TW201251533A - Print circuit board and method of manufacturing the same - Google Patents

Abstract

The present invention provides a print circuit board with an excellent yield. A method of manufacturing the print circuit board of the present invention comprises: a step of separating a carrier substrate from a laminate of copper foil (copper foil layer 104) having the carrier substrate laminated on at least one surface (30) of an insulating layer (102); a step of entirely or selectively forming a metal layer (115) on the copper foil layer (104), in which the metal layer is thicker than the copper foil layer (104); and a step of etching at least the copper foil layer (104) to obtain a pattern of a conductive circuit (119) composed of the copper foil layer (104) and the metal layer (115); wherein in the steps for obtaining the conductive circuit (119), the surface (30) of the insulating layer (102) has a Rp of 4.5 μ m or less, and a Rku of 2.1 or more, as determined according to JIS B0601.

Description

201251533 VI. Description of the Invention: Manufacturing Method of Board and Printed Wiring Board TECHNICAL FIELD OF THE INVENTION The present invention relates to printed wiring [Prior Art] High-density integration of electronic components, high-density integration used for these, and small-sized thin type With the advancement of the high-performance of the electronic equipment, the high-density mounting and the like are progressing, and the corresponding printed wiring boards and the like are more conventionally increased, and the density is increased and the multilayer is defective. A conductor circuit pattern formed on a substrate of such a printed wiring board is described in, for example, Patent Document 1. In the method described in Patent Document 1, first, an insulating resin layer is formed on a double-sided steel sheet, and the surface of the insulating resin layer is roughened to form a conductor layer on the surface thereof, followed by an anti-side agent. As a mask: etch = etching, thereby forming a pattern of a conductor layer (conductor circuit pattern). According to the patent document 1, the surface roughness of the insulating resin layer belonging to the underlying layer of the conductor circuit pattern is reduced, whereby the residue of the etching resist can be prevented from remaining, and the wiring of the conductive circuit pattern can be suppressed from being lowered. Further, the surface roughness of the insulating resin layer described in Patent Document 1 is defined by Ra and Rz, and Ra is the average thickness of the center roughness of the mountain side in the graph showing the surface unevenness; Rz represents The average particle size of the total of 1 point of 5 points of the larger side of the mountain side and the thickness of the valley side of the same figure (the following is a graph showing the surface unevenness, which may correspond to the concave 101102463). 4 201251533 The part of the section is called the valley, and the part equivalent to the convex part is called the mountain. Patent Document 1: Japanese Laid-Open Patent Publication No. 2005-5458 [Draft of the Invention] (Problems to be Solved by the Invention) However, in the conventional step of forming a fine conductive circuit pattern, the resin layer is suppressed on the edge of the resin layer. There is a limit in the deviation of the engraved characteristics of the conductor layer. For example, in order to improve the etching characteristics of the conductor layer, it is required to reduce the surface roughness of the conductor layer. However, the inventors of the present invention have found out that Ra and Rz, which are generally used for the surface roughness in the technical region of the printed wiring board, are not properly defined in the surface shape, so even if such Ra and Rz are used as indicators The Ra and Rz of the surface of the insulating resin layer are controlled to be small, and the surface roughness of the conductor layer formed thereon between the products is still deviated. For example, since Ra and Rz belong to an index which does not indicate the width of the mountain, by merely controlling these indexes, the interval between the mountains of the surface of the insulating resin layer of the base may become wide, and thus the conductor layer may be recessed. - Therefore, in the prior art, there is a case where the etching characteristics of such a conductor layer are deviated, and there is room for improvement. (Means for Solving the Problem) According to the present invention, there is provided a method of manufacturing a printed wiring board, comprising: a step of separating the carrier substrate by laminating a copper foil having a carrier substrate on at least one of the insulating layers 101102463 5 201251533 a step of forming a metal layer thicker than the above-mentioned copper on the copper matte; and by at least etching the copper drop, obtaining the copper drop and the metal layer The step of forming the conductive circuit pattern; and in the step of obtaining the conductive circuit pattern, the Rp of the one surface of the insulating layer is 45 μm or less, and the Rku is 2.1 or more. As a result of the study, the inventors of the present invention have found that copper is formed on one surface of the insulating layer on the surface of the insulating layer of the substrate when there is a surface shape pattern of a mountain having a small mountain height, a narrow mountain gap, and an acute angle. The deviation of the etching characteristics of the crucible is reduced. The present inventors have found that, when the index indicating the height of the mountain is small and the index indicating that the interval between the mountains is relatively sharp and sharp is controlled to an appropriate value, the deviation of the tentacles characteristic of the copper formed on the substrate By reducing the Rp indicating the maximum dimension of the mountain and the Rku indicating the sharpness of the mountain (the gap between the mountains is narrow) as the kind of heart; 'Rp is controlled to be 4 5 handsome and Rku is 2) In the above, the surface shape pattern of the surface of the insulating layer can be appropriately controlled, and the deviation of the fineness of the copper pavilion can be suppressed, and the present invention is completed (4). Further, according to the present invention, there is provided a printed wiring board comprising: an insulating layer; and a conductive circuit pattern formed on one surface of the insulating layer and composed of a copper town and a metal layer; 101102463 6 201251533 according to JIS B0601 In the measurement, the RP of the one surface of the insulating layer was 4.5 μm or less and the Rku was 2.1 or more. Since the RP controlled to one surface of the insulating layer is 4.5 μm or less and the Rku is 2.1 or more, the variation in the etching characteristics of the copper foil is suppressed as described above, and the structure having an excellent yield is realized. (Effect of the Invention) According to the present invention, a printed wiring board excellent in yield can be provided. The above and other objects, features, and advantages of the invention will be apparent from the preferred embodiments described herein. Hereinafter, embodiments of the present invention will be described using the drawings. In the drawings, the same components are denoted by the same reference numerals, and the description is omitted as appropriate. (First Embodiment) Fig. 1 is a cross-sectional view showing the order of manufacture of a printed wiring board according to a first embodiment. Hereinafter, the outline of the method of manufacturing the printed wiring according to the first embodiment will be described, and then the description of the manufacturing method will be described. Further, the detailed production conditions, materials, and the like of the first embodiment will be described later in the embodiment. In the method of manufacturing the printed wiring board according to the first embodiment, a laminated board having a carrier, a foil, or a foil (copper foil layer 104) is laminated on at least the surface 3G of the insulating layer 1G2 (with a carrier foil) Copper foil laminate 1 soil steel 1〇) 'Step 101102463 7 201251533 body substrate (carrier layer 1〇6彳8) knife step; on the copper foil layer 104, the whole surface or selectively formed a step of the copper layer + the self-layer 104 thick metal layer 115; and the conductive circuit U9 composed of the copper foil layer 104 and the metal layer U5 by etching the copper foil layer 104 at least The steps of the pattern. In the manufacturing step, after the step of patterning the conductive circuit ι 9 of the lie step is performed, the measurement is performed according to JIS and 01, and the Rp of one surface of the insulating layer m is 4.5_. Below, and Rku is 2.1. the above. In other words, the steps of the method of manufacturing a printed wiring board according to the first embodiment include the following steps. First, as shown in Fig. 1(a), a copper clad laminate 1G having a carrier crucible is prepared. In the copper sheet laminate 1() having the load, the steel falling layer 104 and the carrier layer 1〇6 are attached to both sides of the insulating layer 102. Then, as shown in Fig. 1(b), the carrier layer 106 is pulled and peeled off by a copper box laminate 1 having a carrier. Next, as shown in Fig. i (4), the anti-money layer 112 having a predetermined opening pattern is formed on the remaining copper layer 104. A plating layer (metal layer 115) is formed by plating in the opening pattern of the plating resist 112 and the copper foil layer 1〇4 (Fig. 1(d)). Next, as shown in Fig. 1(e), the plating resist 112 is removed. Thereby, a pattern of a predetermined metal layer 115 can be selectively formed on the copper box. Thereafter, as shown by ffi ! (1), in the region where the metal layer 115 is not covered, the copper foil layer 104 formed on the insulating layer 1 〇 2 is removed by, for example, soft etching. In the soft etching step, Rp of one surface 30 of the insulating layer 102 is below, and Rku is 9 1 , -^ · 1 Us I* 后 after the step of removing the copper foil layer 104, by remaining steel foil layer 104 101102463 8 201251533 The metal layer 115' may form a pattern of conductive circuits 119. According to the above steps, the printed wiring board 1〇1 of the present embodiment is obtained (FIG. 2 is a cross-sectional view of the conductive circuit 119 in the printed wiring board 101 of the first embodiment. As shown in FIG. 2, The printed wiring board 101' of the present embodiment includes an insulating layer 102, a pattern of a conductive circuit 119 formed of a copper foil layer and a metal layer 115 provided on one surface 30 of the insulating layer 102. The printed wiring board 101 is used. Specifically, when the measurement is performed according to JIS B〇6〇1, Rp of one surface 30 of the insulating layer 102 is 4.5 μm or less, and Rku is 2 or more. Hereinafter, Rp indicating the maximum mountain height of the roughness curve is expressed. The Rku of the kurtosis of the thickness curve (Kurtosis) is described with reference to Fig. 14 and Fig. 15. These Rp and Rku are measured as follows: the surface of one face 30 of the insulating layer 1〇2 is thick. The degree is measured according to JIS B0601 (2001), and the cutoff value is set to none. In the present embodiment, the thickness curve refers to a concave-convex curve indicating the surface roughness. This thickness curve is obtained by a commercially available device. In the embodiment of the corpse, the surface of the insulating layer 102 is indicated ( In the figure 3 of the surface), the valley system refers to the portion corresponding to the concave portion, and the mountain system corresponds to the portion corresponding to the convex portion. The so-called maximum mountain height is as shown in Fig. 14 and refers to the reference length & The maximum value of the convex portion (Zpi) of the profile curve. Therefore, reducing Rp means reducing the maximum height of the mountain in one face 30 of the insulating layer 102. Therefore, the dream is reduced by Rp, which can reduce the minimum height and maximum of the mountain. In addition, the kurtosis Rku of the thickness curve is as shown in Fig. 15. Further, the table 101102463 9 201251533 shows the sharpness of the mountain in one of the faces 30 of the insulating layer 102. Therefore, increasing Rku means insulating. In the face 30 of the layer 102, the mountain is made an acute angle. Therefore, by increasing Rku, the width of the mountain can be reduced and the interval between the mountains can be narrowed. Further, Rku is calculated by the following equation. [1] 1 (I [&τ Α 'Λ

Rku=w i^lo2 (x)dx, where Ir: reference length, Z(x): spheroidal waviness curve, Rq: square root of the thickness curve. Conventionally, in the technical field to which the present invention pertains, the surface roughness is usually specified by an index such as Ra or Rz. (For example, refer to Patent Document 1). However, as a result of examination by the inventors of the present invention, it has been found that these indicators cannot be said to sufficiently reflect the surface shape pattern of the substrate. For example, since the Ra system is not an indicator directly indicating the maximum value of the mountain height, even if the Ra index is controlled to be small, the maximum value of the mountain height may become large. Further, the surface pattern of the substrate may have a large difference between the maximum value and the minimum value of the mountain, and a height difference is generated on the surface of the copper foil formed thereon. On the other hand, since the Ra system does not indicate the index of the width of the mountain, it is possible to cause the gap between the mountains of the surface of the insulating resin layer of the base to be widened only by controlling these indexes, and thus it is possible to cause a depression in the conductor layer. Thus, in the prior art, even if such an index is controlled, it is difficult to sufficiently control the surface shape pattern of the substrate. 101102463 10 201251533 Therefore, the surface shape pattern of the conventional substrate has a case where the height of the mountain is high and the interval between the mountains becomes wide, 'on the surface of the copper foil formed on the surface of the substrate having such a surface shape, Since the surface shape is deviated, it is difficult to stabilize the etching characteristics of the copper box in the prior art. - After the applicant of the present invention has recorded, it is found that the parameter of the so-called Rp indicating the maximum height of the mountain in the edge layer 102 of the substrate is reduced, and the sharpness of the mountain (the interval between the mountains is narrow) is indicated. When the parameter of Rku is increased, the etching characteristics of the copper foil layer 1〇4 (the copper case provided on the substrate) are improved, and the pattern of the conductive circuit 119 having a good wiring shape is formed. Based on the above experimental facts, the inventors established the following assumptions. That is, on the surface of the insulating layer 102 of the substrate, the etching of the copper foil layer 104 formed on the insulating layer 1 (2) is performed when the surface shape pattern of the mountain having a small mountain height, a narrow mountain interval, and an acute angle exists. The deviation of the characteristics is reduced. Therefore, after various experiments, it was found that, when both the index indicating the height of the mountain and the index indicating that the interval between the mountains is narrow and an acute angle are controlled to an appropriate value, the copper falling on the substrate is formed. The inventors of the present invention use Rp indicating the maximum height of the mountain, and Rku indicating the inferiority of the mountain (the narrow interval between the mountains) as such an index, by controlling to RP. When the thickness is 4.5 or less and the Rku is at least the above, the surface shape pattern of one surface 3〇 of the insulating layer 1〇2 can be appropriately controlled, and the variation in the variation of the steel-engraving property can be achieved. In the present embodiment, by forming the pattern 101102463 11 201251533 of the mountain having a narrow interval and having an acute angle as the surface shape (4), for example, the number of mosquitoes can be increased. Thereby, since the area of one surface of the insulating layer (10) is increased, the contact area between the insulating layer and the steel box layer is increased by one, and the adhesion between the conductive circuits 119 including the copper box layer 104 can be achieved. In addition, according to the method for manufacturing a printed wiring board of the present embodiment, streaking of one surface 3 of the insulating layer 1〇2 can be suppressed. The mechanism is still true, but _ due to the removal of the insulating layer On the surface 3G, a surface shape pattern of a mountain height and a mountain interval can be formed as the surface shape map $, so that the variation of the stress in the horizontal direction received by the copper box layer HM is less in the insulating layer. Stripe is formed in the insulating layer 102. Here, if the insulating layer _ stripes, in order to remove the residue in the strip level, such as (4) residue, and (4) excess, there is a wiring shape. On the other hand, if the amount of side is insufficient, then the cruelty of the wealth can not be removed, and there is a connection failure. Further, when streaks occur in the edge layer, the holes may be formed in the multilayer wiring structure, and the connection property may be lowered. However, in the present embodiment, since streaking can be suppressed as described above, it is possible to prevent a defect in wiring shape, a connection failure, or a decrease in connection reliability due to such a stripe. In the present embodiment, the upper limit of Rp in the surface 3G of the insulating layer 1 () 2 is 4.5 μm or less, preferably 3.5 μm or less, more preferably 25 μm or less. On the other hand, the lower limit of the RP is not particularly limited, and is, for example, preferably ϋ 5 μηι or more, more preferably 101102463 12 201251533 1, more than a handsome, and more preferably 1.5 μm or more. By setting Rp to the above range, it is possible to reduce defects such as etching residues during formation of fine wiring, and obtain a printed wiring board with good yield. Furthermore, the insulation reliability between the fine wiring circuits is excellent. In the present embodiment, the upper limit of Rku in one surface 30 of the insulating layer 102 is not particularly limited. For example, it is preferably 10 or less, more preferably 8 or more, still more preferably 6 or less. On the other hand, the lower limit of Rku is 2.1 or more, preferably 3.0 or more, and more preferably 3.5 or more. By setting Rku within the above range, since the surface of the substrate becomes fine unevenness, the copper foil layer 104 formed thereon has uniform button characteristics. Therefore, the side etching characteristics of the conductor layer of the copper foil layer 104 or the like can be made uniform. Further, since the contact area is increased, the adhesion to the conductor layer is excellent. Therefore, the printed wiring board 101 of the present embodiment is excellent in heat resistance and insulation reliability between fine wirings. Here, a good wiring shape will be described with reference to FIGS. 2 to 4 . In FIG. 4, the copper foil laminate 1 has an insulating layer 2, a copper foil layer 4, and a metal layer 14. The term "good wiring shape" refers to a shape that is specific to the characteristics in which the residual edge is less conventional. As shown in Fig. 4, the residual side is a portion formed by extruding the copper pig layer 4 in the outer side of the metal layer 14 in the width direction orthogonal to the direction in which the metal layer 14 extends in plan view. The determination as to whether or not the residual edge has occurred will be described with reference to Figs. 2 and 3 . As shown in the figures, for example, in the cross-sectional view, the maximum width of the copper foil layer 104 (14) in the width direction is L1, and the minimum width of the metal layer 115 (14) in the width direction is L2, in LI. —L2 = When AL is greater than 0, it is determined that a residual edge has occurred. In the case of the conductive circuit 119 of the present embodiment, the enthalpy is smaller than the conventional one, and preferably L1 and L2 are the same (Fig. 2(a)), and more preferably u is smaller than L2. When L1 is smaller than L2, the copper (4) 1〇4 of the cross-sectional view has a region in which the width in the plane direction of the ply is smaller than the width in the plane direction of _115 (Fig. 2(b)). The pattern of the conductive circuit ι 9 specified by this kind of U&L2 can be referred to as a good wiring shape. In addition, in the so-called good wiring shape of the present embodiment, the second means that the shape of the metal layer is specific to the characteristics of the desired shape (Fig. 2 (8) and (9) are required to be mixed, and the design is cut as designed. The shape is, for example, a square ridge/shape, etc. Even if iL1 is the same as [2, and further u is smaller than U, the (four) characteristic of the (four) layer 1G4 is improved, so that the shape can be realized. As shown in Fig. 2 (4), the shape may be a rectangular shape having the same width as the metal layer 115, or may be an inverted cone shape as shown in Fig. _. The inverted cone shape of the copper falling layer (10) is a plan view When the first surface (the upper surface 20) faces the second surface (the lower surface 22), the area thereof may be small (where 'may also be formed in one part of the side surface 24 due to the deviation in the manufacturing step), as shown in FIG. Generally, in the cross-sectional view in the width direction, the angle formed by the perpendicular line of the bridging layer 1 () 2 and the side surface 24 (the angle of the counterclockwise) is preferably, for example, 0 degrees or more and 20 degrees or less. More preferably, it is 1 degree or more and 10 degrees or less. Moreover, as the shape of the other copper foil layer 1〇4, it can be figure 6 The plate (semicircular) shape shown may also be a necked shape as shown in Fig. 6(b). By using 101102463 201251533 such a shape of copper, it is possible to make L1 smaller than L2 in the conductive circuit 119. Further, in comparison with the shape of the inverted taper, the bonding area with the insulating layer can be ensured to be more than a certain value. Further, in the printed decorative wire board of the embodiment, the line spacing (hereinafter referred to as L/S) controllability is satisfied. The superiority is described with reference to Fig. 4. Fig. 4 shows the distance S2 and the spacing S1, and the most adjacent conductive circuit 19 in the width direction of the orthogonal direction with respect to the direction in which the conductive circuits 19 and 119 extend. In the manufacturing method of the printed wiring board of the prior art, the etching characteristics of the copper pig layer 4 are deviated, and the residual side or the side of the copper|| layer 4 may be left. (4) 4 is electrically separated from each other regularly, and the spacing S2 must be sufficiently ensured as shown in Fig. 4 (8). In other words, (4) illusion must be matched with U (4) to reduce the printing of the _ miscellaneous manufacturing method, because of this Ll / S2 It is less controllable, so it is difficult to form In contrast, in the method of manufacturing a printed wiring board of the present embodiment, since the etching property of the copper foil layer 104 can be improved, the width of the metal layer II5 can be maintained under a desired shape to control the width. The width of the copper foil layer 104 in the direction. Therefore, since L1 can be made L2 or less (that is, the residual edge disappears), the pitch S1 can be determined by the minimum width L2 of the metal layer 115. The L2 is as described above. Therefore, in the method of manufacturing a printed wiring board according to the present embodiment, such L2/S1 has superior controllability. Therefore, since L/S controllability is excellent, connection failure can be suppressed, and A method of manufacturing a printed wiring board capable of performing fine wiring processing of 101102463 15 201251533 is obtained. Further, in the present embodiment, the etching of the side surface 24 of the copper foil layer 104 is referred to as side etching. When this side is etched, etching is performed in the horizontal direction with respect to the upper surface of the insulating layer 1?. On the other hand, the etching of the upper surface 20 of the copper foil layer 104 is referred to as vertical etching. This longitudinal characterization is carried out in the vertical direction with respect to the upper surface of the insulating layer 102. (Second Embodiment) A method of manufacturing a printed wiring board according to the second embodiment will be described below. In the second embodiment, detailed manufacturing conditions, materials, and the like which are omitted in the third embodiment are exemplified. In the method of manufacturing a printed wiring board according to the second embodiment, the step of forming the metal layer 116 over the entire surface or selectively includes the following steps, which is different from the first embodiment: forming a through-silicon foil layer 104 And a step of the through hole 1〇8 of the copper foil laminate 100 formed by the insulating layer 1〇2; a step of contacting the chemical liquid at least on the inner wall of the through hole 108; and forming the insulating layer 102 by electroless plating The step of electroless plating layer 110 electrically connected to the copper foil layer 1〇4 on the upper surface on the upper surface. Fig. 7 and Fig. 8 are cross-sectional views showing the procedure of a method of manufacturing a printed wiring board according to a second embodiment. First, as shown in Fig. 7 (4), a copper laminated layer 1 having a carrier g on which the carrier layer 106 and the copper layer 1〇4 are bonded to both surfaces of the insulating layer 1〇2 is prepared. 10Π02463 201251533 As a carrier-attached copper-clad laminate 1, for example, a peelable carrier foil layer 1〇6 is laminated on at least one side of the copper-clad laminate 100. The copper-clad laminate 100 (hereinafter also referred to as a laminate) is not particularly limited, and for example, a copper foil layer 104 may be used in at least one area of the insulating layer 102 having an insulating resin layer with a material base (the fiber is omitted in the drawing). Substrate). The laminate may be a single layer or a multilayer structure. That is, as the laminated board, it may be composed only of the core layer, but it may be used to form an additional layer on the core layer. A known one can be applied to such a laminate, and for example, a plurality of sheets in which a prepreg is superposed can be used. The prepreg is not particularly limited. For example, it can be obtained by a method of impregnating a resin composition containing a thermosetting resin, a curing agent, a filler, or the like in a substrate such as a glass cloth. Further, as the laminated board, an extremely thin metal foil having a carrier foil laminated on at least one side and formed by heating and pressing can be used. Further, in the interlayer insulating layer of the build-up layer, the same material as the core layer may be used, or the substrate or the resin composition may be different. In the present embodiment, the insulating layer 1〇2 corresponds to an insulating resin layer constituting the core layer or the buildup layer. An example of using a laminate having an additional layer will be described in detail with reference to the third embodiment. As the resin composition constituting the laminate and the interlayer insulating layer used in the present embodiment, a known resin (hereinafter also referred to as an insulating resin composition) which is used as an insulating material for a printed wiring board can be used, and it is usually used mainly for heat, A thermosetting resin with good chemical resistance. The resin composition is not particularly limited, and is preferably a resin composition containing at least a thermosetting resin. Examples of the thermosetting resin include urea (urea) resin, melamine tree 101102463 17 201251533 fat, cis:: #二醯iimide compound, polysilicic acid (tetra) lipid, unsaturated vinegar resin, and material ring correction. Resin, bisallyl-iminoimide, vinyl-based resin, ethylene-based phenol, benzocyclobutadiene/cyanate resin, epoxy resin, and the like. Among them, the curable resin is preferably a combination of a slope temperature of 200 C or more. For example, it is preferably a spiro ring, a heterocyclic ring, a hydroxyindole type, a biphenyl type, a naphthalene type, an onion type, a novolac type, or 2 or 3:: the above-mentioned oxime resin, cyanate resin (including a prepolymer of a cyanate resin), a cis-butylimine resin, a benzocyclobutene resin, or a resin having a benzofluorene ring. When an epoxy resin and/or an acid acid-based resin is used, the linear expansion becomes small, and the heat resistance is remarkably improved. X. When epoxy resin and cyanate lysate are combined with a high filler filler, it is excellent in flame retardancy, heat resistance, impact resistance, high rigidity and electrical properties (low dielectric constant, low loss factor). The advantages. In this case, it is considered that the glass transition temperature after the hardening reaction of the thermosetting resin is 2 〇〇 (> c or more, and the thermal decomposition temperature of the resin composition after curing becomes high, at 25低The above-mentioned reaction is low in molecular weight, etc. Further, the improvement of flame retardancy is considered to be due to the thermal hardening of the aromatic system, and the benzene ring is higher in the structure of the benzene ring. It is easy to be carbonized (stone), which is caused by carbonization. _L 述树月曰, 'and the product may further contain a flame retardant within a range that does not impair the effects of the present invention'. Preferably, it is a non-halogen-based flame retardant. Examples of the flame retardant include an organic dish-based flame retardant, an organic gas-containing gas compound, and a chemical gas, a polysulfide-based flame retardant, and a metal hydroxide. For example, there are phosphine compounds such as HCA, hca-hq, and HCA-NQ manufactured by Sanko Co., Ltd., and HFB-2006M manufactured by Showa Polymer Co., Ltd., etc., as the phosphorus-based flame retardant of 101102463 201251533. Phosphorus-containing benzopyrene compound, PPQ of Beixing Chemical Industry Co., Ltd. OP930 made by Clariant Co., Ltd., phosphate ester compound of PX200 manufactured by Daeba Chemical Co., Ltd., phosphorus-containing epoxy resin such as FX289 and FX310 manufactured by Toshiro Kasei Co., Ltd., ERF001 manufactured by Dongdu Chemical Co., Ltd., etc. Phosphorus-containing phenoxy resin, etc. As an organic nitrogen-containing phosphorus compound, for example, a phosphate amide compound such as SP670 or SP703 manufactured by Shikoku Chemicals Co., Ltd., and SPB100 manufactured by Otsuka Chemical Co., Ltd. SPE100, a sulphuric acid compound such as FP series manufactured by Fushimi Co., Ltd., etc. As the metal hydroxide, for example, magnesium hydroxide such as UD65〇 and UD653 manufactured by Ube Materials Co., Ltd., and CL310 manufactured by Sumitomo Chemical Co., Ltd. An aluminum hydroxide such as HP_350 manufactured by Showa Denko Co., Ltd., etc. The cyclic oxime resin used for the resin composition may, for example, be a bisphenol A type oxime resin, a bisphenol F type epoxy resin, or a bisphenol E type. Epoxy resin, double-looking S-type J oxidizing resin, double 16M epoxy resin, double-p-type epoxy resin, double-Z-ring material double _ ring_lipid, esoteric varnish epoxy resin, A (four) paint type Wei charm # _ lacquer type epoxy resin 'biphenyl type epoxy resin, Cover type epoxy resin, bismuth-based epoxy tree = aryl-based oxy-epoxy resin, naphthalene-type epoxy resin, naphthalene glycol-type oxime resin, 2-functional to 4-letter and customer #, #脂,双莽I (4), _type epoxy 榭101102463 resin, onion type epoxy resin, stupid epoxy type epoxy resin, dicyclopentadiene 2 19 201251533 Oxygen resin, lower blessing _ epoxy resin, gold (four) Epoxy resin, bismuth type epoxy resin, etc. As the epoxy resin, one of these may be used alone, or two or more kinds having different weight average molecular weights may be used in combination. Further, one or two or more of these may be used in combination with a prepolymer such as the above. Among these epoxy resins, an aryl-based epoxy resin is preferred. Thereby, the heat absorption and flame retardancy of the moisture absorption solder can be further improved. The term "aryl-based epoxy resin" refers to an epoxy resin having more than one aryl stretching wire in a repeating unit. For example, a fluorene-based epoxy resin, a biphenyl-methylene type epoxy resin, or the like is preferable, and a biphenyl dimethylene type epoxy resin is preferable. The biphenyldimethylene type epoxy resin can be represented, for example, by the following general formula (1). X, as the biphenyl dimethylene type epoxy resin, for example, NC_3000, NC_3〇〇〇L, Na3Q(8)_FH manufactured by Nippon Kayaku Co., Ltd. [Chemical 1]

The homo repeating unit η of the biphenyldifluorenylene type epoxy resin represented by the above formula (1) is an arbitrary integer. The lower limit of n is not particularly limited, but is preferably 1 or more, particularly preferably 2 or more. When η is too small, the biphenyl dimethylene type oxygen resin is easily crystallized, and the solubility to a general-purpose solvent is low, which is difficult. The upper limit of η is not particularly limited, but is preferably 1 〇, ^, or less. If η is too large, there is a case where the fluidity of the resin is lowered and the horse is not formed 101102463 20 201251533. % of the varnish-type epoxy resin made of eucalyptus is a heat-expandable property of the phenolic varnish. The phenolic varnish is preferably a condensed aromatic hydrocarbon structure, which further improves heat resistance and low. It has a condensed ring of aromatic naphthalene, anthracene, phenanthrene The novolac type epoxy resin of the disaster structure is similar to the phenolic varnish type epoxy resin which has the structure of a condensed ring-shaped enamel furnace 椹 _ $1, bis, and tetraphenyl, and other aromatic hydrocarbon structures. It has a condensed ring aryl group, so the low heat type '(4) makes the plural aromatic ring regularly superior in fins. In addition, the price of the glass is also higher. Therefore, it is better to know that (4) Qing and 黍: repeating the structure of the 77-reading large 'defective combination, it can be improved, and the % oxygen resin is superior. Cyanide slightly tree installation reliability is superior, the temperature is higher, the step is higher, so there is no _ should be expected =::: butterfly structure _ varnish type epoxy tree wax, which is composed of stupid σ and 曱 compound and condensed ring Aromatic hydrocarbon red, _ varnish _lipid oxylated I. The benzene compound is not particularly limited, and for example, arbitrarily fine, a variety of materials, l2, 4. 2 曱Hope, 2 6-- m, 2,5- 2,3,5·three-two:, 3,4_two, 3,5-two-in-one, etc., 乙等等二\ f基赖's 'mystery' to face, word 101102463 soil phenols, isopropyl phenol, butyl hope, third butyl test, etc. 21 201251533 alkyl phenols, o-phenylphenol, m-phenylphenol, pair Naphthalene glycols such as phenylphenol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, resorcinol, catechol, hydrogen Polyvalent phenols such as quinone, gallic phenol, fluoroglycine, etc., alkyl resorcinol, alkyl An alkyl polyvalent phenol such as a benzenediol or an alkylhydroquinone. Among these, the benzoic acid is preferably used because of the cost surface and the effect on the decomposition reaction. The aldehyde compound is not particularly limited. For example, furfural, paraformaldehyde, tris. mountain, acetaldehyde, propionaldehyde, polyoxyalkylene, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyl aldehyde, hexanal, Allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxyarylene, phenylacetaldehyde, o-quinacridal, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxyl The condensed cyclic aromatic hydrocarbon compound is not particularly limited, and examples thereof include a naphthalene derivative such as methoxynaphthalene or butoxynaphthalene, and an anthracene derivative such as anthracene oxime. , phenanthrene phenanthrene and other phenanthrene derivatives, other fused tetraphenyl derivatives, chess derivatives, anthracene derivatives, triazine derivatives, tetraphenyl derivatives, etc. Novolac type with condensed cyclic aromatic hydrocarbon structure The epoxy resin is not particularly limited, and examples thereof include a decyloxynaphthalene-modified o-nonphenol novolac epoxy resin and a butoxynaphthalene-modified methyl group ( a non-phenol novolac epoxy resin, a decyloxy naphthalene modified novolac epoxy resin, etc. Among these, a novolac type having a condensed cyclic aromatic hydrocarbon structure represented by the following formula (2) is preferred. Further, as the novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure, for example, HP-5000 manufactured by DIC Co., Ltd. can be mentioned. 101102463 22 201251533 [Chemical 2]

Hf- (2) (wherein = condensed ring aromatic hydrocarbon group 'R may be the same or different from each other, and is a hydrocarbon group selected from a gas atom, a sulphonium, a killing number of 1 or more and 10 or less, or a halogen element, benzene The aryl group of earth, bauxite, etc., and the group of the organic group containing a glycidyl ether, η, ρ, and q are 1 or more, and the values of p and q can be in each repeating unit. The same or different.) [Chemical 3] (Α "" (10) (Ar3) (Ar4) (3) (Arrangement (Arl) to (Ar4) in the Ar system (3) in the formula (2) R in the formula (7) may be the same or different from each other, and is an aromatic group selected from a hydrogen atom, a carbon number of 1 or more and 10 or less, a phenyl group, a phenyl group, a aryl group, and the like, and a glycidyl ether. Further, as the epoxy resin other than the above, a naphthol type epoxy resin, a naphthalene: alcohol type epoxy resin, a bifunctional to 4-functional itoxy type naphthalene resin, and a naphthyl ether type are preferable. A naphthalene type epoxy resin such as an epoxy resin, whereby the heat resistance and low bulging property of the 101102463 23 201251533 can be further improved. Further, since the π_π overlapping yarn of the naphthalene ring is higher than the benzene ring, 2 especially low thermal expansion property , low heat shrinkage Furthermore, due to the multi-ring structure, the straightening effect is high, and since the glass transition temperature is particularly high, the heat shrinkage change before and after the reflow is small. The Cai-type epoxy resin can be, for example, the following general formula (4_υ) Further, as the naphthol type nucleating resin, for example, ESN-375 manufactured by Nippon Steel Chemical Co., Ltd. can be used. The naphthalenediol type epoxy resin can be represented, for example, by the following formula (4-2). The epoxy resin can be, for example, HP-4032D. 2-functional to 4-functional epoxy type naphthalene resin, which can be, for example, the following formula (4-3) (4-4) (4-5). In the case of the bifunctional to tetrafunctional epoxy group-type naphthalene resin, for example, hp_4700 and HP-4770 manufactured by DIC Co., Ltd. may be mentioned. The naphthene ether type epoxy resin may be, for example, represented by the following general formula (4-6). The naphthalene ether type epoxy resin is exemplified by HP-6000 manufactured by DIC Co., Ltd. [Chem. 4]

(4-1) (n represents an average of 1 or more and 6 or less, and R represents a glycidyl group or a niobium group having 1 or more carbon atoms and 1 or less carbon atoms.)

(4-2) 101102463 24 201251533 [Chem. 6]

[Chemistry 7]

(4-6) (wherein R1 represents a hydrogen atom or a fluorenyl group, and R2 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aralkyl group, a naphthyl group or a naphthalene group containing a glycidyl ether group; The base, 〇 and m are each an integer of 0 to 2, and at least one of 〇 or m is 1 or more.) The cyanate resin used in the above resin composition can be, for example, a cyanogen halide compound and a phenol compound. Obtained by carrying out the reaction. Specific examples of the cyanate resin include a novolac type cyanate resin such as a phenol novolak type cyanate resin or a cresol novolac type cyanate resin, and a naphthol aralkyl type cyanate resin. , dicyclopentadiene type cyanate resin, biphenyl cyanate resin, double 101102463 25 201251533

A bisphenol-type cyanate resin such as a tetradecyl bisphenol F phenol A type cyanate resin or a bisphenol AD type cyanate resin type cyanate resin. Among them, it is preferable to contain a secret varnish type cyanogen resin, a naphthene aromatic resin j=_fat, a dicyclopentadiene type cyanate s resin, a biphenyl oleic acid vinegar's preferred resin. The composition contains 10% by weight or more of cyanic acid vinegar resin in the total solid content of the resin composition. Thereby, the prepreg can be improved: thermal (breaking temperature, thermal decomposition temperature). X, the coefficient of thermal expansion of the prepreg (especially the coefficient of thermal expansion in the thickness direction of the prepreg) can be lowered. If the coefficient of thermal expansion in the thickness direction of the prepreg is lowered, the stress strain of the multi-brush wiring can be alleviated. Furthermore, in the wiring board having the fine connection portion, the connection reliability can be greatly improved. The preferred one of the varnish-type cyanate resin used in the above resin composition is exemplified by the following (4) varnish-type cyanate condensate represented by the following formula (7). Preferably, the combination uses a 4-fold average molecular weight of 2 or more, preferably 2, 〇〇〇^1〇, 0〇〇. 2, 2〇〇^3, 50〇 of a nitrogen acid, and a weight average molecular weight yx, Preferably, the "clear varnish type cyanate s" resin (10) represented by the formula (5) of the formula 〜5 is not particularly indicated, and the """ indicates an upper limit and a lower limit). Further, in the present embodiment, the weight average molecular weight is deposited on the value measured by the osmotic chromatography method. [化8] 101102463 26 201251533

In the formula (5), η represents an integer of 0 or more. Further, as the cyanate resin, the cyanate resin represented by the following general formula (6) is also suitably used. The gas ester resin represented by the following general formula (6) is obtained by a pair of naphthols such as X-naphthol or β-naphthol and p-nonanediol, α,α'-dimethoxy group. The naphthol aralkyl resin obtained by the reaction of hydrazine or 1,4-bis(2-hydroxy-2-propyl)benzene is condensed with cyanic acid, and the η of the general formula (6) is 1 or more. When the η is 10 or less, the resin viscosity is not high, and the impregnation property to the substrate is good, and the performance as a laminate can be suppressed from being lowered. Further, intramolecular polymerization and washing are less likely to occur during the synthesis. The liquid separation is improved to prevent the output from decreasing.

In the formula (6), R represents a hydrogen atom or a fluorenyl group, R may be the same or different, and η represents an integer of 1 or more. Further, as the cyanate resin, a dicyclopentadiene type cyanate resin represented by the following general formula (7) is also suitably used. The dicyclopentadiene type cyanate resin represented by the following general formula (7) is preferably such that η of the following general formula (7) is 0 or more and 8 101102463 27 201251533 or less. When n is 8 or less, the resin viscosity is not high, and the impregnation property to the substrate is good, and the performance as a laminate can be prevented from being lowered. Further, by using a dicyclopentadiene type cyanate resin, it is excellent in low hygroscopicity and chemical resistance. [化10]

Further, the resin composition may further contain a curing accelerator. For example, if the curing resin is an epoxy resin or a lyophilized resin, a hardening accelerator such as an aging resin or a % oxygen or a resin is used. The benzene-lipid is not particularly limited, and examples thereof include a benzene (10) paint resin, a 22 varnish resin, a bismuth A lacquer resin, and an aryl-based styrofoam resin. Modified soluble benzene _ fat, by tung oil, linseed oil, walnut oil and other modified oil modified soluble secret stupid _ fat and other soluble secret type stupid _ material. As the above benzene-lipid, it is preferred to use a benzene varnish or a toluene varnish resin. The towel is preferably a biphenyl-based modified silk varnish resin from the viewpoint of heat resistance of the moisture-absorbing article. One of these may be used in combination, or two or more kinds having different weight average molecules may be used in combination, or one or two or more kinds of prepolymers may be used together with the above-mentioned hardening accelerator of 0 101102463 28 201251533. It is not particularly limited, and examples thereof include an organic metal salt such as zinc naphthalate, cobalt naphthalate, tin octylate, cobalt octylate, cobalt acetoacetate (11), triethyl sulfonium acetonide (111), and triethylamine. a tertiary amine such as tributylamine, di-σ丫 bicyclo[2,2,2]octane, 2-mercaptoimidazole, 2-phenylimidazole, 2-phenyl-4-indenyl D-methane , 2-ethyl-4-ethylimidate, ι-benzyl-2-methyl taste. Sit, 1-benzyl-2-phenylimidine. Sitting, 2-11 base microphone. Sodium, cyanoethyl 2 - ethyl 4 - methylimidazole, 1-cyanoethyl 2 -undecyl imidazole, 2-phenyl 4 - fluorenyl-5-hydroxyimidazole, 2-benzene Imidazoles such as benzyl-4,5-dihydroxyimidazole, 2,3-dihydro-m-pyrrole (1,2_a) benzimidazole, phenolic compounds such as phenol, bisphenol A, nonylphenol, acetic acid, benzene A mixture of citric acid, salicylic acid, an organic acid such as p-toluenesulfonic acid, a rust salt compound, or the like. The derivative may be used singly or in combination of two or more of them. Further, the thermosetting resin may contain a maleimide compound from the viewpoint of heat resistance. The maleimide compound is not particularly limited as long as it has one or more maleimide groups in one molecule. Specific examples thereof include a group of phenyl maleimide, N-hydroxyphenyl maleimide, bis(4-pipetenediamine phenyl)methane, and 2, 2_Bis{4-(4-methylene-2-imide phenoxy)phenyl}propane, bis(3,5-indolyl 4-cis-butylene sulfhydryl), bismuth, double 3_ethyl_5_mercaptobutyleneimine phenyl) substituted, bis(3,5-diethyl_4_cis-butenediamine phenyl)-methyl, polyphenyl fluorene a succinimide imine, a prepolymer of such a cis-butadiene diamine compound, or a prepolymer of a cis-butadiene diimine compound and an amine compound 101102463 29 201251533. Further, 'the above thermosetting resin may contain a phenoxy resin, a polyvinyl alcohol resin, a polyethylenimine, a polyamide, a polyamide, or the like from the viewpoint of adhesion to the metal foil. Imine, polyether sulfone resin, polyphenylene ether resin. The phenoxy resin' may, for example, be a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, or a phenoxy resin having a biphenyl skeleton. Further, a phenoxy resin having a structure of a plurality of such skeletons may also be used. Among these, a phenoxy resin having a biphenyl skeleton and a bisphenol s skeleton is preferably used in the phenoxy resin. Thereby, the glass transition temperature of the phenoxy resin can be increased by the rigidity of the biphenyl skeleton, and the adhesion between the phenoxy resin and the metal can be enhanced by the presence of the bisphenol s skeleton. As a result, the heat resistance of the insulating layer 102 can be improved, and when the multilayer substrate is manufactured, the adhesion of the wiring portion (the conductive circuit 118) to the insulating layer 1〇2 can be improved. Further, it is preferred to use a phenoxy resin having a double-presence A skeleton and a double-fragile F skeleton in the present oxyresin. Thereby, when the multilayer substrate is manufactured, the adhesion of the wiring portion to the insulating layer 102 can be further improved. As a commercially available product of a stupid oxy-resin, for example, FX280 manufactured by Tohto Kasei Co., Ltd., and YX8100, YX6954, YL6974 'YL7482, YL7553, YL6794, YL7213, and YL7290 manufactured by Japan Epoxy Resin Co., Ltd. are available. The molecular weight of the phenoxy resin is not particularly limited, and is preferably a weight average molecular weight of 5,000 to 70,000, more preferably 1 Å, 〇〇〇 〇 6 〇, and 0 0 101102463 30 201251533 The content thereof is not particularly limited, and is preferably from 1 to 40% by weight, more preferably from 5 to 30% by weight, based on the total of the resin composition. As a commercially available product of a polyethylene glycol oxime resin, for example, an electric chemical industry (unit) can be used to charge butyraldehyde 4000-2, 5000-A, 6000-C, and 6000-EP, and Sekisui Chemical Industry Co., Ltd. LEC BH series, BX series, KS series, BL series and BM series. Particularly preferred is a glass transfer temperature of 80. (The above is a commercial product of polyimine, polyamine, and polyamidamine.) For example, "VYLOMAX HR11NN (registered trademark)" and "HR-16NN" manufactured by Toyobo Co., Ltd. "HR15ET", "KI-9300", which is made from Hitachi Chemical Co., Ltd., and other products, such as "Neopulim C-1210" manufactured by Mitsubishi Gas Chemical Co., Ltd., and New Japan Physical and Chemical Corporation. Soluble polyimine "RICACOATSN20 (registered trademark)" and "RiCACOATPN20 (registered trademark)", polyether phthalimide "ULTEM (registered trademark)" manufactured by Japan GE Plastics Co., Ltd., DIC (share) system "V8000" and "V8002" and "v8〇〇5", "BPAM155" manufactured by Nippon Kayaku Co., Ltd., etc. As a commercial product of polyethersulfone resin, a known product can be used, for example, Sumitomo

Chemical company PES4100P, PES4800P, PES5003P and PES5200P. As the polyphenylene ether resin, for example, poly(2,6-dimercapto-fluorene, 'phenylene) oxide, poly(2,6-diethyl-1,4-extension) oxidation , poly(2-methyl-ethylidene-1,4-phenylene) oxide, poly(2.methyl-6-propylyi-4-phenylene) oxide, poly(2,6- Dipropyl-1,4-extended base oxide, poly(I-ethyl propylene 101102463 31 201251533 -1,4-phenylene) oxide, and the like. As a commercial item, for example, "Noryl ΡΧ 9701 (registered trademark)" (quantitative average molecular weight Μη = 14,000) and "Noryl 640-111 (registered trademark)" (quantitative average molecular weight Mn = 25,000) manufactured by GE本GE Plastics Co., Ltd., and "SA202" (number average molecular weight Mn = 20,000) manufactured by Asahi Kasei Co., Ltd. can be used by a known method to reduce the molecular weight. Among these, a reactive oligomeric phenylene oxide which is modified by a functional group is preferably used. Thereby, since the compatibility with the thermosetting resin can be improved and the three-dimensional crosslinked structure between the polymers is formed, the mechanical strength is excellent. For example, 2,2',3,3,5,5,-hexamethylenebiphenyl-4,4,-diol 2,6_ described in JP-A-2006-28111 A reaction product of a dimethyl phenol polycondensate and gas methyl styrene. Such a reactive oligomeric phenylene oxide can be produced by a known method. Further, a commercially available product can also be used. For example, 〇PE_2st 22〇〇 (manufactured by Mitsubishi Gas Chemical Co., Ltd.) can be suitably used. The weight average molecular weight of the reactive oligomeric phenylene oxide is preferably 2,000 to 20,000, more preferably tOO^^ooo. If the weight average molecular weight of the reactive oligomeric phenylene oxide exceeds 20 Å, it is difficult to dissolve in the volatile solvent. On the other hand, if the weight average molecular weight is less than 2, the surface is too high, and the elastic modulus or flexibility of the cured product is bad. The heat in the resin composition used in the embodiment is different. The amount of the sclerosing tree is not particularly limited as long as it is appropriately adjusted in accordance with the purpose, and the thermosetting resin is preferably ΐ() to 9 (% by weight) in the total solid content of the tree mash. ^ 101102463 32 201251533 Optimum 20 to 70% by weight 'more preferably 25 to 50% by weight (hereinafter, "~" means that the upper limit and the lower limit are included unless otherwise specified). Further, when an epoxy resin and/or a cyanic acid-based resin is used as the thermosetting resin, the epoxy resin is preferably 5 to 50% by weight, based on the total solid content of the resin composition. The resin is more preferably 5 to 25% by weight. Further, in the total solid content of the resin composition, the cyanate resin is preferably 5 to 50% by weight, and the cyanic acid resin is more preferably 10 to 25% by weight. The resin composition preferably contains an inorganic filler from the viewpoint of low thermal expansion and mechanical strength. The inorganic filler is not particularly limited, and examples thereof include talc, calcined clay, uncalcined clay, mica, glass, and the like, and oxides such as titanium oxide, aluminum oxide, cerium oxide, and cerium oxide. , carbonates such as calcium carbonate, magnesium carbonate, hydrotalcite, aluminum hydroxide, bauxite (AIO(OH)), commonly known as "water" in bauxite (ie, Α12〇3 · xH2) 〇 'here' X=1 to 2), magnesium hydroxide, hydroxide hydroxide 'sulfur_, sulfur, sulfite sulfate or sulfite-Dendrobium zinc, methyl ore, _ Lu, Ship 35, Occupational, etc., acid salt, nitrogen, nitrogen (four), tantalum, carbon nitride and other nitrides, tannic acid recording, titanate conversion titanate. 4 Use this material in combination of two or more. Among these, preferred are hydroxide, continuation, cerium emulsified aluminum, bauxite, digas, cerium, molten cerium oxide, talc, yttrium talc, and alumina. From the viewpoint of low thermal expansion properties and insulation reliability, fit is a nitric oxide eve, and more preferably a spherical wafer 101102463 33 201251533 (iv) dioxo. Further, in terms of fuel economy, it is preferably a hydroxide. Further, in the above (4), the amount of the inorganic filler can be increased in the resin composition by using a substrate which is easily impregnated even if the inorganic filler is used. When the inorganic filler in the second composition of the tree is at a high concentration, the bit wear resistance is deteriorated, but when the machine filler is water and soil, the particle size of the inorganic filler is not particularly large from the viewpoint of good drill wear resistance. For example, it is possible to use an inorganic filler having a uniform particle diameter as a monodisperse. It is also possible to use an inorganic filler having an average particle diameter of polydisperse, and a combination of an inorganic filler having an average particle diameter of monodisperse and/or polydisperse. Or two or more. The average particle diameter of the inorganic filler is not particularly limited, and is preferably 〇.1μΐΏ~5 ()μηη, particularly preferably G 1μιη to 3 Zheng m<> if the particle diameter of the inorganic filler is less than the above lower limit value, Further, since the degree of the resin composition is increased, there is a case where the workability at the time of preparation of the prepreg is affected. In addition, when it exceeds the above upper limit, a phenomenon such as sedimentation of the inorganic filler may occur in the resin composition. Further, the average particle diameter can be measured by a laser diffraction/scattering type particle size distribution measuring apparatus (a general machine such as Shimadzu Corporation and SALD-7000). The content of the inorganic filler is not particularly limited, and is preferably from 1% by weight to 9% by weight, more preferably from 30% by weight to 8% by weight, based on the total solid content of the above resin composition. %~75 weight ❶/. . When the cyanate resin and/or its prepolymer is contained in the above resin composition, the content of the inorganic filler is preferably from 50 to 75% by weight based on the total solid content of the resin composition. If the content of the filler in the inorganic 101102463 34 201251533 exceeds the above upper limit value, the fluidity of the filament is extremely poor, which is not preferable; if the filament is above the lower limit, the strength of the insulating layer composed of the resin composition is insufficient, which is not good. . Further, as the resin composition used in the present embodiment, a rubber component 'for example' may be blended as a rubber particle which can be used in the present embodiment, and examples thereof include a core-shell type rubber and a crosslinked (10) nitrile. Dinger __ child, parent biphenyl B: 3⁄4 butyl; rubber particles, propylene rubber particles, poly-stone particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and the shell layer of the outer layer is composed of a glassy polymer, and the core layer of the inner layer is a two-layer structure composed of a rubber-like polymer; The shell layer of the outer layer is composed of a glassy polymer. The intermediate layer is composed of a rubber-like polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer layer is composed of, for example, methyl-acid A, a polymer or the like, and the rubber-like polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include, for example, Stafn〇id aC3832, AC3816N (manufactured by Ganz Chemical Co., Ltd.), and metablen 0\Μ426 (®σσ, manufactured by Mitsubishi Screw Co., Ltd.). Specific examples of the cross-linked propylene carbonate rubber (NBR) particles include xer_9i (average particle diameter: 0.5 μm, manufactured by JSR Co., Ltd.). Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include, for example, xsk-5〇o (average particle diameter of 0 5 μηι, manufactured by Shibuya Co., Ltd.). Specific examples of the rubber particles of the acrylic rubber 101102463 35 201251533 include, for example, METABLEN W300A (average particle diameter Ο.ίμηι), W450A (average particle diameter 〇.2 μιη) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like. The polysiloxane particles are not particularly limited as long as they are rubber elastic fine particles formed of an organic polysiloxane, and may be, for example, fine particles composed of a polyoxyxene rubber (organic polyoxyalkylene crosslinked elastomer), and A core-shell structured particle coated with a polyfluorinated oxygen of a three-dimensional crosslinked type body by a core portion composed of a two-dimensionally crosslinked host. As the polyoxyxene rubber microparticles, ΚΜΡ-605, ΚΜΡ-600, ΚΜΡ-597, ΚΜΡ-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), TORAYFILE-500, TORAYFILE-600 (manufactured by Toray Dow Corning Co., Ltd.) can be used. And other commercial products. The resin composition may further contain a coupling agent. The coupling agent enhances the wettability of the interface between the thermosetting resin inorganic fillers, thereby uniformly setting the tree sap and the inorganic filler to the substrate, and improving the heat resistance, particularly after moisture absorption. The solder is heat-resistant and formulated. The coupling agent is not particularly limited, and examples thereof include an epoxy decane coupling agent, a cationic decane coupling agent, an amino decane coupling agent, a titanate coupling agent, and a polyoxo-oxygen type coupling agent. Thereby, the wettability with the interface with the inorganic filler can be improved, whereby the heat resistance can be further improved. The amount of the coupling agent to be added is not particularly limited, and is preferably 0.05 to 3 parts by weight, particularly preferably 2 to 2 parts by weight, based on 1 part by weight of the inorganic filler. If the content is less than the above lower limit, the inorganic filler may not be sufficiently coated, so that the effect of improving the heat-generating property may be lowered. If the above-mentioned upper limit is exceeded, the effect of the reaction may be affected, and the bending strength may be affected. Reduced situation. In the resin composition used in the embodiment, an antifoaming agent, a leveling agent, a UV absorber, a foaming agent, an antioxidant, a flame retardant, a flame retardant such as a polyfluorene oxide powder, or the like may be added as needed. An additive other than the above components such as an ion trapping agent. The resin composition preferably contains at least an epoxy resin, a cyanate resin, and an inorganic filler from the viewpoint of easily achieving low-line expansion, high rigidity, and high heat resistance of the prepreg. In the solid portion of the resin composition, it is preferable to contain 5 to 50% by weight of the epoxy resin, 5 to 5 % by weight of the cyanate resin, and 10 to 90% by weight of the inorganic filler, and more preferably contain a ring. The oxygen resin 5 to 25 was reset to %, and the cyanate resin was 10 to 25 parts by weight. /. And inorganic filler material 3〇~8〇 weight %. The prepreg used in the present embodiment is a base material obtained by impregnating or coating a varnish of a resin composition on a substrate, and can be used as a base material for a material-based electrical insulating material. Examples of the material f of the substrate include inorganic fibers such as E glass, D glass, T glass, s glass, or Q glass, organic fibers such as polyimine, polystyrene, or tetrafluoroethylene, and the like. Mixtures, etc. These base materials have, for example, a woven fabric, a non-woven fabric, a roving (four) (four), a rhyme, and a surface scale. The material and shape may be selected depending on the use or performance of the target molded article, and may be used alone or in combination of two or more materials and shapes. . The thickness of the substrate is not particularly limited. Usually, it is about 0.01 to 0.5 mm. From the viewpoint of U or moisture resistance H, in terms of workability, it is preferred to use a surface treatment processor or a mechanical machine such as a stone smelting coupling agent 101102463 37 201251533. Sexual opening treatment and implementation of flattening. Further, the prepreg is usually impregnated or coated on the substrate in a manner such that the resin content thereof is 20 to 90% by weight after drying, depending on 12 to 220. (: The temperature is heated and dried for 1 to 20 minutes, and it is obtained in a semi-hardened state (B-stage state). Further, 'the prepreg can be usually overlapped by 1 to 2 pieces, and then placed on both sides thereof. The ultra-thin copper foil of the body foil is laminated and heated to form a laminate. The thickness of the plurality of prepreg layers varies depending on the application, and is usually 〇〇3 to 2 mm thick. The laminating method can be applied to a conventional laminate, for example, using multi-stage pressing, multi-stage vacuum pressing, continuous forming, a south autoclave forming machine, etc., at a normal temperature of 1 〇〇 to 25 〇. 匸, pressure 0·2 〜 lOMPa, The lamination is carried out under the conditions of a heating time of 1 to 5 hours, or by a vacuum lamination apparatus or the like under the conditions of lamination conditions of 50 to 150 ° C, 0.1 to 5 MPa, and a vacuum pressure of 1.0 to 760 mmHg. The ultra-thin copper foil (copper foil layer 104) having a carrier foil is formed by a bump-like electro-chemical layer on the roughened surface of the ultra-thin foil (referred to as Japanese patent special opening + for example) 5_〇2974〇) formation or oxidation treatment 4 original place i, silver The roughening surface is processed by engraving. Therefore, this is

The surface roughness of the roughened surface of the ultra-thin copper box used in the embodiment is preferably the upper limit of the average roughness (Rz) of the point of JIS B0601 which is preferably 5 瓜 Τ ιμιη yp; The 'lower limit' is not particularly limited, and is preferably 〇·1 μmη or more. Further, the arithmetic mean roughness (four) is preferably 1 or less, more preferably 0. 5 μιη or less. 101102463 38 201251533 In addition, in the present embodiment, the copper foil as the copper box layer 1〇4 is inevitably mixed in the manufacturing step, and the steel is formed to contain the added metal component of the recording or the material, and there is no In particular, the total value of the content of the metal steel constituting the copper (10) layer (10) is preferably 90% by weight or more, more preferably 2% by weight, and more preferably 5% by weight or more. It can be used in combination with a single type. In addition, it is also possible to replace the metal foil of the copper enamel layer just ‘,,’ early, and foil. S' uses nickel foil or aluminum as a conventional copper-forming method, and is usually formed into a copper crucible having a thickness of about three. However, this formation method deals with the case where the orientation of the underlying metal layer (for example, an electrode) is continued: a copper foil having a desired crystal face of the steel falling... If the film thickness of the steel foil is thick, for example, when it is made to have more than The crystal grains tend to be coarsened in the thickness direction. In contrast, in the formation of the steel foil layer 1〇4 of the present embodiment, a peeling layer is formed on the electrode, and a steel box layer is formed on the peeling layer, whereby the copper box layer 104 can be suppressed. Continuing the alignment of the lower electrode; ^, by appropriately controlling the copper foil layer ι〇4 which is in contact with the peeling layer, the orientation of the layered surface of the copper box layer 1〇4 is continued. To the other side. Thereby, the alignment 104 can be formed. The steel layer of the aligned steel box 101102463 The film thickness of the copper pig layer is not particularly limited, and is preferably 〇>^, preferably. .5, above and 3 handsome. By setting the film thickness of Steel No. 2, No. 39 201251533 within this range, the particle size of the crystal grains of the copper foil layer 104 can be made uniform. Thereby, the orientation change of the copper foil layer 104 can be suppressed in the film thickness direction. By the above, the alignment of the upper surface 20 of the copper foil layer 104 can be controlled, for example, from the lower surface 22 of the copper foil layer 1〇4 to the upper surface 20, the ratio of the crystal faces (that is, the alignment) is the same; for example, XRD can be used. The ratio of the plane direction (200) measured by the film method, or the ratio of the plane direction (200) and the plane orientation (220) is the same. The term "same" as used herein refers to a tolerance in the manufacturing step, for example, the ratio of the plane orientation (2 〇〇) of the lower surface 22 of the copper foil layer 104, which is ± 5% of the ratio of the surface direction (200) of the upper surface thereof. Within. Therefore, the ratio of the plane orientation of the lower surface 22 of the copper foil layer 104 measured by the xRD film method is equivalent to the ratio of the upper surface 20 of the copper foil layer ι4. In addition, in the upper surface 20 of the copper foil layer 104 after the formation of the copper foil laminate 1 by heat and pressure molding, the copper foil layer before the heat and pressure molding is maintained in the coordination property (the carrier foil which can be obtained by the separation method) The value of the copper foil). The heating and press forming conditions as described herein are, for example, 1 hour at 20 CTC and a pressure of 3 MPa. The reason for maintaining the ratio is not clear, but it is presumed that the crystal grain size of the crystal grain in the copper foil layer 1〇4 is small, and the average particle diameter has a certain degree of uniformity. Therefore, even before and after the etching step of the copper foil layer 104 to be described later, the surface orientation of the copper foil layer 1 〇4, the surface of the ruthenium 20 (that is, the junction with the metal layer 116 (for example, the electroless plating layer 11 〇)) The ratio of 2〇〇), or the ratio of face orientation (2〇〇) and face orientation (22〇) is the same. The copper foil layer 104 is preferably a crystal grain having an average length of a long side of 101102463 201251533 2μηη or less. The shape of the crystal grains in the copper foil layer 1 〇 4 is, for example, a columnar shape or a triangular pyramid shape. Therefore, the maximum length of the crystal grains of the copper foil layer 1 〇 4 is taken as the long side in the cross-sectional view. The average length of the long side is between FIB_SIM (Focused Ion Beam Scanning Ion Microscope) or FIB-SEM (Focused Ion Beam Scanning Electron Microscope), which is between 10,000 and 12,000 times. The average of the cross-sectional images of 〇μιη was calculated, and the average value of the total of three visual field images was calculated. Thereby, the etching characteristics of the copper foil layer 104 are improved. Further, in the copper foil layer 1 〇4 of the present embodiment, the area ratio □ occupied by the crystal grains having an average length of 2 μm or less in the long side is preferably 8% by number or more, and more preferably 85°. More than 90% above. This area ratio is subjected to image processing on the field of view of the same cross-sectional image as described above, and the average value of the total of three fields of view is calculated. Thereby, the etching characteristics of the copper foil layer 1〇4 are improved. Here, a detailed method of forming the peelable copper foil used for the copper foil layer 104 will be described. The method for producing the copper foil used in the present embodiment is not particularly limited. For example, when a peelable copper foil having a carrier is produced, an inorganic material such as a metal which is a release layer is formed on a carrier foil having a thickness of 10 to 50 μm. A compound or an organic compound layer is subjected to a plating treatment on the release layer to form a copper foil. As a condition of the plating treatment, for example, when a copper sulfate bath is used, it can be set to 50 to 100 g/L of sulfuric acid, 30 to 〇0 g/L of copper, and 2 (rc to 8 (rc, current density of 0.5 to 1 〇). 〇A/dm2 conditions; when using a copper pyrophosphate bath, it can be set to coke 101102463 41 201251533 potassium phosphate 100~700g/L, copper 10~50g/L, temperature 30°C~6 (TC, pH8~12 The current density is 1 to 1 〇A/dm2. Further, various additives may be added to the bath in consideration of the physical properties or smoothness of the steel foil. Further, the peelable metal foil is a metal having a carrier. The foil and the carrier are exfoliable metal ruthenium. The inorganic compound or the organic compound layer of the release layer-based metal or the like may be peeled off even if it is subjected to heat treatment between 10 0 and 300 ° C even when laminated. As the metal oxide, for example, a mixture of zinc, chromium, nickel, copper, molybdenum, an alloy, a metal, a metal compound, or the like can be used. As the organic compound, it is preferred to use an organic compound selected from nitrogen-containing compounds. One or more of a sulfur organic compound and a carboxylic acid The above nitrogen-containing organic compound is preferably a nitrogen-containing organic compound having a substituent. Specifically, it is preferred to use 1,2,3-benzotriazole which is a triazole compound having a substituent (hereinafter referred to as "BTA" "), carboxybenzotriene (hereinafter referred to as

-1H-1,2,4-triazole (hereinafter referred to as "ATA") or the like.

Imidazole thiol (hereinafter referred to as "BIT") and the like. As the acid retardant, it is particularly preferable to use a single lye, and among them, oleic acid, linoleic acid, and linoleic acid are preferably used. As described above, the desired orientation can be achieved on the upper surface 20 of the steel foil layer 104 of the present embodiment by increasing the formula of the method of controlling the untwisting and subtracting the (four) material control system 101102463 42 201251533. In addition, at least the lower surface of the copper foil layer 104 used in the present embodiment (the surface in contact with one surface of the insulating layer 102) is at a practical level or higher in order to make the adhesion between the copper foil layer 1〇4 and the insulating layer 102. Surface treatment can also be carried out. The rough treatment of the metal foil used for the copper foil layer 104 may be, for example, any one of rustproof sound, chromic acid treatment, and decane coupling treatment, or a combination thereof. = Any of the surface strict means is appropriately selected in conjunction with the resin material constituting the insulating layer 102. The rust-preventing treatment can be carried out by forming a film on a metal drop by, for example, plating an alloy of nickel, tin, zinc, chromium, platinum, or the like, or an alloy thereof. . From the viewpoint of cost, it is preferably electric forging. In order to facilitate the precipitation of metal ions, a necessary amount of a modifier such as a naphthate, a tartrate or a sulfamic acid may be added. The bath is usually used in an acidic area and is carried out at room temperature (e.g., pit) to sail temperature. The ore-covering condition is suitably selected from a current density of 0.1 to 10 OA/dm2, and an energization time of _second, preferably _second (four). The amount of the anti-recording treatment metal varies depending on the kind of the metal, and the total amount is preferably from 10 to 2000 mm. If the treatment is too thick, (4) the electrical property is lowered. If it is too thin, the peel strength between the resin and the resin is lowered. Further, when the resin composition constituting the insulating layer 1〇2 contains a ruthenium oxychloride resin, it is preferable to carry out the _ treatment H combination by the metal containing, and the thermal deterioration test or the moisture resistance deterioration test in the 101102463 43 201251533 It is useful to reduce the peel strength less. As the chromic acid treatment, an aqueous solution containing hexavalent chromium ions is preferably used. The chromic acid treatment may be a simple impregnation treatment, but it is preferably carried out by a cathode treatment. Che Yujia is based on heavy bismuth chromate 1~5〇g/L, pHi~13, bath temperature 〇~6〇. 〇, current density 0.1~5A/dm2, electrolysis time o. ^ioo seconds conditions. It can also replace sodium dichromate or chromic acid. Further, it is preferable that the above-mentioned complex acid treatment is superposed on the above-mentioned shutdown treatment so that the adhesion between the insulating resin composition layer (insulating layer 102) and the metal foil (copper box layer 1〇4) can be further improved. As the decane coupling agent to be used in the above decane coupling treatment, for example, 3-glycidoxypropyltrimethoxywei, 2-(3,4-epoxycyclohexyl)ethyltrioxyloxy or the like can be used. Epoxy-functional wei, 3-aminopropyltrimethoxy oxime, N-2-(aminoethyl)-3-aminopropyltrimethoxy-based, N_2-(aminoethyl)3 -Aminopropyl fluorenyl dimethoxy wei, such as amine functional Wei, ethylene triterpenoid A, Wei, ethylene phenyl trimethoxyton, ethylene ginseng (2 - methoxy ethoxy) Ke) Wei et al. olefinic functional Wei, 3_ propyleneoxypropyl 曱 曱 魏 魏 丙烯 丙烯 丙烯 # 能 ################################################## The functional group of Wei, 3, propyl trimethoxy, etc., functional Wei, etc. These may be separate (4) or may be mixed in multiples (4). These couplings are sprayed on a solvent such as water and dissolved in a concentration of ' ' ' 藉 ' ' ' ' ' ' ' 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 101 Adhesive to metal foil. These zephyr coupling agents form a film on the metal foil by condensing and bonding with the hydroxyl group of the rust-preventing metal of the metal pig surface. After the coupling treatment of Shi Xi, the bonding is stabilized by heating, ultraviolet irradiation, or the like. In the heat treatment, for example, 100 to 2 Torr (temperature of TC, drying of 2 to 60 seconds) is preferably carried out. Ultraviolet irradiation is preferably carried out, for example, in a range of wavelengths of 2 〇〇 to 400 nm and 200 to 2500 mJ/cm 2 . The decane coupling treatment is preferably carried out on the outermost layer of the metal foil. When the cyanate resin is contained in the insulating resin composition constituting the insulating layer 102, it is preferably treated with an amine-based coupling agent. It is useful to reduce the peel strength in the heat-resistant deterioration test or the moisture-resistant deterioration test. Further, the decane coupling agent used as the decane coupling treatment is preferably 60 to 200 C, more preferably 80 to 150. : heating, and chemically reacting with the insulating resin composition constituting the insulating layer 1〇2, whereby the functional group in the insulating resin composition is chemically reacted with the functional group of the decane coupling agent, thereby obtaining superiority. For example, for the epoxy resin-containing insulating resin composition, it is preferred to use an amine-based functional Shixiyuan coupling agent, which is because the epoxy group and the amine group are easily heated by heat. shape It is a strong chemical bond, and this bond is extremely detrimental to heat or moisture. Thus, as a combination forming a chemical bond, an epoxy group, an epoxy group, an epoxy group, an epoxy group, a group, and a ring can be exemplified. Oxy-perylene, epoxy group, yl-oxyl-cyano group, amino group, amine group, amine group, amino group, cyano group, etc. 101102463 45 201251533 In addition, the insulation used in this embodiment The insulating resin of the resin composition is preferably used in an epoxy resin which is liquid at normal temperature. In this case, since the viscosity at the time of melting is greatly lowered, the wettability of the adhesive interface is improved, and epoxy resin and decane couple are likely to occur. As a result of the chemical reaction of the mixture, a strong peel strength can be obtained. Specifically, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin having an epoxy equivalent of about 200 is preferable. Further, when the insulating resin composition contains a curing agent, it is particularly preferable to use a thermosetting latent curing agent as a curing agent, that is, a functional group in the insulating resin composition and a functional group of a decane coupling agent. Chemical reaction Preferably, the curing agent is selected according to a method in which the reaction temperature of the functional group in the insulating resin composition and the functional group of the decane coupling agent is lower than the temperature at which the hardening reaction of the insulating resin composition starts. The reaction between the functional group in the compound and the functional group of the Shixiyuan coupling agent is preferentially performed, and the adhesion between the metal foil (copper foil layer 104) and the insulating resin composition layer (insulating layer 1〇2) is selectively made high. Examples of the thermosetting latent curing agent for the insulating resin composition containing an epoxy resin include solid dispersion such as dicyandiamide, diterpene compound, imidazole compound, and amine-epoxy adduct. - a reactive block-type curing agent such as a heat-dissolving hardener, a urea compound, a phosphonium salt, a tri-vaporized boron-amine salt, or a block carboxylic acid compound. By laminating the prepreg containing the above-mentioned insulating resin composition, the ultra-thin copper fl' having a carrier foil which is finely and uniformly roughened and subjected to the above surface treatment by the above method Hua, Qingcheng has a carrier __ laminate 1Q as shown in Fig. 7(4) 101102463 46 201251533. Next, as shown in Fig. 7(b), by pulling off the carrier (four) layer 1G6', a copper box laminate 1 having a copper layer on both sides of the insulating layer can be obtained. At this time, the upper limit of Ra of the surface facing the surface of the steel box on which the carrier box layer is facing (the surface that is also in contact with (4)) is Ι.Ομιη or less, better than Q4gm, and the special kiss. the following. The lower limit of Ra is not particularly limited, and is preferably 〇.G5_ or more. On the other hand, the upper limit of Rz of the surface is preferably 4 () μηη or less, more preferably 2 or less, and more preferably less than ΟμΟη. The lower limit of RZ is not particularly limited, and is not limited thereto. The copper foil layer 104 may be formed on at least one side of the insulating layer 1〇2 or may be formed on the insulating layer 102. Whole face or - Qiu points. . In the present embodiment, by reducing the thickness of the surface of the carrier, reducing the crystal (4) of the bulk copper, and reducing the uniformity of the particles, the method can be appropriately controlled. Rp and Rku in one of the surface layers 1 of the insulating layer 1〇 of the embodiment are within the above range. Next, as shown in Fig. 7(c), a through hole (10) for interlayer connection is formed on the copper pig laminate (10). In the method of forming the through hole (10), it is possible to form a through hole ι 8 having a hole (four) 1 () () μm or more by various known means, for example, from the viewpoint of productivity, it is suitable to form a drill or the like. When the through hole 1 () 8 is ΓΠμΓΠ, it is suitable for a solid laser such as a gas laser such as a carbon dioxide gas or an excimer or a solid laser such as YAG. Then, the catalyst core can be provided on at least the copper tank layer 1〇4. However, in the present embodiment, 101102463 47 201251533, the catalyst core is provided on the entire surface of the copper foil layer 104 and on the inner wall surface of the through hole 1〇8. The catalyst core is not particularly limited, and for example, a noble metal ion or a platinum colloid can be used. Next, an electroless plating layer is formed using the catalyst core as a core. However, before the electroless plating treatment, the surface of the copper foil layer 1〇4 or the through hole 1〇8 may be formed, for example, by Decontamination of liquid medicine, etc. The decontamination treatment is not particularly limited, and a wet method using an oxidizing agent solution having an organic decomposition action or the like can be used, and an active species (plasma, radical, etc.) having a strong oxidation effect can be directly irradiated to the object to be removed. A known method such as a dry method such as a plasma method of an organic residue. Specific examples of the decontamination treatment by the wet method include a method in which a swelling treatment on the surface of the resin is carried out, followed by a treatment, followed by a neutralization treatment. Next, as shown in Fig. 7(d), a thin layer of electroless plating layer 110 is formed by electroless plating on the copper foil layer 1〇4 to which the catalyst core is applied and the inner wall of the through hole 108. The electroless plating layer 11 is formed by electrically connecting the mi layer 104 on the upper surface of the insulating layer 1 2 to the copper box layer 104 on the lower surface thereof. In the case of electroless plating, for example, copper sulfate, furfural, a neutralizing agent, sodium hydroxide or the like can be used. Further, after the electroless plating, it is preferred to carry out heat treatment at 100 to 250 Torr to stabilize the recording film. From the viewpoint of forming a film capable of suppressing oxidation, it is particularly preferably a heat treatment of 12 G to 18 Gt:. Further, the average thickness of the electroless ore layer 110 may be a thickness which can be plated as described below, and for example, 〇·Ι~ΙμΓΠ is sufficient. Further, the through hole may be filled with a conductive paste or an insulating paste, or may be filled by plating with an electric pattern. 101102463 48 201251533 Next, as shown in Fig. 7(e), a plating resist 112 having a predetermined opening pattern is formed on the electroless plating layer 11 provided on the copper foil layer 1〇4. This opening pattern corresponds to a conductive circuit pattern to be described later. Therefore, the plating resist 112 is provided to cover the non-circuit forming region on the copper foil layer 104. In other words, the plating resist 112 is not formed on the beacon hole 108 and the conductor circuit forming region on the copper foil layer 1〇4. The plating resist 112 is not particularly limited, and a known material can be used, but a liquid or dry film can be used. In the case of forming a fine wiring, as the plating resist 112, a photosensitive dry film or the like is preferably used. When the plating resist 112 is formed, for example, a photosensitive dry film is laminated on the electroless plating layer 110, the non-circuit forming region is exposed to light hardening, and the unexposed portion is dissolved and removed by the developing solution. Further, the remaining hardened photosensitive dry film will become the plating resist 112. The thickness of the plating resist 112 is preferably set to a film thickness equal to or thicker than the thickness of the conductor (plating layer 114) to be plated later. Next, as shown in Fig. 8(a), at least the inside of the opening pattern of the residual layer 112 and the electroless plating layer 11 are formed, and the plating layer 114 is formed by a plating treatment. At this time, the copper foil layer 104 functions as a power supply layer. In the present embodiment, the plating layer 114 may be continuously provided on the upper surface of the insulating layer 102, the inner wall of the through hole 1〇8, and the lower surface thereof. The plating method is not particularly limited, and a known method used for a general printed wiring board can be used. For example, a method of immersing in a plating solution such as copper sulfate or the like, and a method of flowing a current or the like to the plating solution can be used. . The thickness of the plating layer 1H is not particularly limited, and may be used as a circuit conductor. For example, it is preferably in the range of 1 to ΙΟΟμπι, preferably in the range of 5 to 5 μm. Plating layer 101102463 49 201251533 114 can be a single layer or have a multi-layer construction. The material of the layer m is not particularly limited, and for example, copper, a steel alloy, a 42 alloy, a lock, iron, a complex, tungsten, gold, solder, or the like can be used. Next, as shown in Fig. 8 (b), the plating resist 112 is removed using an inert stripping solution or sulfuric acid or a commercially available plating stripping solution or the like. Next, as shown in Fig. 8(c), the electroless bond layer 110 and the copper box layer other than the region where the money-coated cladding layer 4 is formed are just removed. The method of removing the copper pulp 1〇4 is, for example, a soft #刻 (fast side) or the like. Thereby, a pattern of the conductive circuit 118 formed by laminating the copper beryllium layer ι 4 and the metal layer electroless ore cladding layer 11 and the cladding layer can be formed. The cross-sectional shape of the conductive circuit 118 of the printed wiring board 2 according to the second embodiment may be an inverted tapered shape as shown in FIG. 9 (4) and a vertical cross-sectional shape as shown in FIG. 9 as shown in FIG. b) any of the fish plate (half-groove) shape shown or the neck-shaped shape shown in Fig. 9(c). Here, the etching liquid used for the soft etching of this embodiment will be described. The etching liquid is not particularly limited, and when a conventional diffusion control type etching liquid is used, the fine portion of the wiring tends to deteriorate in circuit formation property due to deterioration of liquid exchange. Therefore, it is preferable to use the reaction of the copper etch solution as the type of reaction control, not the diffusion control type. If the reaction of copper and the etching solution is reaction control, the etching rate does not change even if the diffusion is enhanced above it. Even if there is no difference in the _ speed between the liquid exchange and the poor. As such a reaction control etching liquid, for example, hydrogen peroxide and an acid having no element 101102463 50 201251533 as a main component can be mentioned. * Since _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Further, if the halogenated 7G element is mixed into the New Zealand liquid, the cardiac reaction tends to become diffusion control. As a acid containing no south, nitric acid, sulfuric acid, organic acid, etc. can be used, and sulfuric acid is preferred because of its low cost. Further, in the case of bribe and Wei hydrogen, the stability of _ speed is higher. The respective concentrations are preferably 5 to 300 g/L and 5 to 200 g/L. For example, a persulfate recording, a sodium persulfate, a persulfate steel system, etc. are mentioned. Thus, by appropriately selecting the silver engraving characteristics or the _ condition of the (four) layer (10), the conductive circuit 118 of a desired shape can be obtained. As a result, the printed wiring board having the conductive circuit 118 formed on both surfaces of the insulating layer 1 2 can be obtained. In the method of manufacturing a printed wiring board according to the second embodiment, the same operational effects as those of the first embodiment can be obtained. + As shown in Fig. 1), the solder resist layer no may be formed so as to cover one portion of the insulating layer 1G2 and one of the conductive circuits 118. As the solder resist layer 0, for example, a photosensitive resin which can contain a filler or a substrate having excellent insulating properties, a thermosetting resin, and a heat-resistant resin composition can be used, and then the solder resist layer 120 is provided. Further, a first money layer 122 and a second key layer 124 are formed on the conductive circuit (10) of the opening. Thereby, the metal layer 116 can be formed into a multilayer structure of two or more layers. As the first key coating layer 122 and the second mineral coating layer 124, a gold ore layer can be used. The method of the method of the method is not particularly limited. For example, 0,1 to 10 Κη electroless nickel plating is performed on the plating layer n4, and electroless nickel plating is performed after the substitution of gold plating 101102463 201251533 0.01 to 0.5 μmη. Forging gold 〇 1~2gm and other methods. The printed wiring board 202 shown in Fig. 8 (d-1) can be obtained by the above. Further, as shown in Fig. 8 (d-2), the first plating layer 122 and the second plating layer 124 may be formed around the conductive circuit 118 without forming the solder resist layer 12A. As the first plating layer 122 and the second plating layer 124, for example, a laminated body of a nickel plating layer and a clock gold layer can be used. With the above, the printed wiring board 204 of Fig. 8 (d_2) can be obtained. Further, a semiconductor wafer (not shown) is mounted on such printed wiring boards 200, 2, and 204 to obtain a semiconductor device. (Third Embodiment) Next, a method of manufacturing a printed wiring board according to a third embodiment will be described. Fig. 1 to Fig. 12 are cross-sectional views showing a procedure of a manufacturing procedure of a method of manufacturing a printed wiring board according to a third embodiment. In the method of manufacturing a printed wiring board according to the third embodiment, for example, the printed wiring boards 2, 2, and 204 obtained in the second embodiment are used as the inner layer circuit board, and the additional layer is formed on the inner layer circuit board. . (4) The printed wiring board obtained from item 8 (8) is used as the inner layer circuit! The inner layer circuit of the printed wiring board 2 (the conductive circuit is called the implementation of the meter). The so-called roughening process refers to the surface of the conductor circuit _ = 2; treatment, etc. As the roughening treatment, for example, the release = two treatment 'or the known treatment of ruthenium hydrogen peroxide system _ 灭 灭 4 can be used to make the layer of edge layer i3Q of the structure of the money edge. 101102463 52 201251533 The adhesion between the conductive circuits 118 of the printed wiring board 200 is improved. The inner circuit board can also be replaced by the printing method obtained in the second embodiment, and is not particularly limited, and can be used by a plated through hole method or The build-up method and the like include a pre-extracted body or a substrate-free tree (4), etc., which is a conductor circuit layer of the inner layer circuit, which can be formed by a conventional circuit forming method. The multi-layer printed (four)-line slab can be formed by drilling, laser processing, or the like by laminating the laminated body (the laminated body obtained by laminating a plurality of prepregs) and the metal foil laminated plate. a hole, and then electrically connecting the inner layers of the two sides by plating or the like Next, as shown in FIG. 10(a), an insulating layer 103 (prepreg) and a copper foil layer having a carrier foil layer 107 are disposed on both sides of the printed wiring board 200 on which the surface of the conductor circuit is roughened. 105 (very thin copper foil having a carrier foil) Next, as shown in Fig. 10 (b), a multilayer laminated plate is formed by subjecting a laminated body which overlaps these layers to heat and pressure treatment. Next, as shown in Fig. As shown in (c), the carrier foil layer 107 is peeled off. Next, as shown in FIG. 10(d), one portion of the insulating layer 130 and the copper foil layer 1〇5 is removed to form a hole 109. The bottom surface exposes a part of the surface of the conductive circuit 118. The method of forming the hole 109 is not particularly limited, and for example, a solid laser such as a gas laser such as carbonic acid gas or an excimer or a solid laser such as YAG can be used to form a blind hole having a diameter of ΙΟΟμηι or less. The method of the through hole, etc., the hole 109 is shown as a non-through hole in Fig. 10, but may be a through hole. Further, in the case of a through hole, a drilling machine may be used even in the case of laser irradiation. And 101102463 53 201251533 is formed. Next, as shown in Figure 11 (a), in the above An electroless plating layer of a thin layer is formed on the inner wall of the conductive circuit ΐΐ8 of the catalyst core, and on the inner wall of the hole 98, and the electroless plating layer I11 and the electroless plating layer 11 are formed. The crucible is formed in the same manner. Before the electroless plating, as described above, the chemical liquid can be removed, and the first decontamination treatment can be performed. Further, the thickness of the electroless recording layer 110 is the thickness which can be electroplated as follows. That is, 0.1~Ipm is enough. In addition, the hole 1〇9 (blind through hole) can be filled with a conductive paste or an insulating paste, or can be filled by electric pattern plating in advance. Next, as shown in Fig. 11(b) In the electroless plating layer 11 (), a plating resist 113 having an opening pattern corresponding to the conductor circuit pattern is formed. In other words, the non-circuit forming portion is masked by forming the plating resist 113'. As the plating resist 113, the same as the above-described plating resist 112 can be used. The thickness of the plating resist 113 is preferably set to a film thickness equal to or thicker than the thickness of the conductor circuit to be plated later. Next, as shown in Fig. 11 (c), a plating layer I32 is formed inside the opening pattern of the plating resist 113. The plating layer 132 may be formed on the conductive circuit 118 inside the hole 1〇9 or may be formed on the electroless plating layer ill inside the opening pattern. For the plating to form the plating layer 132, the same method as the plating layer u4 described above can be used. The thickness of the plating layer 132 may be, for example, a circuit conductor, and is preferably in the range of, for example, 1 to 1 〇 0 μη, more preferably 5 to 5 Å. Next, as shown in Fig. 12 (a), in the same manner as the above-mentioned plating resist 112, the peeling of the anti-cavity layer 113 is carried out in 101102463 54 201251533. Next, as shown in _12(b), the copper box layer 1〇5 and the electroless plating layer (1) are removed by soft silver etching (fast (four)) in the same manner as the above-described copper/white layer 104. Thereby, a conductive circuit pattern composed of the copper tank layer 105, the electroless ore cladding layer 111, and the plating layer 132 can be formed. Further, on the conductive circuit 118, a via hole and a pad electrically connected to the conductive circuit 118 can be formed by the plating layer 132. By the above, the printed wiring board 2〇1 is obtained. Further, as shown in Fig. 12(c-i), the solder resist layer 121 may be formed on the insulating layer 13A, the plating layer 132 of the conductive circuit pattern, and a portion of the plating layer 132 of the pad. As the solder resist layer 121, the same as the above-described anti-corrugated layer 12 can be used. Then, on the plating layer 132 having the opening portion of the solder resist layer 121, for example, the first plating layer 123 and the second plating layer 125 composed of a nickel plating layer and a gold plating layer can be further formed. Thus, the printed wiring board 203 shown in Fig. 12 (c-1) can be obtained. Further, as shown in Fig. 12 (c-2), the first plating layer I23 and the second plating layer 125 may be formed around the conductive circuit pattern and around the pad without forming the solder resist layer 121. Thus, the barbed wiring board 205 shown in Fig. 12 (c-2) can be obtained. In the third embodiment, the same effects as those of the first and second embodiments can be obtained. Further, a modification of the method of manufacturing the printed wiring board of the embodiment will be described with reference to Fig. 13 . In the above-described first to third embodiments, the metal layer is selectively formed on the copper box. However, in the present modification, the difference is that the metal layer is formed on the entire surface of the copper foil 101102463 55 201251533. Hereinafter, a method of manufacturing the printed wiring board of the present modification will be described. First, as shown in Fig. 13 (a), a copper laminated plate 1 having a carrier crucible is prepared. In the (4) laminated board 1G having the carrier fl, the copper layer H) 4 and the carrier layer 1〇6 are attached to both sides of the insulating layer ig2. Next, as shown in Fig. 13 (8), the carrier (4) should be pulled out from the steel-backed laminate 1 having the load (4). Next, as shown in Fig. 13 (c), a metal layer 115 (plating layer) is formed by a keying process on the entire surface of the copper box layer 1〇4. Next, as shown in Fig. 13 (4), a plating resist 112 having a predetermined opening ® is formed on the flat metal layer 115. As shown in Fig. 13(e), the Meng layer 115 and the copper box layer 1〇4 in the open pattern of the anti-mirror layer η are removed by, for example, button etching. Thereafter, the plating resist 112 is removed as shown in Fig. 1 (1). Thereby, a pattern of the conductive circuit 119 composed of the copper box layer and the metal layer 115 can be formed. By the above steps, the printed wiring board 1〇1 of the present modification can be obtained. As described above, according to the present embodiment, it is possible to provide a method of manufacturing a printed wiring board having fine processing of a very thin copper case having a carrier, a shape of a fine circuit, and excellent insulation reliability, and the printed wiring board. The method of manufacturing a printed wiring board according to the present embodiment is not limited to the case where a conductor circuit layer is formed on both surfaces of a substrate for a printed wiring board, and may be applied to a case where a conductor circuit layer is formed only on one surface of a substrate for a printed wiring board. . Further, it is also applicable to the case where the double-sided printed wiring board is used as the inner layer circuit board and the multilayer printed wiring board of the third embodiment as shown in Fig. 8(c). Therefore, any one of a single-sided printed wiring board, a double-sided printed wiring board, and a multilayer printed wiring board can be manufactured by the method of manufacturing the printed wiring board of the present invention. In the following, an electrolytic copper foil having a carrier foil of the present invention and a copper foil laminated board using the copper f white are produced, and an embodiment of a method for producing a printed wiring board of the present invention will be described. Here, the description will be focused on the case where an electrolytic copper foil is used for the carrier foil. Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited thereto. (Example) (Production of metal foil 1) In a carrier foil, an electrolytic steel foil of 18 μm thick (manufactured by Mitsui Metals, Ltd., surface roughness of 3EC-VLP' glossy surface was Ra=〇2_, Rz=1 5μιη) The glossy side sequentially forms a joint interface layer and an extremely thin copper foil layer. As a manufacturing condition, the carrier foil was first immersed in an acid washing tank (dilute sulfuric acid solution, 15 〇g/L, liquid temperature: 3 Torr. 20) for 20 seconds to remove oil, oxide film, and the like on the surface. Then, the groove is formed at the interface of the interface (carboxybenzotriazole solution, 5 g/L, liquid temperature 4 〇{>c, pH 5), and the interface layer is formed on the shiny surface of the carrier box. Crushed in the forming channel of copper (copper sulfate solution; sulfuric acid concentration i5〇g/L, copper concentration 65g/L' gelatin concentration 1〇ppm, chloride ion 2〇鹏液温45. (7), edge to carrierϋ The anode electrode (6) of the single-sided 'parallel arrangement plate is electrolyzed according to the smooth ore-covering condition of current density 15A/dm2 to form a 15_block steel layer. Then 'on the surface of the block steel layer, the edge is immersed in A fine copper grain forming tank (copper sulfate solution; sulfuric acid concentration (10) g/L, copper concentration 丨 之 sulfur 101102463 57 201251533 acid solution, liquid temperature 25eC), one side of the carrier foil is placed in parallel with the anode electrode of the flat plate (lead) Electrolysis is carried out according to the ore-burning conditions of a current density of 10 A/dm2, and then immersed in a money tank for preventing the fine copper particles from falling off (copper sulfate solution; sulfuric acid concentration: 150 g/L, copper concentration: 65 g/L, liquid) Temperature 45. In the middle, electrolysis is performed under smooth plating conditions with a current density of 20 A/dm2. A fine roughening of 0.5 μm was formed to prepare a very thin copper foil having a total thickness of 2.0 μm, and then impregnated in a rust-preventing treatment tank (zinc sulfate solution; sulfuric acid concentration: 70 g/L, zinc concentration: 20 g/L, liquid temperature: 40 C) Electrolysis was performed at a current density of 15 A/dm 2 and rust-preventing treatment was performed using zinc. Here, as the anode electrode, a soluble anode using a zinc plate was used, followed by 'impregnation in a chromic acid treatment tank (chromic acid solution; The chromic acid concentration was 5 g/L, pH 11.5 'liquid temperature 5 5 C) for 4 seconds. Finally, it was heated in a drying chamber to the ambient temperature U (rc in a furnace for 60 seconds) to obtain a carrier. The copper foil of the box is also subjected to the impregnation washing in the washing tank which can be washed in water for about 30 seconds. (Manufacture of metal foil 2) In carrier foil, electrolytic copper of 12 μm thick Foil (manufactured by Furukawa Electric Industrial Co., Ltd., the surface roughness of the surface of the F2-WS 'gloss surface is Ra=〇.2pm, rz=i 2gm), and the joint interface layer and the ultra-thin steel foil layer are sequentially formed. First, the carrier foil is immersed in the acid cleaning tank (dilute sulfuric acid solution, 丨5 〇g / L, liquid temperature 3 〇艺) In the middle of 20 seconds, the surface oil, oxide film, etc. are removed. Then, the groove is formed at the joint interface (carboxy stupid triazole solution, 5 g/L, liquid temperature 4 〇. (:, pH 5), the gloss of the carrier The interface layer is formed on the surface. Then, it is immersed in the formation groove of 101102463 58 201251533 block copper (copper sulfate solution; sulfuric acid concentration 150g/L, copper concentration 65g/L, gelatin concentration l〇ppm, vaporization ion 2〇 Ppm, liquid temperature 45. In the crucible, the anode electrode (lead) of the flat plate was placed in parallel on one side of the carrier foil, and electrolysis was performed under smooth plating conditions of a current density of 20 A/dm 2 to form a 15 μm layer of the bulk steel layer. Next, on the surface of the bulk copper layer, it is immersed in a fine copper particle forming bath (copper sulfate solution; sulfuric acid solution having a sulfuric acid concentration of 1 〇〇g/L, a copper concentration of 18 g/L, and a liquid temperature of 25. On one side of the carrier foil, the anode electrode (lead) of the flat plate is placed in parallel, and electrolysis is performed according to the sintering conditions of a current density of 10 A/dm 2 . Then, the plated groove (copper sulfate) for preventing the fine copper particles from falling off is immersed. The solution has a sulfuric acid concentration of 150 g/L, a copper concentration of 65 g/L, and a liquid temperature of 45. In the crucible, electrolysis is performed under smooth plating conditions of a current density of 20 A/dm 2 to form a fine coarsening of 0.5 μm, and a total thickness of 2.0 μm is produced. Thin copper foil. Then, immersed in anti-rust treatment tank (zinc sulfate solution; sulfuric acid concentration 7〇g/L, zinc concentration 20g/L, liquid temperature 40°C), electrolysis according to current density 15A/dm2 and use of zinc The rust-preventing treatment is carried out. Here, as the anode electrode, a soluble anode using a re-plating plate is used. Next, it is immersed in a chromic acid treatment tank (chromic acid solution; chromic acid concentration: 5 g/L 'pH ll. 4 seconds in temperature 55 ° C). Finally, in the drying tank, it took 60 seconds to pass the electric heater. The copper foil having the carrier foil was obtained in a furnace having an ambient temperature of 11 Torr. Further, in the step of each tank, the impregnation washing was performed in a water washing tank which can be washed with water for about 30 seconds. (Manufacture of 3) In the carrier foil, in a 12 μm thick electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd., 101102463 59 201251533 F2-WS, the surface roughness of the glossy surface is Ra=〇2μιη, Rz=1 2μηι) The joint interface layer and the extremely thin (four) layer are sequentially formed. As a manufacturing condition, the carrier foil is first immersed in an acid cleaning tank (dilute sulfuric acid solution, 15 〇g/L, liquid temperature 3 〇. 〇中20#) Oil, oxide film, etc. Next, a groove is formed at the joint interface (carboxy stupid triazole solution, 5 g/L, liquid temperature 4 & c, pH 5), and a joint interface layer is formed on the surface of the carrier. Then, immersed in the formation of the block copper 1 (copper pyrophosphate solution; potassium pyrophosphate concentration 32 〇 g / L, copper concentration 80 g / L, gelatin concentration i 〇 ppm, pH 8 5, liquid temperature 4 液In the middle of the crucible, the anode electrode (lead) of the flat plate is arranged in parallel with the carrier, and the current is 7A. /dm smooth plating conditions for electrolysis, followed by dipping in the bulk copper forming tank 2 (copper sulfate solution; sulfuric acid concentration 1 〇〇 g / L, copper concentration 200 g / L, gelatin concentration i 〇 ppm, chlorine 2 〇ppm, liquid temperature 45 In the <>c), the anode electrode (lead) of the flat plate is placed in parallel on one side of the carrier foil, and electrolyzed according to the smooth mineralization condition of the current consumption ΙΟΑ/dm2 to form a bulk copper layer of i 5 μη. Next, on the surface of the bulk copper layer, it is immersed in a fine copper particle forming bath (copper sulfate solution; sulfuric acid concentration 100 g/L, copper concentration 18 g/L sulfuric acid solution, liquid temperature 25. 〇, while the carrier foil On one side, the anode electrode (lead) of the flat plate is arranged in parallel, and electrolysis is performed according to the sintering conditions of the current density l〇A/dm2. Then, one side is immersed in the plating tank (copper sulfate solution for preventing the fine copper particles from falling off). ; sulfuric acid concentration 150g / L, copper concentration 65g / L, liquid temperature 45 ° C), while performing electrolysis under smooth plating conditions of current density 20A / dm2, forming a fine roughening of 〇.5μιη 'total thickness 2.0μιη Very thin copper foil. Next, impregnation 101102463 60 201251533 in the anti-rust treatment tank (zinc sulfate solution; sulfuric acid concentration 70g / L, zinc concentration 2〇g / L, liquid temperature 40 ° C) 'current density 15A / dm2 The anodic treatment is carried out by electrolysis, and the anode electrode is a solubilized anode using a zinc plate. Then, it is impregnated in a chromic acid treatment tank (chromic acid solution; chromic acid concentration: 5 g/L, pH 1.5). , liquid temperature 55 C) for 4 seconds. Finally, it is passed in the drying treatment tank for 60 seconds. After heating to a temperature of 11 〇 in the furnace by an electric heater, a copper foil having a carrier foil is obtained. Further, in the step of each tank, it is washed in a water washing tank which can be washed for about 30 seconds. (Example 1) 5% by weight of a naphthalene modified phenol novolac epoxy resin (manufactured by DIC Corporation, ΗΡ-5000) as an epoxy resin, and a biphenyl aralkyl type phenol resin as a phenol vulcanizing agent (Ming Chenghua Co., Ltd., ΜΕΗ7851·4Η) 8.5 parts by weight, phenolic novolac type cyanate resin (primaset T30, manufactured by L0NZA Co., Ltd.) 17 heavy bruises, spherical sulphur dioxide dioxide (made by Admatechs Co., Ltd.) , SOAR, average particle size 〇.5μιη) 65.5 parts by weight, epoxy group Wei (Xiyue Chemical Industry Co., Ltd. 'KBM-4G3) G. 5 parts by weight, mixed in methyl ethyl _. Then use 'high speed The stirring device was subjected to Na, and adjusted to a nonvolatile content of 7 〇% by weight. 'Modified resin varnish. The above resin varnish was impregnated into a glass woven fabric (base weight 104 g, thick, E-glass woven fabric manufactured by Nitto Spinning Co., Ltd.) WE7_11E, 5 (The rc heating furnace is dried for 2 minutes to obtain a prepreg so that the varnish solid content is About 5% by weight of the prepreg. The above prepreg is overlapped by two sheets, and the extremely thin 1〇1102463 201251533 steel foil (metal foil 1) with a load of 3 MPa and a temperature of 2202⁄4 is heated and formed. In the hour, the laminated sheet having the insulating layer is thick. 2〇mnl having copper foil on both sides 0 (printed wiring board) The carrier foil of the laminated board obtained in the example is peeled off (Fig. 7(b)), as shown in Fig. 7 (c), as shown in (c), by a carbon dioxide gas laser (Mitsubishi Electric Corporation's 'ML605GTX3-5100U2), a through-hole of a diameter of 75 μm is opened through a percolation of 60 g/L and hydrogen peroxide. In a 45 g/L aqueous solution, it was immersed for 2 minutes at a temperature of 80 ° C to carry out a desmutting treatment. Then, it was immersed in a hetero-solution (manufactured by Uemura Kogyo Co., Ltd., MAT-2B/MAT-2A) at a temperature of 55 C for 5 minutes, and a catalyst was used, and THUR-CUP PEA-6A manufactured by Uemura Industrial Co., Ltd. was used, and the temperature was 36. . (: Dip for 15 minutes to form an electroless plating layer 7.7μπι (Fig. 7(d)). On the surface of the electroless plating layer, the thickness of the film is 25 μm by the hot roll laminator, and the external line is sensitive. A dry film (sunfort UFG-255, manufactured by Asahi Kasei Co., Ltd.), which uses a glass mask (manufactured by Topic Co., Ltd.) which has a minimum line width/line width of 2〇/2〇μηη, is aligned, and is exposed by an exposure device ( The Ono Tester EV-0800) was exposed to light and developed in an aqueous solution of sodium carbonate to form a plating resist (Fig. 7(e)). Next, an electroless plating layer was used as the electrode for the electric layer, according to 3 A/dm2, 25 Electroplating copper (8 丨 _HL manufactured by Okuno Pharmaceutical Co., Ltd.) was formed in a minute to form a copper wiring pattern having a thickness of about 20 μm (Fig. 8 (4), and then, using a peeling machine, a monoethanolamine solution (R_1 制 manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used. The above-mentioned anti-plating 101102463 62 201251533 mask peeling (Fig. 8 (b;)). Then, the electroless plating layer and the base copper foil (2 μm) belonging to the power supply layer were quickly etched (CPE-800 manufactured by Mitsubishi Gas Chemical Co., Ltd., Liquid temperature: 30 ° C, sprayer pressure 0.23 MPa) was treated for 180 seconds to remove A pattern of L/S=20/20 pm (pattern etching) was formed to obtain a printed wiring board (Fig. 8(c)). Finally, as shown in Fig. 8 (dl), a solder resist layer (sun ink) was formed on the surface of the circuit. Co., Ltd., PSR4000/AUS308), nickel plating layer (ICP NICORON GM, manufactured by Okuno Pharmaceutical Co., Ltd.) is formed at a temperature of 8 (TC is immersed for 12 minutes to form 2.5 μm, and then metallized (FLASH GOLD 330, manufactured by Okuno Pharmaceutical Co., Ltd.) The film was formed by dipping at a temperature of 80 ° C for 9 minutes to obtain a printed wiring board. Further, as shown in Fig. 8 (d-2), a solder resist layer was not formed on the surface of the circuit. Example 2) The same procedure as in Example 1 was carried out except that the ultra-thin copper foil having the carrier foil was changed to the metal foil 2. (Example 3) Except that the ultra-thin copper foil having the carrier foil was changed to the metal foil 3, The same as in the first embodiment except that the rapid etching conditions of the electroless plating layer and the base copper foil (2 μm) belonging to the power supply layer were changed as described below. Electroless plating layer and base copper foil (2μιη) by quick spare 101102463 63 201251533 Engraving (CPE-800, manufactured by Mitsubishi Gas Chemical Co., Ltd., liquid temperature: 30 ° C, sprayer pressure 0.23 MPa) was removed for 240 seconds to form L/S=20/2 (^m pattern (pattern (Example 5) The same procedure as in Example 1 was carried out except that the resin composition used for the laminated board was changed. A biphenyl aryl-based epoxy resin as an epoxy resin (Japan) Chemical Industry Co., Ltd. 'NC-3000' 11 parts by weight, bis-xenylenediamine compound (BMI-70, manufactured by KI Chemical Industry Co., Ltd.) 20 parts by weight, 4,4'-diaminodiphenyl-methyl 3.5 parts by weight, 65 parts by weight of aluminum hydroxide (HP-360 manufactured by Showa Denko), and 0.05 parts by weight of epoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., ΚΒΜ-403) were mixed and dissolved in methyl ethyl ketone. Subsequently, stirring was carried out using a high-speed stirring device to adjust to 70 parts by weight of the nonvolatile matter. /〇, modulating resin varnish. The resin varnish was impregnated into a glass woven fabric (base weight 104 g, thickness 87 μmη, 曰 纺 Ε Ε , ,, WEA-116E), and dried in a 15 (TC oven) for 2 minutes to obtain a prepreg. The varnish solid content is about 50% by weight of the prepreg. The above prepreg weight is #2, and the extremely thin copper poise (metal poise 1) having the carrier box is superposed. The pressure is 3 MPa and the temperature is 20 (TC is heated and added). When the press forming was performed, the insulating layer was a laminate having copper foil on both sides of a thickness of 20 mm. (Comparative Example 1) (Manufacture of metal foil 4) 101102463 64 201251533 In carrier foil, electrolytic copper foil of 35 μm thick (Furu Electric) Made by the industrial company, the shiny surface of the F2_WS 'gloss surface is Ra=0.2pm, Κ·ζ=1.2μιη) sequentially forms the joint interface layer and the ultra-thin copper foil layer. As a manufacturing condition, the carrier box is first dipped. Crushed in an acid washing tank (dilute sulfuric acid solution, 150 g / L, liquid temperature 30. 20 seconds in the crucible to remove the surface oil, oxide film, etc.. Then, dipped in the joint interface to form a tank (carboxy benzotriazole solution, 5g/L, liquid temperature 4〇〇c, pH5), forming a bonding boundary on the shiny surface of the carrier Then, while immersing in the forming channel of the bulk copper (copper sulfate solution; sulfuric acid concentration 150 g/L, copper concentration 65 g/L 'liquid temperature 45 ° C), 'one side of the carrier foil' is arranged in parallel The anode electrode (lead) of the flat plate is electrolyzed according to the smooth plating conditions of a current density of 2 A/dm 2 to form a bulk copper layer of 1.5 μm, and then, on the surface of the bulk copper layer, is immersed in a fine copper grain forming groove. (Copper sulfate solution; sulfuric acid concentration 100g/L, copper concentration i8g/L sulfuric acid solution, liquid temperature 25. In the middle, the anode electrode (10) of the flat plate is arranged in parallel with the single side of the carrier J, according to the current density SAW (4) Electrolytic electrolysis. Next, immersed in a plating tank for preventing fine copper particles from falling off (sulfur_solution; rhythm concentration 15 gorges, copper concentration 65 g/L, liquid temperature 45. 〇, one side according to current density The smoothing condition of 1〇A/dm2 is electrolyzed to form fine coarsening of 〇.5μηι, and the total thickness is 2_very thin (4). Then, it is sewn in the treatment tank (automatic zinc solution; sulfuric acid concentration 70g/L 'zinc Concentration 2〇g/L 'liquid temperature 4〇.〇, according to the current density lOA/dm2 for electrolysis and feed into Line _ treatment π this, as the anode electrode, hiding as a soluble anode using the board. Then, impregnated with chromic acid 101102463 65 201251533, tank (chrome bismuth / liquid, pure acid concentration pure, p with .5 , the liquid temperature hunger 4 & winter 'in the drying treatment tank for a duration of (9) seconds by the use of electric heaters to add,, the brothers in the 110 C furnace, to get the copper box with the carrier pig. Also, in each The step between the tanks was carried out in a water-washable washing tank for about 30 seconds of impregnation washing. A printed wiring board was obtained in the same manner as in Example 1 except that the extremely thin copper crucible having the carrier case was changed to the metal crucible 4. (Comparative Example 2) (Production of Metal Foil 5) In a carrier foil, a 35 μm thick electrolytic copper foil (manufactured by Furukawa Electric Co., Ltd., F2 WS surface roughness of r (four) 2 (four), Rz = 12 μm) The bonding interface layer and the extremely thin copper bead are formed. As a manufacturing condition, first, the carrier 4 was immersed in a gH clean tank (dilute sulfuric acid solution, i5Qg/L, liquid temperature: 3 Torr. The surface oil, oxide film, etc. were removed for 20 seconds in the crucible. Then, the impregnation was formed at the joint interface. a tank (carboxybenzotriazole solution, 5 g/L, liquid temperature 4 (rc, pH 5), forming a joint interface layer on the shiny surface of the carrier. Then, the edge is immersed in the bulk copper forming groove 1 (pyrophosphate) Copper solution; potassium pyrophosphate concentration 32〇g/L, copper degree 80g/L, 25% ammonia water 2ml/L, pH 8.5, liquid temperature 40. In the middle, one side of the carrier is arranged on one side, and the anode of the plate is arranged in parallel. The electrode (6) was electrolyzed according to a smooth ore-covering condition of a current intensity of 1.5 A/dm, and then immersed in a bulk copper forming tank 2 (copper sulfate solution; sulfuric acid concentration 1 〇〇 g/L, copper concentration 200 g/ L, liquid temperature 45. In the crucible, the anode electrode (lead) of 101102463 66 201251533 flat plate is placed in parallel on one side of the carrier foil, and electrolyzed according to the smooth plating conditions of current density 3A/dm2 to form a block of 1.5 μm a copper layer. Then, on the surface of the bulk copper layer, one side is immersed in a fine copper grain forming groove (copper sulfate solution). a liquid; a sulfuric acid solution having a sulfuric acid concentration of 100 g/L, a copper concentration of 18 g/L, and a liquid temperature of 25. In the crucible, the anode electrode (lead) of the flat plate is placed in parallel on one side of the carrier foil, and the current density is 5 A/dm. Electroplating was carried out under the plating conditions, and then immersed in a plating tank (copper sulfate solution; sulfuric acid concentration of 15 〇g/L, copper concentration of 65 g/L, and liquid temperature of 45) for preventing the fine copper particles from falling off. The smooth plating conditions of a current density of 1 〇A/dm2 were electrolyzed to form a finely roughened 0.5 μm, and a very thin copper foil having a total thickness of 2.0 μm was produced. Then, it was immersed in a rust-preventing treatment tank (zinc sulfate solution; sulfuric acid concentration: 70 g) /L, zinc concentration 20g / L, liquid temperature 4 (TC), electrolysis according to the current density of 15A / dm, and use the word for anti-recording treatment. Here, as the anode electrode, a dissolved anode using a zinc plate is used. Then, immersed in a chromic acid treatment tank (chromic acid solution; chromic acid concentration 5g/L, pH 11.5, liquid temperature 55 <>c)$ 4 seconds. Finally, it was heated in a drying treatment tank for 6 seconds by a heater to a furnace having an ambient temperature of 1 UTC to obtain a copper foil having a carrier foil. Further, between the steps of the respective tanks, the impregnation washing was carried out for about 3 seconds in a water washing tank which can be washed with water. A printed wiring board was obtained in the same manner as in Example 1 except that the ultra-thin copper foil having the carrier foil was changed to the metal foil 5. (Evaluation) Using the printed wiring boards obtained in the respective examples and comparative examples, the following evaluations were carried out. The evaluation item is presented together with the content, and the results obtained are shown in the table. 101102463 67 201251533 【1 <Comparative Example 2 I 0.48 OO XX cn oi XX Comparative Example 11 0.39 CN — OO rn O) τ-Ή XXXX Example 5 0.40 oo rn 〇〇ο 〇〇 Example 4 0.44 in cn 〇〇ο 〇〇Implementation Example 3 0.45 rn 〇〇〇〇 Example 2 0.42 00 ΓΟ 〇〇〇〇 Example 1 0.38 inch (N <N 00 (N 〇〇o 〇〇#% average roughness (Ra) 〇 om) Ten point average roughness (RzXlim) Maximum mountain height (RpXpm) kurtosis (Rku) 〇jm) (2) Fast money engraving The appearance of the surface of the insulating layer and the presence or absence of copper residue (3) Thin foil shape during processing of fine lines of LS (4) AL (L1-L2) (5) Determination of the line-to-line BHAST of LS20 (1) Surface of the insulating layer Roughness (Rp, Rku) °°9 £9 inch Z0H2 201251533 (Evaluation) The following evaluations were carried out using the printed wiring boards obtained in each of the examples and the comparative examples. The evaluation item is presented together with the content, and the results obtained are shown in the table. Further, the SEM images of Example 1 and Comparative Example 1 are shown in Figs. 16 and 17 . ' (1) Surface roughness of the insulating layer (Rp, Rku) - Using a color 3D laser microscope (manufactured by KEYENCE, device name W-9710), the thickness is measured according to jIS B0601 ·· 2〇〇1 (no cutoff value) The maximum mountain degree Rp of the degree curve and the kurtosis (sharpness) Rku of the roughness curve. The measurement system is made for any 20 points (20 places) of the measurement piece, which is 1 〇〇μιηχ1〇〇μηη according to the observation field of view. In addition, the laminate obtained above (the carrier foil of the figure was peeled off, and the ultra-thin copper foil was subjected to a full-surface etching by a gas-feeding etching liquid as a sample. (2) Surface of the insulating layer after rapid etching The scanning electron microscope (manufactured by JEOL Ltd., device name: JSM-6060LV) was used to determine the appearance and the presence or absence of copper. The SEM image was observed from the top. The wiring of the above printed wiring board was processed. The latter (Fig. 8(c)) has just been completed as a sample. Each symbol is such as 卞$° 〇: the surface of the insulating layer has no streaks, pits and copper residues. X: The insulating layer has a stripe-like appearance. Pit and copper residue (3) Thin copper foil when LS is finely twisted The scanning electron microscope (manufactured by Sakamoto Electronics Co., Ltd., device name: 101102463 69 201251533 JSM-6060LV) was used to determine the SEM image viewed from directly above. Further, the wiring processing in the manufacturing process of the above printed wiring board was completed. The latter (Fig. 8(c)) is used as a sample. Each symbol is as follows: 〇: There is no residual edge near the insulating layer of the wiring circuit X: There is a residual edge near the insulating layer of the wiring circuit (4) AL=L1-L2 Using scanning electrons Microscope (manufactured by JEOL Ltd., device name: JSM-6060LV) 'The cross-sectional shape of the wiring was observed, and the maximum width of the thin copper foil was calculated as the minimum width of the L-electric pattern plating as L2, and the calculation was performed. Wiring board (Fig. 8(c)).

(5) LS20 (L/S=2C^m/20pm) The electrical insulation reliability between the BHAST fine wirings is determined by continuous measurement under the conditions of voltage application of 10 V, temperature of 130 ° C, and humidity of 85%. Evaluation. Further, the sample was obtained by using the printed wiring board obtained in the above embodiment (Fig. 12 (b)). Further, the point at which the insulation resistance value becomes less than 1 〇 8 Ω is used as the end point. Each symbol is as follows. 〇: 100 hours or more X: less than 100 hours This application claims priority based on Japanese Patent Application No. 2011-14127, filed on Jan. 26, 2011, the entire disclosure of which is hereby incorporated herein. 101102463 70 201251533 [Brief Description of the Drawings] Fig. 1 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board according to a third embodiment. Figure 2 is a schematic representation of the first! A cross-sectional view of a portion of a printed wiring board of an embodiment. Fig. 3 is a cross-sectional view schematically showing a printed wiring board for explaining a residual side. Fig. 4 is a plan view schematically showing a printed wiring board for explaining the effects of the i-th embodiment. Fig. 5 is a cross-sectional view for explaining a wiring shape of the i-th embodiment. Figure 6 is a schematic representation of the first! A cross-sectional view showing a modification of the wiring shape of the embodiment. Fig. 7 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board according to a second embodiment. Fig. 8 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board according to a second embodiment. Fig. 9 is a cross-sectional view schematically showing a modification of the wiring shape of the second embodiment. Fig. 10 is a cross-sectional view showing an example of a method of manufacturing a printed wiring board according to a third embodiment. Fig. 11 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board according to a third embodiment. Fig. 12 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board according to a third embodiment of the present invention, 101102463 71 201251533. Fig. 13 is a cross-sectional view schematically showing a modification of the method of manufacturing the printed wiring board of the embodiment. Fig. 14 is a schematic view showing Rp showing one of the parameters showing the thickness. Fig. 15 is a schematic diagram for explaining Rku showing one of the parameters showing the thickness. Fig. 16 is a view showing SEM images of Examples and Comparative Examples. Fig. 17 is a view showing SEM images of Examples and Comparative Examples. [Description of main component symbols] 1 Copper-clad laminate 2 Insulation layer 4 Copper foil layer 10 Copper foil laminate with carrier foil 14 Metal layer 19 Conductive circuit 20 Top 22 Bottom 24 Side 30-face 100 Copper-clad laminate 101 Printed wiring board 102 Insulation layer 104 Copper foil layer 101102463 72 201251533 105 Copper foil layer 106 Carrier foil layer 107 Carrier foil layer 108 Through-hole 109 Hole 110 Electroless plating layer 111 Electroless plating layer 112 Anti-plating layer 113 Anti-mine layer 114 Plating layer 115 metal layer 116 metal layer 118 conductive circuit 119 conductive circuit 120 solder resist layer 121 solder resist layer 122 first plating layer 123 first plating layer 124 second plating layer 125 second plating layer 130 insulating layer 132 plating Layer 200, 201, 202, 203, 204 Printed wiring board 101102463 73

Claims (1)

201251533 VII. Patent application scope: 1. A method for manufacturing a printed wiring board, comprising: a step of separating the carrier substrate by a laminate having a copper box having a carrier substrate laminated on at least an insulating layer; a step of forming a metal layer thicker than the copper box on the copper box; or performing a etching process on at least the copper box to obtain a conductive circuit composed of the copper drop and the metal layer Step of patterning; in the above step of obtaining the conductive circuit pattern, when the measurement is performed according to jisb deletion, the __Rp of the insulating layer is 4 Å or less, and Rku is 2.1 or more. 2. The method of manufacturing a printed wiring board according to the above aspect of the invention, wherein Ra in the basin and the surface of the copper facing the surface of the insulating layer are Ι.Ομηι or less. 3. The method for manufacturing a printed wiring board according to the second aspect of the present invention, wherein the copper > white has crystal grains having an average length of 2 Å or less on the long side, as in the third item of the patent application. In the method of manufacturing a printed wiring board, the area ratio of the upper side of the long side and the average length of the long side of 2 哗 or less is 8〇% or more. The method for producing a printed wiring board according to the first aspect of the invention, wherein the surface of the carrier substrate facing the surface is 1 (the point average roughness (RZ) is 〇·1 μmη or more and 5 ' 6. The method of manufacturing a printed wiring board according to the first aspect of the invention, wherein the step of forming the metal layer entirely or selectively forms a package. The opening pattern is formed on the copper matrix. The step of resisting the anti-mine layer is wide. The step of forming the plating layer of the metal layer on the copper box in the above-mentioned opening pattern, and the step of removing the above-mentioned anti-plating layer by ', ', and up; The above-mentioned step of the above-mentioned conductive circuit pattern includes a step of softly engraving the above-mentioned steel line. The method for manufacturing a printed wiring board according to the first aspect of the invention, wherein the surface is selectively formed on the t-plane Before the step of the metal layer, the step further comprises: forming a through hole or a non-through hole in the laminated plate; and stepping the inner wall of the through hole or the non-through hole to contact the liquid medicine And a step of forming an electroless plating layer on at least the steel drop and the inner wall of the through hole or the inner wall of the non-through hole by electroless ore coating. 8. A printed wiring board comprising: • an insulating layer; and a conductive circuit pattern is formed on one surface of the insulating layer and is composed of a copper layer and a metal layer; when the SB0601 is measured, the surface of the insulating layer is 4.5 μm or less, and the plate is The printed wiring board of the eighth aspect of the invention, wherein the metal layer contains two or more plating films. 10. The printed wiring board according to claim 8 of the patent application, wherein In the plan view, when the maximum width of the copper foil in the width direction orthogonal to the direction in which the conductive circuit pattern extends is L1, and the minimum width of the metal layer is L2, the L1 system and the L2 are used. 11. The printed wiring board according to claim 10, wherein the area of the copper foil is from the first surface of the copper foil toward the second surface in plan view. Change 101102463 76