TW201242448A - Copper foil and copper-clad laminate obtained using same - Google Patents

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 μ m, has an I(220)/I(200) of 0.11 or less after annealed at 350 C for 0.5 hours, and has a work hardening coefficient of 0.3-0.45 after annealed at 350 C for 0.5 hours.

Description

201242448 VI. Description of the Invention: [Technical Field] The present invention relates to a copper foil used in, for example, a flexible printed wiring board (FPC), and at least laminated the copper foil to a resin layer Single-sided copper clad laminate. [Prior Art] As a circuit for driving an electronic device such as a digital camera or a mobile phone, a flexible printed wiring board (FPC: Flexible Printed Circuit) or a COF (chip 0f flexible circuit) is used. The FPC or COF is used for a copper-clad laminate of a single-sided or double-sided layer of a resin layer, and a circuit pattern is formed on the copper foil. Further, in order to reduce the size and function of such an electronic device, a method of folding and storing the FPC into a narrow space in the casing is employed. For example, in the case of COF used in the periphery of a liquid crystal display, the copper wiring of the COF is folded back to the inner side of the liquid crystal substrate in order to make the bezel (so-called "edge") thin. However, when the FPC or the COF is folded, there is a problem that the copper foil portion is subjected to a large deformation load and is liable to cause cracking. Therefore, it is revealed that there are columnar copper crystal particles and 25. The electrodeposited copper foil having an elongation ratio of 5% or more constitutes Fpc, thereby obtaining an FPC in which the wiring pattern is less likely to be broken (Patent Document 1). [Patent Document 1] Japanese Laid-Open Patent Publication No. 2007-335541. SUMMARY OF THE INVENTION In the prior art, it is considered that the flexibility of the copper foil of CCL is related to the elongation of the copper foil. Therefore, as described in the above-mentioned patent document, the elongation is large. 201242448 Electrolytic copper flute. However, the inventors of the present invention have found that the bending property of CCL is not improved even if a rolled copper pig having a large elongation is used. In other words, the present invention has been made to solve the problems described above, and an object of the present invention is to provide a copper foil which is excellent in flexibility when used for a copper-clad laminate, and a copper-clad laminate using the same. It is found that as a factor for improving the bendability of CCL, it is not the elongation of the copper foil but the work hardening index (η value). To achieve the above object, the copper foil of the present invention has a thickness of 5 to 30/zm and is carried out at 350 °C. After 0.5 hours of annealing, I (22 〇) (2 〇〇) is 〇u or less, and the work hardening index after annealing for 0.5 hours at TC is 〇3 or more and 0.45 or less. The semi-softening temperature of the copper foil of the present invention. Preferably, it is ΐ5〇β〇 or less. Further, the steel slab of the present invention is preferably composed of oxygen-free steel or refined copper, or oxygen-free copper or refined copper, which contains a total of 5 〇〇 mass ppm or less. One or more of the constituent groups. 1 The copper drop of the present invention is preferably selected from the group consisting of Ag, Sn, In, Ti, ZnZr, and Fep as a total of 2〇5〇〇 mass PPm in the oxygen-free copper or the refined copper. One or more elements in the group of 81~., outside, and 乂. Used in the above steel box When the area layer has a resin layer and the total thickness is 5 - or less, and the width is 3 or more and 5 or less, the above: When the exposed surface is the outer side (10) degree close to the f-curve, the upper and lower cracks are preferably better. It is 4 or more times. 'White 1 4 201242448 It is preferable that the total processing degree of the final cold pressing delay is 85% or more, and the oil film equivalent of the last 3 passes of the above final cold rolling is set as follows. , the oil film equivalent of the previous pass before the last pass is set to 2500 or less 'Set the oil film equivalent of the pass before the last pass to 3 〇〇〇〇 or less'. Set the last equivalent of the film equivalent to 3 5% or less. Here, after the hot rolled ingot is cast, the copper foil is produced by cold rolling, and cold rolling and annealing are alternately performed in the cold rolling, and the cold rolling is performed after the final annealing. In the copper-clad laminate of the present invention, the copper foil is laminated on at least one side of the resin layer. According to the present invention, it is possible to obtain a copper ruthenium which is excellent in flexibility when used for a copper-clad laminate. Embodiments Hereinafter, the present invention is directed to the present invention. In addition, the % of the present invention is a mass % unless otherwise specified. The copper foil of the embodiment of the present invention has a thickness of 5 to 3 〇 ym and is 35 〇 for 0.5 hour. The ratio of the integrated intensity of the diffracted peak of the X-ray diffraction after annealing (1〇〇2〇〇) to the integrated intensity of the diffraction peak of 1 (220) is (2) (〇川为为 below ou, and the assignment is performed 0 5 The work hardening index after annealing is 0.3 or more and 45 or less. · <Work hardening index (η value)> The work hardening index (η value) is a plastic deformation above the point of the drop point by the following formula UH〇llomon The exponent η of the relationship between the stress and strain of the F e + if morph Q domain. 201242448 [True stress] = [material constant] χ [true strain] n (!), the greater the work hardening index, the more difficult it is to deform locally, and the more difficult it is to break during deformation. Further, the material having a high work hardening index is excellent in drawing workability, and is suitable for producing a copper clad laminate by pressurizing and adding a layer of copper to at least one side of the resin layer, and evaluating the bending of the copper clad laminate. In the case of sex, the copper foil which is a work hardening number of 〇3 or more is less likely to undergo local deformation and is deformed by the entire curved portion, so that the copper drop is difficult to break. However, the material having a work hardening index exceeding 〇 45 has a low strength after annealing and is inferior in workability, so it is not suitable for use as a copper clad laminate. The work hardening index of 5 5 0 C. The reason of the work hardening index after 5 hours of annealing is because the heating condition for the production of copper clad laminate is Xiao S. 0 production. ^ 'Resin in the laminated steel sheet In the case where the resin composition is coated on a steel crucible and hardened (in the case where the resin layer and the copper drop do not sandwich the second test layer), the resin is cured under the above heating conditions. Further, as a factor for improving the bendability of the copper foil, it is considered that the reason why the copper foil is not stretched by 4 β and the work hardening index (η value) is as follows is as follows. The work hardening index indicates the value of the work hardening behavior of the material. ^ The larger the value, the more the material has the property of work hardening. Here, if the material is locally deformed by the tensile deformation of the island 断裂, the material having a large coefficient is subjected to work hardening, and the shrinkage portion becomes; Therefore, the other part is replaced by the non-variable six v °卩' starting to deform. By repeating this step, the material is evenly uniformed _

It shape. On the other hand, the elongation is a macroscopically used index without considering this condition. 201242448, even if the elongation is larger, the processing hardening index is not necessarily large. Previously, as an index of the ease of uniform deformation of such a material as a whole, for example, a stretch processing order of a material having a thickness, a work hardening index is used. However, a material thinner than (4) is not subjected to drawing processing or the like. In the present invention, it has been considered that the work hardening index is used as an index. The whole is also bent by uniform deformation without breaking. Also, the hardness index of the G·5 after annealing is two or more and less than 45. The reason for this is that the film is formed into a wide layer, and the film and the copper I are laminated on the third layer by the second layer. The work hardening index increases due to (4) crystallization. Therefore, if the work hardening phase of the 350 t low temperature re-distribution I 2 υ υ c is 0.3 or more, then at 35 〇t, in order to fully align the above annealing. : The work hardening index of the second. Private children, r brothers are re-crystallized, the softening temperature of the copper car is preferably 1 50. (: the following. Half (thickness) Stretching: t 'In the drawing of a material having a thickness like a structural member: for example, the material is deformed by the whole sentence, that is, the work hardening index Mb is processed. The thin material does not stretch. Therefore, the work hardening index has not been used as the index Z. Therefore, the thickness of the copper box of the present invention is defined as 5~, and the thickness ratio of the steel foil is 5 to 30 m. In the case of 111 ,, since the proportion of the crystal grains toward the surface of the material of 201242448 becomes large, the difference introduced by the deformation does not accumulate at the grain boundary, and the proportion released from the surface of the material becomes high. Therefore, the copper berth The work hardening index becomes lower than that of a relatively thick material. On the other hand, the work hardening index is determined by the ease of movement of the difference between the set and the difference introduced into the material due to deformation. When there is a precipitate which is a source of the difference ring or a solid solution element and a grain boundary which hinder the movement of the difference row, the work hardening index becomes large. However, if a solid solution element which seriously affects the degree of the displacement movement is added, In the case of a precipitate, the amount of precipitates may be reduced. Therefore, the copper foil for the flexible wiring board is not preferable. (Composition) The copper of the month is preferably JIS-H3. The fine copper specified by the alloy number cU(10) or the alloy of the JIS_H3100 alloy number ^〇2〇, oxy copper as the composition. If it is not similar to the above pure copper, the conductivity of the copper foil is not It is lowered and is suitable for FPC or c〇F. The oxygen concentration contained in the rolled copper is G.G1 to G G5 f in the case of refined copper, and 0.001% by mass or less in the case of oxygen-free copper. Further, the oxygen-free copper may be an oxygen-free copper as defined by the alloy number cl〇1 of Jis-H3510. The progress may be ≥10,500 ppm by mass or less selected from the group consisting of Ag and Sn. If the copper foil is added, the addition of ^ or h will hinder the movement of the difference, so the work hardening coefficient becomes large. If the total addition amount in the rolled copper foil exceeds 5 〇〇 mass ppm, the electrical conductivity decreases and the next day The degree rises and it becomes difficult to suppress the copper foil of 201242448 at the time of final annealing. Generally difficult situation recrystallization annealing of Ag is then oxidized and the surface quality of the 2G

The lower limit of the total amount of addition of Sn is not particularly limited, and is not more than ppm. Further, the above-mentioned steel or the above-mentioned oxygen-free copper may further contain one or more selected from the group consisting of A n, & ςί τ ^ Ζη, Zr, Fe, Ρ, Ni, and ” ^ (10). The method of controlling the work hardening of (4) after Q. 5 hours annealing at 3 耽 is 0.3 or more, and the total plus 2 of the final cold pressing delay is set to 85% or more, and the final adjustment is performed. The oil film equivalent of the last three passes of the cold rolling. Specifically, the oil film equivalent of the previous pass before the last pass of the final cold rolling is set to 25 〇〇〇 or less, and the oil film equivalent of one pass before the last pass is set. When it is 3 GGGG or less, the oil film equivalent of the last pass is 35,000 or less. Further, if the thickness of the material is thin, the oil film equivalent tends to increase, so the value of the oil film equivalent of the last three passes gradually increases. For the last 3 passes of different thicknesses, the appropriate oil film equivalent must be set. In the final cold rolling, 'If the rolling oil viscosity and material lodging stress are equal in all passes, the oil film equivalent system and (calendering speed) bite into The angle is proportional. The same degree of processing When the thickness of the material becomes thinner, the bite angle becomes smaller. Therefore, the closer to the last pass, the greater the oil film equivalent becomes. Further, in order to ensure productivity, the closer to the last length of the material, the more it is needed. Increasing the calendering speed, so there is a tendency that the oil film equivalent becomes larger as it approaches the last pass. And 'If the oil film equivalent in the middle pass of the final cold rolling is large, 201242448 will even be the equivalent of the last pass. If the inhibition is low, the effect of the work hardening index of 〇.3 or higher cannot be obtained. According to this reason, the oil film equivalent of the last 3 passes of the final cold rolling is managed. To reduce the oil film equivalent, the last pass is made. The degree of calendering can be 25% or more. Further, the above oil film equivalent is expressed by the following formula: (oil film equivalent) (calendering oil viscosity, dynamic viscosity of 40t; cSt) X (calendering speed; m/min) (fall of material) Stress; kg / _2: X (roll bite angle; rad ) } The rolling oil viscosity can be set to about 4.0 to 8.0 cSt, the rolling speed can be set to 200 to 600 m / min, and the bite angle of the roll is set to, for example, 〇〇 〇〇5~ 0.005rad Preferably, it is 0.001 to 〇〇4ra (J. <1 (220) / 1 (2〇〇) > In the copper drop of the present invention, (220) (2〇〇) is set to 〇η or less. Although the pure copper type recrystallized aggregate structure is characterized by (2 〇〇). The surface faces the copper falling surface direction 'but the (2 〇〇) plane is also oriented toward the rolling parallel direction and the rolling right angle direction. X...like curved gong In the case of the rolling, the crankshaft is taken in the direction of the flattening direction or the right angle of the rolling. At this time, the main sliding surface of the copper/deformation copper is generated, that is, the {111} plane produces multiple slips, and the work hardening index is southerly. . On the other hand, if the & = azimuth turns outside the (_) plane does not produce sufficient multiple slip, the $ method obtains a harder phase than the inn. For the above reasons, the more crystals having an orientation of 1} with respect to the bending axis, the more excellent the copperness is. Here, 'because of the pure copper type recrystallized aggregate structure {〇〇1} side 10 201242448 ND direction (the calendering surface normal ^ ^ ; KD direction 'the direction of the Ding direction, so you can use the ND side that is easy to measure ^. The diffraction intensity of the door (2〇〇) surface is used as an index instead of the RD or D direction of the bending direction. = The treatment of the copper flute of the present invention and the heat treatment corresponding to the formation of ccl (annealing at 350t) After (5), the "(10) wide (200) is ο. η or less. In the annealing environment, in order to prevent surface oxidation, a non-oxidizing environment is preferable. Further, it is necessary to sufficiently anneal for the following reasons. Since the recrystallized structure is obtained, it is preferable to set the semi-softening temperature of (4) to 15 or less. In order to sufficiently obtain the recrystallized structure, it is necessary to adjust the composition and workability of the copper drop and appropriately control the recrystallization temperature, but if copper is used, When the composition is within the above range, the recrystallization temperature can be set to & i2〇~i5〇C, and the semi-softening temperature is below 150 °C. Here, since there is no recrystallized structure remaining. Processed strain and processed = It is difficult to carry out the work hardening caused by the f-bend deformation, the number of work hardening becomes small, and the bendability is deteriorated. When the work hardening index is set to a large value, the state after the 'steel build-up' CCL must be In the state where the hardening is not applied, P is the state in which the processing should have been removed. In other words, although the copper foil is subjected to heat treatment in the CCL manufacturing process, the strain is removed due to the heat treatment, and only the Further, when the half softening temperature of the copper foil is i 5 〇 ° C or less, the recrystallization of the copper impurities can be expected even by the heat treatment to the extent of the CCL production process, and the work hardening index can be made large. Further, the single-layer layer of the copper foil used in the embodiment of the present invention has a resin layer and a total thickness of 50 μm or less and a width of 3 mm or more and 5 mm of 201242448 or less, and the outer surface of the copper foil is the outer side of the rabbit ice field. When the 180 degree tight bend is performed, the number of bends to the copper foil break is better than that of the *copper (four) area layer =::: is upper;.... The sample under test is a simulated copper clad laminate, which is 18 degrees tightly bonded. Number of bends The bending property of the copper-clad laminate is evaluated. The resin layer may be a polyimide, a polyethylene terephthalate (PET), a thermosetting resin such as an epoxy resin or a phenol resin, and a saturated resin. a thermoplastic resin such as a polystyrene resin, but is not limited thereto. Further, a varnish in which the resin layer components are dissolved in a solvent (for example, a polyamidamine precursor, that is, a polyamidite solution, may be used. Applying to one side of the copper network and heating, thereby removing the solvent to cause the reaction (for example, hydrazine imidization reaction) to proceed and harden it. 1 80 degree close-fitting bending system with the crease parallel to the width direction of itself The sample is folded back and the sample is pressed and flattened by a hand press. Further, the copper foil portion of the cross section of the bent portion was observed by an optical microscope for the presence or absence of breakage. If there is no breakage, the sample after the close bending is opened, and after being stretched flat by using a hand press, it is folded back again at the same portion and crushed by a hand press. Thus, the number of times of bending to the copper foil fracture was obtained. In the copper clad laminate of the present invention, the copper layer is deposited on at least one side of the resin layer. Since the copper foil according to the embodiment of the present invention is excellent in flexibility, the copper-clad laminate using the same is excellent in flexibility. For example, the copper clad laminate of the present invention can be suitably used for the purpose of bending 9 to 180 degrees with a radius of 5 mm or less. Example 12 201242448 Melting oxygen-free copper (JISH0500) or fine copper (jish〇5〇〇) >------- A / 茜 To add the element shown in 纟 2, pray, make thickness from ❼ 2〇mm, width 6. _ cast money. After the cast spinning is hot-rolled to a thickness of 1 (), the cold rolling and annealing are appropriately repeated to prepare a copper drop. In order to adjust the softening temperature, the total degree of processing of the final cold pressing delay is set to 85% or more, and in order to reduce the surface roughness, the final cold rolling is performed using a roll having a smooth surface (in the direction of the shaft axis Ra^.^m). Causeway. Adjusting the calendering oil viscosity to about S.OcSt, rolling speed 2〇〇~6〇〇m/min, and the bite angle of the roll 0.003~0.03rad, so that the last 3 passes of the final cold rolling The equivalent of the oil film equivalent & 35 〇〇〇卩 (the oil film equivalent of the previous pass before the last pass is 25000 or less, before the last pass, the i-time oil film preparation is less than 30,000, the last pass of the oil film equivalent It is 35 〇〇〇 or less). <Process Hardening Index> The obtained steel foil was annealed at 2 Torr (rCx 〇.5 hours and 35 〇<t χ〇5 hours, respectively, and subjected to a tensile test (in accordance with JIS_Z2241) to obtain work hardening. Index. In addition, the value of self-elongation from 2% to the maximum stress point is used because the work hardening index must be obtained by using the mean elongation and stress of the material after the fall. Moreover, the minimum flat method is used to approximate the measured elongation. And the double logarithmic curve of the true strain and the true stress obtained by the stress, and the work hardening index is obtained according to the slope of the curve. The true strain and the true stress are obtained by the following formula [true strain] = In ( 1 + [strain] ]) [Real stress (1+[true strain])χ[stress] Furthermore, the elongation at break is obtained in this tensile test. Therefore, the elongation at break of Table 1, Table 13 201242448 2 is 350 °C. 〇. Value after annealing for 5 hours. <Semi-softening temperature> The obtained copper foil was annealed in a non-oxidizing atmosphere at a temperature of 1 〇〇 to 4 〇〇 ° c χ θ. 5 hours, respectively, and subjected to a tensile test. Find the strength (tensile strength) corresponding to the heat treatment conditions. After annealing The annealing temperature at which the strength becomes the intermediate value of the strength of the rolling rise (annealing) and the state of the state which has been completely softened (annealed at 3 ° C for 3 minutes) is set to a semi-softening temperature. <Bending of a copper clad laminate Folding times> Next, a single-sided CCL is formed by casting a film of a polyimine layer having a thickness of about 2 Å on one side of the obtained copper foil. Specifically, the obtained copper is obtained. One side of the foil was chemically treated (plated), and the polyimide varnish (U-varnish A) was coated on the surface with a thickness of 20 am. The hot air circulation type is dried in a hot air tank for 3 minutes, and is heated to the crucible step by step in 2 seconds. The resin is hardened (醯iminated) to form a resin layer (polyimine) Layer), thereby producing a single-sided CCL. The 180-degree close-bend bending system is carried out in the following order, and the single-sided CCL is cut in such a manner that the width of the single-sided CCL is 3.2 mm, the length is 3 mm, and the longitudinal direction of the test piece is parallel to the rolling direction. As a test piece, the resin layer is inside and is made into a ring shape, and The machine is flattened and subjected to 18-degree tight bending. Then, the optical slanting portion of the curved portion of the curved portion is observed by an optical microscope. If there is no fracture, the sample after the tight bending is opened, and the hand press is stretched. After being flat, it is folded back again at the same portion and flattened by a hand press. Thus, the number of times of bending to the copper foil break is obtained. 14 201242448 <Number of sliding bending of steel foil> Next, the obtained steel foil is made The test piece $Shibai 乂 width U.Tmm, length 200mm and the length of the 1 Wen 4 sensitive piece of blood ^ u B. 彳, soil extension direction parallel to cut out as a test piece, and to 20 (TCi 隹; ^ , Λ, ! ^ . ^ TD ^ Ding 〇 / knife clock heated to recrystallize. By the figure I don't have ipc (US printed mines, 14 forces a D. Industry Association, The Institute of

Pnnted Circuits) The sliding bend is used to measure the number of IPC sliding bends. The device combines the vibration transmitting and oscillating member 3 with the oscillating driving body 4 and the test piece 1 is a total of 4 points of the portion of the screw 2 and the front end of the 3 It is fixed at #胃, *疋方,装置. When the right vibrating portion 3 is driven up and down, the intermediate portion of the test piece 1 is bent in a hairpin shape by a specific ώ. In this test, the number of breaks to the time when the test is repeated is repeated according to the following conditions. The test was carried out under the conditions of radius of curvature r··2.5mm, vibrating line ”.” m cut 仃 spear king. 25mm, 1500 times/min. The degree of x, T, and the 17th method set the radius of curvature r to 〇. 9mn^ This is the same as the other embodiments in which the bending applied to the copper foil is the same as the other embodiments thicker than the embodiment 17. < I ( 220 ) /1 ( 2〇〇) > The obtained copper foil is annealed in a non-oxidizing environment after 35 〇»c 〇5 7|main> hrs, and then x-ray diffraction of the calendering surface is performed, and the (220) plane and (200) are obtained by the knife. The integral value of the diffraction peak intensity of the surface (1). The results obtained are shown in Tables and Table 2. Dan, in the composition of Table 1, Table 2, 0FC and TPC respectively

Non-oxygen-free steel and refined copper (JIS H3100) 'Ag l〇0ppm TPC system is expressed as 1% by mass of Ag added to the fine January. Furthermore, the oxygen-free copper specified in JIS H3100 (1) JIS H0500 stipulated in the 2012 20120448 is the alloy number C1020. Further, the fine copper specified in JIS H3100 is the alloy number C1 100 as the fine copper specified in JIS H0500. 16 201242448 Ιτ^τ

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The number of distortions is 4 or more, and the bending property is excellent. Yu Yu ( 220 ) /1 ( 200 ) is a work hardening index of 0.11 L after fire, and the total processing degree of the final cold press delay of less than 8 5 % when the 1 80 degree close bending is performed is not compared with Comparative Example 3 In the case of 5, 6, or 7, '35. After the 小时 5 hour annealing, the work hardening index was less than 0.3, and the bending time when the 丨8 密 degree of close bending was performed was less than 4 times, and the bendability was deteriorated. Further, in the case of Comparative Example 1, since the addition amount of Sn in the copper foil exceeds 5 〇〇 mass ppm, the semi-softening temperature exceeds 150 ° C ' and the work hardening index does not reach 〇·3. Again, the semi-weighted temperature exceeds 150. In the case of Comparative Examples 1, 6, and 7, the work hardening index after annealing for 0.5 hours at TC did not reach 〇3, and the number of bends when the 仃1 80 degree was tightly bent was less than 4 times, and the bending property was not obtained. Deterioration. As the oil film equivalent in the last 3 passes of the final cold rolling, the oil film equivalent of the previous pass before the last pass exceeds 25 〇〇〇, and the oil film equivalent of 1 pass before the last pass exceeds 3 〇〇〇〇. In the case of Comparative Example 2 in which the oil film equivalent of the last pass exceeds 35,000, the number of bends at the time of 180 degree close bending is less than four times, and the bendability is deteriorated. In the oil film equivalent of the last three passes of the final cold rolling In the case of Comparative Example 4 in which the oil film equivalent of the previous pass before the last pass exceeds 25 ', the number of bends when the 180-degree tight bend is performed is less than 4 times, and the bendability is deteriorated. In the case of Comparative Examples 1 to 7, the 6-valence of the previous bending property, that is, the IPC sliding bending number was also the same as in the respective examples, and the bending property of the copper-clad laminate was not evaluated in the sliding bending 201242448 test. Figure 1 shows the use of IPC sliding Diagram of the sliding bending method of the curved device. [Description of main component symbols] 1 Test piece 2 Screw 3 Vibration transmission member 4 Oscillating drive body r Radius of curvature 20

Claims (1)

201242448 VII. Patent application scope: I A copper foil with a thickness of 5 to 30 m, and I (220) /1 (2〇〇) after annealing at 350 ° C is 011 or less, and 35加工t>c The work hardening index after annealing for 0.5 hours is 〇3 or more. 2. The copper foil of claim 1 of the patent application has a semi-softening temperature of j 50 ° C or less. 3. For the towel, please refer to paragraph (1) or (4) of the patent range, which consists of oxygen-free copper or stainless steel, or a group of Ag and Sn in total of 5 〇〇 mass ppm or less in oxygen-free copper or refined copper. More than one species in the middle. 4. In the fourth or second item of claim 2, the oxygen-free copper or stainless steel contains a total of 20 to _ppm of an element selected from the group consisting of Ag, Sn, in, and above. 5. The copper 29 of the item in the item m of the patent application, wherein the sample having the resin layer in the single-area layer and having a total thickness of less than the core claw and having a width of 3 mm or more and 5 mm or less is used as the copper foil. Exposed: When the outer side is 180 纟 tightly bent, the number of times of bending to the copper foil is four or more. 0. If the patent application scope is i-th wang Τ ΊΠ: 2 the total processing degree of the pressure delay is 85% or more, and the final cold rolling: < the oil film equivalent in the second pass is set to the following conditions for calendering; "In the middle, the oil film equivalent of the previous pass before the last pass is 25 〇〇〇 or less, and the 犋 a 人 — 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人 人201242448 7. A copper-clad laminate which is formed by laminating a copper foil according to any one of claims 1 to 6 on at least one side of a resin layer.