JP2018008496A - Metal-clad laminate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-clad laminate that can prevent a breakage of a graphite sheet, included as a heat radiation material in an insulating layer, and also makes it possible to confirm a position of the graphite sheet in the insulating layer, and a method of producing the same.SOLUTION: A metal-clad laminate has a conductor layer, and an insulating layer placed on the conductor layer. The insulating layer has a base material having electric insulation properties, and a graphite sheet and a guide member embedded in the base material. The guide member and the graphite sheet have a specific physical relationship. The guide member contains metal.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a metal-clad laminate and a method for producing the same.

  Aiming at the realization of a ubiquitous society, the speed of information transmission continues to advance. A printed wiring board used for processing high-speed signals can be produced, for example, by forming a conductor pattern on a metal-clad laminate. As such a metal-clad laminate, conventionally, a metal-clad laminate comprising a conductor layer and an insulating layer made of a liquid crystal polymer resin, a fluororesin, or the like has been provided. For example, in Patent Document 1, in a multilayer metal-clad laminate formed by alternately laminating conductor layers and insulating layers, the insulating layer is formed of a thermosetting resin layer and a liquid crystal polymer resin layer. It is disclosed.

  A metal-clad laminate including an insulating layer made of a liquid crystal polymer resin or a fluororesin has an advantage that it can have a low dielectric constant and a low dielectric loss tangent. For this reason, a printed wiring board excellent in high-speed signal transmission can be produced from this metal-clad laminate.

JP 2011-216841 A

  However, as the high-speed signal is further increased in speed and complexity, and the printed wiring board is made thinner, high heat dissipation is required for the metal-clad laminate.

  Then, the inventors examined improving heat dissipation by sticking a graphite sheet, which is a heat dissipation material, to the surface of the metal-clad laminate via an adhesive or the like. However, when a graphite sheet is attached to the surface of a metal-clad laminate, the thickness increases, making it difficult to achieve a reduction in thickness. Furthermore, since the graphite sheet is easily damaged, scaly fragments are easily peeled off from the graphite sheet. Therefore, the handling property at the time of processing of the metal-clad laminate having a graphite sheet on the surface is low, and it is difficult to produce, for example, a flexible printed wiring board from the metal-clad laminate.

  Therefore, as a result of further studies, the inventors have embedded the graphite sheet in the insulating layer of the metal-clad laminate, thereby reducing the thickness of the metal-clad laminate and suppressing the breakage of the graphite sheet. An attempt was made to further improve handling. However, if the graphite sheet is buried in the insulating layer, the position of the graphite sheet becomes unclear, and accordingly, conductor wiring may be formed on the laminated board or the laminated board may be cut according to the position of the graphite sheet. There is a problem that it is difficult.

  An object of the present invention is to provide a metal-clad laminate and a method for manufacturing the metal-clad laminate, in which the insulating layer includes a graphite sheet as a heat dissipation material, can suppress damage to the graphite sheet, and can easily check the position of the graphite sheet in the insulating layer. It is.

  A metal-clad laminate according to an embodiment of the present invention includes a conductor layer and an insulating layer overlapping the conductor layer. The insulating layer includes a base material having electrical insulation, and a graphite sheet and a guide member embedded in the base material. The guide member and the graphite sheet are in a specific positional relationship. The guide member includes a metal.

  In the embodiment, it is preferable that the metal-clad laminate includes a second conductor layer that overlaps the insulating layer.

  In the embodiment, it is preferable that the graphite sheet and the guide member are arranged in a direction orthogonal to the thickness direction of the insulating layer.

  In the embodiment, the guide member is preferably a metal foil.

  In the embodiment, it is preferable that the metal-clad laminate further includes a guide mark visible from the outside, and the guide mark and the guide member have a specific positional relationship.

  In the embodiment, the guide mark is preferably a hole.

  In the one embodiment, the base material preferably includes a cured product of a thermosetting resin composition.

  In the one embodiment, the base material includes a first layer and a second layer, the first layer includes a thermoplastic resin composition, and the second layer includes It is preferable to consist of a cured product of a thermosetting resin composition.

  In the embodiment, it is preferable that the graphite sheet and the guide member are embedded in the second layer.

  In the embodiment, the thermoplastic resin composition preferably includes at least one component selected from the group consisting of a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin.

In the embodiment, the thermosetting resin composition includes an epoxy compound (A), a bismaleimide (B), and a polyphenylene having a substituent (c2) having a carbon-carbon double bond at the terminal. An ether resin (C) and a block copolymer (D) represented by the following formula (1),
PS-X-PS (1)
Each PS in the formula (1) is a polystyrene block, X in the formula (1) is a polyolefin block, and the polyolefin block contains at least one of an isoprene unit and a hydrogenated isoprene unit, The total of the polyolefin blocks in the block copolymer (D) with respect to the entire block copolymer (D) is in the range of 70 to 90% by mass, and the loss tangent tan δ of the block copolymer (D) The temperature at which shows a maximum value is preferably −20 ° C. or higher.

  In the embodiment, the amount of the polyphenylene ether resin (C) with respect to the thermosetting resin composition is preferably in the range of 8 to 35% by mass.

  In the embodiment, the amount of the bismaleimide (B) with respect to the thermosetting resin composition is preferably in the range of 3 to 20% by mass.

  In the embodiment, the amount of the epoxy compound (A) with respect to the thermosetting resin composition is preferably in the range of 3 to 10% by mass.

  In the method for manufacturing a metal-clad laminate according to an embodiment of the present invention, the metal-clad laminate includes a conductor layer, an insulating layer overlying the conductor layer, and a second conductor layer overlying the insulating layer. The insulating layer includes a base material having electrical insulation, a graphite sheet and a guide member embedded in the base material, and the guide member and the graphite sheet are in a specific positional relationship, The guide member includes a metal. In the manufacturing method, the first metal foil, the first resin sheet, the graphite sheet and the guide member, the second resin sheet, and the second metal foil are stacked in this order and hot pressed, Producing the conductor layer made of metal foil, the base material made of the cured product of the first resin sheet and the cured product of the second resin sheet, and the second conductor layer made of the second metal foil The process of carrying out is included.

  In the embodiment of the method for manufacturing the metal-clad laminate, the method for manufacturing the metal-clad laminate includes a step of detecting a position of the guide member in the insulating layer, It is preferable to further include a step of forming guide marks that are in a positional relationship and are visible from the outside.

  According to the present invention, it is possible to obtain a metal-clad laminate and a method for manufacturing the same, in which the insulating layer includes a graphite sheet as a heat dissipating material and can suppress damage to the graphite sheet, and can easily check the position of the graphite sheet in the insulating layer. it can.

It is sectional drawing which shows a part of metal-clad laminated board in 1st embodiment of this invention. It is sectional drawing which shows a part of metal-clad laminated board in 1st embodiment of this invention. It is a plane sectional view showing a metal tension laminate sheet in a first embodiment of the present invention. It is sectional drawing which shows a part of metal-clad laminated board in 2nd embodiment of this invention.

<Metal-clad laminate>
With reference to FIG. 1, the metal-clad laminate 1 which concerns on one Embodiment of this invention is demonstrated.

  The metal-clad laminate 1 according to an embodiment of the present invention includes a conductor layer 10 (11) and an insulating layer 20 that overlaps the conductor layer 10 (11).

  The insulating layer 20 includes a base material 21 having electrical insulation, a graphite sheet 22 and a guide member 23 embedded in the base material 21.

  The guide member 23 and the graphite sheet 22 are in a specific positional relationship. The guide member 23 contains a metal.

  Since the metal-clad laminate 1 includes the insulating layer 20 including the graphite sheet 22 that is a heat dissipation material, the heat dissipation of the metal-clad laminate 1 can be improved. In addition, since the graphite sheet 22 is embedded in the base material 21 having electrical insulation in the insulating layer 20, breakage of the graphite sheet 22 can be suppressed, and the handleability of the metal-clad laminate 1 can be improved. Therefore, for example, a flexible printed wiring board can be produced from the metal-clad laminate 1. Furthermore, when the graphite sheet 22 is embedded in the base material 21 as compared with the case where the graphite sheet 22 is attached to the surface of the metal-clad laminate 1, the metal laminate 1 can be made thinner, and thereby Heat dissipation can be increased.

  Further, since the guide member 23 having a specific positional relationship with the graphite sheet 22 is buried in the base material 21, the position of the graphite sheet 22 in the insulating layer 20 can be easily confirmed. Since the guide member 23 contains a metal, the position of the guide member 23 can be easily detected by, for example, an X-ray detector. For this reason, the position of the graphite sheet 22 can be specified from the positional relationship between the graphite sheet 22 and the guide member 23.

  As described above, in the metal laminate 1, the insulating layer 20 includes the graphite sheet 22 as a heat dissipation material in the base material 21, so that the graphite sheet 22 can be prevented from being damaged. The position of the graphite sheet 22 can be easily confirmed.

  A metal-clad laminate 1 according to a first embodiment of the present invention will be described with reference to FIGS. 1 is a cross-sectional view of the metal-clad laminate 1 taken along a cutting line AA in FIG.

  The metal-clad laminate 1 of the first embodiment includes at least one conductor layer 10 and an insulating layer 20.

  The conductor layer 10 may be a metal foil such as a copper foil, or may be a conductor wiring. The thickness of the conductor layer 10 is in the range of 2 to 105 μm, for example. As the copper foil, for example, 2 μm with a carrier foil of 18 μm copper foil can be used.

  The metal-clad laminate 1 of this embodiment has two conductor layers 10. The metal-clad laminate 1 includes a first conductor layer 11, an insulating layer 20 that overlaps the first conductor layer 11, and a second conductor layer 12 that overlaps the insulating layer 20. That is, in the metal-clad laminate 1, the first conductor layer 11, the insulating layer 20, and the second conductor layer 12 are laminated in this order.

  The insulating layer 20 includes a base material 21, a graphite sheet 22 and a guide member 23 embedded in the base material 21. The thickness of the insulating layer 20 is preferably in the range of 12 to 200 μm, for example. When the thickness of the insulating layer 20 is within this range, the graphite sheet 22 and the guide member 23 can be easily embedded in the base material 21 of the insulating layer 20. Moreover, since it can prevent that the thickness of the insulating layer 20 becomes large too much because the thickness of the insulating layer 20 exists in this range, it becomes easy to ensure sufficient heat dissipation by the graphite sheet 22. FIG. The thickness of the insulating layer 20 is more preferably in the range of 12 to 150 μm.

  As described above, the base material 21 has electrical insulation. The base material 21 preferably contains a cured product of the thermosetting resin composition. When the base material 21 contains the cured product of the thermosetting resin composition, the metal-clad laminate 1 can be provided with excellent heat resistance. More preferably, the base material 21 includes a cured product of the composition (X) which is a thermosetting resin described later. In this case, the insulating layer 20 including the base material 21 can be molded at a low temperature, and the insulating layer 20 can have high heat resistance. Further, when the base material 21 contains a cured product of the composition (X), the insulating layer 20 can be reduced in dielectric constant and dielectric loss tangent, and therefore produced using the metal-clad laminate 1 and the material as a material. The printed wiring board can have good high-frequency characteristics.

  The base material 21 may contain a thermoplastic resin composition. When the base material 21 includes the thermoplastic resin composition, the metal-clad laminate 1 can be given flexibility. Examples of the thermoplastic resin composition include a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin. When the thermoplastic resin composition contains at least one component selected from the group consisting of a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin, the insulating layer 20 has a low dielectric constant and a low dielectric loss tangent. Is possible. In this case, the metal-clad laminate 1 and the printed wiring board produced using the metal-clad laminate 1 can have good high frequency characteristics.

  The graphite sheet 22 is obtained by processing graphite into a sheet shape. The graphite sheet 22 is embedded in the base material 21. Since the graphite sheet 22 is embedded in the base material 21, damage to the graphite sheet 22 can be suppressed, and the handleability of the metal-clad laminate 1 can be improved.

  As shown in FIG. 3, the metal-clad laminate 1 has a plurality of graphite sheets 22, but may have only one graphite sheet 22 or two or more. In FIG. 3, a plurality of graphite sheets 22 having the same size are regularly arranged in a plan view. Of course, the shape and size of the plurality of graphite sheets 22 may be the same or different. Moreover, the some graphite sheet 22 may be arrange | positioned regularly and may be arrange | positioned irregularly. In FIG. 3, the shape of the graphite sheet 22 is a quadrangle. When the graphite sheet 22 is square, the metal-clad laminate 1 is easily cut when being cut in accordance with the position of the graphite sheet 22. When the graphite sheet 22 is a quadrangle, the size of the graphite sheet 22 in a plan view is preferably in the range of 10 to 500 mm for the long side and 2 to 300 mm for the short side. Moreover, it is preferable that the thickness of the graphite sheet 22 exists in the range of 10-70 micrometers, for example.

  The guide member 23 is embedded in the base material 21. The guide member 23 is embedded in the base material 21, so that the thickness of the metal-clad laminate 1 is not excessively large compared to the case where the guide member 23 is provided on the surface of the metal-clad laminate 1. be able to. Further, the guide member 23 and the graphite sheet 22 are in a specific positional relationship. That is, if the position of the guide member 23 in the insulating layer 20 is specified, the position of the graphite sheet 22 in the insulating layer 20 is also specified. As long as it is such a relationship, the guide member 23 and the graphite sheet 22 may be in any positional relationship. The positional relationship between the graphite sheet 22 and the guide member 23 is arbitrarily determined by, for example, a person who is involved in the development or manufacture of the metal-clad laminate 1.

  The guide member 23 contains a metal. Examples of the metal included in the guide member 23 include copper, aluminum, and stainless steel. Since the guide member 23 contains a metal, the position of the guide member 23 in the insulating layer 20 can be easily detected by, for example, an X-ray detector. The graphite sheet 22 cannot be detected by an X-ray detector or the like, but if the position of the guide member 23 can be detected, the position of the graphite sheet 22 can be confirmed by the positional relationship between the graphite sheet 22 and the guide member 23. The guide member 23 is preferably a metal foil. Examples of metal foil include copper foil, aluminum foil, and stainless steel foil. Since the guide member 23 is a metal foil, the metal-clad laminate 1 can be easily manufactured.

  When the insulating layer 20 includes a plurality of graphite sheets 22, the insulating layer 20 preferably includes at least two guide members 23. For example, in the metal-clad laminate 1 shown in FIG. 3, the insulating layer 20 includes two guide members 23, which are respectively disposed at two opposing corners of the insulating layer 20 in plan view. When the insulating layer 20 includes at least two guide members 23, the positions of the plurality of graphite sheets 22 can be easily specified. When the insulating layer 20 includes the two guide members 23, the two guide members 23 are preferably disposed at two end portions that face each other in plan view of the insulating layer 20.

  The shape of the guide member 23 is a quadrangle in FIG. 3, but may have other shapes. When the guide member 23 is a quadrangle, the size of the guide member 23 in a plan view is preferably in the range of 2 to 10 mm for the long side and 2 to 10 mm for the short side. Moreover, it is preferable that the thickness of the guide member 23 exists in the range of 10-70 micrometers, for example.

  Moreover, it is preferable that the thickness of the graphite sheet 22 and the thickness of the guide member 23 are the same. Since the thickness of the graphite sheet 22 and the thickness of the guide member 23 are the same, the metal-clad laminate 1 can be easily manufactured.

  The graphite sheet 22 and the guide member 23 are preferably arranged in a direction orthogonal to the thickness direction of the insulating layer 20. That is, as shown in FIG. 3, the graphite sheet 22 and the guide member 23 are preferably arranged in a plan view. If the graphite sheet 22 and the guide member 23 overlap in plan view, the thickness of the insulating layer 20 tends to increase. Therefore, it is preferable that the graphite sheet 22 and the guide member 23 are arranged so as not to overlap in a plan view.

  The shortest distance between the guide member 23 and the graphite sheet 22 is, for example, in the range of 1 to 50 mm.

  It is preferable that the metal-clad laminate 1 further includes a guide mark 30 that is visible from the outside. The guide mark 30 and the guide member 23 are in a specific positional relationship. That is, if the position of the guide mark 30 is specified, the position of the guide member 23 in the insulating layer 20 is also specified. As long as it is such a relationship, the positional relationship between the guide mark 30 and the guide member 23 may be anything. The positional relationship between the guide member 23 and the guide mark 30 is arbitrarily determined by, for example, a person who is involved in the development or manufacture of the metal-clad laminate 1.

  If the metal-clad laminate 1 is provided with a visually recognizable guide mark 30, it is possible to visually confirm the guide mark 30 and confirm its position without directly confirming the position of the guide member 23 using an X-ray inspection machine or the like. For example, the position of the graphite sheet 22 can be specified based on the positional relationship between the guide mark 30 and the guide member 23 and the positional relationship between the guide member 23 and the graphite sheet 23. Therefore, it is easy to form conductor wiring on the metal-clad laminate 1 or cut the metal-clad laminate 1 in accordance with the position of the graphite sheet 22.

  When the insulating layer 20 includes a plurality of guide members 23, the guide marks 30 are preferably formed in at least two places in the metal-clad laminate 1. When the insulating layer 20 includes a plurality of guide members 23, the metal-clad laminate 1 preferably includes a plurality of guide marks 30 corresponding to the plurality of guide members 23, respectively. In this case, each of the plurality of guide marks 30 and the corresponding guide member 23 are in a specific positional relationship. In this case, when the plurality of guide marks 30 are visually observed, the positions of the plurality of guide members 23 can be specified, so that the positions of the plurality of graphite sheets 22 can be easily confirmed.

  The guide mark 30 is, for example, a mark such as a figure, a character, or a pattern printed on the conductor layer 10 at a specific position with respect to the guide member 23, or a hole 31 provided at a specific position with respect to the guide member 23. It may be. However, the guide mark 30 is not limited to a mark or hole to be printed, and may be a mark that is visible from the outside.

  The guide mark 30 is preferably a hole 31. For example, in FIG. 2, the guide mark 30 which is the hole 31 which penetrates the metal-clad laminated board 1 in the position where the guide member 23 is arrange | positioned is formed. However, the hole 31 formed as the guide mark 30 may not penetrate the metal-clad laminate 1, and may be, for example, the hole 31 provided only in the conductor layer 10. 21 may be a hole 31 that passes through 21 and does not pass through the guide member 23. It is preferable that the hole 31 penetrates the metal-clad laminate 1. In this case, the guide mark 30 can be visually recognized from both surfaces of the metal-clad laminate 1.

  A metal-clad laminate 1 according to a second embodiment of the present invention will be described with reference to FIG. Below, about the structure similar to the metal-clad laminated board 1 which concerns on 1st embodiment, the same code | symbol is attached | subjected in a figure and detailed description is abbreviate | omitted.

  In the second embodiment, the metal-clad laminate 1 includes a conductor layer 10 (11) and an insulating layer 20 that overlaps the conductor layer 10 (11).

  The insulating layer 20 includes a base material 21 having electrical insulation, a graphite sheet 22 and a guide member 23 embedded in the base material 21.

  The guide member 23 and the graphite sheet 22 are in a specific positional relationship. The guide member 23 contains a metal.

  In the second embodiment, the base material 21 includes a first layer 211 and a second layer 212. That is, in the second embodiment, the insulating layer 20 includes the first layer 211, the second layer 212, the graphite sheet 22, and the guide member 23.

  In the metal-clad laminate 1 shown in FIG. 4, the base material 21 includes two first layers 211 and a second layer 212 between the two first layers 211. That is, the base material 21 includes a first image 211, a second layer 212, and a first layer 211, which are stacked in this order.

  The first layer 211 includes a thermoplastic resin composition. Since the insulating layer 20 includes the first layer 211 containing the thermoplastic resin composition, flexibility can be imparted to the insulating layer 20. Examples of the thermoplastic resin composition include a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin. When the thermoplastic resin composition contains at least one component selected from the group consisting of a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin, the insulating layer 20 has a low dielectric constant and a low dielectric loss tangent. Is possible. In this case, the metal-clad laminate 1 and the printed wiring board produced using the metal-clad laminate 1 can have good high frequency characteristics.

  The second layer 212 is made of a cured product of a thermosetting resin composition. Since the insulating layer 20 includes the second layer 212 made of a cured product of the thermosetting resin composition, heat resistance can be imparted to the insulating layer 20. It is preferable that the 2nd layer 212 contains the hardened | cured material of the composition (X) which is a thermosetting resin composition mentioned later. In this case, the second layer 212 can be formed at a low temperature, and the insulating layer 20 can have high heat resistance. Furthermore, when the second layer 212 contains a cured product of the composition (X), the dielectric layer of the insulating layer 20 can be lowered and the dielectric loss tangent can be lowered. The printed wiring board manufactured in this way can have good high frequency characteristics.

  Since the base material 21 includes the first layer 211 containing the thermoplastic resin composition and the second layer 212 made of a cured product of the thermosetting resin composition, the heat resistance of the metal-clad laminate 1 and Both flexibility can be improved.

  In the second embodiment, the graphite sheet 22 and the guide member 23 are embedded in the second layer 212. In this case, heat resistance and flexibility can be improved while maintaining heat dissipation and handling of the metal-clad laminate 1.

  The thickness of the first layer 211 is preferably in the range of 1 to 25 μm, for example. As shown in FIG. 4, when the base material 21 includes two first layers 211, the thickness of each first layer 211 is preferably in the range of 1 to 25 μm. Thereby, it can suppress that the softness | flexibility of the metal-clad laminated board 1 falls, or thickness becomes large too much. The thickness of the second layer 212 is preferably in the range of 10 to 100 μm, for example. Thereby, while ensuring the heat dissipation of the metal-clad laminated board 1, the graphite sheet 22 and the guide member 23 can be favorably embedded in the second layer 212.

  In the first embodiment and the second embodiment of the present invention, the metal-clad laminate 1 includes two conductor layers 10 and one insulating layer 20, but is not limited thereto. The metal-clad laminate 1 may include only one conductor layer 10 or may include three or more conductor layers 10. When the metal-clad laminate 1 has two or more conductor layers 10, it is possible to form conductor patterns, conductor wirings, etc. on both surfaces of the metal-clad laminate 1. When the metal-clad laminate 1 has only one conductor layer 10, the metal-clad laminate 1 may have only the first conductor layer 11 and only the second conductor layer 12. It may be. The metal-clad laminate 1 may include two or more insulating layers 20. When the metal-clad laminate 1 includes a plurality of insulating layers 20, at least one insulating layer 20 among the plurality of insulating layers 20 may include the base material 21, the graphite sheet 22, and the guide member 23.

<Thermosetting resin composition>
In the metal-clad laminate 1 according to the first embodiment of the present invention, as described above, the base material 21 may include a cured product of the thermosetting resin composition. In the metal-clad laminate 1 according to the second embodiment of the present invention, as described above, the second layer 212 in the base material 21 is made of a cured product of a thermosetting resin composition. These thermosetting resin compositions preferably include a thermosetting resin composition (hereinafter referred to as composition (X)) described later. Hereinafter, the composition (X) will be described.

  The composition (X) contains an organic material. In addition, when the composition (X) contains an organic solvent, the organic solvent is not included in the organic material.

  The organic material is represented by the following formula (1): epoxy compound (A), bismaleimide (B), polyphenylene ether resin (C) having a substituent (c2) having a carbon-carbon double bond at the terminal. Block copolymer (D).

PS-X-PS (1)
Each PS in the formula (1) is a polystyrene block, and X in the formula (1) is a polyolefin block. The polyolefin block has at least one of an isoprene unit and a hydrogenated isoprene unit.

  The sum total of the polyolefin block in a block copolymer (D) with respect to the whole block copolymer (D) exists in the range of 70-90 mass%.

  Furthermore, the temperature at which the loss tangent tan δ of the block copolymer (D) exhibits a maximum value is −20 ° C. or higher. The loss tangent tan δ of the block copolymer (D) is measured by dynamic viscoelasticity measurement. The dynamic viscoelasticity is calculated from a value measured by, for example, a viscoelasticity measuring device “DMS6100” manufactured by Seiko Instruments Inc.

  In the present embodiment, the composition (X) contains the epoxy compound (A), bismaleimide (B) and polyphenylene ether resin (C), thereby reducing the dielectric constant of the cured product of the composition (X). In addition, a low dielectric loss tangent can be achieved. Moreover, the cured | curing material has favorable softness | flexibility because composition (X) contains a block copolymer (D). For this reason, the insulating layer 20 containing hardened | cured material can have favorable flexibility. Furthermore, the composition (X) can be molded at a low temperature such as a temperature within the range of 180 to 200 ° C. This is presumably because the molecules of the block copolymer (D) can react even at a low temperature, and the polyphenylene ether resin (C) and the block copolymer (D) can react at a low temperature. . Furthermore, the cured product of the composition (X) can also have good heat resistance.

  Therefore, the composition (X) can be molded at a low temperature, and the cured product can have a low dielectric constant and a low dielectric loss tangent, and can also have high heat resistance.

  The epoxy compound (A) will be described. When the composition (X) contains the epoxy compound (A), the cured product of the composition (X) can have particularly high heat resistance. Furthermore, cured | curing material can have favorable adhesiveness with a metal and a resin material because composition (X) contains an epoxy compound (A).

  The epoxy compound (A) preferably contains a polyfunctional epoxy resin having a naphthalene skeleton. Examples of the polyfunctional epoxy resin having a naphthalene skeleton include a novolac type epoxy resin, a trifunctional type epoxy resin, an aralkyl type epoxy resin, and a cresol type cocondensation type epoxy resin. The epoxy compound (A) comprises a bisphenol A type epoxy resin, a polyphenol type epoxy resin, a polyglycidylamine type epoxy resin, an alcohol type epoxy resin, an alicyclic epoxy resin, and a novolac type epoxy resin having a phenol skeleton and a biphenyl skeleton. You may contain the at least 1 type of polyfunctional epoxy resin selected from a group.

  The amount of the epoxy compound (A) with respect to the organic material in the composition (X) is preferably in the range of 3 to 10% by mass. When the amount of the epoxy compound (A) is 3% by mass or more, the cured product can have particularly high heat resistance and can have particularly high adhesion to a metal and a resin material. Moreover, the favorable softness | flexibility of hardened | cured material can be maintained because this quantity is 10 mass% or less. The amount of the epoxy compound (A) is more preferably in the range of 3 to 7% by mass.

  The bismaleimide (B) will be described. When the composition (X) contains the bismaleimide (B), the cured product of the composition (X) can have higher heat resistance.

  The bismaleimide (B) is preferably a monomer. In this case, the solubility of the bismaleimide (B) in the organic material in the composition (X) is good, and the cured product can have higher heat resistance.

  The bismaleimide (B) is preferably 4,4′-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, and 1 , 6'-bismaleimide- (2,2,4-trimethyl) hexane, which contains at least one component selected from the group consisting of. In this case, the dielectric loss is particularly reduced.

  The amount of bismaleimide (B) with respect to the organic material in the composition (X) is preferably in the range of 3 to 20% by mass. When the amount of the bismaleimide (B) is 3% by mass or more, the cured product can have particularly high heat resistance. Moreover, hardened | cured material can have a favorable softness | flexibility as this quantity is 20 mass% or less. The amount of this bismaleimide (B) is more preferably in the range of 3 to 15% by mass, and still more preferably in the range of 3 to 10% by mass.

  The polyphenylene ether resin (C) will be described. The polyphenylene ether resin (C) has, for example, a polyphenylene ether chain (c1) and a substituent (c2) bonded to the terminal of the polyphenylene ether chain (c1). The substituent (c2) has a carbon-carbon double bond.

  The substituent (c2) is, for example, a substituent (c21) represented by the following formula (6) or a substituent (c22) represented by the following formula (7).

In the formula (6), n is an integer of 0 to 10, Z is an arylene group, and R ^{1 to} R ³ are each independently hydrogen or an alkyl group. When n in the formula (6) is 0, Z is directly bonded to the end of the polyphenylene ether chain (c1) in the polyphenylene ether resin (C).

In the formula (7), R ⁴ is hydrogen or an alkyl group.

  Regarding the substituent (c21), specific examples of Z in the formula (6) include a divalent monocyclic aromatic group such as a phenylene group and a divalent polyfunctional aromatic group such as a naphthylene group. At least one hydrogen in the aromatic ring in Z may be substituted with an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, or an alkylcarbonyl group.

  The substituent (c21) preferably has a vinylbenzyl group. The substituent (c21) is, for example, a substituent represented by the following formula (61) or a substituent represented by the following formula (62).

  The polyphenylene ether chain (c1) has, for example, a structure represented by the following formula (8).

In the formula (8), m is a number in the range of 1 to 50, and R ^{5 to} R ⁸ are each independently hydrogen, alkyl group, alkenyl group, alkynyl group, formyl group, alkylcarbonyl group, alkenylcarbonyl. Or an alkynylcarbonyl group.

Carbon number of an alkyl group becomes like this. Preferably it is 1-18, More preferably, it is 1-10. More specifically, the alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a hexyl group, or a decyl group. The carbon number of the alkenyl group is preferably 2 to 18, more preferably 2 to 10. More specifically, the alkenyl group is, for example, a vinyl group, an allyl group or a 3-butenyl group. The carbon number of the alkynyl group is preferably 2-18, more preferably 2-10. More specifically, the alkynyl group is, for example, an ethynyl group or a prop-2-yn-1-yl group (also referred to as a propargyl group). The carbon number of the alkylcarbonyl group is preferably 2-18, more preferably 2-10. More specifically, the alkylcarbonyl group is, for example, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, a hexanoyl group, an octanoyl group, or a cyclohexylcarbonyl group. The carbon number of the alkenylcarbonyl group is preferably 3-18, more preferably 3-10. More specifically, the alkenylcarbonyl group is, for example, an acryloyl group, a methacryloyl group or a crotonoyl group. The alkynylcarbonyl group preferably has 3 to 18 carbon atoms, more preferably 3 to 10 carbon atoms. More specifically, the alkynylcarbonyl group is, for example, a propioloyl group. Particularly preferably, R ^{5 to} R ⁸ are each independently hydrogen or an alkyl group.

  The number average molecular weight of the polyphenylene ether resin (C) is preferably in the range of 1000 to 7000. In this case, the cured product of the composition (X) has particularly excellent dielectric properties, and can achieve a high glass transition temperature, improved adhesion, and improved heat resistance in a well-balanced manner. In addition, this number average molecular weight is computed from the analysis result by the gel permeation chromatography of polyphenylene ether resin (C).

  The number of substituents (c2) per molecule in the polyphenylene ether resin (C) is preferably in the range of 1.5 to 3. When the number of the substituents (c2) is 1.5 or more, the crosslinking density of the reaction product of the elastomer (A) and the polyphenylene ether resin (C) is sufficiently high, so that the heat resistance of the cured product is particularly improved. Yes. When the number of the substituents (c2) is 3.0 or less, excessive reactivity of the composition (X) is suppressed, so that the storage stability of the composition (X) and the composition (X) The fluidity during molding can be improved. This number is preferably in the range of 1.7 to 2.7, more preferably in the range of 1.8 to 2.5.

  The intrinsic viscosity of the polyphenylene ether resin (C) is preferably in the range of 0.03 to 0.12 dL / g. If the intrinsic viscosity is 0.03 dL / g or more, the dielectric constant and dielectric loss tangent of the cured product can be particularly lowered. Moreover, if intrinsic viscosity is 0.12 dL / g or less, the fluidity | liquidity at the time of shaping | molding of a composition (X) can improve especially. This intrinsic viscosity is more preferably in the range of 0.04 to 0.11 dL / g, and still more preferably in the range of 0.06 to 0.095 dL / g. The intrinsic viscosity is a viscosity at 25 ° C. of a solution prepared by dissolving polyphenylene ether resin (C) in methylene chloride at a concentration of 0.18 g / 45 ml. This viscosity is measured with a viscometer such as AVS500 Visco System manufactured by Schott.

  The amount of the component having a molecular weight of 13000 or more in the polyphenylene ether resin (C) with respect to the polyphenylene ether resin (C) is preferably 5% by mass or less. In this case, the fluidity at the time of molding the composition (X) is particularly improved, and the curability of the composition (X) can be particularly improved. The amount of the component having a molecular weight of 13,000 or more is more preferably in the range of 0 to 5% by mass, and still more preferably in the range of 0 to 3% by mass. It is particularly preferable if the polyphenylene ether resin (C) does not contain a component having a molecular weight of 13,000 or more.

  The amount of the component having a molecular weight of 13,000 or more in the polyphenylene ether resin (C) relative to the polyphenylene ether resin (C) is calculated from the molecular weight distribution of the polyphenylene ether resin (C) obtained by gel permeation chromatography.

  The amount of the polyphenylene ether resin (C) with respect to the composition (X) is preferably in the range of 8 to 35% by mass. When the amount of the polyphenylene ether resin (C) is 8% by mass or more, the cured product can have higher heat resistance. Moreover, hardened | cured material can have a higher softness | flexibility as this quantity is 35 mass% or less. This amount is more preferably in the range of 10 to 30% by mass, and still more preferably in the range of 10 to 25% by mass.

  The polyphenylene ether resin (C) is synthesized, for example, by the following method.

  First, polyphenylene ether is prepared. Polyphenylene ether is, for example, a copolymer of monomers containing 2,6-dimethylphenol and at least one of bifunctional phenol and trifunctional phenol, and poly (2,6-dimethyl-1,4-phenylene oxide). , Containing at least one.

  More specifically, for example, polyphenylene ether is represented by the following formula (81).

  In the formula (81), s is a number of 0 or more, t is a number of 0 or more, and the sum of s and t is a number of 1 or more. s is preferably a number in the range of 0 to 20, t is preferably a number in the range of 0 to 20, and the total value of s and t is preferably a number in the range of 1 to 30.

  The polyphenylene ether resin (C) can be synthesized by substituting the terminal hydroxyl group of the polyphenylene ether with the substituent (c2). For this purpose, for example, polyphenylene ether is reacted with a compound represented by the following formula (63).

In Formula (63), n is an integer of 0 to 10, Z is an arylene group, and R ^{1 to} R ³ are each independently hydrogen or an alkyl group. X is a halogeno group, and more specifically, for example, a chloro group, a bromo group, an iodo group, or a fluoro group. X is particularly preferably a chloro group. In addition, when n in Formula (63) is 0, Z is directly bonded to X.

  The compound represented by the formula (63) contains, for example, at least one of p-chloromethylstyrene and m-chloromethylstyrene.

  Preferably, polyphenylene ether and the compound represented by formula (63) are reacted in a solvent in the presence of an alkali metal hydroxide. In this case, the reaction can proceed efficiently because the alkali metal hydroxide acts as a dehalogenating agent. The alkali metal hydroxide is sodium hydroxide, for example. The solvent is for example toluene.

  It is also preferable to react the polyphenylene ether and the compound represented by the formula (63) in a solvent in the presence of an alkali metal hydroxide and a phase transfer catalyst. In this case, the reaction can proceed more efficiently. The phase transfer catalyst is a quaternary ammonium salt such as tetra-n-butylammonium bromide.

  The temperature at the time of reaction between the polyphenylene ether and the compound represented by the formula (63) is preferably in the range of room temperature to 100 ° C, more preferably in the range of 30 to 100 ° C. The time of this reaction is preferably It is in the range of 0.5 to 20 hours, more preferably in the range of 0.5 to 10 hours.

  The block copolymer (D) will be described. The block copolymer (D) is represented by the formula (1) as described above. The polystyrene block in the block copolymer (D) is a block composed of polystyrene chains. As described above, the polyolefin block in the block copolymer (D) has at least one of an isoprene unit and a hydrogenated isoprene unit.

The isoprene unit is a unit represented by C ₅ H ₈ derived from isoprene. Specifically, the isoprene unit includes a 3,4-isoprene unit represented by the following formula (11), a 1,2-isoprene unit represented by the following formula (12), and 1,4 represented by the following formula (13). -It can contain at least one unit selected from the group consisting of isoprene units.

The hydrogenated isoprene unit has a structure in which the isoprene unit is hydrogenated, and is represented by C ₅ H ₁₀ . Specifically, the hydrogenated isoprene unit includes a 3,4-hydrogenated isoprene unit represented by the following formula (14), a 1,2-hydrogenated isoprene unit represented by the following formula (15), and the following formula (16). And at least one unit selected from the group consisting of 1,4-hydrogenated isoprene units.

  The reason why the reactivity between the polyphenylene ether resin (C) and the block copolymer (D) is good is that the substituent (c2), the isoprene unit and the hydrogenated isoprene unit have high reactivity. Inferred.

  In order to have particularly good reactivity between the polyphenylene ether resin (C) and the block copolymer (D), the polyolefin block is composed of 3,4-isoprene units, 1,2-isoprene units, 3,4-water. It is preferable to have at least one unit selected from the group consisting of an added isoprene unit and a 1,2-hydrogenated isoprene unit.

  In order for the cured product of the composition (X) to have particularly good heat resistance, the polyolefin block preferably has a hydrogenated polyisoprene unit. The reason why the heat resistance is improved is presumed that the hydrogenated polyisoprene block does not have an unsaturated double bond, so that the unsaturated double bond hardly remains in the cured product.

  The polyolefin block may further have units other than the isoprene unit and the hydrogenated isoprene unit. Examples of units other than isoprene units and hydrogenated isoprene units include hydrogenated polybutadiene.

  However, in order for the reactivity between the molecules of the block copolymer (D) and the reactivity between the polyphenylene ether resin (C) and the block copolymer (D) to be particularly good, isoprene with respect to the entire polyolefin block. The total amount of units and hydrogenated isoprene units is preferably 90% by mass or more. It is particularly preferable if the total amount of 3,4-isoprene unit, 1,2-isoprene unit, 3,4-hydrogenated isoprene unit, and 1,2-hydrogenisoprene unit with respect to the entire polyolefin block is 60% by mass or more. .

  As above-mentioned, the total amount of the polyolefin block in a block copolymer (D) with respect to the whole block copolymer (D) exists in the range of 70-90 mass%. When the total amount of the polyolefin block is 70% by mass or more, the reactivity between the molecules of the block copolymer (D) and the reactivity between the polyphenylene ether resin (C) and the block copolymer (D) are good. And the reaction product produced by the reaction between the molecules of the block copolymer (D) and the reaction between the polyphenylene ether resin (C) and the block copolymer (D) has a sufficiently high crosslinking density. sell. For this reason, hardened | cured material can have high heat resistance. Moreover, a block copolymer (D) can have the outstanding compatibility with polyphenylene ether resin (C) because the total amount of a polyolefin block is 90 mass% or less. The total amount of the polyolefin block is more preferably in the range of 70 to 88% by mass, and still more preferably in the range of 75 to 88% by mass.

  Further, as described above, the temperature at which the loss tangent tan δ of the block copolymer (D) exhibits a maximum value is −20 ° C. or higher. For this reason, the tackiness of the dried or semi-cured product of the composition (X) can be suppressed, and the cured product can have high heat resistance. The temperature at which the loss tangent tan δ exhibits the maximum value is more preferably −10 ° C. or higher, and further preferably 10 ° C. or higher.

  It is preferable that the quantity of block copolymer (D) with respect to the organic material in composition (X) exists in the range of 40-80 mass%. When this amount is 40% by mass or more, the cured product can have high flexibility. Further, when the amount of the block copolymer (D) is 80% by weight or less, the cured product may have higher heat resistance and may have a low linear expansion coefficient.

  The composition (X) preferably contains a flame retardant. In this case, the cured product of the composition (X) can have good flame retardancy. The flame retardant contains, for example, at least one of a halogen flame retardant and a phosphorus flame retardant. The halogen flame retardant contains, for example, at least one of a bromine flame retardant and a chlorine flame retardant. Examples of brominated flame retardants include pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, tetrabromobisphenol A, and hexabromocyclododecane. Examples of chlorinated flame retardants include chlorinated flame retardants such as chlorinated paraffin. Examples of the phosphorus flame retardant include at least one component selected from the group consisting of a phosphate ester, a phosphazene compound, a phosphinate flame retardant, and a melamine flame retardant, for example. Examples of phosphate esters include condensed phosphate esters and cyclic phosphate esters. Examples of phosphazene compounds include cyclic phosphazene compounds. Examples of phosphinate flame retardants include phosphinic acid metal salts, and examples of phosphinic acid metal salts include dialkylphosphinic acid aluminum salts. Examples of the melamine flame retardant include melamine phosphate and melamine polyphosphate.

  The flame retardant preferably contains a brominated flame retardant, and more preferably contains an incompatible bromine-containing compound. The incompatible bromine-containing compound can impart high flame retardancy to the cured product even in a small amount, and it is difficult to lower the glass transition temperature of the cured product, so that good heat resistance of the cured product can be maintained. The amount of bromine in the incompatible bromine-containing compound with respect to the organic material in the composition (X) is preferably in the range of 8 to 20% by mass. In this case, the cured product can have favorable flame retardancy, and good fluidity of the composition (X) and good heat resistance of the cured product can be maintained.

  The composition (X) may contain an inorganic filler. When the composition (X) contains an inorganic filler, the cured product of the composition (X) may have particularly high heat resistance and flame retardancy.

  In general, since the crosslinked density of a cured product of a resin composition containing an elastomer is low, the cured product has a high coefficient of thermal expansion, and in particular, has a high coefficient of thermal expansion at a temperature higher than the glass transition temperature. However, when the composition (X) contains an inorganic filler, the cured product of the composition (X) may have good dielectric properties, heat resistance and flame retardancy, and increase in the viscosity of the composition (X). In addition, the thermal expansion coefficient of the cured product can be reduced. In particular, the thermal expansion coefficient of the cured product at a temperature higher than the glass transition temperature can be reduced. Furthermore, the cured product can have high toughness.

  The inorganic filler can contain at least one material selected from the group consisting of silica, alumina, talc, aluminum hydroxide, magnesium hydroxide, titanium oxide, mica, aluminum borate, barium sulfate, and calcium carbonate, for example.

  The inorganic filler may be surface-treated with a silane coupling agent of vinyl silane type, styryl silane type, methacryl silane type, or acryl silane type. In this case, the metal-clad laminate 1 including the insulating layer 20 containing the cured product of the composition (X) can have high heat resistance during moisture absorption and high interlayer peel strength.

  When the composition (X) contains an inorganic filler, the amount of the inorganic filler with respect to the composition (X) is preferably in the range of 10 to 150% by mass, more preferably in the range of 10 to 100% by mass. More preferably, it is in the range of 20 to 100% by mass.

  The composition (X) may further contain additives other than the above components. Examples of additives include silicone antifoaming agents and antifoaming agents such as acrylic ester antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes, pigments, lubricants, and wetting and dispersing agents. Contains a dispersant. The composition (X) may contain a solvent, if necessary. An example of the solvent includes toluene.

<Thermoplastic resin composition>
In the metal-clad laminate 1 according to the first embodiment of the present invention, as described above, the base material 21 may include a thermoplastic resin composition. In the metal-clad laminate 1 according to the second embodiment of the present invention, as described above, the first layer 211 in the base material 21 includes a thermoplastic resin composition. These thermoplastic resin compositions will be described.

  The thermoplastic resin composition includes at least one component selected from the group consisting of a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin. In the metal-clad laminate 1, the thermoplastic resin composition may be layered. Hereinafter, a layer containing a liquid crystal polymer resin is called a liquid crystal polymer resin layer, a layer containing a polyimide resin is called a polyimide layer, a layer containing a polyamideimide resin is called a polyamideimide layer, and a layer containing a fluororesin is called a fluororesin layer. . These words are considered common nouns herein.

  Each of the liquid crystal polymer resin layer, the polyimide resin layer, the polyamideimide resin layer, and the fluororesin layer is produced from, for example, a resin liquid containing a resin as a material or a sheet material containing a resin. The sheet material may have a base material such as glass cloth inside thereof and may be reinforced with this base material. The sheet material may be, for example, a prepreg.

  Liquid crystal polymer resins include, for example, polycondensates of ethylene terephthalate and parahydroxybenzoic acid, polycondensates of phenol and phthalic acid and parahydroxybenzoic acid, and polycondensates of 2,6-hydroxynaphthoic acid and parahydroxybenzoic acid. It can contain at least one component selected from the group consisting of condensates.

  When producing a liquid crystal polymer resin layer, for example, a liquid crystal polymer resin is formed into a sheet shape to produce a sheet material, and this resin layer can be produced by stacking the sheet material on a metal foil or the like.

  The polyimide resin is obtained, for example, by preparing a resin liquid containing a polyimide resin as follows. First, polyamic acid is produced by polycondensation of tetracarboxylic dianhydride and a diamine component. The tetracarboxylic dianhydride preferably contains 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride. The diamine component is selected from the group consisting of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, and 4,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] sulfone. It is preferable to contain at least one component. Subsequently, the polyamic acid is heated in a solvent. The solvent contains at least one component selected from components consisting of N-methyl-2-pyrrolidone, methyl ethyl ketone, toluene, dimethylacetamide, dimethylformamide, and methoxypropanol, for example. The heating temperature is, for example, in the range of 60 to 250 ° C., preferably in the range of 100 to 200 ° C., and the heating time is, for example, in the range of 0.5 to 50 hours. Thereby, the polyamic acid is imidized by a cyclization reaction, and a polyimide resin is generated. Thereby, the resin liquid containing a polyimide resin is obtained.

  When producing a polyimide resin layer, for example, the resin layer containing a polyimide resin is applied onto a metal foil or the like, and then heated and dried to produce the same layer.

  The polyamideimide resin can be obtained, for example, by adjusting a resin liquid containing a polyamideimide resin as follows. First, a mixture is prepared by mixing trimellitic anhydride, 4,4′-diisocyanato-3,3′-dimethylbiphenyl, tolylene 2,4-diisocyanate, diazabicycloundecene, and N, N-dimethylacetamide. To do. By heating and reacting this mixture, a mixed liquid containing polyamideimide is obtained. Subsequently, the mixed solution is cooled. Further, bismaleimide is blended into this mixed solution. Thereby, the resin liquid containing a polyamideimide is obtained.

  When producing a polyamide-imide resin layer, for example, a resin solution containing a polyamide-imide resin is applied onto a metal foil or the like, and then heated and dried to produce the same layer.

  The fluororesin includes, for example, polytetrafluoroethylene.

<Method for producing metal-clad laminate>
With reference to FIGS. 1-4, the manufacturing method of the metal-clad laminated board 1 of this embodiment is demonstrated.

  The manufacturing method of the metal-clad laminate of this embodiment is obtained by stacking the first metal foil, the first resin sheet, the graphite sheet 22 and the guide member 23, the second resin sheet, and the second metal foil in this order. By hot pressing, from the first conductor layer 11 made of the first metal foil, the base material 21 made of the cured product of the first resin sheet and the cured product of the second resin sheet, and the second metal foil The process of producing the 2nd conductor layer 12 which becomes.

  In order to manufacture the metal-clad laminate 1 shown in FIG. 1, a resin sheet (hereinafter referred to as a first resin sheet) containing a component of one metal foil (hereinafter referred to as a first metal foil) and a base material 21. ), A graphite sheet 22, a guide member 23, a resin sheet containing the components of the base material 21 (hereinafter referred to as the second resin sheet), and another metal foil (hereinafter referred to as the second metal foil) in this order. After being stacked, the metal-clad laminate 1 can be manufactured by, for example, hot pressing them. In this case, the first metal foil and the second metal foil become the first conductor layer 11 and the second conductor layer 12 in the metal-clad laminate 1, respectively. Further, the cured product of the first resin sheet and the cured product of the second resin sheet become the base material 21 in the metal-clad laminate 1.

  The components of the first resin sheet and the second resin sheet may be the same or different, but are preferably the same. The components of the first resin sheet and the second resin sheet preferably include a thermosetting resin composition, and more preferably include the above-described composition (X). The first resin sheet and the second resin sheet may be a sheet material of a thermoplastic resin composition.

  The graphite sheet 22 and the guide member 23 are arranged on the first resin sheet so as to have a specific positional relationship with each other. It is a preferable aspect that the graphite sheet 22 and the guide member 23 are arranged on the first resin sheet so as not to overlap each other. Moreover, it is preferable that the guide member 23 is arrange | positioned at at least two places on a 1st resin sheet.

  When the first resin sheet and the second resin sheet are cured by sandwiching the graphite sheet 22 and the guide member 23 between the first resin sheet and the second resin sheet and performing hot pressing, the graphite sheet 22 And the guide member 23 are embedded in a base material 21 made of a cured product of the first resin sheet and a cured product of the second resin sheet.

  In addition, the metal-clad laminated board 1 which has the conductor layer 10 only on one side can also be produced by removing all the 2nd conductor layers 12 by an etching process etc.

  In another method for manufacturing the metal-clad laminate 1 shown in FIG. 1, for example, a metal foil with a resin can be used.

  When using the metal foil with resin to manufacture the metal-clad laminate 1 shown in FIG. 1, first, one metal foil (hereinafter referred to as the first metal foil) is prepared, and the first metal foil is formed on the first metal foil. Then, after applying the resin liquid containing the components of the base material 21, the resin liquid is dried or semi-cured by an appropriate method such as drying or heating. Accordingly, a resin-coated metal foil (hereinafter referred to as a first resin sheet) including a dried or semi-cured resin liquid (hereinafter referred to as a first resin sheet) containing a component of the base material 21 on the first metal foil. Metal foil). The first resin-attached metal foil is obtained by stacking a resin sheet material containing the components of the base material 21 on the first metal foil as the first resin sheet, and then hot-pressing them as necessary. It can also be produced.

  Next, another metal foil (hereinafter referred to as the second metal foil) is prepared, and the components of the base material 21 are formed on the second metal foil in the same procedure as that for producing the first metal foil with resin. A resin-coated metal foil (hereinafter referred to as a second resin-coated metal foil) comprising a dried resin resin or a semi-cured product (hereinafter referred to as a second resin sheet) is prepared. Of course, the second resin-attached metal foil is also a second resin sheet on which a resin sheet material containing the components of the base material 21 is stacked as a second resin sheet, and these are hot-pressed as necessary. By doing so, it can be manufactured.

  Next, the graphite sheet 22 and the guide member 23 are arranged on the first resin sheet of the first metal foil with resin. These arrangements are as described above. Then, a metal-clad laminate is obtained by heat-pressing the second resin-coated metal foil so that the second resin sheet is on the graphite sheet 22 and the guide member 23 side on the graphite sheet 22 and the guide member 23. 1 can be produced.

  In this case, the first metal foil of the first metal foil with resin and the second metal foil of the second metal foil with resin are respectively the first conductor layer 11 and the second conductor layer 12 in the metal-clad laminate 1. It becomes. The cured product of the first resin sheet in the first metal foil with resin and the cured product of the second resin sheet in the second metal foil with resin become the base material 21 in the metal-clad laminate 1. The graphite sheet 22 and the guide member 23 are sandwiched between the first resin sheet and the second resin sheet, so that the graphite sheet 22 and the guide member are cured when the first resin sheet and the second resin sheet are cured. 23 are embedded in a base material 21 made of a cured product of the first resin sheet and a cured product of the second resin sheet.

  When the component of the base material 21 contains a thermosetting resin composition, each of the first resin sheet and the second resin sheet contains a dried or semi-cured product of the thermosetting resin composition. Moreover, when the component of the base material 21 contains a thermoplastic resin composition, each of the first resin sheet and the second resin sheet contains a thermoplastic resin composition.

  In addition, the graphite sheet 22 and the guide member 23 are disposed on the first resin sheet of the first metal foil with resin, and the resin sheet material including the component of the base material 21 is stacked thereon, and then, The metal-clad laminate 1 having the conductor layer 10 only on one side can be produced by, for example, hot pressing.

  In order to manufacture the metal-clad laminate 1 shown in FIG. 4, one metal foil (hereinafter referred to as a first metal foil), a first resin sheet, a graphite sheet 22, a guide member 23, and a second resin sheet The metal-clad laminate 1 can be manufactured by stacking other metal foils (hereinafter referred to as second metal foils) in this order and then, for example, hot pressing them. When the metal-clad laminate 1 shown in FIG. 4 is manufactured, each of the first resin sheet and the second resin sheet is a sheet material containing a dried or semi-cured product of a thermosetting resin composition (hereinafter referred to as heat). A curable sheet material) and a sheet material containing a thermoplastic resin composition (hereinafter referred to as a thermoplastic sheet material). That is, the metal-clad laminate 1 shown in FIG. 4 includes a first metal foil, a thermoplastic sheet material, a thermosetting sheet material, a graphite sheet 22 and a guide member 23, a thermosetting sheet material, a thermoplastic sheet material, and The second metal foil can be manufactured by laminating in this order and hot pressing.

  In this case, the first metal foil and the second metal foil become the first conductor layer 11 and the second conductor layer 12 in the metal-clad laminate 1, respectively. Further, the cured product of the first resin sheet and the cured product of the second resin sheet become the base material 21 in the metal-clad laminate 1. The thermoplastic sheet material contained in the first resin sheet and the thermoplastic sheet material contained in the second resin sheet become the first layer 211 in the base material 21. The cured product of the thermosetting sheet material contained in the first resin sheet and the cured product of the thermosetting sheet material contained in the second resin sheet become the second layer 212 in the base material 21.

  The components of the thermosetting sheet material contained in the first resin sheet and the second resin sheet are preferably the same. It is preferable that the component of a thermosetting sheet material contains the above-mentioned composition (X). The components of the thermoplastic sheet material contained in the first resin sheet and the second resin sheet are preferably the same. The component of the thermoplastic sheet material preferably includes at least one component selected from the group consisting of a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin.

  The graphite sheet 22 and the guide member 23 are disposed on the thermosetting sheet material included in the first resin sheet so as to have a specific positional relationship with each other. These arrangements may be the same as in the case of manufacturing the metal-clad laminate 1 shown in FIG.

  The graphite sheet 22 and the guide member 23 are sandwiched between thermosetting sheet materials included in the first resin sheet and the second resin sheet. For this reason, the graphite sheet 22 and the guide member 23 are embedded in the second layer 212 made of a cured product of the thermosetting sheet material when the thermosetting sheet material is cured.

  In addition, the metal-clad laminated board 1 which has the conductor layer 10 only on one side can also be produced by removing all the 2nd conductor layers 12 by an etching process etc.

  As another method for manufacturing the metal-clad laminate 1 shown in FIG. 4, for example, a first conductor layer 11 such as a metal foil is first prepared, and the first layer 211 is formed on the first conductor layer 11. Form. The first layer 211 is made from, for example, the resin liquid or sheet material already described. That is, the first layer 211 can be formed on the first conductor layer 11 by applying a resin liquid containing the component of the first layer 211 on the first conductor layer 11 and then drying. . In addition, the 1st layer 211 can also be produced by carrying out the hot press, after laminating | stacking the sheet material containing the component of the 1st layer 211 on the 1st conductor layer 11. FIG.

  Next, the second layer 212 is formed over the first layer 211. For example, after coating the composition (X) on the first layer 211, the coating film of the composition (X) is heated and dried or semi-cured. The graphite sheet 22 and the guide member 23 are placed on the dried or semi-cured coating film, and then the composition (X) is further applied thereon and cured by heating. Thereby, the second layer 212 can be manufactured. The composition (X) can be molded at a low temperature. For this reason, the drying or semi-curing of the composition (X) can be performed, for example, by a heat treatment under the conditions of a heating temperature of 100 to 160 ° C. and a heating time of 5 to 10 minutes. Moreover, hardening of (X) of a composition can be performed by the heat processing on the conditions within the range of the heating temperature of 160 to 200 degreeC, and the time of heating for 30 to 120 minutes, for example. Through this process, the graphite sheet 22 and the guide member 23 are embedded in the second layer 212.

  Next, the first layer 211 and the second conductor layer 12 are further formed on the second layer 212. For example, the first layer 211 is formed by applying a resin solution containing the components of the first layer 211 on the second layer 212 made of the cured product of the composition (X), and then applying a metal foil or the like thereon. The first conductor layer 12 and the second conductor layer 12 can be formed on the second layer 212 by stacking and drying the second conductor layer 12. In addition, the first layer 211 and the second conductor layer 12 are produced by superposing the resin sheet containing the components of the first layer 211 and the metal foil on the second layer 212 and then performing hot pressing. You can also. Thereby, the metal-clad laminate 1 shown in FIG. 4 can be produced. A single-sided metal-clad laminate may be produced without laminating the second conductor layer 12.

  As another method for manufacturing the metal-clad laminate 1 shown in FIG. 4, for example, a metal foil with a resin can be used.

  In order to manufacture a metal foil with a resin, for example, a metal foil is prepared, and a first layer 211 and a second layer 212 to be the base material 21 are formed on the metal foil. The first layer 211 is made from, for example, the resin liquid or sheet material already described. For example, the first layer 211 can be manufactured by applying a resin solution on a metal foil and then drying. The first layer 211 can also be produced by stacking sheet materials on the metal foil and then hot pressing them.

  Next, the second layer 212 is formed over the first layer 211. For example, after applying the composition (X) onto the first layer 211, the second layer 212 can be produced by heating or drying or semi-curing the coating film of the composition (X). In addition, you may produce the 2nd layer 212 by laminating | stacking the resin sheet containing the dried material or semi-hardened | cured material of composition (X) on the 1st layer 211. FIG. The composition (X) can be molded at a low temperature. Therefore, the drying or semi-curing of the composition (X) can be performed, for example, by a heat treatment under the conditions of a heating temperature of 100 to 160 ° C. and a heating time of 5 to 10 minutes. Moreover, hardening of (X) of a composition can be performed by the heat processing on the conditions within the range of the heating temperature of 160 to 200 degreeC, and the time of heating for 30 to 120 minutes, for example. Thereby, metal foil with resin can be produced.

  The graphite sheet 22 and the guide member 23 are arranged on a resin in a dry or semi-cured state of a resin-coated metal foil having a metal foil to be the first conductor layer 11. And the metal-clad laminate 1 shown in FIG. 4 is produced by superposing the metal foil with resin containing the metal foil used as the 2nd conductor layer 12 produced similarly on the graphite sheet 22 and the guide member 23, and heat-pressing. can do. At this time, the graphite sheet 22 and the guide member 23 are embedded in the second layer 212 by being sandwiched between the second layers 212 of two resin-coated metal foils.

  Next, a method for forming the guide mark 30 shown in FIG. 2 in the method for manufacturing the metal-clad laminate 1 shown in FIGS. 1 and 4 will be described.

  The manufacturing method of the metal-clad laminate 1 according to the present embodiment includes a step of detecting the position of the guide member 23 in the insulating layer 20 and a guide mark 30 that is in a specific positional relationship with the position and is visible from the outside. Further comprising the step of:

  In the metal-clad laminate 1 formed as described above, the graphite sheet 22 and the guide member 23 are buried in the base material 21, and therefore their positions cannot be confirmed from the outside. Therefore, for example, the position of the guide member 23 is detected using an X-ray inspection machine or the like.

  After detecting the position of the guide member 23, a guide mark 30 that is visible from the outside is formed on the metal-clad laminate 1. The guide marks 30 are preferably formed in at least two places in the metal-clad laminate 1. The guide mark 30 is formed, for example, by making a hole 31 in the metal laminate 1 with a drill. The drill hole may be about 10 mm in diameter.

  In FIG. 2, the hole 31 passes through the metal laminated plate 1, but the hole 31 may not be penetrated through the metal laminated plate 1 and may be opened only in one conductor layer 10. 10 and the base material 21 may be opened to the front of the guide member 23.

  In FIG. 2, the hole 31 is provided through the guide member 23, but the guide member 23 remains in the base material 21. The guide member 23 is preferably left in the base material 21, but the hole 31 may be provided so that the guide member 23 does not remain.

  In FIG. 2, a hole 31 penetrating the metal-clad laminate 1 is provided as a guide mark 30 at a position overlapping the guide member 23 in plan view, but the guide mark 30 is connected to the guide member 23 in plan view. You may be provided in the position which does not overlap. That is, the guide mark 30 may be formed so as to have a specific positional relationship with the guide member 23. The guide mark 30 is preferably provided so as not to overlap the graphite sheet 22 in plan view.

  In FIG. 2, a hole 31 is formed as the guide mark 30, but the guide mark 30 may be a mark such as a figure, a character, or a pattern printed on the surface of the metal-clad laminate 1 by etching or the like. .

  The position of the graphite sheet 22 in the metal-clad laminate 1 based on the positional relationship between the guide mark 30 and the guide member 23 and the positional relationship between the guide member 23 and the graphite sheet 22 with the position of the visually visible guide mark 30 as a reference. Can be specified. According to the position of the graphite sheet 22, a printed wiring board can be produced by forming a conductor wiring on the metal-clad laminate 1 or cutting the metal-clad laminate 1 and then forming a conductor wiring. Is possible.

1 Metal-clad laminate 10 Conductor layer 20 Insulating layer 21 Base material 22 Graphite sheet 23 Guide member

Claims (16)

A conductor layer, and an insulating layer overlying the conductor layer,
The insulating layer includes a base material having electrical insulation, a graphite sheet and a guide member embedded in the base material,
The guide member and the graphite sheet are in a specific positional relationship,
The guide member includes a metal,
Metal-clad laminate. A second conductor layer overlying the insulating layer;
The metal-clad laminate according to claim 1. The graphite sheet and the guide member are arranged in a direction orthogonal to the thickness direction of the insulating layer,
The metal-clad laminate according to claim 1 or 2. The guide member is a metal foil,
The metal-clad laminate according to any one of claims 1 to 3. A guide mark that is visible from the outside is further provided.
The guide mark and the guide member are in a specific positional relationship.
The metal-clad laminate according to any one of claims 1 to 4. The guide mark is a hole,
The metal-clad laminate according to claim 5. The base material includes a cured product of a thermosetting resin composition,
The metal-clad laminate according to any one of claims 1 to 6. The base material includes a first layer and a second layer,
The first layer includes a thermoplastic resin composition;
The second layer is composed of a cured product of a thermosetting resin composition.
The metal-clad laminate according to any one of claims 1 to 7. The graphite sheet and the guide member are embedded in the second layer,
The metal-clad laminate according to claim 8. The metal-clad laminate according to claim 8 or 9, wherein the thermoplastic resin composition includes at least one component selected from the group consisting of a liquid crystal polymer resin, a polyimide resin, a polyamideimide resin, and a fluororesin. The thermosetting resin composition comprises an epoxy compound (A), a bismaleimide (B), a polyphenylene ether resin (C) having a substituent (c2) having a carbon-carbon double bond at the end, and the following formula: A block copolymer (D) represented by (1),
PS-X-PS (1)
Each PS in the formula (1) is a polystyrene block,
X in the formula (1) is a polyolefin block,
The polyolefin block contains at least one of an isoprene unit and a hydrogenated isoprene unit,
The total of the polyolefin blocks in the block copolymer (D) with respect to the entire block copolymer (D) is in the range of 70 to 90% by mass,
The temperature at which the loss tangent tan δ of the block copolymer (D) exhibits a maximum value is −20 ° C. or higher.
The metal-clad laminate according to any one of claims 7 to 10. The amount of the polyphenylene ether resin (C) with respect to the thermosetting resin composition is in the range of 8 to 35% by mass.
The metal-clad laminate according to claim 11. The amount of the bismaleimide (B) with respect to the thermosetting resin composition is in the range of 3 to 20% by mass.
The metal-clad laminate according to claim 11 or 12. The amount of the epoxy compound (A) with respect to the thermosetting resin composition is in the range of 3 to 10% by mass.
The metal-clad laminate according to any one of claims 11 to 13. A method for producing a metal-clad laminate,
The metal-clad laminate includes a conductor layer, an insulating layer overlying the conductor layer, and a second conductor layer overlying the insulating layer,
The insulating layer includes a base material having electrical insulation, a graphite sheet and a guide member embedded in the base material,
The guide member and the graphite sheet are in a specific positional relationship,
The guide member includes a metal,
In the manufacturing method, the first metal foil, the first resin sheet, the graphite sheet and the guide member, the second resin sheet, and the second metal foil are stacked in this order and hot pressed, Producing the conductor layer made of metal foil, the base material made of the cured product of the first resin sheet and the cured product of the second resin sheet, and the second conductor layer made of the second metal foil Including the step of
A method for producing a metal-clad laminate. Detecting the position of the guide member in the insulating layer;
Further forming a guide mark that is in a specific positional relationship with the position and is visible from the outside,
The method for producing a metal-clad laminate according to claim 15.

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