TW201251532A - 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 (101) of the present invention comprises: a step of separating a carrier substrate from a laminate of copper foil having the carrier substrate laminated on at least one surface of an insulating layer (102); a step of entirely or selectively forming a metal layer (115) on a 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 the surface (upper surface (20)) of the copper foil layer (104) adjacent to the metal layer (115) has a ratio of the peak intensity for the orientation (200) relative to the sum of the peak intensities for the orientations (111), (200), (220) and (311) being 26% or less as determined by XRD (X-ray Diffraction) in thin films.

Description

201251532 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] This is a method of manufacturing a printed wiring board and a printed wiring board. [Prior Art]

Ik is required to increase the high-performance of electronic equipment, high-density integration of electronic components, and progress toward high-density safety, etc., and the high-density Anshang corresponding printed wiring boards are more conventionally increased, and Small, ancient, and multi-layered. A method of forming a conductor circuit layer having a high density and a high pattern accuracy on a substrate of such a printed wiring board has been started, and a semi-additive method has been started. A method of producing a printed wiring board using the semi-additive method is described in, for example, Patent Document 1 and Patent Document 2. In the manufacturing methods described in Patent Documents 1 and 2, first, a plating resist pattern is formed on the double-sided copper deposited layer, and then the anchor layer is filled in the opening portion of the plating resist pattern, and then the key pattern is removed. Thereafter, the lower layer steel foil is etched by using a pattern of a plating layer as a mask to form a conductive circuit pattern composed of a plating layer and a copper foil. Patent Document 1: Japanese Laid-Open Patent Publication No. 2003-69218. Patent Document 2: Japanese Patent Laid-Open Publication No. 2003-403 No. (Summary of the Invention) (Problems to be Solved by the Invention) However, in the conventional step of forming a fine conductive circuit pattern There is still room for improvement in the difficulty of the 101102461 4 201251532 wiring shape to the desired shape. That is, the conventional conductive circuit pattern is composed of the upper layer (money cladding) and the lower layer (two layers of copper magic). In the upper layer and the lower layer, the surface orientation or constituent material of the upper layer is different. Therefore, even if the etching condition is adjusted in conjunction with the upper layer, the etching speed in the lower layer becomes faster or slower. As a result, the upper layer is viewed from above. In the region from the side wall of the (money coating) to the outside, a part of the lower layer (copper foil) may be left by extrusion (hereinafter referred to as a residual edge). However, if the residual edge of the lower layer is removed, the amount of etching is increased. On the other hand, the upper layer (plating layer) is excessively cut, so that there is a case where the wiring shape is poor in the conventional step of forming a conductive circuit pattern. 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 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 above-mentioned copper layer on the whole surface of the pig; and a step of obtaining a conductive circuit pattern composed of the copper foil and the metal layer by etching at least the copper foil; The sum of the peak intensities of the plane orientations (1U), (2〇〇), (22〇), and (311) measured by the XRD film method in the surface of the copper foil that is in contact with the metal layer The ratio of the peak intensity of the above-mentioned plane orientation (2〇0) is 26% or less. 101102461 ς 201251532 The present inventors conducted various experiments in order to control the etching rate of the lower layer (copper foil), and as a result, found that it was in the upper layer. By reducing the ratio of the face orientation (m) to the orientation of the face (200), it is possible to obtain a lower layer (copper foil) having better residual characteristics than conventionally known. Insights When the ratio of the crystal face (2〇〇) in the upper layer (the surface in contact with the metal layer) is set to be less than or equal to a predetermined value, a conventionally good wiring shape can be realized, and the present invention is completed. According to another aspect of the invention, there is provided a printed wiring board comprising: an insulating layer; a conductive circuit pattern s is disposed on the insulating layer, and a copper enamel and a metal layer are laminated; and the cymbal of the gong is connected to the metal layer The ratio of the peak intensity of the plane orientation (200) of the surface orientation (111), (10), (22G), and (311) of the ^^ when the bee is strongly produced is 26% or less. Month, located at 200), because the surface of the steel foil (the surface that is in contact with the metal layer) is not below the predetermined value, so as described above, it is easy to form a conventional two-effect: wiring shape. Excellent Yield (4) Manufacture = According to the present invention [Embodiment<]' can provide a yield superior printed wiring board. The above objectives and 目的 10Π02461 /, purpose, features and advantages are described in the following by means of the 201251532 preferred embodiment and _1. Embodiments of the present invention will be described below using the drawings. Further, in the formula, the same reference numerals are attached to the same <constitutive elements, and the description is omitted as appropriate. (First Embodiment) Fig. 1 is a cross-sectional view showing the procedure of a method of manufacturing a printed wiring board in a first state. The manufacturing method/sleeve of the printed wiring board 101 of the first embodiment is composed of a copper/self-stacked laminate having a carrier substrate on one surface of at least the insulating layer 102 (I (4) laminated layer) Plate 1G), the step of separating the carrier substrate (carrier v from layer 106); on the steel ruthenium layer, the entire surface or selection! · the step of forming a 1 () 4 thick metal layer m; > A step of patterning the copper layer 104 to obtain a pattern of the conductor circuit 119 composed of the steel box layer 1〇4 and the metal layer 115. In the manufacturing step, in the surface (upper surface 2〇) of the copper foil layer 1〇4 which is in contact with the metal layer 115, the plane orientation when measured by the XRD (X-ray Diffracti〇n) film method (1) The sum of the peak intensities of 丨i), (200), (220), and (311) is 26% or less of the peak intensity of the plane orientation (2〇〇).

Fig. 2 is an enlarged cross-sectional view showing the conductor circuit 119 in the printed wiring board 1〇1 of the first embodiment. As shown in Fig. 2, the printed wiring board 1 (H' of the present invention includes: an insulating layer 102; a pattern of a conductive circuit 119 formed of a copper foil layer 104 and a metal layer 115 provided on the insulating layer 1? The surface orientation (111), (200), (220) of the surface of the copper foil layer 1〇4 which is in contact with the metal layer 115 (the upper surface 2〇) with respect to the thin film method by XRD 101102461 7 201251532 The ratio of the peak intensity of (311) to the peak intensity of the above-mentioned plane orientation (200) is specifically 26% or less. In the present embodiment, the 'XRD thin film method uses a condition that the incident angle is 〇2 to 1 。. The peak intensity obtained by the thin film method is the maximum value corresponding to the intensity of each plane orientation. Specifically, a fully automatic powder X-ray diffraction apparatus (PW1700 type manufactured by Philips) is used, and Cu-Κα ray is used as the The incident angle (a) according to the X-ray is incident on the surface of the sample (in this case, the surface of the carrier foil that has been peeled off) at the factory angle, and is obtained by scanning from the Θ2Θ. The detected face orientations (ul), (200), (220) and (311) In the case of the thin film method, since the incident angle is fixed, in order to distinguish θ, a is used to represent θ, and 2 Θ is meant to mean the position of the counter tube with respect to the incident ray, which is the same as the usual method. Therefore, the film method is different from the conventional method, and the depth of X-rays can be suppressed to the minimum required, and the crystal structure can be performed within a range of nanometers to several micrometers of the sample surface. Therefore, in order to accurately evaluate the crystal orientation of the copper foil layer of 0.1 to 5. Ομηα thick, it is necessary to perform X-ray diffraction of the above-mentioned thin film method. Further, 'the copper metal (for example, copper powder) measured by the XRD thin film method The main crystal planes are known to be composed of plane orientations (111), (200), (220), and (311). The values of these peak intensities are proportional to the area of the crystal faces. According to this fact, copper The total value of the wave front strengths of the surface orientations of the foils (111), (200), (220), and (311) 101102461 8 201251532 is proportional to the total of the areas of the various crystal faces on the foil. Therefore, the relative The ratio of the peak intensities of the plane orientations (111), (2〇〇), (22〇), and (3ΐι) to the peak intensities of the 'plane orientations' can be said to represent the plane orientation (2GG) relative to the main crystal on the copper box. The area ratio of the surface area of the surface is also the order of the surface area (111) > plane orientation (2〇〇) 〉 plane orientation (22G). The smaller the atomic surface density, the easier it is to show silver. The degree of the degree of the degree is higher. Therefore, the (4) characteristic in (4) becomes the order of the plane orientation (220) > plane orientation (10)) > the plane orientation (1). That is, it can be said that the plane orientation (22 〇) and the plane orientation (200) are higher than the plane orientation (1 U). From the above, the ratio of the peak intensities of the plane orientations (2〇〇) to the surface orientations ((1)), (200), (220), and (311) measured by the XRD film method is low. However, the area ratio of the surface orientation _) becomes lower, which indicates that the upper characteristics of the steel box are lower. Thus, the ratio of the peak intensities shows the same technical significance as the ratio of the area of the primary area, and therefore, these are sometimes referred to as ratios. In the present specification, the contact with the side surface 24 in the copper box layer 104 is referred to as a side note. In the side, the upper surface of the insulating layer 102 is etched in the horizontal direction. On the other hand, the entanglement of the upper 2 铜 of the copper box layer 1 〇 4 is referred to as a vertical singularity. In the vertical (four), the upper surface of the insulating layer (10) is first-ordered in the vertical direction. In the following description of the manufacturing method of the printed wiring board according to the first embodiment, 101102461 201251532, the effect of the manufacturing method will be described with respect to the conventional manufacturing method. Further, the detailed production conditions, materials, and the like of the first embodiment will be described in detail in the paragraph of the second embodiment. The steps of the method of manufacturing a printed wiring board according to the first embodiment include the following steps. That is, first, as shown in Fig. 1 (a), a copper foil laminate 10 having a carrier foil is prepared. In the copper laminated laminate 1 having a carrier foil, a copper foil layer 104 and a carrier foil layer 1 are attached to both sides of the insulating layer 102. Next, as shown in Fig. 1(b), the carrier foil layer 106 is removed by stripping or the like from a copper foil laminate 1 having a carrier foil. Next, as shown in Fig. 1(c), a plating resist 112 having a predetermined opening pattern is formed on the remaining copper foil layer 104. A plating layer (metal layer 115) is formed in the opening pattern of the plating resist 112 and on the copper foil layer 1 4 by plating (Fig. i(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 foil layer 1〇4. At this time, in the region where the metal layer 115 is not covered, the ratio of the peak intensity of the plane orientation (200) in the upper surface 20 of the copper foil layer 104 is 26% or less. Thereafter, as shown in (9), the _ layer immediately in the region not covered with the metal layer (1) is removed by, for example, soft touch. After the removal step of the copper town f1510, the pattern of the conductive circuit 119 can be formed by the residual steel, 104 and metal. By the above steps, the present embodiment is obtained. Fig. 2). The P-wiring wiring board 101 (FIG. 1) The residual side which occurs in the method of the printed wiring board manufacturing method 201251532, which is known from the Japanese Patent Publication No. 101102461, is described with reference to FIG. 3. The manufacturing method of the conventional printed wiring board is shown in FIG. The following steps are included, that is, 'as described above' is formed on the flat-shaped copper foil layer 4 and is formed into a metal layer 14' having an upper layer of a predetermined pattern, with the metal layer 14 as a cover, The underlying copper foil layer 4 is used. However, according to the review by the inventors of the present invention, in the conventional method of manufacturing a printed wiring board, the surface orientation of the layer 4 and the metal layer W in the constituent material or the upper surface is used. The difference is also different. Therefore, even if such etching conditions are adjusted to the condition that the metal layer 14 is not removed, the speed of the copper (four) 4 (four) is slow, or copper _ * occurs. Further, there is a possibility of the residual edge (Fig. 3(a)). If such a residual edge exists, the distance μ between the conductive circuits 19 (hereinafter referred to as the pitch S2) is narrowed, and it is difficult to form a fine wiring pattern. For the purpose of widening the spacing S2, in order to remove the residual edge When the amount of copper _ 104 _ is increased to the lower layer, the metal layer 刻 is diced (Fig. 3(b)). If the shape of the metal layer 14 is deformed, the shape (wiring shape) of the conductive circuit μ becomes Μ The inventors of the present invention have further reviewed, in order to control the i-worm rate of the lower layer (copper box), it has been found from various experimental results that the lower surface 20 is used to make the plane orientation ( 111) It is easier to be reduced by the ratio of the plane orientation _) of the shot, and the lower layer (copper box) superior in characteristics to the characteristics can be obtained. / The mechanism is not clear that the value can be _, in the upper part of the copper (four) HM 20, by reducing the ratio of the (4) superior surface orientation (), the ratio of the surface orientation (200) in the side 24] 〇1丨02461 201251532 becomes higher Therefore, the speed of etching on the side of the side surface 24 can be increased. According to the above-described embodiment, in the present embodiment, the ratio of the surface orientation (200) having excellent etching characteristics is set to be equal to or less than a predetermined value on the upper surface of the copper foil layer 1〇4. As a result, since the etching characteristics of the side of the copper foil layer 1〇4 can be improved, a conventionally good wiring shape can be realized, and as a result, a printed wiring board excellent in yield can be obtained. 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 extruded in the outer side of the metal layer 铜 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, when the cross-sectional view is '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 L1 -L2 = When AL is greater than 0, it is determined that a residual edge has occurred. In this case, in the conductive circuit 119 of the present embodiment, it is preferable that the ratio of L1 is smaller than that of the conventional L1 and L2 (Fig. 2(a))' is more preferably L1 is smaller than L2. When L1 is smaller than L2, the cross-sectional copper foil layer 104 has a region in which the width of the steel layer ι4 is smaller than the width of the metal layer 115 (Fig. 2(b)). The shape of the conductive circuit 119 specified by the types L1 and L2 is a good wiring shape. 101102461 12 201251532 In addition, the so-called good wiring shape, the second means that the shape of the metal 曰 is specific to the characteristics of the desired shape (Fig. 2 (a) and (8)). The frequency required here is «the shape of the design, for example, the shape of the square. Even when L1盥L2 is opposite to 盥1, and τ1 is the same, and L1 is the same, and L1 is smaller than L2, the remnant characteristics of the side of the (four) layer are improved, so that the shape can be realized. Further, as shown in Fig. 2 (8), the cross-sectional shape of the copper beryllium layer 104 may have a rectangular shape having the same width as the metal layer 115, or may be an inverted pyramid shape as shown in Fig. 2(b). The copper beak layer of the inverted taper shape is formed from the first surface (upper surface 20) toward the second surface (lower surface 22) in a plan view, and the area thereof may be small (where 'the deviation may be due to manufacturing steps) Concavities and convexities are formed in one of the side faces 24). Further, as shown in FIG. 5, when viewed in the cross section in the width direction, the angle formed by the perpendicular line of the insulating layer 102 and the side surface 24 (counterclockwise angle) is preferably, for example, G degrees or more. More preferably, it is above the temperature and below 10 degrees. Further, the shape of the other copper box layer 1〇4 may be a fish plate (semicircle) shape as shown in Fig. 6 (4), or may be a shape as shown in Fig. 6(b). By using the layer 1G4 of such a shape, U can be made smaller than L2' in the conductive circuit ι 9 and further in contact with the inverted tapered shape, and the adhesion area with the insulating layer (10) can be made constant or more. In addition, in the printed wiring board of the present embodiment, the line pitch (hereinafter referred to as (four) controllability is superior, and the description will be made using FIG. 4. The distance S2 and the pitch S1 shown in FIG. 4 are the surface relative to the conductive circuit 101102461. 13 201251532 19' 119 The direction in which the extension extends is the distance between the most adjacent conductive circuits 19 and 119 in the width direction of the orthogonal direction. In the conventional method of manufacturing a printed wiring board, the etching condition of the copper foil layer 4 It is adjusted to the shape of the metal layer 14, so the length of the residual edge extending on the outer side of the metal layer will become longer or shorter. In order to make such a residual edge frequently separated, it must be as shown in Fig. 4. As shown in (b), it is necessary to sufficiently ensure the pitch "in other words, the pitch S2 must be adjusted in accordance with the fluctuation of L1. In the method of manufacturing a printed wiring board, it is difficult to form such a controllability of L1/S2. In contrast, in the method of manufacturing a printed wiring board according to the present embodiment, since the copper bead layer can be improved in shape, the shape of the metal layer ι 5 can be maintained under a desired shape. The width of the layer _4 in the width direction is made. Therefore, since L1 can be made L2 or less (that is, the residual edge disappears), the spacing si can be determined by the minimum width of the metal layer 11S. In the method of manufacturing a P-wiring wiring board according to the present embodiment, such L2/S1 has superior controllability. Therefore, since L/S controllability is excellent, it can be suppressed. In the second embodiment, the method for manufacturing a printed wiring board that can be subjected to fine wiring processing is described in the second embodiment. The detailed manufacturing conditions, materials, and the like which are omitted in the embodiment are exemplified. 101102461 14 201251532 The manufacturing method of the printed wiring board according to the second embodiment is a step of forming the metal layer 116 over the entire surface or selectively. The steps of the steps are different from those of the first embodiment: a step of forming a through hole 1〇8 penetrating through the copper foil laminate 1〇〇 composed of the copper material 104 and the insulating layer 102; at least the inner wall of the through hole 108 Make medicine a step of contacting; and forming an electroless bond layer 110 electrically connecting the upper surface of the insulating layer 102 and the steel foil layer on the back surface by electroless plating. FIGS. 7 and 8 show the second embodiment. A cross-sectional view of a step sequence of a method of manufacturing a printed wiring board of the form. First, as shown in Fig. 7(a), a carrier (4) 1 and 6 and a layer having a carrier are bonded to both surfaces of the insulating layer 1〇2. As a copper box laminate having a carrier case, for example, a carrier layer 1 () 6 of a peelable at least-area layer of the copper box laminate 100. The steel_layer substrate At least 100 (hereinafter sometimes referred to as a laminate) of the insulating layer 1 2 having an insulating resin layer is not particularly limited, and for example, a copper foil layer 104 having an area layer may be used (the fibrous substrate is omitted in the drawing) ). The laminate may be a single layer having a multilayer construction. That is, as the laminated board, it is also possible to use only the core (four) or the additional layer formed on the core layer. Such a laminate can be applied, for example, a person who overlaps a plurality of prepregs or the like can be used. The prepreg is not limited. For example, a resin composition containing a thermal resin, a curing agent, a filler, or the like may be impregnated into a substrate such as a glass cloth. Further, as the laminated sheet, it is possible to use an extremely thin metal foil having a carrier of 101101461 15 201251532 on at least one side and heat-press molding. In addition, the interlayer insulation layer of the additional layer can make the phase-reducing _ material, the village is pure or the tree test is different. In the present embodiment, the insulating layer 102 corresponds to an insulating resin layer constituting the core layer or the buildup layer, and may be either a single layer or a multilayer structure. An example in which a laminated board having an additional layer is used 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 sometimes referred to as an insulating resin composition) which is used as an insulating material for a printed wiring board can be used. The thermosetting resin composition having a good chemical resistance and chemical resistance is not particularly limited, and is preferably a resin composition containing at least a thermosetting resin. Examples of the thermosetting resin include, for example, urea (urea) resin, trimeric amine resin, cis-imine compound, polyxian, non-residual and poly-resin, resin having a ring, and bis(tetra) group. Neviimide compound, Ethyl fresh lion, B County "_lipid, benzocyclobutylene resin, cyanate lysate, epoxy tree material. Among them, the curable resin is preferably a glass transition temperature of 20 Gt or more. For example, it is preferably a spiro ring, a hybrid, a trimethyl form, a biphenyl type, a naphthalene type 1, a secret varnish type; or a trifunctional or higher epoxy resin, a grade g resin (including a practice) Self-adhesive resin prepolymer), cis-butadiene imine compound, stupid cyclopentide, resin with stupid ring. When using epoxy resin and / or cyanate - lipid, the line expansion The heat resistance of the heat is improved. In addition, if the epoxy resin and/or the epoxy resin and/or the atmosphere are combined with the filling material, the flame retardancy, heat resistance, t-carrying, and Advantages of rigidity and electrical characteristics (low dielectric constant, low loss factor). The glass transition temperature of the thermosetting resin is 200° C. or higher, and the thermal decomposition temperature of the resin composition after curing becomes high, and the low molecular weight of the reaction residue at 250° C. or higher is reduced. Further, the improvement of the flame retardancy is considered to be caused by the fact that the aromatic thermosetting resin has a high proportion of the benzene ring in its structure, so that the stupid ring is easily carbonized (graphitized) to cause carbonization. The resin composition may further contain a flame retardant in a range that does not impair the effects of the present invention, and is preferably a non-halogen flame retardant from the environmental viewpoint. As the flame retardant, for example, an organic phosphorus system is difficult. A flammable agent, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyfluorene-based flame retardant, a metal hydroxide, etc. Examples of the organic phosphorus-based flame retardant include HCA and HCA-HQ manufactured by Sanguang Co., Ltd. A phosphine compound such as HCA-NQ, a phosphorus-containing stupid compound of HFB-2006M manufactured by Showa Polymer Co., Ltd., a PPQ manufactured by Beixing Chemical Industry Co., Ltd., and an OP930 'Da Ba Chemical Co., Ltd. manufactured by Clariant Co., Ltd. (shared) PX200 and other phosphoric acid a compound, a phosphorus-containing epoxy resin such as FX289 or FX310 manufactured by Toshiro Kasei Co., Ltd., a phosphorus-containing phenoxy resin such as ERF001 manufactured by Tosho Kasei Co., Ltd., etc. As an organic nitrogen-containing phosphorus compound, for example, four Phosphate decylamine compounds such as SP670 and SP703 manufactured by Guohuacheng Industrial Co., Ltd., SPB100 manufactured by Otsuka Chemical Co., Ltd., SPE100's FP series of FP series manufactured by Fushimi Co., Ltd., etc. For example, the hydroxides such as UD650 and UD653 manufactured by Ube Materials 101102461 17 201251532, and the aluminum hydroxide of CUIO 'Showa Electric Co., Ltd.' manufactured by Sumitomo Chemical Co., Ltd., such as HP_35〇, may be used.

Examples of the epoxy resin used in the resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and bisphenol M. Bisphenol type epoxy resin such as epoxy resin, bisphenol p type epoxy resin, bisphenol Z type epoxy resin, novolac type of phenol novolac type oxime resin, nonylphenol novolak type epoxy resin Epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, biphenyl aralkyl type epoxy resin, etc., aryl alkoxy epoxy resin, naphthol type epoxy resin, naphthalene glycol type epoxy A naphthalene type epoxy resin such as a bifunctional to bifunctional to 4-functional epoxy type naphthalene resin, a epoxidized resin, a bis-naphthyl epoxy resin, or a naphthyl aralkyl epoxy resin. Epoxy resin, phenoxy epoxy resin, dicyclopentadiene epoxy resin, reduced-type epoxy resin, diamond-based epoxy resin, and children's resin. As the epoxy resin, one of these may be used alone, or two or more kinds of different weight average molecular weights may be used in combination. Further, these or the like may be used in combination of two or more kinds of prepolymers. Among these epoxy resins, an aryl-based epoxy resin is preferred. Thereby, the heat resistance and flame retardancy of the moisture absorption solder can be further improved.曰 _Aryl (tetra)-based epoxy resin refers to an epoxy resin having an aryl group in the repeating unit. For example, a 34-epoxy H-methylene type epoxy resin can be mentioned. Among these, a biphenyl diol 101102461 201251532 base epoxy resin is preferred. The biphenyl diindenylene type epoxy resin can be represented, for example, by the following formula (1). Further, examples of the biphenyl dimethylene type epoxy resin include NC-3000, NC-3000L, and NO3000_FH manufactured by Nippon Kayaku Co., Ltd. [Chemical 1]

The average repeating I position η of the biphenyl dimethylene type epoxy resin represented by the above formula (1) is an arbitrary integer. The lower limit of n is not particularly limited, and is preferably 1 or more, particularly preferably 2 or more. When η is too small, the biphenyl dimethylene type epoxy resin is easily crystallized and has low solubility in a general-purpose solvent, so that it is difficult to handle. The upper limit of η is not particularly limited, but is preferably 10 or less, and particularly preferably 5 or less. When η is too large, the fluidity of the resin may be lowered to cause a molding failure or the like. Thermal expansion property The epoxy resin other than the above is preferably a secret varnish type epoxy resin having a condensed cyclic aromatic hydrocarbon structure. Thereby, it is possible to further improve the heat-resistance and low-viscosity epoxidized epoxy resin having a condensed-ring aromatic hydrocarbon structure, such as naphthalene, onion, phenanthrene, benzene-thick, bis-benzene and stupid. Condensed ring aromatic _ structured secret varnish type Wei resin. The varnish type epoxy resin having a condensed ring aromatic hydrocarbon structure has a low thermal expansion property because the plural aromatic rings are regularly arranged. Further, since the glass transition temperature is also high, heat resistance is excellent. Furthermore, since the molecular weight of the repeating structure is 101102461 201251532, the flame retardancy is superior to the conventional awake-clear type epoxy resin, and the combination with the cyanate resin can improve the fragility of the cyanate resin. weakness. Therefore, by using a cyanate resin in combination, the glass transition temperature is further increased, so that the lead-free mounting reliability is excellent. A novolac type epoxy resin having a condensed cyclic aromatic hydrocarbon structure is a mixture of a phenolic compound, a formaldehyde compound, and a condensed cyclic aromatic hydrocarbon compound, and a phenol novolak type phenol resin is epoxyated. The phenol compound is not particularly limited, and examples thereof include phenol such as phenol, o-cresol, m-nonylphenol, p-nonylphenol, 2,3-diinol, 2,4-dioxan, and 2,5-. Dinonylphenols such as diterpene phenol, 2,6-dioxanol, 3,4-dioxanol, 3,5-dioxanol, tridecylphenol such as 2,3,5-tridecylphenol Ethylphenols such as o-ethylphenol, m-ethylphenol, p-ethylphenol, alkylphenols such as isopropylphenol, butylphenol, and tert-butylphenol, o-phenylphenol, and Naphthalene glycols such as phenylphenol, p-phenylphenol, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, resorcinol, ortho Polyvalent phenols such as hydroquinone, hydroquinone, gallic phenol, fluoroglycine, and alkyl polyvalent phenols such as alkyl resorcinol, alkyl catechol, and alkyl hydroquinone. Among these, benzene is preferred from the cost side and the effect on the decomposition reaction. The aldehyde compound is not particularly limited, and examples thereof include furfural, p-nonaldehyde, and trisole. Mountain, acetaldehyde, propionaldehyde, polyfurfural, trichloroacetaldehyde, hexamethylenetetramine, furfural, glyoxal, n-butyl aldehyde, hexanal, allyl aldehyde, benzaldehyde, crotonaldehyde, Acrolein, trimeric furfural, phenylacetaldehyde, o-benzaldehyde, salicylaldehyde, dihydroxybenzaldehyde, 101102461 20 201251532 trihydroxybenzaldehyde, 4-hydroxy-3-hydroxylaldehyde to formaldehyde, and the like. The condensed ring aromatic hydrocarbon compound is not particularly limited, and examples thereof include a naphthalene derivative such as a nonoxynaphthalene or a butoxynaphthalene, an anthracene derivative such as an anthracene oxime, or a phenanthrene derivative such as methoxyphenanthrene. A thick tetraphenyl derivative, a chopstick derivative, an anthracene derivative, a triazine derivative, and a tetraphenyl derivative. The novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure is not particularly limited, and examples thereof include a decyloxynaphthalene-modified o-nonphenol novolac epoxy resin and a butoxynaphthalene-modified fluorenyl group (p-). Phenolic novolac epoxy resin and decyloxy naphthalene modified phenolic varnish epoxy resin. Among these, a novolac type epoxy resin having a condensed ring aromatic hydrocarbon structure represented by the following formula (2) is preferred. Further, as the acetal varnish type epoxy resin having a condensed cyclic aromatic hydrocarbon structure, for example, HP-5000 manufactured by DIC Co., Ltd. can be used. [Chemical 2]

(wherein Ar is a condensed cyclic aromatic hydrocarbon group, and R may be the same or different from each other, and is a hydrocarbon group selected from a hydrogen atom, a carbon number of 1 or more and 10 or less, an aromatic group such as a fluorene element, a phenyl group or a benzyl group; The group of the organic group containing a glycidyl ether, η, ρ and q are integers of 1 or more, and the values of p and q may be the same or different in each repeating unit.) 101102461 21 201251532 [Chemical 3]

Cam)

(Ar3)

(Ar2)

(Ar4) (3) The structure shown by (10) in the formula (7) (10) to (ΑΜ) in the formula (3), (wherein R may be the same or different from each other, and is selected from a hydrogen atom, a carbon number ^ An aryl group of 10 or less, an aryl group such as a phenyl group or a phenyl group, and a group containing an organic group of a benzoxypropyl ether.) Wide = epoxy resin other than the above, preferably a naphthol type epoxy tree Month: a naphthalene type epoxy resin such as a naphthyl alcohol type, a bifunctional to a tetrafunctional to tetrafunctional epoxy type Cai resin, or a naphthoquinone type epoxy resin. In this way, heat resistance and low touch can be further improved. Further, since the π_π t stacking effect of the naphthalene ring is higher than that of the benzene ring, it is particularly low in low expansion and low in heat shrinkage. Furthermore, due to the polycyclic structure & the straight-right effect, since the glass transition temperature is particularly high, the change in heat shrinkage before and after reflow is small. The naphthol type epoxy resin can be represented, for example, by the following general formula (4-1). Further, as the Cai-type epoxy resin, for example, esn_375 manufactured by Shinkai Iron Chemical Co., Ltd. can be mentioned. The naphthalene type epoxy resin can be represented, for example, by the following formula (4-2). The naphthalene diol type epoxy resin may, for example, be HP-4032D manufactured by DIC Co., Ltd. The bifunctional to 4-functional epoxy type naphthalene resin can be represented, for example, by the following formula (4-3) (4-4) (4-5). As a bifunctional to tetrafunctional epoxy type naphthalene resin, 101102461 22 201251532 is exemplified by HP-4700 and HP-4770 manufactured by DIC Corporation. The naphthene ether type epoxy resin can be represented, for example, by the following general formula (4-6). As the naphthene ether type epoxy resin, for example, HP-6000 manufactured by DIC Co., Ltd. can be mentioned. [Chemical 4]

(4-1) (η represents a number of 1 or more and 6 or less on average, and R represents a glycidyl group or a hydrocarbon group having 1 or more and 10 or less carbon atoms.)

101102461 23 201251532 (4-6) (:: number: represents a hydrogen atom or a sulfhydryl group) R2 independently represents a hydrogen atom, a carbon atom, a ruthenium and a ruthenium group, an aryl group, a zeoliyl group or a ring-containing group. The naphthyl I of the oxypropyl ether group is m). An integer of ~2, and. Or at least any one of m is a cyanic acid-based resin used for the cyanide compound, and can be obtained, for example, by reacting the self-chemical example, (4) with the ruthenium, and obtaining a specific resin such as cyanate as a cyanate resin. Secret varnish Wei acid § resin, A 35 miscellaneous varnish type (four) ^ ice and other secret type cyanine dynamic resin, naphthalene silk type cyanate Θ曰 child J 曰, a xm 丄, clothing a thin cyanate Resin, biphenyl cyanate resin, bismuth A-type cyanate S resin, double-prevention AD type cyanate resin, tetramethyl bisphosphonate, etc. Resin, etc. Among the hydrazines, etc., it is preferred to contain a novolac type cyanate resin, a naphthol aralkyl cyanide SxSa resin, a dicyclopentadienyl cyanate lysate, a biphenyl phthalic acid granule and a 4c excellent resin composition. The cyanate resin having a δ content of 10% by weight or more based on the total solid content of the resin composition. Thereby, the heat resistance (glass (four) shift temperature, thermal decomposition temperature) of the prepreg can be improved. Further, 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 direction of the bulk thickness is lowered, the stress of the multilayer printed wiring should be reduced. Further, in the multi-layer printing cloth 101102461 24 201251532 wire board having a fine interlayer connection portion, the large cap can improve the connection reliability. The novolak-type cyanate resin used in the composition of the present invention is preferably a novolac type cyanate resin represented by the following formula (5). Preferably, a novolak type vinegar of the formula (5) having a weight average molecular weight of 2,000 or more, preferably 2,000 to 1 Torr, 〇〇〇, more preferably 2,2 〇 0 to 3, and 5 Å is used in combination. The resin and the novolac type cyanate resin having a weight average molecular weight of 15 Å or less, preferably not more than the formula (5) of 2004, 300 (hereinafter, unless otherwise specified, "~" means that the upper limit is included. Further, in the present embodiment, the weight average molecular weight is a value measured by gel permeation chromatography in terms of polystyrene.

In the formula (5), η represents an integer of 〇 or more. In addition, as a cyanate resin, it is also suitable to use the following general formula (6).

The resin is obtained by condensing cyanohydrin into the hydrazine. - put /,

101102461 25 201251532 It is not easy to cause intramolecular polymerization at the time of the formation, and the liquid separation property during washing is improved, and the production is prevented from being lowered. [Chemistry 9]

In the formula (6), R represents a hydrogen atom or a fluorenyl group, the scales may be the same or different, and n represents an integer of 1 or more. Further, as the cyanate resin, a cyclopentadiene 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 〇 or more and 8 or less in the following general formula (7). When η 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]

The thermosetting resin is an epoxy tree. Further, the tree residue may further contain a curing accelerator. For example, if 9 or chaotic acid ester resin, phenol resin 101102461 26 201251532 曰 or phthalate resin can be used for the hardening promotion limitation, and phenolic phenol resin is not particularly exemplified by, for example, benzoic acid: varnish resin phenol AW (four) varnish Resin, double, main (four) 〇, ~, Na, aryl base (four) material _ fat and other secret two (four) resin, unmodified soluble benzene resin, by tung oil, sub-thorn 7, walnut oil, etc. After the change (four) oil modified soluble benzene _ lipid and other secret type benzene _ fat and so on. As the above-mentioned benzene resin, it is preferred that the benzene viscous varnish or the toluene varnish rhyme H is preferably a bismuth varnish varnish resin from the viewpoint of (four) solder _ sex. In the case of j or the like, one type may be used alone or two or more types of different weight average molecular weights may be used in combination, or two or more types of prepolymers may be used in combination with the above-mentioned hardening accelerator. For example, such as zinc naphthalate, potassium oxalate, tin octoate, octane, bis-ethylidene-acrylic acid (III), triethyl aryl-based cobalt (III) and other organic metal salts, triethylamine, tributyl Amine, diterpene bicyclo[2,2,2], etc., 3, amines, 2_mercaptopurine, 2•phenyl mouth rice. Sit, 2_phenylidene methylimidazole, 2_ethylideneethylimidazole, 1-benzyl-2-methylimidazole, 1-pyryl-2-phenylene, 2-10-decyl (tetra), 1 • Cyanoethyl 2·ethyl·4_ methyl “m. Sit, 1-cyanoethyl 2_ eleven base, 2_ stupid base _5_ carbazol, 2-phenyl-4,5_dipyridyl (tetra), 2,3_two Gas] Η_scale (i, 2_a) benzopyrene and other __, face, double ^, sulfhydryl _ pure compound, acetic acid, benzoic acid, salicylic acid, phthalic acid, etc. , a rust salt compound or the like or a mixture thereof. In addition, one of 101102461 27 201251532 may be used alone, and two or more of them may be used in combination with derivatives thereof. 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 N-phenyl maleimide, N-phenylphenyl maleimide, and bis('s-butylene diimide phenyl) oxime. 2,2-bis{4-(4-maleoximineimine)oxyphenylpropane, bis(3,5-monodecyl-4-methylene-2-imideimidephenyl) , bis(3_ethyl_5_methyl_4_methyleneimine phenyl) decane, bis(3,5-diethyl-4-m-butyleneimine phenyl) A prepolymer of blister, butadiene diamine, or a prepolymer of a maleimide compound and an amine compound, or the like. Further, the thermosetting resin may contain a phenoxy resin, a polyvinyl alcohol resin, a polyimine, a polyamine, a polyamide, or the like, from the viewpoint of adhesion to the metal foil. Imine, polyether sulfone resin, poly-strand ether resin. Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a naphthyl (tetra)phenoxy resin, and a biphenyl f (tetra) strepoxy resin. Further, a phenoxy resin having a configuration of a plurality of such racks can also be used. Among these, a phenoxy resin having a biphenyl skeleton and a bisphenol January shelf is preferably used in the phenoxy resin. Thereby, the glass transition temperature of the rigidity-preparable phenoxy resin having a biphenyl skeleton can increase the adhesion between the phenoxy resin and the metal due to the presence of the double age s skeleton. As a result, it is possible to improve the heat resistance of the insulating layer 102 to 101102461 28 201251532 and to improve the adhesion of the wiring portion (conductive circuit 118) to the insulating layer 1〇2 when manufacturing the multilayer substrate. Further, it is preferred to use a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton in the phenoxy resin. 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 phenoxy resin, for example, FX280 manufactured by Tohto Kasei Co., Ltd., and YX8l, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213, and YL7290 manufactured by Japan Epoxy Resin Co., Ltd., etc., may be mentioned. The molecular weight of the phenoxy resin is not particularly limited, and it is preferably those having a weight average molecular weight of 5,000 to 70,000, more preferably 10,000 to 60,000. The content of the present invention 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 polyvinyl alcohol-based 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 ° Ca. For example, "VYLOMAX HR11NN (registered trademark)" and "HR-MNNjJHRlSETj", manufactured by Toyobo Co., Ltd., and Hitachi Chemical Industry Co., Ltd., are commercially available as Polyimine, Polyamide, and Polyamidamine. ) Polyacrylamide imine "KS-9300" and the like. For example, "Neopulim C-1210" manufactured by Mitsubishi Gas Chemical Co., Ltd., and Soluble Polysaccharide 101102461 29 201251532 by the Nippon Chemical and Chemical Co., Ltd., the imine "RICACOAT SN20 (registered trademark)" and "RICAC〇ATpN2〇" "Registered Trademarks"", Polyurethane Imine, "ULTEM (Registered Trademark)", manufactured by GE Plastics Co., Ltd., "V8000", "V8002" and "V8005", and Japanese Chemicals (shares) "BPAM155" and so on. As a commercial product of a polyether hard resin, a well-known thing can be used, for example, Sumitomo

Chemical company PES4100P, PES4800P, PES5003P and PES5200P. Examples of the polyphenylene ether resin include poly(2,6-dimercapto·anthracene, 4-extended base) oxide and poly(2,6-diethyl-1,4-extended base). Oxide, poly(2-indenyl-6-ethyl-1,4-phenylene) oxide, poly(2-fluorenyl-6-propyl-anthracene), oxide (2,6-Dipropyl-1,4-phenylene) oxide, poly(2-ethylpropyl-1,4-phenylene) oxide, and the like. As a commercial item, for example, "Noryl PX9701 (registered trademark)" (quantitative average molecular weight Mn = 14,000) and "Noryl 640-111 (registered trademark)" (quantitative average molecular weight Mn = 25,000) manufactured by GE Plastics Co., Ltd., and Asahi Kasei The company's "2" 2 (quantitative average molecular weight Mn = 20,000) can be used by a known method to reduce the molecular weight. Among these, it is preferred to use a functional group to modify the terminal end-modified reactive oligomeric phenyl oxide. 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-dimethyl group described in JP-A-2006-28111 A reaction product of a benzene polycondensate and a gas methyl acetophenone. 101102461 30 201251532 Such a reactive oligomeric phenyl 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 2G'_m'GGG~15,_. If the weight average molecular weight of the reactive oligomeric phenylene oxide (4) is 2G, _' coffee is added to the volatile solvent. On the other hand, if the weight average molecular weight is less than 2, _, the crosslink density is too high, and (4) the elastic modulus of the cured product or the flexible material is good. The amount of the thermosetting resin 9 in the resin composition used in the present embodiment can be appropriately adjusted in accordance with the purpose thereof, and is not particularly limited. The total amount of the resin composition is 'thermosetting resin'. It is preferably iG to 9Q% by weight, more preferably 20 to 70% by weight, still more preferably 25 to 50% by weight. Further, when an epoxy resin and/or a cyanide resin is used as the thermosetting resin, the epoxy resin is more than the weight of the total amount of the above-mentioned ingredients. /. The epoxy resin is more preferably 5 to 25% by weight. Further, in the total solid content of the resin plant, the cyanate resin is preferably 5 or more preferably more preferably 10 to 25% by weight. s. 'Nitroleumate The above resin composition is composed of a low thermal expansion and an inorganic filler. There are no special inorganic fillers such as talc, burnt clay, unfired clay, φ, oxidized, oxidized, oxidized, etc., salt, sour, side, hydrotalcite, etc. :" 二一乳虱化化铝,水铝土101102461 201251532 (AIO(OH) ' is often referred to as "class" water and soil water (also known as

Al2〇3 xH2〇'in this ' χ=ι to 2), hydroxides such as hydroxide, hydroxide, etc., sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite, zinc borate, Borates of bismuth bismuth borate, aluminum borate, calcium borate, sodium borate, etc., nitrides of nitrides such as aluminum nitride, boron nitride, tantalum nitride, and carbon nitride, such as barium titanate and barium titanate Wait. One of these may be used alone or in combination of two or more. Among these, magnesium hydroxide, aluminum hydroxide, bauxite, silica, sulphur dioxide, talc, calcined talc, and oxygen (10) are preferred. From the viewpoint of low heat expansion property and insulation reliability, it is particularly preferable to be trioxide #, more preferably spherical molten dioxane. Further, in terms of _ sex, it is preferably hydrazine. Further, in the present embodiment, since the base material which is impregnated even by the inorganic filler is used, the amount of the inorganic filler can be increased in the resin composition. When the inorganic filler in the resin or the product is in a concentration, the bit abrasion property is deteriorated. However, when the inorganic filler is water and soil, it is preferable from the viewpoint of satisfactory drill wear resistance. (4) The inorganic filler is not particularly limited, and the inorganic filler having a uniform average particle diameter may be used, or an inorganic filler having an average particle diameter of polydisperse may be used. The average particle diameter of the inorganic filler, which is one or two or more kinds of the inorganic filler, is not particularly limited, and is preferably 〇1μηι to 5 0μπι, and particularly preferably Q ～3_. When the particle size of the inorganic filler is above the lower limit, the viscosity of the composition of the composition is changed to 101102461 32 201251532, so that 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 (manufactured by Shimadzu Corporation, general equipment such as SALD-7000). The content of the inorganic filler is not particularly limited. It is preferably from 1% by weight to 90% by weight, more preferably from 3% by weight to 8% by weight, and more preferably from 50% by weight of the total solid content of the above resin composition. Weight% to 75% by weight. When the cyanate resin and/or its prepolymer are contained in the above resin composition, the content of the inorganic filler is preferably from 5 to 75% by weight based on the total solid content of the resin composition. When the content of the inorganic filler exceeds the above upper limit, the fluidity of the resin composition is extremely poor, which is not preferable. If the lower limit is not exceeded, the strength of the insulating layer composed of the resin composition is insufficient. good. Further, the resin composition used in the present embodiment may be blended with a rubber component. For example, as a rubber particle which can be used in the present embodiment, for example, core-shell type rubber particles and crosslinked acrylonitrile are used. Diene rubber particles, crosslinked styrene butadiene rubber particles, acrylic rubber particles, polyfluorene oxide particles, and the like. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and for example, the outer layer is composed of a glassy polymer, and 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 rubbery polymer, and the core layer is a three-layer structure composed of 101102461 33 201251532 glassy polymer. The glassy polymer layer is composed of a polymer such as methyl acrylate, and the rubbery polymer layer is made of, for example, an acrylic acid τ polymer (τ-based rubber). Specific examples of the core-shell type rubber particles include, for example, ac 3832.

AC3816N (trade name Ganz Chemical Co., Ltd.), METABLEN KW_4426 (trade name Mitsubishi Luorong (share) system). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles can be exemplified by (average particle diameter: 0.5 μm η JSR). Specific examples of the cross-linking of the bismuth-thin rubber (SBR) particles include, for example, XSK-500 (average particle diameter 〇 5 μmη, manufactured by a dish). Specific examples of the acrylic rubber particles include METABLEN W300A (average particle diameter Ο.ίμιη) and W450A (average particle diameter 〇.2_ (manufactured by Mitsubishi)). 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, KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), TORAYFILE-500, and TORAYnLE-600 (manufactured by Toray Dow Corning Co., Ltd.) can be used. And other commercial products.

The resin composition described above may further contain a coupling agent. The coupling agent enhances the wettability of the interface between the thermosetting resin inorganic fillers, and the resin and the inorganic filler are uniformly fixed to the substrate for improving the heat, especially after moisture absorption. The solder is heat-resistant and formulated. The coupling agent is not particularly limited, and examples thereof include an epoxy group coupling agent, a cationic Wei coupling agent, an amine-based Wei coupling agent, a titanic acid 1 (tetra) mixture, and a polyoxanol type coupling. Thereby, the wettability with the interface with the inorganic filler can be improved, whereby the heat resistance can be further improved. The above-mentioned occasional addition is not particularly limited, and is preferably G. by weight based on 100 parts by weight of the inorganic filler. G5 to 3 parts by weight, particularly preferably (U to 2 parts by weight. If the amount of 3 is less than the above lower limit value), since the inorganic filler is not sufficiently coated, the effect of improving heat resistance is lowered (4), and if the amount exceeds the upper limit The value may affect the reaction, and may have a decrease in bending strength, etc. In the resin composition used in the present embodiment, defoaming and homogenization may be added as needed; an external absorbent, a foaming agent, Additives other than the above-mentioned components, such as an antioxidant, a flame retardant, a polysulfide powder, and the like, and ion trapping (4), in the above-mentioned composition of the tree, it is easy to realize low-line expansion of the prepreg and high From the viewpoint of rigidity and high heat-generating, it is preferable to contain at least an epoxy resin, an oleic acid vinegar resin, and an inorganic filler. Among them, in the solid content of the resin composition, it is preferable to contain an oxidizing resin 5 5% by weight, cyanate resin 5 to 5 % by weight, and inorganic filler 10 to 90% by weight, more preferably 5 to 25 % by weight of epoxy resin, 10 to 25% by weight of cyanate resin and Inorganic filler material 3〇~8〇% by weight. 101102461 35 201251532 The prepreg used in the embodiment is a varnish in which a resin composition is impregnated or applied to a substrate, and as the substrate, various known materials used for a laminate for electrical insulating materials can be used. Examples of the material f include, for example, an inorganic fiber such as E glass, D glass, T surface, s glass or Q glass, organic fibers such as polyimine, polyg or tetrafluoroethylene, and the like. Mixtures, etc. These substrates have a shape such as woven fabric, non-woven fabric, roving, dicing, surface surname, etc., and the material f and shape may be selected depending on the use or performance of the target molded article, and may be used as needed. The thickness of the material of the two or more materials and the shape is not particularly limited, and is usually 0. 01~0. For those of about 5 mm, in terms of m or soup resistance and edifying, it is preferable to use a Wei coupler or the like: a surface treatment person or a mechanical fiber opening treatment, and a fan-flat field. The pre/separation is usually made by impregnating or coating the resin on the substrate in such a manner that the resin content thereof becomes 20 to 90 ^stem % after drying, and the solution is made by using the β2 dry ^1~2〇 minutes. In the hardened state (B-stage state), the film can be heated and twisted by superimposing the prepreg on a sheet of usually 1 to 2 G, and then placing an extremely thin copper foil having a carrier foil thereon. The stratified layer is used to obtain a laminate. The thickness of the prepreg layer of the plurality of sheets varies depending on the use, and is usually G. G3 ~ 2mm thick. As a lamination method, a method of laminating sheets of Tongwei can be applied, for example, multi-stage pressing, multi-stage vacuum pressing, continuous forming, high-pressure dad molding machine, etc., at a normal temperature of 1 〇〇 to □. c, pressure 0. 2~lOMPa, heating time 〇 w hours of conditions for lamination or use of a real-life lamination device, etc. depending on the lamination conditions 50~150 ° C, 0. 1 to 5 MPa, true 101102461 36 201251532 The conditions of the air pressure of 1·0 to 760 mmHg were laminated. . The layer layer used in the present embodiment is the peak intensity of the plane orientation (200) measured by the XRD film method in the above-mentioned 2〇 (surface opposite to the side of the insulating side H) 2 as described above. The ratio of the peak intensity to the plane orientation (1) (2GG) (22G) and (311) is 26% or less, preferably 25% or less, and more preferably 24%. By making the ratio of the plane orientation (thinness) within the above range, the side surname characteristic of the copper falling layer 1〇4 can be improved. In addition, the ratio of the sum of the surface orientations (2〇〇) and (22〇) of the upper surface 20 of the copper y white layer 104 is relative to the plane orientation (out), (200), (220), and (311). The sum of the peak intensities is preferably 32% or less, more preferably less, and even more preferably 30% or less. By setting the ratio of the sum of the peak intensities of the plane orientations (2〇〇) and (10)) to the above range, the side-cut characteristics of the copper-based layer 4 can be further improved. Therefore, a printed wiring board excellent in the degree of use can be obtained, so that the yield of the manufacturing method can be improved. As a method of forming a conventional steel box, a copper box having a film thickness of about 2 ton is usually formed by treatment on the electrode. However, in this formation method, there are cases where the (iv) continuation of the underlying metal layer (e.g., electrode) is orthogonal, and it is difficult to form _ having the desired crystal plane. In addition, when the film thickness of the copper box is thick, for example, 30 μm or more, the crystal grains tend to be coarsened in the thickness direction, and the ratio of the surface orientation (22 〇) of the upper surface of the copper particles tends to be high. Therefore, conventionally, by increasing the ratio of the superior orientation (220) of the surname to the face orientation (111), it is desirable to increase the longitudinal rigidity of the copper box to enhance the lower copper box relative to the upper layer. Metal 101102461 37 201251532 Layer etch rate. In contrast, in the method of forming the copper box layer 104 of the electrode shape/form, the right Tailu &  A copper layer 104 is formed on the release layer. This is because of the alignment of the lower electrode with the steel box layer 104. In other words, it is appropriate to control the alignment of one side of the copper (10) 104 which is in contact with the peeling layer to continue the layered surface of the Hi layer 1G4, so that the alignment of the surface can be made one side. Thereby, a copper layer 104 having a desired alignment property can be formed. In the present embodiment, the ratio of the surface orientation _) which is superior to the surface characteristics of the copper foil layer 104 is set to be lower than a predetermined value, so that the steel ruthenium layer in the step described later can be used. 1〇4's fiber characteristics. Thereby, a well-formed good wiring shape can be realized, and as a result, a printed wiring board excellent in yield can be obtained. Further, a method of forming the detailed copper box layer 1〇4 will be described later. Further, the film thickness of the copper box layer 1〇4 is not particularly limited, but is preferably 〇 ΐμηη or more, and is preferably 5 or less, more preferably 5 or more and _ or less, and more preferably 2 or less. By setting the thickness of the copper foil layer 1〇4 to this range, the particle diameters of the crystal grains of the copper fg layer 104 can be made uniform. Thereby, the orientation change of the copper box layer 1〇4 can be suppressed. By the above, the alignment of the upper surface of the copper foil layer 104 can be controlled, for example, the ratio (i.e., the alignment) of the 20' crystal plane from the lower 22 of the copper fg layer 104 to the upper surface can be the same; for example, the plane orientation can be 2〇〇) The ratio, or the plane orientation (2〇〇) and the plane orientation (220) are the same. Here, the same means that the tolerance in the manufacturing step is allowed, for example, the ratio of the plane orientation (2〇〇) of the lower surface 22 of the copper foil layer 104 is 101102461 38 201251532, which is the ratio of the plane orientation (200) of the upper surface 20 Within ±5%. 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 the ratio of the upper surface 20 of the copper foil layer 104. Further, in the upper surface 20 of the copper foil layer 104 on which the copper foil laminate 1 is formed by heat and pressure forming, the ratio of the plane orientation (200), or the plane orientation (2 〇〇) and the plane orientation (220) The ratio is a value which maintains the copper foil layer (the peelable copper foil with a carrier foil) before heat press molding. In other words, in the upper surface 20 of the heat-press-formed copper foil layer 104, the ratio of the plane orientation (200) is 26% or less, preferably 24% or less, more preferably 23% or less; on the other hand, the plane orientation (thin) and the surface The ratio of the orientation (220) is preferably 32% or less, more preferably 31% or less, still more preferably 30% or less. The heating and press forming conditions as described herein are, for example, 2 Torr for 1 hour and a pressure of 3 MPa. The reason for maintaining the ratio is not clear, but it is presumed that the average particle diameter of the crystal grains in the copper and metallurgy layers 104 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 1 4 described later, the surface orientation (200) of the upper surface of the copper foil layer 104 (that is, the contact surface with the metal layer ι 6 (for example, the electroless plating layer 11 〇)) The ratio, or the ratio of face orientation (2〇〇) and face orientation (22〇), can be the same. The copper foil layer 104 of the present embodiment preferably has crystal grains having an average length of 2 μm or less on the long sides. The shape of the crystal grains in the copper foil layer is, for example, a columnar shape or a double 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 101102461 39 201251532 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 cross-sectional image of the cross-section μιη was averaged, and the average value of the total of three visual field images was calculated. Thereby, the character of the bronze floor 104 is improved. In the copper foil layer 1〇4 of the present embodiment, the area ratio of the crystal grains having an average length of 2 μm or less in the long side is preferably 8% or more, more preferably 85% or more. Even better 90°/. the 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. Further, the ultra-thin copper foil (copper foil layer 104) having a carrier foil used in the present embodiment is an electrode layer in which a roughened surface of an ultra-thin copper foil is convex-shaped (referred to as a baking layer). For example, the roughening surface treatment by the formation or oxidation treatment, reduction treatment, etching, or the like of Japanese Patent Laid-Open No. Hei 9-195-96. Therefore, the surface roughness of the roughened surface of the ultra-thin copper foil used in the present embodiment is preferably the upper limit of the 10-point average roughness (Rz) shown in JIS B0601, preferably 5 or less. 2. 0 μιη or less; on the other hand, the lower limit is not particularly limited, and is preferably Ο. Ίμιη above. Furthermore, the arithmetic mean roughness (Ra) is preferably less than the claw, more preferably 0. 5μιη below. Further, the 'four-layer steel 104 has a block portion and a convex portion formed on one side of the block portion by performing the formation of a bump-shaped electrode layer or roughening surface treatment (hereinafter also referred to as a convex portion). To roughen the foot part). 101102461 201251532 In addition, in the present embodiment, the copper foil layer 104 may be a copper foil composed of steel (except for the incorporation of inevitably in the production step), and may be an additive metal component containing nickel or aluminum. In this case, the content of copper is not particularly limited, and is preferably 90% by weight or more, more preferably % by weight or more, and still more preferably 99% by weight based on the total weight of the total metal components constituting the copper foil layer 104. Further, as the metal component to be added, it may be used alone or in combination with a plurality of types of materials, or a copper foil layer 1〇4 may be used instead, and a metal foil such as a nickel foil or an aluminum foil may be used. Before and after the heat treatment, the difference in Vickers hardness of the copper foil layer 1〇4 is preferably 〇Hv or more and 5ΌΗν or less, more preferably 0Hv or more and 30Hv or less. By the difference in Vickers hardness of the copper foil layer 1〇4 When it is set to the upper limit or less, it is possible to suppress the progress of recrystallization of the copper foil layer 1 to 4 due to heating, and the crystal grain size is increased, and the etching rate is slow, or the strain accumulation of the thin circuit after etching can be suppressed. The copper layer 104 is at 230. The Vickers hardness after heat treatment for 1 hour is preferably 180 Hv or more and 240 Hv or less, more preferably 185 Hv or more and 235 Hv or less. By setting the Vickers hardness after heating to 18 〇Hv or more, heating can be suppressed. When the recrystallization of the thin copper layer (copper foil layer 1〇4) progresses and the crystal grain size becomes large, the linearity of the circuit after etching can be suppressed. On the other hand, 'by setting the Vickers hardness after heating When it is 24 〇Hv or less, it is possible to suppress the case where the thin copper layer becomes too hard and becomes brittle. Thereby, it is possible to suppress cracking during operation and to improve the thermal shock resistance of the formed fine wiring. 101102461 41 201251532. In the form, the Vickers hardness can be measured by the following method. That is, the Vickers hardness is measured in accordance with JIS Z 2244 in the following order using a micro hardness tester (model MVK-2H) manufactured by Akashi Co., Ltd. at 23 °C. 1) The ultra-thin copper foil having the support formed into the thin copper layer was placed in an oven (nitrogen atmosphere) heated to 230 ° C for 1 hour, and then cut into 10 x 10 mm square. (2) The cutting sample was loaded according to the load speed. 3μιη / sec, test negative The indentation was applied under the conditions of a weight of 5 gf and a holding time of 15 seconds, and the Vickers hardness was calculated from the measurement result of the indentation. (3) The average value of the arbitrary five-point Vickers hardness was measured as the Vickers hardness value of the present embodiment. The etching rate of the copper foil layer 104 (thin copper foil) is 〇. 68μιη/ηΰη and above 25μιη/ιτύη Following 'better 〇·68μηι/ιηίη above and 1. 24μιη/ηήη below, and even better. 69μιη/ιηίη and above 1. Below 23pm/min. The etching rate of the copper germanium layer 104 of the present embodiment is only indicated by the etching rate of the bulk portion and the etching rate of the copper foil layer 1〇4, which is specifically determined by the following etching conditions. 95% sulfuric acid, i〇〇〇cc pure water and 20cc 34. 5% hydrogen peroxide water, and a temperature of 3 (TC ± rc of sulfuric acid / hydrogen peroxide water, impregnating the laminate. In the present embodiment, 'by etching the copper foil layer 104 to the lower limit value In the above, the etching residue of the copper foil layer 1〇4 can be reduced, and the wiring shape is good, and the etching rate of the copper foil is set to be lower than the upper limit value, so that 101102461 42 201251532 can be suppressed from forming a cut σ in the copper/self layer 104 (four). The entanglement between the wiring and the insulating layer also suppresses the occurrence of abnormal necking in the copper portion and the bulk portion of the layer 104 when the button is inscribed to the roughened portion of the copper box layer 104. In the fourth embodiment, the (4) (4) fan rate can be measured by the following method: 1. The carrier case (carrier (4) 1〇6) is removed, and a substrate with a very thin copper flute is laminated on both sides ((4) laminated plate _, cut into The sample piece is obtained by 4Qmmx8Gmm and the sample piece is measured by the vernier caliper and read to 2 points below the decimal point, and the area of the sample piece is different.  On a horizontal drying line, the sample piece was subjected to a machine and dried for 1 minute. 3.  The initial weight WG of the sample piece (including the substrate weight) was measured. 4.  Prepare an etchant. 4-1 . Weighing 95% sulfuric acid (manufactured by Wako Pure Chemical Industries Co., Ltd., special grade) 6〇g, placed in a beaker. 4-1 : Put pure water into a beaker and make a total of 1 〇〇〇 cc. 4-3: Stir by a magnetic stirrer for 3 minutes at 3 〇 ±lt. 4-4 . Weighing 34. 5% hydrogen peroxide water (manufactured by Kanto Chemical Co., Ltd., Deer Grade) 20cc was placed in a beaker. 5. Dip in the above etching solution (liquid temperature 3 〇 ± n, stirring conditions: magnetic stirrer, 250 rpm) 〇 6. The weight W1 (including the weight of the substrate) after the treatment was measured every 30 seconds until the bulk layer of the extremely thin foil was completely etched. 101102461 43 201251532 7. Calculate the side weight (WO — W i) / (the area of the two sides of the impregnation = m2), draw the time (seconds) according to the axis, and the etching quality (g/m2) of the Y axis, in the second of 〇~丨The slope κ is calculated according to the least squares method. The conversion formula of the silver engraving rate of the present embodiment is shown below. The etch rate (pm/min) = K(g/sec · m2) + 8. 92 (copper specific gravity g/cm3) x 60 (sec/min) In the present embodiment, the grain size of the steel foil layer 1〇4 is reduced, the change in Vickers hardness after heat is reduced, and the roughened foot portion is improved. The etch rate increases the etch rate of the copper foil layer 104 (especially the bulk portion). Further, the etching speed of the crucible portion is generally slower than that of the portion of the material, but can be improved, for example, by reducing the electrolytic density. The stomach describes the detailed method of the peelable copper used in the copper layer 104. Further, 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, a metal which is a release layer is formed on a carrier foil having a thickness of 10 to 50 μm. The inorganic compound or organic compound layer is subjected to a plating treatment on the release layer to form a copper foil. As a condition for the plating treatment, for example, when a sulfuric acid steel bath is used, it may be 50 to 100 g/L of sulfuric acid, 30 to 100 g/L of copper, and 2 to 8 Torr of temperature. 〇, current density 0. 5~100A/dm conditions' When using a coke-breaking steel bath, it can be set to axe, potassium citrate 100~700g/L, copper 10~50g/L, temperature 303⁄4~60°C, pH8~12, The current density is 1 to ΙΟΑ/dm2. Further, various additives may be added to the above bath in consideration of the physical properties of the steel box or the slidability of 101102461 44 201251532'. x, the so-called detachable metal Μ ' is a metal enamel having a body, and the carrier is a peelable metal. In this embodiment, the steel pig is formed on the peeling layer by, for example, having an average molecular weight of white 15 to 35 ppm of gelatin of 5 Å or less is used as an additive to carry out cathodic electrolysis treatment with copper sulphate. In this case, the bismuth of steel (10) is formed by using the sulphate formed as a cathode and using the above copper sulphate. The ferry is subjected to electrolytic treatment, and the separation is carried out on the separation layer. If the method of forming the copper fl is used, the mechanical strength of (four degrees) can be increased or decreased at a high temperature, and a copper foil excellent in etching property and excellent in workability can be formed. This effect is caused by the fineness of the crystal constituting the copper by the addition of gelatin. When the average molecular weight of the gelatin is ≤ or less, recrystallization of the thin copper layer by heating can be suppressed. Thereby, the crystallization of the crystal after heating is performed. Regarding the fact that it has not been fully explained, it can be considered that by setting the molecular weight of Mingsheng to below the fixed value, gelatin is easily taken into the crystal grain boundary during plating, and as a result, the progress of recrystallization can be suppressed. . The average molecular weight of the daily turnover is preferably ° 5 〇〇 5 5''. By setting the average molecular weight of the daily turnover to 500 or more, it is possible to prevent the gelatin added to the sulfuric acid steel money bath from being decomposed into an organic compound by the amino acid or the like in the acidic solution. Thereby, the effect of preventing the recrystallization from being lowered into the crystal grain boundary can be suppressed. The gelatin concentration in the copper sulfate plating bath is preferably 15 to 35 qing. When the gelatin concentration is 15 ppm or more, recrystallization inhibition due to heating can be sufficiently obtained. 101102461 45 201251532 Effect. Therefore, a fine crystalline state can be maintained after heating. When the gelatin concentration is 35 ppm or less, the internal stress of the copper network formed by the borrowing and coating can be suppressed. Thereby, it is possible to suppress the curl of the ultra-thin copper foil having the carrier foil and the occurrence of defects during transportation. As the copper sulfate ore bath, it is suitable to use, for example, a sulfuric acid acidic copper sulfate plating bath containing copper sulfate 5 hydrate, sulfuric acid, gelatin and gas. The concentration of the copper sulfate hydrate in the copper sulfate plating bath is preferably 5 〇g/L to 3 〇〇g/L, more preferably 100 g/L to 200 g/L. The sulfuric acid concentration is preferably 4 〇 to i6 〇 g/L, more preferably 80 g/L to 120 g/L. The concentration of gelatin is as described above. The concentration of chlorine is preferably from 1 to 20 ppm, more preferably from 3 to 10 ppm. The solvent of the plating bath is usually water. The temperature of the plating bath is preferably from 20 to 60 ° C, more preferably from 30 to 50 ° C. The current density at the time of electrolytic treatment is preferably 1 to 15 A/dm 2 and more preferably 2 to i 〇 A/dm 2 . In the case of forming a copper box, in order to prevent the occurrence of pinholes before the electrolytic treatment using the copper sulfate plating bath described above, a strike plating using a so-called distribution bath is preferably used. Examples of the key bath used for the underplating include a copper pyrophosphate plating bath, a copper citrate plating bath, and a copper citrate plating bath. The copper pyrophosphate plating bath ' is preferably, for example, a plated copper containing copper pyrophosphate and potassium pyrophosphate. The concentration of copper pyrophosphate in the copper pyrophosphate plating bath is preferably from 60 g/L to 110 g/L, more preferably from 70 g/L to 90 g/L. The concentration of potassium pyrophosphate is preferably from 240 g/L to 470 g/L, more preferably from 300 g/L to 4 〇〇g/L. The solvent for the plating bath is usually water. The pH of the plating bath is preferably 8. 0~9. 0, better 8. 2~8. 8. In order to adjust the pH value, ammonia water or the like may be added (the same applies hereinafter). The temperature of the plating bath is preferably 101102461 46 201251532 20 to 60 ° C, more preferably 30 to 50 ° C. The current density during electrolytic treatment is preferably 0. 5~ΙΟΑ/dm2, preferably 1~7A/dm2. The electrolytic treatment time is preferably 5 to 4 seconds, more preferably 10 to 30 seconds. The copper citrate ore bath is preferably a plating bath containing, for example, copper sulfate 5 hydrate and citrate 3 sodium dihydrate. The concentration of the copper sulfate 5 hydrate in the sulphuric acid steel plating bath is preferably from 10 g/L to 50 g/L, more preferably from 2 g/L to 40 g/L. The concentration of the sodium citrate dihydrate 2 hydrate is preferably 2 〇 g / L ~ 60 g / L, more preferably 30 g / L ~ 50 g / L. The solvent of the plating bath is usually water. The pH of the plating bath is preferably 5. 5~7. 5, better 6. 0~7. 0. The temperature of the plating bath is preferably 2 〇 6 (rc, more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 〇 5 to 8 A / dm 2 , more preferably 1 to 4 A / dm 2 . Preferably, it is 5 to 40 seconds, more preferably 1 to 3 seconds. As the copper citrate, it is preferably, for example, containing copper sulfate 5 hydrate, sulfuric acid recorded 6 hydrate and citric acid 3 sodium 2 hydrate. The plating bath. The concentration of copper sulfate 5 hydrate in the copper citrate recording bath is preferably i 〇 g / L 〜 5 〇 g / L, more preferably 20 g / L ~ 40 g / L. Nickel sulfate 6 hydrate The concentration is preferably lg / L ~ 1 〇 g / L, more preferably 3g / L ~ 8g / L. The concentration of sodium citrate dihydrate is preferably 2 〇 g / L ~ 60g / L, more preferably 30g / L~50g/L. The solvent of the plating bath is usually water. The pH of the plating bath is preferably 5. 5~7·5, better 6. 0~7·〇. The temperature of the plating bath is preferably 2 〇 to 6 (rc, more preferably 30 to 5 (rc. The current density during electrolytic treatment is preferably 0. 5~8A/dm2, better i^A/dm2. The electrolytic treatment time is preferably 5 to 4 seconds, more preferably 10 to 30 seconds. The inorganic compound or the organic compound layer of the above-mentioned release layer-based metal material, if 101102461 47 201251532 is heat-treated even if it is subjected to heat treatment between 100 and 300 ° C when laminated, a known product "as a metal oxide can be used. For example, a mixture of zinc, chromium, nickel, copper, molybdenum, an alloy system, a metal and a metal compound or the like is used. As the organic compound, one or more selected from the group consisting of a nitrogen-containing organic compound, a sulfur-containing organic compound, and a carboxylic acid are preferably used. The above nitrogen-containing organic compound is preferably a nitrogen-containing organic compound having a substituent. Specifically, it is preferred to use a 1,2,3-benzane (hereinafter referred to as "BTA") which has a substituent and a triazole compound, and a stagnation and a triple sigma (hereinafter referred to as "CBTA"). ), Ν', Ν'-bis(benzotriazolylhydrazino)urea (hereinafter referred to as "BTD-U"), 1Η-1,2,4-triazole (hereinafter referred to as "ΤΑ") and 3 _Amino-1Η-1,2,4-triazole (hereinafter referred to as "ΑΤΑ") and the like. As the sulfur-containing organic compound, cetylbenzothiazole (hereinafter referred to as "ΜΒΤ"), sulfur-based cyanuric acid (hereinafter referred to as "tca"), and 2-benzimidazolethiol (hereinafter referred to as "sulfonated organic compound") are preferably used. "BIT") and so on. As the acid repellent, it is particularly preferable to use a monoacid, and among them, oleic acid, linoleic acid, and linoleic acid are preferably used. As described above, by appropriately controlling the electrolytic density, reducing the film thickness, and the like, the desired alignment property can be achieved on the copper ruthenium layer 1G4 of the present embodiment. Further, at least the lower surface 22 (the surface in contact with the surface of the insulating layer H) 2 of the steel sheet layer 1〇4 used in the present embodiment is made practical for the adhesion between the steel material and the insulating layer 102. Above the level, surface treatment can also be carried out. 101102461 48 201251532 The rough processing of the metal foil used for the copper foil layer 104 may be, for example, any one of a money-proof sound, a chromic acid treatment, a decane coupling treatment, or a combination thereof. n J - Any one of the surface treatment means is appropriately selected in conjunction with the tree sap material constituting the insulating layer 102. The rust-preventing treatment can form a film on the metal foil by sputtering, electroplating, or electroless plating, for example, by using any one of nickel, tin, rhodium, chrome, bismuth, and the like. Throughout. From the perspective of cost, it is preferably electricity. In order to facilitate the precipitation of metal ions, a necessary amount of a distating agent such as citrate, tartar, under-salt or %-amino acid may be added. The plating solution is usually used in an acidic region, and the temperature is set at a temperature of, for example, 25 c) to 803⁄4, and the current density is 0. 1 ~ ΙΟΑ / dm, power-on time 丨 ~ 6 〇 seconds, preferably 丨 ~ such as the range of seconds is appropriate. The amount of the rust-preventing metal varies depending on the kind of the metal, and is preferably 1 〇 to 2 〇〇 - in total. If the anti-scaling treatment is too thick, it will cause a hindrance of the surname and a decrease in the electric resistance. (6) If the thickness is too thin, the peel strength between the resin and the resin is lowered. In addition, when the resin composition constituting the insulating layer 1G2 contains a cyanic acid vinegar resin, the ruthenium is protected from hearing by a metal containing nickel. In the case of this combination, it is less useful to reduce the peel strength in the deterioration resistance test or the deterioration resistance test. 、 As the chromic acid treatment, an aqueous solution containing hexavalent chromium ions is preferably used. The chromic acid treatment can be used for the early pure impregnation treatment, but it is preferably treated by the cathode into the π ^ good system by the heavy acid sodium. 1~50g/L, pH1~13, bath temperature 〇~60〇c, 101102461 49 201251532 Current density 0. 1~5A/dm2, electrolysis time can replace the secret rhyme, (4) secret 13⁄4 face X seconds piece. It is also preferable to use the above-mentioned rust-preventing treatment for the above-mentioned chromic acid. Thereby, the composition layer (insulating layer 102) and the metal j can be used to lift the insulating resin. The dense adhesion between S 'Shaw layer 1G4) is used as the 3-glycidoxypropyltrimethoxy Wei, 2, (3: ring using, for example, ethylene trimethoxy group (10) ring used in the above decane coupling treatment. Oxygen functional money, 3: amine core: = burned, called aminoethyl) 3_aminopropyl trimethoxy alcohol, called silk ethyl) 3-aminopropyl methyl dimethoxy money Ethyl functionalities (IV), 3_ propylene oxide, etc., such as amino-functional functional money t-dilute tridecyloxy Wei, Ethyl-based tri-f-oxygen, ethyl hexamethylenedioxyethoxy) a propylidene functional group, a propyl group, a propyl group, a methoxy group, a propyl group, a methoxy group Mercapto functional decane and the like. These may be used singly or in combination of plural kinds. These coupling agents can be dissolved in a solvent such as water at a concentration of 1 to 15 g/L, and the resulting solution is coated or electroformed on a metal foil at a temperature of from room temperature to 50 ° C to form a decane. The coupling agent is attracted to the metal foil. These oxime coupling agents form a film on the metal foil by condensation bonding with the hydroxyl group of the rust-preventing metal of the metal falling surface. After the decane coupling treatment, the bonding is stabilized by heating, % external irradiation, or the like. In the heat treatment, it is preferably dried at a temperature of, for example, 100 to 2 ° C for 2 to 60 seconds. Ultraviolet rays 101102461 50 201251532 Irradiation is preferably carried out, for example, in the range of wavelengths of 200 to 400 nm and 2 to 25 μm/cm 2 . Further, 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 decane-based coupling agent. This combination is useful for reducing the peel strength in the heat deterioration resistance test or the moisture resistance deterioration test. Further, the decane coupling agent used in the decane coupling treatment is preferably a chemical reaction with an insulating resin composition constituting the insulating layer 1〇2 by heating at 60 to 200 C, more preferably 80 to 150 °C. Thereby, the functional group in the above insulating resin composition is chemically reacted with the functional group of the shihua coupling agent to obtain superior adhesion. For example, for the epoxy resin-containing insulating resin composition, a decane coupling agent containing an amino functional decane is preferably used. The reason is that the epoxy group and the amine group easily form a strong chemical bond by heat, and the bond is extremely stable to heat or moisture. As such, as a chemical bond. The combination may, for example, be an epoxy group-amino group, an epoxy group, an epoxy group, an epoxy group, a sulfhydryl group, a J ethoxy group, an epoxy group, an epoxy group, an epoxy group, an epoxy group, an amino group, an amino group, a hydroxyl group, Amino-carboxyl, amino-cyano and the like. Further, the insulating resin of the insulating resin composition used in the present embodiment is preferably used in an epoxy resin which is liquid at normal temperature. In this case, since the viscosity at the time of refining is largely lowered, the wettability of the bonding interface is obtained. The chemical reaction between the epoxy resin and the decane coupling agent is likely to occur, and as a result, a strong peel strength can be obtained. Specifically, it is preferably a bisphenol A type ring having an epoxy equivalent of about 2 101 101102461 51 201251532 an oxygen resin, a bisphenol F type epoxy resin, or a phenol novolak type epoxy resin. Further, when the insulating resin composition contains a curing agent, it is particularly preferred to use a thermosetting latent curing agent as the curing agent. That is, in the case where the functional group in the insulating resin composition is chemically reacted with the functional group of the decane coupling agent, it is preferred that 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 hardening agent is selected as a method of setting the temperature at which the hardening reaction of the insulating resin composition starts. Thereby, the reaction of the functional group in the insulating resin composition with the functional group of the decane coupling agent is preferentially and selectively performed, and the metal foil (copper v white layer 104) and the insulating resin composition layer (insulating layer 1 〇 2) The adhesion is high. The thermosetting latent curing agent for the insulating resin composition containing an epoxy resin may, for example, be a solid dispersion such as dicyandiamide, a diterpene compound, an imidazole compound or an amine/epoxy adduct. A reactive block type hardener such as a dissolved hardener, a urea compound, a rust salt, a boron trichloride/amine salt, or a block carboxylic acid compound is heated. The prepreg containing the above-mentioned insulating resin composition is laminated with the roughened surface by fine and uniform rough treatment, and the surface-treated ultra-thin copper foil having the carrier foil is subjected to the above method. When integrated, a copper foil laminate having a carrier foil as shown in Fig. 7(a) is formed, and as shown in Fig. 7(b), by removing the carrier foil layer 106, The copper-free laminate 1 〇〇 on both sides of the insulating layer 1 〇 2 has a steel and smelting layer 104. Moreover, it is not limited to this state. As such, the copper foil layer 104 may be formed on at least one side of the insulating layer 102 or may be formed on the entire surface or a portion of the insulating layer 102. 101102461 52 201251532 Next, as shown in Fig. 7(c), a through hole 1〇8 for interlayer connection from the upper side of the copper foil to the lower surface is formed on the copper foil laminate 1(). In the method of forming the through-holes 108, various known means can be used. For example, when the through-holes 1〇8 having a pore diameter of ΙΟΟμηι or more are formed, from the viewpoint of productivity, it is suitable to use a method such as a drill to form one turn. In the case of the following through holes 1 to 8, a gas laser such as a carbon dioxide gas or an excimer or a solid laser such as YAG is preferably used. Then, the catalyst core can be provided on at least the copper foil layer 1〇4. However, in the present embodiment, the catalyst core is provided on the entire surface of the copper box 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, f metal ions or gels can be used. Next, the electroless plating layer is formed by using the catalyst core as a core. However, before the electroless ore coating treatment, the surface of the copper _1〇4 or the through hole (10) may be subjected to, for example, a shirt by inspection. Wait. As a decontamination treatment, it is particularly limited, and it is possible to remove (4) a wet method using an oxidizing agent solution having an organic decomposition phase and an active species ((4), a free-shirt having a strong oxidation effect on the object to be removed). (10) A well-known method such as a dry method such as a money method. (4) The cutting of H (4), for example, after the swelling treatment by the surface of the fat, the method of performing the neutralization treatment by the alkali treatment, followed by the neutralization treatment. Next, as shown in Fig. 7(d), a thin layer of the electrolytic plating layer m is formed by the electroless ruthenium treatment on the copper (4) to the catalyst core and the through holes (10) and (4). The electroless (four) layer (10) is electrically connected to the copper layer 10 on the upper surface of the insulating layer 101102461 53 201251532. In the case of electroless plating, for example, copper sulfate, formaldehyde, a neutralizing agent, sodium hydroxide or the like can be used. Further, after the electroless plating, it is preferred to carry out heat treatment of 1 〇〇 to 25 〇 t > c to stabilize the film. From the viewpoint of forming a film capable of suppressing oxidation, it is particularly preferably 120 to 18 (heat treatment of rc. Further, the average thickness of the electroless plated layer 110 may be a thickness which can be plated as described below, for example, 0. 1~ is enough. Further, the inside of the through hole 108 may be filled with a conductive paste or an insulating paste, or may be filled by plating with an electric pattern. Next, as shown in Fig. 7(e), a plating resist 112 having a predetermined opening pattern is formed on the electroless plating layer 110 provided on the copper foil layer 1A4. 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 layer 104. In other words, the anti-recording layer 112 is not formed on the through hole 1〇8 and the conductor circuit forming region on the copper foil layer 104. 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 the fine wiring, it is preferable to use a photosensitive dry film or the like as the anti-mine layer 112. When the plating resist ι is formed, for example, a photosensitive dry film is laminated on the electroless plating layer 11 to expose the non-circuit forming region to light-harden, and the tree light portion is dissolved and removed by the (four) liquid. Further, the remaining hardened squeaky dry film will become the bell layer 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 (mineral layer 114) to be coated thereafter. Next, as shown in Fig. 8(a), at least the inside of the opening pattern 101102461 54 201251532 of the resist layer 112 and the electroless plating layer 110 are formed, and the plating layer 114 is formed by a plating process. 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 114 is not particularly limited, and may be used as a circuit conductor. For example, the range of 1 to ΙΟΟμηη, preferably 5 to 5 〇μηι is preferable. The plating layer 1M may be a single layer or have a multilayer structure. The material of the plating layer U4 is not particularly limited, and for example, copper, a copper alloy, a 42 alloy, nickel, iron, chromium, tungsten, gold, solder, or the like can be used. Next, as shown in Fig. 8 (b), the plating resist 112 is removed using an alkaline stripper or sulfuric acid or a commercially available plating stripper or the like. Next, as shown in Fig. 8(c), the electroless plating layer no and the copper foil layer 104 other than the region in which the plating layer U4 is formed are removed. The method of removing the copper foil layer 1〇4 is, for example, soft etching (rapid etching) or the like. Thereby, a pattern of the conductive circuit 118 formed by laminating the copper tank layer 104 and the metal layer 116 (electroless plating layer u 〇 and plating layer ΐ 4) can be formed. The cross-sectional shape of the conductive circuit U8 of the printed wiring board 2 according to the second embodiment is not limited to a rectangular shape as shown in FIG. 9 but also has an inverted tapered shape as shown in FIG. 9 (4) and a mesh 9 (8). Any of the illustrated fish plate (semi-idle) shape or the necked shape shown in Fig. 9(c).乂101102461 55 201251532 于========================================================================================================== The difference is made and the circuit forms a tendency to (4). Therefore, the liquid is preferably used in the type of copper and in accordance with the reaction control, not the humulus and temple diffusion control type. If the anti-y reaction control of steel and (iv) liquid is controlled, then even if the diffusion is enhanced above it, the _speed is still not. Even if the etching rate between the preferred portion and the poor portion where the liquid exchange does not occur is taken as the _reaction (four) etchant, for example, hydrogen peroxide and no teeth are included: by =. Since hydrogen peroxide is used as the oxidant, the degree can be strictly controlled. In addition, if (4) * t into _ 70, then the solution reaction becomes easy to become diffusion control. As the non-reading/reading, it is possible to use succinic acid, sulfuric acid, organic acid, etc., and sulfuric acid is cheap and the parent is better in terms of the stability of the sulfuric acid and chlorine peroxide as the main component and the stability of the liquid. The respective concentrations are 5 to 2,500 g/bu, such as persulfate, sodium persulfate, sodium persulfate, and the like. Thus, by appropriately selecting the cooking characteristics or the (4) conditions of the steel, the conductive circuit 118 of the desired shape can be paid. According to the above, two (four) of the money edge layer (10) can be obtained as the printed wiring board 2 of the conductive circuit m. Further, in the manufacturing method of the printed wiring board of the second embodiment, the same operational effects as those of the first embodiment can be obtained. Further, as shown in Fig. 8 (CM), the solder resist layer 12 may be formed so as to cover one portion of the insulating layer 102 and a portion of the conductive circuit 118. As the solder resist layer 101102461 56 201251532 120, for example, a heat-resistant resin composition such as a photosensitive resin, a thermosetting resin, or a thermoplastic resin which can contain a filler or a substrate having excellent insulating properties can be used. Next, the first plating layer 112 and the second plating layer 124 are further formed on the conductive circuit 118 having the opening portion of the solder resist layer 12A. Thereby, the metal layer 116 is formed into a multilayer structure of two or more layers. As the first plating layer 112 and the second plating layer 124, the gold plating layer is used for the first plating layer 112 and the second plating layer 124. The method of gold plating may be a conventional method without particular limitation. For example, on the plating layer I14, 0. 1~ΙΟμιη around electroless plating 'for substitution gold plating 0. 01~0. After about 5 μm, a method of electroless gold plating of about 0.1 to 2 μm is performed. According to the above, the printed wiring board 202 shown in Fig. 8 (d-1) can be obtained. Further, as shown in Fig. 8 (d-2), the solder resist layer 120 may not be formed, and the first plating layer 122 and the second plating layer 124 may be formed around the conductive circuit 118. As the first plating layer 122 and the second clock layer 124, for example, a laminated body of a nickel plating layer and a gold plating layer can be used. By the above, the printed wiring board 204 of Fig. 8 (d-2) can be obtained. Further, a semiconductor wafer (not shown) is mounted on the printed wiring boards 200, 202, 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. Figs. 10 to 12 are cross-sectional views showing the steps of manufacturing steps of the method of manufacturing the printed wiring board according to the third embodiment. In the method of manufacturing a printed wiring board according to the third embodiment, for example, the printed wiring boards 101102461 57 201251532 200, 202, and 2〇4 obtained in the second embodiment are used as the inner layer circuit board, and the built-in layer is further formed on the inner layer circuit board. By. First, the printed wiring board 2 〇 所得 obtained in Fig. 8(c) is used as the inner layer circuit board. The inner layer circuit (conductive circuit 118) of the printed wiring board 200 is subjected to roughening processing. Here, the roughening treatment means that the surface of the conductor circuit is subjected to a chemical treatment, a plasma treatment, or the like. As the roughening treatment, for example, a blackening treatment by oxidation reduction or a chemical liquid treatment 4 using a known sulfuric acid-hydrogen peroxide-based roughening liquid can be used. Thereby, the adhesion between the interlayer insulating material constituting the insulating layer 130 and the conductive circuit 118 of the printed wiring board 200 can be improved. Further, the inner layer circuit board may be replaced by the printed wiring board 2A obtained in the second embodiment, and is not particularly limited, and a pre-reformed or substrate may be laminated by a plated through hole method or an additive method. A general multilayer printed wiring board such as a resin composition layer. The conductor circuit layer that becomes the inner layer circuit can be formed by a conventional circuit formation method. Further, in the multilayer printed wiring board, it is possible to form a laminated body (a laminated body obtained by laminating a plurality of prepregs) and a metal foil laminated board 'by drilling, laser processing, or the like. The through holes are then electrically connected to the inner layers of the two sides by plating or the like. Next, as shown in Fig. 1 (4), an insulating layer ι 3 (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. 1〇5 (very thin copper foil with carrier foil). Then, as shown in Fig. 10 (b), a multilayer laminated plate is formed by subjecting the laminated body which overlaps these layers to heat and pressure treatment. Next, as shown in FIG. 10(c), the 101,052,461, 2012, 2012,523,320 carrier foil layer 107 is peeled off. Next, as shown in Fig. 10 (d), a part of the insulating layer 13 and the copper foil layer 1 〇 5 is removed to form a hole 109 on the bottom surface of the hole 109 to expose a part of the surface of the conductive circuit 118. The method of forming the hole 109 is not particularly limited. For example, a solid laser that uses a gas laser such as carbonic acid gas or a stimulator or a solid magnetic laser such as a crucible can be used. Further, the hole 109 is shown as a non-through hole in Fig. 1Q, but may be a through hole. Moreover, in the case of a cross-track, even a laser ride is formed. q 踬 加工 Next, as explained in the ®11(8), a thin layer of I thunder plating is formed on the upper guide, on the inner wall of the hole 109, and on the copper foil shore ag 105. The electroless plating layer ηι is formed by electrolysis. Before the electroless plating, if the coating is applied to the coating, the same can be applied to the decontamination of the chemical solution. Moreover, the thickness of the electroless_coating layer (10) may be as follows: (the thickness of the U~_ is sufficient. =, the lower hole may be made), and the conductive paste or the insulating paste 109 may be filled inside (blind-pass plating) Filling. The error-free electrical pattern is then, as shown in Fig. 11 (8), in the case of electrolessness, when the conductor circuit pattern has an open D-dip θ, the formation phase is formed by the formation of the anti-plating layer 113' Layer 113. In other words, 113' can be used in the same manner as the above-mentioned anti-clock layer 112. 'The thickness of the anti-plating layer is preferably not the thickness of the conductor 丨13 with the post-mineral coating. The thickness of the material is (four) degrees or more. The film thickness of 201251532. Next, as shown in Fig. 11(c), a plating layer 132 is formed inside the opening pattern of the wrought layer 113. The plating layer 132 may be formed on the conductive circuit 118 inside the hole 〇9' Alternatively, it may be formed on the electroless gold-clad layer 111 inside the opening pattern. The electric money for forming the plating layer 132 may be the same as that of the above-mentioned mineral coating layer 114. The thickness of the plating layer I 132 may be used as a circuit. The conductor may be, for example, a range of 1 to ΙΟΟμηη, more preferably a range of 5 to 5 μm. Then, as shown in FIG. 12(a), the plating resist 113 is peeled off in the same manner as the plating resist U2. Next, as shown in FIG. 12(b), copper is used in the same manner as the above-described copper foil layer 104. The foil layer 1〇5 and the electroless plating layer ηι are removed by soft etching (rapid etching), whereby the conductive layer composed of the copper foil layer 1〇5, the electroless plating layer 111, and the bell layer 132 can be formed. Further, on the conductive circuit 118, a through 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. Still as shown in Fig. 12(cl) As shown, a solder resist layer 121 may be formed on the insulating layer 13 、, 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 solder resist layer described above may be used. The layer 12 is the same. Then, on the plating layer 132 having the opening portion of the solder resist layer 121, the first plating layer 123 and the second plating layer made of, for example, a mineral nickel layer and a gold plating layer can be further formed. The layer 125 is obtained by the above, and the printed wiring board 203 shown in Fig. 12 (〇1) is obtained. Further, as shown in Fig. 12 (c-2), it may be invisible. The solder resist layer 121 is formed around the electric circuit pattern of the guide 101102461 60 201251532 and around the crucible, and forms the first and second cladding layers 123 and 125. The above is shown in Fig. 12(c_2). In the third embodiment, the same effects as in the second embodiment and the second embodiment can be obtained. Further, a modification of the method of manufacturing the printed wiring board according to the embodiment will be described with reference to FIG. In the third embodiment, the metal is selectively formed on the copper box, but in the present modification, the difference is that the metal layer is formed over the entire surface of (4). Hereinafter, a method of manufacturing the printed wiring board of the present modification will be described. First, a copper box laminate 1 having a carrier case is prepared as shown in Fig. 13 (4). In the steel-layered board 1G having the mi, the copper pavilion layer 104 and the carrier tank layer 106 are attached to both sides of the insulating layer. Next, as shown in the figure, the carrier is pulled by the steel laminate 1G having the carrier fl. Next, as shown in Fig. 13 (4), a gold layer 115 is formed by a clock coating on the entire surface of the copper (four) 1 4 ( Money cover). Next, as shown in Fig. 13 (d), a subtracted layer 112 having a predetermined opening pattern is formed on the flat metal layer 115. Next, the metal layer 115 and the copper falling layer 104 in the opening pattern of the anti-bond layer are removed by, for example, 4 ® (). Thereafter, the anti-money layer 112 is removed as shown in Fig. 13 (1). Thereby, a pattern of the conductive circuit 119 composed of the copper pig layer (10) and the metal layer US can be formed. By the above steps, the printed wiring board 101 of the present modification can be obtained. 101102461 201251532 As described above, according to the present embodiment, it is possible to provide a fine circuit having a carrier case, a fine circuit, a shape of a fine circuit, a method of manufacturing a brush wiring board, and a printed wiring board. The method of manufacturing the printed wiring board according to the present embodiment is not limited to the case where the conductor circuit layer is formed on both surfaces of the substrate for the printed board, and may be applied to the case of the single-sided dicing circuit (4) of the printed wiring board. Further, as shown in Fig. 8(c), the double-sided printed wiring board is used as the multilayer printed wiring board of the third embodiment of the inner layer electric board. Therefore, any one of a single-sided printing board, a double-sided printed wiring board, and a multilayer printed wiring board can be manufactured by the manufacturing method of the printed wiring board of embodiment. In the following, an electrolytic copper box having a carrier case according to the present invention and a copper-layer laminated board using a copper-clad copper are used for the production of the printed circuit board. Here, the invention will be described in detail based on the examples and comparative examples in the case of using the electrolytic copper house in "fl", but the present invention is not limited thereto. (Example) (Manufacturing of Metal Foil 1) The carrier was dropped in an electrolytic copper crucible of 18 μm thick (manufactured by Mitsui Metals, Inc., 3EC VLP, the surface roughness of the glossy surface was Ra = 〇. The surface of 2jim and Rz=l» sequentially forms the joint layer φ layer and extremely thin copper coins. For the secrets, the carrier oil is first immersed in an acid-washing tank (diluted sulfuric acid solution, (9) heart, liquid temperature 3% for 20 seconds to remove the surface oil, oxide film, etc.. Then, immersed in 101102461 62 201251532 & interface forming groove (slow-base stupid and di-sal solution, 5g / L, liquid temperature centimeter, c, forming a joint interface layer on the shiny surface of the carrier fl. Then, - immersed in the formation of the block copper (Copper sulfate solution; sulfuric acid concentration 150g/L, copper concentration 65g/L, gelatin concentration 5ppm, chloride ion l〇ppm, liquid temperature 45. In the middle, one side of the (four) one side, parallel plate anode electrode (5) Electrolyzing according to the smooth plating conditions of a current density of 20 A/dm 2 to form a bulk copper layer of 15 μm, and then, on the surface of the bulk copper layer, while being immersed in fine copper particles to form a groove (copper sulfate solution; A sulfuric acid bath having a sulfuric acid concentration of 1〇〇g/L and a copper concentration of 18g/L, and a liquid temperature of 25. In the middle of the crucible, the anode electrode (lead) of the flat plate is arranged in parallel with the single side of the carrier foil. /dm2 is electroplated under electroplating conditions. Then, it is impregnated for preventing fine copper particles. Colonies plated grooves (copper sulfate solution; 15〇g sulfuric acid concentration / L, 65 g of copper concentration / L, solution temperature 45〇C), and while the plating current density condition by 20A / dm2 electrolytically smoothed, 0 is formed. 5μιη finely roughened to a total thickness of 2. Ομπι ultra-thin copper foil. Then, immersed in the anti-rust treatment tank (sulfuric acid solution; sulfuric acid concentration 7〇g/L, zinc concentration 20g/L, liquid temperature 40°C) 'electrolysis according to current density i5A/dm2 and anti-rust treatment using zinc . Here, as the anode electrode, a soluble anode using a zinc plate is used. Then 'dip in the chromic acid treatment tank (chromic acid solution; chromic acid concentration 5g / L, pH11. 5, liquid temperature 55 ° C) for 4 seconds. Finally, it was heated in a drying treatment tank for 60 seconds by means of an electric heater to an ambient temperature of 11 (rc) to obtain a copper foil having a carrier foil. Further, in the step of each tank, it was washed with water. In the washing tank, the impregnation washing is carried out for about 30 seconds. 101102461 63 201251532 (Manufacture of metal foil 2) In the carrier, it is called the thick electrolytic copper book (made by Furukawa Electric Industrial Co., Ltd., F2-WS 'glossy surface) The surface roughness is 2, and the bonding interface layer and the extremely thin steel layer are sequentially formed on the glossy surface of Rz=丨2 (4). As a manufacturing condition, the carrier II is first immersed in an acid cleaning tank (dilute sulfuric acid solution, 15 〇g). /L, liquid temperature 30. Remove the surface oil, oxide film, etc. for 20 seconds in the crucible. Then, immerse in the joint interface to form a tank (carboxy benzobisazole solution, 5 g / L, liquid temperature 4 〇, pH 5) Forming a bonding interface layer on the shiny surface of the carrier foil. Then, immersing in the forming channel of the bulk copper (copper sulfate solution; sulfuric acid concentration 15 〇 g / L, copper concentration 65 g / L, gelatin concentration 5 ppm, vapor ion 3〇ppm, liquid temperature 45. In the middle, one side of the carrier foil, parallel with The anode electrode (lead) of the plate is electrolyzed according to the smooth plating conditions of a current density of 25 A/dm 2 to form a bulk copper layer of 丨 5 μm, and then, on the surface of the bulk copper layer, is impregnated with fine copper particles. In the tank (copper sulfate solution; sulfuric acid concentration l〇〇g/L, copper concentration I8g/L of sulfur valley liquid, liquid temperature 25 ° C), the anode electrode (lead) of the flat plate is arranged in parallel on one side of the carrier foil. Electrolysis is carried out according to the sintering conditions of current density ΙΟΑ/dm2, and then immersed in a plating tank for preventing fine copper particles from falling off (copper sulfate solution; sulfuric acid concentration 15 〇g/L, copper concentration 65 g/L, The liquid temperature is 45. In the middle, the electrolysis is performed under the smooth plating conditions of a current density of 20 A/dm 2 to form 0. Fine micronization of 5 μm to produce a very thin copper foil with a total thickness of 2 μm. Then, immersed in the anti-recording treatment tank (zinc sulfate solution; sulfuric acid concentration 70g / L, zinc concentration 20g / L, liquid temperature 40 ° 〇, electrolysis according to current density i5A / dm2 and use zinc to prevent 101102461 64 201251532 rust treatment Here, as the anode electrode, a soluble anode using a zinc plate is used. Next, it is impregnated in a chromic acid treatment tank (chromic acid solution; chromic acid concentration: 5 g/L, ρΗ11·5, liquid temperature: 55 ° C) 4 seconds. Finally, it was heated in a drying treatment tank for 60 seconds by means of an electric heater to the ambient temperature ii (TC furnace to obtain a copper foil with a carrier foil. Again, between the steps of each tank, It can be washed in a water washing tank for about 30 seconds. (Manufacture of metal foil 3) In a carrier foil, a 12 μm thick electrolytic copper foil (Furui Electric Industrial Co., Ltd., F2-WS 'glossy surface) The roughness is Ra=〇2μιη, Ι1ζ=1. A bonding interface layer and an ultra-thin copper foil layer are sequentially formed on the gloss surface of 2 μm. As a manufacturing condition, the carrier foil is first immersed in an acid cleaning bath (dilute sulfuric acid solution, l5 〇g/L, liquid temperature 30, hydrazine for 20 seconds to remove surface oil, oxide film, etc.. Forming a tank (carboxybenzotriazole solution, 5 g/L, liquid temperature 40 ° C, pH 5), forming a joint interface layer on the shiny surface of the carrier foil. Then, while immersing in the forming channel of the bulk copper (copper pyrophosphate) Solution; potassium pyrophosphate concentration 25 〇 g / L, copper concentration 25 g / L, pH ll, liquid temperature 45. In the 〇, one side of the carrier foil, parallel plate anode electrode (lead), according to current density 1 〇 The smooth plating conditions of A/dm2 were electrolyzed to form 1. 5gm block copper layer. Next, on the surface of the bulk copper layer, it is immersed in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentration: 100 g/L, copper concentration i8 g/L of sulfuric acid solution, liquid temperature of 25. On one side, the anode electrode (lead) of the flat plate is placed in parallel, and electrolysis is performed according to the sintering conditions of current ΙΟΑ/dm. Then, it is immersed in the plating tank (sulfuric acid) for preventing the peeling of fine copper particles for 101102461 65 201251532 Copper solution; sulfuric acid concentration 150g / L, copper concentration 65g / L, liquid temperature 45 ° C), while the current density of 20A / dm2 smooth plating conditions for electrolysis, forming 〇. The fineness of 5 μm is finely formed to produce a very thin copper foil having a total thickness of 2.0 μm. Subsequently, it was immersed 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 carried out 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 is used. Next, dipped in a chromic acid treatment tank (chromic acid solution; chromic acid concentration 5 g / L, pH 11. 5, liquid temperature 55. 〇 4 seconds. Finally, it was heated in a drying treatment tank for 6 seconds by means of an electric heater to a furnace of an ambient temperature of 1 HTC 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 30 seconds in a water washing tank which can be washed with water. (Example 1) A naphthalene modified phenol novolac epoxy resin (manufactured by DIC Corporation, ΗΡ·50〇〇) as an epoxy resin was used. 5 parts by weight of a styrene-type alkyl resin as a phenol vulcanizing agent (Minghe Chemical Co., Ltd., MEH7851-4H) 8. 5 parts by weight, benzene aging varnish type cyanate resin (primaset PT-30, manufactured by LONZA Co., Ltd.), 17 parts by weight, spherical molten cerium oxide (manufactured by Admatechs Co., Ltd., SO 25R average particle size 〇 5 (im) 65 5 parts by weight, epoxy-based stone shochu (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-4() 3) G. 5 parts by weight of 'dissolved in mercaptoethyl ketone was dissolved. Subsequently, the mixture was stirred using a high-speed stirring device to adjust the amount of nonvolatile matter to 7 wt% to prepare a resin varnish. 101102461 66 201251532 On the tree varnish, it is impregnated into glass woven fabric (basis center of gravity, thickness 87μιη, 曰^:: 螭 螭 ’ ’ WEA_U6E), according to (9). . The furnace was dried for 2 minutes to obtain a pre-collision of the varnish solid content in the prepreg of about 5 g% by weight. The above prepreg weight #2 pieces were superposed and stacked with a carrier ^ pole 0 thin copper box (metal box υ, according to pressure, temperature shoe for heating and pressure forming for 1 hour, the insulating layer was thick. The two sides of the 2〇_ have a steel box of the lumber (Fig. 7(a)). The laminate of the laminate obtained in the example was removed (Fig. 7(b)), as shown in Fig. 7(c), by a carbon dioxide gas laser on a very thin metal box (Mitsubishi Electric Co., Ltd., paper) 6(^乂3_51001; 2) 1 through a 75-hole diameter through hole, in an aqueous solution of potassium permanganate 60g / L and sodium hydroxide 45g / L, by dipping at 80 ° C for 2 minutes, decontamination After that, the in-situ solution (manufactured by Uemura Industrial Co., Ltd., MAT-2B/MAT-2A) was immersed for 5 minutes at a temperature of 55 C, and the catalyst was applied, and THUR-CUP PEA-6A manufactured by Uemura Industrial Co., Ltd. was used. Immersion at a temperature of 36 ° C for 15 minutes to form an electroless plating layer. 7μηη (Fig. 7(d)). On the surface of the electroless plating layer, a UV-sensitive dry film (SUNFORT UFG-255, manufactured by Asahi Kasei Corporation) having a thickness of 25 μm was bonded to the surface of the electroless plating layer, and the minimum line width/line width was 2玻璃/2〇pm pattern of glass mask (manufactured by Topic Co., Ltd.), the position is aligned, exposed by an exposure device (Ono EV-0800), and developed in an aqueous solution of carbon steel to form an anti-mine mask (Fig. 7 (e)). Then, the electroless plating layer was used as the electrode layer electrode, and electroplating copper (81-HL manufactured by Okuno Pharmaceutical Co., Ltd.) was carried out according to 101102461 67 201251532 3A/dm2, 25 minutes to form a copper wiring pattern having a thickness of about 20 μm (Fig. 8(a) ). Next, the above-mentioned plating resist was peeled off by a monoethanolamine solution (R-100, manufactured by Mitsubishi Gas Chemical Co., Ltd.) using a peeling machine (Fig. 8 (b〇). Then, the electroless plating layer belonging to the power feeding layer and Base copper foil (2μιη) by rapid etching (Mitsubishi Gas Chemical Co., Ltd. CPE-800, liquid temperature: 30 ° C, sprayer pressure. 23 MPa) was removed by treatment for 180 seconds to form a pattern of L/S = 20/2 (^m pattern (etched in a pattern) to obtain a printed wiring board (Fig. 8(c)). Finally, as shown in Fig. 8 (dl) In the same manner, a solder resist layer (PSR4000/AUS308, manufactured by Sun Ink Co., Ltd.) was formed on the surface of the circuit, and a nickel plating layer (ICP NICORON GM, manufactured by Okuno Pharmaceutical Co., Ltd.) was immersed at a temperature of 80 ° C for 12 minutes to form 2. 5 μm, and then metal plating (FLASH GOLD 330, manufactured by Okuno Pharmaceutical Co., Ltd.) was immersed at a temperature of 80 ° C for 9 minutes to form 0·05 μm, thereby obtaining a printed wiring board. Further, as shown in Fig. 8 (d-2), a solder resist layer is not formed on the surface of the circuit. (Example 2) The same as Example 1 except that the ultra-thin copper foil having the carrier foil was changed to the metal foil 2. (Example 3) 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 3. (Example 4) 101102461 68 201251532 The same as Example 1 except that the conditions of the rapid plating of the electroless plating layer and the base copper foil (2 μm) belonging to the power supply layer were changed as described below. The electroless plating layer and the base copper foil (2μιη) belonging to the power supply layer were quickly etched (CPE-800 manufactured by Mitsubishi Gas Chemical Co., Ltd., liquid temperature: 30 〇c, sprayer pressure 0. 23 MPa) was removed by treatment for 240 seconds to form a pattern of L/s = 2 〇 / 2 〇 (pattern etching) to obtain a printed wiring board. (Example 5) The same as Example 1 except that the resin composition used for the laminate was changed. 11 parts by weight of a biphenyl aryl-based epoxy resin (manufactured by Nippon Kayaku Co., Ltd., NC-3000) as an epoxy resin, and a bis-butylene diimide compound (BMI-70, manufactured by KI Chemical Industry Co., Ltd.) 20 parts by weight of 4,4'-diaminodiphenyl decane 3. 5 parts by weight, aluminum hydroxide (HP-360, manufactured by Showa Denko), 65 parts by weight, epoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403). 5 parts by weight was dissolved and dissolved in mercaptoethyl ketone. Subsequently, the mixture was stirred with a high-speed stirring device to adjust to a nonvolatile content of 70% by weight to prepare a resin varnish. The above resin varnish was impregnated into a glass woven fabric (base weight l 4 g, thickness 87 μηι, 曰 纺 Ε , ,, WEA-116E), and pre-impregnated by 15 (drying in a TC oven for 2 minutes). The varnish solid content in the body is about 50% by weight of the prepreg. The prepreg is superposed on two sheets, and the extremely thin copper crucible (metal foil 1) having the carrier foil is superposed, and the pressure is 3 MPa and the temperature is 200 ° C. Heat and pressure forming for 1 hour' to obtain a thick layer of insulating layer. 2 〇 mm on both sides with a laminate of copper foil 101102461 69 201251532 board. (Comparative Example 1) (Manufacture of Metallic Foil 4) & Carrier's Electrolysis at 35μηι Thickness (4) (The surface roughness of F2 WS' glossy surface made by Furukawa Electric Co., Ltd. is Ra=〇#m, Rz=1 2μιη The bonding interface layer and the ultra-thin copper junction layer are sequentially formed on the glossy surface. As a manufacturing condition, first, the carrier foil was immersed in an acid cleaning tank (dilute sulfuric acid solution, 150 g/L, liquid temperature 30, and enthalpy for 20 seconds to remove surface oil, oxide film, etc.), and then impregnated at the joint interface. a groove (a slow-base benzotriazine solution, 5 g / L, liquid temperature, pH 5), forming a joint interface layer on the shiny surface of the carrier. Then, while immersing in the formation of the bulk copper (copper sulfate solution; Sulfuric acid concentration 15〇g/L, copper concentration 65g/L 'liquid temperature 45 C) 'On one side of the carrier foil, the anode electrode (8) of the flat plate is arranged in parallel, and electrolysis is performed according to the smooth forging condition of current density 2A/dm2 Forming 1. 5 μιη block copper layer. Next, on the surface of the bulk copper layer, while immersing in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentration 100 g / L, copper concentration 18 g / L sulfuric acid solution, liquid temperature 25 〇 c) +, while the carrier On one side of the box, the anode electrode (lead) of the flat plate was placed in parallel, and electrolysis was performed for 7 seconds according to the sintering conditions of current density ΙΟΑ/dm2. Next, it is immersed in a plating tank (copper sulfate solution; sulfuric acid concentration: 150 g/L, copper concentration: 65 g/L, liquid temperature of 45 in a crucible), and smoothing by current density ΙΟΑ/dm2 while immersing in a plating tank for preventing fine copper particles from falling off. The material is subjected to electrolysis, and the micro-dimension of 5 μm is applied to produce a very thin copper foil with a total thickness of 2·〇μιη. Then, it is immersed in an anti-scaling treatment tank (sulfur 101102461 70 201251532 zinc acid solution; sulfuric acid concentration 70 g/L, The zinc concentration is 20 g/L, and the liquid temperature is 40. 〇, electrolysis is performed according to the current density ΙΟΑ/dm2, and rust-preventing treatment is performed using zinc. Here, as the anode electrode, a soluble anode using a zinc plate is used. Chromic acid treatment tank (chromic acid solution; chromic acid concentration 5g / L, pH11. 5, liquid temperature 55. 〇) 4 seconds. Finally, it was heated in a drying treatment tank for 6 seconds by means of an electric heater to a furnace having an ambient temperature of 11 ° C 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 30 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 4. (Comparative Example 2) (Manufacturing of metal crucible 5) In the carrier foil, the surface roughness of the F2-WS' glossy surface of the 35 μη thick electrolytic copper foil (Fuji Electric Co., Ltd.) was Ra=〇2jxm, Rz=1 2μιη The glossy side sequentially forms a joint interface layer and an extremely thin copper foil layer. As a manufacturing condition, first, the carrier foil was immersed in an acid washing tank (diluted sulfuric acid solution, 15 〇g/L, liquid temperature: 3 Torr. The enthalpy was removed for 20 seconds to remove the surface oil, oxide film, etc.) The joint interface forms a groove (carboxybenzotriazole solution, 5 g/L, liquid temperature 4 ,, pH 5), and forms a joint interface layer on the shiny surface of the carrier foil. Then, the groove 1 is formed by immersing in the bulk copper ( Copper pyrophosphate solution; potassium pyrophosphate concentration 32 〇 g / L, copper / Chen 80 g / L, 25% ammonia 2 ml / L, pH 8. 5, liquid temperature 40 ° C), one side of the carrier Ι ’ single side 'parallel arrangement of the plate anode electrode (10)), according to the current density 101102461 71 201251532 degrees 1. The smooth plating conditions of 5A/dm2 were electrolyzed, and then immersed in the formation tank 2 of the bulk copper (copper sulfate solution; sulfuric acid concentration l〇〇g/L, copper concentration 200 g/L, liquid temperature 45 ° C) In the middle side, the anode electrode (lead) of the flat plate is placed on one side of the carrier foil, and electroplated according to the smooth plating conditions of a current density of 3 A/dm 2 to form 1. 5μηι block copper layer. Next, on the surface of the bulk copper layer, while being immersed in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentrate I00g/L, copper concentration 18 g/L sulfuric acid solution 'liquid temperature 25 乞), while supporting the carrier On one side of the thread, the anode electrode (lead) of the flat plate is arranged in parallel, and electrolysis is performed according to the burning condition of a current density of 5 A/dm 2 . Next, while being immersed in a plating tank (copper sulfate solution; sulfuric acid concentration: 15 〇g/L, steel concentration: 65 g/L, liquid temperature: 45 ° C) for preventing the dropping of fine copper particles, the current density is 1 The smooth plating conditions of 〇A/dm2 were electrolyzed to form 0. 5μΐη finely roughened to make a total thickness 2. 0μιη extremely thin copper enamel. Next, it was immersed in a rust-preventing treatment tank (zinc sulfate solution, sulfuric acid concentration: 70 g/L, zinc concentration: 20 g/L, and liquid temperature of 4 Torr. 电解, electrolysis was carried out at a current density of 15 A/dm 2 and the lin was treated. As a positive electrode, it is set as a soluble anode using a refill plate. Next, it is immersed in a complex acid treatment tank (chromic acid solution; chromic acid concentration 5 g/L, pH ii. 5, liquid temperature 55 χ:) * 4 seconds. In the end, when the money is processed, the second-time electric heater is heated to the ambient temperature of 11 (the furnace of the TC, and the copper box with the carrier box is obtained. Also, in the step of each tank, it is possible to ride on the water. The water (four) towel was fed in (4) three-times of immersion washing. The printed circuit board was obtained in the same manner as in the first embodiment except that the ultra-thin copper foil having the carrier foil was changed to the metal foil 5. (Evaluation) The printed wiring boards obtained in the examples and the comparative examples were evaluated as follows. The evaluation items are shown together with the contents, and the results are shown in Table 1. (1) The XRD film method uses a fully automatic powder X-ray diffraction device (manufactured by Philips Corporation). ~1700 type) 'Measured by Cu-Κα ray as the source of the ray. The peak integration of the ray around the plane orientations (111), (200), (220) and (311) detected by the 2Θ scan is obtained. In addition, the sample was obtained by using a copper foil having a carrier foil obtained in the production example by a vacuum press, and a thin foil surface before and after heat treatment under conditions of 2 ° C, 1 hour, and pressure of 3 MPa was used as a sample surface. Detailed measurement conditions Next. <Measurement conditions> X-ray source: Cu-Ka voltage: 40 kV Current: 50 mA Incident angle: l. Odeg Diffraction angle: 30 to 120 deg Scanning speed: 0.02 deg/sec (2) Crystal grain of copper foil (long The FIB-FESEM (Big Cluster Ion Beam Processing Observation Device FB2000A, Hitachi, Ltd., Electric Field Radiation Scanning Electron 101102461 73 201251532 Microscope S-45GG) was used to modulate the sample profile after the cluster ion beam was applied. According to the SEM image, the field of view is 10000 times, and any 3 points are observed. Further, in the sample, the surface of the thin copper foil before and after the heat treatment was carried out by using a steel box having a carrier box obtained in the production example by a vacuum press at 200 ° C for 1 hour and a pressure of 3 MPa as a sample surface. (3) Shape of thin copper foil during fine processing of LS The scanning electron microscope (manufactured by JEOL Ltd., device name: JSM-6060LV) was used, and the wiring shape was observed obliquely above the line (4). Further, the sample used was a printed wiring board (Fig. 8(c)). Each symbol is as follows: 〇: The thin copper foil portion has no residual edge X. The thin copper box portion has a residual edge (4) AL=L1-L2 Using a scanning electron microscope (manufactured by JEOL Ltd., device name: JSM-6060LV), Observing the cross-sectional shape of the wiring 'calculates the maximum width of the thin copper foil as u and the minimum width of the electrical pattern plating, and calculates it. Further, the sample used was a printed wiring board (Fig. 8(c)).

(5) LS20 (L/S-20pm/20gin) between the wires BHasT The electrical insulation reliability between the fine wirings is evaluated by continuous measurement under the conditions of a voltage of 1〇v, a temperature of 130 C, and a humidity of 85%. 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 108 Ω is used as the end point. 101102461 201251532 Each symbol is as follows. ◎: More than 200 hours. 〇: 100 hours or more and 200 hours or less. X: Less than 100 hours. 101102461 75 201251532 [11 Reference material of copper powder secondary CN On loo.o I 1 1 1 1 1 1 I Example 2 CO CO CO uS (N v〇v〇σ; 卜 a\ vd CS 〇\ oi m oblique direction 2 Δμτη XX Before heating ρ 00 vd <N m vd cn 〇 v v v v (N ο tb| 交 1 1 1 1 1 m m m 〇 N IS IS IS IS IS IS IS IS IS s s s s s s s s s s s s ^ ^ ^ ^ Jm 2.9"m 1 XX before heating ρ in 00 VO CN m VO ΓΟ Os ο Example 5 IS S 卜 m ii Os (N % 4»L base SBC batch ' 1.7//m 〇〇〇 before heating ro ( N Ό Os < N < N < n xn CN si v〇rn <NC\ (N 1 u Example 4 ί S s vn 寸 p Ov CN 卜 discontinuous short or triangular cone 1. 8βτη 〇1 〇 before heating n Os liS ^r\ v〇ON v〇rn (N 〇l On <N Example 3 s§ v〇m vd vb ... 00 ON <N n 00 (N discontinuous short or triangular cone 1.9"m 〇in 〇Before heating 〇1 Bu 2 00 ΓΛ 00 00 On 〇gj Example 2 -1 ^ CN VO Cn 00 <^iv〇〇oo Os Inch 2 m Discontinuous short or triangular cone 1.5/ /m 1 〇〇 before heating t to (N Ό i/S v〇ro 00 〇 \ in wo <N (N real Example 1 § p 〇l ?! r-; (N discontinuous short or triangular cone 1.8μηι 〇ο 〇 before heating m <N v〇Os Ri ^Ti wn <n vd <Ί On VO (111) (200) (220) (311) "^10 (20〇y{(l 1 !>+<200>K220)+<311)} {(200>K200)}/ {(111>H200&gt ;H220)+(311)} Evaluation item rO ? % If 璁€ Surface orientation (200) peak intensity ratio (%) S' | |g ® butterfly · O target § m M # v8 W Crystal shape crystal size LS20 Thin foil shape AL (L1-L2) in the processing of thin wires 9L t9 inch 30ΪΪ01 in line LS20 201251532 This application claims priority based on Japanese Patent Application No. 2011-14126, which was filed on the U. 'Quot all of its disclosures here. 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 first embodiment. Fig. 2 is a cross-sectional view schematically showing a part of a printed wiring board according to a second 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 first embodiment. Fig. 6 is a cross-sectional view schematically showing a modification of the wiring shape of the second 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. 101102461 77 201251532 FIG. 11 is a cross-sectional view schematically showing an example of a method of manufacturing a printed wiring board according to the 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. Fig. 13 is a cross-sectional view schematically showing a modification of the method of manufacturing the printed wiring board of the first embodiment. [Main component symbol description] 1 Copper foil laminate 2 Insulation layer 4 Copper foil layer 10 Copper foil laminate with carrier foil 14 Metal layer 19 Conductive circuit 20 Upper 22 Lower 24 Side 100 Copper enamel board 101 Printed wiring board 102 Insulation Layer 104 Copper foil layer 105 Copper foil layer 106 Carrier foil layer 101102461 78 201251532 107 108 109 110 111 112 113 114 115 116 118 119 120 121 122 123 124 ' 125 130 132 Carrier foil layer through-hole electroless plating layer electroless Plating layer plating resistance plating layer metal layer metal layer conductive circuit conductive circuit solder resist layer solder resist layer 1st ore layer 1st plating layer 2nd plating layer 2nd bond layer insulating layer plating layer 200 , 201, 202 ' 203 ' 204 ' 205 printed wiring board 101102461 79

Claims (1)

201251532 VII. Patent application scope: 1. A method for 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; a step of forming a metal layer thicker than the copper box over the entire surface of the copper 4; and etching the copper box to obtain a conductive circuit pattern composed of the copper foil and the metal layer a step of: summing the surface orientations (111), (200), (220), and (311) of the surface of the copper foil that is in contact with the metal layer with respect to the surface orientation (111), (200), (220), and (311) measured by the XRD film method The ratio of the peak intensity of the plane orientation (200) is 26% or less. 2. The method of manufacturing a printed wiring board according to the first aspect of the invention, wherein the surface orientation (200) and (on the surface of the copper junction in contact with the metal layer with respect to the peak intensity) The ratio of the sum of the peak intensities of 220) is 32% or less. 3. The method of producing a printed wiring board according to the first aspect of the invention, wherein the copper foil has crystal grains having an average length of 2 μm or less on a long side. 4. The method of manufacturing a printed wiring board according to the third aspect of the invention, wherein the area ratio of the crystal grains of the long side having an average length of 2 μm or less is 80% or more. 5. The method of manufacturing a printed wiring board according to the first aspect of the invention, wherein the film thickness of the copper foil is Ο.ίμιη or more and 5 μηι or less. 101102461 80 201251532 6*, in the patent application (4) 1, selectively forming the above metal; the manufacturing method of the wiring board, which has the step of forming on the above-mentioned, comprising: the step of resisting the plating of the pattern of the above-mentioned opening pattern a step of patterning the metal layer of the metal layer in the above-mentioned Ijjjg; gamma, a step of removing the above-mentioned plating layer; and obtaining a step of soft etching the conductive circuit pattern. The "^ step includes the step of forming the above-mentioned metal layer by selectively performing the above-mentioned step of selectively forming the above-mentioned metal layer, and the step of including: forming a f-we or a track in the above-mentioned laminated plate; The inner wall of the through hole or the non-through hole contacts the chemical liquid; and the electroless plating is formed on at least the copper bead and the inner wall of the through hole or the inner wall of the non-through hole by electroless plating The steps of the layer. 8. A printed wiring board comprising: an insulating layer; and a conductive circuit pattern formed on the insulating layer, wherein a copper foil and a metal layer are laminated; and a surface of the copper foil that is in contact with the metal layer The ratio of the peak intensities of the plane orientations (111), (200), (220), and (311) measured by the XRD film method to the peak intensity of the surface orientation (200) is 26%. the following. 9. The printed wiring board according to claim 8, wherein the metal layer contains two or more plating films. 10. The printed wiring board according to claim 8, wherein the maximum width of the copper foil in the width direction orthogonal to the direction in which the conductive circuit pattern extends is set to L1 in a cross-sectional view, When the minimum width of the metal layer is L2, the L1 is the same as L2 or smaller than L2. 11. The printed wiring board according to claim 10, wherein the area of the copper foil is changed from the first surface of the copper foil to the second surface in a plan view, and the area of the copper foil is changed to 101102461.