WO2020066144A1

WO2020066144A1 - Low-dielectric substrate material

Info

Publication number: WO2020066144A1
Application number: PCT/JP2019/023074
Authority: WO
Inventors: 将義中村; 亮人松富; 慧三島
Original assignee: 日東電工株式会社
Priority date: 2018-09-28
Filing date: 2019-06-11
Publication date: 2020-04-02
Also published as: TW202012159A; JP2020049905A

Abstract

This low-dielectric substrate material is provided with a porous resin layer and a metal layer in sequence in the thickness direction. If the pressure to impart 10% residual strain S, described hereinafter, is the 10% strain pressure P, this 10% strain pressure P is at least 4.5 MPa at 180°C. Residual strain S: the initial thickness T0 of the porous resin layer is measured, then the pressure P is applied to the low-dielectric substrate material for 30 minutes in the thickness direction, then the pressure P is released, and the post-release thickness T1 of the porous resin layer is measured. The initial thickness T0 and the post-release thickness T1 are substituted into the following formula (1) to obtain the residual strain S. Residual strain S (%) = ([T0 – T1] / T0) × 100

Description

Low dielectric substrate material

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.

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.

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.

基板 Also, a substrate made of a porous material is 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. For example, a metal foil laminate obtained by forming a resin porous layer as an insulating material on a first copper foil and further pressing the second copper foil via an adhesive layer has been proposed. (For example, see Patent Document 1 below).

JP-A-2004-82372

However, the conventional porous body including Patent Literature 1 is a substrate material of an FPC that transmits data at a conventional speed or wireless communication conforming to “third generation (3G)” or “fourth generation (4G)” standards. Can be used as
When the second copper foil is pressed into the porous resin layer, the porous resin layer is largely distorted in the thickness direction, and if the distortion remains, the second copper foil cannot be accurately patterned. There is a defect.

However, a method for easily and industrially producing a metal foil laminate having a porous body has not yet been established so far.

The object of the present invention is to provide a low-dielectric substrate material that can be easily mass-produced industrially and that can accurately pattern a metal layer.

Thus, the present inventors have conducted intensive studies in order to achieve the above-mentioned object. As a result, the present inventors have succeeded in using a porous resin layer having a remarkably high porosity, can be easily mass-produced industrially, and accurately pattern a metal layer. We have invented a low dielectric substrate material that can be used.

The present invention (1) is a low dielectric substrate material provided with a porous resin layer and a metal layer in the thickness direction in order. A low dielectric substrate material having a% strain pressure P of 4.5 MPa or more at 180 ° C. is included.

The residual strain S: measuring the initial thickness T0 of the porous resin layer, subsequently applying a pressure P to the low dielectric substrate material in the thickness direction for 30 minutes, and then releasing the pressure P, After the release of the porous resin layer, the thickness T1 is measured. Then, the residual strain S is obtained by substituting the initial thickness T0 and the post-release thickness T1 into the following equation (1).

Residual strain S (%) = ([T0−T1] / T0) × 100
The present invention (2) includes the low dielectric substrate material according to (1), wherein the porosity of the porous resin layer is 60% or more.

The present invention (3) includes the low dielectric substrate material according to (1) or (2), wherein the porous resin layer has closed cells.

(5) Since the low dielectric substrate material has a metal layer, it can be patterned as an antenna corresponding to the fifth generation (5G) standard or a wiring of a high-speed FPC substrate. Specifically, even if the metal layer is patterned under etching conditions that can be mass-produced industrially, an antenna or wiring of a high-speed FPC board that can conform to the fifth generation (5G) can be formed with excellent accuracy.

In addition, when the porous resin layer has a closed cell structure in a high ratio, it is possible to suppress a decrease in pattern accuracy due to penetration of an etching solution used for patterning.
That is, since the etchant penetrates into the porous resin layer, it is possible to prevent the portion of the metal layer protected by the resist from being removed by the etchant.
Furthermore, in order to manufacture an antenna circuit board or the like from a low-dielectric substrate material, when the low-dielectric substrate material of the present invention is plated with a drill or a laser and then plated, the plating liquid immersion is suppressed, A metal layer having a uniform thickness can be formed on the surface of the hole. Here, the plating solution immersion is a phenomenon in which the plating solution enters from the porous resin layer exposed by the drilling.

Therefore, in the process of manufacturing the low dielectric substrate material, when the metal layer is bonded to the porous resin layer via the adhesive layer by pressing, it is necessary to apply pressure such that the pores of the porous resin layer are not crushed. is there. However, if the applied pressure is too low, the metal layer and the porous resin layer are not sufficiently bonded. Then, the inventor has found a pressure at which the maintenance of the pores of the porous resin layer and the adhesion of the metal layer and the porous resin layer can both be achieved.

However, when the pressure P at which the residual strain S of 10% is given is as low as less than 4.5 MPa at 180 ° C., even when the metal layer is pressed against the porous resin layer at a low pressure, the relatively large residual strain S is obtained. (Residual strain S exceeding at least 10%) is applied to the porous resin layer. In that case, it is not suitable as a substrate material that can sufficiently and surely cope with the fifth generation (5G) wireless communication and high-speed FPC.

On the other hand, in this low dielectric substrate material, since the pressure P at which a residual strain S of 10% is applied is as high as 4.5 MPa or more at 180 ° C., the metal layer is laminated on the porous resin layer at a general pressure of about 3 MPa. In this case, only a small residual strain S of at most 10% (within 10%) is given to the porous resin layer. As a result, since the pores of the porous resin layer are hardly destroyed by the pressurization, the metal layer can be accurately patterned on the wiring.

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. 3A and 3B are diagrams for explaining the measurement for obtaining the residual strain. FIG. 3A shows a mode for obtaining the initial thickness of the low dielectric substrate material, and FIG. 3B shows a mode for compressing the low dielectric substrate material. 3C shows an embodiment in which the low dielectric substrate material is released from compression and has residual strain. FIG. 4 shows the relationship between pressure and residual strain when obtaining a residual strain of 10%. FIG. 5 is a cross-sectional view of a modified example (an embodiment including a porous resin layer, an adhesive layer, and a second metal layer) of the low dielectric substrate material shown in FIG. FIG. 6 is a cross-sectional view of a modified example (an embodiment including a first metal layer, a porous resin layer, and a second metal layer) of the low dielectric substrate material shown in FIG. FIG. 7 is a sectional view of a modified example (an embodiment including a porous resin layer and a second metal layer) of the low dielectric substrate material shown in FIG. FIG. 8 is a cross-sectional view of a modification (an embodiment including a first metal layer and a porous resin layer) of the low dielectric substrate material shown in FIG. 1. FIG. 9 is an image processing diagram obtained by observing a cross section of the low dielectric substrate material of Example 1 with an optical microscope.

<One embodiment>
A low dielectric substrate material provided with one embodiment of the porous resin layer of the present invention will be described with reference to FIGS.

[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.

(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.

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 5 and a second metal layer 6 as an example of a metal layer disposed on one surface in the thickness direction of the adhesive layer 5. 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.

[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 first metal layer 3 forms the other surface in the thickness direction of the low dielectric substrate material 1. 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.

(Porous resin layer)
The porous resin layer 4 has one surface and the other surface opposed in the thickness direction, and has a substantially plate (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. One surface of the porous resin layer 4 is adhered to the second metal layer 6 via the adhesive layer 5.

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, and preferably mainly has a closed cell structure. The fact that the porous resin layer 4 has a closed cell structure can be confirmed using a penetrant such as that used in a penetrant inspection test (JIS Z 2343-1 etc.) specified in JIS. Preferably, a permeate having a contact angle to the polymer surface of 25 ° or less and a viscosity of 2.4 mm ^{2 / s (} 37.8 ° C.) is used. That is, the porous resin layer 4 is cut almost perpendicularly to the surface to expose a cross section, the cross section is immersed in a penetrant such as a red penetrant for 5 minutes, and then the liquid immersion length (permeate penetrates from the cross section). Distance). The liquid immersion length of the porous resin layer 4 in the low dielectric substrate material 1 is desirably 500 μm or less, and more desirably 300 μm or less. In this case, the proportion of closed cells is, for example, more than 50%, preferably 80% or more, more preferably 90% or more, and for example, less than 100%. When the liquid immersion length is equal to or less than the above upper limit, it is possible to prevent the second metal layer 6 disposed on one side in the thickness direction of the porous resin layer 4 from becoming nonuniform. Discontinuity can be prevented.

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.

Further, when the ratio of the closed cells exceeds the lower limit described above, when the first metal layer 3 is pressed against the porous resin layer 4 and laminated, the 10% strain pressure P for giving the residual strain S10% is set. Can be higher. In other words, the residual strain S at the time of pressing can be reduced.

空 The porosity of the porous resin layer 4 is, for example, 60% or more, more preferably 70% or more, further preferably 80% or more, and particularly preferably 85% or more. In addition, the porosity of the porous resin layer 4 is, for example, less than 100%, and further, 99% or less. 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
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.

(4) When the porosity of the porous resin layer 4 is equal to or more than the lower limit described above, the porous resin layer 4 can have a low dielectric constant that can sufficiently cope with the fifth generation (5G) standard and high-speed 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 FPC.

On the other hand, if the porosity is equal to or more than the above lower limit, the 10% strain pressure P when the residual strain S is 10% tends to be low, as described later. In other words, the residual strain S during pressing tends to increase. However, in the low dielectric substrate material 1, the above tendency can be suppressed because the porous resin layer 4 is configured so that the 10% strain pressure P when the residual strain S is 10% is reduced. As a result, even after pressing, the first metal layer 3 and the second metal layer 6 can be accurately patterned.

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, the holes 10 are identified, the hole diameter is calculated, and a histogram is formed. In the image analysis, ImageJ is used as analysis software.

The dielectric constant of the porous resin layer 4 at a frequency of 60 GHz is appropriately adjusted depending on the porosity and the type of the resin described below, and specifically, is, for example, 2.5 or less, preferably 2.0 or less, Also, for example, it is more than 1.0. The dielectric constant of the porous resin layer 4 is actually measured by a resonator method using a frequency of 60 GHz.

If the dielectric constant of the porous resin layer 4 is equal to or less than the above upper limit, the low dielectric substrate material 1 has a low dielectric constant, and is useful as a fifth generation (5G) standard or a high-speed FPC substrate material. Can be used.

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.

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.

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.

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. The details of the above-mentioned preferable physical properties of the resin and the manufacturing method thereof 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.

厚み The thickness of the porous resin layer 4 is, for example, 2 μm or more, preferably 5 μm or more, and for example, 1,000 μm or less, preferably 500 μm or less.

The ratio of the thickness of the porous resin layer 4 to the thickness of the low dielectric substrate material 1 is, for example, 0.05 or more, preferably 0.10 or more, more preferably 0.2 or more, and further preferably, It is more than 0.5, particularly preferably 0.6 or more, and for example, 0.95 or less, preferably 0.9 or less, more preferably 0.85 or less.

The thickness of the porous resin layer 4 depends on the total thickness of the low dielectric substrate material 1 and the thickness of the layers other than the porous resin layer 4 (specifically, the first metal layer 3, the adhesive layer 5, and the second metal layer 6). It is calculated as a value obtained by subtracting the thickness.

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.

[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.

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 μm or more, preferably 5 μm or more, and is, for example, 50 μm or less, preferably 25 μm or less.

[Second metal layer]
The second metal layer 6 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 second metal layer 6 forms one surface in the thickness direction of the low dielectric substrate material 1. 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 μm or more, preferably 20 μm or more, Also, for example, it is 5,000 μm or less, preferably 2,000 μm or less.

(Production method of low dielectric substrate material)
Next, a method of manufacturing the low dielectric substrate material 1 will be described.

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.

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.

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.

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.

In particular, the number of parts by mass (mixing ratio) of the porogen is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and preferably 300 parts by mass with respect to 100 parts by mass of the precursor. Or less, more 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). 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.

(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.

If the nucleating agent is solid at normal 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, less than 5,000 nm, preferably 2,000 nm or less. Preferably, it is less than 1,000 nm, for example, 1 nm or more.

核 The nucleating agent may be prepared in advance as a slurry dispersed in a solvent (PTFE).

(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.

(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.

(4) Thereafter, the precursor is cured by heating to form a resin having porosity, specifically, the porous resin layer 4.

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.

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.

により Thereby, 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 FPC.

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.

Next, the first metal layer 3 is patterned by photolithography to form the other-side wiring 18 such as a ground wiring, for example.

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.

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. Accordingly, the low dielectric substrate material 1 can have a low dielectric constant that can be used for an antenna substrate for wireless communication of the fifth generation (5G) standard or high-speed FPC.

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 high-speed FPC board. . 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 or the high-speed FPC board that can be adapted to the fifth generation (5G) is excellent. It can be formed with high precision.

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, in the low dielectric substrate material 1, the other-side wiring 18 and the one-side wiring 17 can be accurately formed from the first metal layer 3 and the second metal layer 6.

<Outstanding features>
Next, salient features of the porous resin layer 4 in the low dielectric substrate material 1 will be described with reference to FIGS. 3A to 4.

3A to 3C, the thickness and the like of the low-dielectric substrate material 1 are exaggerated in order to visually recognize the residual strain S. Including.

では In the low dielectric substrate material 1, when the pressure giving the following residual strain S of 10% is 10% strain pressure P, the 10% strain pressure P is 4.5 MPa or more at 180 ° C.

Residual strain S: As shown in FIGS. 1 and 3A, first, the initial thickness T0 of the porous resin layer 4 in the low dielectric substrate material 1 is measured, and then, as shown in FIG. The substrate material 1 is applied in the thickness direction for 30 minutes, and thereafter, as shown in FIG. 3C, the pressure P is released, and the post-release thickness T1 of the porous resin layer 4 in the low dielectric substrate material 1 is measured. After that, the residual strain S is obtained by substituting the initial thickness T0 and the post-release thickness T1 of the porous resin layer 4 into the following equation.

Residual strain S (%) = ([T0−T1] / T0) × 100
The above pressure application and release are performed at 180 ° C.

The application of the 10% strain pressure P to the low dielectric substrate material 1 is performed by, for example, a press 2 having two flat plates as shown in FIG. 3B. At this time, among the layers in the low dielectric substrate material 1, mainly the thickness of the porous resin layer 4 is significantly reduced. On the other hand, since the layers other than the porous resin layer 4, specifically, the first metal layer 3, the adhesive layer 5, and the second metal layer 6 are hard at room temperature (23 ° C.), a 10% strain pressure P After application to the low dielectric substrate material 1, does not substantially change (do not become thin) (become substantially the same thickness) from before the application.

Specifically, when the residual strain S of the low dielectric substrate material 1 after the pressure release does not become 10% and becomes, for example, less than 10%, then the pressure is increased by a pressure P2 higher than the previous pressure P1. Release and test (retest) to 10%. Further, as shown in FIG. 4, when the retest at the pressure P2 exceeds 10% (flow of the arrow), the pressure P1 of less than 10% (the pressure at the time of the first test) P1 and the corresponding strain ( An approximation line (calibration curve) L passing through the pressure exceeding 10% (pressure at the second test) P2 and the corresponding distortion (open point) is obtained, and the residual distortion is obtained from this. A 10% strain pressure P that becomes S10% is estimated.

Conversely, if the residual strain S of the low dielectric substrate material 1 after the pressure release exceeds 10%, then pressurization and release are performed at a pressure P1 lower than the previous pressure P2 so as to be 10%. Test (retest). When the retest at the pressure P1 is less than 10% (flow indicated by a broken arrow), the pressure (pressure at the first test) P2 exceeding 10% and the corresponding distortion (open dots). And an approximate line (calibration curve) L passing through the pressure (pressure at the time of the second test) P1 which is less than 10% and the distortion (dotted black dot) corresponding thereto P1, and the residual distortion S10% is obtained from this. Estimate the 10% strain pressure P.

If the 10% strain pressure P at which 10% residual strain S is applied to the low dielectric substrate material 1 is 4.5 MPa or more at 180 ° C., it is selected as the low dielectric substrate material of the present invention. Conversely, if it is less than 4.5 MPa, it is excluded from the low dielectric substrate material of the present invention.

If the 10% strain pressure P that gives 10% residual strain S to the low dielectric substrate material 1 is less than 4.5 MPa, the low dielectric substrate material 1 is usually subjected to the process (specifically, the second metal layer 6 Since the pressure (assumed pressure) applied during the laminating process is about 4.5 MPa, if the low dielectric substrate material 1 of the comparative example is loaded at a pressure exceeding the assumed pressure P, a low dielectric The residual strain S applied to the substrate material 1 exceeds 10%. That is, a large residual strain S is given to the low dielectric substrate material 1. Therefore, the following problem occurs.

That is, when the porous resin layer 4 has a residual strain S exceeding 10%, the first metal layer 3 and the second metal layer 6 arranged on both sides in the thickness direction of the porous resin layer 4 are precisely patterned. Can not.

Here, the numerical value of 10% of the residual strain S is accurately transferred from the first metal layer 3 and the second metal layer 6 disposed on both sides in the thickness direction of the porous resin layer 4 to the other wiring 18 and the one wiring 17. It means the limit value that can be formed (patterned).

Specifically, when the 10% strain pressure P giving 10% residual strain S is as low as less than 4.5 MPa, when the second metal layer 6 is pressed against the porous resin layer 4 at a low pressure, a comparison is made. The porous resin layer 4 has an extremely large residual strain S (at least 10% residual strain S). Therefore, patterning from the first metal layer 3 and the second metal layer 6 to the other wiring 18 and the one wiring 17 cannot be accurately performed. The low dielectric substrate material 1 provided with such a porous resin layer 4 is not suitable as a substrate material that can sufficiently and reliably cope with the fifth generation (5G) wireless communication and high-speed FPC.
On the other hand, when pressure is applied at a low pressure, the adhesive force between the first metal layer 3 and the porous resin layer 4 and the adhesive force between the porous resin layer 4 and the second metal layer 6 are reduced. Not suitable.

However, in the low dielectric substrate material 1, since the 10% strain pressure P giving 10% residual strain S is as high as 180 ° C. and 4.5 MPa or more, the second metal layer 6 is generally applied to the porous resin layer 4. When pressurization is performed at a moderate pressure (about 3 MPa), only 10% (within 10%) of residual strain S is applied to the porous resin layer 4 at most, so that pores in the porous resin layer are almost destroyed by the pressurization. As a result, it is useful as a low-dielectric substrate material that can sufficiently and reliably cope with wireless communication of the fifth generation (5G) standard and high-speed FPC.

In addition, since the low dielectric substrate material 1 has a high 10% strain pressure P that gives a residual strain S of 10% of 4.5 MPa, the second metal layer 6 is pressed against the porous resin layer 4 at a high pressure, for example. By forming, the low dielectric substrate material 1 in which the second metal layer 6 adheres to the porous resin layer 4 can be easily manufactured. As a result, the low dielectric substrate material 1 can be easily and industrially mass-produced.

The low dielectric substrate material 1 is applied in the thickness direction at a temperature of 180 ° C., preferably at a strain pressure P of 10% of more than 4.5 MPa, more preferably 4.6 MPa or more, and even more preferably 4.7 MPa or more. When pressed, the residual strain S becomes 10%.

The configuration (method) for forming the low dielectric substrate material 1 in which the 10% strain pressure P for giving the residual strain S of 10% is 4.5 MPa or more is not particularly limited, and any method commonly used by those skilled in the art is adopted. Is done. As an example, as described above, the porous resin layer 4 has the pores 10 having a closed cell structure, and the ratio of the closed cells is, for example, more than 50%, preferably 80% or more, more preferably , 90% or more. In addition to or instead of the above, the material of the porous resin layer 4 can be selected from, for example, a polyimide resin, a fluorinated polyimide resin, a polycarbonate resin, and a polyetherimide resin. It is more preferable from the viewpoint of the properties and mechanical strength. The polyimide resin is a material most suitable for lamination (press bonding) by pressure included in the manufacturing process of the low dielectric substrate material 1 including the porous resin layer 4 having a closed cell structure.

In the low dielectric substrate material 1, for example, a 10% strain pressure P for giving a residual strain S of 10% is 10.0 MPa or less.

<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.

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).

Also, in one embodiment, as shown in FIG. 1, the low dielectric substrate material 1 includes the first metal layer 3, but for example, as illustrated in FIG. 5, the low dielectric substrate material 1 may not include the first metal layer 3. Specifically, the low dielectric substrate material 1 includes a porous resin layer 4, an adhesive layer 5, and a second metal layer 6 in this order in the thickness direction.

(5) The porous resin layer 4 shown in FIG. 5 forms the other surface in the thickness direction of the low dielectric substrate material 1. The other surface in the thickness direction of the porous resin layer 4 is exposed toward the other side in the thickness direction.

初期 Both the initial thickness T0 and the released thickness T1 measured when obtaining the residual strain S in the low dielectric substrate material 1 shown in FIG. 5 are the thicknesses of the porous resin layer 4.

(6) Also, as shown in FIG. 6, the low dielectric substrate material 1 does not have to include the adhesive layer 5.

As shown in FIG. 6, the low-dielectric substrate material 1 includes the first metal layer 3, the porous resin layer 4, and the second metal layer 6 in order from one side in the thickness direction to one side in the thickness direction.

一方 One side in the thickness direction of the porous resin layer 4 shown in FIG. 6 is in direct contact (close contact) with the other side in the thickness direction of the second metal layer 6.

初期 Both the initial thickness T0 and the post-release thickness T1 measured when obtaining the residual strain S in the low dielectric substrate material 1 shown in FIG. 6 are the thicknesses of the porous resin layer 4.

Further, as shown in FIG. 7, the low dielectric substrate material 1 does not include the first metal layer 3 and the adhesive layer 5, but includes the porous resin layer 4 and the second metal layer 6 in order toward one side in the thickness direction. be able to.

初期 Both the initial thickness T0 and the post-release thickness T1 measured when obtaining the residual strain S in the low dielectric substrate material 1 shown in FIG. 7 are the thicknesses of the porous resin layer 4.

In the embodiment of FIG. 1, the second metal layer 6 is given as an example of the metal layer. However, as shown in FIG. 8, the first metal layer 3 is used as an example of the metal layer instead of the second metal layer 6. Can also be mentioned.

In the modification of FIG. 8, the low dielectric substrate material 1 includes the first metal layer 3 and the porous resin layer 4 in order from one side in the thickness direction to one side in the thickness direction.

一方 One surface in the thickness direction of the porous resin layer 4 shown in FIG. 8 forms one surface in the thickness direction of the low dielectric substrate material 1. One surface in the thickness direction of the porous resin layer 4 is exposed on one side in the thickness direction.

初期 Both the initial thickness T0 and the post-release thickness T1 measured when obtaining the residual strain S in the low dielectric substrate material 1 shown in FIG. 8 are the thicknesses of the porous resin layer 4.

The method for obtaining the low dielectric substrate material 1 shown in FIG. 8 is not limited to the method of forming the first metal layer 3 on one surface in the thickness direction as exemplified in one embodiment. For example, the first metal layer 3 and the porous resin The layers 4 may be stuck together. In this case, the 10% strain pressure P at which the residual strain S becomes 10% is as high as 4.5 MPa or more at 180 ° C. In this case, the first metal layer 3 and the porous resin layer 4 are subjected to high pressure. The remaining strain S of the porous resin layer 4 can be reduced even after the bonding by the press of the first step, and thereafter, the other-side wiring 18 (see FIG. 2) can be accurately patterned from the first metal layer 3, and the fifth generation (5G) This is useful as a low-dielectric substrate material that can sufficiently and reliably cope with wireless communication of the standard of (1) and high-speed FPC. Therefore, such a low dielectric substrate material 1 can be easily and industrially mass-produced.

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.

Example 1
First, a first metal layer 3 made of copper and having a thickness of 12 μm was prepared.

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 is prepared by blending 200 parts by weight of a porogen comprising MM400, weight average molecular weight 400), 3 parts by weight of a nucleating agent comprising PTFE having an average particle diameter of 1,000 nm or less, and NMP (N-methylpyrrolidone). did. 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 by heating at 100 ° C. for 15 minutes, then at 120 ° C. for 15 minutes to remove NMP, and then by supercritical extraction. Then, the porous agent was removed, followed by heating at 380 ° C. for 2 hours under vacuum to imidize the polyimide resin, thereby forming a porous resin layer 4 made of polyimide on one surface of the first metal layer 3.

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 60 GHz was 1.5.

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.

Next, a second metal layer 6 made of copper and having a thickness of 12 μm was bonded to one surface of the adhesive layer 5 in the thickness direction.

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.

厚み The thickness of the low dielectric substrate material 1 was 149 μm as the total thickness of the first metal layer 3, the porous resin layer 4, the adhesive layer 5, and the second metal layer 6.

On the other hand, the thickness T0 of the porous resin layer 4 is 120 μm, which is a value obtained by subtracting the total thickness of the first metal layer 3, the adhesive layer 5, and the second metal layer 6 from the thickness of the low dielectric substrate material 1 described above. did.

Example 2
As shown in FIG. 8, a low dielectric substrate material 1 was manufactured in the same manner as in Example 1 except that the adhesive layer 5 and the second metal layer 6 were not provided on the printed circuit board 1. That is, the printed circuit board 1 includes the first metal layer 3 having a thickness of 12 μm and the porous resin layer 4 having a thickness of 120 μm in this order.

厚み The thickness of the low dielectric substrate material 1 was 132 μm.

On the other hand, the thickness T0 of the porous resin layer 4 was 120 μm as a value obtained by subtracting the thickness of the first metal layer 3 from the thickness of the low dielectric substrate material 1.

Comparative Example 1
A low-dielectric substrate material 1 was produced in the same manner as in Example 2, except that polypropylene glycol (grade: D400, weight average molecular weight 400, manufactured by NOF Corporation) was changed from polyoxyethylene dimethyl ether as a porosifying agent. .

Evaluation <10% strain pressure P>
A 10% strain pressure P when a residual strain of 10% was applied to the low dielectric substrate material 1 was determined. The 10% strain pressure P was determined based on the method described with reference to FIG. 4 in one embodiment. Table 1 shows the results.
<Measurement of liquid penetration>
(Evaluation of liquid immersion)
The cross section of the porous resin layer 4 was cut with a razor and exposed. After being immersed in a red penetration liquid (NRC-ALII manufactured by Taiyo Bussan Co., Ltd.) for 5 minutes, the penetration liquid adhering to the surface was wiped off. The porous resin layer 4 was further cut perpendicular to the exposed cross section, and the liquid immersion length was measured with an optical microscope. Table 1 shows the results. FIG. 9 shows an image processing diagram obtained by observing a cross section of the low dielectric substrate material of Example 1 with an optical microscope.

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.

(5) The low-dielectric substrate material is preferably used for manufacturing a high-frequency antenna or a high-speed transmission substrate conforming to the fifth generation (5G) standard.

REFERENCE SIGNS LIST 1 Low dielectric substrate material 3 First metal layer 4 Porous resin layer 6 Second metal layer S Residual strain T1 Thickness after release (porous resin layer)
T0 Initial thickness (porous resin layer)
P 10% strain pressure

Claims

A low dielectric substrate material comprising a porous resin layer and a metal layer in the thickness direction,
A low dielectric substrate material characterized in that the 10% strain pressure P is 4.5 MPa or more at 180 ° C. when the pressure giving the following residual strain S of 10% is 10% strain pressure P.
The residual strain S: measuring the initial thickness T0 of the porous resin layer, subsequently applying a pressure P to the low dielectric substrate material in the thickness direction for 30 minutes, and then releasing the pressure P, After the release of the porous resin layer, the thickness T1 is measured. Then, the residual strain S is obtained by substituting the initial thickness T0 and the post-release thickness T1 into the following equation (1).
Residual strain S (%) = ([T0−T1] / T0) × 100
The low dielectric substrate material according to claim 1, wherein the porosity of the porous resin layer is 60% or more.
The low dielectric substrate material according to claim 1, wherein the porous resin layer has closed cells.