TW569656B - Method for manufacturing a flexible printed wiring board, and a flexible printed wiring board obtained through the manufacturing method - Google Patents

Abstract

To provide a flexible printed wiring board excellent in a migration resistance. A method for manufacturing a flexible printed wiring board by way of circuit-etching a copper clad laminate, wherein the method comprising the steps of, after etching, (a) removal step of residual metallic component, namely pickling a circuit-etched substrate to remove metallic component from residual carboxyl metallic salt on a surface of a base material resin exposed in the gaps among circuits formed on the substrate, thereby converting into a carboxyl group; and (b) re-ring-closure step, namely heating the residual-metallic-component-removed substrate for 10 to 80 minutes under a high temperature atmosphere at 180 to 200 DEG C, thereby ring-closing the surface of a polyimide resin film exposed in the gaps among circuits formed on the substrate.

Description

569656 Case No. 91132587 Λ _____ Ά Revision V. Description of the invention (1) Technical field to which the invention belongs The present invention relates to a method for manufacturing a flexible printed wiring board using a so-called double-layer flexible copper-clad laminate. Three layers of tapes, such as the previous technology, are used for narrow lines, dense resin films, not double-layered, polyfluorene, polyfluorene, and practical. Combined with electroless method to form peeling strong factor technique, electric special foil laminating circuit board as a device to enhance the 醯 imine layer as the extensive copper layer and method. It is also difficult to use imine to achieve the method or decompose the copper film and the copper layer. Imine resin is soft and flexible, and has excellent mechanical strength and heat resistance. It has been widely used in the manufacture of flexible printed circuit boards using adhesives and copper substrates, and can be described as a type of flexible printed automatic bonding (TAB) products. Electronic products require a high degree of compactness, space, and flexible printed circuits are required to be thin and miniaturized. Degree, folding strength, omission of the adhesive layer, and the provision of a double-layer substrate with a copper layer directly on the poly surface. A method of forming a copper plate by using an adhesive on the surface of a polyimide resin film, although there are a vapor deposition method, a scale washing method, a ore layer method, etc., but a vapor deposition method is used to vapor-deposit a double-layer substrate forming a copper layer. Lack of adhesion and poor migration resistance. Acrylic acid precursor Polyvinylamine is applied to copper, and the substrate produced by high = 醯 is prone to warp and curl. Therefore, the most commonly used is plating & 'general electrolytic plating demineralization method And electric ore method, but the copper layer of Yidian still lacks the dense manpower of polyimide resin film, the degree is low, and the reliability of the substrate is lacking. However, instead of the above method, there are already succinimide resins.

2169-5304-PFl (Nl) .ptc Page 7

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Plug No. 911325fL 5. Description of the invention (2) The better adhesion of the layer, as proposed by the direct metallization method disclosed in Japanese Patent Laid-Open Nos. 200 1 -73 1 59. DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, it is a common demand to form a fine-pitch circuit which is different from a general rigid circuit board and a flexible printing. Printed circuit board 'The above-mentioned flexible printed circuit board's TAB products are extremely fine', but in the construction of flexures with good anti-migration performance, the structure is dispersed and gathered, which means that the anti-migration is good. During the production of the osmium imine, the direct conductivity of the printed circuit board is assured due to its excellent transferability. The printed circuit board of the resin-based adjacent wire is severely caused by the double-layer metal connection of the substrate. In addition, the means can be used for electrical and electronic equipment when they are energized in step circuit boards, and the copper component of the TAB product's circuit expands the surface or inside of the board to form a bridge. There is a short circuit between the roads, causing malfunctions and no problems. Therefore, a substrate that does not easily migrate can be a plate, and the migration resistance is not excellent. Therefore, the polyimide resin 铜 and copper layers still have a double-layer substrate with excellent migration resistance during the chemical conversion process. Therefore, the present inventors have made a method for manufacturing the mobility of a rigid printed wiring board. Before elaborating the present invention, the results of careful research have come to mind. When a flexible printed wiring board is devised, the present invention will be described below. ’In order to easily understand the present invention, the following inventions can greatly improve the resistance

2169-5304-PFl (Nl) .ptc Page 8 569656

Shift phenomenon. Opinions are currently divergent regarding migration. With reference to the general saying, apt. There is no exact explanation on the mechanism of the growth, but the inventors believe that the following theory should be compared with the copper layer that has a way or applied in this specification, which will affect the circuit, but it should happen is the above There are factors that can affect the size. Existing substrate resin copper atomic migration has become "from a weak point, especially copper with less internal strain, forming melts to remove strain and other results, but it still cannot happen that its surface is" inner copper layer or not In order to make the inner ring or the surface of the present invention or the flexible seal that releases the current migrate to the inside, it should be completely free of all kinds of methods.

The ease of migration depends on the amount of strain that is enclosed inside the plating that constitutes the electrode (hereafter, Hidden strain theory). However, the present inventors have recognized that the built-in strain of the plating layer on the surface is easy to migrate. That is to say, the release of strain energy in the migrating part. At this time, the built-in should be easy to know, but there must still be someone who triggers the release operation to think that 'the promoting factor is a weak current flowing through the inside of the circuit without a weak current that promotes the force of strain (hereinafter, this specification refers to internal strain Release said. "). The manufacturing of brushed circuit boards, TAB products, etc., simply uses a coating film with reduced internal strain when forming a copper layer, or melt processing afterwards. Although the migration resistance has been improved, migration phenomenon must be eliminated.

Therefore, the present invention is based on the premise of recognizing the internal strain release from a weak current, and seeks to limit the weak current flowing through the surface or inside of the substrate resin that promotes the migration phenomenon and promotes the promotion of copper atomic migration to the minimum. In order to limit the weak current (very weak leakage current) flowing through the surface or inside of the substrate resin to the minimum, the surface resistance of the substrate resin should be increased as much as possible,

2169-5304-PFl (Nl) .ptc page 9 569656 case number 91132587 5. Description of the invention (4) Volume resistance. Also, if metal components such as copper are exposed on the surface of the substrate resin between the circuit and the circuit, the leakage current will increase, which should promote migration. Therefore, metal components remaining on the surface of the substrate resin exposed between the circuits should be removed as much as possible. Based on the above ideas, the following invention has finally been devised. The scope of the patent application is, "A method for manufacturing a flexible printed circuit board" is a method for manufacturing a flexible printed circuit board from a flexible copper surface layer a board using a polyimide resin film as a base material, which is characterized by: · Including the steps shown in the first figure. First, step S1 3 is a circuit etching step of engraving the flexible copper laminate to form a circuit. Then, step s5 and 5 etch the substrate of the circuit to The pickling process removes the residual metal component from the carboxylic acid metal salt on the surface of the polyimide resin film exposed between the gaps of the lines formed on the substrate to convert it to a residual metal component removal step of the carboxyl group. Then, Step S17: After the residual metal component removal step, the substrate is heat-treated in a high-temperature gas environment to 200 C for 10 minutes to 80 minutes, so that the surface of the polyimide resin film exposed on the circuit formed on the substrate is closed-loop processed. Then the closed-loop step. To understand the present invention, the following matters are explained first. In this specification, 2 70 17 brush circuit boards "refers to the copper layer and the polyimide resin film layer, and the copper layer Resin film layer @ Metal resistance and anti-clock layer are also covered. The concept of all products such as the automatic bonding of the inner sheet—flexible substrate (CGF) is also covered in this so-called "flexible copper". The "surface laminate" also includes the above-mentioned flexible 2169-5304-PFl (Nl) .ptc page 10 569656 __Case No. 91132587__ year, month, day, amendment_ V. Description of the invention (5) All manufacturing materials for printed wiring boards. In the circuit etching step, an alkaline copper etchant is used for the circuit etching of the copper-faced laminate, and then the copper component is etched to remove the part, and the polyimide resin of the base material is exposed on the surface. The surface of the exposed base polyimide resin must be exposed to the etchant. Polyimide resins used as the base material of copper-clad laminates all have a chemical structure of a cyclic imine ring. When exposed to an alkaline etching solution, the imine ring may have a ring opening phenomenon. The evidence of the occurrence of the ring opening will be described in detail later in the manufacturing method of the double-layer flexible substrate using the direct metallization method, which will exemplify the ring opening phenomenon of polyimide resin. When the direct metallization method forms a seed layer (referred to as a "metal film" in this specification), the polyimide resin film inevitably undergoes ring opening. Therefore, if the surface of the substrate exposed on the gap of the circuit formed on the substrate has a ring-opening phenomenon of the polyimide ring in the polyimide resin or the presence of metal ions contained in the etching solution, etc. The carboxyl group and metal ions produce a metal salt of acid acid, and the surface of the polyimide resin has a residual metal component. Therefore, the substrate on which the circuit is etched is subjected to acid cleaning to remove the surface of the substrate resin film exposed from the gaps of the lines formed on the substrate, and the residual metal components from the acid metal salt. This is referred to as "removal of residual metal components" in this specification. 'As described above, after the metal component is removed from the carboxylic acid metal salt on the surface of the substrate, the surface of the polyimide resin is in a ring-opened state of the imine ring. After being placed in the open-loop state, migration is easy to occur after all. Therefore, the substrate after the removal of the residual gold ^ is subjected to a heat treatment at a high-temperature ambient gas of 80 to 200 t for 10 to 80 minutes to be exposed on the substrate. Gap formed on the circuit ^

569656

Poly-imide resin cavity: 矣 & u Chufeng trace *, closed-loop surface treatment. This is called the reclosed step. This special step :: Fine, also described in the following description using the double-layer flexible base of the direct metallization method, and the method of polyimide resin, as an example, added to the scope of another patent That is, "A method for manufacturing a flexible printed wiring board including the direct metallization method 20 of the following S21 to S25 / is described in the second figure. The direct metallization method 20 first gathers the polymer in step S21. The test of the imine resin film is performed as the ring-opening treatment of the sulfonium imine ring to form a ring-opening step on the surface. Next, step S2 2 neutralizes and neutralizes the carboxyl group formed by the ring-opening with an acid solution. In step S23, the neutralized carboxyl group is brought into contact with the metal ion-containing solution to adsorb metal components, and a metal ion adsorption step is formed on the surface of the polyimide resin film. Next, step S24 is formed in the polyimide resin. A metal thin film forming step of reducing the carboxylic acid metal salt on the surface of the amine resin film to form a metal thin film on the surface of the polyimide resin film. Then, step S25 is formed on the metal thin film formed on the surface of the polyimide resin film. Electrochemical method A step of forming a copper layer for a circuit for forming a copper layer of a circuit. A method for manufacturing a flexible printed circuit board by using the obtained double-layer flexible copper surface laminated board composed of the conductor layer and the polyimide resin layer firstly The step of engraving the circuit of the circuit formed by the flexible copper laminate (step S26). Next, the substrate on which the circuit has been etched is treated with pickling to remove the accumulation of gaps in the circuit formed on the substrate by the external circuit. Residual metal component from the carboxylic acid metal salt surface on the surface of the imine resin film to convert it to a carboxyl residual metal component removal step (step S27). Finally, the substrate after the residual metal component removal step is completed at 180 ° C to High temperature of 200 ° c

2169-5304-PFl (Nl) .ptc Page 12 569656 __Case No. 9132587_Year_Month__ V. Description of the invention (7) Heat treatment in a body environment for 10 minutes to 80 minutes' to expose the substrate The step of closing the loop on the surface of the polyimide resin film of the gap formed in the circuit is a closed loop process (step S28). The manufacturing method of the flexible printed wiring board is a double-layer flexible copper surface laminate (above or below or simply referred to as a "double-layer substrate") composed of a conductor layer and a polyimide resin layer called a direct metallization method. ".) Method of manufacturing a flexible printed wiring board. The steps are described below in the order in which they appear in the scope of the patent application. In the direct metallization method, in order to form a conductor layer, the surface of the polyimide resin film must be subjected to a ring-opening treatment. Therefore, the manufacturing method described above is particularly effective. First, the steps S21 to S25 constituting the direct metallization method 20 will be described. Step S 2 1 is a ring-opening step in which a polyfluorene imide resin film is treated as a ring-opening treatment of the fluoreneimine ring to form a carboxyl group on the surface. This so-called polyimide resin film uses the commercially available KAPTON film (made by TORAY DUPONT (stock)) of the Η type and EN type, and the effect of the present invention is obvious _ UPI LEX S (宇 部 兴 产 (股份有限公司) The same effect can be obtained at the same time. The alkali treatment is to immerse the polyimide resin film in the test solution, or spray the test solution on the surface of the polyimide resin film. The liquid used for this test is preferably a potassium hydroxide solution or a sodium hydroxide solution. This is because subsequent neutralization is easy to perform, and there is little surface residue. but

The concentration of the alkali solution used is high, and the polymerization can be easily performed in a short time. However, the subsequent closed-loop steps described later are performed to the extent that open-loop processing is performed.环 Imine resin film can be ring-opened. ‘In the manufacturing method related to the present invention, it is necessary’ that the ring-closure treatment should not be made difficult. Therefore, an alkali solution concentration of 3.

569656 Case No. 91132SS7 V. Description of the invention (8) The condition of 0 mol / liter to 10.0 mol / liter, and the temperature of the solution is 2 hours, 10 minutes to 10 minutes. If the processing conditions can be checked under these conditions, the polyimide resin film will also be turned into a closed loop, and then the closed loop cannot be performed smoothly. Another =: Second, it is inferior to the alkali treatment conditions in the above range, and the ring opening process proceeds smoothly. The judgment of whether 30% of the ring has been opened is to use Fourier transform to absorb light ^ (ft ^ ir). Observe that the closed-loop polyimide resin does not have 丨 cyclic amine (c = o) absorption, ^ ... 554cnfl near the ring-opening amidine (N-men absorbed, sweat is more specific to the amidine ring 1 774cnrl (c = 0), 1 720cnrl (c = o) and Γ and its absorption disappeared, you can confirm. It should be that the absorption from coo can be observed near 1 579crl, 1371crl, i 344cmi. All these spectra can be observed with alkali treated polyimide resin film. When step S21%, usually enter Neutralization step of water washing step S22 of the ring-opened polyimide resin film. This is the step of ring opening to form a carboxyl group, and the surface of the polyamidoimide resin after strong alkalization is neutralized with an acid solution. The neutralization solution is preferably hydrochloric acid. After the neutralization treatment, sufficient water washing can completely remove the residue on the surface of the polyimide resin. In this neutralization, a hydrochloric acid solution concentration of 3.0 moles / liter to 6.0 mol / L, solution temperature of 20 ° C to 35 ° C, processing time of 1 minute to 2 minutes. After neutralization = washing with water 70. The uFT_IR analysis of the polyfluorene imide resin film at the neutralization stage can confirm the absorption of 1 647cm-1 of cycloamine (C = 0), and the opening near i 554cnrl.

569656 Case No. 91132587 Amendment V. Description of the invention (9) Cycloperamide (N-Η) absorption. In addition, the absorption of the carboxyl group (COO) seen at 1 579cm-1, 1371cm-1, and 1 344cm-1 shifted to the vicinity of 1711cm-1, 1319cm-1 \ 1 296cnr1, which should have CO OH because the carboxyl group was neutralized. Structure. In the next step S23, the neutralized carboxyl group is brought into contact with a solution containing metal ions, and the metal ions are adsorbed on the surface of the polyimide resin to form a metal carboxylic acid salt. The metal ion-containing solution used here is, for example, a copper sulfate solution when it is adsorbed by copper ions. At this time, conditions such as a copper sulfate solution concentration of 0.1 mol / liter to 1.0 mol / liter, a solution temperature of 20 ° C to 50 ° C, and a processing time of 30 seconds to 2 minutes can be used. Therefore, the following is a detailed description using copper carboxylate as an example. In addition, when nickel or cobalt is used, the formed circuit can be maintained at a high peel strength. When the adsorption amount of metal ions on the polyimide resin film at the end of step S23 is based on copper, the copper sulfate solution is used at about 100 to 400 mg / m2. The analysis method of the copper ion adsorption amount is to dissolve the adsorbed copper ions with a 5% by weight nitric acid solution, and the solution is analyzed by an ion plasma luminescence spectrometer (I CP). The same applies to other metal ions such as nickel and cobalt. 2. In step S23, metal ions are adsorbed to form a metal acid salt on the surface of the polyimide resin film. After water washing, the carboxylic acid metal salt formed on the surface of the polyimide resin film is reduced in step S24, and the polyimide is formed on the polyimide resin film. A metal thin film is formed on the surface of the resin film. This is the metal thin film forming step. In addition, repeating the above steps S23 and S24 to form a thick metal frame, which can increase the intimacy of the polyimide resin film and the conductor layer finally obtained. Β Ό ° ° The reduction system at this time makes the formation of a betrayal The surface of the polyimide resin film of the acid metal salt is brought into contact with the reducing agent. For example, the reducing agent of copper metaborate can be used at a concentration of 0.1% as disclosed in JP-A-2001-731 59.

2169-5304-PFHNn.Dtc 569656 Amendment No. 91132587 V. Description of the invention (10) Methylamine from 003 mol / liter to 0.05 mol / liter. The reducing agents, hypophosphorous acid, and dicarboxylic acid of the carboxylic acid metal salt are specifically limited. 〖J & The type is arbitrarily selected, and there is no special step S24 after the reduction is completed. Taking polyimide film layer as an example, it can form 80 to 380 mg / force, and the thickness of the steel is measured. Using the ICP device used to measure the copper ion absorption, the analysis is converted to the weight per square meter. The method of knife analysis ... After Jiuyuan finishes washing with water, the surface of the polyimide resin film forms gold and is a thin film (steel film). . The metal thin film is used for the growth of the copper layer of the electrochemical hand J: electricity, that is, the copper layer-shaped 乂 layer for the circuit of step S25. "I electrochemical method" means that the copper layer is grown by electroless copper ore layer, electrolytic steel layer, or a combination of electroless copper plating and electrolytic copper plating to increase the thickness X to obtain the thickness of the copper layer that can form a circuit. There are no special restrictions on the composition of non-electrolytic steel in cold and copper baths and other plating conditions. x thus completes the formation of the conductor layer. Therefore, the conductor layer can also have metals other than copper such as copper and cobalt under the copper layer. After the direct metallization method described in steps S21 to S25 above, a two-layer substrate composed of a conductor layer and a polyimide resin layer is obtained. Therefore, in the present invention, the first step S26 is circuit etching, and an anti-etching layer is formed on the surface of the copper layer of the double-layer substrate, and the circuit shape is exposed, developed, and etched to form a substrate with circuit circuits. The conventional manufacturing method is at the stage where the circuit is etched, and then washed and dried to obtain a product flexible printed wiring board. After the circuit was etched, the polyimide resin film in the exposed part was analyzed by FT-IR, and it was confirmed that the ring-opened amine (〇〇) absorption of 165 cnrl, naiiHii page 16 2169-5304-PFl (Nl) .ptc 569656 Case No. 91132587 V. Description of the invention (11) Cyclopramidine (N_H) absorption near 1 547cm-1. In addition, the absorption of the carboxyl group (C00) near 1707cnfl and 1 30 8 CIT1 reappeared. The present invention further includes step S27. The substrate after the circuit is etched, and the surface of the substrate resin film exposed on the substrate formed by the gaps of the wiring formed on the substrate is removed by acid pickling to convert the residual metal component from the carboxylic acid metal salt into a rebel Residual metal component removal step. In addition, it includes step (c), 'Residual A metal component removal step. The substrate is heat-treated for 10 to 80 minutes under a high-temperature ambient gas of 1 80 to 200 t to gather the gaps of the circuits formed on the substrate.再 Imine resin film surface closed loop treatment and then closed loop step. The pickling treatment in step S27 is preferably performed using hydrochloric acid. The finally attached ^ acid component 'can be completely removed by washing with water. As a result, the surface of the polyimide can be completely free of metal components. Here, the conditions of using a hydrochloric acid solution concentration of mol / mol to 6.0 mol / liter, a solution temperature of room temperature, and a processing time of π seconds to 5 minutes are preferred. If the pickling conditions above the above conditions are used, even the copper forming the circuit will be eroded and it is difficult to maintain the electricity: Under the pickling treatment conditions that are inferior to the above-disclosed range, the conversion of the metal component to the carboxyl group cannot proceed smoothly . When the polyimide resin film exposed at the stage of pickling treatment is analyzed by FT-IR, it can be confirmed that 1 649cnfl of ring-opened fluorenamine = absorption, and ring-opened fluoramine (N_H) absorption near ipice, 17lcri Absorption of fluorenyl (CO) occurs. Therefore, the X-ray diffraction method and the wavelength two electron probe microanalysis (EPMA) methods were used to analyze the presence of metal components and residuals, and no copper components were detected.

569656

Λ ___ JL Amendment Gu 911325S7 V. Description of the invention (12) The base of the acid washing treatment, water washing treatment, and residual metal component removal step f. Go to step S28 and close the loop step. In the re-closed loop step, the substrate after the residual metal removal step is removed is heated at a high temperature of 1 80 ° C to 200 ° C for 10 to 80 minutes. By heating, the exposed polyfluoride imide resin film surface exists in a ring-opened closed loop. When heating under the above conditions, the polyimide resin film itself is likely to deteriorate. On the other hand, under the heating conditions below the disclosed range, the closed-loop operation is insufficient. After the closed-loop operation, the polyimide resin film in the exposed part was tested by T-IR analysis. It can be seen in the ring-opened polyimide resin film 1 649CIT1 ring-opened amine (c = o) absorption, near 1541cnrl Ring-opening amidine (n_h) absorption was confirmed to be completely absent from nHcr !, 1371cnrl & 1 344crl carboxyl (c〇〇) absorption, and 1778cnrl, 1 724cnrl & 1 379cm-1, which is unique to amidine ring, was observed. absorb. This is proof that the closed-loop operation has proceeded smoothly. The flexible printed wiring board obtained by the above manufacturing method has a very large surface resistance compared to the conventionally known products. Taking the surname confirmed by the present inventors as an example, it is manufactured by the conventional direct metallization method. If the surface resistivity is not more than 2.5 × 1 〇ιιohm / □ without further closed-loop treatment, the volume resistivity is 1. 8x1 013 ohm · cm. the following. In contrast, the surface resistivity of the flexible printed wiring board obtained by the manufacturing method related to the present invention is in! 〇χΐ 〇15 or more, and volume resistivity of 4 · 8χΐ15 ohm · cm or more. The flexible printed wiring board is subjected to constant temperature and humidity treatment (8 5 t / 8 5% RH / 50 hours) After measuring the surface resistivity and volume resistivity. As a result, 2169-5304-PFl (Nl) .ptc Page 18 569656 Λ Case No. 91132587 V. Description of the invention (13) When manufactured by the conventional direct metallization method, the surface resistivity is 1.1x1 〇13 ohm / □ or less The volume resistivity is lower than 2 · 7x1 〇 " ohm · cm. Relatively, the flexible printed circuit board obtained by the manufacturing method related to the present invention has a surface resistivity of more than 6 · 8 × 1014 ohm / ，. Above 14 乂 1015 ohm.cm, it is still a very large value. Therefore, since the values of surface resistivity and volume resistivity are large, a great improvement in anti-migration performance can be expected. The results will be described in the following embodiments. In this specification, the measurement of surface resistance and volume resistivity is performed using a two-layer substrate with a copper layer on both sides, as follows. The surface resistance is the insulation resistance between the electrodes located on the surface of the substrate, and the volume resistance is set in the thickness direction of the substrate. When the cube is 1 cubic centimeter, the electricity between the electrodes on the two opposite sides = two. Therefore, it is used for measurement. The sample is a pair of etched 100 millimeters to 100 millimeters. The center of the sample forms a circular main electrode with a diameter of 50 millimeters. ”10 mm-spaced concentric circular arc-shaped electric main electrode with a width of 10 mm: The back side of the polyimide resin film is etched to make a counter electrode with a concentric diameter of 83 mm in diameter. The counter current on the back is = Use the t electrode and the round sinker, and the circuit is electric S, to form a body guard function, and apply a voltage. Therefore, when the bottle resistance resistor is obtained, the circuit is connected to the main electrode and used as the guard electrode measurement_ # φ 'I The voltage applied between the electrodes is calculated using the arc rate and the product resistivity 'using the conversion formula [Ancient X Ray H area made by RHI Chemical Co., Ltd.] V plate thickness. This measurement system uses three or two = 依依 川 κ _ The method is. As the material constituting the insulating layer ^ The material of the circuit board is ⑽imine resin film 枓, and the surface is formed with circuits, not only the general 2169-5304-PFl (Nl) .ptc page 19 569656 __ _Case No. 91132587_ Amendment 5 、 Explanation of invention (14) It is called flexible printed circuit board (FPC) products, and it is also used to collectively refer to tape and tape automatic bonding products (TAB) used in liquid crystal display drivers, etc. Flexible printed wiring boards such as substrates (COF).

Yet another application for a patent is a method for manufacturing a flexible printed wiring board including a direct metallization method 30 including the following steps 531 to S 35, as shown in the second figure. First, in step S31, the polyfluorene imide resin film is subjected to an alkali treatment to perform a ring-opening treatment of the fluorene imine ring to form a ring-opening of a carboxyl group on the surface. Then, step S 3 2 neutralizes the ring-opened alkyl group with an acid solution. Next, in step S33, the neutralized carboxyl group is brought into contact with the metal ion-containing solution to adsorb the metal to become a metal ion adsorber which forms a metal acid salt on the surface of the polyimide resin film. Then, step S 34 reduces the carboxylic acid metal salt formed on the surface of the polyimide resin film to form a metal thin film on the surface of the polyimide resin film, which is a thin film forming step. Next, step S35 is a step of forming a copper layer for a circuit on the metal thin film formed on the surface of the polyimide resin film to form a copper layer for forming a circuit by an electrochemical method.

The method for manufacturing a flexible printed wiring board with the obtained double-layer flexible copper-faced laminate composed of the conductor layer and the polyimide resin layer is characterized in that it includes the following steps S 3 6 to S 3 9 and the direct metal is used. The pre-heating and pre-heating of the flexible copper-faced laminate obtained by the chemical method (step S36). Next, the pre-heated double-layered flexible steel surface laminated board is etched to form a circuit etch of the circuit (step S37). Next, the substrate after the circuit is etched is treated with acid to remove the residual metal component from the carboxylic acid metal salt on the surface of the polyimide resin film exposed between the gaps of the lines formed on the substrate to convert it into a carboxyl group. Residual metal components are removed (step S38). Finally, the residual metal component is removed

569656 Cable No. 91132587 ± _Η Revision V. Description of the invention (15) Except the step, the substrate is heat-treated in a high-temperature gas environment at 180 ° C to 20 0 ° C for 10 to 80 minutes to form an exposed substrate. The surface of the circuit gap is closed and then closed-looped (step S 3 9). The manufacturing method is the same as the above-mentioned manufacturing method of the flexible printed wiring board, except that before the circuit etching, the pre-heating of the double-layer flexible copper surface laminate obtained by the direct metallization method is performed in advance. + Step S 3 6 is different. Therefore, the same and repeated portions are omitted, and only the pre-heating step S36 will be described. Assuming this pre-heating step, when processed into a flexible printed wiring board, there is no thermal shock exceeding 300 C 'or the circuit does not peel off in an ambient gas at this temperature. Therefore, with the pre-heating step, the adhesion between the conductor layer and the polyimide layer should be significantly improved, and the ability to resist high temperature circuit peeling should be improved. In this pre-heating step, the double layer obtained by the direct metallization method The substrate should be heated at 90 ° C to 160 ° C for 0.5 to 4 hours. Deviating from the above-mentioned "temperature" conditions, if the heating is insufficient, the pre-heating effect must not be prevented, and the circuit peeling cannot be prevented. The excessive heating will promote the degradation of the polyimide resin side, and the ability to resist circuit peeling will inevitably deteriorate. In addition, the pre-heating method is preferably a method in which the temperature is gradually increased from room temperature and maintained for a certain time after reaching the target temperature. If the double-layer substrate is sent sharply from 90 ° C to an ambient gas temperature of 160 ° C, even mild / thermal shock. For example, alkali treatment of polyimide resin film causes ring opening of fluorene imine to form a carboxyl group, and neutralization with an acid solution causes the neutralized carboxyl group to contact with a solution containing cobalt ion to form on the surface of polyimide resin film. Cobalt carboxylate is reduced to form a cobalt thin film on the surface of the polyimide resin film.

569656 91132fSS7 V. Description of the invention (16): Correction Use of electrochemical methods to form electricity

The pre-heated substrate with a difference of I is used to judge that the circuit is peeled when heated for 20 seconds: the two are heated at 350 Ct for 5 minutes without circuit peeling f. Even those who are pre-heated even if they are: ΓΓ? Circuit boards, depending on their use, may be applied with a variety of ^ β〒 hanging terminal plating of tin plating, multi-layered

Seal: m: interlayer conductive copper and other layers. In addition, "Left: Path: the use of layer key scratch recording. Therefore, the so-called plating treatment steps in this specification are not limited to: special types of plating. Such plating treatments are also performed after the circuit is etched. The same as the above When the manufacturing method of the invention is used as the basic flow, after the circuit of the flexible printed wiring board manufacturing method is etched, the plating treatment can be applied at any stage, and the migration resistance can be maintained well. Therefore, the scope of the patent application is based on the above three flexures. A method for manufacturing a flexible printed circuit board with a plated layer, which is a method for manufacturing a flexible printed circuit board, is a method for manufacturing a printed circuit board with a key layer that is plated at any stage after the circuit etching step. Specifically, The following plating treatment steps are provided. First, the present invention is basically "when manufacturing a flexible printed wiring board with a polyimide resin film-based copper-clad laminate" by (a) I engraving the scratch Circuit etching step of forming a circuit with a copper surface layer to form a circuit, (b) the substrate after the circuit is etched, and the circuit exposed on the substrate is removed by pickling. Gap of the substrate resin film, the residual metal component from the carboxylic acid metal salt is converted into a residual metal component removal step of the buffer group. (C) The substrate after the residual metal component removal step is at 180 ° C to 200 C. Heat treatment in the south temperature gas environment 10 to 8

2l69-5304-PFl (Nl) .ptc Page 22 569656 Revised case number 91132587 V. Description of the invention (17), the polyimide resin used as the gap of the circuit formed on the substrate is exposed to the closed-loop treatment of the surface Closed-loop steps to manufacture flexible printed wiring boards. In this case, the plating process step may be provided between the circuit etching step and the step of removing the residual metal by two steps. Or, 'is provided between the step of removing the residual metal component and the step of re-closing. It can also be set after the re-closed loop step is completed. ; n; its-person's inspection, using the above-mentioned direct metallization method to obtain the double-layer flexible steel surface laminate composed of the conductor layer and the poly 2 amine resin layer, and then etching the ^ layer of the flexible copper surface laminate to form a circuit The circuit etching step, (b), the substrate after the road is etched with a pickling place ^ except for the surface of the substrate resin film exposed in the gap formed on the substrate, the residual gold from the carboxylic acid metal salt = component, (C) ^: Removal step of residual metal component converted to carboxyl group, (c) ^: After the second removal step, the substrate is heat-treated under a high-temperature gas frame for 10 to 80 minutes, and is used to aggregate the gaps of the circuits formed on the substrate. The closed-loop process of the closed-loop process of the surface of the imine resin film, and the configuration of the plating process step when manufacturing a flexible printed circuit board. At this time, the same as the above, the plating process step may be set between the circuit etching step and the remaining step of removing. Or, it is provided between the step of removing the residual metal component and the step of re-closing. It can also be set after the re-closed loop step is completed. Let's examine again. Using the conductor layer and imine resin layer obtained from the direct metallization method described above, a two-layer flexible copper-faced laminate made of the above-mentioned direct metallization method is used. The pre-heated pre-addition step is used to etch the pre-heated double-layered copper-clad laminate to form a circuit circuit. (C) The substrate after the circuit is etched, and the exposed substrate is removed by pickling. The surface of the substrate resin film of the gap of the circuit, 23 p.23 2l69-5304-PFl (Nl) .ptc 569656 case number 91132587

V. Explanation of the invention (18) Residual metal component from metal carboxylic acid metal salt Step of metal component removal, (d) Residual metal & residue converted into carboxyl group 10 to 8 for circuit formation formed on the substrate. The test of the minute ’s 碰 卩 俨 碰 夕 夕 俨 俨 俨 俨 狮 俨 狮 狮 门 隙 隙 隙 酿 酿 酿 酿 酿 酿 酿 酿 酿 酿 酿 酿 裱 裱 裱 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤 步骤;;; 生 枝 amp amp King? Niu Xixi Xianfan.ni ^ The configuration of step j at the plating layer when expressing the printed circuit board. At this point, 'as mentioned above, the circuit etching step and the residual metal component are rich, and it is gone. And between the two knife removal steps. Or, the remaining metal component removing step and the re-closed loop + step are completed. Close% steps between. It can also be set at the re-closed loop. The above-mentioned coating removal step and re-closed are used. However, strictly speaking, sex has a great impact. When any of the logical steps is configured as a ring step, it can be described below the plating step. It has a better anti-migration configuration than the absence of residual metal. The optimal configuration for anti-migration coating step is to set the plating treatment step between the circuit etching step and the residual metal component removal step. When using this plating step configuration, a residual metal component removal step is subsequently provided, and the surface of the polyimide resin film exposed on the gap formed by the circuit at the moment of the circuit can be almost free of residual liquid metal components. As a result, optimum anti-migration performance can be obtained. The second step is to set the plating process step after the re-closed loop step. That is, the completion of the "re-closing step" means that the polyimide ring of the polyimide resin film exposed in the gap formed by the circuit etching is closed, and the metal component of the plating solution is difficult to remain in the polyimide resin film. surface. Compared with the previous two configurations, when the plating treatment step is set between the residual metal component removal step and the re-closed-loop step, the migration resistance improvement effect is the most effective.

2169-5304-PFl (Nl) .ptc Page 24 569656 __Case No. 91132587 Car Moon Day Amendment_ V. Description of the invention (19) Small. That is, at the time when the residual metal component removing step is completed, the polyimide ring system of the polyimide resin film exposed in the gap of the circuit formed by the circuit name is in a ring-opened state. Therefore, if a ore layer treatment is applied immediately thereafter, the surface of the polyfluorene imide resin film is liable to leave metal components of the plating solution due to the presence of the ring-opened fluorene imine ring. Therefore, if the step of directly entering the re-closed loop is performed directly, the possibility of the metal component remaining on the surface of the polyimide resin film exposed from the circuit gap becomes higher, and the effect of improving the migration resistance becomes smaller. However, in order to avoid misunderstanding, it is emphasized again that even if the key layer processing step is set between the residual metal component removal step and the re-closed loop step, compared with the previous two configurations, although the improvement effect of the migration resistance is small, it can still ensure that it is better than the conventional one. Know the product's higher resistance to migration. Embodiments Hereinafter, the present invention will be described in more detail by using an embodiment in which a flexible printed wiring board is manufactured using the manufacturing method according to the present invention. First Embodiment: This embodiment adopts a so-called direct metallization double-layer substrate, and the double-layered substrate is used here. And it is still the same. First, the polyfluorene ADB formed a carboxyl group on the surface. The film was sold under the brand name KAPTON. The alkali treatment was based on the hydrogen method to produce a flexible printed circuit board made of a copper layer and a polyimide resin layer. The double-layer substrate with copper layers on both sides of the amine resin film was transferred and the results were verified. The following sequence is ;;: The diamine resin film is alkali-treated to ring-open the imine ring, and then the ring-opening step is performed. Polyimide resin 200H (made by TORAY DUPGNT (stock)) used here. Potassium oxide concentration is 5.0 mol / L, warm. ^

2169-5304-PFl (Nl) .ptc Page 25 569656 Amendment No. 911325S7 5. Description of the invention (20), soak in the liquid for 5 minutes. When the alkali treatment is completed, wash with water. The attached potassium hydroxide solution was removed from the surface of the polyimide resin film. ^ FT-IR analysis to determine whether the ring-opened polyimide resin has observed 1-647CHT1 ring-opened amine (〇0) absorption, and 1 554CIT1 near ring-opened amine (NH) absorption The disappearance of the absorption of the specific imine ring 1774cnfl (C = 0), HZOcnrKOO) and 1Mlcm-KC-NC) can be confirmed. In addition, absorption near the carboxyl group (co) was observed in the vicinity of 1,579cnrl, 1371cnrl, and 1344cnrl. Next, after the 'ring-opening step is completed, the washed polyimide resin film is treated with a neutralization step. The ring is opened to form a carboxyl group, and the strongly alkaline polyimide resin film 'is immersed in an acid solution to be neutralized. The solution used for the neutralization was a hydrochloric acid solution ', and the conditions were that the concentration of the hydrochloric acid solution was 6.0 mol / liter, and the solution temperature was 25 ° C. The treatment time was 1 minute. After neutralization, wash with water. At the completion of this neutralization phase, the polyimide resin film was analyzed by FT-IR, and it was confirmed that the ring-opened fluoramine (C = 0) absorption of 1 647 cm-1, and the ring-opened fluoramine (NH near 554 cm-i) (NH )absorb. In addition, the absorption of the carboxyl group (C00) seen at 1 579cm-i, 1371cm-i, and 1 344cnfl has shifted to the vicinity of i7iicm-i '1319CIT1, 1 29 6cm_1. When the neutralization step is completed, in the copper adsorption step, the neutralized carboxyl group of the polyimide resin film is brought into contact with the copper-containing solution, and the copper ions are adsorbed to the carboxyl group to form copper carboxylate on both sides of the polyimide resin film. salt. The copper-containing solution used here was a copper sulfate solution 'having a copper concentration of 0.05 mol / liter and a solution temperature of 25 ° C, and immersed in the solution for 1 minute. Then wash with water to remove the residue

2169-5304-PFl (Nl) .ptc Page 26 569656 Case No. HIj2587_ V. Description of the invention (21) A sulfuric acid steel solution on the surface of an amine resin film. Subsequently, in the copper film formation step, ^ ¥ π # $ = = copper ions formed on the surface of the 5 ^ imine tree in the step of adsorption _ brewing fine π ^ & π # ^ ^ copper The salt is reduced to form a copper thin film on the surface of the polyimide tree. Too much you ^ ^ ^ ^ ^ The reduction of the rich bismuth form will form a ^^ imine resin film of copper carboxylate salt η π > 跏 # π such as, 々ν + degree · 〇1 Mo Er / L, solution temperature 25 C immersed in a solution of lice 化 纳 ^ ^ ^ ^ ^ ^ ,,, a: times / pack 5 knives know 'in contact with the reducing agent. After that, it is washed with water 'to remove the reducing agent attached to the surface. In this embodiment, a steel fence is formed as early as this. / 5 Mist 4, 隹 —έ 士 里 ^ and attached steps and copper film formation steps 形成 Γ 丁. At the stage after the completion of the copper ion adsorption step, the total amount of steel ions adsorbed on the polyimide resin film reached 22,000 millimeters, and finally 154 can be formed on the copper film formation step ^ ^ + lipid film 45. The milli-reduced formula is almost dimer-dimeric polyimide tree 41 (see figure 4). The steel thin film layer with a thickness of 1,000 grams without weight S ”is then formed in the copper layer for the circuit, and the polyimide resin film surface of the copper thin film formed in the copper thin film forming step is electroplated with a copper component by electrolytic method, and additional copper is electroplated Thin film to 9 micron thick copper layer. The solution used for electrolysis here is a solution of copper sulfate with a sulfuric acid concentration of 150 g / liter, copper 65 g / liter, and a liquid temperature of 45, and an insoluble anode DSE board for the pole system. The current density is 3 amps / square inch. Electroplating conditions Electrolysis 丨 6 minutes. After the plating is added, it is sufficiently washed with water to remove the attached copper sulfate solution. By the above direct metallization method, a double-layer substrate having a copper layer on both sides in a state where the copper layer and the polyimide resin layer are directly bonded is obtained. Then, an etching resist layer is formed on the surface of the copper layer of the double-layer substrate, and the electrical resistance for forming the above-mentioned resistance measurement sample and anti-migration amount test sample is formed by exposure, development, and etching.

2169-5304-PFl (Nl) .ptc Page 27 569656

Case No. 91132587 After the etching step, the exposed polyimide resin film was analyzed by FT— 丨 R, and it was confirmed that the ring-opened amine (C = 0) absorption of 1 650cm-1, i 547cirl near Ring-opening ammonium (NH) absorption, absorption of several bases (COO) near 1 707C1T1 and 1 308CIT1 reappeared. & In the next remaining metal component removal step of the circuit-etched substrate, the surface of the polyimide resin film exposed from the gaps of the lines formed on the substrate is removed by pickling, and the residual copper component from the copper carboxylate is removed. Turn it into a losing ground. The pickling treatment performed here was performed by immersing the circuit-etched substrate for 5 minutes with a hydrochloric acid solution at a concentration of 2.0 mol / liter. It was then washed with water to remove the attached hydrochloric acid component. The resistance measurement sample produced by the etching of the circuit is also the same as above, and its description is omitted to avoid repetition. On the other hand, the anti-migration test sample circuit is a comb pattern with a width of 50 microns and a circuit gap of 70 microns. The number of circuits is such that the circuits arranged in the shape can interact with the positive and negative electrodes. At the stage of removing the residual metal components, the polyimide resin film of the exposed part was analyzed by FT-IR, and it can be confirmed that the absorption of 649cm-1 ring-opened ammonium (00) and the ring opened near 1541cm-1 Amine (N-H) absorption, and

2169-5304-PFl (Nl) .ptc Page 28 1

71 4cm 1 and 1 298 ^ 11-1 near the absorption of the slow base (c〇〇) appeared. Then X-ray diffraction method and wavelength-dispersed electronic probe microanalysis (EPMA) were used to analyze the presence or absence of adsorption of metal components, and copper components and other metal components could not be detected 'to confirm that the pickling removal had been carried out. Then, the closed-loop operation is performed on the substrate after the residual metal component removing step is completed. In this re-closed loop step, the residual metal components are removed to 569656 ____ Case No. 91132587_ Month R 胄 ____ V. Description of the invention (23) The substrate after the step is removed is made under a high temperature ambient gas of 180 ° C Heat treatment for 60 minutes, in the presence of no circuit pattern, exposed carboxyl ring on the surface of the polyimide resin film in a ring-open state. FT-IR analysis was used to confirm the closed loop of the polyimide resin film in the exposed part. It can be seen in the ring-opened polyimide resin film 1 649cnr1 ring-opened amine (C = 0) absorption, 1541cm-1 Nearby ring-opened amidine (N_H) absorption, the absorption of carboxyl groups (c〇〇) at 1714cm-1, 1371cm-1, and 1 3 44cm-1 could not be confirmed at all, but the unique 1 7 7 8 c nr1, 1 7 2 4 c m-1 and 1 379 cm-1. Therefore, it proves that the closed-loop operation has proceeded smoothly. Measure the resistance using the sample for resistance measurement obtained by the above manufacturing method. As a result, the surface resistivity was 1.0 × 10 15 ohm / □, and the volume resistivity was 4 · 8 × 1 015 ohm · cm. In addition, the surface resistivity and volume resistivity after constant temperature and humidity treatment (85 ° C / 85% RH / 50 hours) were measured. As a result, the surface resistivity was 6.8 × 1014 ohm / □, and the volume resistivity was 丨 4 × 5 ohm · cm. The anti-migration test was performed in a thermostatically-wet tank with a temperature of 85 ° C and a humidity of 85%. Using the above-mentioned sample for the anti-migration test, a voltage of 60 volts was applied to measure the time required to generate a leakage current. As a result, the time required for generating the leakage current is more than 1,000 hours. As for the NanWen circuit peeling prevention ability, a sample for resistance to migration test was used, which was exposed to an ambient gas at a temperature of 350 ° C for 20 seconds, and peeling of the circuit was observed. Second Embodiment: This embodiment shows' like the first embodiment, using a 50 micron thick polyimide resin film, the so-called direct metallization method is used to produce a double layer composed of a copper layer and a polyimide resin layer. Substrate, and using this double-layer substrate to make a flexible print

2169-5304-PFl (Nl) .ptc Page 29 569656

V. Description of the invention (24) The result of brushing the circuit board. However, the difference is that a pre-heating step is provided just before the double-layer substrate 5 \ 1 is finished. Therefore, the manufacturing process is almost the same as that of the first embodiment, and repeated descriptions are omitted, and only the pre-heating steps are described. By the direct metallization method as in the first embodiment, a double-layer substrate having a copper layer on both sides in a state where the copper layer and the polyimide resin layer are directly bonded is obtained. The double-layer substrate is then sent to a heating furnace in a dry state for pre-heat treatment. At this time, the temperature of the ambient gas is heated from room temperature to a temperature of 10 ° C / min to 120 ° C. After being held in the ambient gas for 60 minutes, it is slowly cooled to 0 and then doubled at the end of the preheating step. An etching resist layer is formed on the surface of the copper layer of the multi-layer substrate, and the remaining steps of forming the circuit for the resistance measurement sample and the anti-migration amount test sample are performed by exposure, development, and etching. The subsequent steps and the results of FT-IR analysis are also the same as those of the first embodiment, so the descriptions are omitted. The resistance was measured using a sample for resistance measurement like the first embodiment. As a result, the surface resistivity was 1.0 · 10 × 15 ohm / □, and the volume resistivity was 4.9 × 10 × 15 ohm · cm. In addition, the surface resistivity and volume resistivity after constant temperature and humidity treatment (85 ° C / 85% RH / 5 0 hours) were measured. As a result, the surface resistivity was 6.7 × 1014 ohm / □, and the volume resistivity was 1.4 × 1015 ohm · cm. The anti-migration test was performed in a constant temperature and humidity tank with a temperature of 85 ° C and a humidity of 85%. Using the sample for the anti-migration test, a voltage of 60 volts was applied to measure the time required to generate a leakage current. As a result, the time required for generating the leakage current is more than 1,000 hours. As for the high temperature circuit peeling prevention ability,

2169-5304-PFl (Nl) .pt Page 30 569656 No. 91〗 Milk 7 V. Description of the invention (25) Transfer test sample, observation at 3 5 n ° r, silo ^ No circuit peeling . Secondly, exposure to ambient gas for 5 minutes is still a good product. Compared with the first embodiment, the third embodiment is the third embodiment: This embodiment shows that the n-polyimide resin film T is ㈡ :: appearance mode 'using a 50 micron thick imine resin The double-junction metallization method of layer construction results in the production of a double-layer substrate consisting of a copper layer and a polycaffeine + β w, and the use of the double-layer substrate to produce a flexible printed circuit board. As a Taiyin you ^ π β μ, +, ^ ^ 1 A consistent application mode is used in the manufacture of double-layer substrates, replacing the copper ion adsorption steps described above, 1, / K ^ ^ and attached steps, cobalt Ion adsorption step to make the polyfluorene

Yaru: The copper foil M 雔 s A ^ ^ ^ on both sides of the resin film, a double-layer substrate of another layer. In addition, the results of migration tests are presented ... The steps are explained in order below. FT tH: 'ring step, neutralization step, FT-IR after ring opening and after neutralization are analytical results, which are the same as those of the first embodiment.

After the completion of the Bt step, the polyimide tree is contacted with a solution containing cobalt ions in the ion adsorption step, and cobalt is adsorbed on the carboxyl group to form on both sides of the polyimide resin. Cobalt carboxylate. The diamond-containing solution used here was a cobalt sulfate solution of 0.05 mol / liter and a solution temperature of 25 t. The solution was immersed in the solution for 15 minutes. Then, it was washed with water to remove the solution remaining on the surface of the polyimide resin film. After the cobalt film formation step, the slow acid salt formed on the surface of the polyimide resin film in the cobalt ion adsorption step is reduced to form a thin film on the surface of the polyimide resin film. The reduction of this embodiment is performed by forming a polymer of cobalt metaborate salt. The imine resin film is immersed in a sodium borohydride solution having a concentration of 0.01 mol / liter and a solution temperature of 25 C for 5 minutes, and is contacted with a reducing agent.

2169-5304-PFl (Nl) .ptc page 31 569656 correction

__ Case No. 91132587 V. Description of the invention (26) Then wash with water to remove the reducing agent attached to the surface. In this embodiment, the primary ion adsorption step and the cobalt thin film formation step are repeated several times. As a result, the total amount of cobalt ions adsorbed on the polyimide resin film reached 2034 mg / m 2 at the final stage of the cobalt adsorption step, and finally on the polyimide resin film during the reduction stage of the cobalt film formation step. It can form a cobalt thin film layer with a thickness of 142 mg / m 2. Then, in the step of forming a copper layer for a circuit, the surface of the polyimide resin film of the cobalt thin film formed in the step of forming the cobalt thin film was electro-deposited with a copper component by electrolytic method, and an additional copper thin film was formed to a thickness of 9 micron. The solution and electrolytic conditions used for electrolysis here are adjusted to 85 g / L to 90 g / L copper pyrophosphate, 330 g / L potassium pyrophosphate, 4 ml / L ammonia, p ratio (P207 / Cu) = 6.5 to 6 · 8, ρΗ = 8 · 6 to 8 · 9, the solution temperature is 55 ° C, the current density is 33 amps per square inch. After the electroplating is completed, wash it thoroughly with water to remove the attached copper pyrophosphate solution. By the above direct metallization method, a double-layer substrate with a copper layer on both sides is obtained in a state where the copper layer is directly bonded to the polyimide resin layer through the cobalt thin film layer. The double-layer substrate is then sent to a heating furnace in a dry state for pre-heating treatment. At this time, the ambient gas system was heated from room temperature to 150 ° C at a temperature increasing rate of 10 ° c / minute, and then kept in the ambient gas for 60 minutes, and then slowly cooled. Then, an etching resist layer is formed on the surface of the copper layer of the double-layer substrate after the pre-heating step, and the etching step of forming the above-mentioned resistance measurement sample and anti-migration amount test circuit by exposure, development, and etching is performed. . The result of FT-IR analysis after the circuit money is carved is also the same as the first embodiment. Circuit #lithography of the substrate, in the residual metal component removal step, to

2169-5304-PFl (Nl) .ptc Page 32 569656 Case No. 91132587 5. Description of the invention (27) The acidic washing treatment and water washing treatment in the first embodiment remove the attached hydrochloric acid component. The resistance measurement sample and the anti-migration test sample manufactured by circuit etching are also the same as those in the first embodiment, and descriptions thereof are omitted to avoid repetition. At the stage of removing the residual metal components, the results of FT-IR analysis of the polyimide resin film at the exposed parts, the results of the χ-ray diffraction method, and the EpM analysis are also the same as those of the first embodiment, without cobalt components and other The detection of gold lip components confirmed that the pickling removal had been carried out. Then, after the step of removing the residual metal components, the closed-loop operation is performed in the closed-loop step. This re-closing step is a method similar to the first embodiment, in which the carboxyl group existing on the surface of the exposed polyimide resin film in a ring-open state exists in a circuitless pattern. The closed-loop FT-IR analysis results are also the same as in the first embodiment. 0 The electric resistance Γη is measured using the sample for resistance measurement obtained by the above manufacturing method. The surface resistivity is 1 · 〇Xl015 ohm / □, volume. Resistivity is 5.0XUF ohm.cm. In addition, the surface resistivity and volume resistivity after constant temperature and humidity treatment (85 ° c / 85% RH / 50 hours) were measured. The area resistivity is 6.5x10h ohm / □, and the volume resistivity is ΐ 4χΐ ° 〇 欧 5 欧, even t. The anti-migration test was performed at a constant temperature of 85t and a clearness of 85%: in a wet tank. Using the above-mentioned sample for anti-migration test, & 6 pressure was applied to measure the time required to generate a leakage current. Social fruit takes 10 minutes. . Hours to two; ^ is the sample for migration test used to generate leakage current, at 35 (rc temperature of the ambient gas stop: force: buckle, still no observation of circuit peeling. / Knife state 'is an extremely good product m, increase the number of the second embodiment is 1, then the number of martial arts is compared

569656

—__ Case No. 91132587 V. Description of the invention (28) Yes, compared with the second embodiment, it presents a more stable circuit peeling strength ', which is a product with excellent peeling prevention ability at South temperature. Fourth Embodiment: This embodiment adopts the method of the first embodiment as a basic process, and a tin plating step is provided directly after the circuit etching step. Therefore, only the plating process steps added to the process of the first embodiment will be described in detail, and the other parts will be omitted to avoid repetition. As in the first embodiment, the copper layer and the polyimide resin layer are directly bonded by a direct metallization method through a ring opening step, a neutralization step, a copper ion adsorption step, a copper thin film forming step, and a copper layer forming step for a circuit. In this state, a two-layer substrate with a copper layer on both sides. Then, an etching resist layer is formed on the surface of the copper layer of the double-layer substrate, and the etching step of forming the above-mentioned sample for resistance measurement and the circuit for measuring the amount of anti-migration is performed by exposure, development, and etching. After the circuit is etched, a tin plating step is set up to experimentally tin the circuit. The tin plating is made of SHIPLEY FAR EAST (stock) LT-34 tin plating solution, and the plating is performed at a solution temperature of 75 ° C to a thickness of about 1 micron. After the formation of the tin layer, the polyimide resin film in the exposed part was analyzed by FT-IR, and it was confirmed that the ring-opening fluorene (c = 0) absorption at 1 650 cm-1 and the ring-opening amine (NH) near 1 547CHT1 Absorption, and the absorption of carboxyl groups (COO) near 1 707 cm-1 and 1 308 CHT1 reappeared. Comparing the results of FT-IR analysis after circuit etching in the first embodiment, the same as when ore tin was applied. In the substrate after the ore tin processing step, in the next remaining metal component removing step, the surface of the polyimide resin film exposed from the gaps of the lines formed on the substrate is removed by pickling, and the residual tin component from the tin carboxylate salt is removed. ,will

569656 --- Case No. 91132587__year month day__ amendment V. The description of invention (29) is converted to carboxyl group. The pickling treatment performed here was performed using a hydrochloric acid solution of a concentration of mol / liter, the temperature of the solution was room temperature, and the substrate on which the circuit was etched was bubbled in the solution for 5 minutes. It was then washed with water to remove the attached hydrochloric acid component. Since the resistance measurement sample and the anti-migration test sample manufactured in this way are the same as those in the first embodiment, description thereof is omitted. At the stage of removing the residual metal component, the polyimide resin film of the exposed part was analyzed by FT-IR. As in the first embodiment, it was confirmed that the absorption of 1 649 cm of ring-opened amidine (c = 〇), 1 541 cm- The absorption of ring-opened ammonium amine (NH) near 1, and the carboxyl group (C00) near i7i4cm-i and 1 298CDT1 appeared. The X-ray diffraction method and the wavelength-dispersed electron probe microanalysis (EPMA) were used to analyze the presence or absence of adsorption of metal components. The tin components and other metal components could not be detected, and it was confirmed that the pickling and removal had been carried out. Then, the closed-loop operation is performed on the substrate after the residual metal component removing step is completed. The results of the FT-IR analysis of this re-closed-loop step and the confirmation of whether the closed-loop has been closed are also the same as in the first embodiment, and will not be described in detail, but it has been proved that the closed-loop has proceeded smoothly. The resistance was measured using the sample for resistance measurement obtained by the above manufacturing method. As a result, the surface resistivity was 丨 · 〇χ1015 ohm / □, and the volume resistivity was i · 7χ1015 ohm · cm. In addition, the surface resistivity and volume resistivity were measured after constant temperature and humidity treatment (85 ° c / 85% RH / 5 0 hours). As a result, the surface resistivity was 6.6 × 1014 ohm / □, and the volume resistivity was 14 乂 1015 ohm · cm. The anti-migration test was carried out in a constant temperature humidity tank at a temperature of 85 ° C and a humidity of 85%. The above-mentioned sample for the anti-migration test was applied with a voltage of 60 volts to measure the time required to generate a leakage current. As a result, a leakage current is generated.

569656 Case number 91132587 V. Description of the invention (30)

± ___ A said correction takes more than 100 hours. As for the high-temperature circuit peeling prevention ability, a sample for the anti-migration test was exposed to an ambient gas at a temperature of 350 ° C for 20 seconds, and peeling of the circuit was observed. Fifth Embodiment. This embodiment uses the method of the first embodiment as a basic process, and a tin plating step is provided after the re-closed loop step. Therefore, only the plating process steps added to the manufacturing process of the first embodiment will be described in detail, and other parts will be omitted to avoid weight. As in the first embodiment, the copper layer and the polyimide resin layer are directly bonded by a direct metallization method through a ring opening step, a neutralization step, a copper ion adsorption step, a copper thin film forming step, and a copper layer forming step for a circuit. A double-layer substrate with a copper layer on both sides. Then, an etching resist layer is formed on the surface of the copper layer of the double-layer substrate, and the remaining steps of forming a circuit for the resistance measurement sample and the anti-migration amount test sample are performed by exposure, development, and etching. Then, as in the first embodiment, a step of removing residual metal components is performed, and a closed-loop step is performed. After performing the re-closed loop step, a tin plating step is set up to experimentally tin the circuit. Tin plating is a LT-34 ^ tin solution manufactured by SHIPLEY FAR EAST (stock), and is plated at a solution temperature of 75 ° C to a thickness of approximately} microns. After the formation of the tin-plated layer, the exposed polyimide resin film is analyzed by FT-IR, as in the first embodiment without tinning. In order to avoid repeating its detailed description, it is omitted to prove that the closed-loop operation has been smooth. get on. χ, using the χ-ray diffraction long-dispersion electronic probe microanalysis (ερμα) to analyze the presence or absence of adsorption residues of ore tin solution, especially no money and other components

569656

Even if it exists, it should be below the detection limit. Use the above manufacturing method to get resistance.士士洛 主; Φ's resistance $ test sample for measuring resistance, resistance, mouth fruit ’surface resistivity is 1 · 0 X1 0 丨 5 鼢 妩 / gate _ _ ^ 5.2xl0i5 ohm.cm. In addition, the surface resistivity and volume resistivity after the temperature and humidity treatment (85 ° C / 85% RH / 50 hours) are measured in the volume resistivity (□, the volume resistivity is measured here.) The rate is 5.9x10 "ohm / □, and the volume resistivity is 13 xi ohms. Cm. The anti-migration test is performed in a constant temperature and humidity tank with a temperature of 85t and a humidity of 85%. Using the above-mentioned sample for anti-migration test, apply 6 The time required to generate a leakage current was measured at a voltage of volts. As a result, the time required to generate a leakage current was about 600 to 700 hours. However, in terms of the ability to prevent peeling of high-temperature circuits, only the anti-migration test sample was used at 3 5 〇 Exposure to ambient air at a temperature of 20 seconds, peeling of the circuit has been observed. Comparative Example 1: After the etching step of the first embodiment is completed, there is no remaining metal component removal step and re-closed-loop step, and it is performed just like the re-closed-loop step. After heat treatment, samples for resistance measurement and anti-migration test are produced. Therefore, the metal components of the polyimide resin film on the exposed portions are still left after etching. Imine tree The membrane was analyzed by FT-IR for polyimide resin membranes, absorption of cyclamidine (c = 〇) near 1 647 cm-1, absorption of cyclamamine near 1 554 (^ 1 -10), and 1371 ( : The absorption of carboxyl group (COO) seen near 111-1 has disappeared. However, there are peaks of absorption of carboxyl group (COO) near 1 3 6 CIT1. Based on the results, it is judged that heating should cause a certain closed-loop phenomenon. But it cannot be completely closed loop.

2169-5304-PFl (Nl) .ptc Page 37 569656 Case No. 91132587 V. Description of the invention (32) The surface of the polyimide resin film exposed after heating is dispersed by X-ray diffraction and wavelength Two types of electronic probe microanalysis (EPMA) are used to analyze the presence or absence of adsorption of metal components. As a result, it was confirmed that the copper component remained at 0. Then, resistance measurement and anti-migration test were performed in the same manner as in the embodiment. As a result, the surface resistivity was 1.0 × l 015 ohm / □, the volume resistivity was 2.6 × 1015 ohm · cm, and the surface resistivity after constant temperature and humidity treatment (85 ° c / 85% RH / 50 hours) was 3 · 9 × 1014 ohms / □, the volume resistivity is 1 · Oxl 015 ohms · cm, which is lower than the value obtained in the above embodiment. As a result of the anti-migration test, the time required to generate a leakage current was about 420 hours. As for the ability to prevent peeling of high-temperature circuits, only the samples for the anti-migration test were exposed to an ambient gas at a temperature of 350 ° C for 20 seconds, and peeling of the circuit was observed. Comparative Example 2: After the etching step of the first embodiment is completed, only the residual metal component removing step is performed, there is no further closed-loop step, and only the dryer is used to prepare a sample for resistance measurement and a sample for resistance to migration test. Therefore, the surface of the polyimide resin film exposed by the etching has no metal component remaining, but no closed-loop operation is performed. Then, resistance measurement and anti-migration test were performed in the same manner as in the embodiment. As a result, the surface resistivity was 1.βχ1011 ohm / □, the volume resistivity was 7.2x1013 ohm · cm, and the surface resistivity after constant temperature and humidity treatment (85 ° C / 85% RH / 50 hours) was 9.6x1 012 Ohm / □, the volume resistivity of 3 · 3 × 10 ohm · cm is lower than the value obtained in the above embodiment.

2169-5304-PFl (Nl) .ptc Page 38 569656

5. Description of the invention (33) The result of the anti-migration test is that the time required to generate a leakage current is about 35 hours. As for the high-temperature circuit peeling prevention ability, only the sample for the anti-migration test was exposed to an ambient gas at a temperature of 350 ° C for 20 seconds, and peeling of the circuit was observed. 》 Comparative Example 3: After the remaining steps of the first embodiment are completed, no residual metal component removal step and re-closed-loop step are performed. 'The heat treatment is similar to the re-closed-loop step, and the tin-plating treatment is performed as in the fifth embodiment. In the step, a sample for resistance measurement and a sample for anti-migration test are prepared. That is, with the ore tin step as the final step of Comparative Example 1, the metal component of the polyimide resin film surface on the exposed portion after etching is still left. Therefore, the polyimide resin film exposed at the etched position was analyzed by FT-IR, and the ring-opened fluoramine (c = 〇) near 1647c m_1 was absorbed, and the ring-opened fluoramine (N-Η) near 1554cm-1 Absorption, and the absorption of enemy base (C00) seen near 1 37 1 cm-1 has disappeared. However, absorption of the carboxyl group (C00) occurred near 13 16 cm-1. From this result, it can be judged that heating should cause a certain closed-loop phenomenon, but it cannot be completely closed-loop. In addition, the surface of the polyimide resin film exposed after heating was analyzed by X-ray diffraction method and wavelength-dispersed electronic probe microanalysis (EPMA) for the presence or absence of adsorption of metal components. As a result, it was confirmed that the copper component and the tin component of the plating solution remained. Then, resistance measurement and anti-migration test were performed in the same manner as in the embodiment. As a result, the surface resistivity was 1.0 × 10 ohm / □, the volume resistivity was 2 · 3 × 1015 ohm · cm, and the temperature and temperature were constant (85 ° C / 85% RH / 50 hours).

2169-5304-PFl (Nl) .ptc Page 39 569656 ----- Case No. __Che Yueyue __ Amendment ___ 5. When the invention description (34)) the surface resistivity after 3. Oxl 014 ohm / □, the volume resistivity is 8 · 9 X1 014 ohm · cm, which is lower than the value obtained in the above embodiment. As a result of the anti-migration test, the time required to generate a leakage current was about 4,000 hours. As for the NanWen circuit peeling prevention ability, only the sample for the anti-migration test was exposed to an ambient gas at a temperature of 350 ° C for 20 seconds, and the peeling of the circuit was observed. Comparing the first embodiment to the third embodiment described above, and comparative examples 1 and 2 and comparative examples 2, it can be seen that the flexible printed wiring board obtained by the manufacturing method of the embodiment exhibits a much higher flexibility than the comparative example. Resistance to migration of flexible printed wiring boards. Further, comparing the fourth embodiment and the fifth embodiment with Comparative Example 3, it can be seen that even if a plating step is provided, it exhibits higher anti-migration properties than a conventional non-closed-loop processor '. From the above, ① remove the residual metal components from the surface of the polyimide resin and perform a closed-loop treatment to improve the surface resistance and volume resistance; ② no metal components remain on the surface of the polyimide resin film exposed between the circuits, these two elements The improvement in anti-migration is of great help. It is also known that the ability to prevent peeling of high-temperature circuits varies greatly depending on the presence or absence of preheating. ADVANTAGEOUS EFFECTS OF THE INVENTION By using the method for manufacturing a flexible printed wiring board according to the present invention, even if a flexible printed wiring board is manufactured by using a double-layer substrate obtained by a direct metallization method, a circuit pattern is formed by engraving, and the resin exposed on the portion from which copper has been removed …, The metal component remains, and the substrate resin is inevitable due to the etching solution. Once the ring-opening process of the necessary steps of the direct metallization method is opened, it is ^ 569656 _ Case No. 91132587_ year month day amendment Description of the invention (35) Lipid surface can also be closed loop. As a result, the surface resistance and volume resistivity become larger, and the anti-migration property is improved. In addition, since the pre-heating step is provided in the process of manufacturing the flexible printed circuit board, the ability to prevent high-temperature circuit peeling can be greatly improved. Therefore, the reliability of the quality of printed circuit board products has been greatly improved.

2169-5304-PFl (Nl) .ptc Page 41 569656 Case No. 91132587 Amend the diagram briefly to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the embodiments are given in conjunction with the drawings Detailed description is as follows: FIG. 1 is a flowchart showing a method for manufacturing a flexible printed wiring board according to the present invention. FIG. 2 is a flowchart showing a method of manufacturing a flexible printed wiring board by a direct metallization method according to an embodiment of the present invention. FIG. 3 is a flowchart showing a method of manufacturing a flexible printed wiring board by a direct metallization method according to another embodiment of the present invention. FIG. 4 is a schematic view showing a flexible printed wiring board according to the present invention.

Illustration. DESCRIPTION OF SYMBOLS 41 copper thin film layer; 4 5 polyimide resin film.

Claims (1)

569656 1 · A kind of flexible printed circuit board made from copper and copper, which is based on the method of using a flexible copper surface layer using a polyurethane film as a substrate, I & ^ 1㈢ The flexible printed circuit board is manufactured by pressing, and the characteristics of the flexible printed circuit board include the following steps: (a) the step of engraving the flexible copper laminate, forming a circuit corrosion of the circuit (b), and etching the circuit The remaining metal component of the metal salt of carboxylic acid is a component removing step between the gaps of the circuit formed on the completed substrate, and is acid-washed to remove the exposed polyimide resin film surface to convert it to a carboxyl group. Residual gold . After the residual metal component removal step is completed, the substrate is heat-treated under a warm gas atmosphere at a temperature of 0 minutes to 80 minutes to perform a closed-loop treatment on the surface of the polyimide resin film exposed on the gaps of the circuits formed on the substrate. Then close the bad steps. 2 · —A method for manufacturing a flexible printed wiring board including the direct metallization method of the following steps ① to ⑤, which is performed by: ① Polyimide resin film is alkali-treated as a ring-opening treatment of the imine ring, in The ring-opening step of forming a carboxyl group on the surface, ③ contacting the neutralized carboxyl group with a metal ion-containing solution to adsorb metal components, and a metal ion adsorption step of forming a carboxylic acid metal salt on the surface of the polyimide resin film, ④ the carboxyl group formed on the surface of the polyimide resin film A metal thin film forming step of reducing an acid metal salt to form a metal thin film on the surface of a polyimide resin film, Page 43 569656 ⑤ On the circuit film of the copper layer of gold formed on the surface of the polyimide resin film and used to form a circuit through electrochemical methods, a conductor layer and a polyimide resin layer constituting layer formed by a copper layer are formed. The method for manufacturing a flexible printed circuit board by a press plate is characterized by describing each step (a) to (c), which is inferior to that. It includes the following (a) step of electrically engraving the circuit formed by the flexible copper laminate, ~ Electro-lattice etching (b) The substrate after the circuit is etched is treated with acid to remove the residual metal components from the anti-acid metal salt on the surface of the polyimide resin film exposed between the gaps of the lines formed on the substrate. Residual metal component removal step converted to carboxyl group, (c) The substrate K18 (rcs20 (° C) ° C) is subjected to heat treatment in a high temperature gas environment for 10 minutes to 80 minutes after the residual metal component removal step, so as to be exposed on the substrate. The closed circuit of the circuit formed on the surface of the polyimide resin film is then closed again. 3. A method of manufacturing a flexible printed wiring board including a direct metallization method of the following steps ① to ⑤, which is through, ① gather The imine resin film is treated with alkali as the ring-opening treatment of the imine ring. The ring-opening step of forming a carboxyl group on the surface, ② the ring-opened carboxyl group is neutralized with an acid solution and the neutralization step, ③ the neutralized carboxyl group and the A metal ion adsorption step of contacting a solution of metal ions to adsorb metal components, forming a metal salt of a carboxylic acid on the surface of a polyimide resin film, 2169-5304-PFl (Nl) .ptc Page 44 569656 --- Case No. 911325R7 ^ __ Year Month and Amendment VI. Application for Patent ④ Reduce the carboxylic acid metal salt formed on the surface of polyimide resin film to The metal thin film forming step of forming a metal thin film on the surface of the polyimide resin film, ⑤ forming copper for the circuit on the metal thin film formed on the surface of the polyimide resin film to form a copper layer of a circuit formed by an electrochemical method. In the step of forming a layer, the method for manufacturing a flexible printed wiring board with a double-layer flexible copper surface laminate composed of a conductor layer and a polyimide resin layer is known, and includes the following (a) to (d) step, (a) the pre-heating pre-heating step of the flexible copper-faced laminate obtained by the direct metallization method, (b) the circuit etching step of forming a circuit circuit of the 14-layer pre-heated double-layer flexible copper-faced laminate, (c) The substrate on which the circuit has been etched is treated with pickling to remove exposed metal components on the surface of the polyimide resin film between the gaps of the lines formed on the substrate to convert it to carboxyl groups. Residual metal component removal step, the substrate after the residual metal component removal step is at 180 ° C to 200 = Heat treatment in a gas environment for 10 to 80 minutes to close the surface of the polyimide resin film exposed on the gap between the base fa: ί ί circuit as a closed-loop treatment 4. A method as described in any of claims 1 to 3 A tortuous H-method as a basic printed circuit board with plating 2169-5304-PFl (Nl) .ptc Page 45 569656 _Case No. 91132587_ Year Month Amendment_ VI. Patent Application Scope It is provided with a plating treatment step at any stage after the circuit etching step. 5. A flexible printed wiring board obtained by the method for manufacturing a flexible printed wiring board according to any one of claims 1 to 4 of the scope of patent application. 2169-5304-PFl (Nl) .ptc Announcement on page 46 of this year ^ Month 屮 Amendment before the application date: 1L Ι / Λ. Classification, application number: 91132587 ^ ^ V \ f \ \ (the above reasons Note from this Office) Invention patent specification π %% Printed circuit board (the polymerization method and the flexible printed circuit obtained from the manufacturing method are only in Chinese. A FLEXIBLE PRATED WIRING BOARD, AND A METHOD PRINTED ffIRING B0ARD OBTAINED THROUGH THE MANUFACTURING Name (Chinese) 1. Yokota Toshiko-2. Matsumi Hideaki 3. Tusui! ^ Name (English) 1. Y0K0TA, Toshiko 2. MATSUSHIMA, Hideaki 3. DOBASHI, Makoto Inventors (4 people) Nationality (Chinese and English) 1. Japan JP 2. Japan JP 3. Japan JP Domicile (Chinese) HL 士 HL 私 ϋ ϋ 士 没 不 玉 赞 Uhara, Iwo Mitsui Metals & Mining Co., Ltd. Jade shame on the tail ★ Employment City 丨 333-2 Mitsui Metals Co., Ltd. ^ In the company's general research institute 3. The country I333-2 Mitsui Metals Mining Co., Ltd., Harami, Saitama, Japan (English) Person) name or Yin name _ ( (Text) _ Name or name (English) " Τ1Ί, Chinese and English) 1. Mitsui Mining & Mining Co., Ltd. 1. Mitsui Mining & Smelting Co., Ltd. In a camp No. 1, 1-chome, Osaki, Shinagawa-ku, Tokyo, Japan (this address is the same as the person who was previously responsible)