Resin composition, resin film, metal-clad laminate, circuit board, electronic device, electronic apparatus, and method for producing resin film

Abstract

To provide a resin composition having superior dielectric characteristics and film-forming properties, a resin film, a metal-clad laminate, a circuit board, an electronic device, and an electronic apparatus produced from the resin composition, and a method for producing the resin film.SOLUTION: The resin composition comprises (A) a polyphenylene ether 10, (B) an inorganic filler 11, and (C) a binder resin 12, wherein the amount of (C) the binder resin 12 is 3 pts.mass or more and 100 pts.mass or less based on a total of 100 pts.mass of (A) the polyphenylene ether 10 and (B) the inorganic filler 11.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a resin film, a metal-clad laminate, a circuit board, an electronic device, an electronic equipment, and a method for producing a resin film. [Background technology]

[0002] With the recent increase in the volume of information and communication, information communication in the high frequency band has become more prevalent. This has created a demand for electrical insulating materials with better electrical properties, particularly low dielectric constants and low dielectric loss tangents, to reduce transmission loss in the high frequency band.

[0003] Conventionally, thermosetting resins such as phenolic resin, epoxy resin, and polyimide resin have been used for printed wiring boards. Although these resins have a good balance of various performance characteristics, their dielectric properties in the high frequency range are insufficient. Polyphenylene ether (PPE) has attracted attention as a new material that can solve this problem, and attempts are being made to apply it to copper-clad laminates and other products.

[0004] Patent Document 1 discloses a resin composition containing a modified polyphenylene ether compound terminally modified with a substituent having a carbon-carbon unsaturated double bond and an inorganic filler such as silica. It describes that the modified polyphenylene ether compound has a weight-average molecular weight of 2000 to 2300, and contains a curing agent and an initiator.

[0005] Patent Document 2 discloses a curable resin composition containing polyphenylene ether and inorganic particles. The polyphenylene ether contains a low-molecular-weight polyphenylene ether component having a number-average molecular weight of 1500 to 3100 and a high-molecular-weight polyphenylene ether component having a number-average molecular weight of 19000, and further contains a monomer having two or more vinyl groups in the molecule and a reaction initiator. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2021 / 024924 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-1277 Summary of the Invention [Problem to be solved by the invention]

[0007] The resin compositions described in Patent Documents 1 and 2 use low-molecular-weight polyphenylene ethers of 2000 to 2300 or 1500 to 3100. To improve the heat resistance of a resin film formed from a low-molecular-weight resin composition, the resin composition must be cured with a curing agent or a reaction initiator. However, the use of a curing agent or a reaction initiator increases the dielectric loss tangent of the resin film formed, resulting in deterioration of the dielectric properties.

[0008] In order to improve the heat resistance of polyphenylene ether without curing it, it is necessary to use a high molecular weight polyphenylene ether. However, since high molecular weight polyphenylene ether has poor solvent solubility and cannot be made into a varnish, when a high molecular weight polyphenylene ether is used, film formation becomes difficult and the quality of the film deteriorates.

[0009] The present invention aims to provide a resin composition having excellent dielectric properties and film-forming properties, a resin film, a metal-clad laminate, a circuit board, an electronic device, and an electronic device obtained from the resin composition, and a method for producing a resin film having excellent dielectric properties and film-forming properties. [Means for solving the problem]

[0010] The resin composition according to the present invention contains (A) polyphenylene ether, (B) inorganic filler, and (C) binder resin, and the amount of the (C) binder resin per 100 parts by mass of the total amount of the (A) polyphenylene ether and the (B) inorganic filler is within the range of 3 parts by mass or more and 100 parts by mass or less.

[0011] The resin film according to the present invention contains (A) polyphenylene ether, (B) inorganic filler, and (C) binder resin, and the amount of the (C) binder resin relative to 100 parts by mass of the total amount of the (A) polyphenylene ether and the (B) inorganic filler is within the range of 3 parts by mass or more and 100 parts by mass or less.

[0012] The metal-clad laminate of the present invention comprises an insulating resin layer consisting of a single layer or multiple layers, and a metal layer laminated on one or both sides of the insulating resin layer, and at least one layer of the insulating resin layer is made of the above-mentioned resin film.

[0013] The circuit board of the present invention comprises an insulating resin layer consisting of a single layer or multiple layers, and a conductor circuit layer laminated on one or both sides of the insulating resin layer, and at least one layer of the insulating resin layer is made of the above-mentioned resin film.

[0014] The electronic device of the present invention includes the circuit board described above.

[0015] An electronic device of the present invention includes the electronic device described above.

[0016] The method for producing a resin film of the present invention is a method for producing a resin film containing (A) polyphenylene ether, (B) inorganic filler, and (C) binder resin, and includes a step of mixing the (A) polyphenylene ether and the (B) inorganic filler in a solid state in a solvent.

[0017] The method for producing a resin film of the present invention is a method for producing a resin film containing (A) polyphenylene ether, (B) inorganic filler, and (C) binder resin, and includes a step of heat-treating the (A) polyphenylene ether in a solid state at a temperature equal to or higher than the glass transition temperature of the (A) polyphenylene ether. [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a resin composition that is excellent in dielectric properties and film-forming properties.

[0019] According to the present invention, it is possible to provide a resin film, a metal-clad laminate, a circuit board, an electronic device, and an electronic equipment obtained from the resin composition.

[0020] According to the present invention, a resin film having excellent dielectric properties and film-forming properties can be produced. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic diagram showing the manufacturing process of a resin film and a metal-clad laminate using a resin composition according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0022] Hereinafter, an embodiment of the present invention will be described in detail with reference to the drawings. Similar components are designated by similar reference numerals, and the description thereof will be omitted as appropriate.

[0023] 1. Embodiment (1) Resin composition The resin composition according to this embodiment contains (A) polyphenylene ether, (B) inorganic filler, and (C) binder resin.

[0024] (A) Polyphenylene ether The polyphenylene ether may be an unmodified polyphenylene ether, a modified polyphenylene ether, or a mixture thereof. In the aromatic rings constituting the main chain of the polyphenylene ether, one or more hydrogen atoms bonded to each aromatic ring may be substituted with a substituent such as an alkyl group, an alkenyl group, an alkynyl group, a formyl group, an alkylcarbonyl group, an alkenylcarbonyl group, an alkynylcarbonyl group, an aryl group which may have a substituent, an amino group which may have a substituent, a nitro group, or a carboxyl group. The phenolic hydroxyl group at the terminal of the main chain of the modified polyphenylene ether may be substituted with a substituent such as a benzyl group, an allyl group, a propargyl group, a glycidyl group, a vinylbenzyl group, or a methacryl group. The modified polyphenylene ether may be a polymer alloy with polystyrene, nylon, polypropylene, polyphenylene sulfide, polyphthalamide, or the like. Specific examples of polyphenylene ethers include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), and copolymers of 2,6-dimethylphenol and other phenols.

[0025] The weight-average molecular weight of the polyphenylene ether is preferably 5,000 or more. If the weight-average molecular weight of the polyphenylene ether is less than 5,000, the strength and heat resistance of the resin film made from the resin composition will be insufficient, necessitating the addition of a reaction initiator or curing agent to cure the resin. However, the reaction initiator or curing agent undesirably deteriorates the dielectric properties. If the weight-average molecular weight of the polyphenylene ether is 5,000 or more, the strength and heat resistance of the resin film made from the resin composition can be ensured without impairing the dielectric properties of the resin composition. The weight-average molecular weight of the polyphenylene ether is preferably 100,000 or less, more preferably 50,000 or less. If the weight-average molecular weight of the polyphenylene ether exceeds 100,000, the melt fluidity and processability will decrease, which is undesirable. The weight-average molecular weight of the polyphenylene ether is more preferably 8,000 or more and 19,000 or less, which increases the strength and heat resistance of the resin film made from the resin composition and improves its dielectric properties.

[0026] The polyphenylene ether is preferably thermoplastic. Thermoplastic polyphenylene ether does not require additives such as reaction initiators or curing agents that cause deterioration of dielectric properties, and can improve dielectric properties. In addition, the processability of a resin film made from the resin composition is improved, making it easier to laminate the resin film with other substrates or to drill holes.

[0027] The polyphenylene ether preferably has a relative dielectric constant of 4 or less at 10 GHz, for example, 2.42 to 2.43. The polyphenylene ether (A) preferably has a dielectric loss tangent of 0.005 or less at 10 GHz, more preferably 0.003 or less. When the relative dielectric constant and dielectric loss tangent of the resin composition are within the above ranges, the dielectric properties can be improved.

[0028] The polyphenylene ether preferably has a glass transition temperature of 180°C or higher and 250°C or lower. When heated to a temperature higher than the glass transition temperature, the polyphenylene ether melts and becomes fluid, and can form a resin film made of the resin composition. The glass transition temperature of polyphenylene ether is, for example, 214°C.

[0029] (B) Inorganic filler The inorganic filler is a component that reduces the thermal expansion of a resin film made of a resin composition. By including the inorganic filler, warping of the resin film made of the resin composition can be suppressed and dimensional stability can be improved.

[0030] The inorganic filler preferably has a relative dielectric constant of 6 or less at 10 GHz when measured by a cavity resonator perturbation method in an environment of a temperature of 22°C to 24°C and a relative humidity of 45% to 55% RH, thereby improving the dielectric properties of the resin composition.

[0031] Examples of inorganic fillers that satisfy the above-mentioned relative dielectric constant include silica, boron nitride, aluminum fluoride, and magnesia. The inorganic filler may be surface-treated with a silane coupling agent or the like.

[0032] The shape of the inorganic filler is not particularly limited, but may be spherical, crushed powder, needle-like, short fiber-like, or the like.

[0033] The particle size of the inorganic filler is not particularly limited, but is preferably 0.1 μm or more and 20 μm or less. When the particle size is within the above range, the film-forming properties of the resin film obtained from the resin composition can be improved. More preferably, the particle size is 0.5 μm or more and 15 μm or less, which can further improve the film-forming properties.

[0034] (C) Binder resin The binder resin is a resin that acts as a binder to bind the polyphenylene ether and inorganic filler together in the resin film manufacturing process described below, and can ensure the film formability of the resin film, mitigate thermal shrinkage of the resin film to reduce thermal stress, and suppress cracking and wrinkling of the resin film to improve film quality.

[0035] The binder resin preferably has a dielectric loss tangent of 0.005 or less at 20 GHz when measured with a split post dielectric resonator (SPDR) in an environment at a temperature of 22°C to 24°C and a relative humidity of 45% to 55% RH, thereby improving the dielectric properties of the resin composition.

[0036] Examples of binder resins that satisfy the above-mentioned dielectric loss tangent include resins having structural units containing an aliphatic chain or alicyclic skeleton, such as polyimides, polyamides, maleimides, polyolefins (polyethylene, polypropylene, etc.), polyesters, polyurethanes, polystyrene, polystyrene elastomers, cycloolefin polymers (COP), polymethylpentene (PMP), copolymers of the above polymers, and cycloolefin copolymers (COC). Because the binder resin has a low glass transition temperature and tends to soften at high temperatures, when blended with polyphenylene ether, stress is relieved at the interface, preventing embrittlement of the molded product, and the dielectric loss tangent is easily reduced by the effects of molding.

[0037] The temperature (Td1) at which the binder resin shows a 1% reduction rate in thermogravimetric analysis is preferably equal to or higher than the glass transition temperature of the polyphenylene ether. In the resin film manufacturing process described below, the resin composition may be heated to a temperature equal to or higher than the glass transition temperature of the polyphenylene ether. When the temperature (Td1) at which the binder resin shows a 1% reduction rate in thermogravimetric analysis is equal to or higher than the glass transition temperature of the polyphenylene ether, heat resistance can be improved. The temperature (Td1) at which the binder resin shows a 1% reduction rate in thermogravimetric analysis is also referred to as the thermal decomposition temperature (Td1) of the binder resin.

[0038] (D) Mass ratio of each component In the resin composition of this embodiment, the amount of the (C) binder resin relative to 100 parts by mass of the combined total of (A) polyphenylene ether and (B) inorganic filler is within the range of 3 parts by mass to 100 parts by mass. When the amount of the binder resin is within this range, the film-forming properties of the resin film are improved, thermal shrinkage of the resin film is alleviated, reducing thermal stress, and cracking and wrinkling of the resin film are suppressed, thereby improving film quality. If the amount of the binder resin is less than 3 parts by mass, the effects of ensuring the film-forming properties of the resin film and alleviating thermal shrinkage of the resin film to suppress cracking and wrinkling are not fully achieved. If the amount of the binder resin exceeds 100 parts by mass, the influence of the binder resin on properties such as dielectric properties increases and the thermal expansion coefficient of the resin film deteriorates, which is undesirable. The amount of the binder resin is preferably within the range of 4 parts by mass to 70 parts by mass, and more preferably within the range of 4 parts by mass to 50 parts by mass. This improves the film-forming properties of the resin film, alleviates thermal shrinkage of the resin film, and further suppresses cracking and wrinkling.

[0039] In the resin composition of this embodiment, the amount of (B) inorganic filler per 100 parts by mass of the total amount of (A) polyphenylene ether and (C) binder resin is preferably within the range of 150 parts by mass or more and 600 parts by mass or less. When the amount of the inorganic filler is within this range, the thermal expansion of a resin film made from the resin composition can be reduced. If the amount of the inorganic filler is less than 150 parts by mass, the effect of reducing thermal expansion becomes insufficient, and if it exceeds 600 parts by mass, voids will form in the resin film, making it embrittlement, which is undesirable. It is more preferable that the amount of the inorganic filler is within the range of 200 parts by mass or more and 500 parts by mass or less. This further improves the film formability of a resin film made from the resin composition and reduces thermal expansion.

[0040] (E) Additives The resin composition of the present embodiment may contain other additives such as a flame retardant, an antifoaming agent, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a dye, a pigment, a lubricant, a dispersant, etc., to the extent that the additives do not deteriorate the dielectric properties, etc. The resin composition does not contain additives that deteriorate the dielectric properties, such as a reaction initiator and a curing agent.

[0041] The resin composition of this embodiment is a composite of a high-molecular-weight polyphenylene ether that does not require a reaction initiator or a curing agent and can improve dielectric properties such as the dielectric constant and the dielectric loss tangent, and an inorganic filler that can reduce thermal expansion, and further contains a binder resin that is low in dielectric constant and highly heat-resistant in order to improve film formability and film quality. The resin composition of this embodiment is excellent in dielectric properties and film formability.

[0042] (2) Resin film The resin film according to this embodiment contains (A) polyphenylene ether, (B) inorganic filler, and (C) binder resin, and the amount of the (C) binder resin per 100 parts by mass of the total amount of the (A) polyphenylene ether and the (B) inorganic filler is in the range of 3 parts by mass to 100 parts by mass. The resin film according to this embodiment is made of the resin composition according to this embodiment.

[0043] In the resin film of this embodiment, the amount of inorganic filler per 100 parts by mass of the total solid content of the resin film is preferably 60 parts by mass or more. When the amount of inorganic filler is within the above range, the thermal expansion of the resin film can be reduced. When the amount of inorganic filler exceeds 85 parts by mass, voids are generated in the resin film, which is undesirable, making the resin film embrittlement. It is more preferable that the amount of inorganic filler is within the range of 65 parts by mass or more and 83 parts by mass or less. This improves the film formability of the resin film and reduces thermal expansion.

[0044] The resin film of this embodiment is constructed by combining the above-mentioned high molecular weight polyphenylene ether and inorganic filler, and further adding a binder resin, and the resin composition of this embodiment has excellent dielectric properties and film-forming properties.

[0045] (3) Single-sided metal-clad laminate and double-sided metal-clad laminate The metal-clad laminate of this embodiment has an insulating resin layer consisting of a single layer or multiple layers and a metal layer laminated on one or both sides of the insulating resin layer. A single-sided metal-clad laminate has a metal layer on one side of the insulating resin layer, and a double-sided metal-clad laminate has a metal layer on both sides. At least one layer of the insulating resin layer is made of the above-mentioned resin film. When the insulating resin layer consists of multiple layers, the insulating resin layer can be configured by laminating multiple resin layers made of the above-mentioned resin composition, or it may include a resin layer made of a resin other than the above-mentioned resin composition.

[0046] The metal layer is made of a metal such as copper or aluminum, and a foil of these metals can be used. The thickness of the metal foil is not particularly limited, but is, for example, 3 μm to 200 μm, and preferably 3 μm to 105 μm.

[0047] (4) Circuit boards, electronic devices, and electronic equipment The circuit board of this embodiment has a single or multiple insulating resin layer and conductor circuit layers laminated on one or both sides of the insulating resin layer, at least one of which is made of the resin film described above.

[0048] The circuit board of this embodiment is formed by processing the metal layer of the single-sided metal-clad laminate and the double-sided metal-clad laminate into a circuit pattern to form a conductor circuit layer.

[0049] An electronic device of this embodiment includes the above-described circuit board, and an electronic apparatus of this embodiment includes the above-described electronic device.

[0050] (5) Methods for producing resin films and metal-clad laminates FIG. 1 is a schematic diagram showing the steps for producing a resin film and a metal-clad laminate using a resin composition according to an embodiment.

[0051] As shown in 101 in FIG. 1 , (A) polyphenylene ether 10, (B) inorganic filler 11, and (C) binder resin 12 are mixed in a container 20. As described above, polyphenylene ether 10 has a high molecular weight and poor solvent solubility, and is supplied as powder-like solid particles. The inorganic filler 11 is made of silica or the like and is supplied as solid particles, similar to polyphenylene ether 10. The binder resin 12 is solvent-soluble and is supplied in a varnish-like state by mixing it with a solvent 13. By mixing the solid polyphenylene ether 10 and the solid inorganic filler 11 with the binder resin 12 that has been made into a varnish state by containing the solvent 13, a slurry is obtained in which the solid polyphenylene ether 10, the solid inorganic filler 11, and the binder resin 12 are dispersed and dissolved in the solvent 13.

[0052] Next, as shown in 102 of FIG. 1, the slurry obtained above is applied to a substrate 14 made of a metal foil or the like to form a coating film of the slurry in which solid polyphenylene ether 10, solid inorganic filler 11, and binder resin 12 are dispersed and dissolved in a solvent 13.

[0053] Next, as shown in 103 in Fig. 1, the coating film of the above-mentioned slurry is dried by carrying out a heat treatment to volatilize the solvent 13. As a result of the volatilization of the solvent 13, the solid-state polyphenylene ether 10 and the solid-state inorganic filler 11 are exposed, and the strength of the coating film is reduced, but the binder resin 12 binds the solid-state polyphenylene ether 10 and the solid-state inorganic filler 11 on the substrate 14, so that the strength of the coating film can be ensured.

[0054] Next, as shown in 104 of FIG. 1 , the solid polyphenylene ether 10 is heat-treated at a temperature equal to or higher than the glass transition temperature of the polyphenylene ether 10. The glass transition temperature of the polyphenylene ether 10 is, for example, 214°C, and the heat treatment is performed, for example, at a temperature equal to or higher than the glass transition temperature of the polyphenylene ether 10 and equal to or lower than the thermal decomposition temperature (Td1) of the binder resin 12. More preferably, the heat treatment is performed at 230°C or higher and 300°C or lower. Specifically, the heat treatment is performed at 280°C. The solid polyphenylene ether 10 is melted and fluidized by the heat treatment, becoming a polyphenylene ether film 10A. In this way, inorganic filler 11 is dispersed inside the polyphenylene ether film 10A, and a resin film 15 containing the binder resin 12 is produced, and a single-sided metal-clad laminate 16 is produced in which the resin film 15 and the substrate 14 are laminated together. When solid-state polyphenylene ether 10 melts and fluidizes to become polyphenylene ether film 10A, cracks or wrinkles may occur in resin film 15 due to thermal shrinkage. However, in the method for producing resin film 15 of this embodiment, binder resin 12 alleviates the thermal shrinkage of resin film 15, reducing thermal stress and suppressing cracks and wrinkles in resin film 15, thereby improving film quality.

[0055] Next, as shown in 105 in FIG. 1, two single-sided metal-clad laminates 16A and 16B are laminated together from the resin film side to produce a double-sided metal-clad laminate 17.

[0056] (6) Actions and Effects The resin composition of this embodiment and the resin film 15 made from the resin composition are configured by combining a high-molecular-weight polyphenylene ether 10 that does not require a reaction initiator or a curing agent and can improve dielectric properties such as the relative dielectric constant and the dielectric loss tangent, and an inorganic filler 11 that can reduce thermal expansion, and further adding a binder resin 12 that is low in dielectric constant and highly heat-resistant to improve film formability and film quality.

[0057] Because high-molecular-weight polyphenylene ether has poor solubility in solvents, it is mixed in a solid state with an inorganic filler in a solvent to form a slurry, which is then applied to a substrate and dried. The presence of a binder resin during this process improves the coating strength and film-forming properties. The resulting mixture is then heat-treated at or above the glass transition temperature of the high-molecular-weight polyphenylene ether to form a film. The presence of the binder resin during this process alleviates thermal shrinkage of the resin film, reducing thermal stress and suppressing cracking and wrinkling of the resin film, thereby improving film quality.

[0058] The resin composition and resin film of this embodiment are excellent in dielectric properties and film-forming properties.

[0059] 2. Working Example The features of the present invention will be described in more detail below with reference to examples. However, the scope of the present invention is not limited to these examples. In the following examples, various measurements and evaluations are as follows, unless otherwise specified.

[0060] In the following examples and comparative examples, a solid powder sample (PPE resin powder) was used as the polyphenylene ether (PPE resin), a silica filler was used as the inorganic filler, and a soluble polyimide was used as the binder resin. Dispersion compositions and resin compositions were prepared from these, and single-sided copper-clad laminates, double-sided copper-clad laminates, and polyphenylene ether resin films (PPE resin films) were then prepared from these.

[0061] [Measuring the average particle size (D50) of silica filler and PPE resin powder] Using a laser diffraction particle size distribution analyzer (Malvern, trade name: Mastersizer 3000), particle sizes were measured by laser diffraction / scattering under the conditions of THF as a dispersion medium and a particle refractive index of 1.54, and the average particle size (D50) was calculated.

[0062] [Measurement of weight-average molecular weight (Mw) of polyimide] The weight-average molecular weight was measured by gel permeation chromatography (HLC-8220GPC, manufactured by Tosoh Corporation). Polystyrene was used as a standard substance, and tetrahydrofuran was used as a developing solvent.

[0063] [Measurement of coefficient of thermal expansion (CTE)] A PPE resin film cut to a size of 3 mm x 20 mm was placed in a thermomechanical analyzer (Hitachi High-Technologies Corporation, product name: TMA / SS6100). The distance between the device and the jig (effective measurement length) was 15 mm. Next, the temperature was raised from 30°C to 210°C at a constant rate while applying a 5.0 g load. After holding at that temperature for 10 minutes, the film was cooled at a rate of 5°C / min, and the average thermal expansion coefficient (thermal expansion coefficient) from 200°C to 100°C was determined.

[0064] [Measurement of dielectric loss tangent] The dielectric loss tangent (Df) of the PPE resin film at a frequency of 20 GHz was measured using a vector network analyzer (manufactured by Agilent, product name: E8363C) and a split post dielectric resonator (SPDR resonator).

[0065] In addition, a dielectric constant measurement device (Kanto Electronics Application Development Co., Ltd.) using a cavity resonator perturbation method was set to the dielectric constant measurement mode (TM020) to measure the dielectric constant (Dk) and dielectric loss tangent (Df) of the silica filler particles at a frequency of 10 GHz. The silica filler was in powder form and was filled into a sample tube (inner diameter 1.68 mm, outer diameter 2.28 mm, height 8 cm) for measurement.

[0066] The PPE resin film and silica filler used for the measurement were left to stand for 48 hours under conditions of temperature: 22 to 24°C and humidity: 45 to 55%, and then the measurement was performed in a humidity-controlled state.

[0067] [Peel strength measurement] The copper foil on one side of the double-sided copper-clad laminate was circuitized at 10 mm intervals in the direction of the PPE resin coating, with a width of 1 mm, and then cut into 8 cm wide x 4 cm long pieces. The copper foil on the other side was left uncircuited. Peel strength was measured using a Tensilon tester (manufactured by Toyo Seiki Seisakusho, product name: Strograph VE-1D). The copper foil on the cut measurement sample was fixed to an aluminum plate with double-sided tape on the side with the copper foil remaining on the entire surface, and the circuit-processed copper foil was peeled off in a 180° direction at a rate of 50 mm / min. The median strength when 10 mm had been peeled off from the PPE resin layer was determined and used as the peel strength.

[0068] [Measurement of thermal decomposition temperature (Td1)] A PPE resin film weighing 10 to 20 mg was heated at a constant rate from 30°C to 550°C in a nitrogen atmosphere using a thermogravimetric analyzer (TG) (SEIKO, TG / DTA7200), and the weight change was measured. The weight at the starting temperature was set to zero, and the temperature at which the weight loss rate reached 1% was defined as the thermal decomposition temperature (Td1).

[0069] [Storage modulus measurement] The PPE resin film was cut into a size of 5 mm x 70 mm and measured using a dynamic viscoelasticity measuring device (DMA, manufactured by TA Instruments, product name: RSA G2) at a temperature increase rate of 4°C / min from 30°C to 400°C and a frequency of 10 Hz. The storage modulus at 50°C and the maximum value of the storage modulus between 180 and 260°C were obtained from the measurements.

[0070] [Evaluation of film-forming properties] The dispersion composition was applied to the surface of copper foil using a bar coater so that the thickness of the coating film after drying would be 60 to 70 μm, and then dried in a hot air oven at 90°C for 1 minute and then at 120°C for 3 minutes to obtain a laminate of copper foil and the dried coating film. After drying, the surface of the coating film was observed, and those that did not peel from the copper foil were marked with "Good", and those that did peel were marked with "Poor".

[0071] [Evaluation of film appearance] The PPE resin films obtained by etching the double-sided copper-clad laminate were rated "Good" if they had no defects in appearance such as unevenness or cracks on the film surface, and "Poor" if they did.

[0072] The compounds used in the following synthesis examples and for preparing the dispersion compositions are shown below. PPE resin powder: Polyphenylene ether powder XYRON (XYRON is a registered trademark) S203A manufactured by Asahi Kasei Corporation (average particle size (D50): 7 to 8 μm, glass transition temperature: 214°C, Td1: 326°C) Silica filler: Amorphous silica filler SC70-2 manufactured by Nippon Steel Chemical & Material Co., Ltd. (average particle size (D50): 11.7 μm, specific surface area: 1.1 m) 2 / g treated with 0.12% by weight of silica with hexamethyldisilazane, relative permittivity (10 GHz): 3.26, dielectric dissipation factor (10 GHz): 0.0008 THF: tetrahydrofuran NMP: N-methyl-2-pyrrolidone xylene BTDA: 3,3',4,4'-benzophenonetetracarboxylic dianhydride BAFL: 9,9-bis(4-aminophenyl)fluorene DDA: aliphatic diamine with 36 carbon atoms manufactured by Croda Japan (trade name: PRIAMINE 1074, amine value: 205 mg KOH / g, mixture of dimer diamines with cyclic and chain structures, dimer content: 95% by weight or more) Copper foil: CF-T9DA-SV-12 manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd.

[0073] [Synthesis Example 1: Preparation of Soluble Polyimide Varnish] A 500 mL four-neck flask equipped with a nitrogen inlet tube, stirrer, thermocouple, Dean-Stark trap, and condenser was charged with 38.45 g of BTDA (0.119 mol), 31.50 g of DDA (0.059 mol), 20.47 g of BAFL (0.059 mol), 127 g of NMP, and 84 g of xylene, and mixed at 40°C for 30 minutes to prepare a polyamic acid solution. The polyamic acid solution was heated to 180°C and stirred for 4 hours, after which the distilled water and xylene were removed from the system. The mixture was then cooled to 100°C, 51 g of xylene was added, stirred, and further cooled to 30°C to prepare a soluble polyimide varnish (solids content: 31.0 wt%, weight average molecular weight: 70,086) in which imidization was completed.

[0074] The soluble polyimide varnish was applied to a substrate, dried, and then peeled off to obtain a polyimide film. The storage modulus of the polyimide film was measured to be 2.0 GPa at 50°C and a maximum of 3.0 MPa in the temperature range from 180°C to 260°C. The dielectric constant and dielectric dissipation factor of the humidified polyimide film were measured at 20 GHz and found to be 2.7 and 0.0015, respectively. The 1% thermal weight loss of the polyimide film was measured to be 422°C.

[0075] Example 1: Dispersion Composition 1A 4.60 g of PPE resin powder, 13.6 g of silica filler, and 20.2 g of THF were weighed and placed in a 100 ml polypropylene container. The mixture was stirred for 20 minutes using a planetary mixer (SK-350G, manufactured by Shashin Kagaku Co., Ltd.) at a revolution speed of 1060 rpm and a rotation speed of 1060 rpm. 6.54 g of soluble polyimide varnish 1 was then added as a binder to the container and stirred for 4 minutes under the same conditions to obtain a dispersion composition 1A according to Example 1. The mass ratios of the components in dispersion composition 1A are shown in Table 1.

[0076] Example 2: Dispersion Composition 2A The components in the mass ratios shown in Table 1 were placed in a 100 ml polypropylene container, and the procedure was the same as in Example 1 to obtain a dispersion composition 2A according to Example 2.

[0077] Example 3: Dispersion Composition 3A Each component in the mass ratio shown in Table 1 was placed in a 100 ml polypropylene container, and the procedure was the same as in Example 1 to obtain a dispersion composition 3A according to Example 3.

[0078] [Comparative example: Dispersion composition 4A] The components in the mass ratios shown in Table 1 were added to a 100 ml polypropylene container, and a dispersion composition 4A according to the comparative example was obtained in the same manner as in Example 1. In the comparative example, no soluble polyimide varnish was used.

[0079] [Table 1]

[0080] [Example 1: Resin composition 1B, single-sided copper-clad laminate 1C, double-sided copper-clad laminate 1D, PPE resin film 1E] Dispersion composition 1A was coated on copper foil, and then dried using a hot air oven at 90 ° C. for 1 minute and 120 ° C. for 3 minutes. Next, using a hot air oven under a nitrogen atmosphere (oxygen concentration 0.1% by volume or less), the temperature was raised from 40 ° C. to 240 ° C. at 10 ° C. / min, from 240 ° C. to 280 ° C. at 5 ° C. / min, and held at 280 ° C. for 5 minutes to melt the coating of the dried dispersion composition 1A. Then, nitrogen heat treatment was performed to cool to 40 ° C. to obtain a single-sided copper-clad laminate 1C in which copper foil was laminated on one side of a resin film made of resin composition 1B. Two single-sided copper-clad laminates 1C were prepared, stacked resin-side up, and placed in a batch press. They were heated under vacuum from 40°C to 280°C over 40 minutes. Upon reaching 280°C, a pressure of 8 MPa was applied. The temperature was held at 280°C for 5 minutes, then cooled to 40°C over 40 minutes. The pressure was released upon reaching 40°C, yielding double-sided copper-clad laminate 1D with an 80 μm thick dielectric layer. The copper foil was etched away from double-sided copper-clad laminate 1D using an aqueous ferric chloride solution to yield PPE resin film 1E. The mass ratios of the components in resin composition 1B are shown in Table 2.

[0081] [Example 2: Resin composition 2B, single-sided copper-clad laminate 2C, double-sided copper-clad laminate 2D, PPE resin film 2E] Using dispersion composition 2A according to Example 2, resin composition 2B according to Example 2, single-sided copper-clad laminate 2C, double-sided copper-clad laminate 2D, and PPE resin film 2E were obtained in the same manner as in Example 1. The mass ratios of each component in resin composition 2B are shown in Table 2.

[0082] [Example 3: Resin composition 3B, single-sided copper-clad laminate 3C, double-sided copper-clad laminate 3D, PPE resin film 3E] Using dispersion composition 3A of Example 3, resin composition 3B of Example 3, single-sided copper-clad laminate 3C, double-sided copper-clad laminate 3D, and PPE resin film 3E were obtained in the same manner as in Example 1. The mass ratios of each component in resin composition 3B are shown in Table 2.

[0083] [Comparative Examples: Resin Composition 4B, Single-Sided Copper-Clad Laminate 4C, Double-Sided Copper-Clad Laminate 4D, PPE Resin Film 4E] Comparative Example Resin Composition 4B, a single-sided copper-clad laminate 4C, a double-sided copper-clad laminate 4D, and a PPE resin film 4E were obtained using Comparative Example Dispersion Composition 4A in the same manner as in Example 1. Table 2 shows the mass ratios of each component in Resin Composition 4B.

[0084] Table 2 also shows the parts by mass of polyimide per 100 parts by mass of polyphenylene ether (PPE) and silica filler for resin compositions 1B to 4B, the parts by mass of silica filler per 100 parts by mass of polyphenylene ether (PPE) and polyimide, and the parts by mass of silica filler per 100 parts by mass of the total solids content of the resin film.

[0085] [Table 2]

[0086] When the above single-sided copper-clad laminates 1C to 4C were produced, the presence or absence of peeling between the resin composition and the copper foil was observed, and no peeling occurred in the single-sided copper-clad laminates 1C to 3C of Examples 1 to 3. Peeling occurred in the single-sided copper-clad laminate 4C of the comparative example.

[0087] The peel strength of the copper foil was measured for the double-sided copper-clad laminates 1D to 4D, and all of the double-sided copper-clad laminates 1D to 4D had good peel strength.

[0088] The dielectric loss tangent and CTE of the above PPE resin films 1E to 4E were evaluated. The results are shown in Table 3. All of the PPE resin films 1E to 4E had good dielectric loss tangent and CTE.

[0089] Furthermore, when the PPE resin films 1E to 4E were produced, their appearances were observed, and no defects in appearance were found in the PPE resin films 1E to 3E according to Examples 1 to 3. However, the PPE resin film 4E according to the comparative example had a defect in appearance.

[0090] [Table 3]

[0091] Although the embodiments of the present invention have been described in detail above for the purpose of illustration, the present invention is not limited to the above-described embodiments and various modifications are possible. [Explanation of symbols]

[0092] 10 Polyphenylene ether 10A Polyphenylene ether film 11 Inorganic fillers 12 Binder resin 13 Solvents 14 Base material 15 Resin film 16, 16A, 16B Single-sided metal clad laminate 17 Double-sided metal-clad laminate 20 containers

Claims

1. (A) polyphenylene ether; (B) an inorganic filler; (C) a binder resin; Contains The amount of the binder resin (C) relative to 100 parts by mass of the total amount of the polyphenylene ether (A) and the inorganic filler (B) is in the range of 3 parts by mass or more and 100 parts by mass or less. Resin composition.

2. The temperature (Td1) at which the binder resin (C) exhibits a 1% reduction rate in thermogravimetric analysis is equal to or higher than the glass transition temperature of the polyphenylene ether (A). The resin composition according to claim 1.

3. The amount of the inorganic filler (B) relative to 100 parts by mass of the total amount of the polyphenylene ether (A) and the binder resin (C) is in the range of 150 parts by mass or more and 600 parts by mass or less. The resin composition according to claim 1.

4. The inorganic filler (B) has a relative dielectric constant of 6 or less at 10 GHz when measured by a cavity resonator perturbation method in an environment of a temperature of 22° C. or more and 24° C. or less and a relative humidity of 45% RH or more and 55% RH or less. The resin composition according to claim 1.

5. The weight average molecular weight of the polyphenylene ether (A) is 5,000 or more. The resin composition according to claim 1.

6. The polyphenylene ether (A) is thermoplastic. The resin composition according to claim 1.

7. The binder resin (C) has a dielectric loss tangent of 0.005 or less at 20 GHz when measured using a split post dielectric resonator (SPDR) in an environment of a temperature of 22° C. or higher and 24° C. or lower and a relative humidity of 45% RH or higher and 55% RH or lower. The resin composition according to claim 1.

8. (A) polyphenylene ether; (B) an inorganic filler; (C) a binder resin; Contains The amount of the binder resin (C) relative to 100 parts by mass of the total amount of the polyphenylene ether (A) and the inorganic filler (B) is in the range of 3 parts by mass or more and 100 parts by mass or less. Resin film.

9. The amount of the inorganic filler (B) relative to 100 parts by mass of the total solid content of the resin film is 60 parts by mass or more. The resin film according to claim 8.

10. an insulating resin layer consisting of a single layer or multiple layers; a metal layer laminated on one or both surfaces of the insulating resin layer, At least one of the insulating resin layers is made of the resin film according to claim 8 or 9. Metal-clad laminate.

11. an insulating resin layer consisting of a single layer or multiple layers; a conductor circuit layer laminated on one side or both sides of the insulating resin layer, At least one of the insulating resin layers is made of the resin film according to claim 8 or 9. Circuit board.

12. An electronic device comprising the circuit board according to claim 11.

13. An electronic device comprising the electronic device according to claim 12.

14. (A) polyphenylene ether; (B) an inorganic filler; (C) a binder resin; A method for producing a resin film containing a step of mixing the (A) polyphenylene ether and the (B) inorganic filler in a solid state in a solvent; A method for manufacturing a resin film.

15. (A) polyphenylene ether; (B) an inorganic filler; (C) a binder resin; A method for producing a resin film containing a step of heat-treating the polyphenylene ether (A) in a solid state at a temperature equal to or higher than the glass transition temperature of the polyphenylene ether (A). A method for manufacturing a resin film.

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