TW202212469A - Resin film, method for producing same, printed wiring board, coverlay, and multilayer body - Google Patents

Abstract

The present invention provides: a resin film which is produced from a polyarylene ether ketone resin and has improved thermal dimensional stability without deteriorating heat resistance and low dielectric characteristics, while being suppressed in increase of the relative dielectric constant or tan[delta] due to high humidity; a method for producing this resin film; a printed wiring board; a coverlay; and a multilayer body. A resin film 2 which is used for a printed wiring board 1 or the like and contains a polyarylene ether ketone resin, a fluorine-based resin and a synthetic mica, wherein: the total content of the polyarylene ether ketone resin and the fluorine-based resin is set to 100 parts by mass; the content of the synthetic mica is set to a value from 10 parts by mass to 80 parts by mass; the mass ratio of the polyarylene ether ketone resin to the fluorine-based resin, namely (polyarylene ether ketone resin)/(fluorine-based resin) is set to a value from 98/2 to 50/50; and the relative crystallinity of the polyarylene ether ketone resin is set to 80% or higher.

Description

Resin film and method for producing the same, printed wiring board, coverlay, and laminate

The present invention relates to a resin film that can improve dimensional stability under heating or contribute to reduction in water absorption and the like, a method for producing the same, a printed wiring board, a coverlay film, and a laminate.

In the fields of electrical, electronic, telecommunications, precision machinery, etc., although materials with lower dielectric constant and dielectric tangent are being studied, in the field of mobile telecommunications, high-frequency circuits are used to manufacture 5G mobile communication systems (5G). As for the substrate, a material having a lower dielectric constant and a lower dielectric tangent is strongly sought (refer to Patent Documents 1 and 2). In response to this demand, efforts have been made to study materials lower than the dielectric constant and the dielectric tangent, and as a result, the proposal of a poly(arylene ether ketone, PAEK) resin has been attracting attention.

Polyaryletherketone resin is a thermoplastic crystalline resin with excellent electrical insulating properties, mechanical properties, heat resistance, chemical resistance, radiation resistance, hydrolysis resistance, low water absorption, and recyclability. In view of this excellent property, poly(arylene ether ketone resin) is attracting attention from a wide range of fields such as audio, automobile, energy, semiconductor, medical, aerospace and space, in addition to the fields of electrical, electronic, telecommunication, precision machinery, etc. .

If a resin film for, for example, a high-frequency circuit board is produced from this polyaryletherketone resin, the ratio of the resin film in the frequency range of 800 MHz to 100 GHz is 3.5 or less, and the dielectric tangent is 0.007 or less. , excellent low dielectric properties can be obtained. Moreover, even if it floats for 10 second in the solder bath of 288 degreeC, it is also possible to obtain the excellent heat resistance which does not deform|transform. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2017-502595 [Patent Document 2] Japanese Patent Publication No. 6-27002

[The problem to be solved by the invention]

However, the resin film made of poly(arylene ether ketone) resin has excellent low dielectric properties, heat resistance, low water absorption, etc., but its dimensional stability is deteriorated due to heating. The dimensional characteristics of the heated layers are very different, so it becomes a problem for newly generated curled laminates or deformation.

As a method for improving the heating dimensional stability of a resin film made of a polyaryletherketone resin, it is considered that (1) a molding material comprising a polyaryletherketone resin, hexagonal boron nitride and talc is used to form a A method of resin film (refer to Japanese Patent No. 5896822), (2) a method of biaxially stretching a resin film containing polyether ether ketone in an amount of 90% by mass or more (refer to Japanese Patent No. 5847522), and the like.

However, in the case of the method (1), since the uniform dispersibility of the hexagonal boron nitride is deteriorated, the problem that the quality of the mechanical properties and the dielectric properties are not stabilized newly arises. In the case of the method (2), although it is possible to form the metal layer on the resin film, the resin film and the metal layer are bonded with an adhesive, or the metal layer is laminated on the resin film through a seed layer to form However, the thermal fusion of the resin film and the metal layer causes the biaxial stretching to fall off due to the melting of the resin film, which leads to curling or deformation of the laminate after lamination.

On the other hand, although the resin film made of poly(arylene ether ketone) resin is originally low in water absorption, if the water absorption is further reduced, the increase in the specific permittivity or tanδ due to high humidity can be suppressed. It can be expected to prevent deterioration of transmission characteristics.

The present invention has been accomplished in view of the above, and is intended to provide a film that does not degrade low dielectric properties and heat resistance of a film made of a poly(arylene ether ketone) resin, can improve heating dimensional stability, and can suppress high A resin film, a method for producing the same, a printed wiring board, a coverlay film, and a laminate having an increase in specific permittivity or tanδ due to moisture are intended. [means to solve the problem]

As a result of diligent research, the present inventors have completed the present invention by focusing on the combination, use, and the like of a polyarylidene ether ketone resin, a fluorine-based resin, and a synthetic mica.

That is, in the present invention, in order to solve the above-mentioned problems, there is provided a resin film characterized by comprising a polyarylene ether ketone resin, a fluorine-based resin, and a synthetic mica, and a polyarylene ether ketone resin and a fluorine-based resin. The total content of Mica is set to 100 parts by mass, and the content of synthetic mica is set to 10 parts by mass to 80 parts by mass, and the mass ratio of the polyarylene ether ketone resin to the fluorine-based resin is set to the polyaryl ether ketone resin. /Fluorine-based resin=98/2~50/50, and the relative crystallinity of the poly(arylene ether ketone) resin is set to be 80% or more.

Furthermore, the fluorine-based resin is preferably at least any one of perfluoroalkoxyalkane resin, polytetrafluoroethylene resin, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, and ethylene-tetrafluoroethylene copolymer resin. Further, the fluorine-based resin preferably has an ester group, a carbonate group, a hydroxyl group, an epoxy group, a carboxyl group, a carbon dioxide group, a carbofluoride group, an acid anhydride residue, a carbonyl group, an alkoxycarbonyl group, a formyl halogen group, and Among the functional groups of the cyanate group, at least one functional group.

Further, the melting point of the fluorine-based resin is preferably 200°C or higher and 400°C or lower. In addition, the synthetic mica preferably has an average particle diameter of 0.5 μm or more and 50 μm or less. In addition, the aspect ratio of the synthetic mica is preferably 5 or more and 200 or less. In addition, the content of synthetic mica may be 25 parts by mass or more and 60 parts by mass or less. In addition, the mass ratio of the polyarylene ether ketone resin and the fluorine-based resin can be set as polyarylidene ether ketone resin/fluorine-based resin=98/2 to 70/30.

Furthermore, in order to solve the above-mentioned problems, the present invention provides a method for producing a resin film, which is the method for producing a resin film according to any one of claims 1 to 8, characterized by containing at least a poly(arylene ether) Ketone resin, fluorine-based resin, and synthetic mica, and the total content of poly(arylene ether ketone resin and fluorine-based resin) is set to 100 parts by mass by melt-kneading, and the content of synthetic mica is set to 10 parts by mass or more 80 The molding material of less than mass parts, and the molding material is extruded through the die of the extrusion molding machine to form a resin film, and the resin film is contacted with a cooling roller to cool, and the relative crystallinity of the resin film is set as 80 %above.

Moreover, in this invention, in order to solve the said subject, it is a printed wiring board characterized by having the resin film as described in any one of Claims 1-8. Moreover, in this invention, in order to solve the said subject, it is a coverlay film characterized by having the resin film as described in any one of Claims 1-8.

In addition, in order to solve the above-mentioned problems, the present invention is a laminate characterized by comprising the resin film as described in any one of claims 1 to 8, and the resin film is laminated on at least one of both sides of the resin film. The next layer of the face. Furthermore, the present invention, in order to solve the above-mentioned problems, is a laminate characterized by comprising the resin film according to any one of claims 1 to 8, and the resin film is laminated on at least one side of both sides of the resin film. surface metal layer.

Here, although the synthetic mica within the scope of the patent application is classified into non-swelling, swelling, lipophilic, etc., it is preferably non-swelling. In addition, the resin film includes a resin sheet in addition to the resin film, and is transparent, opaque, translucent, unstretched, uniaxially stretched, or biaxially stretched, and there is no particular problem. In addition to printed wiring boards, cover films, and laminates, this resin film can also be used for impregnation, acoustic vibration plates, and temperature and humidity sensors. Furthermore, the adhesive layer of the laminate is not particularly problematic in terms of insulating properties or conductivity, and can be laminated on the opposing metal layer.

According to the present invention, since the relative crystallinity of the poly(arylene ether ketone) resin is more than 80%, the low dielectric properties and heat resistance of the resin film will not be reduced, and the heating dimensional stability can be improved. In addition, by blending the fluorine-based resin, the water absorption rate of the resin film can be reduced, and the increase in the specific permittivity or the dielectric tangent (tan δ) due to high humidity can be suppressed. Furthermore, the reduction of the linear expansion coefficient of the resin film can be expected by blending the synthetic mica. [Inventive effect]

According to the present invention, there is an effect that the heating dimensional stability can be improved without deteriorating the low dielectric properties and heat resistance of the film made of the polyarylene ether ketone resin. In addition, by blending the fluorine-based resin, the increase in the specific permittivity or the dielectric tangent (tan δ) due to high humidity can be suppressed, or the specific permittivity can be lowered.

According to the invention described in claim 2, since it is easy to disperse, and it is difficult to cause poor molding of the resin film, a good resin film can be formed and low water absorption can be imparted. According to the invention of Claim 3, the adhesiveness with the metal of a resin film can be improved. According to the invention recited in claim 4, when the melting point of the fluorine-based resin is 200°C or higher, the generation of gas accompanying the decomposition of the resin during the molding of the resin film can be suppressed, and the molding failure of the resin film can be prevented. In addition, when the melting point of the fluorine-based resin is 400° C. or lower, the unmelted matter of the fluorine-based resin is reduced, and the molding of the resin film is facilitated.

According to the invention set forth in claim 5, since the average particle diameter of the synthetic mica is 0.5 μm or more and 50 μm or less, the synthetic mica can be dispersed slightly uniformly in the poly(arylene ether ketone) resin, and the reduction in the toughness of the resin film can be expected to be prevented. Also, it is possible to prevent the synthetic mica from protruding from the resin film and to make the resin film rough. According to the invention described in claim 6, since the aspect ratio of the synthetic mica is 5 or more and 200 or less, it becomes possible to further reduce the coefficient of linear expansion.

According to the invention described in claim 7, since the content of synthetic mica is 25 parts by mass or more and 60 parts by mass or less, in addition to a reduction in the coefficient of linear expansion, the adhesion to the metal layer can be further improved. According to the invention set forth in claim 8, since the mass ratio of the polyaryletherketone resin to the fluorine-based resin is polyaryletherketone resin/fluorine-based resin=98/2 to 70/30, it can be expected to be comparable to that of copper The adhesion of the metal layer of the foil is improved. In addition, the generation of corrosive gas due to the decomposition of the fluororesin can be suppressed to a minimum, and the corrosion and deterioration of the extruder or T-die of the resin film manufacturing apparatus can also be suppressed.

According to the invention described in claim 9, since the resin film is formed by the melt extrusion molding method, the thickness accuracy, productivity, and operability of the resin film can be improved, and the manufacturing equipment can be simplified.

According to the invention described in claim 10, a printed wiring board for high-frequency circuits capable of transmitting and receiving high-frequency signals of large capacity at high speed can be obtained. In addition, by using the related printed wiring board, it can contribute to the realization of the 5G mobile communication system. According to the invention described in claim 11, it is possible to protect the wiring pattern of the circuit board by the cover film electrically, mechanically, chemically, and thermally.

According to the invention of claim 12, since the adhesive layer is laminated on at least one side of the resin film, the resin film of the present invention and the thermoplastic resin and/or thermosetting resin composition having adhesiveness to the metal layer are obtained. Laminates of composition become possible. According to the invention described in claim 13, since the adhesive layer is laminated on at least one side of the resin film, a laminate composed of a copper-clad laminate, a conductive composite material, or the like can be obtained.

Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1 or FIG. 2, a printed wiring board 1 of the present embodiment includes a thin-ribbon-shaped resin film 2 in a laminated structure, and A high-frequency circuit board for 5G mobile communication system (5G) laminated on the metal layer 3 of the resin film 2, the resin film 2 is made of polyaryletherketone resin containing thermoplastic resin, low water absorption, etc. The molding material 4 of mica excellent in fluorine-based resin, electrical insulating properties, etc. is produced, and as mica with good compatibility with fluorine-based resin, synthetic mica which contributes to dimensional stability is selected.

The resin film 2 is formed into a thin film having a thickness of 2 μm or more and 1000 μm or less by a molding method using a molding material 4 containing a poly(arylene ether ketone) (PAEK) resin. The molding material 4 is prepared by adding 10 parts by mass to 80 parts by mass of non-swellable synthetic mica that contributes to dimensional stability in a total content of 100 parts by mass of the polyarylene ether ketone resin and the fluorine-based resin. In addition to the above-mentioned resin or synthetic mica, calcium carbonate, amorphous silicon, talc, boron nitride, antioxidants, light stabilizers, ultraviolet rays can be optionally added to the molding material 4 within the range that does not impair the characteristics of the present invention. Absorbents, plasticizers, lubricants, flame retardants, antistatic agents, heat resistance enhancers, inorganic compounds, organic compounds, etc.

The polyaryletherketone resin of the molding material 4 is a crystalline resin composed of an arylidene group, an ether group and a carbonyl group, and has a higher melting point Tm than a fluorine-based resin. For example, Japanese Patent No. 5709878 or Japanese Patent The resins described in Gazette No. 5847522, or the document [Asahi Research Center Co., Ltd.: Super Enpla・PEEK (top) developed for advanced applications], etc. The blending mass ratio of the poly(arylene ether ketone) resin and the fluorine-based resin is set at poly(aryl(arylene ether ketone) resin/fluorine-based resin = 98/2~50/50, preferably poly(aryl(arylene ether ketone) resin/ Fluorine resin=98/2~70/30. The polyaryletherketone resin may be used in an amount of not less than 60 parts by mass and not more than 96 parts by mass, preferably not less than 60 parts by mass and not more than 95 parts by mass, from the experimental results.

Specific examples of the polyarylidene ether ketone resin include polyether ether ketone (PEEK) resin having a chemical structure represented by chemical formula (1), polyether ketone (PEK) having a chemical structure represented by chemical formula (2), for example. ) resin, polyetherketoneketone (PEKK) resin with chemical structure represented by chemical formula (3), polyetheretherketoneketone (PEEKK) resin with chemical structure represented by chemical formula (4), or chemical structure with chemical formula (5) The polyetherketone ether ketone ketone (PEKEKK) resin and so on.

Among these polyarylene ether ketone resins, polyether ether ketone resins and polyether ketone ketone resins are preferred from the viewpoints of availability, cost, and formability of the resin film 2 . Specific examples of polyether ether ketone resins include product names made by Victrex: Victrex Powder series, Victrex Granules series, product names made by Daicel-Evonik: VESTAKEEP series, and products made by Solvay Specialty Polymers: KetaSpire PEEK series. In addition, as a specific example of the polyether ketone ketone resin, a product name: KEPSTAN series manufactured by Arkema Co., Ltd. is applied.

The polyarylene ether ketone resin may be used alone or in combination of two or more. Moreover, the polyarylidene ether ketone resin may be a copolymer having two or more chemical structures represented by chemical formulae (1) to (5). The polyarylene ether ketone resin is usually used in a form suitable for molding, such as powder, granule, and pellet form. In addition, although the method for producing the poly(arylene ether ketone) resin is not particularly limited, for example, the literature [Asahi Research Center Co., Ltd.: Super Enpla and PEEK (above) )] recorded in the method of production.

The fluorine-based resin of the molding material 4 is a resin containing fluorine atoms, and is classified into polytetrafluoroethylene (PTFE) resin, perfluoroalkoxyalkane (PFA) resin, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, Ethylene-tetrafluoroethylene copolymer (ETFE) resin, perfluoroethylene-propylene copolymer (FEP) resin, vinylidene fluoride (PVDF) resin, polychlorotrifluoroethylene (PCTFE) resin, ethylene-chlorotrifluoroethylene copolymer (ECTFE) resin.

Among them, perfluoroalkoxyalkane resins, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymers, ethylene-tetrafluoroethylene copolymer resins and polyaryletherketone resins are easily dispersed when kneaded. Better to click. In addition, among these fluorine-based resins, polytetrafluoroethylene has a relatively high melting point, and it is difficult to cause foaming due to decomposition of the fluorine-based resin when it is mixed with the poly(arylene ether ketone resin) to form the resin film 2. It is preferable from the viewpoint of the so-called poor forming, such as film perforation.

The fluorine-based resin has an ester group, a carbonate group, a hydroxyl group, an epoxy group, a carboxyl group, a carbon dioxide group, a carboxyl fluoride group, an acid anhydride residue, a carbonyl group, and an alkoxy group because the adhesion to the metal layer 3 is improved. At least one functional group among the functional groups of a carbonyl group, a formyl halide group and a cyanate group. As a fluorine-type resin which has these functional groups, the product name EA-2000, AH-2000, AH-5000 etc. which are excellent in AGC company's adhesiveness and dispersibility are mentioned, for example. In addition, as types of fluorine-based resins having such functional groups, perfluoroalkoxyalkane resins, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymers, and ethylene-tetrafluoroethylene copolymer resins can be used. It is preferable from the viewpoints of dispersibility during kneading with the poly(arylene ether ketone) resin and adhesion to the metal layer 3 .

The content of the fluorine-based resin is 2 parts by mass or more and 50 parts by mass or less, preferably 2 parts by mass or more and 30 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. This is because when the content of the fluorine-based resin is less than 2 parts by mass, the effect of reducing the specific permittivity and water absorption of the resin film 2 cannot be obtained. Conversely, when the content exceeds 50 parts by mass, it becomes difficult to form the resin film 2 satisfactorily, and the adhesion and dispersibility with the metal layer 3 decreases. Regarding the water absorption rate of the resin film 2, the weight of the test piece before and after the water immersion was measured with an electronic balance according to the JIS K 7209A method, and the change rate of the weight was defined as the water absorption rate.

The water absorption of the fluorine-based resin may be 0.30% or less, preferably 0.28% or less, and more preferably 0.27% or less. This is because if the water absorption rate is 0.30% or less, it can be expected to suppress an increase in the specific permittivity or tanδ in a high-humidity environment. The lower limit of the water absorption rate is not particularly limited.

The melting point Tm of the fluorine-based resin is preferably 200°C or higher and 400°C or lower, more preferably 200°C or higher and 360°C or lower, and even more preferably 220°C or higher and 340°C or lower. This is because when the melting point Tm of the fluorine-based resin is 200° C. or higher, the generation of gas accompanying the decomposition of the resin during the molding of the resin film 2 can be suppressed at least, and the molding failure of the resin film 2 can be prevented. In addition, when the melting point Tm of the fluorine-based resin is 400° C. or lower, the unmelted matter of the fluorine-based resin is reduced, and the molding of the resin film 2 is facilitated. Specific examples of such fluorine-based resins include AGC's product name EA-2000, which is excellent in adhesiveness and dispersibility, AH-2000, AH-5000, and L-173JE, which can expect stable electrical properties.

Furthermore, when the resin material is measured by thermogravimetry (TGA) at a heating rate of 10° C./min, if the molding process is performed at a temperature where the weight reduction rate of the measured sample is less than 5%, the molding of the resin film 2 can be suppressed. bad.

The mica (also referred to as Mica) of the forming material 4 is a plate-like crystal belonging to the mica family of the folic acid mineral, and has a characteristic that the bottom surface is completely cleaved. This mica is classified into two types: natural mica (Muscovite, biotite, phlogopite, etc.) produced in nature, and artificially produced synthetic mica using talc as the main raw material. It is widely used as an industrially excellent electrical insulating material. use.

The natural mica is not suitable for the production of the resin film 2 for high-frequency circuit boards with stable quality because the composition or structure is different depending on the origin, and also contains a large amount of impurities. On the other hand, since synthetic mica is artificially produced mica, and has a constant composition or structure, it has few impurities, and is suitable for the production of high-quality resin films 2 for high-frequency circuit boards that are stable in heating and dimensional stability. In addition, since the hydroxyl group of synthetic mica is substituted with fluorine [F group], it is more excellent in heat resistance and low water absorption than natural mica. Accordingly, the mica used in the present invention is better than natural mica and synthetic mica.

When the mica is synthetic mica, it is possible to easily reduce the coefficient of linear expansion due to its excellent dispersibility, and it is possible to suppress the difference in the partial property values of the molded product. In this regard, when a fluorine-based resin is included, the dispersion of inorganic fillers and other resin materials tends to be difficult, but synthetic mica is sufficient even in kneading of polyaryletherketone resin and fluorine-based resin. tendency to disperse. This is considered to be because the synthetic mica has an F group and interacts with the resin material contained in the fluorine-based resin having an F atom, thereby securing dispersibility.

In addition, when the fluorine-based resin has a functional group, the dispersibility tends to be further improved. This is considered to be because the polarity of the functional group of the fluorine-based resin interacts with the metal species or polar group which the synthetic mica has. In addition, when the dispersibility is improved, it is possible to suppress the molding failure in which the aggregates protrude on the surface of the resin film. Moreover, since the synthetic mica of the inorganic filler which contributes to the reduction of the linear expansion coefficient is dispersed, it contributes to the reduction of the linear expansion coefficient of the resin film 2, and also reduces the difference of the partial characteristic value of the resin film 2 of the molded product. In particular, the partial difference between the dielectric properties and the linear expansion coefficient of the resin film 2 is reduced.

Synthetic mica is classified into non-swelling mica and swellable mica by the difference in behavior with respect to water. Non-swelling mica is a type of synthetic mica that hardly changes in dimensional stability even if it comes into contact with water. On the other hand, the swellable mica is a synthetic mica which absorbs moisture in the air, swells, and causes cleavage. When the swellable mica is used, since the swellable mica contains moisture, there is a possibility that the resin film 2 for high-frequency circuit boards may foam during molding. Therefore, the synthetic mica that can be used in the present invention is preferably a non-swelling mica excellent in dimensional stability and water resistance when heated, and more preferably a synthetic mica heat-treated at 600°C or higher.

The non-swelling synthetic mica is not particularly limited, but the synthetic mica represented by the following general formula is suitably used. General formula:

Here, X is a cation that closes the interlayer with a coordination number of 12, Y is a cation that closes an octahedral seat with a coordination number of 6, and Z is a cation that closes the tetrahedron with a coordination number of 4. [X: Na ⁺ , K ⁺ , Li ⁺ , Rb ⁺ , Ca ²⁺ , Ba ²⁺ and Sr ²⁺ , Y: Mg ²⁺ , Fe ²⁺ , Ni ²⁺ , Mn ² substituted by two or more ions ⁺ , Co ²⁺ , Zn ²⁺ , Ti ²⁺ , Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Li ⁺ , Z: Al ³⁺ , Fe ³⁺ , Si ⁴⁺ , Ge ⁴⁺ , B ³⁺ ].

Examples of the non-swelling synthetic mica include phlogopite (KMg ₃ (AlSi ₃ O ₁₀ )F ₂ ), fluorotetrasilica (KMg _2.5 (Si ₄ O ₁₀ )F ₂ ), and Potassium Teniolite. (KMg ₂ Li(Si ₄ O ₁₀ )F ₂ ). Among these, non-swelling fluorotetrasilica is the most suitable. As a specific example of this synthetic mica, non-swellable fluorotetrasilica mica [product name: Micromica MK series] manufactured by Katakura Coop Agri Co., Ltd., which is high-purity and finely powdered, is excellent in heat resistance. Moreover, as a specific example of a fluorophlogopite, the fluorophlogopite [PDM series] by TOPY Industrial Co., Ltd., etc. are mentioned.

As a method for producing synthetic mica, methods such as (1) a melting method, (2) a solid-phase reaction method, and (3) an intercalation method are exemplified. (1) The melting method is to mix raw materials such as silicon, magnesia, alumina, fluoride, feldspar, koranite, oxides or carbonates of various metals, and melt them at a high temperature of 1300°C or more. The production method of slow cooling and the solid-phase reaction method of (2) use talc as the main raw material, and add alkali fluoride and silicon fluoride to this talc, and then add oxides or carbonates of various metals including transition metals. The production method in which the mixture is mixed and reacted at around 1000° C., and the embedding method in (3) are produced by the embedding method using talc as a main raw material.

The average particle diameter of the synthetic mica is 0.5 μm or more and 50 μm or less, preferably 1 μm or less and 30 μm or less, more preferably 2 μm or more and 20 μm or less, and even more preferably 3 μm or more and 10 μm or less. This is because when the average particle diameter of the synthetic mica is less than 0.5 μm, the synthetic mica particles are easily aggregated and the uniform dispersibility in the poly(arylene ether ketone) resin decreases.

On the other hand, when the average particle diameter of synthetic mica exceeds 50 micrometers, the toughness of the resin film 2 may fall. In addition, when the average particle diameter of the synthetic mica exceeds 50 μm, the synthetic mica protrudes from the surface of the resin film 2 and the surface of the resin film 2 is rough, which interferes with the transmission characteristics.

The aspect ratio of synthetic mica should be 5 or more and 200 or less. Here, the aspect ratio refers to the value obtained by dividing the diameter of the particles by the thickness when the synthetic mica is a scaly powder. The specific aspect ratio of the synthetic mica is 5 or more and 200 or less, preferably 10 or more and 150 or less, more preferably 30 or more and 100 or less, and even more preferably 35 or more and 90 or less.

This is because when the aspect ratio is less than 5, the improvement effect of reducing the heating dimensional stability, and the anisotropy of the mechanical properties in the extrusion direction and the width direction of the resin film 2 and the heating dimensional stability are increased. , for inappropriate reasons. This is because when the aspect ratio exceeds 200, the toughness of the resin film 2 is lowered. The aspect ratio of the synthetic mica can be obtained from the average of the measured values of the length and thickness in the plane direction of the synthetic mica by measurement with SEM (Scanning Electron Microscope).

The synthetic mica is 10 parts by mass or more and 80 parts by mass or less, preferably 15 parts by mass or more and 75 parts by mass or less, more preferably 20 parts by mass or more and 70 parts by mass or less, relative to 100 parts by mass of the poly(arylene ether ketone) resin, Still more preferably, it is added in the range of 25 mass parts or more and 65 mass parts or less from the viewpoint of improvement of adhesiveness. This is because when the amount of synthetic mica added is less than 10 parts by mass, the effect of preparing the resin film 2 for dimensional stability under heating becomes insufficient.

On the other hand, when the amount of synthetic mica added exceeds 80 parts by mass, heat is remarkably generated during the preparation of the molding material 4, and the polyaryletherketone resin may be thermally decomposed. In addition, it is because the toughness of the resin film 2 obtained from the molding material 4 is lost and the resin film 2 becomes significantly brittle, and the resin film 2 may be damaged during molding. In addition, it is because the synthetic mica cannot be sufficiently dispersed in the resin due to the increase in the amount of addition, and the surface of the resin film tends to protrude as a part of the aggregate. In addition, it is because the specific permittivity or the dielectric tangent (tan δ) is increased more than necessary due to the increase in the amount of synthetic mica added. Furthermore, when the amount of synthetic mica added exceeds 65 parts by mass, the strength of the base material of the resin film 2 may be weakened, and the adhesiveness described in the examples may be weakened.

Synthetic mica can be used in the range that does not impair the properties of the resin film 2, for example, a silane coupling agent (vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl) can be used. Oxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyl Oxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryl Aryloxypropyltriethoxysilane, 3-propenyloxypropyltrimethoxysilane, N-2(aminoethyl)-3-aminopropylmethyldimethoxysilane, N- 2(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane -N-(1,3-Dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl - Hydrochloride of 3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-(trimethoxysilylpropyl) Isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.], silane agents [methyltrimethoxysilane, dimethyldimethoxysilane, Phenylsilane, dimethoxydiphenylsilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilylsilane)hexane , trifluoropropylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyltriethoxysilane, phenyltriethoxysilane, n-propyltriethoxysilane , hexyl triethoxy silane, octyl triethoxy silane, hexamethyldisilazane, imidazole silane, etc.], titanate coupling agent [isopropyl triisostearyl titanate, isopropyl Propyl ginseng (dioctyl pyrophosphate) titanate, isopropyl tris (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (di-tridecyl phosphite) ) titanate, tetrakis(2,2-diallyloxy-1-butyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetic acid hydrochloride titanate, bis(dioctyl pyrophosphate) oxyacetic acid titanate, isopropyl trioctyl titanate, isopropyl dimethyl acryl isostearyl titanate, isopropyl dimethyl acrylate Propyl tridodecylbenzenesulfonyl titanate, isopropyl isostearyl diacryloyl titanate, isopropyl tris (dioctyl phosphate) titanate, isopropyl tris Cumyl phenyl titanate, tetraisopropyl bis (dioctyl phosphite) titanate, etc.], aluminate coupling agent [acetoxy alkoxy aluminum diisopropionate, etc.] The various coupling agents of the composition are processed.

Polyaryletherketone resin, fluorine-based resin, and synthetic mica are melt-kneaded for a predetermined time to form the molding material 4 for the resin film 2, but as a method for preparing the molding material 4, (1) Polyaryletherketone resin, fluorine-based resin, and fine powdered synthetic mica are mixed with stirring, and fluorine-based resin and synthetic mica are added to melted polyaryletherketone, and these are melt-kneaded to prepare molding material 4 (2) The polyarylene ether ketone resin, the fluorine-based resin, and the fine powdered synthetic mica are stirred and mixed at room temperature (a temperature between 0°C and 50°C) and then melt-kneaded to prepare a molding material. 4 methods. Although any of the methods (1) and (2) may be used, the method (1) is most suitable from the viewpoint of dispersibility or workability.

When specifically explaining the method of (1), in order to prepare the molding material 4, first, the polyaryletherketone resin is prepared by mixing the polyaryletherketone resin with a mixing roll, a pressure kneader, a Banbury mixer, a single-screw extruder, a multi-screw Extruder (two-screw extruder, three-screw extruder, four-screw extruder, etc.) is melted in a melt-kneading machine, and fluorine-based resin and synthetic mica are added to this poly(aryl ether ketone) resin, The molding material 4 is prepared by melt-kneading and dispersing it.

The temperature at the time of preparation of the melt-kneading machine is not particularly limited as long as it can be melt-kneaded and dispersed without decomposing the polyaryletherketone resin, but it is the melting point of the polyaryletherketone resin or higher. And less than the range of thermal decomposition temperature. Specifically, it may be in the range of 350°C or higher and 420°C or lower, preferably 370°C or higher and 400°C or lower.

This is based on the fact that when the melting point of the polyaryletherketone resin is less than the melting point of the polyaryletherketone resin, the polyaryletherketone resin cannot be melt-extruded and the molding material 4 containing the polyaryletherketone resin cannot be melted. In the case of the thermal decomposition temperature, there is a possibility that the polyarylene ether ketone resin may be violently decomposed. The prepared molding material 4 is usually extruded into a block, strip, sheet, or rod, and then used in a pulverizer or a cutter into a form suitable for molding, such as a block, a granule, or a granule.

Next, when the method of (2) is specifically described, in order to agitate and mix the polyarylene ether ketone resin, the fluorine-based resin, and the synthetic mica to obtain a stirred mixture, a drum mixer, a Henschel mixer, or a V-type mixer can be used. , Knott mixer, ribbon mixer or universal mixer, etc. In this case, the shape of the poly(arylene ether ketone) resin is preferably a powder shape that can disperse the fluorine-based resin or synthetic mica more uniformly. As a method of pulverizing into powder, for example, a shear pulverization method, an impact pulverization method, a collision pulverization method, a freeze pulverization method, a solution pulverization method, etc. are mentioned.

The molding material 4 is prepared by mixing the agitated mixture of poly(aryl ether ketone resin, fluorine-based resin, and synthetic mica) with a mixing roll, a pressure kneader, a Banbury mixer, a single-screw extruder, a multi-screw extruder ( The melt-kneading machine such as twin-screw extruder, triple-screw extruder, quadruple-screw extruder, etc.) is melt-kneaded and dispersed to prepare.

The temperature of the melt-kneader at the time of preparation is not particularly limited as long as it can be melt-kneaded and dispersed without decomposing the polyaryletherketone resin, but it is the melting point of the polyaryletherketone resin. Above and below the range of the thermal decomposition temperature. Specifically, for the same reason as in the case of the method (1), the range may be 350°C or higher and 420°C or lower, preferably 370°C or higher and 400°C or lower. The prepared molding material 4 is usually extruded into blocks, strips, sheets, and rods, and then used in a pulverizer or a cutter into a form suitable for molding, such as blocks, granules, and granules.

The molding material 4 is formed into the resin film 2 by various molding methods such as melt extrusion molding, rolling molding, or casting molding. Among these molding methods, the melt extrusion molding method is most suitable from the viewpoint of improvement of workability and simplification of equipment. In this melt extrusion molding method, as shown in FIG. 2 , the molding material 4 is melt-kneaded by a melt extrusion molding machine 10 such as a uniaxial extrusion molding machine or a biaxial extrusion molding machine, and the molding material 4 is melted and extruded from the melt extrusion molding machine 10. A method of continuously extruding a belt-shaped resin film 2 in the direction of a plurality of cooling rolls 16 and pressing rolls 17 from the T-die 13 .

As shown in FIG. 2 , the melt extrusion molding machine 10 is composed of, for example, a uniaxial extruder or a biaxial extruder, and melts and kneads the input molding material 4 to extrude it in the direction of the T-die 13 . out of the way to function. A raw material input port 11 for the molding material 4 is provided at the rear of the upper portion of the upstream side of the melt extrusion molding machine 10, and this raw material input port 11 is connected to supply helium gas, neon gas, argon gas, and krypton gas as necessary. The inert gas supply pipe 12 of the inert gas such as nitrogen gas, carbon dioxide gas, etc., by the inflow of the inert gas from the inert gas supply pipe 12, the oxidative deterioration of the poly(arylene ether ketone resin) of the molding material 4 is effectively prevented or Oxygen crosslinking.

The temperature of the melt extrusion molding machine 10 is not particularly limited as long as it is possible to form the resin film 2 without decomposing the polyaryletherketone resin, but it is not less than the melting point of the polyaryletherketone resin and What is necessary is just to fall below the range of thermal decomposition temperature. Specifically, it is adjusted to 350°C or higher and 420°C or lower, preferably 370°C or higher and 400°C or lower. This is because when the temperature of the melt extrusion molding machine 10 is lower than the melting point of the polyaryletherketone resin, the polyaryletherketone resin cannot be melted, and the molding of the resin film 2 becomes difficult. On the contrary, the thermal decomposition temperature In the above case, the polyarylene ether ketone resin is strongly decomposed.

The T-die 13 is attached to the front end of the melt extrusion molding machine 10 through the connecting pipe 14, and functions to continuously extrude the belt-shaped resin film 2 downward. The temperature at the time of extrusion of the T-die 13 is in the range not less than the melting point of the polyaryletherketone resin and less than the thermal decomposition temperature. Specifically, it is adjusted to 350°C or higher and 420°C or lower, preferably 370°C or higher and 400°C or lower. This is because when the melting point of the polyaryletherketone resin is less than the melting point, the melt extrusion molding of the molding material 4 containing the polyaryletherketone resin is disturbed. On the contrary, when the thermal decomposition temperature is exceeded, there are Fear of violent decomposition of poly(aryl ether ketone) resin.

A gear pump 15 is preferably installed in the connecting pipe 14 upstream of the T-die 13 . The gear pump 15 transfers the melt-kneaded molding material 4 to the T-die 13 at a constant flow rate with high precision by the melt extrusion molding machine 10 .

The plurality of cooling rolls 16 are composed of, for example, metal rolls whose diameters can be expanded and rotated as compared with the pressing rolls 17. They are supported in a row from the underside of the T-die 13 to the downstream direction by an arrangement shaft, and are held between adjacent extruded rolls. The resin film 2 is held between the pressure rollers 17 and between the adjacent cooling rollers 16 and 16, and the resin film 2 is cooled together with the pressure roller 17, while the thickness is controlled within a predetermined range. .

Each cooling roll 16 is adjusted to be equal to or higher than the [glass transition point + 20° C.] of the polyaryletherketone resin and less than the melting point of the polyaryletherketone resin, preferably the [glass transition point of the polyaryletherketone resin]. Transition point+30°C] or higher than [glass transition point+160°C] of polyaryletherketone resin, more preferably polyarylene ether above [glass transition point+50°C] of polyaryletherketone resin [Glass transition point+140°C] or lower of ketone resin, more preferably [glass transition point+60°C] or higher of polyaryletherketone resin [glass transition point+120°C] of polyaryletherketone resin temperature range, sliding contact with the resin film 2.

In the description of this point, when the temperature of each cooling roll 16 is less than [glass transition point + 20° C.] of the poly(arylene ether ketone) resin, the relative crystallinity of the resin film 2 is less than 80%. There is a problem that good heating dimensional stability or soldering heat resistance cannot be obtained. On the other hand, when the temperature of each cooling roll 16 is equal to or higher than the melting point of the polyarylene ether ketone resin, the resin film 2 may stick to the cooling roll 16 during production of the resin film 2 and may be broken. The temperature adjustment or cooling method of each cooling roll 16 includes a method using a heat medium such as air, water, oil, or the like, an electric heater, or an induction heating.

A plurality of pressing rollers 17 are supported by a pair of rotatable shafts from below the T-die 13 of the melt extrusion molding machine 10 in the downstream direction thereof, and hold a plurality of cooling rollers 16 arranged in a row, and press them on the cooling rollers 16. Connect the resin film 2. The pair of pressing rollers 17 is located downstream of the pressing roller 17 on the downstream side, and a winding machine 18 for the resin film 2 is provided, and between the bobbins 19 of the winding machine 18, at least it can be raised and lowered. A slit blade 20 is arranged on the side of the resin film 2 to form a slit, and between the slit blade 20 and the winding machine 18, a tension is applied to the resin film 2, so that the necessary number of axes can be rotated. It is supported by a tension roller 21 for smooth winding.

In order to improve the adhesion between the resin film 2 and the cooling roller 16, the peripheral surface of each pressure contact roller 17 is coated with at least natural rubber, isoprene rubber, butadiene rubber, norbornene rubber, propylene, if necessary. The rubber layer of nitrile butadiene rubber, nitrile rubber, urethane rubber, polysiloxane rubber, fluorine rubber, etc., and inorganic compounds such as silicon or alumina are selectively added to the rubber layer. Among these, the use of polysiloxane rubber or fluororubber having excellent heat resistance is preferable.

If necessary, a metal elastic roller with a metal surface is used as the pressure contact roller 17 , and when this metal elastic roller is used, the polyarylene ether ketone resin film 2 having an excellent surface smoothness can be formed. As specific examples of the metal elastic roll, a sleeve roll, an air knife roll [manufactured by DYMCO: product name], a UF roll (roll) [manufactured by Hitachi Shipbuilding Co., Ltd.: product name], and the like are suitable.

Such a pressure-bonding roll 17 is the same as the cooling roll 16, and is adjusted to be equal to or higher than the [glass transition point + 20°C] of the polyaryletherketone resin and less than the melting point of the polyaryletherketone resin, preferably a polyaryletherketone resin. [Glass transition point + 30°C] of arylene ether ketone resin or higher than [glass transition point + 160° C] of poly(arylene ether ketone) resin, more preferably [glass transition point + 160°C] of polyarylene ether ketone resin [Glass transition point+140°C] or lower of polyaryletherketone resin above 50°C, more preferably polyaryletherketone resin above [glass transition point+60°C] of polyaryletherketone resin The temperature range of [glass transition point + 120° C.] is in sliding contact with the resin film 2 .

The temperature of the pressing roller 17 is adjusted to the relevant temperature range because the relative crystallization of the resin film 2 is adjusted to 80% or more. That is, when the temperature of the pressure-bonding roller 17 is less than [glass transition point + 20° C.] of the poly(arylene ether ketone) resin film 2, the relative crystallinity of the poly(arylene ether ketone) resin film 2 becomes low. When it is over 80%, there is a problem that good heating dimensional stability or soldering heat resistance cannot be obtained. In addition, when the temperature of the pressure-bonding roll 17 is equal to or higher than the melting point of the polyarylene ether ketone resin, the resin film 2 is attached to the cooling roll 16 during the production of the resin film 2, and there is a possibility of breakage.

The temperature adjustment or cooling method of each pressing roller 17 is the same as that of the cooling roller 16 and is not limited, for example, a method using a heat medium such as air, water, and oil, or an electric heater or dielectric heating, etc. can be mentioned.

As described above, in the case of manufacturing the resin film 2 for high-frequency circuit boards, as shown in FIG. 2 , first, the inertness of the molding material 4 indicated by the arrow is supplied to the raw material inlet 11 of the melt extrusion molding machine 10 . While feeding the gas, the polyaryletherketone resin, fluorine-based resin, and synthetic mica of the molding material 4 are melt-kneaded by the melt extrusion molding machine 10, and the high-temperature resin film 2 is continuously extruded from the T-die 13. in the shape of a ribbon.

At this time, the water content before melt extrusion of the molding material 4 is adjusted to 2000 ppm or less, preferably 1000 ppm or less, more preferably 100 ppm or more and 500 ppm or less. This is because when the water content exceeds 2000 ppm, the polyaryletherketone resin may be foamed immediately after extrusion from the T-die 13 .

When the resin film 2 is extruded, it is wound on the pressure roller 17, a plurality of cooling rollers 16, the pressure roller 17, the tension roller 21, and the bobbin 19 of the winding machine 18 in order, and the high temperature resin film 2 is passed through After the cooling roller 16 is cooled, the resin film 2 can be produced by cutting both sides of the resin film 2 with the slit blades 20 and winding the bobbins 19 of the winding machine 18 in order to produce a resin film for high-frequency circuit boards. 2. When the resin film 2 is manufactured, fine irregularities can be formed on the surface of the resin film 2 within the range that does not lose the effect of the present invention, and the friction coefficient of the surface of the resin film 2 can be reduced.

The thickness of the resin film 2 is not particularly limited as long as it is 2 μm or more and 1000 μm or less, but it is preferably 10 μm or more and 700 μm or less from the viewpoints of sufficiently securing the thickness of the high-frequency circuit board, workability, and thinning. More preferably, it is 20 μm or more and 400 μm or less, and even more preferably 25 μm or more and 125 μm or less.

The resin film 2 has a specific permittivity in the frequency range of 800MHz or more and 100GHz or less, preferably 1GHz or more and 90GHz or less, more preferably 10GHz or more and 85GHz or less, and more preferably 25GHz or more and 80GHz or less. From the viewpoint of the realization of communication, it may be 3.6 or less, preferably 3.3 or less, more preferably 3.1 or less, and even more preferably 3.0 or less. Although the lower limit of this specific permittivity is not particularly limited, it is practically 1.5 or more.

Specifically, the resin film 2 preferably has a specific permittivity of 3.4 or less at a frequency of 1 GHz, a specific permittivity of 3.5 or less at a frequency of 28 GHz or less, and a specific permittivity of 3.6 or less at a frequency of 76.5 GHz. . This is because when the relative permittivity of the resin film 2 exceeds 3.7 in the frequency range of 800 MHz or more and 100 GHz or less, the transmission speed of electrical signals is reduced, which is not suitable for high-speed communication.

The resin film 2 has a dielectric tangent in the frequency range of 800 MHz or more and 100 GHz or less, preferably 1 GHz or more and 90 GHz or less, more preferably 10 GHz or more and 85 GHz or less, and more preferably 25 GHz or more and 80 GHz or less. Therefore, it is 0.007 or less, preferably 0.006 or less, more preferably 0.005 or less, and still more preferably 0.0043 or less. Although the lower limit of the dielectric tangent is not particularly limited, it is practically 0.0001 or more.

Specifically, the dielectric tangent of the resin film 2 may be 0.004 or less at a frequency of 1 GHz, a dielectric tangent of 0.005 or less at a frequency of 28 GHz or less, and a dielectric tangent of 0.007 or less at a frequency of 76.5 GHz or less. These are the reasons why the dielectric tangent in the frequency range of 800MHz or more and 100GHz or less exceeds 0.007, which is not suitable for large-capacity communication because the loss increases and the signal transmission rate decreases.

Although there are no particular restrictions on the measurement methods of these specific permittivity and dielectric tangent, reflection and transmission methods such as coaxial probe method, coaxial S-parameter method, waveguide S-parameter method, and available space S-parameter method can be used. (S-parameter) method, measurement method using stripline (ring) resonator, perturbation method using cavity resonator, measurement method using split post dielectric resonator, using cylindrical type (split cylinder) (Split cylinder) cavity resonator measurement method, measurement method using multi-frequency balanced disc resonator, measurement method using interrupted cylindrical waveguide cavity resonator, using Fabry-Perot resonance Methods such as the resonator method such as the open resonator method of the device.

In addition, the Fabry-Perot method using the open type interferometer, the method of obtaining the specific permittivity and the dielectric tangent of high frequency numbers by the cavity resonator perturbation method, and the mutual inductance bridge can be used. The 3-terminal measurement method of the circuit, etc. Among these, the Fabry-Perot method or the cavity resonator perturbation method, which are excellent in high resolution, are most suitable for selection.

The relative crystallinity of the resin film 2 is 80% or more, preferably 90% or more, more preferably 95% or more, and still more preferably 100%. This is because when the relative crystallinity of the resin film 2 is less than 80%, a problem occurs in the heating dimensional stability of the resin film 2 or the soldering heat resistance. In addition, it is because if the relative crystallinity is 80% or more, it can be expected that the heating dimensional stability can be secured for use as a high-frequency circuit board.

The crystallinity of the resin film 2 can be represented by the relative crystallinity. The relative degree of crystallinity of the resin film 2 was calculated by the following formula from the result of thermal analysis measured at a heating rate of 10° C./min using a differential scanning calorimeter.

ΔHc：再結晶化峰值的熱量(J/g) ΔHm：熔解峰值的熱量(J/g) Relative degree of crystallinity (%)=

ΔHc: Heat of recrystallization peak (J/g) ΔHm: Heat of melting peak (J/g)

The heating dimensional stability of the resin film 2 can be expressed by the coefficient of linear expansion. The linear expansion coefficient is 1 ppm/°C or more and 50 ppm/°C or less, preferably 10 ppm/°C or more and 50 ppm/°C or less, and more preferably 10 ppm/°C or more and 49 ppm/°C or less, more preferably 22 ppm/°C or more and 48 ppm/°C or less. This is because when the coefficient of linear expansion deviates from the range of 1 ppm/°C or more and 50 ppm/°C or less, curling or warping is likely to occur during lamination of the resin film 2 and the metal layer 3, and further, the resin film 2 and the metal layer are likely to be curled. 3 Danger of peeling off.

The mechanical properties of the resin film 2 can be evaluated by the tensile elastic modulus at 23°C. The tensile modulus of elasticity of the resin film 2 at 23°C is preferably 3500N/ ^mm2 or more and 10000N/ ^mm2 or less, preferably 3800N/ ^mm2 or more and 8880N/ ^mm2 or less, more preferably 3900N/ ^mm2 or more and 6300N/mm2 ² or less range. This is because when the tensile elastic modulus is less than 3500 N/mm ² , the rigidity of the resin film 2 is deteriorated, and wrinkles are generated in the resin film 2 during the manufacture of the high-frequency circuit board, which may cause deformation of the resin film 2 . On the contrary, it is the reason that when it exceeds 10000 N/mm ² , it takes a long time to form the resin film 2, and the cost reduction cannot be expected.

The heat resistance of the resin film 2 is desirably evaluated by soldering heat resistance when considering the low cost of manufacturing a high-frequency circuit board. Specifically, the resin film 2 was floated in a solder bath of 288° C. for 10 seconds, and when the occurrence of deformation or wrinkles was observed in the resin film 2 , the heat resistance was evaluated as a problem, and no deformation was observed in the resin film 2 or the occurrence of wrinkles, it was evaluated as no problem in terms of heat resistance.

Next, in the case of manufacturing a high-frequency circuit board, a high-frequency circuit board can be manufactured by forming a metal layer 3 on the manufactured resin film 2, and then forming a wiring pattern of a conductive circuit on the metal layer 3. The metal layer 3 can be formed on both the front and back surfaces, the front surface and the back surface of the resin film 2, and the wiring pattern of the conductive circuit can be formed from the back. As the conductor used in the metal layer 3, generally, for example, metals such as copper, gold, silver, chromium, iron, aluminum, nickel, tin, etc. having low resistance, or alloys of these metals can be cited.

Examples of the method for forming the metal layer 3 include (1) a method of thermally fusing the resin film 2 and a metal film such as copper foil to form the metal layer 3, and (2) a method of forming the metal layer 3 by fusing the resin film 2 with a metal film such as copper foil Next, the method of forming the metal layer 3, (3) forming a seed crystal layer on the resin film 2, and laminating on this crystal layer to form a metal thin film, and using these seed crystal layers and the metal thin film as the metal layer 3 method etc.

The method of (1) is a method of forming the metal layer 3 by sandwiching the resin film 2 and the metal film between a press molding machine or rolls, and heating and pressing them. In this method, the thickness of the metal thin film may be within a 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 40 μm or less.

On the surface of the resin film 2 or the metal film, fine irregularities can be formed by increasing the fusion strength during thermal fusion. Further, the surface of the resin film 2 or the metal film may be subjected to corona irradiation treatment, ultraviolet irradiation treatment, plasma irradiation treatment, frame irradiation treatment, ITRO irradiation treatment, oxidation treatment, hairline processing, sand mat processing, or the like. Surface treatment. In addition, the surface of the resin film 2 or the metal film may be treated with a silane coupling agent, a silane agent, a titanate-based coupling agent, or an aluminate-based coupling agent.

The method of (2) is to arrange epoxy resin adhesive, bismaleimide resin adhesive, phenol resin adhesive, and siloxane modified polyamide between the resin film 2 and the metal film. A method of forming a metal thin film on the resin film 2 by heating and pressurizing an adhesive, such as an imine resin adhesive, after being sandwiched between a press molding machine or between rolls. In this method, the thickness of the metal thin film may be within a 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 40 μm or less. In addition, the thickness of the adhesive may be within a range of 0.3 μm or more and 100 μm or less, preferably 1 μm or more and 50 μm or less, and more preferably 3 μm or more and 30 μm or less.

The surface of the resin film 2 or the metal film can be formed with fine irregularities in the same manner as described above, from the viewpoint of improving the bonding strength. Further, the surface of the resin film 2 or the metal film is subjected to corona irradiation treatment, ultraviolet irradiation treatment, plasma irradiation treatment, frame irradiation treatment, ITRO irradiation treatment, oxidation treatment, hairline processing, sand mat processing, or the like. Surface treatment doesn't matter. In addition, the surface of the resin film 2 or the metal film may be treated with a silane coupling agent, a silane agent, a titanate-based coupling agent, or an aluminate-based coupling agent in the same manner as described above.

The method of (3) is to form a seed crystal layer to be used next on the resin film 2 by sputtering, vapor deposition, or plating, etc., and heat fusion of the metal film on this crystal layer. A method of forming the seed crystal layer and the metal thin film as the metal layer 3 by forming the seed crystal layer and the metal thin film by the vapor deposition method or the plating method. As the seed layer, for example, metals such as copper, gold, silver, chromium, iron, aluminum, nickel, tin, and zinc, or alloys of these metals can be used. The thickness of the seed layer is usually in the range of 0.1 μm or more and 2 μm or less.

When the seed layer is formed on the resin film 2, the anchor layer can be formed for the purpose of improving the bonding strength. Although a metal such as nickel or chromium can be used as the anchor layer, nickel which is most suitable for excellent environmental properties is preferable.

As the metal thin film, for example, metals such as copper, gold, silver, chromium, iron, aluminum, nickel, tin, and zinc, or alloys of these metals can be used. The metal thin film may be a single layer composed of only one type of metal, or may be a multiple layer or multiple layers composed of two or more kinds of metals. The thickness of the metal thin film is not particularly limited, but may be 0.1 μm or more and 50 μm or less, preferably 1 μm or more and 30 μm or less.

The metal layer 3 composed of the seed layer and the metal thin film is 0.2 μm or more and 50 μm or less, preferably 1 μm or more and 30 μm or less, more preferably 5 μm or more and 20 μm or less, and even more preferably 5 μm or more and 10 μm or less. The seed layer and the metal thin film can be the same metal or different metals. In addition, on the surface of the metal thin film, in order to prevent corrosion of the surface, a metal protective layer such as gold or nickel may be formed.

Among these methods of forming the metal layer 3 , the method (1) of resin-thermally fusing the resin film 2 and the metal film is the most suitable. This is because in the case of the method (2), since it is necessary to bond the resin film 2 and the metal film with an adhesive, the dielectric properties of the adhesive are reflected, resulting in an increase in the specific permittivity or dielectric of the high-frequency circuit substrate. Tangent, or because it is necessary to form an adhesive layer, incur the high cost of this part. Moreover, according to the method of (3), the formation process of the metal layer 3 becomes complicated, and the reason for high cost is incurred.

The wiring pattern of the conductive circuit can be formed by necessary methods such as etching method, plating method, or printing method. In this wiring pattern formation method, the occurrence of undercuts and fine wiring is minimized, and the use of sulfuric acid-hydrogen peroxide-based etchants, ferric chloride etchants, etc., which enable good wiring formation, is possible. By forming such a wiring pattern of a predetermined shape, a high-frequency circuit board having excellent low dielectric properties and suppressing signal loss can be produced.

According to the above, since the relative crystallinity of the resin film 2 or the polyarylene ether ketone resin is 80% or more, the heating dimensional stability can be greatly improved. Accordingly, even if the metal layer 3 is laminated, it is assumed that the high-frequency circuit board can be prevented from being curled or deformed. In addition, since the water absorption rate of the resin film 2 can be reduced by blending the fluorine-based resin, the increase in the specific permittivity or tanδ due to high humidity can be suppressed, and by this suppression, the deterioration of the transmission characteristics can be greatly prevented. .

Furthermore, since the resin film 2 is formed by the molding material 4 containing the poly(arylene ether ketone) resin, in addition to obtaining excellent heat resistance, the specific permittivity of the resin film 2 in the frequency range of 800 MHz to 100 GHz can be obtained. It becomes 3.6 or less, and the dielectric tangent becomes 0.007 or less, and the value of a specific permittivity and a dielectric tangent can become lower than before. Accordingly, it becomes possible to obtain a high-frequency circuit board capable of transmitting and receiving high-frequency signals of large capacity at high speed.

In addition, by using high-frequency circuit boards, it is possible to greatly contribute to the realization of 5G mobile communication systems. Furthermore, since the melting temperature of the fluorine-based resin is lower than that of the polyaryletherketone resin, the melting temperature of the molding material 4 can be lowered to be lower than the melting temperature of the polyaryletherketone resin monomer. By this reduction in temperature, when manufacturing a two-layer copper clad laminate (CCL), for example, lamination can be performed at a low temperature.

Furthermore, since the non-swelling synthetic mica is blended with the molding material 4, a reduction in the coefficient of linear expansion can be expected. Accordingly, the heating dimensional stability of the resin film 2 can be improved, and the difference in heating dimensional characteristics with the metal layer 3 made of copper foil can be suppressed. The frequency circuit substrate is curled or deformed.

Next, since FIG. 3 shows the second embodiment of the present invention, in this case, on the front and back sides of the resin film 2, metal films made of copper foil for wiring patterns, etc. are respectively laminated by thermal fusion. , and through the pair of metal thin films, the metal layer 3 is formed. Since other parts are the same as those of the above-described embodiment, the description thereof will be omitted. In this embodiment, the same functions and effects as those of the above-mentioned embodiment can be expected, and since the metal layers 3 are formed on both sides of the resin film 2, it becomes clear that the wiring density of the high-frequency circuit board or the high-frequency circuit board can be increased. multi-layering becomes easier.

Next, since FIG. 4 shows the third embodiment of the present invention, in this case, on the surface of the circuit board 5, the resin film 2 covering the wiring pattern 6 is laminated and bonded through the adhesive layer 7, and the resin film is bonded 2 is performed so as to become the cover film 8 for circuit protection. Since other parts are the same as those of the above-described embodiment, the description thereof will be omitted. In the present embodiment, the same functions and effects as those of the above-described embodiment can be expected, and it is clear that the wiring pattern 6 of the circuit board 5 can be electrically, mechanically, chemically, and thermally protected by the cover film 8 .

Next, since FIG. 5 shows the fourth embodiment of the present invention, in this case, the adhesive layer 9 is laminated on the surface of the resin film 2 to form a flexible two-layer structure laminate 30, and this laminate is The bonding layer 9 of 30 is laminated and bonded to the metal layer 3 made of copper foil or the like, and the metal layer 3 is used for electrical connection with the wiring pattern 6 of the circuit board 5 .

The adhesive layer 9 is laminated by printing or coating of an adhesive composed of an adhesive thermoplastic resin composition or a thermosetting resin composition, but is not particularly limited. In addition, it may be a conductive type in which a conductive polymer or the like is blended. Since other parts are the same as those of the above-described embodiment, the description thereof will be omitted. In this embodiment, the same functions and effects as those of the above-described embodiment can be expected, and the application of the resin film 2 can be expanded. In addition, only by connecting the metal layer 3 to the adhesive layer 9 of the laminate 30 of the two-layer structure, the laminate 30 having the three-layer structure of the metal layer 3 on the surface can be easily obtained.

Furthermore, in the above-described embodiment, one type of synthetic mica is used alone, but two or more types may be used in combination. In addition, the metal layer 3 to be laminated on one resin film 2 is not limited in any way, and the metal layer 3 can be re-laminated on a plurality of resin films 2 of the laminated structure. In addition, the metal layer 3 is laminated on the surface of the resin film 2 by a thermal fusion method, and the metal layer 3 is formed by lamination, but it is not limited and can be formed by a vapor deposition method or a plating method.

In addition, the printed wiring board 1 or the resin film 2 can be used in a collision avoidance millimeter-wave radar device for an automobile, an advanced operation support system (ADAS), artificial intelligence (AI), and the like. Furthermore, by laminating the metal layer 3 made of copper foil or the like on the surface of the resin film 2, a flexible conductive laminate 30 can be formed, and on the surface of the resin film 2, an adhesive layer 9 can be laminated to form Bendable insulating laminate 30 . [Example]

Hereinafter, the Example and the comparative example about the resin film of this invention and its manufacturing method are demonstrated. [Example 1] First, a commercially available polyetheretherketone resin (manufactured by Victrex, product name: Victrex Granules 381G (hereinafter abbreviated as "381G") was prepared as a polyaryletherketone resin in order to manufacture a resin film for high-frequency circuit boards. )], the polyether ether ketone resin was dried with a dehumidifying hot air dryer heated to 160°C for more than 12 hours.

When the polyether ether ketone resin is dried in this way, the polyether ether ketone resin is put into the vicinity of the screw base of the same-direction rotating twin-screw extruder [ϕ42mm, L/D=38, Belstruf Co., Ltd. product name: K660]. The funnel of the first supply port.

In addition, the fluorine-based resin and the non-swelling synthetic mica were forcibly injected from the second supply port of the side feeder in the partition wall of the exhaust port opened by the atmospheric pressure of the rotating twin-screw extruder in the same direction. As the fluorine-based resin, a PFA resin having a functional group, that is, a high melting point type having a melting point of 300° C. [manufactured by AGC Corporation, product name: EA-2000] was selected. In addition, as the non-swelling synthetic mica, commercially available fluorotetrasilica mica having an average particle diameter of 3 μm and an aspect ratio of 35 [manufactured by Katakura Coop Agri, product name: Micromica MK-100DS] was selected.

Put in polyether ether ketone resin, if press into fluorine resin and non-swelling synthetic mica, rotate the two-screw extruder in the same direction. . Discharge per hour: melt and knead under the condition of 20kg/hr, and extrude into strips.

The molten state of the polyether ether ketone resin was observed by visual observation by rotating the exhaust port of the twin-screw extruder in the same direction. The polyetheretherketone resin, the fluorine-based resin, and the synthetic mica were added so as to be 10 parts by mass of the fluorine-based resin and 25 parts by mass of the synthetic mica with respect to 90 parts by mass of the polyetheretherketone resin. If the twin-screw extruder is rotated in the same direction to extrude a strip-shaped extruded product, the air-cooled solidified extruded product is cut into pellets to produce a molding material.

Next, the obtained molding material was put into a uniaxial extruder with a T-die with a width of 900 mm and melt-kneaded, and the melt-kneaded molding material was continuously extruded from the T-die to extrude the high frequency The resin film for the circuit board is extruded into a belt shape. The single-shaft extruder is set as L/D=32, compression ratio: 2.5, screw: full spiral screw type. The temperature of the uniaxial extruder was 380 to 400°C, the temperature of the T-die was 400°C, and the temperature of the connecting pipe and gear pump connecting the uniaxial extruder and the T-die was adjusted to 400°C. When the molding material was charged into the uniaxial extruder, nitrogen gas was supplied at 18 L/min through an inert gas supply pipe.

In this way, if a resin film for high-frequency circuit substrates is formed, the resin film is sequentially wound on a pair of pressure-bonding rollers made of polysiloxane rubber as shown in Figure 2 at 200°C, 230°C, and 250°C. A plurality of metal rolls of cooling rolls, and a 6-inch bobbin of a winding machine located in the downstream of these, and clamped between the crimping rolls and the metal rolls, and the two sides of the continuous resin film are Slit blade cutting, winding in order on a bobbin, to manufacture a resin film with a length of 100m, a width of 650mm, and a thickness of 50μm. A slit blade for cutting both sides of the resin film can be raised and lowered between the pressure roller and the bobbin, and between the bobbin and the slit blade, a tension roller for tensioning the resin film can be rotatably supported by a shaft. .

When a resin film was produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion of the resin film were evaluated and summarized in Table 1. The dielectric properties were evaluated by the specific permittivity and dielectric tangent, the heating dimensional stability was evaluated by the coefficient of linear expansion, and the heat resistance was evaluated by the soldering heat resistance.

･Water absorption of resin film The water absorption rate of the resin film was measured according to the JIS K 7209A method under the conditions of 23° C. water immersion×336h.

･Dielectric properties of resin films [Frequency: around 1GHz] Frequency of the resin film: The dielectric properties in the vicinity of 1 GHz were measured by the cavity resonator perturbation method using a network analyzer [Network analyzer MS46122B manufactured by Anritsu Corporation]. The measurement of the dielectric properties in the vicinity of 1 GHz was performed in accordance with ASTMD2520, except that the cavity resonator was changed to a cavity resonator of 1 GHz [Model manufactured by Keycom Corporation; TMR-IA]. The measurement of dielectric properties was carried out in an environment of temperature: 23°C±1°C and humidity 10%RH±5%RH.

･Dielectric properties of resin films [Frequency: around 28GHz] Frequency of resin films for high-frequency circuit boards: Dielectric properties around 28 GHz were obtained by using a network analyzer [Network analyzer MS46122B manufactured by Anritsu Corporation] by Fabry-Perot (Fabry-Perot), a type of open resonator method. -Pérot) method. As the resonator, an open-type resonator [manufactured by Keycom: Fabry-Perot Resonator Model No. DPS03] was used.

For the measurement, a resin film for a high-frequency circuit board was placed on a sample stage of an open resonator tool, and a vector network analyzer was used to measure by the Fabry-Perot method, which is one of the open resonator methods. Specifically, the specific permittivity and the dielectric tangent are measured by the resonance method using the difference in the number of resonance frequencies between the state where the resin film is not placed on the sample stage and the state where the resin film is placed. The specific frequency used for the measurement of the dielectric properties was 28.29 GHz.

Measurement of Dielectric Properties Specifically, the dielectric properties in the vicinity of 28 GHz were measured by a predetermined measuring apparatus in an environment of temperature: 24° C. and humidity 10%. As a predetermined measurement device, a network analyzer [Network analyzer MS46122B manufactured by Anritsu Corporation] was used in the vicinity of 28 GHz.

･Relative crystallinity of resin film The relative crystallinity of the resin film was measured by weighing about 8 mg of the sample from the resin film, and a differential scanning calorimeter [SII Nano Technologies Co., Ltd. product name: EXSTAR7000 series X-DSC7000] was used to measure the temperature at a temperature increase rate of 10°C/min. The range is measured from 20°C to 380°C. The calorific value (J/g) of the crystal melting peak and the calorific value (J/g) of the recrystallization peak obtained at this time were calculated using the following equations.

於此，ΔHc表示於樹脂薄膜之10℃/分鐘的昇溫條件下之再結晶化峰值的熱量(J/g)，ΔHm表示於樹脂薄膜之10℃/分鐘的昇溫條件下之結晶熔解峰值的熱量(J/g)。 Relative degree of crystallinity (%)=

Here, ΔHc represents the heat value of the recrystallization peak (J/g) under the heating condition of 10°C/min of the resin film, and ΔHm represents the heat quantity of the crystal melting peak under the heating condition of the resin film at 10°C/min. (J/g).

･Tensile elastic modulus of resin film Regarding the tensile modulus of elasticity of the resin film, according to JIS K 7127, under the conditions of a tensile speed of 50 mmmm/min and a measurement environment of 23° C., five test pieces were prepared from the resin film and measured, and the average value was used. The measurement is carried out in the extrusion direction and the width direction of the resin film.

･Coefficient of Linear Expansion of Resin Film The linear expansion coefficient of the resin film is measured with respect to the extrusion direction and the width direction (the direction perpendicular to the extrusion direction) of the resin film. Specifically, when measuring the linear expansion coefficient in the extrusion direction of the resin film, when measuring the linear expansion coefficient in the extrusion direction of 20 mm x width direction 4 mm and the width direction, cut out the extrusion direction of 4 mm x width direction 20 mm. size and measure. When the coefficient of linear expansion is measured, in the tensile mode using a thermomechanical analyzer [manufactured by Hitachi High-Technologies Corporation: SII//SS7100], the ratio of load: 50 mN, heating rate: 5°C/min. From 25°C to 250°C, the temperature is increased at a rate of heating rate: 5°C/min. to measure the temperature change of the dimensions, and the linear expansion coefficient [ppm/°C] is obtained from the gradient in the range from 25°C to 125°C. .

･Soldering heat resistance of resin film Soldering heat resistance of resin film: After the resin film was floated in a solder bath at 288°C for 10 seconds and cooled to room temperature, the presence or absence of deformation or wrinkle of the resin film was visually observed and evaluated for ○x. ○: No deformation or wrinkle was observed in the resin film × : When deformation or wrinkles are observed in the resin film

･Dispersibility of resin film The dispersibility of the resin film is measured by preparing 10m from the formed resin film, and visually inspecting the appearance of the resin film to observe the presence or absence of protruding aggregates. : 547-401] measurement, the thickness of the resin film containing the aggregate was measured, and ○× was evaluated. The term "agglomerate" as used herein refers to what protrudes from the resin film.

○: No agglomerates, or the thickness X of the resin film in the portion where no agglomerates exist relative to the thickness of the resin film containing the agglomerates, less than X±10 μm ×: The thickness X of the resin film in the portion where the aggregates do not exist relative to the thickness of the resin film containing the aggregates is X±10 μm or more

･Adhesion of resin film The adhesiveness of the resin film was measured by the following procedure. First, by preparing a copper foil cut into 320mm × 230mm [Mitsui Metal Mining Co., Ltd. product name TQ-M7-VSP thickness 12μm], and on both sides of the cut 300 × 210mm resin film, the copper foil ( Mud) surface and lamination, and these laminates were sandwiched by a SUS plate with a thickness of 1 mm, and the hot plate was set at 345 ° C with a hot stamping machine, under the conditions of a surface pressure of 4 MPa and 5 minutes for thermocompression bonding and taken out to produce a laminate.

When a laminate is produced, the laminate is cut out as a test body with a width of 25 mm, using JIS Z 0237:2009 (Adhesive Tape and Adhesive Sheet Test Method) as a reference, at a peeling speed of 0.3 mm/min and a peeling angle of 180°, The test body was fixed to the support, and the copper foil was fixed to the drawing jig, and the peel strength when the copper foil was drawn from the test body was measured to measure the adhesion strength (adhesion). Regarding the specific adhesion, it was evaluated according to the following criteria: ◎○△×.

⊚: Adhesion is 9 N/cm or more, and the reliability in the circuit board production step is very high. ○: Adhesion is 7 N/cm or more, and there is no practical problem. △: Adhesion is 5 N/cm or more and less than 7 N/cm, and there is no problem in practical use, but there is a risk that a problem may occur. ×: Adhesion is less than 5 N/cm, and practical problems occur.

[Example 2] Basically, it is the same as Example 1, but the addition amount of the non-swelling synthetic mica is changed to 45 parts by mass. [Example 3] Basically the same as in Example 1, but the non-swelling synthetic mica is a commercially available fluorotetrasilica mica with an average particle diameter of 5 μm and an aspect ratio of 40 [manufactured by Katakura Coop Agri Co., Ltd., product name: Micro mica MK -100] 45 parts by mass.

[Example 4] Basically the same as in Example 1, except that the polyetheretherketone resin, fluorine-based resin, and synthetic mica were adjusted to 95 mass parts of polyetheretherketone resin, 5 mass parts of fluorine-based resin, and 45 mass parts of synthetic mica. change.

[Example 5] Basically the same as in Example 1, except that the polyether ether ketone resin, fluorine-based resin, and synthetic mica were changed to 75 parts by mass of the polyether ether ketone resin, 25 parts by mass of the fluorine-based resin, and 45 parts by mass of the synthetic mica. Add to.

[Example 6] Basically, it was the same as Example 1, except that the polyarylidene ether ketone resin was changed to a commercially available polyether ether ketone resin (manufactured by Victrex, product name: Victrex Granules 450G (hereinafter abbreviated as "450G")]. In addition, the non-swelling synthetic mica was changed to a commercially available fluorotetrasilica mica having an average particle diameter of 12 μm and an aspect ratio of 90 [manufactured by Katakura Coop Agri Co., Ltd., product name: Micromica MK-300].

Micro mica MK-300 is a particle powder passed through a 325 mesh sieve by a well-known particle classification method. Then, the polyether ether ketone resin, the fluorine-based resin, and the synthetic mica were added so as to be 10 parts by mass of the fluorine-based resin and 45 parts by mass of the synthetic mica with respect to 90 parts by mass of the polyether ether ketone resin.

[Example 7] Basically, it is the same as Example 1, but the addition amount of the non-swelling synthetic mica is changed to 65 parts by mass. If a resin film was produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion of the resin film were evaluated and summarized in Table 2.

[Example 8] Basically, it was the same as Example 1, except that the fluorine-based resin was changed to a mid-melting point type having a melting point of 240° C. having a functional group [manufactured by AGC Corporation, product name: AH-2000]. Further, the polyether ether ketone resin, the fluorine-based resin, and the synthetic mica were added so as to be 10 parts by mass of the fluorine-based resin and 45 parts by mass of the synthetic mica with respect to 90 parts by mass of the polyether ether ketone resin. If a resin film was produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion of the resin film were evaluated and summarized in Table 2.

[Example 9] Basically, it is the same as Example 1, but the fluorine-based resin is changed to a high melting point type [manufactured by AGC Corporation, product name: L-173JE] having a melting point of 328°C. This L-173JE is a secondary aggregate of polytetrafluoroethylene (PTFE) resin and has an average particle diameter of 9.3 μm. Further, the polyether ether ketone resin, the fluorine-based resin, and the synthetic mica were added so as to be 10 parts by mass of the fluorine-based resin and 45 parts by mass of the synthetic mica with respect to 90 parts by mass of the polyether ether ketone resin. If a resin film was produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion of the resin film were evaluated and summarized in Table 2.

[Example 10] Basically, it is the same as Example 1, but the fluorine-based resin is changed to a high melting point type [manufactured by AGC Corporation, product name: L-173JE] having a melting point of 328°C. Furthermore, the polyether ether ketone resin, the fluorine-based resin, and the synthetic mica were added so as to be 40 parts by mass of the fluorine-based resin and 35 parts by mass of the synthetic mica relative to 60 parts by mass of the polyether ether ketone resin.

These polyetheretherketone resins, fluorine-based resins, and synthetic mica systems rotate in the same direction as the barrel of the twin-screw extruder. A molding material was prepared by melt-kneading under the condition of /hr. If a resin film was produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion of the resin film were evaluated and summarized in Table 2.

[Example 11] Basically the same as in Example 1, except that the polyether ether ketone resin, fluorine-based resin, and synthetic mica were changed to 40 mass parts of fluorine-based resin and 35 mass parts of synthetic mica relative to 60 mass parts of polyether ether ketone resin. Add to.

These polyetheretherketone resins, fluorine-based resins, and synthetic mica systems rotate in the same direction as the barrel of the twin-screw extruder. A molding material was prepared by melt-kneading under the condition of /hr. If a resin film was produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion of the resin film were evaluated and summarized in Table 2.

[Comparative Example 1] First, a commercially available polyetheretherketone resin (manufactured by Victrex, product name: Victrex Granules 381G (hereinafter referred to as "381G") was prepared as a polyaryletherketone resin in order to manufacture a resin film for high-frequency circuit boards ”)], and the polyetheretherketone resin was dried with a dehumidifying hot air dryer heated to 160°C for more than 12 hours.

When the polyether ether ketone resin is dried in this way, the polyether ether ketone resin is put into the vicinity of the screw base of the same-direction rotating twin-screw extruder [ϕ42mm, L/D=38, Belstruf Co., Ltd. product name: K660]. The funnel of the first supply port.

In addition, only the non-swelling synthetic mica was forcibly injected through the second supply port of the side feeder next to the exhaust port opened by the atmospheric pressure of the rotating twin-screw extruder in the same direction, and the fluorine-based resin was omitted. As the non-swelling synthetic mica, commercially available fluorotetrasilica mica with an average particle diameter of 3 μm [manufactured by Katakura Coop Agri, product name: Micromica MK-100DS] was selected.

If polyetheretherketone resin is put in, and non-swelling synthetic mica is pressed into it, the temperature of the barrel of the twin-screw extruder is rotated in the same direction: 350℃~370℃, the number of revolutions of the screw: 150rpm, each Discharge amount per hour: melt kneading under the condition of 20kg/hr, and extrude into strip.

The molten state of the polyether ether ketone resin was observed by visual observation by rotating the exhaust port of the twin-screw extruder in the same direction. This polyetheretherketone resin and synthetic mica were added so that it might become 45 mass parts of synthetic mica with respect to 100 mass parts of polyetheretherketone resins. If the twin-screw extruder is rotated in the same direction to extrude a strip-shaped extruded product, the air-cooled solidified extruded product is cut into pellets to produce a molding material.

Next, the obtained molding material was put into a uniaxial extruder with a T-die with a width of 900 mm, and melt-kneaded. The resin film for the substrate is extruded into a belt shape. The single-shaft extruder is set as L/D=32, compression ratio: 2.5, screw: full spiral screw type. The temperature of the uniaxial extruder was 380 to 400°C, the temperature of the T-die was 400°C, and the temperature of the connecting pipe and gear pump connecting the uniaxial extruder and the T-die was adjusted to 400°C. When the molding material was charged into the uniaxial extruder, nitrogen gas was supplied at 18 L/min through an inert gas supply pipe.

In this way, if a resin film for high-frequency circuit substrates is formed, the resin film is sequentially wound on a pair of pressure-bonding rollers made of polysiloxane rubber as shown in Figure 2 at 200°C, 230°C, and 250°C. A plurality of metal rolls of cooling rolls, and a 6-inch bobbin of a winding machine located in the downstream of these, and clamped between the crimping rolls and the metal rolls, and the two sides of the continuous resin film are Slit blade cutting, winding in order on a bobbin, to manufacture a resin film with a length of 100m, a width of 650mm, and a thickness of 50μm. A slit blade for cutting both sides of the resin film can be raised and lowered between the pressure roller and the bobbin, and between the bobbin and the slit blade, a tension roller for tensioning the resin film can be rotatably supported by a shaft. .

If a resin film is produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile elasticity, heat resistance, dispersibility, and adhesion of the resin film are the same as in the examples, and are evaluated separately. and recorded in Table 3. The dielectric properties were evaluated by the specific permittivity and dielectric tangent, the heating dimensional stability was evaluated by the coefficient of linear expansion, and the heat resistance was evaluated by the soldering heat resistance.

[Comparative Example 2] Basically the same as in Comparative Example 1, except that the non-swelling synthetic mica was changed to a commercially available fluorotetrasilica mica with an average particle diameter of 5 μm [manufactured by Katakura Coop Agri Co., Ltd., product name: Micromica MK-100] 45 mass share.

[Comparative Example 3] Basically, it is the same as that of Comparative Example 1, but as molding materials, polyetheretherketone resin and fluorine-based resin are used, and non-swelling synthetic mica is omitted. The fluorine-based resin is a high melting point type with a melting point of 300°C [manufactured by AGC Corporation, product name: EA-2000]. Then, the polyether ether ketone resin and the fluorine-based resin were added so as to be 10 parts by mass of the fluorine-based resin with respect to 90 parts by mass of the polyether ether ketone resin.

[Comparative Example 4] Basically, it is the same as in Comparative Example 1, but polyetheretherketone resin, fluorine-based resin, and non-swelling synthetic mica were prepared, and these were used as 10 parts by mass of fluorine-based resin relative to 90 parts by mass of polyetheretherketone resin. and 100 parts by mass of synthetic mica. The fluorine-based resin is a high melting point type with a melting point of 300°C [manufactured by AGC Corporation, product name: EA-2000]. In addition, as the non-swelling synthetic mica, commercially available fluorotetrasilica mica with an average particle diameter of 3 μm (manufactured by Katakura Coop Agri, product name: Micromica MK-100DS) was selected.

[Comparative Example 5] Basically, it is the same as in Comparative Example 4, but the fluorine-based resin and the non-ferrous material are forcibly injected through the second supply port of the side feeder on the side of the gas outlet opened by the atmospheric pressure of the rotating twin-screw extruder in the same direction. Swelling synthetic mica. The non-swelling synthetic mica was changed to commercially available fluorotetrasilica mica with an average particle size of 5 μm [manufactured by Katakura Coop Agri Co., Ltd., product name: Micromica MK-100].

The polyether ether ketone resin, the fluorine-based resin, and the synthetic mica were added so as to be 10 parts by mass of the fluorine-based resin and 45 parts by mass of the synthetic mica with respect to 90 parts by mass of the polyether ether ketone resin. Moreover, the cooling temperature of the several metal rolls of a cooling roll was all changed to 150 degreeC, and the resin film whose relative crystallinity degree was 60% was manufactured.

[Comparative Example 6] Basically the same as in Comparative Example 4, except that the polyether ether ketone resin, the fluorine-based resin, and the synthetic mica were changed to 60 parts by mass of the fluorine-based resin and 30 parts by mass of the synthetic mica relative to 40 parts by mass of the polyether ether ketone resin. Add to. These polyetheretherketone resins, fluorine-based resins, and synthetic mica systems rotate in the same direction as the barrel of the twin-screw extruder. A molding material was prepared by melt-kneading under the condition of /hr. Although a resin film is produced by this molding material, the resin film cannot be formed by opening holes in the resin film.

[Comparative Example 7] Basically, it was the same as that of Comparative Example 6, except that the fluorine-based resin was changed to a high melting point type [manufactured by AGC Corporation, product name: L-173JE] with a melting point of 328°C. This L-173JE is a secondary aggregate of polytetrafluoroethylene (PTFE) resin and has an average particle diameter of 9.3 μm. In addition, the polyether ether ketone resin, the fluorine-based resin, and the synthetic mica were added so as to be 60 parts by mass of the fluorine-based resin and 30 parts by mass of the synthetic mica relative to 40 parts by mass of the polyether ether ketone resin.

[Comparative Example 8] It is basically the same as in Comparative Example 1, but the fluorine-based resin and carbonic acid are forcibly injected from the second supply port of the side feeder on the side of the gas outlet opened by the atmospheric pressure of the rotating twin-screw extruder in the same direction. Calcium, omit synthetic mica. The fluorine-based resin is a high melting point type with a melting point of 300°C [manufactured by AGC Corporation, product name: EA-2000]. In addition, the calcium carbonate was made into WHITONP-10 (manufactured by Toyo Fine Chemical Co., Ltd., product name) with an average particle diameter of 2.5 μm and an aspect ratio of 8 in the market. Then, the polyether ether ketone resin, the fluorine-based resin, and the calcium carbonate were added so as to be 10 parts by mass of the fluorine-based resin and 43 parts by mass of the calcium carbonate relative to 90 parts by mass of the polyether ether ketone resin.

If a resin film is produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile elasticity, heat resistance, dispersibility, and adhesion of the resin film are the same as those in the examples, and are evaluated and evaluated separately. Recorded in Table 4.

[Comparative Example 9] Basically the same as in Comparative Example 8, but forcedly press-fitted from the second supply port of the side feeder next to the exhaust port opened by the atmospheric pressure of the rotating twin-screw extruder in the same direction Fluorine resin and natural mica, omitting synthetic mica. The natural mica (KAl ₂ (AlSi ₃ )O ₁₀ (OH) ₂ ) of muscovite was defined as SJ-005 (manufactured by Yamaguchi Mica Co., Ltd., product name) with an average particle diameter of 4.4 μm and an aspect ratio of 35 in the market. . Further, the polyether ether ketone resin, the fluorine-based resin, and the natural mica were added so as to be 10 parts by mass of the fluorine-based resin and 45 parts by mass of the natural mica relative to 90 parts by mass of the polyether ether ketone resin.

If a resin film is produced, the water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile elasticity, heat resistance, dispersibility, and adhesion of the resin film are the same as those in the examples, and are evaluated and evaluated separately. Recorded in Table 4.

[Evaluate] When used as the resin film of each example, excellent water absorption, dielectric properties, heating dimensional stability, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion of the resin film can be obtained. In the case of the resin films of Examples 7 and 10, although the adhesiveness was slightly lowered, it was in a range that did not cause any practical problems.

In contrast, in the case of the resin films of the comparative examples, problems occurred in water absorption, dielectric properties, dimensional stability under heating, relative crystallinity, tensile modulus, heat resistance, dispersibility, and adhesion. In particular, in the case of the resin film of Comparative Example 3, since the non-swelling synthetic mica was omitted, the value of the coefficient of linear expansion was increased, which caused a serious problem. In addition, in the case of the resin film of Comparative Example 4, although the linear expansion coefficient of the resin film was reduced, among the synthetic mica, the synthetic mica that could not be dispersed in the polyetheretherketone resin or the fluorine-based resin appeared on the surface of the resin film. Aggregates with a thickness of 10 μm or more relative to the lipid film. In addition, the resin film is very easily broken due to the low toughness, and the adhesion to the copper foil is also problematic. In addition, the specific permittivity has become high.

In the case of Comparative Example 6, since the fluororesin exceeds 50 parts by mass and contains 60 parts by mass, if synthetic mica with excellent dispersibility is used as a filler, the heat generation during chain mixing caused by the uniaxial extrusion molding machine is very high, or it may be With the gasification of the fluorine-based resin, the pores of the resin film begin to open, and eventually the resin film cannot be formed. Moreover, in the case of Comparative Example 7, although the film formation of the resin film was possible, since the polytetrafluoroethylene contained more than 50 parts by mass, the dispersibility was lowered and the adhesion was deteriorated. Furthermore, in Comparative Example 9, since not synthetic mica but natural mica was added, the dispersibility was lowered and the linear expansion coefficient of the resin film was deteriorated. [Industrial Availability]

The resin film of the present invention, its manufacturing method, printed wiring board, cover film, and laminate are used in the fields of audio, electricity, electronics, telecommunications, precision machinery, automobiles, energy, semiconductors, medical, aerospace, and the like .

1: Printed wiring board 2: Resin film 3: Metal layer 4: Forming material 5: circuit substrate 6: Wiring pattern 8: cover film 9: Next layer 10: Melt extrusion molding machine (extrusion molding machine) 13: T-die (mold) 16: cooling roll 17: Crimping roller 30: Laminate

1 is an explanatory cross-sectional view schematically showing an embodiment of a resin film and a printed wiring board according to the present invention. [ Fig. 2] Fig. 2 is an overall explanatory view schematically showing an embodiment of the resin film according to the present invention and its manufacturing method. [ Fig. 3] Fig. 3 is an explanatory cross-sectional view schematically showing a second embodiment of the resin film and the printed wiring board according to the present invention. [ Fig. 4] Fig. 4 is an explanatory cross-sectional view schematically showing an embodiment of the coverlay film of the present invention. [ Fig. 5] Fig. 5 is an explanatory cross-sectional view schematically showing an embodiment of the laminate of the present invention.

1: Printed wiring board

2: Resin film

3: Metal layer

Claims (13)

A resin film is characterized by containing a polyaryletherketone resin, a fluorine-based resin and synthetic mica, and the total content of the polyaryletherketone resin and the fluorine-based resin is set at 100 parts by mass, and the synthetic mica is The content is set to 10 parts by mass or more and 80 parts by mass or less, the mass ratio of the polyarylidene ether ketone resin and the fluorine-based resin is set to polyarylidene ether ketone resin/fluorine-based resin=98/2~50/50, and the The relative crystallinity of the polyaryletherketone resin is set to be above 80%. The resin film of claim 1, wherein the fluorine-based resin is a perfluoroalkoxyalkane resin, a polytetrafluoroethylene resin, a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer, and an ethylene-tetrafluoroethylene copolymer resin at least any of them. The resin film of claim 1 or 2, wherein the fluorine-based resin has an ester group, a carbonate group, a hydroxyl group, an epoxy group, a carboxyl group, a carbon dioxide group, a carbonyl fluoride group, an acid anhydride residue, At least one functional group among the functional groups of carbonyl, alkoxycarbonyl, haloformyl and cyanate. The resin film according to claim 1 or 2, wherein the melting point of the fluorine-based resin is 200°C or higher and 400°C or lower. The resin film according to claim 1 or 2, wherein the synthetic mica has an average particle diameter of 0.5 μm or more and 50 μm or less. The resin film according to claim 1 or 2, wherein the aspect ratio of the synthetic mica is 5 or more and 200 or less. The resin film according to claim 1 or 2, wherein the content of synthetic mica is 25 parts by mass or more and 60 parts by mass or less. The resin film according to claim 1 or 2, wherein the mass ratio of the polyaryletherketone resin to the fluorine-based resin is polyaryletherketone resin/fluorine-based resin=98/2~70/30. A method for producing a resin film, which is the method for producing a resin film according to any one of claims 1 to 8, characterized by at least containing poly(arylene ether ketone) resin, fluorine-based resin and synthetic mica, and melt-kneading The total content of the polyarylidene ether ketone resin and the fluorine-based resin is set to 100 parts by mass, and the content of the synthetic mica is set to be 10 parts by mass to 80 parts by mass of the molding material, and the molding material is extruded. The die of the molding machine is extruded to form a resin film, and the resin film is brought into contact with a cooling roll to cool, thereby setting the relative crystallinity of the resin film to 80% or more. A printed wiring board characterized by having the resin film according to any one of claims 1 to 8. A cover film characterized by having the resin film according to any one of claims 1 to 8. A laminate characterized by having the resin film according to any one of claims 1 to 8, and an adhesive layer laminated on at least one side of both sides of the resin film. A laminate characterized by having the resin film according to any one of claims 1 to 8, and a metal layer laminated on at least one side of both sides of the resin film.

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