WO2012128099A1 - Copper foil and copper-clad laminate obtained using same - Google Patents
Copper foil and copper-clad laminate obtained using same Download PDFInfo
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- WO2012128099A1 WO2012128099A1 PCT/JP2012/056269 JP2012056269W WO2012128099A1 WO 2012128099 A1 WO2012128099 A1 WO 2012128099A1 JP 2012056269 W JP2012056269 W JP 2012056269W WO 2012128099 A1 WO2012128099 A1 WO 2012128099A1
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- copper foil
- copper
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- oil film
- work hardening
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- 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
- C22C9/10—Alloys based on copper with silicon as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/02—Alloys based on copper with tin as the next major constituent
-
- 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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- 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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—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 copper foil used for, for example, a flexible printed circuit (FPC) and a copper-clad laminate in which this copper foil is laminated on at least one surface of a resin layer.
- FPC flexible printed circuit
- a flexible printed circuit (FPC) or a chip of flexible circuit (COF) is used as a circuit for driving an electronic device such as a digital camera or a mobile phone.
- the FPC and COF are formed by using a copper clad laminate (CCL) in which a copper foil is laminated on one side or both sides of a resin layer and forming a circuit pattern on the copper foil.
- CCL copper clad laminate
- a method is adopted in which the FPC is folded and accommodated in a narrow space inside the case. For example, in the case of a COF used around a liquid crystal display, the copper wiring of the COF is folded back to the back side of the liquid crystal substrate in order to make the bezel (so-called “frame”) thin.
- the bendability of a copper foil of CCL has a correlation with the elongation of the copper foil. Therefore, as described in Patent Document 1, an electrolytic copper foil having a large elongation is used.
- the present inventors have found that even when a rolled copper foil having a large elongation is used, the bendability of CCL may not be improved. That is, the present invention has been made to solve the above-described problems, and an object thereof is to provide a copper foil excellent in bendability when used in a copper-clad laminate and a copper-clad laminate using the same. .
- the copper foil of the present invention has a thickness of 5 to 30 ⁇ m, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and after annealing at 350 ° C. for 0.5 hour
- the work hardening index is 0.3 or more and 0.45 or less.
- the semi-softening temperature of the copper foil of the present invention is preferably 150 ° C. or lower.
- the copper foil of the present invention is made of oxygen-free copper or tough pitch copper, or the oxygen-free copper or tough pitch copper contains one or more kinds of Ag and Sn in total of 500 mass ppm or less.
- the copper foil of the present invention is one or more selected from the group of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper A total of 20 to 500 ppm by mass of elements is preferable.
- the copper foil When the total thickness of the resin layers laminated on one side of the copper foil is 50 ⁇ m or less and the width is 3 mm or more and 5 mm or less, and the copper foil is subjected to close contact bending with the exposed surface of the copper foil as the outside, the copper foil It is preferable that the number of times of bending until rupture is 4 or more.
- the total degree of work at the time of final cold rolling is 85% or more, and the oil film equivalent in the final three passes in the final cold rolling is rolled under the following conditions.
- the oil film equivalent of the second pass before the final pass 25000 or less, the oil film equivalent of the previous pass of the last pass; 30000 or less, the oil film equivalent of the final pass;
- cold rolling and annealing are alternately performed in the cold rolling.
- the last cold rolling performed after the last annealing is referred to as “final cold rolling”.
- the copper clad laminate of the present invention is formed by laminating the copper foil on at least one surface of the resin layer.
- a copper foil excellent in bendability can be obtained when used for a copper clad laminate.
- the copper foil according to the embodiment of the present invention has an integrated intensity I (200) of (200) diffraction peak and an integral of I (220) diffraction peak by X-ray diffraction after annealing at 350 ° C. for 0.5 hour at a thickness of 5-30 ⁇ m.
- the ratio I (220) / I (200), which is the ratio to the strength, is 0.11 or less, and the work hardening index after annealing at 350 ° C. for 0.5 hours is 0.3 or more and 0.45 or less.
- the work hardening index (n value) is represented by an index n when the relationship between stress and strain in the plastic deformation region above the yield point is approximated by the following formula 1 (Hollomon formula).
- [True stress] [material constant] ⁇ [true strain] n (1)
- a material having a high work hardening index is excellent in drawing workability and suitable for press working.
- the copper foil having a work hardening index of 0.3 or more is not locally deformed. It is unlikely that the copper foil will break, because the entire bent part is deformed.
- a material having a work hardening index exceeding 0.45 is not suitable for a copper clad laminate because the strength after annealing is low and the handleability deteriorates.
- the reason for defining the work hardening index after annealing at 350 ° C. for 0.5 hour is that the heating conditions for producing the copper clad laminate are about this level.
- the resin layer of a copper clad laminated board is obtained by applying and curing a resin composition on a copper foil (in the case of a two-layer CCL in which no adhesive layer is interposed between the resin layer and the copper foil), the above heating conditions Thus, the resin is cured.
- the work hardening index is one of the values indicating the work hardening behavior of a material. The larger this value, the easier the material is to work harden.
- the material is subjected to tensile deformation, the material is locally constricted and fractured.
- the constricted portion is work hardened and the constricted portion is hardly deformed. Therefore, instead of the constricted portion that is difficult to deform, the other portions begin to deform. By repeating this, the entire material is uniformly deformed.
- the elongation is an index captured macroscopically without considering such a situation, even if the elongation is large, the work hardening index is not always large.
- the work hardening index after annealing at 200 ° C. for 0.5 hour is preferably 0.3 or more and 0.45 or less. This is because a laminating temperature at the time of producing a three-layer CCL in which a film is used as a resin layer and a film and a copper foil are laminated via an adhesive layer is about 200 ° C. Since the work hardening index increases when the copper foil is recrystallized by heating, if the work hardening index is 0.3 or more at 200 ° C. lower than 350 ° C., a work hardening index of 0.3 or more can be obtained even at 350 ° C. Further, in order to obtain a recrystallized structure sufficiently by the annealing, the semi-softening temperature of the copper foil is preferably 150 ° C. or less.
- a work hardening index which is an index of the ease of uniform deformation of the entire material, is used in drawing a thick material such as a structural member, but it is as thin as a copper foil. Since the material is not subjected to processing such as drawing, the work hardening index was not used as an index. For these reasons, the thickness of the rolled copper foil of the present invention is regulated to 5 to 30 ⁇ m.
- the work hardening index of copper foil becomes low compared with a comparatively thick material.
- the work hardening index is determined by the amount of dislocations introduced into the material by deformation and the ease of movement of dislocations. That is, the work hardening index increases if there are precipitates that can cause dislocation loops, solid solution elements that hinder the movement of dislocations, and grain boundaries.
- the addition of a solid solution element that greatly hinders the movement of dislocations or an alloy element that can generate precipitates causes a decrease in conductivity, and thus is not preferable as a copper foil for flexible wiring boards.
- the copper foil of the present invention preferably has a composition of tough pitch copper standardized to alloy number C1100 of JIS-H3100 or oxygen-free copper standardized to alloy number C1020 of JIS-H3100.
- the oxygen concentration contained in the rolled copper foil is 0.01 to 0.05 mass% for tough pitch copper and 0.001 mass% or less for oxygen-free copper.
- oxygen-free copper standardized to JIS-H3510 alloy number C1011 can be used as oxygen-free copper.
- one or more elements selected from the group consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V are added to the tough pitch copper or the oxygen-free copper.
- a total of 20 to 500 ppm by mass may be contained.
- the total work degree during final cold rolling should be 85% or more, and the oil film in the final three passes in final cold rolling Adjusting the equivalent weight can be mentioned.
- the oil film equivalent of the last two passes in the final cold rolling 25000 or less, the oil film equivalent of the one before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less. Since the oil film equivalent tends to increase as the material thickness decreases, the oil film equivalent value in the final three passes gradually increases. Therefore, it is necessary to set an appropriate oil film equivalent for the final three passes having different thicknesses.
- the oil film equivalent is proportional to (rolling speed) / (engagement angle). If the degree of processing is the same, the biting angle decreases as the material thickness decreases, and therefore the oil film equivalent tends to increase as it approaches the final pass. In order to maintain productivity, it is necessary to increase the rolling speed as the material passes closer to the final pass, and the oil film equivalent tends to increase as the material approaches the final pass.
- the rolling degree of the final pass should be 25% or more.
- the oil film equivalent is represented by the following formula.
- (Oil film equivalent) ⁇ (rolling oil viscosity, kinematic viscosity at 40 ° C .; cSt) ⁇ (rolling speed; m / min) ⁇ / ⁇ (yield stress of material; kg / mm 2 ) ⁇ (roll biting angle; rad ) ⁇
- the rolling oil viscosity can be about 4.0 to 8.0 cSt, the rolling speed is 200 to 600 m / min, and the biting angle of the roll is, for example, 0.0005 to 0.005 rad, preferably 0.001 to 0.04 rad.
- I (220) / I (200) is 0.11 or less.
- the pure copper-type recrystallized texture is characterized in that the (200) plane faces in the direction of the copper foil surface. At this time, the (200) plane also faces in the rolling parallel direction and the direction perpendicular to the rolling. In general, when bending a copper foil, the bending axis is taken in the direction parallel to the rolling or the direction perpendicular to the rolling. At this time, due to the deformation applied to the copper foil, the ⁇ 111 ⁇ surface, which is the main sliding surface of the copper, causes multiple slips. A high work hardening index can be obtained.
- the crystal orientation other than the (200) plane when the crystal orientation other than the (200) plane is dominant, sufficient multiple slip does not occur and a high work hardening index cannot be obtained.
- the more crystals having the ⁇ 001 ⁇ orientation with respect to the bending axis the better the copper foil becomes.
- the recrystallized texture of the pure copper type has the ⁇ 001 ⁇ direction in each of the ND direction (rolling surface normal direction), RD direction, and TD direction
- the RD direction and TD direction which are bending directions are Alternatively, the (200) plane diffraction intensity in the ND direction, which can be easily measured, can be used as an index.
- the copper foil of this invention makes I (220) / I (200) after the process (annealing at 350 degreeC for 0.5 hour) equivalent to the heat processing equivalent at the time of CCL formation 0.11 or less.
- the annealing atmosphere is preferably a non-oxidizing atmosphere in order to prevent surface oxidation.
- the semi-softening temperature of the copper foil is preferably set to 150 ° C. or lower.
- the composition and processing degree of the copper foil it is necessary to adjust the composition and processing degree of the copper foil and appropriately control the recrystallization temperature, but if the copper foil composition and the processing degree are defined in the above range, The recrystallization temperature becomes about 120 to 150 ° C., and the semi-softening temperature can be made 150 ° C. or less.
- the non-recrystallized structure has a work strain remaining, and since it has already been work hardened, it is difficult to work harden by bending deformation, the work hardening index becomes small, and the bendability deteriorates.
- the state in which the copper foil is laminated on the CCL is a state in which the work hardening is not performed, that is, a state in which the work strain is removed.
- the copper foil undergoes a heat treatment in the CCL manufacturing process, but the strain is removed by the heat treatment, and it is necessary to recrystallize.
- the semi-softening temperature of copper foil is 150 degrees C or less, recrystallization of copper foil can be anticipated also by the heat processing received to a CCL manufacturing process, and a work hardening index
- exponent can be enlarged.
- the total thickness of the resin layers laminated on one side of the copper foil according to the embodiment of the present invention is 50 ⁇ m or less, and a sample having a width of 3 mm or more and 5 mm or less is used, and 180 ° adhesion bending is performed with the exposed surface of the copper foil as the outside.
- the number of times of bending until the copper foil breaks is preferably 4 times or more.
- polyimide As the resin layer, polyimide; PET (polyethylene terephthalate); thermosetting resin such as epoxy resin and phenol resin; thermoplastic resin such as saturated polyester resin can be used, but is not limited thereto.
- varnish for example, polyamic acid solution of polyimide precursor
- a solvent is applied to one side of a copper foil, and the solvent is removed by heating to react (for example, imidization reaction). May be allowed to proceed and cured.
- the 180-degree close contact bending is performed by folding the sample so that the crease is parallel to its own width direction, and crushing and stacking with a hand press. And the presence or absence of a fracture
- the copper clad laminate of the present invention is formed by laminating the above copper foil on at least one side of the resin layer. Since the copper foil which concerns on embodiment of this invention is excellent in bendability, the copper clad laminated board using this is also excellent in bendability.
- the copper clad laminate of the present invention can be suitably used for bending 90 to 180 degrees with a radius of 5 mm or less.
- Oxygen-free copper (JIS H0500) or tough pitch copper (JIS H0500) was dissolved, and the elements shown in Tables 1 and 2 were added as necessary, followed by casting to produce an ingot having a thickness of 20 mm and a width of 60 mm. After hot rolling the ingot to a thickness of 10 mm, cold rolling and annealing were repeated as appropriate to produce a copper foil. In order to adjust the softening temperature, use a roll with a smooth surface (Ra ⁇ 0.1 ⁇ m in the roll axis direction) in order to reduce the surface roughness to a total workability of 85% or more during final cold rolling. Final cold rolling was performed to produce a copper foil.
- the rolling oil viscosity is set to about 4.0 to 8.0 cSt, the rolling speed is adjusted to 200 to 600 m / min, and the roll bite angle is set to 0.003 to 0.03 rad, and the oil film equivalent in the final three passes in the final cold rolling is 35,000 for all.
- ⁇ Work hardening index> The obtained copper foils were annealed at 200 ° C. for 0.5 hours and 350 ° C. for 0.5 hours, respectively, and then subjected to a tensile test (based on JIS-Z2241) to obtain a work hardening index. Note that the work hardening index needs to be obtained using the uniform elongation and stress after the material yields, so the value from the elongation of 2% to the maximum stress point was used. Then, a logarithmic graph of true strain and true stress obtained from the measured elongation and stress was approximated by the method of least squares, and a work hardening index was obtained from the slope of the graph. True strain and true stress were determined by the following formulas.
- ⁇ Semi-softening temperature> The obtained copper foils were annealed in a non-oxidizing atmosphere at 100 to 400 ° C. for 0.5 hours, respectively, and then subjected to a tensile test to determine the strength (tensile strength) against the heat treatment conditions.
- the annealing temperature at which the strength after annealing was an intermediate value between the strength after rolling (before annealing) and the strength after being completely softened (annealed at 300 ° C. for 30 minutes) was defined as the semi-softening temperature.
- a polyimide layer having a thickness of about 20 ⁇ m was formed on one side of the obtained copper foil by a casting method to produce a single-sided CCL.
- one side of the obtained copper foil was subjected to chemical treatment (plating), and a polyimide resin precursor varnish (U-Vanice A made by Ube Industries) was applied to this surface to a thickness of 20 ⁇ m. After that, it is dried for 30 minutes in a hot air circulation high temperature bath set at 130 ° C., and heated up to 350 ° C. over 2000 seconds and cured (imidized) to form a resin layer (polyimide layer).
- Single-sided CCL was prepared.
- this single-sided CCL is 3.2 mm wide, 30 mm long, cut out so that the length direction of the test piece is parallel to the rolling direction, and made into a test piece, looped with the resin layer side inside, and crushed with a hand press 180 degree close contact bending was performed. And the presence or absence of the fracture
- the obtained copper foil was cut out to have a width of 12.7 mm and a length of 200 mm so that the length direction of the test piece was parallel to the rolling direction, and it was recrystallized by heating at 200 ° C. for 30 minutes. I let you. This was measured for the number of IPC sliding bends using an IPC (American Printed Circuit Industry Association) slide bending apparatus shown in FIG.
- This apparatus has a structure in which a vibration transmission member 3 is coupled to an oscillation driver 4, and the test piece 1 is fixed to the apparatus at a total of four points including a screw 2 portion and an end portion 3 indicated by arrows. .
- the intermediate part of the test piece 1 is bent into a hairpin shape with a predetermined radius of curvature r.
- the number of times to break when bending was repeated under the following conditions was obtained.
- the test was performed under the conditions of a radius of curvature r: 2.5 mm, a vibration stroke: 25 mm, and a vibration speed: 1500 times / minute.
- the radius of curvature r was 0.9 mm. This is because the amount of strain applied to the copper foil at the time of bending is made equal to that of another example thicker than Example 17.
- OFC and TPC indicate oxygen-free copper and tough pitch copper (JIS H3100), respectively, and Ag100 ppm TPC indicates that 100 mass ppm of Ag is added to tough pitch copper.
- the oxygen-free copper specified in JIS H3100 and the oxygen-free copper specified in JIS H0500 are both the same in alloy number C1020.
- the tough pitch copper specified in JIS H3100 and the tough pitch copper specified in JIS H0500 are both the same in alloy number C1100.
- the oil film equivalent in the last two passes As the oil film equivalent in the final three passes in the final cold rolling, the oil film equivalent in the last two passes; over 25000, the oil film equivalent in the previous one in the final pass; over 30000, the oil film equivalent in the final pass; 35000
- the number of bendings when the 180-degree contact bending was performed was less than 4, and the bendability deteriorated.
- the number of times of bending when 180 degree contact bending is performed is less than four times. The bendability deteriorated.
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Abstract
The present invention provides both a copper foil which imparts excellent bendability when used in copper-clad laminates and a copper-clad laminate which is obtained using the copper foil. The copper foil has a thickness of 5-30 µm, has an I(220)/I(200) of 0.11 or less after annealed at 350ºC for 0.5 hours, and has a work hardening coefficient of 0.3-0.45 after annealed at 350ºC for 0.5 hours.
Description
本発明は、例えばフレキシブル配線板(FPC:Flexible Printed Circuit)に使用される銅箔、及びこの銅箔を樹脂層の少なくとも片面に積層した銅張積層板に関する。
The present invention relates to a copper foil used for, for example, a flexible printed circuit (FPC) and a copper-clad laminate in which this copper foil is laminated on at least one surface of a resin layer.
デジタルカメラや携帯電話などの電子機器を駆動させる回路として、フレキシブル配線板(FPC:Flexible Printed Circuit)やCOF(chip of flexible circuit)が用いられている。このFPCやCOFは、樹脂層の片面又は両面に銅箔を積層した銅張積層板(CCL)を用い、銅箔に回路パターンを形成してなる。
そして、このような電子機器を小型化、高機能化するために、ケース内の狭い空間にFPCを折りたたんで収容する方法がとられる。例えば液晶ディスプレイ周辺に用いられるCOFの場合には、ベゼル(いわゆる「額縁」)を細くするために、COFの銅配線を液晶基板の裏側へ折り返している。 As a circuit for driving an electronic device such as a digital camera or a mobile phone, a flexible printed circuit (FPC) or a chip of flexible circuit (COF) is used. The FPC and COF are formed by using a copper clad laminate (CCL) in which a copper foil is laminated on one side or both sides of a resin layer and forming a circuit pattern on the copper foil.
In order to reduce the size and increase the functionality of such an electronic device, a method is adopted in which the FPC is folded and accommodated in a narrow space inside the case. For example, in the case of a COF used around a liquid crystal display, the copper wiring of the COF is folded back to the back side of the liquid crystal substrate in order to make the bezel (so-called “frame”) thin.
そして、このような電子機器を小型化、高機能化するために、ケース内の狭い空間にFPCを折りたたんで収容する方法がとられる。例えば液晶ディスプレイ周辺に用いられるCOFの場合には、ベゼル(いわゆる「額縁」)を細くするために、COFの銅配線を液晶基板の裏側へ折り返している。 As a circuit for driving an electronic device such as a digital camera or a mobile phone, a flexible printed circuit (FPC) or a chip of flexible circuit (COF) is used. The FPC and COF are formed by using a copper clad laminate (CCL) in which a copper foil is laminated on one side or both sides of a resin layer and forming a circuit pattern on the copper foil.
In order to reduce the size and increase the functionality of such an electronic device, a method is adopted in which the FPC is folded and accommodated in a narrow space inside the case. For example, in the case of a COF used around a liquid crystal display, the copper wiring of the COF is folded back to the back side of the liquid crystal substrate in order to make the bezel (so-called “frame”) thin.
しかしながら、FPCやCOFを折り畳んだ際、銅箔部分に大きな変形荷重が加わり、破断し易くなるという問題がある。
そこで、柱状の銅結晶粒子を含み、25℃における伸び率5%以上の電解銅箔からFPCを構成することで、配線パターンが破断し難いFPCが得られることが報告されている(特許文献1)。 However, when FPC or COF is folded, there is a problem that a large deformation load is applied to the copper foil portion and it is easy to break.
Thus, it has been reported that an FPC in which the wiring pattern is not easily broken can be obtained by forming the FPC from an electrolytic copper foil containing columnar copper crystal particles and having an elongation of 5% or more at 25 ° C. (Patent Document 1). ).
そこで、柱状の銅結晶粒子を含み、25℃における伸び率5%以上の電解銅箔からFPCを構成することで、配線パターンが破断し難いFPCが得られることが報告されている(特許文献1)。 However, when FPC or COF is folded, there is a problem that a large deformation load is applied to the copper foil portion and it is easy to break.
Thus, it has been reported that an FPC in which the wiring pattern is not easily broken can be obtained by forming the FPC from an electrolytic copper foil containing columnar copper crystal particles and having an elongation of 5% or more at 25 ° C. (Patent Document 1). ).
従来、CCLの銅箔の曲げ性は銅箔の伸びと相関があると考えられており、そのため上記特許文献1に記載されているように、伸びの大きい電解銅箔が用いられている。
ところが、伸びの大きい圧延銅箔を用いても、CCLの曲げ性が向上しない場合があることを本発明者らは見出した。
すなわち、本発明は上記の課題を解決するためになされたものであり、銅張積層板に用いたときに曲げ性に優れた銅箔及びそれを用いた銅張積層板の提供を目的とする。 Conventionally, it has been considered that the bendability of a copper foil of CCL has a correlation with the elongation of the copper foil. Therefore, as described in Patent Document 1, an electrolytic copper foil having a large elongation is used.
However, the present inventors have found that even when a rolled copper foil having a large elongation is used, the bendability of CCL may not be improved.
That is, the present invention has been made to solve the above-described problems, and an object thereof is to provide a copper foil excellent in bendability when used in a copper-clad laminate and a copper-clad laminate using the same. .
ところが、伸びの大きい圧延銅箔を用いても、CCLの曲げ性が向上しない場合があることを本発明者らは見出した。
すなわち、本発明は上記の課題を解決するためになされたものであり、銅張積層板に用いたときに曲げ性に優れた銅箔及びそれを用いた銅張積層板の提供を目的とする。 Conventionally, it has been considered that the bendability of a copper foil of CCL has a correlation with the elongation of the copper foil. Therefore, as described in Patent Document 1, an electrolytic copper foil having a large elongation is used.
However, the present inventors have found that even when a rolled copper foil having a large elongation is used, the bendability of CCL may not be improved.
That is, the present invention has been made to solve the above-described problems, and an object thereof is to provide a copper foil excellent in bendability when used in a copper-clad laminate and a copper-clad laminate using the same. .
本発明者らは種々検討した結果、CCLの曲げ性を向上させる因子として、銅箔の伸びではなく加工硬化指数(n値)が重要であることを見出した。
上記の目的を達成するために、本発明の銅箔は、厚み5~30μm、350℃で0.5時間焼鈍後のI(220)/I(200)が0.11以下で、350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下である。 As a result of various studies, the present inventors have found that work hardening index (n value) is important as a factor for improving the bendability of CCL, not the elongation of copper foil.
In order to achieve the above object, the copper foil of the present invention has a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and after annealing at 350 ° C. for 0.5 hour The work hardening index is 0.3 or more and 0.45 or less.
上記の目的を達成するために、本発明の銅箔は、厚み5~30μm、350℃で0.5時間焼鈍後のI(220)/I(200)が0.11以下で、350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下である。 As a result of various studies, the present inventors have found that work hardening index (n value) is important as a factor for improving the bendability of CCL, not the elongation of copper foil.
In order to achieve the above object, the copper foil of the present invention has a thickness of 5 to 30 μm, I (220) / I (200) after annealing at 350 ° C. for 0.5 hour is 0.11 or less, and after annealing at 350 ° C. for 0.5 hour The work hardening index is 0.3 or more and 0.45 or less.
本発明の銅箔の半軟化温度が150℃以下であることが好ましい。
又、本発明の銅箔は、無酸素銅若しくはタフピッチ銅からなり、又は無酸素銅若しくはタフピッチ銅にAg及びSnの群からなる1種以上を合計500質量ppm以下含むことが好ましい。
本発明の銅箔は、無酸素銅又はタフピッチ銅にAg、Sn、In、Ti、Zn、Zr、Fe、P、Ni、Si、Te、Cr、Nb、及びVの群から選ばれる一種以上の元素を合計で20~500質量ppm含むことが好ましい。
前記銅箔の片面に樹脂層を積層した合計厚みが50μm以下で、幅3mm以上5mm以下の試料を用い、前記銅箔の露出面を外側として180度密着曲げを行った場合に、前記銅箔が破断するまでの曲げ回数が4回以上であることが好ましい。 The semi-softening temperature of the copper foil of the present invention is preferably 150 ° C. or lower.
Moreover, it is preferable that the copper foil of the present invention is made of oxygen-free copper or tough pitch copper, or the oxygen-free copper or tough pitch copper contains one or more kinds of Ag and Sn in total of 500 mass ppm or less.
The copper foil of the present invention is one or more selected from the group of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper A total of 20 to 500 ppm by mass of elements is preferable.
When the total thickness of the resin layers laminated on one side of the copper foil is 50 μm or less and the width is 3 mm or more and 5 mm or less, and the copper foil is subjected to close contact bending with the exposed surface of the copper foil as the outside, the copper foil It is preferable that the number of times of bending until rupture is 4 or more.
又、本発明の銅箔は、無酸素銅若しくはタフピッチ銅からなり、又は無酸素銅若しくはタフピッチ銅にAg及びSnの群からなる1種以上を合計500質量ppm以下含むことが好ましい。
本発明の銅箔は、無酸素銅又はタフピッチ銅にAg、Sn、In、Ti、Zn、Zr、Fe、P、Ni、Si、Te、Cr、Nb、及びVの群から選ばれる一種以上の元素を合計で20~500質量ppm含むことが好ましい。
前記銅箔の片面に樹脂層を積層した合計厚みが50μm以下で、幅3mm以上5mm以下の試料を用い、前記銅箔の露出面を外側として180度密着曲げを行った場合に、前記銅箔が破断するまでの曲げ回数が4回以上であることが好ましい。 The semi-softening temperature of the copper foil of the present invention is preferably 150 ° C. or lower.
Moreover, it is preferable that the copper foil of the present invention is made of oxygen-free copper or tough pitch copper, or the oxygen-free copper or tough pitch copper contains one or more kinds of Ag and Sn in total of 500 mass ppm or less.
The copper foil of the present invention is one or more selected from the group of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V in oxygen-free copper or tough pitch copper A total of 20 to 500 ppm by mass of elements is preferable.
When the total thickness of the resin layers laminated on one side of the copper foil is 50 μm or less and the width is 3 mm or more and 5 mm or less, and the copper foil is subjected to close contact bending with the exposed surface of the copper foil as the outside, the copper foil It is preferable that the number of times of bending until rupture is 4 or more.
最終冷間圧延時の総加工度が85%以上であり、かつ前記最終冷間圧延における最終3パスでの油膜当量を以下の条件として圧延してなることが好ましい。但し、最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下とする。ここで、インゴットを熱間圧延後、冷間圧延を経て銅箔を製造する際、冷間圧延において冷間圧延と焼鈍とを交互に行う。そして、最後の焼鈍後に最後に行う冷間圧延を「最終冷間圧延」とする。
It is preferable that the total degree of work at the time of final cold rolling is 85% or more, and the oil film equivalent in the final three passes in the final cold rolling is rolled under the following conditions. However, the oil film equivalent of the second pass before the final pass: 25000 or less, the oil film equivalent of the previous pass of the last pass; 30000 or less, the oil film equivalent of the final pass; Here, after manufacturing the copper foil through cold rolling after hot rolling the ingot, cold rolling and annealing are alternately performed in the cold rolling. The last cold rolling performed after the last annealing is referred to as “final cold rolling”.
本発明の銅張積層板は、前記銅箔を、樹脂層の少なくとも片面に積層してなる。
The copper clad laminate of the present invention is formed by laminating the copper foil on at least one surface of the resin layer.
本発明によれば、銅張積層板に用いたときに曲げ性に優れた銅箔が得られる。
According to the present invention, a copper foil excellent in bendability can be obtained when used for a copper clad laminate.
以下、本発明の実施形態に係る銅箔について説明する。なお、本発明において%とは、特に断らない限り、質量%を示すものとする。
本発明の実施形態に係る銅箔は、厚み5~30μm、350℃で0.5時間焼鈍後のX線回折による(200)回折ピークの積分強度I(200)と、I(220)回折ピークの積分強度との比であるI(220)/I(200)が0.11以下、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下である。 Hereinafter, the copper foil which concerns on embodiment of this invention is demonstrated. In the present invention, “%” means “% by mass” unless otherwise specified.
The copper foil according to the embodiment of the present invention has an integrated intensity I (200) of (200) diffraction peak and an integral of I (220) diffraction peak by X-ray diffraction after annealing at 350 ° C. for 0.5 hour at a thickness of 5-30 μm. The ratio I (220) / I (200), which is the ratio to the strength, is 0.11 or less, and the work hardening index after annealing at 350 ° C. for 0.5 hours is 0.3 or more and 0.45 or less.
本発明の実施形態に係る銅箔は、厚み5~30μm、350℃で0.5時間焼鈍後のX線回折による(200)回折ピークの積分強度I(200)と、I(220)回折ピークの積分強度との比であるI(220)/I(200)が0.11以下、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下である。 Hereinafter, the copper foil which concerns on embodiment of this invention is demonstrated. In the present invention, “%” means “% by mass” unless otherwise specified.
The copper foil according to the embodiment of the present invention has an integrated intensity I (200) of (200) diffraction peak and an integral of I (220) diffraction peak by X-ray diffraction after annealing at 350 ° C. for 0.5 hour at a thickness of 5-30 μm. The ratio I (220) / I (200), which is the ratio to the strength, is 0.11 or less, and the work hardening index after annealing at 350 ° C. for 0.5 hours is 0.3 or more and 0.45 or less.
<加工硬化指数(n値)>
加工硬化指数(n値)は、降伏点以上の塑性変形域における応力とひずみとの関係を、以下の式1(Hollomonの式)で近似した場合の指数nで表される。
[真応力]=[材料定数]×[真ひずみ]n (1)
加工硬化指数が大きいほど局所変形が起こりにくく、変形を行ったときに破断しにくい。又、加工硬化指数が高い材料は絞り加工性に優れ、プレス加工に適する。そして、銅箔を、樹脂層の少なくとも片面に積層して銅張積層板を製造し、この銅張積層板の曲げ性を評価した場合に、加工硬化指数が0.3以上の銅箔は局所変形が起こりにくく、曲げ部全体で変形を担うので、銅箔が破断しにくいと考えられる。但し、加工硬化指数が0.45を超える材料は、焼鈍後の強度が低く取り扱い性が悪化するため、銅張積層板用として適当でない。 <Work hardening index (n value)>
The work hardening index (n value) is represented by an index n when the relationship between stress and strain in the plastic deformation region above the yield point is approximated by the following formula 1 (Hollomon formula).
[True stress] = [material constant] × [true strain] n (1)
As the work hardening index is larger, local deformation is less likely to occur and is less likely to break when deformed. In addition, a material having a high work hardening index is excellent in drawing workability and suitable for press working. And when copper foil is laminated on at least one side of the resin layer to produce a copper clad laminate, and the bendability of this copper clad laminate is evaluated, the copper foil having a work hardening index of 0.3 or more is not locally deformed. It is unlikely that the copper foil will break, because the entire bent part is deformed. However, a material having a work hardening index exceeding 0.45 is not suitable for a copper clad laminate because the strength after annealing is low and the handleability deteriorates.
加工硬化指数(n値)は、降伏点以上の塑性変形域における応力とひずみとの関係を、以下の式1(Hollomonの式)で近似した場合の指数nで表される。
[真応力]=[材料定数]×[真ひずみ]n (1)
加工硬化指数が大きいほど局所変形が起こりにくく、変形を行ったときに破断しにくい。又、加工硬化指数が高い材料は絞り加工性に優れ、プレス加工に適する。そして、銅箔を、樹脂層の少なくとも片面に積層して銅張積層板を製造し、この銅張積層板の曲げ性を評価した場合に、加工硬化指数が0.3以上の銅箔は局所変形が起こりにくく、曲げ部全体で変形を担うので、銅箔が破断しにくいと考えられる。但し、加工硬化指数が0.45を超える材料は、焼鈍後の強度が低く取り扱い性が悪化するため、銅張積層板用として適当でない。 <Work hardening index (n value)>
The work hardening index (n value) is represented by an index n when the relationship between stress and strain in the plastic deformation region above the yield point is approximated by the following formula 1 (Hollomon formula).
[True stress] = [material constant] × [true strain] n (1)
As the work hardening index is larger, local deformation is less likely to occur and is less likely to break when deformed. In addition, a material having a high work hardening index is excellent in drawing workability and suitable for press working. And when copper foil is laminated on at least one side of the resin layer to produce a copper clad laminate, and the bendability of this copper clad laminate is evaluated, the copper foil having a work hardening index of 0.3 or more is not locally deformed. It is unlikely that the copper foil will break, because the entire bent part is deformed. However, a material having a work hardening index exceeding 0.45 is not suitable for a copper clad laminate because the strength after annealing is low and the handleability deteriorates.
ここで、350℃で0.5時間焼鈍後の加工硬化指数を規定した理由は、銅張積層板を製造する際の加熱条件がこの程度であるためである。なお、銅張積層板の樹脂層が樹脂組成物を銅箔に塗布、硬化して得られる場合(樹脂層と銅箔との間に接着層が介在しない2層CCLの場合)、上記加熱条件で樹脂の硬化を行うことになる。
Here, the reason for defining the work hardening index after annealing at 350 ° C. for 0.5 hour is that the heating conditions for producing the copper clad laminate are about this level. In addition, when the resin layer of a copper clad laminated board is obtained by applying and curing a resin composition on a copper foil (in the case of a two-layer CCL in which no adhesive layer is interposed between the resin layer and the copper foil), the above heating conditions Thus, the resin is cured.
なお、銅箔の曲げ性を向上させる因子として、銅箔の伸びではなく加工硬化指数(n値)が重要である理由は以下のとおりと考えられる。
まず、加工硬化指数は、材料の加工硬化挙動を示す値のひとつであり、この値が大きいほど、材料は加工硬化しやすい性質を持つ。ここで、材料は引張変形を受けると、局部的にくびれを起こして破断するが、加工硬化係数が大きい材料では、くびれを起こした部分が加工硬化し、くびれ部が変形しにくくなる。そのため、変形しにくいくびれ部に代わって、それ以外の部分が変形しはじめる。これを繰り返すことで、材料全体が均等に変形する。一方、伸びはそのような状況を考慮せずにマクロ的に捕らえた指標なので、伸びが大きいものでも加工硬化指数が大きいとは限らない。 The reason why the work hardening index (n value) is important as a factor for improving the bendability of the copper foil, not the elongation of the copper foil, is considered as follows.
First, the work hardening index is one of the values indicating the work hardening behavior of a material. The larger this value, the easier the material is to work harden. Here, when the material is subjected to tensile deformation, the material is locally constricted and fractured. However, in a material having a large work hardening coefficient, the constricted portion is work hardened and the constricted portion is hardly deformed. Therefore, instead of the constricted portion that is difficult to deform, the other portions begin to deform. By repeating this, the entire material is uniformly deformed. On the other hand, since the elongation is an index captured macroscopically without considering such a situation, even if the elongation is large, the work hardening index is not always large.
まず、加工硬化指数は、材料の加工硬化挙動を示す値のひとつであり、この値が大きいほど、材料は加工硬化しやすい性質を持つ。ここで、材料は引張変形を受けると、局部的にくびれを起こして破断するが、加工硬化係数が大きい材料では、くびれを起こした部分が加工硬化し、くびれ部が変形しにくくなる。そのため、変形しにくいくびれ部に代わって、それ以外の部分が変形しはじめる。これを繰り返すことで、材料全体が均等に変形する。一方、伸びはそのような状況を考慮せずにマクロ的に捕らえた指標なので、伸びが大きいものでも加工硬化指数が大きいとは限らない。 The reason why the work hardening index (n value) is important as a factor for improving the bendability of the copper foil, not the elongation of the copper foil, is considered as follows.
First, the work hardening index is one of the values indicating the work hardening behavior of a material. The larger this value, the easier the material is to work harden. Here, when the material is subjected to tensile deformation, the material is locally constricted and fractured. However, in a material having a large work hardening coefficient, the constricted portion is work hardened and the constricted portion is hardly deformed. Therefore, instead of the constricted portion that is difficult to deform, the other portions begin to deform. By repeating this, the entire material is uniformly deformed. On the other hand, since the elongation is an index captured macroscopically without considering such a situation, even if the elongation is large, the work hardening index is not always large.
従来、このような材料全体の均等な変形のしやすさの指標として、厚みのある材料の絞り加工において、加工硬化指数が用いられる例はあるものの、銅箔のように薄い材料は絞り加工などの加工を行わないので、加工硬化指数を指標とすることはこれまでなかった。本発明においては、銅箔の加工硬化指数を大きくすれば、CCLの180度密着曲げにおいても、曲げ部全体が均等に変形することによって破断を起こさずに曲がると考えた。
Conventionally, as an index of the ease of uniform deformation of the entire material, there is an example where work hardening index is used in drawing of a thick material, but thin material such as copper foil is drawn. In the past, no work hardening index was used as an index. In the present invention, it was considered that if the work hardening index of the copper foil is increased, even in the 180 degree close contact bending of the CCL, the entire bent portion is uniformly deformed and does not break.
さらに、200℃で0.5時間焼鈍後の加工硬化指数も0.3以上0.45以下であることが好ましい。これは、樹脂層としてフィルムを用い、フィルムと銅箔とを接着層を介して積層した3層CCLの製造時のラミネート温度が200℃程度であるからである。加工硬化指数は加熱によって銅箔が再結晶することによって大きくなるため、350℃より低温の200℃で加工硬化指数が0.3以上であれば、350℃でも0.3以上の加工硬化指数が得られる。また、上記焼鈍で充分に再結晶組織を得るためには、銅箔の半軟化温度は150℃以下であることが好ましい。
Furthermore, the work hardening index after annealing at 200 ° C. for 0.5 hour is preferably 0.3 or more and 0.45 or less. This is because a laminating temperature at the time of producing a three-layer CCL in which a film is used as a resin layer and a film and a copper foil are laminated via an adhesive layer is about 200 ° C. Since the work hardening index increases when the copper foil is recrystallized by heating, if the work hardening index is 0.3 or more at 200 ° C. lower than 350 ° C., a work hardening index of 0.3 or more can be obtained even at 350 ° C. Further, in order to obtain a recrystallized structure sufficiently by the annealing, the semi-softening temperature of the copper foil is preferably 150 ° C. or less.
(厚み)
なお、従来、構造部材のような厚みのある材料の絞り加工において、材料全体の均等な変形のしやすさの指標である加工硬化指数が用いられた例はあるが、銅箔のように薄い材料は絞り加工などの加工を行わないので、加工硬化指数を指標に用いることはなかった。
このようなことから、本発明の圧延銅箔の厚みを5~30μmに規定する。 (Thickness)
Conventionally, there is an example in which a work hardening index, which is an index of the ease of uniform deformation of the entire material, is used in drawing a thick material such as a structural member, but it is as thin as a copper foil. Since the material is not subjected to processing such as drawing, the work hardening index was not used as an index.
For these reasons, the thickness of the rolled copper foil of the present invention is regulated to 5 to 30 μm.
なお、従来、構造部材のような厚みのある材料の絞り加工において、材料全体の均等な変形のしやすさの指標である加工硬化指数が用いられた例はあるが、銅箔のように薄い材料は絞り加工などの加工を行わないので、加工硬化指数を指標に用いることはなかった。
このようなことから、本発明の圧延銅箔の厚みを5~30μmに規定する。 (Thickness)
Conventionally, there is an example in which a work hardening index, which is an index of the ease of uniform deformation of the entire material, is used in drawing a thick material such as a structural member, but it is as thin as a copper foil. Since the material is not subjected to processing such as drawing, the work hardening index was not used as an index.
For these reasons, the thickness of the rolled copper foil of the present invention is regulated to 5 to 30 μm.
又、銅箔の厚みが5~30μmと比較的薄い場合、材料表面に面した結晶粒の割合が多くなるため、変形によって導入された転位は結晶粒界に蓄積せず、材料表面から解放される割合が高くなる。このため銅箔の加工硬化指数は、比較的厚い材料に比べて低くなる。一方、加工硬化指数は、変形によって材料中に導入される転位の量と、転位の移動し易さとによって決まる。つまり、転位ループの発生源となるような析出物や、転位の移動を妨げる固溶元素及び結晶粒界が存在すると加工硬化指数は大きくなる。しかしながら、転位の移動を大きく妨げる程度の固溶元素や、析出物を生成しうる程度の合金元素の添加は導電率の低下を招くため、フレキシブル配線板用銅箔として好ましくない。
Also, when the copper foil thickness is relatively thin, 5-30 μm, the proportion of crystal grains facing the material surface increases, so dislocations introduced by deformation do not accumulate at the crystal grain boundaries and are released from the material surface. The ratio becomes higher. For this reason, the work hardening index of copper foil becomes low compared with a comparatively thick material. On the other hand, the work hardening index is determined by the amount of dislocations introduced into the material by deformation and the ease of movement of dislocations. That is, the work hardening index increases if there are precipitates that can cause dislocation loops, solid solution elements that hinder the movement of dislocations, and grain boundaries. However, the addition of a solid solution element that greatly hinders the movement of dislocations or an alloy element that can generate precipitates causes a decrease in conductivity, and thus is not preferable as a copper foil for flexible wiring boards.
(組成)
本発明の銅箔は、JIS-H3100の合金番号C1100に規格するタフピッチ銅又はJIS-H3100の合金番号C1020に規格する無酸素銅を組成とすることが好ましい。上記した純銅に近い組成とすると、銅箔の導電率が低下せず、FPCやCOFに適する。圧延銅箔に含まれる酸素濃度は、タフピッチ銅の場合は0.01~0.05質量%、無酸素銅の場合は0.001質量%以下である。
また、無酸素銅としてJIS-H3510の合金番号C1011に規格する無酸素銅を用いることもできる。
さらに、Ag及びSnの群から選ばれる1種以上を合計500質量ppm以下含有してもよい。圧延銅箔にAg又はSnを添加すると転位の移動を妨げるため、加工硬化係数が大きくなる。圧延銅箔へのAg又はSnの合計添加量が500質量ppmを超えると、導電率が低下すると共に再結晶温度が上昇し、最終焼鈍において銅箔の表面酸化を抑えつつ再結晶焼鈍することが困難になる場合がある。なお、AgとSnの合計添加量の下限は特に規定しないが、通常、合計20質量ppm以上である。
又、上記タフピッチ銅又は上記無酸素銅に、Ag、Sn、In、Ti、Zn、Zr、Fe、P、Ni、Si、Te、Cr、Nb、及びVの群から選ばれる一種以上の元素を合計で20~500質量ppm含有してもよい。 (composition)
The copper foil of the present invention preferably has a composition of tough pitch copper standardized to alloy number C1100 of JIS-H3100 or oxygen-free copper standardized to alloy number C1020 of JIS-H3100. When the composition is close to that of the pure copper described above, the conductivity of the copper foil does not decrease and is suitable for FPC and COF. The oxygen concentration contained in the rolled copper foil is 0.01 to 0.05 mass% for tough pitch copper and 0.001 mass% or less for oxygen-free copper.
In addition, oxygen-free copper standardized to JIS-H3510 alloy number C1011 can be used as oxygen-free copper.
Furthermore, you may contain 1 or more types chosen from the group of Ag and Sn in total 500 mass ppm or less. When Ag or Sn is added to the rolled copper foil, the movement of dislocation is hindered, so that the work hardening coefficient is increased. When the total amount of Ag or Sn added to the rolled copper foil exceeds 500 ppm by mass, the electrical conductivity decreases and the recrystallization temperature increases, and recrystallization annealing may be performed while suppressing surface oxidation of the copper foil in the final annealing. It can be difficult. In addition, although the minimum in particular of the total addition amount of Ag and Sn is not prescribed | regulated, Usually, it is 20 mass ppm or more in total.
In addition, one or more elements selected from the group consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V are added to the tough pitch copper or the oxygen-free copper. A total of 20 to 500 ppm by mass may be contained.
本発明の銅箔は、JIS-H3100の合金番号C1100に規格するタフピッチ銅又はJIS-H3100の合金番号C1020に規格する無酸素銅を組成とすることが好ましい。上記した純銅に近い組成とすると、銅箔の導電率が低下せず、FPCやCOFに適する。圧延銅箔に含まれる酸素濃度は、タフピッチ銅の場合は0.01~0.05質量%、無酸素銅の場合は0.001質量%以下である。
また、無酸素銅としてJIS-H3510の合金番号C1011に規格する無酸素銅を用いることもできる。
さらに、Ag及びSnの群から選ばれる1種以上を合計500質量ppm以下含有してもよい。圧延銅箔にAg又はSnを添加すると転位の移動を妨げるため、加工硬化係数が大きくなる。圧延銅箔へのAg又はSnの合計添加量が500質量ppmを超えると、導電率が低下すると共に再結晶温度が上昇し、最終焼鈍において銅箔の表面酸化を抑えつつ再結晶焼鈍することが困難になる場合がある。なお、AgとSnの合計添加量の下限は特に規定しないが、通常、合計20質量ppm以上である。
又、上記タフピッチ銅又は上記無酸素銅に、Ag、Sn、In、Ti、Zn、Zr、Fe、P、Ni、Si、Te、Cr、Nb、及びVの群から選ばれる一種以上の元素を合計で20~500質量ppm含有してもよい。 (composition)
The copper foil of the present invention preferably has a composition of tough pitch copper standardized to alloy number C1100 of JIS-H3100 or oxygen-free copper standardized to alloy number C1020 of JIS-H3100. When the composition is close to that of the pure copper described above, the conductivity of the copper foil does not decrease and is suitable for FPC and COF. The oxygen concentration contained in the rolled copper foil is 0.01 to 0.05 mass% for tough pitch copper and 0.001 mass% or less for oxygen-free copper.
In addition, oxygen-free copper standardized to JIS-H3510 alloy number C1011 can be used as oxygen-free copper.
Furthermore, you may contain 1 or more types chosen from the group of Ag and Sn in total 500 mass ppm or less. When Ag or Sn is added to the rolled copper foil, the movement of dislocation is hindered, so that the work hardening coefficient is increased. When the total amount of Ag or Sn added to the rolled copper foil exceeds 500 ppm by mass, the electrical conductivity decreases and the recrystallization temperature increases, and recrystallization annealing may be performed while suppressing surface oxidation of the copper foil in the final annealing. It can be difficult. In addition, although the minimum in particular of the total addition amount of Ag and Sn is not prescribed | regulated, Usually, it is 20 mass ppm or more in total.
In addition, one or more elements selected from the group consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V are added to the tough pitch copper or the oxygen-free copper. A total of 20 to 500 ppm by mass may be contained.
350℃で0.5時間焼鈍後の銅箔の加工硬化指数を0.3以上に管理する方法としては、最終冷間圧延時の総加工度を85%以上とし、さらに最終冷間圧延における最終3パスにおける油膜当量を調整することが挙げられる。具体的には、最終冷間圧延における最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下とする。
なお、材料厚みが薄くなると油膜当量は大きくなる傾向にあるため、最終3パスにおける油膜当量の値は、徐々に大きくなる。そこで、それぞれ厚みの異なる最終3パスについて、適正な油膜当量を設定する必要がある。
最終冷間圧延において圧延油粘度と材料降伏応力が全パスで等しいとすると、油膜当量は、(圧延速度)/(噛み込み角)に比例する。加工度が同じ場合、材料厚みが薄くなると噛み込み角は小さくなるために、最終パスに近づくほど油膜当量は大きくなる傾向にある。また生産性を保つためには、材料長さの長い最終パスに近づくほど圧延速度を上げる必要があり、これによっても最終パスに近づくほど油膜当量は大きくなる傾向にある。 As a method of managing the work hardening index of copper foil after annealing at 350 ° C for 0.5 hour to 0.3 or more, the total work degree during final cold rolling should be 85% or more, and the oil film in the final three passes in final cold rolling Adjusting the equivalent weight can be mentioned. Specifically, the oil film equivalent of the last two passes in the final cold rolling: 25000 or less, the oil film equivalent of the one before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less.
Since the oil film equivalent tends to increase as the material thickness decreases, the oil film equivalent value in the final three passes gradually increases. Therefore, it is necessary to set an appropriate oil film equivalent for the final three passes having different thicknesses.
If the rolling oil viscosity and the material yield stress are equal in all passes in the final cold rolling, the oil film equivalent is proportional to (rolling speed) / (engagement angle). If the degree of processing is the same, the biting angle decreases as the material thickness decreases, and therefore the oil film equivalent tends to increase as it approaches the final pass. In order to maintain productivity, it is necessary to increase the rolling speed as the material passes closer to the final pass, and the oil film equivalent tends to increase as the material approaches the final pass.
なお、材料厚みが薄くなると油膜当量は大きくなる傾向にあるため、最終3パスにおける油膜当量の値は、徐々に大きくなる。そこで、それぞれ厚みの異なる最終3パスについて、適正な油膜当量を設定する必要がある。
最終冷間圧延において圧延油粘度と材料降伏応力が全パスで等しいとすると、油膜当量は、(圧延速度)/(噛み込み角)に比例する。加工度が同じ場合、材料厚みが薄くなると噛み込み角は小さくなるために、最終パスに近づくほど油膜当量は大きくなる傾向にある。また生産性を保つためには、材料長さの長い最終パスに近づくほど圧延速度を上げる必要があり、これによっても最終パスに近づくほど油膜当量は大きくなる傾向にある。 As a method of managing the work hardening index of copper foil after annealing at 350 ° C for 0.5 hour to 0.3 or more, the total work degree during final cold rolling should be 85% or more, and the oil film in the final three passes in final cold rolling Adjusting the equivalent weight can be mentioned. Specifically, the oil film equivalent of the last two passes in the final cold rolling: 25000 or less, the oil film equivalent of the one before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less.
Since the oil film equivalent tends to increase as the material thickness decreases, the oil film equivalent value in the final three passes gradually increases. Therefore, it is necessary to set an appropriate oil film equivalent for the final three passes having different thicknesses.
If the rolling oil viscosity and the material yield stress are equal in all passes in the final cold rolling, the oil film equivalent is proportional to (rolling speed) / (engagement angle). If the degree of processing is the same, the biting angle decreases as the material thickness decreases, and therefore the oil film equivalent tends to increase as it approaches the final pass. In order to maintain productivity, it is necessary to increase the rolling speed as the material passes closer to the final pass, and the oil film equivalent tends to increase as the material approaches the final pass.
そして、最終冷間圧延における中間パスでの油膜当量が大きいと、最終パスで油膜当量を低く抑えても加工硬化指数を0.3以上にする効果を得ることができない。このようなことから、最終冷間圧延における最終3パスにおける油膜当量を管理している。
油膜当量を低減するために、最終パスの圧延加工度を25%以上にするのが良い。 If the oil film equivalent in the intermediate pass in the final cold rolling is large, the work hardening index cannot be increased to 0.3 or more even if the oil film equivalent is kept low in the final pass. For this reason, the oil film equivalent in the final three passes in the final cold rolling is managed.
In order to reduce the oil film equivalent, the rolling degree of the final pass should be 25% or more.
油膜当量を低減するために、最終パスの圧延加工度を25%以上にするのが良い。 If the oil film equivalent in the intermediate pass in the final cold rolling is large, the work hardening index cannot be increased to 0.3 or more even if the oil film equivalent is kept low in the final pass. For this reason, the oil film equivalent in the final three passes in the final cold rolling is managed.
In order to reduce the oil film equivalent, the rolling degree of the final pass should be 25% or more.
なお、上記油膜当量は下記式で表される。(油膜当量)={(圧延油粘度、40℃の動粘度;cSt)×(圧延速度;m/分)}/{(材料の降伏応力;kg/mm2)×(ロール噛込角;rad)}
圧延油粘度は4.0~8.0cSt程度、圧延速度200~600m/分、ロールの噛込角は例えば0.0005~0.005rad、好ましくは0.001~0.04radとすることができる。 The oil film equivalent is represented by the following formula. (Oil film equivalent) = {(rolling oil viscosity, kinematic viscosity at 40 ° C .; cSt) × (rolling speed; m / min)} / {(yield stress of material; kg / mm 2 ) × (roll biting angle; rad )}
The rolling oil viscosity can be about 4.0 to 8.0 cSt, the rolling speed is 200 to 600 m / min, and the biting angle of the roll is, for example, 0.0005 to 0.005 rad, preferably 0.001 to 0.04 rad.
圧延油粘度は4.0~8.0cSt程度、圧延速度200~600m/分、ロールの噛込角は例えば0.0005~0.005rad、好ましくは0.001~0.04radとすることができる。 The oil film equivalent is represented by the following formula. (Oil film equivalent) = {(rolling oil viscosity, kinematic viscosity at 40 ° C .; cSt) × (rolling speed; m / min)} / {(yield stress of material; kg / mm 2 ) × (roll biting angle; rad )}
The rolling oil viscosity can be about 4.0 to 8.0 cSt, the rolling speed is 200 to 600 m / min, and the biting angle of the roll is, for example, 0.0005 to 0.005 rad, preferably 0.001 to 0.04 rad.
<I(220)/I(200)>
本発明の銅箔において、I(220)/I(200)を0.11以下とする。純銅型の再結晶集合組織は銅箔表面方向に(200)面が向くことが特徴であるが、このとき圧延平行方向および圧延直角方向にも(200)面が向く。又、一般的に銅箔を曲げる場合、圧延平行方向または圧延直角方向に曲げ軸を取るが、このとき銅箔にかかる変形によって銅の主すべり面である{111}面が多重すべりを生じ、高い加工硬化指数が得られる。一方、 (200)面以外の結晶方位が支配的である場合には、充分な多重すべりが起こらず、高い加工硬化指数が得られない。以上の理由から、曲げ軸に対して{001}方位をもつ結晶が多いほど、曲げ性に優れた銅箔となる。
ここで、純銅型の再結晶集合組織は、ND方向(圧延面法線方向)、RD方向、TD方向の各方向に{001}方位を向けることから、曲げ方向であるRD方向やTD方向を代用して測定の容易なND方向の(200)面回折強度を指標として用いることができる。
なお、本発明の銅箔は、CCL形成時相当の熱処理に相当する処理(350℃で0.5時間焼鈍)後のI(220)/I(200)を0.11以下とする。焼鈍雰囲気としては、表面酸化を防止するため、非酸化性雰囲気が好ましい。 <I (220) / I (200)>
In the copper foil of the present invention, I (220) / I (200) is 0.11 or less. The pure copper-type recrystallized texture is characterized in that the (200) plane faces in the direction of the copper foil surface. At this time, the (200) plane also faces in the rolling parallel direction and the direction perpendicular to the rolling. In general, when bending a copper foil, the bending axis is taken in the direction parallel to the rolling or the direction perpendicular to the rolling. At this time, due to the deformation applied to the copper foil, the {111} surface, which is the main sliding surface of the copper, causes multiple slips. A high work hardening index can be obtained. On the other hand, when the crystal orientation other than the (200) plane is dominant, sufficient multiple slip does not occur and a high work hardening index cannot be obtained. For the above reasons, the more crystals having the {001} orientation with respect to the bending axis, the better the copper foil becomes.
Here, since the recrystallized texture of the pure copper type has the {001} direction in each of the ND direction (rolling surface normal direction), RD direction, and TD direction, the RD direction and TD direction which are bending directions are Alternatively, the (200) plane diffraction intensity in the ND direction, which can be easily measured, can be used as an index.
In addition, the copper foil of this invention makes I (220) / I (200) after the process (annealing at 350 degreeC for 0.5 hour) equivalent to the heat processing equivalent at the time of CCL formation 0.11 or less. The annealing atmosphere is preferably a non-oxidizing atmosphere in order to prevent surface oxidation.
本発明の銅箔において、I(220)/I(200)を0.11以下とする。純銅型の再結晶集合組織は銅箔表面方向に(200)面が向くことが特徴であるが、このとき圧延平行方向および圧延直角方向にも(200)面が向く。又、一般的に銅箔を曲げる場合、圧延平行方向または圧延直角方向に曲げ軸を取るが、このとき銅箔にかかる変形によって銅の主すべり面である{111}面が多重すべりを生じ、高い加工硬化指数が得られる。一方、 (200)面以外の結晶方位が支配的である場合には、充分な多重すべりが起こらず、高い加工硬化指数が得られない。以上の理由から、曲げ軸に対して{001}方位をもつ結晶が多いほど、曲げ性に優れた銅箔となる。
ここで、純銅型の再結晶集合組織は、ND方向(圧延面法線方向)、RD方向、TD方向の各方向に{001}方位を向けることから、曲げ方向であるRD方向やTD方向を代用して測定の容易なND方向の(200)面回折強度を指標として用いることができる。
なお、本発明の銅箔は、CCL形成時相当の熱処理に相当する処理(350℃で0.5時間焼鈍)後のI(220)/I(200)を0.11以下とする。焼鈍雰囲気としては、表面酸化を防止するため、非酸化性雰囲気が好ましい。 <I (220) / I (200)>
In the copper foil of the present invention, I (220) / I (200) is 0.11 or less. The pure copper-type recrystallized texture is characterized in that the (200) plane faces in the direction of the copper foil surface. At this time, the (200) plane also faces in the rolling parallel direction and the direction perpendicular to the rolling. In general, when bending a copper foil, the bending axis is taken in the direction parallel to the rolling or the direction perpendicular to the rolling. At this time, due to the deformation applied to the copper foil, the {111} surface, which is the main sliding surface of the copper, causes multiple slips. A high work hardening index can be obtained. On the other hand, when the crystal orientation other than the (200) plane is dominant, sufficient multiple slip does not occur and a high work hardening index cannot be obtained. For the above reasons, the more crystals having the {001} orientation with respect to the bending axis, the better the copper foil becomes.
Here, since the recrystallized texture of the pure copper type has the {001} direction in each of the ND direction (rolling surface normal direction), RD direction, and TD direction, the RD direction and TD direction which are bending directions are Alternatively, the (200) plane diffraction intensity in the ND direction, which can be easily measured, can be used as an index.
In addition, the copper foil of this invention makes I (220) / I (200) after the process (annealing at 350 degreeC for 0.5 hour) equivalent to the heat processing equivalent at the time of CCL formation 0.11 or less. The annealing atmosphere is preferably a non-oxidizing atmosphere in order to prevent surface oxidation.
又、以下の理由により、焼鈍によって充分に再結晶組織を得る必要があることから、銅箔の半軟化温度を150℃以下にすることが好ましい。充分に再結晶組織を得るためには、銅箔の組成と加工度を調整して再結晶温度を適切に管理する必要があるが、銅箔の組成と加工度を上記範囲に規定すれば、再結晶温度が120~150℃程度となり、半軟化温度を150℃以下とすることができる。
ここで、未再結晶組織は加工ひずみが残留しており、すでに加工硬化しているために曲げ変形による加工硬化がしにくく、加工硬化指数が小さくなり、曲げ性が悪くなる。加工硬化指数を大きな値にするには、銅箔をCCLに積層した状態が加工硬化してない状態、すなわち加工ひずみが除去された状態である必要がある。言い換えれば、CCL製造過程で銅箔は熱処理を受けるが、その熱処理によりひずみが除去され、再結晶することが必要となる。そして、銅箔の半軟化温度が150℃以下であれば、CCL製造過程で受ける程度の熱処理によっても銅箔の再結晶が期待でき、加工硬化指数を大きくすることができる。 Moreover, since it is necessary to obtain a recrystallized structure sufficiently by annealing for the following reasons, the semi-softening temperature of the copper foil is preferably set to 150 ° C. or lower. In order to sufficiently obtain a recrystallized structure, it is necessary to adjust the composition and processing degree of the copper foil and appropriately control the recrystallization temperature, but if the copper foil composition and the processing degree are defined in the above range, The recrystallization temperature becomes about 120 to 150 ° C., and the semi-softening temperature can be made 150 ° C. or less.
Here, the non-recrystallized structure has a work strain remaining, and since it has already been work hardened, it is difficult to work harden by bending deformation, the work hardening index becomes small, and the bendability deteriorates. In order to increase the work hardening index, it is necessary that the state in which the copper foil is laminated on the CCL is a state in which the work hardening is not performed, that is, a state in which the work strain is removed. In other words, the copper foil undergoes a heat treatment in the CCL manufacturing process, but the strain is removed by the heat treatment, and it is necessary to recrystallize. And if the semi-softening temperature of copper foil is 150 degrees C or less, recrystallization of copper foil can be anticipated also by the heat processing received to a CCL manufacturing process, and a work hardening index | exponent can be enlarged.
ここで、未再結晶組織は加工ひずみが残留しており、すでに加工硬化しているために曲げ変形による加工硬化がしにくく、加工硬化指数が小さくなり、曲げ性が悪くなる。加工硬化指数を大きな値にするには、銅箔をCCLに積層した状態が加工硬化してない状態、すなわち加工ひずみが除去された状態である必要がある。言い換えれば、CCL製造過程で銅箔は熱処理を受けるが、その熱処理によりひずみが除去され、再結晶することが必要となる。そして、銅箔の半軟化温度が150℃以下であれば、CCL製造過程で受ける程度の熱処理によっても銅箔の再結晶が期待でき、加工硬化指数を大きくすることができる。 Moreover, since it is necessary to obtain a recrystallized structure sufficiently by annealing for the following reasons, the semi-softening temperature of the copper foil is preferably set to 150 ° C. or lower. In order to sufficiently obtain a recrystallized structure, it is necessary to adjust the composition and processing degree of the copper foil and appropriately control the recrystallization temperature, but if the copper foil composition and the processing degree are defined in the above range, The recrystallization temperature becomes about 120 to 150 ° C., and the semi-softening temperature can be made 150 ° C. or less.
Here, the non-recrystallized structure has a work strain remaining, and since it has already been work hardened, it is difficult to work harden by bending deformation, the work hardening index becomes small, and the bendability deteriorates. In order to increase the work hardening index, it is necessary that the state in which the copper foil is laminated on the CCL is a state in which the work hardening is not performed, that is, a state in which the work strain is removed. In other words, the copper foil undergoes a heat treatment in the CCL manufacturing process, but the strain is removed by the heat treatment, and it is necessary to recrystallize. And if the semi-softening temperature of copper foil is 150 degrees C or less, recrystallization of copper foil can be anticipated also by the heat processing received to a CCL manufacturing process, and a work hardening index | exponent can be enlarged.
さらに、本発明の実施形態に係る銅箔の片面に樹脂層を積層した合計厚みが50μm以下で、幅3mm以上5mm以下の試料を用い、銅箔の露出面を外側として180度密着曲げを行った場合に、銅箔が破断するまでの曲げ回数が4回以上であることが好ましい。
銅箔の片面に樹脂層を積層した合計厚みが50μm以下の試料は、銅張積層板を模したものであり、その180度密着曲げの曲げ回数は、銅張積層板の曲げ性を評価したことになる。
樹脂層としては、ポリイミド;PET(ポリエチレンテレフタレート);エポキシ樹脂、フェノール樹脂等の熱硬化性樹脂;飽和ポリエステル樹脂等の熱可塑性樹脂を用いることができるがこれらに限定されない。又、これら樹脂層の成分を溶剤に溶かしたワニス(例えば、ポリイミドの前駆体のポリアミック酸溶液)を銅箔の片面に塗布し、加熱することで溶媒を除去して反応(例えばイミド化反応)を進行させ、硬化させてもよい。 Furthermore, the total thickness of the resin layers laminated on one side of the copper foil according to the embodiment of the present invention is 50 μm or less, and a sample having a width of 3 mm or more and 5 mm or less is used, and 180 ° adhesion bending is performed with the exposed surface of the copper foil as the outside. In this case, the number of times of bending until the copper foil breaks is preferably 4 times or more.
A sample having a total thickness of 50 μm or less, in which a resin layer is laminated on one side of a copper foil, imitates a copper-clad laminate, and the number of bends of 180-degree contact bending evaluated the bendability of the copper-clad laminate. It will be.
As the resin layer, polyimide; PET (polyethylene terephthalate); thermosetting resin such as epoxy resin and phenol resin; thermoplastic resin such as saturated polyester resin can be used, but is not limited thereto. In addition, varnish (for example, polyamic acid solution of polyimide precursor) in which the components of these resin layers are dissolved in a solvent is applied to one side of a copper foil, and the solvent is removed by heating to react (for example, imidization reaction). May be allowed to proceed and cured.
銅箔の片面に樹脂層を積層した合計厚みが50μm以下の試料は、銅張積層板を模したものであり、その180度密着曲げの曲げ回数は、銅張積層板の曲げ性を評価したことになる。
樹脂層としては、ポリイミド;PET(ポリエチレンテレフタレート);エポキシ樹脂、フェノール樹脂等の熱硬化性樹脂;飽和ポリエステル樹脂等の熱可塑性樹脂を用いることができるがこれらに限定されない。又、これら樹脂層の成分を溶剤に溶かしたワニス(例えば、ポリイミドの前駆体のポリアミック酸溶液)を銅箔の片面に塗布し、加熱することで溶媒を除去して反応(例えばイミド化反応)を進行させ、硬化させてもよい。 Furthermore, the total thickness of the resin layers laminated on one side of the copper foil according to the embodiment of the present invention is 50 μm or less, and a sample having a width of 3 mm or more and 5 mm or less is used, and 180 ° adhesion bending is performed with the exposed surface of the copper foil as the outside. In this case, the number of times of bending until the copper foil breaks is preferably 4 times or more.
A sample having a total thickness of 50 μm or less, in which a resin layer is laminated on one side of a copper foil, imitates a copper-clad laminate, and the number of bends of 180-degree contact bending evaluated the bendability of the copper-clad laminate. It will be.
As the resin layer, polyimide; PET (polyethylene terephthalate); thermosetting resin such as epoxy resin and phenol resin; thermoplastic resin such as saturated polyester resin can be used, but is not limited thereto. In addition, varnish (for example, polyamic acid solution of polyimide precursor) in which the components of these resin layers are dissolved in a solvent is applied to one side of a copper foil, and the solvent is removed by heating to react (for example, imidization reaction). May be allowed to proceed and cured.
180度密着曲げは、折り目が自身の幅方向に平行になるように試料を折り返し、ハンドプレスで潰して重ねて行う。そして、曲げ部の断面の銅箔部分の破断の有無を光学顕微鏡で観察する。破断がなければ、密着曲げ後の試料を開き、ハンドプレスを用いて平らに伸ばした後に、同じ場所でもう一度折り返してハンドプレスで潰す。このようにして、銅箔が破断するまでの曲げ回数を求める。
The 180-degree close contact bending is performed by folding the sample so that the crease is parallel to its own width direction, and crushing and stacking with a hand press. And the presence or absence of a fracture | rupture of the copper foil part of the cross section of a bending part is observed with an optical microscope. If there is no break, the sample after close contact bending is opened, stretched flat using a hand press, then folded back at the same place and crushed with a hand press. In this way, the number of times of bending until the copper foil breaks is determined.
本発明の銅張積層板は、上記した銅箔を、上記樹脂層の少なくとも片面に積層してなる。本発明の実施形態に係る銅箔は、曲げ性に優れるため、これを用いた銅張積層板も曲げ性に優れる。例えば、本発明の銅張積層板は、半径5mm以下で90~180度折り曲げる用途に好適に使用できる。
The copper clad laminate of the present invention is formed by laminating the above copper foil on at least one side of the resin layer. Since the copper foil which concerns on embodiment of this invention is excellent in bendability, the copper clad laminated board using this is also excellent in bendability. For example, the copper clad laminate of the present invention can be suitably used for bending 90 to 180 degrees with a radius of 5 mm or less.
無酸素銅(JIS H0500)またはタフピッチ銅(JIS H0500)を溶解し、必要に応じて表1、表2に示す元素を添加して鋳造し、厚さ20mm、幅60mmのインゴットを作製した。インゴットを厚さ10mmまで熱間圧延後に冷間圧延と焼鈍を適宜繰り返して銅箔を作製した。軟化温度を調整するため、最終冷間圧延時の総加工度を85%以上とし、かつ表面粗さを低減するために、表面が平滑(ロール軸方向でRa≦0.1μm)なロールを用いて最終冷間圧延し、銅箔を製造した。圧延油粘度を4.0~8.0cSt程度とし、圧延速度200~600m/分、ロールの噛込角0.003~0.03radの範囲で調整し、最終冷間圧延における最終3パスでの油膜当量をいずれも35000以下(最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下)となるようにした。
Oxygen-free copper (JIS H0500) or tough pitch copper (JIS H0500) was dissolved, and the elements shown in Tables 1 and 2 were added as necessary, followed by casting to produce an ingot having a thickness of 20 mm and a width of 60 mm. After hot rolling the ingot to a thickness of 10 mm, cold rolling and annealing were repeated as appropriate to produce a copper foil. In order to adjust the softening temperature, use a roll with a smooth surface (Ra ≦ 0.1μm in the roll axis direction) in order to reduce the surface roughness to a total workability of 85% or more during final cold rolling. Final cold rolling was performed to produce a copper foil. The rolling oil viscosity is set to about 4.0 to 8.0 cSt, the rolling speed is adjusted to 200 to 600 m / min, and the roll bite angle is set to 0.003 to 0.03 rad, and the oil film equivalent in the final three passes in the final cold rolling is 35,000 for all. The oil film equivalent before the final pass; 25000 or less, the oil film equivalent before the final pass; 30000 or less, the oil film equivalent of the final pass; 35,000 or less.
<加工硬化指数>
得られた銅箔を、それぞれ200℃×0.5時間、及び350℃×0.5時間で焼鈍した後に引張試験(JIS-Z2241に準拠)を行い、加工硬化指数を求めた。なお、加工硬化指数は、材料が降伏した後の均一伸びと応力とを用いて求める必要があるため、伸び2%から最大応力点までの値を用いた。そして、測定した伸び及び応力から求めた真ひずみと、真応力との両対数グラフを最小自乗法で近似し、グラフの傾きから加工硬化指数を求めた。真ひずみと真応力は以下の式で求めた。
[真ひずみ]=ln(1+[ひずみ])
[真応力]=(1+[真ひずみ])×[応力]
なお、この引張試験で破断伸びも求めた。従って、表1、表2の破断伸びは350℃×0.5時間で焼鈍した後の値である。 <Work hardening index>
The obtained copper foils were annealed at 200 ° C. for 0.5 hours and 350 ° C. for 0.5 hours, respectively, and then subjected to a tensile test (based on JIS-Z2241) to obtain a work hardening index. Note that the work hardening index needs to be obtained using the uniform elongation and stress after the material yields, so the value from the elongation of 2% to the maximum stress point was used. Then, a logarithmic graph of true strain and true stress obtained from the measured elongation and stress was approximated by the method of least squares, and a work hardening index was obtained from the slope of the graph. True strain and true stress were determined by the following formulas.
[True strain] = ln (1+ [Strain])
[True stress] = (1+ [true strain]) x [stress]
The elongation at break was also determined by this tensile test. Accordingly, the elongation at break in Tables 1 and 2 is a value after annealing at 350 ° C. × 0.5 hours.
得られた銅箔を、それぞれ200℃×0.5時間、及び350℃×0.5時間で焼鈍した後に引張試験(JIS-Z2241に準拠)を行い、加工硬化指数を求めた。なお、加工硬化指数は、材料が降伏した後の均一伸びと応力とを用いて求める必要があるため、伸び2%から最大応力点までの値を用いた。そして、測定した伸び及び応力から求めた真ひずみと、真応力との両対数グラフを最小自乗法で近似し、グラフの傾きから加工硬化指数を求めた。真ひずみと真応力は以下の式で求めた。
[真ひずみ]=ln(1+[ひずみ])
[真応力]=(1+[真ひずみ])×[応力]
なお、この引張試験で破断伸びも求めた。従って、表1、表2の破断伸びは350℃×0.5時間で焼鈍した後の値である。 <Work hardening index>
The obtained copper foils were annealed at 200 ° C. for 0.5 hours and 350 ° C. for 0.5 hours, respectively, and then subjected to a tensile test (based on JIS-Z2241) to obtain a work hardening index. Note that the work hardening index needs to be obtained using the uniform elongation and stress after the material yields, so the value from the elongation of 2% to the maximum stress point was used. Then, a logarithmic graph of true strain and true stress obtained from the measured elongation and stress was approximated by the method of least squares, and a work hardening index was obtained from the slope of the graph. True strain and true stress were determined by the following formulas.
[True strain] = ln (1+ [Strain])
[True stress] = (1+ [true strain]) x [stress]
The elongation at break was also determined by this tensile test. Accordingly, the elongation at break in Tables 1 and 2 is a value after annealing at 350 ° C. × 0.5 hours.
<半軟化温度>
得られた銅箔を、それぞれ100~400℃×0.5時間で非酸化性雰囲気にて焼鈍した後に引張試験を行い、熱処理条件に対する強度(引張り強さ)を求めた。焼鈍後の強度が、圧延上がり(焼鈍前)の強度と、完全に軟化(300℃で30分間焼鈍)した状態の強度の中間の値となる焼鈍温度を、半軟化温度とした。 <Semi-softening temperature>
The obtained copper foils were annealed in a non-oxidizing atmosphere at 100 to 400 ° C. for 0.5 hours, respectively, and then subjected to a tensile test to determine the strength (tensile strength) against the heat treatment conditions. The annealing temperature at which the strength after annealing was an intermediate value between the strength after rolling (before annealing) and the strength after being completely softened (annealed at 300 ° C. for 30 minutes) was defined as the semi-softening temperature.
得られた銅箔を、それぞれ100~400℃×0.5時間で非酸化性雰囲気にて焼鈍した後に引張試験を行い、熱処理条件に対する強度(引張り強さ)を求めた。焼鈍後の強度が、圧延上がり(焼鈍前)の強度と、完全に軟化(300℃で30分間焼鈍)した状態の強度の中間の値となる焼鈍温度を、半軟化温度とした。 <Semi-softening temperature>
The obtained copper foils were annealed in a non-oxidizing atmosphere at 100 to 400 ° C. for 0.5 hours, respectively, and then subjected to a tensile test to determine the strength (tensile strength) against the heat treatment conditions. The annealing temperature at which the strength after annealing was an intermediate value between the strength after rolling (before annealing) and the strength after being completely softened (annealed at 300 ° C. for 30 minutes) was defined as the semi-softening temperature.
<銅張積層板の折曲回数>
次に、得られた銅箔の片面に、キャスト法で厚み約20μmのポリイミド層を製膜し、片面CCLを作製した。具体的には、得られた銅箔の片面を化学処理(めっき)し、この面にポリイミド樹脂の前駆体ワニス(宇部興産製U-ワニスA)を厚さ20μmになるように塗布した。この後、130℃に設定した熱風循環式高温槽で30分乾燥し、段階的に350℃まで2000秒かけて昇温して硬化(イミド化)して樹脂層(ポリイミド層)を形成し、片面CCLを作製した。
180度密着曲げは以下の手順で行った。まず、この片面CCLを幅3.2mm、長さ30mmで試験片の長さ方向が圧延方向と平行になるように切り出して試験片とし、樹脂層面を内側にしてループ状にし、ハンドプレスで潰して180度密着曲げを行った。そして、曲げ部の断面の銅箔部分の破断の有無を光学顕微鏡で観察した。破断がなければ、密着曲げ後の試料を開き、ハンドプレスを用いて平らに伸ばした後に、同じ場所でもう一度折り返してハンドプレスで潰した。このようにして、銅箔が破断するまでの曲げ回数を求めた。 <Number of bending of copper clad laminate>
Next, a polyimide layer having a thickness of about 20 μm was formed on one side of the obtained copper foil by a casting method to produce a single-sided CCL. Specifically, one side of the obtained copper foil was subjected to chemical treatment (plating), and a polyimide resin precursor varnish (U-Vanice A made by Ube Industries) was applied to this surface to a thickness of 20 μm. After that, it is dried for 30 minutes in a hot air circulation high temperature bath set at 130 ° C., and heated up to 350 ° C. over 2000 seconds and cured (imidized) to form a resin layer (polyimide layer). Single-sided CCL was prepared.
180 degree contact bending was performed according to the following procedure. First, this single-sided CCL is 3.2 mm wide, 30 mm long, cut out so that the length direction of the test piece is parallel to the rolling direction, and made into a test piece, looped with the resin layer side inside, and crushed with a hand press 180 degree close contact bending was performed. And the presence or absence of the fracture | rupture of the copper foil part of the cross section of a bending part was observed with the optical microscope. If there was no break, the sample after close contact bending was opened and stretched flat using a hand press, then folded back at the same place and crushed with a hand press. In this way, the number of bendings until the copper foil broke was determined.
次に、得られた銅箔の片面に、キャスト法で厚み約20μmのポリイミド層を製膜し、片面CCLを作製した。具体的には、得られた銅箔の片面を化学処理(めっき)し、この面にポリイミド樹脂の前駆体ワニス(宇部興産製U-ワニスA)を厚さ20μmになるように塗布した。この後、130℃に設定した熱風循環式高温槽で30分乾燥し、段階的に350℃まで2000秒かけて昇温して硬化(イミド化)して樹脂層(ポリイミド層)を形成し、片面CCLを作製した。
180度密着曲げは以下の手順で行った。まず、この片面CCLを幅3.2mm、長さ30mmで試験片の長さ方向が圧延方向と平行になるように切り出して試験片とし、樹脂層面を内側にしてループ状にし、ハンドプレスで潰して180度密着曲げを行った。そして、曲げ部の断面の銅箔部分の破断の有無を光学顕微鏡で観察した。破断がなければ、密着曲げ後の試料を開き、ハンドプレスを用いて平らに伸ばした後に、同じ場所でもう一度折り返してハンドプレスで潰した。このようにして、銅箔が破断するまでの曲げ回数を求めた。 <Number of bending of copper clad laminate>
Next, a polyimide layer having a thickness of about 20 μm was formed on one side of the obtained copper foil by a casting method to produce a single-sided CCL. Specifically, one side of the obtained copper foil was subjected to chemical treatment (plating), and a polyimide resin precursor varnish (U-Vanice A made by Ube Industries) was applied to this surface to a thickness of 20 μm. After that, it is dried for 30 minutes in a hot air circulation high temperature bath set at 130 ° C., and heated up to 350 ° C. over 2000 seconds and cured (imidized) to form a resin layer (polyimide layer). Single-sided CCL was prepared.
180 degree contact bending was performed according to the following procedure. First, this single-sided CCL is 3.2 mm wide, 30 mm long, cut out so that the length direction of the test piece is parallel to the rolling direction, and made into a test piece, looped with the resin layer side inside, and crushed with a hand press 180 degree close contact bending was performed. And the presence or absence of the fracture | rupture of the copper foil part of the cross section of a bending part was observed with the optical microscope. If there was no break, the sample after close contact bending was opened and stretched flat using a hand press, then folded back at the same place and crushed with a hand press. In this way, the number of bendings until the copper foil broke was determined.
<銅箔の摺動屈曲回数>
次に、得られた銅箔を、幅12.7 mm,長さ200 mmで試験片の長さ方向が圧延方向と平行になるように切り出して試験片とし、200℃で30分間加熱して再結晶させた。このものを、図1に示すIPC(アメリカプリント回路工業会)摺動屈曲装置により,IPC摺動屈曲回数の測定を行った。この装置は,発振駆動体4に振動伝達部材3を結合した構造になっており,試験片1は,矢印で示したねじ2の部分と3の先端部の計4点で装置に固定される。振動部3が上下に駆動すると,試験片1の中間部は,所定の曲率半径rでヘアピン状に屈曲される。本試験では,以下の条件下で屈曲を繰り返した時の破断までの回数を求めた。
曲率半径r:2.5 mm,振動ストローク:25mm,振動速度:1500回/分の条件で試験を行った。ただし、実施例17は曲率半径r:0.9mmとした。これは屈曲時に銅箔にかかるひずみ量を、実施例17より厚い他の実施例と同等とするためである。 <Number of sliding and bending of copper foil>
Next, the obtained copper foil was cut out to have a width of 12.7 mm and a length of 200 mm so that the length direction of the test piece was parallel to the rolling direction, and it was recrystallized by heating at 200 ° C. for 30 minutes. I let you. This was measured for the number of IPC sliding bends using an IPC (American Printed Circuit Industry Association) slide bending apparatus shown in FIG. This apparatus has a structure in which avibration transmission member 3 is coupled to an oscillation driver 4, and the test piece 1 is fixed to the apparatus at a total of four points including a screw 2 portion and an end portion 3 indicated by arrows. . When the vibration part 3 is driven up and down, the intermediate part of the test piece 1 is bent into a hairpin shape with a predetermined radius of curvature r. In this test, the number of times to break when bending was repeated under the following conditions was obtained.
The test was performed under the conditions of a radius of curvature r: 2.5 mm, a vibration stroke: 25 mm, and a vibration speed: 1500 times / minute. However, in Example 17, the radius of curvature r was 0.9 mm. This is because the amount of strain applied to the copper foil at the time of bending is made equal to that of another example thicker than Example 17.
次に、得られた銅箔を、幅12.7 mm,長さ200 mmで試験片の長さ方向が圧延方向と平行になるように切り出して試験片とし、200℃で30分間加熱して再結晶させた。このものを、図1に示すIPC(アメリカプリント回路工業会)摺動屈曲装置により,IPC摺動屈曲回数の測定を行った。この装置は,発振駆動体4に振動伝達部材3を結合した構造になっており,試験片1は,矢印で示したねじ2の部分と3の先端部の計4点で装置に固定される。振動部3が上下に駆動すると,試験片1の中間部は,所定の曲率半径rでヘアピン状に屈曲される。本試験では,以下の条件下で屈曲を繰り返した時の破断までの回数を求めた。
曲率半径r:2.5 mm,振動ストローク:25mm,振動速度:1500回/分の条件で試験を行った。ただし、実施例17は曲率半径r:0.9mmとした。これは屈曲時に銅箔にかかるひずみ量を、実施例17より厚い他の実施例と同等とするためである。 <Number of sliding and bending of copper foil>
Next, the obtained copper foil was cut out to have a width of 12.7 mm and a length of 200 mm so that the length direction of the test piece was parallel to the rolling direction, and it was recrystallized by heating at 200 ° C. for 30 minutes. I let you. This was measured for the number of IPC sliding bends using an IPC (American Printed Circuit Industry Association) slide bending apparatus shown in FIG. This apparatus has a structure in which a
The test was performed under the conditions of a radius of curvature r: 2.5 mm, a vibration stroke: 25 mm, and a vibration speed: 1500 times / minute. However, in Example 17, the radius of curvature r was 0.9 mm. This is because the amount of strain applied to the copper foil at the time of bending is made equal to that of another example thicker than Example 17.
<I(220)/I(200)>
得られた銅箔を、350℃×0.5時間で非酸化性雰囲気にて焼鈍した後,圧延面のX線回折を行い、それぞれ(220)面及び(200)面の回折ピーク強度の積分値(I)を求めた。 <I (220) / I (200)>
The obtained copper foil was annealed in a non-oxidizing atmosphere at 350 ° C. for 0.5 hour, and then X-ray diffraction was performed on the rolled surface, and the integrated values of diffraction peak intensities on the (220) plane and (200) plane, respectively ( I).
得られた銅箔を、350℃×0.5時間で非酸化性雰囲気にて焼鈍した後,圧延面のX線回折を行い、それぞれ(220)面及び(200)面の回折ピーク強度の積分値(I)を求めた。 <I (220) / I (200)>
The obtained copper foil was annealed in a non-oxidizing atmosphere at 350 ° C. for 0.5 hour, and then X-ray diffraction was performed on the rolled surface, and the integrated values of diffraction peak intensities on the (220) plane and (200) plane, respectively ( I).
得られた結果を表1、表2に示す。なお、表1、表2の組成において、OFC及びTPCは、それぞれ無酸素銅及びタフピッチ銅(JIS H3100)を示し、Ag100ppmTPCは、タフピッチ銅にAgを100質量ppm添加したものを示す。
なお、JIS H3100に規格されている無酸素銅とJIS H0500に規格されている無酸素銅はいずれも合金番号C1020で同じである。また、JIS H3100に規格されているタフピッチ銅とJIS H0500に規格されているタフピッチ銅はいずれも合金番号C1100で同じである。 The obtained results are shown in Tables 1 and 2. In the compositions of Tables 1 and 2, OFC and TPC indicate oxygen-free copper and tough pitch copper (JIS H3100), respectively, and Ag100 ppm TPC indicates that 100 mass ppm of Ag is added to tough pitch copper.
The oxygen-free copper specified in JIS H3100 and the oxygen-free copper specified in JIS H0500 are both the same in alloy number C1020. Moreover, the tough pitch copper specified in JIS H3100 and the tough pitch copper specified in JIS H0500 are both the same in alloy number C1100.
なお、JIS H3100に規格されている無酸素銅とJIS H0500に規格されている無酸素銅はいずれも合金番号C1020で同じである。また、JIS H3100に規格されているタフピッチ銅とJIS H0500に規格されているタフピッチ銅はいずれも合金番号C1100で同じである。 The obtained results are shown in Tables 1 and 2. In the compositions of Tables 1 and 2, OFC and TPC indicate oxygen-free copper and tough pitch copper (JIS H3100), respectively, and Ag100 ppm TPC indicates that 100 mass ppm of Ag is added to tough pitch copper.
The oxygen-free copper specified in JIS H3100 and the oxygen-free copper specified in JIS H0500 are both the same in alloy number C1020. Moreover, the tough pitch copper specified in JIS H3100 and the tough pitch copper specified in JIS H0500 are both the same in alloy number C1100.
表1、表2から明らかなように、I(220)/I(200)が0.11以下、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上である実施例1~20の場合、180度密着曲げを行ったときの曲げ回数が4回以上であり、曲げ性に優れたものとなった。
一方、最終冷間圧延時の総加工度を85%未満とした比較例3、5,6,7の場合、350℃で0.5時間焼鈍後の加工硬化指数が0.3未満となり、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。なお、比較例1の場合、銅箔中のSnの添加量が500質量ppmを超えたために半軟化温度が150℃を超え、加工硬化指数が0.3未満となったものと考えられる。
また半軟化温度が150℃を超えた比較例1、6,7の場合、350℃で0.5時間焼鈍後の加工硬化指数が0.3未満となり、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。 As is clear from Tables 1 and 2, in Examples 1 to 20 where I (220) / I (200) is 0.11 or less and the work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 or more, 180 The number of times of bending when performing close contact bending was 4 times or more, and the bending property was excellent.
On the other hand, in Comparative Examples 3, 5, 6, and 7 in which the total degree of work during the final cold rolling was less than 85%, the work hardening index after annealing at 350 ° C. for 0.5 hours was less than 0.3, and the 180 degree adhesive bending was performed. The number of bendings performed was less than 4 and the bendability deteriorated. In addition, in the case of the comparative example 1, since the addition amount of Sn in copper foil exceeded 500 mass ppm, it is thought that the semisoftening temperature exceeded 150 degreeC and the work hardening index became less than 0.3.
In Comparative Examples 1, 6, and 7 where the semi-softening temperature exceeded 150 ° C, the work hardening index after annealing at 350 ° C for 0.5 hour was less than 0.3, and the number of bendings when the 180 ° contact bending was performed was 4 times. As a result, the bendability deteriorated.
一方、最終冷間圧延時の総加工度を85%未満とした比較例3、5,6,7の場合、350℃で0.5時間焼鈍後の加工硬化指数が0.3未満となり、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。なお、比較例1の場合、銅箔中のSnの添加量が500質量ppmを超えたために半軟化温度が150℃を超え、加工硬化指数が0.3未満となったものと考えられる。
また半軟化温度が150℃を超えた比較例1、6,7の場合、350℃で0.5時間焼鈍後の加工硬化指数が0.3未満となり、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。 As is clear from Tables 1 and 2, in Examples 1 to 20 where I (220) / I (200) is 0.11 or less and the work hardening index after annealing at 350 ° C. for 0.5 hour is 0.3 or more, 180 The number of times of bending when performing close contact bending was 4 times or more, and the bending property was excellent.
On the other hand, in Comparative Examples 3, 5, 6, and 7 in which the total degree of work during the final cold rolling was less than 85%, the work hardening index after annealing at 350 ° C. for 0.5 hours was less than 0.3, and the 180 degree adhesive bending was performed. The number of bendings performed was less than 4 and the bendability deteriorated. In addition, in the case of the comparative example 1, since the addition amount of Sn in copper foil exceeded 500 mass ppm, it is thought that the semisoftening temperature exceeded 150 degreeC and the work hardening index became less than 0.3.
In Comparative Examples 1, 6, and 7 where the semi-softening temperature exceeded 150 ° C, the work hardening index after annealing at 350 ° C for 0.5 hour was less than 0.3, and the number of bendings when the 180 ° contact bending was performed was 4 times. As a result, the bendability deteriorated.
最終冷間圧延における最終3パスでの油膜当量として、最終パスの2つ前の油膜当量;25000を超え、最終パスの1つ前の油膜当量;30000を超え、最終パスの油膜当量; 35000を超えた比較例2の場合、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。
最終冷間圧延における最終3パスでの油膜当量のうち、最終パスの2つ前の油膜当量が25000を超えた比較例4の場合、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。 As the oil film equivalent in the final three passes in the final cold rolling, the oil film equivalent in the last two passes; over 25000, the oil film equivalent in the previous one in the final pass; over 30000, the oil film equivalent in the final pass; 35000 In the case of the comparative example 2 that exceeded, the number of bendings when the 180-degree contact bending was performed was less than 4, and the bendability deteriorated.
In the case of Comparative Example 4 in which the oil film equivalent of the last three passes in the final cold rolling exceeds 25000, the number of times of bending when 180 degree contact bending is performed is less than four times. The bendability deteriorated.
最終冷間圧延における最終3パスでの油膜当量のうち、最終パスの2つ前の油膜当量が25000を超えた比較例4の場合、180度密着曲げを行ったときの曲げ回数が4回未満となって曲げ性が劣化した。 As the oil film equivalent in the final three passes in the final cold rolling, the oil film equivalent in the last two passes; over 25000, the oil film equivalent in the previous one in the final pass; over 30000, the oil film equivalent in the final pass; 35000 In the case of the comparative example 2 that exceeded, the number of bendings when the 180-degree contact bending was performed was less than 4, and the bendability deteriorated.
In the case of Comparative Example 4 in which the oil film equivalent of the last three passes in the final cold rolling exceeds 25000, the number of times of bending when 180 degree contact bending is performed is less than four times. The bendability deteriorated.
なお、比較例1~7の場合も、従来の屈曲性の評価であるIPC摺動屈曲回数は各実施例と同等であり、摺動屈曲試験では銅張積層板の曲げ性を評価できないことがわかる。
In the case of Comparative Examples 1 to 7, the number of IPC sliding bends, which is the conventional evaluation of bendability, is the same as each example, and the bendability of the copper clad laminate cannot be evaluated by the slide bend test. Recognize.
Claims (7)
- 厚み5~30μm、350℃で0.5時間焼鈍後のI(220)/I(200)が0.11以下で、かつ350℃で0.5時間焼鈍後の加工硬化指数が0.3以上0.45以下の銅箔。 Copper foil having a thickness of 5 to 30 μm, I (220) / I (200) after annealing for 0.5 hours at 350 ° C. of 0.11 or less, and a work hardening index of 0.3 to 0.45 after annealing for 0.5 hours at 350 ° C.
- 半軟化温度が150℃以下である請求項1に記載の銅箔。 The copper foil according to claim 1, which has a semi-softening temperature of 150 ° C or lower.
- 無酸素銅若しくはタフピッチ銅からなり、又は無酸素銅若しくはタフピッチ銅にAg及びSnの群からなる1種以上を合計500質量ppm以下含む請求項1又は2に記載の銅箔。 The copper foil of Claim 1 or 2 which consists of oxygen-free copper or tough pitch copper, or contains 1 or more types which consist of a group of Ag and Sn in oxygen-free copper or tough pitch copper in total 500 mass ppm or less.
- 無酸素銅又はタフピッチ銅にAg、Sn、In、Ti、Zn、Zr、Fe、P、Ni、Si、Te、Cr、Nb、及びVの群から選ばれる一種以上の元素を合計で20~500質量ppm含む請求項1又は2に記載の銅箔。 Oxygen-free copper or tough pitch copper and 20 to 500 in total of one or more elements selected from the group consisting of Ag, Sn, In, Ti, Zn, Zr, Fe, P, Ni, Si, Te, Cr, Nb, and V The copper foil of Claim 1 or 2 containing mass ppm.
- 前記銅箔の片面に樹脂層を積層した合計厚みが50μm以下で、幅3mm以上5mm以下の試料を用い、前記銅箔の露出面を外側として180度密着曲げを行った場合に、前記銅箔が破断するまでの曲げ回数が4回以上である請求項1~4のいずれかに記載の銅箔。 When the total thickness of the resin layers laminated on one side of the copper foil is 50 μm or less and the width is 3 mm or more and 5 mm or less, and the copper foil is subjected to close contact bending with the exposed surface of the copper foil as the outside, the copper foil The copper foil according to any one of claims 1 to 4, wherein the number of times of bending until breakage is 4 or more.
- 最終冷間圧延時の総加工度が85%以上であり、かつ前記最終冷間圧延における最終3パスでの油膜当量を以下の条件として圧延してなる請求項1~5のいずれかに記載の銅箔。
但し、最終パスの2つ前の油膜当量;25000以下、最終パスの1つ前の油膜当量;30000以下、最終パスの油膜当量; 35000以下 The total work degree at the time of final cold rolling is 85% or more, and the oil film equivalent in the final three passes in the final cold rolling is rolled under the following conditions. Copper foil.
However, the oil film equivalent before the final pass; 25000 or less, the oil film equivalent before the final pass; 30000 or less, the oil film equivalent of the final pass; 35000 or less - 請求項1~6のいずれかに記載の銅箔を、樹脂層の少なくとも片面に積層してなる銅張積層板。 A copper-clad laminate obtained by laminating the copper foil according to any one of claims 1 to 6 on at least one surface of a resin layer.
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JP2014214376A (en) * | 2013-04-30 | 2014-11-17 | 株式会社Shカッパープロダクツ | Rolled copper foil, flexible copper-clad laminated plate, and flexible printed wiring board |
US9232650B2 (en) | 2012-11-09 | 2016-01-05 | Jx Nippon Mining & Metals Corporation | Surface treated copper foil and laminate using the same |
KR20180114532A (en) | 2016-07-12 | 2018-10-18 | 후루카와 덴키 고교 가부시키가이샤 | Electrolytic copper foil |
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JP5362899B1 (en) * | 2012-09-10 | 2013-12-11 | Jx日鉱日石金属株式会社 | Surface-treated copper foil and laminate using the same |
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