Resin composition and molded article

Abstract

A resin composition and a molded article containing the same, the resin composition containing: a polyimide resin (A) containing a repeating structural unit represented by formula (1) and a repeating structural unit represented by formula (2), 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 20-70 mol%; and a resin represented by a predetermined formula (5) or an acid-modified product (B) thereof. The ratio [(B) / {(A) + (B)}] of the content mass of the component (B) to the total content mass of the component (A) and the component (B) is greater than 0.50. (In the formula, R1 represents a divalent group having 6-22 carbon atoms and containing at least one alicyclic hydrocarbon structure. And R2 is a divalent chain aliphatic group having 5-16 carbon atoms. And each of X1 and X2 independently represents a tetravalent group having 6-22 carbon atoms and containing at least one aromatic ring. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded article. Background Art

[0002] Polyimide resins are useful engineering plastics having high heat stability, high strength, and high solvent resistance due to the rigidity of the molecular chain, resonance stabilization, and strong chemical bonding, and are applied to a wide range of fields.

[0003] Polyimide resins have high heat resistance, but on the other hand, they have problems of not exhibiting thermoplasticity and having low moldability. In recent years, however, polyimide resins having thermoplasticity have also been reported. In addition to the heat resistance inherent to polyimide resins, thermoplastic polyimide resins also have excellent moldability. Therefore, thermoplastic polyimide resins can also be applied to molded articles used in harsh environments where general thermoplastic resins such as nylon and polyester cannot be used.

[0004] As one of the molecular designs for imparting thermoplasticity to polyimide resins, a method of incorporating a flexible structure such as an aliphatic structure into the main chain is known. The aliphatic structure has the advantages of being able to relatively easily impart thermoplasticity to polyimide and being likely to exhibit low dielectric properties due to its large volume. On the other hand, compared with the aromatic structure, it has poor oxidation resistance, and as a result, there is a problem of reducing the high flame retardancy originally possessed by polyimide. Therefore, in order to apply such thermoplastic polyimide resins to uses requiring high flame retardancy, research has also been conducted on adding flame retardants to improve flame retardancy.

[0005] For example, Patent Document 1 discloses that a resin composition containing a polyimide resin having a specific structure and a metal salt of hypophosphorous acid-based flame retardant has excellent moldability and can achieve both high flame retardancy and good appearance.

[0006] A method of modifying a resin by using two or more resin components instead of using additives such as flame retardants is also known. For example, Patent Document 2 discloses that a resin composition containing specified polyimide resin particles and at least one selected from a thermoplastic resin and a thermosetting resin can improve various properties such as heat resistance and mechanical properties while maintaining the light weight of the resin.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: International Publication No. 2019 / 220968

[0010] Patent Document 2: International Publication No. 2021 / 100716 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] The disclosed technology of Patent Document 2 is a technology for improving heat resistance, mechanical properties, etc. by including a polyimide resin in a thermoplastic resin or a thermosetting resin while maintaining the state of particles without thermal melting, and has not achieved an improvement in the flame retardancy of the resin composition.

[0013] An object of the present invention is to provide a resin composition and a molded article in which the amount of a flame retardant used is small or which can exhibit high flame retardancy even without using a flame retardant.

[0014] Means for Solving the Problems

[0015] The present inventors have found that the above problems can be solved by a resin composition containing an aromatic resin having a specific structure and a polyimide resin obtained by combining specific different polyimide structural units at a specific ratio.

[0016] That is, the present invention relates to the following.

[0017] [1] A resin composition containing: a polyimide resin (A) containing a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content ratio of the repeating structural unit of the formula (1) to the total of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) is 20 to 70 mol%; and a resin represented by the following formula (5) or an acid-modified product thereof (B), and the proportion [(B) / {(A)+(B)}] of the content mass of the foregoing component (B) to the total content mass of the foregoing component (A) and the foregoing component (B) is greater than 0.50.

[0018]

[0019] (R1 is a divalent group having 6 to 22 carbon atoms containing at least 1 alicyclic hydrocarbon structure, R2 is a divalent linear aliphatic group having 5 to 16 carbon atoms, and X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least 1 aromatic ring.)

[0020]

[0021] (R 51 ~R 55 and R 61 ~R 64 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and R 65 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more.)

[0022] [2]The resin composition according to [1] above, wherein the total content of the component (A) and the component (B) in the resin composition is 50% by mass or more.

[0023] [3]The resin composition according to [1] or [2] above, wherein the intrinsic viscosity of the component (B) measured in chloroform at 30 °C is 0.20 to 0.60 dL / g.

[0024] [4]The resin composition according to any one of [1] to [3] above, wherein the resin composition is obtained by melt-kneading at a temperature higher than the melting point of the component (A).

[0025] [5]The resin composition according to any one of [1] to [4] above, wherein the pellets formed from the resin composition have a microphase-separated structure.

[0026] [6]A molded article comprising the resin composition according to any one of [1] to [5] above.

[0027] [7]The molded article according to [6] above, wherein the molded article is an injection-molded article.

[0028] [8]The molded article according to [6] or [7] above, wherein the oxygen index of the molded article having a thickness of 4 mm measured according to JIS K 7201:1995 is 28 or more.

[0029] Effects of the Invention

[0030] According to the present invention, it is possible to provide a resin composition and a molded article in which the amount of the flame retardant used is small or high flame retardancy can be exhibited even without using the flame retardant. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a schematic diagram showing a method for producing a specimen (ultrathin section) used in field emission scanning transmission electron microscope (FE-STEM) observation.

[0032] Figure 2 It is a micrograph when observing a cross section cut in a direction orthogonal to the flow direction (MD) of the resin composition (pellets) of Example 1 using FE-STEM.

[0033] Figure 3 It is a schematic diagram for explaining a method for producing a test piece used in evaluating the adhesiveness between a film and a copper foil.

[0034] Figure 4 It is a schematic diagram for explaining a method for evaluating the adhesiveness between a film and a copper foil and the tensile adhesive strength. DETAILED DESCRIPTION OF THE INVENTION

[0035] [Resin Composition]

[0036] The resin composition of the present invention contains: a polyimide resin (A) which includes a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is 20 to 70 mol%; and a resin represented by the following formula (5) or its acid-modified product (B), and the proportion [(B) / {(A)+(B)}] of the content mass of the foregoing component (B) relative to the total content mass of the foregoing component (A) and the foregoing component (B) is greater than 0.50.

[0037]

[0038] (R1 is a divalent group having 6 to 22 carbon atoms containing at least 1 alicyclic hydrocarbon structure, R2 is a divalent linear aliphatic group having 5 to 16 carbon atoms, and X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least 1 aromatic ring.)

[0039]

[0040] (R 51 ~R 55 and R 61 ~R 64 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and R 65 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more.)

[0041] The resin composition of the present invention contains, in a specified ratio: a polyimide resin (A) formed by combining specific different polyimide structural units in the above-specified ratio, and a resin represented by the above formula (5) or its acid-modified product (B), so that the amount of the flame retardant used is small, or high flame retardancy can be exhibited even without using it.

[0042] The reason for obtaining the above effect in the present invention is not yet clear, but it is considered as follows.

[0043] The resin composition of the present invention is a resin composition in which the above mass ratio [(B) / {(A)+(B)}] exceeds 0.50 and the content ratio of aromatic rings is high. Therefore, for example, when a molded body formed from this resin composition is subjected to a combustion test, it is considered that char formation is promoted on the surface of the molded body and it becomes difficult to burn. In addition, as described later, it is considered that component (A) and component (B) form a microphase-separated structure in the resin composition or the molded body, and it is considered that at the phase separation interface between component (A) and component (B), the aromatic rings in component (A) and the aromatic structural parts in component (B) partially form a charge transfer complex and are thermally stabilized.

[0044] In addition, by containing component (A) and component (B), the resin composition of the present invention can achieve extremely low dielectric constant and dielectric loss tangent (hereinafter, these are also collectively referred to as "low dielectric properties") as a resin material. Furthermore, the adhesiveness to metal foils such as copper foil is also good.

[0045] <Polyimide resin (A)>

[0046] The polyimide resin (A) used in the present invention contains a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content ratio of the repeating structural unit of formula (1) with respect to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is 20 to 70 mol%.

[0047]

[0048] (R1 is a divalent group having 6 to 22 carbon atoms containing at least 1 alicyclic hydrocarbon structure, R2 is a divalent linear aliphatic group having 5 to 16 carbon atoms, and X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least 1 aromatic ring.)

[0049] The polyimide resin (A) used in the present invention is a thermoplastic resin, and as its form, powder or pellets are preferred. The thermoplastic polyimide resin is different from, for example, a polyimide resin that is formed by closing the imide ring after molding in the state of a polyimide precursor such as polyamic acid and does not have a glass transition temperature (Tg), or a polyimide resin that decomposes at a temperature lower than the glass transition temperature.

[0050] The repeating structural unit of formula (1) will be described in detail below.

[0051] R1 is a divalent group having 6 to 22 carbon atoms containing at least 1 alicyclic hydrocarbon structure. Here, the alicyclic hydrocarbon structure means a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound can be saturated or unsaturated, and can be a monocyclic or polycyclic ring.

[0052] As the alicyclic hydrocarbon structure, cycloalkane rings such as cyclohexane rings, cycloolefin rings such as cyclohexene rings, bicycloalkane rings such as norbornane rings, and bicycloolefin rings such as norbornene rings can be exemplified, but are not limited thereto. Among them, cycloalkane rings are preferred, cycloalkane rings having 4 to 7 carbon atoms are more preferred, and cyclohexane rings are further preferred.

[0053] R1 has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms.

[0054] R1 contains at least 1 alicyclic hydrocarbon structure, preferably 1 to 3.

[0055] R1 is preferably a divalent group represented by the following formula (R1-1) or (R1-2).

[0056]

[0057] (m 11 and m 12 are each independently an integer of 0 to 2, preferably 0 or 1, m 13 to m 15 are each independently an integer of 0 to 2, preferably 0 or 1.)

[0058] R1 is particularly preferably a divalent group represented by the following formula (R1-3).

[0059]

[0060] It should be noted that 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 can be cis or trans, and in addition, the ratio of cis to trans can be any value.

[0061] X1 is a tetravalent group having 6 to 22 carbon atoms and containing at least 1 aromatic ring. The above aromatic ring can be a monocyclic ring or a fused ring, and examples include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited thereto. Among them, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

[0062] X1 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.

[0063] X1 contains at least 1 aromatic ring, preferably 1 to 3.

[0064] X1 is preferably a tetravalent group represented by any one of the following formulas (X-1) to (X-4).

[0065]

[0066] (R 11 to R 18 are each independently an alkyl group having 1 to 4 carbon atoms. p 11 to p 13Each independently is an integer from 0 to 2, preferably 0. p 14 , p 15 , p 16 and p 18 Each independently is an integer from 0 to 3, preferably 0. p 17 is an integer from 0 to 4, preferably 0. L 11 ~L 13 Each independently is a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms. )

[0067] It should be noted that X1 is a tetravalent group having 6 to 22 carbon atoms containing at least 1 aromatic ring. Therefore, R in formula (X-2) 12 , R 13 , p 12 and p 13 are selected in such a way that the carbon number of the tetravalent group represented by formula (X-2) falls within the range of 10 to 22.

[0068] Similarly, L in formula (X-3) 11 , R 14 , R 15 , p 14 and p 15 are selected in such a way that the carbon number of the tetravalent group represented by formula (X-3) falls within 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 are selected in such a way that the carbon number of the tetravalent group represented by formula (X-4) falls within the range of 18 to 22.

[0069] X1 is particularly preferably a tetravalent group represented by the following formula (X-5) or (X-6).

[0070]

[0071] The repeating structural unit of formula (2) will be described in detail below.

[0072] 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 further preferably 8 to 10 carbon atoms. Here, the chain aliphatic group refers to a group derived from a chain aliphatic compound, and the chain aliphatic compound can be saturated or unsaturated, can be straight-chain or branched-chain, and can contain heteroatoms such as oxygen atoms.

[0073] R2 is preferably an alkylene group having 5 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, further preferably 7 to 12 carbon atoms, and particularly preferably 8 to 10 carbon atoms. The above alkylene group can be a straight-chain alkylene group or a branched-chain alkylene group, and is preferably a straight-chain alkylene group.

[0074] R2 is preferably at least one selected from octamethylene and decamethylene, and particularly preferably octamethylene.

[0075] In addition, as another preferred embodiment of R2, a divalent linear aliphatic group having 5 to 16 carbon atoms containing an ether group can be cited. The number of carbon atoms is preferably 6 to 14, more preferably 7 to 12, and further preferably 8 to 10. Among them, a divalent group represented by the following formula (R2-1) or (R2-2) is preferred.

[0076]

[0077] (m 21 and m 22 are each independently an integer from 1 to 15, preferably 1 to 13, more preferably 1 to 11, and further preferably 1 to 9. m 23 ~m 25 are each independently an integer from 1 to 14, preferably 1 to 12, more preferably 1 to 10, and further preferably 1 to 8.)

[0078] It should be noted that since R2 is a divalent linear aliphatic group having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and further preferably 8 to 10 carbon atoms), m 21 and m 22 in the formula (R2-1) are selected in such a way that the number of carbon atoms of the divalent group represented by the formula (R2-1) falls within the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and further 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 further preferably 8 to 10).

[0079] Similarly, m 23 ~m 25 in the formula (R2-2) are selected in such a way that the number of carbon atoms of the divalent group represented by the formula (R2-2) falls within the range of 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and further preferably 8 to 10 carbon atoms). That is, m 23 +m 24 +m 25 is 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and further preferably 8 to 10 carbon atoms).

[0080] X2 is defined in the same manner as X1 in formula (1), and the preferred embodiments are also the same.

[0081] The content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is 20 to 70 mol%. When the content ratio of the repeating structural unit of formula (1) is within the above range, the polyimide resin can be sufficiently crystallized even in a general injection molding cycle. If the content ratio is less than 20 mol%, the moldability is reduced. If it is higher than 70 mol%, the crystallinity is reduced, and thus the heat resistance is reduced.

[0082] From the viewpoint of exhibiting high crystallinity, the content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 65 mol% or less, more preferably 60 mol% or less, and further preferably 50 mol% or less.

[0083] Among them, the content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 20 mol% or more and less than 40 mol%. If it is within this range, the crystallinity of the polyimide resin (A) becomes high, and a resin composition with more excellent heat resistance can be obtained.

[0084] From the viewpoint of moldability, the above content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, and further preferably 32 mol% or more. From the viewpoint of exhibiting high crystallinity, it is more preferably 35 mol% or less.

[0085] The content ratio of the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) relative to all the repeating structural units constituting the polyimide resin (A) is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, further preferably 80 to 100 mol%, and still more preferably 85 to 100 mol%.

[0086] The polyimide resin (A) 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) relative to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 25 mol% or less. On the other hand, the lower limit is not particularly limited, and it may be higher than 0 mol%.

[0087] From the viewpoint of improving heat resistance, the above content ratio is preferably 5 mol% or more, more preferably 10 mol% or more. On the other hand, from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more preferably 15 mol% or less.

[0088]

[0089] (R3 is a divalent group having 6 to 22 carbon atoms and containing at least 1 aromatic ring. X3 is a tetravalent group having 6 to 22 carbon atoms and containing at least 1 aromatic ring.)

[0090] R3 is a divalent group having 6 to 22 carbon atoms and containing at least 1 aromatic ring. The above-mentioned aromatic ring may be a monocyclic ring or a fused ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited thereto. Among them, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

[0091] The carbon number of R3 is 6 to 22, preferably 6 to 18.

[0092] R3 contains at least 1 aromatic ring, preferably 1 to 3.

[0093] In addition, a monovalent or divalent electron-withdrawing group may be bonded to the above-mentioned aromatic ring. Examples of the monovalent electron-withdrawing group include a nitro group, a cyano group, a p-toluenesulfonyl group, a halogen, a haloalkyl group, a phenyl group, an acyl group, etc. Examples of the divalent electron-withdrawing group include, in addition to a fluoroalkylene group (for example, -C(CF3)2-, -(CF2) p -(where p is an integer of 1 to 10)) such a fluoroalkylene group, -CO-, -SO2-, -SO-, -CONH-, -COO-, etc.

[0094] R3 is preferably a divalent group represented by the following formula (R3-1) or (R3-2).

[0095]

[0096] (m 31 and m 32 are each independently an integer of 0 to 2, preferably 0 or 1, m 33 and m 34 are each independently an integer of 0 to 2, preferably 0 or 1. R 21 、R 22 and R 23 are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. p 21 、p 22 and p 23 are integers of 0 to 4, preferably 0. L 21 is a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.)

[0097] In addition, since R3 is a divalent group having 6 to 22 carbon atoms and containing at least 1 aromatic ring, m 31 、m 32 、R 21 and p 21It is selected such that the number of carbon atoms of the divalent group represented by the formula (R3-1) falls within the range of 6 to 22.

[0098] Similarly, L in the formula (R3-2) 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 are selected such that the number of carbon atoms of the divalent group represented by the formula (R3-2) falls within the range of 12 to 22.

[0099] X3 is defined in the same manner as X1 in the formula (1), and the preferred manner is also the same.

[0100] The polyimide resin (A) may further contain a repeating structural unit represented by the following formula (4).

[0101]

[0102] (R4 is a divalent group containing -SO2- or -Si(R x )(R y )O-, R x and R y each independently represent a linear aliphatic group having 1 to 3 carbon atoms or a phenyl group. X4 is a tetravalent group having 6 to 22 carbon atoms containing at least 1 aromatic ring.)

[0103] X4 is defined in the same manner as X1 in the formula (1), and the preferred manner is also the same.

[0104] The terminal structure of the polyimide resin (A) is not particularly limited, and preferably has a linear aliphatic group having 5 to 14 carbon atoms at the terminal.

[0105] This linear aliphatic group may be saturated or unsaturated, and may be linear or branched. When the polyimide resin (A) has the above specific group at the terminal, a resin composition excellent in heat aging resistance can be obtained.

[0106] Examples of the saturated linear aliphatic group having 5 to 14 carbon atoms include: n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, lauryl, n-tridecyl, n-tetradecyl, isopentyl, neopentyl, 2-methylpentyl, 2-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, isooctyl, 2-ethylhexyl, 3-ethylhexyl, isononyl, 2-ethyloctyl, isodecyl, isododecyl, isotridecyl, isotetradecyl, etc.

[0107] Examples of the unsaturated chain aliphatic group having 5 to 14 carbon atoms include 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, and the like.

[0108] Among them, the above-mentioned chain aliphatic group is preferably a saturated chain aliphatic group, more preferably a saturated straight-chain aliphatic group. In addition, from the viewpoint of obtaining heat aging resistance, the above-mentioned chain aliphatic group preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, further preferably 8 or more carbon atoms, preferably 12 or less carbon atoms, more preferably 10 or less carbon atoms, and further preferably 9 or less carbon atoms. The above-mentioned chain aliphatic group may be only 1 type, or 2 or more types.

[0109] The above-mentioned chain aliphatic group is particularly preferably at least one selected from the group consisting of n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isononyl, n-decyl, and isodecyl, more preferably at least one selected from the group consisting of n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, and isononyl, and most preferably at least one selected from the group consisting of n-octyl, isooctyl, and 2-ethylhexyl.

[0110] In addition, from the viewpoint of heat aging resistance, the polyimide resin (A) preferably has only a chain aliphatic group having 5 to 14 carbon atoms at the terminal in addition to the terminal amino group and the terminal carboxyl group. When having a group other than the above at the terminal, its content is preferably 10 mol% or less, more preferably 5 mol% or less, relative to the chain aliphatic group having 5 to 14 carbon atoms.

[0111] From the viewpoint of exhibiting excellent heat aging resistance, relative to a total of 100 mol% of all repeating structural units constituting the polyimide resin (A), the content of the above-mentioned chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and further preferably 0.2 mol% or more. In addition, in order to ensure a sufficient molecular weight and obtain good mechanical properties, relative to a total of 100 mol% of all repeating structural units constituting the polyimide resin (A), the content of the above-mentioned chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) is preferably 10 mol% or less, more preferably 6 mol% or less, and further preferably 3.5 mol% or less.

[0112] The content of the above-mentioned chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) can be determined by depolymerizing the polyimide resin (A).

[0113] The polyimide resin (A) preferably has a melting point of 360°C or lower and a glass transition temperature of 150°C or higher. From the viewpoint of heat resistance, the melting point of the polyimide resin (A) is more preferably 280°C or higher, further preferably 290°C or higher, and from the viewpoint of exhibiting high formability, it is preferably 345°C or lower, more preferably 340°C or lower, and further preferably 335°C or lower. In addition, from the viewpoint of heat resistance, the glass transition temperature of the polyimide resin (A) is more preferably 160°C or higher, more preferably 170°C or higher, and from the viewpoint of exhibiting high formability, it is preferably 250°C or lower, more preferably 230°C or lower, and further preferably 200°C or lower.

[0114] The melting point and glass transition temperature of the polyimide resin (A) can both be measured using a differential scanning calorimeter.

[0115] In addition, for the polyimide resin (A), from the viewpoints of improving crystallinity, heat resistance, mechanical strength, and chemical resistance, the heat of the crystallization exothermic peak (hereinafter also simply referred to as "crystallization heat") observed when the polyimide resin is melted and cooled at a cooling rate of 20°C / minute as measured by a differential scanning calorimeter is preferably 5.0 mJ / mg or more, more preferably 10.0 mJ / mg or more, and further preferably 17.0 mJ / mg or more. The upper limit value of the crystallization heat is not particularly limited and is usually 45.0 mJ / mg or less.

[0116] Specifically, the melting point, glass transition temperature, and crystallization heat of the polyimide resin (A) can be measured using the methods described in the examples.

[0117] The logarithmic viscosity of a 0.5 mass% sulfuric acid solution of the polyimide resin (A) at 30°C is preferably in the range of 0.2 to 2.0 dL / g, more preferably in the range of 0.3 to 1.8 dL / g. If the logarithmic viscosity is 0.2 dL / g or more, sufficient mechanical strength can be obtained when the resulting resin composition is made into a shaped body, and if it is 2.0 dL / g or less, the formability and operability become good. The logarithmic viscosity μ is calculated by the following formula using a Cannon-Fenske viscometer to measure the flow times of concentrated sulfuric acid and the above polyimide resin solution at 30°C.

[0118] μ = ln(ts / t0) / C

[0119] t0: Flow time of concentrated sulfuric acid

[0120] ts: Flow time of the polyimide resin solution

[0121] C: 0.5 (g / dL)

[0122] The weight-average molecular weight Mw of the polyimide resin (A) is preferably in the range of 10,000 to 150,000, more preferably 15,000 to 100,000, still more preferably 20,000 to 80,000, even more preferably 30,000 to 70,000, and even more preferably 35,000 to 65,000. When the weight-average molecular weight Mw of the polyimide resin (A) is 10,000 or more, the mechanical strength of the obtained molded body becomes good; when it is 40,000 or more, the stability of the mechanical strength becomes good; and when it is 150,000 or less, the moldability becomes good.

[0123] The weight-average molecular weight Mw of the polyimide resin (A) can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.

[0124] (Method for producing the polyimide resin (A))

[0125] The polyimide resin (A) can be produced by reacting a tetracarboxylic acid component with a diamine component. The tetracarboxylic acid component contains a tetracarboxylic acid having at least one aromatic ring and / or its derivative, and the diamine component contains a diamine having at least one alicyclic hydrocarbon structure and a linear aliphatic diamine.

[0126] The tetracarboxylic acid having at least one aromatic ring is preferably a compound in which four carboxyl groups are directly bonded to the aromatic ring, and an alkyl group may be included in the structure. In addition, the above tetracarboxylic acid preferably has 6 to 26 carbon atoms. As the above tetracarboxylic acid, pyromellitic acid, 2,3,5,6-tetramethylpyromellitic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, etc. are preferred. Among them, pyromellitic acid is more preferred.

[0127] As derivatives of tetracarboxylic acids containing at least one aromatic ring, anhydrides or alkyl esters of tetracarboxylic acids containing at least one aromatic ring can be cited. The above tetracarboxylic acid derivatives preferably have 6 to 38 carbon atoms. As the acid anhydride of tetracarboxylic acid, examples include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-tetramethylpyromellitic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. As the alkyl esters of tetracarboxylic acids, examples include dimethyl pyromellitate, diethyl pyromellitate, dipropyl pyromellitate, diisopropyl pyromellitate, dimethyl 2,3,5,6-tetramethylpyromellitate, dimethyl 3,3',4,4'-diphenylsulfone tetracarboxylate, dimethyl 3,3',4,4'-benzophenone tetracarboxylate, dimethyl 3,3',4,4'-biphenyltetracarboxylate, dimethyl 1,4,5,8-naphthalenetetracarboxylate, etc. In the above alkyl esters of tetracarboxylic acids, the alkyl preferably has 1 to 3 carbon atoms.

[0128] The tetracarboxylic acid containing at least one aromatic ring and / or its derivatives can use at least one compound selected from the above alone, or can use two or more compounds in combination.

[0129] The carbon number of the diamine containing at least one alicyclic hydrocarbon structure is preferably 6 to 22. For example, 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), carvone diamine, limonene diamine, isophorone diamine, norbornane diamine, bis(aminomethyl)tricyclo[5.2.1.0 2,6 decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, etc. These compounds can be used alone or two or more of them can be used in combination. Among them, 1,3-bis(aminomethyl)cyclohexane can be preferably used. It should be noted that the diamine containing an alicyclic hydrocarbon structure usually has constitutional isomers, but the ratio of cis-form / trans-form is not limited.

[0130] The chain aliphatic diamine can be linear or branched, preferably having 5 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 7 to 12 carbon atoms. Further, if the carbon number of the chain part is 5 to 16, an ether bond may be contained therein. As the chain aliphatic diamine, for example, 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, 2,2'-(ethylenedioxy)bis(ethylamine), etc. are preferred.

[0131] One kind or a mixture of two or more kinds of the chain aliphatic diamines can be used. Among them, a chain aliphatic diamine having 8 to 10 carbon atoms is preferably used, and in particular, at least one selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine is preferably used.

[0132] When producing the polyimide resin (A), the molar ratio of the input amount of the diamine containing at least one alicyclic hydrocarbon structure to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is preferably 20 to 70 mol%. This molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, still more preferably 32 mol% or more, and from the viewpoint of exhibiting high crystallinity, it is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably less than 40 mol%, and still more preferably 35 mol% or less.

[0133] Further, the above diamine component may contain a diamine containing at least one aromatic ring. The carbon number of the diamine containing at least one aromatic ring is preferably 6 to 22, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,2-diethynylbenzene diamine, 1,3-diethynylbenzene diamine, 1,4-diethynylbenzene diamine, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 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, 1,5-diaminonaphthalene, etc.

[0134] In the above, the input amount of the diamine containing at least 1 aromatic ring is preferably 25 mol% or less with respect to the total amount of the diamine containing at least 1 alicyclic hydrocarbon structure and the linear aliphatic diamine in terms of molar ratio. On the other hand, the lower limit is not particularly limited, and it may be higher than 0 mol%.

[0135] From the viewpoint of improving heat resistance, the above molar ratio is preferably 5 mol% or more, more preferably 10 mol% or more. On the other hand, from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more preferably 15 mol% or less.

[0136] In addition, from the viewpoint of reducing the coloring of the polyimide resin (A), the above molar ratio is preferably 12 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and even more preferably 0 mol%.

[0137] When producing the polyimide resin (A), regarding the input amount ratio of the above tetracarboxylic acid component and the above diamine component, it is preferably 0.9 to 1.1 moles of the diamine component relative to 1 mole of the tetracarboxylic acid component.

[0138] In addition, when producing the polyimide resin (A), in addition to the above tetracarboxylic acid component and the above diamine component, a capping agent may be mixed. As the capping agent, at least 1 selected from the group consisting of monoamines and dicarboxylic acids is preferred. The amount of the capping agent used is only required to be an amount capable of introducing a desired amount of end groups into the polyimide resin (A). Relative to 1 mole of the above tetracarboxylic acid and / or its derivative, it is preferably 0.0001 to 0.1 mole, more preferably 0.001 to 0.06 mole, and further preferably 0.002 to 0.035 mole.

[0139] Among them, as the capping agent, a monoamine capping agent is preferred. From the viewpoint of improving heat aging resistance by introducing the above linear aliphatic group having 5 to 14 carbon atoms at the end of the polyimide resin (A), a monoamine having a linear aliphatic group having 5 to 14 carbon atoms is more preferred, and a monoamine having a saturated straight-chain aliphatic group having 5 to 14 carbon atoms is further preferred.

[0140] The capping agent is particularly preferably at least 1 selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine, more preferably at least 1 selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably at least 1 selected from the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.

[0141] As the polymerization method for producing the polyimide resin (A), a known polymerization method can be applied, and the method described in International Publication No. 2016 / 147996 can be used.

[0142] <The resin represented by the formula (5) or its acid-modified product (B)>

[0143] The resin composition of the present invention contains a polyimide resin (A) and contains the resin represented by the following formula (5) or its acid-modified product (B).

[0144]

[0145] (R 51 ~R 55 and R 61 ~R 64 are each independently a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and R 65 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. n is the number of repeating structural units and is a number of 10 or more.)

[0146] In the formula (5), R 51 ~R 55 and R 61 ~R 65 The alkyl group having 1 to 4 carbon atoms among them can be either linear or branched, and examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl. Among them, methyl, ethyl, n-propyl, or isopropyl is preferred, and methyl is more preferred.

[0147] In the formula (5), R 51 , R 53 , R 61 and R 63 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or methyl, and still more preferably a hydrogen atom.

[0148] R 52 , R 54 , R 62 and R 64 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or methyl, and still more preferably methyl.

[0149] R 65 is preferably a hydrogen atom.

[0150] In the formula (5), n is a number of 10 or more, more preferably 20 or more.

[0151] As the resin represented by the above formula (5), a resin represented by the following formula (5-1), that is, poly(2,6-dimethyl-1,4-phenylene ether), is preferred.

[0152]

[0153] (In the formula, n is the same as above.)

[0154] As the acid-modified product of the resin represented by the formula (5), a resin obtained by modifying the resin represented by the formula (5) with a carboxylic acid or a carboxylic acid derivative can be mentioned. From the viewpoint of reactivity with the resin represented by the formula (5), the carboxylic acid or the carboxylic acid derivative is preferably an unsaturated carboxylic acid and its derivative.

[0155] Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid, etc. In addition, examples of the derivative of the unsaturated carboxylic acid include acid anhydride, ester, amide, imide, metal salt, etc., and acid anhydride is preferably used among them.

[0156] Among the above, from the viewpoints of exhibiting high flame retardancy and availability, the acid-modified product of the resin represented by the formula (5) is preferably a resin obtained by modifying the resin represented by the formula (5) with maleic acid or a maleic acid derivative (maleic acid-modified product of the resin represented by the formula (5)), and more preferably a resin obtained by modifying the resin represented by the formula (5) with maleic anhydride.

[0157] As the maleic acid-modified product of the resin represented by the formula (5), a resin having a structure represented by the following formula (5-2) and / or the following formula (5-3) can be mentioned.

[0158]

[0159]

[0160] (In the formula, R 51 ~R 55 , R 61 , R 63 , R 64 , R 65 and n are the same as above.)

[0161] From the viewpoints of obtaining low dielectric characteristics, improving thin film formability, and availability, the acid modification rate in the acid-modified product of the resin represented by the formula (5) is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 3.0% by mass, further preferably 0.1 to 2.0% by mass, and even more preferably 0.2 to 1.0% by mass. The acid modification rate here means the content (% by mass) of the structure derived from the acid in the acid-modified product. For example, when the acid-modified product of the resin represented by the formula (5) is a resin obtained by modifying the resin represented by the formula (5) with maleic anhydride, the acid modification rate means the content (% by mass) of the structure derived from maleic anhydride in the acid-modified product.

[0162] From the viewpoints of exhibiting high flame retardancy and availability, component (B) is preferably the resin represented by the above formula (5) or its maleic acid-modified product, more preferably the resin represented by the above formula (5), and further preferably the resin represented by the above formula (5-1), i.e., poly(2,6-dimethyl-1,4-phenylene ether).

[0163] From the viewpoints of exhibiting high flame retardancy and improving moldability, the intrinsic viscosity of component (B) measured in chloroform at 30 °C is preferably 0.20 to 0.60 dL / g, more preferably 0.30 to 0.50 dL / g, and further preferably 0.30 to 0.45 dL / g.

[0164] As the resin represented by the above formula (5), commercially available products such as "PX100F" (poly(2,6-dimethyl-1,4-phenylene ether), Tg = 207 °C, intrinsic viscosity at 30 °C measured in chloroform = 0.37 dL / g), "PX100L" (poly(2,6-dimethyl-1,4-phenylene ether), Tg = 210 °C, intrinsic viscosity at 30 °C measured in chloroform = 0.47 dL / g) manufactured by Polyxylenol Singapore Pte Ltd can also be used.

[0165] As commercially available products of the resin (maleic acid-modified product) obtained by modifying the resin represented by the above formula (5) with maleic anhydride, "Iupiace PME-80" (maleic anhydride modification rate 0.38 mass%) manufactured by Mitsubishi Engineering-Plastics Corporation, etc. can be cited.

[0166] <Content>

[0167] From the viewpoints of exhibiting high flame retardancy and obtaining low dielectric properties, the proportion of the content of component (B) in the resin composition relative to the total content of components (A) and (B) [(B) / {(A)+(B)}] is greater than 0.50, preferably 0.60 or more, more preferably 0.65 or more, further preferably 0.70 or more, still further preferably 0.75 or more, and still further preferably 0.80 or more. In addition, the upper limit is less than 1.00, and from the viewpoint of exhibiting high flame retardancy, it is preferably 0.99 or less, more preferably 0.98 or less, and further preferably 0.95 or less.

[0168] The content of component (A) in the resin composition is not particularly limited as long as it is in the range where the above [(B) / {(A)+(B)}] is greater than 0.50. From the viewpoints of exhibiting high flame retardancy and obtaining low dielectric properties, it is preferably 1 to 45 mass%, more preferably 2 to 40 mass%, further preferably 5 to 30 mass%, and still further preferably 5 to 25 mass%.

[0169] The content of component (B) in the resin composition is not particularly limited as long as [(B) / {(A)+(B)}] is in a range greater than 0.50. From the viewpoints of exhibiting high flame retardancy and obtaining low dielectric properties, it is preferably 30 to 99.5% by mass, more preferably 40 to 99.5% by mass, further preferably 50 to 99.5% by mass, still further preferably 60 to 98% by mass, still further preferably 70 to 95% by mass, and still further preferably 75 to 95% by mass.

[0170] <Additive>

[0171] In the resin composition of the present invention, additives such as fillers, reinforcing fibers, matting agents, plasticizers, antistatic agents, anti-coloring agents, anti-gelation agents, coloring agents, sliding property improvers, antioxidants, conductive agents, resin modifiers, compatibilizers, etc. can be compounded as needed.

[0172] When using the above additives, their compounding amounts are not particularly limited. From the viewpoints of maintaining high flame retardancy and exhibiting the effects of the additives, in the resin composition, they are usually 50% by mass or less, preferably 0.0001 to 30% by mass, more preferably 0.001 to 15% by mass, and further preferably 0.01 to 10% by mass.

[0173] In addition, in the resin composition of the present invention, resins other than component (A) and component (B) can be compounded within a range that does not hinder its properties. As such resins, thermoplastic resins with high heat resistance are preferred, and examples thereof include polyamide resins, polyester resins, polyimide resins other than polyimide resin (A), polycarbonate resins, polyetherimide resins, polyamideimide resins, polyphenylene etherimide resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, polyarylate resins, liquid crystal polymers, polyetheretherketone resins, polyetherketone resins, polyetherketoneketone resins, polyetheretherketoneketone resins, polybenzimidazole resins, fluorine-based resins, etc. As fluorine-based resins, polytetrafluoroethylene, perfluoroalkyl vinyl ether copolymers, tetrafluoroethylene-ethylene copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. can be mentioned.

[0174] Among them, from the viewpoints of heat resistance, moldability, strength, and solvent resistance, one or more selected from the group consisting of polyetherimide resins, polyphenylene sulfide resins, and polyetheretherketone resins are preferred. From the viewpoint of low water absorption, liquid crystal polymers are preferred. From the viewpoint of obtaining high flame retardancy, one or more selected from the group consisting of polyphenylene sulfide resins, polytetrafluoroethylene, and perfluoroalkyl vinyl ether copolymers are preferred.

[0175] When resins other than component (A) and component (B) are used in combination, as long as it is within a range that does not hinder the properties of the resin composition, their compounding amounts are not particularly limited.

[0176] However, from the viewpoint of obtaining the effects of the present invention, the total content of component (A) and component (B) in the resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, still further preferably 70% by mass or more, still further preferably 80% by mass or more, still further preferably 90% by mass or more, still further preferably 95% by mass or more, and 100% by mass or less.

[0177] The resin composition of the present invention can exhibit high flame retardancy even when the content of the flame retardant is small. From this viewpoint, the content of the flame retardant in the resin composition is preferably 5% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, still further preferably 0.5% by mass or less, still further preferably 0.2% by mass or less, still further preferably 0.1% by mass or less, still further preferably 0.05% by mass or less, still further preferably 0.02% by mass or less, still further preferably less than 0.01% by mass, and still further preferably 0% by mass.

[0178] Examples of the above-mentioned flame retardants include existing flame retardants such as halogen-based flame retardants, phenol-based flame retardants, phosphorus-based flame retardants, metal oxide-based flame retardants, metal hydroxide-based flame retardants, metal salt-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, and boron compound-based flame retardants.

[0179] From the viewpoint of forming a pellet form, the resin composition of the present invention preferably does not contain a solvent. Specifically, the content of the solvent in the resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less.

[0180] <Morphology of the resin composition>

[0181] The resin composition of the present invention can be in any form. From the viewpoints of exhibiting high flame retardancy by forming the microphase separation structure described later and obtaining low dielectric properties, those obtained by melt-kneading at a temperature higher than the melting point of component (A) are preferred, and pellets obtained by melt-kneading at a temperature higher than the melting point of component (A) are more preferred. That is, it is preferred to apply a heat history to component (A) in the resin composition of the present invention, and this resin composition is different from a resin composition containing component (A) in a powder state.

[0182] The resin composition of the present invention is thermoplastic. Therefore, for example, after adding component (A), component (B), and various optional components as needed and performing dry blending, or feeding component (B) and optional components separately from positions different from the feeding of component (A) into the extruder, melt-kneading is performed in the extruder and the strand is extruded, and the strand is cut, thereby granulating. In addition, by introducing the granules into various molding machines and performing thermoforming by the method described later, a molded body having a desired shape can be easily manufactured.

[0183] In the manufacturing process and thermoforming process of the above-mentioned granules, a resin composition containing a flame retardant usually easily causes bleeding, thermal decomposition, coloring, whitening, etc. of the flame retardant. However, the resin composition of the present invention has the advantage that these adverse conditions do not occur.

[0184] From the viewpoints of exhibiting high flame retardancy and obtaining low dielectric characteristics, the granules formed from the resin composition of the present invention and the molded body obtained by molding the resin composition preferably have a microphase separation structure. The microphase separation structure is a micron- to nanometer-scale phase separation structure formed by the phase separation of component (A) and component (B), and can be a sea-island structure or a co-continuous structure, and a sea-island structure is preferred. In the sea-island structure, depending on the mass ratio of component (A) and component (B) in the granules, the optional component can form the "sea".

[0185] Regarding whether the granules or the molded body has a microphase separation structure, it can be determined by observing the surface or cross section of the granules or the molded body with a scanning transmission electron microscope (STEM).

[0186] [Molded body]

[0187] The present invention provides a molded body containing the above resin composition. The shape of the molded body is not particularly limited, and examples thereof include a sheet, a film, a strand, a filament, etc. They can be intermediate members of industrial products or final products.

[0188] The resin composition of the present invention is thermoplastic, and therefore the molded body of the present invention can be easily manufactured by thermoforming. As the thermoforming method, injection molding, extrusion molding, blow molding, blow molding, hot pressing, vacuum molding, pressure-air molding, laser molding, welding, fusion welding, etc. can be cited. As long as it is a molding method that undergoes a hot melting process, any method can be used for molding.

[0189] From the viewpoint of the moldability of the above resin composition, the molded article of the present invention is preferably an injection molded article. In the case of injection molding the above resin composition, it is possible to perform molding without setting the molding temperature and the mold temperature during molding to a high temperature, and thus it is preferable. For example, in injection molding, the molding temperature can be preferably 400°C or lower, more preferably 360°C or lower, and the mold temperature can be preferably 260°C or lower, more preferably 220°C or lower for molding.

[0190] As a method for manufacturing a molded article, for example, the following method can be cited: after drying the pellets produced by the above method, the pellets are introduced into various molding machines for thermoforming to manufacture a molded article having a desired shape.

[0191] <Flame retardancy>

[0192] The resin composition and the molded article of the present invention have high flame retardancy. Specifically, the oxygen index of the above molded article having a thickness of 4 mm, measured according to JIS K 7201:1995, is preferably 28 or more, more preferably 28.5 or more, further preferably 29 or more, still further preferably 30 or more, and still further preferably 32 or more.

[0193] As one of the indexes of flame retardancy, the degree of flame retardancy can be confirmed by measuring the oxygen index. The oxygen index represents the oxygen concentration required to continue combustion, and when it exceeds 21, combustion in air cannot continue under normal conditions. In addition, generally, high flame retardancy is exhibited when the oxygen index is 27 or more.

[0194] Specifically, the oxygen index can be measured by the method described in the examples.

[0195] <Low dielectric properties>

[0196] The resin composition and the molded article of the present invention have low dielectric properties. For example, it is possible to achieve a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.005 or less at a measurement frequency of 10 GHz. The dielectric constant is preferably 2.90 or less, more preferably 2.85 or less, further preferably 2.70 or less, still further preferably 2.50 or less, and the dielectric loss tangent is preferably 0.004 or less, more preferably 0.003 or less. Specifically, the dielectric constant and the dielectric loss tangent can be measured by the method described in the examples.

[0197] <Adhesiveness>

[0198] The resin composition and the molded article of the present invention also have good adhesiveness to metal foils such as copper foils. Therefore, the resin composition and the molded article of the present invention can also be used for metal foil laminates such as copper-clad laminates. The adhesiveness of the molded article formed from the resin composition of the present invention to the copper foil can be evaluated by the method described in the examples.

[0199] <Use>

[0200] The resin composition and the molded article of the present invention are preferably used for applications that require high flame retardancy and low dielectric constant and low dielectric loss tangent, such as being applicable to 5G, or components related to the sixth-generation mobile communication system (6G) using a frequency band of 70G to 300GHz (smartphones, flexible printed circuit boards, metal foil laminates such as copper-clad laminates, antennas, antenna substrates, etc.), various antennas other than the above (microwave antennas, millimeter-wave antennas, waveguide slot antennas, horn antennas, lens antennas, printed antennas, triplate antennas, microstrip antennas, patch antennas, etc.), various antenna substrates (antenna substrates for 77GHz automotive millimeter-wave radars, antenna substrates for terahertz radars, antenna substrates for aircraft radars, antenna substrates for tracked special vehicles, antenna substrates for WiGig, etc.), wire coating materials (low-dielectric wire coating materials, etc.), bonding sheets, insulating films, raw materials for carbon fiber reinforced plastics (CFRP), high-frequency circuit boards, printed wiring boards, chip-on-film (COF) flexible substrates, multi-layer laminates, LED-mounted substrates, industrial robot substrates, communication substrates for household robots, semiconductor element materials, wafers for high-frequency devices, Wi-fi chips, wireless communication devices, transmission lines (coaxial lines, strip lines, microstrip lines, coplanar lines, parallel lines, etc.), coatings for bearings, heat-insulating shafts, trays, various belts (seamless belts, etc.), heat-resistant low-dielectric belts, heat-resistant low-dielectric tubes, various sensors (contact sensors, etc.), various radars (automotive radars, aerospace radars, etc.), radomes, optical communication modules (TOSA / ROSA), cable mobile terminals or digital home appliances for 8k-TV (tablet terminals, notebook PCs, thin TVs, roll-up TVs, digital cameras, smart glasses, smart watches, etc.), base stations (macro cell base stations, small cell base stations, C-RAN base stations, etc.), unmanned aerial vehicles (commercial unmanned aerial vehicles, long-distance mobile unmanned aerial vehicles, etc.), surveillance cameras, indoor or outdoor servers, artificial satellites, communication equipment for space stations, etc.

[0201] Examples

[0202] Next, examples are listed to illustrate the present invention in more detail, but the present invention is not limited thereto. In addition, various measurements and evaluations in each manufacturing example and example are carried out as follows.

[0203] <Infrared spectroscopic analysis (IR measurement)>

[0204] The IR measurement of the polyimide resin was carried out using "JIR-WINSPEC50" manufactured by JEOL Ltd.

[0205] <Logarithmic viscosity μ>

[0206] After drying the polyimide resin at 190 to 200 °C for 2 hours, a polyimide resin solution obtained by dissolving 0.100 g of the polyimide resin in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Chemical Co., Inc.) was used as a measurement sample, and the measurement was carried out at 30 °C using a Cannon-Fenske viscometer. The logarithmic viscosity μ was calculated by the following formula.

[0207] μ = ln[(ts / t0) / C]

[0208] t0: Flow time of concentrated sulfuric acid

[0209] ts: Flow time of the polyimide resin solution

[0210] C: 0.5 g / dL

[0211] <Melting point, glass transition temperature, crystallization temperature, heat of fusion, heat of crystallization>

[0212] The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, heat of fusion Hm, and heat of crystallization Hc of the resin used in each example alone or the resin composition obtained in each example were measured using a differential scanning calorimeter device ("DSC-25" manufactured by TA Instruments). In the measurement of the crystallization temperature Tc, resin powder was used for the polyimide resin, and pellets were used as the measurement sample for the crystalline thermoplastic resin composition.

[0213] Under a nitrogen atmosphere, a heat history under the following conditions was applied to the measurement sample. The conditions of the heat history were the first heating (heating rate 10 °C / minute), subsequent cooling (cooling rate 20 °C / minute), and subsequent second heating (heating rate 10 °C / minute).

[0214] Regarding the melting point Tm, the peak top value of the endothermic peak observed in the second heating was read to determine it. The glass transition temperature Tg was determined by reading the value observed in the second heating. The crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling. It should be noted that regarding Tm, Tg, and Tc, in the case where multiple peaks were observed, the peak top values of each peak were read.

[0215] The heat of fusion Hm (mJ / mg) is calculated from the area of the heat of fusion peak (endothermic peak) near the melting point observed when the test sample is heated at a heating rate of 10 °C / min to a temperature above the melting point to be melted and then cooled at a cooling rate of 20 °C / min and melted again at a heating rate of 10 °C / min. In addition, the heat of crystallization Hc (mJ / mg) is calculated from the area of the crystallization exothermic peak observed when the test sample is heated at a heating rate of 10 °C / min to a temperature above the melting point to be melted and then cooled at a cooling rate of 20 °C / min.

[0216] <Semicrystallization time>

[0217] The semi-crystallization time of the polyimide resin is measured using a differential scanning calorimeter device ("DSC-6220" manufactured by SIINanoTechnologyInc.).

[0218] After maintaining the polyimide resin at 420 °C for 10 minutes in a nitrogen atmosphere to completely melt it and then performing a quenching operation at a cooling rate of 70 °C / min, the time taken from the appearance of the observed crystallization peak to reaching the peak top is calculated. It should be noted that in Table 1, when the semi-crystallization time is 20 seconds or less, it is recorded as "<20".

[0219] <Weight-average molecular weight>

[0220] The weight-average molecular weight (Mw) of the polyimide resin is measured using a gel permeation chromatography (GPC) measuring device "Shodex GPC-101" manufactured by Showa Denko K.K. under the following conditions.

[0221] Column: Shodex HFIP-806M

[0222] Mobile phase solvent: hexafluoroisopropanol (HFIP) containing 2 mM sodium trifluoroacetate

[0223] Column temperature: 40 °C

[0224] Mobile phase flow rate: 1.0 mL / min

[0225] Sample concentration: approximately 0.1 mass%

[0226] Detector: IR detector

[0227] Injection volume: 100 μm

[0228] Standard curve: standard PMMA

[0229] <Heat distortion temperature (HDT)>

[0230] Using only the resins used in each example or the resin compositions obtained in each example, injection-molded articles with dimensions of 80 mm × 10 mm × 4 mm in thickness were manufactured by the methods described below for measurement.

[0231] The measurement was carried out in accordance with JIS K7191-1,2:2015, and a flatwise test was performed. Specifically, using an HDT test device "Auto-HDT3D-2" (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the heat distortion temperature was measured under the conditions of a distance between supports of 64 mm, a load of 1.80 MPa, and a heating rate of 120 °C / hour.

[0232] <Dielectric constant, Dissipation factor>

[0233] Using only the resins used in each example or pellets of the resin compositions obtained in each example, injection-molded articles with a thickness of 1.5 mm were fabricated by the methods described below. The articles were machined to produce test pieces with dimensions of 60 mm × 1.5 mm × 1.5 mm in thickness for measurement. Using a "PNA network analyzer N5222B" manufactured by Keysight Technologies and a cavity resonator "CP531" manufactured by Kanto Electronics Application Development Co., Ltd., the dielectric constant and dissipation factor were measured at a temperature of 23 °C, a humidity of 50%, and a measurement frequency of 10 GHz by the cavity resonance perturbation method in accordance with IEC 62810. The measured values are the average values for n = 2. The test pieces were conditioned at a temperature of 23 °C and a humidity of 50% for more than 24 hours and then quickly used for measurement.

[0234] <Oxygen index>

[0235] Using the resin compositions manufactured in each example, injection-molded articles with dimensions of 80 mm × 10 mm × 4 mm in thickness were fabricated by the methods described below. The molded articles were used as test pieces, and the oxygen index was measured using a candle-type combustion tester D (manufactured by Toyo Seiki Seisakusho Co., Ltd.) by the method based on JIS K 7201:1995.

[0236] Production Example 1 (Production of Polyimide Resin 1)

[0237] Into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and 4-blade impellers, 500 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Emulsion Co., Ltd.) and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Company, Inc.) were introduced. After purging with nitrogen, stirring was carried out at 150 rpm to form a homogeneous suspension. On the other hand, using a 500 mL beaker, 49.79 g (0.35 mol) of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc., cis / trans ratio = 7 / 3) and 93.77 g (0.65 mol) of 1,8-octamethylenediamine (manufactured by Kanto Chemical Co., Inc.) were dissolved in 250 g of 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. This mixed diamine solution was slowly added using a piston pump. Exotherm occurred during the dropping, but the internal temperature was adjusted to be 40 °C to 80 °C. The entire process of dropping the mixed diamine solution was under a nitrogen purge state, and the rotational speed of the stirring blades was 250 rpm. After the dropping was completed, 130 g of 2-(2-methoxyethoxy)ethanol and 1.284 g (0.010 mol) of n-octylamine (manufactured by Kanto Chemical Co., Inc.) as a capping agent were added and further stirred. At this stage, a pale yellow polyamic acid solution was obtained. Next, after setting the stirring speed to 200 rpm, the polyamic acid solution in the 2 L separable flask was heated to 190 °C. During the heating process, precipitation of polyimide resin powder and dehydration accompanied by imidization were confirmed between 120 and 140 °C in the liquid temperature. After holding at 190 °C for 30 minutes, it was cooled to room temperature and filtered. The obtained polyimide resin powder was washed with 300 g of 2-(2-methoxyethoxy)ethanol and 300 g of methanol, filtered, and then dried in a dryer at 180 °C for 10 hours to obtain 317 g of powder of crystalline thermoplastic polyimide resin 1 (hereinafter also simply referred to as "polyimide resin 1").

[0238] The IR spectrum of polyimide resin 1 was measured, and as a result, characteristic absorptions of the imide ring were confirmed at ν(C=O) 1768, 1697 (cm -1 ). The logarithmic viscosity was 1.30 dL / g, Tm was 323 °C, Tg was 184 °C, Tc was 266 °C, the heat of fusion was 26.7 mJ / mg, the heat of crystallization was 30.0 mJ / mg, the half-crystallization time was 20 seconds or less, and Mw was 55,000.

[0239] Production Example 2 (Production of polyimide resin 2)

[0240] Into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and 4-blade impellers, 769 g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Emulsion Co., Ltd.) and 174.50 g (0.80 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Company, Inc.) were introduced. After purging with nitrogen, stirring was carried out at 150 rpm to form a homogeneous suspension solution. On the other hand, using a 500 mL beaker, 22.76 g (0.16 mol) of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Company, Inc., cis / trans ratio = 7 / 3) and 92.33 g (0.64 mol) of 1,8-octamethylenediamine (manufactured by Kanto Chemical Co., Inc.) were dissolved in 250 g of 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. This mixed diamine solution was slowly added using a piston pump. Exotherm occurred upon dropping, but the internal temperature was adjusted to be in the range of 40 °C to 80 °C. The entire process of dropping the mixed diamine solution was under a nitrogen purge state, and the rotational speed of the stirring blades was 250 rpm. After the dropping was completed, 10 g of 2-(2-methoxyethoxy)ethanol and 1.027 g (0.008 mol) of n-octylamine (manufactured by Kanto Chemical Co., Inc.) as a capping agent were added and further stirred. At this stage, a pale yellow polyamic acid solution was obtained. Next, after setting the stirring speed to 200 rpm, the polyamic acid solution in the 2 L separable flask was heated to 185 °C. During the heating process, precipitation of polyimide resin powder and dehydration accompanied by imidization were confirmed between 120 and 140 °C of the liquid temperature. After holding at 185 °C for 30 minutes, it was cooled to room temperature and filtered. The obtained polyimide resin powder was washed with 600 g of methanol, filtered, and then dried at 185 °C for 10 hours using a dryer to obtain 256 g of a powder of crystalline thermoplastic polyimide resin 2 (hereinafter also simply referred to as "polyimide resin 2").

[0241] The Tm of polyimide resin 2 was 344 °C, the Tg was 166 °C, the Tc was 299 °C, the heat of fusion was 40 mJ / mg, the heat of crystallization was 35 mJ / mg, and the Mw was 36,000.

[0242] The compositions and evaluation results of the polyimide resins obtained in Production Examples 1 to 2 are shown in Table 1. It should be noted that the mol% of the tetracarboxylic acid component and the diamine component in Table 1 are values calculated from the input amounts of the respective components during the production of the polyimide resin.

[0243] [Table 1]

[0244] Table 1

[0245]

[0246] *1: Mole percentage of the repeating structural unit of formula (1) in the polyimide resin relative to the total of the repeating structural units of formula (1) and the repeating structural unit of formula (2)

[0247] The abbreviations in Table 1 are as follows.

[0248] ·PMDA: Pyromellitic dianhydride

[0249] ·1,3-BAC: 1,3-Bis(aminomethyl)cyclohexane

[0250] ·OMDA: 1,8-Octamethylenediamine

[0251] ·n-OcA: n-Octylamine

[0252] Example 1 (Production and evaluation of resin composition and molded article)

[0253] The powder of the polyimide resin 1 obtained in Production Example 1 and the powder of poly(2,6-dimethyl-1,4-phenylene ether) (Polyxylenol Singapore Pte Ltd's "PX100F", Tg = 207°C, intrinsic viscosity at 30°C measured in chloroform = 0.37 dL / g) as component (B) were dry-blended in the proportions shown in Table 2, and then melt-kneaded and extruded using a co-rotating twin-screw kneading extruder (PARKER CORPORATION's "HK-25D", screw diameter 25 mmΦ, L / D = 41) under the conditions of a barrel temperature of 330 - 340°C and a screw rotation speed of 120 rpm. The strand extruded from the extruder was air-cooled and then pelletized using a pelletizer (Hoshi Plastics Co., Ltd.'s "Fan Cutter FC-Mini-4 / N"). The obtained pellets were dried at 80°C for 12 hours and then used for injection molding.

[0254] Using an injection molding machine (FANUC Corporation's "Roboshotα-S30iA"), injection molding was carried out at a barrel temperature of 360°C, a mold temperature of 180°C, and a molding cycle of 72 seconds to produce an injection molded article of a specified shape for the above evaluation.

[0255] Using the obtained pellets or injection molded article, various evaluations were carried out by the above methods. The results are shown in Table 2.

[0256] Example 2, Comparative Examples 2 - 4

[0257] The powder of the polyimide resin 1 obtained in Production Example 1 and the powder of poly(2,6-dimethyl-1,4-phenylene ether) “PX100F” were used in the ratios shown in Table 2, and injection molding was carried out within the range of a molding cycle of 65 seconds to 72 seconds (Example 2: 73 seconds, Comparative Example 2: 65 seconds, Comparative Example 3: 67 seconds, Comparative Example 4: 77 seconds). Except for this, pellets and injection molded articles were produced in the same manner as in Example 1, and various evaluations were carried out. The results are shown in Table 2.

[0258] Comparative Example 1

[0259] The powder of the polyimide resin 1 obtained in Production Example 1 was melt-kneaded and extruded using a LABO PLASTMILL (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a barrel temperature of 360 °C and a screw rotation speed of 150 rpm. After the strand extruded from the extruder was air-cooled, it was pelletized using a pelletizer (“Fan Cutter FC-Mini-4 / N” manufactured by Hoshi Plastics Co., Ltd.). The obtained pellets were dried at 150 °C for 12 hours and then used for injection molding.

[0260] Using an injection molding machine (“ROBOSHOTα-S30iA” manufactured by FANUC Corporation), injection molding was carried out at a barrel temperature of 350 °C, a mold temperature of 200 °C, and a molding cycle of 50 seconds to produce an injection molded article having a specified shape for the above evaluation (HDT measurement).

[0261] Using the obtained pellets or injection molded articles, various evaluations were carried out by the above methods. The results are shown in Table 2.

[0262] [Table 2]

[0263] Table 2

[0264]

[0265] As shown in Table 2, it was found that the molded articles formed from the resin compositions of Examples 1 to 2 had a higher oxygen index and higher flame retardancy than the molded articles of Comparative Examples 1 to 4.

[0266] Comparative Examples 5 to 6, Examples 3 to 4

[0267] The polyimide resin 2 obtained in Production Example 2 and the powder of poly(2,6-dimethyl-1,4-phenylene ether) (Polyxylenol Singapore Pte Ltd “PX100L”, Tg = 210 °C, intrinsic viscosity at 30 °C measured in chloroform = 0.47 dL / g) as component (B) were used in the ratios shown in Table 3. Except for this, pellets and injection molded articles were produced in the same manner as in Example 1, and the oxygen index was measured. The results are shown in Table 3.

[0268] [Table 3]

[0269] Table 3

[0270]

[0271] As shown in Table 3, it can be seen that the molded article formed from the resin composition of Examples 3 to 4 has a higher oxygen index and is highly flame retardant compared to the molded articles of Comparative Examples 5 to 6.

[0272] The details of each component shown in Tables 2 to 3 are as described below.

[0273] <Component (A)>

[0274] · Polyimide resin 1: Crystalline thermoplastic polyimide resin 1 obtained in Production Example 1

[0275] · Polyimide resin 2: Crystalline thermoplastic polyimide resin 2 obtained in Production Example 2

[0276] <Component (B)>

[0277] · PX100F: Poly(2,6-dimethyl-1,4-phenylene ether), "PX100F" manufactured by Polyxylenol Singapore Pte Ltd, Tg = 207 °C, intrinsic viscosity at 30 °C measured in chloroform = 0.37 dL / g

[0278] · PX100L: Poly(2,6-dimethyl-1,4-phenylene ether), "PX100L" manufactured by Polyxylenol Singapore Pte Ltd, Tg = 210 °C, intrinsic viscosity at 30 °C measured in chloroform = 0.47 dL / g

[0279] Furthermore, the morphology of the pellets obtained in Example 1 was confirmed by the following method.

[0280] Using an ultramicrotome ("EMUC7" manufactured by Leica Microsystems), as Figure 1 shown, the pellets obtained in Example 1 were cut in a direction orthogonal to the flow direction (MD) of the pellets (i.e., in a manner to form a TD cross-section) to produce ultrathin sections. In Figure 1 , 1 is the pellet and 2 is the ultrathin section.

[0281] After staining the slice in the gas phase of ruthenium tetroxide for 30 minutes, a field emission scanning transmission electron microscope (FE-STEM, "Gemini SEM500" manufactured by Carl Zeiss) was used at an acceleration voltage of 30 kV, column mode: Normal, aperture size: 20 μm, working distance: 3.6 mm, detection signal: aSTEM A, observation magnification: 10,000 times, and transmission observation was performed using a STEM detector ( Figure 2 ). In Figure 2 's observation image, the dark part corresponds to the stained part, and the bright part corresponds to the non-stained part. In the observation image, it was judged that the part with a deep color was composed of resin (B) that was easily stained by ruthenium tetroxide.

[0282] From Figure 2 , it can be seen that in the pellets obtained in Example 1, the polyimide resin (A) and the resin (B) form a microphase separation structure (sea-island structure). In addition, it is speculated that the polyimide resin (A) forms the island part and the resin (B) forms the sea part.

[0283] Example 1A (Production and evaluation of a film, and evaluation of the adhesiveness between the film and a copper foil)

[0284] <Production of a film>

[0285] After drying the pellets of the resin composition obtained in Example 1 at 150 °C for 10 hours, they were put into a single-screw extrusion molding machine equipped with a T die head having a width of 150 mm, and melt-kneaded at a resin temperature of 350 to 360 °C. The melt-kneaded resin composition was continuously extruded from the T die head of the single-screw extrusion molding machine, and then cooled with a metal roll as a cooling roll at 140 °C to obtain a film with a thickness of 70 μm.

[0286] Here, the temperature of the single-screw extrusion molding machine was set to 335 to 340 °C, and the temperature of the T die head was set to 335 °C.

[0287] <Adhesiveness between the film and the copper foil>

[0288] Three 10 cm × 10 cm films and a 10 cm × 10 cm × 12 μm thick copper foil 4 (rolled copper foil, "TQ-MS-VSP" of JX Metals Co., Ltd.) prepared by the above method were prepared. As Figure 3 shown in (a) of Figure 3(in (a), d = 1 cm). Place another release paper on it and perform heat sealing using a thermal tilt testing machine (manufactured by Toyo Seiki Seisaku-sho, Ltd., heater: upper side). The heat sealing conditions are 250 °C, 0.4 MPa (gauge pressure) for 60 seconds.

[0289] After heat sealing, remove the release paper and cut along the MD direction of the film shown in Figure 3 (a) of to produce a strip-shaped test piece with a width of 1 cm ( Figure 3 (b) of). Figure 3 In (b), the bonding area between the film 3' and the copper foil 4' is 1 cm 2 .

[0290] Next, hold the short side of the film 3' of the obtained test piece. As shown in Figure 4 , when hanging it with the long side parallel to the direction of gravity, if the lower copper foil 4' does not fall within 30 seconds, it is judged to have adhesiveness.

[0291] <Tensile Adhesion Strength>

[0292] Produce a test piece in the same manner as in the evaluation of the "adhesiveness between the film and the copper foil" above for evaluation. On the fixture of a universal testing machine ("Strograph VG" manufactured by Toyo Seiki Seisaku-sho, Ltd.), set the above test piece with the film on the upper side and the copper foil on the lower side, with the long side parallel to the direction of gravity. According to JIS K 6849-1994, conduct a tensile shear test under the conditions of temperature: 23 °C, test range: 200 N, test speed: 5 mm / minute, and obtain the tensile adhesion strength (N / cm 2 ).

[0293] Example 2A

[0294] Except for changing the resin composition used in the production of the film to the resin composition obtained in Example 2, produce a film in the same manner as in Example 1A and conduct evaluation. The results are shown in Table 4.

[0295] [Table 4]

[0296] Table 4

[0297]

[0298] As can be seen from Table 4, the film formed from the resin composition of the present invention has adhesiveness to the copper foil, and thus can also be used for metal foil laminates such as copper-clad laminates.

[0299] Industrial Applicability

[0300] According to the present invention, there can be provided a resin composition and a molded article that use a small amount of a flame retardant or exhibit high flame retardancy even without using a flame retardant.

[0301] Explanation of reference numerals

[0302] 1 pellet

[0303] 2 ultra-thin section

[0304] 3, 3' film

[0305] 4, 4' copper foil

Claims

1. A resin composition comprising: a polyimide resin (A) containing a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the content ratio of the repeating structural unit of formula (1) relative to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) being 20 to 70 mol%; and a resin represented by the following formula (5) or its acid-modified product (B), the content mass ratio of the component (B) relative to the total content mass of the component (A) and the component (B) [(B) / {(A)+(B)}] being greater than 0.50, R1 is a divalent group having 6 to 22 carbon atoms containing at least 1 alicyclic hydrocarbon structure; R2 is a divalent linear aliphatic group having 5 to 16 carbon atoms; X1 and X2 are each independently a tetravalent group having 6 to 22 carbon atoms containing at least 1 aromatic ring; R 51 ~R 55 and R 61 ~R 64 Each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and R 65 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; n is the number of repeating structural units and is a number of 10 or more.

2. The resin composition according to claim 1, wherein, the total content of the component (A) and the component (B) in the resin composition being 50% by mass or more.

3. The resin composition according to claim 1 or 2, wherein The intrinsic viscosity of the component (B) measured in chloroform at 30 °C is 0.20 to 0.60 dL / g.

4. The resin composition according to any one of claims 1 to 3, wherein, The resin composition is obtained by melt-kneading at a temperature higher than the melting point of the component (A).

5. The resin composition according to any one of claims 1 to 4, wherein, The pellets formed from the resin composition have a microphase-separated structure.

6. A molded article comprising the resin composition according to any one of claims 1 to 5.

7. The shaped body according to claim 6, wherein, The molded article is an injection molded article.

8. The shaped body according to claim 6 or 7, wherein, The oxygen index of the molded article with a thickness of 4 mm measured according to JIS K 7201:1995 is 28 or more.

Images