TW200847867A - Printed wire board and manufacturing method thereof, and electrolytic copper foil for copper-clad lamination board used for manufacturing the same - Google Patents

Abstract

The present invention provides a printed wire board formed with wires on an insulation substrate, the printed wire board being characterized in that the wires have a layer configuration stacked with a first copper layer and a second copper layer, the first copper layer side is laminated to the insulation substrate, and the average crystalline grain size of the second copper layer is bigger than that of the first copper layer. Moreover, a manufacturing method is provided, which includes preparing a metal-clad lamination board having a conductive layer of a layer configuration allowing to form the wire having the aforementioned structure on a surface of an insulation substrate, forming an etching pattern on a surface of the second copper layer of the conductive layer, performing an etching processing to form wires, and then removing the etching pattern to form a printed wire board. Thereby, the present invention provides a printed wire board easy to be formed with fine wires, and particularly, the present invention provides a printed wire board easy to be formed with fine wires and excellent in bending resistance.

Description

200847867 '9. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method for manufacturing a printed wiring board and the printed wiring board, and to electrolysis of a copper-clad laminate for use in the manufacture of the printed wiring board. Technology] Cold. With the popularity of mobile devices such as mobile phones, personal computers, music players, and portable devices in recent years, the lightness and smallness of electronic devices has continued. Moreover, the mobile devices have a plurality of types of display and display functions, and various display devices are used, and the mainstream display device is a liquid crystal display panel. As a method of mounting an electronic component such as a driver and an LS^ of the liquid crystal display panel, a film carrier tape (hereinafter referred to as a "film carrier tape", or "TABCTape Automated bonding") is used. ; tape reel automatic bonding) with J*" and FPC (Flexible Print Circuit) mounting method, wherein the above-mentioned electronic component mounting film mounting tape includes a C0F (Chip On film; film flip chip) band,

Package, tape carrier, BGA (BaU GHdArray; ball grid > ASIC (Application Specific Integrated

Circuit; specific application integrated circuit) with etc. Therefore, these printed wiring boards are required to further finer lines. In the production of the above-mentioned COF tape or the like, copper is used as a main conductor, and a wiring is formed by an etching method. To miniaturize the lines formed here and to make the subsequent surface mounting easier, it is necessary to increase the wiring (etching factc) r). Therefore, it is necessary to shorten the setting of the secret engraving (〇ver 320099 6 200847867 • etching), and it has been tried to make the copper layer forming the line and the insulating substrate have smooth surfaces and a thin steel layer. Also, in the electrolytic copper foil, various organic additives have been used in the manufacturing process to reduce the crystal grain size of copper, and to achieve a low profile with the insulating substrate. ). However, even if the bonding surface of the insulating substrate is set to be flat, the line formed is narrower than the bottom width due to the undercut generated during the etching. Therefore, if the pitch of the C0F tape or the like is further narrowed, the top width required for the connection of the components cannot be ensured. That is, it is necessary to form a line with a better money engraving factor than conventional knowledge, otherwise the line may not be miniaturized. On the other hand, the TAB tape such as the COF tape and the TCP tape and the flexible circuit board of the FPC are mounted on the electronic device in a bent state, and the bending operation is repeated. In addition, when the circuit boards are subjected to vibration during transportation, vibrations accompanying the operation of the electronic device, etc., when the wiring is formed by the conductor Lu, which is poor in flexibility, there is a disconnection in the bent portion of the line. tendency. In addition, the history of the liquid crystal drive driver represented by the reference TAB tape is the pursuit of wealth and flexibility from the beginning. However, as described above, when the miniaturization of the line is regarded as a priority, the crystal grain size of the electrolytic copper fS is made finer to lower the surface of the insulating substrate. When the crystal grains of copper are reduced in this manner, the tensile strength is increased, but the elongation tends to decrease. In other words, it is difficult to obtain an annealing effect even if it is heated by the influence of an additive which is shifted at the boundary of the crystal grain by I. As described above, it becomes the first place to sacrifice the formation ability of the fine circuit by sacrificing the resistance of 320099 7 200847867. For example, in order to reduce the area of the frame in the liquid helium panel, the output line of the Tab π output is connected to the line of the liquid crystal panel at the end of the liquid crystal panel, so that it is possible to think about the current resistance and the bending property. The tendency to be better than the learner is stronger. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Printing line of the printing line φ, the grain size of the grain of the steel foil, and the structure of the structure of the surface of the copper-clad board = the thickness of the edge of the substrate is sequentially reduced = rs:;:c:::r, r^£ p^^a"- The purpose of the technique is to provide a copper box pattern having a high current density to a high power, which is formed by continuously or stepwise forming a flow from low electricity. The different configurations of the box, the copper foil of the ^ ^ to the side of the hard copper box, the money engraved in the =, 's ν white' and from the pattern with the hard-to-engraving pattern applied not, 30 ίΓ oblique steel falling, The state is moderated. In the heat treatment of the knives and the like, the structure is inclined. If the above-mentioned patent documents i and patent documents are used, it is a factor of the factor that is used as long as the technology is the same. Further, the invention is well formed and has a good etching. Patent Document 1: Japanese Patent Laid-Open No. 5 δ Publication No. 320099 8 200847867 Patent Document 2: Japanese Laid-Open Patent Publication No. Hei. The problem to be solved is that the technical contents disclosed in the above patent documents are applied to a circuit such as a circuit board for a liquid crystal driver of a movable machine, and the risk of disconnection of the line as described above may not be reduced.

Therefore, in the hard printed circuit board and the flexible printing, the general-purpose health material "Ink Cai Road Board" (10) is a technology that maintains a good etch factor. Also, in (10) with 'TCP band and FPC +, the system requires _ kind in the line =

A product that improves bending resistance. j U (Means for Solving the Problem) Therefore, the inventor of the present invention (4) invented the following points for the purpose of making the line of the printed circuit board and the resistance and bending properties as a flexible printed wiring board. Invention. The printed wiring board of the present invention: the printed wiring palladium of the present invention and the ?I edge plate are formed on the surface of the insulating substrate to form a wire, and the second layer and the second copper layer are formed in the first layer. In the layer configuration, the first copper layer side and the uniform crystal grain size are bonded to the first substrate; and the second copper layer is flat crystal (four). The average crystal grain size of the steel layer is also large. In the average tanned wiring board of the copper layer having the average crystal grain size of the printed copper of the present invention, it is preferable that the first copper layer is 〇·ϊ. β 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。. 320099 9 200847867 In the printed wiring board of the present invention, the thickness of the copper foil is 5% to 5 mm of the thickness of the second copper layer. In the printed wiring board of the present invention, the n-th sub-metal: ' is the second copper-layer ratio (the η-υ-metal layer of the ''/〇〇-metal layer is provided in the present invention The print has a large average crystal grain size. In the cross-sectional shape, the input i = 'the other end of the line at any position of the top 丄 = the thickness of the road is I to make the calculation of the upper surface of the line It is 25 or more. 卩 The following formula (1) [Math 1] Etch factor =

Wb_wt (1) In the printed wiring board of the present invention, the substrate for the board is used as a (4) flexible printed wiring board, and a printed circuit board which can be recorded and processed. In the printed circuit board of the present invention, the base material for the laminated board is used, and the hard printed circuit board is formed into a plate shape by using the printed circuit board. The method of manufacturing a printed wiring board of the present invention is characterized in that the method of manufacturing a printed wiring board is characterized by the following steps. For convenience of explanation, it is called a manufacturing method.绕 Γ Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α Α 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 准备 覆 覆 覆 覆 覆 覆 覆 覆 覆 覆The average crystal grain size is larger than the average crystal grain size of the steel layer 320099 10 200847867, and is bonded to the insulating substrate; the first copper layer side agent is attached to the front material. The surface of the second copper layer of the bulk layer forms a etched resistance to perform nG: the material has a metal-clad laminate J of the former etched pattern, and the etching resist pattern body is not formed to dissolve and remove the (four) line m layer. Second, the pattern of the money resist which is present on the surface of the aforementioned line is removed to obtain a printed wiring board. In the above-mentioned manufacturing method, it is preferable that the copper-clad layer is used in the description of the step A in the description, and the laminated board is made of the copper-clad laminate. a layer composed of a layer of a second copper layer and having a second crystal layer having a larger crystal grain size than the average crystal grain size of the first steel layer: a crystal grain controlled electrolytic copper box, and the i-th In the first manufacturing method, it is preferable that the copper-clad laminate is a front-end; the metal-clad laminate used in the step f, the copper-clad laminate is a laminate Brother 1 copper layer and by 17 〇. An electrolytic copper box made of a layer of a second copper layer which is heated by π minutes or more and recrystallized to 18 〇t, and the first copper layer is subjected to 17th generation to 1δ0I at the time of molding of the metal-clad laminate. When the insulating substrate is bonded to the electrolytic copper foil at a degree of 15 knives or more, the average crystal grain size of the second copper layer is larger than the average crystal grain size of the first μ layer. Further, in the manufacturing method of the above-mentioned music, it is preferable to use the copper-clad laminate 320099 11 200847867 as the metal-clad laminate used in the aforementioned step A, which is an electroless-time-coated method on an insulating substrate. Forming a first copper layer thereon, and forming a second copper layer which is recrystallized on the second copper layer as a conductor layer by heating at 170 c to 180 ° C for 15 minutes or more, and then applying i The temperature of 7 〇C to 180 C is heated for 15 minutes or more, whereby the average crystal grain size of the second copper layer is made larger than the average crystal grain size of the second copper layer. Further, in the above-described second method of manufacturing, it is preferable that the core of the second copper 4 is a copper copper method using an acidic copper sulfate liquid, and the copper sulfate plating liquid has a copper concentration of 〇. 8m〇1/liter to Hoi/liter, free sulfuric acid concentration 〇·8m〇l/liter to I 2m〇1/liter, chlorine concentration 5ppm to 5〇ppm, and the use of the acidic copper sulfate mirror solution 1 / 2 Each amount of activated carbon treatment. Further, as another method of manufacturing a printed wiring board of the present invention, the vehicle is a coating method using a printed wiring board characterized by the following steps a to f. For convenience of explanation, it is referred to as a second manufacturing method. Step a: manufacturing a preliminary copper-clad laminate having only a second copper layer on the surface of the insulating substrate; Step b: forming a plating resist pattern on the surface of the second copper layer of the preliminary copper-clad laminate ^Step c: copper plating is performed on the surface of the first copper layer of the preliminary copper-clad laminate which is not formed with the plating resist J to form a second copper layer; the step d· will be described as plating resistance The agent pattern is removed and used as an initial printed wiring board; 320099 12 200847867 y e. The first printed circuit board obtained by the step d is subjected to heat treatment to crystallize the second copper layer; and f: after the crystallization of the second copper layer has been macrocrystallized. The preliminary printed wiring board is subjected to the engraving treatment, and the exposed portion of the portion where the second copper layer is not formed is removed. In the second manufacturing method, 'preferably' the formation of the second copper layer is an electric ore method using an acidic copper sulfate clock solution, and the copper concentration of the acidic copper sulfate is G. .8mc) 1 liter to l 2mc) i / liter, free sulfur ppm, and the acidity has been used ^ Acid copper plating solution to the capacity of the person to be treated with activated carbon. In the manufacturing method of the second aspect, it is preferable that the force-handling treatment in the step π, the work π / the e e step e is heated at a temperature of not to the temperature of the c-c for more than 15 minutes. The electrolytic copper is used for the metallizing; the electrolytic copper box is provided with a layer of the i-th copper layer, and the first working angle after the twisting at 175 ° C for 15 minutes is . _ Upper and lower than the average diameter is l.O/zni or more, 5. Μπι below. Thousand L-day granules (effect of the invention) Hunting the circuit board of the invention obtained by the present invention. In addition, as a flexible printed circuit line, the (four) factor (four) of the road is good (4), and it also plays a good sound = 320099 13 200847867, even if the liquid crystal drive n of the smashing machine is mounted, the wiring such as the printed wiring board is fine. The risk of disconnection is still low. Further, the manufacturing method of the printed wiring board is most suitable as a method of efficiently obtaining the above printed wiring board. [Embodiment] The following is a form of a method of manufacturing a printed wiring board and a printed wiring board of the present invention. The "manufacturing method" is divided into an i-th manufacturing method and a second manufacturing method. <Form of Printed Wiring Board of the Present Invention> The printed wiring board of the present invention is a printed wiring board having a line formed on the surface of the insulating substrate. The wiring system has a layer structure in which an i-th copper layer and a second copper layer are laminated. And the first copper layer side is bonded to the insulating substrate, and the average crystal grain size of the second copper layer is larger than the average crystal grain size of the i-th steel layer. In the printed wiring board of the layer-structured wiring, it is easy to refine the wiring by using the manufacturing method described later, and it is excellent in bending resistance when it is used as a flexible printed wiring board. The average crystal grain size of the copper layer has an average crystal grain size larger than the average crystal grain size of the first copper layer, whereby the bending resistance as a flexible printed wiring board is remarkably improved. Consider the bending resistance test of the admixture printed circuit board, so that it is suitable to withstand repeated and bending stress until the circuit is broken. When subjected to repeated bending stress, if it is in the profile of the flexible printed circuit board At the time of the change, the amount of displacement that changes with the curvature (the amount of displacement that changes with the expansion and contraction) becomes larger as the outer surface becomes larger, and the smaller the center is, the smaller the center portion is. Therefore, it is usually estimated that 320099 24 200847867 == on the flexible printed circuit The plate-curved action granulation boundary occurs while the 'rupture propagation will occur along the crystal plate, so the tester produces. Therefore, in the printed circuit of the present invention, there are few crystal grain boundaries that become the fracture propagation path for the larger extension of the father. The line of the layer is formed into a layer, and the product is made to have the same resistance as the average crystal grain size of the second copper layer. The diameter system and the formation of the low-round temple plane 2::= metal layer of the crystal grain of the moon, the printed circuit board of the second layer only constitutes the hair: crystal grain size is small, in order to seek the guide = sticky surface Low wheel corridor, and can be formed with excellent: - Good: Two: Γ is a kind of printed circuit board that can obtain good (four) ^ /, 艮 good etching characteristics at the same time.

In the printed wiring board of the present invention, the average particle diameter of the second copper layer is greater than or equal to 1.0 mvm, and the average particle diameter of the second steel layer is U 2 m to 5. The average particle size referred to here refers to the use of the test

Anning Electron Microscope; Scanning Electron Microscope), nB Soon Beam (Ion Beam) device, or metal microscope to observe the section length of the channel thickness (4), and determine the crystal length of each copper layer existing in the dry circumference. The average value of the diameter and the short diameter. Here, the measurement method using the above-described method for observing the crystal grain size was carried out by a thermal method to measure the crystal grain size of the broken crystal. Therefore, under the strict thought of 320099 15 200847867, in the i-th steel layer, the average crystal grain is excluded. In the case of the above, the average crystal grain size of the copper layer is changed to the magic speed. The figure 1 shows a representative example of the crystal of the copper layer. : The average crystal grain size of the 22nd is best to "❹. = The average layer diameter of the phantom layer is also determined by the average length and the short diameter of the first layer. When the average crystal grain size is not 曰曰0. In 2, as a line with a good (four) engraving factor, the representative of the crystal of the copper layer of the wind. , by change! : The metal layer of each layer of the first copper layer and the second copper layer of i is capable of having a uniform crystal grain size. In addition, the dream is made by the force of 2 to have a different degree of flat = month:. Even if the crystal grain size just after the production is i = the recrystallization operation due to heating is generated separately, this will be described in detail in the production method described later. I. In the printed wiring board of the present invention, the thickness of the second copper layer is 5% to 5 of the thickness of the 罘1 copper layer, and the average crystallization of the second copper layer is the copper layer and the second steel layer. ^ 斤f sounds. When considering the combination with the i-th copper layer::° and the larger 5.0" combination, the test is long; the crystal grain size is the smallest 〇._ The thickness of the second copper layer exceeds ;丨钢: ^^ 二度. As a result, if the enthalpy of the j-day is 500%, the speed of the layered plate of the gold plate 320099 16 200847867 is faster, and the first copper layer side of the etchable layer is etched during the etching of the core and the enamel. Erosion ", brother 1 steel j ® 〇 〇 1- 1- 1- 1- 1- 1- 1- 1- 同 同 同 同 同 同 同 同 同 龙 龙 龙 龙 龙 龙 龙 龙 々 々 々 々 々 々 々 々 々 々 々 In addition: the money engraving factor observed on the aJ surface will deteriorate, so if the thickness of the layer is 5%, then there is no mouth == degree is not satisfied with the second copper layer TM in the first copper plate. Η-. The level of the secondary metal layer:::: The stratified metal layer has an average crystal grain size larger than that of the I 9 a ^ and the 日 日 。. The difference in the average crystal grain size of the layer of the thicker Γ layer As shown above, when the observation is large and the surface is observed, the step difference is two, and it becomes larger, and there is a difference in the copper layer of the line. In this case, the second part of the first (four) 9 is The wire diameter 妓 becomes the average crystal grain size close to the copper layer of the brother 1 , and therefore, the number of layers is required to be (4) silk, and is effective. Also, in the printed wiring board of the present invention, the cross section of the + 4 position is obtained. In the shape, the thickness of the top 1 U, , and /, any surface has a thickness of 1, the etching factor of the line is opened, and the cross-sectional shape of the line is displayed again. Figure 3 Schematic [Math 2] Engraving factor 2 xTc

Wb_Wt

CD (4) factor indicates that (4) the shape of the section is close to the rectangle ' 320099 17 200847867 , : how the difference between the top width of the upper surface of the line and the bottom width of the lower surface of the line is small: the top surface of the upper surface is thin The bottom width of the surface (five) is rational 'and the value of this % (four) factor is close to infinity). Therefore, H is the same as the method for producing the copper (II) copper layer and the second copper layer, and the following method is used. The factor of (4) is set to 2 5 = upper is preferably set to 3. G or more. On the other hand, when the second copper layer is coated by the pattern ore (corresponding to the following second manufacturing method), the = engraving factor is set to 3.〇 or more, and more preferably 4.0 or more. =: Because the top width of the upper surface of the line is wider, it is more desirable to obtain a wider mounting area for electronic cigarettes and women's clothing. The linearity of the line is also important. Specifically, in the line of the transmission ^, the upper end line (_ Une) and the bottom end line (bott〇m view:; err^ at the end, the shape without the unevenness is ideal. In addition, when the side stress is attached, when The possibility that the line width is widened and the starting point is increased. If the above situation is considered, for example, the variability required for the formed line width is about 10%. The left side is used for the manufacturing thickness of the aforementioned (10) band. ::The pitch of the line (line width + interval width) is 4. /zm -Γ1= When the line width variability exceeds (10), the second power ===.5 tends. Therefore, in order to be easy, install It is very important to set the flexible printing 320099 18 200847867 circuit board with excellent bending resistance, and it is very important to set it to 25 or more. ^Bee's description of the absolute and soil boards used in (4) of the printed wiring board of the present invention. The circuit provided by the printed circuit board of the present invention can be applied to a holding printed circuit board or a hard printed (four) circuit board. When engraved on the Czech brush and the = board, the silk screen (4) is widely used for the imine. (pQiyimide)

Mm mm ^(p〇iyimide-amide)#m *m >

The resin (four), the liquid crystal polymer resin, and the like are provided with a flexible film. When it is suitable for poetry hard printed circuit boards, it can be cured by heating. = = reversed glass containing glass - epoxy (glass_epGxy) resin prepreg Prepreg), glass-polyimide (glass_p〇lyimide) resin A known hard insulating substrate material such as a prepreg or a BT resin prepreg. <Production Mode 1 of Printed Wiring Board of the Present Invention> Here, the form of the first manufacturing method will be described. The first manufacturing method of the printed wiring board of the present invention is characterized by comprising the following steps A to D. Hereinafter, each step will be described. • Step A: / In this step, a metal-clad laminate is provided, and the metal-clad laminate has a body layer formed of a layer in which a first copper layer and a second copper layer are laminated on the surface of the insulating substrate, and The average crystal grain size of the second steel layer has an average crystal grain size larger than the average crystal grain size of the first copper layer, and the first copper layer side is bonded to the insulating substrate. The method of manufacturing the metal-clad laminate is intended to employ several methods. The method for producing the first metal-clad laminate is a method using an electrolytic copper foil. 19 320099 200847867 The electrolytic steel foil at this time is a layer in which a first copper layer and a second steel layer are laminated, and the average crystal grain size of the second copper layer is larger than that of the first copper layer. The average crystal size of the particle size is large. The electrolytic copper system as used herein means that the average crystal grain size of the first copper layer and the average crystal grain size of the second copper layer are clearly different at the stage. Therefore, the electrolysis is based on the formation conditions of the "three-layer" and the second copper layer, and the electrolytic solution of the copper electrolyte or the like. However, the electrolytic copper falling here refers to the copper which is produced by electrolysis. For example, a case where any one of the first copper layer or the second copper layer is produced by an electroless ore coating method or a physical mineralization method on one side of the surface of the copper unboxing case is also included. The above-mentioned electrolytic copper flute has the smaller average crystal grain size! The copper layer is formed by hot pressing or an adhesive layer adhered to the above insulating substrate! y: Metal-clad laminate. The manufacturing method of the second metal-clad laminate is made of the soil. ':】;:=: The electrolytic copper composed of the layer of the layer is two = D 2 copper layer is fine and even isot for 15 minutes or more 6" heat Recrystallization. ^ ^ That is, in the stage of electrolytic copper foil, the difference between the average of the $j copper layer and the average crystal grain size of the second copper layer cannot be distinguished: in the P metal layer. When the i-th steel layer side of the electrolytic copper box is subjected to a temperature of from C to 18 Gt for 15 minutes or more and the insulating substrate is bonded to the electrolytic layer, the average crystal grain size of the second copper layer becomes: That is, by recrystallizing the crystal structure of the copper added with the IS 2 copper layer at the time of lamination, the average crystal grain size is larger than that of the layer 320099 20 200847867. In order to obtain the above, The copper crystal structure of the second copper layer is an electroplated copper method using an acidic copper sulfate plating solution, and the copper sulfate plating solution has a copper concentration of 〇.8 mol/liter to liter, and a free sulfuric acid concentration of 0. 8mol / liter to 1 · 2m 〇 i / liter, chlorine concentration is "talk to 5 〇卯 melon, and enough to use The acidic copper sulfate plating solution has a capacity of 1/2 or more and is treated with activated carbon. It is characterized here that a part of the above copper sulfate plating solution is treated with activated carbon. In other words, a copper plating solution which is cleaner than a general copper electrolytic solution which is industrially used for the production of an electrolytic copper box is used, whereby the dog can obtain electrolysis which is recrystallized by heating from 17 to 180 Torr for 15 minutes or more. Copper foil. The 1/2 volume or more of the acidic copper sulfate plating solution is applied to the X-active H-rope treatment button. When 1 liter of copper ore liquid is prepared, a liter or more is subjected to / tongue-type filtration and reuse. When the amount of activated carbon treated in the acidic copper sulfate plating solution is less than 1/2 capacity, recrystallization does not occur even if it is heated at about 17 Torr to i8 〇t: for about 15 minutes, or even if recrystallization occurs, The amount of variation in crystal grain size will also be large and unsatisfactory. If the electrolysis conditions are further explained, it is preferable to use a dimensionally stable anode (8) - Stable Anode (DSA) for the anode and set the liquid temperature to 4 Torr. The electrolysis is carried out at a current male of 5 A/dm 2 to 70 μ/dm, and the acidic copper sulfate liquid and the electrolysis conditions in the case of forming the second copper layer in which recrystallization occurs are the same as follows. Preferably, the heat treatment is set to 17 〇. 〇 to 18 (rc is 15 knives or more. Such a copper layer having a good low-temperature annealing property greatly changes its mechanical properties after heating 10 knives for 4 knives. Heating with 丨70〇c χ1 〇 minutes causes the change in crystal grain size to start. However, if the temperature is increased by i7 (320099 21 200847867 for more than 15 minutes, it will become the average crystallizer of the i-th copper layer. , = layer = average crystal grain is too high, heating time is too high, but the right heating temperature is further ^ t H, the crystal structure of the first steel layer also appears to be Ding, then, ... and the tendency of macrocrystallization, Therefore, heating 170 C to 180 〇c, adding 埶眭p bow 祆 - and the mouth is 疋 若, ... ~ _ is preferably set to 15 minutes to 30 minutes. iR ^ ^ mr, milk (ep〇Xy) 糸 resin as The insulating base 11! hane is an adhesive next to the insulating layer, and the heating conditions are the same as the following. The manufacturing method of the laminated board does not use the electrolytic copper method. That is, the 'first layer is formed on the insulating substrate by the electroless plating method. The steel layer is formed by the electroless plating method, so it can be directly insulated from the insulation. The i-th copper layer is formed on the surface of the substrate. The electroless ore coating at this time is applied to the electrolytic plating of copper, and any known electroless plating method can be used. Next, the method of the above name is used to "17" to 180. (: In; ft 15 minutes or more heating, by which the second copper layer is formed on the first copper layer to serve as a conductor layer. Thereafter, as described above, the temperature is 1701: 18 (the temperature of rc is 15 minutes or longer). By heating, the average crystal grain size of the second copper layer is larger than the average crystal grain size of the first copper layer, and is used as a copper clad laminate. Step B: At this step An etching resist pattern is formed on the surface of the second copper layer of the conductor layer. The etching resist for forming the etching resist pattern is ink, dry film, or liquid resistance 320099 22 200847867 Any known agent such as a agent is & micro The fish is straightforward m, in order to take into account the agent of the other line. For the resolution of the use of =, it is better to select the liquid resistance 'wash::=: agent, the surface of the second copper layer is acid-washed. The surface is cleaned and dried, and the body is hindered by the work. _ Coating /. Then the coating liquid is exposed and the agent is slaughtered, and two: the soil is attached to the resist film π Lusheng 剞 (2) wood and Into the cheek image to remove the unnecessary portion, the metal-coated step C on the surface is provided with a money-etching resist pattern, in order to perform the rhyme processing on the cladding sheet having the aforementioned pattern of the resisting agent However, all the parts that have not formed the etch resist pattern will be straightened to make the line (4) into the line. The process is used in the manufacture of the stencil. The dad is also used in the manufacture of the slab. An acid acid salt or an alkaline etching solution prepared by mixing copper chloride or ferric chloride. The specific ', ❿ is more suitable to use the liquid quality management material 2 t "疋 处理 ' ' ^ ^ Do not belong to the etchant. And, in the etch imaginary = fixed time is better to use the former (four) ^ :: two (4) The data of 12 is the benchmark and is set to be the child of the copper layer of the rice cooker. In order to minimize the production of the undercut of the brother 1 layer, it is better to set the time to 0% to 10%. In step D., the printed circuit board is obtained by removing (4) resist == which exists on the surface of the aforementioned line. The specific method of paste removal has been widely known, as long as the corresponding money etching agent is selected ί 320099 23 200847867 It can be used by the presenter. For example, after using the liquid resist described in the θ k A field after the use, it is stripped using an inspective second system like a smectic solution. The bamboo etching resist pattern is given. Expansion <Production Form 2 of Printed Wiring Board of the Present Invention> Step 2: The second and second manufacturing methods are characterized by including the following steps a to 2, in order to avoid repeated description, and the description of the first method The part that is repeated is omitted as much as possible. In the step a: the layer is formed on the surface of the insulating substrate to have only the first copper: ... ν, and the steel laminate. The first copper layer has a small average tantalum grain size, and a method of bonding the electrolytic copper crucible to the insulating substrate can be employed. Further, it is also possible to directly open/form the S-edge substrate using an electroless (four) method, a physical vapor deposition method, or the like. As long as there is a crystal structure in which the crystal grain size of the towel is not changed greatly in the step described later. However, in order to obtain a certain degree of bonding strength between the i-th copper layer and the insulating substrate, when electrolytic copper is used, and the method is hot pressing, and is used as a flexible printed wiring board, it is preferable to use a casting. The method produces a copper clad laminate. Moreover, when a thinner 笫1 copper layer is obtained, it is also preferable to use a layer of electrolytic copper.

ArAc Poise 0 Step b In this step, a plating resist pattern is formed on the surface of the first steel layer of the preliminary copper-clad laminate. The plating resist pattern referred to herein can be a known resist such as an ink, a dry film or a liquid resist, similarly to the etching resist. When a thin copper plating layer is formed, if a liquid resist is used, it is easy to obtain 24 32 〇〇 99 200847867 • A fine wiring pattern is obtained. However, Lunan, which is coated with steel reed, will be considered in the following steps; "two two = •, dry film should be used. In the use of dry;,: 'If considering the resolution, etc., the system is 'sweet to t The surface of the first layer is cleaned and dried by washing, and the film is attached by using a laminating machine to dry film + LV β λ χ R. The film is exposed on the dry film. a pattern, and performing development to remove unnecessary portions, and plating a copper-clad laminate of a resist pattern. Step C: η ί = in the middle of the preliminary copper-clad laminate which is not formed with a plating resist pattern The first copper sound # s clothing surface is plated with copper and formed along the shape of the line:::: By using the pattern clock method, the cross-sectional shape of the line formed as the second copper layer can be formed close to In the case of the ideal shape, it is said that it is easy to obtain the formation of the second copper layer having an excellent _ factor at this time as long as it is capable of forming a temperature of 15 minutes or more after heating and then crystallization. For the method of low-temperature annealing of copper layer, the method of using electrolytic bell steel is no electricity ^ Any of the steel method and the physical vapor deposition method may be used. However, in consideration of the productivity and cost, it is preferable to use the above acidic sulfuric acid to perform copper plating under the same conditions. / 步骤 and step d ·· In this step, the plating resist pattern is removed as a preliminary printed wiring board. Since the removal of the mineral resist pattern can be applied to 320099 25 200847867, the same concept as the removal of the etching resist pattern, The explanation is omitted, and the description thereof is omitted. Step e: · 隹-ft shot' is to heat the crystal of the second copper layer by the preliminary brushing of the brush board obtained in (4) (4). The conditions are the same as described above, and thus the description thereof is omitted here. Step f: In this step, the printed wiring board of the second steel layer has been subjected to a etch process of the step 2, and the second copper is not formed. The first copper layer of the plate is dissolved and removed, and the printed circuit line L i can also be formed in the second copper layer formed along the circuit shape, and the metal resist layer of a metal such as tin can be formed into a thin ore. Two: When using the first etching method, just use The copper etching method, that is, the functional copper layer of the plating resist, functions as the first copper layer, and has the second time of the larger average crystal grain size. Line = the shaft material set in the tamper (4) is better to use the data obtained by 对崎; == as the benchmark and set to reduce the width of the first copper layer: cut phenomenon = °:;: 7 is the copper The consumption of the layer is reduced, and the etching time is more suitable for 320099 26 200847867. It is set to 0% to 10%. Retirement, regardless of the manufacturing form, after the formation of the line, plating, Sn -Bi, Au, etc. metal or plating containing σ to the metal. Then, in addition to the terminal portion of the line, a solder mask or a film is used to form an insulation on the line. Protect the layer and get a printed circuit board. Further, the key pad of the above terminal portion may be formed after the formation of the insulating protective film. 〈Present of the electrolytic copper foil of the present invention> The electrolytic copper foil of the present invention is used for the average crystal grain control of the second copper layer after heating at 175 Cxl for 5 minutes for the preparation of the above-mentioned metal-clad laminate The average crystal grain size of the copper layer of 0·l#m or more and the private layer is 1.0/ζιη or more and 5〇//m or less. The electrolytic copper foil having the above-described configuration can be produced by using two types of electrolytic solutions having different electrolyte solutions as electrolytic solutions for the production of electrolytic steel foil and using a two-stage electrolytic step. For example, the second layer system (4) uses a copper concentration of 0.8 m〇l/liter to liter, a free sulfuric acid concentration of 〇.8 m〇i / liter to 1.2 mol/liter, and a chloride ion concentration of 3 to 1 〇卯m. And gelatin is a copper electrolyte having a concentration of 〇3 to 5 ppm, and is formed by electrolysis at a liquid temperature of 40 to 60 C and a current density of 5 to 50 A/dm 2 . The second copper layer is formed using a copper concentration of 〇8 m〇1/liter to 1.2 m〇l/liter, a free sulfuric acid concentration of 〇8 m〇1/liter to 12 liters, and a chloride ion concentration of 5 ppm to 50 ppm. Copper electrolyte. Further, when the acidic copper sulfate electrolyte solution is supplied to the electrolytic cell, 1/2 of the supply amount is applied to the electrolytic solution which has been treated with activated carbon, and is 4 Torr to 6 Torr. The second liquid layer can be formed by electrolysis of the liquid temperature of 〇 and the current density of 5 320099 27 200847867. _· ® The equipment required for the electrolytic copper fi described above can be obtained by adjusting various types of materials that have been fortunately used for the manufacture of electrolytic copper boxes with mounting layers. Further, the second copper layer is formed on the i-th copper layer, or the second copper layer is formed on the second copper layer to select the thickness of each layer. [Examples] The present invention is shown by the following examples, but the present invention is not limited by the following examples. [Example 1] - In Example 1, 'the first copper layer having an average crystal grain size of G 5 #m and a thickness of a core, and an average of the surface of the elongated polyimine film having a thickness of 35 (four) was used. The crystal grain size is 2 () and the thickness is FCCL (Flexible Copper clad Laminate; ^ • Copper-clad laminate). The FCCL was acidified with dilute sulfuric acid having a sulfuric acid concentration of 3 〇 / liter, then washed with water and dried, and a commercially available liquid photoresist ink (etching resist ink) was applied to the surface of the second copper layer. The FCCL on which the liquid resist coating film was formed was dried, and the wiring pattern was projected to expose. The line pattern used for evaluation is a straight line with a line spacing of 3 〇. After the exposure, development was carried out using an aqueous solution of sodium carbonate, and an unnecessary portion of the resist was peeled off, washed with water, and dried to obtain an FCCL having an etching resist pattern. 320099 28 200847867 ' The FCCL· having an etching resist pattern obtained by etching is subjected to etching treatment to obtain a printed wiring board having a line pitch of 30&quot;. The cross-sectional shape of the line of the printed wiring board was subjected to a perfect score of 10 points and an etching factor was obtained. In addition, the ΜΙΤ folding test was carried out to obtain other characteristics. In the ΜΙΤ folding test, the test piece 4 shown in Fig. 4 was produced, and the test piece 4 was formed on the insulating substrate 6 to form a wiring pattern. The portion 8 of the folding end test was formed with the insulating protective layer 5. The test piece was subjected to a folding test using the ΜΙΤ folding test apparatus of Fig. 5, setting the bending curvature r: 咐. M;; 何重. ^ The fracture is detected by detecting the conduction terminals 9 at both ends: = strict production, at 1 parity and test results, the average engraving factor is 5.3 (copper layer: again #顶见12/ Zm / bottom width 1). The condition for breaking the wire by the MIT folding test was 2 times. The contents of the above-mentioned contents are combined with the evaluation and test results of Comparative Example 1 [Comparative Example 1] In Comparative Example 1, the crystal grain size having a degree of 以 is provided as _, and is used for =: The FCCL used for the purpose is the starting material. The method for forming the line for the evaluation of the C0F (four) system is common to the case 1. In order to avoid repeated explanations, the above evaluations and test results are shown as follows. The silver engraving factor averages 320099 29 200847867 2·0 (copper layer thickness 8/zm/top width 7//m/bottom width 15 // m). The condition for breaking the wire by the MIT folding test was 15 times. [Table 1] Line circuit profile----- ΜIΤ folding test copper layer thickness top width bottom width engraving factor β m β m times -------- 200 Example 1 β m 丨--- 15 5 3 Comparative Example 1 8 7 15 2· 0 150 <Control of Comparative Example 1 and Comparative Example 1> According to the above table, the cross-sectional shape of the line obtained in Example 为 is a good rectangular shape, and (4) the factor system 2.7 times the etching factor of the cross-sectional shape of the line obtained by the prior art obtained by the comparative example. Further, the bending resistance in the MIT test showed a durability of about 13 times. Therefore, it is apparent that it is advantageous to have a metal layer having a crystal grain size from the side of the insulating substrate to the surface of all the reeds, and to have a shape and a bending resistance of the printed wiring line. [Example 2] The average crystal grain size 铜1 of copper in addition to the first copper layer was set, and the average crystal grain size of the second copper layer was set to 1; 1_·β The same fccl as in Example 1. "I* and the line pattern obtained with the line spacing of 3Mm except for the use of the above-mentioned FCCL, the line pattern of the line pattern having a line spacing of 3 Mm =: a full-hearted evaluation of the cross-sectional shape of the line of the printed wiring board, and The etching factor is obtained. It is 32〇〇99 30 200847867 In addition, the other characteristics of the MIT folding test are obtained. The name of the printed circuit board is + the main q U is 5.0, and the MIT is broken until the disconnection occurs. The number of times of the test was 165. [Example 3] The disk was used in addition to the average crystal grain size of copper in which the first copper layer was set to m and the average crystal grain size of the second copper layer was set to 35 mm. Example 1 The same FCCL. ', • A printed wiring board having a line pattern having a line pitch of 30 New points was obtained in the same manner as in the example except that the above-described muscle was used. The cross-sectional shape is evaluated as a perfect score, and the residual factor is obtained. In addition, the MIT folding test is performed to obtain other characteristics. The MIT folding test with an etching factor of 4 6 until the disconnection occurs. of Off-times of 23 billion times [Example 4]

m The average crystal grain size of copper in addition to the first copper layer was set to i, and the average crystal grain of the second copper layer was set to be "9". Every day is the same FCCL as in Example 1. /, = Printed wiring board using a line pattern having a line pitch of m, which is the same as that of the above-mentioned FCCL. The cross-sectional shape of the line of the printed wiring board was evaluated as a perfect value, and an etching factor was obtained. In addition, the MIT folding test was carried out to obtain other characteristics. The printed circuit board has an engraving factor of 2.6. However, when the average crystal grain size of the third and third layers of the copper layer is 1.0/zm or more, the distribution of the crystal size becomes wider, and the value of the individual engraving factor is thus varied within the range of 2·〇 to 3.6. 'The range of variation is getting bigger. In addition, the number of bends of the MIT folding test up to the occurrence of the breakage was 180 times. [Example 5] Example 1 was used except that the average crystal grain size of copper in which the first copper layer was set was 〇5 #m, the average of the second copper layer was set, and the crystal grains (4) 〇9//m were used. The same FCCL. ...other than the FCCL described above, the other examples! The printing of the line having the line pattern of the line pitch 3G#m is obtained in the same manner: the road board. The cross-sectional shape of the line of the printed wiring board was evaluated as a perfect value, and an etching factor was obtained. In addition, the MIT folding test was carried out to obtain other characteristics. Up to now = the printing factor of the printed circuit board is 3.°, but the number of f-curves of the ΜΠ folding test until the occurrence of the broken wire is 155 times, and the average crystal grain size of the sound is less than one time. Α Μ 虽 虽 虽 虽 虽 ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ ΜΙΤ After trying to study, the average crystal grain size of the gentleman crystals forming the first copper layer from the τ ten-hook, and σ-yang particle size ratios If the particle size of the larger 愔ι 〗 layer exceeds ^ and is larger, the average crystal of the copper layer is _, but the average value of the sub-particles tends to be broader and wider, and it becomes easy to become:: etch factor The distribution of the values is easy to form and it is difficult to form a homogeneous line. In addition, when the average crystal grain size of the 2nd copper layer of 320099 32 200847867 is lower than that of 丨(4), the number of times of the breakage in the m-folding test is better. The effect may not be able to say that it is already a dog. On the other hand, when the average crystal grain size of the copper crystal of the i-th copper layer is not more than Ο.Ο/zm, and the average crystal grain size of the copper crystal of the second steel layer is in the range of 5/zm, there is no The above tendency. Therefore, for the average crystal grain size of the copper crystals forming the first (fourth) and the second, the average crystal grain size of 1. 0 /z m is a limit point at which the obtained line is changed. [Industrial Applicability] The printed wiring board obtained by the present invention is formed on an insulating substrate: the t:r system has a good etching factor and is a product having excellent bending resistance as a flexible printed wiring. Therefore, it is easy to make the wiring of the printed wiring board or the like for the liquid crystal driver mounting of the line machine 4 thin, and the risk of disconnection of the circuit is also reduced. ^ t, the process of the printed wiring board can use conventional manufacturing equipment to: Lu, and because it does not need to invest in new equipment, it can provide economical and good quality printed circuit boards. /, [Simplified description of the drawings] Fig. 1 is a photograph showing an example of a copper layer having fine crystals. Fig. 2 is a photograph showing an example of a copper layer having a giant crystal. Figure 3 is a schematic diagram showing the cross-sectional shape of the line. Fig. 4 is a schematic view showing a test piece for the MIT folding test. Fig. 5 is a schematic view showing the MIT test device. [Main component symbol description] 320099 33 200847867 -1 Top width (Wt) 2 Lower end width (Wb) 3 Total thickness of copper layer (Tc) 4 Μ IT test piece for folding test 5 Insulation protective layer 6 Insulation substrate 7 Copper line 8 Fold-resistant test part 9 Conduction detection terminal 10 Test piece 11 Bending device 12 Bending device mounting table 13 Plunger 14 Clamp for applying load 15 Conductor 16 Test piece exposed portion (length 50mm to 70mm) 17 Bending angle (135° ±5°) 18 bending angle (135°±5°) 34 320099

Claims (1)

200847867 X. Patent application scope · 1. A printed wiring board having a line formed on the surface of an insulating substrate; the line having a layer of an i-th steel layer and a second steel layer laminated, and the first copper The layer side is bonded to the insulating substrate; and the average crystal grain size of the second copper layer is larger than the average crystal grain size of the layer. 2. For the printed circuit board of the patent range of μ, wherein the average crystal grain size of the copper of the front copper layer is 〇1&quot; the average crystal grain size of the copper of the second copper layer which is not above the above is "." m. Main b· 0 3· Ϊ申: Patent printed circuit board of the first or second printed circuit board, wherein the thickness of the 5 22 copper layer is 5% of the thickness of the first copper layer to刷 围 第 第 第 第 第 第 第 刷 刷 刷 刷 刷 刷 ♦ ♦ ♦ ♦ 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1) The average gentleman's granules of the secondary metal layer obtained a large average crystal grain size. Spoon, - 曰曰 5H (4) The printed circuit board of any of items 1 to 4, in which the 线路 line has a cross-sectional shape at any position thereof, and the thickness of the line 2 is made T. When the page width of the upper surface of the line is Wt and the bottom width of the surface is Wb, the residual factor calculated by the following formula (1) is 2 · 5 or more and the residual factor = -_^ χΤ. ο Wb_Wt 320099 35 (1) 200847867 6.=Application for the special section! In the printed circuit board of any of the five items, the substrate for the flexible printed wiring board is used as the insulating substrate. 8. A printed wiring board according to any one of the items U5, wherein a substrate for a hard printed wiring board is used as an insulating substrate. - A method for manufacturing a printed wiring board, which is a manufacturing method of the fourth to fourth item of the patent application range (4), characterized in that it comprises the following steps A to D: • (d) preparing a metallized laminate, The metal-clad laminate system. , Ba, and 'the surface of the earth plate is provided with a conductor layer composed of a layer of the i-th steel layer and the second copper layer, and the average crystal grain size of the second copper layer is inferior to the average of the copper layer of the brother 1 The first crystal layer has a larger average crystal grain size, and the first copper layer side is bonded to the insulating substrate; and step B: a resistant pattern is formed on the surface of the second copper layer of the conductor layer; Step C· A metal-clad laminate having the above-mentioned (four) resist pattern is subjected to engraving treatment to dissolve and remove a portion of the conductor layer of the unshaped wire etching to form a line; and v-D will exist on the surface of the aforementioned line The etch resist pattern is removed to obtain a printed wiring board. 9. The method for manufacturing a printed wiring board according to the eighth aspect of the invention, wherein the copper-clad laminate (4) is a metal-clad laminate used in the above step A, and the copper-clad laminate is used in a laminate. a copper foil having a layer of a first copper layer and a second copper layer and having an average crystal grain size larger than an average crystal grain size of the first copper layer, and an electrolytic layer of 320099 36 200847867, And the first copper layer side is bonded to the insulating substrate. 10. The method of manufacturing a printed wiring board according to the eighth aspect of the invention, wherein the copper-clad laminate is used as the metal-clad laminate used in the above step A, and the copper-clad laminate is laminated. An electrolytic copper foil comprising a layer of a second copper layer which is recrystallized by a force σ heat of 15 minutes or more at 0 C to 18 0 C, and is formed in the formation of a metal-clad laminate. The first copper layer side is subjected to 17 generations to 180 degrees. The temperature of the crucible is 15 minutes or longer, and the insulating substrate is bonded to the electrolytic projection I, whereby the average crystal grain size of the second copper layer is made larger than the first! The average crystal grain size of the copper layer is also large as the average crystal grain size. 11. The method of manufacturing a printed wiring board according to claim 8, wherein the double-layered copper laminate is used as the metal-clad laminate used in the foregoing step A. The steel-clad laminate is electrolessly plated. A first copper layer is formed on the insulating substrate, and a second re-crystallized second # copper layer is formed on the second steel layer by heating at 170 to 18{rc for 15 minutes or more as a conductor layer. And then applying a temperature of 17{rc to 18th generation for 15 minutes or more to heat, whereby the average crystal grain size of the second copper layer has an average crystal grain size larger than the average crystal grain size of the i-th copper layer. . 12. The method for manufacturing a printed wiring board according to claim 1G, wherein the second copper layer is formed by an electroplating copper method using an acidic copper sulfate plating solution, and the acidic copper sulfate plating solution is Use a copper concentration of 〇.8mol/L to L2mol/L, a free sulfuric acid concentration of 〇8 mol/μl to 1.2 mol/L, a chlorine concentration of 5 ppm to 5 〇ppm, 320099 37 200847867 and the acidity has been used Activated carbon processor for sulfuric acid steel plating bath. 1/2 capacity or more The method for manufacturing a printed circuit board according to any one of the patents (4) r, (the following steps a to f: 1 is 3 = a: manufacturing) a preliminary copper-clad laminate having only the i-th copper sound on the surface of the insulating substrate; 曰 step b: forming a plating resist pattern on the fourth surface of the preliminary copper-clad laminate; ^ ▲Step C: Forming a second copper layer on the surface of the i-th copper layer of the preliminary copper-clad laminate which is not formed with the resist pattern; and forming a second copper layer; step d: printing the circuit board by removing the plating resist pattern; In the first step, the primary copper layer is crystallized by the preliminary heating of the printed circuit board obtained in the step d, and the step f is followed by the crystallization of the second copper layer. The preliminary printed wiring board which has been subjected to the agglomeration is subjected to an etching treatment, and the exposed second copper layer of the portion where the second copper layer is not formed is dissolved and removed as a printed wiring board. 14· Patent Application No. 13 Manufacturing method of printed circuit board, in which 'description The second copper layer is formed by a copper bond method using an acidic copper sulfate plating solution, and the copper sulfate plating solution has a copper concentration of 〇. 8 mol/liter to i.2 mol/liter, and the free sulfuric acid concentration is 〇· 8ιη〇] [/ liter to 1.2 mol / liter, chlorine concentration of gppm to 50ppm, and 38 320099 200847867 used 1/2 capacity or more of the acidic copper sulfate plating solution to be treated with activated carbon. The method for producing a printed wiring board according to claim 13, wherein the heat treatment in the step e is heated at a temperature of 170 ° C to 180 ° C for 15 minutes or more. 16. An electrolytic copper foil is The manufacturer of the metal-clad laminate according to the ninth aspect of the invention, wherein the copper-clad laminate has a layer in which a first copper layer and a second copper layer are laminated, and is heated at 175 C x l for 5 minutes. The average crystal grain size of the copper layer is 0·1 // m or more and less than h 〇/zm, and the average crystal grain size of the second copper layer is 1·0 // m or more and 5·〇m or less. 320099 39