JP2018133416A - Circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high frequency circuit board that achieves both reduction in a dielectric constant of an insulating layer for forming a high frequency circuit and excellent adhesion of an insulating layer for forming a high frequency circuit to an inner layer substrate.SOLUTION: In a high frequency circuit board including an inner layer substrate and an insulating layer bonded to the inner layer substrate, when a dielectric constant of the inner layer substrate is Dk (A), and a dielectric constant of a high frequency circuit forming insulating layer is Dk (B), Dk(A) and Dk(B) satisfy an expression, which is Dk(B)≤Dk(A)-0.8, and the peel strength of the high frequency circuit forming insulating layer to the inner layer substrate is 0.5 kgf/cm or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a circuit board, a resin composition used as a material for an insulating layer of the circuit board, and an adhesive film formed using the resin composition.

  Circuit boards widely used in electronic devices are required to have finer wiring and higher density in order to reduce the size and increase the functionality of electronic devices. As a structure of a circuit board, particularly a circuit board (high frequency circuit board) on which a high frequency device is mounted, an insulating layer is provided on at least one main surface of a core board (inner layer board), and a conductor layer (wiring) is provided on the insulating layer. Is provided. There is also known a high-frequency circuit board having a multilayer wiring structure in which a plurality of insulating layers and conductor layers are provided on one main surface of the core board. A manufacturing method of a high-frequency circuit board having such a multilayer wiring structure is based on a build-up method in which a multilayer wiring structure is formed by alternately forming insulating layers and conductor layers on the main surface of a core substrate and stacking them. Manufacturing methods are known.

  In the method of manufacturing a high-frequency circuit board by a build-up method, the insulating layer is, for example, a resin composition layer (adhesive film) with a support including a support and a resin composition layer, and the resin composition layer is used as a core substrate. It can form by laminating | stacking and thermosetting a resin composition layer. Next, a via hole can be formed by drilling the formed insulating layer (see, for example, Patent Document 1).

  One of the factors of electric signal attenuation in the circuit board is that the dielectric constant of the insulating layer is large. In order to suppress the attenuation of the electric signal due to the large dielectric constant of the insulating layer, it is required to make the dielectric constant smaller.

  In high-frequency circuit boards that transmit high-frequency electrical signals, transmission loss due to the high dielectric constant of the high-frequency circuit-forming insulating layer is significant. For high-frequency circuit boards that are required to transmit high-frequency electrical signals such as for servers In particular, it is required to further reduce the dielectric constant of the insulating layer for forming a high-frequency circuit.

Japanese Patent Laid-Open No. 2016-35969

  The high-frequency circuit board is manufactured using an inner layer substrate having a relatively low dielectric constant and a relatively high dielectric constant, such as a glass epoxy substrate, in order to reduce costs while ensuring electrical characteristics.

  However, in such a conventional high-frequency circuit board, if the dielectric constant of the high-frequency circuit forming insulating layer is made smaller in view of the required electrical characteristics, the adhesion of the high-frequency circuit forming insulating layer to the inner layer substrate is ensured. In some cases, the high-frequency circuit forming insulating layer may be peeled off from the inner layer substrate.

  As a result, the reliability of a device (semiconductor device) provided with such a high-frequency circuit board may be impaired.

  Therefore, in a high-frequency circuit board using a relatively inexpensive inner layer substrate, the dielectric constant of the high-frequency circuit forming insulating layer can be further reduced, and high adhesion to the inner layer substrate of the high-frequency circuit forming insulating layer can be ensured. Therefore, a high-frequency circuit board with improved reliability is demanded.

  The present invention has been made in view of the above problems. As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by a high frequency circuit board adopting a predetermined configuration, and have completed the present invention.

That is, the present invention provides the following [1] to [16].
[1] an inner layer substrate;
A high frequency circuit board comprising a high frequency circuit forming insulating layer bonded to the inner layer board,
When the dielectric constant of the inner layer substrate is Dk (A) and the dielectric constant of the high-frequency circuit forming insulating layer is Dk (B), Dk (A) and Dk (B) are expressed by the following formula:
Dk (B) ≦ Dk (A) −0.8
And the peel strength of the insulating layer for forming a high frequency circuit with respect to the inner layer substrate is 0.5 kgf / cm or more.
[2] Only one insulating layer for forming a high-frequency circuit is provided, or two or more insulating layers for forming a high-frequency circuit are provided on one main surface side of the inner layer substrate. The high-frequency circuit board described.
[3] The high-frequency circuit board according to [1] or [2], wherein the insulating layer for forming a high-frequency circuit has a thickness of 20 to 200 μm.
[4] The high-frequency circuit board according to any one of [1] to [3], wherein the inner layer substrate has a thickness of 50 to 4000 μm.
[5] The inner layer substrate includes a glass epoxy substrate, and the insulating layer for high frequency circuit formation bonded to the glass epoxy substrate is a cured body obtained by thermosetting a resin composition including the component (A) epoxy resin. , [1] to [4].
[6] The inner layer substrate includes one or more insulating layers obtained by curing a material containing an epoxy resin, and the insulating layer for high-frequency circuit formation is bonded to the insulating layer, and the insulating layer for high-frequency circuit formation includes: The high-frequency circuit board according to any one of [1] to [5], which is a cured body obtained by thermosetting a resin composition containing the component (A) epoxy resin.
[7] The high-frequency circuit board according to [5] or [6], wherein the resin composition further includes a component (B) curing agent and a component (C) inorganic filler.
[8] The high frequency circuit board according to [7], wherein the resin composition further includes an organic filler (D).
[9] The component (D) organic filler is one or more organic fillers selected from the group consisting of cycloolefin polymer particles, polyphenylene ether particles, polystyrene particles, and fluorine-based polymer particles. [8] A high-frequency circuit board according to 1.
[10] The high-frequency circuit board according to [9], wherein the component (D) organic filler is fluoropolymer particles.
[11] The high-frequency circuit board according to [9] or [10], wherein the resin composition further includes a component (E) a resin having a vinyl group.
[12] The high-frequency circuit board according to any one of [9] to [11], wherein the resin composition further includes a component (F) indene coumarone resin.
[13] The high-frequency circuit board according to [12], wherein the resin composition further includes a component (H) silane compound.
[14] The high-frequency circuit board according to any one of [1] to [13], wherein the Dk (A) is 4.0 or more.
[15] The high-frequency circuit board according to any one of [1] to [14], wherein the Dk (B) is 3.5 or less.
[16] The high-frequency circuit board according to [15], wherein the Dk (B) is 3.0 or less.

  According to the present invention, in a high-frequency circuit board using a relatively inexpensive inner layer substrate, the dielectric constant of the high-frequency circuit forming insulating layer further formed on the inner layer substrate can be further reduced, and high adhesion to the inner layer substrate can be achieved. It is possible to provide a high-frequency circuit board that is provided with an insulating layer for forming a high-frequency circuit and has excellent reliability.

FIG. 1 is a schematic diagram for explaining the configuration of the high-frequency circuit board according to the first embodiment. FIG. 2 is a schematic diagram for explaining the configuration of the high-frequency circuit board according to the second embodiment. FIG. 3 is a schematic diagram for explaining the configuration of the high-frequency circuit board according to the third embodiment.

  Embodiments of the present invention will be described below with reference to the drawings. It should be noted that the drawings only schematically show the shape, size, and arrangement of the components to the extent that the invention can be understood. The present invention is not limited to the following description, and each component can be appropriately changed without departing from the gist of the present invention. In the drawings used for the following description, the same components are denoted by the same reference numerals, and overlapping descriptions may be omitted. Further, the configuration according to the embodiment of the present invention is not necessarily manufactured or used in the arrangement shown in the drawing.

[High-frequency circuit board]
As described above, the high-frequency circuit board of the present invention is a high-frequency circuit board including an inner layer substrate and a high-frequency circuit forming insulating layer bonded to the inner layer substrate, and the dielectric constant of the inner layer substrate is Dk (A). And when the dielectric constant of the high-frequency circuit forming insulating layer is Dk (B), Dk (A) and Dk (B) satisfy the formula: Dk (B) ≦ Dk (A) −0.8, and The high-frequency circuit board is such that the peel strength of the insulating layer for forming a high-frequency circuit with respect to the inner layer board is 0.5 kgf / cm or more.

  Here, the “high frequency circuit board” means a circuit board that can be operated even with an electric signal in a high frequency band. Here, the “high frequency band” means a band of 1 GHz or more. The high-frequency circuit board of the present invention can be effectively operated even with an electrical signal in the band of 28 GHz to 80 GHz.

  First, each of the inner layer substrate and the high frequency circuit forming insulating layer provided on the inner layer substrate provided in the high frequency circuit substrate will be described.

<Inner layer substrate>
The inner layer substrate includes a core substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. The inner layer substrate may be the core substrate itself. A conductor layer (semiconductor layer) may be directly provided on one side or both sides of the first main surface and the second main surface facing each other of the core substrate. You may be provided in the insulating layer provided in the surface and / or the 2nd main surface. The inner layer substrate may have a multilayer structure in which two or more insulating layers and / or conductor layers are laminated. The inner layer substrate includes a multilayer substrate in which two or more conductor layers are electrically connected to each other by a wiring provided in a via hole or a through hole. The inner layer substrate may comprise any suitable additional components such as passive elements.

  As the core substrate, a glass epoxy substrate, a BT resin base material, and a thermosetting polyphenylene ether base material are preferable from the viewpoint of electrical characteristics, availability, and cost, and a glass epoxy substrate is particularly preferable. An example of a glass epoxy substrate that can be suitably used for a high-frequency circuit board is “R-1766” manufactured by Panasonic Electric Works Co., Ltd. Moreover, “R-1661” manufactured by Panasonic Electric Works Co., Ltd. is an example of an inner layer substrate that is a multilayer substrate that can be suitably used for a high-frequency circuit substrate.

  The thickness of the inner layer substrate that can be used for the high-frequency circuit board is usually 50 μm to 4000 μm. From the viewpoint of improving the mechanical strength and reducing the height (reducing thickness) of the high-frequency circuit board, preferably 200 μm to 3200 μm.

<Insulating layer for high-frequency circuit formation>
The high-frequency circuit forming insulating layer applied to the high-frequency circuit board is a cured product layer obtained by thermosetting a resin composition described later. The insulating layer for forming a high-frequency circuit made of such a cured product can be suitably applied particularly to an insulating layer for a high-frequency circuit substrate. The insulating layer for forming a high-frequency circuit is provided not only with the wiring for configuring the high-frequency circuit that transmits the electric signal in the high-frequency band described above but also with the wiring for transmitting the electric signal in the lower-frequency band. You can also.

  In the high-frequency circuit board, the insulating layer for forming a high-frequency circuit may be provided with only one layer on the inner layer substrate, or may be provided with two or more layers. In the case where two or more insulating layers are provided, it can be provided as a build-up layer in which conductor layers (wiring layers) and high-frequency circuit forming insulating layers are alternately laminated. In particular, when a glass epoxy substrate such as “R-1766” is used as the core substrate, two or more high-frequency circuit insulating layers may be provided on one main surface side of the core substrate.

  As described above, the inner layer substrate that can be included in the high-frequency circuit board of the present invention can have various configurations. Here, a specific arrangement relationship between the high-frequency circuit forming insulating layer and the inner layer substrate will be described. (I) When the inner layer substrate is the core substrate itself, the high-frequency circuit insulating layer is directly bonded to the main surface of the core substrate. (Ii) When the inner layer substrate includes a core substrate and a conductor layer provided on the main surface of the core substrate, the high-frequency circuit insulating layer is bonded to the main surface and the conductor layer of the core substrate. (Iii) When the inner layer substrate includes a core substrate and an insulating layer provided on the main surface of the core substrate, the high-frequency circuit insulating layer is bonded to the insulating layer. (Iv) When the inner layer substrate includes a core substrate, an insulating layer provided on the main surface of the core substrate, and a conductor layer provided on the insulating layer, the high-frequency circuit insulating layer is bonded to the insulating layer and the conductor layer. To do.

  The thickness of the insulating layer applied to the high frequency circuit board is usually 20 μm to 200 μm, and preferably 50 μm to 150 μm from the viewpoint of improving electrical characteristics and reducing the height of the high frequency circuit board.

  The insulating layer is for electrically connecting a conductor layer provided in the inner layer substrate and a conductor layer provided in the insulating layer, or for electrically connecting conductor layers provided in two or more insulating layers. One or more via holes may be provided.

  It is preferable that the dielectric constant Dk (B) of the insulating layer applied to the high-frequency circuit board is lower. Dk (B) is preferably 3.5 or less, more preferably 3.3 or less, and even more preferably 3.0 or less, from the viewpoint of making it smaller than the transmission loss of high-frequency electrical signals. . The dielectric constant can usually be 2 or more. The dielectric constant can be measured according to the method described in <Evaluation of dielectric constant> described later.

  As described above, when the dielectric constant of the inner substrate is Dk (A), it is preferable that Dk (A) and Dk (B) satisfy the formula: Dk (B) ≦ Dk (A) −0.8. Here, the dielectric constant of the inner layer substrate means a measured value in a mode in which a conductor layer (wiring layer) that the inner layer substrate can have is removed from both surfaces of the inner layer substrate.

  Select the material of the inner layer substrate, that is, the material of the core substrate to which the high frequency circuit insulating layer is bonded, and the material of the insulating layer to be bonded to the high frequency circuit insulating layer from among the insulating layers that the inner layer substrate can be provided so as to satisfy the above formula And if the material of the resin composition for forming the insulating layer for high frequency circuits is selected, the transmission loss of a high frequency electric signal can be made smaller.

  Dk (A) is not particularly limited. Dk (A) is preferably 4.0 or more from the viewpoint of cost and availability.

  The high-frequency circuit insulating layer preferably exhibits a lower dielectric loss tangent. The dielectric loss tangent is preferably 0.010 or less, more preferably 0.009 or less, more preferably 0.008 or less, from the viewpoint of heat generation prevention during transmission of a high-frequency signal, signal delay and signal noise reduction. More preferably, it is 0.007 or less, 0.006 or less, or 0.005 or less. The dielectric loss tangent can usually be 0.001 or more.

  The high-frequency circuit insulating layer exhibits good adhesion to the inner layer substrate, that is, the core substrate and the insulating layer included in the inner layer substrate. The peel strength with respect to the inner layer substrate is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and further preferably 0.6 kgf / cm or more. Evaluation of the peel strength with respect to the inner layer substrate can be measured according to the method described in [Measurement of peel strength] described later.

  The high-frequency circuit insulating layer exhibits good adhesion to the conductor layer included in the inner layer substrate, that is, excellent peel strength with respect to the conductor layer. The peel strength with respect to the conductor layer is preferably 0.4 kgf / cm or more, more preferably 0.5 kgf / cm or more, and further preferably 0.6 kgf / cm or more. Evaluation of the peel strength with respect to the conductor layer can be measured according to the method described in [Measurement of peel strength] described later.

  Here, a configuration example of the high-frequency circuit board of the present invention will be described with reference to FIG. 1, FIG. 2, and FIG.

  First, a configuration example of a high-frequency circuit board according to the first embodiment will be described with reference to FIG. FIG. 1 is a schematic diagram for explaining the configuration of the high-frequency circuit board according to the first embodiment.

  As shown in FIG. 1, the high-frequency circuit board 10 of the first embodiment includes a core substrate 22 that is an inner layer substrate 20. The core substrate 22 has a first main surface 22a (20a) and a second main surface 22b (20b) facing each other.

  The first main surface 22a is provided with a high-frequency circuit insulating layer 30 so as to be bonded to and cover the core substrate 22. A high-frequency circuit conductor layer (wiring layer) 40 is provided on the surface of the high-frequency circuit insulating layer 30. The high-frequency circuit conductor layer 40 may include not only a wiring for configuring a high-frequency circuit for transmitting a high-frequency band electrical signal but also a wiring for transmitting a lower-frequency band electrical signal. Good.

  An insulating layer 50 is provided on the second main surface 22b so as to be bonded thereto. A conductor layer (wiring layer) 60 is provided on the surface of the insulating layer 50.

  Further, in this configuration example, the through hole 12 penetrating the inner layer substrate 20, that is, the core substrate 22, the high frequency circuit insulating layer 30 and the insulating layer 50 in the thickness direction is provided. A through-hole wiring 12 a is provided in the through-hole 12. In this configuration example, a part of the high-frequency circuit conductor layer 40 and a part of the conductor layer 60 are electrically connected by the through-hole wiring 12a.

  Next, a configuration example of the high-frequency circuit board according to the second embodiment will be described with reference to FIG. FIG. 2 is a schematic diagram for explaining the configuration of the high-frequency circuit board according to the second embodiment.

  As shown in FIG. 2, the high-frequency circuit board 10 of the second embodiment includes an inner layer board 20. In this configuration example, the inner layer substrate 20 includes a core substrate 22, a first conductor layer (wiring layer) 24, and a second conductor layer (wiring layer) 26. Here, the first conductor layer 24 is provided on the first main surface 22 a of the core substrate 22, that is, the first main surface 20 a of the inner layer substrate 20. The second conductor layer 26 is provided on the second main surface 22 b of the core substrate 22, that is, the second main surface 20 b of the inner layer substrate 20.

  The first main surface 22a provided with the first conductor layer 24 is bonded to the core substrate 22 and the first conductor layer 24 so as to cover them, that is, to be bonded to the first main surface 20a of the inner layer substrate 20. A high-frequency circuit insulating layer 30 is provided on the substrate. A high-frequency circuit conductor layer 40 is provided on the surface of the high-frequency circuit insulating layer 30.

  The high frequency circuit insulating layer 30 is provided with a via hole 32 penetrating the high frequency circuit insulating layer 30 in the thickness direction. A via hole wiring 32 a is provided in the via hole 32. In this configuration example, a part of the high-frequency circuit wiring 40 and a part of the first conductor layer 24 are electrically connected by the via-hole wiring 32a.

  The second main surface 22b provided with the second conductor layer 26 is joined to the core substrate 22 and the second conductor layer 26, that is, the second main surface 20b of the inner layer substrate 20 and covers the insulating layer 50 so as to cover them. Is provided. A conductor layer 60 is provided on the surface of the insulating layer 50.

  The low frequency circuit insulating layer 50 is provided with a via hole 52 penetrating the low frequency circuit insulating layer 50 in the thickness direction. A via hole wiring 52 a is provided in the via hole 52. In this configuration example, a part of the low-frequency circuit conductor layer 60 and a part of the second conductor layer 26 are electrically connected by the via-hole wiring 52a.

  Further, in this configuration example, the through hole 12 penetrating the core substrate 22, the high-frequency circuit insulating layer 30 and the insulating layer 50 in the thickness direction is provided. A through-hole wiring 12 a is provided in the through-hole 12.

  Next, a configuration example of the high-frequency circuit board according to the third embodiment will be described with reference to FIG. FIG. 3 is a schematic diagram for explaining the configuration of the high-frequency circuit board according to the third embodiment.

  As shown in FIG. 3, the high-frequency circuit board 10 of the third embodiment includes an inner layer substrate 20. In this configuration example, the inner layer substrate 20 includes a core substrate 22, a first conductor layer 24, a second conductor layer 26, an interlayer insulating layer 27, and a third conductor layer (wiring layer) 28. Here, the first conductor layer 24 is provided on the first main surface 22 a of the core substrate 22. The second conductor layer 26 is provided on the second main surface 22 b of the core substrate 22. The interlayer insulating layer 27 is provided so as to be bonded to and cover the core substrate 22 and the first conductor layer 24. The third conductor layer 28 is provided so as to be joined to the interlayer insulating layer 27.

  The high-frequency circuit insulating layer 30 is provided so as to be bonded to and cover the interlayer insulating layer 27 and the third conductor layer 28, that is, to be bonded to the first main surface 20 a of the inner layer substrate 20. A high-frequency circuit conductor layer 40 is provided on the surface of the high-frequency circuit insulating layer 30.

  The interlayer insulating layer 27 is provided with a via hole 29 that penetrates the interlayer insulating layer 27 in the thickness direction. In the via hole 29, a via hole wiring 29a is provided. In this configuration example, a part of the high-frequency circuit wiring 40 and a part of the third conductor layer 28 are electrically connected by the via-hole wiring 29a.

  An insulating layer 50 is provided on the second main surface 22b on which the second conductor layer 26 is provided, that is, the second main surface 20b of the inner layer substrate 20 so as to be bonded thereto. A conductor layer 60 is provided on the surface of the insulating layer 50.

  The insulating layer 50 is provided with a via hole 52 that penetrates the insulating layer 50 in the thickness direction. A via hole wiring 52 a is provided in the via hole 52. In this configuration example, a part of the conductor layer 60 and a part of the second conductor layer 26 are electrically connected by the via-hole wiring 52a.

  Further, in this configuration example, the through-hole 12 penetrating the core substrate 22, the interlayer insulating layer 27, the high-frequency circuit insulating layer 30 and the insulating layer 50 in the thickness direction is provided. A through-hole wiring 12 a is provided in the through-hole 12.

[Method for manufacturing high-frequency circuit board]
Next, a method for manufacturing a high-frequency circuit board will be described. First, the adhesive film used for this manufacturing method is demonstrated.

<Adhesive film>
The adhesive film includes a support and a resin composition layer that is provided on the support and includes a resin composition to be described later.

Support Examples of the support include a film made of a plastic material, a metal foil, and a release paper. The support is preferably a film made of a plastic material or a metal foil.

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as “PET”) and polyethylene naphthalate (hereinafter sometimes referred to as “PEN”). Examples include polyester, polycarbonate (hereinafter sometimes referred to as “PC”), acrylic polymer such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. It is done. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and polyethylene terephthalate is particularly preferable because it is inexpensive and excellent in availability.

  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 only of copper may be used, and a foil made of a copper alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) is used. May be.

  The support may be subjected to mat treatment, corona treatment, and antistatic treatment on the surface to be bonded to the resin composition layer.

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent that can be 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, polyolefin resins, urethane resins, and silicone resins. Is mentioned. As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7”, “Lumirror T6AM” manufactured by Toray Industries, Inc., and the like.

  The thickness of the support is not particularly limited. The thickness of the support is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using 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.

Resin Composition Layer The resin composition layer provided in the adhesive film is a thin film obtained by semi-curing a resin varnish coating. The adhesive film is prepared, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish to a support using a die coater or the like, and drying the resin varnish coating film to some extent. It can manufacture by setting it as a physical layer.

  Examples of the organic solvent used for forming the resin composition layer include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate. Mention may be made of esters, carbitols such as cellosolve and butyl carbitol, 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 of the coating film of the resin varnish can be carried out 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 a resin varnish containing 30% by mass to 60% by mass of the organic solvent is used, the resin varnish coating is applied at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. The resin composition layer can be formed by drying.

  In the adhesive film, a surface of the resin composition layer that is not bonded to the support (the surface opposite to the support) may be further laminated with a protective film according to the support. it can. The thickness of the protective film is not particularly limited. The thickness of the protective film is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion or scratches of dust or the like to the surface of the resin composition layer. The adhesive film can be stored in a roll. When an adhesive film has a protective film, it can be used by peeling off and removing the protective film.

  The minimum melt viscosity of the resin composition layer (or resin composition) in the adhesive film is preferably 1000 poise or more from the viewpoint of stably maintaining the thickness even when the resin composition layer is thin. More preferably, it is 1500 poise or more, and further preferably 2000 poise or more. The minimum melt viscosity of the resin composition layer is preferably 12000 poise or less, more preferably 10,000 poise or less, still more preferably 8000 poise or less, particularly preferably, from the viewpoint of improving circuit embedding properties. It is less than 5000 poise.

  The “minimum melt viscosity of the resin composition layer” refers to the minimum viscosity exhibited when the resin composition layer is melted. Specifically, when the resin composition layer is heated and melted at a constant rate of temperature increase, the melt viscosity initially decreases as the temperature rises, and then the melt viscosity increases as the temperature rises over a period of time. . The lowest melt viscosity is the minimum melt viscosity at which the melt viscosity is the lowest. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelastic method.

<Prepreg>
The insulating layer on the high-frequency circuit board may be formed using a prepreg instead of the adhesive film described above. The prepreg can be formed by impregnating a sheet-like fiber base material with a resin composition described later.
The prepreg may contain only one sheet-like fiber base material, or may contain two or more sheet-like fiber base materials.

  The material of the sheet-like fiber base material used for the prepreg is not particularly limited. As the sheet-like fiber substrate, those commonly used as prepreg substrates such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of thinning the high-frequency circuit board, the thickness of the sheet-like fiber base material is preferably 200 μm or less, more preferably 150 μm or less, further preferably 120 μm or less, and even more preferably 100 μm or less. is there. Since the depth of plating for forming the conductor layer can be kept small, it is preferably 800 μm or less, more preferably 70 μm or less, and even more preferably 60 μm or less. The thickness of a sheet-like fiber base material can be normally 4 micrometers or more, can be 6 micrometers or more, and can be 8 micrometers or more. When the “nonvolatile component” is referred to for the prepreg, the “nonvolatile component” does not include the “sheet-like fiber substrate”.

  The prepreg can be produced by a known method such as a hot melt method or a solvent method.

  The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

A high frequency circuit board can be manufactured by the manufacturing method including the following process (I) and process (II) using an adhesive film.
Step (I) Step of laminating an adhesive film on the inner layer substrate so that the resin composition layer of the adhesive film is bonded to the inner layer substrate Step (II) Step of thermosetting the resin composition layer to form an insulating layer

  Lamination | stacking of the adhesive film to an inner layer board | substrate can be performed by the thermocompression bonding process heated, for example, pressing an adhesive film to an inner layer board | substrate from the support body side. Examples of the member used in the thermocompression bonding process (also referred to as “thermocompression bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). Instead of pressing the thermocompression bonding member directly against the support of the adhesive film and pressing it, an elastic material such as heat-resistant rubber is used so that the adhesive film sufficiently follows the irregularities on the main surface of the inner layer substrate. It is preferable to press it.

  Lamination of the inner layer substrate and the adhesive film can 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 in the range of 80 ° C to 140 ° C. The pressure for thermocompression bonding is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the time for thermocompression bonding is preferably in the range of 20 seconds to 400 seconds. More preferably, it is 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 Co., Ltd. and a vacuum applicator manufactured by Nikko Materials Co., Ltd.

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

  The support may be removed between step (I) and step (II), or may be removed after step (II).

  In step (II), the laminated (and smoothing) resin composition layer is thermoset to form an insulating layer.

  The conditions for thermosetting the resin composition layer are not particularly limited, and conditions usually employed when forming the insulating layer of the high-frequency circuit board can be employed.

  The thermosetting conditions of the resin composition layer include, for example, a curing temperature in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C., more preferably in the range of 170 ° C. to 200 ° C.), and a curing time of 5 It can be in the range of minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  When manufacturing a high-frequency circuit board, any one of (III) a step of drilling an insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer is further performed. May be. These steps (III) to (V) can be performed according to various methods known to those skilled in the art, which are used for manufacturing a high-frequency circuit board. When the support is removed after step (II), the support is removed between step (II) and step (III), between step (III) and step (IV), or step It can be carried out between (IV) and step (V).

  In another embodiment, the insulating layer according to the high-frequency circuit board of the present invention may be formed using the prepreg already described instead of the adhesive film. The formation of the insulating layer using the prepreg can be basically performed by the same process as in the case of using the adhesive film.

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, a laser, plasma, or the like according to the composition of the resin composition used for forming the insulating layer. What is necessary is just to determine the dimension and shape of a hole suitably according to the design of a high frequency circuit board.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are normally used when forming the insulating layer of the high-frequency circuit board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid is not particularly limited. Examples of the swelling liquid include an alkaline solution and a surfactant solution. The swelling liquid is preferably an alkaline solution, and the alkaline solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. The swelling treatment with the swelling liquid is not particularly limited. The swelling treatment can be performed, for example, by immersing the insulating layer in a swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. The oxidizing agent is not particularly limited. Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening 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 oxidizing agents include alkaline permanganic acid solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. Moreover, as a neutralization liquid, acidic aqueous solution is preferable. As a commercial item of a neutralization liquid, Atotech Japan Co., Ltd. product "Reduction Solution Securigant P" is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface of the insulating layer 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, it is preferable to immerse the insulating layer subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes.

  In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 280 nm or less, more preferably 250 nm or less, still more preferably 200 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, 95 nm or less, or 90 nm or less. The Ra value is preferably 0.5 nm or more, and more preferably 1 nm or more. 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 Co., Ltd. may be mentioned.

  Step (V) is a step of forming a conductor layer.

  The 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). Above all, from the viewpoint of versatility of forming the conductor layer, cost, easiness of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper -Nickel alloy, copper-titanium alloy alloy layer is preferable, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper single metal layer, or nickel-chromium alloy alloy layer is more preferable, copper A single 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 3 μm to 200 μm, preferably 10 μm to 100 μm.

  In one embodiment, the conductor layer can be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known method such as a semi-additive method, a modified-semi-additive method, or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by the modified semi-additive method will be described.

  First, a copper foil layer is formed on the surface of the insulating layer. As the copper foil layer, for example, the copper foil used as a support for the adhesive film may be used as it is, or the copper foil may be used with a thinner thickness by, for example, an etching process. Next, using the copper foil layer as a seed layer, a mask pattern exposing a part of the seed layer is formed so as to correspond to a desired wiring pattern. After the metal layer is formed on the exposed seed layer by electrolytic plating, the mask pattern is removed. Thereafter, an unnecessary seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  When the high-frequency circuit board includes two or more high-frequency circuit insulating layers and wiring layers (build-up layers), the above-described high-frequency circuit insulating layer forming step and conductor layer forming step are repeated once more. By implementing this, a high frequency circuit board having a multilayer wiring structure that can function as a high frequency circuit can be manufactured.

[Resin composition]
Hereinafter, the resin composition which can be used suitably for formation of the adhesive film and prepreg for manufacturing the high frequency circuit board of this invention is demonstrated.

  The component of the resin composition for forming the insulating layer for high-frequency circuit is the component of the inner-layer substrate used from the viewpoint of increasing the adhesion (peel strength) of the insulating layer for high-frequency circuit, which is a cured product of the resin composition, to the inner-layer substrate. In consideration of the material, it is preferable to select a material having the same structure and the same characteristics (for example, the magnitude of polarity) as the material of the inner layer substrate.

  For example, when the core substrate to be bonded to the high frequency circuit insulating layer includes an epoxy resin such as a glass epoxy substrate as a material and / or the insulating layer provided in the inner layer substrate, the insulating layer to be bonded to the high frequency circuit insulating layer is made of epoxy resin. When it is included, the resin composition preferably contains the component (A) epoxy resin. For example, when the core substrate to be bonded to the high-frequency circuit insulating layer is a BT resin substrate and / or the insulation provided in the inner layer substrate When the insulating layer that is a layer and is bonded to the high-frequency circuit insulating layer contains a resin having a carbodiimide group or a resin having a triazine skeleton, the resin composition contains a resin having a carbodiimide group or a resin having a triazine skeleton It is preferable that the core substrate bonded to the high-frequency circuit insulating layer is a polyphenylene ether substrate. / Or an insulating layer lining the substrate is provided when the insulating layer to be bonded to the high-frequency circuit insulating layer contains a resin having a polyphenylene ether skeleton, a resin composition preferably contains a resin having a polyphenylene ether skeleton.

  By selecting the resin composition in this way, even if an inner layer substrate that is inexpensive and highly available is used, the adhesion of the insulating layer for a high frequency circuit to the inner layer substrate can be ensured.

<Component (A) Epoxy Resin>
The resin composition may contain a component (A) epoxy resin. Examples of the epoxy resin include bixylenol type epoxy resin, 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 novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy 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 component (A) is preferably an aromatic skeleton-containing epoxy resin from the viewpoint of reducing the average linear thermal expansion coefficient. The bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, and di More preferably, it is at least one selected from cyclopentadiene type epoxy resins, and biphenyl type epoxy resins are more preferable. The aromatic skeleton is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles.

  The epoxy resin is preferably 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, it is preferable to contain an epoxy resin having three or more epoxy groups in one molecule and solid at 20 ° C. (referred to as “solid epoxy resin”). The epoxy resin may contain only a solid epoxy resin, and has two or more epoxy groups in one molecule, and is liquid at 20 ° C. (referred to as “liquid epoxy resin”) and solid. And an epoxy resin. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL”, “825” manufactured by Mitsubishi Chemical Corporation. “Epicoat 828EL” (bisphenol A type epoxy resin), “jER807”, “1750” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “630”, “630LSD” (glycidylamine type epoxy) Resin), “ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), “EX-721” (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, "Ceroki" manufactured by Daicel Corporation Id 2021P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure)," ZX1658 "," ZX1658GS "(liquid 1,4-) manufactured by Nippon Steel Chemical Co., Ltd. Glycidylcyclohexane). 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, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable.

  Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. (Cresol novolac type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “HP-7200H”, “EXA-” 7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN-502H "manufactured by Nippon Kayaku Co., Ltd. "(Trisphenol type epoxy resin)", "NC7000L" (Naphthol novolak type epoxy) ), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolak type) Epoxy resin), “YX4000H”, “YX4000”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation “PG-100”, “CG-500” manufactured by Gas Chemical Co., Ltd., “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin), Mitsubishi Chemical Co., Ltd. "JER1010" (solid screw Phenol A type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. 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 an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By making the quantitative ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) the adhesiveness can be made suitable when used in the form of an adhesive film, and ii) the adhesive film is used in the form of an adhesive film. In some cases, sufficient flexibility can be obtained, handling properties can be improved, and iii) an effect that a cured product 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 1: 0.5 to 1:10 by mass ratio. A range is more preferable, and a range of 1: 1 to 1: 8 is even more preferable.

  The content of the epoxy resin in the resin composition is preferably 5% by mass or more, more preferably 10% when the nonvolatile component is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is at least 20% by mass, more preferably at least 20% by mass. The content of the epoxy resin is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less, provided that the effects of the present invention can be obtained.

  The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By setting it as this range, the crosslinked density of hardened | cured material is enough and it can be set as an insulating layer with small surface roughness. The epoxy equivalent is the mass of a resin containing 1 equivalent of an epoxy group, and can be measured according to JIS K7236.

  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.

<Component (B) Curing Agent>
The resin composition contains a component (B) curing agent. The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. Examples of the component (B) curing agent include phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, cyanate ester curing agents, and carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. Component (B) is preferably at least one selected from phenolic curing agents, naphthol curing agents, active ester curing agents, carbodiimide curing agents, and cyanate ester curing agents, and active ester curing agents It is preferable that

  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. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include “MEH-7700”, “MEH-7810”, “MEH-7785”, “MEH-7785H” manufactured by Meiwa Kasei Co., Ltd., Nippon Kayaku Co., Ltd. ) “NHN”, “CBN”, “GPH”, Nippon Steel & Sumikin Co., Ltd. “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” ", TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

  From the viewpoint of obtaining an insulating layer for a high frequency circuit that is excellent in adhesion to the conductor layer, an active ester curing agent is preferable as the component (B). There is no restriction | limiting in particular as an active ester type hardening | curing agent. The active ester curing agent generally has two or more ester groups with high reaction activity in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compound esters. A compound is preferably used. As the active ester curing agent, a compound obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound is preferable. 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 carboxylic acid compounds that can be used 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 that can be used include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, and o-cresol. , M-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone Phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compound, and phenol novolac. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

  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 a phenol novolac, and a benzoylated product of a phenol novolac. An active ester compound containing naphthalene structure and an active ester compound containing dicyclopentadiene type diphenol structure are more preferable. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Examples of commercially available active ester curing agents include “EXB9451”, “EXB9460”, “EXB9460S”, and “HPC-8000-65T” manufactured by DIC Corporation, which are active ester compounds containing a dicyclopentadiene-type diphenol structure. ”,“ HPC-8000H-65TM ”,“ EXB-8000L-65TM ”,“ EXB9416-70BK ”manufactured by DIC, which is an active ester compound containing a naphthalene structure, and an active ester compound containing an acetylated product of phenol novolac. “DC808” manufactured by Mitsubishi Chemical Corporation and “YLH1026”, “YLH1030”, and “YLH1048” manufactured by Mitsubishi Chemical Corporation, which are active ester compounds containing a benzoylated product of phenol novolak, can be mentioned.

  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.

  Examples of the cyanate ester curing agent 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-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins Some triazine of prepolymer.

  Specific examples of cyanate ester curing agents include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (one of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. And a prepolymer in which a part or all of the triazine is converted into a trimer).

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

  The quantity ratio between the epoxy resin and the curing agent is a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] and is in the range of 1: 0.1 to 1: 1. Is more preferable, and is preferably 1: 0.2 to 1: 0.9, more preferably 1: 0.3 to 1: 0.8. 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 totaling the values obtained by dividing the mass of the nonvolatile component 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 mass of the non-volatile component of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent to such a range, the heat resistance of the cured product of the resin composition is further improved.

  The content of the curing agent in the resin composition is not particularly limited. The content in the resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less when the nonvolatile component is 100% by mass. Moreover, content of the hardening | curing agent in a resin composition becomes like this. Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 7 mass% or more.

<Component (C) Inorganic filler>
The resin composition may further contain a component (C) inorganic filler. The material of the inorganic filler is not particularly limited. Examples of the inorganic filler material include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, Magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide , Barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. 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 20 μm or less, more preferably 10 μm or less, and still more preferably from the viewpoint of improving the embedding property of the conductor layer and obtaining an insulating layer for high-frequency circuits with a low surface roughness. Is 5 μm or less, more preferably 3 μm or less, and even more preferably 1 μm or less. The average particle diameter is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “SP60-05”, “SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., “YC100C” manufactured by Admatechs Corporation, “ “YA050C”, “YA050C-MJE”, “YA010C”, “UFP-30” manufactured by Denka Corporation, “Sylfil NSS-3N”, “Sylfil NSS-4N”, “Sylfil NSS-5N” manufactured by Tokuyama Corporation, Examples include “SC2500SQ”, “SO-C4”, “SO-C2”, and “SO-C1” manufactured by Admatechs Corporation.

  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 a measurement sample, a sample in which an inorganic filler is 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.

  Inorganic fillers are aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, titanate coupling agents, etc., from the viewpoint of improving moisture resistance and dispersibility. It is preferable to treat with one or more surface treatment agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by Co., Ltd., "KBM-103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long chain) Epoxy type silane coupling agent).

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. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably at 0.02 mg / ^{m 2} or more, more preferably 0.1 mg / ^{m 2} or more, More preferably, it is 0.2 mg / m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin varnish and the melt viscosity when the resin varnish is in sheet form, the amount of carbon per unit surface area of the inorganic filler is preferably 1 mg / m ² or less, It is more preferably 0.8 mg / m ² or less, and further preferably 0.5 mg / m ² or less.

  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, first, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. Next, after removing the supernatant and drying the non-volatile components, 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.

  From the viewpoint of obtaining an insulating layer having a low dielectric constant, the content of the inorganic filler in the resin composition is preferably 10% by mass or more, more preferably 10% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. Is 20% by mass or more, more preferably 30% by mass or more, or 40% by mass or more. The content of the inorganic filler in the resin composition is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably from the viewpoint of improving the mechanical strength of the insulating layer, particularly the adhesion strength. Is 70% by mass or less.

<Component (D) Organic filler>
The resin composition may contain a component (D) organic filler.

  The particle size of component (D) is not particularly limited. The average particle size of the component (D) is excellent in dispersibility in the resin composition, is preferably 5 μm or less, more preferably 4 μm or less, and further preferably 3 μm or less. The average particle diameter of the component (D) is preferably 0.05 μm or more, more preferably 0.08 μm or more, and further preferably 0.10 μm or more. Therefore, the component (D) preferably has an average particle size of 0.05 μm to 5 μm, more preferably 0.08 μm to 4 μm, and even more preferably 0.10 μm to 3 μm.

  The component (D) is not particularly limited on the condition that the dielectric constant of the high-frequency circuit insulating layer can be reduced. Examples of the component (D) include fluororesin, fluororubber, polyethylene, polypropylene, polystyrene, polycarbonate, norbornene resin, addition copolymer resin with olefins, polyphenylene ether, bismaleimide / triazine / resin, and polyetherimide. , Particles containing a material selected from polyimide, polyetheretherketone, and liquid crystal polymer. Suitable components (D) include, for example, fluorine-based polymer particles, cycloolefin polymer particles, polyphenylene ether particles, and polystyrene particles. Among these, from the viewpoint of reducing the dielectric constant of the high-frequency circuit insulating layer, fluorine-based polymer particles containing a fluorine resin are preferable.

  Examples of the fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene-perfluorodioxide. Sole copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). These resins may be used alone or in combination of two or more.

  From the viewpoint of further reducing the dielectric constant of the high-frequency circuit insulating layer, it is preferable to use PTFE as the fluororesin. In other words, as the component (D), it is preferable to use PTFE particles which are fluorine-based polymer particles containing PTFE as the fluorine-based resin.

  The weight average molecular weight of PTFE is preferably 5000000 or less, more preferably 4000000 or less, and still more preferably 3000000 or less.

  Commercial products may be used as the fluorine-based polymer particles. Specific examples of PTFE particles, which are commercially available fluoropolymer particles, include “Lublon L-2” manufactured by Daikin Industries, Ltd., “Lublon L-5” manufactured by Daikin Industries, Ltd., and “Lublon manufactured by Daikin Industries, Ltd.” L-5F ", Asahi Glass Co., Ltd." FluonPTFE L-170JE ", Asahi Glass Co., Ltd." FluonPTFEEL-172JE ", Asahi Glass Co., Ltd." FluonPTFE L-173JE ", Kitamura" KTL-500F " "KTL-2N" manufactured by Kitamura Co., Ltd., "KTL-1N" manufactured by Kitamura Co., Ltd., and "TLP10F-1" manufactured by Mitsui DuPont Fluorochemical Co., Ltd.

  Component (D) may contain, for example, surface-treated particles. Examples of the surface treatment include surface treatment with a surface treatment agent. The surface treatment agent is not particularly limited. In addition to surfactants such as nonionic surfactants, amphoteric surfactants, cationic surfactants and anionic surfactants, the surface treatment agents include inorganic fine particles. When the component (D) is a fluoropolymer particle containing a fluororesin, it is preferable to use a fluorosurfactant as the surface treatment agent from the viewpoint of affinity. Specific examples of the fluorosurfactant include “Surflon S-243” (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Seimi Chemical Co., Ltd., “Megafac F-251” manufactured by DIC Corporation, DIC Corporation ) "Megafuck F-477", DIC Corporation "Megafuck F-553", DIC Corporation "Megafuck R-40", DIC Corporation "Megafuck R-43", DIC “Megafac R-94” manufactured by Co., Ltd., “FTX-218” manufactured by Neos Co., Ltd., “Furgent 610FM” manufactured by Neos Co., Ltd., and “Futgent 730LM” manufactured by Neos Co., Ltd. may be mentioned.

  The content of the component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 15% by mass from the viewpoint of effectively reducing the dielectric constant of the high-frequency circuit insulating layer. More preferably, it is the above. The content of component (D) is preferably 60% by mass or less, more preferably 55% by mass or less, and further preferably 45% by mass or less, 35% by mass or less, and 30% by mass or less. . Therefore, the content of the component (D) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 35% by mass, and further preferably 15% by mass to 30% by mass. .

<Component (E) Resin having an unsaturated hydrocarbon group>
The resin composition preferably contains a component (E) a resin having an unsaturated hydrocarbon group. By including a component (E), the compatibility of a resin composition can be improved and a resin composition with favorable melt viscosity can be obtained. A component (E) may be used individually by 1 type, and may be used 2 or more types.

  The component (E) is not particularly limited as long as it has an unsaturated hydrocarbon group. The unsaturated hydrocarbon group is preferably an acrylic group, a methacryl group, a styryl group, or an olefin group. Here, the “olefin group” refers to an aliphatic hydrocarbon group having a carbon-carbon double bond in the molecule. Examples of the olefin group include an allyl group, a vinyl group, and a propenyl group. That is, the component (E) is preferably a resin having one or more unsaturated hydrocarbon groups selected from the group consisting of an acryl group, a methacryl group, a styryl group, an allyl group, a vinyl group, and a propenyl group. Component (E) preferably has an aromatic ring in its structure. Especially, it is preferable that a component (E) is a compound (resin) represented by following formula (1) or (4) from a viewpoint of improving the stability at the time of a preservation | save.

In formula (1), R < ¹ > -R < ⁶ > represents a hydrogen atom and a C1-C4 alkyl group each independently. A represents a group represented by the following formula (2) or the following formula (3).

  In formula (2), E represents a group represented by the following formula (E-1), (E-2) or (E-3).

In formula (3), R ^{7 to} R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. E represents the following formula (E-1), (E-2) or (E-3). a and b are integers of 0 to 100, and at least one of a and b represents an integer that is not 0.

In formulas (E-1) to (E-3), R ^{15 to} R ³⁴ each independently represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. G represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In formula (1), R < ¹ > -R < ⁶ > represents a hydrogen atom and a C1-C4 alkyl group each independently. R ^{1 to} R ⁶ are preferably hydrogen atoms. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group.

Examples of the alkyl group having 6 or less carbon atoms according to R ^{7 to} R ¹⁴ in formula (3) and R ^{15 to} R ³⁴ in formulas (E-1) to (E-3) include, for example, a methyl group, Examples include ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, and hexyl group. R ^{7 to} R ¹⁴ are preferably a hydrogen atom or a methyl group.

  a and b are integers of 0 to 100, and at least one of a and b represents an integer that is not 0. a and b are preferably integers of 0 to 50, and more preferably integers of 0 to 10.

  G represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms. Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples of the alkenylene group having 2 to 20 carbon atoms include a vinylene group, a propenylene group, and a butenylene group. Examples of the alkynylene group having 2 to 20 carbon atoms include an ethynylene group, a propynylene group, and a butynylene group.

  The vinyl group in the resin having a vinyl group may have a substituent. The alkyl group, phenyl group, and divalent hydrocarbon group may also have a substituent.

Such a substituent is not particularly limited. Examples of the substituent include a halogen atom, a group represented by —OH, —O—C _1-6 alkyl group, —N (C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _{6-6. 10} aryl group, group represented by —NH ₂ , group represented by —CN, —C (O) O—C _1-6 alkyl group, group represented by —COOH, —C (O) H And a group represented by —NO ₂ .

The meaning of such a substituent _{"C 1-6"} and _{"C 6-10",} explain these words to generalize as _{"C p-q".} “C _p-q ” (where p and q are positive integers and p <q is satisfied) means that the number of carbon atoms of the organic group described immediately after this wording is p to q. Represents. Specifically, for example, “C _1-6 alkyl group” represents “an alkyl group having 1 to 6 carbon atoms”.

  The substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). Examples of the secondary substituent include the same groups as those already described.

  Specific examples of the component (E) include compounds represented by the following formula. The present invention is not limited to this.

In the formula, R ^{1 to} R ⁶ , E, a, and b are as defined in the formula (1) or the formula (3), and preferred ranges thereof are also the same.

  Specific examples of the component (E) include “OPE-2St 2200 (number average molecular weight 2200)”, “OPE-2St 1200 (number average molecular weight 1200)” (styrene-modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd., “YL7776 (number average molecular weight 331)” (bixylenol diallyl ether resin) manufactured by Mitsubishi Chemical Corporation may be mentioned.

  The number average molecular weight of the component (E) is preferably in the range of 100 to 10000 from the viewpoint of preventing volatilization during drying of the resin varnish and preventing the melt viscosity of the resin composition from excessively increasing, A range of 200 to 3000 is more preferable.

  The number average molecular weight is measured by gel permeation chromatography (GPC) method (polystyrene conversion). Specifically, the number average molecular weight by the GPC method 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 ", using chloroform or the like as a mobile phase, measuring at a column temperature of 40 ° C, and calculating using a standard polystyrene calibration curve.

  The content of the component (E) is preferably 30% by mass or less, more preferably 25% by mass or less when the nonvolatile component is 100% by mass from the viewpoint of obtaining a resin composition having good compatibility. More preferably, it is 20 mass% or less, or 15 mass% or less. The content of the component (E) is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more when the nonvolatile component is 100% by mass.

  By including the component (E), the resin composition can more uniformly disperse the component (D) already described (particularly, the fluorine-based polymer particles) in the resin composition. As a result, since the uniformity of the resin composition is improved, the adhesion to the core substrate can be further improved, thereby improving the electrical characteristics such as the dielectric constant of the formed insulating layer, and the reliability of the device Can be improved.

<Ingredient (F) Inden Coumarone Resin>
The resin composition preferably contains the component (F) indene coumarone resin. By including the component (F), the compatibility is improved and a resin composition having a good balance of physical properties can be obtained. The coumarone skeleton contained in the component (F) is highly compatible with highly polar epoxy resins and curing agents, and the indene skeleton and coumarone skeleton are highly compatible with low polarity vinyl resins. Therefore, it functions as a compatibilizing agent between a resin having a high polarity and a resin having a low polarity, and the compatibility of the entire resin composition is considered to be improved.

  Examples of the component (F) include a copolymer of indene and coumarone, and a copolymer of indene, coumarone and styrene.

  The content ratio of the coumarone structure in the indene coumarone resin is preferably 5 mol% or more, more preferably 8 mol% or more, and further preferably 10 mol% or more. The content ratio of the coumarone structure in the indene coumarone resin is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less.

  The content ratio of the indene structure in the indene coumarone resin is preferably 30 mol% or more, more preferably 35 mol% or more, and further preferably 40 mol% or more. The content ratio of the indene structure in the indene coumarone resin is preferably 80 mol% or less, more preferably 75 mol% or less, and further preferably 70 mol% or less.

  When the indencoumarone resin is a copolymer of indene, coumarone and styrene, the content ratio of the styrene structure is preferably 20 mol% or more, more preferably 25 mol% or more, and further preferably 30 mol%. That's it. When the indene coumarone resin is a copolymer of indene, coumarone and styrene, the content ratio of the styrene structure is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol%. It is as follows.

  Specific examples of indene coumarone resins include “H-100”, “V-120S”, and “V-120” manufactured by Nikko Chemical Co., Ltd.

  From the viewpoint of obtaining a resin composition with good compatibility, the content of the component (F) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% when the non-volatile component is 100% by mass. It is at least mass%. The content of the component (F) is 20% by mass or less, preferably 15% by mass or less, more preferably from the viewpoint of obtaining a resin composition having a good melt viscosity and an insulating layer having excellent base adhesion. It is 10 mass% or less or 8 mass% or less.

  When the resin composition according to the present invention contains the component (F), the compatibility is improved and the melt viscosity can be improved. As a result, the dielectric constant of the insulating layer for high-frequency circuits formed using the resin composition can be further lowered, and the adhesion to the inner layer substrate and the adhesion to the conductor layer can be improved. Reliability can be improved.

  The resin composition may contain any one of the said component (E) and a component (F), and may contain both.

<Component (G) Curing accelerator>
The resin composition may contain a component (G) curing accelerator. Examples of the curing accelerator include a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, a guanidine curing accelerator, a metal curing accelerator, and a peroxide curing accelerator. As the curing accelerator, a phosphorus curing accelerator, an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator include More preferred. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. As the phosphorus curing accelerator, triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5,4,0) -undecene is mentioned. As the amine curing accelerator, 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole (2P4MZ), 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1 - Noethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'- Undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2, 4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dode -2-methyl-3-benzyl-imidazolium chloride, 2-methyl-imidazoline, adduct of 2-phenyl-imidazo imidazole compounds such as phosphorus and imidazole compound and an epoxy resin. As the imidazole curing accelerator, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

  A commercially available product may be used as the imidazole curing accelerator. Examples of commercially available imidazole-based curing accelerators include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl), and the biguanide. As the guanidine curing accelerator, dicyandiamide and 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferable.

  Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  Examples of the peroxide curing accelerator include cyclohexanone peroxide, tert-butyl peroxybenzoate, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydro Examples thereof include peroxide, cumene hydroperoxide, and tert-butyl hydroperoxide.

  A commercially available product can be used as the peroxide curing accelerator. As a peroxide type hardening accelerator, NOF Corporation "Park mill D" is mentioned, for example.

  The content of the curing accelerator in the resin composition is not particularly limited. The content of the curing accelerator is preferably 0.01% by mass to 1% by mass when the nonvolatile component is 100% by mass.

<Component (H) Silane Compound>
The resin composition may contain a component (H) silane compound. As the silane compound, a fluorine-based silane compound is preferable. As the component (H) silane compound, 3,3,3-trifluoropropyltrimethoxysilane is preferable, and 3,3,3-trifluoropropyltrimethoxysilane is more preferable. Examples of commercially available silane compounds include “KBM-7103” manufactured by Shin-Etsu Chemical Co., Ltd.

  By containing the component (H) silane compound in the resin composition, the component (C) and the component (D) already described can be more uniformly dispersed in the resin composition. As a result, the uniformity of the resin composition is improved, and the electrical characteristics such as the dielectric constant of the formed insulating layer and the physical characteristics such as adhesion can be further improved.

<Component (I) Thermoplastic Resin>
The resin composition may contain component (I) a 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, polycarbonate resin, polyetheretherketone resin, A polyester resin is mentioned. As the thermoplastic resin, a phenoxy resin is preferable. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The polystyrene-reduced weight average molecular weight of the thermoplastic resin is preferably in the range of 8000 to 70000, more preferably in the range of 10,000 to 60000, and still more preferably in the range of 20000 to 60000. 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 equivalent weight average molecular weight of the thermoplastic resin is “LC-9A / RID-6A” manufactured by Shimadzu Corporation as a measuring device, and “Shodex K-” manufactured by Showa Denko KK as a column. 800P / K-804L / K-804L ", using chloroform or the like as the mobile phase, measuring the column temperature at 40 ° C, and calculating 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” (bisphenol) manufactured by Mitsubishi Chemical Corporation. Other examples include “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YX6954BH30”, “YX7553”, “YX7553BH30”, “YL7769BH30” manufactured by Mitsubishi Chemical Corporation. , “YL6794”, “YL7213”, “YL7290”, “YL7891BH30”, and “YL7482”.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin. As the polyvinyl acetal resin, a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd., Examples include SRECEC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

  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 hydroxy group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  A commercially available product may be used as the polyamideimide resin. Specific examples of commercially available polyamide-imide resins include “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  A commercially available product may be used as the polyethersulfone resin. Specific examples of commercially available polyethersulfone resins include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  A commercially available product may be used as the polysulfone resin. Specific examples of commercially available polysulfone resins that can be used include “P1700” and “P3500” manufactured by Solvay Advanced Polymers.

  Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. In a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

  When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% by mass to 15% by mass, more preferably 0.6% by mass when the nonvolatile component is 100% by mass. It is -12 mass%, More preferably, it is 0.7 mass%-10 mass%.

<Ingredient (J) Flame Retardant>
The resin composition may contain a component (J) flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  A commercially available product may be used as the flame retardant. Examples of commercially available flame retardants include “HCA-HQ” manufactured by Sanko Co., Ltd. and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.

  When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. The content of the flame retardant is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and further preferably 0 when the nonvolatile component is 100% by mass. 0.5 mass% to 10 mass%.

<Component (K) Optional Additive>
The resin composition may further contain an optional additive as necessary. Examples of such optional additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and resins such as thickeners, antifoaming agents, leveling agents, adhesion promoters, and colorants. An additive is mentioned.

[Semiconductor device]
The semiconductor device according to the high-frequency circuit board of the present invention includes the already described high-frequency circuit board. In other words, the semiconductor device of the present invention can be manufactured using the high-frequency 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 can be manufactured by mounting a component (semiconductor chip) on a conductive portion of the high-frequency circuit board. “Conducting part” means “a part where an electric signal can be transmitted in the high-frequency circuit board”, and the part is embedded in the thickness of the high-frequency circuit board even if it is the surface of the high-frequency circuit board. It may be a place. 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. Specifically, the semiconductor chip mounting method includes a wire bonding mounting method, a flip chip mounting method, a mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a non-conductive property. There is a mounting method using a film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a high-frequency circuit board and the wiring of the semiconductor chip and the high-frequency circuit board are connected”. .

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

<Measurement method and evaluation method>
First, a measurement method and an evaluation method according to the example will be described.

1. Measurement of Dielectric Constant Resin varnish obtained in Examples and Comparative Examples described later is dried on the surface of a release-treated PET film (“PET501010” manufactured by Lintec Corporation) as a support. It apply | coated uniformly using the die-coater so that the thickness of a composition layer might be 40 micrometers, and it dried for 6 minutes at 80 to 110 degreeC (average 95 degreeC). Then, it heat-processed for 90 minutes at 200 degreeC, and obtained the hardened | cured material film by peeling a support body.

  The obtained cured product film was cut into a strip shape having a length of 80 mm and a width of 2 mm to obtain an evaluation sample.

  The dielectric constant of this evaluation sample was measured at a measurement frequency of 10 GHz and a measurement temperature of 23 ° C. by a cavity resonance perturbation method using “HP 8362B” manufactured by Agilent Technologies.

  Each of the two evaluation samples was measured, and an average value was calculated as a measured value of the dielectric constant Dk (B) of the evaluation sample (cured product of the resin composition).

  Also, a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R-1766” manufactured by Panasonic Electric Works Co., Ltd.) was coated on both sides with an aqueous ferric chloride solution. The copper foil was removed, and the dielectric constant of the glass cloth base epoxy resin substrate (core substrate) was measured at a measurement temperature of 23 ° C. at 10 GHz. As a result, the dielectric constant of the core substrate was 4.3.

2. Measurement of peel strength (peel strength) between insulating layer for high-frequency circuit and conductor layer (1) Formation of copper foil (adhesive film) with resin composition layer Copper the resin composition obtained in Examples and Comparative Examples On the surface of “MT18Ex” foil manufactured by Mitsui Kinzoku Kogyo Co., Ltd., which is a foil, it is uniformly applied using a die coater so that the thickness of the resin composition layer after drying is 40 μm. It dried at (average 95 degreeC) for 6 minutes, and obtained copper foil with a resin composition layer.

(2) Lamination of copper foil (adhesive film) with resin composition layer The obtained copper foil (2 sheets) with resin composition layer was batch-type vacuum pressure laminator (Nikko Materials Co., Ltd. “2 stage” Build-up laminator CVP700 "), and the resin composition layer is a glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic Electric Works Co., Ltd.“ R ” -1766 ") and laminated on both sides so as to contact both sides. Lamination was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding for 30 seconds at an atmospheric temperature of 100 ° C. and a pressure of 0.74 MPa. Next, hot pressing was performed for 60 seconds at an atmospheric temperature of 100 ° C. and a pressure of 0.5 MPa.

(3) Formation of cured body with copper foil The laminated body in which the laminated copper foil with the resin composition layer is laminated on the core substrate is subjected to a heat treatment at 200 ° C. for 90 minutes to cure the resin composition layer. By making it into a cured body (insulating layer for high-frequency circuits), a cured body with copper foil was formed.

(4) Formation of conductor layer (laminate) (electroplating)
After peeling carrier copper foil from the cured body with copper foil obtained in the above step (3), copper sulfate electrolytic plating (electroplating) was performed to form a conductor layer so that the thickness was 25 μm. Next, the heat processing for 30 minutes were performed at 180 degreeC, and the laminated board which has a conductor layer (copper layer) on both surfaces was obtained. Using this laminate, the peel strength (peel strength) of the conductor layer was measured.

(5) Measurement of peel strength peeling strength between high-frequency circuit insulating layer and conductor layer A strip-shaped cut having a width of 10 mm and a length of 100 mm is made in the formed conductor layer, and one end in the length direction is peeled off. When grabbed with a gripping tool ("Autocom type testing machine AC-50CSL" manufactured by TS E Co., Ltd.) and peeled off 35mm in the vertical direction (length direction) at a speed of 50mm / min. The peel strength (kgf / cm) which is the load of was measured. In both cases, the peeled surface was an interface between the high-frequency circuit insulating layer and the copper foil (“MT18Ex” foil manufactured by Mitsui Kinzoku Co., Ltd.).
The results are shown in Table 2.

3. Measurement of peel strength (peel strength) between inner layer substrate (core substrate) and high frequency circuit insulating layer (1) Preparation of inner layer substrate Glass cloth base epoxy resin double-sided copper clad laminate (copper foil thickness 18 μm, The core substrate was obtained by removing the copper foil on both sides of the substrate having a thickness of 0.8 mm and “R-1766” manufactured by Panasonic Electric Works Co., Ltd. with an aqueous ferric chloride solution.

(2) Formation of copper foil (adhesive film) with resin composition layer The resin compositions obtained in Examples and Comparative Examples were dried on the surface of “MT18Ex” manufactured by Mitsui Kinzoku Kogyo Co., Ltd., which is a copper foil. It apply | coated uniformly using a die-coater so that the thickness of a resin composition layer might be 40 micrometers, and it dried for 6 minutes at 80 to 110 degreeC (average 95 degreeC), and obtained copper foil with a resin composition layer.

(3) Lamination of copper foil (adhesive film) with resin composition layer The obtained copper foil (2 sheets) with resin composition layer was batch-type vacuum pressure laminator (Nikko Materials "2-stage build-up laminator" CVP700 ") was laminated on both surfaces of the core substrate so that the resin composition layer was in contact with the core substrate. Lamination was carried out by pressure bonding for 30 seconds at a pressure of 0.74 MPa with the temperature of the rubber press section of the first chamber being 100 ° C. with the pressure reduced to 30 hPa or less by reducing the pressure for 30 seconds. Subsequently, the temperature of the metal press part of the second chamber was 100 ° C., the pressure was 0.5 MPa, and hot pressing was performed for 60 seconds.

(4) Formation of cured body with copper foil Cured by curing the resin composition layer by heat-treating the laminate in which the copper foil with the resin composition layer is laminated on the core substrate at 200 ° C. for 90 minutes. A cured body with copper foil was formed as a body (insulating layer for high-frequency circuit).

(5) Formation of conductor layer (laminate) (electroplating)
After peeling the carrier foil from the cured body with copper foil obtained in the above step (4), copper sulfate electrolytic plating (electroplating) was performed to form a conductor layer so that the thickness was 25 μm. Next, the heat processing for 30 minutes were performed at 180 degreeC, and the laminated board which has a conductor layer (copper layer) on both surfaces was obtained. Using this laminate, the peel strength (peel strength) of the insulating layer for high-frequency circuits was measured.

(6) Measurement of peel strength of insulating layer for high-frequency circuit A strip-shaped cut having a width of 10 mm and a length of 100 mm is made in the formed conductor layer, and one end in the length direction is peeled off to grasp a gripping tool (Tea Corporation Peel strength (kgf), which is the load when 35mm is peeled off in the vertical direction (length direction) at a speed of 50mm / min. / Cm) was measured.

  Here, when the peeling surface is between the high-frequency circuit insulating layer and the conductive layer, that is, when only the conductive layer is peeled off from the laminated plate, the gap between the inner substrate and the high-frequency circuit insulating layer is The peel strength was judged to be higher.

A case where the peel strength was 0.5 kgf / cm or more was judged as “good”, and a case where the peel strength was less than 0.5 kgf / cm was judged as “poor”.
The results are shown in Table 2.

[Example 1]
Solvent naphtha containing 25 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 190) and 15 parts of liquid bisphenol A type epoxy resin (“jER828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187) It melt | dissolved by stirring, heating to 25 parts, and cooled to normal temperature after that.

  Spherical silica surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) on the resulting mixed solution (“SO-C2” manufactured by Admatechs Co., Ltd.), average particle size of 0.5 μm ) 190 parts and 120 parts of PTFE particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm) were mixed and dispersed by kneading with three rolls.

  In the obtained mixed liquid, 61.5 parts of an active ester curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 and containing 65% by mass of non-volatile components), Resin having a vinyl group (“OPE-2St 2200” manufactured by Mitsubishi Gas Chemical Co., Inc., toluene solution containing 60% by mass of a non-volatile component) 25 parts, Inden Coumarone resin (“H-100” manufactured by Nikkiso Chemical Co., Ltd.) ) 15 parts, 8 parts of 2-phenyl-4-methylimidazole (2.5 mass% MEK solution of “2P4MZ” manufactured by Shikoku Kasei Co., Ltd.), which is a curing accelerator, are mixed and uniformly mixed with a rotary mixer. Disperse to prepare a resin varnish 1, and as already described, using the obtained resin varnish 1, uniformly applied so that the thickness of the resin composition layer after drying is 40 μm, and the resin composition On drying layer Thus, an adhesive film 1 was produced.

[Example 2]
10 parts of bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent 190) and naphthalene type epoxy resin (DIC "HP6000", epoxy equivalent 260) 21 parts Prepared a resin varnish 2 in the same manner as in Example 1, and produced an adhesive film 2 using the resin varnish 2.

[Example 3]
Resin varnish 3 was prepared in the same manner as in Example 1 except that 2 parts of 3,3,3-trifluoropropyltrimethoxysilane (“KBM-7103” manufactured by Shin-Etsu Chemical Co., Ltd.) was further used. The adhesive film 3 was produced using

[Example 4]
30.8 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, active group equivalent is about 223 and 65% by mass of non-volatile components), and further contains a triazine skeleton The same as in Example 1 except that 28 parts of a phenolic curing agent (“LA-3018-50P” manufactured by DIC Corporation, 2-hydroxypropanol solution having a hydroxyl group equivalent of about 151 and containing 50% non-volatile components) was used. Thus, a resin varnish 4 was prepared, and an adhesive film 4 was produced using the resin varnish 4.

[Example 5]
30.8 parts of an active ester-based curing agent (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having an active group equivalent of about 223 and a non-volatile component of 65% by mass) is added to the active ester-based curing agent. (DIC Corporation "EXB-9416-70BK", a methyl isobutyl ketone solution having an active group equivalent of about 274 and containing 70% by mass of a non-volatile component). Then, a resin varnish 5 was prepared, and an adhesive film 5 was produced using the resin varnish 5.

[Example 6]
An active ester type curing agent (“HPC-8000-65T” manufactured by DIC Corporation), a naphthalene type curing agent (“SN485” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), a phenol equivalent is 215, and a nonvolatile component is 60% by mass. MEK solution containing) 33.3 parts and triazine skeleton-containing phenol novolac type curing agent (“LA7054” manufactured by DIC Corporation, MEK solution having a phenol equivalent of 125 and containing 60% by mass of non-volatile components) changed to 18.3 parts A resin varnish 6 was prepared in the same manner as in Example 1 except that the adhesive film 6 was produced using the resin varnish 6.

[Example 7]
250 parts of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish 7 was prepared in the same manner as in Example 1 except that 50 parts of PTFE particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle diameter 3 μm) were used, and an adhesive film 7 was prepared using the resin varnish 7. Was made.

[Example 8]
50 parts of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish 8 was prepared in the same manner as in Example 1 except that 200 parts of PTFE particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm) were used. Was made.

[Example 9]
A resin varnish 9 was prepared in the same manner as in Example 1 except that 5 parts of a carbodiimide compound (“V-03” manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution containing 50% by mass of a nonvolatile component) was additionally used as a curing agent. And the adhesive film 9 was produced using this.

[Example 10]
A curing accelerator ("2P4MZ" manufactured by Shikoku Kasei Co., Ltd., 2-phenyl-4-methylimidazole, a MEK solution containing 2.5% by mass of a non-volatile component), a curing accelerator (4-dimethylaminopyridine (DMAP), A resin varnish 10 was prepared in the same manner as in Example 1 except that it was changed to 2 parts (MEK solution containing 10% by mass of nonvolatile components), and an adhesive film 10 was prepared using the resin varnish 10.

[Comparative Example 1]
Resin having a vinyl group ("OPE-2St 2200" manufactured by Mitsubishi Gas Chemical Co., Inc., toluene solution containing 60% by mass of non-volatile components), 40 parts of indene coumarone resin ("H-100" manufactured by Nikko Chemical Co., Ltd.) ) 15 parts, 50 parts of toluene and 20 parts of methyl ethyl ketone were mixed and dissolved by stirring while heating, and then cooled to room temperature. 50 parts of spherical silica (“SO-C2” manufactured by Admatechs Co., Ltd., average particle size 0.5 μm) surface-treated with a phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), PTFE 50 parts of particles (“Lublon L-2” manufactured by Daikin Industries, Ltd., average particle size 3 μm) were mixed and dispersed with a high-speed rotating mixer.

  The resulting mixture was mixed with 6 parts of a 5% by weight toluene solution of dicumyl peroxide (“Park Mill D” manufactured by NOF Corporation) as a radical generator, and mixed uniformly with a rotary mixer to obtain a resin. The varnish 11 was prepared and the adhesive film 11 was produced using this.

[Comparative Example 2]
35 parts of naphthylene ether type epoxy resin (epoxy equivalent 250, “HP6000” manufactured by DIC Corporation) and 15 parts of liquid bisphenol A type epoxy resin (“jER828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187) The mixture was dissolved by stirring while heating to 30 parts, and then cooled to room temperature.

  In the resulting solution, 20 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, MEK solution containing 30% by mass of nonvolatile components), phenylaminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) ) 180 parts of crystalline silica ("IMSIL A-8" manufactured by Unimin, average particle size 1.38 [mu] m) surface-treated with a high-speed rotary mixer was mixed. Thereafter, 32 parts of a methyl ethyl ketone solution containing 50% by mass of a non-volatile component of a phenol novolac curing agent (“TD2090” manufactured by DIC Corporation, hydroxyl equivalent 105), a phenol novolac curing agent containing triazine skeleton (“LA-” manufactured by DIC Corporation). 7054 ", 10 parts of a MEK solution having a hydroxyl group equivalent of 125 and containing 60% by mass of a non-volatile component), 2-phenyl-4-methylimidazole (" 2P4MZ "manufactured by Shikoku Kasei Co., Ltd.) as a curing accelerator. 8 parts of a 5% by mass MEK solution was added and mixed uniformly with a rotary mixer to prepare a resin varnish 12, which was used to produce an adhesive film 12.

  Table 1 shows the components used in the resin varnishes according to Examples and Comparative Examples. In addition, Table 2 shows measured values and evaluations (evaluation of peel strength, and evaluation of compatibility between insulating layer adhesion and electrical characteristics) according to the examples and comparative examples.

  As is apparent from Table 2, the insulating layers according to Examples 1 to 10 are such that Dk (A) and Dk (B) satisfy the formula: Dk (B) ≦ Dk (A) −0.8, and the inner layer substrate. The peel strength of the insulating layer (insulating layer for high-frequency circuit) with respect to is 0.5 kgf / cm or more. That is, the reduction of Dk (B) to about 2.5 to 3.1 and the excellent adhesion of the insulating layer to the inner layer substrate could be achieved at the same time.

  Therefore, even if a relatively inexpensive inner layer substrate is used and operated in a high frequency band of, for example, 28 GHz to 80 GHz, stable bonding between the inner layer substrate and the insulating layer can be ensured, and for high frequency circuits in a use environment. It is possible to suppress the problem that the insulating layer peels off from the inner layer substrate and does not function as a high frequency circuit substrate, and to further improve the reliability of the device such as suppression of deterioration of electrical characteristics over time and lifetime. Can be expected.

  On the other hand, according to Comparative Example 1 containing no component (A), the insulating layer is swollen, the adhesion is insufficient, the dielectric constant of the insulating layer is reduced, and the core substrate, that is, the inner layer substrate, is reduced. It was not possible to achieve both excellent adhesion of the insulating layer.

  Further, according to Comparative Example 2 that does not contain the components (D), (E), and (F), the reduction of Dk (B) is insufficient, the dielectric constant of the insulating layer is reduced, and the core substrate, that is, the inner layer It was impossible to achieve both excellent adhesion of the insulating layer to the substrate.

DESCRIPTION OF SYMBOLS 10 High frequency circuit board 12 Through hole 12a Through-hole wiring 20 Inner layer board 20a, 22a 1st main surface 20b, 22b 2nd main surface 22 Core substrate 24 1st conductor layer (wiring layer)
26 Second conductor layer (wiring layer)
27 Interlayer insulation layer 28 Third conductor layer (wiring layer)
29, 32, 52 Via hole 29a, 32a, 52a Wiring in via hole 30 High frequency circuit insulating layer 40 High frequency circuit conductor layer (wiring layer)
50 Insulating layer 60 Conductor layer (wiring layer)

Claims (16)

An inner layer substrate;
A high frequency circuit board comprising a high frequency circuit forming insulating layer bonded to the inner layer board,
When the dielectric constant of the inner layer substrate is Dk (A) and the dielectric constant of the high-frequency circuit forming insulating layer is Dk (B), Dk (A) and Dk (B) are expressed by the following formula:
Dk (B) ≦ Dk (A) −0.8
And the peel strength of the insulating layer for forming a high frequency circuit with respect to the inner layer substrate is 0.5 kgf / cm or more.   2. The high-frequency circuit according to claim 1, wherein only one layer of the high-frequency circuit forming insulating layer is provided, or two or more high-frequency circuit forming insulating layers are provided on one main surface side of the inner layer substrate. Circuit board.   The high frequency circuit board according to claim 1 or 2, wherein a thickness of the high frequency circuit forming insulating layer is 20 to 200 µm.   The high frequency circuit board according to any one of claims 1 to 3, wherein the inner layer substrate has a thickness of 50 to 4000 µm.   The said inner layer board | substrate contains a glass epoxy board | substrate, The said insulating layer for high frequency circuit formation joined to this glass epoxy board | substrate is the hardening body which heat-cured the resin composition containing a component (A) epoxy resin. 5. The high frequency circuit board according to any one of 1 to 4.   The inner layer substrate includes one or more insulating layers obtained by curing a material containing an epoxy resin, the high-frequency circuit forming insulating layer is bonded to the insulating layer, and the high-frequency circuit forming insulating layer includes a component (A The high frequency circuit board according to any one of claims 1 to 5, which is a cured product obtained by thermosetting a resin composition containing an epoxy resin.   The high-frequency circuit board according to claim 5 or 6, wherein the resin composition further comprises a component (B) curing agent and a component (C) inorganic filler.   The high-frequency circuit board according to claim 7, wherein the resin composition further includes a component (D) organic filler.   The component (D) organic filler is one or more organic fillers selected from the group consisting of cycloolefin polymer particles, polyphenylene ether particles, polystyrene particles, and fluorine-based polymer particles. High frequency circuit board.   The high-frequency circuit board according to claim 9, wherein the component (D) organic filler is fluoropolymer particles.   The high frequency circuit board according to claim 9 or 10, wherein the resin composition further comprises a resin having a component (E) vinyl group.   The high-frequency circuit board according to claim 9, wherein the resin composition further contains a component (F) indene coumarone resin.   The high frequency circuit board according to claim 12, wherein the resin composition further contains a component (H) silane compound.   The high frequency circuit board according to any one of claims 1 to 13, wherein the Dk (A) is 4.0 or more.   The high-frequency circuit board according to claim 1, wherein the Dk (B) is 3.5 or less.   The high-frequency circuit board according to claim 15, wherein the Dk (B) is 3.0 or less.

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