KR20140009323A - Printed wiring board and method for manufacturing printed wiring board - Google Patents

Abstract

Provides a printed wiring board with excellent product yield. A process of separating a carrier base material from the laminated board in which the copper foil with a carrier base material (copper foil layer 104) was laminated on at least one surface 30 of the insulating layer 102, and the copper foil layer 104 on the copper foil layer 104. Forming a thicker metal layer 115 on the entire surface or selectively, and obtaining a pattern of the conductive circuit 119 composed of the copper foil layer 104 and the metal layer 115 by etching the copper foil layer 104 at least. In the process of obtaining the electrically conductive circuit 119, when measured by JIS B0601, Rp in the one surface 30 of the insulating layer 102 is 4.5 micrometers or less, and Rku is 2.1 or more.

Description

Manufacturing method of printed wiring board and printed wiring board {PRINTED WIRING BOARD AND METHOD FOR MANUFACTURING PRINTED WIRING BOARD}

The present invention relates to a printed wiring board and a manufacturing method of the printed wiring board.

With the demand for high functionalization of electronic devices, high density integration of electronic components, and high density mounting have progressed, and the printed wiring boards for high density mounting used in these have been increased in comparison with the prior art, so that the compactness, the density and the multilayering are increased. It's going on.

The method of forming a conductor circuit pattern on the board | substrate of such a printed wiring board is described in patent document 1, for example.

In the method of patent document 1, first, an insulating resin layer is formed on a double-sided copper clad laminated board, and the surface of this insulating resin layer is roughened, a conductor layer is formed on this surface, and an etching resist is continued. It is described to form a pattern (a conductor circuit pattern) of a conductor layer by performing etching using as a mask. This patent document 1 describes that by reducing the roughness of the surface of the insulating resin layer that is the underlying layer of the conductor circuit pattern, the residue of the etching resist can be prevented from remaining and the decrease in the degree of wiring of the conductive circuit pattern can be suppressed. It is.

Moreover, the roughness of the surface of the insulated resin layer of patent document 1 is Ra which shows the average roughness with respect to the center roughness of the mountain side of the chart figure which shows the unevenness | corrugation of the surface, and the roughness of the mountain side of the same figure is 5 points and valley side. It is prescribed | regulated as Rz which shows the average roughness of ten points | pieces in total of five points with a big roughness (Hereinafter, in the chart which shows the unevenness | corrugation of a surface, the part corresponded to a recessed part, and calculated the part corresponded to a valley and a convex part. May be called).

Japanese Patent Laid-Open No. 2005-5458

However, in the process of forming the conventional fine conductive circuit pattern, there existed a limit in suppressing the imbalance of the etching characteristic of the conductor layer on an insulated resin layer. For example, to improve the etching characteristics of the conductor layer, it is required to reduce the surface roughness of the conductor layer.

However, as a result of the investigation by the present inventors, since Ra and Rz which show the surface roughness normally used in the technical field of a printed wiring board do not exactly define the shape of a surface, these Ra and Rz are employ | adopted as an index, and an insulating resin layer Even if Ra and Rz on the surface of the metal were controlled small, it was found that an imbalance occurred in the surface roughness of the conductor layer formed thereon between products. For example, since Ra and Rz are indices that do not indicate the width of the acid, the spacing of the acids on the surface of the underlying insulating resin layer may be widened only by controlling these indices, thereby denting the conductor layer. There may be a place.

Therefore, in the prior art, an imbalance may arise in the etching characteristic of a conductor layer, and there existed room for improvement.

According to the present invention,

Separating the carrier substrate from a laminate in which copper foil with a carrier substrate is laminated on at least one surface of the insulating layer,

Forming a metal layer thicker than the copper foil on the entire surface or selectively on the copper foil;

A step of obtaining a conductive circuit pattern composed of the copper foil and the metal layer by etching at least the copper foil,

In the said process of obtaining the said electrically conductive circuit pattern, when it measures by JISB0601, the manufacturing method of the printed wiring board with Rp of 4.5 micrometers or less and Rku of 2.1 or more is provided in the said one surface of the said insulating layer.

MEANS TO SOLVE THE PROBLEM As a result of this study, when the surface height pattern which a mountain height is small, the space | interval of a mountain is narrow, and an acid of an acute angle exists on one surface of the insulating layer of the base material exists, it is formed on one surface of an insulating layer. It was thought that the imbalance of the etching characteristics of the was reduced.

The inventors controlled the appropriate values of both the indicator indicating that the height of the acid was small and the indicator indicating that the interval of the acid was narrow and acute, but the imbalance of the etching characteristics of the copper foil formed on the base was reduced. As an index, Rp, which represents the maximum height of the mountain, and Rku, which represents the degree of sharpening of the mountain (the gap between the mountains is narrow), are adopted, and Rp is controlled to 4.5 µm or less and Rku to 2.1 or more, so that It becomes possible to control a surface-shaped pattern suitably, and discovers that the suppression of the imbalance of the etching characteristic of copper foil can be implement | achieved, and came to completion of this invention.

In addition, according to the present invention,

The insulating layer

It is provided on one surface of the said insulating layer, and is provided with the conductive circuit pattern comprised from copper foil and a metal layer,

When measured by JIS B0601, the printed wiring board which Rp in the said one surface of the said insulating layer is 4.5 micrometers or less, and Rku is 2.1 or more is provided.

Since Rp on one surface of the insulating layer is 4.5 µm or less and Rku is controlled to 2.1 or more, an imbalance in the etching characteristics of the copper foil is suppressed as described above, and a structure excellent in product yield is realized.

According to this invention, the printed wiring board excellent in the product yield can be provided.

The above-mentioned object and other objects, features, and advantages are further clarified by the preferred embodiments described below and the accompanying drawings attached thereto.
1: is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 1st Embodiment.
FIG. 2: is sectional drawing which shows a part of printed wiring board of this embodiment typically.
3 is a cross-sectional view schematically showing a printed wiring board for explaining the remaining of the lower portion.
It is a top view which shows typically the printed wiring board for demonstrating the effect of 1st Embodiment.
It is sectional drawing for demonstrating the wiring shape of 1st Embodiment.
It is sectional drawing which shows typically the modification of the wiring shape of 1st Embodiment.
It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 2nd Embodiment.
It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 2nd Embodiment.
It is sectional drawing which shows typically the modification of the wiring shape of 2nd Embodiment.
It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 3rd Embodiment.
It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 3rd Embodiment.
It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 3rd Embodiment.
It is sectional drawing which shows typically the modification of the manufacturing method of the printed wiring board of this embodiment.
It is a schematic diagram explaining Rp which is one of the parameters which show surface roughness.
It is a schematic diagram explaining Rku which is one of the parameters which show surface roughness.
It is a figure which shows the SEM image of an Example and a comparative example.
It is a figure which shows the SEM image of an Example and a comparative example.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described using drawing.

In addition, in all drawings, the same code | symbol is attached | subjected to the same component, and description is abbreviate | omitted suitably.

(First Embodiment)

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the process sequence of the manufacturing method of the printed wiring board of 1st Embodiment.

Hereinafter, after explaining the outline of the manufacturing method of the printed wiring board of 1st Embodiment, the effect of this manufacturing method is demonstrated. In addition, the detailed manufacturing method conditions, material, etc. of 1st Embodiment are mentioned later in the column of 2nd Embodiment.

The process of the manufacturing method of the printed wiring board of 1st Embodiment is the laminated board (copper laminated board 10 with carrier foil) in which the copper foil with a carrier base material (copper foil layer 104) was laminated on at least one surface 30 of the insulating layer 102. )) Separating the carrier substrate (carrier foil layer 106) from the copper foil layer 104 and forming a metal layer 115 thicker than the copper foil layer 104 on the entire surface or selectively on the copper foil layer 104, and at least the copper foil layer ( By etching 104, the process of obtaining the pattern of the electrically conductive circuit 119 comprised from the copper foil layer 104 and the metal layer 115 is included. After the process of obtaining the pattern of the electrically conductive circuit 119 of this manufacturing process, when measured by JISB0601, Rp in one surface 30 of the insulating layer 102 is 4.5 micrometers or less, and Rku is 2.1 or more.

That is, the process of the manufacturing method of the printed wiring board of 1st Embodiment includes the following processes. First, as shown to Fig.1 (a), the copper clad laminated board 10 with carrier foil is prepared. About this copper clad laminated board 10 with carrier foil, the carrier foil layer 106 is affixed on both surfaces of the insulating layer 102 with the copper foil layer 104. Subsequently, as shown in FIG.1 (b), the carrier foil layer 106 is removed from the copper clad laminated board 10 with carrier foil, etc., and it removes. Subsequently, as shown in FIG. 1C, a resist layer 112 having a predetermined opening pattern is formed on the remaining copper foil layer 104. A plating layer (metal layer 115) is formed by plating in the opening pattern of the resist layer 112 and on the copper foil layer 104 (FIG. 1 (d)). Subsequently, as shown in FIG. 1E, the resist layer 112 is removed. Thereby, the pattern of the predetermined metal layer 115 can be selectively formed on the copper foil layer 104. Subsequently, as shown in FIG. 1 (f), in the region not covered with the metal layer 115, for example, soft etching of the copper foil layer 104 formed on one surface 30 of the insulating layer 102. Remove by In the process of soft etching, Rp in the one surface 30 of the insulating layer 102 is 4.5 micrometers or less, and Rku is 2.1 or more. After the removal process of the copper foil layer 104, the pattern of the conductive circuit 119 can be formed by the copper foil layer 104 and the metal layer 115 which remain. By the above process, the printed wiring board 101 of this embodiment can be obtained (FIG. 1).

2 is an expanded sectional view of the electrically conductive circuit 119 in the printed wiring board 101 of 1st Embodiment. As shown in FIG. 2, the printed wiring board 101 of the present embodiment is provided on one surface 30 of the insulating layer 102 and the insulating layer 102, and is formed of the copper foil layer 104 and the metal layer 115. The pattern of the electrically conductive circuit 119 comprised is provided. When this printed wiring board 101 is measured by JIS B0601, it is specified that Rp in the one surface 30 of the insulating layer 102 is 4.5 micrometers or less, and Rku is 2.1 or more.

Hereinafter, Rp representing the maximum peak height of the roughness curve and Rku representing the kurtosis of the roughness curve will be described with reference to FIGS. 14 and 15. These Rp and Rku are obtained by measuring with respect to the surface roughness of the one surface 30 of the insulating layer 102 in the absence of a cutoff value according to JIS B0601 (2001). In the present embodiment, the roughness curve means an uneven curve indicating the surface roughness. This roughness curve is obtained by a commercially available apparatus. In this embodiment, in the figure which shows the unevenness | corrugation of the surface (one surface 30) of the insulating layer 102, the part corresponded to a recessed part means the part corresponded to a valley and a convex part as an acid.

As shown in FIG. 14, the maximum peak height Rp indicates the maximum value of the convex portion Zpi of the contour curve at the reference length lr. For this reason, making Rp small means making the maximum height of an acid small in the one surface 30 of the insulating layer 102. Therefore, by making Rp small, the difference between the minimum height and the maximum height of a mountain can be made small.

Moreover, kurtosis Rku of a roughness curve shows the sharpened state of the acid in the one surface 30 of the insulating layer 102, as shown in FIG. For this reason, increasing Rku means making the acid acute on one surface 30 of the insulating layer 102. Therefore, by increasing Rku, the width of the mountain can be made small, and the distance between the mountains can be narrowed. In addition, Rku is computed by the following formula.

Here, lr: reference length, Z (x): rolling circle waviness curve, and Rq: square root of the roughness curve are shown.

Conventionally, in the technical field to which the present invention belongs, the surface roughness is usually defined by an index of Ra or Rz (see Patent Document 1, for example).

However, as a result of examination by the present inventors, it turned out that these indices cannot fully reflect the surface shape pattern of the lower surface. For example, since Ra is not an indicator that directly indicates the maximum value of the height of the mountain, even if Ra is controlled to be small, the maximum value of the height of the mountain can be increased. And the surface pattern of the base may become large and the difference of the maximum value and minimum value of an acid may arise, and height difference may arise in the surface of the copper foil formed on it. On the other hand, Ra is an index that does not indicate the width of the acid. Therefore, only by controlling these indexes, the spacing of the acids on the surface of the insulating resin layer in the base may be widened, whereby a recess is formed in the conductor layer. There may be work.

As described above, in the prior art, even if such an indicator was controlled, it was difficult to sufficiently adjust the surface shape pattern of the lower surface.

Therefore, since the height of a mountain and the space | interval of a mountain may widen, the surface shape pattern of the conventional lower surface may cause the imbalance in the surface shape to the surface of the copper foil formed on the surface of the lower surface which has such a surface shape. In the prior art, it was difficult to stabilize the etching characteristics of copper foil.

As a result of further investigation, the present inventors further reduced the parameter of Rp indicating the maximum height of the acid in the underlying insulating layer 102 and increased the parameter of Rku indicating the kurtosis (the spacing of the mountains is narrow). The etching characteristic of the copper foil layer 104 (copper foil provided on the lower surface) improved and it discovered that the pattern of the electrically conductive circuit 119 which is a favorable wiring shape was formed.

Based on the above experiments, the present inventors made the following assumptions. That is, the copper foil layer 104 formed on the insulating layer 102 when the acid height is small on the surface of the insulating layer 102 under the ground, the spacing of the mountains is narrow, and there is a surface-shaped pattern in which an acute angle is present. It was considered that the imbalance of the etching characteristics of the () is reduced.

Therefore, as a result of various experiments, it was controlled by appropriate values of both the indicator indicating that the height of the acid was small and the indicator indicating that the distance between the acid was narrow and acute, but the imbalance of the etching characteristics of the copper foil formed on the base was From the reduction, the present inventors employ Rp indicating the maximum height of the acid and Rku indicating the kurtosis (the narrow spacing of the acid) as these indicators, and controlling Rp to 4.5 µm or less and Rku to 2.1 or more, It has been found that it is possible to appropriately control the surface shape pattern of the one surface 30 of the insulating layer 102, and that the suppression of the imbalance in the etching characteristics of the copper foil can be realized, and thus the present invention has been completed.

In this embodiment, the number of acids can be increased, for example, by forming a pattern in which the spacing is narrow and an acute angle is present as the surface shape pattern. Thereby, since the area of the one side 30 of the insulating layer 102 increases, the contact area of the insulating layer 102 and the copper foil layer 104 also increases. Thereby, the printed wiring board 101 excellent in the adhesiveness of the electrically conductive circuit 119 containing the insulating layer 102 and the copper foil layer 104 becomes possible.

Moreover, according to the manufacturing method of the printed wiring board of this embodiment, generation | occurrence | production of a stripe in the one surface 30 of the insulating layer 102 can be suppressed. Although this mechanism is not clear, since the surface-shaped pattern can form a surface-shaped pattern with a uniform acid height and an interval of the acid on one surface 30 of the insulating layer 102, the insulating layer 102 is a copper foil layer. Since the unbalance of the stress in the horizontal direction received from 104 becomes small, it is inferred that the generation | occurrence | production of a stripe in the insulating layer 102 can be suppressed.

Here, when streaks occur in the insulating layer 102, the etching may be excessive in order to remove the residues (for example, the etching residues) in the streaks, and the wiring shape may be poor. There is a risk of poor connection due to failure to remove the residue. Moreover, when streaks generate | occur | produce in the insulating layer 102, a void may arise in a multilayer wiring structure, and connection reliability may fall.

However, in this embodiment, since generation | occurrence | production of a stripe can be suppressed as mentioned above, the defect of wiring shape, connection defect, or fall of connection reliability resulting from such a stripe can be prevented.

In this embodiment, the upper limit of Rp in the one surface 30 of the insulating layer 102 is 4.5 micrometers or less, More preferably, it is 3.5 micrometers or less, More preferably, it is 2.5 micrometers or less. On the other hand, although the lower limit of Rp is not specifically limited, For example, Preferably it is 0.5 micrometer or more, More preferably, it is 1.0 micrometer or more, More preferably, it is 1.5 micrometers or more. By carrying out Rp in the said range, defects, such as an etching residue at the time of fine wiring formation, are reduced, and a printed wiring board can be obtained with a favorable product yield. Furthermore, the insulation reliability between fine wiring circuits is excellent.

In addition, in this embodiment, although the upper limit of Rku in the one surface 30 of the insulating layer 102 is not specifically limited, For example, Preferably it is 10 or less, More preferably, it is 8 or less, More preferably, Is 6 or less. On the other hand, the lower limit of Rku is 2.1 or more, More preferably, it is 3.0 or more, More preferably, it is 3.5 or more. By carrying out Rku in the said range, since the surface of a base becomes minute unevenness | corrugation, the etching characteristic of the copper foil layer 104 formed on it becomes uniform. For this reason, the side etching characteristic of conductor layers, such as the copper foil layer 104, can also be made uniform. Moreover, since contact area increases, adhesiveness with a conductor layer improves. Therefore, the printed wiring board 101 of this embodiment is excellent in heat resistance and the insulation reliability between fine wirings.

Here, the preferable wiring shape is demonstrated using FIGS. In FIG. 4, the copper clad laminate 1 has an insulating layer 2, a copper foil layer 4, and a metal layer 14. The favorable wiring shape refers to the shape specified by the characteristic that the lower part remains less compared with the former first. As shown in FIG. 4, this lower part remains so that the copper foil layer 4 may protrude in the area | region of the outer side of the metal layer 14 in the width direction orthogonal to the extending direction of the metal layer 14 in planar view. Say the part. Determination as to whether or not this bottom portion remains has been described with reference to FIGS. 2 and 3. As shown in these figures, for example, in cross section, the maximum width of the copper foil layers 104 and 4 in the width direction is set to L1, and the minimum width of the metal layers 115 and 14 in the width direction is set to L1. When L2 is set to L2, when L2-L1 = ΔL is greater than 0, it is determined that the bottom portion remains. In this case, in the conductive circuit 119 according to the present embodiment, ΔL may be smaller than the conventional one, more preferably L1 and L2 are the same (FIG. 2 (a)), and still more preferably L1. This is smaller than L2. When L1 is smaller than L2, the copper foil layer 104 in the cross section has a region in which the width in the planar direction of the copper foil layer 104 becomes smaller than the width in the planar direction of the metal layer 115 (Fig. 2 (b)). ). The shape of the conductive circuit 119 specified by such L1 and L2 becomes a favorable wiring shape.

In addition, the favorable wiring shape in this embodiment refers to what is specified by the characteristic that the shape of the 2nd metal layer 115 is maintaining the desired shape (FIG. 2 (a) and (b)). The desired shape here means the shape as it is, and points out, for example, a square shape. Even when L1 is the same as L2 and L1 is smaller than L2, the etching characteristics of the copper foil layer 104 are improved, and such a shape can be realized.

In addition, as a cross-sectional shape of the copper foil layer 104, as shown in FIG.2 (a), it may be rectangular shape which has the same width | variety as the metal layer 115, and may be an inverted taper shape as shown in FIG.2 (b). . The reverse tapered copper foil layer 104 may have a smaller area from the first surface (upper surface 20) to the second surface (lower surface 22) in plan view (however, the manufacturing step) Unevenness may be formed in a part of the side surface 24 due to an imbalance at the side). In addition, as shown in FIG. 5, in the cross section of the width direction, the angle (the left rotation angle) formed by the repair line with respect to the insulating layer 102 and the side surface 24 is, for example, preferably 0 degrees or more. It is 20 degrees or less, More preferably, they are 1 degree or more and 10 degrees or less.

In addition, the shape of the other copper foil layer 104 may be a shape in which the center shown in FIG. 6 (a) is bulging, or the concave shape shown in FIG. 6 (b) may be used. By using the copper foil layer 104 of such a shape, L1 can be made smaller than L2 in the conductive circuit 119, and furthermore, the contact area with the insulating layer 102 can be secured more than a certain level compared with the reverse taper shape. Become.

In addition, in the printed wiring board of this embodiment, what is excellent in a line-and-space (henceforth L / S) controllability is demonstrated using FIG.

Spaces S2 and S1 shown in FIG. 4 represent distances between the conductive circuits 19 and 119 that are adjacent to each other in the width direction in the direction perpendicular to the direction in which the conductive circuits 19 and 119 extend.

In the conventional manufacturing method of a printed wiring board, an imbalance occurred in the etching characteristic of the copper foil layer 4, and the lower part of the copper foil layer 4 and the etching residue may generate | occur | produce. In order to always separate and electrically isolate such copper foil layer 4, as shown in FIG.4 (b), it was necessary to ensure sufficient space S2. In other words, the space S2 needs to be adjusted to the variation of L1. In the conventional manufacturing method of the printed wiring board, since the controllability of such L1 / S2 is low, it was difficult to form fine wiring.

On the other hand, in the manufacturing method of the printed wiring board of this embodiment, since the etching characteristic of the copper foil layer 104 can be improved, the copper foil layer 104 in the width direction while maintaining the shape of the metal layer 115 to a desired shape. It becomes possible to control the width of. For this reason, since L1 can be made into L2 or less (namely, since the remainder of a lower part disappears), the space S1 can be determined by the minimum width L2 of the metal layer 115. As mentioned above, this L2 can be set as the design value. Therefore, in the manufacturing method of the printed wiring board of this embodiment, such controllability of L2 / S1 is excellent. Therefore, since L / S controllability is excellent, the manufacturing method of the printed wiring board which can process fine wiring while suppressing a connection defect is obtained.

In addition, in this embodiment, the etching with respect to the side surface 24 in the copper foil layer 104 is called side etching. In this side etching, etching advances in the horizontal direction with respect to the upper surface of the insulating layer 102.

In addition, the etching with respect to the upper surface 20 of the copper foil layer 104 is called longitudinal etching. In this longitudinal etching, etching advances in the direction perpendicular to the upper surface of the insulating layer 102.

(Second Embodiment)

Hereinafter, the manufacturing method of the printed wiring board of 2nd Embodiment is demonstrated. In 2nd Embodiment, the detailed manufacturing method conditions, material, etc. which were abbreviate | omitted in 1st Embodiment are illustrated.

The manufacturing method of the printed wiring board of 2nd Embodiment has the through-hole which penetrates the copper clad laminated board 100 comprised from the copper foil layer 104 and the insulating layer 102 by the process of forming the metal layer 116 on a whole surface, or selectively. 108 is formed, a step of contacting at least the inner wall of the through hole 108 with the chemical liquid, and electroless plating electrically connecting the copper foil layer 104 on the upper and rear surfaces of the insulating layer 102 by electroplating. The point which further includes the process of forming the electroless plating layer 110 differs from 1st Embodiment.

FIG.7 and FIG.8 is sectional drawing which shows the process sequence of the manufacturing method of the printed wiring board of 2nd Embodiment.

First, as shown to Fig.7 (a), the copper clad laminated board 10 with carrier foil which bonded the copper foil layer 104 with the carrier foil layer 106 on both surfaces of the insulating layer 102 is prepared.

As the copper clad laminated board 10 with carrier foil, this copper clad laminated board 100 in which the peelable carrier foil layer 106 is laminated | stacked on at least one surface of the copper clad laminated board 100 (henceforth a lamination board is called. ) Although not particularly limited, for example, one in which the copper foil layer 104 is laminated on at least one surface of the insulating layer 102 having the insulating resin layer containing the substrate can be used (fiber substrate is omitted in the drawing). Although this laminated sheet may be a single | mono layer, it may have a multilayered structure. That is, although it may be comprised only from a core layer as a laminated board, you may use what the buildup layer is formed on the core layer. A well-known thing can be applied to such a laminated board, For example, what laminated | stacked several sheets of prepreg, etc. can be used. Although this prepreg is not specifically limited, For example, it can obtain by the method of impregnating the resin composition containing thermosetting resin, a hardening | curing agent, a filler, etc. in base materials, such as glass cloth. And as a laminated board, what superimposed the ultra-thin metal foil with carrier foil on at least one surface, and heat-moulded etc. can be used. Moreover, although the thing of the same material as a core layer may be used for the interlayer insulation layer of a buildup layer, a base material or a resin composition may differ. In this embodiment, the insulating layer 102 is corresponded to the insulating resin layer which comprises a core layer or a buildup layer. The example which uses the laminated board provided with a buildup layer is mentioned later in 3rd Embodiment.

The resin composition which comprises the laminated board and interlayer insulation layer used for this embodiment can use well-known resin (henceforth an insulated resin composition) used as an insulation material of a printed wiring board, and thermosetting property with favorable heat resistance and chemical-resistance is normally favorable Resin is mainly used. The said resin composition is not specifically limited, It is preferable that it is a resin composition in which a thermosetting resin is contained at least.

Examples of the thermosetting resin include urea (urea) resins, melamine resins, maleimide resins, polyurethane resins, unsaturated polyester resins, resins having a benzoxazine ring, bisallynalideimide compounds, vinylbenzyl resins, and vinylbenzyl ethers. Resin, benzocyclobutene resin, cyanate resin, epoxy resin and the like. Among these, the combination whose curable resin becomes glass transition temperature 200 degreeC or more is preferable. For example, a spiro ring containing, heterocyclic, trimethylol type, biphenyl type, naphthalene type, antran type, novolak type 2 or trifunctional or more epoxy resin, cyanate resin (including the prepolymer of cyanate resin) , Resin having maleimide resin, benzocyclobutene resin and benzoxazine ring is preferable. When using an epoxy resin and / or a cyanate resin, linear expansion becomes small and heat resistance improves remarkably. In addition, when the epoxy resin and / or cyanate resin are combined with a high-filling filler, there is a merit of being excellent in flame retardancy, heat resistance, impact resistance, high rigidity and electrical characteristics (low dielectric constant, low dielectric loss tangent). Here, the improvement of heat resistance is that the glass transition temperature becomes 200 degreeC or more after the hardening reaction of the said thermosetting resin, the thermal decomposition temperature of the resin composition after hardening becomes high, and low molecular weights, such as the reaction residue in 250 degreeC or more, are reduced. It seems to be due to. Moreover, since the flame retardancy improvement is aromatic thermosetting resin, since the ratio of the benzene ring is high in structure, it is thought that this benzene ring is easy to carbonize (graphite) and the carbonization part arises.

Although the said resin composition may contain a flame retardant further in the range which does not impair the effect of this invention, a non-halogen-type flame retardant is preferable from an environmental viewpoint. As a flame retardant, an organophosphorus flame retardant, an organic nitrogen containing phosphorus compound, a nitrogen compound, a silicone flame retardant, a metal hydroxide, etc. are mentioned, for example. As organophosphorus flame retardants, phosphorus-containing benzoxazine compounds such as HCA, HCA-HQ and HCA-NQ manufactured by Sanko Co., Ltd. and HFB-2006M manufactured by Showa Polymer Co., Ltd. Phosphoric acid ester compounds, such as PPQ by the company, OP930 by Clariant, PX200 by Daihachi Chemical, FX289, FX310 by Toto Kasei Co., Ltd., Toto Kasei Co., Ltd. And phosphorus-containing phenoxy resins such as ERF001. Examples of the organic nitrogen-containing phosphorus compounds include phosphate ester amide compounds such as SP670 and SP703 manufactured by Shikoku Chemical Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Corporation. Pazen compounds, and the like. Examples of the metal hydroxides include magnesium hydroxides such as UD650 and UD653 manufactured by Ube Materials, Inc., CL310 manufactured by Sumitomo Chemical Co., Ltd., and aluminum hydroxides such as Showa Electric Co., Ltd. and HP-350.

As an epoxy resin used for the said resin composition, for example, bisphenol-A epoxy resin, bisphenol F-type epoxy resin, bisphenol E-type epoxy resin, bisphenol S-type epoxy resin, bisphenol M-type epoxy resin, bisphenol P-type epoxy resin, bisphenol Bisphenol-type epoxy resins, such as a Z-type epoxy resin, a phenol novolak-type epoxy resin, a novolak-type epoxy resin, such as a cresol novolak-type epoxy resin, a biphenyl type epoxy resin, a xylylene type epoxy resin, and a biphenyl aralkyl type epoxy resin Naphthalene, such as an aryl alkylene type epoxy resin, a naphthol type epoxy resin, a naphthalene diol type epoxy resin, a bifunctional to tetrafunctional epoxy type naphthalene resin, a naphthylene ether type epoxy resin, a naphthyl type epoxy resin, a naphthalene aralkyl type epoxy resin, etc. Epoxy resin, anthracene epoxy resin, phenoxy epoxy resin, dish As there may be mentioned diene-type epoxy resin, epoxy resin nenhyeong norbornyl, adamantyl tanhyeong epoxy resin, fluorene type epoxy resins.

As the epoxy resin, one of these may be used alone, or two or more kinds having different weight average molecular weights may be used in combination. Moreover, you may use together one or two or more types of these, and these prepolymers.

Especially among these epoxy resins, an aryl alkylene type epoxy resin is preferable. Thereby, moisture absorption solder heat resistance and flame retardance can be improved further.

An aryl alkylene type epoxy resin means the epoxy resin which has one or more aryl alkylene groups in a repeating unit. For example, xylylene-type epoxy resin, biphenyl dimethylene-type epoxy resin, etc. are mentioned. Among these, biphenyl dimethylene type | mold epoxy resin is preferable. Biphenyl dimethylene type | mold epoxy resin can be represented by following General formula (1), for example. Moreover, as biphenyl dimethylene type | mold epoxy resin, NC-3000, NC-3000L, and NC-3000-FH by a Japanese powder company can be mentioned, for example.

The average repeating unit n of the biphenyl dimethylene type | mold epoxy resin represented by the said General formula (1) is arbitrary integers. The lower limit of n is not particularly limited, but is preferably 1 or more, and particularly preferably 2 or more. When n is too small, biphenyl dimethylene type | mold epoxy resin will become easy to crystallize, and since the solubility to general purpose solvents falls comparatively, handling may become difficult. Although the upper limit of n is not specifically limited, 10 or less are preferable and 5 or less are especially preferable. When n is too large, the fluidity | liquidity of resin may fall and it may become a cause of molding defects.

As an epoxy resin of that excepting the above, the novolak-type epoxy resin which has a condensed cyclic aromatic hydrocarbon structure is preferable. Thereby, heat resistance and low thermal expansion property can be improved further.

The novolak type epoxy resins having a condensed cyclic aromatic hydrocarbon structure are naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, triphenylene and tetraphen, and other novolac epoxy resins having a condensed cyclic aromatic hydrocarbon structure. . The novolak-type epoxy resin having a condensed ring aromatic hydrocarbon structure is excellent in low thermal expansion because a plurality of aromatic rings can be arranged regularly. Moreover, since glass transition temperature is also high, it is excellent in heat resistance. Furthermore, since the molecular weight of the repeating structure is large, it is excellent in flame retardancy compared with the conventional novolak-type epoxy resin, and by combining with the cyanate resin, the weakness of the weakness of the cyanate resin can be improved. Therefore, by using together with cyanate resin, since glass transition temperature becomes higher, it is excellent in the mounting reliability corresponding to lead-free.

The novolak-type epoxy resin which has a condensed cyclic aromatic hydrocarbon structure epoxidizes the novolak-type phenol resin synthesize | combined from a phenolic compound, a formaldehyde compound, and a condensed cyclic aromatic hydrocarbon compound.

Although a phenolic compound is not specifically limited, For example, cresols, such as a phenol, o-cresol, m-cresol, and p-cresol, 2, 3- xylenol, 2, 4- xylenol, 2, 5- Xylenols, such as xylenol, 2, 6- xylenol, 3, 4- xylenol, 3, 5- xylenol, trimethyl phenols, such as 2, 3, 5- trimethyl phenol, o-ethyl phenol , ethyl phenols such as m-ethyl phenol and p-ethyl phenol, alkyl phenols such as isopropyl phenol, butyl phenol and t-butyl phenol, o-phenyl phenol, m-phenyl phenol, p-phenyl phenol, catechol, 1 Naphthalene diols, such as 5-, 5- dihydroxy naphthalene, 1, 6- dihydroxy naphthalene, and 2, 7- dihydroxy naphthalene, a resorcinol, catechol, hydroquinone, a pyrogarol, fluoroglucin, etc. Alkyl polyhydric phenols, such as polyhydric phenols, an alkylresolecin, alkyl catechol, and alkyl hydroquinone, are mentioned. Among them, phenol is preferred from the viewpoint of cost and the effect imparted to the decomposition reaction.

The aldehyde compound is not particularly limited, but for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyl Aldehyde, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, dihydroxybenzaldehyde, trihydroxybenzaldehyde, 4-hydroxy-3-aldehyde Methoxyaldehyde paraformaldehyde and the like.

Although a condensed cyclic aromatic hydrocarbon compound is not specifically limited, For example, naphthalene derivatives, such as methoxy naphthalene and butoxynaphthalene, anthracene derivatives, such as methoxy anthracene, phenanthrene derivatives, such as methoxyphenanthrene, and other tetracene derivatives , Chrysene derivatives, pyrene derivatives, derivative triphenylene and tetraphene derivatives.

Although the novolak-type epoxy resin which has a condensed cyclic aromatic hydrocarbon structure is not specifically limited, For example, a methoxy naphthalene modified ortho cresol novolak epoxy resin, butoxy naphthalene modified meta (para) cresol novolak epoxy resin, and methoxy naphthalene A modified novolak epoxy resin etc. are mentioned. Among these, the novolak-type epoxy resin which has a condensed cyclic aromatic hydrocarbon structure represented by following formula (2) is preferable. Moreover, as a novolak-type epoxy resin which has a condensed cyclic aromatic hydrocarbon structure, HP-5000 by DIC Corporation is mentioned, for example.

(In the formula, Ar is a condensed cyclic aromatic hydrocarbon group, R may be the same or different from each other, a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or an aryl group such as a halogen element, a phenyl group, a benzyl group, and glycidyl ether) And n, p and q are integers of 1 or more, and the values of p and q may be the same or different for each repeating unit.)

(Ar in Formula (2) is a structure represented by (Ar1)-(Ar4) in Formula (3), R in Formula (3) may mutually be same or different, and is a hydrogen atom, a C1-C10 hydrocarbon group. Or an aryl group such as a halogen element, a phenyl group, or a benzyl group, and an organic group including glycidyl ether.)

Moreover, as an epoxy resin of that excepting the above, naphthalene type epoxy resins, such as a naphthol type epoxy resin, a naphthalene diol type epoxy resin, a bifunctional to tetrafunctional epoxy type naphthalene resin, and a naphthylene ether type epoxy resin, are preferable. Thereby, heat resistance and low thermal expansion property can be improved further. Moreover, since the (pi)-(pi) stacking effect of a naphthalene ring is higher than a benzene ring, it is especially excellent in low thermal expansion property and low thermal contractility. In addition, because of the polycyclic structure, the rigidity effect is high, and the glass transition temperature is particularly high, so that the heat shrinkage change before and after reflow is small.

A naphthol type epoxy resin can be represented by following General formula (4-1), for example. Moreover, as a naphthol type epoxy resin, ESN-375 by Shin-Ill Iron Chemical Co., Ltd. is mentioned, for example.

A naphthalenediol type epoxy resin can be represented by following formula (4-2), for example. As naphthalene diol type epoxy resin, DIC Corporation HP-4032D is mentioned, for example. The bifunctional to tetrafunctional epoxy-type naphthalene resin can be represented by the following formulas (4-3), (4-4) and (4-5), for example. As a bifunctional to tetrafunctional epoxy-type naphthalene resin, DIC Corporation HP-4700 and HP-4770 are mentioned, for example.

A naphthylene ether type epoxy resin can be represented by following General formula (4-6), for example. As a naphthylene ether type epoxy resin, DIC Corporation HP-6000 is mentioned, for example.

(n represents an average of 1 or more and 6 or less, and R represents a glycidyl group or a C1 or more and 10 or less hydrocarbon group.)

(In formula, R <^1> represents a hydrogen atom or a methyl group, R <^2> represents a hydrogen atom, a C1-C4 alkyl group, an aralkyl group, a naphthalene group, or a glycidyl ether group containing naphthalene group each independently, o and m is an integer of 0-2 each, and at least one of o or m is 1 or more.)

The cyanate resin used for the said resin composition can be obtained by making a cyanide halogen compound and phenol react, for example. Specific examples of the cyanate resin include novolak cyanate resins such as phenol novolac cyanate resins, cresol novolac cyanate resins, naphthol aralkyl type cyanate resins, dicyclopentadiene type cyanate resins, And bisphenol cyanate resins such as biphenyl cyanate resin, bisphenol A cyanate resin, bisphenol AD cyanate resin, and tetramethylbisphenol F cyanate resin.

Especially among these, it is preferable to contain novolak-type cyanate resin, a naphthol aralkyl type cyanate resin, a dicyclopentadiene type cyanate resin, and a biphenyl type cyanate resin. Moreover, it is preferable that a resin composition contains 10 weight% or more of this cyanate resin in the total solid of a resin composition. Thereby, the heat resistance (glass transition temperature, thermal decomposition temperature) of a prepreg can be improved. In addition, the thermal expansion coefficient of the prepreg (particularly, the thermal expansion coefficient in the thickness direction of the prepreg) can be reduced. When the thermal expansion coefficient in the thickness direction of the prepreg decreases, the stress distortion of the multilayer printed wiring can be reduced. Moreover, in the multilayer printed wiring board which has a fine interlayer connection part, the connection reliability can be improved significantly.

As a preferable thing among the novolak-type cyanate resin used for the said resin composition, the novolak-type cyanate resin represented by following formula (5) is mentioned. The weight average molecular weight is 2000 or more, More preferably, 2,000-10,000, More preferably, the novolak-type cyanate resin represented by Formula (5) of 2,200-3,500 and a weight average molecular weight are 1500 or less, More preferably, 200-1,300 It is preferable to use the novolak-type cyanate resin represented by phosphorus formula (5) in combination (Hereinafter, "-" shows including an upper limit and a lower limit unless otherwise specified). In addition, in this embodiment, a weight average molecular weight is the value measured by the gel permeation chromatography method of polystyrene conversion.

In formula (5), n represents the integer of 0 or more.

Moreover, as cyanate resin, the cyanate resin represented by following General formula (6) is also used suitably. The cyanate resin represented by the following general formula (6) includes naphthols such as α-naphthol or β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, and 1,4-di (2). It is obtained by condensing naphthol aralkyl resin and cyanic acid obtained by reaction, such as -hydroxy-2-propyl) benzene. N of General formula (6) is 1 or more, but it is more preferable that it is 10 or less. When n is 10 or less, resin viscosity does not become high and impregnation with a base material is favorable, and the fall of the performance as a laminated board can be suppressed. In addition, intramolecular polymerization hardly occurs at the time of synthesis, and the liquid-liquidity at the time of water washing is improved, and the fall of water quantity can be prevented.

In formula (6), R represents a hydrogen atom or a methyl group, R may be same or different, and n represents an integer of 1 or more.

Moreover, the dicyclopentadiene type cyanate resin represented by following General formula (7) is also used suitably as cyanate resin. As for dicyclopentadiene type cyanate resin represented by following General formula (7), it is more preferable that n of following General formula (7) is 0 or more and 8 or less. When n is 8 or less, resin viscosity does not become high and impregnation with a base material is favorable, and the fall of the performance as a laminated board can be suppressed. Moreover, it is excellent in low hygroscopicity and chemical-resistance by using dicyclopentadiene type cyanate resin.

n represents the integer of 0-8.

In addition, the resin composition may further contain a curing accelerator. For example, if a thermosetting resin is an epoxy resin or a cyanate resin, the hardening accelerator of a phenol resin, an epoxy resin, or a cyanate resin can be used. Although a phenol resin is not specifically limited, For example, novolak-type phenol resins, such as a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, an arylalkylene type novolak resin, an unmodified resolphenol resin, copper oil, Resol type phenol resins, such as oil-modified resol phenol resin modified | modified with amani oil, walnut oil, etc. are mentioned. As said phenol resin, a phenol novolak or a cresol novolak resin is preferable. Especially, biphenyl aralkyl modified phenol novolak resin is preferable at the point of moisture absorption solder heat resistance.

One type of these may be used alone, or two or more types having different weight average molecular weights may be used in combination, or one or two or more types thereof and prepolymers thereof may be used in combination.

Although the said hardening accelerator is not specifically limited, For example, organometallic salts, such as zinc naphthenate, cobalt naphthenate, tin octylic acid, octylic acid cobalt, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), etc. , Tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole , 2-ethyl-4-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2- Ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimide Imidazoles such as dozol, 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole, phenol compounds such as phenol, bisphenol A, nonylphenol, acetic acid, benzoic acid, salicylic acid, paratoluenesul Organic acids such as phonic acid, onium salts Or it may be a mixture. One type may be used independently including derivatives in these, and two or more types may be used together including these derivatives.

Moreover, the said thermosetting resin may contain the maleimide compound from the heat resistant point. The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidephenyl) methane, 2,2-bis {4- (4-maleimidephenoxy) -phenyl} propane, bis (3,5-dimethyl-4-maleimidephenyl) methane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, bis (3,5-diethyl-4-maleimidephenyl) methane, Polyphenylmethane maleimide, the prepolymer of these maleimide compounds, or the prepolymer of a maleimide compound and an amine compound, etc. are mentioned.

Moreover, the said thermosetting resin may contain phenoxy resin, polyvinyl alcohol-type resin, polyimide, polyamide, polyamideimide, polyether sulfone resin, and polyphenylene ether resin from an adhesive point with metal foil.

As a phenoxy resin, the phenoxy resin which has a bisphenol skeleton, the phenoxy resin which has a naphthalene skeleton, the phenoxy resin which has a biphenyl skeleton, etc. are mentioned, for example. Moreover, the phenoxy resin of the structure which has multiple types of these skeletons can also be used.

Among these, it is preferable to use the phenoxy resin which has a biphenyl skeleton and bisphenol S skeleton as a phenoxy resin. Thereby, while the glass transition temperature of a phenoxy resin can be made high by the rigidity which a biphenyl skeleton has, the adhesiveness of a phenoxy resin and a metal can be improved by presence of a bisphenol S skeleton. As a result, the heat resistance of the insulating layer 102 can be improved, and the adhesion of the wiring portion (the conductive circuit 118) to the insulating layer 102 can be improved when the multilayer substrate is manufactured. Moreover, it is also preferable to use the phenoxy resin which has bisphenol A frame | skeleton and bisphenol F frame | skeleton as phenoxy resin. Thereby, the adhesiveness to the insulating layer 102 of a wiring part can be improved further at the time of manufacture of a multilayer board | substrate.

Commercially available products of phenoxy resins include To280 Chemical Co., Ltd. FX280 and FX293, Japan Epoxy Resin Co., Ltd. YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213, and YL7290. Although the molecular weight of a phenoxy resin is not specifically limited, It is preferable that it is 5,000-70,000, and, as for a weight average molecular weight, it is more preferable that it is 10,000-60,000.

When using a phenoxy resin, the content is not specifically limited, It is preferable that it is 1-40 weight% of the whole resin composition, and it is more preferable that it is 5-30 weight%.

Commercially available products of polyvinyl alcohol-based resins include Denki Chemical Industries, Ltd., butane 4000-2, 5000-A, 6000-C and 6000-EP, Sekisui Chemicals, Inc. Esrek BH series, BX series , KS series, BL series, and BM series. In particular, it is especially preferable that glass transition temperature is 80 degreeC or more.

Commercially available products of polyimide, polyamide, and polyamideimide include "Biromax HR11NN" and "HR-16NN" "HR15ET" manufactured by Toyo Spinning Co., Ltd. and polyamideimide "Hitachi Chemical Co., Ltd." KS-9300 ”etc. are mentioned. `` Neoprim C-1210 (registered trademark) '' manufactured by Mitsubishi Gas Chemical Co., Ltd., soluble polyimide `` Lika coat SN20 (registered trademark) '' and `` Lika coat PN20 (registered trademark) '' manufactured by Nippon Ewha Co., Ltd., Polyetherimide "Ultem (registered trademark)" manufactured by GE Plastics Co., Ltd., "V8000" and "V8002" and "V8005" manufactured by DIC Corporation, and "BPAM155" manufactured by Nippon Gunpowder Co., Ltd. have.

As a commercial item of a polyether sulfone resin, a well-known thing can be used, For example, PES4100P, PES4800P, PES5003, PES5200P, etc. by Sumitomo Chemical Co., Ltd. are mentioned.

Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2,6-diethyl-1,4-phenylene) oxide, and poly (2- Methyl-6-ethyl-1,4-phenylene) oxide, poly (2-methyl-6-propyl-1,4-phenylene) oxide, poly (2,6-dipropyl-1,4-phenylene) Oxide, poly (2-ethyl-6-propyl-1,4-phenylene) oxide, and the like. As a commercial item, for example, Japan G.E. "Noryl PX9701 (registered trademark)" (number average molecular weight Mn = 14,000) made by plastic company, "Noryl 640-111 (registered trademark)" (number average molecular weight Mn = 25,000), and "SA202" made by Asahi Kasei Corporation (number average molecular weight) Mn = 20,000) and the like, and these can be used by reducing the molecular weight by a known method.

Among these, the reactive oligophenylene oxide which modified | denatured the terminal by the functional group is preferable. As a result, the compatibility with the thermosetting resin can be improved to form a three-dimensional crosslinked structure between the polymers, so the mechanical strength is excellent. For example, 2,2 ', 3,3', 5,5'-hexamethylbiphenyl-4,4'-diol-2,6-dimethylphenol polycondensate described in Japanese Patent Laid-Open No. 2006-28111 And reaction products of chloromethylstyrene.

Such reactive oligophenylene oxide can be produced by a known method. Moreover, a commercial item can also be used. For example, OPE-2st 2200 (made by Mitsubishi Gas Chemical Co., Ltd.) can be used suitably.

It is preferable that it is 2,000-20,000, and, as for the weight average molecular weight of reactive oligophenylene oxide, it is more preferable that it is 4,000-15,000. If the weight average molecular weight of reactive oligophenylene oxide exceeds 20,000, it will become difficult to melt | dissolve in a volatile solvent. On the other hand, when a weight average molecular weight is less than 2,000, since crosslinking density becomes high too much, a bad influence will arise on the elasticity modulus and flexibility of hardened | cured material.

Although the quantity of the thermosetting resin in the resin composition used for this embodiment may be suitably adjusted according to the objective, it does not specifically limit, It is preferable that it is 10-90 weight% in the total solid of a resin composition, Furthermore, 20-70 It is preferable that it is 25% by weight, and still more 25-50 weight% (Hereafter, "-" shows including an upper limit and a lower limit, unless it mentions specially.).

Moreover, when using an epoxy resin and / or a cyanate resin as a thermosetting resin, it is preferable that an epoxy resin is 5-50 weight% in the total solid of the said resin composition, and it is more preferable that an epoxy resin is 5-25 weight%. Do. Moreover, it is preferable that cyanate resin is 5-50 weight% in the total solid of a resin composition, and it is more preferable that cyanate resin is 10-25 weight%.

It is preferable to contain an inorganic filler in the said resin composition from the point of low thermal expansion and mechanical strength. The inorganic filler is not particularly limited, but for example, talc, calcined clay, unbaked clay, mica, silicate such as glass, oxides such as titanium oxide, alumina, silica, fused silica, calcium carbonate, magnesium carbonate, hydrotalcite, etc. Carbonate, aluminum hydroxide, boehmite (AlO (OH)), boehmite commonly referred to as "similar" boehmite (ie, Al ₂ O ₃ xH ₂ O, where x = 1 to 2), magnesium hydroxide, calcium hydroxide Such as metal hydroxides, barium sulfate, calcium sulfate, sulfate such as calcium sulfite or sulfite, zinc borate, barium metaborate, borate such as aluminum borate, calcium borate, sodium borate, aluminum nitride, boron nitride, silicon nitride, carbon nitride, etc. And nitrides such as nitride, strontium titanate and barium titanate. One type of them may be used alone, or two or more types may be used in combination.

Among these, magnesium hydroxide, aluminum hydroxide, boehmite, silica, fused silica, talc, calcined talc, and alumina are preferable. Silica is particularly preferable in view of low thermal expansion and insulation reliability, and more preferably spherical fused silica. Moreover, aluminum hydroxide is preferable at the point of flame resistance. Moreover, in this embodiment, since the base material which is easy to impregnate even if it is an inorganic filler is used, the quantity of an inorganic filler can be increased in the said resin composition. When the inorganic filler is in high concentration in the resin composition, the drill wear property is deteriorated. However, when the inorganic filler is boehmite, the drill wear property is preferable.

Although the particle diameter of an inorganic filler is not specifically limited, Inorganic filler whose average particle diameter is monodisperse can also be used, and the inorganic filler which polydispersion of an average particle diameter can be used. Moreover, you may use together one type or two types or more of the inorganic filler whose average particle diameter is monodispersion and / or polydispersion. Although the average particle diameter of the said inorganic filler is not specifically limited, 0.1 micrometer-5.0 micrometers are preferable, and 0.1 micrometer-3.0 micrometers are especially preferable. Since the viscosity of a resin composition becomes it high that the particle size of an inorganic filler is less than the said lower limit, workability at the time of prepreg preparation may be influenced. Moreover, when it exceeds the said upper limit, the phenomenon, such as sedimentation of an inorganic filler, may arise in a resin composition. In addition, an average particle diameter can be measured using a laser diffraction / scattering type particle size distribution measuring apparatus (general apparatuses, such as SALD-7000 by Shimadzu Corporation).

Although content of an inorganic filler is not specifically limited, It is preferable that it is 10 weight%-90 weight% in the total solid of the said resin composition, Furthermore, it is 30 weight%-80 weight%, Furthermore, it is 50 weight%-75 weight% It is preferable. When containing cyanate resin and / or its prepolymer in the said resin composition, it is preferable that content of the said inorganic filler is 50 to 75 weight% in the total solid of a resin composition. If the content of the inorganic filler exceeds the above upper limit, the fluidity of the resin composition may be extremely poor, and if it is less than the lower limit, the strength of the insulating layer made of the resin composition may not be sufficient, which may be undesirable.

Moreover, the resin composition used for this embodiment can also mix | blend a rubber component, For example, a preferable example of the rubber particle which can be used in this embodiment is a core-shell rubber particle, crosslinked acrylonitrile butadiene rubber particle, crosslinked styrene butadiene Rubber particles, acrylic rubber particles, silicon particles, and the like.

The core-shell rubber particles are rubber particles having a core layer and a shell layer, for example, a two-layer structure in which the shell layer of the outer layer is made of a glassy polymer, and the core layer of the inner layer is made of a rubbery polymer, or the shell layer of the outer layer is a glassy polymer. And a three-layer structure in which the intermediate layer is composed of a rubbery polymer and the core layer is composed of a glassy polymer. The glassy polymer layer is composed of, for example, a polymer of methyl methacrylate, or the like, and the rubbery polymer layer is composed of, for example, a butyl acrylate polymer (butyl rubber) or the like. Specific examples of the core-shell rubber particles include starpiroid AC3832, AC3816N (trade name, manufactured by Gantz Chemical Co., Ltd.), and metabrene KW-4426 (trade name, manufactured by Mitsubishi Rayon Corporation). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle diameter of 0.5 µm, manufactured by JSR Corporation), and the like.

Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter of 0.5 µm, manufactured by JSR Corporation), and the like. Specific examples of the acrylic rubber particles include metabrene W300A (average particle diameter of 0.1 µm), W450A (average particle diameter of 0.2 µm) (manufactured by Mitsubishi Rayon Corporation), and the like.

The silicon particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane, and for example, the core part composed of fine particles made of silicone rubber (organo polysiloxane crosslinked elastomer) itself and silicon of a two-dimensional crosslinked main body may be used. And core shell structural particles coated with silicon. As silicone rubber microparticles | fine-particles, KMP-605, KMP-600, KMP-597, KMP-594 (made by Shin-Etsu Chemical Co., Ltd.), trefil E-500, trefil E-600 (made by Toray Dow Corning Co., Ltd.). Commercially available products, such as), can be used.

You may further contain a coupling agent in the said resin composition. A coupling agent is mix | blended in order to improve the wettability of the interface of a thermosetting resin and an inorganic filler, to fix a resin and an inorganic filler uniformly with respect to a base material, and to improve heat resistance, especially the solder heat resistance after moisture absorption.

Although the said coupling agent is not specifically limited, For example, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, a silicone oil type coupling agent, etc. are mentioned. Thereby, wettability with the interface of an inorganic filler can be made high, and heat resistance can be improved more by it.

Although the addition amount of the said coupling agent is not specifically limited, 0.05-3 weight% is preferable with respect to 100 weight% of inorganic fillers, and 0.1-2 weight% is especially preferable. When content is less than the said lower limit, since an inorganic filler cannot fully be coat | covered, the effect of improving heat resistance may fall, and when it exceeds the said upper limit, reaction may be affected and bending strength etc. may fall.

If necessary, additives other than the above components, such as an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, a silicone powder, and an ion trapping agent, may be added to the resin composition used in the present embodiment.

It is preferable that the said resin composition contains at least an epoxy resin, a cyanate resin, and an inorganic filler from the point which is easy to implement | achieve low linear expansion, high rigidity, and high heat resistance of a prepreg. Especially, it is preferable to contain 5-50 weight% of epoxy resins, 5-50 weight% of cyanate resins, and 10-90 weight% of inorganic fillers in solid content of a resin composition, 5-25 weight% of epoxy resins, It is more preferable to contain 10 to 25 weight% of cyanate resin and 30 to 80 weight% of an inorganic filler.

The prepreg used for this embodiment is formed by impregnating or coating the varnish of a resin composition to the base material, and the well-known thing used for the laminated board for various electrical insulation materials can be used as a base material. Examples of the material of the substrate include inorganic fibers such as E glass, D glass, T glass, S glass or Q glass, organic fibers such as polyimide, polyester or tetrafluoroethylene, and mixtures thereof. These substrates have the shape of, for example, woven fabrics, nonwovens, rovings, chopped strands, surfacing mats, etc., but the materials and shapes are selected according to the use and performance of the intended molding, Or use from two or more types of materials and shapes is possible. Although there is no restriction | limiting in particular in the thickness of a base material, Usually, what is surface-treated with a silane coupling agent etc. using the thing of about 0.01-0.5 mm, and what mechanically opened and flattened it are suitable from the viewpoint of heat resistance, moisture resistance, and workability. Do. In addition, the prepreg is usually impregnated or coated with a resin so that the resin content is 20 to 90% by weight after drying, followed by drying by heating for 1 to 20 minutes at a temperature of 120 to 220 ° C. You can get it. Moreover, laminated | stacked board can be obtained by laminating | stacking this prepreg normally 1-20 sheets, and heat-pressing and laminating | stacking in the structure which further arrange | positioned the ultra-thin copper foil with carrier foil on both surfaces. Although the thickness of a plurality of prepreg layers differs depending on a use, the thing of thickness of 0.03-2 mm is preferable normally. As a lamination method, the method of a normal laminated board can be applied, For example, using a multistage press, a multistage vacuum press, continuous molding, an autoclave forming machine, etc., normal temperature 100-250 degreeC, pressure 0.2-10 MPa, heating time 0.1 It can laminate | stack on the conditions of -5 hours, or can laminate on the conditions of lamination conditions 50-150 degreeC, 0.1-5 Mpa, and vacuum pressure 1.0-760 mmHg using a vacuum laminating apparatus.

In addition, the ultra-thin copper foil (copper foil layer 104) with carrier foil used for this embodiment is a electrodeposition layer (a yake plating) of the shape of a hump on the rough surface of the ultra-thin foil. For example, Japanese Unexamined Patent Publication No. 5-029740 Coarsening process is performed by formation, oxidation treatment, reduction treatment, etching, or the like. Therefore, it is preferable that the upper limit of the 10-point average roughness Rz shown to JIS B0601 is 5.0 micrometers or less, and, as for the surface roughness of the roughening surface of the ultra-thin copper foil used for this embodiment, it is more preferable that it is 2.0 micrometers or less, On the other hand, Although it does not specifically limit, 0.1 micrometer or more are preferable. Moreover, it is preferable that arithmetic mean roughness Ra is 1.0 micrometer or less, and it is more preferable that it is 0.5 micrometer or less.

In addition, in the present embodiment, the copper foil layer 104 may be a copper foil containing an additive metal component such as nickel or aluminum, in addition to copper foil made of copper (except for the inevitably mixed material in the manufacturing process). In the case of copper content, although it does not specifically limit, 90 weight% or more is preferable with respect to the total value of the weight of all the metal components which comprise the copper foil layer 104, 95 weight% or more is more preferable, 99 weight% or more Moreover, as an addition metal component, you may use individually and may use multiple types together). Instead of the copper foil layer 104, metal foils such as nickel foil and aluminum foil may be used.

As a conventional copper foil formation method, the copper foil of about 30 micrometers thick was formed on the electrode by plating process. However, in this formation method, it was difficult for copper foil to inherit the orientation of the lower metal layer (for example, electrode), and to make copper foil which has a desired crystal surface. Moreover, when the film thickness of copper foil is thick, it exists in the tendency for a crystal grain to coarsen toward thickness direction, for example, when it is 30 micrometers or more.

On the other hand, in the formation method of the copper foil layer 104 of this embodiment, the peeling layer is formed on an electrode, and the copper foil layer 104 is formed on this peeling layer. For this reason, it can suppress that the copper foil layer 104 inherits the orientation of the lower electrode. In other words, since the crystal plane of the copper foil layer 104 constitutes a layer by appropriately controlling the orientation on one surface of the copper foil layer 104 in contact with the release layer, the orientation on one surface can be inherited to the other surface. Become. Thereby, the copper foil layer 104 which has desired orientation can be formed.

Although the film thickness of the copper foil layer 104 is not specifically limited, Preferably it is 0.1 micrometer or more and 5 micrometers or less, More preferably, they are 0.5 micrometer or more and 3 micrometers or less. By making the film thickness of the copper foil layer 104 into this range, the particle size of the crystal grain of the copper foil layer 104 can be prepared. Thereby, fluctuation | variation in the orientation in the film thickness direction of the copper foil layer 104 can be suppressed.

By the above, the orientation on the upper surface 20 of the copper foil layer 104 can be controlled, for example, the ratio of the crystal surface (that is, the orientation property from the lower surface 22 to the upper surface 20 of the copper foil layer 104). ) May be the same, for example, the ratio of the plane orientation 200 measured by the XRD thin film method, or the ratio of the plane orientation 200 and the plane orientation 220 to be the same. The same thing as said here allows a difference in a manufacturing process, for example, the ratio of the surface orientation 200 in the lower surface 22 of the copper foil layer 104 is the surface orientation 200 in the upper surface 20. It means within ± 5% of the ratio of. Therefore, it can be said that the ratio of the surface orientation of the lower surface 22 of the copper foil layer 104 measured by the XRD thin film method is equivalent to the ratio of the upper surface of the copper foil layer 104.

Moreover, even in the upper surface 20 of the copper foil layer 104 after forming the copper clad laminated board 100 by heat press molding, the orientation has the value of the copper foil layer (copper foil with carrier foil of a peelable type) before heat press molding, have. As conditions for heat press molding here, it is set as 1 h and pressure 3 MPa at 200 degreeC, for example. Although the reason why a ratio is maintained in this way is not clear, it is inferred that the average particle diameter of the crystal grain in the copper foil layer 104 is small, this average particle diameter is equipped to some extent, and the like.

Therefore, even before and after the etching process of the copper foil layer 104 described later, the upper surface 20 of the copper foil layer 104 (that is, the contact surface with the metal layer 116 (for example, the electroless plating layer 110)). It can be said that the ratio of the surface orientation 200 and the ratio of the surface orientation 200 and the surface orientation 220 are the same.

It is preferable that the copper foil layer 104 of this embodiment has the crystal grain whose average length of a long side is 2 micrometers or less. As a shape of the crystal grain in the copper foil layer 104, it becomes a columnar shape and a triangular pyramid shape, for example. For this reason, the maximum length of the crystal grain of the copper foil layer 104 is made into a long side at the time of a cross section. The average length of this long side is 10 μm in length and 10 μm in width between approximately 10,000 and 12,000 times using Focused Ion Beam Scanning Ion Microscope (FIB-SIM) or Focused Ion Beam Scanning Electron Microscope (FIB-SEM). An average is computed from the cross-sectional image of, and it computes as an average value of three visual field images in total. Thereby, the etching characteristic of the copper foil layer 104 improves.

Moreover, in the copper foil layer 104 of this embodiment, the area ratio occupied by the crystal grain whose long side average length is 2 micrometers or less becomes like this. Preferably it is 80% or more, More preferably, it is 85% or more, More preferably, Is 90% or more. This area ratio image-processes the visual field of the above-mentioned cross-sectional image, and calculates it as an average value of three visual fields in total. Thereby, the etching characteristic of the copper foil layer 104 improves.

Here, the detailed formation method of the peelable type copper foil used for the copper foil layer 104 is demonstrated.

It does not specifically limit as a manufacturing method of the copper foil used for this embodiment, For example, when manufacturing the peelable type copper foil which has a carrier, metal etc. which become a peeling layer on carrier foil of thickness 10-50 micrometers, etc. Inorganic compound or organic compound layer is formed, and copper foil is formed by plating process on the peeling layer. As the conditions of the plating treatment, for example, when a copper sulfate bath is used, sulfuric acid 50-100 g / L, copper 30-100 g / L, liquid temperature 20 ° C.-80 ° C., current density 0.5-100 A / dm 2, When a pyrophosphoric acid copper bath is used, potassium pyrophosphate 100 to 700 g / L, copper 10 to 50 g / L, liquid temperature 30 ° C. to 60 ° C., pH 8 to 12, and current density of 1 to 10 A / dm 2 can be used. have. Moreover, you may add various additives in the said bath in consideration of the physical property and smoothness of copper foil. In addition, the metal foil of the peelable type is a metal foil which has a carrier, and is a metal foil which can remove a carrier.

The said peeling layer is an inorganic compound or organic compound layers, such as a metal substance, and if it can peel even if it receives the heat processing between 100-300 degreeC at the time of lamination | stacking, a well-known thing can be used. As the metal oxide, for example, zinc, chromium, nickel, copper, molybdenum, alloys, mixtures of metals and metal compounds are used. It is preferable to use what consists of 1 type (s) or 2 or more types chosen from a nitrogen containing organic compound, a sulfur containing organic compound, and a carboxylic acid as an organic compound.

It is preferable that the said nitrogen containing organic compound is a nitrogen containing organic compound which has a substituent. Specifically, 1,2,3-benzotriazole (hereinafter referred to as "BTA") which is a triazole compound having a substituent, carboxybenzotriazole (hereinafter referred to as "CBTA"), N ', N' -Bis (benzotriazolylmethyl) urea (hereinafter referred to as "BTD-U"), 1H-1,2,4-triazole (hereinafter referred to as "TA") and 3-amino-1H-1 , 2,4-triazole (hereinafter, referred to as "ATA") and the like are preferably used.

Examples of the sulfur-containing organic compound include mercaptobenzothiazole (hereinafter referred to as "MBT"), thiocyanuric acid (hereinafter referred to as "TCA"), and 2-benzimidazole thiol (hereinafter referred to as "BIT"). ) And the like are preferable.

It is preferable to use monocarboxylic acid especially as carboxylic acid, and it is preferable to use an oleic acid, a linoleic acid, a linoleic acid, etc. especially.

As described above, desired orientation can be realized on the upper surface of the copper foil layer 104 of the present embodiment by appropriately controlling the production method, such as increasing the electrolytic density or decreasing the film thickness.

In addition, the adhesion between the copper foil layer 104 and the insulating layer 102 is at a practical level or at least on the lower surface 22 (surface in contact with one surface of the insulating layer 102) of the copper foil layer 104 used in the present embodiment. Surface treatment may be performed in order to make it more than that. As a roughening process with respect to the metal foil used for the copper foil layer 104, any one of antirust process, chromate process, silane coupling process, or a combination thereof is mentioned, for example. Any surface treatment means can be appropriately selected in accordance with the resin material constituting the insulating layer 102.

The antirust treatment can be carried out by forming a thin film on metal foil by, for example, sputtering, electroplating or electroless plating of any one of metals such as nickel, tin, zinc, chromium, molybdenum and cobalt or alloys thereof. Can be. In terms of cost, electroplating is preferable. In order to facilitate precipitation of metal ions, a complexing agent such as citrate, tartarate, sulfamic acid and the like may be added. The plating solution is usually used in an acidic region and is carried out at a temperature of room temperature (for example, 25 ° C) to 80 ° C. Plating conditions are suitably selected from the range of the current density of 0.1-10 A / dm <2>, energization time 1-60 second, Preferably 1-30 second. Although the amount of antirust treatment metal differs according to the kind of metal, 10-2000 micrograms / dm <2> in total is suitable. If the antirust treatment is too thick, etching inhibition and electrical properties are lowered, and if too thin, the peel strength with the resin may be a factor.

Moreover, when cyanate resin is included in the resin composition which comprises the insulating layer 102, it is preferable that antirust process is performed by the metal containing nickel. In this combination, the fall of peeling strength in a heat resistant deterioration test and a moisture deterioration test is small, and it is useful.

As the chromate treatment, an aqueous solution containing hexavalent chromium ions is preferably used. The chromate treatment is possible by a simple dipping treatment, but is preferably carried out by cathodic treatment. It is preferable to carry out on the conditions of 0.1-50 g / L sodium dichromate, pH 1-13, bath temperature 0-60 degreeC, current density 0.1-5 A / dm <2>, and electrolysis time 0.1-100 second. It can also be carried out using chromic acid or potassium dichromate instead of sodium dichromate. In addition, the chromate treatment is preferably superimposed on the rust prevention treatment. Thereby, adhesiveness of the insulated resin composition layer (insulating layer 102) and metal foil (copper foil layer 104) can be improved more.

As a silane coupling agent used for the said silane coupling process, epoxy functional silanes, such as 3-glycidoxy propyl trimethoxysilane and 2- (3, 4- epoxycyclohexyl) ethyl trimethoxysilane, for example. Amino functional silanes such as 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, Acrylic functional silanes, such as olefin functional silanes, such as a vinyl trimethoxysilane, a vinylphenyl trimethoxysilane, and a vinyl tris (2-methoxyethoxy) silane, and 3-acryloxypropyl trimethoxysilane, 3-metha Methacryl functional silanes, such as kryloxypropyl trimethoxysilane, and mercapto functional silanes, such as 3-mercaptopropyl trimethoxysilane, etc. are used. These may be used independently or may be used in mixture of multiple. These coupling agents are dissolved and used in a solvent such as water at a concentration of 0.1 to 15 g / L, and the silane coupling agent is adsorbed onto the metal foil by applying or electrodeposition the obtained solution to the metal foil at a temperature of room temperature to 50 ° C. A film is formed on metal foil by these silane coupling agents condensing-bonding with the hydroxyl group of the antirust process metal of the metal foil surface. After the silane coupling treatment, such bonding is stabilized by heating, ultraviolet irradiation or the like. In heat processing, it is preferable to perform the temperature of 100-200 degreeC, and drying for 2 to 60 second, for example. It is preferable to perform ultraviolet irradiation in the range of wavelength 200-400 nm and 200-2500 mJ / cm <2>, for example. Moreover, it is preferable to perform a silane coupling process to outermost layer of metal foil. When cyanate resin is included in the insulated resin composition which comprises the insulating layer 102, it is preferable to process with the coupling agent of an aminosilane system. This combination is useful because the peel strength of the heat resistance deterioration test and the moisture resistance deterioration test is small.

Moreover, as a silane coupling agent used for a silane coupling process, Preferably it is 60-200 degreeC, More preferably, it chemically reacts with the insulating resin composition which comprises the insulating layer 102 by heating of 80-150 degreeC. It is preferable. Thereby, the functional group in the said insulated resin composition and the functional group of a silane coupling agent chemically react, and it becomes possible to obtain more excellent adhesiveness. For example, it is preferable to use the silane coupling agent containing an amino functional silane about the insulated resin composition containing an epoxy group. This is due to the formation of a chemical bond in which the epoxy group and the amino group are easily formed by heat, and the bond is extremely stable against heat and moisture. Thus, as a combination which forms a chemical bond, an epoxy group-an amino group, an epoxy group-an epoxy group, an epoxy group-mercapto group, an epoxy group-a hydroxyl group, an epoxy group-a carboxyl group, an epoxy group-a cyanate group, an amino group-a hydroxyl group, an amino group-a carboxyl group, an amino group-a cyanate And the like are exemplified.

Moreover, it is preferable to use a liquid epoxy resin at normal temperature as an insulation resin of the insulation resin composition used for this embodiment. In this case, since the viscosity at the time of melting falls largely, wettability in an adhesive interface improves and an epoxy resin is used. Chemical reaction of and a silane coupling agent tends to occur, and as a result, firm peel strength is obtained. Specifically, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and phenol novolac type epoxy resins having an epoxy equivalent of about 200 are preferable.

Moreover, when an insulated resin composition contains a hardening | curing agent, it is preferable to use especially a heat-hardening type latent hardening | curing agent as a hardening | curing agent. That is, when the functional group in the insulating resin composition and the functional group of the silane coupling agent react chemically, the curing agent is selected so that the reaction temperature of the functional group in the insulating resin composition and the functional group of the silane coupling agent becomes lower than the temperature at which the curing reaction of the insulating resin composition is started. It is desirable to. Thereby, reaction of the functional group in an insulated resin composition and the functional group of a silane coupling agent is performed preferentially and selectively, and adhesiveness of a metal foil (copper foil layer 104) and an insulated resin composition layer (insulating layer 102) becomes higher. As a thermosetting latent hardening | curing agent with respect to the insulated resin composition containing an epoxy resin, solid dispersion-heat dissolving type hardening | curing agent and urea, such as a dicyandiamide, a dihydrazide compound, an imidazole compound, an amine-epoxy adduct, for example, Reactive group block type hardening | curing agents, such as a compound, an onium salt, a boron trichloride amine salt, and a block carboxylic acid compound, are mentioned.

The prepreg and rough surface containing the above insulating resin composition are finely and uniformly roughened, and the ultra-thin copper foil with carrier foil subjected to the surface treatment is laminated and integrated by the method described above, and FIG. The copper clad laminated board 10 with carrier foil shown to the above can be obtained. Subsequently, as shown in FIG.7 (b), by removing this carrier foil layer 106, the copper clad laminated board 100 which has the copper foil layer 104 on both surfaces of the insulating layer 102 is obtained. At this time, it is preferable that the upper limit of Ra of the surface (that is, the surface which contacts copper foil) of the carrier foil layer 106 facing the surface of copper foil is 1.0 micrometer or less, It is more preferable that it is 0.4 micrometer or less, It is especially preferable that it is 0.2 micrometer or less Do. Although the lower limit of Ra is not specifically limited, 0.05 or more are preferable. On the other hand, it is preferable that the upper limit of Rz in the surface is 4.0 micrometers or less, It is more preferable that it is 2.0 micrometers or less, It is especially preferable that it is 1.0 micrometer or less. Although the lower limit of Rz is not specifically limited, 0.1 micrometer or more is preferable. In addition, it is not limited to this aspect, The copper foil layer 104 should just be formed in at least 1 surface of the insulating layer 102, and may be formed in the whole surface or one part of the insulating layer 102. FIG.

In the present embodiment, the insulating layer 102 of the present embodiment is controlled by appropriately controlling the manufacturing method such as reducing the roughness of the surface of the carrier foil and making the grain size of the grains small and uniform, or even small and uniform. Rp and Rku on one side 30 of can be in the above range.

Next, as shown in FIG.7 (c), the through hole 108 for interlayer connection is formed in the copper clad laminated board 100. Then, as shown to FIG. As the method for forming the through hole 108, various known means can be used. For example, when forming the through hole 108 having a hole diameter of 100 µm or more, a means for using a drill or the like from the viewpoint of productivity may be used. When forming the through-hole 108 which is suitable and 100 micrometers or less, the means which use gas lasers, such as a carbon dioxide gas and an excimer, and solid-state lasers, such as YAG, are suitable.

Next, although a catalyst nucleus can be provided on at least the copper foil layer 104, in this embodiment, a catalyst nucleus is provided on the front surface of the copper foil layer 104, and on the inner wall surface of the through hole 108. As shown in FIG. Although it does not specifically limit as this catalyst nucleus, For example, a noble metal ion and a palladium colloid can be used. Subsequently, an electroless plating layer is formed using this catalyst nucleus as a nucleus, but smear removal using, for example, chemicals is performed on the surface of the copper foil layer 104 and the through hole 108 before the electroless plating treatment. You may carry out. The desmear treatment is not particularly limited, such as a wet method using an oxidizing agent solution having an organic decomposition effect or the like, and a plasma method for removing an organic residue by irradiating active species (plasma, radicals, etc.) with strong direct oxidation to the object. Known methods such as a dry method can be used. As a wet desmear process, after performing swelling process of a resin surface specifically, the method of etching by alkali treatment, and then carrying out neutralization treatment is mentioned.

Next, as shown in FIG.7 (d), the thin electroless plating layer 110 is formed on the copper foil layer 104 which provided the catalyst nucleus, and on the inner wall of the through-hole 108 by an electroless plating process. The electroless plating layer 110 electrically connects the copper foil layer 104 on the upper surface of the insulating layer 102 and the copper foil layer 104 on the lower surface thereof. For electroless plating, for example, those containing copper sulfate, formalin, a complexing agent, sodium hydroxide and the like can be used. Moreover, it is preferable to perform 100-250 degreeC heat processing after electroless plating, and to stabilize a plating film. The heat treatment at 120 to 180 ° C is particularly preferable in that a film capable of inhibiting oxidation can be formed. Moreover, the average thickness of the electroless plating layer 110 should just be a thickness which can perform the following electroplating, for example, it is enough about 0.1-1 micrometer. The inside of the through hole 108 may be filled with a conductive paste or an insulating paste, or may be filled with electric pattern plating.

Next, as shown in FIG. 7E, a resist layer 112 having a predetermined opening pattern is formed on the electroless plating layer 110 provided on the copper foil layer 104. This opening pattern is corresponded to the electrically conductive circuit pattern mentioned later. For this reason, the resist layer 112 is provided so that the non-circuit formation area | region on the copper foil layer 104 may be covered. In other words, the resist layer 112 is not formed on the through hole 108 and the conductor circuit forming region on the copper foil layer 104. The resist layer 112 is not particularly limited and known materials can be used, but liquid and dry films can be used. In the case of forming fine wirings, it is preferable to use a photosensitive dry film or the like as the resist layer 112. In order to form the resist layer 112, for example, a photosensitive dry film is laminated on the electroless plating layer 110, the non-circuit formation region is exposed and photocured, and the unexposed portion is dissolved and removed with a developer. In addition, the cured photosensitive dry film remaining becomes the resist layer 112. It is suitable for the thickness of the resist layer 112 to be about the same as the thickness of the conductor (plating layer 114) plated after that, or to make it thicker.

Next, as shown in FIG. 8A, the plating layer 114 is formed by electroplating at least on the inside of the opening pattern of the resist layer 112 and on the electroless plating layer 110. At this time, the copper foil layer 104 serves as a power feeding layer. In this embodiment, the plating layer 114 may be provided continuously over the upper surface of the insulating layer 102, the inner wall of the through-hole 108, and the lower surface. Although it does not specifically limit as such electroplating, The well-known method used by a normal printed wiring board can be used, For example, the method, such as making a current flow through this plating liquid in the state immersed in plating liquids, such as copper sulfate, can be used. have. Although the thickness of the plating layer 114 is not specifically limited, What is necessary is just to be usable as a circuit conductor, For example, it is preferable that it is the range of 1-100 micrometers, and it is more preferable that it is the range of 5-50 micrometers. The plating layer 114 may be a single layer or may have a multilayer structure. Although it does not specifically limit as a material of the plating layer 114, For example, copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, soldering etc. can be used.

Next, as shown in Fig. 8B, the resist layer 112 is removed using an alkaline stripping solution, sulfuric acid or a commercially available resist stripping solution.

Next, as shown in FIG. 8C, the electroless plating layer 110 and the copper foil layer 104 other than the region where the plating layer 114 is formed are removed. As a method of removing this copper foil layer 104, soft etching (flash etching) etc. are used, for example. Thereby, the pattern of the electrically conductive circuit 118 comprised by laminating | stacking the copper foil layer 104 and the metal layer 116 (electroless plating layer 110 and plating layer 114) can be formed.

As a cross-sectional shape of the electrically conductive circuit 118 of the printed wiring board 200 of 2nd Embodiment, in addition to a normal square shape as shown in FIG. 9, it is shown in the reverse taper shape shown in FIG. 9 (a), FIG. The fish cake shape shown or the concave shape shown in FIG. 9 (c) may be sufficient.

Here, the etching liquid used for the soft etching of this embodiment is demonstrated below. Although it does not specifically limit as etching liquid, When using the conventional diffusion rate type etching liquid, since the exchange | exchange of liquid worsens by the minute part of wiring, there exists a tendency for circuit formation property to deteriorate. For this reason, as for etching liquid, it is preferable to use the type in which reaction of copper and etching liquid advances not in a diffusion rate but into reaction rate. If reaction of copper and etching liquid is in the reaction rate, even if it diffuses further, etching speed will not change. That is, there is no difference in etching speed between the place where the liquid exchange is good and the place where the liquid is bad. As such a reaction rate etching liquid, what has a main component is an acid which does not contain hydrogen peroxide and a halogen element, for example. Since hydrogen peroxide is used as the oxidizing agent, precise etching rate control is possible by managing the concentration. Moreover, when a halogen element mixes in etching liquid, a dissolution reaction will become easy to become a diffusion rate. As the acid containing no halogen, nitric acid, sulfuric acid, organic acid and the like can be used, but sulfuric acid is preferable because it is inexpensive. In addition, when sulfuric acid and hydrogen peroxide are main components, it is preferable to set each concentration to 5-300 g / L and 5-200 g / L from a viewpoint of an etching rate and liquid stability. For example, ammonium persulfate, sodium persulfate, a sodium persulfate system, etc. are mentioned.

Thus, by selecting the etching characteristic and etching conditions of the copper foil layer 104 suitably, the electrically conductive circuit 118 of a desired shape is obtained. By the above, the printed wiring board 200 in which the electrically conductive circuit 118 was formed in both surfaces of the insulating layer 102 is obtained. Moreover, also in the manufacturing method of the printed wiring board 200 of 2nd Embodiment, the effect similar to 1st Embodiment is acquired.

As shown in FIG. 8 (d-1), the solder resist layer 120 may be formed so as to cover the insulating layer 102 and a part of the conductive circuit 118. As the soldering resist layer 120, the filler or base material which is excellent in insulation may be included, for example, and heat resistant resin compositions, such as photosensitive resin, a thermosetting resin, and a thermoplastic resin, are used. Next, you may further form the 1st plating layer 122 and the 2nd plating layer 124 on the electrically conductive circuit 118 in which the opening part of the soldering resist layer 120 is provided. As a result, the metal layer 116 may have a multilayer structure of two or more. As the first plating layer 122 and the second plating layer 124, a gold plating layer can be employed. As a method of gold plating, a conventionally well-known method may be sufficient and it does not specifically limit, For example, electroless nickel plating is performed on the plating layer 114 about 0.1-10 micrometers, and substitution gold plating is about 0.01-0.5 micrometers. After implementation, there are methods such as electroless gold plating of about 0.1 to 2 µm. By the above, the printed wiring board 202 shown to FIG. 8 (d-1) is obtained.

In addition, as shown in FIG. 8 (d-2), the first plating layer 122 and the second plating layer 124 may be formed around the conductive circuit 118 without forming the solder resist layer 120. As these 1st plating layer 122 and the 2nd plating layer 124, you may employ | adopt the laminated body of a nickel plating layer and a gold plating layer, for example. By the above, the printed wiring board 204 shown to FIG. 8 (d-2) is obtained.

A semiconductor chip (not shown) can be mounted on these printed wiring boards 200, 202, and 204 to obtain a semiconductor device.

(Third Embodiment)

Next, the manufacturing method of the printed wiring board of 3rd Embodiment is demonstrated.

10-12 is sectional drawing which shows the procedure of the manufacturing process of the manufacturing method of the printed wiring board of 3rd Embodiment. The manufacturing method of the printed wiring board of 3rd Embodiment uses the printed wiring board 200, 202, and 204 obtained by 2nd Embodiment as an inner layer circuit board, and forms a buildup layer further on this inner layer circuit board, for example.

First, the printed wiring board 200 obtained by FIG. 8 (c) is used as an inner circuit board. The inner layer circuit (conductive circuit 118) of this printed wiring board 200 is subjected to a roughening process. Here, roughening process means giving chemical liquid process, plasma process, etc. to the conductor circuit surface. As the roughening treatment, for example, a blackening treatment using redox or a chemical liquid treatment using a known roughening liquid of sulfuric acid-hydrogen peroxide can be used. Thereby, the adhesiveness of the interlayer insulation material which comprises the insulating layer 130, and the electrically conductive circuit 118 of the printed wiring board 200 can be improved. In addition, the inner circuit board is not particularly limited in place of the printed wiring board 200 obtained in the second embodiment, but is usually formed by laminating a prepreg or a resin composition layer containing no base material by a plating through hole method, a buildup method, or the like. It is also possible to use a multilayer printed wiring board. You may form the conductor circuit layer used as an inner layer circuit by a conventionally well-known circuit formation method. Moreover, in a multilayer printed wiring board, through-holes are formed by drilling, laser processing, etc. to the laminated body used as the core layer (the laminated body obtained by laminating | stacking two or more prepregs), and the laminated board with metal, and then forming by a plating etc. Both inner layer circuits may be electrically connected.

Next, as shown in Fig. 10 (a), the copper foil layer 105 (carrier) with the insulating layer 130 (prepreg) and the carrier foil layer 107 is provided on both sides of the printed wiring board 200 having the conductor circuit surface harmonized, respectively. Place ultra-thin copper foil with foil). Next, as shown in FIG.10 (b), a multilayer laminated board is formed by heat-pressing the laminated body which piled up these. Subsequently, as shown in FIG.10 (c), the carrier foil layer 107 is peeled off.

Next, as shown in FIG.10 (d), a part of the insulating layer 130 and the copper foil layer 105 is removed, and the hole 109 is formed. A portion of the surface of the conductive circuit 118 is exposed at the bottom of the hole 109. Although it does not specifically limit as a method of forming this hole 109, For example, the method of forming the blind via hole of 100 micrometers or less of hole diameters using gas lasers, such as a carbon dioxide gas and an excimer, and solid-state lasers, such as YAG, etc. Can be used. In addition, although the hole 109 is shown as a non-through hole in FIG.10 (d), it may be a through hole. In the case of through-holes, a laser drilling machine may be used for laser irradiation.

Next, as shown in FIG. 11A, a thin electroless plating layer 111 is formed on the conductive circuit 118 to which the above-described catalyst nucleus has been applied, on the inner wall of the hole 109, and on the copper foil layer 105. do. The electroless plating layer 111 is formed in the same manner as the electroless plating layer 110 described above. As described above, before the electroless plating, a desmear treatment such as smear removal with a chemical liquid may be performed. In addition, the thickness of the electroless plating layer 110 should just be the thickness which can perform the following electroplating, and is enough in about 0.1-1 micrometer. The inside of the hole 109 (blind via hole) may be filled with a conductive paste or an insulating paste, or may be filled with electric pattern plating.

Next, as shown in FIG. 11B, a resist layer 113 having an opening pattern corresponding to the conductor circuit pattern is formed on the electroless plating layer 110. In other words, by forming the resist layer 113, the non-circuit forming portion is masked. As this resist layer 113, the same thing as the resist layer 112 mentioned above can be used. It is suitable for the thickness of the resist layer 113 to be about the same as the thickness of the conductor circuit to plate after that, or to make it thicker.

Next, as shown in FIG.11 (c), the plating layer 132 is formed in the opening pattern of the resist layer 113. Next, as shown in FIG. The plating layer 132 may be formed on the conductive circuit 118 inside the hole 109 or may be formed on the electroless plating layer 111 inside the opening pattern. Electroplating for forming the plating layer 132 may use the same method as the above-described plating layer 114. What is necessary is just to be able to use the thickness of this plating layer 132 as a circuit conductor, For example, it is preferable that it is the range of 1-100 micrometers, and it is more preferable that it is the range of 5-50 micrometers.

Next, as shown in Fig. 12A, the resist layer 113 is peeled off in the same manner as the resist layer 112 described above. Next, as shown to FIG. 12 (b), the copper foil layer 105 and the electroless plating layer 111 are removed by soft etching (flash etching) similarly to the copper foil layer 104 mentioned above. Thereby, the electrically conductive circuit pattern comprised from the copper foil layer 105, the electroless plating layer 111, and the plating layer 132 can be formed. In addition, vias and pads electrically connected to the conductive circuit 118 can be formed by the plating layer 132. The printed wiring board 201 is obtained by the above.

12 (c-1), a solder resist layer 121 may be formed on the insulating layer 130, on the plating layer 132 of the conductive circuit pattern, and on a part of the plating layer 132 of the pad. . As the solder resist layer 121, the same solder paste layer 120 as that described above may be used. Next, you may further form the 1st plating layer 123 and the 2nd plating layer 125 which consist of a nickel plating layer and a gold plating layer, for example on the plating layer 132 in which the opening part of the soldering resist layer 121 is provided. . By the above, the printed wiring board 203 shown to FIG. 12 (c-1) is obtained.

As shown in Fig. 12C-2, the first plating layer 123 and the second plating layer 125 described above are formed around the conductive circuit pattern and around the pad without forming the solder resist layer 121. You may form. By the above, the printed wiring board 205 shown to FIG. 12 (c-2) is obtained. Also in 3rd Embodiment, the same effect as 1st and 2nd Embodiment is acquired.

Moreover, the modification of the manufacturing method of the printed wiring board of this embodiment is demonstrated using FIG.

Although the metal layer was selectively formed on the copper foil in the above-mentioned first to third embodiments, the point of forming the metal layer on the entire surface on the copper foil is different in this modification.

Hereinafter, the manufacturing method of the printed wiring board of this modification is demonstrated.

First, as shown to Fig.13 (a), the copper clad laminated board 10 with carrier foil is prepared. About this copper clad laminated board 10 with carrier foil, the carrier foil layer 106 is affixed on both surfaces of the insulating layer 102 with the copper foil layer 104. Subsequently, as shown in FIG.13 (b), the carrier foil layer 106 is removed from the copper clad laminated board 10 with carrier foil. Subsequently, as shown to FIG. 13 (c), the metal layer 115 (plating layer) is formed on the whole surface of the copper foil layer 104 by plating process. Subsequently, as shown in FIG. 13 (d), a resist layer 112 having a predetermined opening pattern is formed on the plane-shaped metal layer 115. Subsequently, as shown in FIG. 13E, the metal layer 115 and the copper foil layer 104 in the opening pattern of the resist layer 112 are removed by, for example, etching. Thereafter, the resist layer 112 is removed as shown in Fig. 13F. Thereby, the pattern of the electrically conductive circuit 119 comprised from the copper foil layer 104 and the metal layer 115 can be formed. By the above process, the printed wiring board 101 of this modification is obtained.

As mentioned above, according to this embodiment, it becomes possible to provide the manufacturing method of the printed wiring board excellent in the fine circuit processing of the ultra-thin copper foil with carrier foil, the shape of a fine circuit, and insulation reliability, and this printed wiring board.

The manufacturing method of the printed wiring board of this embodiment can be applied not only when forming a conductor circuit layer on both surfaces of a board | substrate for printed wiring boards, but also when forming a conductor circuit layer only on one surface of a board | substrate for printed wiring boards. Moreover, as shown in FIG.8 (c), the case of the multilayer printed wiring board of 3rd Embodiment can also be applied using a double-sided printed wiring board as an inner layer circuit board. Therefore, by the manufacturing method of the printed wiring board of this embodiment, both a single-sided printed wiring board, a double-sided printed wiring board, and a multilayer printed wiring board can be manufactured.

EMBODIMENT OF THE INVENTION Hereinafter, the electrolytic copper foil with carrier foil which concerns on this invention, and the copper clad laminated board using this copper foil are manufactured, and embodiment of the manufacturing method of the printed wiring board of this invention is described. Here, it demonstrates centering around the case where an electrolytic copper foil is used for carrier foil. Although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this.

Example

( Metal foil  1, manufacture)

Bonding interface layer and ultra-thin copper foil layer are formed in the carrier foil on the glossy surface of 18 micrometer-thick electrolytic copper foil (made by Mitsui Metal Co., Ltd., 3EC-VLP, gloss surface Ra = 0.2 micrometer, Rz = 1.5 micrometer) did. As a manufacturing condition, carrier foil was first immersed in an acid washing tank (dilute sulfuric acid solution, 150g / L, liquid temperature 30 degreeC) for 20 second, and the oil component, oxide film, etc. of the surface were removed. Next, it immersed in the joining interface formation tank (carboxybenzotriazole solution, 5g / L, 40 degreeC of liquid temperature, pH5), and formed the joining interface layer on the gloss surface of carrier foil. Next, an anode electrode of a flat plate with respect to one surface of the carrier foil while being immersed in a bulk copper forming tank (copper sulfate solution; sulfuric acid concentration 150 g / L, copper concentration 65 g / L, gelatin concentration 10 ppm, chloride ion 20 ppm, liquid temperature 45 ° C.). (Lead) was arrange | positioned in parallel, and it electrolyzed on the smooth plating conditions of a current density of 15 A / dm <2>, and formed the bulk copper layer of 1.5 micrometers. Next, the anode of the plate with respect to one side of the carrier foil while immersing in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentration 100g / L, sulfuric acid solution of 18g / L, sulfuric acid solution 25 ℃) on the surface of the bulk copper layer Electrodes (lead) were arrange | positioned in parallel and were electrolyzed by the small plating conditions of 10 A / dm <2> of current densities. Next, while immersing in a lid plating tank (copper sulfate solution; sulfuric acid concentration 150 g / L, copper concentration 65 g / L, liquid temperature 45 ° C.) for preventing fine copper particles from falling off, under smooth plating conditions of a current density of 20 A / dm 2. Electrolysis was carried out to form a fine roughness of 0.5 mu m to produce a total thickness of 2.0 mu m ultrathin copper foil. Next, it was immersed in an antirust treatment tank (zinc sulfate solution; sulfuric acid concentration 70g / L, zinc concentration 20g / L, liquid temperature 40 degreeC), electrolytically with a current density of 15A / dm <2>, and antirust process was performed using zinc. Here, it was set as the soluble anode which used the zinc plate as an anode electrode. Next, it was immersed for 4 second in the chromate treatment tank (chromic acid solution; chromic acid concentration 5g / L, pH 11.5, liquid temperature 55 degreeC). Finally, the copper foil with a carrier foil was obtained by passing through the inside of the furnace heated to the atmospheric temperature of 110 degreeC with the heater in the drying process for 60 second. In addition, it is immersed and washed in the water washing tank which can wash about 30 seconds between processes for each tank.

( Metal foil  2, manufacture)

Bonding interface layer and ultra-thin copper foil layer are formed in the carrier foil on the glossy surface of 12 micrometer-thick electrolytic copper foil (made by Furukawa Electric Co., F2-WS, and surface roughness of Ra = 0.2 micrometer, Rz = 1.2 micrometer) did. As a manufacturing condition, carrier foil was first immersed in an acid washing tank (dilute sulfuric acid solution, 150g / L, liquid temperature 30 degreeC) for 20 second, and the oil component, oxide film, etc. of the surface were removed. Next, it was immersed in the joining interface formation tank (carboxybenzotriazole solution, 5 g / L, 40 degreeC of liquid temperature, pH 5), and the joining interface layer was formed in the gloss surface of carrier foil. Next, an anode electrode of a flat plate with respect to one surface of the carrier foil while being immersed in a bulk copper forming tank (copper sulfate solution; sulfuric acid concentration 150 g / L, copper concentration 65 g / L, gelatin concentration 10 ppm, chloride ion 20 ppm, liquid temperature 45 ° C.). (Lead) was arrange | positioned in parallel, and it electrolyzed on the smooth plating conditions of 20 A / dm <2> of current density, and formed the bulk copper layer of 1.5 micrometers. Next, the anode of the plate with respect to one side of the carrier foil while immersing in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentration 100g / L, sulfuric acid solution of 18g / L, sulfuric acid solution 25 ℃) on the surface of the bulk copper layer Electrodes (lead) were arrange | positioned in parallel and were electrolyzed by the small plating conditions of 10 A / dm <2> of current densities. Next, while immersing in a lid plating tank (copper sulfate solution; sulfuric acid concentration 150 g / L, copper concentration 65 g / L, liquid temperature 45 ° C.) for preventing fine copper particles from falling off, under smooth plating conditions of a current density of 20 A / dm 2. Electrolysis was performed to form a fine roughness of 0.5 mu m to produce ultrathin copper foil having a total thickness of 2.0 mu m. Next, it was immersed in an antirust treatment tank (zinc sulfate solution; sulfuric acid concentration 70g / L, zinc concentration 20g / L, liquid temperature 40 degreeC), electrolytically with a current density of 15A / dm <2>, and antirust process was performed using zinc. Here, it was set as the soluble anode which used the zinc plate as an anode electrode. Next, it was immersed for 4 second in the chromate treatment tank (chromic acid solution; chromic acid concentration 5g / L, pH 11.5, liquid temperature 55 degreeC). Finally, the copper foil with a carrier foil was obtained by passing through the inside of the furnace heated to the atmospheric temperature of 110 degreeC with the heater in the drying process for 60 second. In addition, it is immersed and washed in the water washing tank which can wash about 30 seconds between processes for each tank.

( Metal foil  3, manufacture)

Bonding interface layer and ultra-thin copper foil layer are formed in the carrier foil on the glossy surface of 12 micrometer-thick electrolytic copper foil (made by Furukawa Electric Co., F2-WS, and surface roughness of Ra = 0.2 micrometer, Rz = 1.2 micrometer) did. As a manufacturing condition, carrier foil was first immersed in an acid washing tank (dilute sulfuric acid solution; 150 g / L, liquid temperature 30 degreeC) for 20 second, and the oil component, oxide film, etc. of the surface were removed. Next, it was immersed in the joining interface formation tank (carboxybenzotriazole solution; 5 g / L, 40 degreeC of liquid temperature, pH 5), and the joining interface layer was formed in the gloss surface of carrier foil. Next, bulk copper forming tank 1 (copper pyrophosphate solution; potassium pyrophosphate concentration 320g / L, copper concentration 80g / L, gelatin concentration 10ppm, chloride ion 10ppm, 25% ammonia water 2ml / L, pH 8.5, liquid temperature 40 degreeC) ), While the anode electrode (lead) of the flat plate is arranged in parallel with one surface of the carrier foil, and is electrolyzed under smooth plating conditions of a current density of 7 A / dm 2, and then the bulk copper forming bath 2 (copper sulfate solution; sulfuric acid) Concentrated 100 g / L, copper concentration 200 g / L, gelatin concentration 10 ppm, chloride ion 20 ppm, liquid temperature 45 ° C.), while the anode electrode (lead) of the plate was placed in parallel with one side of the carrier foil, the current density was 10 A / Electrolysis was carried out under a smooth plating condition of d 2 m 2 to form a bulk copper layer of 1.5 μm. Next, the anode of the plate with respect to one side of the carrier foil while immersing in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentration 100g / L, sulfuric acid solution of 18g / L, sulfuric acid solution 25 ℃) on the surface of the bulk copper layer Electrodes (lead) were arrange | positioned in parallel and were electrolyzed by the small plating conditions of 10 A / dm <2> of current densities. Next, while immersing in a lid plating tank (copper sulfate solution; sulfuric acid concentration 150 g / L, copper concentration 65 g / L, liquid temperature 45 ° C.) for preventing fine copper particles from falling off, under smooth plating conditions of a current density of 20 A / dm 2. It electrolyzed and formed 0.5 micrometer fine roughness, and produced ultra-thin copper foil of 2.0 micrometers in total thickness. Next, it was immersed in an antirust treatment tank (zinc sulfate solution; sulfuric acid concentration 70g / L, zinc concentration 20g / L, liquid temperature 40 degreeC), electrolytically with a current density of 15A / dm <2>, and antirust process was performed using zinc. Here, it was set as the soluble anode which used the zinc plate as an anode electrode. Next, it was immersed for 4 second in the chromate treatment tank (chromic acid solution; chromic acid concentration 5g / L, pH 11.5, liquid temperature 55 degreeC). Finally, the copper foil with a carrier foil was obtained by passing the inside of the furnace heated to the atmospheric temperature of 110 degreeC with the heater in the drying process over 60 second. In addition, it is immersed and washed in the water washing tank which can wash about 30 seconds between processes for each tank.

( Example  One)

8.5 weight part of biphenyl aralkyl type phenol resins (Meiwa Kasei Co., Ltd., MEH7851-4H) as a phenol hardening agent, a naphthalene modified cresol novolak epoxy resin (made by DIC Corporation, HP-5000) as an epoxy resin 17 weight part of cyanate resin (made by LONZA company, Primaset PT-30), 65.5 weight part of spherical fused silica (made by Admatex company, SO-25R, average particle diameter: 0.5 micrometer), epoxy silane (made by Shin-Etsu Chemical Co., Ltd., KBM-) 403) 0.5 part by weight was dissolved in methyl ethyl ketone. Next, it stirred using the high speed stirring apparatus and adjusted so that it may be 70 weight% of non volatile matters, and the resin varnish was prepared.

The resin varnish was impregnated into a glass woven fabric (basic weight 104 g, thickness 87 탆, Nittobo E glass woven fabric, WEA-116E), dried in a heating furnace at 150 ° C. for 2 minutes, and the varnish solid content in the prepreg was about 50% by weight. Prepreg was obtained.

The two prepregs were stacked, and the ultra-thin copper foil (metal foil 1) with carrier foil was piled up and heat-molded by pressure at 3MPa and the temperature of 200 degreeC for 1 hour, and the insulating layer obtained the laminated board which has copper foil on both surfaces of thickness 0.20mm.

(Printed wiring board)

Carrier foil of the laminated sheet obtained in the Example was peeled off (FIG. 7 (b)), and it showed diameter 75 by carbon dioxide gas laser (ML605GTX3-5100U2 by Mitsubishi Electric Corporation) from ultra-thin metal foil phase, as shown to FIG. 7 (c). The through-hole of micrometer was opened, it was immersed in aqueous solution of 60 g / L potassium permanganate and 45 g / L sodium hydroxide for 2 minutes at 80 degreeC of liquid temperature, and was desmeared.

Subsequently, the solution is immersed in a palladium solution (Kamimura Kogyo Co., Ltd., MAT-2B / MAT-2A) at a liquid temperature of 55 ° C. for 5 minutes, and a catalyst is used, using Kamimura Kogyo Co., Ltd., through-cupper PEA-6A, It was immersed for 15 minutes at 36 degreeC of liquid temperature, and 0.7 micrometer of electroless plating layers were formed (FIG. 7 (d)).

A glass with a 25 mm-thick ultraviolet photosensitive dry film (manufactured by Asahi Chemical Co., Ltd., Sanport UFG-255) bonded to the surface of this electroless plating layer by a hot roll laminator and a pattern having a minimum line width / line of 20/20 μm drawn. Using a mask (manufactured by Topic Co., Ltd.), the position was adjusted, and the resultant was exposed with an exposure apparatus (Onosoki EV-0800) and developed with an aqueous solution of sodium carbonate to form a resist mask (Fig. 7 (e)). Next, electrolytic copper plating (Okuno Pharmaceutical Co., Ltd. 81-HL) was performed for 25 minutes at 3 A / dm <2> for 25 minutes using an electroless plating layer as a feed layer electrode, and the pattern of the copper wiring of thickness about 20 micrometers was formed (FIG. 8 (a)). ). Next, the said resist mask was peeled off with the monoethanolamine solution (R-100 by Mitsubishi Gas Chemical Corporation) using a peeler (FIG. 8 (b)). Then, the electroless plating layer and the base copper foil (2 µm), which are the feed layer, were removed by treatment for 180 seconds by flash etching (CPE-800 manufactured by Mitsubishi Gas Chemical Co., Ltd., liquid temperature: 30 ° C, spray pressure 0.23 MPa), and L / S = 20/20 µm. Phosphorus pattern was formed (pattern etching) and the printed wiring board was obtained (FIG. 8 (c)).

Finally, as shown in Fig. 8 (d-1), a solder resist (PSR4000 / AUS308, manufactured by Toyo Ink Co., Ltd.) is formed on the circuit surface, and the nickel plating layer (ICP Nicolon GM, manufactured by Okuno Pharmaceutical Co., Ltd.) is subjected to a liquid temperature of 80 ° C. Was immersed for 12 minutes at 2.5 占 퐉, and then a gold plated layer (Flash Gold 330, manufactured by Okuno Pharmaceutical Co., Ltd.) was immersed at 80 占 폚 for 9 minutes to form 0.05 占 퐉 to obtain a printed wiring board. As shown in Fig. 8 (d-2), a solder resist may not be formed on the circuit surface.

( Example  2)

It carried out similarly to Example 1 except having changed the ultra-thin copper foil with carrier foil into the metal foil 2.

( Example  3)

It carried out similarly to Example 1 except having changed the ultra-thin copper foil with carrier foil into the metal foil 3.

( Example  4)

It carried out similarly to Example 1 except having changed the conditions of the flash etching of the electroless plating layer which is a power supply layer, and base copper foil (2 micrometers) as follows.

The electroless plating layer and base copper foil (2 micrometers) which are a power supply layer were removed by processing for 240 second by flash etching (CPE-800 by Mitsubishi Gas Chemical Co., Ltd., liquid temperature: 30 degreeC, spray pressure 0.23 MPa), and L / S = 20/20 A micrometer pattern was formed (pattern etching) and the printed wiring board was obtained.

( Example  5)

It carried out similarly to Example 1 except having changed the resin composition used for a laminated board. As an epoxy resin, 11 weight part of biphenyl aralkyl type epoxy resins (made by Nippon Kayaku Co., Ltd.), 20 weight part of bismaleimide compounds (BMI-70 by Keikasei Co., Ltd.), 4,4'- diamino di 3.5 weight part of phenylmethane, 65 weight part of aluminum hydroxides (HP-360 by Showa Denko), and 0.5 weight part of epoxy silanes (KBM-403 by Shin-Etsu Chemical Co., Ltd.) were mixed and dissolved in methyl ethyl ketone. Next, it stirred using the high speed stirring apparatus and adjusted to 70 weight% of non volatile matters, and prepared the resin varnish.

The resin varnish was impregnated into a glass woven fabric (a basis weight of 104 g, a thickness of 87 μm, manufactured by Nittobo E glass woven fabric, WEA-116E), dried for 2 minutes in a heating furnace at 150 ° C., and the varnish solid content in the prepreg was about 50% by weight. Prepreg was obtained. The two prepregs were stacked, and the ultra-thin copper foil (metal foil 1) with carrier foil was piled up and heat-molded by pressure at 3MPa and the temperature of 200 degreeC for 1 hour, and the insulating layer obtained the laminated board which has copper foil on both surfaces of thickness 0.20mm.

( Comparative Example  One)

( Metal foil  4, manufacture)

Bonding interface layer and ultra-thin copper foil layer are formed in the carrier foil on the glossy surface of 35 micrometer-thick electrolytic copper foil (made by Furukawa Electric Co., F2-WS, the surface roughness of a glossy surface Ra = 0.2 micrometer, Rz = 1.2 micrometer) did. As a manufacturing condition, carrier foil was first immersed in an acid washing tank (dilute sulfuric acid solution, 150g / L, liquid temperature 30 degreeC) for 20 second, and the oil component, oxide film, etc. of the surface were removed. Next, it immersed in the joining interface formation tank (carboxybenzotriazole solution, 5g / L, 40 degreeC of liquid temperature, pH5), and formed the joining interface layer on the gloss surface of carrier foil. Next, the anode electrode (lead) of a flat plate is arrange | positioned in parallel with one side of carrier foil, immersing in a bulk copper forming tank (copper sulfate solution; sulfuric acid concentration 150g / L, copper concentration 65g / L, liquid temperature 45 degreeC), Electrolysis was carried out under smooth plating conditions with a current density of 2 A / dm 2 to form a bulk copper layer of 1.5 μm. Next, the anode of the plate with respect to one side of the carrier foil while immersing in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentration 100g / L, sulfuric acid solution of 18g / L, sulfuric acid solution 25 ℃) on the surface of the bulk copper layer The electrodes (leads) were placed in parallel and electrolyzed for 7 seconds under a small plating condition of a current density of 10 A / dm 2. Next, while immersing in a lid plating tank (copper sulfate solution; sulfuric acid concentration 150 g / L, copper concentration 65 g / L, liquid temperature 45 ° C.) for preventing fine copper particles from falling off, under smooth plating conditions with a current density of 10 A / dm 2. Electrolysis was performed to form a fine roughness of 0.5 mu m to produce ultrathin copper foil having a total thickness of 2.0 mu m. Next, it was immersed in an antirust treatment tank (zinc sulfate solution; sulfuric acid concentration 70g / L, zinc concentration 20g / L, liquid temperature 40 degreeC), electrolytically with a current density of 10A / dm <2>, and antirust process was performed using zinc. Here, it was set as the soluble anode which used the zinc plate as an anode electrode. Next, it was immersed for 4 second in the chromate treatment tank (chromic acid solution; chromic acid concentration 5g / L, pH 11.5, liquid temperature 55 degreeC). Finally, the copper foil with a carrier foil was obtained by passing the inside of the furnace heated to the atmospheric temperature of 110 degreeC with the heater in the drying process over 60 second. In addition, it is immersed and washed in the water washing tank which can wash about 30 seconds between processes for each tank.

Except having changed the ultra-thin copper foil with carrier foil into the metal foil 4, it carried out similarly to Example 1, and obtained the printed wiring board.

( Comparative Example  2)

( Metal foil  5, manufacture)

Bonding interface layer and ultra-thin copper foil layer are formed in the carrier foil on the glossy surface of 35 micrometer-thick electrolytic copper foil (made by Furukawa Electric Co., F2-WS, the surface roughness of a glossy surface Ra = 0.2 micrometer, Rz = 1.2 micrometer) did. As a manufacturing condition, carrier foil was first immersed in an acid washing tank (dilute sulfuric acid solution; 150 g / L, liquid temperature 30 degreeC) for 20 second, and the oil component, oxide film, etc. of the surface were removed. Next, it was immersed in the joining interface formation tank (carboxybenzotriazole solution; 5 g / L, 40 degreeC of liquid temperature, pH 5), and the joining interface layer was formed in the gloss surface of carrier foil. Next, the carrier foil was immersed in a bulk copper forming tank 1 (copper pyrophosphate solution; potassium pyrophosphate concentration 320 g / L, copper concentration 80 g / L, 25% ammonia water 2 ml / L, pH 8.5, liquid temperature 40 ° C). The anode electrode (lead) of the flat plate is arranged in parallel with one surface, and it is electrolyzed under the smooth plating conditions of a current density of 1.5 A / dm 2, and then the bulk copper forming bath 2 (copper sulfate solution; sulfuric acid concentration 100 g / L, copper concentration) While immersing in 200 g / L, liquid temperature of 45 DEG C), the anode electrode (lead) of the flat plate is placed in parallel with one surface of the carrier foil, and is electrolyzed under smooth plating conditions of a current density of 3 A / dm &lt; 2 &gt; Formed. Next, the anode of the plate with respect to one side of the carrier foil while immersing in a fine copper particle forming tank (copper sulfate solution; sulfuric acid concentration 100g / L, sulfuric acid solution of 18g / L, sulfuric acid solution 25 ℃) on the surface of the bulk copper layer Electrodes (lead) were arrange | positioned in parallel and were electrolyzed under the small plating conditions of 5 A / dm <2> of current densities. Next, while immersing in a lid plating tank (copper sulfate solution; sulfuric acid concentration 150 g / L, copper concentration 65 g / L, liquid temperature 45 ° C.) for preventing fine copper particles from falling off, under smooth plating conditions with a current density of 10 A / dm 2. Electrolysis was performed to form a fine roughness of 0.5 mu m to produce ultrathin copper foil having a total thickness of 2.0 mu m. Next, it was immersed in an antirust treatment tank (zinc sulfate solution; sulfuric acid concentration 70g / L, zinc concentration 20g / L, liquid temperature 40 degreeC), electrolytically with a current density of 15A / dm <2>, and antirust process was performed using zinc. Here, it was set as the soluble anode which used the zinc plate as an anode electrode. Next, it was immersed for 4 second in the chromate treatment tank (chromic acid solution; chromic acid concentration 5g / L, pH 11.5, liquid temperature 55 degreeC). Finally, the copper foil with a carrier foil was obtained by passing through the inside of the furnace heated to the atmospheric temperature of 110 degreeC with the heater in the drying process for 60 second. In addition, it is immersed and washed in the water washing tank which can wash about 30 seconds between processes for each tank.

Except having changed the ultra-thin copper foil with carrier foil into the metal foil 5, it carried out similarly to Example 1, and obtained the printed wiring board.

(evaluation)

The following evaluation was performed using the printed wiring board obtained by each Example and the comparative example. An evaluation item is shown with the content and the obtained result is shown in Table 1.

(evaluation)

The following evaluation was performed using the printed wiring board obtained by each Example and the comparative example. An evaluation item is shown with the content and the obtained result is shown in Table 1. Moreover, SEM image of Example 1 and the comparative example 1 is shown to FIG. 16 and FIG.

(1) Surface roughness of the insulating layer (Rp, Rku)

Using a 3D laser microscope (device name VK-9710, manufactured by Keyence), the maximum peak height Rp of the roughness curve and the kurtosis (sharpness) Rku of the roughness curve were measured according to JISB0601: 2001 (no cutting value). The measurement performed the observation visual field surface at 100 micrometers x 100 micrometers about arbitrary 20 points (20 places) of a measurement piece, and made it the average value. In addition, peeling removal and the ultra-thin copper foil of the carrier foil of the said laminated board (FIG. 7 (a)) which made the whole surface etch with the copper chloride etching liquid were made into the sample.

(2) State of insulating layer surface after flash etching and presence or absence of copper residue

A scanning electron microscope (manufactured by Nippon Electronic Co., Ltd., apparatus name: JSM-6060LV) was used to determine from the SEM image observed from directly above. In addition, the thing immediately after wiring process (FIG. 8 (c)) was made into the sample in the manufacturing process of the said printed wiring board.

Each code is as follows.

(Circle): There is no stripe pattern, crater, and copper residue on the surface of insulating layer

X: Stripe shape, crater, or copper residue on the surface of an insulating layer

(3) Shape of pulsating foil at the time of thin wire processing of LS

A scanning electron microscope (manufactured by Nippon Electronic Co., Ltd., apparatus name: JSM-6060LV) was used to determine from the SEM image observed from directly above. In addition, the thing immediately after wiring process (FIG. 8 (c)) was made into the sample in the manufacturing process of the said printed wiring board.

Each code is as follows.

(Circle): No lower part remains in the vicinity of the insulation layer of a wiring circuit.

X: The lower part remains in the vicinity of the insulating layer of a wiring circuit

(4) ΔL = L1-L2

The cross-sectional shape of the wiring was observed using a scanning electron microscope (manufactured by Japan Electronics Co., Ltd .: JSM-6060LV), and the maximum width of the foil was calculated by calculating L1 and the minimum width of the electrical pattern plating by calculating L2. In addition, the sample used the printed wiring board (FIG. 8 (c)).

(5) Line BHAST of LS20 (L / S = 20㎛ / 20㎛)

Electrical insulation reliability between fine wirings was evaluated by continuous measurement under conditions of an applied voltage of 10V and a temperature of 130 ° C and a humidity of 85%. In addition, the sample used the printed wiring board (FIG. 12 (b)) obtained by the said Example. In addition, it terminated when the insulation resistance value became less than 10 <^8> ohms.

Each code is as follows.

○: More than 100 hours

X: It was less than 100 hours.

This application claims the priority based on Japanese Patent Application No. 2011-14127 for which it applied on January 26, 2011, and includes all that published here.

Claims (11)

Separating the carrier substrate from a laminate in which copper foil with a carrier substrate is laminated on at least one surface of the insulating layer,
Forming a metal layer thicker than the copper foil on the entire surface or selectively on the copper foil;
A step of obtaining a conductive circuit pattern composed of the copper foil and the metal layer by etching at least the copper foil,
In the said process of obtaining the said conductive circuit pattern, when measured by JIS B0601, Rp in the said 1 surface of the said insulating layer is 4.5 micrometers or less, and Rku is 2.1 or more, The manufacturing method of the printed wiring board. The method according to claim 1,
The manufacturing method of the printed wiring board in which Ra on the surface of the said copper foil opposing the said one surface of the said insulating layer is 1.0 micrometer or less. The method according to claim 1 or 2,
The said copper foil is a manufacturing method of the printed wiring board which has a crystal grain whose average length of a long side is 2 micrometers or less. The method according to claim 3,
The cross-sectional view WHEREIN: The manufacturing method of the printed wiring board whose area ratio which the said crystal grain which the average length of the said long side is 2 micrometers or less occupies is 80% or more. The method according to any one of claims 1 to 4,
The manufacturing method of the printed wiring board whose 10-point average roughness Rz of the surface of the said carrier base material which opposes the surface of the said copper foil is 0.1 micrometer or more and 5.0 micrometers or less. The method according to any one of claims 1 to 5,
The process of forming the metal layer on the front surface or selectively
Forming a resist having an opening pattern on the copper foil;
Forming a plating layer to be the metal layer by plating in the opening pattern and on the copper foil;
Removing the resist;
The step of obtaining the conductive circuit pattern includes a step of soft etching the copper foil. The method according to any one of claims 1 to 6,
Prior to the process of forming the metal layer on the front surface or selectively
Forming a through hole or a non-penetrating hole in the laminate;
Contacting the chemical liquid with at least an inner wall of the through hole or the non-penetrating hole;
The method of manufacturing a wiring board further comprising the step of forming an electroless plating layer on at least the copper foil and the inner wall of the through hole or on the inner wall of the non-penetrating hole by electroless plating. With insulation layer,
It is provided on one surface of the said insulating layer, and is provided with the conductive circuit pattern comprised from copper foil and a metal layer,
The printed wiring board with Rp of 4.5 micrometers or less, and Rku of 2.1 or more when measured by JIS B0601. The method according to claim 8,
The printed wiring board in which the said metal layer contains two or more plating films. The method according to claim 8 or 9,
In the planar view, when the maximum width of the said copper foil in the width direction orthogonal to the extending | stretching direction of the said conductive circuit pattern is made into L1, and the minimum width of the said metal layer is made into L2, said L1 is the same as L2, or L2 Small printed wiring board. The method of claim 10,
The printed wiring board in which the area of the said copper foil becomes small toward the 2nd surface from the 1st surface of the said copper foil in planar view.

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