JP6413654B2 - Circuit board and manufacturing method thereof - Google Patents

Description

  The present invention relates to a circuit board and a manufacturing method thereof.

  Circuit boards widely used in various electronic devices are required to have finer and higher density circuit wiring in order to reduce the size and increase the functionality of electronic devices. As a circuit board manufacturing technique, a manufacturing method based on a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer substrate is known. In the manufacturing method based on the build-up method, the insulating layer is formed by laminating the resin composition layer on the inner layer substrate using, for example, an adhesive film including a support and a resin composition layer provided on the support. It is formed by thermosetting the material layer. Next, the formed insulating layer is drilled with a laser to form a via hole, and desmear treatment is performed to remove resin residue (smear) inside the via hole and roughen the surface of the insulating layer simultaneously (for example, Patent Document 1).

JP 2008-37957 A

  In order to further increase the density of circuit wiring, it is desired to reduce the diameter of via holes. The via hole is generally formed by drilling with a laser, and as the laser, a carbon dioxide laser, which has a high drilling speed and is advantageous in terms of manufacturing cost, is mainly used at present. However, there is a limit to reducing the diameter of the via hole. For example, it is difficult to form a via hole having an opening diameter of 25 μm or less with a carbon dioxide laser.

  Examples of the laser that can be used for forming the via hole include an excimer laser (abbreviation of Excited Dimer Laser) in addition to the carbon dioxide gas laser. Excimer lasers are not widely used to form via holes, but generally, since a strong ultraviolet laser is obtained, unlike infrared lasers such as carbon dioxide lasers, heat is not generated. Therefore, finer processing is possible and it is expected to contribute to the reduction of the diameter of the via hole.

  On the other hand, the dielectric constant of the insulating layer is being reduced to cope with high-speed signal transmission, and it is preferable to include an inorganic filler in the insulating layer.

  The present inventors have attempted to form a small-diameter via hole by an excimer laser in an insulating layer containing an inorganic filler. As a result, it has been found that the laser workability is lowered, the shape of the via hole (also simply referred to as “via shape”) may be deteriorated, and the amount of smear inside the via hole may be increased. In particular, it becomes a big problem when the content of the inorganic filler in the insulating layer is increased to achieve an insulating layer having a low dielectric constant. It was also found that the same problem occurs when the arithmetic average roughness (Ra) of the insulating layer forming the via hole by the excimer laser is high. Deterioration of the via shape causes a decrease in conduction reliability, and an increase in the amount of smear inside the via hole requires a desmear treatment under severe conditions, which hinders miniaturization of circuit wiring.

  An object of the present invention is to provide a technique capable of forming a small-diameter via hole having a favorable via shape and a small amount of internal smear in an insulating layer containing an inorganic filler when manufacturing a circuit board. .

The present invention includes the following contents.
[1] A circuit board including an insulating layer in which a via hole having an opening diameter of 15 μm or less is formed,
The arithmetic average roughness (Ra) of the surface of the insulating layer is 150 nm or less,
The insulating layer contains an inorganic filler, and the average number of inorganic fillers having a particle diameter of 3 μm or more contained in a region having a width of 15 μm is 1.0 or less in a cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer. Circuit board.
[2] The circuit board according to [1], wherein Ra on the surface of the insulating layer is 100 nm or less.
[3] The circuit board according to [1] or [2], wherein an opening diameter of the via hole is 12 μm or less.
[4] In the cross section of the insulating layer in the direction perpendicular to the surface of the insulating layer, the resin area A ₁ and the inorganic filler area A _{2 in} a region having a width of 15 μm are 0.1 ≦ A ₂ / (A ₁ + A ₂ ) The circuit board according to any one of [1] to [3].
[5] The circuit board according to any one of [1] to [4], wherein an opening diameter D of the via hole and a minimum diameter D _min of the via hole satisfy 0.65 ≦ D _min / D.
[6] The circuit board according to any one of [1] to [5], wherein the insulating layer includes an inorganic filler surface-treated with a silane compound including an organic group having an aromatic ring.
[7] The circuit board according to any one of [1] to [6], wherein the inorganic filler is silica.
[8] A semiconductor device including the circuit board according to any one of [1] to [7].
[9] (A) A step of laminating an adhesive film including a support and a resin composition layer provided on the support on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate;
(B) including a step of thermally curing the resin composition layer with the support attached thereto to form an insulating layer; and (C) forming a via hole having an opening diameter of 15 μm or less in the insulating layer by an excimer laser. In the method for manufacturing a circuit board, the insulating layer formed in the step (B) includes an inorganic filler, and particles included in a region having a width of 15 μm in a cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer. A method for producing a circuit board, wherein the average number of inorganic fillers having a diameter of 3 μm or more is 1.0 or less.
[10] The method according to [9], wherein the support is removed before step (C).
[11] The method according to [9] or [10], wherein the arithmetic average roughness (Ra) of the surface of the insulating layer is 150 nm or less.
[12] In the cross section of the insulating layer in the direction perpendicular to the surface of the insulating layer, the resin area A ₁ and the inorganic filler area A _{2 in} the region having a width of 15 μm are 0.1 ≦ A ₂ / (A ₁ + A ₂ ) The method according to any one of [9] to [11].
[13] The method according to any one of [9] to [12], wherein the via hole opening diameter D and the via hole minimum diameter D _min satisfy 0.65 ≦ D _min / D.
[14] The method according to any one of [9] to [13], wherein the insulating layer includes an inorganic filler surface-treated with a silane compound containing an organic group having an aromatic ring.
[15] The method according to any one of [9] to [14], wherein the inorganic filler is silica.

  According to the present invention, when manufacturing a circuit board, a small-diameter via hole having a good via shape and a small amount of internal smear can be formed in an insulating layer containing an inorganic filler.

FIG. 1 is a schematic view for explaining a counting method of an inorganic filler having a particle diameter of 3 μm or more in a region having a width of 15 μm in a cross section of an insulating layer. FIG. 2 is a schematic diagram for explaining the via shape.

  First, the concept of the present invention will be described.

In the present invention, a via hole having a small diameter (for example, an opening diameter of 15 μm or less) is formed in the insulating layer by an excimer laser while satisfying the following conditions (i) and (ii):
(I) Arithmetic average roughness (Ra) of the surface of the insulating layer is 150 nm or less; and (ii) In the cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer, a particle size of 3 μm or more contained in a region having a width of 15 μm The average number of inorganic fillers is 1.0 or less.

  The inventors of the present invention have a favorable via shape in an insulating layer containing an inorganic filler by drilling with an excimer laser while satisfying the above-mentioned specific conditions (i) and (ii) when manufacturing a circuit board. However, a small-diameter via hole having a small amount of internal smear can be formed.

-Condition (i)-
Condition (i) relates to the arithmetic average roughness (Ra) of the surface of the insulating layer. The present inventors have found that when a small-diameter via hole is formed by an excimer laser, Ra on the surface of the insulating layer greatly affects the via shape and smear amount.

  From the viewpoint of forming a small-sized via hole having a good via shape and a small amount of internal smear, the arithmetic average roughness (Ra) of the surface of the insulating layer is 150 nm or less, preferably 140 nm or less, more preferably 130 nm or less. More preferably, it is 120 nm or less, still more preferably 110 nm or less, particularly preferably 100 nm or less, 90 nm or less, 80 nm or less, or 70 nm or less. Although the minimum of this Ra is not specifically limited, From a viewpoint of stabilizing the adhesive strength of an insulating layer and a conductor layer, it can usually be 1 nm or more, 5 nm or more, 10 nm or more, etc. The arithmetic average roughness (Ra) of the surface of the insulating layer can be measured using a non-contact type surface roughness meter. As a specific example of the non-contact type surface roughness meter, “WYKO NT3300” manufactured by Becoins Instruments is cited.

-Condition (ii)-
Condition (ii) relates to the particle size of the inorganic filler in the insulating layer. The present inventors have found that when forming a small diameter via hole by an excimer laser, the particle size of the inorganic filler in the insulating layer greatly affects the via shape and smear amount.

  From the viewpoint of forming a small-sized via hole having a good via shape and a small amount of internal smear, the width in the cross section of the insulating layer in the direction perpendicular to the surface of the insulating layer (also simply referred to as “cross section of the insulating layer”). The average number n of inorganic fillers having a particle diameter of 3 μm or more contained in the 15 μm region is 1.0 or less, preferably 0.9 or less, more preferably 0.8 or less, and even more preferably 0.7 or less, 0.6 or less, or 0.5 or less. The lower limit of the average number n is preferably as low as possible, and may be 0.

  The cross section of the insulating layer can be suitably observed using a FIB-SEM composite apparatus. An example of the FIB-SEM composite device is “SMI3050SE” manufactured by SII Nanotechnology. After cutting out the cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer with FIB (focused ion beam), the cross section can be observed with a scanning electron microscope (SEM) to obtain a cross-sectional SEM image. . The observation width and observation magnification by SEM are not particularly limited as long as an inorganic filler having a particle diameter of 3 μm or more contained in a region having a width of 15 μm in the cross section of the insulating layer can be appropriately counted, and is determined according to the specifications of the apparatus to be used. You can do it.

In obtaining the average number n, the “region having a width of 15 μm” refers to a region having the total thickness t (μm) of the insulating layer × the width of 15 μm in the cross-sectional SEM image. The “inorganic filler having a particle diameter of 3 μm or more” refers to an inorganic filler having a maximum diameter of 3 μm or more in a cross-sectional SEM image. When more than ½ of the maximum diameter of the inorganic filler is in the region having a width of 15 μm, the inorganic filler is determined to be “included in the region having a width of 15 μm”. With reference to FIG. 1, the counting method of an inorganic filler is demonstrated in detail. FIG. 1 shows a cross section of an insulating layer 10 having a thickness t including a resin component 10 and an inorganic filler 12 having a particle diameter of 3 μm or more. In the cross section of the insulating layer shown in FIG. 1, there are three inorganic fillers having a particle size of 3 μm or more, and the maximum diameter of each inorganic filler is indicated by a one-dot chain line. Among the three inorganic fillers, the middle inorganic filler has all of its maximum diameter in the region having a width of 15 μm, and the inorganic filler is determined to be “included in the region having a width of 15 μm”. The left inorganic filler has a width of more than ½ of its maximum diameter in a region having a width of 15 μm, and the inorganic filler is determined to be “included in a region having a width of 15 μm”. It is determined that the right inorganic filler is included in a region having a width of 15 μm and less than ½ of the maximum diameter, and the inorganic filler is not included in a region having a width of 15 μm. Therefore, regarding the cross section of the insulating layer shown in FIG. 1, it is determined that two inorganic fillers having a particle size of 3 μm or more exist in a region having a width of 15 μm. An average number n can be calculated by obtaining a sufficient number (N ₁ ) of cross-sectional SEM images for the insulating layer sample and counting inorganic fillers having a particle size of 3 μm or more contained in a region having a width of 15 μm. . Here, N ₁ is preferably 10 or more. In the present invention, the average number n can be calculated according to the procedure described in <Evaluation of particle diameter of inorganic filler in insulating layer> described later.

  According to the present invention satisfying the above conditions (i) and (ii), a small-diameter via hole having a good via shape and a small amount of internal smear can be formed. As the diameter of the via hole is reduced, the problem of the via shape and the amount of internal smear tends to become remarkable. However, according to the method of the present invention, for example, 15 μm or less, preferably 14 μm or less, more preferably 12 μm or less, A via hole having an opening diameter (top diameter) of preferably 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, or 5 μm or less can be advantageously formed without deterioration of the via shape or the amount of internal smear. The lower limit of the opening diameter of the via hole is not particularly limited, but can usually be 1 μm or more, 2 μm or more, 3 μm or more, and the like.

  As described above, when the inorganic layer contains a certain amount or more of an inorganic filler having a large particle size in the insulating layer, the present inventors deteriorated the laser workability by the excimer laser, and the shape of the via hole (simply referred to as “via shape”). And the amount of smear inside the via hole may increase. In particular, the problem becomes more apparent as the content of the inorganic filler increases. On the other hand, according to the present invention, even when the content of the inorganic filler in the insulating layer is high, a small diameter via hole having a good via shape and a small amount of internal smear is formed in the insulating layer. be able to.

The content of the inorganic filler in the insulating layer can be evaluated using the area ratio of the inorganic filler in the cross section of the insulating layer. In particular, the inorganic filler content in the insulating layer, A ₁ resin area of the region of the width 15μm in the cross section of the insulating _layer, an inorganic filler area when the _{A 2, A 2 / (A} 1 + A 2 ) Can be used for evaluation. The larger the value of A ₂ / (A ₁ + A ₂ ), the higher the inorganic filler content in the insulating layer. From the viewpoint of lowering the dielectric constant of the insulating layer, the value of A ₂ / (A ₁ + A ₂ ) is preferably 0.1 or more (that is, 0.1 ≦ A ₂ / (A ₁ + A ₂ )), more preferably Is 0.2 or more, more preferably 0.3 or more, and even more preferably 0.4 or more. Although the upper limit of the value of A ₂ / (A ₁ + A ₂ ) is not particularly limited, it is preferably 0.9 or less, more preferably 0.8 or less, from the viewpoint of the mechanical strength of the insulating layer. In the present invention, “resin area” means an area occupied by a resin component. The “resin component” for the resin area refers to a component excluding the inorganic filler among the components constituting the insulating layer. The value of A ₂ / (A ₁ + A ₂ ) in the cross section of the insulating layer can be obtained according to the procedure described in <Measurement of resin area and inorganic filler area in cross section of insulating layer> described later.

  In the present invention, a small diameter via hole is formed in the insulating layer by an excimer laser while satisfying the above conditions (i) and (ii).

In general, an excimer laser generates laser light using a mixed gas of a rare gas and a halogen gas. The wavelength of the generated laser light belongs to the ultraviolet region, and generates very little heat compared with an infrared laser such as a carbon dioxide laser. The laser wavelength of the excimer laser varies depending on the type of mixed gas used, and is, for example, 193 nm (ArF), 248 nm (KrF), 308 nm (XeCl), and 351 nm (XeF). In particular, 248 nm (KrF) and 308 nm (XeCl) are preferable. An excimer laser that generates laser light using only a rare gas is also known, and there are 172 nm (Xe ₂ ), 146 nm (Kr ₂ ), and 126 nm (Ar ₂ ) as the laser wavelength of the excimer laser. These are also included in the excimer laser in the present invention.

  Excimer laser drilling conditions (for example, laser wavelength, number of pulses, pulse width, output) are not particularly limited as long as a small diameter via hole having a good via shape and a small amount of internal smear can be formed. Depending on the specifications of the laser processing machine, it can be appropriately determined within the range of general processing conditions. Examples of commercially available excimer laser processing machines include “ELP300 Gen2” manufactured by SUSS MicroTech.

  According to the method of the present invention in which the excimer laser drills while satisfying the above conditions (i) and (ii), the insulating layer containing the inorganic filler (even if the insulating layer has a high inorganic filler content). In addition, a small-diameter via hole having a good via shape and a small amount of internal smear can be formed.

The shape of the via hole will be described with reference to FIG. FIG. 2 shows an inner layer substrate 1 and an insulating layer 10 having a thickness t provided so as to be joined to the inner layer substrate. The insulating layer 10 includes (a) to (c). A typical via hole is formed. In the present invention, the “opening diameter” (D) of the via hole refers to the diameter of the via hole on the surface of the insulating layer (position Z = 0 in FIG. 2). Further, the “minimum diameter” (D _min ) of the via hole refers to the minimum diameter of the via hole in the range where Z is 0 to t. The “maximum diameter” (D _max ) of the via hole refers to the maximum diameter of the via hole in the range where Z is 0 to t. For example, the via hole in FIG. 2A has a forward tapered shape in which the diameter gradually decreases as it proceeds from the insulating layer surface in the depth direction (Z) of the insulating layer. In the via hole (a), the opening diameter D is the maximum diameter _Dmax , and the minimum diameter _Dmin is exhibited at the bottom of the via hole (position Z = t in FIG. 2). When forming a via hole using an excimer laser, the via hole of (a) is generally formed. Also, the via hole (b) or (c) in FIG. 2 may be formed. The via hole (b) has a constant distance (k ₁ t; where k ₁ is a number satisfying 0 <k ₁ <1) in the depth direction (Z) of the insulating layer from the surface of the insulating layer. Gradually decreases, and the diameter gradually increases as it proceeds further in the depth direction. In such a via hole (b), the opening diameter D or the diameter of the via hole bottom (Z = t position) is the maximum diameter _Dmax , and the minimum diameter _Dmin is exhibited at the position of the depth k ₁ t. The via hole of (c) has a constant distance (k ₂ t; where k ₂ is a number satisfying 0 <k ₂ <1) in the depth direction (Z) of the insulating layer from the surface of the insulating layer. Gradually increases, and the diameter gradually decreases as it proceeds further in the depth direction. In such a via hole (c), exhibit a maximum diameter _{D max} at the position of depth _{k 2} t, the diameter of the aperture diameter D or the bottom of the via hole (the position of the Z = t) is the minimum diameter _{D min.}

(A) to both the other via hole (c), from the viewpoint of obtaining good conduction reliability, the minimum diameter _{D min} of the aperture diameter D and the via hole of the via hole, satisfy 0.65 ≦ _{D min} / D Is preferred. This is because if the value of D _min / D is low, it results in deterioration of the penetration of the plating solution into the via hole, which leads to a decrease in conduction reliability. From the viewpoint of obtaining better conduction reliability, the value of D _min / D is preferably 0.66 or more, more preferably 0.68 or more, further preferably 0.70 or more, 0.72 or more, 0.74. These are 0.76 or more, 0.78 or more, or 0.80 or more. The upper limit of the value of D _min / D is 1, and is usually 0.99 or less, 0.98 or less, 0.95 or less, 0.90 or less, and the like. According to the method of the present invention, a small-diameter via hole having a high value of D _min / D can be formed advantageously. The value of D _min / D can be obtained by observing the surface of a via hole opening with a SEM for a sufficient number (N ₂ ) of via holes. Also for the via hole of (c), when the diameter of the bottom of the via hole is smaller than the opening diameter D, the minimum diameter _Dmin can be measured by surface observation with SEM (if the diameter of the bottom of the via hole is not visually recognized, The opening diameter D is the minimum diameter _Dmin ). N ₂ is preferably 10 or more.

In addition, although it is rare that many via holes of (c) are formed, in such a case, the opening diameter D of the via hole and the maximum diameter D _{max of the} via hole satisfy D _max /D≦1.35. Is preferred. The value of D _max / D is preferably 1.30 or less, more preferably 1.20 or less, and still more preferably 1.10 or less or 1.05 or less. The lower limit of the value of D _max / D is 1. The value of D _max / D can be obtained by observing the cross section of the via hole with a SEM for a sufficient number (N ₂ ) of via holes. N ₂ is preferably 10 or more.

  In the present invention, the thickness t (μm) of the insulating layer and the opening diameter D (μm) of the via hole are t ≦ 3D from the viewpoint of forming a small diameter via hole having a good via shape and a small amount of internal smear. It is preferable to satisfy, more preferably t ≦ 2.5D, more preferably t ≦ 2D, t ≦ 1.8D, t ≦ 1.6D, t ≦ 1.4D, t ≦ 1.2D. Or it is even more preferable to satisfy t ≦ 1D. The lower limit of the thickness t of the insulating layer is not particularly limited, but is usually 1 μm or more, 2 μm or more, 3 μm or more, and the like.

  In a preferred embodiment, the insulating layer is formed by thermosetting a resin composition layer containing an inorganic filler.

From the viewpoint of achieving high-speed signal transmission by sufficiently reducing the dielectric constant of the insulating layer, the content of the inorganic filler in the resin composition constituting the resin composition layer is preferably 20% by mass or more, more preferably It is 25% by mass or more.
In addition, in this invention, content of each component which comprises a resin composition is a value when the non-volatile component in a resin composition is 100 mass%.

  When an insulating layer is formed using a resin composition containing an inorganic filler, laser workability with an excimer laser may be reduced, the via shape may be deteriorated, and the amount of smear inside the via hole may be increased. On the other hand, in the present invention in which via holes are formed by an excimer laser while satisfying the specific conditions (i) and (ii), the resin composition having a high inorganic filler content without problems of via shape and smear amount. Can be used. For example, the content of the inorganic filler in the resin composition may be increased to 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more.

  The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of preventing a decrease in mechanical strength of the insulating layer.

  Examples of inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitride. Boron, aluminum nitride, manganese nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, zirconium phosphate, and phosphoric acid Examples thereof include zirconium tungstate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica is particularly suitable. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle diameter of the inorganic filler is preferably 0.6 μm or less, more preferably 0.5 μm or less, still more preferably 0.4 μm or less, from the viewpoint of suitably satisfying the above conditions (i) and (ii). .3 μm or less, 0.25 μm or less, 0.2 μm or less, 0.15 μm or less, or 0.1 μm or less. Although the minimum of the average particle diameter of an inorganic filler is not specifically limited, Usually, it may be 0.01 micrometer or more, 0.02 micrometer or more. Examples of commercially available inorganic fillers having such an average particle diameter include, for example, “UFP-30”, “UFP-40” manufactured by Denki Kagaku Kogyo Co., Ltd., “SO-C2” manufactured by Admatex, “SO-C1”, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C”, “Silfil NSS-3N”, “Silfil NSS-4N”, “Sylfil NSS-5N” manufactured by Tokuyama Corporation Can be mentioned. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  The inorganic filler is treated with at least one surface treatment agent such as a silane compound, an organosilazane compound, an aluminum coupling agent, a titanium coupling agent, or a zirconium coupling agent in order to improve moisture resistance. Is preferred.

In particular, by using an inorganic filler surface-treated with a silane compound containing an organic group having an aromatic ring, the value of A ₂ / (A ₁ + A ₂ ) is high, and the condition (ii) The inventors have found that an insulating layer with a low average number n can be realized. Accordingly, in a preferred embodiment, the resin composition constituting the resin composition layer, and thus the insulating layer, includes an inorganic filler surface-treated with a silane compound containing an organic group having an aromatic ring.

From the viewpoint of realizing an insulating layer having a high value of A ₂ / (A ₁ + A ₂ ) and a low average number n, the organic group having an aromatic ring has 6 to 20 carbon atoms (preferably 6 To 14, more preferably 6 to 12, and still more preferably 6 to 10) aryl group, and particularly preferably a phenyl group.

  The silane compound containing an organic group having an aromatic ring used for the treatment of the inorganic filler is not particularly limited as long as the organic group having an aromatic ring can be introduced onto the surface of the inorganic filler, and an epoxy resin described later. It may further have a reactive group (for example, an amino group, an epoxy group, a mercapto group, etc.) that can react with the resin component. Specific examples of such silane compounds include phenyltrimethoxysilane, diphenyldimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxypropylphenyldiethoxysilane, and mercaptopropylphenyldimethoxysilane. Examples of commercially available silane compounds include “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Etc. A silane compound may be used individually by 1 type, and may be used in combination of 2 or more type.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is 0.02 mg / m ² or more from the viewpoint of realizing an insulating layer having a high value of A ₂ / (A ₁ + A ₂ ) and a low average number n. Preferably, 0.1 mg / m ² or more is more preferable, and 0.2 mg / m ² or more is still more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the film form. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. can be used.

  In one embodiment, the resin composition constituting the resin composition layer includes a thermosetting resin in addition to the inorganic filler. As a thermosetting resin, a conventionally well-known thermosetting resin used when forming the insulating layer of a circuit board can be used, and an epoxy resin is especially preferable. The resin composition constituting the resin composition layer may also contain a curing agent. Accordingly, in one embodiment, the resin composition includes an epoxy resin and a curing agent in addition to the inorganic filler.

-Epoxy resin-
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing ester Carboxymethyl resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition is a solid epoxy resin (also referred to as “solid epoxy resin”) alone at a temperature of 20 ° C., or a solid epoxy resin and an epoxy resin that is liquid at a temperature of 20 ° C. And a liquid epoxy resin ”). The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, phenol novolac type epoxy resin, and epoxy resin having a butadiene structure are preferable, and bisphenol A type epoxy resin Bisphenol F type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032H”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “jER828EL”, “828US” manufactured by Mitsubishi Chemical Corporation. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "ZX1059" (bisphenol A type epoxy resin and bisphenol manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) F-type epoxy resin mixture), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, “Celoxide 2021P” (manufactured by Daicel Corporation) (alicyclic epoxy resin having an ester skeleton) ), "PB-3600" (pig Epoxy resin) having an end structure. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, And bisphenol AF type epoxy resin is more preferable. Specific examples of the solid epoxy resin include “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690”, “N-695” (cresol novolak) manufactured by DIC Corporation. Type epoxy resin), “HP7200”, “HP7200H”, “HP7200HH” (dicyclopentadiene type epoxy resin), “EXA7311”, “EXA7311-G3”, “EXA7311-G4”, “EXA7311-G4S”, “HP6000” (Naphthylene ether type epoxy resin), “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., “NC7000L” (naphthol novolak type epoxy resin), “NC3000H”, “NC3000”, “ NC3000L ”,“ NC3100 ”(Bifeni Type epoxy resin), “ESN475V” (naphthol type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolac type epoxy resin), “YX4000H”, “YL6121” (biphenyl) manufactured by Mitsubishi Chemical Corporation Type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG-100”, “CG-500” manufactured by Osaka Gas Chemical Co., Ltd., Mitsubishi Chemical Corporation ) "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Corporation "jER1010" (solid bisphenol A type epoxy resin), "YL7723", "YL7760" (bisphenol AF type epoxy resin), "jER1031S (Tetraphenylethane type epoxy resin Etc. The. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 5 by mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) moderate tackiness is obtained when used in the form of an adhesive film described later, and ii) used in the form of an adhesive film. In this case, sufficient flexibility can be obtained, handling properties can be improved, and iii) an insulating layer having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.5 to 1: 5 by mass ratio. Is more preferable, the range of 1: 1 to 1: 4.5 is more preferable, and the range of 1: 1.5 to 1: 4.5 is particularly preferable.

  3 mass%-60 mass% are preferable, as for content of the epoxy resin in a resin composition, 5 mass%-55 mass% are more preferable, and 5 mass%-45 mass% are more preferable.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

-Curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and A carbodiimide type hardening | curing agent is mentioned. A hardening | curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion strength with the conductor layer, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferable, and a triazine structure-containing phenol-based curing agent or a triazine structure-containing naphthol-based curing agent is more preferable. Among these, a triazine structure-containing phenol novolac resin or a triazine structure-containing naphthol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with a conductor layer. These may be used alone or in combination of two or more. Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "SN-495", "SN-375", "SN-395", "LA-7052," "LA-7054," "LA-3018," "LA-1356," "TD2090" manufactured by DIC Corporation Or the like.

  Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule. A compound having two or more in the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-cresol. P-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzene Examples include triol, dicyclopentadiene type diphenol compound, phenol novolac and the like. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  Preferable specific examples of the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac. Active ester compounds containing an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. Among them, an active ester compound containing a dicyclopentadiene type diphenol structure, a naphthalene structure More preferred is an active ester compound containing an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. In the present invention, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

  As the active ester curing agent, active ester compounds disclosed in JP-A Nos. 2004-277460 and 2013-40270 may be used, and commercially available active ester compounds may also be used. Commercially available active ester compounds include, for example, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000L-65M” (dicyclopentadiene type diacids) manufactured by DIC Corporation. Active ester compound containing a phenol structure), “9416-70BK” (active ester compound containing a naphthalene structure) manufactured by DIC Corporation, “DC808” (active ester compound containing phenol novolac acetylated product) manufactured by Mitsubishi Chemical Corporation Compound), "YLH1026" (active ester compound containing a benzoylated product of phenol novolak) manufactured by Mitsubishi Chemical Corporation, and "EXB9050L-62M" (phosphorus atom-containing active ester compound) manufactured by DIC Corporation.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Although it does not specifically limit as a cyanate ester type hardening | curing agent, For example, novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, And bisphenol F type, bisphenol S type, and the like) and cyanate ester-based curing agents, and prepolymers in which these are partially triazines. Specific examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidene diphenyl. Dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, Bifunctional cyanate resins such as 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol novolac and cresol novolac Invite from etc. Polyfunctional cyanate resin is, these cyanate resins and partially triazine of prepolymer. Commercial products of cyanate ester curing agents include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. And the like, and the like, and the like.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  From the viewpoint of improving the mechanical strength and water resistance of the resulting insulating layer, the amount ratio of the epoxy resin and the curing agent is a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent]. The range of 1: 0.2 to 1: 2 is preferable, the range of 1: 0.3 to 1: 1.5 is more preferable, and the range of 1: 0.4 to 1: 1.2 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents.

  The resin composition may further contain one or more additives selected from the group consisting of a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler, as necessary.

-Thermoplastic resin-
Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YX7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, “YL7290”, “YL7482” and the like can be mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. .

-Curing accelerator-
Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, phosphorus-based curing accelerators, amine-based curing accelerators, and imidazole-based accelerators. A curing accelerator is preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type. The content of the curing accelerator in the resin composition layer is preferably in the range of 0.05% by mass to 3% by mass when the total of the nonvolatile components of the epoxy resin and the curing agent is 100% by mass.

-Flame retardant-
Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may be used in combination of 2 or more type. Although content of the flame retardant in a resin composition is not specifically limited, Preferably it is 0.5 mass%-10 mass%, More preferably, it is 1 mass%-9 mass%.

-Organic filler-
As the organic filler, any organic filler that can be used in forming the insulating layer of the circuit board may be used. Examples thereof include rubber particles, polyamide fine particles, and silicone particles, and rubber particles are preferable.

  The rubber particle is not particularly limited as long as it is a fine particle of a resin that has been subjected to a chemical crosslinking treatment on a resin exhibiting rubber elasticity and is insoluble and infusible in an organic solvent. For example, acrylonitrile butadiene rubber particles, butadiene rubber particles, Examples include acrylic rubber particles. Specific examples of rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (above, manufactured by Aika Industry Co., Ltd.) Paraloid EXL2655. , EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.) and the like.

  The average particle diameter of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and the particle size distribution of the organic filler is measured by mass using a concentrated particle size analyzer (“FPAR-1000” manufactured by Otsuka Electronics Co., Ltd.). It can be measured by creating a standard and setting the median diameter as the average particle diameter. The content of the organic filler in the resin composition layer is preferably 1% by mass to 10% by mass, more preferably 2% by mass to 5% by mass.

-Other ingredients-
The resin composition may contain other components as necessary. Examples of such other components include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resin additions such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and coloring agents. Agents and the like.

  The method for preparing the resin composition is not particularly limited, and examples thereof include a method in which the compounding components are mixed and dispersed using a rotary mixer or the like after adding a solvent or the like as necessary. In addition, from a viewpoint of reducing the average number n in said condition (ii), you may remove the particle | grains which have a predetermined particle diameter by filtering the resin composition as needed. Therefore, in one embodiment, the insulating layer is formed by thermosetting a layer of a resin composition that has been subjected to a process of removing particles having a particle size of d (μm) or more by filtering. Here, d is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and even more preferably 1 or less. The filtration accuracy of the filter is preferably 4 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, and even more preferably 1 μm or less. Examples of suitable filters that can be used for filtration of the resin composition include “SCP-010”, “SHP-020”, and “SHP-030” manufactured by Loki Techno Co., Ltd.

[Circuit board]
A circuit board obtained based on the concept of the present invention will be described.

The circuit board of the present invention is a circuit board including an insulating layer in which a via hole having an opening diameter of 15 μm or less is formed,
The arithmetic average roughness (Ra) of the surface of the insulating layer is 150 nm or less,
The insulating layer contains an inorganic filler, and the average number of inorganic fillers having a particle diameter of 3 μm or more contained in a region having a width of 15 μm is 1.0 or less in a cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer. It is characterized by that.

  The circuit board of the present invention is characterized in that a small-sized via hole having a good via shape and a small amount of internal smear is formed in an insulating layer containing an inorganic filler.

Preferred range of opening diameter of via hole, shape of via hole (that is, preferred range of D _min / D and D _max / D), preferred Ra value of insulating layer surface, insulating layer thickness, insulating layer cross section The preferred range of the average number n and A ₂ / (A ₁ + A ₂ ) is as described above. The composition of the insulating layer is also as described above. In a preferred embodiment, the insulating layer includes an inorganic filler surface-treated with a silane compound containing an organic group having an aromatic ring. Details of the organic group having an aromatic ring and a suitable silane compound are as described above.

  The circuit board of the present invention further includes a conductor layer (circuit) formed on the surface of the insulating layer. Details of the conductor layer are as described in [Method of manufacturing circuit board] described later. In a preferred embodiment, the circuit board according to the present invention has a ratio (L / S) of a circuit width (line; L) to a width (space; S) between circuits of 10 μm / 10 μm or less (that is, a wiring pitch of 20 μm or less). ) Circuit. In a more preferred embodiment, L / S = 9 μm / 9 μm or less (wiring pitch 18 μm or less), L / S = 8 μm / 8 μm or less (wiring pitch 16 μm or less), L / S = 7 μm / 7 μm or less (wiring pitch 14 μm). Or less), L / S = 6 μm / 6 μm or less (wiring pitch 12 μm or less), L / S = 5 μm / 5 μm or less (wiring pitch 10 μm or less), or L / S = 4 μm / 4 μm or less (wiring pitch 8 μm or less). Circuit.

[Semiconductor device]
A semiconductor device can be manufactured using the circuit board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a circuit board. The “conduction location” is a “location where an electric signal is transmitted on a circuit board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without bumps (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a circuit board and the semiconductor chip and a wiring on the circuit board are connected”. .

[Circuit board manufacturing method]
The method for producing a circuit board according to the present invention is not particularly limited as long as the above-described concept of the present invention can be achieved. Hereinafter, preferred embodiments capable of achieving the concept of the present invention will be exemplified.

In a preferred embodiment, a method for manufacturing a circuit board according to the present invention comprises:
(A) A step of laminating an adhesive film including a support and a resin composition layer provided on the support on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate;
(B) a step of thermosetting the resin composition layer with a support attached thereto to form an insulating layer; and (C) a step of forming a via hole having an opening diameter of 15 μm or less in the insulating layer by an excimer laser. The insulating layer formed in the step (B) contains an inorganic filler, and in the cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer, an inorganic filler having a particle size of 3 μm or more contained in a region having a width of 15 μm. The average number is 1.0 or less.

-Process (A)-
In the step (A), an adhesive film including a support and a resin composition layer provided on the support is laminated on the inner layer substrate so that the resin composition layer is bonded to the inner layer substrate.

  The resin composition constituting the resin composition layer is as described above. The thickness of the resin composition layer is particularly limited as long as the thickness t (μm) of the obtained insulating layer satisfies the above specific relationship (that is, t ≦ 3D) with the opening diameter D (μm) of the via hole. It may be determined appropriately.

  Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), acrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). , Cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. . Examples of commercially available release agents include “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are alkyd resin release agents.

  The arithmetic average roughness (Ra) of the surface of the support that is bonded to the resin composition layer is 150 nm or less from the viewpoint of reducing the Ra value of the surface of the insulating layer formed in the step (B). Preferably it is 140 nm or less, More preferably, it is 130 nm or less, More preferably, it is 120 nm or less, More preferably, it is 110 nm or less, Most preferably, it is 100 nm or less, 90 nm or less, 80 nm or less, or 70 nm or less. Although the minimum of this Ra is not specifically limited, From a viewpoint of obtaining the insulating layer with favorable adhesive strength with a conductor layer, it may be normally 1 nm or more, 5 nm or more, 10 nm or more. The arithmetic mean roughness (Ra) of the surface of the support that is to be bonded to the resin composition layer can be measured by the same method as described for Ra of the surface of the insulating layer.

  Although the thickness of a support body is not specifically limited, Preferably it is 75 micrometers or less, More preferably, it is 60 micrometers or less, 50 micrometers or less, or 40 micrometers or less. Although the minimum of the thickness of a support body is not specifically limited, Usually, it may be 1 micrometer or more, 2 micrometers or more, 5 micrometers or more, etc. In addition, when a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  For the adhesive film, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and this resin varnish is applied on a support using a die coater or the like and further dried to form a resin composition layer. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  In the adhesive film, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off the protective film.

  The “inner layer substrate” used in the step (A) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A substrate on which a patterned conductor layer (circuit) is formed. In addition, when the circuit board is manufactured, an inner layer circuit board as an intermediate product on which an insulating layer and / or a conductor layer is to be formed is also included in the “inner layer board” in the present invention. When the circuit board is a circuit board with a built-in component, an inner layer board with a built-in component may be used.

  Lamination | stacking of an inner layer board | substrate and an adhesive film can be performed by heat-pressing an adhesive film to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the adhesive film to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate, etc.) or a metal roll (SUS roll). In addition, it is preferable not to press the thermocompression bonding member directly on the adhesive film but to press it through an elastic material such as heat resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the adhesive film may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  After lamination, the laminated adhesive film may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

-Process (B)-
In the step (B), the resin composition layer is thermally cured with the support attached thereto to form an insulating layer.

  The conditions for thermosetting are not particularly limited, and the conditions normally employed when forming the insulating layer of the circuit board may be used.

  The thermosetting conditions of the resin composition layer vary depending on the composition of the resin composition used for the resin composition layer, but are not particularly limited as long as an appropriate insulating layer can be finally formed. The curing temperature is preferably in the range of 120 ° C to 240 ° C, more preferably in the range of 150 ° C to 210 ° C, and still more preferably in the range of 160 ° C to 190 ° C. Here, the thermosetting temperature is not necessarily fixed at a predetermined temperature in the above temperature range, and may be changed with time as long as an appropriate insulating layer is finally formed. And may be cured in multiple stages. Moreover, it is preferable that the highest reached temperature of a curing temperature exists in the said range.

  The thermosetting time varies depending on the composition of the resin composition used for the resin composition layer and the thermosetting temperature, but is not particularly limited as long as an appropriate insulating layer is finally formed, for example, 20 minutes to 150 minutes, Preferably it can be 30 minutes to 120 minutes, more preferably 40 minutes to 120 minutes.

  The thermosetting of the resin composition layer is preferably performed under atmospheric pressure (normal pressure).

  As described above, in the present invention, the arithmetic average roughness (Ra) of the surface of the insulating layer is set to 150 nm or less (condition (i)). When the Ra value exceeds 150 nm, there are problems that the laser processability is lowered, the via shape is deteriorated, and the amount of smear inside the via hole is increased. In general, when an insulating layer is formed by thermosetting a resin composition, the inorganic filler is exposed on the surface of the insulating layer due to melting of the resin, or the surface is wavy, resulting in a decrease in smoothness and a low Ra. However, according to the method for producing a circuit board of the present invention in which the resin composition layer is thermally cured with the support attached to the resin composition layer, a low Ra value can be easily achieved. . In addition, increasing the temperature stepwise during thermosetting is also effective for lowering the Ra value. For example, after heating for 10 minutes to 60 minutes at a thermosetting temperature T1 (where 50 ° C. ≦ T1 <150 ° C.), heat for 5 minutes to 90 minutes at a temperature T2 (where 150 ° C. ≦ T2 ≦ 240 ° C.) A technique for performing curing is mentioned. The preferable range of the Ra value is as described above.

  The insulating layer formed in the step (B) includes an inorganic filler, and an average of inorganic fillers having a particle diameter of 3 μm or more contained in a region having a width of 15 μm in a cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer. The number is 1.0 or less (condition (ii)). When the average number (n) exceeds 1.0, there are problems that the laser processability is lowered, the via shape is deteriorated, and the amount of smear inside the via hole is increased. In general, the average number n tends to increase when the inorganic filler content in the insulating layer is high. In reducing the average number n, 1) use of an inorganic filler having a small average particle diameter, 2) use of an inorganic filler surface-treated with a silane compound containing an organic group having an aromatic ring, 3) resin composition It is effective to carry out filtering of materials. The preferred range of the average number n is as described above.

  The support may be removed after step (B). In a preferred embodiment, the support is removed prior to step (C). In addition, when using a very thin (for example, 2 micrometers or less or 1 micrometer or less) metal foil as a support body, you may implement a process (C) in the state which attached the support body to the insulating layer.

-Process (C)-
In step (C), a via hole having an opening diameter of 15 μm or less is formed in the insulating layer by an excimer laser.

  Details of the excimer laser (laser wavelength, etc.) and the opening diameter and shape of the via hole are as described above.

-Process (D)-
The method for manufacturing a circuit board of the present invention may further include (D) a desmear treatment step after the step (C).

  According to the method of the present invention, a small-diameter via hole having a small amount of smear inside a via hole is formed in an insulating layer containing an inorganic filler (even if the inorganic filler content in the insulating layer is high). Can do. Therefore, in the method of the present invention, step (D) may or may not be performed. Even when the step (D) is carried out, the step (D) can be carried out under mild conditions as compared with the normal desmear treatment. Therefore, the surface roughness of the insulating layer due to the desmear process can be suppressed, and an insulating layer having a low surface roughness suitable for forming fine wiring can be realized.

  The desmear treatment is not particularly limited and can be performed by various known methods. In one embodiment, the desmear process may be a wet desmear process using an oxidant solution.

  In the wet desmear process using an oxidant solution, it is preferable to perform a swelling process with a swelling liquid, an oxidation process with an oxidant solution, and a neutralization process with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent solution, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The oxidation treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidant solutions include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

-Process (E)-
The method for manufacturing a circuit board of the present invention may further include (E) a step of forming a conductor layer on the surface of the insulating layer after the step (C).

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

  The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  The thickness of the conductor layer is usually 35 μm or less, preferably 30 μm or less, more preferably 25 μm or less, depending on the desired circuit board design. Although the minimum of the thickness of a conductor layer is not specifically limited, Usually, 3 micrometers or more, Preferably it is 5 micrometers or more.

  In the step (E), the conductor layer may be formed by dry plating, wet plating, or a combination thereof.

  Examples of dry plating include physical vapor deposition (PVD) methods such as vapor deposition, sputtering, ion plating, and laser ablation, and chemical vapor deposition (CVD) methods such as thermal CVD and plasma CVD. Sputtering is preferred. When the conductor layer is formed only by dry plating, the conductor layer (circuit) may be formed by a known method such as a full additive method.

  When the conductive layer is formed by wet plating, the conductive layer may be formed by a combination of electroless plating and electrolytic plating by a semi-additive method, and a plating resist having a pattern opposite to that of the conductive layer is formed. The conductor layer may be formed by a full additive method. In addition, when an extremely thin metal foil is used as the support, the conductor layer may be formed by a modified semi-additive method. These methods may be performed according to procedures known in the art.

  The conductor layer may be formed by combining dry plating and wet plating. For example, a metal layer formed by dry plating can be used as a plating seed layer, and a conductor layer can be formed by a semi-additive method using electrolytic plating or electroless plating.

  In the semi-additive method, an unnecessary plating seed layer is removed by etching or the like to form a conductor layer (circuit) having a desired wiring pattern. At this time, if the surface roughness of the insulating layer is large, it is difficult to remove the plating seed layer in the large roughness region when the unnecessary plating seed layer is removed by etching when forming the wiring pattern. When etching is performed under conditions that can sufficiently remove the seed layer, the dissolution of the wiring pattern becomes significant, which hinders miniaturization of circuit wiring. On the other hand, in the method of the present invention, as described above, since desmear treatment is unnecessary or can be performed under mild conditions, an insulating layer with low surface roughness can be realized. Combined with the effect of realizing a small-diameter via hole having a good via shape and a small amount of smear, the circuit board manufacturing method of the present invention significantly contributes to both high density and miniaturization of circuit wiring. is there.

  The preferred embodiment of the method for producing a circuit board of the present invention has been described above. However, as long as the concept of the present invention can be achieved, the method of the present invention may include steps other than those described above.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to these Examples. In the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

<Measurement and evaluation method>
First, the measurement / evaluation method in the physical property evaluation in this specification will be described.

[Preparation of measurement and evaluation substrate]
(1) Ground treatment of inner layer circuit board Glass cloth base epoxy resin double-sided copper-clad laminate with a circuit formed (copper foil thickness 18 μm, substrate thickness 0.4 mm, “R1515A” manufactured by Panasonic Corporation) Both surfaces were etched by 1 μm with a microetching agent (“CZ8100” manufactured by MEC Co., Ltd.) to roughen the copper surface.

(2) Lamination | stacking of adhesive film The protective film was peeled from the adhesive film produced in the Example and the comparative example. Using the batch type vacuum pressure laminator (Nichigo Morton 2-stage buildup laminator “CVP700”), the resin composition layer is bonded to the inner circuit board using the exposed adhesive film of the resin composition layer. And laminated on both sides of the inner circuit board. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Subsequently, the laminated adhesive film was smoothed by hot pressing at 100 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(3) Curing of resin composition layer After laminating the adhesive film, the resin composition layer was thermally cured to form insulating layers on both sides of the inner circuit board. At that time, for Examples 1 to 4 and Comparative Example 1, the resin composition layer was thermally cured with the support attached thereto, and the support was peeled off after the thermosetting. Regarding Comparative Example 2, the resin composition layer was thermally cured after peeling the support. The obtained substrate is referred to as “evaluation substrate a”.

The thermosetting of the resin composition layer was performed under the following condition B-1 (Examples 1 and 2, Comparative Examples 1 and 2) or Condition B-2 (Examples 3 and 4).
Condition B-1: Thermal curing was performed at 180 ° C. (after being put into an oven at 180 ° C.) for 30 minutes. Thereafter, the substrate was taken out in a room temperature atmosphere.
Condition B-2: Thermal curing was performed at 100 ° C. for 30 minutes (after being put into an oven at 100 ° C.), and then at 170 ° C. (after being transferred to an oven at 170 ° C.) for 30 minutes. Thereafter, the substrate was taken out in a room temperature atmosphere.

(4) Formation of via hole by excimer laser An excimer laser processing machine ("ELP300 Gen2" manufactured by SUS MicroTech) was used to form a small diameter via hole in the insulating layer. Via holes were formed under the following conditions I-1 for Example 1, and under the following conditions I-2 for Examples 2 to 4 and Comparative Examples 1 and 2. The obtained substrate is referred to as “evaluation substrate b”.
Condition I-1: Laser wavelength 248 nm (KrF), frequency 30 Hz, pulse 14, target top diameter 5 μm, scan ablation processing method Condition I-2: Laser wavelength 308 nm (XeCl), frequency 100 Hz, pulse 30, target top diameter 10 μm, Scan ablation processing method

<Measurement of arithmetic average roughness (Ra)>
For the evaluation substrate a, using a non-contact type surface roughness meter (“WYKO NT3300” manufactured by BEIKO INSTRUMENTS), Ra value was obtained from a numerical value obtained with a measurement range of 121 μm × 92 μm using a VSI contact mode and a 50 × lens. . The average value of 10 points randomly selected for each sample was determined.

<Evaluation of particle size of inorganic filler in insulating layer>
About the evaluation board | substrate b, the cross-sectional observation of the insulating layer was performed using FIB-SEM composite apparatus ("SMI3050SE" by SII nanotechnology Co., Ltd.). Specifically, a cross section in a direction perpendicular to the surface of the evaluation substrate was cut out by FIB (focused ion beam), and a cross-sectional SEM image (observation width 30 μm, observation magnification x9000) was obtained. For each sample, 10 randomly selected cross-sectional SEM images were acquired.
For each of the acquired 10 cross-sectional SEM images, a region having a width of 15 μm, that is, a rectangular region having a total length of the insulating layer and a width of 15 μm (total thickness of the insulating layer (vertical) × 15 μm (horizontal)) The number of inorganic fillers having a particle size of 3 μm or more contained in was counted, and an average number n was obtained for 10 cross-sectional SEM images. Here, the “inorganic filler having a particle diameter of 3 μm or more” refers to an inorganic filler having a maximum diameter of 3 μm or more in a cross-sectional SEM image. Further, when more than ½ of the maximum diameter of the inorganic filler was in the region having a width of 15 μm, the inorganic filler was determined to be “included in the region having a width of 15 μm”.

<Measurement of resin area and inorganic filler area in cross section of insulating layer>
About the evaluation board | substrate b, the cross-sectional observation of the insulating layer was performed using FIB-SEM composite apparatus ("SMI3050SE" by SII nanotechnology Co., Ltd.). Specifically, a cross section in a direction perpendicular to the surface of the evaluation substrate was cut out by FIB (focused ion beam), and a cross-sectional SEM image (observation width 30 μm, observation magnification x9000) was obtained. For each sample, 10 randomly selected cross-sectional SEM images were acquired. For each of the acquired 10 cross-sectional SEM images, a region having a width of 15 μm, that is, a rectangular region having a total length of the insulating layer and a width of 15 μm (total thickness of the insulating layer (vertical) × 15 μm (horizontal)) The resin area A ₁ and the inorganic filler area A ₂ were measured, and the value of A ₂ / (A ₁ + A ₂ ) was calculated from the obtained A ₁ value and A ₂ value.
Specifically, the resin area A ₁ and the inorganic filler area A ₂ are obtained by storing an SEM observation image as an image, and using image analysis software, the resin portion is black and the inorganic filler portion other than the resin is white. binarized black and white as the number of bits black portion and the resin area a _1, and the number of bits the white portion and the inorganic filler area a _2.

<Evaluation of via shape>
About the evaluation board | substrate b, the surface of the via-hole opening part was observed using the scanning electron microscope ("S-4800" by Hitachi High-Technologies Corporation). From the obtained image, the opening diameter D of the via hole and the minimum diameter D _min of the via hole were measured. D and D _min were measured for 10 via holes, and the average value of the D _min / D ratio was determined. The via shape was evaluated according to the following evaluation criteria based on the average value of the obtained D _min / D ratios.
Evaluation criteria:
○: D _min / D ratio is 0.65 or more ×: D _min / D ratio is less than 0.65

<Evaluation of smear>
For the evaluation substrate b, the surface of the via hole opening was observed with a scanning electron microscope ("S-4800" manufactured by Hitachi High-Technologies Corporation), and the maximum smear length from the wall surface at the bottom of the via hole was measured from the obtained image. . The smear was evaluated according to the following evaluation criteria.
Evaluation criteria:
○: Maximum smear length is 2 μm or less ×: Maximum smear length is more than 2 μm

<Preparation Example 1> (Preparation of resin varnish 1)
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts of naphthalene type epoxy resin (“HP4032SS” manufactured by DIC Corporation) , Epoxy equivalent of 144) 5 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000L", epoxy equivalent 269) 20 parts, and phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 30 mass % Cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution) was dissolved by heating in 15 parts of solvent naphtha and 5 parts of MEK with stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution with a solid content of 60%), naphthol curing agent ( "SN-485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 10 parts of a MEK solution having a hydroxyl equivalent weight of 215 and a solid content of 60%, polyvinyl butyral resin (glass transition temperature of 105 ° C, "KS-1" manufactured by Sekisui Chemical Co., Ltd.) ) 15 parts solid mixed solution of ethanol and toluene with 15% solid content, 1 part amine curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% solid content), flame retardant ( "HCA-HQ" manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxai , 2 parts of average particle diameter), spherical silica surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) (“UFP-40” manufactured by Denki Kagaku Kogyo Co., Ltd.), average particle diameter of 0 .1 μm, 20 parts of carbon per unit surface area of 0.21 mg / m ² ) were mixed and dispersed uniformly with a high-speed rotary mixer, then a cartridge filter (“SCP-010” manufactured by Loki Techno Co., Ltd., filtration efficiency (manufacturer) Nominal value): 1 μm or more of particles were filtered by 99.9% or more) to prepare a resin varnish 1.

<Preparation Example 2> (Preparation of resin varnish 2)
Bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type) 8 parts, bixylenol type epoxy resin (manufactured by Mitsubishi Chemical Corporation) “YX4000HK”, 10 parts of epoxy equivalent of about 185), 10 parts of dicyclopentadiene type epoxy resin (DIC Corporation “HP-7200HH”, epoxy equivalent of 280), and phenoxy resin (“YX7553BH30” made by Mitsubishi Chemical Corporation) 12 parts of cyclohexanone: MEK having a solid content of 30% by mass) was dissolved by heating in 28 parts of solvent naphtha and 5 parts of MEK while stirring. After cooling to room temperature, 10 parts of a triazine skeleton-containing cresol novolac-based curing agent (hydroxyl equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution with a solid content of 50%), 10 parts of active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by mass of non-volatile component in toluene solution), amine curing accelerator (DMAP, solid content of 5% by mass) 1.6 parts of an MEK solution), 1 part of an imidazole-based curing accelerator (1-benzyl-2-phenylimidazole (1B2PZ), MEK solution having a solid content of 5% by mass), a flame retardant (“HCA-” manufactured by Sanko Co., Ltd.) HQ ", average particle size 2 μm) 2 parts, surface treated with N-phenyl-3-aminopropyltrimethoxysilane (“ KBM573 ”manufactured by Shin-Etsu Chemical Co., Ltd.) Spherical silica (Co. Admatechs Ltd., "SO-C2", average particle size 0.5 [mu] m, the carbon amount 0.38 mg ^/ m 2 per unit surface area) 130 parts were mixed, after uniformly dispersed in a high-speed rotary mixer The resin varnish 2 was prepared by filtration with a cartridge filter (“SHP-050” manufactured by Loki Techno Co., Ltd., filtration efficiency (manufacturer nominal value): particles of 3 μm or more were cut 99.9% or more).

<Preparation Example 3> (Preparation of resin varnish 3)
10 parts bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation “YL7723”, epoxy equivalent of about 238), 10 parts of bixylenol type epoxy resin (Mitsubishi Chemical Corporation “YX4000HK”, epoxy equivalent of about 185), biphenyl type Epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 269) 10 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content 30 mass% cyclohexanone: 1: 1 solution of MEK) 10 parts were dissolved by heating in 25 parts of solvent naphtha and 5 parts of MEK while stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent: 125, “LA-7054” manufactured by DIC Corporation, MEK solution with a solid content of 60%), active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223, non-volatile component 65 mass% toluene solution) 15 parts, amine curing accelerator (DMAP, solid content 5 mass% MEK solution) 2 Parts, phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) and N-phenyl-3-aminopropyltrimethoxysilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (1: 1 by weight) Spherical silica surface-treated with a mixture (“SO-C1” manufactured by Admatechs Co., Ltd.), average particle size of 0.25 μm, amount of carbon per unit surface area of 0.35 m / ^M 2) were mixed 100 parts, after uniformly dispersed in a high-speed rotary mixer, a cartridge filter (Co. Rokitekuno Ltd. "SHP-030", filtration efficiency (nominal value by the maker): 2 [mu] m or more particles 99.9 The resin varnish 3 was prepared by filtration.

<Preparation Example 4> (Preparation of resin varnish 4)
1) Spherical silica surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) (“UFP-40” manufactured by Denki Kagaku Kogyo Co., Ltd.), average particle size of 0.1 μm, per unit surface area Instead of 20 parts of carbon (0.21 mg / m ² ), spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd.) surface-treated with phenyltrimethoxysilane (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd.) ² ) The point of using 20 parts of average particle diameter 1 μm and carbon amount per unit surface area 0.30 mg / m ² ) 2) “SHP-150” manufactured by Loki Techno Co., Ltd. (filtration efficiency (manufacturer nominal value): Resin varnish 4 was prepared in the same manner as in Preparation Example 1 except that the particle size of 5 μm or more was cut to 98% or more.

<Preparation Example 1> Preparation of Adhesive Film 1 As a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc.), which was release-treated with an alkyd resin mold release agent (“AL-5” manufactured by Lintec Corporation), A thickness of 38 μm and a softening point of 130 ° C. were prepared. The resin varnish 1 was applied to the release surface of the support with a die coater and dried at 80 ° C. to 110 ° C. (average 100 ° C.) for 1 minute to form a resin composition layer. The thickness of the resin composition layer was 5 μm. Next, a polypropylene film (“Alphan MA-411” manufactured by Oji Specialty Paper Co., Ltd., thickness 15 μm) is used as a protective film on the surface of the resin composition layer not bonded to the support, and the rough surface of the protective film. Were laminated so as to be bonded to the resin composition layer, and the adhesive film 1 was produced.

<Production Example 2> Production of adhesive film 2 As a support, a PET film ("Lumirror T6AM" manufactured by Toray Industries, Inc.), which has been subjected to a release treatment with an alkyd resin mold release agent ("AL-5" manufactured by Lintec Corporation), A thickness of 38 μm and a softening point of 130 ° C. were prepared. The resin varnish 1 was applied to the release surface of the support with a die coater, and dried at 80 ° C. to 110 ° C. (average 100 ° C.) for 1.5 minutes to form a resin composition layer. The thickness of the resin composition layer was 10 μm. Next, a polypropylene film (“Alphan MA-411” manufactured by Oji Specialty Paper Co., Ltd., thickness 15 μm) is used as a protective film on the surface of the resin composition layer not bonded to the support, and the rough surface of the protective film. Were laminated so as to be bonded to the resin composition layer, and an adhesive film 2 was produced.

<Production Example 3> Production of Adhesive Film 3 Adhesive film 3 was produced in the same manner as Production Example 2 except that resin varnish 2 was used instead of resin varnish 1.

<Production Example 4> Production of Adhesive Film 4 Adhesive film 4 was produced in the same manner as Production Example 2 except that resin varnish 3 was used instead of resin varnish 1.

<Production Example 5> Production of adhesive film 5 Adhesive film 5 was produced in the same manner as Production Example 2 except that resin varnish 4 was used instead of resin varnish 1.

<Example 1>
Using the adhesive film 1, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Example 2>
Using the adhesive film 2, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Example 3>
Using the adhesive film 3, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Example 4>
Using the adhesive film 4, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Comparative Example 1>
Using the adhesive film 5, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

<Comparative example 2>
Using the adhesive film 2, an evaluation substrate was prepared according to the above [Preparation of measurement / evaluation substrate], and each evaluation was performed.

The evaluation results are shown in Table 2.

DESCRIPTION OF SYMBOLS 1 Inner layer board | substrate 10 Insulating layer 11 Resin component 12 Inorganic filler

Claims (15)

A circuit board including an insulating layer in which a via hole having an opening diameter of 15 μm or less is formed,
The arithmetic average roughness (Ra) of the surface of the insulating layer is 150 nm or less,
The insulating layer contains an inorganic filler, and the average number of inorganic fillers having a particle diameter of 3 μm or more contained in a region having a width of 15 μm is 1.0 or less in a cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer. Circuit board.   The circuit board according to claim 1, wherein Ra on the surface of the insulating layer is 100 nm or less.   The circuit board according to claim 1, wherein an opening diameter of the via hole is 12 μm or less. In the cross section of the insulating layer in the direction perpendicular to the surface of the insulating layer, the resin area A ₁ and the inorganic filler area A _{2 in} the region having a width of 15 μm satisfy 0.1 ≦ A ₂ / (A ₁ + A ₂ ). The circuit board according to claim 1. 5. The circuit board according to claim 1, wherein an opening diameter D of the via hole and a minimum diameter D _min of the via hole satisfy 0.65 ≦ D _min / D.   The circuit board according to claim 1, wherein the insulating layer includes an inorganic filler surface-treated with a silane compound containing an organic group having an aromatic ring.   The circuit board according to claim 1, wherein the inorganic filler is silica.   A semiconductor device comprising the circuit board according to claim 1. (A) A step of laminating an adhesive film including a support and a resin composition layer provided on the support on the inner layer substrate such that the resin composition layer is bonded to the inner layer substrate;
(B) including a step of thermally curing the resin composition layer with the support attached thereto to form an insulating layer; and (C) forming a via hole having an opening diameter of 15 μm or less in the insulating layer by an excimer laser. In the method for manufacturing a circuit board, the insulating layer formed in the step (B) includes an inorganic filler, and particles included in a region having a width of 15 μm in a cross section of the insulating layer in a direction perpendicular to the surface of the insulating layer. A method for producing a circuit board, wherein the average number of inorganic fillers having a diameter of 3 μm or more is 1.0 or less.   The method according to claim 9, wherein the support is removed before step (C).   The method according to claim 9 or 10, wherein the surface of the insulating layer has an arithmetic average roughness (Ra) of 150 nm or less. In the cross section of the insulating layer in the direction perpendicular to the surface of the insulating layer, the resin area A ₁ and the inorganic filler area A _{2 in} the region having a width of 15 μm satisfy 0.1 ≦ A ₂ / (A ₁ + A ₂ ). The method according to any one of claims 9 to 11. The method according to claim 9, wherein the via hole opening diameter D and the via hole minimum diameter D _min satisfy 0.65 ≦ D _min / D.   The method of any one of Claims 9-13 in which an insulating layer contains the inorganic filler surface-treated with the silane compound containing the organic group which has an aromatic ring.   The method according to any one of claims 9 to 14, wherein the inorganic filler is silica.

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