360 ° C. was loaded for 5 minutes or more in the integration time.
- the copper foil was cut out to a rectangular size of 250 mm in length along the rolling direction (MD direction) and 150 mm in the direction perpendicular to the rolling direction (TD direction), as shown in FIG.
- the tensile elastic modulus of the entire resin layer was 7.5 GPa.
- the single-sided copper clad laminate 4 obtained above is subjected to mechanical and chemical polishing using colloidal silica on the rolled surface 2a of each copper foil 2 from the copper foil A to the copper foil G.
- the azimuth analysis was performed with an EBSP apparatus.
- the apparatuses used were FE-SEM (S-4100) manufactured by Hitachi, Ltd., EBSP apparatus manufactured by TSL, and software (OIM Analysis 5.2).
- the measurement area was an area of approximately 800 ⁇ m ⁇ 1600 ⁇ m, and the measurement acceleration voltage was 20 kV and the measurement step interval was 4 ⁇ m.
- the evaluation of the orientation was shown by the ratio of the measurement points where ⁇ 100> is within 10 ° with respect to the thickness direction of the foil and the rolling direction of the foil to the total measurement points. The number of measurements was made on five different samples of each variety and rounded to the nearest whole number. Further, using the obtained data, the crystal grain size was evaluated by setting the crystal grain boundaries to those having an orientation difference of 15 ° or more between adjacent crystal grains, and the average grain size was determined for the polycrystal. The results are shown in Table 1.
- These copper foils were composed of grains having a cubic orientation in a field of 800 ⁇ 1600 ⁇ m, and crystal grains having different orientations of 5 ⁇ m or less were dispersed in an island shape inside. Since the area ratio of the island-like structure is as small as 2% or less, the recrystallized grains having a cubic orientation are integrated with the same orientation, and the size of the recrystallized grains is the same as the foil thickness in the thickness direction. 9 ⁇ m, and 800 ⁇ m or more in the foil surface. In addition, the recrystallized grains having a cubic orientation of the copper foil F and the copper foil G are not high in area ratio, and therefore exist independently of each other, and the average grain sizes in the foil surface are 25 ⁇ m and 20 ⁇ m, respectively. It was. On the other hand, the electrolytic copper foil B was a polycrystal having an average particle diameter of 1 ⁇ m, and almost no orientation was observed.
- a predetermined mask is put on the copper foil 2 side of the single-sided copper clad laminate 4 obtained above, and etching is performed using an iron chloride / copper chloride solution, as shown in FIG.
- the angle between the wiring direction H and the MD direction is 0 °
- the wiring direction H (H direction) of the linear wiring 2 having a line width (l) of 150 ⁇ m is parallel to the MD direction ( ⁇ 100> axis).
- the wiring pattern was formed so that the space width (s) was 250 ⁇ m.
- MIT flex test was performed according to JIS C5016 using the test flexible circuit board obtained above.
- a schematic diagram of the test is shown in FIG.
- the equipment is manufactured by Toyo Seiki Seisakusho (STROGRAPH-R1), one end of the test flexible circuit board 5 in the longitudinal direction is fixed to the holding jig of the bending test apparatus, and the other end is fixed with a weight.
- the wire 2 on the circuit board 5 is cut off from conduction while being rotated to 135 ⁇ 5 degrees alternately left and right at a vibration speed of 150 times / min. was determined as the number of flexing.
- the main stress applied to the copper circuit is obtained because the ridge line formed in the bent portion is bent so as to be orthogonal to the wiring direction H of the wiring 2 of the test flexible circuit board 5.
- the main strain is a tensile stress or tensile strain parallel to the rolling direction.
- the bending fatigue life depends on the degree of integration of the cube texture, but the copper foil C, the copper foil D, and the copper foil E, which are produced by the same processing method and have substantially the same degree of orientation. It has been found that the bending fatigue life varies greatly.
- a tensile test was performed in parallel with the main stress of bending, the main strain direction, that is, the rolling direction.
- the resin layer was dissolved from the single-sided copper clad laminate 4 before etching, and a tensile test was conducted on the copper foil alone. In the process of dissolving the polyimide, it was confirmed that there was no change in the structure of the copper foil.
- the tensile test uses a sample cut to a length of 150 mm in the rolling direction (MD direction) of the copper foil and a width of 10 mm in the direction perpendicular to the rolling direction in the foil plane, and the distance between the gauge points is 100 mm in the length direction.
- the elongation at break is correlated with the bending fatigue life, not the strength at break.
- copper foil B is large in both strength and elongation at break, this reflects that it is a fine polycrystalline body of crystal grains.
- the fatigue life was inferior.
- the copper foil C with a purity of 99.99% and the copper foil D with a purity of 99.999%, which have the same degree of cube texture accumulation were compared, the fatigue characteristics of the copper foil D with respect to bending were greatly improved.
- the oxygen concentration of these two copper foils is the same, and the amount of copper oxide inside is also small and equal, so it is not due to the difference due to copper oxide but due to the difference in elongation at break due to different purity. .
- the basic crystal axis ⁇ 100> exists in the thickness direction of the metal foil and in the foil plane.
- the main orientation is such that the preferential orientation region with an azimuth difference of 10 ° or less occupies 50% or more with respect to two orthogonal axes with a certain direction, and the ridge line at the bent portion It was found that the breaking elongation of the metal foil in the normal direction relative to the cross section P of the wiring cut in the thickness direction of the metal foil was required to be 3.5% or more.
- the purity is extremely high at 99.999% or more, and by developing the cube orientation, the elongation at break is improved, and the fatigue life against repeated bending in which principal stress and principal strain are applied in that direction. It has been found to be a long flexible circuit board.
- Example 2 for a single-sided copper-clad laminate using copper foil A and copper foil E produced by the same method as in Example 1, as shown in FIG. 6, the wiring of linear wiring 2 having a line width (l) of 150 ⁇ m
- the wiring pattern was formed such that the direction H (H direction) had an angle of 30 ° and 45 ° with respect to the MD direction ([100] axis) and the space width (s) was 250 ⁇ m.
- the test having a width of 150 mm in the longitudinal direction along the wiring direction H of the circuit board and a width of 15 mm in the direction orthogonal to the wiring direction H.
- a flexible circuit board 5 was obtained.
- FIG. 6 shows an example in which the angle formed by the wiring direction H of the test flexible circuit board 5 and the MD direction is cut out at an angle of 45 °.
- the test flex circuit board 5 obtained above was repeatedly subjected to bending fatigue tests under the same conditions as in Example 1. Also, the resin layer is melted from the single-sided copper clad laminate 4 before etching so that the angle formed by the wiring direction H and the MD direction of the flexible circuit board 5 for testing is the same, and the longitudinal direction is rolled.
- a tensile test was performed in the same manner as in Example 1 using a sample of 150 mm ⁇ 10 mm cut so as to have an angle of 30 ° and 45 ° with respect to the direction. That is, the principal stress and principal strain direction in the fatigue test of the copper foil coincide with the tensile direction of the tensile test, and both the copper foil A and the copper foil E have a highly developed cubic texture. In the tensile test, the same crystal orientation is subjected to principal strain and principal stress. Table 2 shows the results of the fatigue test and the tensile test.
- Example 2 From the results of Example 2 above, when the copper foil was highly oriented between the fatigue life of the flexible circuit board against repeated bending of high strain and the breaking elongation of the copper foil constituting the wiring, It was found that there was a high correlation. As seen in Example 1, the polycrystalline body provides higher strength and ductility, but is not effective in high bending applications. Therefore, the relationship between the fatigue life and the elongation at break under conditions that have a highly integrated texture is that the slip system plays an important role, not just copper, but the same slip system. Even a face-centered cubic orientation metal holds, and if the metals have different stacking fault energies, it is expected that the elongation at break can be increased and the fatigue life can be expected to be increased.
- Example 3 The polyamic acid solution a prepared by the same method as in Synthesis Example 1 is applied to a rolled copper foil H having a purity of 99.9 mass% and a thickness of 12 ⁇ m and dried (after curing, a 2 ⁇ m-thick thermoplastic polyimide is formed) ), And polyamic acid b is applied and dried (forms a low thermal expansion coefficient polyimide having a film thickness of 8 ⁇ m after curing), and further polyamic acid a is applied and dried (film thickness after curing). 2 ⁇ m thermoplastic polyimide is formed), as shown in conditions a to d below, the polyimide layer (resin layer) is subjected to heating conditions such that the maximum temperature of 180 to 240 ° C. is added for 10 minutes in the total time. Formed.
- a polyimide layer (resin) having a thickness of 250 ⁇ m along the rolling direction (MD direction) of the copper foil and a rectangular size of 150 mm width in a direction orthogonal to the rolling direction (TD direction) and having a thickness of 12 ⁇ m.
- a predetermined mask is placed on the copper foil side of the single-sided copper-clad laminate 4 obtained above, etching is performed using an iron chloride / copper chloride solution, and a straight line having a line width of 150 ⁇ m and a space width of 250 ⁇ m is based on the IPC standard.
- a low-speed IPC test wiring 2 having a shape-like wiring was formed.
- the maximum temperature of the heating conditions in forming the polyimide layer is set to four levels of 180 ° C. (condition a), 200 ° C. (condition b), 220 ° C. (condition c), and 240 ° C. (condition d).
- the wiring direction (H direction) of the linear wiring 2 is 0 °, 2 °, 2.9 °, 5.7 °, 9.5 °, 11.4 ° with respect to the rolling direction (MD direction). 14 °, 18.4 °, 25 °, 26.6 °, 30 °, 40 °, 45 °, 55 °, 60 °, 63.4 °, 78.6 °, 80 °, 82.9 °, Wiring patterns were formed so as to have angles of 22 levels of 87.1 °, 88 °, and 90 °, respectively.
- the cover material 7 (Arisawa Seisakusho CVK-0515KA: thickness 12.5 ⁇ m) was laminated on the surface of each wiring pattern side using an epoxy adhesive.
- the thickness of the adhesive layer 6 made of an adhesive was 15 ⁇ m in a portion without a copper foil circuit, and 6 ⁇ m in a portion where a copper foil circuit was present. And it cut out so that it might become 15 cm in a length direction along a wiring direction (H direction), and 8 mm in the direction orthogonal to a wiring direction, and the flexible circuit board for a test for setting it as an IPC test sample was obtained.
- a tensile test was performed as follows.
- the resin layer is dissolved from the single-sided copper-clad laminate 4 before etching so that the angle relationship between the wiring direction H and the MD direction of the test flexible circuit board 5 is the same 22 level, and the copper foil is dissolved.
- a rectangular sample having a length of 150 mm and a width of 10 mm, which was cut out so that the longitudinal direction had the above-described 22 level angle with respect to the rolling direction, was prepared. At this time, it was confirmed that there was no change in the structure of the copper foil in the process of dissolving the polyimide.
- the distance between gauge points in the length direction is 100 mm
- the tensile speed is 10 mm / min. Measured with
- a single-sided copper-clad laminate produced under the heat treatment conditions of conditions a to d is 0 °, 2.9 °, 30 °, 63.4 with respect to the rolling direction.
- a total of 20 samples without wiring patterns cut out at 5 angles of 7 ° and 78.6 ° were produced.
- a simulated heat treatment was applied under the same conditions as the circuit formation etching, and a cover material was further laminated under the same conditions.
- these effects on the copper foil structure are minor, and it has been found that the copper foil structure is determined by the heat treatment conditions of conditions a to d at the time of polyimide formation.
- the number of points where the unit cell axis ⁇ 001> is within 10 ° is counted in the thickness direction and the rolling direction of the copper foil, and the ratio to the total number of points is calculated.
- the average value was obtained.
- the results are shown in Table 3.
- the variation between samples under the same heating condition is 1% or less, and it can be said that the same heat treatment condition has the integration degree shown in Table 3 over the entire surface of the copper foil. It was found that the higher the maximum heat treatment temperature and the greater the thermal history, the more recrystallization progressed and the higher the degree of integration of the cubic recrystallization texture.
- the IPC test is a test simulating slide bending, which is one of the bending forms used for mobile phones and the like, as shown in the schematic diagram of FIG.
- the IPC test is a test in which a bent portion is provided with a determined gap length 8 as shown in FIG. 8, one side is fixed by a fixing portion 9, and the slide operating portion 10 on the opposite side is repeatedly reciprocated as shown in the drawing. . Therefore, the substrate is repeatedly bent in a region corresponding to the stroke amount of the reciprocating portion.
- the test was conducted by repeatedly sliding the polyimide layer (resin layer) 1 with the cap length being 1 mm, that is, the bending radius being 0.5 mm and the stroke being 38 mm.
- the circuit breakage life was defined as the number of strokes at which the electrical resistance of the circuit reached twice the initial value.
- the test was conducted on a total of 88 levels in which wiring patterns having 22 levels of angles were formed under the four heat treatment conditions of the above conditions a to d. At each test level, four test pieces were measured, and the average number of strokes at which the circuit was broken was obtained.
- the copper foil after the circuit breaking life when the cross section of the copper foil cut in the thickness direction so as to be orthogonal to the sliding direction is observed with a scanning electron microscope, there is a difference in degree, but the resin layer side and the cover material side It was observed that cracks occurred on the surfaces of the copper foils, and that many cracks were introduced on the surface of the copper foil on the resin layer side, which is outside the bent portion.
- Table 4 shows the average value of circuit break life at each level and the elongation at break in the tensile test.
- the surface index is also shown only in the case of the low index direction of the cross section P of the wiring when the circuit is cut in the length direction (wiring direction), that is, the ridgeline at the bent portion in the thickness direction. .
- the fracture life (fatigue life) in the IPC test is the angle between the circuit length direction (H direction) and the rolling direction (MD direction), that is, the normal direction of the cross section of the wiring when cutting from the ridge line at the bent portion in the thickness direction. And [100] were found to depend greatly on the angle.
- This orientation dependency is manifested under conditions b, c, and d.
- the higher the degree of integration of the cube orientation the greater the fatigue life against repeated bending and the greater the orientation dependency.
- the ⁇ 001> main direction is such that the area where the copper [001] is within an orientation difference of 10 ° occupies an area ratio of 50% or more in the evaluation by the EBSP method with respect to the thickness direction of the metal foil.
- the orientation is preferentially oriented in the thickness direction of the metal foil, and the region within 10 ° of the orientation difference from the [100] axis of copper occupies an area ratio of 50% or more as evaluated by the EBSP method. It was confirmed that the main azimuth was expressed when preferentially oriented in the metal foil plane. In particular, when the thickness direction and the rolling direction show the area ratios of 75% or more and 85% or more, respectively, and the condition c has a high degree of integration of cube orientation, the fatigue life is large and the orientation dependency is also high.
- the effect becomes large, and in the condition d in which the thickness direction and the rolling direction show an area ratio of 98% or more and 99% or more, respectively, and the accumulation degree of the cube orientation is extremely high, the fatigue life is further increased and the orientation dependency is increased. It turns out that the effect is great.
- the normal direction of the wiring cross section P when cutting in the thickness direction from the ridgeline at the bent portion is the ⁇ 100> main orientation of the copper foil.
- the fatigue life of the circuit against bending is higher when it deviates from the above.
- the effect was observed with respect to the main strain direction of the bent portion, that is, with respect to the cross-sectional normal direction of the wiring when cutting from the ridge line in the bent portion in the thickness direction. This was the case with an angle of 9 ° to 87.1 °.
- the cross section P of the wiring when cut in the thickness direction from the ridgeline at the bent portion passes from (20 1 0) to (110) with [001] as the zone axis, and (1 20 0 ).
- the effect is large at 11.4 ° to 78.6 ° with respect to the main strain direction of the bent portion, that is, with respect to the normal direction of the cross section of the wiring when cut from the ridge line in the bent portion in the thickness direction. It was the case with an angle.
- the cross section P of the wiring when it is cut in the thickness direction from the ridgeline at the bent portion ranges from (510) to (110) to (150) with [001] as the zone axis.
- the bending characteristic further has an angle of 26.6 ° to 63.4 ° with respect to the main strain direction of the bent portion, that is, with respect to the normal direction of the cross section of the wiring when cut from the ridge line in the bent portion in the thickness direction. In the case of 30 ° and 60 °, the best results were obtained.
- the cross section P is in the range from (210) to (110) to (120) with [001] as the zone axis, and the most excellent is (40 23 0) and ( 23 40 0) Near.
- the basic crystal axis ⁇ 100> of the unit cell having a face-centered cubic structure has two orthogonal axes of the thickness direction of the metal foil and a certain direction existing in the foil surface.
- the main orientation is such that the preferential orientation regions having an orientation difference of 10 ° or less each occupy 50% or more in area ratio
- the wiring cut from the ridge line in the bent portion in the thickness direction of the metal foil It was found that when the breaking elongation of the metal foil in the normal direction relative to the cross section P is 3.5% or more, the metal foil has good bending fatigue characteristics with respect to bending that generates principal stress and principal strain in the direction.
- the area ratio of the ⁇ 100> preferentially oriented region was 49% or less, even if the elongation at break in that direction showed a value of 3.5% or more, good bending fatigue characteristics were not obtained.
- Example 4 A heat treatment (preliminary heat treatment) for 30 minutes was applied to copper foil C having a purity of 99.99% at five levels of 180 ° C. to 400 ° C. in an Ar stream, and the polyamic acid solution a was applied in the same manner as in Example 1. , Dried (after forming a 2 ⁇ m-thick thermoplastic polyimide film after curing), coated with polyamic acid b and dried (after curing, formed a 9 ⁇ m-thick low thermal expansion polyimide), and further The polyamic acid a is applied and dried (forms a thermoplastic polyimide with a film thickness of 2 ⁇ m after curing), and is heated to a temperature of 300 to 360 ° C.
- a polyimide layer was formed.
- the copper foil was cut out to a rectangular size of 250 mm in length along the rolling direction (MD direction) and 150 mm in the direction perpendicular to the rolling direction (TD direction), as shown in FIG.
- colloidal silica was used on the rolled surface 2a of the copper foil 2, mechanically and chemically polished, and then subjected to orientation analysis using an EBSP apparatus.
- the apparatuses used were FE-SEM (S-4100) manufactured by Hitachi, Ltd., EBSP apparatus manufactured by TSL, and software (OIM Analysis 5.2).
- the measurement area was an area of approximately 800 ⁇ m ⁇ 1600 ⁇ m, and the measurement acceleration voltage was 20 kV and the measurement step interval was 4 ⁇ m.
- the evaluation of the orientation was shown by the ratio of the measurement points where ⁇ 100> is within 10 ° with respect to the thickness direction of the foil and the rolling direction of the foil to the total measurement points.
- the number of measurements was performed on five different samples of each variety, and the percentages after the second decimal place were rounded off. Further, using the obtained data, the crystal grain size was evaluated by setting the crystal grain boundaries to those having an orientation difference of 15 ° or more between adjacent crystal grains, and the average grain size was determined for the polycrystal. The results are shown in Table 5.
- each of the copper foils C had a cubic texture, and both the copper foil surface orientation and the rolling direction had a main orientation of ⁇ 001 ⁇ ⁇ 100>.
- the rolled copper foil was recrystallized by pre-heat treatment and heat at the time of curing of the polyimide, and a recrystallized texture was formed.
- the higher the preliminary heat treatment temperature the greater the degree of orientation of ⁇ 001 ⁇ ⁇ 100>.
- the orientation other than the ⁇ 100> orientation was confirmed by the EBSP apparatus in the same manner as described above.
- the recrystallized residual orientation having an orientation of ⁇ 212> with respect to the rolling direction and an equivalent circle diameter of 5 ⁇ m or less was island-like. Was dispersed.
- a predetermined mask is put on the copper foil 2 side of the single-sided copper clad laminate 4 obtained above, and etching is performed using an iron chloride / copper chloride solution, as shown in FIG.
- the angle between the wiring direction H and the MD direction is 0 °
- the wiring direction H (H direction) of the linear wiring 2 having a line width (l) of 150 ⁇ m is parallel to the MD direction ( ⁇ 100> axis).
- the wiring pattern was formed so that the space width (s) was 250 ⁇ m.
- MIT flex test was performed according to JIS C5016 using the test flexible circuit board obtained above.
- a schematic diagram of the test is shown in FIG.
- the equipment is manufactured by Toyo Seiki Seisakusho (STROGRAPH-R1), one end of the test flexible circuit board 5 in the longitudinal direction is fixed to the holding jig of the bending test apparatus, and the other end is fixed with a weight.
- the wire 2 on the circuit board 5 is cut off from conduction while being rotated to 135 ⁇ 5 degrees alternately left and right at a vibration speed of 150 times / min. was determined as the number of flexing.
- the main stress applied to the copper circuit is obtained because the ridge line formed in the bent portion is bent so as to be orthogonal to the wiring direction H of the wiring 2 of the test flexible circuit board 5.
- the main strain is a tensile stress or tensile strain parallel to the rolling direction.
- a tensile test was performed in parallel with the main stress of bending, the main strain direction, that is, the rolling direction.
- the resin layer was dissolved from the single-sided copper clad laminate 4 before etching, and a tensile test was conducted on the copper foil alone. In the process of dissolving the polyimide, it was confirmed that there was no change in the structure of the copper foil.
- the tensile test uses a sample cut to a length of 150 mm in the rolling direction (MD direction) of the copper foil and a width of 10 mm in the vertical direction in the foil plane, the distance between the gauge points is 100 mm, and the tensile speed is 10 mm / min in the length direction. . Measured with For the measurement, seven samples were prepared for each preliminary heat treatment temperature of the copper foil, and the breaking stress (breaking strength) and the average value of breaking elongation obtained by measuring these were shown in Table 5.
- the elongation at break increased as the integration degree increased in the region where the ⁇ 100> integration degree (%) was 98.0% or more and 99.8% or less.
- the elongation at break was small in the copper foil from which the island-like structure disappeared. This is presumed to be related to the slip surface. From the above, it was confirmed that the elongation at break and the bending fatigue life have a strong correlation. That is, a texture with a ⁇ 100> accumulation degree (%) of 98.0% or more and 99.8% or less is highly developed, and the flexural fatigue life is increased when the elongation at break is 3.5% or more. I understand.
- the flexible circuit board according to the present invention can be widely used in various electronic and electrical devices.
- the circuit board itself is bent, twisted, or deformed according to the operation of the mounted device. , Suitable for use with a bent portion in either.
- the flexible circuit board of the present invention has a bent portion structure with excellent bending durability, it is frequently bent with repeated operations such as sliding bending, bending bending, hinge bending, and sliding bending.
- it is suitable for the case where a bent portion is required in which the radius of curvature is required to be extremely small in order to cope with downsizing of the equipment to be mounted. Therefore, it can be suitably used for various electronic devices such as thin mobile phones, thin displays, hard disks, printers, and DVD devices that require durability.
- Resin layer 2 Wiring (metal foil) 2a: Rolled surface 2b: Side surface 3: Connector terminal 4: Single-sided copper clad laminate 5: Test flexible circuit board 6: Adhesive layer 7: Cover material 8: Gap length 9: Fixing part 10: Slide operating part 21: Method of section P Line direction L: Ridge line P: Cross section of wiring when cut in the thickness direction from the ridge line at the bent portion
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Abstract
Description
(1)樹脂層と金属箔から形成された配線とを備え、配線の少なくとも一箇所に屈曲部を有して使用される可撓性回路基板であって、
金属箔は、面心立方構造を有する金属からなると共に、面心立方構造の単位格子の基本結晶軸<100>が、金属箔の厚さ方向と箔面内に存在するある一方向との2つの直交軸に対して、それぞれ方位差10°以内の優先配向領域が面積率で50%以上を占め、かつ屈曲部における稜線から金属箔の厚み方向に切った配線の断面Pに対する法線方向の金属箔の破断伸びが3.5%以上、20%以下であることを特徴とする可撓性回路基板。
(2)金属箔が、純度99.999質量%以上の銅箔からなる(1)項に記載の可撓性回路基板。
(3)金属箔が銅箔であり、箔面法線方向から見たときの結晶粒径が25μm以上である(1)又は(2)項に記載の可撓性回路基板。
(4)金属箔の厚みが5μm以上、18μm以下である(1)~(3)項のいずれかに記載の可撓性回路基板。
(5)配線の断面Pが、[001]を晶帯軸として(100)から(110)への回転方向における(20 1 0)から(1 20 0)の範囲に含まれたいずれかの面に主方位をなす(1)~(4)項のいずれかに記載の可撓性回路基板。
(6)配線の断面Pが、(100)標準投影図のステレオ三角形において(20 1 0)を表す点と(110)を表す点とで結ばれた線分上にあるいずれかの面である(5)項に記載の可撓性回路基板。
(7)屈曲部における稜線に対して直交する方向に沿って配線が形成されている(1)~(6)項のいずれかに記載の可撓性回路基板。
(8)樹脂層がポリイミドからなる(1)~(7)項のいずれかに記載の可撓性回路基板。
(9)摺動屈曲、折り曲げ屈曲、ヒンジ屈曲及びスライド屈曲からなる群から選ばれたいずれかの繰り返し動作を伴う屈曲部が形成されるように使用される(1)~(8)項のいずれかに記載の可撓性回路基板。
(10)上記(1)~(9)項のいずれかに記載の可撓性回路基板を搭載した電子機器。
(11)樹脂層と金属箔から形成された配線とを備え、配線の少なくとも一箇所に屈曲部を有して使用される可撓性回路基板の屈曲部構造であって、
金属箔は、面心立方構造を有する金属からなると共に、面心立方構造の単位格子の基本結晶軸<100>が、金属箔の厚さ方向と箔面内に存在するある一方向との2つの直交軸に対して、それぞれ方位差10°以内の優先配向領域が面積率で50%以上を占め、かつ、屈曲部における稜線から金属箔の厚み方向に切った配線の断面Pに対する法線方向の金属箔の破断伸びが3.5%以上、20%以下であることを特徴とする可撓性回路基板の屈曲部構造。 The present invention is summarized as follows as a result of intensive studies to solve the above-described problems of the prior art.
(1) A flexible circuit board including a resin layer and a wiring formed from a metal foil, and having a bent portion at least at one place of the wiring,
The metal foil is made of a metal having a face-centered cubic structure, and the basic crystal axis <100> of the unit cell of the face-centered cubic structure is 2 in the thickness direction of the metal foil and a certain direction existing in the foil surface. With respect to two orthogonal axes, the preferential orientation regions having an azimuth difference of 10 ° or less occupy 50% or more in area ratio, and the normal direction with respect to the cross section P of the wiring cut from the ridge line in the bent portion in the thickness direction of the metal foil A flexible circuit board, wherein the breaking elongation of the metal foil is 3.5% or more and 20% or less.
(2) The flexible circuit board according to (1), wherein the metal foil is a copper foil having a purity of 99.999% by mass or more.
(3) The flexible circuit board according to (1) or (2), wherein the metal foil is a copper foil, and the crystal grain size when viewed from the normal direction of the foil surface is 25 μm or more.
(4) The flexible circuit board according to any one of (1) to (3), wherein the thickness of the metal foil is 5 μm or more and 18 μm or less.
(5) Any plane in which the cross section P of the wiring is included in the range of (20 1 0) to (1 20 0) in the rotation direction from (100) to (110) with [001] as the zone axis The flexible circuit board according to any one of (1) to (4), wherein
(6) The cross section P of the wiring is any surface on the line segment connected by the point representing (20 1 0) and the point representing (110) in the stereo triangle of the (100) standard projection view. (5) The flexible circuit board according to item (5).
(7) The flexible circuit board according to any one of (1) to (6), wherein a wiring is formed along a direction orthogonal to the ridge line in the bent portion.
(8) The flexible circuit board according to any one of (1) to (7), wherein the resin layer is made of polyimide.
(9) Any one of items (1) to (8) used so as to form a bent portion with any repetitive motion selected from the group consisting of sliding bending, bending bending, hinge bending, and sliding bending A flexible circuit board according to
(10) An electronic device on which the flexible circuit board according to any one of (1) to (9) is mounted.
(11) A bent portion structure of a flexible circuit board that includes a resin layer and a wiring formed from a metal foil, and is used with a bent portion in at least one portion of the wiring,
The metal foil is made of a metal having a face-centered cubic structure, and the basic crystal axis <100> of the unit cell of the face-centered cubic structure is 2 in the thickness direction of the metal foil and a certain direction existing in the foil surface. The normal orientation direction with respect to the cross section P of the wiring cut in the thickness direction of the metal foil from the ridgeline in the bent portion with respect to the two orthogonal axes, the preferential orientation region having an azimuth difference of 10 ° or less occupies 50% or more in area ratio Bending part structure of flexible circuit board, wherein elongation at break of metal foil is 3.5% or more and 20% or less.
市販圧延銅箔、純度99.9%、厚さ9μm。
[銅箔B]
市販電解銅箔、純度99.9%、厚さ9μm。
[銅箔C]
無酸素銅箔、純度99.99%、厚さ9μm、プロセス条件A。
不純物(mass ppm) 酸素:2、銀:18、リン:2.1、硫黄:4、鉄:1.5
[銅箔D]
精製銅箔、純度99.999%、厚さ9μm、プロセス条件A。
不純物(mass ppm) 酸素:2、銀:5、リン:0.01、硫黄:0.01、鉄0.002
[銅箔E]
精製銅箔、純度99.9999%、厚さ9μm、プロセス条件A。
不純物(mass ppm) 酸素:<1、銀:0.18、リン:<0.005、硫黄:<0.005、鉄:0.002
[銅箔F]
精製銅箔、純度99.9999%、厚さ9μm、プロセス条件B。
不純物(mass ppm) 酸素:<1、銀:0.18、リン:<0.005、硫黄:<0.005、鉄:0.002
[銅箔G]
精製銅箔、純度99.9999%、厚さ9μm、プロセス条件C。
不純物(mass ppm) 酸素:<1、銀:0.18、リン:<0.005、硫黄:<0.005、鉄:0.002
[銅箔H]
市販圧延銅箔、純度99.9%、厚さ12μm。 [Copper foil A]
Commercial rolled copper foil, purity 99.9%, thickness 9 μm.
[Copper foil B]
Commercially available electrolytic copper foil, purity 99.9%, thickness 9 μm.
[Copper foil C]
Oxygen-free copper foil, purity 99.99%, thickness 9 μm, process condition A.
Impurities (mass ppm) Oxygen: 2, Silver: 18, Phosphorus: 2.1, Sulfur: 4, Iron: 1.5
[Copper foil D]
Purified copper foil, purity 99.999%, thickness 9 μm, process condition A.
Impurities (mass ppm) Oxygen: 2, Silver: 5, Phosphorus: 0.01, Sulfur: 0.01, Iron 0.002
[Copper foil E]
Purified copper foil, purity 99.9999%, thickness 9 μm, process condition A.
Impurities (mass ppm) Oxygen: <1, Silver: 0.18, Phosphorus: <0.005, Sulfur: <0.005, Iron: 0.002
[Copper foil F]
Purified copper foil, purity 99.9999%, thickness 9 μm, process condition B.
Impurities (mass ppm) Oxygen: <1, Silver: 0.18, Phosphorus: <0.005, Sulfur: <0.005, Iron: 0.002
[Copper foil G]
Purified copper foil, purity 99.9999%, thickness 9 μm, process condition C.
Impurities (mass ppm) Oxygen: <1, Silver: 0.18, Phosphorus: <0.005, Sulfur: <0.005, Iron: 0.002
[Copper foil H]
Commercial rolled copper foil, purity 99.9%, thickness 12 μm.
銅箔Aと銅箔Hは、市販の圧延銅箔であり、銅箔Bは硫酸銅浴で製造した市販の電解銅箔である。これらはいずれも高屈曲用途品として市販されている銅箔であり、純度は99.9%と市販品としては高いものである。銅箔C~銅箔Gは本発明者らが加工したものであり、所定の純度の銅素材を黒鉛鋳型内で鋳造凝固し、圧延加工して所定の厚さにしたものである。鋳造インゴットの厚さは10mmであり、冷間圧延で1mmまで落とした後、銅箔C、銅箔D、及び銅箔Eについては、300℃、30分の中間焼鈍を実施した後、9μmまで冷間圧延を実施した(プロセス条件A)。また、銅箔Fは中間焼鈍を行わないで、9μmまで冷間圧延を実施した(プロセス条件B)ものである。更に、銅箔Gは、中間焼鈍温度を800℃で行い、9μmまで冷間圧延を実施した(プロセス条件C)。 [Manufacturing method of copper foil]
Copper foil A and copper foil H are commercially available rolled copper foils, and copper foil B is a commercially available electrolytic copper foil produced in a copper sulfate bath. These are all copper foils that are commercially available as high-bending products, and the purity is 99.9%, which is high as a commercial product. Copper foils C to G are processed by the present inventors, and are obtained by casting and solidifying a copper material having a predetermined purity in a graphite mold and rolling it to a predetermined thickness. The thickness of the casting ingot is 10 mm, and after dropping to 1 mm by cold rolling, for copper foil C, copper foil D, and copper foil E, after carrying out intermediate annealing at 300 ° C. for 30 minutes, up to 9 μm Cold rolling was performed (process condition A). Moreover, the copper foil F was cold-rolled to 9 micrometers (process condition B), without performing intermediate annealing. Further, the copper foil G was subjected to an intermediate annealing temperature of 800 ° C. and cold-rolled to 9 μm (process condition C).
(合成例1)
熱電対及び攪拌機を備えると共に窒素導入が可能な反応容器に、N,N-ジメチルアセトアミドを入れた。この反応容器に2,2-ビス[4-(4-アミノフェノキシ)フェニル]プロパン(BAPP)を容器中で撹拌しながら溶解させた。次に、ピロメリット酸二無水物(PMDA)を加えた。モノマーの投入総量が15wt%となるように投入した。その後、3時間撹拌を続け、ポリアミド酸aの樹脂溶液を得た。このポリアミド酸aの樹脂溶液の溶液粘度は3,000cpsであった。 [Synthesis of polyamic acid solution]
(Synthesis Example 1)
N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) was dissolved in the reaction vessel with stirring. Next, pyromellitic dianhydride (PMDA) was added. The total amount of monomers charged was 15 wt%. Thereafter, stirring was continued for 3 hours to obtain a resin solution of polyamic acid a. The solution viscosity of this polyamic acid a resin solution was 3,000 cps.
熱電対及び攪拌機を備えると共に窒素導入が可能な反応容器に、N,N-ジメチルアセトアミドを入れた。この反応容器に2,2'-ジメチル-4,4'-ジアミノビフェニル(m-TB)を投入した。次に3,3',4,4'-ビフェニルテトラカルボン酸二無水物(BPDA)及びピロメリット酸二無水物(PMDA)を加えた。モノマーの投入総量が15wt%で、各酸無水物のモル比率(BPDA:PMDA)が20:80となるように投入した。その後、3時間撹拌を続け、ポリアミド酸bの樹脂溶液を得た。このポリアミド酸bの樹脂溶液の溶液粘度は20,000cpsであった。 (Synthesis Example 2)
N, N-dimethylacetamide was placed in a reaction vessel equipped with a thermocouple and a stirrer and capable of introducing nitrogen. 2,2′-Dimethyl-4,4′-diaminobiphenyl (m-TB) was charged into the reaction vessel. Next, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and pyromellitic dianhydride (PMDA) were added. The total amount of monomers charged was 15 wt%, and the molar ratio of each acid anhydride (BPDA: PMDA) was 20:80. Thereafter, stirring was continued for 3 hours to obtain a resin solution of polyamic acid b. The solution viscosity of this polyamic acid b resin solution was 20,000 cps.
銅箔Aから銅箔Gまでの7種類の銅箔に上記で準備したポリアミド酸溶液aを塗布し、乾燥させ(硬化後は膜厚2μmの熱可塑性ポリイミドを形成)、そのうえにポリアミド酸bを塗布し、乾燥させ(硬化後は膜厚9μmの低熱熱膨張性ポリイミドを形成)、更にその上にポリアミド酸aを塗布し乾燥させ(硬化後は膜厚2μmの熱可塑性ポリイミドを形成)、300~360℃の温度が積算時間で5分以上負荷されるような加熱条件を経て3層構造からなるポリイミド層を形成した。次いで、銅箔の圧延方向(MD方向)に沿って長さ250mm、圧延方向に対して直交する方向(TD方向)に幅150mmの長方形サイズとなるように切り出し、図5に示すように、厚さ13μmのポリイミド層(樹脂層)1と厚さ9μmの銅箔2とを有した片面銅張積層板4を得た。そのときの樹脂層全体の引張弾性率は7.5GPaであった。 [Example 1]
The polyamic acid solution a prepared above is applied to seven types of copper foils from copper foil A to copper foil G, dried (after curing, a 2 μm-thick thermoplastic polyimide film is formed), and then polyamic acid b is applied thereon. And dried (after forming a low thermal expansion coefficient polyimide with a film thickness of 9 μm), and further coated with polyamic acid a and dried (after curing, formed with a polyimide film with a film thickness of 2 μm), 300 ~ A polyimide layer having a three-layer structure was formed through a heating condition in which a temperature of 360 ° C. was loaded for 5 minutes or more in the integration time. Next, the copper foil was cut out to a rectangular size of 250 mm in length along the rolling direction (MD direction) and 150 mm in the direction perpendicular to the rolling direction (TD direction), as shown in FIG. A single-sided copper clad
次に、実施例1と同じ方法で作製した銅箔Aと銅箔Eを用いた片面銅張積層板について、図6に示すように、線幅(l)150μmの直線状の配線2の配線方向H(H方向)がMD方向([100]軸)に対して30°及び45°の角度を有するようにし、かつ、スペース幅(s)250μmで配線パターンを形成した。そして、後述する耐屈曲試験用のサンプルを兼ねるように、JIS 6471に準じて、回路基板の配線方向Hに沿って長手方向に150mm、配線方向Hに直交する方向に幅15mmを有した試験用可撓性回路基板5を得た。図6は、試験用可撓性回路基板5の配線方向HとMD方向とのなす角を45°の角度で切り出した時の例である。 [Example 2]
Next, for a single-sided copper-clad laminate using copper foil A and copper foil E produced by the same method as in Example 1, as shown in FIG. 6, the wiring of
純度99.9mass%であり、厚さ12μmの圧延銅箔Hに、合成例1と同じ方法で準備したポリアミド酸溶液aを塗布して乾燥させ(硬化後は膜厚2μmの熱可塑性ポリイミドを形成)、その上にポリアミド酸bを塗布して乾燥させ(硬化後は膜厚8μmの低熱熱膨張性ポリイミドを形成)、更にその上にポリアミド酸aを塗布して乾燥させ(硬化後は膜厚2μmの熱可塑性ポリイミドを形成)、下記条件a~dに示したように、最高温度180~240℃の温度が積算時間で10分付加されるような加熱条件を経てポリイミド層(樹脂層)を形成した。 [Example 3]
The polyamic acid solution a prepared by the same method as in Synthesis Example 1 is applied to a rolled copper foil H having a purity of 99.9 mass% and a thickness of 12 μm and dried (after curing, a 2 μm-thick thermoplastic polyimide is formed) ), And polyamic acid b is applied and dried (forms a low thermal expansion coefficient polyimide having a film thickness of 8 μm after curing), and further polyamic acid a is applied and dried (film thickness after curing). 2 μm thermoplastic polyimide is formed), as shown in conditions a to d below, the polyimide layer (resin layer) is subjected to heating conditions such that the maximum temperature of 180 to 240 ° C. is added for 10 minutes in the total time. Formed.
純度99.99%の銅箔CにAr気流中で180℃~400℃の5水準の温度で30分間の熱処理(予備熱処理)を加え、実施例1と同じ方法でポリアミド酸溶液aを塗布し、乾燥させ(硬化後は膜厚2μmの熱可塑性ポリイミドを形成)、その上にポリアミド酸bを塗布し、乾燥させ(硬化後は膜厚9μmの低熱熱膨張性ポリイミドを形成)、更にその上にポリアミド酸aを塗布し乾燥させ(硬化後は膜厚2μmの熱可塑性ポリイミドを形成)、300~360℃の温度が積算時間で5分以上負荷されるような加熱条件を経て3層構造からなるポリイミド層を形成した。次いで、銅箔の圧延方向(MD方向)に沿って長さ250mm、圧延方向に対して直交する方向(TD方向)に幅150mmの長方形サイズとなるように切り出し、図5に示すように、厚さ13μmのポリイミド層(樹脂層)1と厚さ9μmの銅箔2とを有した片面銅張積層板4を得た。そのときの樹脂層全体の引張弾性率は7.5GPaであった。 [Example 4]
A heat treatment (preliminary heat treatment) for 30 minutes was applied to copper foil C having a purity of 99.99% at five levels of 180 ° C. to 400 ° C. in an Ar stream, and the polyamic acid solution a was applied in the same manner as in Example 1. , Dried (after forming a 2 μm-thick thermoplastic polyimide film after curing), coated with polyamic acid b and dried (after curing, formed a 9 μm-thick low thermal expansion polyimide), and further The polyamic acid a is applied and dried (forms a thermoplastic polyimide with a film thickness of 2 μm after curing), and is heated to a temperature of 300 to 360 ° C. for a total time of 5 minutes or more. A polyimide layer was formed. Next, the copper foil was cut out to a rectangular size of 250 mm in length along the rolling direction (MD direction) and 150 mm in the direction perpendicular to the rolling direction (TD direction), as shown in FIG. A single-sided copper clad
2:配線(金属箔)
2a:圧延面
2b:側面
3:コネクタ端子
4:片面銅張積層板
5:試験用可撓性回路基板
6:接着層
7:カバー材
8:ギャップ長
9:固定部
10:スライド稼動部
21:断面Pの法線方向
L:稜線
P:屈曲部における稜線から厚み方向に切った際の配線の断面 1: Resin layer 2: Wiring (metal foil)
2a: Rolled surface
2b: Side surface 3: Connector terminal 4: Single-sided copper clad laminate 5: Test flexible circuit board 6: Adhesive layer 7: Cover material 8: Gap length 9: Fixing part 10: Slide operating part 21: Method of section P Line direction L: Ridge line P: Cross section of wiring when cut in the thickness direction from the ridge line at the bent portion
Claims (11)
- 樹脂層と金属箔から形成された配線とを備え、配線の少なくとも一箇所に屈曲部を有して使用される可撓性回路基板であって、
金属箔は、面心立方構造を有する金属からなると共に、面心立方構造の単位格子の基本結晶軸<100>が、金属箔の厚さ方向と箔面内に存在するある一方向との2つの直交軸に対して、それぞれ方位差10°以内の優先配向領域が面積率で50%以上を占め、かつ屈曲部における稜線から金属箔の厚み方向に切った配線の断面Pに対する法線方向の金属箔の破断伸びが3.5%以上、20%以下であることを特徴とする可撓性回路基板。 A flexible circuit board comprising a resin layer and a wiring formed from a metal foil, and having a bent portion in at least one part of the wiring,
The metal foil is made of a metal having a face-centered cubic structure, and the basic crystal axis <100> of the unit cell of the face-centered cubic structure is 2 in the thickness direction of the metal foil and a certain direction existing in the foil surface. With respect to two orthogonal axes, the preferential orientation regions having an azimuth difference of 10 ° or less occupy 50% or more in area ratio, and the normal direction with respect to the cross section P of the wiring cut from the ridge line in the bent portion in the thickness direction of the metal foil A flexible circuit board, wherein the breaking elongation of the metal foil is 3.5% or more and 20% or less. - 金属箔が、純度99.999質量%以上の銅箔からなる請求項1に記載の可撓性回路基板。 The flexible circuit board according to claim 1, wherein the metal foil is made of copper foil having a purity of 99.999 mass% or more.
- 金属箔が銅箔であり、箔面法線方向から見たときの結晶粒径が25μm以上である請求項1又は2に記載の可撓性回路基板。 The flexible circuit board according to claim 1 or 2, wherein the metal foil is a copper foil, and the crystal grain size when viewed from the normal direction of the foil surface is 25 µm or more.
- 金属箔の厚みが5μm以上、18μm以下である請求項1~3のいずれかに記載の可撓性回路基板。 4. The flexible circuit board according to claim 1, wherein the thickness of the metal foil is 5 μm or more and 18 μm or less.
- 配線の断面Pが、[001]を晶帯軸として(100)から(110)への回転方向における(20 1 0)から(1 20 0)の範囲に含まれたいずれかの面に主方位をなす請求項1~4のいずれかに記載の可撓性回路基板。 The cross section P of the wiring has a main orientation on any surface included in the range of (20 1 0) to (1 20 0) in the rotation direction from (100) to (110) with [001] as the zone axis The flexible circuit board according to any one of claims 1 to 4, wherein:
- 配線の断面Pが、(100)標準投影図のステレオ三角形において(20 1 0)を表す点と(110)を表す点とで結ばれた線分上にあるいずれかの面である請求項5に記載の可撓性回路基板。 6. The cross section P of the wiring is any surface on a line segment connected by a point representing (20 1 0) and a point representing (110) in a stereo triangle of (100) standard projection. A flexible circuit board according to claim 1.
- 屈曲部における稜線に対して直交する方向に沿って配線が形成されている請求項1~6のいずれかに記載の可撓性回路基板。 The flexible circuit board according to any one of claims 1 to 6, wherein a wiring is formed along a direction orthogonal to the ridge line in the bent portion.
- 樹脂層がポリイミドからなる請求項1~7のいずれかに記載の可撓性回路基板。 8. The flexible circuit board according to claim 1, wherein the resin layer is made of polyimide.
- 摺動屈曲、折り曲げ屈曲、ヒンジ屈曲及びスライド屈曲からなる群から選ばれたいずれかの繰り返し動作を伴う屈曲部が形成されるように使用される請求項1~8のいずれかに記載の可撓性回路基板。 The flexibility according to any one of claims 1 to 8, which is used so as to form a bent portion with any repetitive motion selected from the group consisting of sliding bending, bending bending, hinge bending, and sliding bending. Circuit board.
- 請求項1~9のいずれかに記載の可撓性回路基板を搭載した電子機器。 An electronic device on which the flexible circuit board according to any one of claims 1 to 9 is mounted.
- 樹脂層と金属箔から形成された配線とを備え、配線の少なくとも一箇所に屈曲部を有して使用される可撓性回路基板の屈曲部構造であって、
金属箔は、面心立方構造を有する金属からなると共に、面心立方構造の単位格子の基本結晶軸<100>が、金属箔の厚さ方向と箔面内に存在するある一方向との2つの直交軸に対して、それぞれ方位差10°以内の優先配向領域が面積率で50%以上を占め、かつ、屈曲部における稜線から金属箔の厚み方向に切った配線の断面Pに対する法線方向の金属箔の破断伸びが3.5%以上、20%以下であることを特徴とする可撓性回路基板の屈曲部構造。 A flexible circuit board bent portion structure comprising a resin layer and a wiring formed from a metal foil, and having a bent portion in at least one portion of the wiring;
The metal foil is made of a metal having a face-centered cubic structure, and the basic crystal axis <100> of the unit cell of the face-centered cubic structure is 2 in the thickness direction of the metal foil and a certain direction existing in the foil surface. The normal orientation direction with respect to the cross section P of the wiring cut in the thickness direction of the metal foil from the ridgeline in the bent portion with respect to the two orthogonal axes, the preferential orientation region having an azimuth difference of 10 ° or less occupies 50% or more in area ratio Bending part structure of flexible circuit board, wherein elongation at break of metal foil is 3.5% or more and 20% or less.
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JP2013207145A (en) * | 2012-03-29 | 2013-10-07 | Jx Nippon Mining & Metals Corp | Copper foil, copper-clad laminate, flexible wiring board, and three-dimensional molding |
CN103358618A (en) * | 2012-03-29 | 2013-10-23 | Jx日矿日石金属株式会社 | Copper foil, copper plated film stacking body, flexible distributing board and stereoscopic forming body |
CN103358618B (en) * | 2012-03-29 | 2015-04-22 | Jx日矿日石金属株式会社 | Copper foil, copper plated film stacking body, flexible distributing board and stereoscopic forming body |
JP2013247017A (en) * | 2012-05-28 | 2013-12-09 | Jx Nippon Mining & Metals Corp | Rolled copper foil for secondary battery negative electrode collector, negative electrode material for lithium ion secondary battery including the same, and lithium ion secondary battery |
KR20140042684A (en) * | 2012-09-28 | 2014-04-07 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Flexible copper-clad laminate |
KR102045089B1 (en) * | 2012-09-28 | 2019-11-14 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Flexible copper-clad laminate |
KR20160038827A (en) * | 2014-09-30 | 2016-04-07 | 신닛테츠 수미킨 가가쿠 가부시키가이샤 | Flexible printed circuit board and electronic device |
JP2016072405A (en) * | 2014-09-30 | 2016-05-09 | 新日鉄住金化学株式会社 | Flexible circuit board, method of use thereof and electronic apparatus |
TWI660649B (en) * | 2014-09-30 | 2019-05-21 | 日商日鐵化學材料股份有限公司 | Flexible circuit board and electronic equipment |
KR102404294B1 (en) * | 2014-09-30 | 2022-05-31 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Flexible printed circuit board and electronic device |
JP2019083321A (en) * | 2018-12-26 | 2019-05-30 | 日鉄ケミカル&マテリアル株式会社 | Flexible circuit board, method of using the same, and electronic device |
WO2024014169A1 (en) * | 2022-07-14 | 2024-01-18 | Jx金属株式会社 | Copper foil, and copper-clad laminate and flexible printed wiring board each using same |
Also Published As
Publication number | Publication date |
---|---|
KR101690491B1 (en) | 2016-12-28 |
CN102782174B (en) | 2015-11-25 |
JPWO2011078259A1 (en) | 2013-05-09 |
CN102782174A (en) | 2012-11-14 |
KR20120108032A (en) | 2012-10-04 |
JP5732406B2 (en) | 2015-06-10 |
TWI571183B (en) | 2017-02-11 |
TW201146101A (en) | 2011-12-16 |
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