Polyphenylene ether resin composition and uses thereof

Abstract

A purpose of the present invention is to provide a polyphenylene ether resin composition having excellent film-forming properties, thermosetting properties, adhesiveness, and ATF resistance. Another purpose of the present invention is to provide: a coating agent, paint, and adhesive comprising the polyphenylene ether resin composition of the present invention; and a laminate, wiring board, metal composite, secondary battery exterior, covered wire for motor coils, and fiber-reinforced composite resin comprising a layer formed from the polyphenylene ether resin composition of the present invention. The present invention relates to a polyphenylene ether resin composition comprising a polyphenylene ether component-containing resin and an organic solvent. The polyphenylene ether component has a radical amount of 100 g-1 or greater as measured by electron spin resonance, a weight average molecular weight of 10,000 or greater, and a structure B represented by general formula (2) in a repeating unit A represented by general formula (1). The structure B content is 1.2 mol% or greater in relation to the total amount of the repeating unit A and the structure B in the polyphenylene ether component. (In the formula, R1 and R2 are each independently a hydrogen atom or a C1-C10 hydrocarbon group that may have a substituent, and each R3 independently represents a C1-C10 hydrocarbon group that may have a substituent.) (In the formula, R1 and R2 are each independently a hydrogen atom or a C1-C10 hydrocarbon group that may have a substituent, each R3 is independently a C1-C10 hydrocarbon group that may have a substituent, and R3' represents a divalent group obtained by removing one hydrogen atom from the R3.)

Description

Polyphenylene ether resin composition and its applications

[0001] The present invention relates to polyphenylene ether resin compositions and their applications (coating agents, paints, adhesives, laminates, wiring boards, metal composites, casings for secondary batteries, insulated wires for motor coils, and fiber-reinforced composite resins).

[0002] Polyphenylene ether (hereinafter also referred to as "PPE") is widely used as a material for products and components in the electrical and electronic, automotive, and food and packaging fields, as well as in various other industrial materials, due to its excellent high-frequency properties, flame retardancy, and heat resistance. In particular, in recent years, its low dielectric properties and heat resistance have led to its application as a modifier in various applications, including electrical and electronic applications such as substrate materials.

[0003] However, generally speaking, high molecular weight PPEs (polymethyl phenylethylennium) with repeating units derived from monovalent phenols, such as 2,6-dimethylphenol, are soluble in highly toxic solvents such as chloroform, but are poorly soluble in aromatic solvents such as toluene, which are known as good solvents, and are insoluble in ketone solvents such as methyl ethyl ketone. Therefore, when used as adhesives or coatings, for example, handling with resin varnish solutions such as toluene or methyl ethyl ketone was difficult.

[0004] Furthermore, in recent years, studies have been conducted to improve the solvent solubility of PPE, and solutions containing PPE are known (see, for example, Patent Documents 1 and 2). Patent Document 1 focuses on the fact that branched PPE has an increased number of hydroxyl groups due to the branched structure, and describes how to improve solvent solubility and crack resistance by modifying some or all of the terminal hydroxyl groups of the PPE with functional groups having unsaturated carbon bonds. Patent Document 2 describes a resin composition containing low molecular weight PPE having a PPE portion in its molecular structure and having at least one p-ethenylbenzyl group or m-ethenylbenzyl group at the end of this molecular structure, and a crosslinking curing agent, and describes that the low molecular weight PPE is soluble in a solvent.

[0005] Patent No. 7497143 Patent No. 4211784

[0006] In Patent Document 1, some or all of the terminal hydroxyl groups of PPE are modified into functional groups having unsaturated carbon bonds. By losing the highly polar hydroxyl groups, it is expected that the adhesion will be insufficient when a composition containing this modified polyphenylene ether is applied to an adhesive layer. In Patent Document 2, low molecular weight PPE is used, so it is expected that it will be insufficient in terms of film-forming ability, mechanical strength, durability, etc.

[0007] Therefore, an object of the present invention is to provide a PPE resin composition that is excellent in film-forming properties, thermosetting properties, adhesive properties, and ATF resistance. Furthermore, an object of the present invention is to provide coating agents, paints, adhesives containing the PPE resin composition of the present invention, and laminates, wiring boards, metal composites, casings for secondary batteries, coated wires for motor coils, and fiber-reinforced composite resins containing layers formed from the PPE resin composition of the present invention.

[0008] The present inventors conducted thorough research on PPE resin compositions and found that the above problems can be solved by using a PPE resin composition having the following configuration, thus completing the present invention.

[0009] [1] A PPE resin composition containing a resin containing a PPE component and an organic solvent, wherein the PPE component has a radical amount of 100 g as measured by electron spin resonance. －１ The PPE resin composition having a weight-average molecular weight of 10,000 or more, having a repeating unit A represented by the following general formula (1) and a structure B represented by the following general formula (2), wherein the content of structure B is 1.2 mol% or more relative to the total amount of repeating unit A and structure B in the PPE component. (In the formula, R １ , R ２ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have substituents, and R ３ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. (In the formula, R １ , R ２ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have substituents, and R３ is, independently of each other, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ ’ represents a divalent group obtained by removing one hydrogen atom from the above R ３ ). [2] The PPE resin composition according to [1], wherein the hydroxyl equivalent of the PPE component is 100 eq / t or more. [3] The PPE resin composition according to [1] or [2], wherein the weight average molecular weight of the PPE component is 100,000 or less. [4] The PPE resin composition according to any one of [1] to [3], wherein the organic solvent is an aromatic hydrocarbon solvent or an amine solvent. [5] A coating agent containing the PPE resin composition according to any one of [1] to [4]. [6] A paint containing the PPE resin composition according to any one of [1] to [4]. [7] An adhesive containing the PPE resin composition according to any one of [1] to [4]. [8] A laminate having a base material and a layer formed from the PPE resin composition according to any one of [1] to [4]. [9] A wiring board having a coating layer formed from the PPE resin composition according to any one of [1] to [4].

[10] A metal composite having a metal structure and a coating layer formed from the PPE resin composition according to any one of [1] to [4].

[11] An exterior for a secondary battery formed from the metal composite according to

[10] .

[12] A coated wire for a motor coil formed from the metal composite according to

[10] .

[13] A fiber-reinforced composite resin having carbon fiber or glass fiber and a coating layer made of the PPE resin composition according to any one of [1] to [4].

[0010] It is a figure which shows typically one Embodiment of the manufacturing method of the PPE resin used by this invention.

[0011] ≪Polyphenylene ether (PPE) resin composition≫ The PPE resin composition of the present invention contains a resin containing a PPE component and an organic solvent. The PPE component has a radical amount measured by an electron spin resonance method of 100 g －１The PPE resin composition has a weight-average molecular weight of 10,000 or more, and contains a repeating unit A represented by the following general formula (1) with a structure B represented by the above general formula (2), wherein the content of structure B is 1.2 mol% or more relative to the total amount (100 mol%) of repeating units A and structure B in the PPE component. With this configuration, the PPE resin composition exhibits excellent solubility when dissolved in organic solvents, and the molded article formed from the PPE resin composition exhibits excellent film-forming properties, thermosetting properties, adhesive properties, and ATF resistance. Conventionally, PPE resins (especially PPE resins containing a high content of PPE components) have been known to be poorly soluble in aromatic solvents such as toluene, which are known as good solvents, and insoluble in ketone solvents such as methyl ethyl ketone. Therefore, it has been considered difficult to handle PPE resins containing high molecular weight PPE components as resin varnish solutions such as toluene or methyl ethyl ketone. The present inventors have newly discovered that, by having a specific configuration, PPE resins can be used as resin varnishes such as toluene despite containing high molecular weight PPE components. The following describes each component included in the PPE resin composition of the present invention.

[0012] <Resin> The resin contained in the PPE resin composition of the present invention contains a PPE component. The PPE component has a repeating unit A (phenylene ether units connected by para bonds) represented by the following general formula (1), and a structure B (a rearrangement structure connected by ortho bonds) represented by the following general formula (2). (In the formula, R １ , R ２ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have substituents, and R ３ Each of these independently represents a hydrocarbon group having 1 to 10 carbon atoms, which may have substituents. (In the formula, R １ , R ２ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have substituents, and R ３ Each is independently a hydrocarbon group having 1 to 10 carbon atoms, which may have substituents, and R ３ ' is the aforementioned R ３represents a divalent group from which one hydrogen atom has been removed.)

[0013] In the general formula (2), "~" indicates that the subsequent structure is not particularly limited. The portion of "~" may be formed from phenylene ether units connected by para bonds, and may also have a portion connected by ortho bonds therein.

[0014] The structure B is formed, for example, by the reaction represented by the following formula, and is sometimes called methylene bridge rearrangement.

[0015] Further, the PPE component may include a structure represented by the following formula (i) or (ii) as a terminal structure.

[0016] R in the general formulas (1), (2), (i), and (ii) １ , R ２ , R ３ Examples of the hydrocarbon group having 1 to 10 carbon atoms in R, R, and R include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, decyl group, etc.; aryl groups having 6 to 10 carbon atoms such as phenyl group, 4-methylphenyl group, 1-naphthyl group, 2-naphthyl group, etc.; aralkyl groups having 7 to 10 carbon atoms such as benzyl group, 2-phenylethyl group, 1-phenylethyl group, etc.

[0017] When the hydrocarbon group has a substituent, examples of the substituent include halogen atoms such as fluorine atom, and alkoxy groups such as methoxy group. Specific examples of the hydrocarbon group having a substituent include, for example, trifluoromethyl group, etc.

[0018] Among these, R, R are preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom, and R is preferably a methyl group. １ , R ２ As for R ３ ', it is the same as R

[0019] The R ３ ' is the same as the R ３represents a divalent group from which one hydrogen atom has been removed, and a methylene group is preferred.

[0020] Specific examples of the repeating unit of the general formula (1) include repeating units derived from 2,6-dimethyl-1,4-phenylene ether, 2,6-diethyl-1,4-phenylene ether, 2-methyl-6-ethyl-1,4-phenylene ether, and 2,6-dipropyl-1,4-phenylene ether. Among these, a repeating unit derived from 2,6-dimethyl-1,4-phenylene ether is preferred.

[0021] The PPE component preferably has a structure B represented by the general formula (2) in a homopolymer having a repeating unit A of the general formula (1) or a copolymer containing two or more different repeating units A of the general formula (1).

[0022] In addition, the PPE component having the structure B can contain a repeating unit a other than the general formula (1) as long as the effects of the present invention are not impaired. In that case, it can be a copolymer containing the repeating unit A of the general formula (1) and a repeating unit a other than the general formula (1) and having the structure B represented by the general formula (2). The content of the repeating unit a other than the general formula (1) is not particularly limited as long as the effects of the present invention are not impaired. For example, it is preferably about 5 mol% or less in the copolymer, and more preferably not contained.

[0023] The content of the structure B in the PPE component is 1.2 mol% or more, preferably 1.5 mol% or more, more preferably 1.7 mol% or more, and further preferably 2 mol% or more with respect to the total amount (100 mol%) of the repeating unit A and the structure B. Also, the content of the structure B is preferably 15 mol% or less, more preferably 12 mol% or less, and further preferably 10 mol% or less. When the content of the structure B is within the above range, the number of bent structures increases, the orientation and re-aggregation of polymer molecules after dissolution in a solvent are reduced, and the solubility in the solvent becomes good.

[0024] The structure B is a nuclear magnetic resonance spectrum ( １In 1H-NMR measurements, it is preferable to show peaks in the ranges of 3.8–4.0 ppm and 6.8–7.0 ppm. Typically, PPE shows a peak around 6.4–6.6 ppm, which is a peak originating from the hydrogen atoms at positions 3 and 5 of the benzene ring in the PPE main chain. PPE having structure B shows peaks in the ranges of 3.8–4.0 ppm and 6.8–7.0 ppm, in addition to the peak around 6.4–6.6 ppm. The chemical shift at 3.8–4.0 ppm is due to R in the structure. ３’ This originates from the proton of the divalent group (e.g., methylene group) shown, and the chemical shift of 6.8 to 7.0 ppm is due to the R at positions 3 and 5 of PPE in structure B. １ , R ２ It originates from the protons of the group (for example, the hydrogen atoms at positions 3 and 5 of the benzene ring bonded to the ortho position via a methylene group).

[0025] The molecular weight of the PPE is preferably 10,000 or more, more preferably 20,000 or more, and more preferably 30,000 or more, with a weight-average molecular weight (Mw) of 10,000 or less, and more preferably 90,000 or less. Having a weight-average molecular weight within this range ensures that the film-forming properties and solution viscosity during dissolution are suitable for processing.

[0026] The number-average molecular weight (Mn) of the PPE component is not particularly limited, but is preferably 4,000 to 30,000, and more preferably 8,000 to 20,000. The molecular weight dispersion (Mw / Mn) is preferably 2.5 to 10.0, and more preferably 3.0 to 8.0.

[0027] The amount of radicals measured by electron spin resonance (ESR) of the aforementioned PPE component was 100 g. －１ That's all, 120g －１ The above is preferable, 150g －１ The above is more preferable, 300g －１ The above is particularly preferable. The amount of radicals is 900 g. －１ The following is preferable: 800g －１ The following is more preferable: 700g －１The following is even more preferable: The radical content being within the aforementioned range results in excellent thermosetting properties and ATF resistance.

[0028] The hydroxyl group equivalent of the PPE component is preferably 100 eq / t or more, more preferably 130 eq / t or more, even more preferably 150 eq / t or more, and particularly preferably 300 eq / t or more. A hydroxyl group equivalent of less than 100 eq / t is undesirable because it may result in poor adhesion. There is no particular upper limit to the hydroxyl group equivalent, but it is preferably 800 eq / t or less, and more preferably 700 eq / t or less.

[0029] The glass transition temperature of the PPE component is not particularly limited, but is preferably 180°C or higher, and more preferably 190°C or higher. A glass transition temperature within this range is preferable because it increases heat resistance. Furthermore, the upper limit of the glass transition temperature is not particularly limited, but is preferably 250°C or lower, more preferably 240°C or lower, and even more preferably 230°C or lower.

[0030] The PPE component used in the present invention may include PPE that does not have the aforementioned structure B. Examples of PPE that does not have the aforementioned structure B include a homopolymer having the repeating unit A of general formula (1), a copolymer containing two or more different repeating units A of general formula (1), and a copolymer having the repeating unit A of general formula (1) and repeating units a other than general formula (1). The content of repeating units a of general formula (1) or less in the copolymer can be as described above.

[0031] The resin used in the present invention contains the PPE component, but the PPE component content is preferably 95% by weight or more, more preferably 98% by weight or more, and even more preferably a resin consisting substantially only of the PPE component (100% by weight). Having the PPE component content in the resin within the above range is preferable because it results in a PPE resin composition with excellent heat resistance, chemical resistance, flame retardancy, ATF resistance, etc.

[0032] The resin used in the present invention may contain resin components other than the PPE component. Examples of resin components other than the PPE component include styrene, polyethylene, polypropylene, polyamides such as polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 66, polyamide 6T, and polyamide 6T / 11, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polycarbonates. However, the content of these components is preferably 5% by weight or less, more preferably 2% by weight or less, and even more preferably none (0% by weight).

[0033] <Organic Solvent> The PPE resin composition of the present invention comprises a resin containing the PPE component and an organic solvent, wherein the resin containing the PPE component is dissolved in the organic solvent.

[0034] Examples of the aforementioned organic solvents include: alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, and butanol; acetic acid ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone-based solvents such as acetone and methyl ethyl ketone; aromatic hydrocarbon-based solvents such as toluene, xylene, and Solvesso® 100 (manufactured by ENEOS Corporation); cyclic ether-based solvents such as dioxane; amine-based solvents such as N-methylpyrrolidone, N-dimethylformamide, and N-dimethylacetamide; and aliphatic hydrocarbon-based solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane. These organic solvents may be used individually or in combination of two or more.

[0035] Among these, aromatic hydrocarbon solvents and amine solvents are preferred from the viewpoint of dissolution at higher concentrations and stability after dissolution, with toluene, xylene, N-methylpyrrolidone, and Solvesso® 100 being more preferred.

[0036] Furthermore, when used as a mixed solvent containing two or more organic solvents, from the viewpoint of dissolution at higher concentrations and stability after dissolution, it is preferable that the organic solvent contains 30% by weight or more of an aromatic hydrocarbon solvent or an amine solvent, more preferably 40% by weight or more, and even more preferably 50% by weight or more.

[0037] The content of the organic solvent is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and even more preferably 200 parts by weight or more, per 100 parts by weight of the resin containing the PPE component. The content of the organic solvent is preferably 2000 parts by weight or less, more preferably 1800 parts by weight or less, even more preferably 1000 parts by weight or less, and particularly preferably 800 parts by weight or less. Having the organic solvent content within this range is preferable from the viewpoint of solubility and film-forming properties.

[0038] Furthermore, the PPE resin composition of the present invention does not require high temperatures when dissolving the resin in an organic solvent, and can be dissolved at room temperature to about 60°C. Also, the solid content concentration of the PPE resin composition solution is not particularly limited and can be set appropriately depending on the intended use of the PPE, but the PPE resin composition solution of the present invention can have a solid content concentration of about 5 to 80% by weight.

[0039] <Other Components> Additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, dulling agents, and antistatic agents may be added to the PPE resin composition of the present invention, to the extent that they do not impair the effects of the present invention.

[0040] <Method for producing PPE resin composition> The PPE resin composition of the present invention can be produced by manufacturing a molten extruded molded body such as PPE pellets by a method that includes the step of melt-extruding a raw material PPE (hereinafter also referred to as "raw material PPE") using an extruder equipped with a cylinder, screw and extrusion nozzle, and then dissolving the molten extruded molded body in the organic solvent.

[0041] Examples of raw material PPE include homopolymers having the repeating unit A of general formula (1), copolymers containing two or more different repeating units A of general formula (1), and copolymers having the repeating unit A of general formula (1) and repeating units a other than general formula (1). The content of repeating units a other than general formula (1) in the copolymer can be those mentioned above. Among these, homopolymers having the repeating unit A of general formula (1) are preferred.

[0042] Examples of homopolymers having the repeating unit A of the general formula (1) include poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2,6-dipropyl-1,4-phenylene ether), but among these, poly(2,6-dimethyl-1,4-phenylene ether) is preferred.

[0043] Commercially available poly(2,6-dimethyl-1,4-phenylene ether) products can also be suitably used. Specifically, examples include PPO630, PPO640, and PPO646 from SABIC Innovative Plastics, PX100L and PX100F from Mitsubishi Engineering Plastics Corporation, and LXN035 and LXN040 from Bluestar.

[0044] The glass transition temperature of the raw material PPE is preferably 170°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher. Furthermore, while there is no particular upper limit to the glass transition temperature, it is preferably 230°C or lower. Having the glass transition temperature of the raw material PPE within this range is preferable because it allows for the production of a PPE melt-extruded molded article with high heat resistance.

[0045] Furthermore, the raw materials used in the present invention may include two or more types of PPE having different glass transition temperatures. Specifically, in addition to PPE with a glass transition temperature of 170°C or higher, PPE with a glass transition temperature of less than 170°C may be included. Adding PPE with a glass transition temperature of less than 170°C reduces the melt viscosity and improves fluidity, but tends to reduce the content of structure B in the PPE.

[0046] In the raw material PPE, the content of PPE having a glass transition temperature of 170°C or higher is preferably 80% by weight or more, more preferably 90% by weight or more, even more preferably 95% by weight or more, and it is particularly preferable that it consists only of PPE having a glass transition temperature of 170°C or higher. Furthermore, there is no particular upper limit to the content of PPE having a glass transition temperature of 170°C or higher, but it is preferably 100% by weight or less. In the present invention, including PPE with a high glass transition temperature (i.e., high molecular weight) within the above range is preferable because it results in excellent mechanical strength, heat resistance, chemical resistance, flame retardancy, etc., of the resulting PPE melt extruded article.

[0047] Furthermore, along with the raw material PPE, resin components other than PPE and additives may be included. The resin components other than PPE and additives are as described above. The content of resin components other than PPE is preferably 5% by weight or less, more preferably 2% by weight or less, and even more preferably none (0% by weight).

[0048] As the extruder equipped with the cylinder, screw, and extrusion nozzle, a single-screw extruder or a twin-screw extruder, which are commonly used in this field, can be used. In the present invention, it is preferable to use a twin-screw extruder. The extruder is not limited to this, and any extruder that can effectively achieve the objective of shearing the polymer is acceptable.

[0049] The nozzle hole diameter of the extrusion nozzle is preferably 2 mm or less, more preferably 1.8 mm or less, and even more preferably 1.5 mm or less. A nozzle hole diameter of 2 mm or less is preferable because it allows for faster cooling of the PPE molten extruded molded body, suppressing surface oxidation, and consequently reducing the amount of insoluble matter during solvent dissolution.

[0050] The peripheral speed of the screw is necessary to generate enough material for the structure B to dissolve in the solvent, and is preferably 10 m / min or more, more preferably 15 m / min or more, and even more preferably 20 m / min or more. The upper limit of the peripheral speed of the screw is not particularly limited, but is preferably 94.2 m / min or less. In the present invention, by increasing the screw rotation speed to make the peripheral speed of the screw 10 m / min or more, it is possible to form PPE that satisfies the structure B content necessary for dissolution in an organic solvent.

[0051] The shape of the screw is not particularly limited; it should be one that can apply a shear force sufficient to cause a rearrangement reaction in the raw material PPE.

[0052] The temperature inside the cylinder (extrusion temperature) is 260°C or higher, preferably 280°C or higher, and more preferably 300°C or higher. Furthermore, the extrusion temperature is preferably 350°C or lower, and more preferably 345°C or lower. By setting the temperature inside the cylinder within the above range, it is possible to form PPE that satisfies the structural B content necessary for dissolution in the solvent, and surface oxidation of the PPE melt extruded molded body can be suppressed. As a result, the amount of insoluble matter during solvent dissolution can be suppressed, which is preferable.

[0053] An example of manufacturing PPE molten extruded products (pellets) will be explained using Figure 1. Raw PPE is fed from the hopper 1 in Figure 1 into an extruder 2 equipped with a cylinder, screw, and extrusion nozzle 5. The molten PPE is discharged from the nozzle, cooled on an air-cooled belt conveyor 3, and pelletized by a pelletizer 4. The extruder 2 may also be equipped with a degassing vent 10. To prevent oxygen from entering the extruder 2, an inert gas may be introduced beyond the degassing vent 10, or a vacuum pump may be attached.

[0054] The discharge rate from nozzle 5 is preferably 3 g / min or more, more preferably 5 g / min or more, and even more preferably 8 g / min or more. Furthermore, there is no particular upper limit to the discharge rate, but it is preferably 50,000 g / min or less, more preferably 40,000 g / min or less, and even more preferably 30,000 g / min or less.

[0055] The shape of the melt-extruded article is not limited to the pellet shape described above, but can be molded into various shapes such as film, sheet, plate, pipe, tube, rod, fiber, nonwoven fabric, paper, or cloth.

[0056] The organic solvents described above can be suitably used in the production of the PPE resin composition of the present invention.

[0057] The resulting PPE resin composition exhibits excellent film-forming properties, thermosetting properties, adhesive properties, and ATF resistance, making it suitable for various applications such as coatings, adhesives, and paints. Because it contains a small amount of insoluble matter during solvent dissolution, it can be used in various applications such as wiring board materials, wire insulation materials, lithium-ion battery package interior coatings, motor coil wire insulation materials, heat-resistant paints, can interior coatings, film capacitors, and insulating paper.

[0058] ≪Coating Agent≫ The coating agent of the present invention contains the PPE resin composition of the present invention. It may also optionally contain additives such as crosslinking agents, viscosity modifiers, adhesion improvers, defoaming agents, plasticizers, water-resistant agents, preservatives, antioxidants, penetrating agents, surfactants, fillers, starch and its derivatives, and latex. These additives may be used individually or in combination of two or more.

[0059] The content of the above-mentioned additive is, for example, 0.01 to 10 parts by weight relative to the total solid content weight of the coating agent.

[0060] The method for producing the coating agent is not particularly limited. For example, a coating agent of a predetermined concentration can be prepared by mixing the PPE resin composition, additives as needed, and stirring thoroughly at room temperature. Furthermore, the concentration of the coating agent may be adjusted by adding the same organic solvent as that contained in the PPE resin composition, or a different organic solvent.

[0061] There are no particular limitations on the coating method for applying the coating agent, and known methods can be used. Examples of coating methods include blade coaters, bar coaters, air knife coaters, slit die coaters, gravure coaters, microgravure coaters, gate roll coaters, and the like.

[0062] There are no particular limitations on the drying equipment used to dry the coating agent after application, and known equipment can be used. Examples of drying equipment include hot air dryers, infrared dryers, gas burners, and hot plates.

[0063] The coating agent of the present invention can be used as a coating agent for the inside and outside of cans, a coating agent for the interior and exterior of automobiles, aircraft, ships, motorcycles, etc., a coating agent for building materials such as flooring, tiles, concrete, exterior and interior walls, and reinforcing bars, a coating agent for electronic devices such as smartphones and personal computers, a coating agent for home appliances such as refrigerators and air conditioners, and the like.

[0064] ≪Paint≫ The paint of the present invention contains the PPE resin composition of the present invention. If necessary, additives such as crosslinking agents, weathering agents, surface modifiers, curing accelerators, antioxidants, anti-yellowing agents, bluing agents, pigments, leveling agents, defoaming agents, thickeners, anti-settling agents, antistatic agents, and anti-fogging agents may be added. These additives may be used individually or in combination of two or more.

[0065] The method for manufacturing the paint is not particularly limited. For example, a paint of a predetermined concentration can be prepared by mixing the PPE resin composition with additives and organic solvents as needed, and stirring and mixing thoroughly at room temperature. The concentration of the paint may also be adjusted by adding the same organic solvent as that contained in the PPE resin composition, or a different organic solvent.

[0066] There are no particular limitations on the method of coating the paint, and any known method can be used. For example, the methods mentioned above in the coating method for coating agents can be adopted.

[0067] There are no particular limitations on the drying equipment used to dry the paint; known equipment can be used. For example, the drying equipment mentioned above for coating agents can be used.

[0068] The paint of the present invention contains a PPE resin composition that is excellent in film-forming properties, thermosetting properties, adhesion, and ATF resistance, and can therefore be used as a paint for heat-resistant applications, as well as for coating the inside of cans, as a paint for mobility such as automobiles, aircraft, ships, and motorcycles, as a paint for building materials such as tiles, concrete, and exterior walls, and as an industrial paint for pre-coated metals and metal products.

[0069] <<Adhesive>> The adhesive of the present invention comprises the PPE resin composition of the present invention. The adhesive of the present invention enables good fixation, bonding, or protection of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.).

[0070] The adhesive of the present invention may contain only the PPE resin composition of the present invention, or it may contain various other additives.

[0071] The adhesive of the present invention contains a PPE resin composition that is excellent in film-forming properties, thermosetting properties, adhesion, and ATF resistance, and can therefore be used as an adhesive for electronic circuit boards, motors, and semiconductor electronics; an adhesive for secondary batteries such as lithium-ion batteries, fuel cells, and all-solid-state batteries; and an adhesive for automobiles such as engine compartments, electronic components, batteries, fuel components, and interior and exterior parts.

[0072] <Laminate> The laminate of the present invention includes a layer formed from a substrate and a PPE resin composition. By using a film substrate as the substrate, a laminated film can be formed.

[0073] As the film substrate, for example, films made of homopolymers or copolymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate, polyamide, polyvinyl chloride, polycarbonate (PC), cycloolefin polymer (COP), polystyrene, polypropylene (PP), polyethylene, polycycloolefin, polyurethane, acrylic (PMMA), and ABS can be used.

[0074] The aforementioned film substrate may be a single-layer film or a laminated film. For ease of processing, the thickness is preferably, for example, 5 μm to 1000 μm. The thickness of the film substrate can be measured, for example, using a film thickness gauge (dial gauge).

[0075] The laminated film can be formed by applying a PPE resin composition to a film substrate and then drying it.

[0076] For the application method and drying equipment, the application method and drying equipment mentioned above for the coating agent can be used.

[0077] The thickness of the layer formed from the PPE resin composition is not particularly limited and can be adjusted as appropriate depending on the application of the laminated film, but for example, a thickness of about 2 μm to 1000 μm is preferred.

[0078] The laminated film of the present invention can be used as an insulating material for motors in aircraft and automobiles, as a laminate constituting printed circuit boards, as a semiconductor manufacturing process film, as a film for film capacitors, as a wire coating material, as a food packaging material, as a medical packaging material, and the like.

[0079] Furthermore, the laminate of the present invention may have a layer formed from the PPE resin composition as an adhesive layer.

[0080] The structure of the laminate may be a two-layer laminate of a substrate / adhesive layer, or a three-layer laminate of a further substrate (substrate / adhesive layer / substrate). The laminate of the present invention can be obtained by applying the PPE resin composition of the present invention to various substrates in accordance with conventional methods, drying to remove the solvent, and then laminating other substrates.

[0081] The thickness of the adhesive layer formed from the PPE resin composition is not particularly limited and can be adjusted as appropriate depending on the application of the laminate, but for example, a thickness of about 2 μm to 300 μm is preferred.

[0082] The laminate of the present invention can be used in printed circuit boards, electrical components, electrical insulating materials such as insulating spacers, heat insulating materials such as heaters, and laminate materials for secondary batteries.

[0083] <<Printed Circuit Board>> The printed circuit board in the present invention is a so-called printed circuit board that includes a laminate formed from a metal foil and a resin substrate as constituent elements, and includes a layer made of the PPE resin composition of the present invention as an adhesive layer. The printed circuit board of the present invention can be obtained by applying the PPE resin composition of the present invention to a substrate for a printed circuit board, drying it, and removing the solvent.

[0084] The wiring board of the present invention is the same as a known wiring board except that it includes a layer made of the PPE resin composition of the present invention as an adhesive layer, and can have any laminated configuration that can be used as a printed wiring board. For example, it can be a printed wiring board composed of four layers: a base film layer, a metal foil layer, an adhesive layer, and a cover film layer. Alternatively, for example, it can be a wiring board composed of five layers: a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer. At least one of the adhesive layers in the above configuration can be formed from the PPE resin composition of the present invention.

[0085] <Metal Composite> The metal composite of the present invention includes a metal structure and a coating layer formed from a PPE resin composition.

[0086] The metal forming the aforementioned metal structure is not particularly limited, but examples include copper, aluminum, nickel, tin, stainless steel, iron, zinc, and the like.

[0087] The shape of the metal structure can be determined according to the intended use of the metal composite, but examples include plate-like (film-like), cable-like, spherical, etc.

[0088] The method for producing the metal composite of the present invention is not particularly limited, but it can be formed by coating a metal structure with a PPE resin composition and then removing the solvent. Known methods can be used for the coating method and solvent removal method.

[0089] The metal composite of the present invention can be used as an outer casing for secondary batteries or as a coated wire for motor coils, as described later.

[0090] <<Enclosure for Secondary Battery>> The enclosure for secondary battery of the present invention includes the metal composite of the present invention described above as a component. Examples of the metal structure include metal plates used as enclosure material for secondary batteries.

[0091] A secondary battery includes a positive electrode, a negative electrode, an electrolyte, and an outer casing material. The PPE resin composition of the present invention can be used as an insulating layer to protect the outer casing material. Metal materials are used as the outer casing material, and examples of metals include iron, aluminum, and stainless steel.

[0092] The structure of a secondary battery is not particularly limited, but it usually comprises a positive electrode, a negative electrode, and a separator provided as needed, and can be in various shapes depending on the intended use, such as paper type, cylindrical type, button type, or laminated type.

[0093] <Insulated Wire for Motor Coils> The insulated wire for motor coils of the present invention includes the aforementioned metal composite as a component. Examples of the metal structure include a metal wire that serves as a conductor.

[0094] The structure of the motor coil insulated wire of the present invention is not particularly limited, but examples include an insulating layer covering a conductor, and an outermost layer made of an outermost cured material on the insulating layer. The PPE resin composition of the present invention can be used as the insulating layer.

[0095] Metal conductors such as copper wire and aluminum wire are used as conductors.

[0096] The insulating layer consists of one or more layers, and a multilayer insulating layer of two or more layers, including a primer layer to improve the adhesion between the conductor and the insulating film, is preferably used.

[0097] The insulating layer is formed on the conductor by applying, drying, baking, etc., the PPE resin composition of the present invention. The thickness of the insulating layer is preferably 5 to 100 μm, and more preferably 10 to 50 μm, from the viewpoint of protecting the conductor. If the insulating film is too thick, the outer diameter of the insulated wire for the motor coil will increase, and consequently the packing ratio of the coil wound with the insulated wire for the motor coil tends to decrease, which is undesirable.

[0098] The insulated wire for motor coils of the present invention is suitably used in the coils of modern, smaller, high-speed motors.

[0099] <<Fiber-reinforced composite resin>> The fiber-reinforced composite resin of the present invention includes carbon fibers or glass fibers and a layer formed from the PPE resin composition of the present invention.

[0100] The method for producing the fiber-reinforced composite resin of the present invention is not particularly limited, but it can be produced by mixing and dispersing carbon fibers or glass fibers in the PPE resin composition of the present invention.

[0101] The carbon fiber or glass fiber content in the fiber-reinforced composite resin of the present invention is not particularly limited, but it is preferably, for example, 10% by weight or more and 70% by weight or less in the fiber-reinforced composite resin.

[0102] <<Other Uses>> Furthermore, the film made from the PPE resin composition of the present invention can also be used as a membrane for water electrolysis.

[0103] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The evaluation methods for physical properties, etc. in the following examples are as follows, and unless otherwise specified, the measurement of physical properties, etc. means measurement at room temperature (20-25°C) / relative humidity 40-50%.

[0104] (1) The number-average molecular weight (Mn), weight-average molecular weight (Mw), and Mw / Mn were all determined using gel permeation chromatography (GPC). The measurement conditions were as follows: 4 mg of the sample was weighed, and 4 mL of chloroform was added to prepare the sample solution. The sample solution was filtered through a 0.2 μm membrane filter, and the obtained sample solution was subjected to GPC measurement under the following conditions. Molecular weight was calculated on a standard polystyrene basis. Instrument: HLC-8420GPC (Tosoh Corporation) Detector: Differential refractive index detector (Tosoh Corporation) Column: TSKgel SuperHM-H + TSKgel SuperH2000 (Tosoh Corporation) Solvent: Chloroform Temperature: 40°C Flow rate: 0.6 mL / min Sample concentration: 1.0 mg / mL Injection volume: 20 μL Calibration curve: Polystyrene standard Filter: PTFE 0.2 μm (GL Sciences Co., Ltd.) Data processing device: EcoSEC Elite-WS (Tosoh Corporation)

[0105] (2) Approximately 2.0 g of PPE pellets obtained in the examples and comparative examples (however, in Comparative Example 1, raw material PPE) was accurately weighed into a two-necked flask for hydroxyl group equivalents. 10 mL of pyridine was added and completely dissolved. Then, 5 mL of the acetylating agent (a solution of 25 g of acetic anhydride dissolved in pyridine and made to a volume of 100 mL) was accurately added, and the mixture was heated at 60°C for 2 hours to acetylate the hydroxyl groups. After the reaction was complete, 10 mL of pyridine was added to the reaction solution to dilute it, and the unreacted acetic anhydride was decomposed by reprecipitation purification with 200 mL of warm water. The two-necked flask was then washed with 5 mL of ethanol. 10 drops of phenolphthalein solution were added as an indicator to the warm water used for reprecipitation purification, and the mixture was titrated with a 0.5 mol / L potassium hydroxide ethanol solution. The endpoint was reached when the indicator remained pink for 15 seconds. A blank test was performed using the same procedure without the sample. The hydroxyl value was calculated using the following formula (unit: mgKOH / g). Hydroxyl value (mgKOH / g) = [{(b-a) × F × 28.05} / S] + D (In the above formula, each letter represents the following: S: Sample amount (g) a: Amount of 0.5 mol / L potassium hydroxide ethanol solution consumed (mL) b: Amount of 0.5 mol / L potassium hydroxide ethanol solution consumed in the blank test (mL) F: Factor of 0.5 mol / L potassium hydroxide ethanol solution D: Acid value (mgKOH / g)) From the hydroxyl value obtained above, the hydroxyl group equivalent (eq / t) was calculated using the following formula: Hydroxyl group equivalent (eq / t) = Hydroxyl value / 56.1 × 1,000,000

[0106] (3) Glass transition temperature (Tg) Using a differential scanning calorimetry analyzer (model: DSC-Q100) manufactured by TA Instruments Inc., 2 mg of the obtained PPE pellet was measured in a nitrogen atmosphere from 30°C to 250°C at a heating rate of 10°C / min. The temperature at the intersection of the extension of the baseline below the glass transition temperature and the tangent line showing the maximum slope in the transition region was defined as the glass transition temperature (Tg).

[0107] (4) Content of structure B in PPE at a resonance frequency of 600 MHz １The analysis was performed using 1H-NMR. A BRUKER NMR spectrometer (model name: AVANCE-NEO600) was used, and the measurements were performed as follows: 10 mg of PPE pellets obtained in the examples and comparative examples were dissolved in deuterated chloroform, and the solution was filled into an NMR tube within 2 hours for measurement. Deuterated chloroform was used as the locking solvent, with a waiting time of 1 second, a data acquisition time of 4 seconds, and 64 integration cycles. Deuterated benzene may also be used as the solvent. The content of structure B was analyzed as follows: R at positions 3 and 5 of PPE. １ , R ２ The peak originates from the proton of the base, and R in structure B. ３’ The peak integral values ​​of the peaks originating from the protons of the divalent group (methylene group, etc.) shown as T1 and T2 were used, and the content of structure B was calculated using the following formula: Structure B content (mol%) = (T2 / (T1 + T2)) × 100

[0108] (5) Radical content The radical content was measured by ESR (electron spin resonance) under the following conditions and procedure. Using an electron spin resonance spectrometer (ESR, JEOL Ltd., JES-FA100), the radical content in the PPE pellets obtained in the examples and comparative examples (however, in Comparative Example 1, raw material PPE) was measured under the following conditions. Bulk density of 0.1 to 0.2 g / cm³ ３ A 0.1g sample was packed to achieve this. However, depending on the sample shape, it may vary from 0.1 to 0.2g / cm³. ３ If it does not fall within that range, use 0.2 g / cm³. ３ It's okay if it's more. Radical amount (g) －１The value was calculated using the following formula. Normalized intensity of sample = Signal intensity of sample / Manganese intensity Normalized intensity of blank = Signal intensity of blank / Manganese intensity Radical amount = (Normalized intensity of sample - Normalized intensity of blank) / Sample weight (Measurement conditions) Sample tube: EPW-005J (manufactured by Shigemi Co., Ltd.) Manganese intensity: Two integral values ​​in the range of 320 to 322 mT Signal intensity of sample and blank: Two integral values ​​in the range of 322.1 to 329.3 mT Magnetic Field: 325.8 ± 7.5 mT Microwave Power: 0.1 mW Sweep Time: 4 min Modulation Width: 0.12 mT Amplitude: 1000 Time Constant: 0.3 sec Mn Marker: 800 Scans: 2

[0109] (6) Peripheral speed of the screw The peripheral speed of the screw was determined by the following formula: Peripheral speed of the screw (m / min) = Screw diameter (mm) × 0.00314 × Screw rotation speed (rpm)

[0110] Example 1 Poly(2,6-dimethyl-1,4-phenylene ether) (PPO (trademark registered) 640, glass transition temperature (Tg): 221°C, manufactured by SABIC Innovative Plastic) was extruded using a twin-screw extruder manufactured by Technovel Co., Ltd. (product name: KZW15TW-30MG). The twin-screw extruder has four cylinder zones, and the cylinders from the hopper side were designated as cylinder 1, 2, 3, and 4. Cylinder 1 was set to 280°C, and cylinders 2-4 and the cylinder head were set to 330°C. The screw rotation speed was set to 400 rpm (screw peripheral speed: 18.8 m / min). The discharge rate was 20 g / min. A vent was attached to cylinder 3, and the vent was evacuated.

[0111] A nozzle with a diameter of φ0.8 mm was attached downstream of the extruder, and the extruded resin was dropped onto a metal conveyor, picked up at 100 m / min, cut with a strand cutter, and obtained pellets. The physical properties of the obtained pellets are shown in Table 1.

[0112] Based on the measurement method for "(4) Content of structure B in PPE" of the obtained PPE pellets, １ ¹H-NMR measurements were performed. As a result, when deuterated chloroform was used at 7.28 ppm, peaks were observed around 6.9 ppm, 6.48 ppm, and 3.87 ppm. The peak around 6.9 ppm corresponds to the protons at positions 3 and 5 of PPE generated by the rearrangement (i.e., in structure B), the peak around 6.48 ppm corresponds to the protons at positions 3 and 5 of PPE in the main chain, and the peak around 3.87 ppm corresponds to the methylene group in the methylene bridge generated by the rearrangement. The content of rearrangement B in PPE was 1.2 mol%.

[0113] 100 g of the obtained PPE pellets and 400 g of toluene were placed in a four-necked flask equipped with a stirrer and reflux condenser, and the temperature was raised to 70°C. After raising the temperature, stirring was started and continued for 2 hours. After cooling, the mixture was removed to obtain a PPE resin composition (PPE resin solution).

[0114] Examples 2-16, Comparative Examples 2 and 3: PPE pellets were obtained in the same manner as in Example 1, except that the raw materials used, discharge volume, extrusion temperature, screw rotation speed, and venting conditions were changed as shown in Table 1. The physical properties of the obtained pellets are shown in Table 1. In Table 1, "PX100F" is poly(2,6-dimethyl-1,4-phenylene ether) (PX100F, glass transition temperature (Tg): 210°C, manufactured by Mitsubishi Engineering Plastics Corporation), LXN035 is poly(2,6-dimethyl-1,4-phenylene ether) (LXN035, glass transition temperature (Tg): 208°C, manufactured by Bluestar Inc.), and SA90 is poly(2,6-dimethyl-1,4-phenylene ether) (SA90, glass transition temperature (Tg): 150°C, manufactured by SABIC Corporation). Furthermore, the solution used to produce the PPE resin composition (PPE resin solution) from the obtained pellets, and the amount used (amount of solvent per 100 g of pellets), are as shown in Table 1. In Table 1, "NMP" is N-methylpyrrolidone and "MEK" is methyl ethyl ketone. In Comparative Example 2, the PPE pellets did not dissolve in toluene. Note that "-" in Table 1 below indicates that the corresponding component was not used.

[0115] Comparative Example 1 In Comparative Example 1, the evaluation was performed using raw material PPE (i.e., it was not fed into the melt extruder), but the raw material PPE did not dissolve in toluene.

[0116] The following evaluations were performed using the PPE resin composition obtained above.

[0117] <Solubility> The solubility of the PPE resin compositions prepared in the examples and comparative examples was evaluated according to the following criteria. ○: No increase in viscosity was observed even after storing the PPE resin composition at room temperature for 3 days. △: An increase in viscosity was observed after storing the PPE resin composition at room temperature for 3 days. ×: The PPE did not dissolve in the solvent, or dissolved but solidified immediately afterward.

[0118] <Film-forming properties> The PPE resin soluble compositions prepared in the examples and comparative examples were applied to a 50 μm thick polyolefin film (manufactured by Toyobo Co., Ltd., Pyrene®) to a thickness of 25 μm after drying, and dried at 130°C for 5 minutes. After drying, film-forming properties were confirmed according to the following evaluation criteria. Note that in Comparative Examples 1 and 2, film-forming properties could not be evaluated because the PPE pellets were insoluble in the organic solvent. ○: Film formed. △: Film formed, but some defects were observed. ×: Film did not form, or even if film formed, it was brittle and could not be lifted.

[0119] <Thermosetting Properties> The PPE resin soluble compositions prepared in the Examples and Comparative Examples were applied to a 100 μm thick polytetrafluoroethylene film (manufactured by Chuko Chemical Industries, Ltd., Tubeflow®) to a thickness of 25 μm after drying, and dried at 130°C for 5 minutes. After drying, the film was heat-treated in an oven heated to 200°C for 1 hour. After heat treatment, a 20 mm x 50 mm sample was cut out, the polyphenylene ether sample was peeled off the polytetrafluoroethylene film, and its weight was measured (X). This sample piece was immersed in toluene at 25°C for 1 hour, filtered through a nylon mesh, and then dried at 100°C for 1 hour, and its dry weight was measured (Y). The degree of thermosetting properties Z was calculated using the following formula and evaluated according to the following evaluation criteria. Note that in Comparative Examples 1 and 2, thermosetting properties could not be evaluated because the PPE pellets were insoluble in the organic solvent. Z = Y / X × 100 (Evaluation Criteria) ○: Z was 50% or more. △: Z was between 20% and 50%. ×: Z was less than 20%.

[0120] <Adhesion> The PPE resin soluble compositions prepared in the Examples and Comparative Examples were applied to rolled copper foil (manufactured by JX Metals Corporation, BHY series) with a thickness of 18 μm so that the thickness after drying was 25 μm. To bond this polyphenylene ether-coated copper foil to the rolled copper foil, it was pressed at 170°C under a pressure of 2 MPa for 30 seconds to bond them. Then, it was pressed at 200°C and 3 MPa for 1 hour to obtain a sample for evaluating peel strength. The peel strength was measured by performing a 90° peel test at 25°C with a tensile speed of 50 mm / min. This test indicates the adhesive strength at room temperature. Note that in Comparative Examples 1 to 3, it was not possible to prepare test samples, so the adhesion could not be evaluated. (Evaluation Criteria) ○: 0.3 N / mm or more △: 0.2 N / mm or more and less than 0.3 N / mm ×: Less than 0.2 N / mm

[0121] <ATF Resistance> The PPE resin soluble compositions prepared in the Examples and Comparative Examples were applied to a 100 μm thick polytetrafluoroethylene film (manufactured by Chuko Chemical Industries, Ltd., Tubeflow®) to a thickness of 25 μm after drying, and dried at 130°C for 5 minutes. After drying, the film was heat-treated in an oven heated to 200°C for 1 hour. After heat treatment, a 20 mm x 50 mm sample was cut out, the polyphenylene ether sample was peeled off the polytetrafluoroethylene film, and its weight was measured (X). ATF (automatic transmission fluid, manufactured by Toyota Motor Corporation) was placed in a sealed metal container and heated to 150°C. The sample piece was then placed in the container and treated for 24 hours. After that, the ATF was wiped off, and the sample was left to stand at room temperature and humidity overnight before its weight was measured. The percentage change in weight of the sample piece after immersion was calculated compared to the sample piece before immersion, and this was displayed according to the following criteria as an indicator of ATF resistance. Note that in Comparative Examples 1 to 3, it was not possible to prepare test samples, and therefore ATF resistance could not be evaluated. ○: Weight change rate was less than 2%. △: Weight change rate was 2% or more and less than 5%. ×: Weight change rate was 5% or more.

[0122]

[0123] As shown in Table 1, the PPE pellets obtained in the examples exhibited excellent solubility when dissolved in organic solvents, allowing for the production of a PPE resin composition. Furthermore, the molded articles formed from the PPE resin composition of the present invention exhibited excellent film-forming properties, thermosetting properties, adhesive properties, and ATF resistance. On the other hand, the raw material PPE of Comparative Example 1 lacked structure B and radicals, resulting in poor solvent solubility. Consequently, test samples could not be prepared, and various evaluations could not be performed. Comparative Example 2 had low levels of structure B and radicals, resulting in poor solubility. Test samples could not be prepared, and various evaluations could not be performed. Comparative Example 3 had low levels of Mn and Mw in the PPE components, resulting in poor film-forming properties. Test samples could not be prepared for adhesion and ATF resistance, making evaluation impossible.

[0124] 1. Hopper 2. Extruder 3. Air-cooled belt conveyor 4. Pelletizer 5. Extrusion nozzle 10. Vent for degassing

Claims

1. A polyphenylene ether resin composition containing a resin containing a polyphenylene ether component and an organic solvent, wherein the polyphenylene ether component has a radical amount measured by electron spin resonance method of 100 g －１ or more and a weight average molecular weight of 10,000 or more, has a structure B represented by the following general formula (2) in a repeating unit A represented by the following general formula (1), and the content of the structure B is 1.2 mol% or more based on the total amount of the repeating unit A and the structure B in the polyphenylene ether component. A polyphenylene ether resin composition. (In the formula, R １ and R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ each independently represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.) (In the formula, R １ and R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ ' represents a divalent group obtained by removing one hydrogen atom from the R ３ .) 2. The polyphenylene ether resin composition according to claim 1, wherein the hydroxyl group equivalent of the polyphenylene ether component is 100 eq / t or more.

3. The polyphenylene ether resin composition according to claim 1, wherein the weight-average molecular weight of the polyphenylene ether component is 100,000 or less.

4. The polyphenylene ether resin composition according to claim 1, wherein the organic solvent is an aromatic hydrocarbon solvent or an amine solvent.

5. A coating agent containing the polyphenylene ether resin composition according to any one of claims 1 to 4.

6. A paint containing the polyphenylene ether resin composition according to any one of claims 1 to 4.

7. An adhesive containing the polyphenylene ether resin composition according to any one of claims 1 to 4.

8. A laminate having a base material and a layer formed from the polyphenylene ether resin composition according to any one of claims 1 to 4.

9. A wiring board having a substrate for a wiring board and a coating layer formed from the polyphenylene ether resin composition according to any one of claims 1 to 4.

10. A metal composite having a metal structure and a coating layer formed from the polyphenylene ether resin composition according to any one of claims 1 to 4.

11. An outer casing for a secondary battery formed from the metal composite described in claim 10.

12. A coated wire for a motor coil formed from the metal composite according to claim 10.

13. A fiber-reinforced composite resin having a coating layer made of carbon fibers or glass fibers and the polyphenylene ether resin composition according to any one of claims 1 to 4.

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