Resin components, thin films, optical lenses, diffractive optical elements, ion-conducting membranes, battery separators, secondary batteries, circuit boards, and vibrating plates.

Abstract

The objective of this invention is to provide a resin composition with good dispersibility and low impurity content. The means to solve this objective is a resin composition whose main components are aromatic polyamine and / or aromatic polyamine acid. When the powder is prepared into an aqueous dispersion of 100 ppm by mass and the average hydrodynamic radius measured by dynamic light scattering is defined as rA (nm), and the average hydrodynamic radius after ultrasonic treatment of the dispersion is defined as rB (nm), rA / rB is greater than 1 and rB is between 100 nm and 10000 nm.

Description

Technical Field

[0001] This invention relates to resin compositions with aromatic polyamide and / or aromatic polyamide as the main components, and thin films, optical lenses, diffractive optical elements, ion-conducting membranes, battery separators, secondary batteries, circuit boards, and vibrating plates using the resin compositions. Prior Technology

[0002] Aromatic polyimides, obtained from aromatic polyamines and aromatic polyamides, play an important role as materials in the fiber, electronics, and automotive industries due to their excellent mechanical properties and heat resistance. In the manufacture of components made of aromatic polyamine resins, solutions and powders are used for ease of handling and molding.

[0003] The excellent physical properties of aromatic polyamides and / or aromatic polyamides originate from the π-π interactions between aromatic groups and the strong inter-chain interactions generated by the hydrogen bonds between amide groups. On the other hand, these polymers have low dispersibility and solubility when in solid form, and lack processability.

[0004] Research is underway to improve the processability of resin compositions. For example, patent documents 1 and 2 have proposed a polyimide resin precursor powder that controls the degree of polymerization and the amide content.

[0005] On the other hand, for example, Patent Document 3 discloses a polymer microparticle with controlled particle size distribution and particle size. Also, for example, Patent Document 4 discloses a method for manufacturing polyamide-based resin powder with a small particle size distribution. [Previous Technical Documents] [Patent Literature]

[0006] Patent Document 1: Japanese Patent Application Publication No. 5-271539 Patent Document 2: Japanese Patent Application Publication No. 2020-12103 Patent Document 3: Japanese Patent Application Publication No. 2013-237857 Patent Document 4: Japanese Patent Application Publication No. 2021-113275 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] However, the resin powders disclosed in Patent Documents 1 and 2 limit the molecular structure of polyamide in order to improve processability (dispersibility and solubility in solvents), making them difficult to apply to highly rigid aromatic polyamides.

[0009] Furthermore, the polymer microparticles disclosed in Patent Document 3 are manufactured in an emulsion of a good solvent and a poor solvent in order to control the particle shape of the powder. In this case, sometimes the polymer in contact with the poor solvent will rapidly agglomerate and no powder can be obtained. Therefore, the applicable polymers are limited to resins with high solubility, such as amorphous non-aromatic polyamides and polyether amides.

[0010] Furthermore, the resin powder obtained by the manufacturing method described in Patent Document 4 has a relatively large particle size because the particle size is controlled by the stirring speed and the addition speed of the undesirable solvent. Sometimes the solubility is reduced and the impurity content increases.

[0011] Furthermore, any of the patent documents 1 to 4 require handling small-sized powders and particles from the manufacturing process, and sometimes the filter cloth will become clogged, or the powder will scatter, which reduces operability.

[0012] The purpose of this invention is to provide a resin composition, as well as films, optical lenses, diffractive optical elements, ion-conducting membranes, battery separators, secondary batteries, circuit boards, and vibrating plates, that are made primarily of aromatic polyamides and / or aromatic polyamide acids with low solubility and high cohesion, and which have excellent dispersion, solubility and operability. [Methods used to solve problems]

[0013] The features of the present invention for achieving the above objectives are as follows: (1) A resin composition, wherein aromatic polyamine and / or aromatic polyamine acid are used as the main components, and when the powder is made into an aqueous dispersion of 100 ppm by mass and the average hydrodynamic radius measured by dynamic light scattering is set as r A (nm), and the average hydrodynamic radius after ultrasonic treatment of the dispersion is set as r B (nm), r A / r B is greater than 1 and r B is between 100 nm and 10000 nm. (2) A resin composition, wherein aromatic polyamide is the main component, and when the powder is made into an aqueous dispersion of 100 ppm by mass and the average hydrodynamic radius measured by dynamic light scattering is set as r A (nm), and the average hydrodynamic radius after ultrasonic treatment of the dispersion is set as r B (nm), the ratio of r A to r B is greater than 3 and the ratio of r B is greater than 100 nm and less than 5000 nm. (3) The resin composition as described in (1) or (2) wherein the multilayer adsorption (BET) specific surface area determined by gas adsorption method is above 50 m2 / g and below 90 m2 / g. (4) The resin composition described in any of (1) to (3) wherein, when the number average molecular weight determined by gel permeation chromatography (GPC) is set as Mn and the mass average molecular weight is set as Mw, the ratio of Mw / Mn is 1.0 or more and 2.5 or less. (5) A film made using a resin composition as described in any one of (1) to (4). (6) An optical lens made of a resin composition as described in any one of (1) to (4). (7) A diffractive optical element made of a resin composition as described in any one of (1) to (4). (8) An ion-conducting membrane, which is made using a resin composition as described in any one of (1) to (4). (9) A battery separator made of a resin composition as described in any one of (1) to (4). (10) A secondary battery comprising an ion-conducting membrane as described in (8) or a battery separator as described in (9). (11) A circuit board made of a resin composition as described in any one of (1) to (4). (12) A vibrating plate made of a resin composition as described in any one of (1) to (4). [Effects of the Invention]

[0014] According to the present invention, a resin composition with good dispersibility, mainly composed of aromatic polyamines and / or aromatic polyamides, can be provided. Therefore, the resin composition of the present invention can balance the workability and solubility of powders, and even aromatic polyamines and / or aromatic polyamides with low solubility and high cohesion can produce fibers, molded articles, films, etc. with high rigidity, high heat resistance and low impurity content.

[0015] According to the present invention, thin films with low molecular weight components and low impurity content can be provided. Therefore, thin films, laminates, etc., with good rigidity and long-term stability can be obtained.

[0016] According to the present invention, optical lenses and / or diffractive optical elements with excellent transparency and shape stability can be provided. Therefore, when the optical lenses and / or diffractive optical elements of the present invention are used as sensors or as waveguide elements for AR devices, sensors and devices with excellent sensitivity and brightness can be manufactured.

[0017] According to the present invention, an ion-conducting membrane and / or battery separator with low impurity content and excellent mechanical strength can be provided. Since it is a thin film with excellent safety and low resistance in terms of heat resistance, deformation resistance, impact resistance, etc., excellent battery characteristics can be obtained, for example, when the ion-conducting membrane and / or battery separator of the present invention are mounted in a secondary battery.

[0018] According to the present invention, a circuit board with excellent heat resistance and dimensional stability can be provided. According to the present invention, a diaphragm with excellent rigidity and creep characteristics can be provided. Therefore, when mounted in, for example, audio speakers, actuators, microphones, etc., excellent transient characteristics, excellent output from the high frequency range to the ultrasonic range, and / or sensitivity can be obtained. Simple Explanation of the Diagram

[0019] none Implementation

[0020] [The form in which the invention is carried out]

[0021] The resin composition of this invention uses aromatic polyamide and / or aromatic polyamide as the main components. Here, "main component" refers to the component most abundant in the resin composition. The amount of the component is not particularly limited, but preferably it is 70% by mass or more, more preferably 85% by mass or more, of the total resin composition. Within these ranges, the high rigidity derived from aromatic polyamide is better utilized. As an aromatic polyamide, it is preferred to have a structural unit represented by any one of the following chemical formulas (I) to (V).

[0022] Chemical formula (I):

[0023] R1 is -H, an aliphatic group with 1 to 5 carbon atoms, -CF3, -CCl3, -OH, -F, -Cl, -Br, -OCH3, a silyl group, or a group containing an aromatic ring.

[0024] Chemical formula (II):

[0025] R2 and R3 are -H, aliphatic groups with 1 to 5 carbon atoms, -CF3, -CCl3, -OH, -F, -Cl, -Br, -OCH3, silyl, or groups containing aromatic rings.

[0026] Chemical formula (III):

[0027] R 4 is a group containing Si, a group containing P, a group containing S, a halogenated hydrocarbon group, a group containing an aromatic ring, or a group containing an ether bond (wherein, structural units having these groups can coexist in a mixture within the molecule).

[0028] Chemical formula (IV):

[0029] R5 is any basis.

[0030] Chemical formula (V):

[0031] R6 can be any aromatic group or any alicyclic group. As an aromatic polyamide, it is preferred to have a structural unit represented by any one of the following chemical formulas (VI) to (X).

[0032] Chemical formula (VI):

[0033] R7 can be -H, an aliphatic group with 1 to 5 carbon atoms, -CF3, -CCl3, -OH, -F, -Cl, -Br, -OCH3, a silyl group, or a group containing an aromatic ring.

[0034] Chemical formula (VII):

[0035] R8 and R9 are -H, aliphatic groups with 1 to 5 carbon atoms, -CF3, -CCl3, -OH, -F, -Cl, -Br, -OCH3, silyl, or groups containing aromatic rings.

[0036] Chemical formula (VIII):

[0037] R 10 is a group containing Si, a group containing P, a group containing S, a halogenated hydrocarbon group, a group containing an aromatic ring, or a group containing an ether bond (wherein, structural units having these groups can coexist in a mixture within the molecule).

[0038] Chemical formula (IX):

[0039] R11 is any basis.

[0040] Chemical formula (X):

[0041] R 12 is a group containing Si, a group containing P, a group containing S, a halogenated hydrocarbon group, a group containing an aromatic ring, or a group containing an ether bond (wherein, structural units having these groups can coexist in the molecule).

[0042] The resin composition of this invention, aimed at improving rigidity and thermal dimensional stability, may also include thermosetting resins, UV-curing resins, hydrolyzed / condensed resins, alkoxysilane compounds, and other organic-inorganic hybrid resins. Furthermore, it may also contain particles. Here, the so-called particles can be either inorganic or organic particles, but for the purpose of improving hardness and thermal dimensional stability, inorganic particles are preferred. Inorganic particles are not particularly limited and may include oxides, silicates, nitrides, borides, chlorides, and carbonates of metals or semi-metals, specifically including silicon dioxide (SiO₂), aluminum oxide (Al₂O₃), zinc oxide (ZnO), zirconium dioxide (ZrO₂), titanium dioxide (TiO₂), antimony trioxide (Sb₂O₃), and indium tin oxide (ITO). Furthermore, for the purpose of controlling coloring or deterioration, it may also contain organic or inorganic pigments and dyes, or antioxidants.

[0043] The resin composition of the present invention may also contain polymers other than aromatic polyamides for the purpose of adjusting mechanical properties and solubility. Specifically, examples include: vinyl polymers, polyesters, polyimides, polyethers, polysulfides, polyurethanes, polycarbonates, polyacetals, polysiloxanes and their copolymers.

[0044] In cases where it is necessary to identify the chemical structure and composition ratio of aromatic polyamides and other components constituting the resin composition of the present invention, the components separated by column chromatography and / or distillation can be analyzed by combining nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), mass spectrometry (MS), elemental analysis, etc.

[0045] The resin composition of this invention is characterized in that, when preparing an aqueous dispersion of 100 ppm by mass, the average hydrodynamic radius determined by dynamic light scattering is defined as rA (nm), and the average hydrodynamic radius after ultrasonic treatment of the dispersion is defined as rB (nm), wherein rA / rB is greater than or equal to 1 and rB is greater than or equal to 100 nm and less than or equal to 10000 nm. By having rA / rB greater than or equal to 1 and rB greater than or equal to 100 nm and less than or equal to 10000 nm, the workability is improved due to the large particle size before dispersion, and high dispersibility and solubility can be obtained. To obtain the above effects, it is preferable that rA / rB is greater than or equal to 3 and rB is greater than or equal to 100 nm and less than or equal to 5000 nm, more preferably that rA / rB is greater than or equal to 4 and rB is greater than or equal to 100 nm and less than or equal to 3500 nm, and even more preferably that rA / rB is greater than or equal to 5 and rB is greater than or equal to 100 nm and less than or equal to 2500 nm. When the particle size rB is less than 100 nm, the generated microparticles are too fine, which sometimes leads to poor operability, lower degree of polymerization, and reduced rigidity. The specific surface area of ​​the resin composition of this invention, as determined by the Biosorption Spectrometry (BET) method, is preferably 50 m² / g or higher and 90 m² / g or lower. More preferably, it is 55 m² / g or higher and 90 m² / g or lower, and even more preferably, it is 65 m² / g or higher and 90 m² / g or lower. By achieving a specific surface area of ​​50 m² / g or higher, dispersibility can be improved and the amount of impurities in the composition can be reduced. If the specific surface area is greater than 90 m² / g, microparticle formation may occur, sometimes resulting in poor workability.

[0046] Regarding the number average molecular weight Mn and weight average molecular weight Mw determined by gel permeation chromatography (GPC), the Mw / Mn ratio of the resin composition of the present invention is preferably 1.0 to 2.5. More preferably, the Mw / Mn ratio is 1.0 to 2.3, and even more preferably, the Mw / Mn ratio is 1.0 to 2.1. By keeping the Mw / Mn ratio between 1.0 and 2.5, the amount of volatile impurities can be reduced, the amount of low molecular weight components that function as plasticizers can be reduced, and the rigidity of the molded article can be improved. When the Mw / Mn ratio is greater than 2.5, the amount of low molecular weight oligomers and unreacted monomers that are byproducts of polymerization will remain as impurities in the composition.

[0047] Next, the method for manufacturing resin compositions with aromatic polyamides and / or aromatic polyamides as the main components of the present invention will be described, but the present invention is not limited to the following method.

[0048] As a method for obtaining the resin composition of the present invention, firstly, for example, dichlorodiamine and diamine are used as raw materials, and aromatic polyamides are polymerized by low-temperature solution polymerization in an aprotic polar solvent. Here, the so-called aprotic polar solvent is a polar solvent that does not have proton (hydrogen cation) donation capability, and examples include: pyrrolidone solvents such as N-methyl-2-pyrrolidone (NMP), methylamine solvents such as N,N-dimethylformamide, acetamide solvents such as N,N-dimethylacetamide, urethane solvents such as dimethyl sulfoxide, ether solvents such as tetrahydrofuran, lactone solvents such as γ-butyrolactone, ester solvents such as ethyl acetate, and nitrile solvents such as acetonitrile. It is preferable to use these solvents alone or as a mixture. To suppress the deactivation of dichlorodimethylamine, the water content of the solvent used in polymerization is preferably below 500 ppm by mass, more preferably below 200 ppm by mass. Furthermore, when the molar ratio of dichlorodimethylamine to diamine differs significantly, the polymer may sometimes have a low molecular weight and fail to produce powder when unsuitable organic solvents are added. Therefore, it is preferable to adjust the molar ratio so that one component is 96.0–99.8% of the other, more preferably 97.0–99.8%. The polymerization reaction of aromatic polyamides is accompanied by heat generation, and it is preferable to keep the solution temperature during polymerization below 40°C, more preferably below 30°C. If the solution temperature exceeds 40°C, side reactions will occur, preventing the degree of polymerization from increasing sufficiently. By adding a poorly functioning organic solvent that cannot dissolve the polymer to this polymerization solution, the resin composition of the present invention can be obtained. Here, examples of poorly functioning organic solvents that cannot dissolve the polymer include hydrocarbon solvents such as hexane and cyclohexane, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone, and ether solvents such as THF and diethyl ether. The combination of aprotic polar solvent and poorly functioning organic solvent used for polymerization is preferably a mixture of both. From the perspective of increasing the degree of polymerization of the resin composition, acetylamine-based solvents, pyrrolidone-based solvents, methine-based solvents, or mixtures containing any of these are preferred as aprotic polar solvents. Specific solvent systems include, but are not limited to, systems in which 2-propanol is added to a mixture of DMAc and THF, systems in which 2-propanol is added to a mixture of NMP and THF, and systems in which decane is added to a mixture of DMAc and THF. There are no particular limitations on the method of including organic-inorganic hybrid resins or particles in the resin composition. It is preferable to add them directly to the polymerization solution after the polymerization step, as a solution dispersed in a poor organic solvent. If added before the polymerization step, the particles may hinder the polymerization reaction, and sometimes the polymer may be reduced in molecular weight or the resin composition may not be obtained.

[0049] The resin composition of this invention is suitable for use as a raw material for fibers, molded articles, films, etc. It is particularly preferred for use as a film raw material because it can produce films with high rigidity and low impurity content. Therefore, it is suitable for use as a raw material for various applications such as display materials, sensor substrates, circuit boards, optical waveguide substrates, semiconductor assembly substrates, transparent conductive films, phase difference films, touch panel substrates, solar cells, packaging materials, adhesive tapes, bonding tapes, and decorative materials.

[0050] The film of this invention is characterized by using the aforementioned resin composition as a raw material. By using the aforementioned resin composition as a raw material, compared to conventional products, the low molecular weight components of the polymer constituting the film are reduced, resulting in a film with excellent rigidity and long-term stability. Furthermore, it reduces the amount of impurities contained in the film and suppresses coloring or turbidity. The thickness of the film of this invention is not particularly limited, but is preferably 1 μm to 100 μm, more preferably 3 μm to 80 μm. From the viewpoint of shape stability and mechanical strength, the Young's modulus of the film of this invention is preferably 8.0 GPa to 12.0 GPa. The long-term heat resistance temperature of the film of this invention is preferably 160°C or higher, more preferably 170°C or higher. To ensure that the long-term heat resistance temperature is within the above range, it is preferable to use a resin composition free of low-polymerization components, byproducts, and impurities as a raw material. In this invention, the so-called long-term heat resistance temperature is the temperature at which the Young's modulus is halved relative to its value at 25°C; a higher long-term heat resistance temperature indicates better long-term stability. The thin film of the present invention can be obtained by coating a resin solution, obtained by dissolving the aforementioned resin composition, onto a substrate to form a film. There are no limitations on the solvent used to dissolve the resin; examples that easily yield a homogeneous solution include pyrrolidone-based solvents such as N-methyl-2-pyrrolidone, methylamine-based solvents such as N,N-dimethylformamide, acetamide-based solvents such as N,N-dimethylacetamide, and dimethyl sulfoxide. Examples of film-forming methods for the thin film of the present invention include: a dry-wet method involving a pre-drying step, a washing step in a wet bath, and then heat treatment; a dry method involving solvent drying without a washing step; or a wet method involving introducing the film into a wet bath without a solvent drying step and then heat treatment. While the specific method used for film formation is not critical, from the viewpoint of simplicity and processability in forming thin films on any object, a dry method is preferred.

[0051] As for the method of coating onto the substrate, well-known methods such as metal interface or die coating, roller coating, wire rod coating, and gravure coating can be selected. As for the substrate, any material that will not be corroded by the raw material solution and will not deform or deteriorate when heated for solvent drying is acceptable; examples include: glass plates, thin-film glass, resin films, metal plates, quartz plates, and silicon wafers. Furthermore, the surface structure of the substrate can be smooth, fine-textured, or has lenticular or diffraction grating patterns. Methods for solvent drying include hot air, infrared radiation, and microwave radiation, among others, with no particular limitation. The preferred drying temperature is 50–400°C. For improving thermal dimensional stability, it is even more preferable to include a step in the drying process with a temperature range of 150–400°C. To prevent surface roughness caused by rapid solvent evaporation, it is even more preferable to pre-dry at 50–200°C followed by intermittent solvent drying at 200–400°C.

[0052] The optical lens and diffractive optical element of the present invention are characterized by using the aforementioned resin composition as a raw material. By using the aforementioned resin composition as a raw material, coloring or devitrification caused by impurities can be suppressed, and shape stability can be improved. Furthermore, since aromatic polyamines and aromatic polyacrylic acids have high dielectric constants, they can exhibit excellent refractive indices. In the case of high refractive indices, it is preferable that the structure of aromatic polyamines and / or aromatic polyacrylic acids contains functional groups with high dielectric constants or functional groups that reduce molecular volume. Examples of such functional groups include, for example, halogen groups (Br, I), groups containing sulfur atoms, hydroxyl groups, and other groups that can form hydrogen bonds. Therefore, when used in applications such as sensor lenses or AR devices, sensitivity and brightness can be improved. As a method for manufacturing optical lenses, examples include encapsulating the aforementioned resin solution in a molding die shaped into an optical component, or casting it onto a substrate shaped into an optical lens and then desolventizing it under high temperature conditions. Alternatively, the resin composition can be molded into rods or plates, then cut and ground to form an optical lens. As a method for manufacturing diffractive optical elements, examples include: coating the aforementioned resin solution onto a substrate having a diffraction grating pattern and drying the solvent; and forming a diffraction grating pattern by cutting a resin composition into a plate shape using a laser or similar method.

[0053] The optical lens and diffraction optical element of the present invention are suitable for use as optical components such as lenses for semiconductor sensors, optical waveguide circuits, and AR devices.

[0054] The ion-conducting membrane and battery separator of the present invention are characterized by using the aforementioned resin composition as a raw material. This resin composition differs from conventional polyamide resins, particularly in that it is free of byproducts and inorganic salts. Therefore, it prevents the presence of impurities, ensuring that ions moving within the membrane are not captured or reacted, thus stabilizing ion conductivity. Furthermore, by reducing the amount of low molecular weight components, mechanical strength is increased, preventing breakage under compression, bending stress, impact, etc., and making it easier to maintain membrane performance.

[0055] The ion-conducting membrane and battery separator of the present invention can be a single-layer thin film or a laminated thin film formed on at least one side of an electrode material or a porous substrate. In the case of forming a single-layer thin film, it can be manufactured using the same method as the aforementioned thin film.

[0056] In the case of forming a multilayer thin film with an electrode material, the electrode can be either a positive or negative electrode, and can be used on lithium metal electrodes or carbon electrodes, etc. For example, when used on a lithium metal negative electrode, by forming the thin film of the present invention directly on the lithium negative electrode, the thin film functions as a protective film and can improve ion conductivity and dendrite resistance.

[0057] In the case of forming a laminated thin film with a porous substrate, the porous substrate can be a porous membrane, nonwoven fabric, or a porous membrane sheet made of fibrous material, and may also have through pores. The resin constituting the porous substrate is preferably a resin with good electrical insulation, electrical stability, and stability even in an electrolyte. Furthermore, from the viewpoint of providing a shutdown function, the resin used is preferably a thermoplastic resin, and more preferably a thermoplastic resin with a melting point below 200°C. The shutdown function referred to here is the function that, when the lithium-ion battery abnormally heats up, the porous structure is sealed due to the melting caused by heat, thus stopping ion movement and power generation.

[0058] The porous substrate is preferably a polyolefin-based porous substrate containing polyolefins, and more preferably a polyolefin-based porous substrate containing polyolefins with a melting point below 200°C. Examples of polyolefins include polyethylene, polypropylene, and copolymers and mixtures thereof. Examples include: a single-layer polyolefin-based porous substrate containing 90% by mass or more polyethylene, and a multi-layer polyolefin-based porous substrate composed of polyethylene and polypropylene. The membrane resistance of the ion-conducting membrane and battery separator of the present invention can be obtained by measuring the AC impedance of the resin membrane impregnated with electrolyte solution by clamping it with an SUS metal plate. Here, the electrolyte solution is an electrolyte solution in which LiPF6, as the solute, is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate in a 1:1 (volume ratio) solution to achieve a concentration of 1.0 mol / L. The AC impedance measurement is performed after doping treatment by allowing the membrane to stand at 50°C for 12 hours, and then at 25°C with a voltage amplitude of 10 mV and a frequency of 10 Hz to 5,000 kHz. The membrane resistance (Ω) can be obtained by Cole-Cole plot. The membrane resistance of the ion-conducting membrane and battery separator of the present invention, measured under the above conditions, is preferably in the range of 0.05 to 50.0 Ω·cm². By keeping the membrane resistance within the above range, when used as a solid electrolyte membrane, high ion conductivity, excellent output characteristics, and cycling characteristics can be obtained. If the membrane resistance is greater than 50.0 Ω·cm², when used as a solid electrolyte membrane, the ionic conductivity will be low, the output characteristics will be reduced, or the capacity decay will be greater during repeated use. In order to keep the membrane resistance within the above range, it is preferable to form a small free volume in the thin film that allows lithium ions to move. For example, aromatic polyamides and / or aromatic polyamide acids preferably have fluorine atoms or macrocyclic structures in their molecular structure. The ion-conducting membrane and battery separator of this invention are suitable for use in secondary batteries, vehicles, aircraft, and electronic devices. Furthermore, in this invention, "vehicle" refers to automobiles, motorcycles, bicycles, electric wheelchairs, electric trolleys, etc., which incorporate a secondary battery as part of their power mechanism. In this invention, "aircraft" refers to manned aircraft, unmanned aerial vehicles, drones, etc., which incorporate a secondary battery as part of their propulsion mechanism. In this invention, "electronic device" refers to an entire device that incorporates a secondary battery as an energy storage device; optoelectronic devices and information terminal devices are all examples of electronic devices.

[0059] The circuit board of the present invention is characterized by using the aforementioned resin composition as a raw material. By using the aforementioned resin composition as a raw material, the coefficient of linear expansion is reduced, resulting in excellent heat resistance.

[0060] The circuit board of this invention can be obtained by providing wiring portions on a resin film serving as a substrate. The resin film used to form the substrate can be manufactured using the same method as the aforementioned thin film. Reinforcing fibers can also be added to strengthen the substrate. Examples of reinforcing fibers include: glass fiber, metal fiber, other synthetic or natural inorganic fibers; natural fibers such as cotton, hemp, and felt fibers; carbon fiber, etc. Reinforcing fibers can be added as a single type or in combination of two or more types.

[0061] The circuit board of this invention can have wiring portions provided on one or both sides of the resin film. Methods for forming the wiring portions include those that pattern a conductive material on the resin film, such as lamination, metallization, sputtering, vapor deposition, coating, and printing. Conductive materials include metals such as copper, silver, and gold; indium tin oxide (ITO); and conductive resins such as polythiophene, polyaniline, and polypyrrole. Furthermore, to improve the adhesion between the resin film and the conductive material before patterning, surface modification such as plasma treatment can be performed, or an adhesive can be applied to the resin film beforehand.

[0062] The circuit board of this invention is suitable for mounting on precision machines and flexible machines.

[0063] The diaphragm of this invention is characterized by using the aforementioned resin composition as a raw material. By using the aforementioned resin composition as a raw material, a high Young's modulus can be obtained, resulting in a diaphragm with excellent latency characteristics and superior high-frequency output. The film thickness of the diaphragm of this invention is preferably between 5 μm and 50 μm. With a film thickness of 5 μm or more, high mechanical strength and good operational performance can be obtained. By keeping the film thickness below 50 μm, good transient characteristics are easily obtained.

[0064] The vibrating plate of this invention can be a smooth thin film, or any shape such as conical or corrugated. In the case of a smooth thin film, it can be manufactured using the same method as the aforementioned thin film. For forming any shape, methods include: cutting, stacking, bending, etc., of the smooth thin film; transferring the shape by pressing it into a mold; or directly obtaining a film of any shape by coating the aforementioned solution onto a mold, etc. The vibrating plate of this invention is suitable for use as a component in speaker horns, microphones, ultrasonic actuators, and ultrasonic sensors. [Example]

[0065] The following examples further illustrate the present invention.

[0066] The methods for measuring physical properties and evaluating effects in this invention are carried out according to the following methods.

[0067] (1) Ultrasonic treatment The ultrasonic treatment of the solution is carried out using the following apparatus and conditions. Immerse the glass tube containing 10 mL of the sample solution in an ultrasonic cleaner (BRANSONIC220, output / frequency: 75W / 45kHz, manufactured by Yamato Scientific Co., Ltd.) filled with water and vibrate.

[0068] (2) Average hydrodynamic radius (average particle size) The cumulative average particle size was determined by dynamic light scattering using the following apparatus and conditions for a solution in which 100 ppm of the resin composition was dispersed in pure water. The particle size obtained from the solution without ultrasonic treatment is denoted as rA (nm), and the particle size after ultrasonic treatment for 1 hour is denoted as rB (nm). Device: ELSZ-1000 (manufactured by Otsuka Electronics Co., Ltd.) Test conditions: in accordance with JIS-Z8826 (2005).

[0069] (3) Specific surface area The following apparatus and conditions were used to determine the resin composition after it had been degassed under reduced pressure for 12 hours at room temperature in a glass cell. Device: BELSORP-max (manufactured by Bell Japan) Adsorbate: Krypton Dead volume measurement gas: Helium Measurement temperature: 77K Saturated vapor pressure: 0.331 kPa Surface area analysis method: Multilayer adsorption (BET) multipoint method Test conditions: in accordance with JIS-Z8830 (2013). (4) Average molecular weight The resin composition was dissolved in the test solvent at 60°C to a concentration of 1.0 g / L. The solution was filtered through a 0.5 μm filter, and the number average molecular weight Mn and mass average molecular weight Mw were determined using the following apparatus and conditions. Apparatus: Gel permeation chromatography system No. GPC-26 (manufactured by Toray Research Center) Detector: Differential refractive index detector RID-20A (manufactured by Shimadzu Corporation) Column: 2 tubes of TSKgelα-M (φ7.8mm×30cm, manufactured by TOSOH) Determination solvent: Dimethylacetamide with 0.05M lithium chloride and 0.1% by mass phosphoric acid was added. Flow rate: 0.8 mL / mm Column temperature: 40℃ Injection volume: 0.2 mL Standard sample: Monodisperse polystyrene (manufactured by TOSOH). (5) Confirm solubility The solubility of the resin composition is evaluated as follows. The resin composition was added to NMP to form a 10% (w / w) solution and then ultrasonically treated at 60°C. The solution was evaluated as "good" if it was completely dissolved visually after 10 minutes of ultrasonic treatment; "acceptable" if any residue remained and was further ultrasonically treated for 20 minutes until completely dissolved; and "unacceptable" if any residue remained.

[0070] (6) Confirm operability The angle of repose is used as an indicator of the workability of resin compositions. The smaller the angle of repose, the higher the flowability and jetting properties of the resin composition, and the more difficult it becomes to work with. The angle of repose of each resin composition is determined using the funnel injection method (free stacking method) as follows. In an atmospheric environment with temperature and humidity adjusted to 25°C and 60%RH, a funnel with an inner diameter of 5mm is used to allow the resin composition to flow from a height of 15cm onto a measuring stage with a diameter of 5cm, causing the resin composition to accumulate into a cone shape. The angle of repose is measured by reading the angle formed by the lateral surface of this cone and the measuring stage (base of the cone) using a protractor.

[0071] (7) Volatile impurities The following apparatus and methods were used to determine the resin composition. Apparatus: TGA-50 thermogravimetric analyzer (manufactured by Shimadzu Corporation), TA-60WS thermal analysis system (manufactured by Shimadzu Corporation) Measurement environment: Nitrogen gas (20 mL / min) Measurement temperature: 25~330℃ Heating rate: 5℃ / min.

[0072] (8) Young's Modulus Tensile tests were conducted on films cut into 10 mm wide and 150 mm long samples using a Robot Tensilon AMF / RTA-100 (Orientec) under conditions of 50 mm clamp spacing, 300 mm / min stretching speed, 23 °C temperature, and 65% relative humidity. The Young's modulus was determined from the resulting load-elongation curves. The tests were performed in both the casting direction (length direction) and the direction perpendicular to it (width direction), with five average values ​​taken in each direction. Table 1 shows the higher Young's modulus value between the two directions. (9) Long-term stability (long-term heat resistance temperature) For samples cut into 10mm wide and 150mm long pieces, a Tensilon RTF1210 universal testing machine (manufactured by AND Corporation) and a constant temperature bath for tensile testing (manufactured by Orientec Corporation) were used. Under conditions of 50mm clamp spacing, 300mm / min tensile speed, and 65% relative humidity, five tensile tests were conducted at 25℃, 50℃, and 70℃ respectively. The Young's modulus at each temperature was measured and taken as its average value. A logarithmic plot of the obtained Young's modulus relative to temperature was plotted. The Arenyi plot was extrapolated using the least squares method to find the temperature at which the Young's modulus relative to 25℃ was halved. This temperature was defined as the long-term heat resistance temperature. Long-term stability was evaluated as follows: conditions with a long-term heat resistance temperature above 170℃ were rated as excellent; conditions below 170℃ but above 160℃ were rated as acceptable; and conditions below 160℃ were rated as unacceptable. The results are shown in Table 1.

[0073] (Example 1) Under a nitrogen atmosphere, 2-chloro-1,4-phenylenediamine (CTPA), representing 85 mol% of the total diamine content, and 4,4'-diaminodiphenyl ether (DPE), representing 15 mol%, were dissolved in a polymerization solvent prepared by mixing dehydrated dimethylacetamide (DMAc) and tetrahydrofuran (THF) in a 1:1 volume ratio. The solution was cooled to 5°C using an ice-water bath. While maintaining the system under a nitrogen atmosphere and in an ice-water bath, 2-chloroterephthalic acid chloride (CTPC), representing 99 mol% of the total diamine content, was added over 30 minutes. After the complete addition, the mixture was stirred for approximately 2 hours to polymerize an aromatic polyamide (polymer A). 2-Propanol, representing 100 vol% of the polymerization solvent, was then added to the resulting solution over 30 minutes. After the dripping was completed, the mixture was stirred for another 30 minutes, and then the solid components were filtered out by suction filtration. The mixture was then dried in a hot air oven at 80°C for 1 hour and then at 120°C for 12 hours to obtain a resin composition with polymer A as the main component. Here, a Safety Oven SPH100 ​​(manufactured by Espec Corporation) was used, and the temperature was maintained at 50% damper for 1 hour after reaching the set temperature. This resin composition was dissolved in NMP to form a 10% by mass solution, which was then cast onto a glass plate at room temperature using a spreader to form a film. This film was dried in a hot air oven at 150°C for 20 minutes, followed by drying at 280°C for 5 minutes to obtain a film with a thickness of 5 μm. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 173°C.

[0074] (Example 2) Except for using 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB) as the diamine (equivalent to 100 mol% of the total diamine content), CTPC (equivalent to 99 mol% of the total diamine content) as the chloroacetate, and decane as a poor solvent, a resin composition with aromatic polyamide (polymer B) as the main component was obtained in the same manner as in Example 1. A film was obtained in the same manner as in Example 1, except that using this resin composition. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 170°C. (Example 3) Except for using a mixed solvent of DMAc (60 vol%) and dibutyl ether (40 vol%) as the polymerization solvent and ethanol as a poor solvent, a resin composition with polymer A as the main component and a film using the same were obtained in the same manner as in Example 1. The physical properties of the obtained resin composition and film are shown in Table 1. In addition, the long-term heat resistance temperature of the film is 174°C.

[0075] (Example 4) Except for using a mixed solvent of DMAc (80 vol%) and THF (20 vol%) as the polymerization solvent and ethanol as a poor solvent, a resin composition with polymer A as the main component and a film using the same were obtained in the same manner as in Example 1. The physical properties of the obtained resin composition and film are shown in Table 1. In addition, the long-term heat resistance temperature of the film is 169°C.

[0076] (Example 5) Except for using a mixed solvent of DMAc (90 vol%) and THF (10 vol%) as the polymerization solvent and 2-propanol as a poor solvent, a resin composition with polymer A as the main component and a film using the same solvent were obtained in the same manner as in Example 1. The physical properties of the obtained resin composition and film are shown in Table 1. In addition, the long-term heat resistance temperature of the film is 168°C. (Example 6) Except for using a mixed solvent of NMP (95 vol%) and THF (5 vol%) as the polymerization solvent and 2-propanol as a poor solvent, a resin composition with polymer A as the main component and a film using the same were obtained in the same manner as in Example 1. The physical properties of the obtained resin composition and film are shown in Table 1. The long-term heat resistance temperature of the film obtained using this resin composition is 168°C.

[0077] (Example 7) Under a nitrogen atmosphere at room temperature, TFMB (100 mol% of the total diamine) was dissolved in a polymerization solvent prepared by mixing dehydrated dimethylacetamide (DMAc) and tetrahydrofuran (THF) in a 1:1 volume ratio. 4,4'-(hexafluoroisopropylidene) phthalic anhydride (6FDA) (99 mol% of the total diamine) was added over 30 minutes. After the total amount was added, the mixture was stirred for approximately 2 hours to polymerize aromatic polyacrylic acid (polymer C). The resulting solution was cooled using an ice-water bath, and 2-propanol (100 vol% of the polymerization solvent) was added over 30 minutes as a poor solvent. After the addition was complete, the mixture was stirred for another 30 minutes. The solid components were then filtered out by vacuum filtration and dried in a hot air oven at 80°C for 1 hour and then at 100°C for 12 hours to obtain a resin composition with polymer C as the main component. Here, a Safety Oven SPH100 ​​(manufactured by Espec Corporation) was used in the hot air oven. The temperature was maintained at 50% airflow and the set temperature was reached for 1 hour before use. The resin composition was dissolved in NMP to form a 10% by mass solution, which was then cast onto a glass plate at room temperature using a spreader to form a film. This film was dried in a hot air oven at 150°C for 20 minutes, followed by drying at 280°C for 5 minutes, and then heat-treated at 350°C for 10 minutes to obtain a film with a thickness of 5 μm. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 181°C.

[0078] (Example 8) The resin composition obtained in the same manner as in Example 2 was dissolved in NMP to a concentration of 10% by mass. This solution was then cast onto a glass plate at room temperature using a spreader to form a film. The film was dried in a hot air oven at 150°C for 20 minutes and then at 280°C for 3 minutes to obtain a film with a thickness of 3 μm. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 170°C.

[0079] (Example 9) The resin composition obtained in the same manner as in Example 2 was dissolved in NMP to a concentration of 10% by mass. This solution was then cast onto a glass plate at room temperature using a spreader to form a film. The film was dried in a hot air oven at 150°C for 20 minutes and then at 280°C for 3 minutes to obtain a film with a thickness of 1 μm. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 164°C.

[0080] (Example 10) The resin composition obtained in the same manner as in Example 2 was dissolved in NMP to a concentration of 10% by mass. This solution was then cast onto a glass plate at room temperature using a spreader to form a film. The film was dried in a hot air oven at 150°C for 20 minutes and then at 280°C for 5 minutes to obtain a film with a thickness of 50 μm. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 176°C.

[0081] (Example 11) The resin composition obtained in the same manner as in Example 2 was dissolved in NMP to a concentration of 10% by mass. This solution was then cast onto a glass plate at room temperature using a spreader to form a film. The film was dried in a hot air oven at 150°C for 20 minutes and then at 280°C for 7 minutes to obtain a film with a thickness of 78 μm. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 176°C.

[0082] (Example 12) The resin composition obtained in the same manner as in Example 2 was dissolved in NMP to a concentration of 10% by mass. This solution was then cast onto a glass plate at room temperature using a spreader to form a film. The film was dried in a hot air oven at 150°C for 20 minutes and then at 280°C for 10 minutes to obtain a film with a thickness of 97 μm. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 178°C.

[0083] (Comparative Example 1) Under a nitrogen gas flow, 85 mol% of CTPA (a diamine) and 15 mol% of DPE were dissolved in dehydrated N-methyl-2-pyrrolidone (NMP), and the liquid temperature was cooled to 5°C in an ice-water bath. While maintaining the system under a nitrogen gas flow and in an ice-water bath, 99 mol% of CTPC (relative to the total diamine) was added over 30 minutes. After the total amount was added, the mixture was stirred for approximately 2 hours to polymerize an aromatic polyamide (polymer A). The resulting polymer solution was added to a large volume of pure water while stirring, causing polymer A to solidify into a fibrous form. Polymer A was then removed and pulverized in a mixer for 5 minutes, dried in an 80°C hot air oven for 1 hour, and then dried in a 120°C vacuum oven for 12 hours to obtain a resin composition with polymer A as the main component. A film was obtained similarly to that in Example 1, except using this resin composition. The properties of the obtained resin composition and film are shown in Table 1. In addition, the long-term heat resistance temperature of this film is 155℃.

[0084] (Comparative Example 2) The resin composition obtained in the same manner as in Comparative Example 1 was dissolved in NMP. The resulting polymer solution (8% by mass) was coated onto a 100 μm polyethylene terephthalate (PET) film using a die coater to form a film with a thickness of approximately 120 μm. The film was then treated in conditioned air at 30°C and 85% RH for 2 minutes. Next, after peeling off the opaque film from the PET film, the film was immersed in a 60°C water bath for 2 minutes for solvent extraction. The film was then dried in a tenter frame initially at 90°C for 1 minute. Finally, it was heat-treated in a hot air oven at 250°C for 2 minutes to obtain a porous film. This film was pulverized using a mixer to obtain a resin composition with polymer A as the main component. A film was obtained in the same manner as in Example 1, except that using this resin composition. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 150°C.

[0085] (Comparative Example 3) The polymer polymerized in the same manner as in Comparative Example 1 was separated using a separating GPC (Prominence, manufactured by Shimadzu Corporation) to isolate only the components with an intensity range exceeding 20% ​​of the maximum peak intensity detected by a differential refractive index detector (RID-10A, manufactured by Shimadzu Corporation), thus obtaining a polymer solution. This polymer solution was then added to a large volume of pure water while stirring, causing polymer A to solidify into a fibrous form. Polymer A was then removed, pulverized, dried in an 80°C hot air oven for 1 hour, and then dried in a 120°C vacuum oven for 12 hours to obtain a resin composition with polymer A as the main component. A film was obtained using this resin composition, similar to Example 1. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of this film is 168°C.

[0086] (Comparative Example 4) Except that the grinding time in the mixer was set to 1 minute, a resin composition using the obtained polymer A as the main component was obtained in the same manner as in Comparative Example 1. A film was obtained in the same manner as in Example 1, except that the resin composition was used. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of the film is 153°C.

[0087] (Comparative Example 5) The polymer solution obtained in the same manner as in Comparative Example 1 was diluted with NMP to achieve a polymer content of 0.1% by mass. While stirring the diluted solution, a large amount of pure water was added dropwise to suspend the solution, and then the solution was filtered to obtain a resin composition with polymer A as the main component. A film was obtained in the same manner as in Example 1, except that a different resin composition was used. The properties of the obtained resin composition and film are shown in Table 1. Furthermore, the long-term heat resistance temperature of the film is 157°C.

[0088] [Table 1] resin composition film polymer r A / r B (-) r B (nm) BET specific surface area (m 2 / g) M w / M n (-) Solubility Angle of repose (°) Residual volatile matter (quality%) Film thickness (μm) Young's module (GPa) Long-term stability Example 1 A 6.7 2410 71 2.1 good 50 0.5 5 9.1 good Example 2 B 5.2 2350 68 2.5 good 48 0.7 5 8.6 good Example 3 A 6.5 102 75 1.8 good 51 0.5 5 9.3 good Example 4 A 5.0 2480 51 2.6 good 45 2.7 5 8.4 Can Example 5 A 4.8 3320 47 2.8 Can 42 3.4 5 8.3 Can Example 6 A 3.1 4740 48 2.7 Can 35 3.1 5 8.3 Can Example 7 C 3.0 3560 51 2.3 good 37 2.8 5 6.5 good Example 8 B 5.2 2350 68 2.5 good 48 0.7 3 8.6 good Example 9 B 5.2 2350 68 2.5 good 48 0.7 1 8.5 Can Example 10 B 5.2 2350 68 2.5 good 48 0.7 50 8.3 good Example 11 B 5.2 2350 68 2.5 good 48 0.7 78 8.2 good Example 12 B 5.2 2350 68 2.5 good 48 0.7 97 8.0 good Comparative Example 1 A 2.8 5830 46 2.6 No 55 4.0 5 8.6 No Comparative Example 2 A 2.8 5100 53 2.8 No 53 2.9 5 8.4 No Comparative Example 3 A 2.4 5810 38 2.2 No 53 3.4 5 8.9 good Comparative Example 4 A 2.0 10200 42 2.6 No 62 4.7 5 8.5 No Comparative Example 5 A 1.2 95 93 2.9 good 18 0.6 5 8.2 No

[0089] none

Claims

1. A resin composition having aromatic polyamide as the main component, wherein when the powder is made into an aqueous dispersion of 100 ppm by mass and the average hydrodynamic radius measured by dynamic light scattering is defined as rA (nm), and the average hydrodynamic radius after ultrasonic treatment of the dispersion is defined as rB (nm), the ratio of rA to rB is 3 or more and the ratio of rB is 100 nm or more and 5000 nm or less.

2. The resin composition of claim 1, wherein the multilayer adsorption (BET) specific surface area determined by gas adsorption method is 50 m2 / g or more and 90 m2 / g or less.

3. The resin composition of claim 1, wherein when the number average molecular weight determined by gel permeation chromatography (GPC) is set as Mn and the mass average molecular weight is set as Mw, the ratio of Mw / Mn is 1.0 or more and 2.5 or less.

4. A film made using a resin composition as claimed in claim 1.

5. An optical lens made using a resin composition as claimed in claim 1.

6. A diffractive optical element made using a resin composition as claimed in claim 1.

7. An ion-conducting membrane made using a resin composition as claimed in claim 1.

8. A battery separator made using a resin composition as claimed in claim 1.

9. A secondary battery comprising an ion-conducting membrane as claimed in claim 7 or a battery separator as claimed in claim 8.

10. A circuit board made using the resin composition as claimed in claim 1.

11. A vibrating plate made of a resin composition as claimed in claim 1.