Resin composition, pellet, and molded body

Abstract

The present invention provides a resin composition, a pellet, and a molded body. A resin composition according to the present disclosure includes: a polyphenylene ether resin composed of a resin represented by formula (1) and / or an acid-modified product thereof; a polyimide resin; a flame retardant; and ceramic particles. The polyimide resin includes a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3). The content ratio of the repeating structural unit represented by formula (2) to a total of 100 mol% of the repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3) is 20-70 mol% inclusive.

Description

Resin composition, pellets, and molded body

[0001] The present invention relates to a resin composition, a pellet, and a molded article, and more particularly to a resin composition containing a polyphenylene ether resin as a main component.

[0002] Polyphenylene ether resin (PPE) is a resin that has excellent properties such as heat resistance, flame retardancy, electrical properties, and dimensional stability, as well as low specific gravity and hydrolysis resistance.

[0003] Resin compositions containing such polyphenylene ether resins (polyphenylene ether resin compositions) have been widely used as materials for various applications, such as electrical components, electronic device components, and vehicle components. Various properties are required of polyphenylene ether resin compositions depending on their applications. For example, when a polyphenylene ether resin composition is used as a spacer between batteries or a bus bar cover material in a battery unit including a battery pack or the like, the polyphenylene ether resin composition is required to have high tracking resistance in addition to the flame retardancy and thin-wall moldability required for the battery spacer or bus bar cover.

[0004] For example, Patent Document 1 discloses a composition that contains 45 to 65% by weight of PPE, 10 to 30% by weight of a polyalkenyl aromatic resin (styrene resin), 1 to 8% by weight of tricalcium phosphate, 3 to 15% by weight of an organic phosphate ester flame retardant, 5 to 10% by weight of titanium oxide, and 3 to 15% by weight of a reinforcing filler, and that exhibits a CTI of 350V or more according to the IEC 60112 standard.

[0005] International Publication No. 2009 / 040751

[0006] Under these circumstances, the present inventors have investigated the possibility of improving the tracking resistance of a polyphenylene ether resin composition by blending a polyimide resin into the polyphenylene ether resin composition. Furthermore, flame retardancy may also be required for polyphenylene ether resin compositions with improved tracking resistance. However, it has been found that blending a flame retardant into a polyphenylene ether resin composition may result in a deterioration in tracking resistance. The present invention aims to solve these problems and to provide a resin composition, pellets, and molded articles that are excellent in tracking resistance and flame retardancy.

[0007] As a result of investigations conducted by the present inventors in light of the above-mentioned problems, it was found that the above-mentioned problems could be solved by using a nonionic phosphorus-based flame retardant as a flame retardant. Specifically, the above-mentioned problems were solved by the following means.

[0008] [1-1] A resin composition comprising a polyphenylene ether resin made of a resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a flame retardant, and ceramic particles, wherein the polyimide resin comprises a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and the content of the repeating structural unit represented by formula (2) is 20 to 70 mol % relative to 100 mol % in total of the repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3). (In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６４ are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ６５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more. (In formulas (2) and (3), R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) [1-2] The resin composition according to [1-1], which contains 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles relative to 100 parts by mass of the polyphenylene ether resin and the polyimide resin combined. [1-3] The resin composition according to [1-1] or [1-2], wherein the flame retardant contains a phosphorus-based flame retardant. [1-4] The resin composition according to any one of [1-1] to [1-3], wherein the ceramic particles contain titanium oxide particles. [1-5] The resin composition according to any one of [1-1] to [1-4], which further contains a lubricant. [1-6] The resin composition according to any one of [1-1] to [1-5], which further contains a lubricant in an amount of 0.1 to 3 parts by mass relative to 100 parts by mass of the polyphenylene ether resin and the polyimide resin combined. [1-7] The resin composition according to any one of [1-1] to [1-6], wherein the mass ratio of the polyphenylene ether resin to the total 100 mass parts of the polyphenylene ether resin and the polyimide resin is 50 to 99 parts by mass. [1-8] The resin composition according to any one of [1-1] to [1-7], wherein the median diameter (D50) of the ceramic particles is 0.01 to 30 μm. [1-9] The resin composition according to any one of [1-1] to [1-8], wherein the resin composition comprises 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles relative to 100 parts by mass of the polyphenylene ether resin and the polyimide resin, wherein the flame retardant comprises a phosphorus-based flame retardant, the ceramic particles comprise titanium oxide particles, and the resin composition further comprises 0.1 to 3 parts by mass of a lubricant relative to 100 parts by mass of the polyphenylene ether resin and the polyimide resin, wherein the median diameter (D50) of the ceramic particles is 0.01 to 30 μm, and the mass ratio of the polyphenylene ether resin relative to 100 parts by mass of the polyphenylene ether resin and the polyimide resin is 50 to 99 parts by mass. [1-10] The resin composition according to any one of [1-1] to [1-9], wherein the resin composition is molded into a test piece of 100 mm × 150 mm × 3.2 mm, and the CTI value measured by a measurement method in accordance with IEC 60112 is 600 V or more.[1-11] The resin composition according to any one of [1-1] to [1-10], wherein the resin composition is molded into a flat plate-like molded article having a thickness of 0.125 μm, and the result of a combustion test in accordance with UL-94 satisfies VTM-0. [1-12] Pellets of the resin composition according to any one of [1-1] to [1-11]. [1-13] A molded article formed from the resin composition according to any one of [1-1] to [1-11]. [1-14] The molded article according to [1-13], which is flat plate-like.

[0009] [2-1] A resin composition comprising a polyphenylene ether resin made of a resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a polyamide resin, and a non-ionic phosphorus-based flame retardant, wherein the content of the ionic phosphorus-based flame retardant is 2.0 parts by mass or less per 100 parts by mass of the polyphenylene ether resin made of a resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin, and the polyimide resin contains a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and the content ratio of the repeating structural unit represented by formula (2) is 20 to 70 mol % per 100 mol % of the total of the repeating structural units represented by formula (2) and formula (3). (In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６４ are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ６５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more. (In formulas (2) and (3), R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) [2-2] The resin composition according to [2-1], wherein the nonionic phosphorus-based flame retardant comprises a nitrogen-containing phosphorus-based flame retardant and / or a phosphate ester. [2-3] The resin composition according to [2-1], wherein the nonionic phosphorus-based flame retardant comprises a phosphazene and / or a phosphate ester. [2-4] The resin composition according to any one of [2-1] to [2-3], wherein a part of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1). [2-5] The resin composition according to any one of [2-1] to [2-4], wherein 1 to 40 mass% of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1). [2-6] The resin composition according to any one of [2-1] to [2-5], wherein the polyamide resin comprises an aliphatic polyamide resin. [2-7] The resin composition according to any one of [2-1] to [2-6], wherein the polyamide resin comprises at least one of polyamide 6, polyamide 66, and polyamide 666. [2-8] The resin composition according to any one of [2-1] to [2-7], wherein the polyamide resin comprises polyamide 6. [2-9] The resin composition according to any one of [2-1] to [2-8], wherein the content of the polyamide resin is 1 to 40 parts by mass per 100 parts by mass of the polyphenylene ether resin comprising a resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin. [2-10] The resin composition according to any one of [2-1] to [2-9], wherein the content of the polyimide resin is 1 to 40 parts by mass per 100 parts by mass of the polyphenylene ether resin comprising a resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin. [2-11] The resin composition according to any one of [2-1] to [2-10], further comprising a lubricant. [2-12] The resin composition according to any one of [2-1] to [2-11], further comprising ceramic particles. [2-13] The resin composition according to [2-12], wherein the ceramic particles comprise titanium oxide particles.[2-14] The resin composition according to any one of [2-1] to [2-14], wherein the nonionic phosphorus-based flame retardant comprises a phosphazene and / or a phosphate ester, 1 to 40 mass% of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1), the polyamide resin comprises at least one of polyamide 6, polyamide 66, and polyamide 666, the content of the polyamide resin is 1 to 40 parts by mass per 100 parts by mass of the polyphenylene ether resin formed from the resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin, the content of the polyimide resin is 1 to 40 parts by mass per 100 parts by mass of the polyphenylene ether resin formed from the resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin, further comprising a lubricant, and further comprising ceramic particles, the ceramic particles comprising titanium oxide particles. [2-15] Pellets of the resin composition according to any one of [2-1] to [2-14]. [2-16] A molded article formed from the resin composition according to any one of [2-1] to [2-14]. [2-17] A flat-plate-shaped molded article formed from the resin composition according to any one of [2-1] to [2-14].

[0010] The present invention makes it possible to provide a resin composition, pellets, and molded articles that are excellent in tracking resistance and flame retardancy.

[0011] 1 shows a photograph of the appearance of the film obtained in Comparative Example 1-1. 2 shows a photograph of the appearance of the film obtained in Example 1-1. 3 shows a photograph of the appearance of the film obtained in Example 1-2.

[0012] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the following present embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment. Note that in this specification, the term "to" is used to mean that the numerical values ​​before and after it are included as the upper and lower limits. "A to B" means A or more and B or less. Furthermore, any combination of the upper and lower limit values ​​of numerical values ​​in this specification can be cited as an example of this embodiment. In this specification, various physical property values ​​and characteristic values ​​are those at 23°C unless otherwise specified.

[0013] The flat-plate-shaped molded body in this specification is intended to include those in the shape of a film or sheet. The terms "film" and "sheet" refer to a generally flat molded body that is thin relative to its length and width, and are not particularly distinguished in this specification. Furthermore, the "film" and "sheet" in this specification may be single-layer or multi-layer, but single-layer is preferred. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they shall be based on the standards as of January 1, 2024, unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification are abolished as of January 1, 2024, they shall be based on the standards at the time of abolition.

[0014] The first resin composition of the present embodiment comprises a polyphenylene ether resin composed of a resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a flame retardant, and ceramic particles, wherein the polyimide resin comprises a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and the content ratio of the repeating structural unit represented by formula (2) is 20 to 70 mol % relative to a total of 100 mol % of the repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3). (In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６４ are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R６５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more. (In formulas (2) and (3), R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２ are each independently a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms.

[0015] This configuration makes it possible to provide a new resin composition with excellent flame retardancy and tracking resistance. It is believed that adding a specific polyimide resin improves tracking resistance. Furthermore, adding a flame retardant improves flame retardancy. Furthermore, adding ceramic particles improves tracking resistance. In particular, tracking failure occurs due to the formation of a carbonized conductive circuit near the surface of a molded product. However, in the first resin composition of this embodiment, it is believed that the ceramic particles can be well dispersed in the resin composition, inhibiting the formation of the carbonized conductive circuit.

[0016] Furthermore, the first resin composition of the present embodiment can have excellent moldability when molded into a flat plate-like molded article such as a film. This is presumably because the incorporation of ceramic particles allows the polyimide resin to be better dispersed, resulting in excellent extrudability when extruding a film and making it less likely for holes or the like to form in the molded film.

[0017] The first resin composition of the present embodiment further uses a phosphorus-based flame retardant as a flame retardant, which tends to improve the moldability of the resin composition. This is presumably because the phosphorus-based flame retardant functions like a plasticizer for the polyphenylene ether resin, thereby reducing the viscosity of the resin composition.

[0018] The second resin composition of the present embodiment comprises a polyphenylene ether resin (hereinafter sometimes simply referred to as "polyphenylene ether resin") composed of a resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a polyamide resin, and a non-ionic phosphorus-based flame retardant, wherein the content of the ionic phosphorus-based flame retardant is 2.0 parts by mass or less per 100 parts by mass of the polyphenylene ether resin composed of a resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin together, and the polyimide resin comprises a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and the content ratio of the repeating structural unit represented by formula (2) is 20 to 70 mol % per 100 mol % of the total of the repeating structural units represented by formula (2) and the repeating structural units represented by formula (3). (In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６４ are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ６５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more. (In formulas (2) and (3), R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２ are each independently a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms.

[0019] This configuration allows for the production of a resin composition with excellent tracking resistance and flame retardancy. Specifically, in the second resin composition of this embodiment, the tracking resistance of the resin composition can be improved by blending a specific polyimide resin with the polyphenylene ether resin. Furthermore, blending a polyamide resin reduces the viscosity of the resin composition in a temperature range above the melting point of the polyamide, and promotes melting of the polyimide, thereby improving processability. The present inventors decided to blend a phosphorus-based flame retardant with the polyphenylene ether resin to improve the flame retardancy of the resin composition. However, they found that blending a phosphorus-based flame retardant tends to deteriorate the tracking resistance. This is because phosphorus-based flame retardants generally promote char formation during combustion of a molded body, suppressing combustion and forming a highly conductive carbonized layer, which tends to deteriorate the tracking resistance. Based on this background, the present inventors conducted further research and found that, among phosphorus-based flame retardants, nonionic phosphorus-based flame retardants are relatively less likely to deteriorate the tracking resistance, while ionic phosphorus-based flame retardants are more likely to deteriorate the tracking resistance. The reason for this is presumed to be that ionic substances such as phosphates diffuse within the resin composition when it comes into contact with an electrolyte during moisture absorption or tracking resistance testing, thereby further deteriorating tracking resistance. Under these circumstances, it was discovered that the above problem could be solved by using a non-ionic phosphorus-based flame retardant as the phosphorus-based flame retardant and reducing the content of, or not incorporating, the ionic phosphorus-based flame retardant.

[0020] Hereinafter, an embodiment of the present invention will be described in detail, but the explanation of the constituent elements described below is one example of an embodiment of the present invention, and the present invention is not limited to these contents. In this specification, when the term "resin composition of the present embodiment" is mentioned, it is intended to include both the first resin composition and the second resin composition.

[0021] <Polyphenylene ether resin> The resin composition of the present embodiment contains a polyphenylene ether resin (sometimes simply referred to as a "polyphenylene ether resin" in this specification) made of a resin represented by formula (1) and / or an acid-modified product thereof, and preferably contains at least a polyphenylene ether resin that is a resin represented by formula (1), and more preferably contains both a polyphenylene ether resin made of a resin represented by formula (1) and an acid-modified product thereof. (In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６４ are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ６５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more.

[0022] In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６５ The alkyl group having 1 to 4 carbon atoms in the formula (I) may be either linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Among these, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is preferred, and a methyl group is more preferred.

[0023] In formula (1), R ５１ , R ５３ , R ６１ , and R ６３ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. ５２ , R ５４ , R ６２ , and R ６４ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a methyl group. ６５ is preferably a hydrogen atom.

[0024] In formula (1), n ​​is a number of 10 or more, more preferably 20 or more, and although there is no particular upper limit, it is 300 or less.

[0025] As the polyphenylene ether resin, poly(2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol / 2,3,6-trimethylphenol random copolymer are particularly preferred. Poly(2,6-dimethyl-1,4-phenylene ether) represented by formula (1-1) is particularly preferred. Polyphenylene ether resins having a specified number of terminal groups and copper content, as described in JP-A-2005-344065, can also be suitably used. (wherein n is the same as defined above.)

[0026] The intrinsic viscosity of the polyphenylene ether resin measured in chloroform at 30° C. is preferably 0.20 to 0.60 dL / g, more preferably 0.30 to 0.50 dL / g, and even more preferably 0.30 to 0.45 dL / g, from the viewpoints of exhibiting high flame retardancy and improving moldability. Two or more types of (a) polyphenylene ether resins having different intrinsic viscosities may be used in combination to achieve an intrinsic viscosity within this range.

[0027] The method for producing the polyphenylene ether resin used in the present embodiment is not particularly limited, and may be any known method, for example, a method of oxidatively polymerizing a monomer such as 2,6-dimethylphenol in the presence of an amine copper catalyst, in which the intrinsic viscosity can be controlled within a desired range by selecting the reaction conditions. The control of the intrinsic viscosity can be achieved by selecting conditions such as the polymerization temperature, polymerization time, and catalyst amount.

[0028] In the resin composition of this embodiment, a portion of the polyphenylene ether resin is preferably an acid-modified product of a resin represented by formula (1). This configuration can improve the compatibility between the polyphenylene ether resin and the polyamide resin. Examples of acid-modified products of the resin represented by formula (1) include resins obtained by modifying the resin represented by formula (1) with a carboxylic acid or a carboxylic acid derivative. As the carboxylic acid or carboxylic acid derivative, unsaturated carboxylic acids and their derivatives are preferred from the viewpoint of reactivity with the resin represented by formula (1). Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, and angelic acid. Examples of derivatives of unsaturated carboxylic acids include acid anhydrides, esters, amides, imides, and metal salts, with acid anhydrides being preferred. Among the above, the acid-modified product of the resin represented by formula (1) is preferably a resin obtained by modifying the resin represented by formula (1) with maleic acid or a maleic acid derivative (maleic acid-modified product of the resin represented by formula (1)) from the viewpoints of exhibiting high flame retardancy and availability.

[0029] Examples of the maleic acid modified resin represented by formula (1) include resins having a structure represented by formula (1-2) and / or formula (1-3). (In formula (1-2), R ５１ ~R ５５ , R ６１ , R ６３ , R ６４ , R ６５ and n each independently have the same meaning as in formula (1).

[0030] Formula (1-3) (In formula (1-3), R ５１ ~R ５５ , R ６１ , R ６３ , R ６４ , R ６５ and n each independently have the same meaning as in formula (1).

[0031] When the polyphenylene ether resin is taken as 100% by mass, the maleinization ratio is preferably 0.005% by mass or more, more preferably 0.015% by mass or more, even more preferably 0.025% by mass or more, even more preferably 0.035% by mass or more, and even more preferably 0.040% by mass or more, and is preferably 0.16% by mass or less, more preferably 0.12% by mass or less, and even more preferably 0.08% by mass or less. The maleinization ratio is measured according to the method described in the examples below.

[0032] The content of the acid-modified resin represented by formula (1) in the resin composition of this embodiment (preferably the first resin composition) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, and even more preferably 10% by mass or more, based on 100% by mass of the polyphenylene ether resin. It is also preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less. By setting the content at or above the lower limit, the compatibility between the polyphenylene ether resin and the polyamide resin tends to be further improved. Furthermore, by setting the content at or below the upper limit, the flame retardancy tends to be improved. The resin composition of this embodiment may contain only one type of acid-modified resin represented by formula (1), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0033] The polyphenylene ether resin used in this embodiment may be a recycled product (including recovered products, material recycled products, chemical recycled products, etc.), a rejected product, or a scrap material from molding a polyphenylene ether resin.

[0034] The content of the polyphenylene ether resin in the first resin composition of the present embodiment is preferably 55% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, and may be 70% by mass or more, and is preferably 90% by mass or less, more preferably 85% by mass or less, and may be 80% by mass or less, based on 100% by mass of the resin composition.

[0035] The content of the polyphenylene ether resin in the second resin composition of this embodiment is preferably 40% by mass or more, more preferably 45% by mass or more, and preferably 75% by mass or less, more preferably 70% by mass or less, and may be 65% by mass or less, based on 100% by mass of the resin composition. The resin composition of this embodiment may contain only one type of polyphenylene ether resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0036] <Polyimide Resin> The resin composition of the present embodiment includes a polyimide resin (sometimes simply referred to as a "polyimide resin" in this specification) that contains a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and in which the content of the repeating structural unit represented by formula (2) is 20 to 70 mol % relative to 100 mol % in total of the repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3). (In formulas (2) and (3), R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２ are each independently a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms.

[0037] The polyimide resin used in this embodiment is a thermoplastic resin, and is preferably in the form of powder or pellets. Thermoplastic polyimide resins are distinguished from polyimide resins that do not have a glass transition temperature (Tg), or polyimide resins that decompose at a temperature lower than the glass transition temperature, and are formed by molding a polyimide precursor such as polyamic acid and then closing the imide ring.

[0038] The repeating unit of formula (2) is described in detail below. １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. Here, the alicyclic hydrocarbon structure refers to a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and may be monocyclic or polycyclic. Examples of alicyclic hydrocarbon structures include, but are not limited to, cycloalkane rings such as a cyclohexane ring, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane, and bicycloalkene rings such as norbornene. Among these, a cycloalkane ring is preferred, a cycloalkane ring having 4 to 7 carbon atoms is more preferred, and a cyclohexane ring is even more preferred. R １ has 6 to 22 carbon atoms, preferably 8 to 17. １ contains at least one alicyclic hydrocarbon structure, preferably 1 to 3.

[0039] R1 is preferably a divalent group represented by formula (R1-1) or formula (R1-2). (In formula (R1-1) and formula (R1-2), m11 and m12 each independently represent an integer of 0 to 2. m13 to m15 each independently represent an integer of 0 to 2.) In formula (R1-1) and formula (R1-2), m11 and m12 each independently represent preferably 0 or 1. m13 to m15 each independently represent preferably 0 or 1.

[0040] R １ is particularly preferably a divalent group represented by formula (R1-3). In the divalent group represented by the above formula (R1-3), the positional relationship of the two methylene groups with respect to the cyclohexane ring may be either cis or trans, and the ratio of cis to trans may be any value.

[0041] In formula (2), X １ is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited to these. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. X １ has 6 to 22 carbon atoms, preferably 6 to 18. １ contains at least one aromatic ring, preferably 1 to 3.

[0042] X １ is preferably a tetravalent group represented by any one of the following formulae (X-1) to (X-4). (In formulas (X-1) to (X-4), R １１ ~R １８ are each independently an alkyl group having 1 to 4 carbon atoms. １１ ~p １３ are each independently an integer of 0 to 2. p14, p15, p16 and p18 are each independently an integer of 0 to 3. p17 is an integer of 0 to 4. L １１ ~L １３ are each independently a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.

[0043] In formulas (X-1) to (X-4), p11 to p13 are each independently preferably 0. p14, p15, p16, and p18 are each independently preferably 0. p17 is preferably 0. １ is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, and therefore, R １２ , R １３ , p12 and p13 are selected so that the number of carbon atoms in the tetravalent group represented by formula (X-2) is in the range of 10 to 22. Similarly, L in formula (X-3)１１ , R １４ , R １５ , p14 and p15 are selected so that the number of carbon atoms of the tetravalent group represented by formula (X-3) is in the range of 12 to 22, and L in formula (X-4) １２ , L １３ , R １６ , R １７ , R １８ , p １６ , p １７ and p １８ is selected so that the number of carbon atoms in the tetravalent group represented by formula (X-4) falls within the range of 18 to 22.

[0044] X １ is particularly preferably a tetravalent group represented by formula (X-5) or (X-6).

[0045] Next, the repeating structural unit of formula (3) will be described in detail below. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms. Here, the chain aliphatic group means a group derived from a chain aliphatic compound, and the chain aliphatic compound may be saturated or unsaturated, linear or branched, and may contain a heteroatom such as an oxygen atom. ２ is preferably an alkylene group having 5 to 16 carbon atoms, more preferably an alkylene group having 6 to 14 carbon atoms, even more preferably an alkylene group having 7 to 12 carbon atoms, and among these, preferably an alkylene group having 8 to 10 carbon atoms. The alkylene group may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group. ２ is preferably at least one selected from the group consisting of an octamethylene group and a decamethylene group, and particularly preferably an octamethylene group.

[0046] Also, R ２Another preferred embodiment of is a divalent chain aliphatic group containing an ether group and having 5 to 16 carbon atoms. The number of carbon atoms is preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10. Among these, a divalent group represented by formula (R2-1) or formula (R2-2) is preferred. (In formulas (R2-1) and (R2-2), m21 and m22 each independently represent an integer of 1 to 15. m23 to m25 each independently represent an integer of 1 to 14.)

[0047] In formula (R2-1), m21 and m22 each independently represent preferably 1 to 13, more preferably 1 to 11, and even more preferably 1 to 9. m23 to m25 each independently represent preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8.

[0048] In addition, R ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms), and therefore m21 and m22 in formula (R2-1) are selected so that the number of carbon atoms in the divalent group represented by formula (R2-1) is within the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms). In other words, m21 + m22 is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10 carbon atoms). Similarly, m23 to m25 in formula (R2-2) are selected so that the number of carbon atoms in the divalent group represented by formula (R2-2) is within the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms). That is, m23+m24+m25 is 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms).

[0049] X ２ is X in formula (2) １ The definitions and preferred embodiments are the same as above.

[0050] The content ratio of the repeating structural unit of formula (2) relative to the total of the repeating structural units of formula (2) and formula (3) is 20 to 70 mol%. When the content ratio of the repeating structural unit of formula (2) is within the above range, the polyimide resin can be sufficiently crystallized even in a typical injection molding cycle. By setting the content ratio to 20 mol% or more, moldability is improved, and by setting it to 70 mol% or less, crystallinity and heat resistance tend to be improved. From the viewpoint of achieving high crystallinity, the content ratio of the repeating structural unit of formula (2) relative to the total of the repeating structural units of formula (2) and formula (3) is preferably 65 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. In particular, the content ratio of the repeating structural unit of formula (2) relative to the total of the repeating structural units of formula (2) and formula (3) is preferably 20 mol% or more but less than 40 mol%. Within this range, the crystallinity of the polyimide resin is high, and a resin composition having better heat resistance can be obtained. From the viewpoint of moldability, the content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 32 mol% or more, and from the viewpoint of achieving high crystallinity, it is even more preferably 35 mol% or less.

[0051] The total content ratio of the repeating structural unit of formula (2) and the repeating structural unit of formula (3) relative to all repeating structural units constituting the polyimide resin is preferably 50 to 100 mol %, more preferably 75 to 100 mol %, even more preferably 80 to 100 mol %, and still more preferably 85 to 100 mol %.

[0052] The polyimide resin may further contain a repeating structural unit of formula (4). In this case, the content ratio of the repeating structural unit of formula (4) to the total of the repeating structural units of formula (2) and formula (3) is preferably 25 mol% or less. On the other hand, there is no particular lower limit, as long as it is greater than 0 mol%. From the viewpoint of improving heat resistance, the content ratio is preferably 5 mol% or more, more preferably 10 mol% or more, while from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more preferably 15 mol% or less. Formula (4) (In formula (4), R ３ is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. ３ is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.

[0053] R ３ R is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. The aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited to these. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. ３ has 6 to 22 carbon atoms, preferably 6 to 18. ３ contains at least one aromatic ring, preferably 1 to 3. The aromatic ring may have a monovalent or divalent electron-withdrawing group bonded thereto. Examples of the monovalent electron-withdrawing group include a nitro group, a cyano group, a p-toluenesulfonyl group, halogen, a halogenated alkyl group, a phenyl group, and an acyl group. Examples of the divalent electron-withdrawing group include a fluorinated alkylene group (e.g., -C(CF ３ ) ２ -, - (CF ２ ) ｐ In addition to halogenated alkylene groups such as - (where p is an integer from 1 to 10), -CO-, -SO ２ -, -SO-, -CONH-, -COO- and the like.

[0054] R ３is preferably a divalent group represented by formula (R4-1) or formula (R4-2). (In formula (R4-1) and formula (R4-2), m31 and m32 each independently represent an integer of 0 to 2. m33 and m34 each independently represent an integer of 0 to 2. R ２１ , R ２２ , and R ２３ are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. p21, p22, and p23 are integers of 0 to 4. L ２１ is a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.

[0055] In formula (R4-1) and formula (R4-2), m31 and m32 are each independently preferably 0 or 1. m33 and m34 are each independently preferably 0 or 1. ３ is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, and therefore, m31, m32, and R ２１ and p21 are selected so that the number of carbon atoms in the divalent group represented by formula (R4-1) is in the range of 6 to 22. Similarly, L in formula (R3-2) ２１ , m33, m34, R ２２ , R ２３ , p22, and p23 are selected so that the divalent group represented by formula (R3-2) has 12 to 22 carbon atoms.

[0056] X ３ is X in formula (2) １ The definitions and preferred embodiments are the same as above.

[0057] The polyimide resin may further contain a repeating structural unit represented by the following formula (5): (In formula (5), R ４ is -SO ２ - or a divalent group containing Si(Rx)(Ry)O-, where Rx and Ry each independently represent a chain aliphatic group having 1 to 3 carbon atoms or a phenyl group. ４is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. ４ is X in formula (2) １ The definitions and preferred embodiments are the same as above.

[0058] Although there are no particular limitations on the terminal structure of the polyimide resin, it is preferable that the polyimide resin has a chain aliphatic group having 5 to 14 carbon atoms at the terminal. The chain aliphatic group may be saturated or unsaturated, and may be linear or branched. When the polyimide resin has the above-mentioned specific group at the terminal, a resin composition with excellent heat aging resistance can be obtained. Examples of saturated chain aliphatic groups having 5 to 14 carbon atoms include an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, a lauryl group, an n-tridecyl group, an n-tetradecyl group, an isopentyl group, a neopentyl group, a 2-methylpentyl group, a 2-methylhexyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, an isooctyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, an isononyl group, a 2-ethyloctyl group, an isodecyl group, an isododecyl group, an isotridecyl group, and an isotetradecyl group. Examples of unsaturated chain aliphatic groups having 5 to 14 carbon atoms include 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, and tetradecenyl groups. Among these, the chain aliphatic groups are preferably saturated chain aliphatic groups, and more preferably saturated linear chain aliphatic groups. Furthermore, from the viewpoint of obtaining heat aging resistance, the chain aliphatic groups preferably have 6 or more carbon atoms, more preferably 7 or more carbon atoms, and even more preferably 8 or more carbon atoms, and preferably have 12 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably have 9 or less carbon atoms. The chain aliphatic groups may be of one type, or two or more types. The chain aliphatic group is particularly preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, an isononyl group, an n-decyl group, and an isodecyl group, further preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, a 2-ethylhexyl group, an n-nonyl group, and an isononyl group, and most preferably at least one selected from the group consisting of an n-octyl group, an isooctyl group, and a 2-ethylhexyl group.From the viewpoint of heat aging resistance, the polyimide resin preferably has, at its terminals, only chain aliphatic groups having 5 to 14 carbon atoms in addition to terminal amino groups and terminal carboxy groups. When a group other than the above is present at its terminals, the content thereof is preferably 10 mol % or less, more preferably 5 mol % or less, relative to the chain aliphatic groups having 5 to 14 carbon atoms.

[0059] From the viewpoint of exhibiting excellent heat aging resistance, the content of the chain aliphatic groups having 5 to 14 carbon atoms in the polyimide resin is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 0.2 mol% or more, based on 100 mol% of the total of all repeating structural units constituting the polyimide resin. Furthermore, in order to ensure a sufficient molecular weight and obtain good mechanical properties, the content of the chain aliphatic groups having 5 to 14 carbon atoms in the polyimide resin is preferably 10 mol% or less, more preferably 6 mol% or less, and even more preferably 3.5 mol% or less, based on 100 mol% of the total of all repeating structural units constituting the polyimide resin. The content of the chain aliphatic groups having 5 to 14 carbon atoms in the polyimide resin can be determined by depolymerizing the polyimide resin.

[0060] The polyimide resin preferably has a melting point of 360°C or lower and a glass transition temperature of 150°C or higher. From the viewpoint of heat resistance, the melting point of the polyimide resin is more preferably 280°C or higher, and from the viewpoint of achieving high moldability, it is preferably 345°C or lower, more preferably 340°C or lower, and even more preferably 335°C or lower. From the viewpoint of heat resistance, the glass transition temperature of the polyimide resin is preferably 160°C or higher, and from the viewpoint of achieving high moldability, it is preferably 250°C or lower, more preferably 230°C or lower, and even more preferably 200°C or lower. The melting point and glass transition temperature of the polyimide resin can both be measured by a differential scanning calorimeter. Furthermore, from the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance, the polyimide resin preferably has a heat value of 5.0 mJ / mg or more, more preferably 10.0 mJ / mg or more, and even more preferably 17.0 mJ / mg or more, of the heat value of the exothermic crystallization peak observed when the polyimide resin is melted and then cooled at a temperature decreasing rate of 20°C / min, as measured by a differential scanning calorimeter. The upper limit of the heat value of crystallization is not particularly limited, but is usually 45.0 mJ / mg or less. The melting point, glass transition temperature, and heat value of crystallization of the polyimide resin can be specifically measured by the methods described in the Examples.

[0061] The logarithmic viscosity of a 0.5% by mass solution of polyimide resin in concentrated sulfuric acid at 30°C is preferably in the range of 0.2 to 2.0 dL / g, more preferably 0.3 to 1.8 dL / g. If the logarithmic viscosity is 0.2 dL / g or higher, sufficient mechanical strength can be obtained when the resulting resin composition is molded into a molded article, while if it is 2.0 dL / g or lower, moldability and handleability are improved. The logarithmic viscosity μ is calculated by measuring the flow times of concentrated sulfuric acid and the polyimide resin solution at 30°C using a Cannon-Fenske viscometer and using the following formula: μ = ln(ts / t0) / C, where t0 is the flow time of concentrated sulfuric acid, ts is the flow time of polyimide resin solution, and C is 0.5 (g / dL).

[0062] The weight-average molecular weight Mw of the polyimide resin is preferably in the range of 10,000 to 150,000, more preferably 15,000 to 100,000, even more preferably 20,000 to 80,000, still more preferably 30,000 to 70,000, and even more preferably 35,000 to 65,000. If the weight-average molecular weight Mw of the polyimide resin is 10,000 or more, the mechanical strength of the resulting molded article will be good; if it is 40,000 or more, the stability of the mechanical strength will be good; and if it is 150,000 or less, the moldability will be good. The weight-average molecular weight Mw of the polyimide resin can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.

[0063] (Method for Producing Polyimide Resin) Polyimide resin can be produced by reacting a tetracarboxylic acid component with a diamine component, wherein the tetracarboxylic acid component contains a tetracarboxylic acid and / or a derivative thereof having at least one aromatic ring, and the diamine component contains a diamine having at least one alicyclic hydrocarbon structure and a chain aliphatic diamine.

[0064] The tetracarboxylic acid containing at least one aromatic ring is preferably a compound in which four carboxy groups are directly bonded to the aromatic ring, and may contain an alkyl group in the structure. The tetracarboxylic acid preferably has 6 to 26 carbon atoms. Examples of the tetracarboxylic acid include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, and 1,4,5,8-naphthalenetetracarboxylic acid. Among these, pyromellitic acid is more preferred.

[0065] Examples of derivatives of tetracarboxylic acids containing at least one aromatic ring include anhydrides or alkyl esters of tetracarboxylic acids containing at least one aromatic ring. The tetracarboxylic acid derivatives preferably have 6 to 38 carbon atoms. Examples of anhydrides of tetracarboxylic acids include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride. Examples of alkyl esters of tetracarboxylic acids include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylate, dimethyl 3,3',4,4'-diphenylsulfonetetracarboxylate, dimethyl 3,3',4,4'-benzophenonetetracarboxylate, dimethyl 3,3',4,4'-biphenyltetracarboxylate, dimethyl 1,4,5,8-naphthalenetetracarboxylate, etc. In the alkyl esters of tetracarboxylic acids, the alkyl group preferably has 1 to 3 carbon atoms.

[0066] As the tetracarboxylic acid and / or derivative thereof containing at least one aromatic ring, at least one compound selected from the above may be used alone, or two or more compounds may be used in combination.

[0067] The diamine containing at least one alicyclic hydrocarbon structure preferably has 6 to 22 carbon atoms, and examples thereof include 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), carvonediamine, limonenediamine, isophoronediamine, norbornanediamine, bis(aminomethyl)tricyclo[5.2.1.02,6]decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodicyclohexylpropane. These compounds may be used alone, or two or more compounds selected from these may be used in combination. Of these, 1,3-bis(aminomethyl)cyclohexane is preferred. Diamines containing an alicyclic hydrocarbon structure generally have structural isomers, but the ratio of cis / trans isomers is not limited.

[0068] The chain aliphatic diamine may be linear or branched, and preferably has 5 to 16 carbon atoms, more preferably 6 to 14, and even more preferably 7 to 12. Furthermore, as long as the chain portion has 5 to 16 carbon atoms, it may contain an ether bond therebetween. Preferred examples of the chain aliphatic diamine include 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 2,2'-(ethylenedioxy)bis(ethyleneamine). The chain aliphatic diamine may be used alone or in combination of two or more. Among these, chain aliphatic diamines having 8 to 10 carbon atoms are preferably used, and in particular, at least one selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine is preferably used.

[0069] In producing a polyimide resin, the molar ratio of the amount of the diamine containing at least one alicyclic hydrocarbon structure charged to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is preferably 20 to 70 mol %. This molar ratio is preferably 25 mol % or more, more preferably 30 mol % or more, and even more preferably 32 mol % or more. From the viewpoint of achieving high crystallinity, it is preferably 60 mol % or less, more preferably 50 mol % or less, even more preferably less than 40 mol %, and even more preferably 35 mol % or less.

[0070] The diamine component may also contain a diamine containing at least one aromatic ring. The diamine containing at least one aromatic ring preferably has 6 to 22 carbon atoms, and examples thereof include ortho-xylylenediamine, meta-xylylenediamine, para-xylylenediamine, 1,2-diethynylbenzenediamine, 1,3-diethynylbenzenediamine, 1,4-diethynylbenzenediamine, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, α,α'-bis(4-aminophenyl)1,4-diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,4-diisopropylbenzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,6-diaminonaphthalene, and 1,5-diaminonaphthalene.

[0071] In the above, the molar ratio of the amount of the diamine containing at least one aromatic ring to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is preferably 25 mol% or less. On the other hand, the lower limit is not particularly limited, as long as it is greater than 0 mol%. From the viewpoint of improving heat resistance, the molar ratio is preferably 5 mol% or more, more preferably 10 mol% or more. On the other hand, from the viewpoint of maintaining crystallinity, the molar ratio is preferably 20 mol% or less, more preferably 15 mol% or less. Furthermore, from the viewpoint of reducing coloration of the polyimide resin, the molar ratio is preferably 12 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, and even more preferably 0 mol%.

[0072] When producing the polyimide resin, the ratio of the amount of the tetracarboxylic acid component to the amount of the diamine component charged is preferably 0.9 to 1.1 moles of the diamine component per mole of the tetracarboxylic acid component.

[0073] Furthermore, when producing a polyimide resin, a terminal-capping agent may be mixed in addition to the tetracarboxylic acid component and the diamine component. The terminal-capping agent is preferably at least one selected from the group consisting of monoamines and dicarboxylic acids. The amount of terminal-capping agent used may be any amount sufficient to introduce the desired amount of terminal groups into the polyimide resin, and is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, and even more preferably 0.002 to 0.035 mol per mol of the tetracarboxylic acid and / or its derivative. Among these, monoamine terminal-capping agents are preferred. From the viewpoint of introducing the aforementioned linear aliphatic group having 5 to 14 carbon atoms to the terminal of the polyimide resin to improve heat aging resistance, monoamines having a linear aliphatic group having 5 to 14 carbon atoms are more preferred, and monoamines having a saturated linear aliphatic group having 5 to 14 carbon atoms are even more preferred. The end-capping agent is particularly preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine, more preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably at least one selected from the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.

[0074] As a polymerization method for producing a polyimide resin, a known polymerization method can be applied, and the method described in WO 2016 / 147996 can be referred to, the contents of which are incorporated herein by reference.

[0075] The polyimide resin used in this embodiment may be a recycled product (including recovered products, material recycled products, chemical recycled products, etc.), a rejected product, or a waste material from polyimide resin molding.

[0076] <Blend of Polyphenylene Ether Resin and Polyimide Resin> Next, the blend ratio of polyphenylene ether resin and polyimide resin in the first resin composition of this embodiment will be described. In the first resin composition of this embodiment, the mass ratio of polyphenylene ether resin relative to 100 parts by mass of the total of polyphenylene ether resin and polyimide resin is preferably 50 to 99 parts by mass. Furthermore, relative to 100 parts by mass of the total of polyphenylene ether resin and polyimide resin, the mass ratio of polyphenylene ether resin is preferably 55 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 85 parts by mass or more, and preferably 95 parts by mass or less. By setting the mass ratio at or above the lower limit, flame retardancy tends to be further improved. Furthermore, by setting the mass ratio at or below the upper limit, tracking resistance tends to be further improved. The first resin composition of the present embodiment may contain only one polyphenylene ether resin and one polyimide resin, or may contain two or more of either one or both. When two or more types are contained, it is preferable that the total amount is in the above range.

[0077] In the first resin composition of the present embodiment, the total amount of the polyphenylene ether resin and the polyimide resin is preferably 70% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, and even more preferably 83% by mass or more, based on 100% by mass of the resin composition, and is preferably 95% by mass or less, and may be 90% by mass or less.

[0078] On the other hand, the content of the polyimide resin in the second resin composition of this embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the total of the polyphenylene ether resin composed of the resin represented by Formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin. It is also preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and may be 15 parts by mass or less, 12 parts by mass or less, or 10 parts by mass or less. By setting the content at or above the lower limit, tracking resistance tends to be further improved. Furthermore, by setting the content at or below the upper limit, flame retardancy tends to be improved. The resin composition of this embodiment may contain only one type of polyimide resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0079] <Polyamide Resin> The second resin composition of this embodiment contains a polyamide resin. By including a polyamide resin, processability can be improved in a temperature range above the melting point of the polyamide. The polyamide resin may be an aliphatic polyamide resin or a semi-aromatic polyamide resin, but an aliphatic polyamide resin is preferred. Examples of aliphatic polyamide resins include one or more of polyamide 6, polyamide 66, polyamide 46, polyamide 666 (a copolymer consisting of a polyamide 6 component and a polyamide 66 component), polyamide 610, polyamide 612, polyamide 410, polyamide 1010, polyamide 11, polyamide 12, and polyamide 9C (a polyamide consisting of a mixed diamine of 1,9-nonanediamine and 2-methyl-1,8-octanediamine and 1,4-cyclohexanedicarboxylic acid). Preferably, the resin composition contains at least one of polyamide 6, polyamide 66, and polyamide 666, and more preferably polyamide 6. The tracking resistance of the resulting molded article tends to be further improved by including polyamide 6. Examples of semi-aromatic polyamide resins include polyamide 4T, polyamide 6T, polyamide 6I, polyamide 6T / 6I, polyamide 9T, polyamide 10T, polyamide 9N (a polyamide comprising a mixed diamine of 1,9-nonanediamine and 2-methyl-1,8-octanediamine and 2,6-naphthalenedicarboxylic acid), and xylylenediamine-based polyamide resins. Examples of xylylenediamine-based polyamide resins include MXD6, which is a polycondensate of metaxylylenediamine and adipic acid, MXD6I, which is a polycondensate of metaxylylenediamine, adipic acid, and isophthalic acid, MP6, which is a polycondensate of metaxylylenediamine, paraxylylenediamine, and adipic acid, MXD10, which is a polycondensate of metaxylylenediamine and sebacic acid, MP10, which is a polycondensate of metaxylylenediamine, paraxylylenediamine, and sebacic acid, and PXD10, which is a polycondensate of paraxylylenediamine and sebacic acid.

[0080] The polyamide resin used in this embodiment may be a recycled product (including recovered products, material recycled products, chemical recycled products, etc.), a rejected product, or a waste material from polyamide resin molding.

[0081] The content of the polyamide resin in the second resin composition of this embodiment is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, even more preferably 10 parts by mass or more, per 100 parts by mass of the polyphenylene ether resin composed of the resin represented by Formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin combined. It is also preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, and may even be 15 parts by mass or less. By setting the content at or above the lower limit, processability tends to be further improved. Furthermore, by setting the content at or below the upper limit, flame retardancy tends to be further improved. The second resin composition of this embodiment may contain only one type of polyamide resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0082] In the second resin composition of the present embodiment, the total amount of the polyphenylene ether resin composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin preferably accounts for 75% by mass or more, more preferably 78% by mass or more, and even more preferably 80% by mass or more, of 100% by mass of the resin composition, and preferably accounts for 95% by mass or less, and even more preferably 93% by mass or less.

[0083] The second resin composition of this embodiment preferably does not substantially contain any resin components other than the polyphenylene ether resin composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin. "Substantially free" means that the content of resin components other than the polyphenylene ether resin composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin in the resin composition is, for example, less than 5% by mass, preferably less than 3% by mass, more preferably less than 1% by mass, and even more preferably less than 0.1% by mass, based on 100% by mass of the resin composition. An example of the second resin composition of this embodiment is one that does not contain a polycarbonate resin.

[0084] <Flame retardant> The first resin composition of this embodiment contains a flame retardant. By containing a flame retardant, the flame retardancy of the resulting molded article can be improved. The type of flame retardant is not particularly limited, and known flame retardants can be used. Examples include phosphorus-based flame retardants, halogen-based flame retardants, and organic metal salt-based flame retardants. Phosphorus-based flame retardants and halogen-based flame retardants are preferred, and phosphorus-based flame retardants are more preferred. By using a phosphorus-based flame retardant, the flame retardancy of the resin composition can be improved more effectively.

[0085] Examples of phosphorus-based flame retardants include metal ethylphosphinate, metal diethylphosphinate, melamine polyphosphate, condensed phosphate esters, and phosphazene compounds. Among these, condensed phosphate esters or phosphazene compounds are preferred, and condensed phosphate esters are more preferred. As the flame retardant, one type of flame retardant may be used alone, or two or more types of flame retardants with different compositions may be used in combination.

[0086] In particular, when a phosphorus-based flame retardant is used as the flame retardant, the phosphorus-based flame retardant is preferably, for example, a phosphoric acid ester represented by formula (3P).

[0087] Formula (3P)

[0088] In formula (3P), R 1 , R 2 , R 3 , R 4each independently represents an aryl group. The aryl group may be substituted or unsubstituted. X represents a divalent aromatic group. The divalent aromatic group may or may not have another substituent. n represents an integer of 0 to 5.

[0089] R 1 , R 2 , R 3 , R 4 Examples of the aryl group represented by each of the above include a phenyl group and a naphthyl group, with a phenyl group being preferred. Examples of the divalent aromatic group represented by X include a phenylene group, a naphthylene group, or a group derived from a bisphenol, with a group derived from a bisphenol being preferred. When X is a group derived from a bisphenol, it is more preferred that it is any of the following groups:

[0090] The R 1 , R 2 , R 3 , R 4 The substituents for each of and X are preferably, for example, an alkyl group, an alkoxy group, or a hydroxy group. When the integer n is 0, the phosphate ester flame retardant represented by formula (3P) is a phosphate ester. When the integer n is any one of 1 to 5, the phosphate ester flame retardant represented by formula (3P) is a condensed phosphate ester. The condensed phosphate ester may be a mixture. In this embodiment, a condensed phosphate ester is preferred.

[0091] Examples of such phosphate ester-based flame retardants include triphenyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, and substitution products, condensates, etc. Commercially available phosphate ester-based flame retardants include, for example, "TPP" (triphenyl phosphate), "CR733S" (resorcinol bis(diphenyl phosphate)), "CR741" (bisphenol A bis(diphenyl phosphate)), "PX-200" (resorcinol bis(dixylenyl phosphate)), and "SR-3000" (non-halogen condensed phosphate ester), all manufactured by Daihachi Chemical Industry Co., Ltd., and "FP-900L" (biphenyl-4,4'-diol bis(diphenyl phosphate)), all manufactured by ADEKA Corporation, and are readily available.

[0092] The content of the flame retardant (preferably a phosphorus-based flame retardant) in the first resin composition of this embodiment is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the polyphenylene ether resin and the polyimide resin combined, and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 13 parts by mass or less. By setting the content at or above the lower limit, the combustion time of the resulting molded article can be shortened and the fluidity of the resin composition tends to be improved. Furthermore, by setting the content at or below the upper limit, the deterioration of the heat resistance and impact resistance of the resulting molded article tends to be more effectively suppressed. The first resin composition of this embodiment may contain only one type of flame retardant (preferably a phosphorus-based flame retardant), or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0093] On the other hand, the second resin composition of the present embodiment contains a nonionic phosphorus-based flame retardant, which can improve the flame retardancy of the resulting molded article without deteriorating its tracking resistance.

[0094] The nonionic phosphorus-based flame retardant is not particularly limited in terms of type, but preferably contains a nitrogen-containing phosphorus-based flame retardant and / or a phosphate ester, and more preferably contains a phosphazene and / or a phosphate ester.

[0095] In this embodiment, nitrogen-containing phosphorus-based flame retardants are particularly preferred. Nitrogen-containing phosphorus-based flame retardants are thought to have a particularly high flame retardancy effect by releasing inert nitrogen gas, and also to inhibit the accumulation of carbonized products resulting from deterioration, making them less likely to deteriorate tracking resistance.

[0096] Examples of nitrogen-containing phosphorus-based flame retardants include phosphazene and phosphoric acid ester amide, with phosphazene being preferred.

[0097] The phosphazene is an organic compound having a -P=N- bond in the molecule, and preferably includes at least one compound selected from the group consisting of a cyclic phosphazene represented by formula (F1), a chain phosphazene represented by formula (F2), and a bridged phosphazene obtained by crosslinking at least one phosphazene selected from the group consisting of formulas (F1) and (F2) with a crosslinking group, and the cyclic phosphazene represented by formula (F1) is preferred.

[0098] Formula (F1) (In formula (F1), a is an integer of 3 to 25, and R ｆ５ and R ｆ６ may be the same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryloxy group, an amino group, a hydroxy group, an aryl group, or an alkylaryl group.

[0099] Formula (F2) (In formula (F2), b is an integer of 3 to 10,000, and R ｆ７ and R ｆ８ may be the same or different and represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryloxy group, an amino group, a hydroxy group, an aryl group, or an alkylaryl group. ｆ９ is -N=P(OR ｆ７ ) ３ group, -N=P(OR ｆ８) ３ group, -N=P(O)OR ｆ７ group, -N=P(O)OR ｆ８ represents at least one selected from the group ｆ１０ is -P(OR ｆ７ ) ４ group, -P(OR ｆ８ ) ４ group, -P(O)(OR ｆ７ ) ２ group, -P(O)(OR ｆ８ ) ２ represents at least one selected from the group:

[0100] In formula (F1) and formula (F2), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group. Of these, an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, or a hexyl group, is preferred, and an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, or a propyl group, is particularly preferred.

[0101] Examples of the cycloalkyl group include cycloalkyl groups having 5 to 14 carbon atoms, such as cyclopentyl and cyclohexyl groups, and cycloalkyl groups having 5 to 8 carbon atoms are preferred.

[0102] Examples of the alkenyl group include alkenyl groups having 2 to 8 carbon atoms, such as a vinyl group and an allyl group. Examples of the cycloalkenyl group include cycloalkenyl groups having 5 to 12 carbon atoms, such as a cyclopentyl group and a cyclohexyl group.

[0103] Examples of the alkynyl group include alkynyl groups having 2 to 8 carbon atoms, such as ethynyl and propynyl groups, and alkynyl groups having an aryl group as a substituent, such as ethynylbenzene groups.

[0104] Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as a phenyl group, a methylphenyl (i.e., tolyl) group, a dimethylphenyl (i.e., xylyl) group, a trimethylphenyl group, and a naphthyl group. Among these, aryl groups having 6 to 10 carbon atoms are preferred, and a phenyl group is particularly preferred.

[0105] Examples of the alkylaryl group include aralkyl groups having 6 to 20 carbon atoms, such as benzyl, phenethyl, and phenylpropyl groups. Of these, aralkyl groups having 7 to 10 carbon atoms are preferred, with benzyl being particularly preferred.

[0106] Among them, R in formula (F1) ｆ５ and R ｆ６ , R in formula (F2) ｆ７ and R ｆ８ However, the aromatic phosphazene is preferably an aryl group or an arylalkyl group, more preferably an aryl group, and further preferably a phenyl group. By using such an aromatic phosphazene, the thermal stability of the resulting resin composition can be effectively improved.

[0107] Examples of the cyclic and / or chain phosphazenes represented by formula (F1) and formula (F2) include (poly)tolyloxyphosphazenes such as phenoxyphosphazene, o-tolyloxyphosphazene, m-tolyloxyphosphazene, and p-tolyloxyphosphazene; (poly)xylyloxyphosphazenes such as o,m-xylyloxyphosphazene, o,p-xylyloxyphosphazene, and m,p-xylyloxyphosphazene; o,m,p-trimethylphenyloxyphosphazene; phenoxy o-tolyloxyphosphazene; and phenoxy m-tolyloxyphosphazene. Examples include (poly)phenoxytolyloxyphosphazenes such as oxyphosphazene and phenoxy p-tolyloxyphosphazene, (poly)phenoxytolyloxyxylyloxyphosphazenes such as phenoxy o,m-xylyloxyphosphazene, phenoxy o,p-xylyloxyphosphazene and phenoxy m,p-xylyloxyphosphazene, and phenoxy o,m,p-trimethylphenyloxyphosphazene, and the like, and preferred are cyclic and / or chain phenoxyphosphazenes.

[0108] The cyclic phosphazene represented by formula (F1) includes R ｆ５ and R ｆ６is a phenyl group. Examples of such cyclic phenoxyphosphazenes include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decafenoxycyclopentaphosphazene, which are obtained by isolating cyclic chlorophosphazenes such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, and decachlorocyclopentaphosphazene from a mixture of cyclic and linear chlorophosphazenes obtained by reacting ammonium chloride with phosphorus pentachloride at a temperature of 120 to 130°C, and then substituting the cyclic chlorophosphazenes with phenoxy groups. Furthermore, the cyclic phenoxyphosphazene is preferably a compound represented by formula (F1) in which a is an integer of 3 to 8, and may also be a mixture of compounds in which a is different.

[0109] The average of the above a is preferably 3 to 5, and more preferably 3 to 4. Among these, a mixture of compounds in which those in which a=3 are 50% by mass or more, those in which a=4 are 10 to 40% by mass, and those in which a=5 or more are 30% by mass or less in total is preferred.

[0110] The chain phosphazene represented by formula (F2) is R ｆ７ and R ｆ８ is a phenyl group. Examples of such chain phenoxyphosphazenes include compounds obtained by ring-opening polymerization of hexachlorocyclotriphosphazene obtained by the above method at a temperature of 220 to 250°C, and substituting the resulting linear dichlorophosphazene having a degree of polymerization of 3 to 10,000 with a phenoxy group. In the linear phenoxyphosphazene, b in formula (F2) is preferably 3 to 1,000, more preferably 3 to 100, and even more preferably 3 to 25.

[0111] Examples of the crosslinked phosphazene include compounds having a crosslinked structure of a 4,4'-diphenylene group, such as a compound having a crosslinked structure of 4,4'-sulfonyldiphenylene (i.e., a bisphenol S residue), a compound having a crosslinked structure of a 2,2-(4,4'-diphenylene)isopropylidene group, a compound having a crosslinked structure of a 4,4'-oxydiphenylene group, and a compound having a crosslinked structure of a 4,4'-thiodiphenylene group.

[0112] The crosslinked phosphazene may be a phosphazene represented by the formula (F2) ｆ７ , R ｆ８ a bridged phenoxyphosphazene in which a cyclic phenoxyphosphazene in which R is a phenyl group is bridged by the above-mentioned bridge group, or ｆ７ , R ｆ８ is a phenyl group, is crosslinked by the above crosslinking group, which is preferred from the viewpoint of flame retardancy, and a bridged phenoxyphosphazene obtained by crosslinking a cyclic phenoxyphosphazene by the above crosslinking group is more preferred. The content of phenylene groups in the bridged phenoxyphosphazene is usually 50 to 99.9%, preferably 70 to 90%, based on the total number of phenyl groups and phenylene groups in the cyclic phosphazene represented by formula (F1) and / or the chain phenoxyphosphazene represented by formula (F2). It is particularly preferred that the bridged phenoxyphosphazene is a compound that does not have a free hydroxyl group in its molecule.

[0113] In this embodiment, the phosphazene is preferably at least one selected from the group consisting of cyclic phenoxyphosphazene represented by formula (F1) and crosslinked phenoxyphosphazene obtained by crosslinking the cyclic phenoxyphosphazene represented by formula (F1) with a crosslinking group, from the viewpoint of flame retardancy and mechanical properties of the resin composition. An example of a commercially available phosphazene product is FP-110 manufactured by Fushimi Pharmaceutical Co., Ltd.

[0114] The phosphate ester is preferably a compound represented by formula (F3) described in the section on the first resin composition above.

[0115] The nonionic phosphorus-based flame retardant used in this embodiment preferably has excellent heat resistance. Specifically, when subjected to thermogravimetric analysis, the 5% mass loss temperature is preferably 300°C or higher, more preferably 350°C or higher, and even more preferably 380°C or higher, and may be 420°C or lower. The 5% mass loss temperature refers to the temperature at which the mass is reduced by 5% when the temperature is increased from room temperature at a rate of 1°C / minute.

[0116] The content of the nonionic phosphorus-based flame retardant in the second resin composition of this embodiment is preferably 3.0 parts by mass or more, more preferably 5.0 parts by mass or more, even more preferably 6.0 parts by mass or more, even more preferably 8.0 parts by mass or more, even more preferably 9.0 parts by mass or more, even more preferably 11.0 parts by mass or more, relative to 100 parts by mass of the polyphenylene ether resin composed of the resin represented by Formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin combined. It is also preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 18 parts by mass or less, and even more preferably 14 parts by mass or less. By setting the content at or above the lower limit, the flame retardancy of the resulting molded article tends to be further improved. Furthermore, by setting the content at or below the upper limit, the tracking resistance of the resulting molded article tends to be further improved. The second resin composition of this embodiment may contain only one type of nonionic phosphorus-based flame retardant, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0117] In particular, the content of the nonionic phosphorus-based flame retardant, which is the nitrogen-containing phosphorus-based flame retardant, in the second resin composition of this embodiment is preferably 3.0 parts by mass or more, more preferably 4.0 parts by mass or more, even more preferably 5.0 parts by mass or more, even more preferably 6.0 parts by mass or more, and even more preferably 9.0 parts by mass or more, per 100 parts by mass of the polyphenylene ether resin composed of the resin represented by Formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin combined. It is also preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 18 parts by mass or less, and even more preferably 14 parts by mass or less. By setting the content at or above the lower limit, the flame retardancy of the resulting molded article tends to be further improved. Furthermore, by setting the content at or below the upper limit, the tracking resistance of the resulting molded article tends to be further improved.

[0118] The second resin composition of this embodiment may contain an ionic phosphorus-based flame retardant, but the content of the ionic phosphorus-based flame retardant is 2.0 parts by mass or less, preferably 1.5 parts by mass or less, more preferably 1.0 part by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of the polyphenylene ether resin composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin. Furthermore, the second resin composition of this embodiment may not contain an ionic phosphorus-based flame retardant. By reducing the content of the ionic phosphorus-based flame retardant in this manner, the tracking resistance of the resulting molded article can be further improved. Examples of ionic phosphorus-based flame retardants include phosphates, and more specifically, phosphinates and diphosphinates. For details, please refer to paragraphs 0036 to 0043 of JP 2023-007062 A, the contents of which are incorporated herein by reference.

[0119] The second resin composition of this embodiment may contain a nitrogen-based flame retardant as a flame retardant other than the phosphorus-based flame retardant. Examples of nitrogen-based flame retardants include melamine isocyanurate, triazine compounds, aminotriazine compounds, melamine, guanamine, melam, melem, and other melamine condensates, and guanidine compounds. Nitrogen-based flame retardants generate inactive nitrogen gas upon thermal decomposition, and their use together with a nonionic phosphorus-based flame retardant tends to improve flame retardancy and tracking resistance. When the second resin composition of this embodiment contains a nitrogen-based flame retardant, the content thereof is preferably 0.1 to 10 parts by mass per 100 parts by mass of the polyphenylene ether resin composed of a resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin combined.

[0120] The second resin composition of this embodiment may or may not contain a flame retardant other than a phosphorus-based flame retardant and a nitrogen-based flame retardant. Preferably, the second resin composition of this embodiment is substantially free of flame retardants other than phosphorus-based flame retardants. "Substantially free" means that the content of flame retardants other than phosphorus-based flame retardants contained in the resin composition is less than 10% by mass of the content of phosphorus-based flame retardants, preferably less than 5% by mass, more preferably less than 3% by mass, even more preferably less than 1% by mass, and even more preferably less than 0.1% by mass.

[0121] <Ceramic Particles> The first resin composition of this embodiment contains ceramic particles. The second resin composition of this embodiment preferably contains ceramic particles. By including ceramic particles, the tracking resistance of a molded article obtained from the first resin composition can be improved. Ceramic particles are usually insulating, and the dispersion of such insulating components tends to effectively suppress the formation of conductive circuits that cause tracking breakdown. Furthermore, the formation of holes during extrusion molding of the first resin composition of this embodiment into a flat-plate molded article (particularly, a film) can be effectively suppressed. It is presumed that the incorporation of ceramic particles allows the polyimide resin to be more effectively dispersed in the molded article. In particular, it is presumed that the inclusion of ceramic particles in the first resin composition of this embodiment allows the polyphenylene ether resin and the polyimide resin to be well dispersed even without the inclusion of a compatibilizer, thereby enabling the molding of a good flat-plate molded article (particularly, a film).

[0122] The median diameter (D50) of the ceramic particles used in this embodiment is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, even more preferably 0.15 μm or more, even more preferably 0.2 μm or more, and preferably 30 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, even more preferably 15 μm or less, and even more preferably 10 μm or less. By setting the diameter to be equal to or greater than the lower limit, tracking resistance tends to be further improved. Furthermore, by setting the diameter to be equal to or less than the upper limit, the impact resistance and toughness of the resulting molded body tend to be improved. The median diameter (D50) is measured according to a laser diffraction / scattering method. When the first resin composition of this embodiment contains two or more types of ceramic particles, the median diameter of the ceramic particles is the median diameter of the mixture.

[0123] The type of ceramic particles is not particularly limited, but is preferably at least one selected from alumina particles, titanium oxide v, yttrium oxide particles, silicon nitride particles, silicon carbide particles, magnesium oxide particles, calcium oxide particles, iron oxide particles, copper oxide particles, chromium oxide particles, boron oxide particles, silicon dioxide particles, and nickel oxide particles, and titanium oxide particles are preferred.

[0124] The ceramic particles may be surface-treated with at least one compound selected from polyorganohydrogensiloxanes and organopolysiloxanes. In this case, the amount of the siloxane compound attached to the ceramic particles is preferably 0.1 to 5 mass % of the ceramic particles.

[0125] The content of ceramic particles in the first resin composition of this embodiment is 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 10 parts by mass or less, preferably 8 parts by mass or less, more preferably 6 parts by mass or less, even more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of the total of the polyphenylene ether resin and the polyimide resin. By setting the content at or above the lower limit, the tracking resistance of the resin composition or molded article tends to be further improved. Furthermore, by setting the content at or below the upper limit, the decrease in impact resistance and toughness of the resulting molded article tends to be more effectively suppressed.

[0126] On the other hand, the content of ceramic particles in the second resin composition of this embodiment is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the polyphenylene ether resin composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin combined. It is also preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 6 parts by mass or less, even more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less. By setting the content at or above the lower limit, the tracking resistance of the resin composition or molded article tends to be further improved. Furthermore, by setting the content at or below the upper limit, the impact resistance and toughness of the resulting molded article tend to be more effectively suppressed. The resin composition of this embodiment may contain only one type of ceramic particle, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

[0127] <Lubricant> The resin composition of this embodiment may contain a lubricant. The incorporation of a lubricant tends to further improve the tracking resistance and flame retardancy of the resulting molded article. This is presumably because the lubricant is less likely to cause carbonized residue on the material surface and also less likely for the resin to remain or adhere to the die outlet during extrusion (suppressing scum), thereby reducing the risk of contamination with components deteriorated by heat or oxidation. Examples of lubricants include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds with a number-average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ketone waxes, and light amides. Aliphatic carboxylic acids, salts of aliphatic carboxylic acids, and esters of aliphatic carboxylic acids and alcohols are preferred, with salts of aliphatic carboxylic acids being more preferred, metal stearates being even more preferred, calcium stearate and zinc stearate being even more preferred, and zinc stearate being even more preferred. For details of the lubricant, please refer to paragraphs 0055 to 0061 of JP 2018-095706 A, the contents of which are incorporated herein by reference.

[0128] When the first resin composition of this embodiment contains a lubricant, the content thereof is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the total of the polyphenylene ether resin and the polyimide resin. It is also preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, even more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less. By setting the content at or above the lower limit, the effect of suppressing the buildup and tracking resistance tend to be further improved. Furthermore, by setting the content at or below the upper limit, it is possible to effectively suppress the lubricant from bleeding out, and it is possible to effectively suppress the appearance defect and the lubricant itself from becoming a cause of buildup. Furthermore, by setting the content at or below the upper limit, it is possible to suppress the amount of gas generated during heat processing.

[0129] On the other hand, when the second resin composition of this embodiment contains a lubricant, the content thereof is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the polyphenylene ether resin composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin combined, preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, even more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less. By setting the content at or above the lower limit, the effect of suppressing the buildup and tracking resistance tend to be further improved. Furthermore, by setting the content at or below the upper limit, the lubricant can be effectively prevented from bleeding out, and poor appearance and the lubricant itself can be effectively prevented from causing buildup. Furthermore, by setting the content at or below the upper limit, the amount of gas generated during heat processing tends to be suppressed. The resin composition of this embodiment may contain only one type of lubricant, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0130] <Stabilizer> The resin composition of the present embodiment may contain a stabilizer. Examples of the stabilizer include a thermal stabilizer and an antioxidant. Examples of the stabilizer include a phenol-based stabilizer, an amine-based stabilizer, a phosphorus-based stabilizer, and a thioether-based stabilizer. Among these, in the present embodiment, it is preferable to contain a phenol-based stabilizer, a phosphorus-based stabilizer, and a thioether-based stabilizer.

[0131] Any known phosphorus stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphite compounds being particularly preferred.

[0132] Examples of the organic phosphite compound include triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonyl phenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite. Specific examples of such organic phosphite compounds include "ADK STAB (registered trademark; the same applies hereinafter) 1178," "ADK STAB 2112," "ADK STAB HP-10," and "PEP-36" manufactured by ADEKA Corporation; "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd.; and "IRGAFOS (registered trademark; the same applies hereinafter) 168" manufactured by BASF.

[0133] As the phenol-based stabilizer, a hindered phenol-based stabilizer is preferably used. Specific examples of hindered phenol stabilizers include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesityle) 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0134] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Specific examples of such hindered phenol stabilizers include "Irganox (registered trademark; the same applies hereinafter) 1010" and "Irganox 1076" manufactured by BASF, and "ADK STAB AO-50" and "ADK STAB AO-60" manufactured by ADEKA Corporation.

[0135] Examples of thioether stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, laurylstearyl thiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and the like. For example, commercially available products such as DSTP "Yoshitomi", DLTP "Yoshitomi", DLTOIB, and DMTP "Yoshitomi" (all manufactured by API Corporation), Seenox 412S (manufactured by Shipro Chemical Co., Ltd.), Adekastab AO-412S (manufactured by ADEKA Corporation), Cyanox 1212 (manufactured by Cyanamid Corporation), and Sumilizer TP-D (manufactured by Sumitomo Chemical Co., Ltd.) can be used (all are trade names).

[0136] The content of the stabilizer in the first resin composition of the present embodiment is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, and usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 1 part by mass or less, relative to 100 parts by mass of the total amount of the polyphenylene ether resin and the polyimide resin. By setting the content of the stabilizer within this range, the effect of adding the stabilizer can be more effectively exhibited.

[0137] On the other hand, the content of the stabilizer in the second resin composition of this embodiment is usually 0.001 parts by mass or more, preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, relative to 100 parts by mass of the total amount of the polyphenylene ether resin composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin, and is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 1 part by mass or less. By setting the content of the stabilizer within the above range, the effect of adding the stabilizer can be more effectively exhibited. The resin composition of this embodiment may contain only one type of stabilizer, or may contain two or more types. When two or more types are contained, it is preferable that the total amount be within the above range.

[0138] <Other Components> The resin composition of the present embodiment may contain other components in addition to those described above. Examples of other components include resin additives and fillers other than ceramic particles.

[0139] Resin additives may include dyes, pigments, weather resistance improvers, nucleating agents, impact modifiers, plasticizers, flow improvers, etc. The total amount of these resin additives is preferably less than 10% by mass, more preferably less than 5% by mass, and even more preferably less than 3% by mass, based on 100% by mass of the resin composition. In addition, the resin composition of this embodiment can be blended with additives described in paragraphs 0047 to 0103 of WO 2021 / 241471 within the scope of the present invention, the contents of which are incorporated herein by reference.

[0140] Examples of fillers other than ceramic particles include glass fiber, carbon fiber, etc. The total amount of fillers other than ceramic particles in the resin composition of this embodiment is preferably less than 10% by mass, more preferably less than 5% by mass, even more preferably less than 3% by mass, and even more preferably less than 1% by mass, based on 100% by mass of the resin composition.

[0141] In the first resin composition of the present embodiment, the polyphenylene ether resin, polyimide resin, flame retardant, and ceramic particles, as well as the lubricant and stabilizer that are blended as needed, preferably account for 90% by mass or more of the resin composition, more preferably 95% by mass or more, even more preferably 97% by mass or more, and may even account for 99% by mass or more.

[0142] In the second resin composition of the present embodiment, the polyphenylene ether resin, polyimide resin, polyamide resin, and flame retardant, which are composed of a resin represented by formula (1) and / or an acid-modified product thereof, as well as the lubricant, ceramic particles, and stabilizer which are blended as necessary, preferably account for 90% by mass or more of the resin composition, more preferably 95% by mass or more, even more preferably 97% by mass or more, and may even account for 99% by mass or more.

[0143] <Physical Properties of Resin Composition> The resin composition of this embodiment preferably has excellent tracking resistance. Specifically, the resin composition is molded into a test piece of 100 mm × 150 mm × 3.2 mm, and the CTI value measured by a measurement method in accordance with IEC 60112 is preferably 400 V or more, more preferably 450 V or more, even more preferably 500 V or more, even more preferably 525 V or more, even more preferably 550 V or more, even more preferably 600 V or more, and particularly preferably 650 V or more. The upper limit of the CTI value is preferably the measurement limit value, for example, 1000 V. The CTI value is measured according to the description of the examples described below.

[0144] The resin composition of this embodiment preferably has excellent flame retardancy. Specifically, the resin composition is molded into a 0.125 μm thick plate-shaped molded article, and the result of a flammability test in accordance with UL-94 preferably satisfies VTM-1 (V-1), more preferably VTM-0 (V-0). The flame retardancy is measured according to the description in the Examples below. Specifically, the resin composition is molded into a 0.4 μm thick plate-shaped molded article, and the result of a flammability test in accordance with UL-94 preferably satisfies V-1, more preferably V-0. Alternatively, the resin composition is molded into a 0.8 μm thick plate-shaped molded article, and the result of a flammability test in accordance with UL-94 preferably satisfies V-1, more preferably V-0. Furthermore, when the resin composition is molded into a plate-like molded article having a thickness of 0.4 μm, and when the resin composition is molded into a plate-like molded article having a thickness of 0.8 μm, the result of a flammability test of the plate-like molded article in accordance with UL-94 preferably satisfies V-1, and more preferably satisfies V-0. The flame retardancy is measured according to the description in the Examples below.

[0145] <Method for Producing Resin Composition> The method for producing the resin composition of this embodiment is not limited, and a wide variety of known methods for producing resin compositions can be used. Examples include premixing the essential components of the resin composition of this embodiment and other components added as needed using various mixers such as a tumbler or Henschel mixer, followed by melt-kneading using a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. The melt-kneading temperature is not particularly limited, but is preferably 330°C or lower, more preferably 320°C or lower, even more preferably 310°C or lower, even more preferably 300°C or lower, and even more preferably 290°C or lower. The lower limit of the melt-kneading temperature is preferably 240°C or higher, and may be 250°C or higher, 260°C or higher, or 270°C or higher. An example of a resin composition is pellets.

[0146] <Molded Article> The molded article of this embodiment is formed from the resin composition or pellets of this embodiment. In this embodiment, the molded article may be produced by pelletizing the resin composition and molding the resulting pellets using various molding methods. Alternatively, the molded article may be produced by directly molding a resin composition melt-kneaded in a kneader without going through pelletization. The above-mentioned resin composition (e.g., pellets) is molded into a molded article using various molding methods. The shape of the molded article is not particularly limited and can be appropriately selected depending on the application and purpose of the molded article. Examples of the shape of the molded article include flat, rod-shaped, cylindrical, annular, circular, elliptical, polygonal, irregular, hollow, frame-shaped, box-shaped, panel-shaped, and button-shaped articles. An example of the molded article of this embodiment is a flat-plate molded article (film, sheet). The thickness of the plate-like molded article of this embodiment is, for example, preferably 10 μm or more, more preferably 25 μm or more, even more preferably 50 μm or more, even more preferably 75 μm or more, even more preferably 100 μm or more, and preferably 2000 μm or less, more preferably 1000 μm or less, even more preferably 750 μm or less, even more preferably 500 μm or less, and even more preferably 250 μm or less. The temperature during film molding is not particularly limited, but is preferably 330 ° C or less, more preferably 320 ° C or less, even more preferably 310 ° C or less, even more preferably 300 ° C or less, and even more preferably 290 ° C or less. The lower limit of the temperature during film molding is preferably 240 ° C or more, and may be 250 ° C or more, 260 ° C or more, or 270 ° C or more.

[0147] The method for molding the molded article is not particularly limited, and conventionally known molding methods can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. The resin composition of this embodiment is particularly suitable for molded articles obtained by injection molding, injection compression molding, and extrusion molding. However, it goes without saying that the resin composition of this embodiment is not limited to molded articles obtained by these methods.

[0148] <Applications> The resin composition, pellets, and molded article of this embodiment are widely used in applications where polyphenylene ether resins, particularly blends of polyphenylene ether resins and polyimide resins, are commonly used. The resin composition, pellets, and molded article of this embodiment are applicable to applications requiring high flame retardancy and tracking resistance, such as electric vehicle battery modules, battery housings, battery cases, battery cell frames, battery cell spacers, battery cell retainers, bus bar holders, bus bar covers, terminal covers, electrical connectors, automotive electrical connectors, relays, charging couplers, charging adapters, and outlets.

[0149] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0150] <Raw Materials> The raw materials shown in Table 1 below were used.

[0151]

[0152] Synthesis Example 1: Production of maleic anhydride-modified polyphenylene ether resin 97.6% by mass of polyphenylene ether resin PX100L (Polyxylenol Singapore Pte. Ltd.) and 2.4% by mass of maleic anhydride CRYSTAL MAN AB (NOF Corporation) were mixed and melt-kneaded using a twin-screw extruder (Shibaura Machine Co., Ltd.: TEM18SS) at a cylinder temperature (extrusion temperature) of 280°C and a screw rotation speed of 450 rpm to obtain maleic anhydride-modified polyphenylene ether resin pellets. After removing unreacted maleic anhydride from the obtained maleic anhydride-modified polyphenylene ether resin pellets by reprecipitation purification, the maleic anhydride addition rate was quantified by neutralization titration using phenolphthalene indicator and 0.1 mol / L sodium methylal, and the maleic anhydride addition rate was found to be 0.39% by mass.

[0153] Synthesis Example 2: Production of Polyimide Resin 1 Into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and a four-paddle blade, 500 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Nyukazai Co., Ltd.) and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Company, Inc.) were introduced, and after flowing nitrogen, the mixture was stirred at 150 rpm to obtain a uniform suspension. Meanwhile, using a 500 mL beaker, 49.79 g (0.35 mol) of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc., cis / trans ratio = 7 / 3) and 93.77 g (0.65 mol) of 1,8-octamethylenediamine (manufactured by Kanto Chemical Co., Inc.) were dissolved in 250 g of 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. This mixed diamine solution was gradually added using a plunger pump. Although heat was generated during the dropwise addition, the internal temperature was adjusted to remain within the range of 40 to 80°C. During the dropwise addition of the mixed diamine solution, nitrogen flow was maintained throughout, and the stirring impeller rotation speed was set to 250 rpm. After the dropwise addition was completed, 130 g of 2-(2-methoxyethoxy)ethanol and 1.284 g (0.010 mol) of n-octylamine (Kanto Chemical Co., Inc.), an end-capping agent, were added and further stirred. At this stage, a pale yellow polyamic acid solution was obtained. Next, the stirring speed was increased to 200 rpm, and the polyamic acid solution in the 2-L separable flask was heated to 190°C. During the temperature increase, precipitation of polyimide resin powder and dehydration associated with imidization were observed between 120 and 140°C. After holding at 190°C for 30 minutes, the solution was allowed to cool to room temperature and then filtered. The obtained polyimide resin powder was washed with 300 g of 2-(2-methoxyethoxy)ethanol and 300 g of methanol, filtered, and then dried in a dryer at 180°C for 10 hours to obtain 317 g of powder of crystalline thermoplastic polyimide resin 1 (hereinafter also simply referred to as "polyimide resin 1"). The IR spectrum of polyimide resin 1 was measured, revealing a ν(C=O) 1768, 1697 (cm －１) characteristic absorption of an imide ring was observed. The inherent viscosity was 1.30 dL / g, Tm was 323°C, Tg was 184°C, Tc was 266°C, the heat of fusion was 26.7 mJ / mg, the heat of crystallization was 30.0 mJ / mg, the crystallization half time was 20 seconds or less, and the Mw was 55,000. The IR spectrum, relative viscosity, Tm, Tg, Tc, heat of fusion, crystallization half time, and weight average molecular weight were measured according to the descriptions in paragraphs 0114 to 0117 of WO 2016 / 084475.

[0154] Synthesis Example 3 A polyimide resin was synthesized according to the description in paragraph 0134 of WO 2016 / 147996. The Tm was 283°C, the Tg was 165°C, the Tc was 237°C, the heat of crystallization was 21.0 mJ / mg, and the crystallization half time was 20 seconds or less.

[0155] Example 1-1, Example 1-2, Example 1-3, Example 1-4, Comparative Example 1-1, Comparative Example 1-2, and Comparative Example 1-3 <Method for producing resin composition> The components shown in Table 1 or Table 2 were mixed in the ratios (parts by mass) shown in Table 3 described below, and the mixture of the components was melt-kneaded using a twin-screw extruder (Shibaura Machine Co., Ltd.: TEM26SX) at a cylinder temperature of 340°C and a screw rotation speed of 200 rpm to obtain a resin composition (pellets). The obtained resin composition (pellets) was used to perform the following evaluations. The results are shown in Table 3.

[0156] <Evaluation of Tracking Resistance> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours and then fed to an injection molding machine ("EC75SX" manufactured by Shibaura Machine Co., Ltd.), and a molded body having dimensions of length x width x thickness = 100 mm x 100 mm x 3 mm was produced in this injection molding machine under conditions of a cylinder temperature of 320°C and a mold temperature of 130°C. Using the produced molded body, the maximum voltage at which tracking failure of the molded body did not occur, i.e., the CTI value (unit: V), was measured by a measurement method in accordance with IEC60112 (electrolyte used: solution A, number of drops: 50).

[0157] <Film formability> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, then fed into a T-die extrusion molding machine (a small extruder manufactured by Technovel Co., Ltd.) and extruded at a cylinder setting temperature of 310°C to 340°C and a screw rotation speed of 25 rpm. The film was then taken up at a cooling roll setting temperature of 140°C and a take-up speed of 0.8 to 1.5 m / min to obtain a film having a thickness of 150 μm and a width of 140 mm. Evaluation was performed according to the following criteria. Evaluation was performed visually by five experts and judged by majority vote. A: 1 or less pinhole B: 2 to 20 pinholes C: 20 or more pinholes D: It was difficult to take up the film.

[0158] <Flame Retardancy> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, then fed into a T-die extrusion molding machine (a small extruder manufactured by Technovel Co., Ltd.) and extruded at a cylinder setting temperature of 310°C to 340°C and a screw rotation speed of 25 rpm. The extrusion was performed at a chill roll setting temperature of 140°C and a take-up speed of 0.8 to 1.5 m / min, yielding a film having a thickness of 125 nm and a width of 140 mm. Films (thickness 0.125 μm) obtained under the same conditions as the film moldability described above were cut into 200 mm x 50 mm pieces and subjected to a vertical flame resistance test (UL-94 VTM test) for sets of five pieces in accordance with the UL-94 standard. The UL-94 standard grades are classified as VTM-0 (V-0), VTM-1 (V-1), VTM-2 (V-2), and non-compliant, in descending order of quality. Each set was graded based on the vertical flame resistance test, and the results are shown in Table 3.

[0159]

[0160] In Table 3 above, the unit of tracking resistance is V. As is clear from the above results, the resin compositions of the present invention were excellent in tracking resistance, film formability, and flame retardancy (Examples 1-1 to 1-4). In particular, by blending a lubricant, tracking resistance and flame retardancy were further improved (Examples 1-2 to 1-4). Also, photographs of the appearance of the films of Comparative Example 1-1, Example 1-1, and Example 1-2 are shown in Figures 1, 2, and 3, respectively.

[0161] Examples 2-1 to 2-10 <Method for producing resin composition> The components shown in Table 1 or Table 2 were mixed in the proportions (parts by mass) shown in Table 4 or Table 5 described below, and the mixture of the components was melt-kneaded using a twin-screw extruder (TEM26SX, manufactured by Shibaura Machine Co., Ltd.) at a cylinder temperature (extrusion temperature) of 280°C and a screw rotation speed of 200 rpm to obtain a resin composition (pellet). The obtained resin composition (pellet) was used to perform the following evaluations. The results are shown in Table 4 or Table 5.

[0162] <Evaluation of Tracking Resistance> Measurement was carried out in the same manner as in Example 1-1.

[0163] <Flame Retardancy> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours and then fed into an injection molding machine ("EC75SX" manufactured by Shibaura Machine Co., Ltd.). In this injection molding machine, plate-like molded articles having a thickness of 0.8 mm and 0.4 mm were produced under conditions of a cylinder temperature of 280°C and a mold temperature of 130°C. The flame retardancy of the plate-like molded articles was evaluated in accordance with the UL-94 standard. The UL-94 standard grades are classified in order of best to worst as V-0, V-1, V-2, and non-compliant. Each set was evaluated based on a grade based on a vertical flammability test, and the results are shown in Table 4 or Table 5.

[0164]

[0165] As is clear from the above results, the molded articles formed from the resin composition of this embodiment maintained good tracking resistance and also had excellent flame retardancy (Examples 2-1 to 2-10). In particular, when polyamide 6 was blended as the polyamide resin, the molded articles had excellent tracking resistance and flame retardancy (comparison of Examples 2-1 to 2-4, 2-6 to 2-9 with Example 2-5).

[0166] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.

Claims

1. A resin composition comprising a polyphenylene ether resin consisting of a resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a flame retardant, and ceramic particles, wherein the polyimide resin comprises a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and the content of the repeating structural unit represented by formula (2) is 20 to 70 mol % relative to 100 mol % of the total of the repeating structural units represented by formula (2) and the repeating structural units represented by formula (3). (In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６４ are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ６５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more. (In formulas (2) and (3), R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２ are each independently a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms.

2. The resin composition according to claim 1, which contains 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles per 100 parts by mass of the polyphenylene ether resin and polyimide resin combined.

3. The resin composition according to claim 1 or 2, wherein the flame retardant comprises a phosphorus-based flame retardant.

4. The resin composition according to claim 1 or 2, wherein the ceramic particles include titanium oxide particles.

5. The resin composition according to claim 1 or 2, further comprising a lubricant.

6. The resin composition according to claim 1 or 2, further comprising a lubricant in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the polyphenylene ether resin and polyimide resin combined.

7. The resin composition according to claim 1 or 2, wherein the mass ratio of the polyphenylene ether resin to the total of 100 parts by mass of the polyphenylene ether resin and the polyimide resin is 50 to 99 parts by mass.

8. The resin composition according to claim 1 or 2, wherein the ceramic particles have a median diameter (D50) of 0.01 to 30 μm.

9. The resin composition according to claim 1, comprising 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles relative to 100 parts by mass of the polyphenylene ether resin and polyimide resin combined, wherein the flame retardant comprises a phosphorus-based flame retardant, the ceramic particles comprise titanium oxide particles, and the resin composition further comprises 0.1 to 3 parts by mass of a lubricant relative to 100 parts by mass of the polyphenylene ether resin and polyimide resin combined, wherein the ceramic particles have a median diameter (D50) of 0.01 to 30 μm, and the mass ratio of the polyphenylene ether resin to 100 parts by mass of the polyphenylene ether resin and polyimide resin combined is 50 to 99 parts by mass.

10. The resin composition according to claim 1, 2 or 9, wherein the resin composition is molded into a test piece of 100 mm x 150 mm x 3.2 mm, and the CTI value measured by a measurement method in accordance with IEC 60112 is 600 V or more.

11. The resin composition according to claim 1, 2 or 9, which is molded into a flat plate-like molded article having a thickness of 0.125 μm, and the result of a flammability test in accordance with UL-94 satisfies VTM-0.

12. A resin composition comprising a polyphenylene ether resin formed from a resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a polyamide resin, and a non-ionic phosphorus-based flame retardant, wherein the content of the ionic phosphorus-based flame retardant is 2.0 parts by mass or less per 100 parts by mass of the polyphenylene ether resin formed from the resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin, and the polyimide resin contains a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and the content ratio of the repeating structural unit represented by formula (2) is 20 to 70 mol % per 100 mol % of the total of the repeating structural units represented by formula (2) and the repeating structural units represented by formula (3). (In formula (1), R ５１ ~R ５５ , and R ６１ ~R ６４ are each independently a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ６５ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more. (In formulas (2) and (3), R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ is a divalent chain aliphatic group having 5 to 16 carbon atoms. １ and X ２ are each independently a tetravalent group containing at least one aromatic ring and having 6 to 22 carbon atoms.

13. The resin composition according to claim 12, wherein the nonionic phosphorus-based flame retardant comprises a nitrogen-containing phosphorus-based flame retardant and / or a phosphoric acid ester.

14. The resin composition according to claim 12, wherein the nonionic phosphorus-based flame retardant comprises a phosphazene and / or a phosphoric acid ester.

15. The resin composition according to any one of claims 12 to 14, wherein a portion of the polyphenylene ether resin is an acid-modified product of the resin represented by formula (1).

16. The resin composition according to any one of claims 12 to 14, wherein 1 to 20 mass% of the polyphenylene ether resin is an acid-modified product of the resin represented by formula (1).

17. The resin composition according to any one of claims 12 to 14, wherein the polyamide resin comprises an aliphatic polyamide resin.

18. The resin composition according to any one of claims 12 to 14, wherein the polyamide resin comprises at least one of polyamide 6, polyamide 66, and polyamide 666.

19. The resin composition according to any one of claims 12 to 14, wherein the polyamide resin comprises polyamide 6.

20. A resin composition according to any one of claims 12 to 14, wherein the content of the polyamide resin is 1 to 40 parts by mass per 100 parts by mass of the total of the polyphenylene ether resin consisting of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin.

21. The resin composition according to any one of claims 12 to 14, wherein the content of the polyimide resin is 1 to 40 parts by mass per 100 parts by mass of the total of the polyphenylene ether resin formed from the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin.

22. The resin composition according to any one of claims 12 to 14, further comprising a lubricant.

23. The resin composition according to any one of claims 12 to 14, further comprising ceramic particles.

24. The resin composition of claim 23, wherein the ceramic particles comprise titanium oxide particles.

25. The resin composition according to claim 12, wherein the nonionic phosphorus-based flame retardant comprises a phosphazene and / or a phosphate ester; 1 to 20% by mass of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1); the polyamide resin comprises at least one of polyamide 6, polyamide 66, and polyamide 666; the content of the polyamide resin is 1 to 40 parts by mass per 100 parts by mass of the polyphenylene ether resin formed from the resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin; the content of the polyimide resin is 1 to 40 parts by mass per 100 parts by mass of the polyphenylene ether resin formed from the resin represented by formula (1) and / or an acid-modified product thereof, the polyimide resin, and the polyamide resin; further comprising a lubricant; and further comprising ceramic particles, the ceramic particles comprising titanium oxide particles.

26. Pellets of the resin composition according to any one of claims 1, 2, 9, 12, 13, 14 and 25.

27. A molded article formed from the resin composition according to any one of claims 1, 2, 9, 12, 13, 14 and 25.

28. The molded article according to claim 27, which is flat.

Images