TWI290816B - Wiring board and method for producing the same - Google Patents

Abstract

A wiring board exhibiting high adhesion between a substrate and a conductive layer, and its production method. A transfer sheet having a protruding/recessed surface of specified surface roughness is formed integrally with the substrate such that the protruding/recessed surface is transferred to the surface of the substrate, and then the transfer sheet is removed from the substrate, thus performing first surface roughening. The substrate surface roughened by the first surface roughing is then chemically roughened using etching liquid, thus performing second surface roughening. Subsequently, a conductive layer is formed on the substrate surface subjected to first and second surface roughening preferably by an additive method.

Description

[Technical Field] The present invention relates to a wiring board and a method of manufacturing the same, and more particularly to a roughening treatment of a substrate which is performed before forming a conductive layer. [Prior Art] In recent years, with the miniaturization and weight reduction of electronic/electrical devices, printed circuit boards combined with them have become thinner, and various improvements have been made to the manufacturing methods thereof.

In order to reduce the thickness of a multilayer printed board, a method of manufacturing a multilayer printed board capable of reducing back warpage and twisting during mounting of a member has been proposed in the Japanese Patent Laid-Open Publication No. Hei 5-136575. In the method, as shown in the eighth (a) and (b), after the resin film 25 having the protective film 26 is placed on the surface of the inner layer substrate 5 having the specific inner layer circuit 4 to form a laminate, the vacuum laminator is used. One piece of the laminate is formed. At this time, the resin film 25 has the function of an insulating layer. It is as follows: As shown in the eighth diagram (c), the protective film 26 is peeled off, and the outer layer circuit 70 is formed on the Lin: lipid film 25 by a stacking method. Therefore, the layer printed board shown in the eighth figure (d) is obtained. In addition, the symbol 7b 72 in the figure is a through-hole key and a blind via for electrically connecting the inner layer circuit 4 and the outer layer circuit 7G. When the multilayer printed board is manufactured in this manner, a thinner insulating layer is formed, and further, since the stacking method is employed, the pattern can be opened. However, there is still room for improvement in the adhesion of the outer layer circuit W. The resin film 25 is used to reduce the rigidity of the multilayer printed board. 5 1290816 [Invention] The main purpose of the present invention is to provide a method for manufacturing a wiring substrate. In order to achieve a high adhesion strength of the conductive layer, the elasticity can be improved corresponding to the improvement of the reliability of the insulation. In other words, the method of the present invention includes a first roughening treatment for physically roughening the surface of a substrate having an electrically insulating woven composition as a main component, and performing a roughening treatment using a magical roughening treatment. The surface of the roughened substrate is subjected to a second roughening treatment of chemical roughening with a meal liquid; and a step of forming a conductive layer on the surface of the substrate roughened by the second roughening treatment. Further, another object of the present invention is to provide a wiring board obtained by the above-described manufacturing method, the wiring board having a feature of embedding a material constituting the conductive layer by the first roughening treatment and the second roughening treatment The unevenness of the roughened surface forms an interface structure between the conductive layer and the substrate. According to the present invention, in addition to significantly increasing the contact area between the conductive layer and the substrate, the anchoring effect of the conductive layer material on the surface of the substrate is utilized to strongly fix the conductive layer on the substrate, so that the conductive layer can be highly painted. Synergy. In the above invention, the first roughening treatment includes a step of forming a sheet having a concave-convex surface having a specific surface roughness and a substrate, and a step of replicating the uneven surface onto the surface of the substrate, and removing the sheet from the substrate to obtain a physical rough surface. The step of the substrate surface. In particular, it is preferable to use a step in which the sheet is made of a metal such as copper, the step of removing the sheet by etching to obtain a surface of the substantially roughened substrate, or the surface coating of 1290816 containing an inorganic filler. The step of removing the sheet of the release agent onto the surface of the physically roughened substrate. - (9) Peeling from the substrate When the first roughening treatment is employed, a high adhesion can be obtained by the treatment effect = or sand method as compared with the case of performing the roughening treatment. The uniformity is high. Therefore, in the above invention, the substrate contains a material which is dispersed in the thunder and is preferentially dissolved by the liquid.], ', and the resin of the rim resin and the granules, so the second roughening treatment The aforementioned particles in the vicinity of the surface of the roughened substrate. This: wins the content, shape, and size of the particles that are dispersed, = null (4) i is introduced into the surface of the substrate by the surface treatment: square = two and size, in particular, to combine the above first rough surface In the case of manufacturing a thin printed circuit board, the optimum roughening treatment can be performed from the viewpoints of improvement in adhesion of the conductive layer and securing of electrical properties. In the implementation of the first and second roughening treatments, the surface roughness Rz (1G point average thickness) of the substrate should be 3 to 15 mm, and the Ra (arithmetic mean thickness) should be 0.1 to 1.0 # m. . When the thickness of the substrate of the prepreg which is obtained by impregnating the fibrous base material with the electrically insulating resin composition is thin, if it exceeds 15/zm or Ra exceeds, the insulation reliability in the depth direction of the wiring board may be lowered. Further, when Rz is less than m or Ra is less than 0.1 / m, the effect of improving the adhesion strength of the conductive layer is small. The formation of the conductive layer should be carried out by a stacking method. In addition to the formation of the above-mentioned boundary 1290816 surface structure, in addition to good believers, but also more (four) into a fine pattern. The other purposes and effects of the soil opening/detailing can be clearly understood from the following exemplifications for carrying out the invention. [Embodiment] Hereinafter, a wiring board and a method of manufacturing the same according to the present invention will be described in detail with reference to FIG. The main component of the substrate used in the present invention is an electrically insulating resin composition. The resin composition is not particularly limited. For example, a dish containing a resin, a brominated epoxy resin, and a bismuth-type epoxidized epoxy tree can be used. Further, the resin composition may contain a curing agent such as dicyandiamide or a hardening accelerator such as 2-ethyl-4-methylammonium saliva, and if necessary, a filler of a dioxide filler and two may be added. An organic solvent such as methylformamide (10)). Further, when the substrate of the prepreg is produced by impregnating the fibrous base material with the electrically insulating resin composition, the rigidity of the printed circuit board can be obtained by the fibrous substrate. In addition, a fibrous base material having a thickness of 〇 or less should be used, which not only ensures moderate rigidity, but also improves the size and thickness of the printed circuit board. Specifically, §, WEA1116" (glass cloth with a thickness of 0. 08_) or "weai〇78" (a glass cloth with a thickness of 〇· 〇 4 mm) manufactured by Nitto Denko can be used. Further, the thickness of the fibrous base material can be appropriately set to the lower limit of the thickness of the substrate, and the lower limit of the thickness can be set, for example, to 19 mm (19 // m). After the resin composition is impregnated into the fibrous substrate, the obtained impregnated body is dried by heating in a dryer to obtain a prepreg in a B-stage state of semi-hardened 8 1290816. Further, in order to effectively carry out the second roughening treatment to be described later, the particles of the material which can be preferentially dissolved in the etching solution used in the second roughening treatment are dispersed in the resin composition. The first figure (a) is the substrate knife before the roughening process, the flat surface state, the substrate! Internally - the particles 2 are dispersed. Further, the SEM photograph of the second figure shows that the surface of the substrate before the third surface roughening treatment is very flat. (The second to fourth figures are indicated by lines, which are represented by photographs), and the second surface is subjected to physical roughening of the surface of the substrate 1. In the first roughening treatment, the uniformity of the treatment efficiency and the treatment effect is applied to the substrate. The replica sheet 8 having the uneven surface having a specific surface thickness and the substrate are formed to form the concave and convex surface to the substrate. The surface of the crucible (first figure (8)) and the step of removing the replica sheet 8 from the substrate 1 to obtain a physically roughened substrate surface (first figure (6)). Specifically, a method in which the substrate 1 and the replica sheet 8 are formed after the formation of the substrate 1 and the replica sheet 8 may be carried out by a method of dissolving and removing the sheet, or a method of removing and removing it by copying.时 When the surface of the substrate is roughened by dissolving and removing the replica sheet 8, the release sheet 8 may be a metal mold such as an electrolytic copper box. At this time, the surface of the substrate 1 to which the electrolytic copper case is bonded shall have (1) ^ (4) Cong average coarse, . 'Field degree' and 0. 3~〇. 7m2Ra (arithmetic mean thickness), and the retanning sheet The surface thickness is copied to the base. The dissolution of the replicated flakes uses an existing copper etching solution. In addition, the release sheet 8 is peeled off to implement the substrate! In the case of roughening, for example, a release agent containing an inorganic filler may be applied to a sheet to prepare a sheet. After the lamination is carried out by using a release agent, it is easy to make a complex (4) • I ^ body and +, as shown in the fifth figure, first, the _-like polyethylene terephthalate is formed with the binder 14 The ester (PET) 13 is bonded to the aluminum foil π and is made into a material of the aluminum foil π. Next, the inorganic filler 10 such as pulverized cerium oxide is mixed with a release agent u such as polypropylene (PP). This blend is applied to the surface of the material 15 of the sheet material 12 to form a replica sheet 8. The average particle diameter of the inorganic filler 10 is not particularly limited, however, it is preferably 1 to 1 Å/m. Further, the surface of the release agent coated with the inorganic filler 10 should have a Ra to (10 point average thickness) and a Ra (arithmetic mean thickness) of 〇·3 to 0·7 m, and the surface The relief is copied to the surface of the substrate. The first figure (b) is a state in which the replica sheet 8 is formed on the surface of the substrate, and the first sheet (c) is a state in which the replica sheet is peeled off and the concave surface on the surface of the replica sheet is copied to the surface of the substrate. Further, the third figure is an SEM photograph of the surface of the substrate after the sheet is peeled off, and the surface of the substrate is formed into a uniform number of micrometers. The first roughening treatment by the above-mentioned replica sheet 8 has an excellent adhesion improving effect and reliability as compared with the case of roughening such as polishing or blasting. That is, when the surface of the substrate is roughened by polishing, the substrate material in the vicinity of the surface is pulverized, and even if a conductive layer is formed thereon, the conductive layer peels off the material of the substrate, and it is difficult to obtain the desired density. Combination, sex. Further, when the surface of the substrate is roughened by mechanical means such as sand blasting, the particles to be blown remain on the surface of the substrate, and the adhesion of the conductive layer formed later may be adversely affected. In addition, the use of grinding or blasting roughening treatment is prone to errors. On the other hand, when the first roughening treatment of the replica sheet is used, the size and shape of the unevenness formed on the substrate by 1290816 are sufficient, and even if the processing area of the substrate is large, the entire substrate can be realized. Very uniform - the advantages of the rational effect. For the above reasons, the first roughening treatment of the present invention is preferably carried out by removing the replica sheet 8 from the substrate 1. In the case of the surface of the substrate roughened by the first roughening treatment, the second roughening treatment using the chemical roughening of the etching liquid is applied. In the second roughening treatment, it is preferable to use a method in which the money engraving solution is preferentially dissolved and distributed in the vicinity of the surface of the substrate on which the particles 20 are dispersed by the first roughening treatment. Hey. For example, a bridging elastomer such as a butadiene-acrylonitrile copolymer or polyvinyl acetal may be used as the particles in which the solution is preferentially dissolved. The content of the particles can be appropriately set. However, for example, the content of the particle component with respect to the entire resin composition is preferably 1 to 2% by mass. In addition, in terms of the average particle diameter of the particles 2溶解 dissolved in the second roughening treatment, it is effective at 0 to 1 to 2//m from the viewpoint of forming fine unevenness on the surface subjected to the first roughening treatment. The range is good. For the solution of the insect-like solution for dissolving the particles 20, at least one of an acid and an oxidizing agent may be used. For example, "CIRCUPOSIT MLB211" manufactured by CYPRES, "EMPRATE MLB497" manufactured by MELTEX, and "EMPRATE MLB-" manufactured by MELTEX Co., Ltd. may be used in combination. Three kinds of 791M" are used as etching solutions. Here, the main component of "CIRCUPOSIT MLB211" is an aqueous solution of ethylene glycol, which has the function of swelling resin. The main component of "EMPRATE MLB497" is an aqueous solution of potassium methacrylate (oxidizing agent) and an aqueous solution of potassium hydroxide, which has a function of dissolving a resin (especially a dissolved component). Permanganate such as potassium permanganate has a strong oxidizing agent at 11 1290816 alkaline. As the solution having a function of dissolving the resin, it is also possible to use a substance having a main component of an aqueous solution of sodium permanate (oxidizing agent) and an aqueous solution of sodium hydroxide. The main component of "EMPRATE MLB-791M" is an aqueous solution of sulfuric acid (acid) and an aqueous solution of hydrogen peroxide, which has the function of neutralizing the alkaline state. When the second roughening treatment is performed, the particles 20 which are copied to the vicinity of the uneven surface of the substrate 1 by the first roughening treatment are preferentially dissolved by the residual solution, as shown in the first diagram (d), the substrate The uneven surface is further formed with fine irregularities. The fourth figure is an SEM photograph of the surface of the substrate after the second roughening treatment on the surface of the first roughening treatment of the third figure, and comparing the third and fourth figures, it is known that the treatment is performed by using the younger one. Each of the unevenness formed is formed by a plurality of fine irregularities due to the second roughening treatment. As described above, by performing the second roughening treatment after the first roughening treatment, the surface area of the substrate can be remarkably increased. Further, when the second roughening treatment is performed on only the substrate having a flat surface, only R1 (10-point average thickness) of 1 to 5/m and Ra of 〇3 to 0.4 m are formed on the surface of the substrate ( The Raman of the arithmetic mean thickness (the arithmetic mean thickness) is preferably combined as described above to form a 1~(1() point average thickness) of 4~12//111 and a Ra of 0·3~0. 7m (1) The roughening treatment for the purpose of the relatively large (thickness of the average thickness), and the surface roughness after the second roughening treatment can be 3 to 15/m. The average thickness of the 〇 point) and Ra·丨~丨· Ravm Ra (arithmetic mean thickness). Next, the conductive layer 7 is formed on the surface of the substrate which is roughened by the second roughening treatment. As shown in the first figure (e), the material constituting the conductive layer is embedded in the surface of the roughened surface by the second roughening treatment and the second roughening treatment 12 1290816. Anchoring effect). The interface structure between the conductive layer 7 and the substrate 1 obtained in this way can not only significantly increase the contact area between the conductive layer and the substrate, but also utilize the conductive layer material to anchor the unevenness of the substrate surface to make the conductive layer Strongly fixed on the substrate. The method of forming the conductive layer and the layer is not particularly limited as long as it is a method for forming the above-described interface structure. However, as will be described later, a stacking method is preferably employed. Further, the stacking method is divided into a full stacking method and a half stacking method, and any one of the methods can be used in the present invention. According to the present invention, in combination with the physical roughening treatment and the chemical roughening treatment, in particular, the third surface roughening of the surface of the substrate is performed by copying the unevenness of the replicated sheet to the substrate. The combination of the treatment and the second roughening treatment for preferentially etching and removing the particles dispersed in the inside of the substrate to chemically roughen the surface of the substrate improves the adhesion between the conductive layer and the substrate, thereby achieving better reliability. Next, an example of a method of manufacturing a multilayer printed wiring board of the present invention will be described. μ As shown in Fig. 6(a), the inner layer substrate 5 of the specific inner layer circuit 4 is pre-wired on both sides, and the prepreg 3 which is formed by the electrical insulating property is formed into a fibrous base material 3 Then, after the replica film is placed on the prepreg, as shown in FIG. 6(b), the laminate is formed into a body by a molding method such as multi-stage vacuum press. The inner layer substrate 5 is formed by, for example, laminating the prepreg 3 () of the necessary number to form a laminate structure. The inner layer circuit 4 is formed by a stacking method or a removal method. In addition, a circuit can be formed on a laminated board such as a copper-clad laminate which is commercially available. Further, it is also possible to arrange the prepreg 30 on the outer surface of the 13 1290816 and perform lamination molding. This black oxygen, where == etc. = prepreg 3. Shape 1:: The straw is removed from the replicated sheet 8, using the surface of the prepreg. Thus: due to the copy of the complex (four) film to the roughening process, (4) _^,, _ bribe the button of the insulating layer and 彳t rate. Further, by using the unevenness of the replica sheet 8 to make use of the surface area formed on the prepreg 3G (insulating layer 6) half == the crucible 30, the depth of the concavity formed is reduced by the thickness of the sheet|C For example, in order to realize the prepreg of the wiring base, if the roughening treatment is used/the undercut is too deep, the insulation reliability in the thickness direction may be lowered. In the roughening treatment, if the thickness is __, the thickness of the +-cured sheet is reduced and there is a problem of insulation reliability. However, by using the above-mentioned complex (four) 4 method, it is only necessary to produce a copy of the uneven surface having the thickness of the special surface. The thin sheet can provide good reproducibility of the prepreg with the same surface thickness, and the quality of the 铋 曰 曰 曰 5 5 5 谷 谷 谷 谷 谷 , , , , , , , , , , , , , , , , , , , , , , , , , , , , Bad rate. Next, the secret engraving solution was subjected to the second roughening treatment. The second roughening treatment can be carried out by impregnating the laminated sheet shown in Fig. 6(C) with the (10) solution impregnation. Further, the type of the etching solution can be changed and performed plural times. For example, the temperature of the (iv) solution can be set to 4G to (10). C, set the immersion time to 1 to 30 minutes. In addition, when the above-mentioned "CiRCUp〇SIT MLB211", "EMPRATE MLB497", and "E_ATE MLB-791M" 1290816 are used in combination, the following solutions are implemented, that is, First, the laminate is immersed in "circup〇sit MLB21l" and the resin is swelled. Next, the laminate is immersed in "EMpRATE MLB497" to carry out the resin transfer. Finally, the laminate is immersed in

"EMPRATE 791M" neutralizes the state under the test. In this way, the second roughening treatment is performed after the first roughening treatment is performed using the copy sheet. However, it is not excluded that the second roughening treatment is performed by using a method other than the replica sheet. Then, the method of the second roughening treatment is carried out. Thereafter, an outer layer circuit 7 is formed on the surface of the insulating layer 6 subjected to the first and second roughening treatments by a stacking method, and if necessary, is formed to connect the inner layer of electricity, 4, and the outer layer of the insulating layer 6. The via hole (4) of the road 7 () is obtained as a multilayer printed circuit board as shown in the sixth figure (4). In addition, the printed circuit board system shown in the sixth figure (4) is difficult. However, the present invention is not limited thereto, and the above-mentioned four-layer board can also be regarded as the inner layer substrate 5, and more layers can be printed in the same steps. Circuit board. Next, an example of a method of manufacturing a printed circuit board in the method of forming the outer layer circuit 70 using the half stack method will be described. First, as shown in the seventh figure (6), the stacking method shown in the seventh figure (a) of the second roughening treatment is performed, and the hole 50 is formed by a drill or the like. And the blind via hole is formed to reach the hole 52 of the inner layer circuit 4. This =, the laminated system shown in the seventh figure (a) is made in the same manner as in the sixth drawing (c), and the repeated description is omitted. Next, as shown in the seventh diagram (c), a plating layer 4 is formed on the surface of the insulating layer 6 composed of the semi-cured sheet 30 by electroless plating. Secondly, as shown in Fig. 15 1290816, Figure 7 (4), in the part that does not have to form the outer layer of electric paste. In addition, as shown in the seventh figure (e), the implementation of electrolytic steel electro-mineralization and demineralization treatment does not form a coal mine. The part of the anti-money (10) is the plating 43. *Electric fresh electricity

Secondly, as shown in the seventh figure (7), 'removing the resistance to the anti-mineral anti-refinement, so that after the de-extracted ore is removed, it will be removed quickly, and the outer layer circuit will be formed as shown in the seventh figure (g). Multilayer printed electricity: board. Electroless electricity (10) and plating 43 are formed on the inner surface of the through hole 52, and via plating 71 and blind via 72 for electrically connecting the inner layer circuit 4 and the outer layer circuit 7 are formed. In addition, it is hardened after moderate implementation. [Examples] Hereinafter, the present invention will be specifically described by way of examples. <Preparation of varnish> In the present embodiment, each component was blended in the amounts shown in Table 1, and three types of varnishes "”~" 3" were prepared. Obtained as follows. First, a stirring apparatus and a cooling tube were placed in a three-necked flask having a capacity of 300 ml, and then, a specific amount of dimethylformamide (DMF) and Methoxy propanol (MP) were added to the flask, and further, Epoxy resin (EPIKURON 850S, manufactured by Dainippon Ink and Chemicals, Inc., 53 wt% and "EPIKURON N690", 13 wt%) were added. The epoxides of "EPIKURON 850S" and "EPIKURON N690" were 190 and 220 respectively. Thereafter, the obtained mixture was heated to 8 (TC) in an oil bath, and the scaly compound shown in [Chemical Formula 1] was added in a ratio of 16 1290816 1 (the chemical formula 1). In the case of c-day, the triphenylbenzene scale is injected at a ratio of 〇2% by mass to the total of 1, and the gas-gas resin is reacted. Further, when a specific epoxide equivalent is reached, the reaction is stopped to obtain Oxygen lie on the surface. In addition, anti-red is carried out = according to nSK7i1995 to detect the amount of epoxide # to determine [Chemical Formula 1]

溴 The brominated epoxy resin used for the preparation of the varnishes 2" and "3" is "YDB-500" manufactured by Tosho Kasei Co., Ltd., and the cresol novolak epoxy resin is "EPIKURON N690" manufactured by Nippon Ink Chemical Industry Co., Ltd. As the hardener, a diazoamine (molecular weight 84, theoretically active hydrogen equivalent 21) was used, and a hardening accelerator was 2-ethyl-4-methylimidazole. Further, dimethylformamide (DMF) using cerium oxide ("SFP-10X" manufactured by Electrochemical Industry Co., Ltd.) as an organic solvent was used as a filler. In addition, the component which is preferentially dissolved and removed by the etching solution used for the second roughening treatment is a bridging elastomer of butadiene-acrylonitrile copolymer (XER-91 manufactured by JSR Corporation: particle diameter 0·1 // m The following) and polyvinylacetal resin ("6000R" manufactured by Electric Chemical Industry Co., Ltd.). 17 1290816 [Table 1] Content (% of Wei Halo) Paint No. 1 2 3 Phosphorus-containing epoxy resin 82 0 0 Brominated epoxy resin 0 49 49 A(phenyl)phenol phenolic enamel paint type epoxy tree month 0 9 9 dicyandiamide — 3~~ 2 2 2-ethyl-4-methylimidazole 0.1 0.1 0.1 cerium oxide 10 10 10 DMF 0 25 25 bridging elastomer 10 10 0 polyvinyl acetal resin 5 5 0 Total 110.1 110.1 95.1 (Preparation of prepreg) The three types of varnish and fibrous substrate shown in Table 1 used in this example are rWEA1116 manufactured by Nippon Textile Co., Ltd. and glass cloth with a thickness of 0.04 mm. RWEA1〇78" manufactured by Nitto Spinning Co., Ltd., combined with the varnish and glass cloth shown in Table 2, and immersed the varnish in a glass cloth, and then dried at 170 ° C in a dryer to obtain a semi-hardened price. State prepreg. (Example 1) A printed circuit board was produced by the following method using a semi-cured 18 1290816 sheet made of varnish, 1, and glass cloth "WEA1116". First, as shown in Fig. 6 (a) and (b), the prepreg 3 配置 is disposed on the surface of the inner substrate 5 in which the inner layer circuit 4 ("R-1566" manufactured by Matsushita Electric Works Co., Ltd.) is not formed, and the replica sheet 8 is used as the triple sheet. "3EG-III" manufactured by Metals Co., Ltd., having a thickness of 18 μπ〇 and a thickness of 18 μm, was laminated on a three-stage vacuum prepreg to form a laminate. In the implementation of the layer formation, the conditions of heating and pressurization are changed in the order of (1) to (7) below. (1) Pressure 0·5 MPa (5 KgF/cm 2 ), hot plate temperature 3 〇 ° c, and hold for 30 minutes. _ (2) The pressure is 0·5 MPa (5 KgF/cm2), and the hot plate temperature is raised to i2 〇 °c. The temperature rise rate is 2 〇C / min. (3) Pressure 〇 · 5MPa (5KgF / cm2), hot plate temperature 12 〇. Hey, keep it for 5 minutes. (4) Pressure 2·0MPa (20KgF/cm2), hot plate temperature 120°C, hold for 20 minutes. (5) The pressure is 2.0 MPa (20 KgF/cm2), and the hot plate temperature is raised to 160 °C. The heating rate was 3 ° C / min. (6) Pressure 2·0MPa (20KgF/cm2), hot plate temperature 160°C, hold for 30 minutes _ clock. (7) Pressure 2·0 MPa (20 KgF/cm2), and the hot plate temperature is cooled to 50 ° C or less with cooling water. • Next, as shown in Fig. 6(c), after the laminate is formed, the replica sheet 8 is removed by etching to complete the first roughening treatment. Further, after the first roughening treatment, the second roughening treatment is performed. The second roughening treatment is carried out in the following order (1) to (3).

(1) The laminate was immersed in a "CIRCUPOSIT 19 1290816 κ MLB211" solution manufactured by CYPRES Co., Ltd. at 75 ° C for 6 minutes. (2) Second, immerse in 80. (In the EMPRAte MLB497" liquid manufactured by LTEX Co., Ltd., the immersion time was 1 minute. (3) The immersion time of 5 minutes was immersed in the "EMpRATE MLB-791M" liquid manufactured by MELTEX Co., Ltd. at 40 °C. After the outer layer circuit 7 is formed by a stacking method, it is cured by a dryer for 17 〇t: and after 120 minutes to obtain a 4-layer printed electric purity of the embodiment shown in the sixth figure (d). After the storage of the copper ore deposit, the treatment is carried out after 120 C, 60 minutes of drying, and then electrolytic copper plating treatment. The plating thickness is 20 ± 2 / / m. (Example 2) In addition to the use of varnish "Γ and glass The four-layer printed circuit board of Example 2 was obtained in the same manner as in Example 1 except that the prepreg made of "WEA1078" and the detachable replica sheet 8 were used instead of the etch-removable sheet of the embodiment. For the production of the replica sheet 8 used, as shown in the fifth figure, a film-like poly(ethylene terephthalate) (PET) 13 having a thickness of 12/m is bonded to the thickness of the dry binder 14 by 25 / / m of the foil 15 to make the sheet 12, and secondly, 1% by mass of polypropylene (pp) This mixture was applied to the surface of the aluminum foil 15 of the above-mentioned sheet material 12 so as to have a thickness of 2 / / Π 粉碎 二 二 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 A 4-layer printed 20 1290816 circuit board of Example 3 was obtained in the same manner as in Example 2 except that a prepreg made of varnish "2" and glass cloth "WEA1078" was used. (Example 4) In addition to using varnish, A four-layer printed circuit board of Example 4 was obtained in the same manner as in Example 2 except that the prepreg made of the glass cloth "WEA1078" was used. (Example 5) The content of the pulverized cerium oxide was 2 Å. A four-layer printed circuit board of Example 5 was obtained in the same manner as in Example 2 except for the % of the replica sheet 8. (Comparative Example 1) Except that the sheet 6 was used, a sheet containing no pulverized silica was used, and the same was carried out. In the same manner as in Example 2, a 4-layer printed circuit board of Comparative Example 1 was obtained. (Comparative Example 2) A printed circuit board of Comparative Example 2 was produced by the following method. First, as shown in the eighth (a) and (b), Resin sheet 25 having protective film 26 as resin sheet The surface of the inner layer substrate 5 of the same type as that of the user of the first embodiment is superimposed on the surface of the inner layer substrate 5 of the first embodiment, and then laminated by vacuum lamination. The protective film is used in this comparative example. In the production of the resin film 25 of 26, a MULTICHET ("M400" manufactured by HELANOTAIX Co., Ltd.) was used, and a polyethylene terephthalate (pET) film having a thickness of 40 /zm was coated with a thickness of about 6 〇 #m. The paint 1' was conveyed at a conveyance speed of 2 〇cm/min while being dried at a temperature of 1 〇〇C, and covered with a polyethylene (PE) film having a thickness of 20/m. Further, the PE film was peeled off before the laminate molding. ^ Next, as shown in the eighth figure (C), after the protective film 26 is peeled off, the outer layer circuit 70 is formed on the road-out tree (4) by a stacking method, and the dryer is hardened by performing a heat treatment for 120 minutes. The four layers of printing shown in Figure 8 (d), the board. The outer layer circuit 7 is formed by electroless copper plating treatment, and the bead yoke 120 C, dried for 60 minutes, and then subjected to electrolytic copper plating treatment. The plating thickness is 20 ± 2 / / m. With respect to the printed circuit boards of Examples 丨 to 5 and Comparative Examples 丨 2 which were produced by the above method, (1) peel strength of the electric ore, and (2) elasticity (3) insulation and evaluation were evaluated. In addition, the ultra-deep surface shape measuring microscope VK-85GG manufactured by the company is used to detect the surface roughness of the substrate before plating (_

Ra). (1) Peel strength The peeling number (4) of the outer layer circuit 70 (copper plating web 10_) was measured to be 5, and the average enthalpy was taken as the peeling strength. The results are as follows: Table = Extraction (2) Elasticity ❺f A total of 8 prepregs used in the respective examples were obtained, and the laminate was molded and used as a sample for evaluation of the modulus of elasticity. Further, in the case of Comparative Example 2, the film of 8 sheets was used, and the obtained sample was formed into a sample for evaluation. Using the DMA method to detect the elastic modulus for the above samples

Ub C). The results are shown in Table 2. (3) Insulation reliability Test the insulation reliability. First, a DC book is applied to the printed circuit board in a temperature of 130 C/rel. humidity, and 22 1290816 detects the pre-test impedance 値 of the insulating layer formed by the prepreg or the resin sheet. Next, the printed circuit board was placed in an environment of a temperature of 13 ° C / a relative humidity of 85%, and after applying 150 VDC for 2 hours, a direct current of 20 V was applied to detect the post-test impedance 绝缘 of the insulating layer. Then, after the test, the ratio of the impedance 値 to the impedance 値 before the test is 50% or less, and it is judged as "><(", the value of 5〇〇/0 or more is determined as "〇", and the number of evaluation samples is 3, The insulation reliability was determined by the number of turns. The results are shown in Table 2.

[Table 2]

_Example Comparative Example 1 2 3 4 5 1 2 淸lacquer No. 1 1 2 3 1 1 1 Glass cloth 1116 1078 1078 1078 1078 1078 1078 Lamination method of insulating layer Multi-stage vacuum stamping vacuum lamination modulus (25 degrees C) ( Kgf/mm2) 1189 908 903 973 899 903 522 (Mpa) 11660 8904 8855 9610 8810 8855 5116 Peel strength (η=5 average 値) (kgf/cm) 0.88 0.85 0.86 0.68 0.89 0.59 0.59 (N/cm) 8.6 8.3 8.4 6.7 8.7 5.8 5.8 Surface thickness (after 2nd roughening treatment) Rz(β m) 11.9 7.2 9.7 3.9 17.1 2.7 2.6 Ra( β m) 0.54 0.29 0.46 0.19 1.30 0.08 0.07 Insulation reliability (test time: 2〇〇 Hour) 〇〇〇〇〇〇〇〇〇〇〇〇 XXX 〇〇〇Οχχ As can be seen from the results of Table 2, Comparative Example 1 in which the first roughening treatment was not performed, and the first and second rough surfaces were not implemented. In Comparative Example 2, Comparative Examples 1 to 5 in which the first and second roughening treatments were carried out had high adhesion. In addition, compare 23 1290816 (4)' because the enamel does not contain pulverized silica dioxide, and the surface is recessed to the surface of the prepreg, which should be the reason for poor adhesion. Further, in the case of (4) f, since the fibrous base material is not used, the rigidity is also inferior. In the case of the fourth embodiment, since the prepreg does not contain particles in which the residual liquid is preferentially dissolved in the first surface treatment, the adhesion effect obtained by the surface treatment is slightly lower than that of the actual age Π3. Actually (4), although the shot is extremely poor, the unevenness of the prepreg contained in the film 8 will be too deep, and the insulation reliability cannot be obtained in this case. Therefore, for the compatibility and the reliability of the insulation can be broken, it should be determined according to the strictness of the prepreg, and the amount of the unevenness (surface thickness) of the prepreg is XX% because it is easier to control (the thickness of the surface of the surface is roughened) And the size of the particles dissolved in the second roughening treatment, so that the printing can be performed on a printed circuit board having different thicknesses: the surface has the most appropriate unevenness of σ, and good reliability is obtained. (1) According to the method for manufacturing a wiring board according to the present invention, the optimum surface state of the adhesion and the reliability of the insulation is high, and the electric power is high: in recent years, the tendency to be thinned is made 24 1290816 [Simple description of the drawing] Figures (a) to (e) are schematic flow diagrams of a two-stage roughening treatment according to a preferred embodiment of the present invention. The second drawing is an SEM photograph of the surface of the substrate before the first roughening treatment. 1 SEM photograph of the surface of the substrate after the roughening treatment. SEM photograph of the surface of the substrate after the roughening treatment of the younger brother. The fifth figure is an outline of an example of the replica sheet used in the first roughening treatment. Sectional view. Xindi /, map ( a) to (d) are schematic process diagrams of a method of manufacturing a printed circuit board according to a preferred embodiment of the present invention. (a) to (g) are other methods of manufacturing a printed circuit board according to a preferred embodiment of the present invention. Fig. 8(a) to (d) are schematic diagrams showing the conventional manufacturing method of a printed circuit board. _ [Main component symbol description] 1 substrate 2 electrically insulating resin composition 3 fibrous substrate 4 Inner layer circuit 5 Inner substrate 6 Insulation layer 7 Conductive layer 8 Replicated sheet 25 Inorganic filler Release agent Sheet material Polyethylene terephthalate adhesive agent Mingί White particle resin film Protective film Prepreg Electrolytic plating Through hole resistance Electroplated resist layer outer circuit through hole electric mine blind through hole 26

Claims (1)

1290816 卜, the scope of application for patents: 1. The method for manufacturing a wiring board, wherein the base 2::====: rough is roughened into a conductive layer by the second roughening treatment. step. The surface shape of the soil 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 2、 配线 配线 配线 配线 配线 配线 配线 配线A method of manufacturing a braided wiring substrate according to the fourth aspect of the invention, wherein the first roughening treatment is performed by forming a sheet having a convex surface having a specific surface roughness and a substrate. a step of converting the unevenness to the surface; and a step of removing the surface of the substrate from the substrate to obtain a surface of the substrate which is physically textured. 4. The method of producing a wiring board according to the third aspect of the invention, wherein the sheet is produced by applying a coating containing an inorganic filler to a thin surface. 5. The method of manufacturing a wiring board according to the first aspect of the invention, wherein the first and second roughening treatments are performed such that the surface roughness RzUG point average thickness is 3 to 15 mm, The (arithmetic mean thickness) is 0.1 to 1. 〇//m. 6. In the method of manufacturing the wiring board according to the first item, the substrate of the above-mentioned substrate is contained in the layer of 12 1290816, and the particles of the material are dispersed, and the second coarse: the second solution is preferentially dissolved and distributed. The first graining treatment is performed to roughen the particles in the vicinity of the surface of the substrate. 7. A method of producing a wiring board according to the patent application, wherein the material constituting the particles comprises a bridging elastomer of a butyl diene-acrylonitrile copolymer and a PQlyvinylacetal resin. 8. A method of manufacturing a wire board for a specific purpose, wherein the above-mentioned "electric layer is formed by stacking a surface of a substrate which is roughened by a second roughening treatment. 9. The method of manufacturing a wiring board according to the third aspect of the invention, wherein the surface layer of the 0-layer material of the surface domain circuit is in contact with the surface of the substrate through the first rough surface region of the substrate. The step of bonding to the above substrate. The ten types of wiring boards are provided with an i-th roughening treatment for physically roughening the surface of the substrate containing the electrically insulating resin composition, and for performing rough surface by the first roughening step. The second roughening treatment for chemically roughening the surface of the substrate by the (four) liquid, and the manufacturing method for forming the conductive layer on the surface of the substrate roughened by the second roughening treatment In the wiring board, the material constituting the conductive layer is described as a guide and a ride formed by the unevenness of the roughened surface by the first roughening treatment and the second roughening treatment. Interface structure between. 11', in the middle of the wiring board of the i-th item, wherein the above-mentioned work 28:29〇816 piece = chemical treatment has a thin step of performing a concave-convex surface having a specific surface thickness, and the substrate is formed by one body The step of replicating the uneven surface to the surface of the substrate and the step of removing the surface of the substrate to obtain a surface of the substrate which is physically roughened. The wiring board of claim 10, wherein the base and =3 have particles dispersed in the electrically insulating resin composition and the etching solution can preferentially material of W 2 , and the second roughening treatment system The particles are preferentially etched by the etching solution, and the particles in the vicinity of the surface of the substrate are roughened by the ruthenium roughening step. The wiring board of claim 10, wherein the surface of the substrate roughened by the i-th and second roughening treatments has an Rz (average thickness of l〇 points) of 3 to i5//m and Ra (arithmetic mean thickness) is the surface thickness of 〇·1 to 1. · #