WO2020066145A1 - Low dielectric substrate material - Google Patents

Low dielectric substrate material Download PDF

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Publication number
WO2020066145A1
WO2020066145A1 PCT/JP2019/023075 JP2019023075W WO2020066145A1 WO 2020066145 A1 WO2020066145 A1 WO 2020066145A1 JP 2019023075 W JP2019023075 W JP 2019023075W WO 2020066145 A1 WO2020066145 A1 WO 2020066145A1
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WIPO (PCT)
Prior art keywords
low dielectric
layer
substrate material
dielectric substrate
porous resin
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PCT/JP2019/023075
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French (fr)
Japanese (ja)
Inventor
亮人 松富
将義 中村
慧 三島
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日東電工株式会社
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Publication of WO2020066145A1 publication Critical patent/WO2020066145A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal

Definitions

  • the present invention relates to a low dielectric substrate material, and more particularly, to a low dielectric substrate material suitably used for manufacturing a high-frequency antenna and a high-speed transmission substrate.
  • Wireless communication of the "fifth generation (5G)” standard can transmit a large amount of data. Moreover, in the wireless communication of the "fifth generation (5G)” standard, the above data can be transmitted at a high speed. In recent years, the use of the "fifth generation (5G)” standard has been increasingly desired. It is rare.
  • a high frequency including a millimeter wave is used. This millimeter wave is easily attenuated by moisture in the atmosphere, and a substrate material having a low dielectric constant is required as a substrate material of a high-frequency antenna that emits a millimeter wave.
  • a substrate material having a low dielectric constant is required as a substrate material of a high-frequency antenna that emits a millimeter wave.
  • millimeter wave radio waves can be efficiently emitted.
  • the communication distance can be extended, the area of the antenna member can be reduced, and power consumption can be reduced.
  • a low dielectric substrate with a low dielectric constant has been developed, and a polyimide resin or a fluorine-based resin has been developed. Substrates using low dielectric resin materials such as resins have been developed.
  • a substrate made of a porous material is also being studied. Since the porous body has air having the lowest dielectric constant 1 in the pores, the porous body has a relatively low dielectric constant.
  • a metal foil laminate provided with such a porous body for example, a metal foil laminate provided with a resin porous layer as an insulating material and metal foils arranged on both sides in the thickness direction has been proposed (for example, And Patent Document 1 below.)
  • the conventional porous body including the above Patent Document 1 is based on the wireless communication of the “third generation (3G)” or “fourth generation (4G)” standard or the FPC that transmits data at the conventional speed. Although it can be used as a plate material, its porosity is low, so it does not have a sufficiently low dielectric constant, but has a low dielectric constant of the level required by the "fifth generation (5G)” standard and high-speed transmission FPC. Absent.
  • the object of the present invention is to provide a low dielectric substrate material having a still lower dielectric constant and good adhesion strength of a metal layer.
  • the present inventors have conducted intensive studies and as a result, have successfully used a porous resin layer having a remarkably high porosity, and have a low dielectric constant that can conform to the fifth generation (5G) standards and high-speed transmission FPC.
  • the present inventors have invented a low dielectric substrate material having good adhesion strength of a metal layer.
  • the present invention [1] includes a porous resin layer, an adhesive layer, and a metal layer in the thickness direction in order, and the thickness d1 of the adhesive layer and the thickness d2 of the porous resin layer are represented by the following formula (1). And a low dielectric substrate material that satisfies the above condition. d1 / d2 ⁇ 0.5 (1)
  • the present invention [2] includes the low dielectric substrate material according to [1], which satisfies the following expression (2).
  • This low dielectric substrate material has a porous resin layer, and when the porous resin layer has a high porosity, it can have a sufficiently low low dielectric constant.
  • the low dielectric substrate material can have a low dielectric constant that can be used for a fifth generation (5G) wireless communication antenna or a high-speed transmission FPC.
  • the low dielectric substrate material includes a porous resin layer, an adhesive layer, and a metal layer in the thickness direction in order, the adhesive strength between the metal layer and the porous resin layer is good.
  • the thickness d1 of the adhesive layer is smaller than the thickness d2 of the porous resin layer, the amount of the adhesive layer having a high dielectric constant is larger than the amount of the porous resin layer having a low dielectric constant. Few. Therefore, the influence of the dielectric constant of the adhesive layer can be suppressed, and the dielectric constant of the low dielectric substrate material can be reduced.
  • FIG. 1 shows a cross-sectional view of one embodiment of the low dielectric substrate material of the present invention.
  • FIG. 2 shows a cross-sectional view of a pattern laminate obtained from the low dielectric substrate material shown in FIG.
  • the low dielectric substrate material 1 has one surface and the other surface facing each other in the thickness direction, and has a shape extending in a surface direction orthogonal to the thickness direction.
  • the low dielectric substrate material 1 is disposed on a first metal layer 3, a porous resin layer 4 disposed on one surface in the thickness direction of the first metal layer 3, and disposed on one surface in a thickness direction of the porous resin layer 4.
  • the semiconductor device includes an adhesive layer and a second metal layer (an example of a metal layer) disposed on one surface in the thickness direction of the adhesive layer. That is, the low dielectric substrate material 1 includes the first metal layer 3, the porous resin layer 4, the adhesive layer 5, and the second metal layer 6 in order from the other side in the thickness direction to one side.
  • low dielectric substrate material 1 includes only first metal layer 3, porous resin layer 4, adhesive layer 5, and second metal layer 6.
  • the first metal layer 3 has one surface and the other surface facing each other in the thickness direction, and has a sheet (plate) shape extending in the surface direction.
  • the material of the first metal layer 3 is not particularly limited, and examples thereof include copper, iron, silver, gold, aluminum, nickel, and alloys thereof (stainless steel, bronze). Preferably, copper is used.
  • the thickness of the first metal layer 3 is, for example, 0.1 ⁇ m or more, preferably 1 ⁇ m or more, and is, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less.
  • the porous resin layer 4 has one surface and the other surface opposed in the thickness direction, and has a sheet shape extending in the surface direction.
  • the other surface of the porous resin layer 4 is in contact (close contact) with one surface of the first metal layer 3.
  • the porous resin layer 4 has many fine pores (pores) 10.
  • the porous resin layer 4 has, for example, one of a closed cell structure and an open cell structure. Preferably, it mainly has a closed cell structure.
  • the ratio of the closed cells is, for example, more than 50%, preferably 80% or more, more preferably 90% or more, and for example, 100%. %.
  • the ratio of the closed cells exceeds the above lower limit, a decrease in pattern accuracy due to the penetration of the etching solution used for patterning the first metal layer 3 and the second metal layer 6 into the porous resin layer 4 is suppressed. be able to. That is, it is possible to prevent the etchant from permeating the porous resin layer 4 to remove even the portions of the first metal layer 3 and the second metal layer 6 protected by the resist. it can.
  • plating immersion refers to a phenomenon in which a plating solution infiltrates from a porous portion exposed by the drilling and a metal is deposited in the porous resin layer 4, and the thickness of the metal layer formed on the hole surface is reduced. It becomes non-uniform or discontinuous, resulting in an exposed portion of the porous resin layer.
  • the porosity of the porous resin layer 4 is 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 85% or more.
  • the porosity of the porous resin layer 4 is less than 100%, preferably less than 99%.
  • the porosity is determined, for example, by image analysis of a cross-sectional SEM photograph of the porous resin layer 4. Alternatively, the porosity is determined by calculation based on the following equation.
  • Porosity (%) (1 ⁇ specific gravity of non-porous resin layer / specific gravity of porous resin layer) ⁇ 100
  • the non-porous resin layer is made of the material of the porous resin layer 4, but is not porous but a dense film.
  • the porous resin layer 4 can have a low dielectric constant that can sufficiently cope with the fifth generation (5G) standard and high-speed transmission FPC.
  • the low dielectric substrate material 1 is useful as a substrate material that can sufficiently comply with the fifth generation (5G) standard and high-speed transmission FPC.
  • the average diameter of the pores 10 in the porous resin layer 4 (that is, the average pore diameter) is, for example, 10 ⁇ m or less, and is, for example, 0.1 ⁇ m or more.
  • the average pore diameter is determined by image analysis of a cross-sectional SEM photograph of the porous resin layer 4. In the image analysis, binarization is performed on the SEM image to identify the holes 10, then the hole diameter is calculated, and a histogram is formed. AnalysisJ uses ImageJ.
  • the dielectric constant of the porous resin layer 4 at a frequency of 10 GHz is appropriately adjusted depending on the porosity and the type of the resin described below. Specifically, for example, the dielectric constant is 2.5 or less, preferably 2.0 or less. Also, for example, it is more than 1.0. The dielectric constant is measured by a resonator method using a frequency of 10 GHz.
  • the low dielectric substrate material 1 has a low dielectric constant, and is useful as a substrate material for fifth generation (5G) standards and high-speed transmission FPCs. Can be used.
  • the material of the porous resin layer 4 is not particularly limited, and examples thereof include resins such as a thermosetting resin and a thermoplastic resin.
  • thermosetting resin for example, polycarbonate resin, thermosetting polyimide resin, thermosetting fluorinated polyimide resin, epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin, thermosetting urethane resin , A fluororesin (a polymer of a fluorine-containing olefin (specifically, polytetrafluoroethylene (PTFE) or the like)), a liquid crystal polymer (LCP), or the like. These can be used alone or in combination of two or more.
  • PTFE polytetrafluoroethylene
  • LCP liquid crystal polymer
  • thermoplastic resin examples include olefin resin, acrylic resin, polystyrene resin, polyester resin, polyacrylonitrile resin, maleimide resin, polyvinyl acetate resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polyamide resin, and polyvinyl chloride.
  • Resin polyacetal resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ketone resin, polyallyl sulfone resin, thermoplastic polyimide resin, thermoplastic fluorinated polyimide resin, thermoplastic urethane resin, poly Examples include ether imide resin, polymethylpentene resin, cellulose resin, liquid crystal polymer, and ionomer. These can be used alone or in combination of two or more.
  • polyimide resin including thermosetting polyimide resin and thermoplastic polyimide resin
  • fluorinated polyimide resin thermosetting fluorinated polyimide resin and thermoplastic fluorinated polyimide resin
  • polycarbonate resins particularly preferably, polyetherimide resin
  • a polyimide resin is used.
  • the polyimide resin is the most suitable material for lamination by pressure, which is included in the process of manufacturing the low dielectric substrate material 1 including the porous resin layer 4 having a closed cell structure.
  • the details of the above-mentioned preferable physical properties and production method of the resin are described in, for example, JP-A-2018-021171, JP-A-2018-021172, and the like.
  • the porous resin layer 4 can have a skin layer (not shown) formed on one surface and the other surface in the thickness direction.
  • the arithmetic average roughness (Ra) on one surface or the other surface in the thickness direction of the porous resin layer 4 is, for example, 0.1 ⁇ m or more, preferably 0.2 ⁇ m or more, and for example, 1.0 ⁇ m or less, preferably, It is 0.7 ⁇ m or less.
  • the maximum height (Rz) of the porous resin layer 4 on one surface or the other surface in the thickness direction is, for example, 1.0 ⁇ m or more, preferably 2.0 ⁇ m or more, and for example, 15.0 ⁇ m or less. Preferably, it is 10.0 ⁇ m or less.
  • the thickness of the porous resin layer 4 is, for example, 2 ⁇ m or more, preferably 5 ⁇ m or more, more preferably 25 ⁇ m or more, further preferably 50 ⁇ m or more, and, for example, 1,000 ⁇ m or less, preferably 500 ⁇ m or less. It is.
  • the layers other than the porous resin layer 4, specifically, the first metal layer 3, the adhesive layer 5 (described later), and the second metal layer 6 (described later) are all On the other hand, for example, it is non-porous, that is, it is dense without substantially having fine pores.
  • the adhesive layer 5 has a sheet shape along the surface direction on one surface in the thickness direction of the porous resin layer 4.
  • the material of the adhesive layer 5 is not particularly limited, and includes various types of adhesives such as a hot melt type adhesive and a thermosetting type adhesive. Specifically, an acrylic type adhesive, an epoxy type adhesive And silicone-based adhesives. Preferably, an acrylic adhesive is used.
  • the thickness of the adhesive layer 5 is, for example, 2 ⁇ m or more, preferably 5 ⁇ m or more, and is, for example, 50 ⁇ m or less, preferably 25 ⁇ m or less.
  • the second metal layer 6 has one surface and the other surface opposed in the thickness direction, and has a sheet shape extending in the surface direction.
  • the other surface of the second metal layer 6 is adhered to one surface of the porous resin layer 4 via the adhesive layer 5.
  • the material and thickness of the second metal layer 6 are the same as those of the first metal layer 3.
  • the thickness of the low dielectric substrate material 1 is the total thickness of the first metal layer 3, the porous resin layer 4, the adhesive layer 5, and the second metal layer 6, for example, 10 ⁇ m or more, preferably 20 ⁇ m or more, Also, for example, it is 5,000 ⁇ m or less, preferably 2,000 ⁇ m or less.
  • each member is stacked (formed) while being conveyed by a roll-to-roll method.
  • the first metal layer 3 is prepared.
  • a foil (metal foil) made of the above-described material is prepared as the first metal layer 3.
  • the porous resin layer 4 is formed on one surface of the first metal layer 3.
  • the porous resin layer 4 is formed (built) on one surface of the first metal layer 3.
  • a varnish containing the above-described resin precursor, a porogen, a nucleating agent, and a solvent is prepared, and then, the varnish is applied to one surface of the first metal layer 3 to be applied.
  • the varnish is applied to one surface of the first metal layer 3 to be applied.
  • the types, blending ratios, and the like of the porosity, nucleating agent, and solvent in the varnish are described in, for example, JP-A-2018-021171, JP-A-2018-021172, and the like.
  • the number of parts by mass (mixing ratio) of the porogen is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 100 parts by mass of the precursor. , 50 parts by mass or more, and for example, 300 parts by mass or less, preferably 250 parts by mass or less.
  • the nucleating agent is a foaming nucleating agent (cell regulator) that becomes a nucleus when the precursor is foamed (porous).
  • a foaming nucleating agent cell regulator
  • a fluororesin polymer of fluorinated olefin
  • poly (chlorotrifluoroethylene) such as poly (chlorotrifluoroethylene)
  • meth monomer unit
  • Copolymers containing acrylic acid esters and the above-mentioned fluorine-containing olefins are also included.
  • the nucleating agent may be in a solid state, a liquid state, or a semi-solid state at room temperature (23 ° C.), and is preferably in a solid state. If the nucleating agent is solid at room temperature, examples of the shape of the nucleating agent include a substantially spherical shape, a substantially plate shape, a substantially needle shape, and an indefinite shape (including a lump shape). No.
  • the average value of the maximum length of the nucleating agent is, for example, 2,000 nm or less, preferably 1,000 nm or less. It is preferably 800 nm or less, more preferably less than 500 nm, and for example, 1 nm or more.
  • the nucleating agent may be prepared in advance as a slurry dispersed in a solvent (PTFE).
  • the porogen is extracted from the precursor (pulled out or removed) by, for example, a supercritical extraction method using supercritical carbon dioxide as a solvent.
  • the precursor is cured to form a porous resin, specifically, the porous resin layer 4.
  • the adhesive layer 5 is disposed on one surface of the porous resin layer 4.
  • an adhesive is applied to one surface of the porous resin layer 4, or an adhesive layer 5 previously formed into a sheet from the adhesive is attached to one surface of the porous resin layer 4.
  • the second metal layer 6 is disposed on one surface of the adhesive layer 5.
  • a foil (metal foil) made of the above-described material is attached to one surface of the adhesive layer 5.
  • the low dielectric substrate material 1 is manufactured.
  • the low dielectric substrate material 1 is used for various applications, for example, and is preferably used for manufacturing a high-frequency antenna or a high-speed transmission board (such as a high-speed transmission FPC) conforming to the fifth generation (5G) standard. Specifically, the low dielectric substrate material 1 is used as a substrate material for a high-frequency antenna or a high-speed transmission FPC.
  • the second metal layer 6 is patterned by photolithography (for example, a subtractive method) as shown in FIG.
  • One-sided wiring 17 such as (differential wiring) and antenna wiring is formed.
  • the first metal layer 3 is patterned by photolithography to form the other-side wiring 18 such as a ground wiring, for example.
  • a pattern laminated material 13 having the other side wiring 18, the porous resin layer 4, the adhesive layer 5, and the one side wiring 17 sequentially in the thickness direction is manufactured.
  • 5G high-frequency antennas and high-speed transmission boards conforming to (5G) standards.
  • this low dielectric substrate material 1 has a porous resin layer 4, and the porous resin layer 4 is 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably, When it has a high porosity of 85% or more, it can have a sufficiently low low dielectric constant.
  • the low dielectric constant is, for example, 2.5 or less, preferably 2.0 or less. Therefore, the low dielectric substrate material 1 can have a low dielectric constant that is compatible with a fifth generation (5G) standard wireless communication antenna substrate and a high-speed transmission FPC.
  • 5G fifth generation
  • the low dielectric substrate material 1 includes the first metal layer 3 and the second metal layer 6, it can be patterned as an antenna corresponding to the fifth generation (5G) standard or a wiring of a substrate of a high-speed transmission FPC. it can. Specifically, even if the first metal layer 3 and the second metal layer 6 are patterned under industrial etching conditions, the wiring of the antenna and the substrate of the high-speed transmission FPC that can be adapted to the fifth generation (5G) is used. It can be formed with excellent accuracy.
  • the porous resin layer 4 has a closed cell structure, and the ratio of the closed cells is more than 50%, further, 80% or more, and further, as high as 90% or more, patterning is performed. It is possible to suppress a decrease in pattern accuracy due to the penetration of the used etching solution. Therefore, the low dielectric substrate material 1 is useful as a substrate material that can sufficiently and surely cope with the fifth generation (5G) standard wireless communication and high-speed transmission FPC.
  • 5G fifth generation
  • a porous resin layer 4, an adhesive layer 4, and a second layer 6 are sequentially provided in the thickness direction. Therefore, the adhesive strength between the porous resin layer 4 and the second metal layer 6 is good.
  • the adhesive force between the porous resin layer 4 and the second metal layer 6 is, for example, 0.3 N / mm or more, preferably 0.6 N / mm or more. 0 N / mm or less.
  • the adhesive strength between the porous resin layer 4 and the second metal layer 6 was 90 ° peel strength when the second metal layer 6 was peeled at an angle of 90 ° with respect to the porous resin layer 4 at 23 ° C. The details will be described in detail in Examples.
  • the thickness d1 of the adhesive layer 5 and the thickness d2 of the porous resin layer 4 satisfy the following expression (1). d1 / d2 ⁇ 0.5 (1)
  • the ratio (d1 / d2) of the thickness d1 of the adhesive layer 5 to the thickness d2 of the porous resin layer 4 is 0.5 or less. In other words, the thickness d1 of the adhesive layer 5 is half or less than the thickness d2 of the porous resin layer 4.
  • the thickness of the adhesive layer 5 having a higher dielectric constant than that of the porous resin layer 4 is sufficiently smaller than the thickness of the porous resin layer 4, the influence of the dielectric constant of the adhesive layer 5 can be reduced. Therefore, the dielectric constant of the low dielectric substrate material 1 can be reduced. Therefore, it can be suitably used as a high-frequency antenna or a high-speed transmission board conforming to the fifth generation (5G) standard.
  • 5G fifth generation
  • a low dielectric substrate material including a resin substrate and a metal layer does not have an adhesive layer, and thus has poor adhesive strength.
  • an adhesive layer is disposed between the resin substrate and the metal layer to improve the adhesive strength, the dielectric constant of the low dielectric substrate material is affected by the dielectric constant of the adhesive layer.
  • the conventional resin substrate is not required to have a low dielectric constant that can be used as a high-frequency antenna or a high-speed transmission board conforming to the fifth generation (5G) standard. No attention was paid to the performance of. However, the necessity of conforming to the fifth generation (5G) standard requires a further reduction in the dielectric of the substrate material. We found that we could meet the demand.
  • the inventor can reduce the dielectric constant of the entire substrate material by reducing the thickness of the adhesive layer and making the dielectric constant of the porous resin layer lower than the adhesive layer dominant.
  • the adhesive layer is too thin, the adhesive force between the resin substrate and the metal layer becomes insufficient, so it is necessary to design the adhesive layer with a thickness that can achieve both sufficient adhesive force and suppression of the dielectric constant. there were. Therefore, the present invention suppresses the improvement of the dielectric constant while ensuring the adhesive force by making the adhesive layer 5 thinner than half of the porous resin layer 4, and as a result, the non-peeling of the second metal layer 6 is prevented. (Adhesive strength of the adhesive layer 4) and low dielectric constant of the low dielectric substrate material 1 are achieved.
  • the ratio (d1 / d2) is 0.3 or less, more preferably 0.1 or less. Further, the ratio (d1 / d2) is, for example, 0.01 or more, preferably 0.03 or more. In the low dielectric substrate material 1, preferably, the following expression (2) is satisfied.
  • the ratio (d2 / d1) of the thickness d2 of the porous resin layer 4 to the thickness d1 of the adhesive layer 5 is preferably 2 or more, more preferably 3 or more, and more preferably 10 or more. Also, it is preferably 150 or less, more preferably 25 or less, and further preferably 20 or less.
  • the ratio is equal to or more than the above lower limit, the adhesive strength between the porous resin layer 4 and the second metal layer 6 is further improved.
  • the above ratio is equal to or less than the above upper limit, the dielectric constant of the low dielectric substrate material 1 becomes lower, which is extremely useful as a substrate material that can conform to the fifth generation (5G) standard and high-speed transmission FPC.
  • the low dielectric substrate material 1 preferably satisfies the following expression (3).
  • the difference (d2 ⁇ d1) between the thickness d2 of the porous resin layer 4 and the thickness d1 of the adhesive layer 5 is preferably 5 ⁇ m or more, more preferably 20 ⁇ m or more, and more preferably 50 ⁇ m or more. And preferably 115 ⁇ m or less, more preferably 100 ⁇ m or less.
  • the dielectric constant of the low dielectric substrate material 1 is further reduced.
  • the adhesive strength between the porous resin layer 4 and the second metal layer 6 is further improved.
  • the thickness d1 of the adhesive layer 5 is, for example, 1 ⁇ m or more, preferably 4 ⁇ m or more, more preferably 5 ⁇ m or more, and, for example, 50 ⁇ m or less, preferably 44 ⁇ m or less. , More preferably 10 ⁇ m or less.
  • the dielectric constant of the adhesive layer 5 at a frequency of 10 GHz is appropriately adjusted depending on the type of the adhesive, and specifically, is, for example, 3.10 or less, preferably 2.80 or less, and more preferably 2.50 or less. , For example, 1.00 or more.
  • the dielectric constant of the adhesive layer 5 is equal to or less than the above upper limit, the dielectric constant of the low dielectric substrate material 1 is further reduced.
  • the dielectric constant of the low dielectric substrate material 1 at a frequency of 10 GHz is, for example, 2.00 or less, preferably 1.80 or less, more preferably 1.60 or less, and is, for example, 1.00 or more.
  • the low dielectric substrate material 1 is manufactured by roll-to-roll.
  • the present invention is not limited to this.
  • the low dielectric substrate material 1 can be manufactured by a batch method (single wafer type).
  • the low dielectric substrate material 1 includes the first metal layer 3.
  • the low dielectric substrate material 1 may not include the first metal layer 3. . That is, in one embodiment, a low-dielectric substrate material of a double-sided metal layer lamination type is used. However, in another embodiment, a low-dielectric substrate material of a single-sided metal layer lamination type may be used.
  • the low dielectric substrate material 1 includes a first release sheet disposed on the other side of the first metal layer 3 and a second release sheet disposed on one side of the second metal layer 6. be able to. That is, the low dielectric substrate material 1 includes the first release sheet, the first metal layer 3, the porous resin layer 4, the adhesive layer 5, the second metal layer 6, and the second release sheet on the other side in the thickness direction. From one side to the other side.
  • the low dielectric substrate material 1 may further include a functional layer interposed between layers or formed on the surface.
  • Example 1 First, a 12.5 ⁇ m-thick first metal layer 3 made of copper was prepared.
  • a varnish was prepared by blending 200 parts by mass of a porogen comprising MM400 and a weight average molecular weight of 400), 3 parts by mass of a nucleating agent comprising PTFE having an average particle diameter of 1000 nm, and NMP (N-methylpyrrolidone).
  • the nucleating agent was prepared in advance as a slurry dispersed in NMP and blended with the polyimide precursor. The total number of NMP in the varnish was adjusted so as to be 150 parts by mass with respect to 100 parts by mass of the polyimide precursor, including those contained in the slurry.
  • This varnish is applied to one surface of the first metal layer 3 and dried at 120 ° C. for 30 minutes to remove NMP, followed by supercritical extraction to remove the porosifier, and then vacuum Heating was performed at 380 ° C. for 2 hours for imidization, and a porous resin layer 4 made of polyimide was formed on one surface of the first metal layer 3.
  • the thickness of the porous resin layer 4 was 120 ⁇ m.
  • the porosity of the porous resin layer 4 was 80%, and the average pore diameter was 7 ⁇ m.
  • the dielectric constant of the porous resin layer 4 at a frequency of 10 GHz was 1.5.
  • an adhesive layer 5 made of an acrylic adhesive and having a thickness of 5 ⁇ m was formed on one surface of the porous resin layer 4.
  • a second metal layer 6 made of copper and having a thickness of 12 ⁇ m was bonded to one surface of the bonding layer 5.
  • the low dielectric substrate material 1 including the first metal layer 3, the porous resin layer 4, the adhesive layer 5, and the second metal layer 6 in this order on one side in the thickness direction is manufactured. did.
  • Examples 2 to 5 A low dielectric substrate material 1 was manufactured in the same manner as in Example 1 except that the thickness d1 of the adhesive layer 5 and the thickness d2 of the porous resin layer were changed to the thicknesses d1 and d2 shown in Table 1.
  • Comparative Examples 1-3 A low dielectric substrate material 1 was manufactured in the same manner as in Example 1 except that the thickness d1 of the adhesive layer 5 and the thickness d2 of the porous resin layer were changed to the thicknesses d1 and d2 shown in Table 1.
  • the adhesive strength between the porous resin layer 4 and the second metal layer 6 was It was measured by performing a 90 ° peel test using a tensile compression tester (“SUZ-50NT-2R2T”, manufactured by Imada Seisakusho) at a peel speed of 50 mm / min. At this time, the adhesive layer 5 was scattered or adhered to the entire surface of the porous resin layer 4, the second metal layer 6, or both.
  • the case where the adhesive force was 0.6 N / mm or more was evaluated as ⁇ .
  • the case where the adhesive strength was 0.3 N / mm or more and less than 0.6 N / mm was evaluated as ⁇ .
  • the case where the adhesive force was less than 0.3 N / mm was evaluated as x.
  • ⁇ Dielectric constant> The relative dielectric constant at 10 GHz of each of the low dielectric substrate materials of the examples and comparative examples was measured using a PNA network analyzer (manufactured by Agilent Technologies, model number "5227A") and an SPDR resonator.
  • Table 1 shows the results of the above evaluation.
  • Ra was 0.444 ⁇ m, 0.399 ⁇ m, and 0.396 ⁇ m, and the average value of Ra was 0.41 ⁇ m.
  • Rz was 4.761 ⁇ m, 8.62 ⁇ m, and 6.502 ⁇ m, and the average value of Rz was 6.63 ⁇ m.
  • the low dielectric substrate material is suitably used for manufacturing a high-frequency antenna and a high-speed transmission substrate.
  • Low dielectric substrate material 4 Porous resin layer 5 Adhesive layer 6 Second metal layer

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Abstract

This low dielectric substrate material comprises, in the following order in the thickness direction, a porous resin layer, ah adhesive layer, and a metal layer. The thickness d1 of the adhesive layer and the thickness d2 of the porous resin layer satisfy formula (1). d1/d2≤0.5 (1)

Description

低誘電基板材Low dielectric substrate material
　本発明は、低誘電基板材、詳しくは、高周波アンテナや高速伝送基板の製造に好適に用いられる低誘電基板材に関する。 The present invention relates to a low dielectric substrate material, and more particularly, to a low dielectric substrate material suitably used for manufacturing a high-frequency antenna and a high-speed transmission substrate.
　従来、いわゆる「第三世代（３Ｇ）」や「第四世代（４Ｇ）」の規格の無線通信が広く利用されている。しかしながら、近年、画像データ等の通信容量がより一層増加する傾向（大容量化の傾向）にあり、上記した規格の無線通信では、大容量のデータを、実用レベルの速度で伝送できない。 Conventionally, so-called “third generation (3G)” and “fourth generation (4G)” wireless communication standards have been widely used. However, in recent years, the communication capacity of image data and the like has tended to further increase (increase in capacity), and large-capacity data cannot be transmitted at a practical level in wireless communication of the above-described standard.
　そこで、いわゆる「第五世代（５Ｇ）」の規格の無線通信の開発が進められている。「第五世代（５Ｇ）」の規格の無線通信であれば、大容量のデータを伝送できる。しかも、この「第五世代（５Ｇ）」の規格の無線通信では、上記のデータを、高速で伝送することもでき、近年、ますます、「第五世代（５Ｇ）」の規格の利用が望まれている。 Therefore, the development of so-called "fifth generation (5G)" wireless communication is being promoted. Wireless communication of the "fifth generation (5G)" standard can transmit a large amount of data. Moreover, in the wireless communication of the "fifth generation (5G)" standard, the above data can be transmitted at a high speed. In recent years, the use of the "fifth generation (5G)" standard has been increasingly desired. It is rare.
　具体的には、「第五世代（５Ｇ）」の規格の無線通信では、ミリ波を含む高周波が用いられる。このミリ波は、大気中の水分で減衰し易く、ミリ波を放出する高周波アンテナの基板材として、誘電率が低い基板材が求められている。低誘電の基板材をアンテナに用いると、ミリ波の電波を効率よく放出することができる。また、低誘電のアンテナ用基板材を用いると、通信距離が延び、しかも、アンテナ部材の小面積化を図ることができ、さらに、低消費電力にもつながる。 Specifically, in the wireless communication of the “fifth generation (5G)” standard, a high frequency including a millimeter wave is used. This millimeter wave is easily attenuated by moisture in the atmosphere, and a substrate material having a low dielectric constant is required as a substrate material of a high-frequency antenna that emits a millimeter wave. When a low dielectric substrate material is used for the antenna, millimeter wave radio waves can be efficiently emitted. In addition, when a low dielectric antenna substrate material is used, the communication distance can be extended, the area of the antenna member can be reduced, and power consumption can be reduced.
　また、近年、ＦＰＣ（フレキシブルプリント回路基板）として、データを高速で伝送する高速伝送ＦＰＣが求められており、この高速伝送ＦＰＣの基板材としても、低誘電の基板材が求められる。 In recent years, a high-speed transmission FPC that transmits data at high speed has been required as an FPC (flexible printed circuit board), and a low-dielectric substrate material is also required as a substrate material of the high-speed transmission FPC.
　上記した要求に応えるために、つまり、大容量のデータ無線通信のアンテナや高速伝送ＦＰＣに備えられる基板材として、誘電率の低い低誘電基板の開発が進められており、ポリイミド系樹脂やフッ素系樹脂などの低誘電樹脂材料を用いた基板が開発されている。 In order to meet the above demands, that is, as a substrate material for a large-capacity data wireless communication antenna or a high-speed transmission FPC, a low dielectric substrate with a low dielectric constant has been developed, and a polyimide resin or a fluorine-based resin has been developed. Substrates using low dielectric resin materials such as resins have been developed.
　一方で、材料が多孔質体である基板も検討されている。多孔質体は、最も低い誘電率１である空気を孔内に有することから、多孔質体は誘電率が比較的低くなる。このような多孔質体を備える金属箔積層板として、例えば、絶縁材である樹脂多孔質層と、その厚み方向両側に配置される金属箔とを備える金属箔積層板が提案されている（例えば、下記特許文献１参照。）。 On the other hand, a substrate made of a porous material is also being studied. Since the porous body has air having the lowest dielectric constant 1 in the pores, the porous body has a relatively low dielectric constant. As a metal foil laminate provided with such a porous body, for example, a metal foil laminate provided with a resin porous layer as an insulating material and metal foils arranged on both sides in the thickness direction has been proposed (for example, And Patent Document 1 below.)
特開２００４－８２３７２号公報JP-A-2004-82372
　しかし、上記特許文献１を含む従来の多孔質体は、「第三世代（３Ｇ）」や「第四世代（４Ｇ）」の規格の無線通信や、従来の速度でデータを伝送するＦＰＣの基板材として利用できるが、その空孔率が低いことから、十分な低誘電率ではなく、「第五世代（５Ｇ）」の規格や高速伝送ＦＰＣで必要とされるレベルの低誘電率を有さない。 However, the conventional porous body including the above Patent Document 1 is based on the wireless communication of the “third generation (3G)” or “fourth generation (4G)” standard or the FPC that transmits data at the conventional speed. Although it can be used as a plate material, its porosity is low, so it does not have a sufficiently low dielectric constant, but has a low dielectric constant of the level required by the "fifth generation (5G)" standard and high-speed transmission FPC. Absent.
　また、上記特許文献１の金属箔積層板では、金属箔が多孔質層から脱落することを抑制するために、これらの間に、十分な膜厚の接着層を配置して、樹脂多孔質体と金属箔とを接着している。しかしながら、「第五世代（５Ｇ）」の規格や高速伝送ＦＰＣで必要とされるレベルの低誘電率では、接着層の誘電率が大きく影響してしまい、上記レベルを達成できない不具合が生じる。 Further, in the metal foil laminate of Patent Document 1, in order to prevent the metal foil from falling off from the porous layer, an adhesive layer having a sufficient film thickness is disposed between the metal foil and the resin porous body. And metal foil. However, the low dielectric constant of the level required for the "fifth generation (5G)" standard and the high-speed transmission FPC has a large influence on the dielectric constant of the adhesive layer, and the above-described level cannot be achieved.
　本発明は、より一層低い誘電率を有し、金属層の接着強度が良好な低誘電基板材を提供することにある。 The object of the present invention is to provide a low dielectric substrate material having a still lower dielectric constant and good adhesion strength of a metal layer.
　そこで、本発明者らは、鋭意検討した結果、空孔率が顕著に高い多孔質樹脂層を使いこなし、第五世代（５Ｇ）の規格や高速伝送ＦＰＣに適合できる低誘電率を有しながら、金属層の接着強度が良好である低誘電基板材を発明するに至った。 Thus, the present inventors have conducted intensive studies and as a result, have successfully used a porous resin layer having a remarkably high porosity, and have a low dielectric constant that can conform to the fifth generation (5G) standards and high-speed transmission FPC. The present inventors have invented a low dielectric substrate material having good adhesion strength of a metal layer.
　本発明［１］は、多孔質樹脂層と、接着層と、金属層とを厚み方向に順に備え、前記接着層の厚みｄ１と、前記多孔質樹脂層の厚みｄ２とが、下記式（１）を満足する、低誘電基板材を含む。
ｄ１／ｄ２≦０．５ （１）
　本発明［２］は、下記式（２）を満足する、［１］に記載の低誘電基板材を含む。 The present invention [1] includes a porous resin layer, an adhesive layer, and a metal layer in the thickness direction in order, and the thickness d1 of the adhesive layer and the thickness d2 of the porous resin layer are represented by the following formula (1). And a low dielectric substrate material that satisfies the above condition.
d1 / d2 ≦ 0.5 (1)
The present invention [2] includes the low dielectric substrate material according to [1], which satisfies the following expression (2).
　　　　２≦ｄ２／ｄ１≦１５０　　（２） {2 ≦ d2 / d1 ≦ 150} (2)
　この低誘電基板材は、多孔質樹脂層を有し、多孔質樹脂層が高い空孔化率を有する場合には、十分に低い低誘電率を有することができる。具体的には、低誘電基板材が、第五世代（５Ｇ）の規格の無線通信のアンテナや、高速伝送ＦＰＣに対応できる低い誘電率を有することができる。 This low dielectric substrate material has a porous resin layer, and when the porous resin layer has a high porosity, it can have a sufficiently low low dielectric constant. Specifically, the low dielectric substrate material can have a low dielectric constant that can be used for a fifth generation (5G) wireless communication antenna or a high-speed transmission FPC.
　この低誘電基板材は、多孔質樹脂層と、接着層と、金属層とを厚み方向に順に備えるため、金属層と、多孔質樹脂層との接着強度が良好である。 Since the low dielectric substrate material includes a porous resin layer, an adhesive layer, and a metal layer in the thickness direction in order, the adhesive strength between the metal layer and the porous resin layer is good.
　また、この低誘電基板材では、接着層の厚みｄ１が、多孔質樹脂層の厚みｄ２よりも薄いため、誘電率が高い接着層の量が、誘電率が低い多孔質樹脂層の量よりも少ない。そのため、接着層による誘電率の影響を抑え、低誘電基板材の誘電率を低くできる。 Further, in this low dielectric substrate material, since the thickness d1 of the adhesive layer is smaller than the thickness d2 of the porous resin layer, the amount of the adhesive layer having a high dielectric constant is larger than the amount of the porous resin layer having a low dielectric constant. Few. Therefore, the influence of the dielectric constant of the adhesive layer can be suppressed, and the dielectric constant of the low dielectric substrate material can be reduced.
　したがって、金属層の脱落を抑制しつつ、第五世代（５Ｇ）の規格の無線通信のアンテナや、高速伝送ＦＰＣに対応できる低い誘電率を有することができる。 Therefore, it is possible to have a low dielectric constant that can support a fifth generation (5G) wireless communication antenna or a high-speed transmission FPC while suppressing the metal layer from falling off.
図１は、本発明の低誘電基板材の一実施形態の断面図を示す。FIG. 1 shows a cross-sectional view of one embodiment of the low dielectric substrate material of the present invention. 図２は、図１に示す低誘電基板材から得られるパターン積層材の断面図を示す。FIG. 2 shows a cross-sectional view of a pattern laminate obtained from the low dielectric substrate material shown in FIG.
　　＜一実施形態＞
　本発明の低誘電基板材の一実施形態を、図１および図２を参照して説明する。 <One embodiment>
One embodiment of the low dielectric substrate material of the present invention will be described with reference to FIGS.
　　［基本態様］
　まず、この低誘電基板材１の基本態様である層構成、製造方法および使用方法等を順に説明する。 [Basic aspect]
First, a layer configuration, a manufacturing method, a usage method, and the like, which are basic aspects of the low dielectric substrate material 1, will be described in order.
　〔低誘電基板材およびその層構成〕
　図１に示すように、低誘電基板材１は、厚み方向に対向する一方面および他方面を有しており、厚み方向に直交する面方向に延びる形状を有する。 (Low dielectric substrate material and its layer structure)
As shown in FIG. 1, the low dielectric substrate material 1 has one surface and the other surface facing each other in the thickness direction, and has a shape extending in a surface direction orthogonal to the thickness direction.
　この低誘電基板材１は、第１金属層３と、第１金属層３の厚み方向一方面に配置される多孔質樹脂層４と、多孔質樹脂層４の厚み方向一方面に配置される接着層５と、接着層５の厚み方向一方面に配置される第２金属層（金属層の一例）６とを備える。つまり、低誘電基板材１は、第１金属層３と、多孔質樹脂層４と、接着層５と、第２金属層６とを厚み方向他方側から一方側に向かって順に備える。好ましくは、低誘電基板材１は、第１金属層３と、多孔質樹脂層４と、接着層５と、第２金属層６とのみを備える。 The low dielectric substrate material 1 is disposed on a first metal layer 3, a porous resin layer 4 disposed on one surface in the thickness direction of the first metal layer 3, and disposed on one surface in a thickness direction of the porous resin layer 4. The semiconductor device includes an adhesive layer and a second metal layer (an example of a metal layer) disposed on one surface in the thickness direction of the adhesive layer. That is, the low dielectric substrate material 1 includes the first metal layer 3, the porous resin layer 4, the adhesive layer 5, and the second metal layer 6 in order from the other side in the thickness direction to one side. Preferably, low dielectric substrate material 1 includes only first metal layer 3, porous resin layer 4, adhesive layer 5, and second metal layer 6.
　〔第１金属層〕
　第１金属層３は、厚み方向に対向する一方面および他方面を有しており、面方向に延びるシート（板）形状を有する。第１金属層３の材料は、特に限定されず、例えば、銅、鉄、銀、金、アルミニウム、ニッケル、それらの合金（ステンレス、青銅）などが挙げられる。好ましくは、銅が挙げられる。第１金属層３の厚みは、例えば、０．１μｍ以上、好ましくは、１μｍ以上であり、また、例えば、１００μｍ以下、好ましくは、５０μｍ以下である。 [First metal layer]
The first metal layer 3 has one surface and the other surface facing each other in the thickness direction, and has a sheet (plate) shape extending in the surface direction. The material of the first metal layer 3 is not particularly limited, and examples thereof include copper, iron, silver, gold, aluminum, nickel, and alloys thereof (stainless steel, bronze). Preferably, copper is used. The thickness of the first metal layer 3 is, for example, 0.1 μm or more, preferably 1 μm or more, and is, for example, 100 μm or less, preferably 50 μm or less.
　〔多孔質樹脂層〕
　多孔質樹脂層４は、厚み方向に対向する一方面および他方面を有しており、面方向に延びるシート形状を有する。多孔質樹脂層４の他方面は、第１金属層３の一方面に接触（密着）している。 (Porous resin layer)
The porous resin layer 4 has one surface and the other surface opposed in the thickness direction, and has a sheet shape extending in the surface direction. The other surface of the porous resin layer 4 is in contact (close contact) with one surface of the first metal layer 3.
　多孔質樹脂層４は、微細な空孔（気孔）１０を多数有している。多孔質樹脂層４は、例えば、独立気泡構造および連続気泡構造のいずれかを有する。好ましくは、独立気泡構造を主として有しており、この場合の独立気泡の割合は、例えば、５０％超過、好ましくは、８０％以上、より好ましくは、９０％以上であり、また、例えば、１００％未満である。独立気泡の割合が上記した下限を上回れば、第１金属層３および第２金属層６のパターンニングで用いられるエッチング液の多孔質樹脂層４への染み込みに起因するパターン精度の低下を抑制することができる。すなわち、エッチング液が多孔質樹脂層４に染み込むことで、第１金属層３および第２金属層６のレジストで保護されている部分までもがエッチング液により除去されることを、抑制することができる。 The porous resin layer 4 has many fine pores (pores) 10. The porous resin layer 4 has, for example, one of a closed cell structure and an open cell structure. Preferably, it mainly has a closed cell structure. In this case, the ratio of the closed cells is, for example, more than 50%, preferably 80% or more, more preferably 90% or more, and for example, 100%. %. When the ratio of the closed cells exceeds the above lower limit, a decrease in pattern accuracy due to the penetration of the etching solution used for patterning the first metal layer 3 and the second metal layer 6 into the porous resin layer 4 is suppressed. be able to. That is, it is possible to prevent the etchant from permeating the porous resin layer 4 to remove even the portions of the first metal layer 3 and the second metal layer 6 protected by the resist. it can.
　さらに、アンテナ回路基板を作製するため、本発明の低誘電基板材にドリルやレーザーなどで穴あけをした上でめっき処理をした際に、めっき液浸が抑制されるため、厚みが均一な金属層を穴の表面に形成することができる。ここでめっき液浸とは、前記穴あけにより露出した多孔部からめっき液が侵入し、多孔質樹脂層４内に金属が析出してしまう現象をいい、穴表面に形成される金属層の厚みが不均一になったり、不連続となり多孔質樹脂層の露出部分ができたりする原因となる。 Furthermore, in order to manufacture an antenna circuit board, when a low dielectric substrate material of the present invention is drilled with a drill or a laser and then plated, plating immersion is suppressed. Can be formed on the surface of the hole. Here, the plating solution immersion refers to a phenomenon in which a plating solution infiltrates from a porous portion exposed by the drilling and a metal is deposited in the porous resin layer 4, and the thickness of the metal layer formed on the hole surface is reduced. It becomes non-uniform or discontinuous, resulting in an exposed portion of the porous resin layer.
　多孔質樹脂層４における空孔率は、６０％以上、より好ましくは、７０％以上、さらに好ましくは、８０％以上、とりわけ好ましくは、８５％以上である。なお、多孔質樹脂層４の空孔率は、１００％未満、好ましくは、９９％未満である。空孔率は、例えば、多孔質樹脂層４の断面ＳＥＭ写真の画像解析により求められる。あるいは、空孔率は、下記式に基づく計算により求められる。 空 The porosity of the porous resin layer 4 is 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 85% or more. The porosity of the porous resin layer 4 is less than 100%, preferably less than 99%. The porosity is determined, for example, by image analysis of a cross-sectional SEM photograph of the porous resin layer 4. Alternatively, the porosity is determined by calculation based on the following equation.
　空孔率（％）＝（１－無孔樹脂層の比重／多孔質樹脂層の比重）×１００
　なお、式中、無孔樹脂層は、多孔質樹脂層４の材料からなるが、多孔質ではなく、緻密質を有するフィルムである。 Porosity (%) = (1−specific gravity of non-porous resin layer / specific gravity of porous resin layer) × 100
In the formula, the non-porous resin layer is made of the material of the porous resin layer 4, but is not porous but a dense film.
　多孔質樹脂層４の空孔率が上記した下限以上であれば、多孔質樹脂層４が、第五世代（５Ｇ）の規格や高速伝送ＦＰＣに十分に対応できる低い誘電率を有することができる。具体的には、低誘電基板材１が、上記したように、第五世代（５Ｇ）の規格や高速伝送ＦＰＣに十分に対応できる基板材として有用となる。 When the porosity of the porous resin layer 4 is equal to or more than the above lower limit, the porous resin layer 4 can have a low dielectric constant that can sufficiently cope with the fifth generation (5G) standard and high-speed transmission FPC. . Specifically, as described above, the low dielectric substrate material 1 is useful as a substrate material that can sufficiently comply with the fifth generation (5G) standard and high-speed transmission FPC.
　多孔質樹脂層４における空孔１０の平均径（つまり、平均孔径）は、例えば、１０μｍ以下であり、また、例えば、０．１μｍ以上である。平均孔径は、多孔質樹脂層４の断面ＳＥＭ写真の画像解析により求められる。画像解析は、ＳＥＭ像に２値化を施し、空孔１０を識別した後、その孔径を算出し、ヒストグラム化する。解析ソフトは、ＩｍａｇｅＪを用いる。 平均 The average diameter of the pores 10 in the porous resin layer 4 (that is, the average pore diameter) is, for example, 10 μm or less, and is, for example, 0.1 μm or more. The average pore diameter is determined by image analysis of a cross-sectional SEM photograph of the porous resin layer 4. In the image analysis, binarization is performed on the SEM image to identify the holes 10, then the hole diameter is calculated, and a histogram is formed. AnalysisJ uses ImageJ.
　多孔質樹脂層４の周波数１０ＧＨｚにおける誘電率は、空孔率および次に述べる樹脂の種類によって適宜調整され、具体的には、例えば、２．５以下、好ましくは、２．０以下であり、また、例えば、１．０超過である。誘電率は、周波数の１０ＧＨｚを用いる共振器法により、実測される。 The dielectric constant of the porous resin layer 4 at a frequency of 10 GHz is appropriately adjusted depending on the porosity and the type of the resin described below. Specifically, for example, the dielectric constant is 2.5 or less, preferably 2.0 or less. Also, for example, it is more than 1.0. The dielectric constant is measured by a resonator method using a frequency of 10 GHz.
　多孔質樹脂層４の誘電率が上記した上限以下であれば、低誘電基板材１が低誘電率を有することとなるので、第五世代（５Ｇ）の規格や高速伝送ＦＰＣの基板材として有用に用いることができる。 If the dielectric constant of the porous resin layer 4 is equal to or less than the upper limit described above, the low dielectric substrate material 1 has a low dielectric constant, and is useful as a substrate material for fifth generation (5G) standards and high-speed transmission FPCs. Can be used.
　多孔質樹脂層４の材料としては、特に限定されず、例えば、熱硬化性樹脂、熱可塑性樹脂などの樹脂が挙げられる。 材料 The material of the porous resin layer 4 is not particularly limited, and examples thereof include resins such as a thermosetting resin and a thermoplastic resin.
　熱硬化性樹脂としては、例えば、ポリカーボネート樹脂、熱硬化性ポリイミド樹脂、熱硬化性フッ化ポリイミド樹脂、エポキシ樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、ジアリルフタレート樹脂、シリコーン樹脂、熱硬化性ウレタン樹脂、フッ素樹脂（含フッ素オレフィンの重合体（具体的には、ポリテトラフルオロエチレン（ＰＴＦＥ）など））、液晶ポリマー（ＬＣＰ）などが挙げられる。これらは、単独使用または２種以上併用することができる。 As the thermosetting resin, for example, polycarbonate resin, thermosetting polyimide resin, thermosetting fluorinated polyimide resin, epoxy resin, phenol resin, urea resin, melamine resin, diallyl phthalate resin, silicone resin, thermosetting urethane resin , A fluororesin (a polymer of a fluorine-containing olefin (specifically, polytetrafluoroethylene (PTFE) or the like)), a liquid crystal polymer (LCP), or the like. These can be used alone or in combination of two or more.
　熱可塑性樹脂としては、例えば、オレフィン樹脂、アクリル樹脂、ポリスチレン樹脂、ポリエステル樹脂、ポリアクリロニトリル樹脂、マレイミド樹脂、ポリ酢酸ビニル樹脂、エチレン－酢酸ビニル共重合体、ポリビニルアルコール樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂、ポリアセタール樹脂、ポリフェニレンオキシド樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリエーテルエーテルケトン樹脂、ポリアリルスルホン樹脂、熱可塑性ポリイミド樹脂、熱可塑性フッ化ポリイミド樹脂、熱可塑性ウレタン樹脂、ポリエーテルイミド樹脂、ポリメチルペンテン樹脂、セルロース樹脂、液晶ポリマー、アイオノマーなどが挙げられる。これらは、単独使用または２種以上併用することができる。 Examples of the thermoplastic resin include olefin resin, acrylic resin, polystyrene resin, polyester resin, polyacrylonitrile resin, maleimide resin, polyvinyl acetate resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polyamide resin, and polyvinyl chloride. Resin, polyacetal resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, polyether sulfone resin, polyether ether ketone resin, polyallyl sulfone resin, thermoplastic polyimide resin, thermoplastic fluorinated polyimide resin, thermoplastic urethane resin, poly Examples include ether imide resin, polymethylpentene resin, cellulose resin, liquid crystal polymer, and ionomer. These can be used alone or in combination of two or more.
　上記した樹脂のうち、機械強度の観点から、好ましくは、ポリイミド樹脂（熱硬化性ポリイミド樹脂および熱可塑性ポリイミド樹脂を含む）、フッ化ポリイミド樹脂（熱硬化性フッ化ポリイミド樹脂および熱可塑性フッ化ポリイミド樹脂）、ポリカーボネート樹脂、ポリエーテルイミド樹脂が挙げられる。特に好ましくは、ポリイミド樹脂が挙げられる。
ポリイミド樹脂は、独立気泡構造を有する多孔質樹脂層４を含む低誘電基板材１の作製工程に含まれる、加圧による積層に最も適した材料である。なお、上記した好適な樹脂の物性および製造方法等の詳細は、例えば、特開２０１８－０２１１７１号公報、特開２０１８－０２１１７２号公報などに記載されている。 Among the above resins, from the viewpoint of mechanical strength, preferably, polyimide resin (including thermosetting polyimide resin and thermoplastic polyimide resin), fluorinated polyimide resin (thermosetting fluorinated polyimide resin and thermoplastic fluorinated polyimide resin) Resins), polycarbonate resins and polyetherimide resins. Particularly preferably, a polyimide resin is used.
The polyimide resin is the most suitable material for lamination by pressure, which is included in the process of manufacturing the low dielectric substrate material 1 including the porous resin layer 4 having a closed cell structure. The details of the above-mentioned preferable physical properties and production method of the resin are described in, for example, JP-A-2018-021171, JP-A-2018-021172, and the like.
　多孔質樹脂層４は、その厚み方向一方面および他方面に形成されるスキン層（図示せず）を有することができる。 The porous resin layer 4 can have a skin layer (not shown) formed on one surface and the other surface in the thickness direction.
　多孔樹脂層４の厚み方向一方面または他方面における算術平均粗さ（Ｒａ）は、例えば、０．１μｍ以上、好ましくは、０．２μｍ以上であり、また例えば、１．０μｍ以下、好ましくは、０．７μｍ以下である。また、多孔質樹脂層４の厚み方向一方面または他方面における最大高さ（Ｒｚ）は、例えば、１．０μｍ以上、好ましくは、２．０μｍ以上であり、また、例えば、１５．０μｍ以下、好ましくは、１０．０μｍ以下である。 The arithmetic average roughness (Ra) on one surface or the other surface in the thickness direction of the porous resin layer 4 is, for example, 0.1 μm or more, preferably 0.2 μm or more, and for example, 1.0 μm or less, preferably, It is 0.7 μm or less. Further, the maximum height (Rz) of the porous resin layer 4 on one surface or the other surface in the thickness direction is, for example, 1.0 μm or more, preferably 2.0 μm or more, and for example, 15.0 μm or less. Preferably, it is 10.0 μm or less.
　多孔質樹脂層４の厚みは、例えば、２μｍ以上、好ましくは、５μｍ以上、より好ましくは、２５μｍ以上、さらに好ましくは、５０μｍ以上であり、また、例えば、１，０００μｍ以下、好ましくは、５００μｍ以下である。 The thickness of the porous resin layer 4 is, for example, 2 μm or more, preferably 5 μm or more, more preferably 25 μm or more, further preferably 50 μm or more, and, for example, 1,000 μm or less, preferably 500 μm or less. It is.
　なお、多孔質樹脂層４以外の層、具体的には、第１金属層３、接着層５（後述）、および、第２金属層６（後述）は、いずれも、多孔質樹脂層４と異なり、例えば、無孔であり、つまり、微細な空孔を実質的に有さず、緻密である。 The layers other than the porous resin layer 4, specifically, the first metal layer 3, the adhesive layer 5 (described later), and the second metal layer 6 (described later) are all On the other hand, for example, it is non-porous, that is, it is dense without substantially having fine pores.
　［接着層］
　接着層５は、多孔質樹脂層４の厚み方向一方面において、面方向に沿うシート形状を有する。 [Adhesive layer]
The adhesive layer 5 has a sheet shape along the surface direction on one surface in the thickness direction of the porous resin layer 4.
　接着層５の材料としては、特に限定されず、ホットメルト型接着剤、熱硬化型接着剤など、種々の型の接着剤が挙げられ、具体的には、アクリル系接着剤、エポキシ系接着剤、シリコーン系接着剤などが挙げられる。好ましくは、アクリル系接着剤が挙げられる。 The material of the adhesive layer 5 is not particularly limited, and includes various types of adhesives such as a hot melt type adhesive and a thermosetting type adhesive. Specifically, an acrylic type adhesive, an epoxy type adhesive And silicone-based adhesives. Preferably, an acrylic adhesive is used.
　接着層５の厚みは、例えば、２μｍ以上、好ましくは、５μｍ以上であり、また、例えば、５０μｍ以下、好ましくは、２５μｍ以下である。 The thickness of the adhesive layer 5 is, for example, 2 μm or more, preferably 5 μm or more, and is, for example, 50 μm or less, preferably 25 μm or less.
　［第２金属層］
　第２金属層６は、厚み方向に対向する一方面および他方面を有しており、面方向に延びるシート形状を有する。第２金属層６の他方面は、接着層５を介して、多孔質樹脂層４の一方面に接着している。第２金属層６の材料および厚みは、第１金属層３のそれらと同様である。 [Second metal layer]
The second metal layer 6 has one surface and the other surface opposed in the thickness direction, and has a sheet shape extending in the surface direction. The other surface of the second metal layer 6 is adhered to one surface of the porous resin layer 4 via the adhesive layer 5. The material and thickness of the second metal layer 6 are the same as those of the first metal layer 3.
　低誘電基板材１の厚みは、第１金属層３、多孔質樹脂層４、接着層５および第２金属層６の総厚みであって、例えば、１０μｍ以上、好ましくは、２０μｍ以上であり、また、例えば、５，０００μｍ以下、好ましくは、２，０００μｍ以下である。 The thickness of the low dielectric substrate material 1 is the total thickness of the first metal layer 3, the porous resin layer 4, the adhesive layer 5, and the second metal layer 6, for example, 10 μm or more, preferably 20 μm or more, Also, for example, it is 5,000 μm or less, preferably 2,000 μm or less.
　〔低誘電基板材の製造方法〕
　次に、低誘電基板材１の製造方法を説明する。 (Production method of low dielectric substrate material)
Next, a method of manufacturing the low dielectric substrate material 1 will be described.
　なお、一実施形態における低誘電基板材１の製造では、例えば、ロールトゥロール法によって、各部材を、搬送しながら積層（形成）する。 In the manufacture of the low dielectric substrate material 1 according to one embodiment, for example, each member is stacked (formed) while being conveyed by a roll-to-roll method.
　具体的には、まず、第１金属層３を準備する。例えば、上記した材料から成る箔（金属箔）を第１金属層３として準備する。 Specifically, first, the first metal layer 3 is prepared. For example, a foil (metal foil) made of the above-described material is prepared as the first metal layer 3.
　次いで、多孔質樹脂層４を第１金属層３の一方面に形成する。例えば、多孔質樹脂層４を、第１金属層３の一方面で作製する（作り込む）。 Next, the porous resin layer 4 is formed on one surface of the first metal layer 3. For example, the porous resin layer 4 is formed (built) on one surface of the first metal layer 3.
　具体的には、まず、上記した樹脂の前駆体と、多孔化剤と、核剤と、溶媒とを含むワニスを調製し、次いで、ワニスを第１金属層３の一方面に塗布して塗膜を形成する。ワニスにおける多孔化剤、核剤および溶媒の、種類および配合割合等は、例えば、特開２０１８－０２１１７１号公報、特開２０１８－０２１１７２号公報などに記載されている。 Specifically, first, a varnish containing the above-described resin precursor, a porogen, a nucleating agent, and a solvent is prepared, and then, the varnish is applied to one surface of the first metal layer 3 to be applied. Form a film. The types, blending ratios, and the like of the porosity, nucleating agent, and solvent in the varnish are described in, for example, JP-A-2018-021171, JP-A-2018-021172, and the like.
　とりわけ、多孔化剤の質量部数（配合割合）は、前駆体１００質量部に対して、例えば、１質量部以上、好ましくは、３質量部以上、より好ましくは、２０質量部以上、さらに好ましくは、５０質量部以上であり、また、例えば、３００質量部以下、好ましくは、２５０質量部以下である。 In particular, the number of parts by mass (mixing ratio) of the porogen is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 100 parts by mass of the precursor. , 50 parts by mass or more, and for example, 300 parts by mass or less, preferably 250 parts by mass or less.
　核剤は、前駆体を発泡（多孔化）させるときに核となる発泡核剤（気泡調整剤）である。また、核剤として、上記公報に記載の核剤（ＰＴＦＥなど）の他に、ポリ（クロロトリフルオロエチレン）などのフッ素樹脂（含フッ素オレフィンの重合体）、さらには、モノマー単位として、（メタ）アクリル酸エステルおよび上記した含フッ素オレフィンを含有する共重合体なども挙げられる。 The nucleating agent is a foaming nucleating agent (cell regulator) that becomes a nucleus when the precursor is foamed (porous). As the nucleating agent, in addition to the nucleating agent (PTFE and the like) described in the above publication, a fluororesin (polymer of fluorinated olefin) such as poly (chlorotrifluoroethylene), and further, as a monomer unit, (meth) ) Copolymers containing acrylic acid esters and the above-mentioned fluorine-containing olefins are also included.
　核剤は、常温（２３℃）で、例えば、固体状、液体状、半固体状のいずれであってよく、好ましくは、固体状である。核剤が常温で固体状であれば、核剤の形状としては、例えば、略球形状、略板形状、略針形状、不定形状（塊状を含む）が挙げられ、好ましくは、略球形状が挙げられる。 (4) The nucleating agent may be in a solid state, a liquid state, or a semi-solid state at room temperature (23 ° C.), and is preferably in a solid state. If the nucleating agent is solid at room temperature, examples of the shape of the nucleating agent include a substantially spherical shape, a substantially plate shape, a substantially needle shape, and an indefinite shape (including a lump shape). No.
　核剤が常温で固体状であれば、核剤の最大長さの平均値（略球形状であれば、平均粒子径）は、例えば、２，０００ｎｍ以下、好ましくは、１，０００ｎｍ以下、より好ましくは、８００ｎｍ以下、さらに好ましくは、５００ｎｍ未満であり、また、例えば、１ｎｍ以上である。 If the nucleating agent is solid at room temperature, the average value of the maximum length of the nucleating agent (or the average particle diameter if it is substantially spherical) is, for example, 2,000 nm or less, preferably 1,000 nm or less. It is preferably 800 nm or less, more preferably less than 500 nm, and for example, 1 nm or more.
　また、核剤は、予め溶媒（ＰＴＦＥ）に分散したスラリーとして調製されていてもよい。 核 The nucleating agent may be prepared in advance as a slurry dispersed in a solvent (PTFE).
　その後、塗膜を加熱により乾燥することにより、溶媒の除去が進行しつつ、核剤を核とした、前駆体と多孔化剤との相分離構造が形成される。 (4) Thereafter, by drying the coating film by heating, a phase separation structure of a precursor and a porogen with a nucleating agent as a nucleus is formed while the removal of the solvent proceeds.
　その後、例えば、超臨界二酸化炭素を溶媒として用いる超臨界抽出法により、多孔化剤を前駆体から抽出する（引き抜く、あるいは、除去する）。 (4) Then, the porogen is extracted from the precursor (pulled out or removed) by, for example, a supercritical extraction method using supercritical carbon dioxide as a solvent.
　その後、前駆体を硬化させて、多孔を有する樹脂、具体的には、多孔質樹脂層４を形成する。 (4) Thereafter, the precursor is cured to form a porous resin, specifically, the porous resin layer 4.
　その後、接着層５を、多孔質樹脂層４の一方面に配置する。例えば、接着剤を多孔質樹脂層４の一方面に塗布したり、あるいは、接着剤から予めシート状に形成した接着層５を多孔質樹脂層４の一方面に貼る。 Then, the adhesive layer 5 is disposed on one surface of the porous resin layer 4. For example, an adhesive is applied to one surface of the porous resin layer 4, or an adhesive layer 5 previously formed into a sheet from the adhesive is attached to one surface of the porous resin layer 4.
　続いて、第２金属層６を、接着層５の一方面に配置する。例えば、上記した材料から成る箔（金属箔）を接着層５の一方面に貼り付ける。 Next, the second metal layer 6 is disposed on one surface of the adhesive layer 5. For example, a foil (metal foil) made of the above-described material is attached to one surface of the adhesive layer 5.
　これにより、低誘電基板材１を製造する。 に よ り Thereby, the low dielectric substrate material 1 is manufactured.
　この低誘電基板材１の用途は、例えば、各種用途に用いられ、好ましくは、第五世代（５Ｇ）の規格に適合する高周波アンテナや高速伝送基板（高速伝送ＦＰＣなど）の製造に用いられる。具体的には、低誘電基板材１は、高周波アンテナや高速伝送ＦＰＣの基板材として用いられる。 The low dielectric substrate material 1 is used for various applications, for example, and is preferably used for manufacturing a high-frequency antenna or a high-speed transmission board (such as a high-speed transmission FPC) conforming to the fifth generation (5G) standard. Specifically, the low dielectric substrate material 1 is used as a substrate material for a high-frequency antenna or a high-speed transmission FPC.
　低誘電基板材１を上記の用途で使用する場合には、第２金属層６を、フォトリソグラフィ（例えば、サブトラクティブ法）によって、図２に示すように、パターンニングして、例えば、信号配線（差動配線など）やアンテナ配線などの一方側配線１７を形成する。続いて、第１金属層３を、フォトリソグラフィによって、パターンニングして、例えば、グランド配線などの他方側配線１８を形成する。 When the low dielectric substrate material 1 is used for the above purpose, the second metal layer 6 is patterned by photolithography (for example, a subtractive method) as shown in FIG. One-sided wiring 17 such as (differential wiring) and antenna wiring is formed. Subsequently, the first metal layer 3 is patterned by photolithography to form the other-side wiring 18 such as a ground wiring, for example.
　これにより、他方側配線１８、多孔質樹脂層４、接着層５および一方側配線１７を厚み方向一方側に向かって順に備えるパターン積層材１３を製造し、このパターン積層材１３を、第五世代（５Ｇ）の規格に適合する高周波アンテナや高速伝送基板に備える。 As a result, a pattern laminated material 13 having the other side wiring 18, the porous resin layer 4, the adhesive layer 5, and the one side wiring 17 sequentially in the thickness direction is manufactured. Provided on high-frequency antennas and high-speed transmission boards conforming to (5G) standards.
　そして、この低誘電基板材１は、多孔質樹脂層４を有し、多孔質樹脂層４が、６０％以上、より好ましくは、７０％以上、さらに好ましくは、８０％以上、とりわけ好ましくは、８５％以上の高い空孔率を有する場合には、十分に低い低誘電率を有することができる。具体的には、低誘電率が、例えば、２．５以下、好ましくは、２．０以下である。従って、低誘電基板材１が、第五世代（５Ｇ）の規格の無線通信のアンテナ基板や、高速伝送ＦＰＣに対応できる低い誘電率を有することができる。 And this low dielectric substrate material 1 has a porous resin layer 4, and the porous resin layer 4 is 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably, When it has a high porosity of 85% or more, it can have a sufficiently low low dielectric constant. Specifically, the low dielectric constant is, for example, 2.5 or less, preferably 2.0 or less. Therefore, the low dielectric substrate material 1 can have a low dielectric constant that is compatible with a fifth generation (5G) standard wireless communication antenna substrate and a high-speed transmission FPC.
　また、低誘電基板材１は、第１金属層３および第２金属層６を備えるので、第五世代（５Ｇ）の規格に対応するアンテナや高速伝送ＦＰＣの基板の配線としてパターンニングすることができる。具体的には、工業的なエッチング条件で、第１金属層３および第２金属層６をパターンニングしても、第五世代（５Ｇ）に適合できるアンテナや高速伝送ＦＰＣの基板の配線を、優れた精度で形成できる。 Further, since the low dielectric substrate material 1 includes the first metal layer 3 and the second metal layer 6, it can be patterned as an antenna corresponding to the fifth generation (5G) standard or a wiring of a substrate of a high-speed transmission FPC. it can. Specifically, even if the first metal layer 3 and the second metal layer 6 are patterned under industrial etching conditions, the wiring of the antenna and the substrate of the high-speed transmission FPC that can be adapted to the fifth generation (5G) is used. It can be formed with excellent accuracy.
　また、多孔質樹脂層４が独立気泡構造を有する場合であって、独立気泡の割合が、５０％超過、さらには、８０％以上、さらには、９０％以上と高い場合には、パターンニングで用いられるエッチング液の染み込みに起因するパターン精度の低下を抑制することができる。そのため、低誘電基板材１は、第五世代（５Ｇ）の規格の無線通信や、高速伝送ＦＰＣに十分かつ確実に対応できる基板材として有用である。 In the case where the porous resin layer 4 has a closed cell structure, and the ratio of the closed cells is more than 50%, further, 80% or more, and further, as high as 90% or more, patterning is performed. It is possible to suppress a decrease in pattern accuracy due to the penetration of the used etching solution. Therefore, the low dielectric substrate material 1 is useful as a substrate material that can sufficiently and surely cope with the fifth generation (5G) standard wireless communication and high-speed transmission FPC.
　＜顕著な特徴点＞
　次いで、この低誘電基板材１における顕著な特徴点を以下に説明する。 <Outstanding features>
Next, salient features of the low dielectric substrate material 1 will be described below.
　この低誘電基板材１では、多孔質樹脂層４と、接着層４と、第２層６とを厚み方向に順に備える。そのため、多孔質樹脂層４と、第２金属層６との接着強度が良好である。 低 In this low dielectric substrate material 1, a porous resin layer 4, an adhesive layer 4, and a second layer 6 are sequentially provided in the thickness direction. Therefore, the adhesive strength between the porous resin layer 4 and the second metal layer 6 is good.
　具体的には、多孔質樹脂層４と、第２金属層６との接着力は、例えば、０．３Ｎ／ｍｍ以上、好ましくは、０．６Ｎ／ｍｍ以上であり、また、例えば、３．０Ｎ／ｍｍ以下である。 Specifically, the adhesive force between the porous resin layer 4 and the second metal layer 6 is, for example, 0.3 N / mm or more, preferably 0.6 N / mm or more. 0 N / mm or less.
　多孔質樹脂層４と第２金属層６との接着力は、２３℃で、第２金属層６を多孔質樹脂層４に対して９０度の角度で剥離するときの９０°剥離強度であって、その詳細は実施例で詳細する。 The adhesive strength between the porous resin layer 4 and the second metal layer 6 was 90 ° peel strength when the second metal layer 6 was peeled at an angle of 90 ° with respect to the porous resin layer 4 at 23 ° C. The details will be described in detail in Examples.
　このため、第２金属層６が低誘電基板材１から脱落することを抑制することができる。特に、第２金属層６を配線１７に形成した際に、配線１７の全部または一部が多孔質樹脂層４からの剥離を抑制することができ、配線１７の断線を抑制することができる。 た め Therefore, it is possible to prevent the second metal layer 6 from falling off from the low dielectric substrate material 1. In particular, when the second metal layer 6 is formed on the wiring 17, the whole or a part of the wiring 17 can be prevented from being separated from the porous resin layer 4, and the disconnection of the wiring 17 can be suppressed.
　また、接着層５の厚みｄ１と、多孔質樹脂層４の厚みｄ２とが、下記式（１）を満足する。
ｄ１／ｄ２≦０．５ （１）
　多孔質樹脂層４の厚みｄ２に対する接着層５の厚みｄ１の比（ｄ１／ｄ２）が０．５以下である。換言すれば、接着層５の厚みｄ１が、多孔質樹脂層４の厚みｄ２の半分またはそれよりも薄い。 The thickness d1 of the adhesive layer 5 and the thickness d2 of the porous resin layer 4 satisfy the following expression (1).
d1 / d2 ≦ 0.5 (1)
The ratio (d1 / d2) of the thickness d1 of the adhesive layer 5 to the thickness d2 of the porous resin layer 4 is 0.5 or less. In other words, the thickness d1 of the adhesive layer 5 is half or less than the thickness d2 of the porous resin layer 4.
　すなわち、多孔質樹脂層４よりも誘電率が高い接着層５の厚みが、多孔質樹脂層４の厚みよりも充分に薄いため、接着層５による誘電率の影響を低減できている。したがって、低誘電基板材１の誘電率を低くすることができる。このため、第五世代（５Ｇ）の規格に適合する高周波アンテナや高速伝送板として好適に使用することができる。 That is, since the thickness of the adhesive layer 5 having a higher dielectric constant than that of the porous resin layer 4 is sufficiently smaller than the thickness of the porous resin layer 4, the influence of the dielectric constant of the adhesive layer 5 can be reduced. Therefore, the dielectric constant of the low dielectric substrate material 1 can be reduced. Therefore, it can be suitably used as a high-frequency antenna or a high-speed transmission board conforming to the fifth generation (5G) standard.
　なお、樹脂基板と金属層とを備える低誘電基板材では、接着層を有しないため、接着力が劣る。一方、接着力向上のため、樹脂基板と金属層との間に接着層を配置すると、低誘電基材材の誘電率が接着層の誘電率の影響を受ける。そして、従来の樹脂基板では、第五世代（５Ｇ）の規格に適合する高周波アンテナや高速伝送板として使用することができる程度の低誘電化は求められていなかったため、接着層についての接着性以外の性能については着目されていなかった。しかしながら、第五世代（５Ｇ）の規格への適合の必要性から、更なる基板材の低誘電化が求められることとなり、発明者は、樹脂基板のみならず、接着層の低誘電化によりこの要求を満たせることを見出した。 Note that a low dielectric substrate material including a resin substrate and a metal layer does not have an adhesive layer, and thus has poor adhesive strength. On the other hand, when an adhesive layer is disposed between the resin substrate and the metal layer to improve the adhesive strength, the dielectric constant of the low dielectric substrate material is affected by the dielectric constant of the adhesive layer. The conventional resin substrate is not required to have a low dielectric constant that can be used as a high-frequency antenna or a high-speed transmission board conforming to the fifth generation (5G) standard. No attention was paid to the performance of. However, the necessity of conforming to the fifth generation (5G) standard requires a further reduction in the dielectric of the substrate material. We found that we could meet the demand.
　具体的には、発明者は、接着層の厚みを薄くして、接着層よりも低い多孔質樹脂層の誘電率を支配的とすることで、基板材全体の誘電率を低下させることができることを見出した。しかしながら、接着層が薄すぎると、樹脂基板と金属層の間の接着力が不十分となるため、充分な接着力と誘電率の抑制を両立できる厚みで、接着層を設計することが必要であった。そこで、本発明は、接着層５を多孔質樹脂層４の半分以下に薄くすることにより、接着力を担保しながら、誘電率の向上を抑制し、その結果、第２金属層６の非剥離（接着層４の接着力）と、低誘電基板材１の低誘電とのバランスを図ることを達成したものである。 Specifically, the inventor can reduce the dielectric constant of the entire substrate material by reducing the thickness of the adhesive layer and making the dielectric constant of the porous resin layer lower than the adhesive layer dominant. Was found. However, if the adhesive layer is too thin, the adhesive force between the resin substrate and the metal layer becomes insufficient, so it is necessary to design the adhesive layer with a thickness that can achieve both sufficient adhesive force and suppression of the dielectric constant. there were. Therefore, the present invention suppresses the improvement of the dielectric constant while ensuring the adhesive force by making the adhesive layer 5 thinner than half of the porous resin layer 4, and as a result, the non-peeling of the second metal layer 6 is prevented. (Adhesive strength of the adhesive layer 4) and low dielectric constant of the low dielectric substrate material 1 are achieved.
　上記式（１）において、上記比（ｄ１／ｄ２）は、０．３以下、より好ましくは、０．１以下である。また、上記比（ｄ１／ｄ２）は、例えば、０．０１以上、好ましくは、０．０３以上である
　また、この低誘電基板材１では、好ましくは、下記式（２）を満足する。 In the above formula (1), the ratio (d1 / d2) is 0.3 or less, more preferably 0.1 or less. Further, the ratio (d1 / d2) is, for example, 0.01 or more, preferably 0.03 or more. In the low dielectric substrate material 1, preferably, the following expression (2) is satisfied.
　　　　２≦ｄ２／ｄ１≦１５０　　（２）
　具体的には、接着層５の厚みｄ１に対する多孔質樹脂層４の厚みｄ２の比（ｄ２／ｄ１）が、好ましくは、２以上、より好ましくは、３以上、より好ましくは、１０以上であり、また、好ましくは、１５０以下、より好ましくは、２５以下、さらに好ましくは、２０以下である。 2 ≦ d2 / d1 ≦ 150 (2)
Specifically, the ratio (d2 / d1) of the thickness d2 of the porous resin layer 4 to the thickness d1 of the adhesive layer 5 is preferably 2 or more, more preferably 3 or more, and more preferably 10 or more. Also, it is preferably 150 or less, more preferably 25 or less, and further preferably 20 or less.
　上記比が上記した下限以上であれば、多孔質樹脂層４と第２金属層６との接着力がより一層優れる。一方、上記比が上記した上限以下であれば、低誘電基板材１の誘電率がより低くなり、第五世代（５Ｇ）の規格や高速伝送ＦＰＣに適合できる基板材として極めて有用となる。 (4) When the ratio is equal to or more than the above lower limit, the adhesive strength between the porous resin layer 4 and the second metal layer 6 is further improved. On the other hand, if the above ratio is equal to or less than the above upper limit, the dielectric constant of the low dielectric substrate material 1 becomes lower, which is extremely useful as a substrate material that can conform to the fifth generation (5G) standard and high-speed transmission FPC.
　また、この低誘電基板材１では、好ましくは、下記式（３）を満足する。 In addition, the low dielectric substrate material 1 preferably satisfies the following expression (3).
　　　　５μｍ≦ｄ２－ｄ１≦１１５μｍ　　（３）
　具体的には、多孔質樹脂層４の厚みｄ２と接着層５の厚みｄ１との差（ｄ２－ｄ１）が、好ましくは、５μｍ以上、より好ましくは、２０μｍ以上、より好ましくは、５０μｍ以上であり、また、好ましくは、１１５μｍ以下、より好ましくは、１００μｍ以下である。 5 μm ≦ d2-d1 ≦ 115 μm (3)
Specifically, the difference (d2−d1) between the thickness d2 of the porous resin layer 4 and the thickness d1 of the adhesive layer 5 is preferably 5 μm or more, more preferably 20 μm or more, and more preferably 50 μm or more. And preferably 115 μm or less, more preferably 100 μm or less.
　上記差が上記した下限以上であれば、低誘電基板材１の誘電率がより一層低くなる。一方、上記比が上記した上限以下であれば、多孔質樹脂層４と第２金属層６との接着力がより一層優れる。 で あ れ ば If the above difference is not less than the above lower limit, the dielectric constant of the low dielectric substrate material 1 is further reduced. On the other hand, when the ratio is equal to or less than the above upper limit, the adhesive strength between the porous resin layer 4 and the second metal layer 6 is further improved.
　また、この低誘電基板材１では、接着層５の厚みｄ１が、例えば、１μｍ以上、好ましくは、４μｍ以上、より好ましくは、５μｍ以上であり、また、例えば、５０μｍ以下、好ましくは、４４μｍ以下、より好ましくは、１０μｍ以下である。 Further, in the low dielectric substrate material 1, the thickness d1 of the adhesive layer 5 is, for example, 1 μm or more, preferably 4 μm or more, more preferably 5 μm or more, and, for example, 50 μm or less, preferably 44 μm or less. , More preferably 10 μm or less.
　接着層５の厚みｄ１が上記した下限以上であれば、多孔質樹脂層４と第２金属層６との接着力がより一層優れる。一方、上記比が上記した上限以下であれば、低誘電基板材１の誘電率がより一層低くなる。 (4) When the thickness d1 of the adhesive layer 5 is equal to or more than the above lower limit, the adhesive strength between the porous resin layer 4 and the second metal layer 6 is further improved. On the other hand, when the above ratio is equal to or less than the above upper limit, the dielectric constant of the low dielectric substrate material 1 is further reduced.
　接着層５の周波数１０ＧＨｚにおける誘電率は、接着剤の種類によって適宜調整され、具体的には、例えば、３．１０以下、好ましくは、２．８０以下、より好ましくは、２．５０以下であり、例えば、１．００以上である。接着層５の誘電率が上記した上限以下であれば、低誘電基板材１の誘電率がより一層低くなる。 The dielectric constant of the adhesive layer 5 at a frequency of 10 GHz is appropriately adjusted depending on the type of the adhesive, and specifically, is, for example, 3.10 or less, preferably 2.80 or less, and more preferably 2.50 or less. , For example, 1.00 or more. When the dielectric constant of the adhesive layer 5 is equal to or less than the above upper limit, the dielectric constant of the low dielectric substrate material 1 is further reduced.
　低誘電基板材１の周波数１０ＧＨｚにおける誘電率は、例えば、２．００以下、好ましくは、１．８０以下、より好ましくは、１．６０以下であり、また、例えば、１．００以上である。 誘 電 The dielectric constant of the low dielectric substrate material 1 at a frequency of 10 GHz is, for example, 2.00 or less, preferably 1.80 or less, more preferably 1.60 or less, and is, for example, 1.00 or more.
　＜変形例＞
　次に、一実施形態の変形例を説明する。以下の各変形例において、上記した一実施形態と同様の部材および工程については、同一の参照符号を付し、その詳細な説明を省略する。また、一実施形態および各変形例を適宜組み合わせることができる。さらに、各変形例は、特記する以外、一実施形態と同様の作用効果を奏することができる。 <Modification>
Next, a modified example of the embodiment will be described. In the following modified examples, the same members and steps as those in the above-described embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted. Further, one embodiment and each modified example can be appropriately combined. Further, each modified example can exhibit the same operational effects as those of the embodiment, except where otherwise noted.
　上記した説明では、低誘電基板材１をロールトゥロールで製造したが、これに限定されず、例えば、バッチ法（枚葉式）で低誘電基板材１を製造することもできる。 In the above description, the low dielectric substrate material 1 is manufactured by roll-to-roll. However, the present invention is not limited to this. For example, the low dielectric substrate material 1 can be manufactured by a batch method (single wafer type).
　また、一実施形態では、低誘電基板材１は、第１金属層３を備えているが、例えば、図示しないが、低誘電基板材１は、第１金属層３を備えていなくてもよい。すなわち、一実施形態では、両面金属層積層型の低誘電基板材であるが、例えば、他の実施形態では、片面金属層積層型の低誘電基板材であってもよい。 Further, in one embodiment, the low dielectric substrate material 1 includes the first metal layer 3. However, for example, although not illustrated, the low dielectric substrate material 1 may not include the first metal layer 3. . That is, in one embodiment, a low-dielectric substrate material of a double-sided metal layer lamination type is used. However, in another embodiment, a low-dielectric substrate material of a single-sided metal layer lamination type may be used.
　また、図示しないが、低誘電基板材１は、第１金属層３の他方側に配置される第１剥離シートと、第２金属層６の一方側に配置される第２剥離シートとを備えることができる。
すなわち、低誘電基板材１は、第１剥離シート、第１金属層３と、多孔質樹脂層４と、接着層５と、第２金属層６と、第２剥離シートとを厚み方向他方側から一方側に向かって順に備えることもできる。 Although not shown, the low dielectric substrate material 1 includes a first release sheet disposed on the other side of the first metal layer 3 and a second release sheet disposed on one side of the second metal layer 6. be able to.
That is, the low dielectric substrate material 1 includes the first release sheet, the first metal layer 3, the porous resin layer 4, the adhesive layer 5, the second metal layer 6, and the second release sheet on the other side in the thickness direction. From one side to the other side.
　なお、図示しないが、低誘電基板材１は、各層間に介在したり、あるいは、表面に形成される機能層をさらに備えることもできる。 Although not shown, the low dielectric substrate material 1 may further include a functional layer interposed between layers or formed on the surface.
　以下に実施例および比較例を示し、本発明をさらに具体的に説明する。なお、本発明は、何ら実施例および比較例に限定されない。また、以下の記載において用いられる配合割合（含有割合）、物性値、パラメータなどの具体的数値は、上記の「発明を実施するための形態」において記載されている、それらに対応する配合割合（含有割合）、物性値、パラメータなど該当記載の上限（「以下」、「未満」として定義されている数値）または下限（「以上」、「超過」として定義されている数値）に代替することができる。 実 施 Examples and comparative examples are shown below to further illustrate the present invention. In addition, this invention is not limited to an Example and a comparative example at all. Specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the mixing ratios (corresponding to them) described in the above-mentioned “Embodiments of the Invention”. The upper limit (values defined as “less than” or “less than”) or the lower limit (values defined as “over” or “exceeding”), such as the content ratio, physical property values, and parameters, may be substituted. it can.
　　実施例１
　まず、銅からなる厚み１２．５μｍの第１金属層３を準備した。 Example 1
First, a 12.5 μm-thick first metal layer 3 made of copper was prepared.
　次いで、特開２０１８－０２１１７２号公報の参考例に記載のポリイミド前駆体溶液１００質量部に、イミド化触媒（２－メチルイミダゾール）４．２質量部、ポリオキシエチレンジメチルエーテル（日油社製　グレード：ＭＭ４００、重量平均分子量４００）からなる多孔化剤２００質量部、ＰＴＦＥからなる平均粒子径１０００ｎｍの核剤３質量部、および、ＮＭＰ（Ｎ－メチルピロリドン）を配合して、ワニスを調製した。核剤は、予めＮＭＰに分散されたスラリーとして調製したものを、ポリイミド前駆体に対して配合した。なお、ワニスにおけるＮＭＰの総配合部数は、上記したスラリー中に含まれるものを併せて、ポリイミド前駆体１００質量部に対して、１５０質量部となるように、調整した。 Next, 4.2 parts by mass of an imidation catalyst (2-methylimidazole) and polyoxyethylene dimethyl ether (Nippon Oil Co., Ltd. grade: 100 parts by mass) in 100 parts by mass of the polyimide precursor solution described in Reference Example of JP-A-2018-021172: A varnish was prepared by blending 200 parts by mass of a porogen comprising MM400 and a weight average molecular weight of 400), 3 parts by mass of a nucleating agent comprising PTFE having an average particle diameter of 1000 nm, and NMP (N-methylpyrrolidone). The nucleating agent was prepared in advance as a slurry dispersed in NMP and blended with the polyimide precursor. The total number of NMP in the varnish was adjusted so as to be 150 parts by mass with respect to 100 parts by mass of the polyimide precursor, including those contained in the slurry.
　このワニスを、第１金属層３の一方面に塗布し、１２０℃で３０分間、乾燥して、ＮＭＰを除去し、続いて、超臨界抽出法により、多孔化剤を除去し、その後、真空下、３８０℃で２時間加熱して、イミド化させて、ポリイミドからなる多孔質樹脂層４を、第１金属層３の一方面で作り込んだ。 This varnish is applied to one surface of the first metal layer 3 and dried at 120 ° C. for 30 minutes to remove NMP, followed by supercritical extraction to remove the porosifier, and then vacuum Heating was performed at 380 ° C. for 2 hours for imidization, and a porous resin layer 4 made of polyimide was formed on one surface of the first metal layer 3.
　多孔質樹脂層４の厚みが、１２０μｍであった。多孔質樹脂層４における空孔率が、８０％、平均孔径が、７μｍであった。また、多孔質樹脂層４の周波数１０ＧＨｚにおける誘電率が、１．５であった。 The thickness of the porous resin layer 4 was 120 μm. The porosity of the porous resin layer 4 was 80%, and the average pore diameter was 7 μm. The dielectric constant of the porous resin layer 4 at a frequency of 10 GHz was 1.5.
　次いで、アクリル系接着剤からなり、厚み５μｍの接着層５を、多孔質樹脂層４の一方面に形成した。 Next, an adhesive layer 5 made of an acrylic adhesive and having a thickness of 5 μm was formed on one surface of the porous resin layer 4.
　次いで、銅からなる厚み１２μｍの第２金属層６を、接着層５の一方面に接着した。 Next, a second metal layer 6 made of copper and having a thickness of 12 μm was bonded to one surface of the bonding layer 5.
　これにより、図１に示すように、第１金属層３と、多孔質樹脂層４と、接着層５と、第２金属層６とを厚み方向一方側に順に備える低誘電基板材１を製造した。 Thereby, as shown in FIG. 1, the low dielectric substrate material 1 including the first metal layer 3, the porous resin layer 4, the adhesive layer 5, and the second metal layer 6 in this order on one side in the thickness direction is manufactured. did.
　　実施例２～５
　接着層５の厚みｄ１および多孔質樹脂層の厚みｄ２を表１に記載の厚みｄ１、ｄ２に変更した以外は、実施例１と同様にして、低誘電基板材１を製造した。 Examples 2 to 5
A low dielectric substrate material 1 was manufactured in the same manner as in Example 1 except that the thickness d1 of the adhesive layer 5 and the thickness d2 of the porous resin layer were changed to the thicknesses d1 and d2 shown in Table 1.
　　比較例１～３
　接着層５の厚みｄ１および多孔質樹脂層の厚みｄ２を表１に記載の厚みｄ１、ｄ２に変更した以外は、実施例１と同様にして、低誘電基板材１を製造した。 Comparative Examples 1-3
A low dielectric substrate material 1 was manufactured in the same manner as in Example 1 except that the thickness d1 of the adhesive layer 5 and the thickness d2 of the porous resin layer were changed to the thicknesses d1 and d2 shown in Table 1.
　評価
　＜厚み＞
　各層の厚みは、ダイヤルゲージ（ＰＥＡＣＯＣＫ社製、「ＵＰＲＩＧＨＴ ＤＩＡＬ　ＧＡＵＧＥ　Ｒ１－２０５」）を用いて測定した。 Evaluation <Thickness>
The thickness of each layer was measured using a dial gauge ("UPRIGHT DIAL GAUGE R1-205" manufactured by PEACOCK).
　＜接着力＞
　各実施例および各比較例において、多孔質樹脂層４と第２金属層６との接着力を、
引張圧縮試験機（今田製作所社製、「ＳＵＺ－５０ＮＴ－２Ｒ２Ｔ」）を用いて、剥離速度５０ｍｍ／分の条件で９０度剥離試験を実施することにより、測定した。なお、このとき、接着層５は、多孔質樹脂層４、第２金属層６、または、これらの両方に点在または全面に接着していた。
接着力が、０．６Ｎ／ｍｍ以上であった場合を〇と評価した。
接着力が、０．３Ｎ／ｍｍ以上、０．６Ｎ／ｍｍ未満であった場合を△と評価した。
接着力が、０．３Ｎ／ｍｍ未満であった場合を×と評価した。 <Adhesive strength>
In each example and each comparative example, the adhesive strength between the porous resin layer 4 and the second metal layer 6 was
It was measured by performing a 90 ° peel test using a tensile compression tester (“SUZ-50NT-2R2T”, manufactured by Imada Seisakusho) at a peel speed of 50 mm / min. At this time, the adhesive layer 5 was scattered or adhered to the entire surface of the porous resin layer 4, the second metal layer 6, or both.
The case where the adhesive force was 0.6 N / mm or more was evaluated as Δ.
The case where the adhesive strength was 0.3 N / mm or more and less than 0.6 N / mm was evaluated as Δ.
The case where the adhesive force was less than 0.3 N / mm was evaluated as x.
　＜誘電率＞
　各実施例および各比較例の低誘電基板材において、１０ＧＨｚにおける比誘電率を、ＰＮＡネットワークアナライザ（アジレント・テクノロジー社製、型名「５２２７Ａ」）およびＳＰＤＲ共振器を用いて測定した。 <Dielectric constant>
The relative dielectric constant at 10 GHz of each of the low dielectric substrate materials of the examples and comparative examples was measured using a PNA network analyzer (manufactured by Agilent Technologies, model number "5227A") and an SPDR resonator.
　上記した評価の結果を表１に示す。 Table 1 shows the results of the above evaluation.
　＜算術平均粗さ（Ｒａ）、最大高さ（Ｒｚ）＞
　実施例１で作製した多孔質樹脂層４を、５０ｍｍ×５０ｍｍの大きさに切り取った試験片を３つ用意し、これらの接着層側の面の算術平均粗さ（Ｒａ）と最大高さ（Ｒｚ）を、走査型共焦点レーザ顕微鏡（オリンパス社製、「ＯＬＳ３０００」）を用いて測定した。 <Arithmetic average roughness (Ra), maximum height (Rz)>
Three test pieces were prepared by cutting the porous resin layer 4 prepared in Example 1 into a size of 50 mm × 50 mm, and the arithmetic average roughness (Ra) and the maximum height (Ra) of the surface on the adhesive layer side were prepared. Rz) was measured using a scanning confocal laser microscope (manufactured by Olympus Corporation, “OLS3000”).
　Ｒａでは、０．４４４μｍ、０．３９９μｍ、０．３９６μｍであり、Ｒａの平均値は、０．４１μｍであった。また、Ｒｚにおいては、４．７６１μｍ、８．６２μｍ、６．５０２μｍであり、Ｒｚの平均値は、６．６３μｍであった。 Ra was 0.444 μm, 0.399 μm, and 0.396 μm, and the average value of Ra was 0.41 μm. In addition, Rz was 4.761 μm, 8.62 μm, and 6.502 μm, and the average value of Rz was 6.63 μm.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示に過ぎず、限定的に解釈してはならない。当該当技術分野の当業者によって明らかな本発明の変形例は、後記請求の範囲に含まれる。 Note that the above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be construed as limiting. Modifications of the invention apparent to those skilled in the art are included in the following claims.
　低誘電基板材は、高周波アンテナや高速伝送基板の製造に好適に用いられる。
１　低誘電基板材
４　多孔質樹脂層
５　接着層　
６　第２金属層
  The low dielectric substrate material is suitably used for manufacturing a high-frequency antenna and a high-speed transmission substrate.
1 Low dielectric substrate material 4 Porous resin layer 5 Adhesive layer
6 Second metal layer

Claims (2)

  1. 　多孔質樹脂層と、接着層と、金属層とを厚み方向に順に備え、
    　前記接着層の厚みｄ１と、前記多孔質樹脂層の厚みｄ２とが、下記式（１）を満足する
    ことを特徴とする、低誘電基板材。
    ｄ１／ｄ２≦０．５ （１）     A porous resin layer, an adhesive layer, and a metal layer are sequentially provided in the thickness direction,
    A low-dielectric substrate material, wherein a thickness d1 of the adhesive layer and a thickness d2 of the porous resin layer satisfy the following expression (1).
    d1 / d2 ≦ 0.5 (1)
  2. 　下記式（２）を満足することを特徴とする、請求項１に記載の低誘電基板材。
    　　　　２≦ｄ２／ｄ１≦１５０　　（２）     2. The low dielectric substrate material according to claim 1, wherein the low dielectric substrate material satisfies the following expression (2).
    2 ≦ d2 / d1 ≦ 150 (2)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022211042A1 (en) * 2021-03-31 2022-10-06
WO2022260085A1 (en) * 2021-06-09 2022-12-15 株式会社村田製作所 Porous resin sheet, porous resin sheet with metal layer, electronic circuit board, method for producing porous resin sheet, method for producing porous resin sheet with metal layer, and method for producing electronic circuit board

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* Cited by examiner, † Cited by third party
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WO2023145345A1 (en) * 2022-01-31 2023-08-03 富士フイルム株式会社 Laminate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012224692A (en) * 2011-04-16 2012-11-15 Nitto Denko Corp Porous resin laminate
JP2014231533A (en) * 2011-02-03 2014-12-11 日東電工株式会社 Porous resin molded body, porous body substrate and production method thereof
JP2017148986A (en) * 2016-02-23 2017-08-31 東京応化工業株式会社 Laminate for wiring board, wiring board, and method for manufacturing laminate for wiring board

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014231533A (en) * 2011-02-03 2014-12-11 日東電工株式会社 Porous resin molded body, porous body substrate and production method thereof
JP2012224692A (en) * 2011-04-16 2012-11-15 Nitto Denko Corp Porous resin laminate
JP2017148986A (en) * 2016-02-23 2017-08-31 東京応化工業株式会社 Laminate for wiring board, wiring board, and method for manufacturing laminate for wiring board

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022211042A1 (en) * 2021-03-31 2022-10-06
WO2022211042A1 (en) * 2021-03-31 2022-10-06 大日本印刷株式会社 Laminate for printed circuit board and junction for multilayer printed circuit board
JP7298786B2 (en) 2021-03-31 2023-06-27 大日本印刷株式会社 Laminate for printed wiring board and joined body for multilayer printed wiring board
WO2022260085A1 (en) * 2021-06-09 2022-12-15 株式会社村田製作所 Porous resin sheet, porous resin sheet with metal layer, electronic circuit board, method for producing porous resin sheet, method for producing porous resin sheet with metal layer, and method for producing electronic circuit board

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