TW201132493A - Copper or copper alloy foil, and method for manufacturing double-sided copper-clad laminate using the same - Google Patents

Abstract

To provide a copper or copper alloy foil which can reduce wrinkles or creases occurring when used for a double-sided copper-clad laminate, and to provide a method for manufacturing a double-sided copper-clad laminate using the same. The copper or copper alloy foils 4 and 6 are used for the double-sided copper-clad laminate 8, satisfy 3/4 10,000*(E<SB>A</SB>*/2) 3/4 ≤YS<SB>A</SB>when [sigma]<SB>A</SB>is (E<SB>A</SB>*[Delta]L<SB>B</SB>)/2*1,000, and have the number of bending times of 400,000 or more, wherein E<SB>A</SB>is Young's modulus (of which the unit is GPa) in a width direction after the copper or copper alloy foil has been held at 350[deg.]C for 30 min and cooled to room temperature; [Delta]L<SB>A</SB>is a dimensional change rate (of which the unit is ppm, and in which shrinkage is defined as positive value) in the width direction of the copper or copper alloy foil which has been heated to 350[deg.]C from room temperature, held at the temperature for 30 min and cooled to room temperature; YS<SB>A</SB>is 0.2% yield strength (of which the unit is MPa) of the copper or copper alloy foil in a tensile test; and the number of bending times is a value measured at an end point at which the electric resistance has increased from the initial stage by 20%, with the use of an IPC sliding bending tester.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a two-layer copper or copper alloy foil suitable for use in a resin layer for a flexible printed circuit board (FPC 'Flexible Printed Circuit), for example. A copper or copper alloy of a double-sided copper clad laminate, and a method of manufacturing a two-sided copper clad laminate using the copper or copper alloy case. [Prior Art] A copper clad laminate (CCl) used in a flexible wiring board (FPC) can be used for a single-sided steel-clad laminate made of a single-layer copper foil for a resin layer, and a resin layer. Two-sided copper-clad laminate made of two-layer copper foil (hereinafter referred to as "two-sided CCL"). The circuit formed on both sides of the CCL is a two-sided flexible wiring board. It is easy to realize the refinement of the circuit and the space saving of the FPC. Therefore, the use of the two-sided CCL tends to increase. In the method for producing a double-sided CCL, there is known a method in which a varnish of a resin composition of a single side of a copper foil is cured and heat-cured, and then a copper foil is thermally bonded to the surface of the resin (Patent Document 1). Further, there are the following methods: a surface of the polyimide film having a thermoplastic polyimide layer on both sides and a back surface, and a thermocompression bonding copper foil; and a polyimide film having a thermoplastic polyimide layer After hot-pressing the copper foil, the thermoplastic polyimide layer is coated on the opposite side of the copper foil, and the other copper foil is thermocompression bonded on the surface; The imide precursor, that is, the varnish, is hardened, and a thermoplastic polyimide layer is formed on the surface of the resin opposite to the copper foil, and the other copper foil is thermocompression bonded to the surface. Patent Document 1: Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The resin laminated copper foil (the first copper oxide) is heated to a temperature equal to or higher than the constitution c at the time of initial lamination, and is temporarily cooled to a further portion, and then after the other copper foil (second copper poise) in the opposite area of the resin layer 'The i-th copper box is also reheated and cooled. However, when the second copper box is laminated and heated, it is cooled. "The length direction of the first copper is parallel and usually in the center in the width direction = wrinkles or creases are formed. Even if the second copper is adjusted. Time: heating conditions (hot crimping conditions, tension, etc.), it is also difficult to completely eliminate: the folds or creases. Moreover, it is considered that the above-mentioned enemy folds or creases are as follows; = Health: due to the application of (10) and When the second copper matte is laminated, the heat is changed: = the copper foil is different in the thickness of the two copper foils which are present when the second copper crucible is heated and then cooled. It is impossible to withstand the stress generated by this. For the purpose of solving the above problems, an object of the invention is to mention two: when used for a double-sided copper-clad laminate, it can suppress the wrinkle copper alloy foil, and the estimation of #田丄J ^ Method of copper or copper alloy falling from two copper-clad laminates. The results of various studies by the inventors found that: even if the application is applied to the (10) and the second copper drop, the size changes. ", the difference between the private and the private ^ ^ ^ and thus the stress generated in the foil , Can adjust the characteristics of the bran two copper foil, the copper foil is not to Alice A h v., Said wrinkles or creases. (4) bundling (bUcking) suppression 201132493 That is, the copper or copper alloy foil of the present invention is used for a double-sided copper-clad laminate, and when (EaxALa) /2χ1〇〇〇, 丨1〇xcta|Sysa, bending The number of times is more than 400,000 times. Among them, EA: the above copper or copper alloy foil is 350. (: The Young's modulus in the width direction after 30 minutes of cooling and cooling to room temperature (unit: GPa); △ L a. The above temperature is raised to 305 ° C and kept for 30 minutes and then cooled to room temperature. The dimensional change rate in the width direction of the copper or copper alloy foil (in ppm, the shrinkage is set to a positive value); YgA: 0.2% safety stress (Proofstress) of the above copper or copper alloy foil in the tensile test (unit Μρ〇; Bending times: Using an IPC sliding bending tester', the foil was cut into strips with a width of 12.5 mm and a length of 200 mm and used at 35 (rc heat treatment for 0.5 hours, with a bend radius of 18 mm). In the case of the claw, it is set to 1.5 mm, and when the pig thickness is 12/zm, it is set to 1 mm, and the test piece load is repeatedly slid 100 times per minute, and the number of times the resistance is 20% from the initial rise is also terminated. Degree R (%) is 93.0% or more, preferably the above copper or copper alloy joints are calendered boxes, and finally cold rolling processing

And the average crystal grain size GS (#m) after the final annealing was gs$3.08xR-260. ΔLa is preferably i45 ppm or less. Forming a resin layer on one side of the above steel or copper alloy foil

Other laminates of the above copper or copper alloy foil coated steel sheets. The manufacturing method of the double-sided copper-clad laminate according to the present invention has the following steps: obtaining the above-mentioned resin-like alloy crucible with a single-sided copper coating on the single-sided copper-clad laminate, and heating, thereby obtaining two sides 201132493 according to the present invention, Sensitive pleats or creases can be suppressed when manufacturing two-sided copper clad laminates. [Embodiment] Hereinafter, a method for producing a double-sided copper-clad laminate using copper or copper alloy crucible according to an embodiment of the present invention will be described. In the present invention, the term "%" means mass% (% by mass) unless otherwise specified. Fig. 1 shows a method of manufacturing a double-sided metal-clad laminate 8. In Fig. 1, first, the first copper or copper alloy crucible 4 in a roll shape is continuously wound up, and one side of the first copper or copper alloy foil 4 to be wound up is applied using an application roller 10, 11, or the like. The varnish-like resin composition 2a is continuously applied in a specific thickness. After the resin composition 2a is cured, it becomes a resin layer h, and the first copper or copper alloy crucible 4 coated with the sapphire composition 2a is introduced into the drying device 15 to harden (or semi-harden) the resin composition 2a. Thus, a resin layer is formed on one surface of the first copper or copper alloy foil 4 to obtain a single-sided copper-clad laminate (first step). Here, the single-sided copper clad laminate may be wound into a roll shape after the completion of the second step, and the second step may be performed. In addition, when the resin layer is formed on one surface of the first copper or copper alloy foil 4, the resin is subjected to heating after the application of the resin composition, and may be, for example, a resin layer as a resin. Thermocompression bonded to the first side of the first copper or steel &amp; Jinzhi 4. Further, usually, the heating temperature in the second step is a temperature higher than the heating temperature in the second step. Then, the second copper or copper alloy foil 6 in the form of a roll is continuously wound up, and the first copper or copper alloy foil 4 and the second steel are continuously passed between the lamination rolls 2, 21 heated to, for example, 350 to 400 °C. Or steel alloy name 6 At this time, the 201132493 2 copper or copper alloy foil 6 is laminated on the resin layer 2 side of the first copper or copper alloy foil 4 and heated to obtain a double-sided steel-clad laminate 8 (second step)^ The double-sided copper clad laminate 8 is appropriately wound into a roll. Further, as shown in Fig. 2, the double-sided copper-clad laminate 8 is formed by laminating a second copper or copper alloy foil 6 on the resin layer 2 side of the second copper or copper alloy foil 4. Examples of the first copper or copper alloy foil 4 and the second copper or copper alloy foil 6 include pure copper, refined copper (JIS-11), oxygen-free copper (JIS-1〇2〇), or such pure copper. In the refined copper 'oxygen-free copper, a total of 4 〇 to 4 〇〇 mass of the claws of Sn and/or Ag is added. The thickness of the first copper or copper alloy foil 4 and the second copper or copper alloy case 6 can be, for example, about 6 to 18 #m. The same applies to the second copper or copper alloy foil 4 and the second copper or copper alloy foil 6. The first copper or copper alloy foil 4 and the second copper or copper alloy foil 6 may be rolled foil or may be an electrolytic cell. As the resin layer 2, a thermosetting resin such as polyimide, PET or epoxy resin, or a thermoplastic resin such as a saturated polyester resin can be used, but it is not limited to these resins. Also, the solvent can be dissolved

The following 'is indicated that when the two-sided CCL is formed on the one side of the i-th copper or steel alloy pig 4 to form the two-sided CCL, the second copper or copper alloy is lost after the layer is formed by the difference in the dimensional changes of 4 and 6. The stress of the two pieces of copper or copper alloy box of the resin. 201132493 First, when the temperature is T] (T1 a rj a -, the heating temperature when the second copper or copper alloy foil 6 is laminated), the two layers are CCL and then cooled by $ τ * , applied to the first copper or copper alloy foil 4, ^ ^ « « « 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 立 σ σ σ σ σ σ σ σ σ = = = = = = = = = = = = = = = = = = = = = = = = = = + △ (" axCT.-T.) +ALa) ) χίοοο (1). In addition, the B size change △ is set to be positive and is in the width direction (continuously from the copper or copper alloy pig roll The change in the width direction of the roll when manufacturing CCL·. Here, the copper or copper alloy foil used for CCL is similar to pure copper, so even if it contains a slight addition component, the coefficient of thermal expansion α (subscript A, subscript A, B denotes that the first copper or copper alloy foil 4 and the second copper or copper alloy foil 6) are considered to be the same (Ο: A and α B ). Therefore, the formula i is expressed by the following formula 2: aA=EAxEB/( EA+EB)x(^LA-ALB)xl〇〇〇(2), wherein EA. The above first copper or copper alloy foil is 35 〇. 匸 is kept for a few minutes and cooled to room temperature, again at 35 ( Rc keeps 3 minutes and However, in the first heating course to room temperature, the rising modulus of the above-mentioned second copper or copper alloy foil in the width direction (unit: Gpa); Eb: by smashing the second copper or copper alloy to 350. : a rising modulus (in units of GPa) in the width direction of the second copper or steel alloy foil produced by the second heat history of holding for 30 minutes and cooling to room temperature; Δ LA : heating from room temperature to 350. (: and maintaining the dimensional change rate in the width direction of the first copper or copper alloy foil after 35 seconds while maintaining the temperature after cooling to room temperature for 3 minutes (the rc is kept for 30 minutes and cooled to room temperature) The unit is ppm, the shrinkage is set to a positive value); Δ lb : the temperature change rate in the width direction of the second copper or copper alloy foil of 201132493 after the temperature is raised from room temperature to 3501, and kept for 30 minutes and cooled to room temperature (unit In the case of ppm, the shrinkage is set to a positive value. Further, the room temperature is 25 to 35. (: (usually 25 ° C). That is, if two sheets of copper or copper alloy foils 4 and 6 are formed, When the number becomes small and the difference in the dimensional change rate (ALa_ALb) of the copper or copper alloy foils 4, 6 becomes small, the stress σ Α becomes It is not easy to produce wrinkles or creases when manufacturing the two-sided CCL. Here, even if the two copper or copper alloy foils 4, 6 are the same, the difference in dimensional change rate occurs, so it is obvious that the difference is not caused by thermal expansion. If the metal is heated, a change in structure such as recrystallization or recovery occurs. Therefore, if the metal is heated and then cooled, it becomes shorter (heat shrinkage) or longer (thermal elongation) than the original size. Further, even if the temporarily heated and cooled metal is heated and cooled again at the same temperature or lower, heat shrinkage or thermal elongation does not occur. Furthermore, these phenomena are generated in both the rolled foil and the electrolytic foil, but the strain caused by the calendering of the rolled foil is larger, and, depending on the composition of the foil, the calendering due to the heat applied during the manufacture of the CCL The tissue changes to recrystallized structure' so that heat shrinkage or thermal elongation becomes large. Fig. 3 shows a state in which the above-described heat extension or heat shrinkage is caused by heat applied when CCl is produced, and wrinkles (creases) are formed in the first copper or copper alloy foil 4. First, when the single-sided copper-clad laminate is produced in the above first step, the first copper or copper alloy crucible 4 is heated and then cooled, and the heat shrinkage is smaller than the original length. Then, when the double-sided copper-clad laminate is produced in the second step, the second copper or copper alloy foil 6 is heated and then cooled, and the heat shrinkage 201132493 is reduced to be smaller than the original length (arrow of Fig. 3). On the other hand, the first copper or copper alloy 4 which is heat-shrinked in the step hardly undergoes heat shrinkage in the second step (arrow of Fig. 3). Therefore, when cooling after heating in the second step, by the second alloy, "the compressive stress is applied to the copper or copper alloy by the force to be contracted, and then the first copper or copper alloy foil 4 cannot withstand the compressive stress. And warping (creating wrinkles or creases), j, when compressive stress is applied to the side of the first copper or copper alloy foil 4, 'if the safety limit stress of the copper collar is greater than the compressive stress (^ of the formula 2) ), it will not cause light curvature 'and it is difficult to produce wrinkles or creases. Usually the I method is used to determine the safety limit stress of the copper box relative to compression, but whether it will cause the boundary value of the light curve can be safe relative to the stretching The limit stress (YS) is substituted. That is, it is considered that the t-th copper or copper alloy foil* is selected so that YS becomes σ A or more, and wrinkles or creases are not generated. The condition for producing a double-sided copper-clad laminate does not cause wrinkles or creases. As a result, it is understood that the first copper or the first copper is selected in the manner of 110 &lt; σ Α|^ YSA (3) with respect to Formula 2 On the other hand, it is difficult to generate wrinkles or creases on the copper alloy foil 4. In the case of the second copper or copper alloy foil 6, when the second copper or copper alloy foil 6 is selected so as to become |10 χ σ Β |^ YSB (4) with respect to σ B of Formula 2, wrinkles are less likely to occur or fold

10 201132493 Traces. However, compressive stress is generally applied to the first copper or copper alloy foil 4. In order to satisfy the formula 3 (or the formula 4), σΑ(σΒ), that is, the difference in the dimensional change rate (ΔLA−Δ“) is preferably as small as possible, so that the first copper or copper alloy crucible 4 is subjected to heat in the first step. The smaller the difference between the heat received by the second copper or copper alloy foil 6 in the second step, the smaller the strain of the second copper or copper alloy foil 4 in the first step, the dimensional change rate. The difference (Δ") also changes to /J. As described above, specific methods for satisfying Expressions 3 and 4 include: j) preheating the first copper or copper alloy foil 4 and the second copper or copper alloy foil 6; 2) on the first copper or copper alloy foil 4 And when the second copper or copper alloy foil 6 is a rolled foil, the rolling is performed with a low degree of work; 3) the pressure delay tension set according to the thickness and mechanical properties of the box does not exceed the limit; 4) the i-th copper or copper An electrolytic foil is used for the alloy foil 4 and the second copper or copper alloy foil 6. However, if it is considered that a compressive stress is generally applied to the i-th copper or copper alloy phase, the method of 1) to 4) may be applied only to the second copper or copper alloy foil 6. Regarding the method of the above 1), it is known that pure copper is a metal having a face-centered cubic structure, and if recrystallization is performed by heating, the cube orientation and the flexibility are improved. The cube-azimuth extension (4) has a lower lift modulus and a 0.2% safety limit stress in the tensile test. In other words, J is most likely to be creased or wrinkled when the two-sided CCL is produced by the copper foil which is extended by δ to such a cube orientation (in the case of the push-step, the second step). According to the inventors of the present invention, it is understood that, for example, pure copper is smashed at 35 (TC is kept for 30 minutes and then cooled, and the body is about 7 〇 GPa, 0.2% safety limit stress is 5: Yang type modulus is strong, and so on, the ancient blade In order to heat the copper or copper even if the safety limit is small, #树&gt; white is heated again to 3 5 〇

After 11 S 201132493 °c, it is cooled and the dimensional change is almost 〇. Therefore, the same one is used as the second steel or steel alloy 4 and the second copper or copper alloy 羯6 (ΕΑπΒ, 丨σΑΗ丨σΒ|), and when ^^〇, the formula 2 is expressed by the following formula 5: = ( ΕαχΔ Lb) / 2x1000 ( 5 ). Further, according to Equations 3 and 5, ΙΙΟΟΟΟχ (ΕαχΔ LB/2) YSA (6) is used, and the two-sided CCL is manufactured by using a copper or copper alloy foil that satisfies the formula 6, that is, "5J- 〇 According to the above experimental results, if Ea = 7 〇 QPa ' YSa = 5 〇 MPa is substituted into Formula 5, Δ Lb = 143 (ppm) can be obtained. In other words, if at least the second copper or steel alloy foil 6 is heated before use, ΔLBgi 43 (ppm) is used, and both of them have flexibility and are less likely to cause creases or wrinkles. The heating conditions of the second copper or copper alloy foil 6 are set to 5 〇 ° c to 200. (The heating may be performed for about 1 second to 10 hours, but is not limited thereto. For example, the heating condition may be maintained at 60 C for 3 hours or at 130 ° C for 3 seconds. That is, the copper or copper alloy is applied in advance. The heat treatment described above may be used to produce both-sided Ccl. Next, in the method of the above 2), the strain of the rolled foil varies depending on the degree of rolling after final annealing, the amount of rolling reduction, the tension, the processing temperature, and the like. However, the amount of shrinkage or tension may vary depending on the thickness of the foil to be processed or the performance of the calender. Further, the higher the processing temperature, the smaller the strain. However, the rolling oil in the rolling functions as a coolant, and it is difficult to specify the processing temperature in an instant. Therefore, the conditions required for the foil are specified according to the degree of calendering. Here,

12 201132493 If the degree of calendering is reduced, the strain of the box becomes small, but when the crystal is recrystallized, it is difficult to expand the cube and the buckling property is lowered, which is not preferable. On the other hand, if the crystal grain size before the dusting is reduced, even if the rolling is performed at the same degree of processing, the orientation of the cube is expanded. According to the above findings, the inventors of the present invention have made it clear that if the final cold processing degree R (%) $ and the average crystal grain size after final annealing (GSUm) is 3 〇 8 x r - 鸠, it will not damage 靑Flexibility' and can prevent creases or wrinkles from occurring. However, if r is too high, the bendability tends to decrease. Therefore, when the copper or copper alloy case is not previously heated before use (in the case where the above method is not performed), R is preferably 98% or less. As described above, in the copper or copper alloy foil of the present invention, the bendability is required to be excellent, and the number of times of bending of the steel or copper alloy foil must be 40,000 or more. Here, the number of bends is made by using the IPC (American Printed Circuit Industry Association) sliding bending tester to cut the foil into the width direction (the direction perpendicular to the rolling direction. In the case of the electrolysis box, it is the same as MD) The test piece obtained in the form of a strip having a length of 250 mm and a length of 200 mm in the direction of the right angle was used after 35 hours of heat treatment for 5 hours. The bending radius is set to 1.5 mm when the foil thickness is 18 β m, and is set to 1 mm when the foil thickness is 12 μm, and the sliding of the test piece load is 100 times per minute. The number of terminations is the resistance of the test piece. The number of bends from the initial rise of 20%. It is known that the number of bending of the copper or copper alloy case is 400,000 times or more, which is equivalent to the number of bending times which are determined to be acceptable in the actual two-sided CCL. For example, in the previous copper foil, there is also an R (%) of 93.3% or more.

13 S 201132493 260 ^ ^ GS ^ ) ^ Gs ^ 3 .〇8xR ^ Γ4〇Λ i2〇〇p-s^^) Full of people. Further, even if a copper foil produced by a known method is used in a known composition and has high bending property (for example, the final rolling is performed in a processed article, the thief is smashed to 4^0 hours. The pre-heating of the left and right also satisfies the above formula 6, and therefore is excellent in f curvature and is suitable for a double-sided copper-clad laminate." The embodiment uses a copper foil (copper alloy foil) of the composition shown in Table 1, to In this manner, the two-sided CCL is produced. Here, the i-th copper foil 4 and the second copper are the same, but are different from the first copper V# 4 and the second copper foil 6 in accordance with the order used in the manufacture of the CCL. In addition, the copper foil is adjusted to have a crystal grain size GS and a degree of processing as shown in Table 1, or a pre-heat treatment is performed. Further, the pre-heat treatment is performed after the following chemical treatment (electroplating), or It is to be carried out before the production of the CCL. First, the chemical treatment (electroplating) of the single side of the first copper junction 4 is carried out, and the varnish of the acrylonitrile resin is applied to the surface in such a manner that the thickness is 25 &quot; Manufactured u-Varnish A). Then, set to 1 30 C heat The mixture was dried in a circulating high-temperature bath for 3 minutes, and the temperature was gradually increased to 35 〇t in 2,000 sec and hardened (醯iminated) to form the resin layer 2, thereby producing a single-sided CCL. Then, the resin of the single-sided CCl was produced. After the side surface is coated with a thermoplastic polyimide (adhesive layer) and dried, the second copper bovine 6' is overlapped and thermoformed by a press heated to 35 〇〇c for 1 〇 to produce a two-sided CCL. Cool to room temperature and visually determine the occurrence of creases or wrinkles in 201132493. 12 5==The steel pig is cut into the width direction of 15 〇, the length direction is _ hardness tester (4) is (10) ― 2: Pre: trace The coordinates of the coordinates are used to determine the distance L before heating. Further, after the copper sputum sample subjected to heat treatment, the same is obtained, and then the w M _ m is finally obtained, and then the coordinates of the two dents are determined. Find the distance L. \ ' - Γ /V rt I / △ La can be positive for (l - L', / τ, 仕 - &gt; 丄々 情形 。 。 。 。 L L L L L 舁 舁 舁The Yang-type modulus Ea of the contracted eight-point rule can be determined by the vibration method according to JIS — Z228〇_丨993. The G 2% safety limit should be obtained. % was obtained by using a tensile tester according to jis~~Z2241 - 1998. The f-curvature was evaluated as follows. First, the copper was cut into a width direction of 12.5 mm and a length direction of 2 mm. The test piece was made into a strip shape, and it was heat-treated at 35 ° C for 5 hours. The bending test was performed using an IPC (American Printed Circuit Industry Association) sliding-bending test machine, and the bending radius was 18 mm. In the case of #m, it is set to 1.5 mm, and when the thickness of the copper foil is 12 V m, it is set to 1 mm. The thinner the thickness of the copper foil, the better the bendability. Therefore, the evaluation is performed on the same basis, and the radius of curvature f may be changed depending on the thickness of the copper foil. Then, the number of times of the reverse sliding of the test piece load per minute was repeated as the number of bends of the test piece from the initial rise of 2%. It is known that the number of bending of the copper or copper alloy foil is 40,000 or more times, which is equivalent to the number of bending times which are qualified in the actual two-sided CCL. The results obtained are shown in Table 1. 15 201132493 [一办] Evaluation of the number of distortions (thousands) 672 v〇Ό 699 539 547 517 499 605 653 1 488 475 432 227 245 232 1 σ\ 〇〇&lt;N rO 360 595 459 Ό «/*) VO 525 318 so ΓΟ wrinkles or ^ creases 〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇〇XXXX 〇〇1 characteristics of knots |1〇χσΑ| (MPa) 卜«Ν CN &lt; N CM m Ό m cs cs σ\ (Ν m 〇〇m σ\ s〇Ό two CN ο v〇— σΑ (MPa) νώ — 卜&lt;Ν fS oo — CN Cs v〇c&lt;i &lt;^i σ\ μ ΡΛ 00 ΓΛ a\ CO v〇ν〇Ο a · rO ν〇r^i &lt;N 卜^ ο 卜^ 〆IT) οο Δ la (ppm) (Ν oo (N Os O &lt;N NO § m \〇? CN OO 艺艺ΓΟ 1 〇〇\ 00 OS &lt;s w-&gt;&lt;Ν οο YSA (MPa) mm »n - VO - as Ό m IT) 00 VO Ρ OO g oo oo 00 210 〇u-&gt; 00 S msg Ea (GPa) - γΛ oo oo OO n OO - CS s CN σ\ 〇\ so 120 〇SO ON Sn JQ g &lt;s 00 ΙΛ 00 Preheating 1 50t&gt;3h 1 60〇Cx3h 1 140〇Cx3s 1 60°C x7 h 1 65°〇3h I 60〇C&gt;&lt;7h 150°Cx3 s I 5 5°Cx3h 140°〇3 s 60°〇5h 65〇C x3 h 璀€ Calendering conditions and particle size 3.08xR -260 1 4A3 I 1 44.6 1 1 45.5 1 46.2 1 45.5 I 46.2 45.5 1 46.5 1 | 46.5 I 44.0 1 43.4 1 31.1 11.0 11.0 1 1 29.5 1 22.7 1 45.5 44.5 45.8 45.8 43.7 43.7 R (%) 98.8 98.9 99.2 99.4 ' 99.2 99.4 99.2 L?9-5 —99.5 1 98.7 I 98.5 1 94.5 95.5 188.0 I 88.0 89.0 1 1 I 94.0 1 L9K8 J | 99.2 | 1 98.9 1 1 99.3 1 99.3 98.6 98.6 GS (βτη) &lt;N »〇CN &lt;N &lt;N &lt;N CN σ\ 00 OO &lt;N OO (N On (S Ό CN 1 ο (N CN oo 2 m thickness (^m) 〇〇&lt;N &lt;N Ν CN &lt;N (N fS CN (N (Ν (Ν Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ (N cs (Ν Composition 190 ppmAg (predium copper) 190 ppmAg (fine copper) 190 ppmAg (fine copper) 300 ppmAg (fine copper) 1 50ppmSn (oxygen free copper) 110 ppmSn (oxygen free copper) 180 ppmSn (oxygen free copper) ) Copper refined copper 50 卯mSn-50 ppmAg (oxygen free copper) 50 ppmSn-50 ppmAg (oxygen free copper) 190 ppmAg (fine copper) 110 ppmSn (oxygen free copper) refined copper fine copper 2000 ppmSn (no gas copper) &gt;99.9% Cu , 50卯mSn (oxygen free copper) ! 190 ppmAg (Pearin) 190 ppmAg (polished copper) 50 ppmSn (oxygen free copper) refined copper 90 ppmSn (oxygen free copper) 500 ppmSn (oxygen free copper) 500 ppmAg (fine copper) type rolled foil 1 calendered foil 1 1 calendered foil 1 Calendered foil 1 calendered foil 1 1 calendered foil 1 calendered foil calendered foil 1 calendered foil 1 calendar foil 1 calendered foil | calendered foil calendered foil calendered foil calendered foil calendered foil electrolytic copper foil | calendered foil | I calendered foil calendered foil calendered foil calendered Foil Calender Foil Calender Foil Calender Foil Example 1 Example 2 Example 3 1 Example 4 1 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 12 Example 13 Comparison Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Comparative Example 12 91 s 201132493 As shown in Table 1, the copper foil was subjected to In the case of Examples 1 to 13 which were previously heat-treated, |1 〇χ σ Α丨 $YSa was obtained, and no wrinkles or creases were formed on both surfaces obtained, and the flexibility was also excellent. Further, in the case of adjusting the rolling conditions of the copper foil so that R is 93% by number or more and 98. 〇〇/° or less, and in the case of Examples 12 and 13 of GSS3.08XR-260, even if the heat treatment is not performed,丨1〇χσ a丨,= There are no wrinkles or creases in the CCL obtained on both sides, and the bending property is also excellent. On the other hand, when R is set to be less than 93.0% and the comparative example 3 of the prior heat treatment is not performed, the bendability is lowered. In the case of Comparative Example 4 using electrolytic copper crucible and not subjected to preheat treatment, the flexibility was also lowered. In the case of Comparative Example 5 in which annealing was performed after obtaining GS of GS &gt; 3.08XR-26, and the ratio of the ruler was set to less than %, the flexibility was also lowered. In the case of Comparative Examples 7 to 10 t which were calendered under the condition that R was more than 98.0% and was not subjected to pre-heat treatment, wrinkles or creases were formed in the obtained two-sided CCL by 丨1〇X(Ja|&gt;YSa. In Comparative Examples 11 and 12 in which the amount of the element (Sn or Ag) added to the copper exceeds 4 〇〇 ppm, the bendability is lowered. [Schematic Description] Fig. 1 shows a two-sided copper-clad laminate according to an embodiment of the present invention. Fig. 2 is a cross-sectional view showing a configuration example of a double-sided copper-clad laminate. Fig. 3 is a view showing a first copper or steel alloy due to a crucible applied during the manufacture of a double-sided copper clad laminate. A diagram of the state of the wrinkles (creases) of the foil.

17 S 201132493 [Description of main component symbols] 2 Resin layer 2a Resin composition 4 First copper or copper alloy foil 6 Second copper or copper alloy foil 8 Double-sided copper clad laminate 10, 11 Application roller 15 Drying device 20 ' 21 Laminating roll 100 wrinkles (creases)

18 S

Claims (1)

201132493 VII. Patent application scope: 1. A copper or steel alloy foil used for two-sided copper clad laminates, and when σ Α = ( Εα χ Δ LA) /2x1000, 丨l〇xcr A|$ YSA, the number of bends is More than 400,000 times, where 'EA: the copper or copper alloy foil is held at 3501 for 30 minutes and cooled to room temperature in the width direction of the Young's modulus (in GPa); △ LA: from room temperature to 350 it And maintaining the dimensional change rate in the width direction of the copper or copper alloy crucible after cooling to room temperature for 3 minutes (in ppm, the shrinkage is set to a positive value); YSA: the copper or copper alloy foil in the tensile test 〇.2〇/〇Proof stress (unit: y[Pa); Bending times: using IPC sliding bending tester, the foil is cut into a width direction of 12.5mm and a length direction of 2〇〇mm It is used in a strip shape and heat-treated at 350 ° C for 0.5 hours, and the bending radius is set to 1.5111111 when the foil thickness is 丨8 in the case of the claw, and 1111111 in the case of the pig; (1111111 in the case of /111, The test piece load is repeatedly slipped 100 times per minute, and the resistance is increased by 20% from the initial bending time. The number is the number of terminations. 2. For the copper or copper alloy foil of the first item of the patent scope, the copper or copper alloy box is a rolled collar, and the final cold rolling degree R (%) is 93% or more. And the average crystal grain size Gs after final annealing ( &quot;^^ is Gs$3 〇8 xR - 260 〇3. For example, the copper or steel alloy 羯 of the i or 2 of the patent application scope, where Δ LA is I45ppm or less. 4_ A method for manufacturing a two-sided copper-clad laminate, which has the following steps: Step 1: It is applied for the patented 笳囹 ,, Guang, the monthly number is not the same as the 201132493 copper of any of the three items a single-sided copper-clad laminate is obtained by forming a resin layer on one side of the copper alloy foil; and a second step: laminating and heating the other copper or copper alloy foil on the resin layer side of the single-sided copper-clad laminate And obtain a two-sided copper-clad laminate. Eight, schema: (such as the next page)