TW200402481A - Method of forming a dielectric filler-contained polyimide film on a surface of a metallic material, method of manufacturing a copper-clad laminate for a capacitor layer formation, and copper clad laminate obtained by the manufacturing method - Google Patents

Abstract

The present invention provides a method of forming a dielectric filler-contained dielectric layer having a superior uniformity of film thickness by employing a dielectric filler-contained polyimide electrodeposition solution. The present invention discloses a method of forming a dielectric filler-contained polyimide film on a surface of a metallic material. The method is characterized by use of dielectric powder as a dielectric filler, which powder has: an average particle size DIA, obtained through image analysis, of 0.05-1.0 μ m; weight cumulative particle size D50, measured with a laser diffraction scattering particle size distribution test, of 0.1-2.0 μ m; cohesion of 4.5 or lower represented by D50/DIA; a substantial sphere; and a perovskite structure.

Description

200402481 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a method for forming a polyimide coating with a dielectric filler on the surface of a metal material such as copper, and a capacitor layer for a printed wiring board. Manufacturing method of copper foil laminated board and copper foil laminated board manufactured by the method By omitting the possibility of using the outer layer, the printed wiring can be made of copper, a copper foil layer, a copper laminated layer, a capacitor electrode, a dielectric layer, and then an electrical capacity. As a vacuum medium ① Make the capacitor thin. ③ It is made in a printed wiring board, especially a multilayer printed wiring board in the same way as forming a circuit shape using a copper foil laminated board, and it is used as a built-in capacitor layer to use a general multilayer printed wiring board that gradually changes. The inner layer part forms a capacitor structure, and capacitors can be arranged on the surface. The miniaturization and high density of the outer layer circuit reduce the surface-mounted components, and it becomes easy to manufacture circuit boards including micro-fine pitch. 2 The laminated capacitor structure uses two capacitors formed by the so-called two-sided dielectric layer :: == two interlayer dielectric structures to form the desired shape state at the target position to the two-sided electric electrodes. The work is a basic quality, and the capacitance is as much as possible: the capacity (C) of the capacity is calculated from C = " 〇 (A: includes): rate. Therefore, 'to increase the capacitance d = area (a). ② Make the dielectric layer: (d) The specific permittivity of the dielectric layer (0 becomes larger. Use this

200402481 V. Description of Invention (2) Any one is acceptable. However, with regard to the trend of thinner, thinner, and thinner devices, it is almost impossible to be thin in a certain printed area. As long as the dielectric layer covers the bone material, the conventional dielectric engraving is used to make the capacitor electrode because it includes the bone surface. At this time, the layer will have a dielectric property of ③ due to the remaining time. Surface area (A). From the recent electrons, it is possible to adopt a wide angle for the printed wiring board and the wiring board area. Regarding (2), the thickness of the dielectric material layer including a glass complex material represented by a prepreg is limited in thickness. The quality layer and only the skeleton material are omitted, & the defect that the liquid pressure of the copper pig layer is removed after a while to be destroyed is bad ^ < The electric machine with the specific permittivity (ε) increased has the same The capacitance of the capacitor (d) changes to the other side of the fabric and other bones in the case of eroding the dielectric. As a result, the structure of the dielectric layer is necessary, and the thickness of the entire layer of the skeleton material becomes thinner, and the dispersion of the tree containing the dielectric filler increases. In order to obtain a thin layer by weaving a skeletal material such as glass fabric, the dielectric is temporarily used in the constituent material of the dielectric layer, and the grease is used to obtain the electrical capacity of the capacitor.

However, as the electrical capacity of the built-in capacitor becomes larger in the dielectric layer, it is waiting to establish a thin thickness and excellent thickness accuracy, and it includes spraying of the last name engraving liquid that is not lower than the last name engraving. Sinking: and a method for manufacturing a copper-clad laminated board for forming a capacitor layer. | Activity To meet such conditions, we have reviewed, for example, Japanese Patent Laid-Open No. 20 0 1 _1 5883 for the production of steel laminates for the formation of capacitor layers. Have

200402481 V. Description of the invention (3) η electric filler containing polyimide electric ore liquid with dielectric filler, a dielectric layer containing a dielectric filler in polyimide resin is formed by electric ore coating method In this dielectric layer, the method of copper foil is more suitable. However, the use of a polyimide plating solution directly on the surface of copper to form a polyimide coating by the electroplating coating method is more advantageous than the coating method in that the film thickness can be reduced, but In reality, it is very difficult, and the son-in-law of the polyimide bond itself has difficulties. In addition, it is very difficult to uniformly disperse the particles of the dielectric filler powder in the polyfluoride imide bonding liquid in the electroplated polyimide coating film. Mass production has not been achieved on the job. From the above, 'the copper foil laminated board used for forming the capacitor layer " electrical shell of the copper shell " uses a polyimide plating solution containing a dielectric filler to obtain a medium having excellent thickness formation accuracy. Electromass technology. SUMMARY OF THE INVENTION Therefore, as a result of careful research, the inventors of the two cases have adopted a method for forming a polyimide coating film containing a dielectric filler on the surface of a metal material such as copper, and a printed wiring board, as shown below. It is conceivable to provide a copper-percent laminated board for forming a capacitor layer, and it is conceivable to provide a copper-clad laminated board which has not been available in the past. In the scope of the patent application, "A method for forming an imine coating film on the surface of a metal material containing a dielectric filler, which is used in a polyfluorene imine plating solution to contain the dielectric filler." Filler polyimide electrical bond liquid W electric ore coating method to form polyimide film containing dielectric filler

Page 9 200402481

On the surface of a metal material, it is characterized in that the dielectric filler has an average particle diameter D1A of 0 · 05 ~ 1 · 〇, and the weight accumulation is obtained by a laser refraction scattered particle size distribution measurement method. The particle size I is 〇 · 2. 2.0, and the value of the degree of agglomeration indicated by the cumulative weight particle size 1 and the average particle size Du obtained by image analysis! 5 () / DIA is 4.5. The following U-shaped 50 having a substantially spherical shape includes a dielectric powder of perovskite structure. ”T S & imine grease coating method is a uniform film formation on the metal with defects such as bubbles, and uniform film formation even for complex shapes. In the past, polyimide was hardly soluble in solvents. Therefore, in the state of polyimide acid of its precursor, electroplating coating was performed. The polyimide was formed by dehydration and cyclization by high-temperature heating. Amine film. However, the 'polyfluorenic acid is easily decomposed and unstable. Therefore, in the present invention, it is preferred to use polyimide having a composition for the anion ion bond coating of a polyblock polyimide which is soluble in a pendant carboxyl group-containing solvent. Therefore, this type of free-flowing imine electric ore liquid can be dispatched in the market, and the commercially available polyimide plating liquid also includes very good performance. In the case of using a far polyfluorene imine battery, and a polyimide coating is to be formed on a metal, the plating properties are different due to the type of metal. Therefore, it is necessary to prepare a polyimide power ore liquid according to the type of metal forming the polyimide-plated holmium coating. In particular, in the case where a polyimide coating is to be formed on a copper material as a metal material by electroplating, if the polyimide colloidal particles in the polyimide plating solution have a small particle diameter, In this case, it is considered that there is no tendency to form a uniform and defect-free good plating film. Therefore, depending on the type of the electroplated polyfluorene imide, it is considered that the amount of the solvent is increased to obtain the glue.

2169-5720-PF (Nl): Ahdiub.Ptd Page 10 200402481 V. Description of the invention (5) Miniaturization of bulk particles. However, the diameter of the colloidal particles in the polyimide plating solution is also related to the thickness of the polyimide coating film formed, so in the end, the purpose is to maintain the thickness of the polyimide coating and the electroplatability. It is balanced and modulated in the appropriate field. In the case of the present invention, it is considered that the dispersion shape of the polyimide electrolyte solution should be determined in consideration of the dispersibility of the dielectric filler in which the polyimide electrolyte is dispersed and mixed. However, from the current technical level, there is a limit to the types of polyimide-containing polyimide-containing electroplating solutions that can form uniform and non-defective good polyimide coatings on metal materials. There is also a limit to the modulation range of this composition. However, "the inventors of the present case" #by improving the state of the dielectric filler "ensured good dispersibility of the dielectric filler powder in the polyimide power ore liquid. The powder of the dielectric filler used in the present invention is made of eight: a polyimide film containing a rhenium dielectric filler, and finally: ^ the function of the dielectric 2 dielectric layer, processed into a capacitor shape When; make; Β TT used. In this dielectric filler, the dielectric of the composite oxide of MUZ state commonly known as PLZT), SrHTa2Q9 (commonly known as ^ (Pe, S, lte) structure: ... 0 051. Powder characteristics of this filler First of all, the particle size must be in the state of 0: 05 ~ U⑽. The particle size mentioned here must form a certain degree of secondary agglutination state. The accuracy is poor, so there is no 1 Λ. Xiao Department of Scanning Electron Display, page 11 2169-5720-mM); .Ahddub.ptd 200402481 V. Description of the invention (6) Observation by micro-mirror (SEM), image analysis of the SEM image The average particle size. In this specification, the particle diameter at this time is represented by Dia. In addition, the analysis of the shirt image of the ancestor of the dielectric filler observed at Benguer = L-type electron microscope (SEM) uses Asahi Engineering Co., Ltd. IP-1 000PC, and the minimum roundness is 10, more 20 The average particle diameter D] A obtained by analyzing the clothes. Ding Yuanzuzu can further obtain: the cumulative particle diameter D50 of the laser refraction disorder particle size weight is 0.002 2.0, and the average particle diameter obtained by image analysis is used to accumulate the particles in D ^ "5. A dielectric powder with a perovskite structure represented by a slightly spherical shape with a value of and below 4.5. The diameter of diacalcite is measured by laser refraction random particle size distribution, which is a 50% particle size accumulated by the weight accumulation of the particles called by the laser diffraction random type Hado-82. Then in the particle size distribution of the weight-filling powder obtained by the Yifa method, the smaller the value of the fine ^ D5G is, the smaller the value of 'D5G' in the invention of dielectric filling, and the value obtained is 0 ·; 1 ~ 2 The ratio of η々 high. When the value of this Dm is less than 0. 1 # ^, the total particle size of the electric filler with a cumulative total particle size of P / P ′ is significantly agglomerated, and which kind of manufacturing method is used to determine the degree of agglutination. On the other hand, if it is impossible to satisfy the following // m, it is necessary for the purpose of the present invention if the value of the cumulative particle size is greater than 0.5. It is impossible to form a built-in capacitor layer for the built-in electricity in the printed wiring board. That is, as a thickness of 10 / ζιη to 25 // m in general, the dielectric layer of the self-laminated laminate is charged, and the upper limit is 2 · 0 // m. To uniformly disperse the dielectric fill

2169-5720-PF (Nl); Ahddub.ptc 苐 page 200200402481 V. Description of the invention (7) In the present invention, the measurement of the weight-accumulating particle diameter D5G is a method of mixing and dispersing the dielectric filler powder in methyl ethyl ketone, This solution was put into a circulator of a laser diffraction random particle size distribution measuring device Micro Trac HRA 9320-XI 00 (manufactured by Nikkiso Co., Ltd.) for measurement. Here, the term "agglutination" is used for the following reasons. That is, the value of the cumulative weighted particle diameter I obtained by using the laser diffraction random particle size distribution measurement method is not considered to be one that directly observes each diameter. Almost all the powders that make up the dielectric powder 疋 each particle is completely separated, so-called monodisperse powder, and a plurality of powder particles are aggregated to become an aggregated state. Laser diffraction random particle size distribution measurement method can be said to use agglomerated powder particles as a particle (aggregated powder particles) to capture the 'different weight cumulative particle size. On the other hand, a scanning electron microscope is used to obtain the average particle diameter d of the observed image of the mediator, and it is directly obtained by the SEM observation image. Therefore, a can be reliably captured. — 次 = 子 ， Conversely, it is impossible to reflect the agglomeration of powder particles. From the above, the inventors of this case use two = particle size as the cumulative particle size of the cloth measurement method ^ and by analysis ^: i ： The average particle diameter DIA 'takes the value calculated by D “Dia as the condensate extreme :: The payer is in a batch of copper powder, assuming that the value of ^ and ~ can be measured with the same accuracy. It can be compared with the measured value of D5. The value is the value of Dia. The second one is that the state of the two sets is centered, and the same result can be obtained.) See the measurement of K at this time. The powder is almost completely free of agglomeration.

200402481 V. Description of the invention (8) m 'will gradually approach the value of Dia indefinitely. The degree of agglomeration is at a stage where the degree of agglomeration becomes 1. It can be said that there is no powder at all. * 篇 ι /: of: Disperse powder. However, in reality, the degree of doubt shows that there is no husband ... Xi situation: in the case of the true ball considered on the theory, there will be no: but in reality, because the powder is not a true ball, it can be obtained Agglutination value less than 1. In the present invention, the degree of agglomeration of the powder of the dielectric filler is more than 4.5 and the degree of Α Ϊ Ϊ is more than 4.5, and then the powder of the dielectric filler is coagulated. : Get W 'and mix it with the above polyfluorene imine plating solution-mixing = manufacturing method for manufacturing dielectric filler powder, even if fermented salt is used to account for "", synthesis method, oxalate method, etc. A manufacturing method may cause a certain agglomeration state which can be avoided, so the above-mentioned degree of agglomeration of the dielectric filler powder may be generated. Especially in the case of the wet method of water 1, it is easy to produce an agglomeration state. The tendency of formation. ^ Separation of the powder in this agglomerated state into one grain by one: dehydration ^ treatment ', so that the aggregation state of the dielectric filler can be in the range of the above-mentioned / pitching degree. ^ A If the purpose is to perform the granulation operation, as a mobile phone for granulation, ^ ^ ^ 用 energy ball milling, high-speed conductor conflict type air-flow pulverization (c '4 + type pulper, standard grinder, media mixing Type grinder, high-quality materials' However, in order to ensure the mixing and dispersibility of the A-imine plating solution described in the dielectric filling, the following should be considered ... 3 Reduced viscosity.

200402481 V. Description of the invention (9) In order to obtain a low concentration of agglomerates containing dielectric fillers, the pursuit is to reduce the viscosity of the dielectric fillers to the powder ^ main electrical grade = = to make it possible to disintegrate, but also not It is a degranulation method in which the specific surface area is increased when :: ^ ^ shells are used during granulation. Based on this knowledge, the inventor's existing two methods are effective. The two results of these two methods suppress the contact between the particles of the dielectric filler powder and the inner wall of the device: the media and other parts to a minimum. The conflict between the two "; =" can fully disintegrate. The point of the method. That is, the contact between the inner wall of the device, the mixing blade, and the pulverizing medium will cause scratches and marks on the surface of the powder, making the surface rough: the degree of sharpness is deteriorated. Then, by To fully impact the powder particles with each other, and to disintegrate the powder particles in a 2-ball aggregation state, you can use the method between the powder particles :: to smooth the surface of the powder particles. One of the impacts between t is The powder of the dielectric filler in the agglomerated state is degranulated by a private grinding method. Here ... the jet grinding method "of the research institute, the South-speed airflow, and the dielectric filler powder is added to this airflow, In the air flow, the powders are caused to collide with each other to perform the granulation operation. Quickly, the dielectric filler powder in the agglomerated state is divided into a suspension in a solvent with stoichiometry, and the granulation process is performed by using a fluid powder that uses =,:, and no fluid. By using the "Li Erli's fluid grinding powder" mentioned here, the suspension can be made as high as drawing a circular orbit. Solvent = foreign, hit, to perform the granulation operation. By this, by mashing the granulation operations, the surname and the mutual name shall be changed. Page 15 ~ 169-5720-Ff (N :); Ahddub.Ptd 200402481

The liquid was washed, filtered, and dried to obtain the dielectric filler powder after the granulation operation. By the method described above, adjustment of the agglomeration degree and smoothing of the powder surface of the dielectric filler powder can be obtained. The polyimide plating solution described above is mixed with a dielectric filler, and is a polyimide plating solution containing a dielectric filler. At this time, the blending ratio of the polyfluorine imide electric ore liquid and the dielectric filler is as described in the scope of the patent application. The content of the dielectric filler in the polyfluorine imide plating solution containing the dielectric filler is 50 g. / L ~ 350g / L is preferred.

When the content of the dielectric filler is less than 50 g / L, the dielectric constant when the capacitor is formed is too low to meet the specific permittivity of 20 currently required on the market. If the content of the dielectric filler is If it exceeds 35 g / L, the content of the polyimide resin in the polyimide coating film containing the dielectric filler is too low, and the adhesion of the copper foil posted thereon becomes poor, and It becomes difficult to form a capacitor. Then, as the dielectric filler, at the present stage, if the manufacturing accuracy of the particles is taken into consideration, it is preferable to use barium titanate among the compound oxides including a perovskite structure. Among the dielectric fillers at this time, either pre-fired barium titanate or non-pre-fired barium titanate can be used. In the case of obtaining a high dielectric constant, it is better to use a burn-in, but it may be selected according to the design quality of the capacitor. The dielectric filler of barium titanate is preferably a crystal structure including cubic crystals. In the crystal structure including barium titanate, there are cubic crystals and tetragonal crystals, and the dielectric filler including the cubic crystal barium titanate is more suitable than the dielectric filler including the cubic crystal barium titanate. Situation, eventually

2169-5720-PF (Nl); Ahddub.ptd page 16 200402481 V. Description of the invention (11) The dielectric constant of the obtained dielectric layer is more stable. Therefore, it can be said that at least barium titanate powder having a crystalline structure of cubic and tetragonal crystals must be used. Using the polyimide plating solution containing a dielectric filler as described above, a polyimide coating film containing a dielectric filler is formed on the surface of a copper material by electroplating, even on the surface of a copper material. In the polyfluorene imide film containing the dielectric filler, the dielectric filler is not unevenly dispersed, and the polyfluorene imide film containing the dielectric filler itself also includes a smooth surface and a uniform film thickness. Become something without defects. Furthermore, if it is claimed that polyimide is used in polyimide electric charge, polyimide electropolyimide coating is 0. 05 ~ 1. 0 // m in nickel or metal. The weight accumulation particle size D5G and the value of the agglomerated degree of permeation (perovski te) #dielectric filler are formed on the surface of the containing material to make the dielectric content better.

According to the scope of the patent, by using "a method of forming a dielectric filler layer on the surface of a metal layer, a dielectric ballast containing a dielectric filler is contained in a letter plating solution, and an electroplating coating method is used. Formed on the surface of a metal material containing a dielectric filler, which is characterized in that: a layer is formed on a copper material; and on the thin metal layer, an average particle size is used. .〇㈣ 'Also, use weight to accrue

Μ 4 β Α The film thickness of the polyimide coating on the metal material filler by electroplating is included in a slightly spherical shape including titanium-calcium-dielectric powder as the dielectric recording liquid containing the dielectric filler; =

219 200402481 V. Description of the invention (12) The polymer containing the dielectric filler and the polymer containing the dielectric filler are formed in advance on the surface of the metal material, and then the point containing the dielectric filler is formed. Because of the same, To avoid the formation of repeated thin layers. A very thin polyimide coating is placed on the metal. The formation of the metal layer on the surface of this specification can be performed by various methods. By providing this thin metal layer, the copper material surface of the polyimide coating film is formed. In the present invention, the possibility of occurrence of defects in the final imine film is increased. By using the above-mentioned method for forming a polyimide coating on an amine coating, the place where the dielectric filler is not on the working dimension plane causes the polyimide containing the dielectric filler and a uniform film thickness, Adhesiveness on the polyfluorene imide film forming the capacitor electric filler, which is the method for forming a fluorene imide film without forming a dielectric layer on the surface of the metal-deficient material. The difference from the method for forming the amine plating film described above is nickel. Or polyimide coating in the form of a thin metal layer of cobalt. Regarding other records, only the difference in gold is used when the electric bell coating method is used. Nickel or a metal with excellent electrical bondability is called a thin metal layer. For metal materials, electrolytic methods, sputtering methods, etc. can be used to form extremely good polymers, even if it is said to be difficult to surface with the electroplating coating method. The polymer containing the dielectric filler has extremely low polymer properties. The uniformity of the film thickness which is much larger than that of the metal material containing the dielectric filler will be biased and the uniformity of the component I will be less, which can reduce the difference in electrical rate from =; 丨. Then, in order to maintain the smooth surface of the moon, it is easy to obtain a uniform material attached to the electrode material containing the dielectric, steel vg, and the like. In this way, by using the free control for the '' as the dielectric

/ 200402481 V. Description of the invention (13): The thickness of the polyimide coating with dielectric filler, the results include excellent electrical appliances _ ^, li ′ can obtain products including high-quality capacitors. '' As mentioned above, the idea of a polycondensate containing a dielectric filler on a metal material: a method of forming technology can be applied to a method for manufacturing a printed wiring board . That is, in the application for a patent, the following is: "_ Kind of copper deposition layer for the formation of a capacitor layer for a printed wiring board composed of a layer having an i-th copper box / polyfiller containing a dielectric filler, and a layer of copper. The manufacturing method of the plate is characterized in that: the polyimide power mineral liquid is used; and the average particle diameter as the dielectric filler is 0 to 0 5 1. 0 ym, and the scattered particle size distribution is by laser refraction The measurement method is used to calculate the weight of the accumulated grains. The value is 0.2. __, and the weight accumulation grains I and the average particle size obtained by image analysis are used to indicate the value of agglomeration. Polyimide electroplating solution containing a dielectric filler obtained by mixing a dielectric powder including perovskite structure with a slightly spherical shape below 4.5, and forming a dielectric containing Copper f with polyimide coating containing dielectric filler and polyimide film formed on one side surface of the second copper film; Polyimide-coated copper with polyimide coating containing dielectric filler It is described that the copper thin polyimide electrical film surface with polyimide film can be bonded and overlapped. "The flow of this manufacturing method is shown in Figure 1 and the surface is 0. In order to" make the description of the manufacturing method easy to understand, In this description, the figure is a very model and is shown as a cross-section. It is not a faithful response, especially the value of the thing implemented in thickness and size. The basic idea is that because of the above for metal materials:

2169-5720-order (N1); Ahddub.ptd

200402481 V. Description of Invention (14) The method for forming polyimide coatings containing dielectric fillers is the same, so only the manufacturing sequence of copper foil laminates will be explained. Referring to FIG. 1, a description will be given of a manufacturing method in which a polyimide coating film 2 containing a dielectric filler is formed on the surface of the first copper film CF1 to form a polyimide coating film containing a dielectric filler. Of copper foil 3. At this time, the polyimide plating film containing the dielectric filler is used to form the polyimide plating film containing the dielectric filler. The polyimide plating solution containing the dielectric filler is added to the polyimide plating solution, and the average value as the dielectric filler is added. The particle diameter DIA is 0 · 〇5 ~ 1 · 0 # m, and the weight-accumulated particle diameter ι is determined by laser refraction scattering particle size distribution measurement method, and the weight accumulation is used. The particle size 'and the average particle size D1A obtained by image analysis / the value of the degree of agglomeration indicated by DIA is less than 4.5, and it is a spherical shape of a dielectric powder including a titanium perovskite structure. Evenly mixed. Then, 'using this polyimide electroplating solution containing a dielectric filler, a polyimide bond film with a dielectric filler is formed by a galvanic coating method, and a polymer with a dielectric filler is attached.醯 Imine coated copper foil 3. On the other hand, on the single-sided surface of the second steel foil CF2, in the end, a 1 to 3 // m thick polyimide film 4 is left, taking into account the solvent removal and resin that occur during drying and pressing. Flow, first make a copper foil 5 with a polyimide film 2 to 3 times the intended thickness. At this time, on one side of the second copper foil CF2, a polyimide film without a dielectric filler is formed by electroplating to form a polyimide film having a thickness of 2 to 3 times the final thickness. 4. This polyimide film 4 includes a function of adhesion when it is bonded to a polyimide coating film 2 containing a dielectric filler as described below. then,

2169-5720-PF (Nl); Ahddub.ptd Page 20,200,402,481 V. Description of the invention (15) Here, 'when the final polyimide film 4 after the stamping process is less than 1 // m' is fully covered It is difficult to include the uneven surface of the copper foil. If the polyimide film 4 is 3 # m or more, the polyimide film 4 itself does not contain a dielectric filler. The dielectric constant of the stratum is significantly low. As mentioned above, in order to obtain the obtained copper foil 3 with a polyimide film containing a dielectric filler and the copper foil 5 with a polyimide film, a polyimide with a dielectric filler is provided. Coated copper foil 3, polyimide film 2 'with dielectric filler, and polyimide of copper foil 5 with polyimide film

The film 4 is bonded together so as to face each other, and by overlaying the layers, a print including the structure of the first copper 羯 CF1 / polyimide dielectric layer containing a dielectric filler 6 / the second copper foil CF2 can be obtained. Copper foil laminated board for forming capacitor layer for wiring board. ^-In addition, in the scope of other patent applications, it is "a capacitor layer of a printed wiring board consisting of a first copper foil / polyimide dielectric layer containing a dielectric filler / a second copper foil layer" The manufacturing method of a copper foil laminated board for forming "is characterized in that: on the surface of the first copper foil, a metal thin layer of nickel or cobalt is formed on the surface of the 4 metal thin layer, and polyimide is mixed, The average particle size of the plating solution and the dielectric filler is 0 · 〇5 ～ 丨 .〇 #

The cumulative weighted particle diameter was determined by the laser refraction scattered particle size distribution measurement method, which was 0 · 2.0, and the cumulative weighted particle diameter 'and the average particle diameter obtained by image analysis were used. Dia < The value of agglutination under 5 U is a slightly spherical shape including a perovskite (per〇vski Shiki structured dielectric powder) containing polyimide containing a dielectric filler plating

200402481 V. Description of the invention (16) liquid, using electroplating to form a polyimide film containing a dielectric filler, a copper foil with a polyimide coating film containing a dielectric filler; and 2 The polyimide film formed on the single-sided surface of the copper film is such that the polyimide-plated film surface of the copper foil with a dielectric filler-containing polyimide coating Copper thin polyimide electrical film surfaces with polyimide film can be bonded and stacked. The flow of this manufacturing method is shown in the pattern of Figure 2. The manufacturing method of the copper foil laminated board for forming the capacitor layer of the printed wiring board is basically the same as the method of manufacturing the copper foil laminated board for forming the capacitor layer of the printed wiring board previously described, but differs only in the following points. . In the case of the first copper foil CF1, a thin metal layer s is formed on the surface of the first copper foil CF1 before the polyimide plating film 2 containing a dielectric filler is formed. Then, similarly, in the case of the second steel foil CF2, a thin metal layer is formed on the surface of the second copper foil CF2 before the polyimide film 4 is formed. The method for forming the thin metal layer S is the same as that described above for the polyimide coating film containing a dielectric filler on a metal material. To avoid repetitive loading, the description is omitted here. ° The manufacturing method used above is the bonding surface of the first copper foil CF1 and the second copper box CF2, which is the surface used when bonding to the dielectric layer 6. In order to achieve the effect of & The dielectric layer 6 includes irregularities. In the picture &, a person with fine copper particles attached is described. The copper used to form the capacitor layer: The copper foil used in the "Laugh" layer, in order to maintain a uniform thickness of the dielectric layer, it is preferred that the roughened surface of the foil be as flat as possible. Therefore, the use of copper outline (very low pr0fiie (VLp) copper knots, rolled steel boxes, etc.

200402481 V. Description of Invention (17) In addition, as shown in the drawing, the copper foils of the amine-plated film are laminated and punched, and the thickness of the copper foils is also shown to produce a material-containing layer. In addition, when the filler is highly dispersed and elastic, the dielectric filler F has a wide range of black spots during spraying. With two pieces of the above-mentioned attached dielectrics, the individual dielectrics are filled, and Xingya can manufacture copper pig laminated boards. Autumn :: The manufacturing method of private coated plate, can :: 的; :: Use the thickness of the above _ ^ ^ Ren ^ Ren Si as a uniform with "quote-bei" electric layer 'and can form extremely thin Dielectric t Ming * The dielectric layer of the steel box laminated board is a dielectric polyimide coating, the 'dielectric layer of polyimide resin: it will be brittle, ▼ prevent the formation of electricity = spraying the contact engraving liquid The occurrence of the resulting damage. [Embodiment] Hereinafter, the present invention will be described by manufacturing a copper foil laminated board for forming a capacitor layer of a printed wiring board. First implementation mode: In this embodiment mode, according to the manufacturing process shown in Fig. 1, a copper pig laminate 21 for forming a capacitor layer of a printed wiring board is manufactured. In this embodiment mode, a very & very low profile (VLP) copper foil with a nominal thickness of 35 Am is used as the first! Copper network cn. First, before the polyimide coating film 2 containing a dielectric filler is formed on the surface of the first copper foil CF1, pickling is performed in FIG. 1 (stage a) for the purpose of quieting the surface of the first copper foil CF1. Treatment and electrolytic degreasing. The pickling process is performed by immersing the first copper foil C F 1 in a sulfuric acid solution having a concentration of 1 M at a liquid temperature of 25 ° C for one minute, and washing with water. Then, 20 g / L of sodium carbonate and 5 g / L of trisodium phosphate were used to remove r * 1 / ^

2169-5720-PF (ND; .Ahddui) .pid

200402481 V. Description of the invention (18) Aqueous fat solution, whose liquid temperature is 50 ° C, is subjected to degreasing treatment at an electrolytic current of 5A / dm2 for 1 minute, washed with water, and dried. Next, preparation of a polyimide plating solution containing a dielectric filler will be described. In this embodiment, polyimide plating solution is used. 25% by weight of cyclohexanone is added to polyimide plating solution q_ed-22-10 manufactured by the Pyre Technology Institute of Japan. The colloid is used. Particle size adjustment. Then, in this polyimide bonding solution, a barium titanate powder including a dielectric filler F having powder characteristics shown below was mixed and dispersed. The mixing ratio is such that the barium titanate is 80% by weight of the polyfluorene imide solid content of the polyfluorine imine plating solution containing the dielectric filler. Powder characteristics of dielectric filler 0 · 2 5 // m 〇 · 5 # m 2 · 〇 Average particle diameter (Dia) Weight cumulative particle diameter (d5 ()) Degree of aggregation (D5Q / d1a) Use as described above And the production; φ ^ ^ 3 of the clothing 有 polyimide 有 with a dielectric filler on the adhesive surface, the electroform coating method is used to make the film 2. At this time, the electroplating coating strip ° C, the temperature of the copper 羯 CF1 is yang · imine electric ore liquid is 25

The current was electrolyzed for 6 minutes, and the steel plate was used as a cathode, and a direct current of 5 V was applied to the copper foil at the same time. The μimide resin and the dielectric filler F were placed on the imide surface and then washed with water. Then, as the final age, keep in the deer atmosphere for 30 minutes, and further increase: j, li 'by increasing the temperature of the atmosphere at 120 ° C to 180 ° C and keeping it at 30

^ 2 200402481 V. Description of the invention (19) minutes. Thus, as shown in Fig. 1 (a-2), a copper foil 3 with a polyimide plating film containing a dielectric filler is manufactured. On the other hand, the second copper box CF2 uses the same copper pig as the first steel reed CF1 to perform pickling treatment and degreasing treatment at the stage of FIG. 1 (b-1) in the same manner as described above. In order to make the thickness of 2 ~ 3 Am finally, the polyimide plating solution containing no dielectric filler is used to form a polyimide film with a thickness of 10m on the surface of the bonding surface. 4. Then, as the final drying treatment, the temperature was maintained in the same temperature atmosphere as above for 30 minutes, and the temperature was further increased to i 800 ° C, and the temperature was maintained for 30 minutes. Thus, as shown in Fig. 1 (b-2), a copper foil 5 with a polyimide film was manufactured. The copper foil 3 with a polyimide coating containing a dielectric filler and the polyimide coating 2 with a dielectric filler and the copper foil 5 with a polyimide coating obtained as described above As shown in FIG. I (c), the polyimide plating film 4 is opposed to each other, and a copper foil laminated board 1 for a capacitor formation layer of a printed wiring board is manufactured by lamination. The lamination conditions at this time are as follows: the punching is 5 kg / cm2, the punching temperature is initially heated at 2 50 ° C for 30 minutes, and the temperature is raised to 300 ° C and maintained for 30 minutes. Fig. 3 is a cross-section of a copper foil laminated board for forming a capacitor layer of a printed wiring board thus obtained, observed with an electron microscope. At this time, the thickness of the dielectric layer 6 bonded to the polyfluorene-imide coating film 2 and the polyfluorene-imide coating film 4 containing the dielectric filler is 10 // m on average. As shown in FIG. 3, it can be clearly seen that it includes a very uniform thickness. ^ —The entire surface of the first steel pig CF i and the second copper foil CF2 on both sides of the copper foil laminated board 1 manufactured as described above, and a dry film was put on the two sides to form an etching light.

2169-5720-PF (Nl); Ahddub.ptd

Page 25 200402481 V. Description of the Invention (20) ^ Resistive layer. Then, on the both sides of the photoresist layer, the developing capacitor circuit is exposed to form a pattern. After that, while the circuit is being vaporized with a vaporized copper etchant, the etching resist is peeled off to manufacture a capacitor circuit. In this case, the dielectric layer 6 is not damaged due to the spray pressure of the etching solution, and a printed wiring board in a good condition can be obtained. Then, 'the result of measuring the specific permittivity of the dielectric layer 6 constituting the capacitor circuit' showed a very good value ε = 24 · 7, and it was understood that a capacitor having a high electric capacity can be obtained. °

Second embodiment: In the present embodiment, the manufacturing process shown in FIG. 2 is used to manufacture: a copper foil laminated board 1 for forming a capacitor layer of a printed wiring board. In this embodiment mode, as in the first embodiment, a very low profile outer foil (very low power (yLp)) having a nominal thickness of 35 / m is used as the first copper drop CF1. First, the process of pickling and degreasing of the first steel foil CF 1 performed at the stage of Fig. 2 (a-1) is the same as that of the first embodiment. After the degreasing treatment is completed, as shown in Fig. 2 (a -2) A thin metal layer 8 of nickel is provided, and then as shown in FIG. 2 (a-3), on the surface of the i-th copper foil ^^^, a polyimide coating film 2 containing a dielectric filler is formed. , As a steel foil 3 with a polyimide coating containing a dielectric filler. The formation of the polyfluorene-imide coating film 2 containing the dielectric filler after the metal thin layer s is provided at this time is also the same as the first embodiment. -Therefore, only the method for forming the thin metal layer S of nickel will be described. In the present embodiment, the thin metal layer s is formed by using nickel borate containing 240 g / L of nickel sulfate and hexahydrate, 45 g / L of gasified nickel and hexahydrate, and nickel borate.

2169-5720-PF (Nl); Ahddub.ptd Page 26,200402481 V. Description of the invention (21) 特 成 iitffPH5 'Liquid temperature 55 ° C' Current density 2A / dm2 Electrolysis 1 ', buckle, shape A 100 A nickel layer is used as the thin metal layer s. On the other hand, the second steel box CF2 uses the same gfc ^ ^ white as copper 羯, which is the same as ^ f1 copper pi CF1 in Figure 2 (b) above, and then pickled. Λ / Λ drying, forming a metal as shown in Figure 2 (b-2): After that, use the above-mentioned polysaline layer liquid without dielectric filler so that the final thickness can be 2 ~ 3. No. 12 (^ 之 ίproduction) Π = drying treatment, which is carried out by increasing the temperature of the gas to 180 ° C and maintaining it for 30 minutes. In this way, as shown in 2 (b-3), a polyimide film is produced. The steel falls 5, ... by making the above obtained with the dielectric filler Ϊ = polyimide containing dielectric filler film 2 and: The copper foil 5, the gate, and the door 〇, are shown to be opposed to each other and laminated. The laminated conditions at this time are the same as in the first embodiment to avoid repetitive descriptions, and explanations are omitted here. Accumulation of capacitor layers for wiring boards: observation with an optical microscope 'Because the thin metal layer s is not visible, it can be observed in the same state as shown in Figure 3. Therefore: Observe the cross section of the copper-clad laminated board i under a microscope. In this embodiment, the thickness of the water-imide coating 2 and the polyimide film 4 containing a dielectric filler can be understood. 9.5, including very smooth and even- = = layer 6 2169-5720-PF (Nl); .Ahddlib ptd page 27 200402481 V. Description of the invention (22) The copper foil laminated board 1 manufactured as above, both sides The entire surface of the first steel drop CF1 and the second copper foil CF2, and a dry film was put on the two sides to form a thin metal layer. Then, a capacitor circuit of 1 cm X 1 cm was exposed and developed on the photoresist layer on the two sides. 'Form a surname engraved pattern. After that, the circuit is engraved with a vaporized copper surname engraving solution, and the etching resist is peeled off to make a capacitor circuit. At this moment, it will not occur due to the etching solution spray pressure If the dielectric layer 6 is destroyed, a printed wiring board in a good state can be obtained. Then, the result of measuring the specific permittivity of the dielectric layer 6 constituting the capacitor circuit shows a very good value ε = 24 · 7, and understand To obtain capacitors with high electrical capacity.

[Industrial Applicability] By using: coating with dielectric fillers related to the present invention to obtain a thin and uniform dielectric layer containing a dielectric filler as a capacitor layer by using electric ore coating, the capacitor layer can be obtained. The capacitance stability has also increased significantly. Polyimide foil laminates containing a dielectric filler can provide high-quality construction materials. The method is to form a polyimide bell film on the surface of a metal material, a polyimide coating film of a chargeable material, and use this layer to achieve a high dielectric constant and increase the amount of the result. Since there are few defects, the product uses the same thinking technology, and uses the key film 2 as a dielectric layer to produce a copper object as a capacitor layer of a printed wiring board.

200402481 Brief description of drawings Figure 1 is a schematic cross-sectional view showing a manufacturing process of a copper foil laminated board for forming a capacitor layer of a printed wiring board. Fig. 2 is a schematic cross-sectional view showing a manufacturing process of a copper foil laminated board for forming a capacitor layer of a printed wiring board. Fig. 3 is an optical microscope observation image of a copper foil laminated board for forming a capacitor layer of a printed wiring board. [Symbol] CF 1st copper foil; CF2 ~ 2nd copper foil; 4 ~ polyimide film; S ~ metal thin layer; 5 ~ copper foil with polyimide film; F ~ dielectric filling 2 ~ polyimide coating with dielectric filler; 6 ~ polyimide dielectric layer with dielectric filler; 3 ~ copper with polyimide coating with dielectric filler Foil.

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Claims (1)

200402481 6. Scope of patent application 1. A method for forming a dielectric filler layer with polyfluorene on the surface of a metal layer, and using a dielectric filler containing a dielectric filler in a polyfluorene imine plating solution A polyimide plating solution is formed on the surface of a metal material by an electroplating coating method to form a polyimide coating film containing a dielectric filler, which is characterized in that: among the dielectric fillers, the average particle diameter Dia is The weight-accumulated particle diameter E was determined by the laser refraction scattered particle size distribution measurement method, and 50 was 0 ·:! ~ 2 · 0, and the weight-accumulated particle diameter ❹ and the average particle size obtained by image analysis were used. The diameter of Dia and the value of the degree of agglomeration represented by Dia are less than 4.5, and the dielectric powder including a perovskite structure has a slightly spherical shape and a spherical shape. 2 · A method of forming a dielectric filler with polyfluorene imide on the surface of a metal layer by using a polyfluorene-containing dielectric filler containing a dielectric filler in a polyfluorine imide plating solution The electroplating solution is formed on the surface of the metal material by a polyimide coating containing a dielectric filler by an electroplating coating method, and / is characterized in that: a thin metal layer of nickel or cobalt is formed on a copper material, and on the metal thin layer, Using the average particle diameter DIA of 〇. 〇5 ~ 1. 〇 # m, the weight-accumulated particle size by the laser refraction scattered particle size distribution measurement method was obtained. The particle size I and the particle size D1A obtained by image analysis, and the value of the degree of agglomeration represented by DIA of DIA below 4.5 are in a slightly dimorphic shape, including perovskite structure. Polyimide containing a dielectric filler as a dielectric filler ^ = Electro-mineral coating method to form a dielectric filler-containing material on the surface of a metal material 200402481 6. Scope of patent application Amine coating. 3. The method of forming a dielectric filler layer having polyfluorene on the surface of a metal layer as described in claim 1 or 2, wherein the dielectric filler is in a polyfluorine-imide plating solution having a dielectric filler. Its content is 50g / L ~ 350g / L. 4. The method of forming a dielectric filler layer having polyfluorene imine on the surface of a metal layer as described in any one of claims 1 to 3, wherein the dielectric filler is pre-sintered rhenium titanate or It is pre-sintered barium titanate. 5. The method for forming a dielectric filler layer having polyfluorene imine on the surface of a metal layer according to any one of claims 1 to 4, wherein the dielectric filler includes only cubic crystals or cubic Barium titanate with a crystalline structure in a mixed state of crystalline and tetragonal crystals. For μ Y species with 1st copper cladding / polyimide dielectric shell with 2nd dielectric filler / 2nd copper foil layer β 口 π, 接 $ 接 ® this-leftover & + ρ A method for manufacturing a copper-clad laminated board for forming a capacitor layer for a wiring board is characterized in that: a polyimide electrolyte solution with a diameter of 0.05 to 1.0 is used. ; The average particle size method of the electric filler is used to obtain the cumulative weight particle diameter D5g of ^, the scattered particle size distribution is used to measure the cumulative particle diameter d5 (), and the degree of agglutination expressed by weight is used in the image analysis g. A value of 4.5 with a passed average particle size of 0.50 / Dia perovskite (perovski te) structure has a slightly spherical shape, including polyimide electric charge of electric filler> Ye '丨 Polyimide-containing polyimide coating film containing dielectric filler is attached to the copper foil containing dielectric plating film by electro-coating method; and "Polyimide containing dielectric filler is included" Polyimide film formed on one side of the second copper film; 200402481 6. The scope of the application for the patent makes the polyimide film with a dielectric filler and the polyimide film with a dielectric filler and the copper thin film with a polyacid film The fluorene imide film surface can be bonded and stacked. / 7 · —a capacitor layer shape of a printed wiring board having a first copper foil / polyimide dielectric layer containing a dielectric filler / a second copper foil layer; a method for manufacturing a foil laminated board, Copper is characterized in that a thin metal layer of nickel or cobalt is formed on the surface of the first copper foil, and a polyimide plating solution mixed with a dielectric filler is used on the surface where the metal thin layer is formed. The average particle diameter DIA is 0.05 to 1.0 / zm, and the weight-accumulated particle diameter i is determined by laser refraction and particle size distribution measurement of the political SL type to be 0.1 to 2 〇 // m, and, The weight-accumulated particle diameter Ds◦ and the average particle diameter DIA obtained by image analysis, and the value of the degree of agglomeration indicated by DIA are less than 4.5, and the shape of the spherical shape includes perovskite (per〇vskite) A polyimide electroplating solution containing a dielectric filler made of a dielectric powder having a structure of) is formed by using a ore coating method to form a polyimide film containing a dielectric filler. Polyimide-coated copper foil; and polyimide film formed on one side of the second copper film, The above-mentioned copper foil with a polyimide coating containing a dielectric filler has a polygimide film surface of the electric filler and the polyimide with a thin copper film with a polyimide film. The electric film surfaces can be bonded and stacked. 8 · A method for manufacturing a copper foil laminated board for forming a capacitor layer of a printed wiring board as claimed in claim 6 or 7, wherein the content of the dielectric filler in a polyimide bond fluid with a dielectric filler is contained The amount is 50 g / L to 35 g / L. 2169-5720-PF (Nl); Ahddub.ptd 200402481 VI. Application Patent Scope 9 · Manufacturing method of copper foil laminated board for forming capacitor layer of printed wiring board according to any one of patent application items 6 to 8, wherein the dielectric filler is pre-sintered Barium titanate or pre-sintered barium titanate. 10. The method for manufacturing a copper foil laminated board for forming a capacitor layer of a printed wiring board according to any one of claims 6 to 9 of the patent application, wherein the dielectric filler includes only cubic crystals or cubic crystals. Barium titanate with a crystal structure mixed with tetragonal crystals. 11. A copper foil base plate for forming a capacitor layer of a printed wiring board, characterized by using a copper pig base layer for forming a capacitor layer of a printed wiring board in any one of claims 6 to 10 of the scope of patent application Obtained by the manufacturing method of the board. 2169-5720-PF (Nl); Ahddub.pid p. 33