TW200838390A - Two-layer flexible substrate, method for manufacturing the two-layer flexible substrate, and flexible printed wiring board manufactured thereof - Google Patents

Abstract

To provide a two-layer flexible substrate which, even when allowed to stand at an elevated temperature of about 150 DEG C, even at an elevated temperature of about 180 DEG C, for a long period of time causes no significant lowering in adhesive strength between an insulating film and a copper layer (hereinafter often referred to as "peel strength"), particularly a two-layer flexible substrate suitable for fine pattern formation/COF mounting, and a method for manufacturing the two-layer flexible substrate. A two-layer flexible substrate comprising an insulating film, a substrate metallic layer provided by a dry-type plating method directly on at least one side of the insulating film without interposing any adhesive agent, and a copper conductor layer having a desired layer thickness on the substrate metallic layer, characterized in that the substrate metallic layer is crystalline and is composed mainly of nickel-chromium or nickel-chromium-molybdenum in which 0.5 to 4.8 atomic% of a nitrogen atom has been dissolved.

Description

[Technical Field] The present invention relates to a two-layer flexible substrate, a method of manufacturing the same, and a flexible printed wiring board obtained from the two-layer flexible substrate, and more particularly, It is especially suitable for fine pattern formation and a two-layer flexible substrate which is less than 15 (the rc level or even 18 (long-term rc temperature is placed at a high temperature for the insulation film and the copper layer). A two-layer flexible substrate mounted on c〇F (film wafer soldering), a method for producing the same, and a flexible printed wiring board obtained from the two-layer flexible substrate. [Prior Art] Various types of electrical equipment, such as monitors, mobile phones, and digital cameras, are required to be thinner, smaller, and lighter. Therefore, electronic components mounted on them are also becoming smaller.

As a substrate for forming an electronic circuit, which is frequently used for such electronic components, a "hard printed wiring board" having a hard plate shape and a flexible and freely bendable "flexible wiring board" (hereinafter also referred to as a film) "Fpc")", ^中' FPG can use its flexibility, and it is used in the L (:D drive wiring board, _, DVD module, mobile phone folds, where flexion is required, so The need for the material is increasing. The material user of the FPC is like a copper-clad laminate of copper (conductor layer) (hereinafter also referred to as ILL).

Further, this CCL can be roughly classified into the following types in which the film and the copper foil (conductor layer) are bonded by a bonding agent. One is to insulate CCL (commonly referred to as 3-layer 96147168 5 200838390 CCL), and the other is to use an insulating film and a copper foil (conductor layer) without using a bonding agent, by casting, lamination, metallization. (metallizing) method, etc., which directly combines it with CCL (commonly referred to as r2 layer CCL). When the three-layer CCL is compared with the two-layer CCL, the three-layer CCL is easy to manufacture in terms of material cost, handling, and the like of the insulating film and the bonding agent, so that the manufacturing cost is relatively low; Two layers of CCL are superior in properties such as properties, film formation, and dimensional stability. Therefore, in recent years, due to the demand for fine patterning and high density of wiring, the two-layer CCL is relatively expensive, but since it can be made thinner, the demand for the two-layer coffee is still expanding. Further, as a method of assembling ic on the FPC, the (10) electrical mounting method for detecting the position of the IC by the light transmitted through the insulator is formed after the wiring is formed on the ca, so the thinness of the material itself and the insulating material are Transparency must be required. Based on this, it is also advantageous to have 2 layers.

First: The second layer of the second layer of manufacturing, the law, can be further advanced - roughly divided into three types. Insulating film, , %, copper or copper drop on the copper by the casting method to solve the problem of the second method of the second method is to laminate the electrical process on the insulating film by lamination (here... The upper layer is composed of a dry ion beam method, a cesium ore method, an ion ore method, a clustering method, a CVD method, a CVD method, etc., and the bottom layer of the film is entirely on the insulating film, and on the (four) cap layer Meng belongs to the above-mentioned q-th system, "the method of copper electroplating to form a copper layer. The third method of each method is usually called metallization. The system ==Fazhong" is freely controlled by the dry process and the key. The thickness of the layer, so the metal sound ^ ^ 溥 filming compared to the casting method and laminated method capacity 96147168 6 200838390 easy: again, 'because of the smoothness of the interface between polyimine and metal layer is higher, it is generally considered suitable for fine patterns. ::The two-layer CCL obtained by the metallization method cannot expect the commonly used anchor effect due to the joint between the metal film interface and the genus and the insulating film, and the interface between the metal and the insulating film. The adhesion strength cannot be fully exerted, so it is sandwiched between the insulating film and the copper layer. ^Medium alloy layer such as Nl Cr, which is a main component, in order to improve the adhesion force. Moreover, when a flexible wiring board having a narrow width and a narrow pitch is obtained, when the amount of chromium in the metal alloy layer is large, The method used is to form a wiring by chemically engraving a solution of a metallized substrate with a solution such as ferric chloride or copper chloride, and then post-treating with a solution containing sulfuric acid or hydrochloric acid, and then potassium hydroxide by a clock H, The step of impregnating the mixed solution of sodium hydroxide to remove the dissolved portion of the metal alloy layer. 2 'The two-layer CCL using the metallization method is carried out at 18 (the same degree of rc) When the heat resistance test is placed, the strength of the 遂 and the combination tends to be greatly reduced as compared with the initial adhesion strength. Therefore, if the liquid photoresist is applied after the application of the liquid photoresist in the pattern forming step, i 〇 is applied. M5 (heat of rc degree, and when the formation of the pattern is 1 ^ = bonding or welding is also applied 25 〇. The degree of 〇, the amount, the two-layer CCL manufactured by the previous metallization method , not suitable for fine pattern shape to warm In addition to the high density of the wiring pattern, the use of the high-voltage environment 96116168 7 200838390 increases the number of printed wirings. The insulation reliability of the substrate tends to be important. As an indicator of this characteristic, a constant temperature and humidity bias test (sometimes also referred to as HHBT test) is adopted. - As a bottom metal layer, a Ni-Cr alloy layer is provided. The two-layer exchangeable substrate 'for example, 'HHBT at a voltage of 4〇v in a constant temperature and humidity chamber of 85°C to 85% R·H·, to a wiring pitch of 3〇# m, for a given insulation resistance value Insulation reliability of more than 10,000 hours can be ensured. In contrast, in the case of a narrow method in which the wiring pitch is 3 〇"m or less, the insulation reliability cannot be maintained. More than 1 0 0 0 hours. As a method for solving the above problems, the patent document 记载 discloses that the ruthenium molecular film is contained in a nitrogen-containing atmosphere by a vacuum deposition method, an ion plating method or a sputtering method, and contains 60% by weight. A metal film containing copper as a main component is formed on the first metal film containing 100% by weight or less of nickel atom-containing nickel, and the two layers of the film thus formed are subjected to 15 (rc, 168 hours) heat, and then The adhesion strength can be improved. Then, in Patent Document 2, the application only describes the film formation in a nitrogen-only environment, and only proposes a range in which the amount of nitrogen in the first metal film is very large. Further, in the invention of Patent Document 2, the discussion on the evaluation of the heat-resistant adhesive strength of 15 (rc, 168 hours of heat-resistant looseness after heat treatment under more severe conditions) is not sufficient. However, It is known that a surface of a polymer film is usually subjected to surface modification treatment by an aqueous alkali solution, a plasma treatment, a electrosonic discharge treatment, or the like, and a copper layer formed by dry plating or wet plating is formed on the film ( 200) face with (1) n 96147168 8 20 0838390 The X-ray diffraction intensity ratio of the surface is changed by 1 (200) / 1 (1 11 ). Further, Patent Document 3 describes an aromatic polyamine which is surface-treated with an aqueous alkali solution. On the sheet-like substrate, a metal thin film is formed by a sputtering method, and a copper layer obtained by electroplating thereon has a χ-ray diffraction intensity ratio of os-iqoovkudslo, which is excellent in etching property. The result is ^, the X film of the metal film on the substrate. However, these are due to the degree of surface modification, so that the surface shape of the polymer film is not modified without surface modification. Japanese Patent Laid-Open No. Hei 2-6-3〇6〇〇9 Patent Document 2 Japanese Patent Laid-Open No. Hei 2-6-3〇32〇6 Patent Literature 3 Japanese Patent Laid-Open Publication No. Hei. No. 2-6-3〇32〇6 [Invention] (The problem to be solved by the invention) φ The instrument of the present invention is 纮 μ μ π _

96147168 9 200838390 The underlying metal consisting of a nitrogen atom of 0.5 to 4.8 atom% of the recording or network structure, and the layer of the substrate layer in the underlying metal layer, which will solve the above-mentioned 4 The two layers of the copper conductor layer with directional heat resistance can also be applied to (4) width, (4) and (4). n substrate. The first invention of the present invention is a two-layer flexible substrate which is attached to a second layer: a surface without a bonding agent, and is directly formed into a lower layer to a genus layer by a dry ore-forming method. The crystals of the desired layer thickness are formed on the layer, wherein the underlying metal layer is a crystal containing mainly 0.5 to 4.8 atom% of a ruthenium atom or a ruthenium. The second invention of the present invention is the first! The two-layer susceptibility substrate of the invention described in the 'the bottom layer of the metal layer of the ff surface and (2, the index of index ratio is ... coffee) / K (111J 21.0). More specifically For the at least one side of the insulator film, the underlying metal layer is directly formed by dry plating without a bonding agent, and the two layers of flexible substrate formed by forming a copper conductor layer having a desired layer thickness on the underlying metal layer The underlying metal layer is composed of a nickel-chromium or nickel-chromium-turned crystal having a solid solution of nitrogen and nitrogen, and the crystalline layer of the underlying metal layer is a (1)1) surface of the fcc structure. The ratio of the index to the (200) plane is in the range of 0. is K(2〇〇)/K(l 11)5 21.0. According to a third aspect of the invention, the two-layer flexible substrate according to the first aspect of the invention, wherein the underlying metal layer is mainly in a state in which nitrogen is present in the vicinity of chromium, and the chemical bonding energy in the XPS state is 396.4 to 396.8. eV and 96147168 200838390 397.2~397. There is a wave ♦ in the position of 4eV. - plate m guangyue is the two-layer manageable group described in the first invention - the unitary lattice volume of the <1 〇曰 层 layer is 100.0 compared to the unsolidified 虱 为 100.0 ~104 5% range. The fifth invention of the present invention is a two-layer serviceable group described in the first aspect of the invention, and (1) 1) Sri of the structure of the copper conductor layer (2G plane: the orientation index ratio is 0·01 «(_/κ(1)υπ〇 The scope of the invention: The sixth invention of the invention is a two-layer t-film that is described in the invention. The membrane is selected from the group consisting of a polyimide film, a bis-naphthalate film, and a liquid crystal polymer. 〈==================================================================================================== The copper wiring pattern is required. The θ-substrate is formed by the surname method. The ninth invention of the present invention applies a DC voltage of 4〇ν to the terminal of 23_ or more which is formed with the pattern, at 85〇c-85. %rh ; In the case of constant temperature and humidity bias test (10) BT test), the flexible wiring board having a resistance of more than one hour is more than one. The invention of the invention 10 is a two-layer programmable substrate method. Forming an underlying metal layer directly on at least one side of the insulator film by a dry type 96147168 11 200838390 plating method through the bonding agent Forming a copper conductor layer of a desired layer thickness; wherein the formation of the underlying metal layer by the dry plating method is a mixed gas of argon and nitrogen having a nitrogen concentration of 55 to 1 vol% Under the circumstances.

According to a tenth aspect of the present invention, there is provided a method for producing a two-layer flexible substrate according to the tenth aspect of the present invention, wherein the obtained underlying metal layer is nickel-chromium or nickel mainly containing 0.5 to 4.0% by atom of a nitrogen atom dissolved therein. Crystallization of _chromium_molybdenum, and the ratio of the orientation index of the (111) plane to the (2〇〇) plane of the crystalline structure of the underlying metal layer is 〇.lgK(2〇〇)/K(111) The range of S21 ;; in more detail, 'at least the surface of the insulator film, the underlying metal layer is directly formed by the dry ore method without the bonding agent, and the copper conductor of the desired layer thickness is formed on the underlying metal layer. The underlayer metal layer formed by the dry (four) method is formed by a mixed gas of argon and nitrogen at a nitrogen concentration of 0.5 to 1 vol%, and the obtained underlying metal m is contained in a solid solution. a crystal of nickel-chromium or nickel-chromium-molybdenum having a nitrogen atom of 0.5 to 4.8 atomic %, and the ratio of the orientation of the 〇11) plane to the (2〇〇) plane of the crystalline structure of the underlying metal layer is G.1 is the scope of ZGGVKUlDgu. According to a twelfth aspect of the invention, in the method of manufacturing the two-layer flexible substrate according to the tenth aspect of the invention, the 'the underlying metal layer' is mainly a nitrogen present in the ς=6 near-state 'in the XPS state analysis' chemical bond The knot can be in the chaos 4~396. 8eV and 397· 2~397. There is a peak at the position of 4eV. According to a thirteenth aspect of the present invention, in the fourth aspect of the invention, the method of the second layer of the second layer of the second layer of the present invention is that the unit cell volume of the underlying metal layer is 100.0 to 104 in a state in which nitrogen is not dissolved. 5% range. A method of manufacturing a two-layer flexible substrate according to the tenth aspect of the present invention, wherein the alignment of the (1) plus (j〇〇) plane of the structure of the copper conductor layer is described in the fourteenth aspect of the present invention. The index ratio is in the range of 0.01^Κ(200)/Κ(111)'7 0 . According to a fifteenth aspect of the present invention, in the second aspect of the present invention, the second layer of the coating layer is a late method, wherein the insulator film is selected from the group consisting of a polyimide film: "& amine film, polyester At least one or more resin films of a film, a polytetrafluoroethylene film, a poly-ruthenium film, a polyethylene naphthalate film, and a liquid crystal polymer film. The sixteenth invention of the present invention is the two-layer serviceable group according to the first aspect of the invention, wherein the dry weaving method is a vacuum evaporation method, a sputtering method, or a scorpion scorpion method. Any of them. (Effect of the Invention) According to the two-layer flexible substrate of the present invention, it is possible to obtain a two-acoustic adhesive-bonded flexible substrate having high adhesion and heat resistance, and is applicable to a narrow width and a narrow width. The flexible wiring board of the wiring part is useful in the Wei industry. [Embodiment] Hereinafter, the present invention will be described in detail. 1) Two-layer flexible substrate The two-layer flexible substrate of this month is attached to at least one side of the insulator film, and the underlying metal layer is directly formed without the bonding agent by Gansian/dry plating. The gold layer layer is also used to form the copper conductor layer of the desired layer thickness. The underlying metal layer is fortunately and the p-characteristic in the von mainly contains solid solution nitrogen atoms 05~4. 8 eyebrows early recorded L chrome 1 , 纟 _. Atom 96147168 13 200838390 A two-layer flexible substrate in which a copper conductor layer having high adhesion and high heat resistance is formed by using the above configuration can be obtained. Here, the underlying metal layer used in the present invention is obtained by the dry (four) method, and the main 3 is recorded as chromium- or chromium-nickel-turned crystal, and the nitrogen atom dissolved in the underlying gold layer must be 〇. .5~48 atomic %. The nitrogen atom dissolved in the underlying metal layer is less than 〇5 atomic %, and the solid solution effect of the nitrogen atom appears to be ' @ 15 (TC heat-resistant adhesion strength and heat-tightness of C. C heat resistance; If the X 'nitrogen atom exceeds 354.8% atomic%, it will be found that the crystallinity is lowered, and 1 18 (the TC heat-resistant adhesion strength is lowered (the causal relationship is not known), which is not preferable. Further, it is used in the present invention. The crystallinity of the underlying metal layer is preferably in the range of 配.丨$ Κ(200;)/Κ(111) $21·0 of the (111) plane and the (200) plane of the fee structure. The index of the orientation of the (cc) surface and the (200) plane of the fcc structure is κ(2〇〇)/κ(111) if it is less than 〇i, °c heat-resistant adhesion strength and 18 (rc heat-resistant adhesion strength) It will be lowered, so it is not good, and the ratio of the index of the (11丨) and (2〇〇) faces of the 'fee structure is more than 21〇, 18 (rc). Here, it is known that the orientation index K (200) and K (lll) are affected by changes in surface roughness and the like due to surface modification of the insulator film in the prior art. Invented Focusing on the change of the orientation index due to the film formation environment of the underlying metal layer even in the case where the surface modification is not performed, in the present specification, the orientation index is measured for the underlying metal layer formed on the surface of the insulator film. 96147168 14 200838390 Further, Κ(200) represents a tangential index obtained from a ridge of a surface of an fcx structure measured by X-ray diffraction (hereinafter also referred to as xrd), and KU(1) represents fcc. The structure of the (1) plane is determined by the w-lson orientation index. Further, the layer thickness of the underlying metal layer used in the present invention is preferably 3 nm or more and 5 Å or less. The layer thickness of the underlying metal layer is not When the thickness is 3μ, even after the subsequent processing steps, the long-term adhesion of the underlying metal layer may also be problematic. On the other hand, if the layer thickness of the underlying metal layer exceeds 5 〇 nm, the underlayer is processed during the wiring portion. The removal of the metal layer may be difficult, and hair-crack and warpage may occur, and the adhesion strength may be lowered, which is not preferable. The group of the underlying metal layer used in the present invention is also used. Become the main record In the case of the underlying metal layer, the ratio of the heat in the metal layer of the test is 12, and the atomic % is preferred. The ratio of chromium to j is less than 12 atom%, and the heat resistance is lowered; The ratio of chrome is too much: two %%, and the removal of the underlying metal layer during processing of the wiring portion will be repeated again: in the case where the usual nickel-based alloy is dry, the ratio of nickel is greater than / IA It #£ itself becomes a ferromagnetic body 'In the case of film formation by magnetron reduction, the film formation speed is lowered, so it is not good. However, the dry nickel amount of the present invention is 93% or less', so the film formation day is performed using magnetron sputtering. Shou can also pass to a good film formation rate. = The thickness of the underlying metal layer containing the recording-chromium alloy is mainly used to improve the heat resistance and durability of the recorded chromium alloy. Also, 96116168 15 200838390 can be used according to the desired target characteristics. The transfer metal element is appropriately added. Furthermore, the composition of the underlying metal layer used in the present invention is a case where the underlying metal layer mainly contains nickel chrome, and preferably the ratio of chromium is 4 to 22% by weight, and the ratio of molybdenum is 5 to 40% by weight. The rest is nickel. First, the reason why the proportion of chromium is required to be 4 to 22% by weight is to prevent a significant decrease in the peeling strength of the heat of the heat due to thermal deterioration. Further, when the proportion of chromium is less than 4% by weight, the heat-resistant peel strength cannot be prevented from being remarkably lowered by thermal deterioration, which is not preferable. Further, if the proportion of chromium is more than 22% by weight, etching becomes difficult, which is not preferable. Therefore, chromium is preferably 4 to 15% by weight, particularly preferably 5 to 12% by weight. Secondly, the reason why the proportion of molybdenum must be 5 to 40% by weight is to improve the reliability of insulation. If the proportion of molybdenum is less than 5% by weight, the effect of addition is hard to be exhibited. The thermal method improves the durability and the reliability of insulation, which is not preferable. Further, when the ratio of molybdenum exceeds 40% by weight, the heat-resistant peel strength tends to be extremely lowered, which is not preferable. 10. Furthermore, in the case of a conventional nickel-based alloy target, if the ratio of nickel is more than 93/〇, the sputtering target itself becomes a ferromagnetic body, and when the film is sputtered by magnetron sputtering, the film formation speed is lowered. It is not good. However, in the dryness of the present invention, the amount of nickel in the formation is 93% or less, that is, the magnetron (4) is used for film formation, and a good film formation rate can be obtained. Further, in order to improve the heat resistance and corrosion resistance of the nickel-chromium-molybdenum alloy, a transfer metal element may be appropriately added in addition to the target characteristics. In the case of the underlying metal layer, in addition to the nickel-chromium-molybdenum alloy, impurities which are contained in an amount of 1% by weight or less which are contained in the case of being produced by a person or the like may be avoided. • The film thickness of the underlying metal layer of the main 3 nickel-chromium-molybdenum is preferably in the range of 3 to 50 nm. If the thickness of the film is 3n [thinness, it may cause problems such as a significant decrease in the peeling strength of the wiring due to the intrusion of the liquid in the wiring portion during the wiring process, etc.], which is not preferable. Further, if the film thickness is more than 5 Å, it is difficult to carry out the film, which is not preferable. The two-layer flexible substrate of the present invention is formed on at least one side of the insulator film, and 10 is not directly formed by a dry plating method via a bonding agent, and a copper layer having a desired layer thickness is formed on the underlying metal layer. The two-layer flexible substrate of the conductor layer forms an underlying metal layer by a dry ore method in a mixed gas of argon gas and nitrogen gas. Further, since the present invention is formed by the above-described manufacturing method, the underlying metal layer is mainly in the state in which nitrogen exists in the vicinity of chromium, and is X-ray-electric (hereinafter, also referred to as the state analysis of the state, the second

396· 4~396· There is a peak of CrN near 8eV, and there is a peak of CrA at the position of 397· 2~397. 4 eV 10. Further, the unit lattice volume of the underlying metal layer is preferably in the range of 100.0 to 104·5% in comparison with the state in which nitrogen is not dissolved. If the unit lattice volume of the underlying metal layer is less than 100.0%, the nitrogen is not completely dissolved, so it is not good. And if the unit lattice volume of the underlying metal layer exceeds 104·5%, then 15〇°C heat-resistance The combined strength and the heat-resistance strength at 180 ° C are lowered, which is not preferable. Here, the unit lattice volume is obtained by the peak position of the (111) plane or the (200) plane of the fcc structure obtained by XRD measurement, and the unit lattice volume is calculated. 96147168 17 200838390 Further, as the insulator film used in the present invention, an imide film, a polyamine film, a polyester film, a polytetraethylene film, a polyphenylene sulfide film, or the like may be mentioned. The polyethylene naphthalate film 曰, the resin film of at least one or more of the polymer film; wherein the wire is preferably used in the high temperature bonding of the material to be recycled. The thickness of the above 缘ε edge film is preferably in the range of 25 to 75/zm. The reason is that, for example, if it is less than 25/m, the workability is too small, and if it exceeds 75, the bendability is lowered. In addition, inorganic materials such as glass (four) fibers are preferred because they do not use substrates containing inorganic materials because they interfere with laser processing and chemical processing. The dry plating method which can be used in the present invention: may be any one of a vacuum vapor deposition method, a sputtering method, or an ion plating method. The two-layer flexible substrate towel of the present invention can further form a copper film layer by dry plating on the underlying metal layer. Further, after the copper film layer is formed by the dry plating method, the copper layer may be formed by wet plating on the copper film a. The orientation index of the underlying metal layer is changed in the above range. ☆ The alignment index of the copper conductor layer on the underlying metal layer is also specialized and cross-linked, so the copper conductor layer The ratio of the index of the (111) plane to the (200) plane of the ice structure is in the range of 0·〇1颂200)/Κ(111)$7·〇. The method of the galvanic coating method is as described above for the vacuum evaporation method m, or any of the ionization methods. Compared with the wet plating method, the film formation rate is higher than 96,147,168, 18, 2008,38,390 k k, which is suitable for forming. The case of a relatively thin copper film layer. On the other hand, when a copper film layer is formed by a dry plating method, and a copper layer is formed by wet plating on the copper film layer, it is suitable for forming a thick copper conductor layer. 2) Method for Producing Two-Layer Flexible Substrate Hereinafter, a method for producing a two-layer flexible substrate of the present invention will be described in detail. In the above invention, it is selected from the group consisting of a polyimide film, a polyamide film, a polyester film, a polytetrafluoroethylene film, a polyphenylene sulfide film, and a polynaphthalene dicarboxylic acid. One or both surfaces of the insulator film of at least one resin film of the ethylene glycol film or the liquid crystal polymer film, the underlayer metal layer is directly formed without a bonding agent, and a desired layer is formed on the underlying metal layer. Thick copper conductor layer. The film usually contains moisture. Before the underlying metal layer mainly containing the nickel-chromium alloy is formed by dry-packing, it is necessary to perform air drying or vacuum drying to remove moisture present in the film. If this step is not sufficient, the adhesion between 10 and the underlying metal layer may be deteriorated. In the case of forming a bottom metal layer mainly containing nickel-chromium or nickel-chromium-molybdenum by dry plating, for example, when forming an underlying metal layer by a roll-to-roll (1) coiling type ore apparatus 5〜10体积%的。 The nitrogen/increase is 0. 5~10% by volume. A mixed gas of nitrogen and argon is maintained at a level of 1.3 Pa in the apparatus, and then wound into the insulator film mounted in the apparatus, and transferred at a speed of, for example, 3 m per minute, a 96147168 19 200838390 side Sputtering is started by supplying electric power from a DC power source for sputtering connected to the cathode, and an underlying metal layer mainly containing nickel-chromium or nickel-chromium-molybdenum is formed on the film. Similarly, a copper target is used as a cathode for sputtering. In the sputtering apparatus, the copper conductor layer is formed on the insulator film on which the underlying metal layer is formed. Then, after the underlying metal layer and the copper film layer are continuously formed in the same vacuum chamber, the underlying metal layer is opened/formed. Take the film out to In the air, when a copper film layer is formed by another sputtering device, sufficient water removal must be performed before the copper film layer is formed. Further, after the copper film layer is formed by dry plating, the copper is formed. On the film layer: in the case of forming a copper layer by a plating method, for example, electroless copper plating treatment can be performed by forming an electroless copper layer on the entire substrate, even if the insulator film is present in a large pinhole. The exposed surface of the film can also be used to make the entire substrate a good conductor, thereby not being affected by the pinhole and the layer thickness of the copper layer plated by the electroless copper plating solution, as long as it can be repaired, It is preferable that the thickness of the copper plating solution is not to be melted by the plating of the pinhole of the substrate®, and it is preferable to form the substrate on which the electroless copper plating layer is formed. :: Secondary copper plating treatment of the layer thickness of the conductor layer required at the end can be obtained. 2 The pinholes of various sizes which are generated when the underlying metal layer is formed are good and the adhesion of the film layer is high. Layer flexible substrate. Electroplated copper treatment Whether it is - copper plating or secondary 96147168 20 200838390 copper plating can be used in the common copper plating method, the layer thickness of the copper film layer formed on the underlying metal layer is the underlying metal layer 'its Thickness must be below 12/zm

Further, in the method for producing a two-layer flexible substrate of the present invention, the surface of the insulating film is not modified as described above, and the influence of the bain property is improved by introducing nitrogen, that is, by the bottom layer. In the metal layer, the amount of the conductor is changed to the ratio of the diffraction intensity of the x-ray, in order to achieve the adhesion (heat resistance) force, and the insulator film of the prior art (the tea patent document j, etc.) The surface is modified with alkali to produce the effect of the anchoring effect, that is, the X-ray diffraction intensity ratio is changed according to the degree of the modification, so as to improve the adhesion (5), and the force is completely different. 3) Flexible printed wiring board Hereinafter, the flexible wiring board of the present invention will be described. The etching method is a step of using a portion selected from the group consisting of: ferric chloride, copper chloride, ammonium persulfate: a liquid residue to remove the copper film, and a hemiplegic solution composed of sulfur sulfonium. The second stage of the step of removing the underlying metal layer of the ruthenium or the recorded underlying metal layer in which the nitrogen atom is dissolved is formed. * Nitrogen is dissolved in the underlying metal layer of the flexible substrate. Therefore, an etching solution such as ferric chloride, copper chloride or ammonium persulfate cannot be removed: large 'This must be an etching solution composed of hydrochloric acid and sulfuric acid. Further, in the above-described flexible printed wiring board, the DC printed circuit is applied between the terminals of the pattern of 23# m or more in the pattern, and the flexible wiring board of the present invention is flexible. The flexible substrate is formed into a flexible wiring substrate of a desired copper wiring pattern by a credit engraving method.

96147168 21 200838390 In the case of constant temperature and humidity bias test in an environment of 85 C -85% R· Η·, the resistance between the terminals is ϊ〇〇〇h or more. [Examples] The examples of the present invention will be described together with the comparative examples. First, the measurement method of the peeling strength is carried out in accordance with the method of ipc-ΤΜ-65〇, Ν〇·2·4·9. Among them, the lead width was set to 1 mm, and the peeling angle was set to 9 〇. . The leads are formed by a removal method or a semi-addition method. Further, as an index of heat resistance, a substrate formed with a lead film of 1 mm was placed in a 15 (TC oven for 168 hours, taken out and placed in a chamber, and placed as an index under more severe conditions). After 240 hours in the oven of 18 ,, it was taken out to room temperature after being taken out, and it was subjected to 9 〇. Evaluation of peel strength. The HHBT test of the insulation reliability test was determined by the removal method according to JPCA-ETG4. The semi-additive method removes the copper film by ferric chloride, and removes the underlying metal layer by etching with 8-12% by weight of hydrochloric acid and 13~17 by weight of sulfuric acid to form a test piece, so that the test is used. The sheet was applied between the terminals with a DC of 40 V, and the resistance was observed for 1 hour in an environment of 85 t: 85% RH. It was judged to be defective at a point where the resistance between the terminals became 1 〇 6 ω or less, and was still 1 经过 after 1000 hours. % or more is determined to be qualified. The index of orientation index is KOOOVKUU), and the diffraction peaks of the (111) plane and the (200) plane of the face-centered cubic fcc structure measured by XRD have a Willson alignment index κ ( 200) and K (111) are obtained. Leaf 96147168 22 200838390 fee configuration ^ The Κα1 position obtained by the Kai_W 7 knife treatment is obtained by using the peak of the (1) υ or (10) plane obtained by XRD measurement. Calculate the unit cell volume by the interval. Setting the surface [Example 1] = Polythene film (thickness manufactured by Toray-DuPont, registered, Kabton 150EN) having a thickness of 38/zm was formed as a layer of the underlying metal layer. It uses a 2 〇 atomic Cr-Ni alloy target (Sumitomo Metal Mine Co., Ltd.) to perform 20Cr-Ni alloy at a film formation rate of (7 (10)/sec in a 2% N2-Ar environment by DC sputtering. Film formation of the underlying metal layer. The thickness of the layer was measured by a transmission electron microscope (TEM: manufactured by Hitachi, Ltd.), and the film thickness was 18 nm. Further, the nitrogen in the underlying metal layer was measured by X-ray electron spectroscopy (XPS: VG-Scientific), and the result was 2 atom%. Further, a chemical bonding energy can be observed in the vicinity of 396·4 to 396·8 eV and around 397_2 to 397·4 eV, and a peak of 0 can be observed on the film on which the NiCr film is formed, and then the film formation of the second layer is performed thereon. A Cu target (manufactured by Sumitomo Metal Mine Co., Ltd.) was used to form a 100 nm thick copper film layer by sputtering, and then electroplated to a film size of 8#. The obtained two-layer flexible substrate had an initial peel strength of 572 N/m, a 150 C heat-resistant peel strength of 501 N/m, and a 180 °C heat-resistant peel strength of 203 N/m. Further, the orientation index of the underlying metal layer is Κ(200)/Κ(1Π), and the orientation index ratio K(200)/K(lll) of the 3' copper film layer is 0.01. 96147168 23 200838390 Also, the unit cell volume of the underlying metal layer is 44 655 χ US·3. After forming a photosensitive resist film on the surface layer of the copper layer surface layer of the conductive metal layer, exposure and development were carried out to form a wiring pitch of 28/m (line 觅··14#m, pitch width: 14/zm) and 23μπι (line width··h] giant 1·12/ζπι) comb-tooth test piece, using this pattern as a masking material, for the copper layer with 40°Be (Baume, Baume) The iron solution was etched and then immersed in an acidic etching solution (CH-1920) (manufactured by MEC) at 50 Torr for 2 minutes, and then the photoresist was removed to prepare a test piece (removal method). Further, after performing the line etching, a tin plating treatment step is provided, and plating is performed on the line. When tin plating is used, the LT-34 manufactured by Shipley FarEast (stock) is used as the tin plating solution, and plating at a solution temperature of 75 ° C is equivalent to 〇.6/zm, make a sample. π was heat treated at 15 〇 C for 1 hour. Thereafter, the three samples were subjected to an instinct test, and the resistance after the test was 1 〇 6 ω or more. [Example 2] A polyimide film having a thickness of 38/zm (manufactured by Toray-DuPont, registered, 軚卡布通150EN) was formed on one surface as a layer of the underlying metal layer, which was 20 atoms. The alloy target (manufactured by Sumitomo Metal Mine Co., Ltd.) was formed into a film of a 20Cr-Ni alloy underlayer metal layer by a DC sputtering method at a film formation rate of 0.77 nm/sec in a 5% N2-Ar environment. The layer thickness was measured by a transmission electron microscope (TEM: manufactured by Hitachi, Ltd.) for the film formation under the same conditions, and it was 18 (10). The nitrogen in the underlying metal layer was measured by X-ray and spring turtle spectrometry (manufactured by XPS·· VG-Scienti fic), and was found to be 4 atom%. In addition, the chemical bonding can be observed in the vicinity of 3 teams of 4 to 396.8 eV and around 397 2 to 397 4 eV. 96116168 24 200838390 o. On the film formed with the NiCr film, the second layer is formed thereon. For the film, a Cu target (manufactured by Sumitomo Metal Mine Co., Ltd.) was used to form a 100 nm thick copper film layer by sputtering, and then electroplated to form a film. The two-layer flexible substrate that was served had an initial peel strength of 567 N/m, a heat-resistant peel strength of 15 〇 ° C of 5 〇 7 N/m, and a heat-resistant peel strength of 18 〇 of 201 N/m. Further, the orientation index of the underlying metal layer is ιο·9, and the ratio of the orientation index of the copper film layer is 2.〇8. Also, the unit cell volume of the underlying metal layer is 45 783 \1〇3. After forming a photosensitive photoresist film on the surface of the copper layer surface layer of the obtained conductive metal layer, exposure and development are performed to form a wiring pitch of 28 " (line width: 14 " 'pitch width: 14") and 23 (four) (line width: u β m, wide pitch: 12 m) comb-tooth test piece, using this pattern as a masking material, for the copper layer with 4 (TBe) of the ferric iron solution for the following: Further, an acidic etching solution (CH_192〇) (manufactured by MEC) was used for 5 minutes. After immersing for 2 minutes, the photoresist was removed to prepare a test piece (removal method). Tin plating treatment, on-line plating: 'In Qianxi, as a tin plating solution, Shipley Far East is used as LT-34 at a solution temperature of 75. 〇 plating is equivalent to 〇.6"m ♦ This sample was heat treated for 150 hours. After that, three samples were tested for insulation sin, either of which had a resistance of 1 〇 6 Ω after the test. [Example 3] ° = thickness 38#m An imide film (made by Toray _ DuPont, registrar Titanium Cabbong 150EN) is formed on one of the faces as the underlying metal layer 9611416 8 25 200838390 The first layer, which is made of 20 atom% Cr-Ni alloy target (manufactured by Sumitomo Metal Mine Co., Ltd.), in a 8%-Ar environment, by DC sputtering at a film formation rate 〇//nm The film formation of the underlying metal layer of the 20Cr-Ni alloy was carried out in a second. The thickness of the layer was measured by a transmission electron microscope (TEM: manufactured by Hitachi, Ltd.) for the film formation under the same conditions. Further, the nitrogen in the underlying metal layer was measured by X-ray electron spectroscopy (XPS·· VG-Scientific), and the result was 4.8 atom%. Further, the chemical bonding energy was around 396·4 to 396·8 eV and 397. · 2~397· 4eV is observed in the vicinity of the mine. On the film on which the NiCr film is formed, the second layer is formed on the film, and the Cu target (manufactured by Sumitomo Metal Mine Co., Ltd.) is used. A 100 nm thick copper film layer was formed by sputtering, and then electroplated to a film thickness of 8 Å ηη. The initial two-layer flexible substrate had an initial peel strength of 573 N/m and a 150 ° C heat-resistant peel strength of 531 N/m. , 18 〇ΐ heat-resistant peel strength is 200 N / m. Also, the underlying metal layer has an index of orientation ratio _ of 20.1, copper The orientation index of the layer is 5.8 (2 〇〇) / κ (ιιι) is 5.86. Further, the unit lattice volume of the underlying metal layer is 46·415 X 1 〇 3 (10), / copper in the obtained conductive metal layer After forming a photosensitive resist film by a dry film of a layer surface area layer, exposure and development were carried out to form a wiring pitch of 28 #m (line width: Η/ζιη, pitch width: 14//111) and 23/zm (line width: u V"1, wide pitch · 12/zm) comb-tooth test piece, using this pattern as a masking material, etching the copper layer with 4 (TBe) ferric solution, and then etching with acid The liquid (CH-1920) (manufactured by MEC Co., Ltd.) was immersed in 501 for 2 minutes, and then the photoresist was removed to prepare a test piece (removal method). 96147168 26 200838390 In addition, the tin plating treatment step is set after the line etching, and the tin on the line is in the tin tin. The tin plating solution is made of ShipleyFarEast (stock) LT-34' at a solution temperature of 75 ° C. The sample was heat-treated at 15 °C for 1 hour at 0·6/zm. Thereafter, the insulation reliability test was performed on three samples, and the resistance after the test was 106 Ω or more. [Comparative Example 1] A polytheneimide film having a thickness of 38/zm (manufactured by Toray-DuPont, registered trademark "Kabong 150EN") is formed on the surface of the first layer as the underlying metal layer. (Sumitomo Metal Mine Co., Ltd.) 'In the Ar environment, the film formation of the underlying metal layer of 20Cr-Ni alloy was carried out by DC sputtering at a film formation rate of nm·7 nm/sec. The thickness of the layer was measured by a penetrating electron micromirror (ΤΈΜ: manufactured by Hitachi, Ltd.), and the result was i8 nm. The X-ray electron spectroscopy (XPS: VG-Scienti fic) was used to measure the underlying metal layer. The result of nitrogen is less than 0.1 atomic %. The chemical bonding energy was not observed near the range of 396·4 to 396.8 eV and around 397.2 to 397.4 eV. On the film on which the NiCr film was formed, the second layer was formed on the film. The target (manufactured by Sumitomo Metal Mine Co., Ltd.) was formed by sputtering to form a thick copper film layer, and then electroplated to form a two-layer flexible substrate with an initial peel strength of 584 Ν/Π1, 150 C. The heat-resistant peel strength is 425 N/m, and the heat-resistant peel strength at 180 ° C is 127 N/m. Further, the orientation index of the underlying metal layer is 配(200) / Κ(111) is 0 'the ratio of the orientation index of the copper film layer Κ (200)/Κ(1Π) is 0. Further, 96147168 27 200838390 The unit cell volume of the underlying metal layer is 44.433 χ i〇W. The obtained conductivity is all horses, ^ is the copper layer surface of the genus layer Laminated dry film: After forming a secondary photoresist film, it is exposed and developed to form a wiring pitch of 'm' for 14" m, pitch width: 14/zm) and 23#m (line width: 11 mask) , a comb-shaped test piece of copper 1 12 " m), using this pattern as a cover

In addition, after the line (four) engraving, the Lai processing step is set. On the line, the mine is made in tin plating, and as the 钖 plating solution, the LT_34 is used, and the plating at the solution temperature of 75 ° C is equivalent to about 6.6iam. Make: Sample two at 15. . Heat treatment η, time. Thereafter, the "successful test of the three samples" was carried out, and the electric resistance after the test was equal to or less than A iq6 为. 5 a is etched with 40 Be (Beau) trivalent iron solution, and then 1 t rhyme αΗ-192{)) (10) (share)) after immersion for 2 minutes, remove the photoresist 'made into Test piece (removal method). [Comparative Example 2] • The first layer of the underlying metal layer was formed on one surface of a polyethylene/imide film having a thickness of 38/zm (manufactured by Toray-DuPont, registered trademark "Kabong 150EN"). Atomic %Cr-Ni alloy dry (Sumitomo Metal Mine Co., Ltd.) in 1 (UN2-Ar environment, by DC sputtering at a film formation rate 〇 7nm / private film formation of 20Cr-Ni alloy underlying metal layer The thickness of the layer was measured by a transmission electron microscope (TEM: manufactured by Seiko Seisakusho Co., Ltd.), and the result was i8 nm. Further, X-ray electron spectroscopy (XPS ·· VG) was used. -Scientific system) The nitrogen in the layer of the layer of the genus is 5 atomic %. Further, the chemical bonding energy is 396. 4~ 96147168 28 200838390 396. Near 8eV and 397. 2~397. The peak can be observed near 4eV On the film on which the NiCr film was formed, the second layer was formed thereon, and a Cu target (manufactured by Sumitomo Metal Mine Co., Ltd.) was used to form a 100 nm thick copper film layer by Qian Zhong Er. Then, the film was formed by electroplating to 8 claws. The initial peel strength of the obtained two-layer flexible substrate was 553 N/m. Heat-resistant peel strength & 4_ / m, 18 〇. The heat-resistant peel strength is 131 N / m. In addition, the orientation index of the underlying metal layer is κ (2 (10) is 22.3, the orientation index of the copper film layer is 8. 45 and ' The unit lattice volume of the underlying metal layer is X i〇w. After the dry film of the copper layer surface area of the obtained conductive metal layer is formed to form a photosensitive film, exposure is performed, and (4) 彡 is formed to form a wiring pitch of 28/zm ( Line width: 14 (four), pitch width: 14 / / m) and 23_ (line width: ", wide pitch: 12 / / 11 〇 comb-tooth test piece, use this pattern as mask =, for copper layer 4 (TBe (Beauty) The ferric iron solution was etched, and then an acid etching solution (CH-1920) (manufactured by MEC) was used to prepare a test piece (removed by the 'resist agent' after 2 minutes of rc immersion for 2 minutes. Method). After the line is left, the tinning process is set, and the tin plating on the line is used for tin plating. When the tin plating solution is used, the LT-34 of ShipleyFarEast (stock) is used for plating at a solution temperature of 75 ° C. It is equivalent to 〇·6Μιη, which makes 4 wood; 1C ΠΠ 〇 15 〇 it heat treatment for 1 hour. Thereafter, three samples were tested for sin and sin. The resistance of any of the tests after the test was 1 〇 6 〇 or more. The results of the above examples and comparative examples are shown in Fig. 1 . Further, the XPS measurement results of the underlying metal layer are shown in Fig. 2. 96147168 29 200838390 It can be seen that in the two-layer flexible substrate of Examples 1 to 3, the underlying metal layer directly formed on the insulator film by dry plating is in the environment in which the underlying 'metal layer is formed. In the mixed gas atmosphere of argon and nitrogen, the nitrogen concentration is in the range of the effect of the present invention, and the obtained underlying metal layer is crystalline, and the nitrogen atom is dissolved in the metal layer in a preferred range in which the effect of the present invention can be exhibited. The aspect ratio index of the (111) plane to the surface of the fcc structure of the underlying metal layer is excellent in satisfying O.iSKMOOyKdiDgU j, i5Q 10C heat-resistant peel strength and 18 〇°c. Further, in the insulation reliability, the distance between 23/zm and above is excellent even if the resistance between the terminals of 1〇6ω or more is maintained after 1 000 hours. On the other hand, in the two-layer flexible substrate of Comparative Examples 1 to 2, the underlying metal layer directly formed on the insulator film by dry plating was used in Comparative Example 1 to form the underlying metal layer. The environment is argon only, and the (200) alignment of the underlying metal layer cannot be expressed. As a result, the heat-resistant peel strength and the heat-resistant peel strength of Φ 18 0 °c are inferior to those of the examples. Further, in Comparative Example 2, although a mixed gas atmosphere of argon and nitrogen is used, the nitrogen concentration is mixed in a large amount from the preferred range of the present invention, and the (111) plane of the fcc structure of the obtained underlying metal layer is obtained. 2〇〇) The orientation of the surface. Although the index ratio becomes larger, the heat-resistant peel strength at 150 ° C is slightly worse than that of the examples, and the heat-resistant peel strength at 180 ° C is remarkably inferior. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a table of the results of an embodiment of the present invention and a comparative example. Fig. 2 is a view showing the results of XPS measurement 96147168 30 200838390 of the underlying metal layer of the embodiment and the comparative example of the present invention.

96147168 31

Claims (1)

200838390 X. Patent application scope: 1 · A two-layer flexible substrate is attached to at least one side of the insulator film, and the underlying metal layer is directly formed by dry plating from the bonding agent to the underlying layer. A copper conductor layer having a desired layer thickness is formed on the genus layer; wherein the α-floor metal layer is a crystal containing nickel-chromium or nickel-chromium-molybdenum mainly containing a nitrogen atom Q·5~U atom% quality. 2. The two-layer flexible substrate according to claim 1, wherein the crystal structure of the underlayer to the genus layer has an index index ratio of (111) plane to (200) plane of the fcc structure at 0·ΒΚ (2〇〇)/κ(1(1)$21〇 range. 3 = 2 layers of flexible substrate of claim 1 of the patent scope, wherein the f layer to the genus layer is mainly a state in which nitrogen exists in the vicinity of chromium. In the XPS state, the chemical bonding can exist at the positions of 396·4~396·8eV and 397·2~397·4eV. · 4·The flexible substrate of the second layer of the first application of the patent scope, In the middle, the unit lattice volume of the genus layer is in the range of 100·0~104·5% compared to the state in which the nitrogen is not dissolved. 茑: Please request the second layer of the first item of the patent range to be flexible. a substrate in which the ratio of the index of the (111) plane to the (2〇〇) plane of the == fee structure is in the range of 0.01 $ κ (200) / κ (111) 57.0. The two-layer flexible substrate of the first item, wherein the body f is selected from the group consisting of a polyaniline film and a polyamine film: a polyester-based face, a phase vinyl film, and a polystyrene ring. Film, poly Ethylene formate film or liquid crystal polymer film, a lipid film. At least one or more of the trees 96147168 32 200838390 a winding substrate, wherein, or any of the ion plating methods, as described in the patent application. The two-layer dry plating method of the first item is a vacuum vapor deposition method or a sputtering method. 8. A flexible printed wiring board in which a substrate is formed by a method to form a copper wiring. In the flexible printing (10) substrate of the 9th item, the flow voltage is applied, and the direct test (HHBT test) is applied between the environments of RH and RH. The end of the plate is constant. 10. The method for producing a two-layer flexible substrate is based on the surface of the insulator film and is formed by directly forming a bottom metal layer by dry plating without using a bonding agent. Forming a copper conductor layer of a desired layer thickness on the underlying metal layer; characterized in that the underlying metal layer formed by the dry plating method is formed by argon and nitrogen having a nitrogen concentration of 55 to 10% by volume. In a mixed gas environment. 11·If applying The method for producing a two-layer flexible substrate according to claim 10, wherein the obtained underlying metal layer is nickel-chromium or nickel-chromium-molybdenum mainly containing 0.5 to 4.8 atom% of a nitrogen atom dissolved therein. Crystalline, and the ratio of the orientation index of the (ln) plane to the (2〇〇) plane of the crystalline structure of the underlying metal layer is 〇.1$ 1 ((200)/1((1 1 1 )$21 The scope of the 〇 · 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 12 Can be found in 396 4~396.8ev and 96147168 33 200838390 397· 2~397. 4eV position has a peak. 13. The method for producing a two-layer flexible substrate according to claim 10, wherein the unit lattice volume of the underlying metal layer is 100.0~1〇4·5 compared to the state in which nitrogen is not dissolved. The range of %. The method for manufacturing a two-layer flexible substrate according to the patent application scope, wherein the ratio of the (m) plane to the (2〇〇) plane of the fcc structure of the copper conductor layer is 〇 · 〇1$Κ(200)/Κ(111)^7·0 range. 15. The manufacturer of a two-layer removable substrate according to the first aspect of the invention, wherein the insulator film is selected from the group consisting of a polyimide film, a polyamide film, a polyester film, and a poly 4 At least one or more resin films of a vinyl fluoride film, a polyphenylene sulfide film, a polyethylene naphthalate film, and a liquid crystal polymer film. 16. A method of producing a two-layer flexible substrate according to claim 10, wherein the dry plating method is any one of a vacuum deposition method, a sputtering method, and an ion plating method. 96147168 34