Resin composition, pellet, and molded article

Abstract

To provide a resin composition excellent in tracking resistance and flame retardancy, pellets of the resin composition, and a molded article formed from the resin composition.SOLUTION: A polyphenylene ether resin, a polyimide resin, a polyamide resin, and a non-ionic phosphorus-based flame retardant, wherein a content of the ionic phosphorus-based flame retardant is 2.0 parts by mass or less with respect to a total of 100 parts by mass of the polyphenylene ether resin, the polyimide resin, and the polyamide resin, the polyimide resin includes a repeating structural unit represented by Formula (2) and a repeating structural unit represented by Formula (3), and a content ratio of the repeating structural unit represented by Formula (2) is 20 to 70 mol% with respect to a total of 100 mol% of the repeating structural unit represented by Formula (2) and the repeating structural unit represented by Formula (3).SELECTED DRAWING: None

Description

[Technical Field]

[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. [Background technology]

[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. Polyphenylene ether resin compositions are required to have various properties 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. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2009 / 040751 Summary of the Invention [Problem to be solved by the invention]

[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 with the polyphenylene ether resin composition. Furthermore, a polyphenylene ether resin composition having improved tracking resistance may also be required to have flame retardancy. 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 the above problems and to provide a resin composition, pellets, and molded articles that are excellent in tracking resistance and flame retardancy. [Means for solving the problem]

[0007] In view of the above problems, the present inventors have conducted research and found that the above problems can be solved by using a nonionic phosphorus-based flame retardant as the flame retardant. Specifically, the above problems were solved by the following means. [1] A flame retardant composition comprising a polyphenylene ether resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a polyamide resin, and a nonionic phosphorus-based flame retardant, 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 the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin; The polyimide resin contains a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), A resin composition in which the repeating structural unit represented by formula (2) is contained in an amount of 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). [ka] (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. [ka] (In formulas (2) and (3), R1 is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. R2 is a divalent chain aliphatic group having 5 to 16 carbon atoms. X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) [2] The resin composition according to [1], wherein the nonionic phosphorus-based flame retardant comprises a nitrogen-containing phosphorus-based flame retardant and / or a phosphate ester. [3] The resin composition according to [1], wherein the nonionic phosphorus-based flame retardant comprises a phosphazene and / or a phosphate ester. [4] The resin composition according to any one of [1] to [3], wherein a part of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1). [5] The resin composition according to any one of [1] to [4], wherein 1 to 40 mass % of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1). [6] The resin composition according to any one of [1] to [5], wherein the polyamide resin contains an aliphatic polyamide resin. [7] The resin composition according to any one of [1] to [6], wherein the polyamide resin comprises at least one of polyamide 6, polyamide 66, and polyamide 666. [8] The resin composition according to any one of [1] to [7], wherein the polyamide resin contains polyamide 6. [9] The resin composition according to any one of [1] to [8], 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.

[10] The resin composition according to any one of [1] to [9], 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 consisting of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin.

[11] The resin composition according to any one of [1] to

[10] , further comprising a lubricant.

[12] The resin composition according to any one of [1] to

[11] , further comprising ceramic particles.

[13] The resin composition according to

[12] , wherein the ceramic particles contain titanium oxide particles.

[14] 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 contains 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 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; 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 composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin; Further comprising a lubricant, Further containing ceramic particles, The resin composition according to any one of [1] to

[14] , wherein the ceramic particles include titanium oxide particles.

[15] Pellets of the resin composition according to any one of [1] to

[14] .

[16] A molded article formed from the resin composition according to any one of [1] to

[14] .

[17] A flat plate-shaped molded article formed from the resin composition according to any one of [1] to

[14] . [Effects of the Invention]

[0008] The present invention makes it possible to provide a resin composition, pellets, and molded articles that are excellent in tracking resistance and flame retardancy. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as upper and lower limits. "A to B" means that the range is A or more and B or less. In addition, any combination of the upper and lower limit values ​​of the numerical values ​​in this specification is an example of this embodiment. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified.

[0010] The flat-plate-shaped molded body in this specification includes 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 either single-layer or multi-layer, but are preferably single-layer. If the measurement methods, etc. described in the standards shown in this specification change from year to year, they will be based on the standards in effect 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 will be based on the standards in effect at the time of abolition.

[0011] The 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 repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3). [ka] (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. [ka] (In formulas (2) and (3), R1 is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. R2 is a divalent chain aliphatic group having 5 to 16 carbon atoms. X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.)

[0012] By adopting such a constitution, a resin composition having excellent tracking resistance and flame retardancy can be obtained. That is, by blending a specific polyimide resin with a polyphenylene ether resin, the tracking resistance of the resin composition can be improved.Furthermore, by blending a polyamide resin, the viscosity of the resin composition can be reduced in a temperature range above the melting point of the polyamide, and melting of the polyimide can be promoted, thereby improving processability. The present inventors decided to incorporate a phosphorus-based flame retardant into a polyphenylene ether resin to improve the flame retardancy of the resin composition. However, they found that incorporating a phosphorus-based flame retardant tends to deteriorate tracking resistance. This is presumably because phosphorus-based flame retardants generally promote char formation and inhibit combustion during combustion of a molded body, leading to the formation of a highly conductive carbonized layer, which tends to deteriorate 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 tracking resistance, while ionic phosphorus-based flame retardants are more likely to deteriorate tracking resistance. The reason for this is presumed to be that ionic substances such as phosphates further deteriorate tracking resistance by diffusing within the resin composition when the resin composition absorbs moisture or comes into contact with an electrolyte during a tracking resistance test. Under these circumstances, it has been discovered that the above problems can be solved by using a non-ionic phosphorus-based flame retardant as the phosphorus-based flame retardant and reducing the content of, or not using, the ionic phosphorus-based flame retardant.

[0013] Hereinafter, the embodiments of the present invention will be described in detail. However, the explanation of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to these contents.

[0014] <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. [ka] (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.

[0015] In formula (1), R 51 ~R 55 , and ,R 61 ~R 65 The alkyl group having 1 to 4 carbon atoms in 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.

[0016] 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. R 52 , R 54 , R 62 , and ,R 64is 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. R 65 is preferably a hydrogen atom.

[0017] 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.

[0018] 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, and poly(2,6-dimethyl-1,4-phenylene ether) represented by formula (1-1) is particularly preferred. Also suitable for use are polyphenylene ether resins having a specified number of terminal groups and copper content, as described in JP-A-2005-344065. [ka] (wherein n is the same as above).

[0019] 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 (a) polyphenylene ether resins with different intrinsic viscosities may be used in combination to achieve this intrinsic viscosity range.

[0020] The method for producing the polyphenylene ether resin used in the present embodiment is not particularly limited, and may be a 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 intrinsic viscosity can be controlled by selecting conditions such as the polymerization temperature, polymerization time, and catalyst amount.

[0021] In the resin composition of the present embodiment, a part of the polyphenylene ether resin is preferably an acid-modified product of the resin represented by formula (1). By adopting such a configuration, the compatibility between the polyphenylene ether resin and the polyamide resin can be improved. The acid-modified resin represented by formula (1) may be a resin 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, an unsaturated carboxylic acid and its derivative 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, angelic acid, etc. 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 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 resin represented by formula (1)) from the viewpoints of exhibiting high flame retardancy and availability.

[0022] 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). Formula (1-2) [ka] (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).

[0023] Formula (1-3) [ka] (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).

[0024] When the polyphenylene ether resin is taken as 100% by mass, the maleation rate 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 maleation rate is measured according to the method described in the Examples below.

[0025] The content of the acid-modified resin represented by formula (1) in the resin composition of this embodiment 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, even more preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on 100% by mass of the polyphenylene ether resin. By ensuring that the content is equal to or greater than the lower limit, the compatibility between the polyphenylene ether resin and the polyamide resin tends to be further improved. Furthermore, by ensuring that the content is equal to or less than the upper limit, the flame retardancy tends to be improved. The resin composition of the present embodiment may contain only one kind of acid-modified resin represented by formula (1), or may contain two or more kinds. When two or more kinds are contained, the total amount is preferably in the above range.

[0026] 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.

[0027] The content of the polyphenylene ether resin in the resin composition of the present embodiment is preferably 40% by mass or more, more preferably 45% by mass or more, and is 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 the present 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.

[0028] <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 units represented by formula (2) and the repeating structural units represented by formula (3). [ka] (In formulas (2) and (3), R1 is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. R2 is a divalent chain aliphatic group having 5 to 16 carbon atoms. X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.)

[0029] 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 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.

[0030] The repeating unit of formula (2) is described in detail below. R1 is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. Here, the alicyclic hydrocarbon structure means 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 the alicyclic hydrocarbon structure include, but are not limited to, cycloalkane rings such as cyclohexane rings, cycloalkene rings such as cyclohexene rings, bicycloalkane rings such as norbornane rings, and bicycloalkene rings such as norbornene rings. Among these, preferred are cycloalkane rings, more preferred are cycloalkane rings having 4 to 7 carbon atoms, and even more preferred are cyclohexane rings. R1 has 6 to 22 carbon atoms, and preferably 8 to 17 carbon atoms. R1 contains at least one alicyclic hydrocarbon structure, and preferably contains 1 to 3 alicyclic hydrocarbon structures.

[0031] R1 is preferably a divalent group represented by formula (R1-1) or formula (R1-2). [ka] (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.

[0032] R1 is particularly preferably a divalent group represented by formula (R1-3). [ka] 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.

[0033] In formula (2), X1 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, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. The number of carbon atoms in X1 is 6 to 22, preferably 6 to 18. X1 contains at least one aromatic ring, preferably 1 to 3 aromatic rings.

[0034] X1 is preferably a tetravalent group represented by any one of the following formulae (X-1) to (X-4). [ka] (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.

[0035] In the formulae (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. Since X1 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, R 12 , R 13 , p12 and p13 are selected so that the tetravalent group represented by formula (X-2) has 10 to 22 carbon atoms. Similarly, L in formula (X-3) 11 , R 14 , R 15 p14 and p15 are selected so that the number of carbon atoms in 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.

[0036] X1 is particularly preferably a tetravalent group represented by formula (X-5) or (X-6). [ka]

[0037] Next, the repeating unit of formula (3) will be described in detail below. R2 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. R2 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 of 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. R2 is preferably at least one selected from the group consisting of an octamethylene group and a decamethylene group, and particularly preferably an octamethylene group.

[0038] Another preferred embodiment of R2 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. [ka] (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.)

[0039] 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.

[0040] Since R2 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), 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). That is, m21+m22 is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10). Similarly, m23 to m25 in formula (R2-2) are selected so that the carbon number of the divalent group represented by formula (R2-2) is in 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).

[0041] X2 is defined in the same manner as X1 in formula (2), and the preferred embodiments are also the same.

[0042] The content ratio of the repeating structural unit of formula (2) to the total of the repeating structural unit of formula (2) and the repeating structural unit of formula (3) is 20 to 70 mol %. When the content ratio of the repeating structural unit of formula (2) is within this 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 is improved, which tends to improve heat resistance. 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, from the viewpoint of exhibiting high crystallinity. In particular, the content ratio of the repeating structural unit of formula (2) to the total of the repeating structural units of formula (2) and formula (3) is preferably 20 mol % or more and less than 40 mol %. Within this range, the crystallinity of the polyimide resin is increased, and a resin composition with even 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.

[0043] The total content ratio of the repeating structural units of formula (2) and the repeating structural units 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 %.

[0044] 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, the content ratio is preferably 20 mol% or less, more preferably 15 mol% or less. Formula (4) [ka] (In formula (4), R3 is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. X3 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.)

[0045] R3 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, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring. Of these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. R3 has 6 to 22 carbon atoms, and preferably 6 to 18 carbon atoms. R3 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(CF3)2-, -(CF2) p In addition to halogenated alkylene groups such as - (where p is an integer of 1 to 10), examples include -CO-, -SO2-, -SO-, -CONH-, -COO-, and the like.

[0046] R3 is preferably a divalent group represented by formula (R4-1) or formula (R4-2). [ka] (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.

[0047] In formula (R4-1) and formula (R4-2), m31 and m32 are each preferably 0 or 1 independently. m33 and m34 each independently represent preferably 0 or 1. Since R3 is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, m31, m32, and R 21 and p21 is selected so that the divalent group represented by formula (R4-1) has 6 to 22 carbon atoms. 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.

[0048] X3 is defined in the same manner as X1 in formula (2), and the preferred embodiments are also the same.

[0049] The polyimide resin may further contain a repeating structural unit represented by the following formula (5). Formula (5) [ka] (In formula (5), R4 is a divalent group containing -SO2- or Si(Rx)(Ry)O-, and Rx and Ry each independently represent a chain aliphatic group having 1 to 3 carbon atoms or a phenyl group. X4 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) X4 is defined in the same manner as X1 in formula (2), and the preferred embodiments are also the same.

[0050] There are no particular restrictions on the terminal structure of the polyimide resin, but 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 specific group at its terminal, a resin composition having 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 the unsaturated chain aliphatic group having 5 to 14 carbon atoms include a 1-pentenyl group, a 2-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 1-heptenyl group, a 2-heptenyl group, a 1-octenyl group, a 2-octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tridecenyl group, and a tetradecenyl group. Among these, the chain aliphatic group is preferably a saturated chain aliphatic group, and more preferably a saturated linear aliphatic group. From the viewpoint of obtaining heat aging resistance, the chain aliphatic group preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms, and even more preferably 9 or less carbon atoms. The chain aliphatic group may be of only one type, or of 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.

[0051] 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 all repeating 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 all repeating units constituting the polyimide resin. The content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin can be determined by depolymerizing the polyimide resin.

[0052] 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, the melting point 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, the glass transition temperature 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 of crystallization of the polyimide resin can be specifically measured by the method described in the Examples.

[0053] The logarithmic viscosity of a 0.5% by mass solution of a 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 can be calculated from the following formula by measuring the flow times of concentrated sulfuric acid and the polyimide resin solution at 30°C using a Cannon-Fenske viscometer: μ=ln(ts / t0) / C t0: Time when concentrated sulfuric acid flows ts: Flow time of polyimide resin solution C: 0.5 (g / dL)

[0054] 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.

[0055] (Method of manufacturing polyimide resin) The 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.

[0056] 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.

[0057] Examples of the derivative of tetracarboxylic acid containing at least one aromatic ring include anhydrides or alkyl esters of tetracarboxylic acid containing at least one aromatic ring. The tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms. Examples of the anhydride of tetracarboxylic acid include pyromellitic acid monoanhydride, pyromellitic acid dianhydride, 2,3,5,6-toluenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and 1,4,5,8-naphthalenetetracarboxylic acid dianhydride. Examples of alkyl esters of tetracarboxylic acids include dimethyl pyromellitate, diethyl pyromellitate, dipropyl pyromellitate, diisopropyl pyromellitate, 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 the above tetracarboxylic acids, the alkyl group preferably has 1 to 3 carbon atoms.

[0058] As the tetracarboxylic acid containing at least one aromatic ring and / or a derivative thereof, at least one compound selected from the above may be used alone, or two or more compounds may be used in combination.

[0059] 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. Among these, 1,3-bis(aminomethyl)cyclohexane is preferably used. Diamines containing an alicyclic hydrocarbon structure generally have structural isomers, but the ratio of cis / trans isomers is not limited.

[0060] 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. When 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. 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.

[0061] When 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 %. The 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, the ratio 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.

[0062] 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.

[0063] 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, while 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, while from the viewpoint of maintaining crystallinity, the molar ratio is preferably 20 mol% or less, more preferably 15 mol% or less. Moreover, 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 %.

[0064] 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.

[0065] When producing the polyimide resin, a terminal blocking agent may be mixed in addition to the tetracarboxylic acid component and the diamine component. The terminal blocking agent is preferably at least one selected from the group consisting of monoamines and dicarboxylic acids. The amount of terminal blocking agent used may be any amount sufficient to introduce a desired number 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 end-capping agents are preferred as end-capping agents, and from the viewpoint of improving heat aging resistance by introducing the aforementioned chain aliphatic group having 5 to 14 carbon atoms into the end of the polyimide resin, monoamines having a chain 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, further 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.

[0066] 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.

[0067] 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.

[0068] The content of the polyimide resin in the 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, per 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. By setting the content at or below the upper limit, flame retardancy tends to be improved. The resin composition of the present 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 in the above range.

[0069] <Polyamide resin> The resin composition of the present embodiment contains a polyamide resin, which can improve processability in a temperature range equal to or higher than the melting point of polyamide. The polyamide resin may be an aliphatic polyamide resin or a semi-aromatic polyamide resin, but is preferably an aliphatic polyamide resin. 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), and preferably contain at least one of polyamide 6, polyamide 66, and polyamide 666, more preferably polyamide 6. By containing polyamide 6, the tracking resistance of the resulting molded article tends to be further improved. Examples of semi-aromatic polyamide resins include polyamide 4T, polyamide 6T, polyamide 6I, polyamide 6T / 6I, polyamide 9T, polyamide 10T, polyamide 9N (a polyamide composed of 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, a polycondensate of metaxylylenediamine and adipic acid, MXD6I, a polycondensate of metaxylylenediamine, adipic acid, and isophthalic acid, MP6, a polycondensate of metaxylylenediamine, paraxylylenediamine, and adipic acid, MXD10, a polycondensate of metaxylylenediamine and sebacic acid, MP10, a polycondensate of metaxylylenediamine, paraxylylenediamine, and sebacic acid, and PXD10, a polycondensate of paraxylylenediamine and sebacic acid.

[0070] 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.

[0071] The content of the polyamide resin in the 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, 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. By setting the content at or below the upper limit, flame retardancy tends to be further improved. The resin composition of the present 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 in the above range.

[0072] In the 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 mass% or more, more preferably 78 mass% or more, and even more preferably 80 mass% or more, of 100 mass% of the resin composition, and preferably accounts for 95 mass% or less, and even more preferably 93 mass% or less.

[0073] The resin composition of this embodiment preferably contains substantially no 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 no" 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. The resin composition of the present embodiment does not contain a polycarbonate resin, for example.

[0074] <Non-ionic phosphorus flame retardant> The resin composition of the present embodiment contains a nonionic phosphorus-based flame retardant. By including the nonionic phosphorus-based flame retardant, the flame retardancy can be improved without deteriorating the tracking resistance of the resulting molded article.

[0075] 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.

[0076] 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.

[0077] Examples of nitrogen-containing phosphorus-based flame retardants include phosphazene and phosphoric acid ester amide, with phosphazene being preferred.

[0078] Phosphazenes are organic compounds having a -P=N- bond in the molecule, and preferably include at least one compound selected from the group consisting of cyclic phosphazenes represented by formula (F1), chain phosphazenes represented by formula (F2), and bridged phosphazenes formed by crosslinking at least one phosphazene selected from the group consisting of formulas (F1) and (F2) with a crosslinking group, with cyclic phosphazenes represented by formula (F1) being preferred.

[0079] Formula (F1) [ka] (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.

[0080] Formula (F2) [ka] (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. R f9 is -N=P(ORf7 ) 3 groups, -N=P(OR f8 ) 3 groups, -N=P(O)OR f7 Group, -N=P(O)OR f8 represents at least one selected from the group R f10 is -P(OR f7 ) 4 groups, -P(OR f8 ) 4 groups, -P(O)(OR f7 ) 2 groups, -P(O)(OR f8 ) represents at least one selected from the following two groups.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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, 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.

[0089] The cyclic phosphazene represented by formula (F1) includes R f5 and R f6 is 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 and 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] In addition, the crosslinked phosphazene is 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 A bridged phenoxyphosphazene obtained by crosslinking a chain phenoxyphosphazene in which R is a phenyl group with the above crosslinking group is preferred from the viewpoint of flame retardancy, and a bridged phenoxyphosphazene obtained by crosslinking a cyclic phenoxyphosphazene with the above crosslinking group is more preferred. The content of phenylene groups in the crosslinked 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 preferable that the crosslinked phenoxyphosphazene is a compound having no free hydroxyl groups in its molecule.

[0094] In this embodiment, the phosphazene is preferably at least one selected from the group consisting of cyclic phenoxyphosphazenes represented by formula (F1) and crosslinked phenoxyphosphazenes obtained by crosslinking the cyclic phenoxyphosphazenes represented by formula (F1) with crosslinking groups, 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.

[0095] The phosphate ester is preferably a compound represented by the following formula (F3). Formula (F3) [ka]

[0096] In formula (3P), R 1 , R 2 , R 3 , R 4 are each independently 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.

[0097] R 1 , R 2 , R 3 , R 4Examples 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, a biphenyl 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: [ka] [ka]

[0098] 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 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, condensed phosphate esters are preferred.

[0099] Specific examples of the condensed phosphate ester represented by the above formula (F3) include various ones such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris(chloroethyl)phosphate, tris(dichloropropyl)phosphate, tris(chloropropyl)phosphate, bis(2,3-dibromopropyl)phosphate, bis(2,3-dibromopropyl)-2,3-dichlorophosphate, bis(chloropropyl)monoctyl phosphate, bisphenol A tetraphenyl phosphate, bisphenol A tetracresyl diphosphate, bisphenol A tetraxylyl diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetracresyl phosphate, and hydroquinone tetraxylyl diphosphate. Commercially available condensed phosphate esters are readily available, such as those sold by Daihachi Chemical Industry Co., Ltd. under the trade names "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), and by Asahi Denka Kogyo Co., Ltd. under the trade names "ADK STAB FP-700" (phenol condensate of 2,2-bis(p-hydroxyphenyl)propane-trichlorophosphine oxide polycondensate (degree of polymerization 1-3)).

[0100] 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 decreases by 5% when the temperature is increased from room temperature at a rate of 1°C / minute.

[0101] The content of the nonionic phosphorus-based flame retardant in the 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, based on 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 resin composition of the present 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 in the above range.

[0102] In particular, the content of the nonionic phosphorus-based flame retardant, which is the nitrogen-containing phosphorus-based flame retardant, in the 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 ensuring that the content is equal to or greater than the lower limit, the flame retardancy of the resulting molded article tends to be further improved. By ensuring that the content is equal to or less than the upper limit, the tracking resistance of the resulting molded article tends to be further improved.

[0103] The 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 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, more specifically phosphinates and diphosphinates. For details, see paragraphs 0036 to 0043 of Japanese Patent Laid-Open No. 2023-007062, the contents of which are incorporated herein by reference.

[0104] The resin composition of the present embodiment may contain a nitrogen-based flame retardant as a flame retardant other than the phosphorus-based flame retardant. Examples of the nitrogen-based flame retardant include melamine isocyanurate, triazine compounds, aminotriazine compounds, melamine condensates such as melamine, guanamine, melam, and melem, and guanidine compounds. Nitrogen-based flame retardants generate inert nitrogen gas when thermally decomposed, and when used together with nonionic phosphorus-based flame retardants, flame retardancy and tracking resistance tend to be improved. When the resin composition of the present embodiment contains a nitrogen-based flame retardant, the content thereof is preferably 0.1 to 10 parts by mass relative to 100 parts by mass in 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.

[0105] The 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 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.

[0106] <Lubricant> The resin composition of this embodiment may contain a lubricant. Addition 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 makes it less likely for the resin to accumulate or adhere to the die outlet during extrusion (suppressing scum), thereby making it less likely for components deteriorated by heat or oxidation to be mixed in. Examples of lubricants include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ketone waxes, and light amides. Of these, aliphatic carboxylic acids, salts of aliphatic carboxylic acids, and esters of aliphatic carboxylic acids and alcohols are preferred, salts of aliphatic carboxylic acids are more preferred, metal stearates are even more preferred, calcium stearate and zinc stearate are even more preferred, and zinc stearate is even more preferred. For details about the lubricant, please refer to paragraphs 0055 to 0061 of JP 2018-095706 A, the contents of which are incorporated herein by reference.

[0107] When the 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, and is 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 sludge formation and tracking resistance tend to be further improved. Furthermore, by setting the content at or below the upper limit, bleeding of the lubricant can be effectively suppressed, and poor appearance and the lubricant itself can be effectively suppressed from causing sludge formation. 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 the present 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 in the above range.

[0108] <Ceramic particles> It is preferred that the material contains ceramic particles. The inclusion of ceramic particles can improve the tracking resistance of molded articles obtained from the resin composition. 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, when the resin composition of this embodiment is extruded into a flat plate-shaped molded product (particularly, a film), the generation of holes and the like can be effectively suppressed. This is presumably because the incorporation of ceramic particles allows the polyimide resin to be more effectively dispersed in the molded product. In particular, it is presumed that the resin composition of this embodiment, by containing ceramic particles, can satisfactorily disperse 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, even without containing a compatibilizer, and thus a good flat plate-shaped molded product (particularly, a film) can be molded.

[0109] 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 at or above the lower limit, tracking resistance tends to be further improved. Furthermore, by setting the diameter at or below 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 the laser diffraction / scattering method. When the resin composition of the present embodiment contains two or more types of ceramic particles, the median diameter of the ceramic particles is the median diameter of the mixture.

[0110] The type of ceramic particles is not particularly limited, but is preferably at least one selected from alumina particles, titanium oxide, 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.

[0111] 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% by mass of the ceramic particles.

[0112] The content of ceramic particles in the 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 prevented from decreasing. The resin composition of the present embodiment may contain only one type of ceramic particles or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0113] <Stabilizer> The resin composition of the present embodiment may contain a stabilizer. The stabilizer includes a heat stabilizer and an antioxidant. Examples of the stabilizer include a phenol-based stabilizer, an amine-based stabilizer, a phosphorus-based stabilizer, a thioether-based stabilizer, etc. Among these, in the present embodiment, it is preferable to include a phenol-based stabilizer, a phosphorus-based stabilizer, and a thioether-based stabilizer.

[0114] Any known phosphorus-based 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.

[0115] Examples of organic phosphite compounds include triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonylphenyl)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.

[0116] 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)tri-p-cresol -4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 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.

[0117] 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.

[0118] Examples of thioether stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, laurylstearyl thiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), and pentaerythritol tetrakis(3-laurylthiopropionate). 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 Kasei Co., Ltd.), Adeka Stab AO-412S (manufactured by ADEKA Corporation), Cyanox 1212 (manufactured by Cyanamid), and SUMILIZER TP-D (manufactured by Sumitomo Chemical Co., Ltd.) can be used (all trade names).

[0119] The content of the stabilizer in the resin composition of this 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, per 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. By setting the content of the stabilizer within this range, the effect of adding the stabilizer can be more effectively exerted. The resin composition of the present embodiment may contain only one stabilizer, or may contain two or more stabilizers. When two or more stabilizers are contained, the total amount is preferably in the above range.

[0120] <Other ingredients> The resin composition of the present embodiment may contain other components in addition to those described above, such as resin additives and fillers other than ceramic particles.

[0121] The resin additives may include dyes, pigments, weather resistance improvers, nucleating agents, impact resistance improvers, 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.

[0122] 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.

[0123] In the 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 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.

[0124] <Physical properties of resin composition> The resin composition of this embodiment preferably has excellent tracking resistance. Specifically, the resin composition is molded into a 100 mm × 150 mm × 3.2 mm test piece, 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 600 V or more, and even more preferably 650 V or more. The upper limit of the CTI value is preferably the measurement limit, for example, 1000 V. The CTI value is measured as described in the Examples below.

[0125] The resin composition of this embodiment preferably has excellent flame retardancy. Specifically, the resin composition is molded into a 0.4 μm thick plate-like molded article, and the result of the combustion 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-like molded article, and the result of the flammability test in accordance with UL-94 preferably satisfies V-1, and more preferably V-0. Furthermore, when the resin composition is molded into a flat plate-shaped molded article having a thickness of 0.4 μm, and when the resin composition is molded into a flat plate-shaped molded article having a thickness of 0.8 μm, it is preferable that the result of the combustion test of the flat plate-shaped molded article in accordance with UL-94 satisfies V-1, and it is more preferable that the result satisfies V-0. The flame retardancy is measured as described in the Examples below.

[0126] <Method of manufacturing 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 employed. Examples include premixing a polyphenylene ether resin, a polyimide resin, or a polyamide resin, a nonionic phosphorus-based flame retardant, and other optional components, using a mixer such as a tumbler or Henschel mixer, followed by melt-kneading using a mixer such as a Banbury mixer, a roll mixer, a Brabender mixer, a single-screw extruder, a twin-screw extruder, or a 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 the resin composition is pellets.

[0127] <Molded body> The molded article of this embodiment is formed from the resin composition or pellets of this embodiment. In this embodiment, a molded article may be produced by pelletizing the resin composition and molding the resulting pellets by various molding methods. Alternatively, a molded article may be produced by directly molding a resin composition that has been melt-kneaded in a kneader, without going through pelletization. The resin composition (e.g., pellets) described above can be molded into a molded article by 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, and examples thereof include flat, rod, cylindrical, ring, circular, elliptical, polygonal, irregular, hollow, frame, box, panel, and button shapes. An example of the molded article of this embodiment is a flat plate-like molded article (film, sheet). The thickness of the flat 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, still more preferably 75 μm or more, still more preferably 100 μm or more, and preferably 2000 μm or less, more preferably 1000 μm or less, still more preferably 750 μm or less, still more preferably 500 μm or less, still more preferably 250 μm or less. The temperature during film molding 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 temperature during film molding is preferably 240° C. or higher, and may be 250° C. or higher, 260° C. or higher, or 270° C. or higher.

[0128] 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.

[0129] <Application> The resin composition, pellets, and molded article of this embodiment can be widely used in applications where polyphenylene ether resins, particularly blends of polyphenylene ether resins and polyimide resins, are generally used. The resin composition, pellets, and molded article of the present embodiment can be used in 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. [Example]

[0130] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed 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.

[0131] <Raw materials> The raw materials shown in Table 1 below were used.

[0132] [Table 1]

[0133] <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 in 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.

[0134] <Synthesis Example 2: Production of Polyimide Resin 1> A 2L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and a four-paddle impeller was charged with 500g of 2-(2-methoxyethoxy)ethanol (Nippon Nyukazai Co., Ltd.) and 218.12g (1.00mol) of pyromellitic dianhydride (Mitsubishi Gas Chemical Co., Ltd.). After nitrogen flow, the mixture was stirred at 150 rpm to form a uniform suspension. A 500mL beaker was used to prepare a mixed diamine solution by dissolving 49.79g (0.35mol) of 1,3-bis(aminomethyl)cyclohexane (Mitsubishi Gas Chemical Co., Ltd., cis / trans ratio = 7 / 3) and 93.77g (0.65mol) of 1,8-octamethylenediamine (Kanto Chemical Co., Ltd.) in 250g of 2-(2-methoxyethoxy)ethanol. The mixed diamine solution was gradually added using a plunger pump. Although the dropwise addition generated heat, the internal temperature was adjusted to remain within the range of 40 to 80°C. During the dropwise addition of the mixed diamine solution, a 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 maintaining the temperature 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 simply referred to as "polyimide resin 1"). The IR spectrum of polyimide resin 1 was measured, and ν(C=O) 1768, 1697 (cm -1The characteristic absorption of the imide ring was observed in the α-methyl-2-propanol copolymer. 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 half-crystallization time was less than 20 seconds, and the Mw was 55,000. The IR spectrum, relative viscosity, Tm, Tg, Tc, heat of fusion, half-crystallization time, and weight-average molecular weight were measured according to the descriptions in paragraphs 0114 to 0117 of WO 2016 / 084475.

[0135] <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 half-crystallization time was 20 seconds or less.

[0136] Examples 1 to 9, Comparative Examples 1 and 2 <Method of manufacturing resin composition> The components shown in Table 1 were mixed in the proportions (parts by mass) shown in Table 2 or Table 3 below, and the mixture of components was melt-kneaded using a twin-screw extruder (Shibaura Machine Co., Ltd.: TEM26SX) at a cylinder temperature (extrusion temperature) of 280°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 2 or Table 3.

[0137] <Evaluation of tracking resistance> The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours and then fed into an injection molding machine (Shibaura Machine Co., Ltd., "EC75SX"), where a molded body measuring 100 mm x 100 mm x 3 mm in length x width x thickness was produced using the injection molding machine under conditions of a cylinder temperature of 280°C and a mold temperature of 130°C. Using the produced molded body, the maximum voltage at which tracking breakdown of the molded body did not occur, i.e., the CTI value (unit: V), was measured using a measurement method in accordance with IEC60112 (electrolyte used: Solution A, number of drops: 50).

[0138] <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 (Shibaura Machine Co., Ltd., "EC75SX"), where plate-shaped molded bodies with thicknesses 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 flat molded articles was evaluated in accordance with the UL-94 standard. UL-94 grades are classified as V-0, V-1, V-2, and non-compliant, in descending order of quality. Each set was graded based on a vertical flame test, and the results are shown in Tables 2 and 3.

[0139] [Table 2] [Table 3]

[0140] 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 1 to 9). In particular, when polyamide 6 was blended as the polyamide resin, the molded articles had excellent tracking resistance and flame retardancy (comparison of Examples 1 to 4, 6 to 9 with Example 5). On the other hand, when the ionic phosphorus-based flame retardant was contained in a large amount (Comparative Examples 1 and 2), the tracking resistance was poor.

[0141] 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. The flame retardant comprises a polyphenylene ether resin formed of a resin represented by formula (1) and / or an acid-modified product thereof, a polyimide resin, a polyamide resin, and a nonionic phosphorus-based flame retardant, the content of the ionic phosphorus-based flame retardant is 2.0 parts by mass or less 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; The polyimide resin contains a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), A resin composition in which the content ratio 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). 【Chemistry 1】 (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. 【Chemistry 2】 (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 , wherein the nonionic phosphorus-based flame retardant comprises a nitrogen-containing phosphorus-based flame retardant and / or a phosphate ester.

3. The resin composition according to claim 1 , wherein the nonionic phosphorus-based flame retardant comprises a phosphazene and / or a phosphoric acid ester.

4. The resin composition according to any one of claims 1 to 3, wherein a part of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1):

5. The resin composition according to any one of claims 1 to 3, wherein 1 to 20 mass% of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1).

6. The resin composition according to any one of claims 1 to 3, wherein the polyamide resin comprises an aliphatic polyamide resin.

7. The resin composition according to any one of claims 1 to 3, wherein the polyamide resin comprises at least one of polyamide 6, polyamide 66, and polyamide 666.

8. The resin composition according to any one of claims 1 to 3, wherein the polyamide resin comprises polyamide 6.

9. The resin composition according to any one of claims 1 to 3, 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.

10. The resin composition according to any one of claims 1 to 3, 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 composed of the resin represented by formula (1) and / or its acid-modified product, the polyimide resin, and the polyamide resin.

11. The resin composition according to any one of claims 1 to 3, further comprising a lubricant.

12. The resin composition according to any one of claims 1 to 3, further comprising ceramic particles.

13. The resin composition according to claim 12, wherein the ceramic particles comprise titanium oxide particles.

14. the nonionic phosphorus-based flame retardant comprises a phosphazene and / or a phosphate ester; 1 to 20 mass % of the polyphenylene ether resin is an acid-modified product of a resin represented by formula (1), the polyamide resin includes 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 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; 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 composed of the resin represented by formula (1) and / or the acid-modified product thereof, the polyimide resin, and the polyamide resin; Further comprising a lubricant, Further containing ceramic particles, The resin composition according to claim 1 , wherein the ceramic particles comprise titanium oxide particles.

15. Pellets of the resin composition according to claim 1, 2 or 14.

16. A molded article formed from the resin composition according to claim 1, 2 or 14.

17. A flat plate-like molded article formed from the resin composition according to claim 1 , 2 or 14 .

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