TW201006337A - Printing wiring cardinal plate and method for producing the same - Google Patents

Abstract

The invention provides a printing wiring cardinal plate with high insulation reliability and corrosion resistance and method for producing the same, namely the conductor wiring is formed with high etching, when etching is performed by ferric chloride solution or hydrochloric acid solution of copper chloride, residual etching draff with ingredients of the base metal layer between the conductor wirings are few, when high voltage is exerted among the conductor wirings. On at least one surface of the insulating resin film A, a metallic layer B with nickel, or nickel-chromium alloy containing nickel above 70 quality percentage and chromium below 15 quality percentage is stacked in series without an adhesive agent; a metallic layer C made of alloy containing chromium over 15 weight percentage, unnecessary part of a metal membrane composed by copper tunica layer D with thickness 10 nm to 35 Mum, chemical etching processing is adopted for selective removal, and then the printing wiring cardinal plate of conductor wirings is formed.

Description

201006337 VI. Description of the invention: • [Technical field to which the invention pertains] 'H _ printed wiring substrate and its manufacturing method, more specifically, dry plating between the film and the copper film layer The coating method has a south-insulating metal substrate and a method for manufacturing the same according to a metal layer having a good (four) property and a metal layer having a high impurity. [Prior Art] The flexible printed wiring board is roughly divided into a three-layer resin film metal film laminated substrate in which a copper foil of a conductor layer is bonded to an insulating resin film by an adhesive (for example, see Patent Document 1). And a two-layer resin film metal film laminated substrate in which a copper film layer as a conductor layer is directly formed on the insulating resin film by a dry plating method or a wet plating method without using an adhesive. However, in recent years, with the increase in the density of electronic devices, a wiring board having a narrow pitch is required, and in the production of the above-mentioned three-layer resin film metal-clad laminate substrate, it will be on the insulating resin film. In the formed copper film layer, the conductor wiring portion is formed by etching in accordance with a desired wiring pattern. However, the side surface of the conductor wiring portion is so-called side etching which is excessively etched. As a result, the cross-sectional shape of the wiring portion is likely to become a trapezoidal shape having a wide lower portion. problem. Therefore, in order to solve this problem, a two-layer resin film metal film laminated substrate has been replaced by the original laminated copper foil (three-layer resin film metal film laminated substrate). The two-layer resin film metal film laminate substrate is formed on the insulating resin film to form a coating layer having a thickness of 098117258 3 201006337. As a means, an electric ore method is generally used. In addition, in order to carry out the electric ore, a thin metal layer is formed on the insulating resin film to impart conductivity to the entire surface, and electric ore is applied thereto (see, for example, Patent Document 2). Further, the thin metal layer formed on the insulating resin film is formed by a dry Wei method such as a vacuum distillation method or an ion ore method. Thus, the adhesion of the insulating resin film to the copper coating layer is formed at the interface thereof.

In the case of a fragile layer such as CuO or Cu2, it is very weak. Therefore, in order to maintain the adhesion strength to the copper film layer required for the printed wiring board, the insulating metal film and the copper coating layer are provided as a base metal layer. Nickel-chromium alloy layer (refer to Patent Document 3). Thereafter, a laminate comprising a base metal layer and a copper coating layer is used as the metal film. The wiring pattern of the two-layer resin film metal film laminate substrate can be formed by a subtractive process. This subtraction method refers to a method of manufacturing a printed wiring board by removing a portion of the metal film of the resin film metal film laminate substrate without using a chemical etching treatment. The chemical surrogate treatment consists of washing with an undesired metal film using a chemical surname and washing with a chemical etching solution. In the chemical etching process, a chemical etching solution or water is generally used in a shower method. The nozzle is sprayed or immersed in a chemical remnant or the like. The chemical etching liquid corresponding to the etching of the copper coating layer is, for example, a solution of a vaporized iron (FeCl3.2H2〇) aqueous solution, a hydrochloric acid acidified copper (CuCl2.2H2〇) water 098117258 4 201006337, and a chemical etching using the substance. Processing can form conductor wiring. k In the chemical silver engraving method using these chemical rhyme solutions, as the underlying metal layer, when a nickel-chromium alloy having a high chromium content is used from the viewpoint of corrosion resistance, chemical etching cannot be sufficiently performed at the edge of the conductor wiring. The underlying metal layer remains between the conductor wirings, and a metal residue which is a residue of the surname is generated, and sufficient etching results may not be obtained. Further, as a problem in terms of insulation reliability, in the index of insulation reliability, a constant temperature and humidity deviation test (hereinafter sometimes referred to as HHBT test: High Temperature High Humidity Bias Test) can be performed. The substrate on which the etching residue was produced or the flexible printed wiring board using the underlying metal layer having a low chromium content clearly showed insufficient insulation reliability in the HHBT test. In other words, when the two-layer resin film metal film-layered substrate having a base metal layer having a high chromium content is subjected to the above-described chemical etching treatment, when the underlying metal ruthenium layer such as a nickel-knot alloy is left as a result of lack of a surname, In the HHBT test, the adjacent conductor wiring has a problem of short-circuiting due to a metal residue composed of a base metal layer component remaining between wirings. On the other hand, in the two-layer resin film metal film laminated substrate having the underlying metal layer having a low chromium content, although no etching residue occurs, the corrosion resistance of the underlying gold-based layer cannot be ensured, so that the HHBT test cannot be ensured. Insulation reliability. Therefore, the opposite characteristics of the etching property and the corrosion resistance of the underlying metal layer are required. Therefore, as one of the means for realizing the insulation reliability, it is necessary to remove the residual (four) residuals between the above-mentioned conductors 098117258 5 201006337, and as a related correction method of the disadvantages, for example, in Patent Document 4, it is proposed that After the chemical treatment of the copper film with the chemical vapor enriched iron solution or the hydrochloric acid acidified copper solution, a type of <2 kinds of acidic _ 彳 过 过 ( 四 四 四The above is processed to dissolve the etching residue between the wirings. Further, in Patent Document 5, it is proposed that the side between the wirings is ruined by using a salt acid and a sulfuric acid, and the mixture is immersed in a mixed liquid of a oxy- oxidized clock and sodium hydroxide. In the patent document 6, it is proposed that the (four) residue between the wirings is treated by using an acidic chemical tobacco material containing a salt acid to sigh H-aged potassium or an over-acid salt (IV) liquid. When an inspective liquid containing potassium ferricyanide or perrhenate is used, the chrome alloy or the chrome-plated alloy of the wiring (4) is removed by a method in which the rhyme of the wiring can be reduced. [Patent Document 1] Japanese Patent Laid-Open No. Hei 8-139448 (Patent Document 3) Japanese Patent Laid-Open Publication No. Hei No. Hei 6-12-63 No. [Patent Document 4] Japanese Patent [Patent Document 5] Japanese Patent No. 3888587 [Patent Document 6] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. However, the recent flexible printed wiring board has a higher density of wiring with a higher density of wiring patterns 098117258 6 201006337, and it is accompanied by high performance, and it is required to use it at a high voltage. As a result, the insulation reliability of the printed wiring board used becomes important, and in order to withstand high voltage, the base metal layer is required to have higher resistance to the surname. Therefore, from the viewpoint of corrosion resistance, it can be seen that the tendency of providing a base layer having a high chromium content of a nickel-chromium alloy is caused by a chemical etching process in which a base metal layer is not left between the conductor wires. There is an increase in enthusiasm. In the case where the conventional two-layer resin film metal film-layered substrate is formed by subtraction to form a conductor wiring pattern, the etching process is performed by using one type of chemical etching solution using a vaporized iron aqueous solution or a hydrochloric acid-acidified copper aqueous solution. The removal of the etching residue and the addition of a new etching treatment step require a new introduction of the equipment, which may cause an increase in equipment cost and liquid management cost, and a decrease in production efficiency due to an increase in steps. The present invention has been made to solve the above problems, and an object thereof is to provide a base metal layer formed on at least one surface of an insulating resin film in the manufacture of a dry plating method and a touch print printing board. When a germanium layer is formed on the underlying metal layer, the printed wiring board having high sidelinity when the conductor wiring is formed and a method for producing the same, specifically, an aqueous solution of ferric chloride or an acid chloride of hydrochloric acid is used to dissolve the water. In the conductor wiring (4), there is little _ residue in the base metal layer component, and when the conductor wiring is raised, the insulation reliability and corrosion resistance are both high. 098117258 7 201006337 (Means for Solving the Problem) The above-mentioned condition was intensively studied by the present inventors, and as a result, it was found that the metal layer B and the metal layer C were laminated without being separated by an adhesive agent on one or both sides of the insulating resin film. The steel coating layer D can realize a printed wiring board which ensures insulation reliability and corrosion resistance. According to a first aspect of the invention, there is provided a printed wiring board which is obtained by chemically removing a resin which is formed by laminating a metal film on at least one surface of an insulating resin film A without interposing an adhesive. The metal film constituting the conductor wiring includes a metal layer B laminated on the surface of the insulating resin film A, and the metal layer B is formed on the surface of the insulating resin film A. The layer b is composed of a recorded or containing 5% by mass of bromine and less than 15% by mass of chrome-based alloy; in the metal layer c of the surface layer of the above-mentioned metal layer B, the metal layer c contains the recorded and chromium-containing 15 An alloy of a mass % or more; and a steel coating layer D having a film thickness of 10 nm to 35/zm in the surface layer of the metal layer c; only the chemical butterfly liquid of the above-mentioned copper film layer D © is used to selectively remove the above In the printed wiring board according to the first aspect of the invention, the conductor wiring of the metal film including the metal layer Β, the metal layer C, and the copper film layer D sequentially laminated is sequentially formed. 'use After the chemical iron solution or the hydrochloric acid acidic copper chloride water-solution is subjected to the chemical remnant treatment, the amount of the gold-based residue remaining on the insulating resin film is measured in the area per unit area of the insulating resin film A. 0. 13 // g/cm2 or less. In the printed wiring board according to the first aspect or the second aspect of the invention, the metal layer B contains hunger 13 mass% or less, titanium § mass% or less, and 锢20 mass% or less, and the balance is recorded or 70% by mass or more of the cancer and less than 15% by mass of the chromium-nickel-chromium alloy and 1% by mass or less of the non-ingredane, and the film thickness is 3 to 20 nm. In the printed circuit board according to any one of the first to third aspects of the present invention, the metal layer C contains chromium in an amount of 15% by mass or more, and nickel 〇. 01 to ❿ 85 mass% and 1 mass% or less. An alloy composed of inevitable impurities, or an alloy containing chromium in an amount of 15% by mass or more, nickel ruthenium, 0.01 to 85% by mass, and molybdenum 〇. 〇1 to 9% by mass of 1% by mass or less of unavoidable impurities. 5 to 37 nm, or a film thickness of 5 nm or more and a total of the metal layer b of 4 Å or less. In the printed wiring board according to any one of the first to third aspects of the invention, the chemical etching liquid does not contain manganese or cyanide. According to a sixth aspect of the invention, in the printed wiring board according to any one of the first to third aspects, the chemical etching liquid is an aqueous solution of an iron oxide or an aqueous solution of acidified acidified copper. The seventh invention is based on the first.* « q% Le Z invented the printing cloth color fee..., the insulating tree moon-day film A is selected from the group consisting of a poly-imine film, a polyamine-based knee, and a polyester system.

Method for producing at least one type of resin of a film, a polytetrafluoroethylene film, a polystyrene (tetra) film, a polynaphthalene-f-acid bismuth film, or a resin film, a method for producing a printed wiring board, The chemical money X is formed without interposing the metal film yf on the at least one surface of the insulating resin 098117258 9 201006337 on the at least one surface of the film A to form an unnecessary portion of the above metal film of the substrate. The conductor wiring member is characterized in that the resin film metal film laminated substrate is formed by forming a nickel layer or a metal layer B having nickel as a main edge on the surface of the above-mentioned resin film A by using dry plating. On the surface of the metal layer B, a metal layer composed of an alloy containing 15% by mass or more, or an alloy of chromium, nickel, and (tetra) having a mass % or more is formed by a dry forming method. After the second metal film of the film thickness 1 () 111 〇 to 35 积 is deposited on the surface of the metal layer C, the metal film _ 1 type liquid is selectively removed. A conductor wiring is formed. According to a ninth aspect of the invention, in the method of manufacturing a printed wiring board according to the eighth aspect of the invention, the chemical etching solution does not contain manganese or cyanide. The above 10th invention is based on the manufacture of the printed wiring board of the eighth invention = 1 = gas (10) water-soluble (four) copper-copper aqueous solution. "Invention, in the printed wiring board of the eighth invention, the copper film layer D is formed by a plating method in a dry reading method to form a copper layer. On the surface of the copper layer to be formed, the manufacturing method of the eighth invention or The printed wiring board sub-plating method according to the eleventh aspect of the invention is the vacuum method, the vacuum method, the hybrid method or the separation effect (invention effect) 098117258

The P brushed wire substrate is provided with an opacity of 15% by mass or more between the money film A and the copper film layer D 201006337, and at the same time, it has excellent resistance and quantity. Between the layers C, the metal layer B containing the '# quantity_alloys is arranged, whereby the metal film can be exchanged for chemical chemistry (4) sputum is removed without _, which can be large and reliable, and its industrial utilization value is extremely high. . [Embodiment] The brush wiring board is manufactured by processing a two-layer resin film metal (hereinafter referred to as a resin film metal film laminated substrate) by a half-addition method. The resin film metal film layering system used in the printed wiring board of the present invention is formed on the at least one surface of the insulating resin film A by the absence of an adhesive. A metal film of layer B, metal layer c, and copper film layer D. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross section of a laminated metal film laminate used in a printed wiring board of the present invention. The gold ride B and the metal layer c correspond to the base metal layer of the two-layer resin film metal film laminate substrate. Further, the tree-laid metal film-layered system is formed by laminating the insulating layer A and the respective metal layers, and since there is no adhesive layer, it corresponds to two resin film metal-clad layer substrates. Hereinafter, each constituent element of the resin film metal film laminated substrate of the present invention will be described in detail. (metal layer B) The metal layer B is on the surface of the insulating tree A. It is placed on the surface of the insulating layer 098117258 201006337. The layer 'containing or containing more than 7G, the metal layer B preferably has a chromium content of H.5 mass k. #量% of the alloy. The amount is below %. When the chromium content is 15% by mass or more, the cover is more immersed in a 14-mass aqueous iron solution or a hydrochloric acid acidic copper chloride, and the gasification is used to remove the metal layer B, and the insulation reliability can be maintained. In addition, the metal layer B may contain 13% by mass or less of molybdenum and 20% by mass or less of molybdenum. The content of 8% or less by mass, such as hunger and titanium, may be added to the selected metal layer B' or a plurality of elements to be added to the alloy of the elemental alloys of the titanium, titanium, and _ elements. The other is an alloy of two elements selected from the group consisting of hunger, chin, and pin, and may be an alloy containing nickel, chromium, and two or more elements selected from the group consisting of Syrian, chin, and (iv). Each element of vanadium, chrysanthemum, and yttrium can improve the coffee property of the metal layer B. When it is a content of 13 or less, titanium content of 8 mass% or less, or (10) mass% or less, water vaporization of iron (four) Wei acid gasification is used. Eclipse by copper water

In the engraving step, the residue of the metal layer B is not generated. In addition, when the addition of π of the metal layer B is composed only of titanium, in the etching step by using an aqueous solution of ferric chloride or an aqueous solution of an acidified copper oxide of hydrochloric acid, a ruthenium of the metal layer 0 is generated. In order to improve heat resistance and wear resistance, a transition metal element may be appropriately added in accordance with the target characteristics. In addition, in the case of the metal layer, in addition to the gold such as 098,117, 258, and 12,063,063, the unavoidable impurities may be contained in the amount of 5% by mass or less which is contained in the metal layer. The method for forming the metal layer B is preferably carried out by using a known vapor deposition method, a reduced ore plating method, or an ion plating method, which is formed by changing the composition of the alloy of the (4) minus component. ❹ When the film thickness of the metal layer B is less than 3 nm, the metal layer C and the metal layer B are not dissolved and remain in the chemical etching process using the ferric chloride aqueous solution or the hydrochloric acid acidic copper chloride aqueous solution during the conductor wiring processing. Between conductor wiring. The reason for this is considered to be that since the metal layer B is not formed in a complete film type, the metal layer c is partially formed directly on the insulating resin film A, or the metal layer c is dissolved together with the metal layer b, and the conductor wiring processing is considered. When the metal layer B is as thin as possible. When the film thickness is more than 2 〇 mQ, when a voltage is applied to the conductor wiring, the composition of the metal layer B gradually dissolves, which tends to be a cause of the road. In addition, the film thickness of the metal layer 推 can be estimated from the formation conditions. For example, ☆ When the sputtering method is used, the film thickness is changed according to the power supplied to the lining cathode and the _ time == condition. The film thickness of gold (four) 1 (metal layer C) β was determined. The metal layer C is formed by a ruthenium of the metal layer β on the insulating resin film a. No, the metal layer C is an alloy containing nickel and chromium as the main component. When the weight is less than G/Hi and the content of the complex is less than 098117258, the corrosion resistance after wiring processing cannot be fully maintained due to the metal 13 201006337 layer. The dissolution of c or copper reduces the insulation reliability. On the other hand, when the chrome θ is more than 70% by mass, chromium may precipitate at the grain boundary, and when the gold ride C is composed only of Cr, the acid resistance is lowered due to the dissolution of hydrochloric acid. If Ruolin has steps and steps, it will cause a decrease in the reliability of the edge, so it is preferably 15 to 7 mass%.浥 In addition, the nickel content of the metal layer G is preferably 0.1 to 8 mass% before the chromium content is ensured. Further, the metal layer C may also contain 〇1 to 4% by mass. Of course, the content of the recorded, chromium and unavoidable mis-f is added to the mass%. Gu also has an effect of improving the recording resistance. When the tumbling content exceeds 40% by mass, the peeling of the heat is extremely lowered, which is not preferable. When the film thickness of the metal layer C is less than 5 nm, the barrier property against copper cannot be ensured, and the insulation reliability is lowered. Further, when the total film thickness of the metal layer B and the metal layer c is larger than 4 Å, the Lang stress becomes high, and fineness and (4) are generated, and the adhesion strength may be lowered. 'The total film thickness of the metal layer B and the metal layer c is preferably small. It is 4〇(10) or less. In addition, the film thickness of the metal layer C can be determined from the formation conditions. For example, when the sputtering method is used, it is known that the film thickness changes linearly according to conditions such as electric power applied to the cathode, time elapsed, and the like. The film is thick. (Copper film layer D) Next, the case where the steel film layer D is formed into a thin copper film layer is formed by a dry plating method of 098117258 201006337. Alternatively, a thin copper-coated film layer may be formed by a dry bond method, and a thin copper film layer may be formed by a wet ore coating method on the thin copper film layer. The film thickness of the copper film layer is preferably from 10 legs to 35 mm. When the film thickness is less than 10 nm, the conductivity of the twisted portion is liable to cause a problem, or there may be a problem of strength. On the other hand, when the film thickness exceeds 35//m, it becomes thick, and fine cracks, warpage, and the like may occur to lower the adhesion strength, which is not preferable. ® After forming a copper film layer by dry plating, when a thick steel film layer is formed by wet plating on the copper film layer, the film thickness can be formed by dry plating. /Π! After the copper film layer on the left and right sides, the layer is laminated by wet plating until it becomes a copper film layer or conductor wiring of a desired film thickness. (Insulating Resin Film) The insulating resin film is selected from the group consisting of a polyimide film, a polyamide film, a polyethylene terephthalate (PET), and a polyethylene naphthalate. Insulation resin film of Sishendan ethylene film, polyphenylene sulfide film, polyethylene naphthalate film or liquid crystal polymer film, heat resistance, dielectric properties, electricity, color edge can be considered The properties and the manufacturing steps of the printed wiring board and the chemical resistance of the subsequent steps are appropriately selected depending on the application. For example, 'the poly-imide film system is Kapton (* main volume trademark) manufactured by Toray Dupont Co., Ltd., UPILEX (registered trademark) manufactured by Ube Industries Co., Ltd., and Zhongyuan Chemical Industry Co., Ltd. APICAL (registered trademark), 东0 (registered trademark) of Toyobo Co., Ltd., etc. In addition, as the arylamine film which is a film of the aromatic polyamine 098117258 15 201006337, there is a Mictr〇n made by Toray (a registered company Teijin Advanced Fihn (10) such as (registered trademark) In addition, in the printed wiring board of the present invention, in addition to the conductive cloth-printed wiring board formed on one surface of the insulating resin film A, it is also possible to form a turn-on printed wiring on both Φ of the insulating resin film A. In addition, a plurality of local-printed wiring boards may be laminated and used as a multilayer printed wiring board.

(Amount of Residue of Metal) Next, the amount of residual metal remaining on the insulating resin film A will be described. If a layer containing metal atoms remains in the wiring, it will become a cause of a short circuit between the materials and a large reduction in insulation reliability. It is also known that the amount of metal residue when the entire surface of the portion which is partially biased is covered by one layer of metal atoms is equivalent to about 15 "g/cm2 ° ❹ Here, in order to understand the nickel-chromium alloy The relationship between the chromium content and the amount of residue on the insulating resin film is determined by forming a bismuth-chromium alloy (corresponding to the metal layer B or the insulating resin film (polyimine film)) The metal layer is ruthenium, and then the substrate formed with the copper film layer by using Wei and the electric ore is etched with a ferric chloride solution. At this time, the complex concentration in the chromium alloy and the nickel remaining on the polyimide film are - The total of the components of the chromium alloy layer, that is, the total of the residual residue amount is shown in Fig. 2. In Fig. 2, the right chromium content is 15% by mass, when the insulating resin film is etched 098117258 16 201006337 For a long period of time, the insulating resin film is 〇.15 core per W, and the value is as described above. 'The amount corresponding to the entire surface of the insulating resin film covered with one layer of metal atoms' is actually partially biased. In part, if a layer containing metal atoms remains between wirings, In the test, with the short-circuit between the wires, the insulation reliability is greatly reduced. 9 In particular, in order to form a high-precision trim line of several tens of pitches, it is required to bribe the metal of the I5 knife. A resin film metal film laminated substrate in which a metal film having a chromium content of 15% by mass or more is formed on the surface of the shovel, and a chemical vapor etching treatment is performed using a vaporized iron aqueous solution to form a printed wiring board. The required metal _ makes the surface of the insulating film is visually exposed 'but the atomic layer of one or more metals remains between the wires', so that sufficient insulation reliability cannot be obtained. On the contrary, the surface content of the insulating resin film is set. When a metal layer of less than 15% by mass is provided on the metal layer of the valence metal layer, even if it is used as a gasified iron solution or hydrochloric acid or copper chloride water ☆ solution of #刻_化学(四)液, It is possible to remove the metal layer which is not required to be used in the chemical etching process. Conversely, when a metal layer of 15 mass% or more in the network 3 is provided on the insulating resin film, a complex content is set on the metal layer. When the genus layer is used, the aqueous solution of iron-hydride or hydrochloric acid is used to dissolve the copper chloride, and the unnecessary portion of the metal having a chromium content of 15% by mass or more is not used. 098 117 117 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 098 D: The unit _ is .13, and further, if the conductor layer of the metal layer B and the metal layer c is removed, the surface of the insulating resin film A is exposed, and the residual light of the __^ is also present in the insulating resin film. By the amount of metal remaining on the lipid film A of the genus, it is possible to find the amount of slag, and therefore, the insulation reliability can be estimated. The amount of residual metal residue on the gelatin insulating resin film A is measured by the following method: (4) _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The surface of A is exposed, and if necessary, the metal component remaining on the surface layer portion of the exposed insulating resin film A, which is the surface layer portion of the printed wiring board from which the conductor wiring is removed, is removed, and the metal component remains. Dissolved solution. An acid is used for the dissolution of the residual metal component, but in the case of metal* quantification, an acid containing a component that hinders the detection spectrum cannot be used. For example, if it is easy to dissolve residual metals such as Ni, Cu, Mo, Ta, Ti, V, Cr, L η fe ' L〇, hydrochloric acid is effective, but the Cl detection spectrum of hydrochloric acid has a hindrance to the above gold 098117258 18 201006337 The tiny detection spectrum of the genus component is therefore not good. Further, although nitric acid does not interfere with the above-mentioned detection spectrum, it is not suitable for the solution to be left on the side of the insulating film after dissolution. Therefore, in the present invention, in order to dissolve the metal component remaining in the surface layer portion of the insulating resin film after the buttoning, a solution of a solution of a rhyme 7G and a peroxide solution of 1% to 30% of chlorine peroxide is used. Dissolution treatment. By this method, quantitative analysis does not hinder the detection of the spectrum, and all the metal components remaining on the insulating film can be completely dissolved. In addition, by using the microwave decomposing device, it is different from indirect heating by a hot plate or the like. "Because the acid in the sealed container is directly heated by the microwave, the heat is leaked to the &" and the contamination from the outside is also Fewer. Therefore, the residual metal forming knife can be decomposed with a small amount of acid in a short time, so that the decomposition and measurement time of the sample is about 5 to 6 hours, and the evaluation can be performed extremely quickly. The metal component such as the turn-to-turn (four) material is quantitatively pure. As an analytical method, it is not limited to use a dielectric-bonded electric 4 ion source mass spectrometer capable of quantifying trace amounts of metal components (hereinafter sometimes referred to as -(6) is preferred. (Chemical etching solution) and the chemical used in this month. The surname of the engraved liquid is the chemical remnant of any kind of ferric chloride or pure (four) copper aqueous solution. The ferric chloride aqueous solution or the hydrochloric acid acidic copper chloride is dissolved in water. The copper is oxidized to the side, and at the same time, the metal layer Β and the metal layer C are removed in the laminated structure of the metal film of the present invention. 098117258 19 201006337 Generally, 'on the viewpoint of corrosion resistance, 'will be on the surface of the insulating resin film A resin film metal film laminate provided with a base metal layer of a nickel-chromium alloy having a high chromium content (metal layer c in the present invention), an aqueous solution of an iron oxide or an aqueous solution of an acidic copper chloride solution for etching a copper coating layer is used. When the printed wiring board is manufactured by chemical refining, 'the unnecessary portion of the underlying metal layer remains unetched and remains, and may become a metal residue due to etching. Especially when the substrate is used. When the chromium content of the metal layer is 15% by mass or more, the metal residue due to etching may be significantly observed, and the underlying metal layer component remains in the thickness of 0.1 to several nm from the surface of the insulating resin film. For the removal, it is necessary to use a solution of a potassium ferricyanide aqueous solution or an aqueous solution of an aqueous solution of an acid anhydride which can dissolve the metal residue. Further, the base metal layer is also passivated by using an aqueous solution of iron oxide. The passivation of the metal layer is a cause of a decrease in the insulation reliability of the metal residue in the etching. On the other hand, the printed wiring board of the present invention is provided with the metal layer B and the metal layer C in this order on the surface of the insulating resin film A. The laminated structure of the copper coating layer D, the metal layer c containing 15% by mass or more of chromium is provided between the insulating resin film 4 and the copper coating layer D, and is interposed between the metal layer c and the insulating resin film A by etching. The chemical etching solution of the copper coating layer D is etched with a chromium-containing metal layer B of less than 15% by mass. Therefore, only the chemical etching liquid corresponding to the copper coating layer D (for example, an aqueous solution of ferric chloride or acidified copper of hydrochloric acid) is used. The solution is subjected to a chemical etching treatment, and an unnecessary portion of the metal film containing the metal layer c may be removed. The metal film provided on the surface of the insulating resin film A is made of metal 098117258 20 201006337 * layer B, metal layer c The laminated structure of the copper film layer D is arranged in order, so that the metal layer B, the metal layer C, and the steel film can be removed without chemical etching treatment using an aqueous solution of potassium ferricyanide or an aqueous solution of alkaline permanganate. The reason for the layer D is unknown. However, when the order of the surface layer of the insulating resin film A is changed to = metal layer C, metal layer B, or copper film group D, an aqueous solution of ferric chloride or an aqueous solution of acidic copper chloride is used. When the chemical etching treatment is performed, the metal residue of the metal layer C component is generated. (2) Manufacturing method of printed wiring board Next, the manufacturing method of the printed wiring board of the present invention is described in detail. m ° ° Resin film metal film laminated substrate system The printed wiring board is manufactured by subtractive or semi-additive. In other words, the metal film of the 匕3 copper-based dielectric layer D, the metal layer c, and the metal layer B on the surface of the resin film-metallized substrate is removed by chemical etching or the like to form a conductor wiring. In the case where the printed wiring board of the present invention is produced by the subtraction method, the description of the subtraction method means that the metal film of the resin film metal film laminated substrate is not required to be removed by chemical side treatment or the like. A method of manufacturing a printed wiring board. The printed wiring board of this month is a surface which remains as a conductor wire in the metal film of the resin film metal film laminated substrate, and is provided with an anti-fourth. That is, the anti-money agent = the shape of the wiring pattern. Then, after the chemical side treatment and water washing using the drying corresponding to the copper coating layer, the unnecessary portion of the metal film 098117258 21 201006337 is rotationally removed to form a conductor wiring. Selectively removes only one chemical etching solution that etches the copper film layer to chemically etch the metal film, so no new one is needed. The etching process step is added, and it is not necessary to reintroduce the device. Equipment costs, liquid-body management costs, and increased working hours. Further, the resist may be a known resist, and it is resistant to the chemical etching liquid, and % may be removed after wiring. The anti-money agent may be formed by screen printing on the surface of the copper coating layer D or by a photosensitive Lu-resist which is cured by irradiation with ultraviolet rays or the like, and is cured to a predetermined shape or the like. In the present invention, the metal film is used to remove unnecessary portions by any of the chemical sputum solutions of the aqueous solution of the vaporized iron or the aqueous solution of the acidified copper oxide in the copper film. The aqueous solution of ferric chloride or the acidic copper chloride hydrochloride is dissolved in water (iv), and the copper layer is oxidized, and the metal layer B and the metal layer C are removed in the laminated structure of the metal film of the present invention. Thus, the 'chemical etching solution does not use permanganate water-soluble cerium or ferricyanide cyanide such as potassium permanganate aqueous solution', so it is not necessary to remove it in the side step, since the chemical etching solution does not contain knots and cyanide. Therefore, the printed wiring board before the gold bonding step is not contained in the cyanide, and the printed wiring board which is subjected to gold plating does not contain a chain. In addition, manganese and cyanide are excluded as manganese and cyanide which are unavoidable impurities. Further, the printed wiring board of the present invention is not subjected to a chemical etching treatment with a chemical etching solution corresponding to the metal layer C of 098117258 22 201006337. In the chemical etching solution corresponding to the metal layer c, the alkaline permanganate aqueous solution removes the surface layer of the insulating resin film A, but since the alkaline permanganate aqueous solution is not used, even if the metal layer c is removed, the insulating resin film The surface has not been removed. In other words, it is known that the conductor cloth and the wire including the metal layer B, the metal layer C, and the copper film layer D are removed by using an aqueous solution of an iron carbide. The unevenness of the surface of the exposed insulating resin film A is determined by an optical contouring machine ( Optical 叩 0 161 *) was measured, and the parameters were smooth below the measurement limit. This means that the surface of the exposed insulating resin film A cannot be dissolved by the chemical rice liquid. The removal of the oxide film formed on the surface of the conductor wiring after forming the conductor wiring can be performed by a known micro (10) method. After the conductor wiring of the printed wiring board is formed, a chemical etching liquid other than the chemical etching liquid corresponding to the copper film is used. , can be selected by the following steps.

Next, a case where the printed wiring board of the present invention is produced by a semi-additive method will be described. The semi-additive method refers to a method of removing the surface of the insulating resin film after securing the film thickness of the wiring on the surface of the metal film of the resin film metal film-clad substrate, where the wiring is to be formed. A metal film for a method of manufacturing a printed wiring board. Specifically, on the surface of the metal film of the resin film metal film-clad substrate, a resist film is formed in a place where wiring is not desired, and a copper material is formed on the surface of the exposed metal film by using an electric key or the like, and is removed by chemical (four) Anti-silver agent and 098117258 23 201006337 The exposed metal film is removed to form a wiring to manufacture a printed wiring board. The resist used herein may be any copper-resistant plating solution, and any known resist may be used. Further, since the removal of the unnecessary metal film is performed on the surface of the copper film layer, it is carried out by the same method as the subtraction method using a chemical etching solution corresponding to copper. In the above, the present invention will be described using a flexible printed wiring board using a flexible insulating resin film. Of course, a rigid printed wiring board made of a material such as an epoxy resin, a phenol resin or a Tef (registered trademark) may be used. this invention. The present invention will be described below by way of examples. Insulating resin film A is a polyimide film with a film thickness of 38/zm (Dongli.

The product name "Kapton 150EN" manufactured by Dupont Co., Ltd.) is sequentially laminated with a metal layer B, a metal layer C, and a copper film layer D to form a resin film metal film laminate substrate. The initial peel strength, the heat-resistant peel strength, the money-etching property, the amount of metal residue after the burn, and the insulation reliability were evaluated for the obtained resin film metal film laminated substrate. The sample described in the following (a), (b), and (c) is used as long as the sample for each characteristic is not particularly limited. (a) Measurement of peel strength The initial peel strength was measured in accordance with the measurement methods of IPC-TM-650 and NUMBER 2.4.9. The measurement conditions were that the angle of peeling was 9 Å. . The sample was formed by the following subtraction method: the wire width was 1 mm, and a photosensitive resist was applied on the surface of the copper film layer D of the resin film metal film laminated substrate (Tokyo 098117258 24 201006337 (share), PMER) P—RH30 PM), exposure was carried out to form a pattern having a width of 1 mm, developed with a sodium carbonate aqueous solution having a concentration of 0.3% by mass, and immersed in a vaporized iron solution (specific gravity: 40° Baume, temperature: 43° C.) After a minute, it was washed with water and dried. The peeling of the resist was carried out using a sodium oxynitride aqueous solution having a concentration of 4% by mass. Further, the heat-resistant peel strength was measured by holding the sample having the same shape as the initial peel strength at 150 C for 168 hours, and after cooling to room temperature, the peeling angle was 90 as the initial peel strength. The peel strength was measured. When the initial peel strength was 600 N/m or more and the peel strength (heat-resistant peel strength) after the heat resistance test was 400 N/m or more, it was judged to be good. (b) Etching property and metal residue amount The etching property was evaluated by cutting a resin film metal film laminate substrate by 3 cm x 3 cm' in a chemical etching solution for 2 minutes, followed by washing with water and drying. Visually, it was confirmed whether or not the metal layer on the insulating resin film remained. When there was a significant residue, it was judged that the wiring was not processed only by the above chemical etching solution. On the other hand, when it is difficult to visually confirm the judgment and the residue cannot be confirmed, in order to measure the amount of metal residue after the etching, the insulating resin film A from which the metal layer is removed and the surface is exposed is subjected to a microwave decomposing apparatus using 5 ml of nitric acid. A solution of 1 ml of hydrogen peroxide is dissolved. The metal component in the obtained solution is quantitatively analyzed by ICP-MS (high-frequency induction plasma luminescence/mass spectrometry) to determine the amount of metal residue (metal layer B and metal). The total amount of layer c). (c) Insulation reliability 098117258 25 201006337 The evaluation of insulation reliability is carried out in accordance with the JPCA to ET04 standards. The measurement sample was applied to the resin film metal film laminated substrate, and the comb wiring having a pitch of m ( (line width 20/zm, interval width 20/m) shown in FIG. 3 was subtracted from the peel strength measurement. The law is formed. The comb-type wiring is such that the overlap length (10) of the comb-shaped conductor is 20 mm. The gap (11a, lib) between the tip end of the comb-shaped conductor and the short-circuit bar (bar) is 5 mm. A potential difference of DC6 〇 v was applied between the wirings, and the temperature was set at a temperature of 85 ° C and a relative humidity of 85% for 1000 hours, and the insulation resistance value was measured by a migration tester (manufactured by IMV Du, trade name: MIG-87). When the resistance value reached 106 Ω or less, it was judged to be a short-circuit defect, and after 1000 hours or more, it was judged to be acceptable after reaching 1 〇 6 Ω or more. (Example 1) A 38 gm thick polyimine film (manufactured by Toray Dupont Co., Ltd., "Kaptonl 50EN") was placed on a sputtering apparatus, and evacuated to a later stage. The yttrium imide film, after removing the moisture in the film, was evacuated to lxl (T4Pa. Then, Ar gas was introduced, and the pressure inside the device was maintained at 0·3 Pa'. Sputtering was performed on one side of the polyimide film. The method is as follows: a Ni-7 mass% Cr layer having a film thickness of 10 nm, a Ni~18 gram mass of a film thickness of 10 nm, a Cr-10 mass% Mo layer, and a film thickness 〇. 1 / m of the copper film layer, Then, a copper layer having a film thickness is formed on the copper film layer by electroplating to obtain an insulating film metal film layered body 1. The peeling strength measurement sample and insulation are produced from the obtained resin film metal film laminated substrate 1. The reliability measurement sample was supplied to each test. 098117258 26 201006337 The initial separation strength was 654 N/m, and the heat-resistant peel strength was 576 N/m, which was good. The 'insulation reliability test was conducted on three samples'. After 10 hours, the resistance is still above 106〇, which is good. #刻性评价系The lipid film metal film laminate substrate 1 was cut out by 3 cm x 乍 as a chemical money engraving liquid system using an aqueous solution of iron oxide (specific gravity 40. Baume, degree of 45C) was etched for 2 minutes, and the metal layer on the insulating resin film was visually observed. In addition, the metal stalk that is slightly left on the surface layer of the insulating tree is a microwave decomposing device, and is dissolved in 5 ml of nitric acid and hydrogen imi, 'liquid, and the solution is obtained. The metal component was analyzed by 1C? MS, and the result was as low as 〇.〇34/zg/cm2, which was good. The results were summarized in Table (. (Example 2) For the metal layer, use a film thickness of 3 nm. In the same manner as in the example i, the sample was prepared in the same manner as in the example i, and the result was as follows: Ni- 7 mass% Cr, metal ❿ + Μ Μ & 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 属 属 属 属 属 属 属 属 属 属In the case of the metal layer, the Ni layer and the metal layer c are made of a metal layer having a thickness of 20 nm, and a metal film obtained by forming a metal film with a film thickness of 20 nm is used. The samples were prepared in the same manner as the implementers, and each test was carried out. The results are not shown in Table 1. (Example 4) 0981172 58 27 201006337 A resin film metal obtained by forming a metal film using a metal layer B with a thickness of 20 nm of Ni- 7 mass% of Cr and a metal layer C of 10 nm by mass of Ni-18 mass% Cr-10 mass% of Mo. A sample was produced in the same manner as in Example 1 except for the film laminate substrate 4, and each test was carried out. The results are shown in Table 1. (Example 5) A metal layer B was used to have a thickness of 15 nm of Ni-7 mass% of Cr or a metal layer. In the same manner as in Example 1, a sample was prepared in the same manner as in Example 1 except that the resin film was used to form a metal film having a thickness of 5 nm and a thickness of 5 nm by mass of Cr-10% by mass. The test was carried out, and the results are shown in Table 1. . (Example 6) A resin film metal film laminated substrate 6 obtained by forming a metal film using a metal layer B of Ni-14 mass% Cr having a thickness of 5 nm and a metal layer C of Ni-20 mass% of a film thickness of 20 nm was used. A sample was produced in the same manner as in Example 1, and various tests were carried out. The results are shown in Table 1. (Example 7) A resin film metal film laminated substrate 7 obtained by forming a metal film using a metal layer B of Ni-7 mass% Cr having a thickness of 15 nm and a metal layer C of Ni-40 mass% Cr having a film thickness of 25 nm was used. A sample was produced in the same manner as in Example 1, and each test was carried out. The results are shown in Table 1. (Example 8) A Ni-7 mass of a film thickness of 10 nm was used in addition to the metal layer B, and a metal layer C was used in a thickness of 5 nm of Ni-70 mass% (:1· 098117258 28 201006337 resin obtained by forming a metal film) In the same manner as in the first embodiment, the sample was produced in the same manner as in the first embodiment, and the results were as shown in Table 1. (Example 9) The Ni-5.6 mass of the film thickness i〇nm was used except for the use of the metal layer B. In the same manner as in the first embodiment, samples were prepared and tested in the same manner as in Example 1 except that the resin film metal film laminate substrate 9 was formed by forming a metal film with a film thickness of i 〇 nm of Ni-20 mass% Cr. The results are shown in Table 1. Φ (Example 10) In the case of using the metal layer B, Ni - 13% by mass of the film thickness l〇nm was used, and the metal layer C was made of Ni 2 mass % of the film thickness of 10 nm (^ A sample was produced in the same manner as in Example 〇 except for the resin film metal film laminated substrate obtained by the metal film, and each test was carried out. The results are shown in Table 1. (Example 11) The film thickness was used except for the use of the metal layer B. Ni of Ni_7_5 mass of nm. /ji, gold genus layer C adopts Ni_2〇% by mass of film thickness In the same manner as in Example 制造, a sample was produced in the same manner as in Example 以外, and each test was carried out, and the results are shown in Table 丨. (Example 12) 'In addition to the resin film metal film laminated substrate 1 For the evaluation of the etching property, an acidic copper chloride aqueous solution (: agricultural sound lmol/bu CuCl2: specific gravity i 3, 〇Rp: 58 〇 mV, temperature: 4 generations) was used for the evaluation of the etchability, and the same as in the first embodiment. Ingredients, riding each test, the remainder (4) in ^ ' 098117258 29 201006337 (Comparative Example 1) except for the use of the metal layer B, a film thickness of 10 nm Ni - 18% by mass Cr - 10% by mass Mo, the metal layer C using a film thickness of 10 nm A sample was produced in the same manner as in Example 1 except that the resin film metal film laminated substrate 13 was formed, and the respective tests were carried out. The results are shown in Table 1. (Comparative Example 2) In addition to the use of the metal layer B A sample was produced in the same manner as in Example 1 except that the resin film metal film laminate substrate 14 obtained by forming the copper film layer D without using the metal layer C having a film thickness of 20 nm and having a Ni 18 mass ° / 〇Cr - 10 mass % Mo was used. Each test was carried out and the results are shown in Table 1. (Comparative 3) The same as in the first embodiment except that the resin layer metal film laminated substrate 15 obtained by forming the copper film layer D without using the metal layer C and having a thickness of 20 nm of Ni-20 mass% (:1) is used. The sample was produced and each test was carried out, and the results are shown in Table 1. (Comparative Example 4) A copper film layer D was formed by using a metal layer B of Ni-7 mass% Cr having a thickness of 10 nm and no metal layer C. A sample was produced in the same manner as in Example 1 except that the resin film metal film laminate substrate 16 was used, and each test was carried out. The results are shown in Table 1. (Comparative Example 5) A resin film metal film layer obtained by forming a metal film using a metal layer B having a thickness of 2 nm of Ni-7 mass% Cr, metal 098117258 30 201006337, and a film thickness of 15 nm of Ni-20 mass% Cr. A sample was produced in the same manner as in Example 1 except for the substrate 17, and each test was carried out. The results are shown in Table 1. (Comparative Example 6) A resin film obtained by forming a metal film using a metal layer B of Ni-7 mass% 0 alloy having a thickness of 10 nm and a metal layer C of Ni-18 mass% Cr-10 mass% Mo having a thickness of 3 nm A sample was produced in the same manner as in Example Φ 1 except for the metal film laminate substrate 18, and each test was carried out. The results are shown in Table 1. (Reference Example) The metal film B is formed of a Ni-7 mass% Cr alloy having a thickness of 5 nm, and the metal layer C is formed by forming a metal film using Ni-20 mass% Cr having a thickness of 100 nm. A sample was prepared in the same manner as in Example 1, and an etching test was performed. The results are shown in Table 1.

098117258 31 201006337 e - ° [I<] 8SZXH860 201006337 It is apparent from Table 1 that the inventive examples 1 to 12 of the inventions 1 to 12 are metal layers having a surface area layer having a chromium content of less than 15% by mass. B, a metal layer C having a chromium content of 15% by mass or more is laminated on the surface of the metal layer B, and a printed wiring board having a copper coating layer is laminated on the surface of the metal layer C, and has a good peeling strength, and the metal residue after etching is also Less, get high insulation reliability. On the other hand, in Comparative Example 1, the metal layer B had a chromium content of more than 15% by mass, and the metal layer C had a complex content of less than 15% by mass. Since the chromium content of the metal layer B exceeds 15% by mass. The metal residue can be observed visually after etching, and it is understood that the insulation reliability cannot be ensured. In Comparative Example 2, the metal layer B having a chromium content of more than 15% by mass is the base metal layer. As in the case of Comparative Example 1, the metal residue was observed by visual observation after the etching, and it was found that the insulation reliability could not be ensured. On the other hand, in Comparative Example 3, the base metal layer was formed only in the metal layer B in the same manner as in Comparative Example 2, and the surface of the polyimide film was observed by visual observation. The surface of the polyimide film was observed to be more than 0.15. /zg/cm2, it can be seen that insulation reliability cannot be ensured. In Comparative Example 4, the chromium content of the metal layer B was 7% by mass, and the etching property and the amount of metal residue were good. However, since the underlying metal layer was composed only of the metal layer B, it was found that the insulation reliability could not be ensured. In Comparative Example 5, the chromium content of the metal layer B and the metal layer C is within the scope of the patent application of the present invention, but since the film thickness of the metal layer B is 2 nm, the amount of metal residue can be measured even if it is full of 098117258 33 201006337. In the case of 〇15-, the insulation reliability can be ensured. In the comparative example, the content of the metal layer B and the metal layer c is within the scope of the patent application of the present invention, but the metal layer is 3 nra, and it is known that the insulation reliability cannot be ensured. The content of 'Jinqi B and metal layer in Mazhong is in the patent garden of the invention. Only the thickness of the metal layer C reaches (10) (10), which is much thicker than the general one, but the visual inspection is good, and the amount of metal collapse is also small. 〇g/cm2 'is good. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a resin film metal film laminate used in a printed wiring board of the present invention. Fig. 2 is a graph showing the relationship between the amount of chromium in the recording-road alloy and the amount of _residue. Fig. 3 is a schematic view showing a comb-tooth wiring used in the evaluation of insulation sinus. [Main component symbol description]

^ Insulating resin film ; Metal layer : Metal layer Copper film layer Short bar Resin film Metal film laminate substrate Comb-shaped conductor 098117258 34 201006337 10 Overlapping length of comb-shaped conductor 10a, 10b Comb wiring 11a, lib Clearance

098117258 35

Claims (1)

201006337 VII. Patent application scope: 1. A printed wiring substrate, the side is treated by chemical (4), selectively removing the metal lining layer formed on at least one surface of the insulating tree a without interposing the adhesive. A metal film constituting the above-mentioned = wiring includes a metal layer b laminated on the surface of the insulating resin film A, and the metal layer is formed by forming a required portion of the substrate. B is composed of cerium or 70% by mass or more of nickel and less than 15% by mass of lanthanum chrome alloy; 'the metal layer C of the surface layer of the above metal layer B, the metal layer c containing nickel and chromium 15% by mass or more of the alloy; and the film thickness of the surface layer of the metal layer c of the above-mentioned metal layer c should be m~35_, and only the chemical remnant of the above-mentioned steel coating layer is used to selectively remove the metal film. No part is needed. 2. The printed wiring board according to item i of the patent application, wherein the conductor wiring of the metal film including the metal layer B, the metal layer C and the copper film layer D sequentially laminated is made into a gasified iron water acid. After the side-by-side treatment, the amount of the metal remaining on the insulating resin film A is 〇. ^ g/cm 2 or less per unit surface of the insulating tree A. 3. The printed wiring board according to claim 1 (4), wherein the gold layer 098117258 36 201006337 is a layer B containing vanadium of 13% by mass or less and less than titanium, and the balance is recorded or containing 7 〇 mass indium and 20% by mass of chromium. Record - chrome alloy and! The mass % or less of nickel and less than 15% by mass are 3 to apply m. The material of the invention is the material of the invention. And the balance is nickel or a chromium-containing alloy containing 70 masses of chrome-chromium alloy and the quality of her under / recorded and less than 15% by mass thick is a quality of her underlying impurities, its membrane 3. such as T印刷 堉 利 范 范 第 第 第 第 第 第 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷 印刷15% by mass or more, nickel Ο.ον^ mass%, molybdenum 〇〇1 to cut mass%] an alloy composed of unavoidable impurities of mass% or less, in the order of &~37nm 'resonance or film thickness 5111" The total amount of the metal layer B is 4 〇 nm or less. 6. The printed wiring board according to any one of the preceding claims, wherein the chemical etching solution contains no manganese or cyanide. 7. The printed wiring board according to any one of the preceding claims, wherein the chemical etching solution is an aqueous solution of ferric chloride or an aqueous solution of acidic copper chloride hydrochloride. 8. The printed wiring board according to claim 1 or 2, wherein the insulating resin film A is selected from the group consisting of a polyimide film, a polyamine system, a polyfluorene system 098117258 37 201006337 film, a poly 4 At least one resin film of a vinyl fluoride fluorene, a polyphenylene sulfide film, a polyethylene naphthalate film, or a liquid crystal polymer domain. 9. A method of manufacturing a printed wiring board by selectively removing a metal film laminated on at least one of the surface Φ of the insulating resin film A without chemically etching. In the case of forming a conductor wiring of the above-mentioned metal film of the layer substrate, the resin film metal-clad layer substrate is formed by forming a nickel by a dry impurity method on the surface of the insulating resin film A. Or a metal layer B containing nickel as a main component, and then, on the surface of the metal layer B, an alloy containing 15% by mass or more of chromium and nickel or 15% by mass or more is formed by a dry ore method. After the metal layer c composed of an alloy of chromium, brocade, and indium, a metal film formed by laminating a copper layer of a film thickness is formed on the surface of the metal layer C, and the metal film is made of a metal The engraving is selectively removed to form a conductor wiring. The method for producing a printed wiring board according to item 9, wherein the chemical liquid does not contain a clock or a cyanide. The method for producing a printed wiring board according to the ninth aspect of the solution, =, the above-mentioned chemical solution is a solution of a gasified iron solution or an acidified copperated water of hydrochloric acid, and the printing wiring of the ninth item is required. In the method of stimulating the substrate, the ruthenium layer D is formed on the surface of the layer by dry-packing, and a copper layer is formed by electro-mineralization. The method of manufacturing a printed wiring board according to claim 9 or 12, wherein the dry plating method is any one of a vacuum deposition method, a sputtering method, and an ion plating method. 098117258 39