WO2016093349A1 - 配向銅板、銅張積層板、可撓性回路基板、及び電子機器 - Google Patents
配向銅板、銅張積層板、可撓性回路基板、及び電子機器 Download PDFInfo
- Publication number
- WO2016093349A1 WO2016093349A1 PCT/JP2015/084822 JP2015084822W WO2016093349A1 WO 2016093349 A1 WO2016093349 A1 WO 2016093349A1 JP 2015084822 W JP2015084822 W JP 2015084822W WO 2016093349 A1 WO2016093349 A1 WO 2016093349A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper
- copper plate
- mass
- less
- oriented
- Prior art date
Links
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
-
- 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
- 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
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/02—Single bars, rods, wires, or strips
-
- 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
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
-
- 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
-
- 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
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
-
- 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
- H05K2201/0302—Properties and characteristics in general
- H05K2201/0317—Thin film conductor layer; Thin film passive component
-
- 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 an oriented copper plate having high strength and high durability against fatigue such as thermal cycling and bending, a copper-clad laminate using the same, a flexible circuit board, and an electronic device on which the circuit board is mounted.
- an oriented copper plate capable of obtaining a flexible circuit board having durability against bending and excellent flexibility, a copper-clad laminate and a flexible circuit board using the same, and a circuit
- the present invention relates to an electronic device mounted with a substrate.
- texture is a recrystallization stable orientation of copper with relatively high purity, and is an orientation that is relatively easy to develop in the texture.
- RD rolling
- ND plate thickness
- TD TD
- Patent Documents 1 and 2 copper foils for flexible circuit boards
- Patent Documents 3 and 4 rectangular copper wires for connecting solar cells
- Patent Document 4 The reason why the cubic texture is formed in the material is to improve the fatigue characteristics (Patent Documents 1 and 2), and to soften by Young's modulus (Patent Document 3) and yield strength reduction (Patent Document 4).
- the metal material constituting such a flexible circuit board copper foil or solar cell connecting flat copper wire is generally subjected to repeated strain.
- the distortion is caused by bending at a hinge part, a slide part, or a bent part of a mobile phone.
- the thermal strain is caused by the difference in thermal expansion coefficient between silicon and copper.
- Patent Document 2 utilizes the fact that the cubic texture is excellent in enhancing the fatigue characteristics of copper foil when a high bending with a small radius of curvature is used, which is incorporated into thin devices such as mobile phones. Furthermore, by utilizing the anisotropy of the mechanical properties, a geometric device was devised to match the direction of the stress with the direction of high elongation at break.
- the cubic texture is generally manufactured by utilizing the recrystallization stable orientation of copper having a relatively high purity. Therefore, the number of dislocations and crystal grain boundaries that essentially have the effect of increasing the strength is small.
- the stable orientation of recrystallization will change due to changes in stacking fault energy, or grain growth will be hindered by precipitates. For example, the formation of a cubic texture is hindered. Therefore, in the copper material having a high cubic texture, the kind and concentration of the alloy element to be added are limited. In particular, no copper alloy system has been found in which the cubic orientation is highly developed at a concentration high enough to cause precipitation strengthening.
- an industrially produced copper material with a developed cubic texture is produced by rolling and recrystallization, and therefore has one of 100 main orientations in the rolling direction. Therefore, the flat direction copper wire for solar cell connection has a longitudinal direction of ⁇ 100>, and unless special measures are taken, the flexible circuit board also has a stress direction of ⁇ 100>.
- the elongation at break is the smallest among the possible orientations. Therefore, although a material having a highly developed cubic texture has excellent fatigue characteristics, the most likely orientation (ie, ⁇ 100>) is an unfavorable orientation in terms of fatigue characteristics. Therefore, for a copper material with a highly developed cubic texture, there is a demand for improvement in strength when stress is applied in the ⁇ 100> direction and improvement in elongation at break.
- the object of the present invention is to newly establish an oriented copper plate having a higher strength and higher elongation at break than conventional materials having the same texture, while the cube texture is highly developed. It is to be.
- Another object of the present invention is to newly establish a flexible circuit board having excellent bending and bending properties using this oriented copper plate.
- the present inventors have achieved the same degree of cubic structure by providing both material structure characteristics of both advanced cubic texture and Cr precipitation.
- the present invention has been completed by finding that the strength is higher than that of a conventional copper material showing accumulation of texture and the elongation at break is higher. That is, this invention makes it a summary to include the following structures. (1) It is a copper plate containing 0.03% by mass or more and 1.0% by mass or less of Cr, and the balance is made of copper and inevitable impurities, and the thickness direction of the copper plate and the specific direction in the copper plate surface are each made of copper.
- the ⁇ 100> preferential orientation region satisfying the crystal axis ⁇ 100> and satisfying an orientation difference of 15 ° or less has a main orientation of ⁇ 100> such that the area ratio occupies 60.0% or more, and the equivalent circle diameter
- Mn 0.4 mass% or less
- Al 0.4 mass% or less
- Zr 0.2 mass% or less
- rare earth element 0.4 mass% or less
- the oriented copper plate according to (1) or (2) further comprising one or two of P: less than 0.01% by mass and Zn: less than 0.1% by mass.
- One or more selected from Ag, Sn, Pd, Ni, Fe, B, Si, Ca, V, Co, Ga, Ge, Sr, Nb, Mo, Rh, Ba, W and Pt The oriented copper plate according to any one of (1) to (3), further containing less than 0.03% by mass in total.
- the bending portion is a bending portion that includes one or two or more repetitive motions selected from helical folding, sliding bending, bending bending, hinge bending, and sliding bending.
- Flexible circuit board (10) An electronic device on which the circuit board according to (8) or (9) is mounted.
- the strength is higher than that of a conventional copper material having the same degree of cube texture accumulation,
- an oriented copper plate having high elongation at break and excellent bending and bending properties can be obtained.
- Such an oriented copper plate can be used in a wide range of wiring materials, circuit board materials, and the like.
- FIG. 1A is a positive electrode dot diagram obtained as a result of EBSD analysis of the copper foil of Sample 1 in Example 1.
- FIG. 1B is a dot diagram of the positive electrode obtained as a result of EBSD analysis of the copper foil of Sample 2 in Example 1.
- 1C is a positive electrode dot diagram obtained as a result of EBSD analysis of the copper foil of Sample 5 in Example 1.
- FIG. FIG. 1D is a positive electrode dot diagram obtained as a result of EBSD analysis of the copper foil of Sample 6 in Example 1.
- FIG. 2 is a stress-strain curve obtained as a result of the tensile test performed on the sample shown in FIG.
- FIG. 3 is a bright-field image of a transmission electron microscope of Sample 6 produced in Example 1.
- FIG. 4 is an image obtained by binarizing the contrast between the Cr precipitate and the matrix and numbering the bright field image of FIG. 3.
- the oriented copper plate of the present invention is a material in which Cr precipitates are dispersed and precipitated in a copper plate on which a highly cubic texture is formed. Due to the precipitation strengthening effect of the Cr precipitates, the copper material has higher strength and higher elongation at break than conventional copper materials having the same degree of cube texture accumulation, and further, an advanced cube texture is formed. Therefore, it is excellent in bending and bending properties and can be used in a wide range of materials such as wiring materials and circuit board materials.
- the degree of integration of the cubic texture of the oriented copper plate of the present invention is such that the preferred orientation region is within an orientation difference of 15 ° with respect to two orthogonal axes of the thickness direction of the oriented copper plate and the specific direction existing in the oriented copper plate surface. Occupies 60.0% or more in area ratio.
- the oriented copper plate of the present invention has a main orientation of ⁇ 100> in the thickness direction of the copper plate and ⁇ 100> in the plane of the copper plate. It can be said that it has That is, the copper plate of the present invention has a ⁇ 100> orientation in the thickness direction of the plate, and a texture called a highly oriented cube orientation having a ⁇ 100> orientation perpendicular to the plate surface as a main orientation. Must be present.
- the degree of integration of the cube orientation is better, and the area of the preferentially oriented region forming the cube texture can be 100%.
- the thickness direction of the oriented copper plate and the inside of the oriented copper plate is preferably 60.0% or more in area ratio, and preferably occupies more than 70.0%. Desirably, more desirably it is more than 80.0%.
- the preferentially oriented region has an area ratio of more than 70.0%, the orientation of the remaining region is often an orientation close to the twin orientation with respect to the cube orientation, and is more mechanical than the crystal grains of other orientations.
- the adverse effect on properties is relatively small. A small amount of copper oxide may be deposited.
- the copper plate is made of a rolled material.
- the specific direction existing in the plane of the oriented copper plate is a direction orthogonal to the rolling direction in the plane of the plate and the rolling direction in the final cold rolling.
- the thickness direction of the oriented copper plate is a direction orthogonal to the rolling surface.
- the cutting method of the plate is arbitrary depending on the product shape, material yield, etc., one side of the plate does not have to be positioned in the rolling direction, and ⁇ 100> main directions in two orthogonal directions in the plane. As long as it has.
- the oriented copper plate does not have to be completely plate-like, for example, it may be a thin and long tape-like wire by slit processing, and the plate-like plane is partially etched, A circuit-like complicated form may be used.
- the thickness of the oriented copper plate is not particularly limited, and includes a plate material having a certain thickness to a very thin material such as a copper foil. However, in order to obtain an advanced cubic texture, it is substantially 3 mm or less. It is necessary to be a copper plate.
- the thickness can be appropriately set depending on the use of the copper plate. For example, when used for wiring of a flexible circuit board having a plastic substrate described later, a typical thickness is 5 ⁇ m or more and 18 ⁇ m or less.
- a typical thickness is preferably 100 ⁇ m or more and 500 ⁇ m or less.
- a typical thickness is preferably 100 ⁇ m or more and 300 ⁇ m or less. Note that the lower limit of the thickness is substantially 3 ⁇ m from the limits of rolling and subsequent process handling.
- the structure of the copper plate of the present invention can be measured and evaluated by an EBSD (Electron Backscattered Diffraction) method that is widely used as a crystal orientation analysis method.
- the EBSD method is attached to a scanning electron microscope (SEM: Scanning Electron Microscope), irradiates an electron beam locally on the surface of the sample, analyzes the diffraction pattern generated by the backscatter diffraction, and analyzes the point. This is a method of orientation.
- SEM Scanning Electron Microscope
- the area ratio of the ⁇ 100> preferred orientation region in which the predetermined crystal axis of the unit cell is within a certain misorientation by taking the measurement points and the measurement area sufficiently large so as to represent the average structure of the copper plate, It can be determined from the ratio of the points where the predetermined crystal axis of the lattice is below a certain misorientation to the total number of points.
- the azimuth information of the EBSD method is three-dimensional, the azimuth information of the copper plate can be evaluated on a polished surface having an arbitrary cross section.
- it is an oriented copper plate.
- the area of the polished surface is limited in the C cross section orthogonal to the plate surface.
- an area having a size of 800 ⁇ m ⁇ 1600 ⁇ m or more is selected and evaluated at intervals of 4 ⁇ m or less in the area.
- the oriented copper plate of the present invention is a copper plate containing Cr of 0.03% by mass to 1.0% by mass with the balance being copper and inevitable impurities and having the above-described texture, and having a highly cubic texture. It has a structure in which Cr precipitates of 4 nm or more and 52 nm or less are deposited at a density of 300 pieces / ⁇ m 3 or more and 12000 pieces / ⁇ m 3 or less.
- size of a precipitate here is the equivalent circle diameter converted from the area of the precipitate when it projects from one direction of a copper plate.
- the crystal structure is almost defined as a highly oriented cubic texture
- the crystal grains forming the cubic texture are coarse, and a technique such as increasing the strength by refining the crystal grains is employed. I can't. Therefore, it is conceivable to adopt a technique of alloying such as solid solution strengthening or precipitation strengthening, but if an alloying element is added to a concentration at which a solid solution strengthening or precipitation strengthening action can be obtained, a high cubic texture cannot be formed. This is because the stable orientation of recrystallization changes due to a change in stacking fault energy, or grain growth is hindered by precipitates. Furthermore, although the main use of copper is a conductive material, increasing the alloying element content increases electrical resistance and makes it unsuitable for that use.
- Cr exhibits a precipitation strengthening effect even at a comparatively low concentration of 0.03% by mass or more, and can precipitate and strengthen a copper plate having a high cubic texture.
- Many alloy elements that precipitate and strengthen copper are known, but only Cr was found as an alloy element compatible with a high degree of cubic texture.
- the Cr concentration is 1.0 mass% or less, preferably less than 0.30 mass%.
- the Cr concentration is less than 0.30% by mass, it is possible to form an advanced texture in which the ⁇ 100> preferred orientation region occupies more than 70.0% in terms of area ratio in the state where Cr is precipitated, Therefore, it is possible to realize a copper-clad laminate and a flexible circuit board that are highly resistant to fatigue such as thermal cycle and bending, and an electronic device on which the circuit board is mounted.
- the main form of the flexible circuit board of the present invention is a composite of copper and resin, particularly polyimide.
- the process of forming the composite in the step of continuously forming or bonding polyimide on the copper foil, it is easier to handle the copper foil if the copper foil before the step has strength. Therefore, after precipitating Cr, cold work is performed, the copper foil is drawn out in a state where precipitation strengthening and work hardening are performed, and recrystallization is performed by heat of imidization treatment or hot press treatment of obtaining a laminate with polyimide. It is desirable to obtain a highly oriented cubic texture. Since this step is usually carried out at a temperature of 400 ° C. or less for several minutes, it is necessary to advance recrystallization with this thermal history. Since the recrystallization temperature rises as the Cr concentration increases, it is desirable in terms of production efficiency that the Cr content is less than 0.20 mass%, particularly for flexible circuit boards.
- the density of Cr precipitates in the copper plate of the present invention is 300 / ⁇ m 3 or more and 12000 / ⁇ m 3 or less, but more desirably in the range of 2000 / ⁇ m 3 or more and 12000 / ⁇ m 3 or less.
- size of the Cr precipitate of the copper plate of this invention is 4 nm or more and 52 nm or less, the deposit smaller than 4 nm and exceeding 52 nm may exist statistically. However, most of the precipitates fall within this range, particularly 8 nm or more and 40 nm or less.
- the effect of the precipitate in the particle size range of the present invention preventing the movement of dislocations contributes most to precipitation strengthening.
- the inevitable impurities are elements brought in from the raw material copper and raw material Cr as impurities, crucibles, and environmental gases.
- inevitable impurities that are likely to be contained in electrolytic copper, oxygen-free copper, tough pitch copper, and scrap copper, which are likely to be used as the raw material of the present invention, will be described.
- elements such as Mn, Al, Ti, Zr, and rare earth elements may be contained up to a certain concentration because they have a relatively small effect of inhibiting the formation of a cubic texture.
- Rare earth elements, Mn, and Al are each acceptable up to 0.4 mass%, and Ti and Zr are each acceptable up to 0.2 mass%.
- the solid solution strengthening action of these elements is smaller than the precipitation strengthening action of Cr, a small amount of rare earth elements, Al, Ti and the like are combined with inevitable impurity elements such as O and S to inhibit the formation of the cube texture. The action may be suppressed.
- Mn International annealed Copper Standard
- IACS International annealed Copper Standard
- the concentrations of Ag, Sn, Pd, Ni, Fe, B, Si, Ca, V, Co, Ga, Ge, Sr, Nb, Mo, Rh, Ba, W, and Pt can vary depending on the raw materials used. These elements are preferably less than 0.03% by mass in total. Among these, Ni and Fe have a strong effect of increasing the electric resistance value, and in order to satisfy IACS (International Copper Standard) 95% or more, the total content must be 0.025% by mass or less. .
- O oxygen
- O oxygen
- P has a deoxidizing action and improves the strength, but inhibits the formation of a cubic texture.
- regulated of this invention it is necessary to be less than 0.01 mass%.
- Zn has a small effect of increasing electrical resistance, but, like P, inhibits the formation of a cubic texture.
- regulated of this invention it needs to be less than 0.1 mass%. That is, in the copper plate in which the prescribed Cr of the present invention is deposited, when P is contained in an amount of 0.01% by mass or more, the copper plate in which the ⁇ 100> preferential orientation region occupies 60.0% or more in area ratio is obtained. I can't get it.
- the remaining copper concentration excluding Cr is desirably 98% by mass or more.
- the upper limit is 99.97% by mass, assuming that no impurities other than 0.03% by mass of Cr are included.
- the size and density of the Cr precipitates described above can be examined using a transmission electron microscope (TEM).
- TEM transmission electron microscope
- the projected image of the precipitate can be observed as a contrast, unlike the cross-sectional observation, and the number within a certain volume can be determined. It can be measured. Further, a projected area can be obtained from this contrast by image analysis, and the equivalent circle diameter of the precipitate converted from the area can be calculated.
- the oriented copper plate of the present invention has a highly oriented ⁇ 100 ⁇ ⁇ 001> texture (cubic texture), it is resistant to metal fatigue, and fine Cr is precipitated inside. Therefore, it is characterized by high strength.
- the material structure affects the fatigue characteristics of the material.
- the structure is fine, the strength and elongation at break are improved, while the crystal grain boundary is a dislocation accumulation surface.
- the mechanical anisotropy of each crystal grain depending on the crystal orientation due to the mechanical anisotropy of each crystal grain depending on the crystal orientation, local deformation occurs when mechanical or thermal stress such as bending or tension is applied, thereby causing microscopic stress concentration. When it happens, it deteriorates fatigue properties. Therefore, it is desirable that there is no grain boundary in the copper plate, it is desirable that it is highly oriented and the three basic crystal axes of copper are aligned, and the cube texture of the present invention is formed for that purpose.
- the cube texture of the present invention is industrially a recrystallized texture using rolling and recrystallization, and thus it is difficult to impart strength, but by the precipitation strengthening of Cr, an advanced cube texture. The strength is increased while maintaining the above.
- the oriented copper plate of the present invention is a material further resistant to metal fatigue and is a copper material having a relatively low alloy concentration, for example, a wiring material for solar cells (interconnector for solar cells), plastic It is useful as a copper clad laminate material using ceramics and ceramics as a substrate.
- a representative member manufactured from a copper-clad laminated material with a plastic substrate is a flexible circuit board, and when it is used in a bent form utilizing its flexibility There are many.
- the flexible circuit board is a form in which a copper plate and a plastic of an insulating layer are joined and a circuit pattern is formed on the copper plate.
- a copper-clad laminate in which an insulating layer is formed on the surface of the copper plate according to the present invention can be used, and among these, a typical copper plate has a thickness of 5 ⁇ m or more, 18 ⁇ m or less, The thickness of the insulating layer is 5 ⁇ m or more and 75 ⁇ m or less.
- the thickness of the insulating layer can be appropriately set according to the use, shape, etc. of the flexible circuit board, but is preferably in the above range from the viewpoint of flexibility, and is in the range of 9 ⁇ m or more and 50 ⁇ m or less.
- the range is 10 ⁇ m or more and 30 ⁇ m or less. If the thickness of the insulating 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 will increase when mounted on a small device as a flexible circuit board. There is a possibility that it will be too much, and a decrease in flexibility may be considered.
- the insulating layer of the copper-clad laminate for a flexible circuit board in the present invention is preferably formed using a resin, and the type of resin forming the insulating layer is not particularly limited.
- a resin for example, polyimide, polyamide, Examples thereof include polyester, liquid crystal polymer, polyphenylene sulfide, polyether ether ketone, and the like.
- polyimide and liquid crystal polymer are preferred because they exhibit good flexibility when used as a circuit board and are excellent in heat resistance.
- a cover material as shown below may be formed on a wiring formed from a copper plate such as a copper foil.
- a cover material it is preferable to design the structure of the cover material and the resin forming the insulating layer in consideration of the balance of stress applied to the wiring. According to the knowledge of the present inventors, for example, when the polyimide resin forming the insulating layer has a tensile modulus of 4 to 6 GPa at 25 ° C.
- the cover material to be used is A structure having two layers of 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, and the tensile elastic modulus of the entire adhesive layer and the polyimide layer being 2 to 4 GPa Is desirable.
- the polyimide forming the insulating layer has a tensile modulus of 6 to 8 GPa at 25 ° C. and a thickness in the range of 12 to 15 ⁇ m
- the cover material to be used is made of a thermosetting resin having a thickness of 8 to 17 ⁇ m. It is desirable that the adhesive layer and the polyimide layer having a thickness of 7 to 13 ⁇ m have two layers, and the tensile elastic modulus of the adhesive layer and the entire polyimide layer is 2 to 4 GPa.
- the ceramic forming the ceramic substrate is typically alumina, alumina zirconia, aluminum nitride, or silicon nitride, and the thickness is 0.2 mm or more and 0.5 mm. It is often the following.
- the thickness of the copper plate is often the same, and the copper plate is bonded to both sides of the ceramic substrate, a circuit pattern is formed on one side, and the other side is used as a solid surface for heat dissipation.
- the joining portion may be joined directly or a metal braze may be formed.
- the copper alloy containing 0.03% by mass or more and 1.0% by mass or less of Cr is cold worked with a reduction in area of 90% or more, and is 400 ° C or more and 700 ° C
- the melting temperature is generally from 1100 ° C. to 1200 ° C.
- Cr may precipitate and grow to a size larger than the size specified in the present invention. In this case, it is necessary to perform a solution treatment.
- the solution treatment temperature is 800 ° C. or higher, preferably 950 ° C. or higher and 1080 ° C. or lower.
- the Cr precipitation process may be at any stage in the process. It may be after melting, in the middle of rolling, or after the final thickness has been reached.
- the temperature required for Cr deposition is 400 ° C. or higher and 700 ° C. or lower. If the temperature is too low, a sufficient amount of precipitates will not be obtained within the time that is established industrially, and even if the temperature is too high, the solid solubility limit will increase, so the amount of precipitates will decrease, and the precipitates will also become coarse and dislocation motion. The pinning effect which inhibits is reduced.
- the aging time for precipitation depends on the temperature, but 30 minutes or more is necessary.
- the precipitation treatment may also serve as an intermediate annealing, and may also serve as a final annealing heat treatment for forming a cubic texture.
- the manufacturing process of the oriented copper plate is not limited, but can be obtained by special rolling and heat treatment under controlled conditions. For example, after performing rolling such as different peripheral speed rolling and cross rolling and introducing shear strain in various directions, primary recrystallization is performed, and then cold rolling of 90% or more is performed under the condition that dynamic recrystallization does not occur. And a plate having a uniform lamellar structure parallel to the rolling direction and having a target thickness can be obtained, and then heated and recrystallized. In this case, the specific direction in the copper plate surface coincides with the rolling direction. As the final plate thickness increases, it becomes difficult to increase the degree of accumulation of the cubic texture, so it is necessary to select process conditions and strictly control them.
- the recrystallization temperature depends on the concentration of Cr and other impurity elements, but must be in the temperature range of 200 ° C. or higher and 700 ° C. or lower.
- the recrystallization heat treatment time for forming the cubic texture does not require as much time as the aging heat treatment for precipitation, but may also serve as the aging heat treatment.
- a method of joining the ceramic substrate and the copper plate is to sinter in a reducing atmosphere around 1500 ° C. with a Mo—Mn powder sandwiched between the ceramic and copper plates.
- an activated metal method in which a metal brazing material such as an Ag-Cu alloy having a melting point lower than that of copper containing an activated metal such as Ti or Zr is sandwiched between a ceramic substrate and a copper plate, and is subjected to liquid phase bonding.
- a direct bonding method in which the surfaces of the copper plates face each other and are brought into contact with each other to form a Cu—Cu 2 O eutectic at the interface at a temperature of 1050 ° C. or higher and then cooled to be bonded.
- the process temperature exceeds 700 ° C., the aging precipitation heat treatment of the copper plate needs to be performed after joining.
- Examples of the method for producing a copper-clad laminate using plastic as a substrate include a casting method, a hot press method, and a laminating method.
- the temperature at which the insulating layer made of resin is formed is at most about 400 ° C., and it is preferable that the copper plate is subjected to aging heat treatment for Cr precipitation before joining with the resin.
- the recrystallization heat treatment for forming the cubic texture may be performed after the copper clad laminate is formed. Since the copper plate used for the copper-clad laminate using plastic as a substrate is in a thin foil state, it is desirable that the copper plate is hard from the viewpoint of handling when forming the insulating layer.
- the aging heat treatment for Cr precipitation may be performed before the cold working of copper, and the heat treatment for forming the cubic texture may utilize the temperature at which the insulating layer is formed.
- the Cr concentration is preferably less than 0.20 mass%.
- a copper plate may be thermally laminated by applying or interposing a thermoplastic polyimide on a polyimide film (so-called laminating method).
- polyimide films used in the laminating method include “Kapton (registered trademark)” (Toray DuPont Co., Ltd.), “Apical” (Kanebuchi Chemical Industry Co., Ltd.), and “Upilex (registered trademark)” (Ube Industries Ltd.) Company).
- the polyimide film and the copper plate are thermocompression bonded, it is preferable to interpose a thermoplastic polyimide resin exhibiting thermoplasticity.
- the thermocompression bonding temperature is preferably 280 ° C. or higher and 400 ° C. or lower.
- a polyimide precursor solution (also referred to as a polyamic acid solution) is applied to a copper plate, and then dried and cured to form an insulating layer.
- the temperature of the heat treatment for imidizing the polyimide precursor solution to form an insulating layer made of a resin is preferably 280 ° C. or higher and 400 ° C. or lower.
- the insulating layer may be formed by laminating a plurality of resins. For example, two or more kinds of polyimides having different linear expansion coefficients may be laminated. From the viewpoint of ensuring the above, it is desirable that all of the insulating layer is substantially formed of polyimide without using an epoxy resin or the like as an adhesive.
- the tensile elastic modulus of the resin forming the insulating layer should be 4 to 10 GPa, preferably 5 to 8 GPa, including the case of consisting of a single polyimide and the case of consisting of a plurality of polyimides. It is good.
- the linear expansion coefficient of the resin forming the insulating layer is preferably in the range of 10 to 30 ppm / ° C.
- the linear expansion coefficient of the entire insulating 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.
- the linear expansion coefficient can be set within a range of 10 to 30 ppm / ° C. by adjusting the thickness ratio thereof.
- a preferred thickness ratio of the low linear expansion polyimide layer to the high linear expansion polyimide layer is in the range of 70:30 to 95: 5.
- the low linear expansion polyimide layer is a main resin layer of the insulating layer, and the high linear expansion polyimide layer is preferably provided so as to be in contact with the copper plate.
- 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 insulating layer of the copper-clad laminate is ceramic or plastic
- the flexible circuit board obtained from the copper-clad laminate in the present invention includes an insulating layer and a wiring formed from an oriented copper plate, 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 uses the copper plate according to the present invention, it has a bent portion structure excellent in bending durability. For this reason, the bending radius is set to 0.
- the flexible circuit board of the present invention is highly oriented and has a high strength copper plate, even for helix folds that are less bent but more severely fold as is done in smartphone mounting. Since it uses, even if a bending part is formed in at least one place of wiring so that it may orthogonally cross with respect to the specific orientation in a copper plate surface, it has the outstanding durability and reliability.
- the oriented copper plate of the present invention is highly oriented, contains a specified alloy component, and precipitates, so that metal fatigue hardly occurs and is excellent in stress and strain. It has durability.
- a flexible circuit board obtained by forming a copper-clad laminate using such an oriented copper plate and etching the copper foil by a known method to form a wiring has a repeated bending and curvature. It is strong enough to withstand bending with a small radius and has excellent flexibility. Therefore, there is no restriction on the design of the flexible circuit board such as considering the shape of the wiring in the bent portion.
- Example 1 First, in order to show the precipitation strengthening of Cr in the oriented copper plate of the present invention, the effect of the present invention was examined using a high-purity copper raw material while the influence of other components was small.
- the raw materials copper and Cr were materials having a purity of 99.9999% by mass or more and 99.99% or more, respectively. A predetermined amount of this was weighed, dissolved in a vacuum of 10 ⁇ 2 Pa or less using a high purity graphite crucible, and cast into a high purity graphite mold cooled through a water-cooled copper hearth. The size of the ingot was 30 mm ⁇ 55 mm ⁇ 12 mm. This was hot-rolled at 700 ° C. to produce a plate having a thickness of 1.5 mm. The number of hot rolling passes was 7, and the 30 mm length direction and the 55 mm direction were alternately crossed 90 °. A hot-rolled sheet having a thickness of 1.5 mm was subjected to intermediate annealing at 300 ° C.
- the copper plate material was cold-rolled to 0.4 mm, adjusted to a width of 40 mm by slitting, and then cold-rolled to a final plate thickness of 12 ⁇ m with a tension rolling mill.
- concentration of Cr was analyzed by ICP issue analysis.
- Samples 1 and 2 There are 12 types of copper foil samples prepared as described above, and the Cr concentration is 0% by mass (Samples 1 and 2), 0.019% by mass (Sample 3), 0.03% by mass (Sample 4), 0.1 mass% (sample 4 to sample 8), 0.19 mass% (sample 9), 0.29 mass% (sample 10), 1.0 mass% (sample 11), 1.1 mass% (sample) 12).
- the Cr concentration of Sample 3 to Sample 12 is an analytical value.
- Samples 1 and 2 are samples prepared by the same method without adding Cr. In this example, high-purity copper was used as the main element, and high-purity graphite was used for the crucible. Therefore, elements other than Cu and Cr were 0.0001% by mass or less, which is the detection limit.
- the texture of the oriented copper plate was obtained by performing orientation analysis using an EBSD device after performing mechanical and chemical polishing using colloidal silica on the rolling surface of each oriented copper plate.
- the equipment used was a FE-SEM (Ultra 55) manufactured by Tsuice, an EBSD apparatus manufactured by TSL, and software (OIM Analysis 5.2).
- the measurement area is an area of approximately 800 ⁇ m ⁇ 1600 ⁇ m, the measurement acceleration voltage is 20 kV, and the measurement step interval is 4 ⁇ m (in this embodiment, the measurement points are measured to form a triangular lattice, and the distance between the measurement points is 4 ⁇ m.
- the total number of measurement points is 92,631 points in the above area).
- the degree of integration of the cube texture of the present invention that is, the evaluation of the ⁇ 100> preferential orientation region is evaluated with respect to both the thickness direction of the copper plate and the rolling direction of the copper plate (specific direction in the copper plate surface).
- ⁇ 100> can be shown as a ratio of measurement points within 15 ° to the total measurement points. The number of measurements was obtained for two different fields of view for each individual cultivar, and was obtained by rounding the percentage to two decimal places. Note that these copper foil samples 1 to 11 have large crystal grains forming the ⁇ 100> preferential orientation region, and some of them exceed the measurement area described above, and the crystal grain size is similar to the sample 13 of Example 2 described later. It was difficult to prescribe.
- the average crystal grain size (area average diameter) excluding the ⁇ 3 grain boundary was calculated for the sample 12 having the smallest crystal grain among the copper foil samples 1 to 12 by the EBSD software, it was calculated to be 10 ⁇ m. Therefore, the average particle diameter of the copper foil samples 1 to 11 is larger than this value.
- Deposits on the copper plate were evaluated using Hitachi FE-SEM (HF-2000) after thinning each copper plate by electrolytic polishing.
- the thickness of the sample in the measurement region was measured at 0.15 ⁇ m and an acceleration voltage of 200 kV.
- the orientation of the copper matrix was confirmed by electron diffraction.
- the identification of the precipitate was determined by electron diffraction and composition analysis using an EDS analyzer.
- the size and density of the precipitates were obtained by subjecting the obtained images to image processing, calculating projected areas one by one for the contrast of the obtained precipitates, and calculating the equivalent circle diameter.
- a tensile test of the copper plate was performed by cutting a test piece having a length of 150 mm and a width of 10 mm in parallel with the rolling direction, with a distance between gauge points of 100 mm and a tensile speed of 10 mm / min.
- the results obtained as a result of the tensile test were expressed in a stress-strain diagram, and the 0.2% proof stress value, strength, and elongation at break were evaluated.
- the stress is a value obtained by dividing the load applied to the load cell by the cross-sectional area of the copper plate before the tensile test, and the strain is the percentage of the moving distance of the crosshead of the tensile tester with respect to the distance between the gauge points.
- 1A to 1D and FIG. 2 are a positive dot diagram and a stress-strain diagram evaluated by EBSD of a representative sample. 1A to 1D and FIG. 2, (1) shows the result of sample 1, (2) shows sample 2, (3) shows sample 5, and (4) shows the result of sample 6.
- FIG. 1A to FIG. 1D are positive electrode dot diagrams obtained as a result of EBSD analysis of the copper plates of Sample 1, Sample 2, Sample 5, and Sample 6.
- FIG. Each point in the positive electrode diagram represents a measurement point.
- ⁇ 100> is aligned in the rolling direction, the plate thickness direction, and the direction perpendicular to these, indicating that a strong recrystallized cubic texture is formed.
- the ratio of the ⁇ 100> preferential orientation region in which ⁇ 100> is within 15 ° with respect to both the foil rolling direction and the foil thickness direction calculated from the measurement points was approximately equal at around 99%.
- the ratio of the ⁇ 100> preferred orientation region was as shown in Table 1.
- FIG. 2 is a stress-strain curve obtained as a result of the tensile test of the samples shown in FIGS. 1A to 1D. Although the textures of the four samples were almost the same, the 0.2% proof stress value, strength, and elongation at break differed greatly. Further, the 0.2% proof stress value, strength, and elongation at break of the samples other than these are as shown in Table 1, and the smallest 0.2% proof stress value and strength among the samples do not contain Cr. Sample 2, which was a sample that was annealed at 390 ° C. for 1 hour. This is thought to be due to the fact that the concentration of defects such as dislocations and vacancies was lowered because recrystallization heat treatment was performed at a high temperature in addition to high purity copper.
- Sample 5 is a sample having a Cr concentration of 0.1% by mass and heat-treated at 390 ° C. for 1 hour, which is the same as Sample 2. From Sample 1 and Sample 2, the slope of the linear portion in the low strain region of the stress-strain curve is 0.2% proof stress and strength are high. This is a Cr precipitation strengthening action. Sample 6 has the same Cr concentration as Sample 5 and was heat-treated at 590 ° C. for 1 hour, although the annealing temperature is high and the concentration of defects such as dislocations and vacancies is low. The strength was further improved.
- FIG. 3 is a TEM bright field image of Sample 6, but a fine granular contrast was observed.
- FIG. 4 is an image obtained by binarizing the contrast and matrix of Cr precipitates in the bright field image 0.697 ⁇ m ⁇ 0.697 ⁇ m field of FIG. 3 and numbering the precipitates. The number of precipitates and individual areas were calculated, and the density and average particle size were calculated. Since the thickness of the TEM sample is 0.15 ⁇ m and is a transmission image, the number of Cr precipitates present in the region of 0.697 ⁇ 0.697 ⁇ 0.15 ⁇ m 3 is counted. As a result, it was found that the density of Cr precipitates in Sample 6 was 2287 / ⁇ m 3 . The size of the precipitate was distributed from 4 nm to 36 nm, and the average diameter was 9.8 nm.
- the Cr precipitates of other samples were evaluated by the same method.
- the difference in 0.2% proof stress, strength, and elongation at break between Sample 5 and Sample 6 is mainly the difference in the precipitation strengthening action of the Cr precipitates, and these values are smaller in Sample 5 than in Sample 6. This is because the Cr precipitation density was small.
- the density of Cr precipitates in each sample shown in Table 1 represents the number per unit volume of Cr precipitates having an equivalent circle diameter of 4 nm to 52 nm.
- the sample 12 has very high 0.2% yield strength, strength, and elongation at break, the area ratio of the ⁇ 100> preferentially oriented region is less than 60.0%, so that the fatigue characteristics are inferior.
- the concentration at which the cubic texture having a ⁇ 100> preferential orientation region of 60.0% or more and the precipitation strengthening of Cr are compatible is 1.0% by mass or less.
- region has 70.0% or more of cube texture and Cr precipitation strengthening is less than 0.30 mass%.
- the concentration at which the cubic texture having a ⁇ 100> preferential orientation region of 80.0% or more and Cr precipitation strengthening are both less than 0.20% by mass.
- the size of the Cr particles in the concentration range in which the cubic texture having a ⁇ 100> preferential orientation region of 60.0% or more and the precipitation strengthening of Cr are compatible was in the range of 4 to 52 nm. It was estimated that the precipitate density at which the cubic texture having a ⁇ 100> preferential orientation region of 60.0% or more and Cr precipitation strengthening are compatible was 12000 / ⁇ m 3 . Further, the lower limit of the Cr concentration showing the effective range of the present invention is determined to be 0.03% by mass or more, in which the 0.2% proof stress, strength and elongation at break are clearly improved as compared with the 6N copper foil.
- Example 2 Using the copper foil samples (orientated copper plates) of Sample 1 to Sample 12 prepared in Example 1, a flexible circuit board was prepared, and a bending (shell folding) test was performed. Moreover, the copper foil which heat-processed the commercially available electrolytic copper foil in nitrogen at 390 degreeC for 1 hour was added as a sample 13 for the comparison.
- the purity of the copper plate of the sample 13 is 99% or more, and as a result of conducting a tensile test under the same conditions as in the examples, the 0.2% yield strength, strength, and elongation at break were 115 MPa, 159 MPa, and 5.8%, respectively. It turned out to be relatively high.
- the measurement area is an area of 80 ⁇ m ⁇ 160 ⁇ m, and has a visual field of measurement acceleration voltage of 20 kV and measurement step interval of 0.4 ⁇ m.
- this sample was polycrystalline, and the crystal grain size (area average diameter) excluding the ⁇ 3 grain boundary was about 2 ⁇ m.
- the ratio of the ⁇ 100> preferred orientation region was calculated by the same method as in Example 1, and as a result, it was 6.8%.
- polyimide precursors constituting the insulating layer of the test flexible circuit board of this example.
- the polyamic acid solution a obtained in Synthesis Example 1 was applied to one side surface of the copper plates of Samples 1 to 12 prepared above and dried (after curing, a 2 ⁇ m-thick thermoplastic polyimide film was formed)
- the polyamic acid b obtained in Synthesis Example 2 is applied and dried (after curing, a low thermal expansion coefficient polyimide film having a thickness of 8 ⁇ m is formed), and the polyamic acid a is further applied and dried (after curing).
- the resin plate (polyimide) having a thickness of 12 ⁇ m and the copper plate layer having a thickness of 12 ⁇ m are cut out to have a rectangular size of 250 mm in length along the rolling direction of the copper plate and a width of 40 mm in a direction orthogonal to the rolling direction.
- a single-sided copper-clad laminate for testing was obtained.
- the tensile elastic modulus of the entire resin layer was 7.5 GPa.
- a predetermined mask is put on the copper plate layer side of the test single-sided copper clad laminate obtained above, and etching is performed using an iron chloride / copper chloride solution, and the line width is 100 ⁇ m and the length is 40 mm.
- a wiring pattern was formed so that the wiring direction of the 10 linear wires was parallel to the rolling direction and the space width was 100 ⁇ m, and a flexible circuit board for testing was obtained.
- all 10 rows of wiring are continuously connected via U-shaped portions, and electrode portions for measuring resistance values are provided at both ends. It was also confirmed that the structure of the copper plate and the precipitation state of Cr hardly change before and after the formation of polyimide and the circuit formation by etching.
- a helix fold test was performed using the test flexible circuit board obtained above.
- the direction of bending is the rolling (wiring) direction, that is, the crease is in the direction perpendicular to the rolling direction, and the wiring is bent so that the wiring is on the inside (that is, the bent portion is orthogonal to the ⁇ 100> orientation in the copper plate surface).
- the roller is moved in parallel with the folded line while controlling the gap to be 0.3 mm using the roller, and after all the 10 rows of wiring are folded, the folded portion is restored to the original position. It opened 180 degrees to the state, and it moved, the part which has a crease
- the flexible circuit board using Sample 12 having a ⁇ 100> preferential orientation region of 55.3% had the same folding life as that of the copper foil on which Cr was not deposited. It has been found that when the ⁇ 100> preferential orientation region is 60.0% or more, more preferably more than 70.0%, the bending resistance is increased in combination with the precipitation strengthening of Cr.
- Example 3 A test was conducted to determine whether the embodiment of the present invention was feasible when the Cr precipitation step and the recrystallization step were separated.
- the raw material copper scrap copper and Cr having a purity of 99.5% or more were used. These were weighed to a predetermined amount, dissolved in a vacuum of 10 ⁇ 2 Pa or less using a high-purity graphite crucible, and cast into a high-purity graphite mold cooled through a water-cooled copper hearth. The size of the ingot was 30 mm ⁇ 55 mm ⁇ 12 mm. This was hot-rolled at 700 ° C. to produce a plate having a thickness of 1 mm.
- the number of hot rolling passes was 7, and the 30 mm length direction and the 55 mm direction were alternately crossed 90 °.
- a 1 mm thick hot-rolled sheet was subjected to intermediate annealing in nitrogen at 650 ° C. for 2 hours.
- the copper plate material was cold-rolled to 0.4 mm, adjusted to a width of 40 mm by slitting, and then cold-rolled to a final plate thickness of 12 ⁇ m with a tension rolling mill.
- the Cr concentration was analyzed by ICP emission analysis. As impurities other than Cr, oxygen was detected by 0.005 mass%, Fe by 0.0016 mass%, Ag by 0.002 mass%, and Mn by 0.0015 mass%. P, Ni, Sn, and Zn were 0.001 mass% or less.
- the amount of Cr impurities in the copper foil (sample 14) prepared without adding Cr was 0.0011% by mass.
- Annealing uses a tubular furnace, inserts copper foil from the outside of the heating zone into the heating soaking zone of the furnace preheated to 400 ° C, and after 5 minutes, the copper foil is taken out of the heating zone and cooled without being oxidized. It was done by the operation. This condition simulates the thermal history of a continuous process for forming polyimide on a copper foil.
- the material structure and mechanical properties of the produced copper foil were examined.
- the material structure was evaluated using an EBSD attached to a field emission scanning electron microscope (FE-SEM), and the precipitates were evaluated using a field emission scanning transmission electron microscope (FE-TEM). Further, the mechanical properties were subjected to a tensile test.
- FE-SEM field emission scanning electron microscope
- FE-TEM field emission scanning transmission electron microscope
- the texture of the oriented copper plate was obtained by performing orientation analysis using an EBSD device after performing mechanical and chemical polishing using colloidal silica on the rolling surface of each oriented copper plate.
- the equipment used was a FE-SEM (Ultra 55) manufactured by Tsuice, an EBSD apparatus manufactured by TSL, and software (OIM Analysis 5.2).
- the measurement area is an area of approximately 800 ⁇ m ⁇ 1600 ⁇ m, the measurement acceleration voltage is 20 kV, and the measurement step interval is 4 ⁇ m (in this embodiment, the measurement points are measured to form a triangular lattice, and the distance between the measurement points is 4 ⁇ m.
- the total number of measurement points is 92,631 points in the above area).
- the degree of integration of the cube texture of the present invention that is, the evaluation of the ⁇ 100> preferential orientation region is evaluated with respect to both the thickness direction of the copper plate and the rolling direction of the copper plate (specific direction in the copper plate surface).
- ⁇ 100> can be shown as a ratio of measurement points within 15 ° to the total measurement points. The number of measurements was obtained for two different fields of view for each individual cultivar, and was obtained by rounding the percentage to two decimal places. All the prepared samples had large crystal grains forming the ⁇ 100> preferred orientation region, and some of the samples exceeded the measurement area.
- Deposits on the copper plate were evaluated using Hitachi FE-SEM (HF-2000) after thinning each copper plate by electrolytic polishing.
- the thickness of the sample in the measurement region was measured at 0.15 ⁇ m and an acceleration voltage of 200 kV.
- the orientation of the copper matrix was confirmed by electron diffraction.
- the identification of the precipitate was determined by electron diffraction and composition analysis using an EDS analyzer.
- the size and density of the precipitates were obtained by subjecting the obtained images to image processing, calculating projected areas one by one for the contrast of the obtained precipitates, and calculating the equivalent circle diameter.
- a tensile test of the copper plate was performed by cutting a test piece having a length of 150 mm and a width of 10 mm in parallel with the rolling direction, with a distance between gauge points of 100 mm and a tensile speed of 10 mm / min.
- the results obtained as a result of the tensile test were expressed in a stress-strain diagram, and the 0.2% proof stress value, strength, and elongation at break were evaluated.
- the stress is a value obtained by dividing the load applied to the load cell by the cross-sectional area of the copper plate before the tensile test, and the strain is the percentage of the moving distance of the crosshead of the tensile tester with respect to the distance between the gauge points.
- the folds of 90 ° and 60 ° in the length direction and the fold angle are set to an acute angle at the center in the length direction, and then the same as the tensile test
- Repeated bending compression tests were performed using the apparatus.
- the center of the creased portion was compressed in the direction of increasing the fold in the vertical direction through a parallel plate, and the distance between the plates was opened by 5 mm, and compression and release were repeated 10 times.
- the maximum load during compression was 10 N, and the time was 5 seconds.
- the maximum value of Cr addition for obtaining the ratio of the ⁇ 100> preferred orientation region of 60.0% or more was 0.38% by mass, and in order to obtain a value exceeding 70.0%, it was less than 0.30% by mass. It was.
- the reason why the Cr addition range in which the high cubic texture and Cr precipitation strengthening are compatible is small is that the thermal history of the final annealing process is small.
- the ratio of the ⁇ 100> preferred orientation region of the copper foil of Sample 14 to which Cr was not added was about 70%, which was small despite the low Cr content. This is because the Cr content is small and the crystal grains become coarse in the intermediate annealing at 650 ° C. for 2 hours, and the uniform working strain is not introduced in the subsequent cold working, so the cube orientation does not develop in the final annealing. This is because.
- the Cr concentration range is 0.38% by mass or less, preferably less than 0.30% by mass, more preferably less than 0.20% by mass, and the optimum value is the heat of the copper foil and polyimide lamination process. It is desirable to maximize the Cr content within a range in which crystal grains that change depending on the history and exhibit a ⁇ 100> preferred orientation can be developed.
- sample 16b was manufactured without performing intermediate annealing that also served as a precipitation treatment at 650 ° C. for the manufacturing method of sample 16 that had excellent results. Cracks after the bending test were not observed for the 60 ° direction bending test piece, but minute cracks were observed for the 90 ° direction bending test piece.
- the ratio of the ⁇ 100> preferred orientation region of this sample 16b was 70.9%, and the strength was 148 Pa.
- the reason why the strength decreased compared to Sample 16 was that the precipitation heat treatment was not performed, so the amount of Cr deposited decreased and the precipitation strengthening action was small.
- the reason why the area ratio of the ⁇ 100> preferred orientation region is reduced compared to Sample 16 is that the amount of solute Cr in copper is large, so that the recrystallization temperature is higher than that of Sample 16, and This is because recrystallization did not proceed sufficiently under the final annealing conditions.
- the bending fatigue property of the sample 16b was smaller than that of the sample 16, because the strength was small, and the ratio of the ⁇ 100> preferred orientation region was reduced, and the mechanical heterogeneity due to the orientation difference for each crystal grain. This is because microscopic stress concentration occurs and cracks are likely to occur.
- Example 4 A test was conducted to examine the influence of impurities other than Cr.
- oxygen-free copper having a purity of 99.96% or more and phosphorous deoxidized copper containing Cr, Zr, Zn, and 2.8% by weight of P were used. These were weighed to a predetermined amount, dissolved in a vacuum of 10 ⁇ 2 Pa or less using a high-purity graphite crucible, and cast into a high-purity graphite mold cooled through a water-cooled copper hearth. The size of the ingot was ⁇ 20 mm ⁇ 100 mm.
- the material structure was evaluated using an EBSD attached to a field emission scanning electron microscope (FE-SEM), and the deposits were evaluated using a field emission scanning transmission electron microscope (FE-TEM).
- FE-SEM field emission scanning electron microscope
- FE-TEM field emission scanning transmission electron microscope
- the texture of the oriented copper plate was obtained by performing orientation analysis using an EBSD device after performing mechanical and chemical polishing using colloidal silica on the rolling surface of each oriented copper plate.
- the equipment used was a FE-SEM (Ultra 55) manufactured by Tsuice, an EBSD apparatus manufactured by TSL, and software (OIM Analysis 5.2).
- the measurement area is an area of approximately 800 ⁇ m ⁇ 1600 ⁇ m, the measurement acceleration voltage is 20 kV, and the measurement step interval is 4 ⁇ m (in this embodiment, the measurement points are measured to form a triangular lattice, and the distance between the measurement points is 4 ⁇ m.
- the total number of measurement points is 92,631 points in the above area).
- the degree of integration of the cube texture of the present invention that is, the evaluation of the ⁇ 100> preferential orientation region is evaluated with respect to both the thickness direction of the copper plate and the rolling direction of the copper plate (specific direction in the copper plate surface).
- ⁇ 100> can be shown as a ratio of measurement points within 15 ° to the total measurement points. The number of measurements was obtained for two different fields of view for each individual cultivar, and was obtained by rounding the percentage to two decimal places.
- the 90 ° bend test was performed using a wiring device (manufactured by NPC: fully automatic wiring device (NTS-150-SM)) for manufacturing a string by wiring cells of a crystalline silicon solar cell.
- NPC fully automatic wiring device
- the tape-shaped plate material is fed out from the bobbin with a constant tension, cut into a length of 320 m, and then embossed using a stepped mold at the center thereof, in a direction perpendicular to the length and thickness direction, Two 90 ° bends, mountain fold and valley fold, can be applied, so that the plate material can have a gap of about 150 ⁇ m in the thickness direction at the center in the length direction, and two adjacent solar cells
- the light receiving surface and the back surface of the cell can be joined with a reduced distance between the cells.
- the ratio of the ⁇ 100> preferred orientation region was 80.0% or more, whereas the sample containing 0.01% by mass of P 22.
- Sample 24 containing 0.1% by mass of Zn a sample having a ⁇ 100> preferred orientation region of 60.0% or more was not obtained.
- the other components should be restricted.
- P is less than 0.01% by mass.
- Zn was found to be limited to less than 0.10% by mass in this example.
- An oriented copper plate having excellent bending and bending properties can be provided, and can be used in a wide range of wiring materials for solar cells, various circuit board materials including plastic or ceramic as an insulating layer, and the like.
- a flexible circuit for a device that forms a bent portion that is frequently bent with repeated operations such as sliding bending, bending bending, hinge bending, and sliding bending, or that requires a very small radius of curvature. It is suitable as a substrate. 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.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
- Laminated Bodies (AREA)
Abstract
Description
(1)Crを0.03質量%以上1.0質量%以下含有し、残部が銅及び不可避不純物からなる銅板であり、銅板の厚さ方向と銅板面内の特定方向とが、それぞれ銅の結晶軸<100>と方位差15°以内の条件を満たす<100>優先配向領域が面積率で60.0%以上を占めるように<100>の主方位を有しており、かつ円相当径で4nm以上52nm以下のCr析出物が300個/μm3以上、12000個/μm3以下であることを特徴とする配向銅板。
(2)Mn:0.4質量%以下、Al:0.4質量%以下、Ti:0.2質量%以下、Zr:0.2質量%以下、希土類元素:0.4質量%以下の1種または2種以上をさらに含有することを特徴とする(1)に記載の配向銅板。
(3)P:0.01質量%未満、Zn:0.1質量%未満の1種または2種をさらに含有することを特徴とする(1)または(2)に記載の配向銅板。
(4)Ag、Sn、Pd、Ni、Fe、B、Si、Ca,V、Co、Ga、Ge、Sr、Nb、Mo、Rh、Ba、WおよびPtから選ばれる1種または2種以上を合計で0.03質量%未満さらに含有することを特徴とする(1)から(3)のいずれかに記載の配向銅板。
(5)(1)から(4)のいずれかに記載の配向銅板表面に形成された絶縁層を有することを特徴とする銅張積層板。
(6)前記配向銅板の厚みが5μm以上18μm以下であり、かつ前記絶縁層が樹脂からなり、その厚みが5μm以上75μm以下である(5)に記載の銅張積層板。
(7)前記樹脂がポリイミドからなる(6)に記載の銅張積層板。
(8)(5)~(7)のいずれかに記載の銅張積層板の配向銅板に形成された所定の配線を有し、さらに、銅板面内の特定方向に対して直交するように、該配線の少なくとも一箇所に屈曲部を有することを特徴とする可撓性回路基板。
(9)前記屈曲部は、はぜ折り屈曲、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選ばれた1つまたは2つ以上の繰り返し動作を伴う屈曲部である(8)に記載の可撓性回路基板。
(10)(8)又は(9)に記載の回路基板を搭載した電子機器。
先ず、本発明の配向銅板におけるCrの析出強化を示すために、高純度の銅原料を使用して、他の成分の影響が小さい状態で本発明の効果を調べた。
実施例1で作製した試料1~試料12の銅箔試料(配向銅板)を使用して、可撓性回路基板を作製して、折り曲げ(はぜ折り)試験を実施した。また、比較のために市販の電解銅箔を窒素中で390℃で1時間熱処理した銅箔を試料13として加えた。
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15質量%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。
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15質量%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。
Cr析出工程と再結晶工程を分けた時に本発明の形態が実現可能かを調べる試験を行った。原料の銅は、純度99.5%以上のスクラップ銅とCrを使用した。これらを所定の量に秤量して、高純度黒鉛坩堝を使用して、10-2Pa以下の真空中で溶解し、水冷銅ハースを介して冷却された高純度黒鉛鋳型に鋳造した。インゴットの大きさは、30mm×55mm×12mmであった。これを700℃で熱間圧延して、厚さ1mmの板を作製した。熱間圧延のパス回数は7回で長さ30mmの方向と55mmの方向を交互に90°クロスさせて実施した。厚さ1mmの熱延板を窒素中で650℃で2時間のCr析出処理を兼ねた中間焼鈍を施した。この銅板材を0.4mmまで冷間圧延して、スリット加工で幅40mmに整えた後、張力圧延機で最終板厚である12μmまで冷間圧延を実施した。最終板厚まで圧延した配向銅板について、Crの濃度をICP発光分析にて分析を行った。Cr以外の不純物として、酸素が0.005質量%、Feが0.0016質量%、Agが0.002質量%、Mnが0.0015質量%検出された。P、Ni、Sn、Znは0.001質量%以下であった。Crを添加せずに作製した銅箔(試料14)のCrの不純物量は0.0011質量%であった。
結果をまとめたものを表3に示した。
Cr以外の不純物の影響を調べる試験を行った。原料は、純度99.96%以上の無酸素銅とCr、Zr、Zn、並びに2.8重量%のPを含むりん脱酸銅を使用した。これらを所定の量に秤量して、高純度黒鉛坩堝を使用して、10-2Pa以下の真空中で溶解し、水冷銅ハースを介して冷却された高純度黒鉛鋳型に鋳造した。インゴットの大きさは、Φ20mm×100mmであった。これをΦ6mmまでスエージ加工をして減面し、クロス圧延で幅出加工を行いながら幅18mm厚さ1.5mmのテープ状板材とした後、冷間圧延で厚さを0.2mmとした後、長さ方向にスリット加工を行い幅1.3mm、厚さ0.2mmのテープ状板材とした。この材料をステンレスボビンに巻いて、真空中で650℃×2時間の析出、再結晶焼鈍を行って最終試料とした。
結果をまとめたものを表4に示した。
Claims (10)
- Crを0.03質量%以上1.0質量%以下含有し、残部が銅及び不可避不純物からなる銅板であり、銅板の厚さ方向と銅板面内の特定方向とが、それぞれ銅の結晶軸<100>と方位差15°以内の条件を満たす<100>優先配向領域が面積率で60.0%以上を占めるように<100>の主方位を有しており、かつ円相当径で4nm以上52nm以下のCr析出物が300個/μm3以上、12000個/μm3以下であることを特徴とする配向銅板。
- Mn:0.4質量%以下、Al:0.4質量%以下、Ti:0.2質量%以下、Zr:0.2質量%以下、希土類元素:0.4質量%以下の1種または2種以上をさらに含有することを特徴とする請求項1に記載の配向銅板。
- P:0.01質量%未満、Zn:0.1質量%未満の1種または2種をさらに含有することを特徴とする請求項1または2に記載の配向銅板。
- Ag、Sn、Pd、Ni、Fe、B、Si、Ca,V、Co、Ga、Ge、Sr、Nb、Mo、Rh、Ba、WおよびPtから選ばれる1種または2種以上を合計で0.03質量%未満さらに含有することを特徴とする請求項1から3のいずれか1項に記載の配向銅板。
- 請求項1から4のいずれか1項に記載の配向銅板表面に形成された絶縁層を有することを特徴とする銅張積層板。
- 前記配向銅板の厚みが5μm以上18μm以下であり、かつ前記絶縁層が樹脂からなり、その厚みが5μm以上75μm以下である請求項5に記載の銅張積層板。
- 前記樹脂がポリイミドからなる請求項6に記載の銅張積層板。
- 請求項5~7のいずれか1項に記載の銅張積層板の配向銅板に形成された所定の配線を有し、さらに銅板面内の特定方向に対して直交するように、該配線の少なくとも一箇所に屈曲部を有することを特徴とする可撓性回路基板。
- 前記屈曲部は、はぜ折り屈曲、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選ばれた1つまたは2つ以上の繰り返し動作を伴う屈曲部である請求項8に記載の可撓性回路基板。
- 請求項8又は9に記載の可撓性回路基板を搭載した電子機器。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/533,195 US9883588B2 (en) | 2014-12-12 | 2015-12-11 | Oriented copper plate, copper-clad laminate, flexible circuit board, and electronic device |
EP15866605.7A EP3231880B1 (en) | 2014-12-12 | 2015-12-11 | Oriented copper plate, copper- clad laminate, flexible circuit board, and electronic device |
JP2016563751A JP6358340B2 (ja) | 2014-12-12 | 2015-12-11 | 配向銅板、銅張積層板、可撓性回路基板、及び電子機器 |
CN201580067345.1A CN107109534B (zh) | 2014-12-12 | 2015-12-11 | 取向铜板、铜箔叠层板、挠性电路板以及电子设备 |
KR1020177015273A KR101915422B1 (ko) | 2014-12-12 | 2015-12-11 | 배향 동판, 동장 적층판, 가요성 회로 기판 및 전자 기기 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014252321 | 2014-12-12 | ||
JP2014-252321 | 2014-12-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016093349A1 true WO2016093349A1 (ja) | 2016-06-16 |
Family
ID=56107526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/084822 WO2016093349A1 (ja) | 2014-12-12 | 2015-12-11 | 配向銅板、銅張積層板、可撓性回路基板、及び電子機器 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9883588B2 (ja) |
EP (1) | EP3231880B1 (ja) |
JP (1) | JP6358340B2 (ja) |
KR (1) | KR101915422B1 (ja) |
CN (1) | CN107109534B (ja) |
TW (1) | TWI582248B (ja) |
WO (1) | WO2016093349A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2018180920A1 (ja) * | 2017-03-30 | 2019-12-12 | Jx金属株式会社 | 圧延銅箔 |
WO2021145043A1 (ja) * | 2020-01-14 | 2021-07-22 | 古河電気工業株式会社 | 銅合金板材およびその製造方法、ならびに電気・電子部品用部材 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI719110B (zh) * | 2016-01-15 | 2021-02-21 | 日商Jx金屬股份有限公司 | 銅箔、覆銅積層板、印刷配線板之製造方法、電子機器之製造方法、傳輸線之製造方法及天線之製造方法 |
TWI814182B (zh) * | 2021-12-21 | 2023-09-01 | 鉑識科技股份有限公司 | 複合銅層及其製備方法 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012026611A1 (ja) * | 2010-08-27 | 2012-03-01 | 古河電気工業株式会社 | 銅合金板材及びその製造方法 |
WO2013031841A1 (ja) * | 2011-08-29 | 2013-03-07 | 古河電気工業株式会社 | 銅合金材料およびその製造方法 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3009383B2 (ja) | 1998-03-31 | 2000-02-14 | 日鉱金属株式会社 | 圧延銅箔およびその製造方法 |
EP1471164B1 (en) * | 2002-01-30 | 2013-01-23 | JX Nippon Mining & Metals Corporation | Copper alloy sputtering target and method for manufacturing the target |
CN101899587B (zh) * | 2006-07-21 | 2012-07-04 | 株式会社神户制钢所 | 电气电子零件用铜合金板 |
US9060432B2 (en) * | 2008-06-30 | 2015-06-16 | Nippon Steel & Sumikin Chemical Co., Ltd. | Flexible circuit board and method for producing same and bend structure of flexible circuit board |
JP4763068B2 (ja) | 2008-06-30 | 2011-08-31 | 新日鐵化学株式会社 | 可撓性回路基板及びその製造方法並びに可撓性回路基板の屈曲部構造 |
JP5446188B2 (ja) | 2008-09-17 | 2014-03-19 | 新日鐵住金株式会社 | 半導体線実装用のインターコネクター及び太陽電池用インターコネクター |
JP5462069B2 (ja) * | 2009-07-27 | 2014-04-02 | 株式会社神戸製鋼所 | 落重特性および母材靭性に優れた高強度厚鋼板 |
CN102812522B (zh) * | 2010-03-17 | 2014-04-02 | 新日铁住金株式会社 | 金属带材料和太阳能电池集电用互连线 |
KR101703679B1 (ko) * | 2010-07-07 | 2017-02-07 | 미츠비시 신도 가부시키가이샤 | 딥 드로잉 가공성이 우수한 Cu―Ni―Si계 동합금판 및 그 제조 방법 |
CN103415635B (zh) * | 2011-03-31 | 2016-07-06 | 新日铁住金化学株式会社 | 铜箔、覆铜层叠板、挠性电路基板及覆铜层叠板的制造方法 |
TW201321527A (zh) * | 2011-08-05 | 2013-06-01 | Furukawa Electric Co Ltd | 二次電池集電體用壓延銅箔及其製造方法 |
CN103917683B (zh) * | 2011-11-11 | 2016-02-24 | 古河电气工业株式会社 | 压延铜箔 |
JP2013194246A (ja) * | 2012-03-15 | 2013-09-30 | Mitsubishi Shindoh Co Ltd | 残留応力の少ないリードフレーム用Cu−Cr−Sn系銅合金板 |
WO2014115307A1 (ja) * | 2013-01-25 | 2014-07-31 | 三菱伸銅株式会社 | 端子・コネクタ材用銅合金板及び端子・コネクタ材用銅合金板の製造方法 |
-
2015
- 2015-12-11 CN CN201580067345.1A patent/CN107109534B/zh active Active
- 2015-12-11 EP EP15866605.7A patent/EP3231880B1/en active Active
- 2015-12-11 JP JP2016563751A patent/JP6358340B2/ja active Active
- 2015-12-11 KR KR1020177015273A patent/KR101915422B1/ko active IP Right Grant
- 2015-12-11 US US15/533,195 patent/US9883588B2/en active Active
- 2015-12-11 TW TW104141761A patent/TWI582248B/zh not_active IP Right Cessation
- 2015-12-11 WO PCT/JP2015/084822 patent/WO2016093349A1/ja active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012026611A1 (ja) * | 2010-08-27 | 2012-03-01 | 古河電気工業株式会社 | 銅合金板材及びその製造方法 |
WO2013031841A1 (ja) * | 2011-08-29 | 2013-03-07 | 古河電気工業株式会社 | 銅合金材料およびその製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3231880A4 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2018180920A1 (ja) * | 2017-03-30 | 2019-12-12 | Jx金属株式会社 | 圧延銅箔 |
WO2021145043A1 (ja) * | 2020-01-14 | 2021-07-22 | 古河電気工業株式会社 | 銅合金板材およびその製造方法、ならびに電気・電子部品用部材 |
JP2021110015A (ja) * | 2020-01-14 | 2021-08-02 | 古河電気工業株式会社 | 銅合金板材およびその製造方法、ならびに電気・電子部品用部材 |
JP2021143428A (ja) * | 2020-01-14 | 2021-09-24 | 古河電気工業株式会社 | 銅合金板材およびその製造方法、ならびに電気・電子部品用部材 |
JP7178454B2 (ja) | 2020-01-14 | 2022-11-25 | 古河電気工業株式会社 | 銅合金板材およびその製造方法、ならびに電気・電子部品用部材 |
Also Published As
Publication number | Publication date |
---|---|
JP6358340B2 (ja) | 2018-07-18 |
KR101915422B1 (ko) | 2018-11-05 |
US20170332489A1 (en) | 2017-11-16 |
US9883588B2 (en) | 2018-01-30 |
TW201625804A (zh) | 2016-07-16 |
CN107109534A (zh) | 2017-08-29 |
EP3231880A1 (en) | 2017-10-18 |
JPWO2016093349A1 (ja) | 2017-11-02 |
EP3231880A4 (en) | 2018-07-11 |
CN107109534B (zh) | 2018-11-09 |
KR20170083076A (ko) | 2017-07-17 |
TWI582248B (zh) | 2017-05-11 |
EP3231880B1 (en) | 2020-10-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5826160B2 (ja) | 圧延銅箔、銅張積層板、フレキシブルプリント配線板及びその製造方法 | |
JP5732406B2 (ja) | 可撓性回路基板及び可撓性回路基板の屈曲部構造 | |
JP6358340B2 (ja) | 配向銅板、銅張積層板、可撓性回路基板、及び電子機器 | |
KR101632515B1 (ko) | 압연 동박 | |
KR101613914B1 (ko) | 우수한 내피로특성을 가지는 Cu―Mg―P계 구리합금판 및 그 제조방법 | |
US20080099110A1 (en) | Rolled copper foil and manufacturing method thereof | |
KR101886824B1 (ko) | 동박, 동장 적층판, 가요성 회로기판 및 동장 적층판의 제조방법 | |
KR102098479B1 (ko) | 플렉시블 프린트 기판용 구리박, 그것을 사용한 구리 피복 적층체, 플렉시블 프린트 기판 및 전자 기기 | |
JP6126799B2 (ja) | 銅箔、銅張積層板、可撓性回路基板、及び銅張積層板の製造方法 | |
JP5479002B2 (ja) | 銅合金箔 | |
JP5865759B2 (ja) | 銅箔、銅張積層板、可撓性回路基板、及び銅張積層板の製造方法 | |
JP4642119B2 (ja) | 銅合金及びその製造方法 | |
JP6643287B2 (ja) | フレキシブルプリント基板用銅箔、それを用いた銅張積層体、フレキシブルプリント基板、及び電子機器 | |
JP5933943B2 (ja) | フレキシブルプリント配線板用圧延銅箔、銅張積層板、フレキシブルプリント配線板及び電子機器 | |
JP2010280191A (ja) | 熱処理用銅箔、熱処理用銅箔の製造方法およびフレキシブルプリント配線板 | |
CN113631741A (zh) | 铜合金板、通电用电子元件及散热用电子元件 | |
JP2010215935A (ja) | 銅合金及びその製造方法 | |
JP2012001786A (ja) | フレキシブル銅張積層板及びその製造方法 | |
JP2007126687A (ja) | 銅合金箔 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15866605 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2015866605 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2016563751 Country of ref document: JP Kind code of ref document: A Ref document number: 20177015273 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15533195 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |