Resin composition, resin molded product, and method for producing the same

Abstract

A resin composition containing: polyimide resin particles (A) including repeating constituent units represented by formula (1) and repeating constituent units represented by formula (2), having a content ratio of repeating constituent units of formula (1) to the total repeating constituent units of formula (1) and repeating constituent units of formula (2) of 20–70 mol%, and a volume average particle size D50 of 5-200 μm; and at least one selected from the group consisting of a thermoplastic resin (B) and a thermosetting resin (C). (R1 is a C6–22 divalent group including at least one alicyclic hydrocarbon structure. R2 is a C5–16 divalent chain aliphatic group. X1 and X2 are each independently a C6–22 tetravalent group including at least one aromatic ring.)

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a resin molded article, and a method for producing the same, and more particularly to a resin composition containing thermoplastic polyimide resin particles and a thermoplastic resin or a thermosetting resin, a resin molded article, and a method for producing the same. [Background technology]

[0002] Polyimide resins are useful engineering plastics with high thermal stability, strength, and solvent resistance due to the rigidity of their molecular chains, resonance stabilization, and strong chemical bonds, and are used in a wide range of fields. Furthermore, because polyimide resins have crystallinity, their heat resistance, strength, and chemical resistance can be further improved, making them promising candidates for use as metal replacements. However, while polyimide resins have high heat resistance, they lack thermoplasticity and have poor moldability.

[0003] Although high-heat-resistant resins such as Vespel (registered trademark) are known as polyimide molding materials (Patent Document 1), they have extremely low fluidity even at high temperatures, making molding difficult and cost-inefficient due to the need for long molding times under high-temperature and high-pressure conditions. In contrast, resins that have a melting point and fluidity at high temperatures, such as crystalline resins, can be molded easily and inexpensively.

[0004] In recent years, thermoplastic polyimide resins have been reported. Thermoplastic polyimide resins have the inherent heat resistance of polyimide resins, but also have excellent moldability. Therefore, thermoplastic polyimide resins can be used in molded articles used in harsh environments, which is not possible with general-purpose thermoplastic resins such as nylon and polyester. For example, Patent Document 2 discloses a thermoplastic polyimide resin containing a predetermined repeating structural unit, which is obtained by reacting a tetracarboxylic acid and / or a derivative thereof containing at least one aromatic ring, a diamine containing at least one alicyclic hydrocarbon structure, and a chain aliphatic diamine.

[0005] In the field of engineering plastics, a technique for compounding two or more thermoplastic resins to form an alloy is known for the purpose of improving physical properties, imparting functions according to applications, etc. Patent Document 3 discloses a thermoplastic polyimide resin containing a predetermined repeating unit, and also describes the use of the polyimide resin in combination with other resins to form a polymer alloy. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-28524 [Patent Document 2] International Publication No. 2013 / 118704 [Patent Document 3] International Publication No. 2016 / 147996 Summary of the Invention [Problem to be solved by the invention]

[0007] As mentioned above, crystalline thermoplastic polyimide resins have high heat resistance, strength, and chemical resistance, and also have a lower specific gravity than metals. Therefore, they are also expected to be used as resin modifiers that can improve heat resistance, mechanical properties, etc. while maintaining the light weight inherent in resin materials. An example in Patent Document 3 describes the production of a resin molded article by alloying a crystalline thermoplastic polyimide resin containing a predetermined repeating unit with a polyether ether ketone resin (PEEK). PEEK is a thermoplastic resin that has high heat resistance like polyimide resin, and the resin molded article is produced by heating and melting the crystalline thermoplastic polyimide resin containing the predetermined repeating unit and PEEK at a temperature equal to or higher than the melting point of the polyimide resin, followed by extrusion and thermoforming. On the other hand, there has been no study on using the polyimide resin to improve the properties of thermoplastic resins with lower heat resistance, such as crystalline thermoplastic resins with low melting points or amorphous thermoplastic resins with low glass transition temperatures, or thermosetting resins.

[0008] In addition, cured thermosetting resins generally have higher heat resistance than thermoplastic resins, but tend to have lower toughness due to their high crosslink density. In aircraft, ships, etc., the strain energy release rate (G 1c ) and other factors related to fracture strength are considered important, and while maintaining the heat resistance of the cured resin, 1c It is desirable to improve this.

[0009] An object of the present invention is to provide a resin composition, a resin molded product, and a method for producing the same, which are made of a thermoplastic resin or a thermosetting resin having low heat resistance and have improved properties such as heat resistance and mechanical properties while maintaining the light weight inherent to the resin. [Means for solving the problem]

[0010] The present inventors have discovered that the above-mentioned problems can be solved by preparing a resin composition in which a crystalline thermoplastic polyimide resin having specific polyimide structural units is contained in a thermoplastic resin or a thermosetting resin in the form of resin particles having a particle size within a specific range. That is, the present invention provides the following [1] to [3]. [1] A resin composition comprising polyimide resin particles (A) having a volume average particle size D50 of 5 to 200 μm, which contain repeating units represented by the following formula (1) and repeating units represented by the following formula (2), wherein the content of the repeating units of formula (1) relative to the total of the repeating units of formula (1) and formula (2) is 20 to 70 mol %: and at least one resin selected from the group consisting of a thermoplastic resin (B) and a thermosetting resin (C). [ka] (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] A resin molded product comprising polyimide resin particles (A) having a volume average particle size D50 of 5 to 200 μm, which contain repeating units represented by the formula (1) and repeating units represented by the formula (2), wherein the content of the repeating units of the formula (1) relative to the total of the repeating units of the formula (1) and the repeating units of the formula (2) is 20 to 70 mol %; and at least one resin selected from the group consisting of a thermoplastic resin (B) and a cured product of a thermosetting resin (C). [3] A method for producing a resin molded product according to the above item [2], comprising a step of molding a resin composition containing the polyimide resin particles (A) and at least one resin selected from the group consisting of the thermoplastic resin (B) and the thermosetting resin (C) at a temperature below the melting point of the polyimide resin particles (A). [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a resin composition, a resin molded product, and a method for producing the same, which are thermoplastic resins such as low-melting-point crystalline thermoplastic resins and low-glass-transition-temperature amorphous thermoplastic resins, or thermosetting resins, in which various properties such as heat resistance and mechanical properties are improved while maintaining the light weight inherent to the resin. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a micrograph of the resin composition (pellets) of Example 1 observed with a field emission scanning electron microscope (FE-SEM). DETAILED DESCRIPTION OF THE INVENTION

[0013] [Resin composition] The resin composition of the present invention contains polyimide resin particles (A) (hereinafter simply referred to as "polyimide resin particles (A)" or "component (A)") that contain repeating structural units represented by the following formula (1) and repeating structural units represented by the following formula (2), wherein the content of the repeating structural units of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is 20 to 70 mol % and that have a volume average particle size D50 of 5 to 200 μm, and at least one resin selected from the group consisting of a thermoplastic resin (B) and a thermosetting resin (C). [ka] (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 the present invention contains a polyimide resin in the form of particles having a predetermined D50, which is obtained by combining specific different polyimide structural units in the above-mentioned specific ratio. This allows for the production of a resin composition and a resin molded article that have improved properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C). Although the reason for this is unclear, it is thought that the polyimide resin particles (A) disperse in the thermoplastic resin (B), the thermosetting resin (C), or their cured products and act as a resin filler, thereby improving various properties such as heat resistance and mechanical properties. In addition, the polyimide resin particles (A) acting as a resin filler can also be expected to improve sliding properties.

[0014] The resin composition of the present invention is a thermoplastic resin composition or a thermosetting resin composition, and its form can be appropriately selected depending on whether a thermoplastic resin (B) or a thermosetting resin (C) is used. When the resin composition of the present invention is a thermoplastic resin composition containing polyimide resin particles (A) and a thermoplastic resin (B), the form of the thermoplastic resin composition is preferably pellets from the viewpoint of handling and processability. More preferably, the thermoplastic resin composition is pellets in which polyimide resin particles (A) described below are dispersed in a matrix composed of a thermoplastic resin (B).

[0015] <Polyimide resin particles (A)> The resin composition of the present invention, from the viewpoint of improving various properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C), contains polyimide resin particles (A) that contain repeating structural units represented by the following formula (1) and repeating structural units represented by the following formula (2), wherein the content of the repeating structural units of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is 20 to 70 mol % and the volume average particle size D50 is 5 to 200 μm. [ka] (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.)

[0016] The polyimide resin constituting component (A) is a thermoplastic resin and is 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, which are formed by molding a polyimide precursor such as polyamic acid and then closing the imide ring. The polyimide resin has crystallinity, and the degree of crystallinity can be determined by the calorific value of the exothermic peak of crystallization (crystallization exothermic value) observed when the polyimide resin is melted and then cooled at a temperature decreasing rate of 20°C / min. Details will be described later.

[0017] The repeating unit of formula (1) 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.

[0018] R1 is preferably a divalent group represented by the following formula (R1-1) or (R1-2). [ka] (m 11 and m 12 are each independently an integer of 0 to 2, preferably 0 or 1. 13 ~m 15 are each independently an integer of 0 to 2, preferably 0 or 1.

[0019] R1 is particularly preferably a divalent group represented by the following 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.

[0020] 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 a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited to these. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. X1 has 6 to 22 carbon atoms, and preferably 6 to 18 carbon atoms. X1 contains at least one aromatic ring, preferably 1 to 3.

[0021] X1 is preferably a tetravalent group represented by any one of the following formulae (X-1) to (X-4). [ka] (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, preferably 0. 14 , p 15 , p 16 and p 18 are each independently an integer of 0 to 3, preferably 0. 17 is an integer of 0 to 4, preferably 0. 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. Since X1 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, R 12 , R 13 , p 12 and p 13is selected so that the number of carbon atoms in the tetravalent group represented by formula (X-2) falls within the range of 10 to 22. Similarly, L in formula (X-3) 11 , R 14 , R 15 , p 14 and p 15 is selected so that the number of carbon atoms of the tetravalent group represented by formula (X-3) is in the range of 12 to 22, and L in formula (X-4) 12 , L 13 , R 16 , R 17 , R 18 , p 16 , p 17 and p 18 is selected so that the number of carbon atoms in the tetravalent group represented by formula (X-4) falls within the range of 18 to 22.

[0022] X1 is particularly preferably a tetravalent group represented by the following formula (X-5) or (X-6). [ka]

[0023] Next, the repeating unit of formula (2) 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.

[0024] 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, preferred are divalent groups represented by the following formula (R2-1) or (R2-2). [ka] (m 21 and m 22 are each independently an integer of 1 to 15, preferably 1 to 13, more preferably 1 to 11, and even more preferably 1 to 9. 23 ~m 25 are each independently an integer of 1 to 14, 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), m in formula (R2-1) 21 and m 22 is selected so that the carbon number of 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, m 21 +m 22 is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, and even more preferably 8 to 10). Similarly, m in formula (R2-2) 23 ~m 25 is 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, m 23 +m 24 +m 25 has 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).

[0025] X2 is defined in the same manner as X1 in formula (1), and the preferred embodiments are also the same.

[0026] The content ratio of the repeating structural unit of formula (1) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 20 to 70 mol %. When the content ratio of the repeating structural unit of formula (1) is within this range, the polyimide resin can be sufficiently crystallized even in a general injection molding cycle. When the content ratio is 20 mol % or more, good moldability is achieved, and when it is 70 mol % or less, good heat resistance can be maintained. The content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is preferably 65 mol % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less, from the viewpoint of achieving high crystallinity. In particular, from the viewpoint of obtaining a resin composition with high crystallinity and excellent heat resistance, the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural units of formula (1) and formula (2) is preferably 20 mol% or more and less than 40 mol%. From the viewpoint of moldability, this content ratio is more preferably 25 mol% or more, even 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.

[0027] The total content ratio of the repeating structural units of formula (1) and the repeating structural units of formula (2) 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 %.

[0028] The polyimide resin may further contain a repeating structural unit of the following formula (3). In this case, the content ratio of the repeating structural unit of formula (3) to the total of the repeating structural units of formula (1) and formula (2) is preferably 25 mol % or less. On the other hand, there is no particular lower limit, as long as it is more 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. [ka] (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.)

[0029] 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 a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited to these. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred. 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.

[0030] R3 is preferably a divalent group represented by the following formula (R3-1) or (R3-2). [ka] (m 31 and m 32are each independently an integer of 0 to 2, preferably 0 or 1. 33 and m 34 are each independently an integer of 0 to 2, preferably 0 or 1. 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. 21 , p 22 and p 23 is an integer of 0 to 4, preferably 0. 21 is a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms. Since R3 is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, m in formula (R3-1) 31 , m 32 , R 21 and p 21 is selected so that the divalent group represented by formula (R3-1) has 6 to 22 carbon atoms. Similarly, L in formula (R3-2) 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 is selected so that the divalent group represented by formula (R3-2) has 12 to 22 carbon atoms.

[0031] X3 is defined in the same manner as X1 in formula (1), and the preferred embodiments are also the same.

[0032] The polyimide resin may further contain a repeating structural unit represented by the following formula (4). [ka] (R4 is -SO2- or -Si(R x )(R y )O-containing divalent group, and R x and R yeach independently represents 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 (1), and the preferred embodiments are also the same.

[0033] The terminal structure of the polyimide resin is not particularly limited. For example, the polyimide resin constituting the polyimide resin particles (A) may be a polyimide resin that is not end-capped. The term "unend-capped polyimide resin" refers to a polyimide resin whose terminal structure consists only of terminal amino groups and terminal carboxy groups derived from the tetracarboxylic acid component and diamine component that are the raw materials of the polyimide resin. If the polyimide resin constituting the polyimide resin particles (A) is not end-capped, crosslinking of the terminal amino groups and terminal carboxyl groups in the polyimide resin particles (A) with the thermoplastic resin (B) or thermosetting resin (C) becomes possible, thereby further improving mechanical properties such as toughness. From this viewpoint, in the resin composition of the present invention, it is more preferable to use the polyimide resin particles (A) composed of an unend-capped polyimide resin in combination with the thermosetting resin (C).

[0034] On the other hand, when the polyimide resin is end-capped, the polyimide resin preferably has a chain aliphatic group having 5 to 14 carbon atoms at the end. 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, 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. Furthermore, when the polyimide resin has a chain aliphatic group having 5 to 14 carbon atoms at its terminal, it preferably has only a chain aliphatic group having 5 to 14 carbon atoms at its terminal in addition to a terminal amino group and a terminal carboxy group, from the viewpoint of heat aging resistance. When a group other than the above is present at the terminal, the content thereof is preferably 10 mol % or less, more preferably 5 mol % or less, relative to the chain aliphatic group having 5 to 14 carbon atoms.

[0035] When the polyimide resin has a chain aliphatic group having 5 to 14 carbon atoms at its terminal, 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, from the viewpoint of exhibiting excellent heat aging resistance. 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.

[0036] The polyimide resin preferably has a melting point of 360°C or less and a glass transition temperature of 150°C or more. The melting point of the polyimide resin is preferably 280°C or higher, more preferably 290°C or higher, from the viewpoint of heat resistance, and is more preferably 345°C or lower, even more preferably 340°C or lower, and even more preferably 335°C or lower, from the viewpoint of exhibiting high moldability. Furthermore, from the viewpoint of heat resistance, the glass transition temperature of the polyimide resin is more preferably 160°C or higher, and even more preferably 170°C or higher, and from the viewpoint of exhibiting high moldability, it is preferably 250°C or lower, more preferably 230°C or lower, and even more preferably 200°C or lower. Furthermore, from the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance, the polyimide resin preferably has a calorific 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, at the exothermic peak of crystallization, 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 (hereinafter simply referred to as "exothermic value of crystallization"). The upper limit of the exothermic value of crystallization is not particularly limited, but is usually 45.0 mJ / mg or less. The melting point, glass transition temperature, and crystallization heat of the polyimide resin can all be measured by a differential scanning calorimeter, specifically by the method described in the examples.

[0037] The logarithmic viscosity of a 5% by mass solution of the 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)

[0038] The weight-average molecular weight Mw of the polyimide resin constituting the polyimide resin particles (A) 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 mechanical strength stability 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.

[0039] (Volume average particle size D50) The polyimide resin particles (A) have a volume average particle size D50 of 5 to 200 μm, more preferably 5 to 150 μm, even more preferably 5 to 100 μm, and even more preferably 5 to 40 μm, from the viewpoint of obtaining a resin composition and a resin molded article that have improved properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C), and from the viewpoint of dispersibility. The D50 of the polyimide resin particles (A) can be measured by a laser diffraction light scattering particle size distribution analyzer, specifically by the method described in the examples.

[0040] The shape of the polyimide resin particles (A) is not particularly limited, but porous is preferred. Porous polyimide resin particles (A) can improve the heat resistance, mechanical properties, and other properties of the resulting resin composition and resin molded article while reducing their weight. Furthermore, a lower dielectric constant can be expected for the resin composition and resin molded article. From the perspective of achieving these effects, it is preferred that the polyimide resin particles (A) be present in the resin composition and resin molded article in the form of porous particles. Therefore, as described below, it is preferred to produce the resin composition and resin molded article without subjecting them to a thermal history above the melting point of the polyimide resin particles (A). The phrase "producing a resin composition and resin molded article without subjecting them to a thermal history above the melting point of the polyimide resin particles (A)" means that all production steps in the production of the resin composition and resin molded article of the present invention are carried out under temperature conditions below the melting point of the polyimide resin particles (A). The porous nature of the polyimide resin particles (A) can be confirmed by observing them with a scanning electron microscope (SEM).

[0041] The D50 of the polyimide resin particles (A) can be adjusted to fall within the above range and the polyimide resin particles (A) can be made porous by producing the polyimide resin particles (A) by the production method described below.

[0042] (specific gravity) The specific gravity of the polyimide resin particles (A) is preferably 0.8 to 1.7, more preferably 0.9 to 1.5, even more preferably 1.0 to 1.4, and even more preferably 1.05 to 1.25, from the viewpoint of obtaining a resin composition and a resin molded article that have improved properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C). The specific gravity of the polyimide resin particles (A) is a value measured at 23° C., and specifically, can be measured by the method described in the Examples.

[0043] (true density) The true density of the polyimide resin particles (A) measured by a gas phase method is preferably 1.0 to 1.8 g / cm from the viewpoint of obtaining a resin composition and a resin molded article having improved properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C). 3 , more preferably 1.1 to 1.6 g / cm 3 , more preferably 1.2 to 1.5 g / cm 3 From the above viewpoints, the true density of the polyimide resin particles (A) measured by a liquid phase method is preferably 0.8 to 1.7 g / cm. 3 , more preferably 0.9 to 1.5 g / cm 3 , more preferably 1.0 to 1.4 g / cm 3 is. True density measurement by the gas phase method can be performed in accordance with the "Method for measuring density and specific gravity by gas displacement method" specified in JIS Z8807:2012. True density measurement by the liquid phase method (pycnometer method) can be performed using n-butyl alcohol as the liquid medium and a wet true density measuring instrument. The true density can be measured specifically by the method described in the Examples.

[0044] Furthermore, the difference (D1-D2) between the true density D1 of the polyimide resin particles (A) measured by the gas phase method and the true density D2 measured by the liquid phase method is 0.05 to 0.7 g / cm 3 It is preferable that the density is 0.08 to 0.5 g / cm 3 More preferably, it is 0.08 to 0.4 g / cm 3 It is more preferable that (D1-D2) indicates the presence of minute pores into which the liquid medium used in the true density measurement by the liquid phase method cannot penetrate.

[0045] (specific surface area) The specific surface area of ​​the polyimide resin particles (A) is preferably 1.0 to 50 m from the viewpoint of ease of handling and from the viewpoint of obtaining a resin composition having excellent fluidity. 2 / g, more preferably 2.0 to 40m 2 / g, more preferably 5.0 to 25m 2 / g. It is presumed that the specific surface area is affected by both the D50 and the pore volume of the polyimide resin particles (A). The specific surface area can be determined by the BET method, specifically by the method described in the Examples.

[0046] (total pore volume) When the polyimide resin particles (A) are porous, the total pore volume thereof is preferably 0.005 to 0.50 cc / g, more preferably 0.01 to 0.30 cc / g, and even more preferably 0.015 to 0.20 cc / g, from the viewpoint of obtaining a resin composition and a resin molded article that have improved properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C). The total pore volume can be specifically measured by the method described in the Examples.

[0047] (average pore diameter) When the polyimide resin particles (A) are porous, the average pore diameter thereof is preferably 5 to 85 nm, more preferably 10 to 80 nm, and even more preferably 20 to 70 nm, from the viewpoint of obtaining a resin composition and a resin molded article that have improved properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C). The average pore diameter can be measured specifically by the method described in the Examples.

[0048] The D50, specific gravity, true density, specific surface area, total pore volume, and average pore diameter of the polyimide resin particles (A) are preferably within the above-mentioned ranges as measured using the polyimide resin particles (A) before being incorporated into the resin composition and resin molded article. In the present invention, when the resin composition and resin molded article are produced without applying a thermal history above the melting point of the polyimide resin particles (A), the shape of the polyimide resin particles (A) in the resin composition and resin molded article is considered to maintain the shape of the polyimide resin particles (A) used unless they are deformed by shear stress. The "shape of the polyimide resin particles (A) used" refers to the D50 and porous state of the polyimide resin particles (A) before being incorporated into the resin composition and resin molded article.

[0049] (Method for producing polyimide resin particles (A)) The polyimide resin particles (A) can be produced by reacting a tetracarboxylic acid component containing at least one aromatic ring-containing tetracarboxylic acid and / or its derivative with a diamine component, and a diamine component containing at least one alicyclic hydrocarbon structure-containing diamine and a chain aliphatic diamine.

[0050] 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.

[0051] 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.

[0052] As the tetracarboxylic acid and / or derivative thereof containing at least one aromatic ring, at least one compound selected from the above may be used alone, or two or more compounds may be used in combination.

[0053] 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[5.2.1.0]diamine, and bis(aminomethyl)tricyclo[5.2.1.0]diamine. 2,6 ]decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, etc. are preferred. 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 preferably used. Note that diamines containing an alicyclic hydrocarbon structure generally have structural isomers, but the ratio of cis / trans isomers is not limited.

[0054] 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.

[0055] When producing polyimide resin particles (A), 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 ratio is more preferably 25 mol % or more, even more preferably 30 mol % or more, and even more preferably 32 mol % or more, and from the viewpoint of achieving high crystallinity, is more preferably 60 mol % or less, even more preferably 50 mol % or less, even more preferably less than 40 mol %, and even more preferably 35 mol % or less.

[0056] 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.

[0057] In the above, the molar ratio of the amount of the diamine containing at least one aromatic ring charged 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. 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 particles (A), the molar ratio is preferably 12 mol % or less, more preferably 10 mol % or less, even more preferably 5 mol % or less, and still more preferably 0 mol %.

[0058] When producing the polyimide resin particles (A), 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.

[0059] When producing the polyimide resin particles (A), 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. When a terminal blocking agent is used, the amount used may be any amount that allows the desired number of terminal groups to be introduced into the polyimide resin constituting the polyimide resin particles (A). The amount used is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.06 mol, even more preferably 0.002 to 0.035 mol, still more preferably 0.002 to 0.020 mol, and even more preferably 0.002 to 0.012 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 terminal of the polyimide resin constituting the polyimide resin particles (A), 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.

[0060] The polymerization method for producing the polyimide resin particles (A) can be any known polymerization method, and is not particularly limited, but examples thereof include solution polymerization, melt polymerization, solid-phase polymerization, and suspension polymerization. Among these, suspension polymerization under high-temperature conditions using an organic solvent is particularly preferred. When suspension polymerization is performed under high-temperature conditions, polymerization is preferably performed at 150°C or higher, more preferably 180 to 250°C. The polymerization time can be appropriately selected depending on the monomer used, but is preferably about 0.1 to 6 hours.

[0061] The method for producing the polyimide resin particles (A) preferably includes a step of reacting the tetracarboxylic acid component with the diamine component in the presence of a solvent containing an alkylene glycol solvent represented by the following formula (I): This makes it possible to easily obtain porous polyimide resin particles having a D50 of 5 to 200 μm. [ka] (Ra1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ra2 is a linear alkylene group having 2 to 6 carbon atoms, and n is an integer of 1 to 3.)

[0062] In formula (I), Ra1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group. In formula (I), Ra2 is a linear alkylene group having 2 to 6 carbon atoms, preferably a linear alkylene group having 2 to 3 carbon atoms, and more preferably an ethylene group. In formula (I), n is an integer of 1 to 3, preferably 2 or 3. Specific examples of the alkylene glycol solvent include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether (also known as 2-(2-methoxyethoxy)ethanol), triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether (also known as 2-(2-ethoxyethoxy)ethanol), ethylene glycol monoisopropyl ether, diethylene glycol monoisopropyl ether, triethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol, and 1,3-propanediol. These solvents may be used alone, or two or more solvents selected from these may be used in combination. Of these solvents, at least one selected from the group consisting of 2-(2-methoxyethoxy)ethanol, triethylene glycol monomethyl ether, 2-(2-ethoxyethoxy)ethanol, and 1,3-propanediol is preferred.

[0063] A suitable method for producing the polyimide resin particles (A) includes, for example, separately preparing a solution (a) containing a tetracarboxylic acid component in a solvent containing the alkylene glycol-based solvent, and a solution (b) containing a diamine component in a solvent containing the alkylene glycol-based solvent, and then adding solution (b) to solution (a) or solution (a) to solution (b) to prepare a solution (c) containing a polyamic acid, and then heating solution (c) to imidize the polyamic acid and precipitate polyimide resin particles in solution (c), thereby obtaining the polyimide resin particles (A). The reaction between the tetracarboxylic acid component and the diamine component can be carried out either under normal pressure or under pressure, but is preferably carried out under normal pressure since it does not require a pressure-resistant vessel. When a terminal-capping agent is used, it is preferable to mix solution (a) and solution (b), add the terminal-capping agent to the mixture, prepare solution (c) containing a polyamic acid, and then heat solution (c); it is more preferable to add the terminal-capping agent after completing the addition of solution (b) to solution (a), prepare solution (c) containing a polyamic acid, and then heat solution (c).

[0064] <Thermoplastic resin (B)> Thermoplastic resin (B) (hereinafter also referred to as "component (B)") is a thermoplastic resin other than the component (A). When the polyimide resin particles (A) are not subjected to a thermal history above their melting point when the resin composition and resin molded article are produced, the shape of the polyimide resin particles (A) used can be maintained and the resin composition and resin molded article can incorporate the polyimide resin particles (A) into the resin composition and resin molded article, provided that they are not deformed by shear stress. From this viewpoint, the thermoplastic resin (B) is preferably at least one selected from the group consisting of the following (B1) and (B2): (B1) Amorphous thermoplastic resin having a glass transition temperature lower than the melting point of the polyimide resin particles (A) (B2) A crystalline thermoplastic resin having a melting point lower than the melting point of the polyimide resin particles (A) or a glass transition temperature lower than the glass transition temperature of the polyimide resin particles (A). In this specification, "amorphous thermoplastic resin" refers to a thermoplastic resin that has a glass transition temperature but no melting point, and "thermoplastic resin without a melting point" refers, more specifically, to a resin whose heat value at the crystallization exotherm peak (crystallization exotherm) observed when the resin is melted and then cooled at a temperature decrease rate of 20°C / min, as measured by a differential scanning calorimeter, is less than 5mJ / mg. Also, "crystalline thermoplastic resin" refers to a thermoplastic resin that has a melting point and whose crystallization exotherm is 5mJ / mg or more.

[0065] (Amorphous thermoplastic resin (B1)) When the thermoplastic resin (B) is an amorphous thermoplastic resin, it is preferably an amorphous thermoplastic resin (B1) (hereinafter also referred to as "amorphous thermoplastic resin (B1)" or "component (B1)") whose glass transition temperature is lower than the melting point of the polyimide resin particles (A). Component (B1) can be melted and molded at a temperature lower than the melting point of component (A), so that a resin composition and a resin molded article containing component (A) can be obtained while maintaining the shape of the component (A) used. Examples of component (B1) include amorphous thermoplastic resins having a glass transition temperature lower than the melting point of component (A), such as polystyrene resins, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene resins, polycarbonate resins, polysulfone resins, polyphenylsulfone resins, polyarylate resins, polyphenylene ether resins, polyethersulfone resins, polyetherimide resins, polyamideimide resins, and polyurethane resins. These may be used alone or in combination of two or more.

[0066] Glass transition temperature Tg of component (B1) B1 (°C) is the melting point of component (A) as Tm from the viewpoint of facilitating incorporation of component (A) into a resin composition and a resin molded article while maintaining the shape of component (A) used. A (℃), (Tm A -30) ° C. or lower, and (Tm A -50) ° C. or less, and (Tm A It is more preferable that the glass transition temperature (Tg) is −100° C. or lower. B1 The lower limit of Tg is not particularly limited, and may be, for example, −125° C. or higher. B1 is preferably −50° C. or higher, more preferably 0° C. or higher, and even more preferably 50° C. or higher.

[0067] (Crystalline thermoplastic resin (B2)) When the thermoplastic resin (B) is a crystalline thermoplastic resin, it is preferably a crystalline thermoplastic resin (B2) (hereinafter also referred to as "crystalline thermoplastic resin (B2)" or "component (B2)") whose melting point is lower than the melting point of the polyimide resin particles (A) or whose glass transition temperature is lower than the glass transition temperature of the polyimide resin particles (A). Component (B2) can also be melted and molded at a temperature lower than the melting point or glass transition temperature of component (A), so that component (A) can be incorporated into resin compositions and resin molded articles while maintaining the shape of the component (A) used. Examples of component (B2) include crystalline thermoplastic resins having a glass transition temperature lower than that of component (A) or a melting point lower than that of component (A), such as polyolefin resins such as polyethylene, polypropylene, and cyclic polyolefins; polyamide resins; polyacetal resins; polyphenylene sulfide resins; polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polycyclohexylene dimethylene terephthalate, and polyglycolic acid; liquid crystal polymers; fluororesins such as polytetrafluoroethylene and polyvinylidene fluoride; polymethylpentene resins; polyurethane resins; etc. These may be used alone or in combination of two or more.

[0068] Melting point Tm of component (B2) B2 The melting point (°C) is not particularly limited as long as it is a temperature below the melting point of component (A), but from the viewpoint of moldability, it is preferably 320°C or lower, more preferably 300°C or lower, even more preferably 280°C or lower, and even more preferably 250°C or lower. B2 The lower limit of the temperature is not particularly limited, but from the viewpoint of heat resistance, it is preferably 50°C or higher, more preferably 100°C or higher, even more preferably 120°C or higher, and still more preferably 140°C or higher. The glass transition temperature Tg of component (B2) B2The glass transition temperature Tg (°C) is not particularly limited as long as it is a temperature below the glass transition temperature of component (A), but from the viewpoint of moldability, it is preferably 170°C or lower, more preferably 150°C or lower, even more preferably 120°C or lower, and even more preferably 100°C or lower. B2 The lower limit of Tg is not particularly limited, and may be, for example, −125° C. or higher. B2 is preferably −50° C. or higher, more preferably −20° C. or higher, and even more preferably 0° C. or higher.

[0069] As the thermoplastic resin (B) used in the present invention, one or more types selected from the group consisting of components (B1) and (B2) can be used. From the viewpoint of incorporating component (A) into a resin composition and a resin molded article while maintaining the shape of the component (A) used, and from the viewpoint of improving heat resistance, mechanical properties, etc., the thermoplastic resin (B) is preferably at least one selected from the group consisting of polystyrene resin, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene resin, polycarbonate resin, polysulfone resin, polyphenylsulfone resin, polyarylate resin, polyphenylene ether resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, polyolefin resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyester resin, liquid crystal polymer, fluororesin, polymethylpentene resin, and polyurethane resin. More preferably, it is at least one selected from the group consisting of polystyrene resin, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene resin, polycarbonate resin, polyphenylsulfone resin, polyphenylene ether resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, polyolefin resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyester resin, fluororesin, and polyurethane resin, even more preferably it is at least one selected from the group consisting of polycarbonate resin, polyolefin resin, polyamide resin, and polyphenylene sulfide resin, even more preferably it is a polyolefin resin, and even more preferably it is a polypropylene resin.

[0070] Furthermore, the polyimide resin particles (A) may contain the aforementioned terminal amino groups, and the use of a thermoplastic resin (B) having a structure capable of reacting with the terminal amino groups can improve the toughness of the resulting resin composition and resin molded article. From this viewpoint, the thermoplastic resin (B) is preferably at least one selected from the group consisting of polyamide resins and polyamideimide resins, and more preferably a polyamide resin. The term "improved toughness" used herein means that the elongation until breakage occurs when a tensile stress is applied to the resin molded article increases, and can be evaluated by, for example, measuring the tensile strain at break.

[0071] Examples of the polyamide resin used as the thermoplastic resin (B) include aromatic ring-containing polyamides and aliphatic polyamides. As the aromatic ring-containing polyamide, from the viewpoint of satisfying the requirements of component (B2), polyamides derived from aromatic ring-containing diamines and aliphatic dicarboxylic acids are preferred, such as polymetaxylylene adipamide (MXD6), polymetaxylylene sebacamide (MXD10), polyparaxylylene adipamide (PXD6), polyparaxylylene sebacamide (PXD10), polymeta / paraxylylene adipamide (MPXD6), and polymeta / paraxylylene sebacamide (MPXD10), and one or more of these can be used. Examples of aliphatic polyamides include polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyundecaneamide (polyamide 11), polydodecanamide (polyamide 12), and polyhexamethylene dodecamide (polyamide 612), and one or more of these can be used. Among the above, aliphatic polyamides are more preferred from the viewpoint of obtaining an effect of improving toughness in the resulting resin composition and resin molded article.

[0072] <Thermosetting resin (C)> The thermosetting resin (C) (hereinafter also referred to as "component (C)") is not particularly limited as long as it is a thermosetting resin capable of dispersing the polyimide resin particles (A), and examples thereof include at least one selected from the group consisting of epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyimide resins, bismaleimide resins, silicone resins, urethane resins, casein resins, furan resins, alkyd resins, and xylene resins. Among these, from the viewpoint of incorporating component (A) into a resin composition or a resin molded product while maintaining the shape of the component (A) used, and from the viewpoint of the dispersibility of component (A), component (C) is preferably at least one selected from the group consisting of epoxy resins, urethane resins, and bismaleimide resins, more preferably at least one selected from the group consisting of epoxy resins and urethane resins, and even more preferably an epoxy resin.

[0073] The epoxy resin used as component (C) may be a two-component curing type epoxy resin composition containing an epoxy group-containing compound as a main component and a curing agent. The epoxy group-containing compound as the main component is preferably a polyfunctional epoxy compound having two or more epoxy groups, and more preferably a polyfunctional epoxy compound containing an aromatic ring or an alicyclic structure in the molecule, from the viewpoint of the mechanical strength of the cured product. Specific examples of polyfunctional epoxy compounds include polyfunctional epoxy compounds having a glycidylamino group derived from metaxylylenediamine; polyfunctional epoxy compounds having a glycidylamino group derived from paraxylylenediamine; polyfunctional epoxy compounds having a glycidylamino group derived from 1,3-bis(aminomethyl)cyclohexane; polyfunctional epoxy compounds having a glycidylamino group derived from 1,4-bis(aminomethyl)cyclohexane; and polyfunctional epoxy compounds having a glycidylamino group derived from diaminodiphenylmethane such as tetraglycidyldiaminodiphenylmethane. Examples of suitable epoxy compounds include polyfunctional epoxy compounds having glycidylamino groups and / or glycidyloxy groups derived from para-aminophenol, polyfunctional epoxy compounds having glycidyloxy groups derived from bisphenol A, such as bisphenol A diglycidyl ether, polyfunctional epoxy compounds having glycidyloxy groups derived from bisphenol F, such as bisphenol F diglycidyl ether, polyfunctional epoxy compounds having glycidyloxy groups derived from phenol novolac, and polyfunctional epoxy compounds having glycidyloxy groups derived from resorcinol. Two or more of the above polyfunctional epoxy compounds can also be used in combination.

[0074] Among the above, from the viewpoint of obtaining a cured product with high heat resistance, the polyfunctional epoxy compound used as the base agent is preferably one containing as a main component at least one selected from the group consisting of polyfunctional epoxy compounds having a glycidylamino group derived from meta-xylylenediamine, polyfunctional epoxy compounds having a glycidylamino group derived from para-xylylenediamine, polyfunctional epoxy compounds having a glycidylamino group derived from diaminodiphenylmethane, polyfunctional epoxy compounds having a glycidyloxy group derived from bisphenol A, and polyfunctional epoxy compounds having a glycidyloxy group derived from bisphenol F. From the viewpoint of obtaining a cured product with high heat resistance, availability, and economy, polyfunctional epoxy compounds having a glycidylamino group derived from diaminodiphenylmethane, such as tetraglycidyldiaminodiphenylmethane, are more preferred.

[0075] The curing agent used in the epoxy resin composition may be any agent having two or more active hydrogens capable of reacting with the epoxy groups in the base resin, and from the viewpoint of curability, a polyamine compound or a modified product thereof is preferred. Specific examples thereof include chain aliphatic polyamine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine, 2-methylpentamethylenediamine, and trimethylhexamethylenediamine; 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, menthenediamine, isophoronediamine, norbornanediamine, tricyclodecanediamine, adamantanediamine, diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-3,6-diethylcyclohexane, and diaminodiethylmethylcyclohexane. Examples of suitable polyamine compounds include polyamine compounds having an alicyclic structure such as cyclohexane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, and 4,4'-diaminodicyclohexylmethane; polyamine compounds having an aromatic ring such as o-xylylenediamine, m-xylylenediamine (MXDA), and p-xylylenediamine (PXDA), phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone; polyamine compounds having a heterocyclic structure such as N-aminomethylpiperazine and N-aminoethylpiperazine; polyetherpolyamine compounds, and their Mannich-modified products, epoxy-modified products, Michael adducts, Michael addition polycondensates, styrene-modified products, and polyamide-modified products. These compounds can be used alone or in combination of two or more.

[0076] Among the above, from the viewpoint of obtaining a resin composition and a resin molded article having high heat resistance and high breaking strength, the epoxy resin used as component (C) is more preferably a two-component curing type epoxy resin composition in which the main component is tetraglycidyldiaminodiphenylmethane and the curing agent is diaminodiphenylsulfone. A cured product of a resin composition containing polyimide resin particles (A) and the epoxy resin composition as thermosetting resin (C) has excellent heat resistance and a strain energy release rate (G 1c ) is improved, and high breaking strength can be achieved. Strain energy release rate (G 1C ) is measured in accordance with ASTM D5045-99 for plane strain fracture toughness (K 1C ) and specifically, it can be determined by the method described in the Examples.

[0077] The content of the curing agent in the epoxy resin composition is an amount such that the ratio of the number of active amine hydrogens in the curing agent to the number of epoxy groups in the main agent (number of active amine hydrogens in the curing agent / number of epoxy groups in the main agent) is preferably 1 / 0.5 to 1 / 2, more preferably 1 / 0.6 to 1 / 1.8, and even more preferably 1 / 0.75 to 1 / 1.5.

[0078] Examples of the urethane resin used as component (C) include two-component curing urethane resin compositions containing a polyol compound such as polyester polyol or polyether polyol, and a polyisocyanate compound. Examples of the bismaleimide resin used as component (C) include two-component curing bismaleimide resin compositions containing a bismaleimide such as 4,4'-bis(maleimide)diphenylmethane and a cyanate compound such as bis(3,5-dimethyl-4-cyanatophenyl)methane.

[0079] (Content) The resin composition of the present invention may contain polyimide resin particles (A) and at least one resin selected from the group consisting of a thermoplastic resin (B) and a thermosetting resin (C), and the thermoplastic resin (B) and the thermosetting resin (C) may be used in combination. The mass ratio [(A) / {(B)+(C)}] of the polyimide resin particles (A) to the total amount of the thermoplastic resin (B) and the thermosetting resin (C) is preferably in the range of 1 / 99 to 99 / 1, more preferably 5 / 95 to 95 / 5, and even more preferably 5 / 95 to 90 / 10, from the viewpoint of improving various properties such as heat resistance and mechanical properties while maintaining the light weight inherent in the thermoplastic resin (B) and the thermosetting resin (C). From the viewpoint of obtaining a resin composition or a resin molded article in which polyimide resin particles (A) are dispersed in a matrix composed of a thermoplastic resin (B), a thermosetting resin (C), or a cured product thereof, the mass ratio [(A) / {(B)+(C)}] is more preferably in the range of 5 / 95 to 80 / 20, even more preferably 5 / 95 to 70 / 30, even more preferably 5 / 95 to 60 / 40, even more preferably 5 / 95 to 50 / 50, and even more preferably 5 / 95 to 40 / 60. When the resin composition of the present invention is a thermoplastic resin composition containing polyimide resin particles (A) and a thermoplastic resin (B), the mass ratio is preferably in the range of 5 / 95 to 60 / 40, more preferably 5 / 95 to 50 / 50, since this provides good strand extrudability from an extruder and allows easy production of pellets.

[0080] In order to obtain the effects of the present invention, the total content of the polyimide resin particles (A), the thermoplastic resin (B), and the thermosetting resin (C) in the resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, with the upper limit being 100% by mass.

[0081] <Additives> The resin composition of the present invention may contain additives such as fillers, matting agents, nucleating agents, plasticizers, antistatic agents, coloring inhibitors, antigelling agents, flame retardants, colorants, sliding property improvers, antioxidants, conductive agents, and resin modifiers, as needed. There are no particular restrictions on the content of the additives, but from the viewpoint of exhibiting the effects of the additives while maintaining the physical properties derived from components (A), (B), and (C), the content of the additives in the resin composition is usually 50% by mass or less, preferably 0.0001 to 30% by mass, more preferably 0.0001 to 15% by mass, even more preferably 0.001 to 10% by mass, and still more preferably 0.01 to 8% by mass.

[0082] [Method of producing resin composition] Although the method for producing the resin composition of the present invention is not particularly limited, from the viewpoint of incorporating the polyimide resin particles (A) used into the resin composition while maintaining their shape, it is preferable to produce the resin composition by mixing the polyimide resin particles (A) with the thermoplastic resin (B) or the thermosetting resin (C) without subjecting them to a thermal history above the melting point of the polyimide resin particles (A). As described above, "producing a resin composition without subjecting it to a thermal history above the melting point of the polyimide resin particles (A)" means that all production steps in the production of the resin composition of the present invention are carried out under temperature conditions below the melting point of the polyimide resin particles (A). Specifically, when the resin composition of the present invention is a thermoplastic resin composition containing polyimide resin particles (A) and a thermoplastic resin (B), it is preferable to knead the polyimide resin particles (A) and the thermoplastic resin (B) at a temperature below the melting point of the polyimide resin particles (A) in the production of the resin composition. For example, in an extruder, a resin composition containing the polyimide resin particles (A) and the thermoplastic resin (B) is kneaded at a temperature set below the melting point of the polyimide resin particles (A). When the extruder has multiple temperature settings, it is preferable that all of the temperature settings be below the melting point of the polyimide resin particles (A). Furthermore, it is preferable to adjust the resin temperature during the kneading process of the resin composition so that it does not exceed the melting point of the polyimide resin particles (A). The kneading temperature is set to a value lower than the melting point of component (A) (Tm) in order to maintain the shape of the component (A) used. A (℃), (Tm A -10) ° C or lower, (Tm A -20) ° C. or lower, and (Tm AIt is more preferable that the temperature is −30° C. or lower. When the thermoplastic resin (B) is an amorphous thermoplastic resin (B1), the kneading temperature is preferably a temperature equal to or higher than the glass transition temperature of the resin. B1 (°C), from the viewpoint of ease of extrusion, it is more preferable to use a temperature of (Tg B1 +5)°C or higher, more preferably (Tg B1 When the thermoplastic resin (B) is a crystalline thermoplastic resin (B2), the temperature is preferably equal to or higher than the melting point of the resin. B2 (°C), from the viewpoint of ease of extrusion, it is more preferable to use (Tm B2 +5)°C or higher, more preferably (Tm B2 +10)℃ or higher.

[0083] Preferably, the resin composition is kneaded under the above temperature conditions, and then the strands are extruded to produce pellets of the thermoplastic resin composition containing the polyimide resin particles (A) used while maintaining their shape. After producing the pellets, a drying step may be carried out if necessary, and the drying temperature in this case is also preferably a temperature below the melting point of the polyimide resin particles (A).

[0084] When the resin composition of the present invention is a thermosetting resin composition containing polyimide resin particles (A) and a thermosetting resin (C), the polyimide resin particles (A) and the thermosetting resin (C) may be mixed in the production of the resin composition at a temperature lower than the melting point of the polyimide resin particles (A). The mixing temperature is set to a temperature lower than the melting point of the component (A) Tm from the viewpoint of maintaining the shape of the component (A) used and suppressing decomposition of the thermosetting resin (C) before curing. A (℃), (Tm A -10) ° C or lower, (Tm A -20) ° C. or lower, and (Tm A -30) ° C. or lower, and (Tm A It is even more preferable that the temperature is equal to or lower than (Tm −50) ° C.A It is even more preferable that the temperature is equal to or lower than (Tm −100) ° C. A It is even more preferable that the mixing temperature is not higher than −120° C. The lower limit of the mixing temperature can be selected depending on the curing speed of the thermosetting resin composition, etc.

[0085] In the production of the resin composition of the present invention, in order to maintain the shape of the component (A) used, the melting point of the component (A) is set to Tm A (℃), all manufacturing processes are A It is more preferable to carry out the process under a temperature condition of −10)°C or lower, (Tm A It is more preferable to carry out the reaction under a temperature condition of (Tm −20)° C. or lower. A It is even more preferable to carry out the reaction under a temperature condition of -30°C or lower.

[0086] [Resin molding] The resin molded article of the present invention contains polyimide resin particles (A) having a volume average particle size D50 of 5 to 200 μm, which contain repeating units represented by the following formula (1) and repeating units represented by the following formula (2), wherein the content of the repeating units of formula (1) relative to the total of the repeating units of formula (1) and formula (2) is 20 to 70 mol %. The resin molded article also contains at least one resin selected from the group consisting of a thermoplastic resin (B) and a cured product of a thermosetting resin (C). [ka] (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 components (A), (B) and (C) and their preferred embodiments are the same as those described in the resin composition. The resin molded article of the present invention is preferably a resin molded article in which polyimide resin particles (A) are dispersed in a matrix composed of a cured product of a thermoplastic resin (B) or a thermosetting resin (C). This allows the polyimide resin particles (A) to act as a resin filler, and is thought to have the effect of improving various properties such as heat resistance and mechanical properties.

[0087] [Method of manufacturing resin molded body] In the production of the resin molded article of the present invention, from the viewpoint of incorporating the polyimide resin particles (A) into the resin molded article while maintaining their shape, it is preferable to produce the resin molded article without subjecting the polyimide resin particles (A) to a thermal history of at least the melting point thereof. From this viewpoint, the method for producing the resin molded article of the present invention preferably includes a step of molding a resin composition containing the polyimide resin particles (A) and at least one resin selected from the group consisting of a thermoplastic resin (B) and a thermosetting resin (C) at a temperature below the melting point of the polyimide resin particles (A).

[0088] The resin composition of the present invention described above can be used to produce the resin molded article. When a resin molded article is produced using a thermoplastic resin composition containing polyimide resin particles (A) and a thermoplastic resin (B), it is preferable to use pellets of the resin composition produced by the above-mentioned method. Before subjecting the pellets to molding, a step of drying the pellets may be carried out, if necessary. The drying temperature for the pellets is preferably a temperature below the melting point of the polyimide resin particles (A) from the viewpoint of incorporating the polyimide resin particles (A) into a resin molded product while maintaining their shape, and is more preferably 200°C or lower, even more preferably 150°C or lower, and even more preferably 120°C or lower from the viewpoint of preventing deterioration of the thermoplastic resin (B). The lower limit of the drying temperature is not particularly limited, but is preferably 40°C or higher, more preferably 60°C or higher, from the viewpoint of drying efficiency. The drying time for the pellets can be appropriately selected depending on the type of thermoplastic resin (B) used, the drying temperature, etc., but is preferably 0.5 to 10 hours, more preferably 2 to 8 hours.

[0089] When a thermoplastic resin composition containing polyimide resin particles (A) and a thermoplastic resin (B) is used as the resin composition, methods for molding the resin molded article include injection molding, extrusion molding, blow molding, heat press molding, vacuum molding, pressure molding, laser molding, ultrasonic heat molding, welding, welding, etc. Among these, injection molding is preferred because it allows molding without setting the molding temperature and the mold temperature during molding to high temperatures.

[0090] When a thermoplastic resin composition containing polyimide resin particles (A) and a thermoplastic resin (B) is used as the resin composition, the thermoplastic resin (B) is preferably at least one selected from the group consisting of the following (B1) and (B2): (B1) Amorphous thermoplastic resin having a glass transition temperature lower than the melting point of the polyimide resin particles (A) (B2) A crystalline thermoplastic resin having a melting point lower than the melting point of the polyimide resin particles (A) or a glass transition temperature lower than the glass transition temperature of the polyimide resin particles (A). The amorphous thermoplastic resin (B1) and the crystalline thermoplastic resin (B2) and preferred embodiments thereof are the same as those described in the resin composition.

[0091] When the thermoplastic resin (B) is an amorphous thermoplastic resin (B1), the method for producing a resin molded product preferably includes a step of extruding a resin composition containing the polyimide resin particles (A) and the amorphous thermoplastic resin (B1) at a temperature lower than the melting point of the polyimide resin particles (A) and equal to or higher than the glass transition temperature of the amorphous thermoplastic resin (B1), from the viewpoint of maintaining the shape of the polyimide resin particles (A) used. The temperature is set to be lower than the melting point of the component (A) Tm from the viewpoint of maintaining the shape of the component (A) used. A (℃), (Tm A -10) ° C. or lower, and (Tm A -20) ° C. or lower, and (Tm AThe lower limit of the temperature is not particularly limited as long as it is equal to or higher than the glass transition temperature of component (B1). B1 (°C), from the viewpoint of ease of extrusion, it is preferable to use a temperature of (Tg B1 +5)°C or higher, more preferably (Tg B1 +10)℃ or higher. In the production of resin molded articles, it is preferable that at least the set temperature during extrusion is within the above range, and when the set temperature is multi-staged, it is preferable that all set temperatures are within the above range. It is also more preferable to adjust the resin temperature during extrusion to be within the above range.

[0092] Furthermore, when the thermoplastic resin (B) is a crystalline thermoplastic resin (B2), the method for producing a resin molded product preferably includes a step of extruding a resin composition containing polyimide resin particles (A) and the crystalline thermoplastic resin (B2) at a temperature lower than the melting point of the polyimide resin particles (A) and higher than the melting point of the crystalline thermoplastic resin (B2), from the viewpoint of maintaining the shape of the polyimide resin particles (A) used. The temperature is set to be lower than the melting point of the component (A) Tm from the viewpoint of maintaining the shape of the component (A) used. A (℃), (Tm A -10) ° C. or lower, and (Tm A -20) ° C. or lower, and (Tm A The lower limit of the temperature is not particularly limited as long as it is a temperature equal to or higher than the melting point of component (B2). B2 (°C), from the viewpoint of ease of extrusion, it is preferable to use a temperature (Tm B2 +5)°C or higher, more preferably (Tm B2 +10)℃ or higher. As described above, in the production of resin molded products, it is preferable that at least the set temperature during extrusion is within the above range, and when the set temperature is multi-staged, it is preferable that all the set temperatures are within the above range. It is also more preferable to adjust the resin temperature during extrusion to be within the above range.

[0093] When a thermoplastic resin composition containing polyimide resin particles (A) and a thermoplastic resin (B) is used as the resin composition, the specific procedure for the method for producing the resin molded article of the present invention may be, for example, the following method. First, polyimide resin particles (A), thermoplastic resin (B), and, if necessary, various optional components are added and dry-blended, and then the mixture is introduced into an extruder, kneaded and extruded at a temperature below the melting point of the polyimide resin particles (A), preferably within the above-mentioned range, to produce pellets. Alternatively, thermoplastic resin (B) may be introduced into the extruder, melted at a temperature below the melting point of the polyimide resin particles (A), preferably within the above-mentioned range, and then polyimide resin particles (A) and, if necessary, various optional components are introduced therein, kneaded and extruded in the extruder, to produce the pellets. The pellets may be dried under the above-mentioned drying conditions as needed, and then introduced into various molding machines such as an injection molding machine and molded at a temperature below the melting point of the polyimide resin particles (A) to produce a resin molded product having a desired shape. After molding, if necessary, post-processing may be performed, such as by short-term ultrasonic heating, to melt and bond the interface between component (A) and component (B).

[0094] When a thermosetting resin composition containing polyimide resin particles (A) and a thermosetting resin (C) is used as the resin composition, the method for producing a resin molded article preferably involves curing and molding the resin composition at a temperature below the melting point of the polyimide resin particles (A), preferably at a temperature in the above range, from the viewpoint of maintaining the shape of the component (A) used. The temperature (curing temperature) is set to be lower than the melting point of the component (A) by Tm A (℃), (Tm A -10) ° C or lower, (Tm A -20) ° C. or lower, and (Tm A -30) ° C. or less, and (Tm A -50) ° C. or less, and (Tm AIt is even more preferable that the temperature is not higher than −100° C. The lower limit of the temperature is not particularly limited as long as it is a temperature at which the thermosetting resin composition can be cured.

[0095] <Application> The resin composition and resin molded article of the present invention have improved properties such as heat resistance and mechanical properties while maintaining the lightweight properties inherent to resin, and can be used in various molded products such as industrial intermediate products such as prepregs, resin binders, matrix resins for fiber-reinforced plastics (FRP), coating agents, laminating adhesives, and materials for 3D printers; sliding members, structural or engine members for aircraft, ships, or vehicles; cooking utensils, stationery, earphone diaphragms, air pillows, and fasteners.

[0096] When the resin composition of the present invention is used in a structural member for an aircraft, ship, or vehicle, from the viewpoint of improving all of the elastic modulus, strength, and toughness, it is preferable that the material constituting the structural member be a fiber-reinforced composite material containing the resin composition of the present invention or a cured product thereof and reinforcing fibers. Examples of reinforcing fibers used in fiber-reinforced composites include glass fibers, carbon fibers, boron fibers, and metal fibers, and one or more of these can be used. Among these, carbon fibers are preferred from the viewpoint of the strength and light weight of the resulting composite. That is, the fiber-reinforced composite is preferably a carbon fiber-reinforced composite (CFRP) containing the resin composition or a cured product thereof and carbon fibers.

[0097] The carbon fibers used in CFRP may be produced using rayon, polyacrylonitrile (PAN), or the like as raw materials, or may be produced by spinning pitch derived from petroleum, coal, or the like. Recycled carbon fiber scraps and recycled carbon fibers obtained by removing resin from CFRP can also be used. Carbon fibers can take various forms, such as monofilaments or multifilaments simply arranged in one direction or alternately crossing each other, fabrics such as knitted or woven fabrics, nonwoven fabrics, or mats. Among these, monofilaments, fabrics, nonwoven fabrics, and mats are preferred, with fabrics being more preferred.

[0098] The average fiber diameter of the carbon fibers is preferably 1 to 100 μm, more preferably 3 to 50 μm, and even more preferably 4 to 20 μm. When the average fiber diameter is within this range, processing is easy and the resulting CFRP has excellent elastic modulus and strength. The average fiber diameter can be measured by observation using a scanning electron microscope (SEM) or the like. 50 or more fibers are randomly selected and their lengths are measured, and the number-average average fiber diameter can be calculated.

[0099] The fineness of the carbon fiber is preferably 20 to 4,500 tex, more preferably 50 to 4,000 tex. When the fineness is within this range, impregnation with the resin composition is easy, and the resulting composite material has excellent elastic modulus and strength. The fineness can be determined by measuring the weight of long fibers of any length and converting it into the weight per 1,000 m. Carbon fibers with a filament count of about 500 to 60,000 are usually preferred.

[0100] The fiber-reinforced composite material can be produced by impregnating reinforcing fibers with the resin composition of the present invention in a conventional manner, and then molding the fibers into a desired shape. [Example]

[0101] The present invention will now be described in more detail with reference to examples, but the present invention is not limited thereto. In addition, various measurements and evaluations in each production example and example were carried out as follows.

[0102] <Infrared spectroscopy (IR measurement)> The IR measurement of the polyimide resin particles was carried out using a JIR-WINSPEC50 manufactured by JEOL Ltd.

[0103] <Logarithmic viscosity μ> The polyimide resin particles were dried at 190 to 200°C for 2 hours, and then 0.100 g of the polyimide resin was dissolved in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Chemical Co., Inc.) to prepare a polyimide resin solution for measurement. Measurement was carried out at 30°C using a Cannon-Fenske viscometer. Logarithmic viscosity μ was calculated using the following formula. μ=ln(ts / t0) / C t0: Time when concentrated sulfuric acid flows ts: Flow time of polyimide resin solution C: 0.5 g / dL

[0104] <Melting point, glass transition temperature, crystallization temperature, heat of crystallization> The melting point Tm and glass transition temperature Tg of the polyimide resin particles and thermoplastic resin described in the Production Examples, as well as the crystallization temperature Tc and crystallization heat value ΔHm of the polyimide resin particles described in the Production Examples, were measured using a differential scanning calorimeter (DSC-6220, manufactured by SII NanoTechnology Inc.). Under a nitrogen atmosphere, the polyimide resin particles or thermoplastic resin were subjected to the following thermal history conditions: first heating (heating rate: 10°C / min), then cooling (cooling rate: 20°C / min), and then second heating (heating rate: 10°C / min). The melting point Tm was determined by reading the peak top value of the endothermic peak observed during the second heating. The glass transition temperature Tg was determined by reading the value observed during the second heating. The crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling. The crystallization heat value ΔHm (mJ / mg) was calculated from the area of ​​the exothermic peak observed during cooling.

[0105] <Crystallization half time> The half-crystallization time of the polyimide resin particles was measured using a differential scanning calorimeter (DSC-6220, manufactured by SII NanoTechnology, Inc.). The polyimide resin was held at 420°C for 10 minutes in a nitrogen atmosphere until it was completely melted, and then rapidly cooled at a rate of 70°C / min. The time required from the appearance of the observed crystallization peak until it reached its peak top was calculated. In Table 1, half-crystallization times of 20 seconds or less are indicated as "<20."

[0106] <Weight average molecular weight> The weight average molecular weight (Mw) of the polyimide resin particles was measured using a gel permeation chromatography (GPC) measuring device "Shodex GPC-101" manufactured by Showa Denko K.K. under the following conditions. Column: Shodex HFIP-806M Mobile phase solvent: HFIP containing 2 mM sodium trifluoroacetate Column temperature: 40℃ Mobile phase flow rate: 1.0mL / min Sample concentration: approximately 0.1% by mass Detector: IR detector Injection amount: 100μm Calibration curve: Standard PMMA

[0107] <Volume average particle size (D50)> The D50 of the polyimide resin particles and the resin particles used in the comparative examples was determined by laser diffraction particle size distribution measurement. The measurement device used was a Malvern Laser Diffraction Light Scattering Particle Size Distribution Analyzer "LMS-2000e." The D50 measurement of the resin particles was carried out using water as the dispersion medium and under ultrasonic conditions to ensure that the resin particles were sufficiently dispersed. The measurement range was 0.02 to 2000 μm.

[0108] <True density (vapor phase method)> The true density of polyimide resin particles was measured by the gas phase method using a measuring device "VM-100" manufactured by Seishin Enterprise Co., Ltd. and helium gas as the gas, in accordance with the "Method for measuring density and specific gravity by the gas displacement method" specified in JIS Z8807:2012.

[0109] <True density (liquid phase method)> The true density of the polyimide resin particles was measured by the liquid phase method (pycnometer method) using an automatic wet true density measuring instrument "AUTO TRUE DENSER MAT-7000" manufactured by Seishin Enterprise Co., Ltd. as the measuring device and n-butyl alcohol as the liquid medium, and the true density was calculated using the following formula.

number

[0110] <Specific surface area> The specific surface area of ​​the polyimide resin particles was determined by measuring the nitrogen adsorption amount under the following conditions and using the BET method from the resulting adsorption isotherm (vertical axis: nitrogen adsorption amount, horizontal axis: relative pressure P / P0). The measurement sample was pretreated by heating at 180°C for 6 hours and degassing under vacuum. Measurement equipment: Quantachrome 4-unit specific surface area and pore distribution measurement equipment NOVA-TOUCH type Gas used: Nitrogen gas Refrigerant: Liquid nitrogen (temperature 77.35K) Measurement relative pressure: 5 x 10 -3 <P / P0<0.99 Isotherm data used to calculate the specific surface area: 0.05 <P / P0<0.3

[0111] <Total pore volume> The total pore volume of polyimide resin particles is calculated by the P / P ratio in the adsorption isotherm, assuming that the pores are filled with liquid nitrogen. 0,max The amount of nitrogen adsorbed was calculated from the amount of nitrogen adsorbed at the

[0112] <Average pore diameter> The average pore diameter of the polyimide resin particles was calculated using the following formula. Average pore diameter D ave =(4V total / S) V total : total pore volume S: Specific surface area (BET method)

[0113] <Strand condition> For the thermoplastic resin compositions of Examples 1 to 3, the state of the strands extruded from the extruder was visually observed and evaluated according to the following criteria. A: Good B: Strand extrusion is possible, but it is brittle and breaks easily. C: Strand extrusion not possible

[0114] <Specific gravity> For the thermoplastic resin (B) used alone in Examples 1 to 3 or the thermoplastic resin compositions obtained in Examples 1 to 3, molded bodies of 80 mm x 10 mm x 4 mm thick were prepared by the method described below, and the specific gravity at 23°C was determined using an electronic hydrometer ("MDS-300" manufactured by Alpha Mirage Co., Ltd.). In this example, the specific gravity of the polyimide resin particles (A) was the absolute value of the true density (liquid phase method) measured by the above-mentioned method. The specific gravity of the polyimide resin particles 1 obtained in Production Example 1 was 1.19.

[0115] The specific gravity of the pellets obtained by melt-kneading the polyimide resin particles 1 obtained in Production Example 1 at a temperature equal to or higher than the melting point thereof was measured by the following method. The polyimide resin particles 1 obtained in Production Example 1 were melt-kneaded using a Labo Plastomill (manufactured by Toyo Seiki Seisakusho, Ltd.) at a cylinder setting temperature of 350°C and a screw rotation speed of 70 rpm to extrude strands, which were then air-cooled and pelletized using a pelletizer (Hoshi Plastics Co., Ltd., "Fan Cutter FC-Mini-4 / N"). The resulting pellets were dried at 150°C for 12 hours, and then their true density (liquid phase method) was measured using the method described above, and this value was taken as the specific gravity. The specific gravity was 1.29.

[0116] <Specific gravity of component (A) in resin molded product> The specific gravity of the component (A) in the resin molded articles obtained in Examples 1 to 3 was calculated according to the following formula. [(specific gravity of resin molded body) - (specific gravity of component (B)) x (mass fraction of component (B)] / (mass fraction of component (A))

[0117] <Tensile strength, tensile modulus and tensile breaking strain> Using the thermoplastic resin (B) alone or the thermoplastic resin composition obtained in each example, 1A type test pieces as defined in JIS K7161-2:2014 were prepared by the method described below and used for measurements. Using a tensile testing machine ("Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd.), tensile tests were performed in accordance with JIS K7161-1:2014 and K7161-2:2014 at a temperature of 23°C, a grip distance of 50 mm, and a test speed of 20 mm / min to measure tensile strength, tensile modulus, and tensile strain at break.

[0118] <Flexural modulus> Using the thermoplastic resin (B) alone or the thermoplastic resin composition obtained in each example, molded articles of 80 mm × 10 mm × 4 mm thickness as specified in ISO 316 were prepared by the method described below and used for measurement. A bending test was performed using a Bendograph (manufactured by Toyo Seiki Seisakusho, Ltd.) at a temperature of 23°C and a test speed of 2 mm / min in accordance with ISO 178 to measure the flexural modulus.

[0119] <Heat distortion temperature (HDT)> Using the thermoplastic resin (B) used in each example alone or the thermoplastic resin composition obtained in each example, a resin molded body of 80 mm x 10 mm x 4 mm thick was produced by the method described below and used for the measurement. The measurement was performed in flatwise in accordance with JIS K7191-1,2:2015. Specifically, the heat distortion temperature was measured using the HDT testing device "Auto-HDT3D-2" (manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the conditions of a support distance of 64 mm, a load of 1.80 MPa, and a heating rate of 120°C / hour.

[0120] <Weight loss temperature> The thermoplastic resin (B) used in each example alone, or pellets of the thermoplastic resin composition or a cured product of the thermosetting resin composition obtained in each example was used for the measurement. A thermogravimetric analyzer (Seiko Instruments Inc., "TG / DTA6200") was used for the measurements. Approximately 10 mg of sample was collected and heated from room temperature to 450°C under conditions of a nitrogen gas flow rate of 100 mL / min and a heating rate of 10°C / min. The temperature at which the weight decreased by 1% by mass, relative to 100% by mass of the sample weight at 100°C, was defined as the 1% weight loss temperature, the temperature at which the weight decreased by 5% by mass, and the temperature at which the weight decreased by 10% by mass, respectively.

[0121] <Dynamic friction coefficient> Using the thermoplastic resin (B) used in each example alone or the thermoplastic resin composition obtained in each example, a resin molded body was produced by the method described below, and the molded body was cut to 30 mm x 30 mm x 3 mm thick and used for measurement. The measurement was performed using a friction and wear tester (MODEL EMF-III-F) manufactured by A&D Co., Ltd. In accordance with JIS K7218 (1986)-A method, the mating material was a S45C ring (contact area 2 cm) at 23°C and 50% RH. 2 ) and a sliding wear test was carried out under the conditions of initial load: 50 N, test speed: 0.5 m / s, and sliding distance: 3 km, and the dynamic friction coefficient was measured.

[0122] <Plane strain fracture toughness (K 1C ), Poisson's ratio, strain energy release rate (G 1C )> The plane strain fracture toughness K 1C The Poisson's ratio and tensile modulus were measured by the following "tensile test". (Bending fracture toughness test) Using the cured products of the thermosetting resin compositions listed in Table 7, resin molded bodies measuring 60 mm x 12 mm x 6 mm thick were produced using the method described below. Test pieces were notched with a 30°t1.0 equiangular milling cutter and then pre-cracked to obtain test pieces, which were then used for measurement. The measurements were performed using an Instron universal testing machine (Model 5966). In accordance with ASTM D5045-99, bending fracture toughness tests were performed at a test speed of 1 mm / min and a support distance of 48 mm (initial value) in a 23°C environment (n=5). (Tensile test) Using the cured products of the thermosetting resin compositions listed in Table 7, resin molded bodies were produced by the methods described below, and test pieces obtained by cutting into 150 mm × 12 mm × 3 mm thick were used for measurement. Measurements were performed using an Instron universal testing machine (Model 5966). Tensile tests were performed in accordance with JIS K7161-2:2014 at a temperature of 23°C, a chuck distance of 115 mm, and a test speed of 1 mm / min (n=3). Strain measurements were performed using a uniaxial strain gauge (Kyowa Electric Industrial Co., Ltd., "KFGS-5-120-C1-23") attached to the center of one side of the test piece.

[0123] Next, the stress diffusion coefficient K Q asked for.

number

[0124] Here, if the following formula (1) is satisfied, P Q Using K Q asked for. P max / P Q <1.1 (1) P max : Maximum load In addition, if the following condition (2) is met, K Q =K 1CIt was decided. B, a, Wa>2.5(K Q / σ y ) 2 ···(2) σ y : Bending offset 0.2% stress (MPa)

[0125] K obtained by the above method 1C , Poisson's ratio, and tensile modulus of elasticity, the strain energy release rate (G 1C ) was calculated.

number

[0126] <Glass transition temperature (Tg)> The Tg of the cured product of the thermosetting resin composition shown in Table 7 was determined by dynamic mechanical analysis (DMA). Using each of the thermosetting resin compositions shown in Table 7, a resin molded body measuring 50 mm x 10 mm x 3 mm thick was produced by the method described below and used for the measurement. The measurements were performed using a dynamic viscoelasticity measuring device (Hitachi High-Tech Science Corporation, "EXSTAR DMS6100"). In accordance with JIS K7244:1998, the storage modulus E', loss modulus E'', and tan δ were measured in a nitrogen gas flow (300 mL / min) at a temperature of room temperature to 300°C, a heating rate of 4.0°C / min, a frequency of 1 Hz, and a bending mode. The peak top temperature (°C) on the high-temperature side of tan δ was taken as Tg and is shown in Table 7.

[0127] <Film tensile strength, tensile modulus, maximum elongation, elongation at break> Using the thermoplastic resin compositions having the compositions shown in Table 8, films were produced by the method described below, and cut into a width of 10 mm for use in the measurements. Using a tensile testing machine (Strograph VG-1E manufactured by Toyo Seiki Co., Ltd.), tensile tests were performed in accordance with JIS K7161-1:2014 and K7161-2:2014 at a temperature of 23°C, a gripping distance of 50 mm, and a test speed of 50 mm / min, and the tensile strength, tensile modulus, maximum elongation, and elongation at break were measured.

[0128] Production Example 1 (Production of Polyimide Resin Particles 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, 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 particles and dehydration associated with imidization were observed between 120 and 140°C. After holding at 190°C for 30 minutes, the solution was allowed to cool to room temperature and then filtered. The obtained polyimide resin particles were 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 polyimide resin particles 1. The IR spectrum of polyimide resin particle 1 was measured, and ν(C=O) 1768, 1697 (cm -1 The characteristic absorption of the imide ring was observed. The inherent viscosity was 1.30 dL / g, Tm was 323°C, Tg was 184°C, Tc was 266°C, the exotherm of crystallization was 21.0 mJ / mg, the half-crystallization time was less than 20 seconds, and Mw was 55,000.

[0129] The composition of the polyimide resin particles 1 obtained in Production Example 1 is shown in Table 1. The mole percentages of the tetracarboxylic acid component and the diamine component in Table 1 are values ​​calculated from the amounts of each component charged when the polyimide resin particles were produced. The polyimide resin particles 1 had a D50 of 17 μm and a specific gravity of 1.19, and were porous. The true density, specific surface area, total pore volume, and average pore diameter of the polyimide resin particles 1 are also shown in Table 1.

[0130] Production Example 2 (Production of Polyimide Resin Particles 2) Polyimide resin particles 2 were produced in the same manner as in Production Example 1, except that n-octylamine, the end-capping agent, was not used, and analyzed by the methods described above. The composition and analysis results of polyimide resin particles 2 are shown in Table 1.

[0131] [Table 1]

[0132] The abbreviations in Table 1 are as follows: PMDA; Pyromellitic dianhydride 1,3-BAC; 1,3-bis(aminomethyl)cyclohexane OMDA; 1,8-octamethylenediamine n-OcA: n-octylamine

[0133] Production Example 3 (Production of Modified Polyethylene Terephthalate Resin 1) A mixture of 6449.5 g (33.2 mol) of dimethyl terephthalate (DMT), 2747.1 g (44.2 mol) of ethylene glycol (EG), 4727.4 g (15.5 mol) of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane (SPG), and 0.03 mol of manganese acetate tetrahydrate per 100 mol of dimethyl terephthalate was heated to 200 °C under a nitrogen atmosphere to carry out a transesterification reaction. After the amount of methanol distilled reached 90% or more of the theoretical amount, 0.02 mol of antimony(III) oxide and 0.05 mol of triphenyl phosphate were added to 100 mol of dimethyl terephthalate. The temperature and pressure were gradually increased, and polymerization was finally carried out at 280 °C and 0.1 kPa or less. The reaction was terminated when an appropriate melt viscosity was reached, yielding a polyester containing 44 mol % SPG residues, 56 mol % EG residues in the diol component, and 100 mol % terephthalic acid residues in the dicarboxylic acid component.

[0134] Example 1 (Preparation and Evaluation of Thermoplastic Resin Composition and Resin Molded Article) The polyimide resin particles 1 obtained in Production Example 1 and pellets of polypropylene (PP) resin (a crystalline thermoplastic resin (B2-1)) (Novatec FY6, manufactured by Japan Polypropylene Corporation, melting point 150-160°C, glass transition temperature 0°C) were used in the proportions shown in Table 2. PP resin pellets were introduced into a co-rotating twin-screw extruder (HK-25D, manufactured by Parker Corporation, screw diameter D = 25 mmΦ, L / D = 41 (L: screw length)) through a hopper at the inlet side. Polyimide resin particles 1 were introduced into the extruder through a side feeder. The extruder was mixed at a cylinder temperature of 200°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The resin temperature, torque, resin pressure, and strand condition were monitored. The resin temperature was measured at the extruder outlet. The strand extruded from the extruder was cooled with water, then pelletized using a pelletizer (Hoshi Plastics Co., Ltd., "Fan Cutter FC-Mini-4 / N") and used for injection molding. Using an injection molding machine (FANUC Corporation's "ROBOSHOT α-S30iA"), injection molding was performed under conditions of a cylinder setting temperature of 200°C, a mold temperature of 50°C, and an injection speed of 62.5 mm / s to produce resin molded bodies of the specified shape to be used for various evaluations. The pellets and resin molded articles obtained were subjected to various evaluations according to the methods described above. The results are shown in Table 2.

[0135] Examples 2 and 3, Comparative Example 1 Pellets and resin molded products were produced in the same manner as in Example 1, except that the formulation of the resin composition, the strand extrusion conditions, and the molding conditions were changed as shown in Table 2, and various evaluations were carried out by the same methods as described above. The results are shown in Table 2.

[0136] [Table 2]

[0137] From Table 2, the following can be seen: The resin moldings of Examples 1 to 3, which contain polyimide resin particles 1 as component (A) and PP resin as crystalline thermoplastic resin (B2-1), had improved tensile modulus, flexural modulus, HDT, and 1% weight loss temperature compared to the resin molding of Comparative Example 1, which consists of only PP resin. In the resin molded articles of Examples 1 to 3, the specific gravity of component (A) in the molded articles was 1.19 to 1.22. This specific gravity was lower than the specific gravity (1.29) of pellets obtained by melt-kneading polyimide resin particles 1, and was the same as or slightly higher than the specific gravity (1.19) of polyimide resin particles 1 blended in the resin composition. This suggests that component (A) did not melt during the production process of the resin compositions and resin molded articles of Examples 1 to 3, and was contained in the resin compositions and resin molded articles while maintaining the shape of the polyimide resin particles 1 used.

[0138] The resin composition (pellets) obtained in Example 1 was cut using a microtome (ULTRACUT E manufactured by REICHERT-JUNG LIMITED), smoothed, and then stained with a ruthenium-based stain. The cut surface was observed using a field emission scanning electron microscope (ZEISS GeminiSEM500) at an accelerating voltage of 1.00 kV and a magnification of 100x (Figure 1). Figure 1 shows that in the resin composition obtained in Example 1, polyimide resin particles 1 are dispersed in a matrix made of PP resin.

[0139] Furthermore, the extrudability of strands was confirmed in the production of the resin compositions (pellets) of Examples 1 to 3. As shown in Table 2, strand extrusion was possible for all of the resin compositions of Examples 1 to 3, but increases in resin temperature, torque, and resin pressure were observed in Example 3 compared to Examples 1 and 2, and the resulting strands were also brittle. Therefore, it can be said that the resin compositions of Examples 1 and 2 have better strand extrudability.

[0140] Example 4 (Preparation and Evaluation of Thermoplastic Resin Composition and Resin Molded Article) The polyimide resin particles 1 obtained in Production Example 1 and polycarbonate (PC) resin (Iupilon S2000, manufactured by Mitsubishi Engineering-Plastics Corporation, glass transition temperature 145-150°C), which is an amorphous thermoplastic resin (B1-1), were used in the proportions shown in Table 3. The PC resin was dried for 5 hours in a dryer at 120°C, and then introduced into a co-rotating twin-screw kneading extruder (HK-25D, manufactured by Parker Corporation) through a hopper on the inlet side. The polyimide resin particles 1 were introduced into the extruder through a side feeder, and the mixture was kneaded under conditions of a cylinder temperature setting of 275°C, a feed rate of 6 kg / h, and a screw rotation speed of 150 rpm, and a strand was extruded. The strand extruded from the extruder was air-cooled, then pelletized using a pelletizer (Hoshi Plastics Co., Ltd., "Fan Cutter FC-Mini-4 / N") and used for injection molding. The obtained pellets were dried in a dryer at 120°C for 4 hours, and then injection-molded using an injection molding machine (FANUC Corporation's "ROBOSHOT α-S30iA") under conditions of a cylinder setting temperature of 270°C, a mold temperature of 100°C, and an injection speed of 62.5 mm / s to produce resin molded bodies of a specified shape to be used for various evaluations. The obtained pellets and resin molded product were subjected to HDT measurement by the above-mentioned method. The results are shown in Table 3.

[0141] Comparative Example 2 A polycarbonate resin, which is the amorphous thermoplastic resin (B1-1), was used alone and dried in a dryer at 120° C. for 4 hours, and then a resin molded body was produced in the same manner as in Example 4. The HDT of the resulting resin molded article was measured by the method described above. The results are shown in Table 3.

[0142] Example 5 (Preparation and Evaluation of Thermoplastic Resin Composition and Resin Molded Article) The polyimide resin particles 1 obtained in Production Example 1 and polyphenylene sulfide (PPS) resin (Toray Industries, Inc., "TORELINA A900," melting point 278°C, glass transition temperature 90°C), which is a crystalline thermoplastic resin (B2-2), were used in the proportions shown in Table 3. The PPS resin was introduced into a co-rotating twin-screw kneading extruder (Parker Corporation, "HK-25D") through a hopper on the inlet side, and the polyimide resin particles 1 were introduced into the extruder through a side feeder. The mixture was kneaded under conditions of a cylinder temperature setting of 290°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The strand extruded from the extruder was cooled with water, then pelletized using a pelletizer (Hoshi Plastics Co., Ltd., "Fan Cutter FC-Mini-4 / N") and used for injection molding. The obtained pellets were dried in a dryer at 130°C for 3 hours, and then injection-molded using an injection molding machine (FANUC Corporation's "ROBOSHOT α-S30iA") under conditions of a cylinder setting temperature of 310°C, a mold temperature of 150°C, and an injection speed of 62.5 mm / s to produce resin molded bodies of the specified shape to be used for various evaluations. The HDT of the resulting resin molded article was measured by the method described above. The results are shown in Table 3.

[0143] Comparative Example 3 A PPS resin, which is the crystalline thermoplastic resin (B2-2), was used alone and dried in a dryer at 130° C. for 3 hours, and then a resin molded body was produced in the same manner as in Example 5. The HDT of the resulting resin molded article was measured by the method described above. The results are shown in Table 3.

[0144] [Table 3]

[0145] Example 6 (Production and Evaluation of Thermoplastic Resin Composition and Resin Molded Article) The polyimide resin particles 1 obtained in Production Example 1 and polyamide resin PA6 (UBE Nylon 1030B manufactured by Ube Industries, Ltd., melting point 215-225°C, glass transition temperature 50°C), which is a crystalline thermoplastic resin (B2-3), were used in the proportions shown in Table 4. PA6 was introduced into a co-rotating twin-screw kneading extruder (HK-25D manufactured by Parker Corporation) through a hopper at the base, and polyimide resin particles 1 were introduced into the extruder through a side feeder. The mixture was kneaded under conditions of a cylinder temperature setting of 260°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The strand extruded from the extruder was cooled with water, then pelletized using a pelletizer (Hoshi Plastics Co., Ltd., "Fan Cutter FC-Mini-4 / N") and used for injection molding. The resulting pellets were dried in a dryer at 80°C for 6 hours and then injection-molded using an injection molding machine (FANUC Corporation's "ROBOSHOT α-S30iA") under conditions of a cylinder temperature of 250°C, a mold temperature of 80°C, and an injection speed of 62.5 mm / s. The resulting injection-molded product was annealed in a dryer at 120°C for 1 hour to produce resin molded products of the specified shape for use in various evaluations. The obtained resin molded article was subjected to HDT measurement and tensile testing by the above-mentioned methods. The results are shown in Table 4.

[0146] Example 7 A resin molded article was produced in the same manner as in Example 6, except that the blending amounts (parts by mass) of polyimide resin particles 1 and polyamide resin PA6 were changed to the amounts shown in Table 4. The obtained resin molded article was subjected to HDT measurement and tensile testing by the above-mentioned methods. The results are shown in Table 4.

[0147] Comparative Example 4 Polyamide resin PA6, which is a crystalline thermoplastic resin (B2-3), was used alone and dried in a dryer at 80° C. for 6 hours. A resin molded body was then produced in the same manner as in Example 6. The obtained resin molded article was subjected to HDT measurement and tensile testing by the above-mentioned methods. The results are shown in Table 4.

[0148] [Table 4]

[0149] As can be seen from Table 4, the resin moldings of Examples 6 and 7, which contain polyimide resin particles 1 and polyamide resin PA6, showed improved HDT and a significant improvement in tensile break strain compared to the resin molding of Comparative Example 4, which consists only of PA6.

[0150] Example 8 (Production and Evaluation of Thermoplastic Resin Composition and Resin Molded Article) The polyimide resin particles 1 obtained in Production Example 1 and polyethylene terephthalate (PET) resin ("RT553C" manufactured by Mitsubishi Chemical Corporation, melting point 250°C, glass transition temperature 81°C), which is a crystalline thermoplastic resin (B2-4), were used in the proportions shown in Table 5. The PET resin was introduced into a co-rotating twin-screw kneading extruder ("HK-25D" manufactured by Parker Corporation) through a hopper at the base, and the polyimide resin particles 1 were introduced into the extruder through a side feeder. The mixture was kneaded under conditions of a cylinder temperature setting of 280°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The strand extruded from the extruder was cooled with water, then pelletized using a pelletizer (Hoshi Plastics Co., Ltd., "Fan Cutter FC-Mini-4 / N") and used for injection molding. The obtained pellets were dried in a dryer at 80°C for 6 hours, and then injection-molded using an injection molding machine (FANUC Corporation's "ROBOSHOT α-S30iA") under conditions of a cylinder setting temperature of 250°C, a mold temperature of 80°C, and an injection speed of 62.5 mm / s to produce resin molded bodies of the specified shape to be used for various evaluations. The obtained resin molded article was subjected to various evaluations using the methods described above. The results are shown in Table 5.

[0151] Comparative Example 5 PET resin, which is the crystalline thermoplastic resin (B2-4), was used alone and dried in a dryer at 130° C. for 3 hours, and then a resin molded body was produced in the same manner as in Example 8. The obtained resin molded article was subjected to various evaluations using the methods described above. The results are shown in Table 5.

[0152] Example 9 (Production and Evaluation of Thermoplastic Resin Composition and Resin Molded Article) Polyimide resin particles 1 obtained in Production Example 1 and modified polyethylene terephthalate (PET) resin 1 (melting point 220-230°C, glass transition temperature 110°C), which is the crystalline thermoplastic resin (B2-5) obtained in Production Example 3, were used in the proportions shown in Table 5. PET resin was introduced into a co-rotating twin-screw kneading extruder ("HK-25D" manufactured by Parker Corporation) through a hopper at the base, and polyimide resin particles 1 were introduced into the extruder through a side feeder. The mixture was kneaded under conditions of a cylinder temperature setting of 265°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The strand extruded from the extruder was cooled with water, then pelletized using a pelletizer (Hoshi Plastics Co., Ltd., "Fan Cutter FC-Mini-4 / N") and used for injection molding. The obtained pellets were dried in a dryer at 80°C for 6 hours, and then injection-molded using an injection molding machine (FANUC Corporation's "ROBOSHOT α-S30iA") under conditions of a cylinder setting temperature of 250°C, a mold temperature of 80°C, and an injection speed of 62.5 mm / s to produce resin molded bodies of the specified shape to be used for various evaluations. The obtained resin molded article was subjected to various evaluations using the methods described above. The results are shown in Table 5.

[0153] Comparative Example 6 PET resin, which is the crystalline thermoplastic resin (B2-5), was used alone and dried in a dryer at 130° C. for 3 hours, and then a resin molded body was produced in the same manner as in Example 9. The obtained resin molded article was subjected to various evaluations using the methods described above. The results are shown in Table 5.

[0154] [Table 5]

[0155] As can be seen from Table 5, the resin moldings of Examples 8 and 9, which contain polyimide resin particles 1 and PET resin or modified PET resin 1, showed improved HDT, flexural strength, and flexural modulus compared to the resin moldings of Comparative Examples 5 and 6, which consisted only of PET resin or modified PET resin 1.

[0156] Example 10 (Preparation and Evaluation of Thermosetting Resin Composition and Resin Molded Product) Using the two-component curing epoxy resin composition (C-1) as the thermosetting resin (C), a thermosetting resin composition and a cured product were prepared by the following method and evaluated. A 100cc disposable cup was charged with 18.6g of bisphenol A liquid epoxy resin ("jER828" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 186g / eq), a base epoxy group-containing compound, preheated to 40°C. 9.5g of polyimide resin particles 1 obtained in Preparation Example 1 was then added, followed by 3.55g of the curing agent 1,3-bis(aminomethyl)cyclohexane ("1,3-BAC" manufactured by Mitsubishi Gas Chemical Co., Inc.). The mixture was mixed for 1 minute at 200 rpm / min using a wooden spatula to prepare a thermosetting resin composition containing polyimide resin particles 1 and a two-component curing epoxy resin composition (C-1) consisting of the base and curing agent. In the two-component curing epoxy resin composition (C-1), the molar ratio of the number of epoxy groups in the base to the number of active amine hydrogens in the curing agent was 1 / 1. The resulting thermosetting resin composition was cured by placing it in a hot air oven at 80°C for 1 hour, and the 5% weight loss temperature and 10% weight loss temperature of the cured product were measured by the above-mentioned method. The results are shown in Table 6.

[0157] Example 11 A thermosetting resin composition and a cured product thereof were prepared in the same manner as in Example 10, except that the amount of polyimide resin particles 1 added was changed to 22.1 g, and the 5% weight loss temperature and 10% weight loss temperature of the cured product were measured by the same method as in Example 10. The results are shown in Table 6.

[0158] [Table 6]

[0159] Example 12 (Preparation and Evaluation of Thermosetting Resin Composition and Resin Molded Product) Using the two-component curing epoxy resin composition (C-2) as the thermosetting resin (C), a thermosetting resin composition and a cured product were prepared by the following method and evaluated. The base epoxy group-containing compound, tetraglycidyldiaminodiphenylmethane (TGDDM) (Sumitomo Chemical Co., Ltd., "Sumiepoxy ELM-434"), was weighed into a 500 mL separable flask and melted by heating to 130 °C in an oil bath. Next, polyimide resin particles 1, previously dried at 150 °C for 1 hour, were added in the amount shown in Table 7, and the mixture was stirred for 3 hours while continuing to heat. After stirring, the mixture was cooled to 110 °C, transferred to a disc cup, and weighed. The curing agent, 4,4'-diaminodiphenyl sulfone (DDS), was added at an equivalent ratio of 1 / 1.43 (the ratio of the number of active amine hydrogens in the curing agent to the number of epoxy groups in the base agent). The mixture was then stirred and mixed in an oven at 110 °C to prepare an epoxy resin composition. The obtained epoxy resin composition was degassed under reduced pressure and poured into a casting mold of a predetermined shape that had been preheated to 110°C. The temperature was increased to 150°C at a rate of 2°C / min, and after heating for 2 hours, the temperature was increased to 180°C and further heated for 2 hours to cure, thereby obtaining test pieces of the desired shape. The test piece dimensions are as follows: For bending fracture toughness testing: 125mm x 115mm x 6mm For dynamic viscoelasticity and Poisson's ratio measurements: 220mm x 100mm x 3mm The obtained test specimen was used to measure the plane strain fracture toughness (K 1C ), strain energy release rate (G 1C The results are shown in Table 7.

[0160] Examples 13 to 15, Comparative Examples 7 to 9 Epoxy resin compositions and cured products were prepared and evaluated in the same manner as in Example 12, except that the type and amount of resin particles used and the drying conditions were changed as shown in Table 7. The results are shown in Table 7.

[0161] [Table 7]

[0162] The ingredients listed in Table 7 are as follows: (A1) Polyimide resin particles 1: Polyimide resin particles obtained in Production Example 1 (A2) Polyimide resin particles 2: Polyimide resin particles obtained in Production Example 2 (without end-capping) (a1) Polyethersulfone resin particles: "Sumikaexcel 4800P" manufactured by Sumitomo Chemical Co., Ltd., D50 = 560 μm (a2) Polyether ether ketone resin particles: "330UPF" manufactured by Jilin Joint Polymer Co., Ltd., D50 = 14 μm (C-2) Two-component curing epoxy resin composition: An epoxy resin composition obtained by mixing tetraglycidyldiaminodiphenylmethane (TGDDM), an epoxy group-containing compound as the base compound, and 4,4'-diaminodiphenylsulfone (DDS), a curing agent, in an equivalent ratio of 1 / 1.43, where the ratio of the number of active amine hydrogens in the curing agent to the number of epoxy groups in the base compound (number of active amine hydrogens in the curing agent / number of epoxy groups in the base compound) is 1 / 1.43.

[0163] Table 7 shows that the cured products of the thermosetting resin compositions of Examples 12 to 15 maintained heat resistance while improving the plane strain fracture toughness and strain energy release rate compared to the cured products of the comparative examples. Furthermore, by using non-terminal-capped polyimide resin particles 2 as the polyimide resin particles, the plane strain fracture toughness and strain energy release rate were further improved.

[0164] Reference Examples 1 and 2 (Preparation of Thermoplastic Resin Films) The polyimide resin particles 1 obtained in Production Example 1 and pellets of polypropylene (PP) resin (Novatec FY6 manufactured by Japan Polypropylene Corporation), which is a crystalline thermoplastic resin (B2-1), were used in the proportions shown in Table 8. The PP resin was previously dried with hot air at 80°C for at least 6 hours before use. PP resin pellets were introduced into a co-rotating twin-screw extruder ("HK-25D" manufactured by Parker Corporation, screw diameter D = 25 mmΦ, L / D = 41 (L: screw length)) through a hopper at the inlet side, and polyimide resin particles 1 were introduced into the extruder through a side feeder. The mixture was mixed at a cylinder temperature of 200°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The strand extruded from the extruder was water-cooled and then pelletized using a pelletizer ("Fan Cutter FC-Mini-4 / N" manufactured by Hoshi Plastics Co., Ltd.). The pellets were then extruded to produce a monolayer film. The extrusion molding was carried out using a Labopla T-die extrusion molding apparatus (manufactured by Toyo Seiki Seisakusho, Ltd.) equipped with an extruder, a T-die, a cooling roll, and a take-up machine under the following conditions. Extruder Screw diameter D: 20mmΦ, L / D=25 (L: screw length) Screw rotation speed: 14 rpm Setting temperature: 190~210℃ T-die Die width: 150mm, lip width: 0.4mm Set temperature: 205℃ Cooling roll Set temperature: 50℃ Pick-up machine Take-up speed: 1.0 m / min The obtained film was evaluated by the above-mentioned methods, and the results are shown in Table 8.

[0165] Reference Examples 3 to 7 (Preparation of Thermoplastic Resin Films) The polyimide resin particles 1 obtained in Production Example 1 and polyamide resin PA6 ("UBE Nylon 1030B" manufactured by Ube Industries, Ltd.), which is a crystalline thermoplastic resin (B2-3), were used in the proportions shown in Table 8. PA6 was pre-dried at 80°C for 10 hours or more before use. PA6 was introduced into a co-rotating twin-screw kneading extruder ("HK-25D" manufactured by Parker Corporation) through a hopper at the base, and polyimide resin particles 1 were introduced into the extruder through a side feeder. The mixture was kneaded at a cylinder temperature of 260°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The strand extruded from the extruder was cooled with water and then pelletized using a pelletizer ("Fan Cutter FC-Mini-4 / N" manufactured by Hoshi Plastics Co., Ltd.). A monolayer film was produced using the pellets by extrusion molding. The extrusion molding was carried out using a Labopla T-die extrusion molding apparatus (manufactured by Toyo Seiki Seisakusho, Ltd.) equipped with an extruder, a T-die, a cooling roll, and a take-up machine under the following conditions. Extruder Screw diameter D: 20mmΦ, L / D=25 Screw rotation speed: 16 rpm Setting temperature: 240~265℃ T-die Die width: 150mm, lip width: 0.4mm Set temperature: 260℃ Cooling roll Set temperature: 48℃ Pick-up machine Take-up speed: 1.0 m / min The obtained film was evaluated by the above-mentioned methods, and the results are shown in Table 8.

[0166] Reference Examples 8 to 9 (Preparation of Thermoplastic Resin Films) The polyimide resin particles 1 obtained in Production Example 1 and the polyamide resin MXD6 (polymetaxylylene adipamide, "S6011" manufactured by Mitsubishi Gas Chemical Company, Inc., melting point 237°C, glass transition temperature 85°C), which is a crystalline thermoplastic resin (B2-6), were used in the proportions shown in Table 8. MXD6 was pre-dried at 80°C for 10 hours or more before use. MXD6 was introduced into a co-rotating twin-screw kneading extruder ("HK-25D" manufactured by Parker Corporation) through a hopper at the base, and polyimide resin particles 1 were introduced into the extruder through a side feeder. The mixture was kneaded at a cylinder temperature of 260°C, a feed rate of 6 kg / h, and a screw rotation speed of 200 rpm, and a strand was extruded. The strand extruded from the extruder was water-cooled and then pelletized using a pelletizer ("Fan Cutter FC-Mini-4 / N" manufactured by Hoshi Plastics Co., Ltd.). A monolayer film was produced using the pellets by extrusion molding. The extrusion molding was carried out using a Labopla T-die extrusion molding apparatus (manufactured by Toyo Seiki Seisakusho, Ltd.) equipped with an extruder, a T-die, a cooling roll, and a take-up machine under the following conditions. Extruder Screw diameter D: 20mmΦ, L / D=25 Screw rotation speed: 40 rpm Setting temperature: 240~260℃ T-die Die width: 150mm, lip width: 0.4mm Set temperature: 260℃ Cooling roll Set temperature: 75℃ Pick-up machine Take-up speed: 1.8 m / min (Reference Example 8), 1.2 m / min (Reference Example 9) The obtained film was evaluated by the above-mentioned methods, and the results are shown in Table 8.

[0167] [Table 8]

[0168] The ingredients listed in Table 8 are as follows: (A1) Polyimide resin particles 1: Polyimide resin particles obtained in Production Example 1 (B2-1) Polypropylene resin: "Novatec FY6" manufactured by Japan Polypropylene Corporation (B2-3) Polyamide resin PA6: UBE Nylon 1030B manufactured by Ube Industries, Ltd. (B2-6) Polyamide resin MXD6: polymetaxylylene adipamide, "S6011" manufactured by Mitsubishi Gas Chemical Company, Inc. [Industrial Applicability]

[0169] According to the present invention, it is possible to provide a resin composition, a resin molded product, and a method for producing the same, which are thermoplastic resins such as low-melting-point crystalline thermoplastic resins and low-glass-transition-temperature amorphous thermoplastic resins, or thermosetting resins, in which various properties such as heat resistance and mechanical properties are improved while maintaining the light weight inherent to the resin.

Claims

1. A resin composition comprising polyimide resin particles (A) having a volume average particle size D50 of 5 to 200 μm, which contain repeating structural units represented by the following formula (1) and repeating structural units represented by the following formula (2), wherein the content of the repeating structural units of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is 20 to 70 mol %; and a thermoplastic resin (B) other than (A), or a thermoplastic resin (B) other than (A) and a thermosetting resin (C), the resin composition contains the polyimide resin particles (A) in a particle state, the polyimide resin constituting the polyimide resin particles (A) is a crystalline thermoplastic polyimide resin, A resin composition, wherein the mass ratio [(A) / {(B)+(C)}] of the polyimide resin particles (A) to the total amount of the thermoplastic resin (B) and the thermosetting resin (C) is in the range of 5 / 95 to 80 / 20. 【Chemical 1】 (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. 2. The resin composition according to claim 1, wherein the polyimide resin particles (A) are porous and have an average pore diameter of 5 to 85 nm.

3. 3. The resin composition according to claim 1, wherein the mass ratio [(A) / {(B)+(C)}] of the polyimide resin particles (A) to the total amount of the thermoplastic resin (B) and the thermosetting resin (C) is in the range of 15 / 85 to 80 / 20.

4. The resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin (B) is at least one selected from the group consisting of the following (B1) and (B2): (B1) Amorphous thermoplastic resin having a glass transition temperature lower than the melting point of the polyimide resin particles (A). (B2) A crystalline thermoplastic resin having a melting point lower than the melting point of the polyimide resin particles (A) or a glass transition temperature lower than the glass transition temperature of the polyimide resin particles (A).

5. The thermoplastic resin (B) is a polystyrene resin, polyvinyl chloride, polyvinylidene chloride, polymethyl methacrylate, acrylonitrile-butadiene-styrene resin, polycarbonate resin, polysulfone resin, polyphenylsulfone resin, polyarylate resin, polyphenylene ether resin, polyethersulfone resin, polyetherimide resin, polyamideimide resin, polyolefin resin, polyamide resin, polyacetal resin, polyphenylene sulfide resin, polyester resin, liquid crystal polymer, fluororesin, polymethylpentene resin, and polyurethane resin. The resin composition according to claim 4, which is at least one selected from the group consisting of resins.

6. The resin composition according to any one of claims 1 to 3, wherein the thermosetting resin (C) is at least one selected from the group consisting of epoxy resins, phenolic resins, urea resins, melamine resins, unsaturated polyimide resins, bismaleimide resins, silicon resins, urethane resins, casein resins, furan resins, alkyd resins, and xylene resins.

7. 7. The resin composition according to claim 6, wherein the epoxy resin is a two-component curing epoxy resin composition containing tetraglycidyldiaminodiphenylmethane as a base resin and diaminodiphenylsulfone as a curing agent.

8. The resin composition according to any one of claims 1 to 7, wherein the polyimide resin constituting the polyimide resin particles (A) is a polyimide resin that is not end-capped.

9. polyimide resin particles (A) comprising a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), wherein the content of the repeating structural unit of formula (1) relative to the total of the repeating structural units of formula (1) and formula (2) is 20 to 70 mol %, and the volume average particle size D50 is 5 to 200 μm; A thermoplastic resin (B) other than the above (A), or A cured product of a thermoplastic resin (B) other than the above (A) and a thermosetting resin (C). A resin molded product containing the resin molded product contains the polyimide resin particles (A) in a particle state, the polyimide resin constituting the polyimide resin particles (A) is a crystalline thermoplastic polyimide resin, a mass ratio [(A) / {(B)+(C)}] of the polyimide resin particles (A) to the total amount of the thermoplastic resin (B) and the thermosetting resin (C) is in the range of 5 / 95 to 80 / 20. 【Chemistry 2】 (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.

10. The method for producing a resin molded article according to claim 9, A method for producing a resin molded product, comprising a step of molding a resin composition containing the polyimide resin particles (A) and the thermoplastic resin (B), or the thermoplastic resin (B) and the thermosetting resin (C), at a temperature below the melting point of the polyimide resin particles (A).

11. The method for producing a resin molded article according to claim 10, wherein the thermoplastic resin (B) is at least one selected from the group consisting of the following (B1) and (B2): (B1) Amorphous thermoplastic resin having a glass transition temperature lower than the melting point of the polyimide resin particles (A). (B2) A crystalline thermoplastic resin having a melting point lower than the melting point of the polyimide resin particles (A) or a glass transition temperature lower than the glass transition temperature of the polyimide resin particles (A).

12. 12. The method for producing a resin molded product according to claim 11, wherein the thermoplastic resin (B) is the amorphous thermoplastic resin (B1), and the method comprises a step of extruding a resin composition containing the polyimide resin particles (A) and the amorphous thermoplastic resin (B1) at a temperature lower than the melting point of the polyimide resin particles (A) and equal to or higher than the glass transition temperature of the amorphous thermoplastic resin (B1).

13. 12. The method for producing a resin molded product according to claim 11, wherein the thermoplastic resin (B) is the crystalline thermoplastic resin (B2), and the method comprises a step of extruding a resin composition containing the polyimide resin particles (A) and the crystalline thermoplastic resin (B2) at a temperature lower than the melting point of the polyimide resin particles (A) and higher than the melting point of the crystalline thermoplastic resin (B2).

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