JP2021042294A - Resin film for high frequency circuit board, method for producing the same, and high frequency circuit board - Google Patents

Abstract

To provide a resin film for a high frequency circuit board that reduces values of dielectric constant and dielectric tangent, can obtain excellent mechanical strength and heat resistance and facilitates the realization of high-capacity/high-speed communication utilizing a frequency band from a MHz band to a GHz band, to provide a method for producing the resin film and to provide a high frequency circuit board.SOLUTION: The resin film 1 for a high frequency circuit board comprises a polyarylene ether ketone resin and a fluorine-containing copolymer in such a blending ratio thereof that the fluorine-containing copolymer is 3 pts.mass to 30 pts.mass based on 100 pts.mass of the polyarylene ether ketone resin. The resin film 1 for a high frequency circuit board has a dielectric constant of 3.3 or less and a dielectric tangent of 0.006 or less each in the range of a frequency of 800 MHz to 100 GHz. As the resin film 1 for a high frequency circuit board is molded by blending 3 pts. mass to 30 pts.mass of the fluorine-containing copolymer contributing to dielectric characteristics, values of dielectric constant and dielectric tangent can be lowered than the conventional ones.SELECTED DRAWING: Figure 1

Description

The present invention relates to a resin film for a high-frequency circuit board used from the MHz band to the GHz band, a method for manufacturing the same, and a high-frequency circuit board.

In recent years, mobile information communication devices such as multifunctional mobile phones and tablet terminals, whose demand is rapidly expanding, and electronic devices such as next-generation televisions are required to send and receive larger volumes of data at higher speeds. Along with this, increasing the frequency of electric signals is being studied. For example, in the field of mobile information and communication, studies on a fifth generation mobile communication system (5G) are being promoted worldwide (see Patent Documents 1 and 2). The communication speed of this 5th generation mobile communication system is several tens of times higher than that of the previous generation, and in order to realize this, a high frequency band of 10 GHz or more is being studied for electric signals. Further, in the field of automobiles, the use of signals in a high frequency band of 60 GHz or more called millimeter waves is being studied as an in-vehicle radar system.

Special Table 2017-507620 Japanese Unexamined Patent Publication No. 2015-210271

However, since the conventional circuit board is not designed and developed on the premise of large-capacity and high-speed communication utilizing the high frequency band, the relative permittivity value of the normal type is as high as about 4.3, and the normal type has a high relative dielectric constant value of about 4.3. The dielectric loss tangent is also as high as about 0.018. Circuit boards for large-capacity and high-speed communication are required to have materials having low dielectric properties such as relative permittivity and dielectric loss tangent, and excellent properties such as heat resistance and mechanical strength. Here, the relative permittivity is a parameter indicating the degree of polarization in the dielectric, and the higher the relative permittivity, the larger the propagation delay of the electric signal. Therefore, in order to increase the propagation speed of the electric signal and enable high-speed calculation, it is preferable that the relative permittivity is low.

Further, the dielectric loss tangent (also referred to as tan δ) is a parameter indicating the amount of the electric signal propagating in the dielectric that is converted into heat and lost. The lower the dielectric loss tangent, the smaller the signal loss and the electric signal. The transmission rate is improved. When the relative permittivity is high, the propagation speed of the electric signal becomes slow, and when the dielectric loss tangent is high, the transmission rate of the electric signal decreases. Further, since the dielectric loss tangent increases as the frequency increases in the high frequency band, it is necessary to use a material having a small value in order to reduce the loss as much as possible. Therefore, for a circuit board used in a high frequency band such as a MHz band to a GHz band, a material having a low relative permittivity and a dielectric loss tangent is strongly desired.

The present invention has been made in view of the above, and it is possible to lower the values of the relative permittivity and the dielectric loss tangent, obtain excellent mechanical strength and heat resistance, and perform large-capacity and high-speed communication utilizing the MHz band to the GHz band. It is an object of the present invention to provide a resin film for a high-frequency circuit board, a method for manufacturing the same, and a high-frequency circuit board, which can facilitate the realization of the above.

In the present invention, in order to solve the above problems, the polyarylene ether ketone resin and the fluorine-containing copolymer are contained, and the compounding ratio of these is such that the fluorine-containing copolymer is contained in 100 parts by mass of the polyarylene ether ketone resin. It is characterized in that it has 3 parts by mass or more and 30 parts by mass or less, has a relative permittivity of 3.3 or less in a frequency range of 800 MHz or more and 100 GHz or less, and has a dielectric loss tangent of 0.006 or less.

The polyarylene ether ketone resin is preferably at least one of a polyether ether ketone resin and a polyether ketone resin.
Further, the fluorine-containing copolymer can be a perfluoroalkoxyalkane.

The fluorine-containing copolymer is a functional group of an ester group, a carbonate group, a hydroxyl group, an epoxy group, a carboxyl group, a carbonyl dioxide group, a carbonyl fluoride group, an acid anhydride residue, a carbonyl group, and an isocyanate group. Of these, at least one can be possessed.
The thickness of the resin film for a high-frequency circuit board is preferably 3 μm or more and 200 μm or less.

Further, in the present invention, in order to solve the above problems, the method for producing a resin film for a high-frequency circuit board according to any one of claims 1 to 5 is used.
A molding material is prepared by melt-kneading at least 100 parts by mass of a polyarylene ether ketone resin and 3 parts by mass or more and 30 parts by mass or less of a fluorine-containing copolymer, and this molding material is extruded from a T-die to be a resin for a high-frequency circuit board. It is characterized in that a film is formed and the resin film for a high frequency circuit board is brought into contact with a cooling roll to be cooled.

Further, in order to solve the above problems, the present invention is characterized in that a metal layer is laminated on at least one of both sides of the resin film for a high frequency circuit board according to any one of claims 1 to 5.

Here, although there are various types of fluorine-containing copolymers in the claims, it is preferable that they are perfluoroalkoxyalkanes having adhesiveness. Further, the resin film for a high-frequency circuit board does not particularly ask whether it is transparent, opaque, translucent or the like. The high frequency circuit board according to the present invention is preferably used in a frequency band of 800 MHz to 100 GHz or less.

According to the present invention, a resin film for a high-frequency circuit board is formed by blending a polyarylene ether ketone resin having excellent mechanical properties and thermal properties with a fluorine-containing copolymer that contributes to a dielectric property, and thus is used for a high-frequency circuit board. The relative permittivity in the frequency range of 800 MHz or more and 100 GHz or less of the resin film is 3.3 or less, and the dielectric loss tangent is 0.006 or less, so that the values of the relative permittivity and the dielectric loss tangent can be made lower than before.

According to the present invention, there is an effect that the relative permittivity and the value of the dielectric loss tangent of the resin film for a high frequency circuit board can be lowered, and excellent mechanical strength and heat resistance can be obtained. Further, when used for a high frequency circuit board, there is an effect that it is possible to easily realize a large capacity and high speed communication utilizing the MHz band to the GHz band.

According to the invention of claim 2, since the polyarylene ether ketone resin is used, the mechanical properties, heat resistance, electrical properties, cold resistance, chemical resistance, solvent resistance, etc. of the resin film for high frequency circuit boards are improved. Can be made to. Further, if a polyetheretherketone resin is selected as the polyarylene ether ketone resin, mechanical properties, heat resistance, electrical properties, cold resistance, chemical resistance, solvent resistance, etc. can be improved and easily obtained. It is expected that the properties and molding will be facilitated, and that the manufacturing cost will be reduced.

According to the invention of claim 3, since the fluorine-containing copolymer is perfluoroalkoxyalkane, excellent heat resistance, slipperiness, chemical resistance, low friction resistance, insulation property, and melt moldability can be obtained. ..
According to the invention of claim 4, it is possible to impart excellent adhesiveness to the fluorine-containing copolymer, and it is possible to obtain an adhesive resin film for a high-frequency circuit board. Further, the polyarylene ether ketone resin and the fluorine-containing copolymer can be appropriately kneaded, and the difference in appearance and characteristics of the resin film for a high-frequency circuit substrate can be reduced.

According to the invention of claim 5, it is possible to secure a sufficient thickness of the high-frequency circuit board, improve the handleability, reduce the thickness of the high-frequency circuit board, and the like.

According to the invention of claim 6, since the resin film for a high-frequency circuit board is extruded by a melt extrusion molding method using a T-die, the thickness accuracy, productivity, and handleability of the resin film for a high-frequency circuit board can be improved. It can be expected to improve and simplify the equipment.
According to the invention of claim 7, since the relative permittivity and the dielectric loss tangent of the resin film for a high frequency circuit board are low, the propagation speed of an electric signal is improved, and the resin film can be used in a high frequency band such as a MHz band to a GHz band. A suitable high frequency circuit board can be obtained.

It is sectional drawing which shows typically the embodiment of the resin film for a high frequency circuit board and the high frequency circuit board which concerns on this invention. It is explanatory drawing which shows typically the embodiment of the manufacturing method of the resin film for a high frequency circuit board which concerns on this invention. It is sectional drawing which shows typically the 2nd Embodiment of the resin film for a high frequency circuit board and the high frequency circuit board which concerns on this invention.

Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIGS. 1 and 2, the resin film 1 for a high-frequency circuit substrate in the present embodiment has at least a polyarylene ether ketone resin and dielectric properties. It is a thin resin film containing 3 parts by mass or more and 30 parts by mass or less of the fluorine-containing copolymer with respect to 100 parts by mass of the polyarylene ether ketone resin. By laminating the metal layer 2 on one side, a high-frequency circuit board mainly for a fifth-generation mobile communication system is formed.

The compounding ratio of the polyarylene ether ketone resin forming the resin film 1 for the high frequency circuit substrate and the fluororesin containing fluorine-based copolymer is such that the fluorine-containing copolymer is 100 parts by mass of the polyarylene ether ketone resin. 3 parts by mass or more and 30 parts by mass or less, preferably 4 parts by mass or more and 25 parts by mass or less of the fluoropolymer, and more preferably 5 parts by mass or more and 20 parts by mass or less of the fluoropolymer.

This is because if the amount of the fluorine-containing copolymer is less than 3 parts by mass, the dielectric property of the resin film 1 for a high-frequency circuit board may not be improved. On the contrary, when it exceeds 30 parts by mass, the dispersibility and moldability of the resin film 1 for a high-frequency circuit board deteriorate, the resin film 1 for a high-frequency circuit board has a poor appearance, and there is a local difference in physical properties. This is because it is likely to occur.

Polyethereneetherketone resin is a thermoplastic resin having good mechanical properties and thermal properties, and is a polyetheretherketone (PEEK) resin, a polyetherketone (PEK) resin, or a polyetheretherketone resin and poly. A mixture of etherketone resins is used. Among these, a relatively inexpensive polyetheretherketone resin, which has excellent mechanical properties, heat resistance, chemical resistance, etc., is the most suitable.

Hereinafter, the polyetheretherketone resin will be described. The polyetheretherketone resin is not particularly limited, but is a crystalline resin having the following repeating units, and the glass transition point is usually 130 ° C. or higher and 160 ° C. or lower. (Measuring method: differential scanning calorimeter), preferably 135 ° C. or higher and 155 ° C. or lower, more preferably 140 ° C. or higher and 150 ° C. or lower. The melting point is usually 320 ° C. or higher and 360 ° C. or lower (measurement method: differential scanning calorimetry), preferably 330 ° C. or higher and 350 ° C. or lower, more preferably 335 ° C. or higher and 345 ° C. or lower, and usually powdery, granular, or granular. , Used in a form suitable for pellet molding.

The structural formula n of the polyetheretherketone resin is preferably 10 or more, preferably 20 or more, from the viewpoint of mechanical properties. This polyetheretherketone resin may be a homopolymer composed of only the repeating unit of [Chemical formula 1], but may have a repeating unit other than [Chemical formula 1]. The ratio of the chemical structure of [Chemical 1] in the polyetheretherketone resin is 50 mol% or more, preferably 70 mol% or more, more preferably 80, based on the total of all the repeating units constituting the polyetheretherketone resin. More than mol% is optimal.

Specific examples of the polyetheretherketone resin include product names manufactured by Victrex, Victorex Powerer series, Victorex Granules series, product names manufactured by Daicel Ebonic, Vestakeep series, and product names manufactured by Solvay Specialty Polymers: Keta. Spire polyether ether ketone series can be mentioned. Examples of the method for producing the polyetheretherketone resin include JP-A-50-27897, JP-A-5l-119797, JP-A-52-38000, and JP-A-54-90296. Examples thereof include the methods described in Japanese Patent Publication No. 55-23574 and Japanese Patent Publication No. 56-2091.

As the polyetheretherketone resin, a block copolymer, a random copolymer, or a modified product with another copolymerizable monomer can also be used as long as the effect of the present invention is not impaired.

The fluorine-containing copolymer has a repeating unit (a) based on tetrafluoroethylene (hereinafter referred to as TFE) and / or chlorotrifluoroethylene (hereinafter referred to as CTFE), a dicarboxylic acid anhydride group, and is in the ring. A repeating unit (b) based on a cyclic hydrocarbon monomer having a polymerizable unsaturated group, and a repeating unit based on other monomers (however, if it overlaps with the repeating units (a) and (b), the monomer is excluded). A melt-moldable adhesive copolymer containing the unit (c).

In the fluorine-containing copolymer, the repeating unit (a) is 50 to 99.89 mol%, and the repeating unit (b) is based on the total molar amount of the repeating unit (a), the repeating unit (b), and the repeating unit (c). ) Is 0.01 to 5 mol%, and the repeating unit (c) is 0.1 to 49.99 mol%. The repeating unit (a) is preferably 50 to 99.47 mol%, the repeating unit (b) is 0.03 to 3 mol%, and the repeating unit (c) is 0.5 to 49.97 mol%, more preferably. The repeating unit (a) is 50 to 98.95 mol%, the repeating unit (b) is 0.05 to 2 mol%, and the repeating unit (c) is 1 to 49.95 mol%.

This is because if the molar% of the repeating unit (a), the repeating unit (b), and the repeating unit (c) is within the relevant range, the heat resistance and chemical resistance of the fluorine-containing copolymer can be expected to be improved. is there. Further, when the molar% of the repeating unit (b) is within the above range, the adhesion of the fluorine-containing copolymer to the resin film 1 for a high-frequency circuit board is excellent. Further, if the molar% of the repeating unit (c) is within the above range, the moldability of the fluorine-containing copolymer is improved, and the mechanical properties such as stress crack resistance are also excellent.

The above-mentioned "cyclic hydrocarbon monomer having a dicarboxylic acid anhydride group and a polymerizable unsaturated group in the ring" (hereinafter, simply abbreviated as a cyclic hydrocarbon monomer) has one or more 5-membered rings or 6-membered rings. A cyclic hydrocarbon composed of a ring, which is a polymerizable compound having a dicarboxylic acid anhydride group and an intracyclically polymerizable unsaturated group. As the cyclic hydrocarbon, a cyclic hydrocarbon having one or more bridged polycyclic hydrocarbons is preferable. That is, a cyclic hydrocarbon composed of an Arihashi polycyclic hydrocarbon, a cyclic hydrocarbon obtained by condensing two or more of the Arihashi polycyclic hydrocarbons, or a cyclic hydrocarbon obtained by condensing an Arihashi polycyclic hydrocarbon with another cyclic hydrocarbon. It is preferable to have.

Further, the cyclic hydrocarbon monomer has one or more polymerizable unsaturated groups in the ring, that is, one or more polymerizable unsaturated groups existing between the carbon atoms constituting the hydrocarbon ring. This cyclic hydrocarbon monomer further has a dicarboxylic acid anhydride group (-CO-O-CO-), and the dicarboxylic acid anhydride group may be bonded to two carbon atoms constituting the hydrocarbon ring, and the ring may be bonded. It may be bonded to two outer carbon atoms. Preferably, the dicarboxylic acid anhydride group is a carbon atom constituting the ring of the cyclic hydrocarbon and is bonded to two adjacent carbon atoms. Further, a halogen atom, an alkyl group, an alkyl halide group, or another substituent may be bonded to the carbon atom constituting the ring of the cyclic hydrocarbon instead of the hydrogen atom.

Specific examples thereof are those represented by the formulas (2) to (9). Here, R in the formulas (3) and (6) to (9) is a halogen atom selected from a lower alkyl group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Indicates an alkyl halide group in which a hydrogen atom in a lower alkyl group is replaced with a halogen atom.

The cyclic hydrocarbon monomer is preferably 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as NAH) represented by the formula (2), represented by the formulas (4) and (5). Cyclic hydrocarbon monomers which are acid anhydrides, and cyclic hydrocarbon monomers whose substituent R is a methyl group in the formulas (3) and (6) to (9). More preferably, it is NAH.

Examples of other monomers include vinyl fluoride, vinylidene fluoride (hereinafter referred to as VdF), CTFE (excluding the case where it is used as a repeating unit (a)), trifluoroethylene, and hexafluoropropylene (hereinafter referred to as HFP). ), CF ₂ = CFOR ^f1 (where R ^f1 is a perfluoroalkyl group having 1 to 10 carbon atoms and may contain oxygen atoms between carbon atoms), CF ₂ = CFOR ^f2 SO ₂ X ¹ (where R ^f2 is the number of carbon atoms) Perfluoroalkylene groups 1 to 10 which may contain an oxygen atom between carbon atoms, X ¹ is a halogen atom or a hydroxyl group), CF ₂ = CFOR ^f2 CO ₂ X ² (where R ^f2 is the same as above, X ² is Hydrogen atom or alkyl group with 1-3 carbon atoms), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ (where p is 1 or 2), CH ₂ = CX ³ (CF ₂ ) _q X ⁴ (where p is 1 or 2) Here, X ³ and X ⁴ are hydrogen atoms or fluorine atoms independently of each other, q is an integer of 2 to 10), perfluoro (2-methylene-4-methyl-1,3-dioxolane), ethylene, propylene, isobutene. Examples thereof include olefins having 2 to 4 carbon atoms, vinyl esters such as vinyl acetate, and vinyl ethers such as ethyl vinyl ether and cyclohexyl vinyl ether. Other monomers may be used alone or in combination of two or more.

Specific examples of CF ₂ = CFOR ^f1 include, for example, CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF _2). ) ₈ F, and the like. Preferably, CF ₂ = CFOCF ₂ CF ₂ CF ₃ . Further, _{as specific examples of CH 2} = CX ³ (CF ₂ ) _q X ⁴ , for example, CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF). ₂ ) ₄ F, CH ₂ = CF (CF ₂ ) ₃ H, CH ₂ = CF (CF ₂ ) ₄ H and the like. Preferably, CH ₂ = CH (CF ₂ ) ₄ F or CH ₂ = CH (CF ₂ ) ₂ F.

Other monomers are preferably VdF, HFP, CTFE (except when used as a repeating unit (a)), CF ₂ = CFOR ^f1 , CH ₂ = CX ³ (CF ₂ ) _q X ⁴ , ethylene. , Propylene, and vinyl acetate, more preferably HFP, CTFE (except when used as the repeating unit (a)), CF ₂ = CFOR ^f1 , ethylene, And CH ₂ = CX ³ (CF ₂ ) _q X ⁴ is one or more selected from the group. Most preferably, HFP or CF ₂ = CFOR ^f1 . Further, as CF ₂ = CFOR ^f1 , ^{a perfluoroalkyl group having R f1} having 1 to 6 carbon atoms is preferable, a perfluoroalkyl group having 2 to 4 carbon atoms is more preferable, and a perfluoropropyl group is most suitable.

Specific examples of the adhesive fluoropolymer include TFE / CF ₂ = CFOCF ₂ CF ₂ CF ₃ / NAH copolymer, TFE / HFP / NAH copolymer, TFE / CF ₂ = CFOCF _2. CF ₂ CF ₃ / HFP / NAH copolymer, TFE / VdF / NAH copolymer, TFE / CH ₂ = CH (CF ₂ ) ₄ F / NAH / ethylene copolymer, TFE / CH ₂ = CH (CF ₂₎ ) ₂ F / NAH / ethylene copolymer, CTFE / CH ₂ = CH (CF ₂ ) ₄ F / NAH / ethylene copolymer, CTFE / CH ₂ = CH (CF ₂ ) ₂ F / NAH / ethylene copolymer , CTFE / CH ₂ = CH (CF ₂ ) ₂ F / NAH / ethylene copolymer and the like.

The melting point of the fluorine-containing copolymer is preferably 150 ° C. or higher and 320 ° C. or lower, and more preferably 200 ° C. or higher and 310 ° C. or lower. The melting point can be adjusted by appropriately selecting the content ratio of the repeating unit (a), the repeating unit (b), and the repeating unit (c) within the above range.

The fluorine-containing copolymer has an ester group, a carbonate group, a hydroxyl group, a carboxyl group, a carbonyl fluoride group, an acid anhydride residue, and a carbonyl as polymer terminal groups in order to appropriately knead the polyarylene ether ketone resin. It is preferable to have at least one functional group of a group and an isocyanate group. This is because if at least one of these functional groups is present, the adhesiveness to a thermoplastic resin other than the fluorine-containing copolymer is excellent. The polymer terminal group having an adhesive functional group can be introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent, or the like at the time of producing the fluorine-containing copolymer.

The fluorine-containing copolymer preferably has a volumetric flow velocity (hereinafter referred to as Q value) in the range of ^{0.1 to 100 mm 3 / sec.} The Q value is an index showing the melt fluidity of the fluorine-containing copolymer and serves as a guideline for the molecular weight. A large Q value indicates a low molecular weight, and a small Q value indicates a high molecular weight.

The Q value is the fluorine-containing copolymer when extruded into an orifice with a diameter of 2.1 mm and a length of 8 mm under a load of 7 kg at a temperature 50 ° C. higher than the melting point of the fluorine-containing copolymer using a flow tester manufactured by Shimadzu Corporation. Extrusion speed. If this Q value is too small, extrusion molding becomes difficult, and conversely, if it is too large, the mechanical strength of the fluorine-containing copolymer decreases. Q value of the fluorocopolymer is preferably from 5 to 500 mm ³ / sec, 10 to 200 mm ³ / sec is more preferable.

The method for producing the fluorine-containing copolymer is not particularly limited, and a radical polymerization method using a radical polymerization initiator is used. As the polymerization method, bulk polymerization, solution polymerization using an organic solvent such as fluorinated hydrocarbon, chlorinated hydrocarbon, fluorinated hydrocarbon, alcohol, hydrocarbon, aqueous medium, and if necessary, an appropriate organic solvent are used. Suspension polymerization used, an aqueous medium, and emulsion polymerization using an emulsifier can be mentioned, and solution polymerization is particularly preferable.

As the radical polymerization initiator, a radical polymerization initiator having a half-life of 10 hours and a temperature of 0 ° C. to 100 ° C., more preferably 20 to 90 ° C. is preferable. Specific examples include azo compounds such as azobisisobutyronitrile, non-fluorinated diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide and lauroyl peroxide, diisopropyl peroxydicarbonate and di-n-propyl peroxide. Peroxy dicarbonates such as dicarbonates, peroxyesters such as tert-butyl peroxypivalate, tert-butyl _{peroxyisobutyrate, and tert-butyl peroxyacetate, (Z (CF 2} ) rCOO) ₂ (where Z is a hydrogen atom , Fluorine atom or chlorine atom, where r is an integer of 1 to 10) includes fluorine-containing diacyl peroxides such as compounds, and inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate. Be done.

When controlling the Q value of the fluorine-containing copolymer, it is also preferable to use a chain transfer agent. Examples of this chain transfer agent include alcohols such as methanol and ethanol, and chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane and 1,1-dichloro-1-fluoroethane. , Pentan, hexane, cyclohexane and other hydrocarbons. Examples of the chain transfer agent for introducing an adhesive functional group into the polymer terminal of the fluorine-containing copolymer include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

The polymerization conditions of the fluorine-containing copolymer are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably 0.1 to 10 MPa, more preferably 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.

The concentration of the cyclic hydrocarbon monomer during the polymerization is preferably 0.01 to 5 mol%, more preferably 0.1 to 3 mol%, and most preferably 0.1 to 1 mol% with respect to all the monomers. If the concentration of the cyclic hydrocarbon monomer is too high, the polymerization rate tends to decrease. Within the above range, the polymerization rate during production does not decrease, and the fluorine-containing copolymer has excellent adhesiveness. During the polymerization, as the cyclic hydrocarbon monomer is consumed in the polymerization, it is preferable to continuously or intermittently supply the consumed amount into the polymerization tank to maintain the concentration of the cyclic hydrocarbon monomer in this range.

The fluorine-containing copolymer obtained by the above production method can be obtained in the form of pellets, powder, or other forms according to a conventional method. Since this fluorine-containing copolymer is excellent in moldability, it can be injection-molded or extrusion-molded, and can be molded into a desired shape. Further, since the above-mentioned fluorine copolymer is excellent in flexibility, the resin film 1 for a high-frequency circuit board using these as an adhesive is peeled off or damaged even if it is bent or drawn. Can be suppressed.

The adhesive fluorine-containing copolymer can be produced as described above, but a commercially available product can also be used. The adhesive commercially available product is not particularly limited, and examples thereof include EA-2000 manufactured by AGC Inc.

The resin film 1 for a high-frequency circuit substrate includes a polyetherketone resin, a fluororesin, a polyimide resin such as a polyimide (PI) resin, a polyamideimide (PAI) resin, and a polyetherimide (PEI) resin, and a polyamide 4T (PA4T). ) Resin, Polyamide 6T (PA6T) Resin, Modified Polyamide 6T (PA6T) Resin, Polyamide 9T (PA9T) Resin, Polyamide 10T (PA10T) Resin, Polyamide 11T (PA11T) Resin, Polyamide 6 (PA6) Resin, Polyamide 66 (PA66) ) Resin, polyamide resin such as polyamide 46 (PA46) resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polyester resin such as polyethylene naphthalate (PEN) resin, polyetherketone (PEK) resin, poly Polyetheretheretherketone (PEEEK) resin, polyetherketoneketone (PEKK) resin, polyetheretherketoneketone (PEEKK) resin, polyetherketone etherketoneketone (PEKEKK) resin, and other polyaralyene etherketone resins, polysalphon (PSU) resins ), Polyetherketone (PES) resin, polysulfone resin such as polyphenylene sulphon (PPSU) resin, polyphenylene sulfide (PPS) resin, polyphenylene sulfite resin, polyphenylene sulfide sulfone resin, polyphenylene sulfide ketone sulfone resin, etc. Sulfide resin, polytetrafluoroethylene (PTFE) resin, polytetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) resin, tetrafluoroethylene-hexafluoropropyl copolymer (FEP) resin, tetrafluoroethylene-ethylene Polymer (ETFE) resin, polychlorotrifluoroethylene (PCTFE) resin, polyvinylidene fluoride (PVDF) resin, fluororesin such as vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene copolymer resin, liquid crystal polymer (LCP) ), Polyetherketone (PC) resin, polyarylate (PAR) resin and the like can be added as needed.

In addition to the above resins, the resin film 1 for high-frequency circuit boards includes antioxidants, light stabilizers, colorants, ultraviolet absorbers, plasticizers, antistatic agents, heat-resistant improvers, as long as the characteristics of the present invention are not impaired. It is possible to selectively add flame retardants, inorganic compounds, organic compounds, resin modifiers and the like.

When the polyetheretherketone resin is selected, the crystallinity of the resin film 1 for a high-frequency circuit board is preferably 15% or more, preferably 20% or more, more preferably 23% or more, still more preferably 25% or more. This is because when the crystallinity of the resin film 1 for a high-frequency circuit board is less than 15%, there is a problem in the solder heat resistance of the resin film. On the contrary, when the crystallinity is 15% or more, it can be expected to secure the mechanical strength that can be used as a high frequency circuit board.

The upper limit of the crystallinity of the resin film 1 for a high-frequency circuit board is not particularly limited, but is preferably 50% or less. This is based on the reason that when the crystallinity of the resin film 1 for a high-frequency circuit board exceeds 50%, a long-time heat treatment is required, which causes a problem in productivity.

The thickness of the resin film 1 for a high-frequency circuit board is 3 μm or more and 200 μm or less, preferably 8 μm or more and 110 μm or less, and more preferably 10 μm from the viewpoint of ensuring a sufficient thickness of the high-frequency circuit board, handleability, and thinning. It is preferably 100 μm or less, more preferably 12.5 μm or more and 100 μm or less.

The mechanical properties of the resin film 1 for a high-frequency circuit board can be evaluated by the maximum tensile strength at 23 ° C., the elongation at tensile break, and the tensile elastic modulus. Maximum tensile strength, 60N / mm ² or more, preferably 90 N / mm ² or more 140 N / mm ² or less, more preferably 100 N / mm ² or more 135N / mm ² or less is good.

Tensile modulus at 23 ° C. in a high-frequency circuit board resin film 1, 2600N / mm ² or more 8000 N / mm ² or less, preferably 2650N / mm ² or more 3900N / mm ² or less, more preferably 2700N / mm ² or more 3850N / The optimum range is ^{mm 2 or less.} This is based on the reason that when the tensile elastic modulus is ^{less than 2600 N / mm 2} , the resin film 1 for a high-frequency circuit board is inferior in rigidity, so that the handleability during processing of the high-frequency circuit board is deteriorated. On the contrary, ^{when it exceeds 8000 N / mm 2} , it takes a long time to mold the resin film 1 for a high frequency circuit board, and the cost reduction cannot be expected.

The elongation at tensile break of the resin film 1 for a high-frequency circuit board is preferably 50% or more, preferably 155% or more and 300% or less, and more preferably 160% or more and 280% or less. This is because when the maximum tensile strength is ^{less than 60 N / mm 2} and the elongation at break is less than 50%, the resin film 1 for high-frequency circuit boards does not have sufficient toughness, so that it may break during processing of high-frequency circuit boards. This is because there is a risk of trouble such as cracking.

The relative permittivity of the resin film 1 for a high-frequency circuit board in the frequency range of 800 MHz or more and 100 GHz or less is 3.3 or less, preferably 2 from the viewpoint of preventing propagation delay of electric signals of the high-frequency circuit board and realizing high-speed communication. It is preferably .60 or more and 3.0 or less, more preferably 2.63 or more and 2.90 or less. Further, the dielectric loss tangent of the resin film 1 for a high-frequency circuit board in the frequency range of 800 MHz or more and 100 GHz or less is 0.006 or less, preferably 0.006 or less, from the viewpoint of preventing propagation delay of the electric signal of the high-frequency circuit board and realizing high-speed communication. It is preferably 0.0017 or more and 0.0058 or less, more preferably 0.0018 or more and 0.0055 or less.

The method for measuring the specific dielectric constant and the dielectric tangent is not particularly limited, but is reflected / transmitted (S) such as a coaxial probe method, a coaxial S parameter method, a waveguide S parameter method, and a free space S parameter method. Parameter) method, measurement method using stripline (ring) resonator, cavity resonator perturbation method, measurement method using split-post dielectric resonator, measurement method using cylindrical (split cylinder) cavity resonator, Measurement methods using multi-frequency balanced disc resonators, measurement methods using cut-off cylindrical waveguide hollow resonators, resonator methods such as open-type resonators using Fabry Perot resonators, etc. Be done.

Further, the Fabry-Perot method using an open interferometer, the method of obtaining the high frequency relative permittivity and the dielectric loss tangent by the cavity resonator perturbation method, the three-terminal measurement method by a mutual induction bridge circuit, and the like can be mentioned. Of these, the Fabry-Perot method, which has excellent high resolution, is the most suitable.

When producing such a resin film 1 for a high-frequency circuit substrate, a pellet molding material 11 containing at least 100 parts by mass of a polyarylene ether ketone resin and 3 parts by mass or more and 30 parts by mass or less of a fluorine-containing copolymer is used. , A known manufacturing method such as a melt extrusion molding method, a calendar molding, or a casting molding method can be adopted. Among these manufacturing methods, the melt extrusion molding method using the T-die 12 is continuously used from the viewpoints of improving the thickness accuracy, productivity, handleability, and simplification of the equipment of the resin film 1 for the high frequency circuit board. Extrusion molding is preferred.

Here, the melt extrusion molding method is a pellet molding material 11 in which a polyarylene ether ketone resin and a fluorine-containing copolymer are melt-kneaded at a temperature equal to or higher than the melt temperature using a mixer, a melt extrusion molding machine 10, or the like. Is a molding method in which the molding material 11 is put into a melt extrusion molding machine 10 and the resin film 1 for a high frequency circuit substrate is continuously extruded from the T die 12. The melt extrusion molding machine 10 can use, for example, a single-screw extrusion molding machine, a twin-screw extrusion molding machine, or the like, and is not particularly limited.

The molding material 11 melt-kneaded and pelletized by a melt extrusion molding machine 10 or the like is continuously extruded onto a band-shaped resin film 1 for a high-frequency circuit board by a T die 12 at the tip of the melt extrusion molding machine 10. The continuous resin film 1 for a high-frequency circuit board is sandwiched between the lower pressure-bonding roll 13 and the plurality of cooling rolls 14 connected to each other to be cooled, and then the tension roll 17 is attached to the take-up pipe 16 of the take-up machine 15. Manufactured by being wound up through.

After the high-frequency circuit board resin film 1 is manufactured, the high-frequency circuit board can be manufactured by forming the metal layer 2 on the high-frequency circuit board resin film 1 and further forming the wiring pattern of the conductive circuit. The metal layer 2 is laminated and formed on the surface of the resin film 1 for a high-frequency circuit board, and a wiring pattern of a conductive circuit is formed later. As the conductor used for the metal layer 2, for example, a metal such as copper, gold, silver, chromium, iron, aluminum, nickel, tin, or an alloy composed of these metals can be used.

The method for forming the metal layer 2 is not particularly limited, but (1) a method for forming the metal layer 2 by heat-sealing the resin film 1 for a high-frequency circuit board and a metal foil, and (2) high frequency. A method of forming a metal layer 2 by adhering a circuit board resin film 1 and a metal foil with an adhesive, (3) depositing a high frequency circuit board resin film 1 and a metal foil to form a metal layer 2. (4) A method of sputtering the metal layer 2 onto the resin film 1 for a high-frequency circuit board.

The method (1) is a method in which a resin film 1 for a high-frequency circuit board and a metal foil are sandwiched between a press molding machine or a roll, and heated and pressed to form a metal layer 2. In the case of this method, as the metal foil, a copper foil such as an electrolytic copper foil or a rolled copper foil is mainly used. The thickness of the metal foil is preferably in the range of 1 μm or more and 100 μm or less, preferably 5 μm or more and 80 μm or less, and more preferably 10 μm or more and 70 μm or less.

The surface of the resin film 1 or metal foil for a high-frequency circuit board can form fine irregularities in order to improve the fusion strength. Further, the surface of the resin film 1 or metal foil for a high frequency circuit substrate is surface-treated by corona irradiation treatment, ultraviolet irradiation treatment, plasma irradiation treatment, frame irradiation treatment, itro irradiation treatment, oxidation treatment, hairline processing, sand mud processing, etc. Is also good. Further, the surface of the resin film 1 for a high frequency circuit substrate or the metal foil can be treated with a silane coupling agent, a silane agent, a titaniumate-based coupling agent, or an aluminate-based coupling agent.

In the method (2), an epoxy resin adhesive, a urethane resin adhesive, an acrylic resin adhesive, and a melamine resin adhesive are used between the resin film 1 for a high frequency circuit board and the metal foil to be the metal layer 2. Place an adhesive such as a phenol resin adhesive, a silicone resin adhesive, a polyimide resin adhesive, or a polystyrene resin adhesive, sandwich it between press molding machines or rolls, and then heat and pressurize the metal foil. This is a method of forming on a resin film 1 for a high-frequency circuit board. The thickness of the metal foil is preferably in the range of 1 μm or more and 100 μm or less, preferably 5 μm or more and 80 μm or less, and more preferably 10 μm or more and 70 μm or less.

Similar to the above, the surface of the resin film 1 or metal foil for a high-frequency circuit board can be formed with fine irregularities from the viewpoint of improving the adhesive strength. In addition, the surface of the resin film 1 or metal foil for a high-frequency circuit substrate is surface-treated by corona irradiation treatment, ultraviolet irradiation treatment, plasma irradiation treatment, frame irradiation treatment, itro irradiation treatment, oxidation treatment, hairline processing, sand mud processing, etc. It doesn't matter. Further, the surface of the resin film 1 for a high frequency circuit substrate or the metal foil may be treated with a silane coupling agent, a silane agent, a titaniumate-based coupling agent, or an aluminate-based coupling agent in the same manner as described above.

In the case of the methods (3) and (4), the metal layer 2 can be laminated and formed by using a dedicated vapor deposition apparatus or sputtering apparatus. Among these methods (3) and (4), if the vapor deposition method of (3) is adopted, a high-frequency circuit board for a fifth-generation mobile communication system can be easily obtained. Further, if the sputtering method (4) is adopted, various metals can be used as the metal layer 2, and high adhesion strength can be obtained.

A required number of wiring patterns for the metal layer 2 can be formed by an etching method, a plating method, a printing method, or the like. As a method for forming this wiring pattern, it is possible to use a sulfuric acid-hydrogen peroxide system, an etching agent for iron chloride, etc., which minimizes the occurrence of undercut and wiring thinning and enables good wiring formation. By forming such a wiring pattern having a predetermined shape, it is possible to manufacture a high-frequency circuit board having excellent low dielectric properties and capable of suppressing signal loss.

According to the above, since the resin film 1 for a high-frequency circuit board is formed by blending a fluorine-containing copolymer that contributes to a dielectric property to a polyarylene ether ketone resin having excellent mechanical properties and thermal properties, it is used for a high-frequency circuit board. The relative permittivity of the resin film 1 in the frequency range of 800 MHz or more and 100 GHz or less is 3.3 or less, and the dielectric loss tangent is 0.006 or less, so that the values of the relative permittivity and the dielectric loss tangent can be made lower than before.

Therefore, it is possible to obtain a high-frequency circuit board capable of transmitting and receiving a large-capacity high-frequency signal at high speed. The use of this high-frequency circuit board can greatly contribute to the realization of a fifth-generation mobile communication board. Further, since the fluorine-containing copolymer has excellent adhesiveness due to the introduction of functional groups in addition to the dielectric properties, the metal layer 2 is easily laminated on the resin film 1 for the high frequency circuit board when manufacturing the high frequency circuit board. It is possible to prevent the metal layer 2 from adhering or peeling or falling off. Further, since the fluorine-containing copolymer is also excellent in slidability, winding and the like at the time of manufacturing the resin film 1 for a high-frequency circuit board becomes extremely easy.

Further, if a polyetheretherketone resin film having a crystallinity of 15% or more, which is excellent in heat resistance, is used for the resin film 1 for a high frequency circuit board, excellent solder heat resistance characteristics can be obtained. Further, if a polyetheretherketone resin film having excellent heat dissipation characteristics is used for the resin film 1 for a high frequency circuit board, the loss can be reduced and the resin film 1 for a high frequency circuit board can be used for a long period of time, so that the high frequency band can be utilized. Realization of high-speed communication is very easy. Further, if an adhesive polyetheretherketone resin film is used instead of the polyimide resin film, the high frequency circuit board can be easily multilayered.

Next, FIG. 3 shows a second embodiment of the present invention. In this case, the metal layers 2 are laminated on both the front and back surfaces of the resin film 1 for a high-frequency circuit board to move the fifth generation. A high frequency circuit board for a communication system is formed. Since the other parts are the same as those in the above embodiment, the description thereof will be omitted.
It is clear that the same effects as those of the above-described embodiment can be expected in this embodiment as well, and that the configuration of the high-frequency circuit board can be diversified.

In the above embodiment, an adhesive fluorine-containing co-weight obtained by introducing a functional group into a semi-crystalline perfluoroalkoxy alkane (tetrafluoroethylene / perfluoroalkoxy ethylene copolymer resin: PFA) capable of thermal melt molding. A non-adhesive perfluoroalkoxy alkane that has shown coalescence but does not introduce a functional group may also be used. This fluorine-containing copolymer can be produced, but a commercially available product can also be used. Examples of commercially available products include AP-210 manufactured by Daikin Industries, Ltd. Further, in the above embodiment, the high frequency circuit board for the fifth generation mobile communication system is shown, but the present invention is not limited to this, and the high frequency circuit board is used as an automobile collision prevention millimeter wave radar device and an advanced driver assistance system. (ADAS), artificial intelligence (AI), etc. may be used.

Hereinafter, examples of the resin film for a high-frequency circuit board and the method for manufacturing the same according to the present invention will be described together with comparative examples.
[Example 1]
First, a polyarylene ether ketone resin and a fluorine-containing copolymer were melt-kneaded at a temperature higher than the melting temperature of 340 ° C. using a melt extrusion molding machine or the like to prepare a pellet molding material. As the polyarylene ether ketone resin, 100 parts by mass of a polyetheretherketone resin of KT-851 NL SP [manufactured by Solvay Specialty Polymers: product name Ketaspire polyetheretherketone series] was used. As the fluorine-containing copolymer, 5 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was used.

After preparing the molding material, the molding material is put into a melt extrusion molding machine consisting of a single-screw extrusion molding machine having a diameter of 40 mm, and a resin film for a high-frequency circuit board is continuously extruded from a T-die having a width of 900 mm at the tip thereof. The continuous resin film for a high frequency circuit board was sandwiched between a crimping roll below and a cooling roll articulated to cool the resin film, and a resin film for a high frequency circuit board having a thickness of 25 μm was produced. Here, the temperature of the melt extrusion molding machine having a diameter of 40 mm was 380 ° C. to 420 ° C., and the temperature of the T die was 400 ° C. The cooling roll was a metal roll at 210 ° C.

Once a resin film for a high-frequency circuit board was obtained, the mechanical properties, dielectric properties, and moldability of this resin film for a high-frequency circuit board were evaluated, and the results are shown in Table 1. Mechanical properties are evaluated by maximum tensile strength, elongation at tensile break, and tensile elastic modulus, and dielectric properties are evaluated by relative permittivity and dielectric loss tangent.

-Mechanical properties of the resin film for high-frequency circuit boards The mechanical properties of the resin film for high-frequency circuit boards were evaluated by the maximum tensile strength at 23 ° C., elongation at tensile break, and tensile elastic modulus. The mechanical properties were measured in the extrusion direction and the width direction (direction perpendicular to the extrusion direction) of the resin film for a high-frequency circuit board. The measurement was carried out in accordance with JIS K7127 under the conditions of a tensile speed of 50 mm / min and a temperature of 23 ° C.

Dielectric characteristics of resin film for high-frequency circuit boards [Frequency: 1 GHz, 10 GHz]
The dielectric property of the resin film for a high-frequency circuit board at a frequency of 1 GHz was measured by a cavity resonator perturbation method using a network analyzer [Network analyzer MS46122B manufactured by Anritsu Co., Ltd.]. For the measurement of the dielectric property at 1 GHz, the cavity resonator is the cavity resonator 1 GHz [Keycom model; TMR-1A], and for the measurement of the dielectric property at 10 GHz, the cavity resonator is the cavity resonator 10 GHz [Keycom model; It was carried out in accordance with ASTMD2520 except that it was changed to TMR-10A]. The measurement of the dielectric property was carried out in an environment of temperature: 23 ° C. ± 1 ° C. and humidity of 50% RH ± 5% RH.

Dielectric characteristics of resin film for high-frequency circuit boards [Frequency: around 28 GHz, around 76.5 GHz]
The frequency of the resin film for a high-frequency circuit board: around 28 GHz and around 76.5 GHz was measured by the Fabry-Perot method, which is a kind of open resonator method, using a vector network analyzer. The resonator is an open type resonator [manufactured by Keycom: Fabry-Perot resonator Model No. DPS03] was used.

In the measurement, a resin film for a high-frequency circuit board was placed on the sample table of the open resonator jig, and the measurement was performed by the Fabry-Perot method, which is a kind of open resonator method, using a vector network analyzer. Specifically, the relative permittivity and the dielectric loss tangent are obtained by a resonance method that utilizes the difference in resonance frequency between the state where the resin film for high-frequency circuit board is not placed on the sample table and the state where the resin film for high-frequency circuit board is placed. And was measured.

The measurement of the dielectric property, specifically, the dielectric property near 28 GHz and 76.5 GHz was measured in an environment of temperature: 24 ° C. and humidity of 45%. As a predetermined measuring device, a vector network analyzer E8631A [manufactured by Agilent Technologies: product name] was used near 28 GHz. At around 76.5 GHz, a vector network analyzer N5227A [manufactured by Agilent Technologies: product name] was used.

-Formability of resin film for high-frequency circuit boards The front and back sides of the manufactured resin film for high-frequency circuit boards were visually observed and evaluated as XX.

[Example 2]
Although basically the same as in Example 1, 10 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was used as the fluorine-containing copolymer. After preparing the molding material, the molding material is put into a melt extrusion molding machine consisting of a single-screw extrusion molding machine having a diameter of 40 mm, and a resin film for a high-frequency circuit board is continuously extruded from a T-die having a width of 900 mm at the tip thereof. The continuous resin film for a high-frequency circuit board was sandwiched between a crimping roll below and a cooling roll connected to the lower surface to cool the resin film, to produce a resin film for a high-frequency circuit board having a thickness of 50 μm.

Once a resin film for a high-frequency circuit board was obtained, the mechanical properties, dielectric properties, and moldability of this resin film for a high-frequency circuit board were evaluated, and the results are shown in Table 1.

[Example 3]
Although basically the same as in Example 1, 10 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was used as the fluorine-containing copolymer. After preparing the molding material, the molding material is put into a melt extrusion molding machine consisting of a single-screw extrusion molding machine having a diameter of 40 mm, and a resin film for a high-frequency circuit board is continuously extruded from a T-die having a width of 900 mm at the tip thereof. The continuous resin film for a high frequency circuit board was sandwiched between a crimping roll below and a cooling roll articulated to cool the resin film, and a resin film for a high frequency circuit board having a thickness of 75 μm was produced.

Once a resin film for a high-frequency circuit board was obtained, the mechanical properties, dielectric properties, and moldability of this resin film for a high-frequency circuit board were evaluated, and the results are shown in Table 1.

[Example 4]
Although basically the same as in Example 1, 20 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was used as the fluorine-containing copolymer. After preparing the molding material, the molding material is put into a melt extrusion molding machine consisting of a single-screw extrusion molding machine having a diameter of 40 mm, and a resin film for a high-frequency circuit board is continuously extruded from a T-die having a width of 900 mm at the tip thereof. The continuous resin film for a high-frequency circuit board was sandwiched between a crimping roll below and a cooling roll connected to the lower surface to cool the resin film, to produce a resin film for a high-frequency circuit board having a thickness of 50 μm.

Once a resin film for a high-frequency circuit board was obtained, the mechanical properties, dielectric properties, and moldability of this resin film for a high-frequency circuit board were evaluated, and the results are shown in Table 1.

[Example 5]
Basically the same as in Example 1, but the fluorine-containing copolymer was changed to 20 parts by mass of pelletized adhesive perfluoroalkoxyalkane [AGC: product name EA-2000], and the thickness was 75 μm. Manufactured a resin film for high-frequency circuit boards. After producing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are shown in Table 1.

[Example 6]
Basically the same as in Example 1, the polyetheretherketone resin was changed to 100 parts by mass of a polyetheretherketone resin of 381G [manufactured by Victrex: product name Victorex Granules series]. Further, as the fluorine-containing copolymer, 10 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was used.

After preparing the molding material, the molding material is put into a melt extrusion molding machine, a resin film for a high frequency circuit board is continuously extruded from a T die at the tip thereof, and the continuous resin film for a high frequency circuit board is pushed downward. A resin film for a high-frequency circuit board having a thickness of 50 μm was produced by sandwiching it between a crimping roll and a cooling roll articulated in the above.
After manufacturing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are summarized in Table 2.

[Example 7]
Although basically the same as in Example 6, 20 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was used as the fluorine-containing copolymer. After preparing the molding material, the molding material is put into a melt extrusion molding machine, a resin film for a high frequency circuit board is continuously extruded from a T die at the tip thereof, and the continuous resin film for a high frequency circuit board is pushed downward. A resin film for a high-frequency circuit board having a thickness of 50 μm was produced by sandwiching it between a crimping roll and a cooling roll articulated in the above.

After manufacturing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are summarized in Table 2.

[Example 8]
Although basically the same as in Example 6, 20 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was used as the fluorine-containing copolymer. After preparing the molding material, the molding material is put into a melt extrusion molding machine, a resin film for a high frequency circuit board is continuously extruded from a T die at the tip thereof, and the continuous resin film for a high frequency circuit board is pushed downward. A resin film for a high-frequency circuit board having a thickness of 100 μm was produced by sandwiching it between a crimping roll and a cooling roll articulated in the above.

After manufacturing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are summarized in Table 2.

[Example 9]
Basically the same as in Example 1, but as a polyarylene ether ketone resin, 100 parts by mass of polyetheretherketone resin of KT-851 NL SP [manufactured by Solvay Specialty Polymers: product name Ketaspire polyetheretherketone series] is used. used. Further, the fluorine-containing copolymer was changed to 10 parts by mass of pelletized perfluoroalkoxyalkane [manufactured by Daikin Corporation: product name AP-210].

After preparing the molding material, the molding material is put into a melt extrusion molding machine, a resin film for a high frequency circuit board is continuously extruded from a T die at the tip thereof, and the continuous resin film for a high frequency circuit board is pushed downward. A resin film for a high-frequency circuit board having a thickness of 50 μm was produced by sandwiching it between a crimping roll and a cooling roll articulated in the above.
After manufacturing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are shown in Table 2.

[Example 10]
Basically the same as in Example 1, the polyetheretherketone resin was changed to 100 parts by mass of a polyetheretherketone resin of 381G [manufactured by Victrex: product name Victorex Granules series]. Further, the fluorine-containing copolymer was changed to 10 parts by mass of pelletized perfluoroalkoxyalkane [manufactured by Daikin Corporation: product name AP-210].

After preparing the molding material, the molding material is put into a melt extrusion molding machine, a resin film for a high frequency circuit board is continuously extruded from a T die at the tip thereof, and the continuous resin film for a high frequency circuit board is pushed downward. A resin film for a high-frequency circuit board having a thickness of 50 μm was produced by sandwiching it between a crimping roll and a cooling roll articulated in the above.

After manufacturing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are shown in Table 2.

[Comparative Example 1]
Basically the same as in Example 1, but the molding material is only 100 parts by mass of the polyetheretherketone resin of KT-851 NL SP [manufactured by Solvay Specialty Polymers: product name Ketaspire polyetheretherketone series], including The fluoropolymer was omitted.

After preparing the molding material, the molding material is put into a melt extrusion molding machine consisting of a single-screw extrusion molding machine having a diameter of 40 mm, and a resin film for a high-frequency circuit board is continuously extruded from a T-die having a width of 900 mm at the tip thereof. The continuous resin film for a high frequency circuit board was sandwiched between a crimping roll below and a cooling roll articulated to cool the resin film, and a resin film for a high frequency circuit board having a thickness of 25 μm was produced.
Once a resin film for a high-frequency circuit board was obtained, the mechanical properties, dielectric properties, and moldability of the resin film for a high-frequency circuit board were evaluated, and the results are shown in Table 3.

[Comparative Example 2]
It was basically the same as in Comparative Example 1, but was manufactured by changing the resin film for a high-frequency circuit board to a thickness of 50 μm.
After manufacturing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are shown in Table 3.

[Comparative Example 3]
It is basically the same as Comparative Example 1, but the molding material is only 100 parts by mass of a polyetheretherketone resin of 381G [manufactured by Victrex: product name Victorex Granules series], and the fluorine-containing copolymer is omitted.

After preparing the molding material, the molding material is put into a melt extrusion molding machine, a resin film for a high frequency circuit board is continuously extruded from a T die at the tip thereof, and the continuous resin film for a high frequency circuit board is pushed downward. A resin film for a high-frequency circuit board having a thickness of 50 μm was produced by sandwiching it between a crimping roll and a cooling roll articulated in the above.
After manufacturing the resin film for high-frequency circuit boards, the mechanical properties, dielectric properties, and moldability of the resin film for high-frequency circuit boards were evaluated, and the results are summarized in Table 3.

[Comparative Example 4]
Basically the same as in Example 1, but as a polyarylene ether ketone resin, 100 parts by mass of polyetheretherketone resin of KT-851 NL SP [manufactured by Solvay Specialty Polymers: product name Ketaspire polyetheretherketone series] is used. Selected. Further, as the fluorine-containing copolymer, 40 parts by mass of pelletized adhesive perfluoroalkoxyalkane [manufactured by AGC: product name EA-2000] was selected.

After preparing the molding material, the molding material is put into a melt extrusion molding machine, a resin film for a high frequency circuit board is continuously extruded from a T die at the tip thereof, and the continuous resin film for a high frequency circuit board is pushed downward. A resin film for a high-frequency circuit board having a thickness of 100 μm was produced by sandwiching it between a crimping roll and a cooling roll articulated in the above.
Once a resin film for a high-frequency circuit board was obtained, the mechanical properties, dielectric properties, and moldability of this resin film for a high-frequency circuit board were evaluated, and the results are summarized in Table 1.

[Rating]
The resin film for the high-frequency circuit substrate of each embodiment was formed by blending 100 parts by mass of the polyarylene ether ketone resin with 3 parts by mass or more and 30 parts by mass or less of the fluorine-containing copolymer, and thus the value of the relative permittivity. Was 3.3 or less, and the dielectric loss tangent was also a low value of 0.006 or less. In terms of moldability, no deformation or wrinkles were observed in the resin film for high-frequency circuit boards.

On the other hand, in the resin film for the high frequency circuit board of each comparative example, since the fluorine-containing copolymer was omitted or excessively blended, the value of the relative permittivity became relatively high, and a large-capacity high frequency signal was produced. It turned out that it is not suitable as a material for a high-frequency circuit board capable of transmitting and receiving at high speed. Further, in the case of the resin film for high frequency circuit board of Comparative Example 4, although the dielectric property was excellent, a big problem occurred in moldability, and it was confirmed that the resin film for high frequency circuit board was deformed and wrinkled.

From the above results, a resin film for a high-frequency circuit board in which 3 parts by mass or more and 30 parts by mass or less of a fluorine-containing copolymer is blended with 100 parts by mass of a polyarylene ether ketone resin has excellent dielectric properties and moldability, and is in the MHz band. It was found that it is most suitable for high frequency circuit boards used in the high frequency band of the GHz band.

The resin film for a high-frequency circuit board and a method for manufacturing the same according to the present invention, and the high-frequency circuit board are used in fields such as information communication and automobile equipment.

1 Resin film for high-frequency circuit board 2 Metal layer 10 Melt extrusion molding machine 11 Molding material 12 T die 13 Crimping roll 14 Cooling roll 15 Winding machine

Claims (7)

It contains a polyarylene ether ketone resin and a fluorine-containing copolymer, and the compounding ratio thereof is 3 parts by mass or more and 30 parts by mass or less of the fluorine-containing copolymer with respect to 100 parts by mass of the polyarylene ether ketone resin. A resin film for a high-frequency circuit substrate, characterized in that the relative permittivity is 3.3 or less and the dielectric loss tangent is 0.006 or less in a frequency range of 800 MHz or more and 100 GHz or less. The resin film for a high-frequency circuit substrate according to claim 1, wherein the polyarylene ether ketone resin is at least one of a polyetheretherketone resin and a polyetherketone resin. The resin film for a high-frequency circuit board according to claim 1 or 2, wherein the fluorine-containing copolymer is a perfluoroalkoxyalkane. The fluorine-containing copolymer is a functional group of an ester group, a carbonate group, a hydroxyl group, an epoxy group, a carboxyl group, a carbonyl dioxide group, a carbonyl fluoride group, an acid anhydride residue, a carbonyl group, and an isocyanate group. The resin film for a high-frequency circuit substrate according to claim 1, 2 or 3, which has at least one type. The resin film for a high-frequency circuit board according to any one of claims 1 to 4, wherein the thickness is 3 μm or more and 200 μm or less. The method for producing a resin film for a high-frequency circuit board according to any one of claims 1 to 5.
A molding material is prepared by melt-kneading at least 100 parts by mass of a polyarylene ether ketone resin and 3 parts by mass or more and 30 parts by mass or less of a fluorine-containing copolymer, and this molding material is extruded from a T-die to be a resin for a high-frequency circuit board. A method for producing a resin film for a high-frequency circuit board, which comprises molding a film and bringing the resin film for a high-frequency circuit board into contact with a cooling roll to cool the film. A high-frequency circuit board characterized in that a metal layer is laminated on at least one of both sides of the resin film for a high-frequency circuit board according to any one of claims 1 to 5.

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