WO2025225252A1 - Resin composition, pellet, and molded body - Google Patents

Abstract

The present invention provides a resin composition having excellent film processability, a pellet, and a molded body (in particular, a film). The present invention includes: a polyphenylene ether resin composed of a resin represented by formula (1) and/or an acid-modified product thereof; a polyimide resin; and a polycarbonate resin. The polyimide resin includes a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3). The content ratio of the repeating structural unit represented by formula (2) to a total of 100 mol% of the repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3) is 20-70 mol% inclusive.

Description

Resin composition, pellets, and molded body

The present invention relates to a resin composition, pellets, and molded articles. In particular, it relates to a resin composition containing a polyphenylene ether resin as a primary component.

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.

Resin compositions containing such polyphenylene ether resins (polyphenylene ether resin compositions) have traditionally been widely used as materials for a variety of applications, including electrical components, electronic device components, and vehicle components. Polyphenylene ether resin compositions are required to have a variety of properties depending on their intended use. For example, when using a polyphenylene ether resin composition as a spacer or bus bar cover material between batteries in a battery unit including an assembled battery, the polyphenylene ether resin composition is required to have high tracking resistance in addition to the flame retardancy and thin-wall moldability required for battery spacers and bus bar covers.

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

International Publication No. 2009/040751

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. However, they have found that when a resin composition obtained by blending a polyphenylene ether resin with a polyimide resin is processed into a film, the film processability may be poor. In particular, they have found that a resin scum is generated.
The present invention aims to solve the above problems and to provide a resin composition, pellets, and molded articles (particularly films) that are excellent in film processability.

In view of the above-mentioned problems, the present inventors have conducted research and found that a resin composition having excellent film processability can be obtained by blending a polycarbonate resin with a resin composition containing a specified polyphenylene ether resin and a specified polyimide resin.
Specifically, the above problems were solved by the following means.
<1> A polyphenylene ether resin comprising a resin represented by formula (1) and/or an acid-modified product thereof, a polyimide resin, and a polycarbonate 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).
(In formula (1), R ₅₁ to R ₅₅ and R ₆₁ to R ₆₄ each independently represent a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ₆₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n represents the number of repeating structural units and is a number of 10 or more.)
(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>, further comprising a lubricant.
<3> The resin composition according to <1> or <2>, further comprising a lubricant in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the total of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin.
<4> The mass ratio of the polyphenylene ether resin to the total 100 parts by mass of the polyphenylene ether resin and the polyimide resin is 50 to 99 parts by mass,
<1><3> The resin composition according to any one of <1> to <3>.
<5> The resin composition according to any one of <1> to <4>, further comprising 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles per 100 parts by mass of the total of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin.
<6> The resin composition according to <5>, wherein the flame retardant includes a phosphorus-based flame retardant.
<7> The resin composition according to <5>, wherein the ceramic particles include titanium oxide particles.
<8> Further, the lubricant is contained in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the total of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin,
the mass ratio of the polyphenylene ether resin to a total of 100 parts by mass of the polyphenylene ether resin and the polyimide resin is 50 to 99 parts by mass;
Further, the composition contains 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles relative to 100 parts by mass of the total of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin,
the flame retardant comprises a phosphorus-based flame retardant;
<7> The resin composition according to any one of <1> to <7>, wherein the ceramic particles include titanium oxide particles.
<9> Pellets of the resin composition according to any one of <1> to <8>.
<10> A molded article formed from the resin composition according to any one of <1> to <8>.
<11> A flat plate-like molded product formed from the resin composition according to any one of <1> to <8>.

The present invention makes it possible to provide resin compositions, pellets, and molded articles (especially films) that have excellent film processability.

1 is a photograph showing the state of the film of Example 1 during extrusion. 1 is a photograph showing the state of the film of Comparative Example 1 during extrusion.

Hereinafter, an embodiment of 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, various physical properties and characteristic values are those at 23° C. unless otherwise specified.

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 vary 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.

The resin composition of the present embodiment comprises a polyphenylene ether resin composed of a resin represented by formula (1) and/or an acid-modified product thereof, a polyimide resin, and a polycarbonate resin, wherein the polyimide resin comprises a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and the content ratio of the repeating structural unit represented by formula (2) is 20 to 70 mol % relative to 100 mol % in total of the repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3).
(In formula (1), R ₅₁ to R ₅₅ and R ₆₁ to R ₆₄ each independently represent a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ₆₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n represents the number of repeating structural units and is a number of 10 or more.)
(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.)

By adopting such a configuration, a resin composition having excellent film processability can be obtained. That is, by blending a predetermined polyimide resin with a predetermined polyphenylene ether resin, the tracking resistance of the resin composition can be improved. However, when a resin composition obtained by blending a predetermined polyimide resin with a predetermined polyphenylene ether resin is extruded into a flat plate-shaped molded product (film), there is a possibility that a scum may be generated.
In this embodiment, in order to solve this problem, a polycarbonate resin is blended in. It is presumed that blending the polycarbonate resin can lower the extrusion temperature of the resin composition and suppress the generation of resin scum.
The resin buildup is caused by volatile matter, moisture, and degradation products in the molten resin, or by poor dispersion of fillers and additives. The higher the melt-kneading temperature (extrusion temperature), the more likely it is that thermal degradation products will form. Polyphenylene ether, in particular, tends to produce resin buildup consisting of thermal degradation products.
In this embodiment, since a polyimide resin is used, the melt-kneading temperature (extrusion temperature) tends to be high. Therefore, it is presumed that when the polyimide resin is heated to a temperature at which it melts, it becomes easy for the resin to produce a sticky substance derived from thermal degradation. In this embodiment, it is presumed that by blending a polycarbonate resin, which is easily mixed with the polyimide resin and has no melting point, the polyimide resin becomes compatible with the polycarbonate resin, making it possible to process the polyimide resin at a temperature lower than its melting point.

The following describes in detail an embodiment of the present invention. However, the following description of the components is an example of an embodiment of the present invention, and the present invention is not limited to these contents.

<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) composed of a resin represented by formula (1) and/or an acid-modified product thereof, and the polyphenylene ether resin is preferably a resin represented by formula (1).
(In formula (1), R ₅₁ to R ₅₅ and R ₆₁ to R ₆₄ each independently represent a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ₆₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n represents the number of repeating structural units and is a number of 10 or more.)

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

In formula (1), R ₅₁ , R ₅₃ , R ₆₁ and R ₆₃ are 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 ₆₄ are 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.

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.

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.
(wherein n is the same as defined above.)

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 achieving high flame retardancy and improving moldability. Furthermore, two or more types of (a) polyphenylene ether resins with different intrinsic viscosities may be used in combination to achieve an intrinsic viscosity within this range.

The method for producing the polyphenylene ether resin used in this embodiment is not particularly limited, and can be any known method, such as oxidative polymerization of a monomer such as 2,6-dimethylphenol in the presence of an amine copper catalyst. By selecting the reaction conditions, the intrinsic viscosity can be controlled within the desired range. Control of the intrinsic viscosity can be achieved by selecting conditions such as polymerization temperature, polymerization time, and catalyst amount.

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 or a derivative thereof is 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 product of the resin represented by formula (1) is preferably a resin obtained by modifying the resin represented by formula (1) with maleic acid or a maleic acid derivative (maleic acid-modified product of the resin represented by formula (1)) from the viewpoints of exhibiting high flame retardancy and availability.

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)
(In formula (1-2), R ₅₁ to R ₅₅ , R ₆₁ , R ₆₃ , R ₆₄ , R ₆₅ and n each independently have the same meaning as in formula (1).)

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

The polyphenylene ether resin used in this embodiment may be recycled products (including recovered products, material recycled products, chemical recycled products, etc.), rejected products, or offcuts from polyphenylene ether resin molding.

<Polycarbonate resin>
The resin composition of the present embodiment contains a polycarbonate resin, which is compatible with the polyimide resin and can lower the melting temperature of the resin composition.
The polycarbonate resin is not particularly limited as long as it contains an —[O—R—OC(═O)]— unit containing a carbonate bond in the molecular main chain (wherein R is an organic group, preferably a hydrocarbon group, more preferably an aliphatic group, an aromatic group, or one containing both an aliphatic group and an aromatic group, and further one having a linear or branched structure). In this embodiment, the polycarbonate resin is preferably an aromatic polycarbonate resin, and more preferably a polycarbonate resin having a bisphenol skeleton. By using such a polycarbonate resin, the obtained molded article can achieve better heat resistance and toughness. In this embodiment, the polycarbonate resin having a bisphenol skeleton preferably contains 90 mol % or more of all structural units of structural units having a bisphenol skeleton, more preferably 90 mol % or more of all structural units of structural units having at least one skeleton of bisphenol A, bisphenol C, and bisphenol AP, and even more preferably 90 mol % or more of all structural units of structural units having a bisphenol A skeleton.

The viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 10,000 or more, more preferably 12,000 or more, and even more preferably 15,000 or more. The upper limit of the viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, still more preferably 25,000 or less, and even more preferably 20,000 or less. By keeping the viscosity average molecular weight below the upper limit, the molding processability of the molded article tends to be further improved.
The viscosity average molecular weight (Mv) means a value calculated from the intrinsic viscosity [η] (unit: dL/g) at 25°C using methylene chloride as a solvent and an Ubbelohde viscometer, using Schnell's viscosity formula, i.e., η = 1.23 × 10 ^-4 × Mv ^0.83 .
When two or more types of polycarbonate resins are used, the viscosity average molecular weight is the viscosity average molecular weight of the mixture.

The method for producing polycarbonate resin is not particularly limited, and polycarbonate resins produced by the conventionally known phosgene method (interfacial polymerization method) or melt method (ester interchange method) can be used. Furthermore, when using the melt method, polycarbonate resins with an adjusted amount of OH groups at the terminal groups can be used.

The polycarbonate resin used in this embodiment may contain recycled products.
Recycled products are polycarbonate resins derived from molded products formed from polycarbonate resin, meaning virgin polycarbonate resins that have been subjected to some kind of molding process, and include polycarbonate resin molded products, rejected polycarbonate resin molded products, scraps from the manufacture of polycarbonate resin molded products, etc. Molded products include injection molded products, extrusion molded products, and molded products formed by other manufacturing methods.
Examples of recycled polycarbonate resin include those obtained by material recycling in which recovered used polycarbonate resin molded articles are crushed and alkaline washed to be reused as fibers, etc., those obtained by chemical recycling (chemical decomposition method), and those obtained by mechanical recycling.
Chemical recycling involves chemically decomposing recovered used polycarbonate resin molded articles, returning them to their raw material level, and resynthesizing the polycarbonate resin.Mechanical recycling, on the other hand, is a method that makes it possible to remove dirt from polycarbonate resin molded articles more reliably than material recycling by carrying out alkaline washing more rigorously than in the material recycling described above, or by vacuum drying at high temperatures.
For example, after foreign matter is removed from used polycarbonate resin molded articles, they are crushed and washed, and then pelletized by an extruder to obtain recycled polycarbonate resin.
Examples of used polycarbonate resin molded articles include disks, sheets (including films), meter covers, headlamp lenses, water bottles, and face plates for gaming and pachinko machines.
Virgin products refer to products other than recycled products.

In addition to the above, for details on polycarbonate resins, please refer to the descriptions in paragraphs [0013] to [0041] of JP 2021-084942 A, the descriptions in paragraphs [0030] to [0035] of JP 2021-119211 A, and the descriptions in paragraphs [0008] to [0064] of JP 2023-012167 A, the contents of which are incorporated herein by reference.

The content of the polycarbonate resin in the resin composition of this embodiment is preferably 1% by mass or more of the resin composition, more preferably 3% by mass or more, even more preferably 5% by mass or more, and even more preferably 8% by mass or more, and is preferably 15% by mass or less, and more preferably 10% by mass or less.
The resin composition of the present embodiment may contain only one type of polycarbonate resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

<Polyimide resin>
The resin composition of the present embodiment includes a polyimide resin (sometimes simply referred to as a "polyimide resin" in this specification) that contains a repeating structural unit represented by formula (2) and a repeating structural unit represented by formula (3), and in which the content of the repeating structural unit represented by formula (2) is 20 to 70 mol % relative to 100 mol % in total of the repeating structural unit represented by formula (2) and the repeating structural unit represented by formula (3).
(In formulas (2) and (3), _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.)

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

The repeating unit of formula (2) will be described in detail below.
_R1 is a divalent group containing at least one alicyclic hydrocarbon structure and having 6 to 22 carbon atoms.
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, cycloalkane rings are preferred, cycloalkane rings having 4 to 7 carbon atoms are more preferred, and cyclohexane rings are even more preferred.
_R1 has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms.
_R1 contains at least one alicyclic hydrocarbon structure, preferably 1 to 3.

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

_R1 is particularly preferably a divalent group represented by formula (R1-3).
In the divalent group represented by the above formula (R1-3), the positional relationship of the two methylene groups with respect to the cyclohexane ring may be either cis or trans, and the ratio of cis to trans may be any value.

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.

_X1 is preferably a tetravalent group represented by any one of the following formulae (X-1) to (X-4).
(In formulas (X-1) to (X-4), R ₁₁ to R ₁₈ each independently represent an alkyl group having 1 to 4 carbon atoms. _{p 11} to p ₁₃ each independently represent an integer of 0 to 2. p14, p15, p16 and p18 each independently represent an integer of 0 to 3. p17 is an integer of 0 to 4. L ₁₁ to L ₁₃ each independently represent a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.)

In 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 containing at least one aromatic ring and having 6 to 22 carbon atoms, _R12 , _R13 , p12, and p13 in formula (X-2) are selected so that the number of carbon atoms of the tetravalent group represented by formula (X-2) falls within the range of 10 to 22.
Similarly, L ₁₁ , R ₁₄ , R ₁₅ , p14 and p15 in formula (X-3) are selected so that the number of carbon atoms in the tetravalent group represented by formula (X-3) falls within the range of 12 to 22, and L ₁₂ , L ₁₃ , R ₁₆ , R 17 , R ₁₈ , p ₁₆ , p ₁₇ and p ₁₈ in formula (X-4) are 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.

_X1 is particularly preferably a tetravalent group represented by formula (X-5) or (X-6).

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 particularly 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.

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.
(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.)

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

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 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, 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).

_X2 is defined in the same manner as _X1 in formula (2), and the preferred embodiments are also the same.

The content ratio of the repeating structural unit of formula (2) relative 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, it becomes possible to sufficiently crystallize the polyimide resin even in a typical injection molding cycle. By setting this 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.
From the viewpoint of achieving high crystallinity, the content ratio of the repeating structural unit of formula (2) relative to the total of the repeating structural unit of formula (2) and the repeating structural unit of formula (3) is preferably 65 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less.
In particular, the content ratio of the repeating structural unit of formula (2) 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 expressing high crystallinity, it is even more preferably 35 mol% or less.

The combined content of the repeating structural units of formula (2) and 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 even more preferably 85 to 100 mol%.

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, the lower limit is not particularly limited, 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)
(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.)

_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. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.
_R3 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
_R3 contains at least one aromatic ring, preferably 1 to 3.
Furthermore, a monovalent or divalent electron-withdrawing group may be bonded to the aromatic ring. 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 halogenated alkylene group such as a fluorinated alkylene group (e.g., -C( _CF3 ) _2- , -( _CF2 ) _p- (where p is an integer of 1 to 10)), as well as -CO-, _-SO2- , -SO-, -CONH-, and -COO-.

_R3 is preferably a divalent group represented by formula (R4-1) or formula (R4-2).
(In formula (R4-1) and formula (R4-2), m31 and m32 each independently represent an integer of 0 to 2. m33 and m34 each independently represent an integer of 0 to 2. R ₂₁ , R ₂₂ , and R ₂₃ each independently represent 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 each independently represent an integer of 0 to 4. L ₂₁ represents a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.)

In formula (R4-1) and formula (R4-2), m31 and m32 each independently represent preferably 0 or 1.
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, _R21 , and p21 in formula (R4-1) are selected so that the divalent group represented by formula (R4-1) has 6 to 22 carbon atoms.
Similarly, L ₂₁ , m33, m34, R ₂₂ , R ₂₃ , p22, and p23 in formula (R3-2) are selected so that the divalent group represented by formula (R3-2) has 12 to 22 carbon atoms.

_X3 is defined in the same manner as _X1 in formula (2), and the preferred embodiments are also the same.

The polyimide resin may further contain a repeating structural unit represented by the following formula (5).
Formula (5)
(In formula (5), _R4 is a divalent group containing —SO ₂ — 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 containing at least one aromatic ring and having 6 to 22 carbon atoms.)
_X4 is defined in the same manner as _X1 in formula (2), and the preferred embodiments are also the same.

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, 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, 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.

From the viewpoint of exhibiting excellent heat aging resistance, the content of the chain aliphatic group 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, relative to 100 mol % of the total of all repeating structural units constituting the polyimide resin. Furthermore, in order to ensure a sufficient molecular weight and obtain good mechanical properties, the content of the chain aliphatic group 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, relative to 100 mol % of the total of all repeating structural 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.

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 more preferably 160° C. or higher, more preferably 170° 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 quantity of the exothermic crystallization peak (hereinafter simply referred to as "crystallization heat quantity") 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, as measured by a differential scanning calorimeter when the polyimide resin is melted and then cooled at a temperature decreasing rate of 20°C/min. The upper limit of the heat quantity 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.

The logarithmic viscosity of a 0.5% by mass solution of polyimide resin in concentrated sulfuric acid at 30°C is preferably in the range of 0.2 to 2.0 dL/g, more preferably 0.3 to 1.8 dL/g. If the logarithmic viscosity is 0.2 dL/g or higher, sufficient mechanical strength can be obtained when the resulting resin composition is molded into a molded article, while if it is 2.0 dL/g or lower, good moldability and handleability can be achieved. 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 during which concentrated sulfuric acid flows, ts: Time during which polyimide resin solution flows, C: 0.5 (g / dL)

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 still 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.

(Method for producing 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.

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 within the structure. Furthermore, the tetracarboxylic acid preferably has 6 to 26 carbon atoms. Preferred tetracarboxylic acids 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.

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

The tetracarboxylic acid and/or derivative thereof containing at least one aromatic ring may be at least one compound selected from the above, and may be a combination of two or more compounds.

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

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

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

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 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.

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.
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 %.

When producing polyimide resin, the ratio of the tetracarboxylic acid component to the diamine component is preferably 0.9 to 1.1 moles of diamine component per 1 mole of tetracarboxylic acid component.

Furthermore, when producing a polyimide resin, a terminal-capping agent may be mixed in addition to the tetracarboxylic acid component and the diamine component. The terminal-capping agent is preferably at least one selected from the group consisting of monoamines and dicarboxylic acids. The amount of terminal-capping agent used may be any amount that allows the desired number of terminal groups to be introduced 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, the terminal blocking agent is preferably a monoamine terminal blocking agent, and from the viewpoint of improving heat aging resistance by introducing the aforementioned chain aliphatic group having 5 to 14 carbon atoms into the terminal of the polyimide resin, a monoamine having a chain aliphatic group having 5 to 14 carbon atoms is more preferred, and a monoamine having a saturated linear aliphatic group having 5 to 14 carbon atoms is even more preferred.
The end-capping agent is particularly preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine, more preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably at least one selected from the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.

Known polymerization methods can be applied as the polymerization method for producing polyimide resins, and the method described in WO 2016/147996 may be taken into consideration, the contents of which are incorporated herein by reference.

The polyimide resin used in this embodiment may be recycled products (including recovered products, material recycled products, chemical recycled products, etc.), rejected products, or offcuts from polyimide resin molding.

<Blend of polyphenylene ether resin, polyimide resin, and polycarbonate resin>
Next, the blend ratio of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin in the resin composition of this embodiment will be described.
In the resin composition of this embodiment, the mass ratio of the polyphenylene ether resin relative to 100 parts by mass of the polyphenylene ether resin and the polyimide resin is preferably 50 to 99 parts by mass. Furthermore, relative to 100 parts by mass of the polyphenylene ether resin and the polyimide resin, the mass ratio of the polyphenylene ether resin is preferably 55 parts by mass or more, more preferably 60 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 85 parts by mass or more, and is preferably 95 parts by mass or less, and may be 90 parts by mass or less. By setting the mass ratio at or above the lower limit, flame retardancy tends to be further improved. Furthermore, by setting the mass ratio at or below the upper limit, tracking resistance tends to be further improved.
The resin composition of the present embodiment may contain only one polyphenylene ether resin and one polyimide resin, or may contain two or more of either one or both. When two or more types are contained, it is preferable that the total amount is in the above range.
In the resin composition of this embodiment, the polycarbonate resin is preferably contained in an amount of 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 7 parts by mass or more, per 100 parts by mass of the total of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin. The amount is preferably 20 parts by mass or less, and more preferably 15 parts by mass or less. By setting the amount to the above lower limit or more, the occurrence of sludge during film molding tends to be more effectively suppressed. By setting the amount to the above upper limit or less, the tracking resistance of the resulting molded article is significantly improved, and a resin composition with excellent flame retardancy is obtained.

In the resin composition of this embodiment, the total amount of polyphenylene ether resin, polyimide resin, and polycarbonate resin is preferably 70% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, and even more preferably 85% by mass or more, based on 100% by mass of the resin composition. It may be 90% by mass or more, and preferably 99% by mass or less, and may be 95% by mass or less, or may be 90% by mass or less.

<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 remain 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 of the lubricant, please refer to paragraphs 0055 to 0061 of JP 2018-095706 A, the contents of which are incorporated herein by reference.
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 total of the polyphenylene ether resin, polyimide resin, and polycarbonate resin. It is also preferably 3 parts by mass or less, more preferably 2.5 parts by mass or less, even more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less. By setting the content at or above the lower limit, the effect of suppressing the buildup and tracking resistance tend to be further improved. Furthermore, by setting the content at or below the upper limit, it is possible to effectively suppress the lubricant from bleeding out, and it is possible to effectively suppress the appearance defect and the lubricant itself from becoming a cause of buildup. Furthermore, by setting the content at or below the upper limit, it is possible to suppress the amount of gas generated during heat processing.
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.

<Ceramic particles>
It is preferable that the resin composition contains ceramic particles. By containing ceramic particles, the tracking resistance of a molded article obtained from the resin composition can be improved. Ceramic particles are usually insulating, and the dispersion of such insulating components tends to effectively suppress the formation of conductive circuits that cause tracking breakdown.
Furthermore, the formation of holes and the like can be effectively suppressed when the resin composition of this embodiment is extruded into a flat-plate-shaped molded product (particularly, a film). 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, containing ceramic particles, can disperse the polyphenylene ether resin, polyimide resin, and polycarbonate resin well even without containing a compatibilizer, and thus a good flat-plate-shaped molded product (particularly, a film) can be molded.

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 a 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.

The type of ceramic particles is not particularly limited, but 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 is preferred, with titanium oxide particles being preferred.

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

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 total of the polyphenylene ether resin, polyimide resin, and polycarbonate resin. 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.

<Flame retardants>
The resin composition of the present embodiment preferably contains a flame retardant, which can improve the flame retardancy of the resulting molded article.
The type of flame retardant is not particularly limited, and known flame retardants can be used. Examples include phosphorus-based flame retardants, halogen-based flame retardants, and organometallic salt-based flame retardants. Phosphorus-based flame retardants and halogen-based flame retardants are preferred, and phosphorus-based flame retardants are more preferred.
By using a phosphorus-based flame retardant, the flame retardancy of the resin composition can be improved more effectively, and the viscosity during heat processing tends to decrease.

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

In particular, when a phosphorus-based flame retardant is used as the flame retardant, it is preferable that the phosphorus-based flame retardant be, for example, a phosphate ester represented by formula (3P).

Formula (3P)

In formula (3P), R ¹ , R ² , R ³ , and R ⁴ each independently represent 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.

Examples of the aryl group represented by each of ^R1 , ^R2 , ^R3 , and ^R4 include a phenyl group and a naphthyl group, with a phenyl group being preferred. Examples of the divalent aromatic group represented by X include a phenylene group, a naphthylene group, or a group derived from a bisphenol, with a group derived from a bisphenol being preferred. When X is a group derived from a bisphenol, it is more preferred that it be any of the following groups:

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

Such phosphate ester-based flame retardants include, for example, triphenyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, and their substituted and condensed derivatives. Commercially available phosphate ester-based flame retardants include, for example, Daihachi Chemical Industry's "TPP" (triphenyl phosphate), "CR733S" (resorcinol bis(diphenyl phosphate)), "CR741" (bisphenol A bis(diphenyl phosphate)), "PX-200" (resorcinol bis(dixylenyl phosphate)), and "SR-3000" (non-halogen condensed phosphate ester), and ADEKA Corporation's "FP-900L" (biphenyl-4,4'-diol bis(diphenyl phosphate)).

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

<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.

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.

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

Hindered phenol stabilizers are preferably used as phenol stabilizers. 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 -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, etc.

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

Examples of thioether stabilizers include dilauryl thiodipropionate, distearyl thiodipropionate, dimyristyl thiodipropionate, laurylstearyl thiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), etc. Commercially available products that can be used include DSTP "Yoshitomi," DLTP "Yoshitomi," DLTOIB, and DMTP "Yoshitomi" (all manufactured by API Corporation), Seenox 412S (Shipro Chemical Co., Ltd.), Adekastab AO-412S (ADEKA Corporation), Cyanox 1212 (Cyanamide Corporation), and Sumilizer TP-D (Sumitomo Chemical Co., Ltd.) (all trade names).

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, polyimide resin, and polycarbonate resin. By setting the content of the stabilizer within this range, the effect of adding the stabilizer can be more effectively exhibited.
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.

<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.

The resin additives may include dyes, pigments, weather resistance improvers, nucleating agents, impact resistance improvers, plasticizers, flowability 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.
Further, the resin composition of the present embodiment can be blended with the additives described in paragraphs 0047 to 0103 of WO 2021/241471 within the scope of the present invention, and the contents thereof are incorporated herein.

Examples of fillers other than ceramic particles include glass fiber and carbon fiber. 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.

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

<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 conforming to IEC 60112 is preferably 500 V or more, more preferably 550 V or more, even more preferably 600 V or more, and even more preferably 650 V or more, and may be 700 V or more depending on the application, etc. The upper limit of the CTI value is preferably the measurement limit value, for example, 1000 V.
The CTI value is measured as described in the Examples below.

The resin composition of this embodiment preferably has excellent flame retardancy. Specifically, when the resin composition is molded into a 0.125 μm thick plate-like molded article, the result of a flammability test in accordance with UL-94 preferably satisfies VTM-1, and more preferably VTM-0.
The flame retardancy is measured as described in the Examples below.

<Method of producing resin composition>
The method for producing the resin composition of this embodiment is not limited, and a wide variety of known methods for producing resin compositions can be used. Examples include a method in which the polyphenylene ether resin, polyimide resin, and polycarbonate resin, as well as other components added as needed, are premixed using various mixers such as a tumbler or Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, or kneader. The melt-kneading temperature is not particularly limited, but is preferably 330°C or lower, more preferably 320°C or lower, even more preferably 310°C or lower, even more preferably 300°C or lower, and even more preferably 290°C or lower. The lower limit of the melt-kneading temperature is preferably 240°C or higher, and may be 250°C or higher, 260°C or higher, or 270°C or higher.
An example of the resin composition is pellets.

<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-shaped molded article (film, sheet). The thickness of the flat plate-shaped molded article of this embodiment is, for example, preferably 10 μm or more, more preferably 25 μm or more, even more preferably 50 μm or more, even more preferably 75 μm or more, even more preferably 100 μm or more, and preferably 2000 μm or less, more preferably 1000 μm or less, even more preferably 750 μm or less, even more preferably 500 μm or less, and even more preferably 250 μm or less.
The temperature during film molding is not particularly limited, but is preferably 330° C. or lower, more preferably 320° C. or lower, even more preferably 310° C. or lower, still 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.

The method for molding the molded article is not particularly limited, and any conventionally known molding method 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, multi-layer 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 (extrusion molded articles, particularly flat extrusion molded articles) obtained by injection molding, injection compression molding, and extrusion molding, and is particularly suitable for molded articles obtained by extrusion molding. However, it goes without saying that the resin composition of this embodiment is not limited to molded articles obtained by these methods.

<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.

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.

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

Synthesis Example 1: Production of Polyimide Resin 1
500 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Nyukazai Co., Ltd.) and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and a four-paddle blade. After nitrogen flow, the mixture was stirred at 150 rpm to obtain a uniform suspension. Meanwhile, a 500 mL beaker was used to prepare a mixed diamine solution by dissolving 49.79 g (0.35 mol) of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., cis/trans ratio = 7/3) and 93.77 g (0.65 mol) of 1,8-octamethylenediamine (manufactured by Kanto Chemical Co., Ltd.) in 250 g of 2-(2-methoxyethoxy)ethanol. This mixed diamine solution was gradually added using a plunger pump. Although heat was generated during the dropwise addition, the internal temperature was adjusted to remain within the range of 40 to 80°C. Nitrogen flow was maintained throughout the dropwise addition of the mixed diamine solution, 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 confirmed between the liquid temperature of 120 and 140°C. After holding at 190°C for 30 minutes, the solution was allowed to cool to room temperature and then filtered. The obtained polyimide resin powder was washed with 300 g of 2-(2-methoxyethoxy)ethanol and 300 g of methanol, filtered, and then dried in a dryer at 180°C for 10 hours to obtain 317 g of powder of crystalline thermoplastic polyimide resin 1 (hereinafter also simply referred to as "polyimide resin 1").
The IR spectrum of Polyimide Resin 1 showed characteristic absorption of the imide ring at ν(C═O) 1768 and 1697 (cm ⁻¹ ). The inherent viscosity was 1.30 dL/g, Tm was 323° C., Tg was 184° C., Tc was 266° C., heat of fusion was 26.7 mJ/mg, heat of crystallization was 30.0 mJ/mg, crystallization half time was 20 seconds or less, and 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.

<Synthesis Example 2>
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.

<Method of producing resin composition>
In each of Example 1 and Comparative Example 1, the components shown in Table 1 were mixed in the proportions (parts by mass) shown in Table 2 below, and the mixture of components was melt-kneaded using a twin-screw extruder (TEM26SX, manufactured by Shibaura Machine Co., Ltd.) at the cylinder temperature (extrusion temperature) shown in Table 2 and a screw rotation speed of 200 rpm to obtain a resin composition (pellet). The obtained resin composition (pellet) was used to perform the following evaluations. The results are shown in Table 2.

<Evaluation of tracking resistance>
The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours and then fed to an injection molding machine ("EC75SX" manufactured by Shibaura Machine Co., Ltd.), and molded bodies measuring length x width x thickness = 100 mm x 100 mm x 3 mm were produced in this injection molding machine under conditions of a cylinder temperature shown in Table 2 and a mold temperature of 130°C. Using the produced molded bodies, the maximum voltage at which tracking failure of the molded bodies did not occur, i.e., the CTI value (unit: V), was measured by a measurement method in accordance with IEC60112 (electrolyte used: solution A, number of drops: 50).

<Film processability>
The pellets obtained by the above manufacturing method were dried at 120°C for 4 hours, and then fed to a T-die extrusion molding machine (a small extruder manufactured by Technovel Co., Ltd.). The cylinder temperature (film processing temperature) was adjusted to the film processing temperature shown in Table 2, and extrusion molding was carried out at a screw rotation speed of 25 rpm. A cooling roll temperature was set to 140°C and the film was taken up at a take-up speed of 0.8 to 1.5 m/min, yielding a film having a thickness of 150 μm and a width of 140 mm.
Photographs of the extrusion from the film of Example 1 and Comparative Example 1 are shown in Figures 1 and 2, respectively. As is clear from Figures 1 and 2, no generation of gum was observed in Example 1 (Figure 1), but gum was generated near the die opening of the extruder in Comparative Example 1 (Figure 2).
The evaluation was made according to the following criteria: The evaluation was made by visual inspection by five experts and judged by majority vote.
A: No eye mucus occurred. B: Eye mucus occurred.

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

As is clear from the above results, the film formed from the resin composition of the present invention had excellent film processability. Furthermore, the molded article formed from the resin composition of the present invention had excellent tracking resistance and flame retardancy (Examples 1 and 2).

Although the present invention has been described in detail using 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 (11)

The composition includes a polyphenylene ether resin composed of a resin represented by formula (1) and/or an acid-modified product thereof, a polyimide resin, and a polycarbonate 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).
(In formula (1), R ₅₁ to R ₅₅ and R ₆₁ to R ₆₄ each independently represent a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 4 carbon atoms, and R ₆₅ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n represents the number of repeating structural units and is a number of 10 or more.)
(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.) The resin composition of claim 1, further comprising a lubricant. The resin composition according to claim 1 or 2 further contains a lubricant in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the polyphenylene ether resin, polyimide resin, and polycarbonate resin combined. the mass ratio of the polyphenylene ether resin to the total 100 parts by mass of the polyphenylene ether resin and the polyimide resin is 50 to 99 parts by mass;
The resin composition according to claim 1 or 2. The resin composition according to claim 1 or 2 further contains 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles per 100 parts by mass of the polyphenylene ether resin, polyimide resin, and polycarbonate resin combined. The resin composition according to claim 5, wherein the flame retardant comprises a phosphorus-based flame retardant. The resin composition according to claim 5, wherein the ceramic particles comprise titanium oxide particles. Further, the lubricant is contained in an amount of 0.1 to 3 parts by mass per 100 parts by mass of the total of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin,
the mass ratio of the polyphenylene ether resin to a total of 100 parts by mass of the polyphenylene ether resin and the polyimide resin is 50 to 99 parts by mass;
Further, the composition contains 5 to 20 parts by mass of a flame retardant and 0.1 to 10 parts by mass of ceramic particles relative to 100 parts by mass of the total of the polyphenylene ether resin, the polyimide resin, and the polycarbonate resin,
the flame retardant comprises a phosphorus-based flame retardant;
The resin composition according to claim 1 , wherein the ceramic particles comprise titanium oxide particles. Pellets of the resin composition described in claim 1, 2, or 8. A molded article formed from the resin composition described in claim 1, 2, or 8. A flat-plate molded article formed from the resin composition of claim 1, 2, or 8.