Thermoplastic polyimide resin, production method for same, and molded article

Abstract

Provided is a thermoplastic polyimide resin that includes a prescribed repeating structural unit and that is obtained by reacting: a tetracarboxylic acid component (A) including a tetracarboxylic dianhydride (A1) represented by formula (A-1); a diamine component (B) including a diamine (B1) represented by formula (B-1) and a diamine (B2) represented by formula (B-2); and an amine (Z) represented by formula (Z-1), wherein the amount of the amine (Z) with respect to 100 parts by mass of the diamine (B2) is 0.10-0.70 parts by mass. Also provided are a production method for the thermoplastic polyimide resin, and a molded article.

Description

Thermoplastic polyimide resin, method for producing the same, and molded article

[0001] This invention relates to thermoplastic polyimide resin, a method for producing the same, and molded articles.

[0002] Polyimide resins are useful engineering plastics with high thermal stability, high strength, and high solvent resistance due to the rigidity of their molecular chains, resonance stabilization, and strong chemical bonding, and are applied in a wide range of fields. While polyimide resins have high heat resistance, they do not exhibit thermoplasticity and have the problem of poor moldability. However, in recent years, thermoplastic polyimide resins have been reported. Thermoplastic polyimide resins have excellent moldability in addition to the heat resistance inherent in polyimide resins. Therefore, thermoplastic polyimide resins can be applied to molded articles used in harsh environments where general-purpose thermoplastic resins such as nylon and polyester could not be used.

[0003] For example, Patent Document 1 proposes a thermoplastic polyimide resin that has a structure derived from a tetracarboxylic acid component and an aliphatic diamine component, and satisfies predetermined conditions, as a polyimide resin that has a good balance of moldability and heat resistance, and further has high solder reflow resistance.

[0004] International Publication No. 2016 / 147996

[0005] Since thermoplastic resin molding materials are subjected to thermoforming after melting, controlling the stagnation behavior during melting is industrially important. Specifically, it is preferable that the viscosity does not decrease due to thermal decomposition of the resin even when the preheating time during melting is extended. Furthermore, from the viewpoint of improving the dimensional stability of the resulting thermoformed article, it is sometimes preferable to observe a moderate increase in viscosity during melting. However, in Patent Document 1, no thermoplastic polyimide resin exhibiting a moderate increase in viscosity during melting has been found.

[0006] The object of the present invention is to provide a thermoplastic polyimide resin having predetermined repeating structural units, without viscosity reduction during melting, and with an appropriate viscosity increase, a method for producing the same, and a molded article.

[0007] The inventors of the present invention have found that a thermoplastic polyimide resin obtained by reacting a specific amount of a specific compound in addition to a specific tetracarboxylic acid component and a diamine component can solve the above problems. That is, the present invention relates to the following. [1] A thermoplastic polyimide resin containing a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), wherein 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 15 to 70 mol%, (R １ is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure. R ２ is a divalent linear aliphatic group having 9 to 14 carbon atoms. X １ and X ２ are each independently a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.) The thermoplastic polyimide resin includes a tetracarboxylic acid component (A) containing a tetracarboxylic dianhydride (A1) represented by the following formula (A-1), (X is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.) A diamine component (B) containing a diamine (B1) represented by the following formula (B-1) and a diamine (B2) represented by the following formula (B-2), H ２ N-R １ -NH ２ (B-1) H ２ N-R ２ -NH ２ (B-2) (R １ and R ２ are the same as above.) It is obtained by reacting an amine (Z) represented by the following formula (Z-1), H ２ N-R ２ -NH-CH ２ CH ３ (Z-1) (R ２(The same as above.) A thermoplastic polyimide resin in which the amount of amine (Z) per 100 parts by mass of diamine (B2) is 0.10 to 0.70 parts by mass. [2] The thermoplastic polyimide resin according to [1], wherein the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural units of formula (1) and the repeating structural units of formula (2) is 15 mol% or more and less than 40 mol%. [3] The thermoplastic polyimide resin according to [1] or [2], wherein the thermoplastic polyimide resin is a crystalline thermoplastic polyimide resin. [4] The R １ A thermoplastic polyimide resin according to any one of [1] to [3], wherein the group is a divalent group represented by the following formula (R1-1) or (R1-2). (m １１ and m １２ Each of these is an integer between 0 and 2, independently of the others. １３ ~m １５ Each of these is an integer between 0 and 2, independently of the others.) [5] The above R ２ A thermoplastic polyimide resin according to any one of [1] to [4], wherein is an alkylene group having 9 to 14 carbon atoms. [6] X in formula (A-1), X in formula (1) １ and X in formula (2) ２ A thermoplastic polyimide resin according to any one of items [1] to [5], wherein is a tetravalent group represented by the following formula (X-5) or (X-6). [7] The thermoplastic polyimide resin according to any one of [1] to [6], wherein the thermoplastic polyimide resin is obtained by reacting the tetracarboxylic acid component (A), the diamine component (B), the amine (Z), and an end-capturing agent. [8] A method for producing the thermoplastic polyimide resin according to any one of [1] to [7], comprising the step of reacting the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z). [9] A method for producing the thermoplastic polyimide resin according to [8], comprising the following steps (I) to (IV) in order. Step (I): A step of mixing the tetracarboxylic acid component (A) and the solvent (C) to prepare a mixture 1. Step (II): A step of mixing the mixture 1 with the diamine component (B) and the amine (Z) to prepare a solution 2 containing a polyimide resin precursor containing polyamic acid. Step (III): A step of heating the solution 2 to imidize the polyimide resin precursor, thereby precipitating polyimide resin powder in the solution, and preparing a slurry 3 containing the polyimide resin powder. Step (IV): A step of separating the slurry 3 into solid and liquid.

[10] A method for producing a thermoplastic polyimide resin according to [9], wherein the solvent (C) contains an alkylene glycol solvent represented by the following formula (C-1). (Ra １ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ra ２ (where n is a linear alkylene group having 2 to 6 carbon atoms, and n is an integer from 1 to 3.)

[11] A method for producing a thermoplastic polyimide resin according to [9] or

[10] , wherein step (II) further comprises the step of adding an end-capturing agent.

[12] A molded article comprising the thermoplastic polyimide resin according to any one of [1] to [7].

[0008] According to the present invention, it is possible to provide a thermoplastic polyimide resin having a predetermined repeating structural unit, without viscosity reduction during melting, and with an appropriate viscosity increase, a method for producing the same, and a molded article.

[0009] [Definition] In this specification, thermoplastic polyimide resin means a polyimide resin having a glass transition temperature. That is, thermoplastic polyimide resin is distinguished from polyimide resins that do not have a glass transition temperature (Tg), which are formed by molding a polyimide precursor such as polyamic acid and then closing the imide ring, or from polyimide resins that decompose at a temperature lower than the glass transition temperature.

[0010] In this specification, the viscosity of a thermoplastic polyimide resin during melting refers to the viscosity measured using a capillary rheometer at a temperature exceeding the melting point of the thermoplastic polyimide resin. The viscosity change of a thermoplastic polyimide resin during melting can be evaluated by the rate of change in viscosity measured after preheating for a certain period of time (15 to 30 min) compared to the viscosity measured at 6 min of preheating under the above conditions at the same extrusion rate (10 mm / min or 100 mm / min). Furthermore, "appropriate viscosity increase during melting of thermoplastic polyimide resin" means that the viscosity change rate at extrusion rates of 10 mm / min and 100 mm / min is in the range of 10 to 100%. The viscosity and viscosity change rate can be measured specifically by the method described in the examples.

[0011] [Thermoplastic Polyimide Resin] The thermoplastic polyimide resin of the present invention (hereinafter also simply referred to as "(the present invention) polyimide resin") comprises repeating structural units represented by the following formula (1) and repeating structural units represented by the following formula (2), wherein the content ratio of repeating structural units of formula (1) to the total of repeating structural units of formula (1) and repeating structural units of formula (2) is 15 to 70 mol%, (R １ R is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ X is a divalent, chain-like aliphatic group having 9 to 14 carbon atoms. １ and X ２ Each of these is independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) The thermoplastic polyimide resin comprises a tetracarboxylic acid component (A) containing a tetracarboxylic dianhydride (A1) represented by the following formula (A-1), (X is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) Diamine component (B) including diamine (B1) represented by the following formula (B-1) and diamine (B2) represented by the following formula (B-2), and H ２ N-R １ -NH ２ (B-1) H ２ N-R ２ -NH ２ (B-2) (R １ , R ２ (This is the same as above.) It is obtained by reacting the amine (Z) shown in the following formula (Z-1) with H ２ N-R ２ -NH-CH ２ CH ３ (Z-1) (R ２ (The same as above.) The amount of amine (Z) per 100 parts by mass of diamine (B2) is 0.10 to 0.70 parts by mass.

[0012] The polyimide resin of the present invention, having the above configuration, is a thermoplastic polyimide resin that does not experience a decrease in viscosity during melting and exhibits a moderate increase in viscosity. The reason for this is not entirely clear, but it is thought to be as follows. Generally, polymers tend to decrease in viscosity when they are heated and melted due to thermal decomposition, etc. In contrast, the thermoplastic polyimide resin of the present invention is presumed to have a structure derived from the amine (Z) at the end or side chain of the polyimide resin, or to have the amine (Z) present in the polyimide resin in a partially amidized state. It is presumed that when the polyimide resin is heated and melted, a crosslinked structure is formed, and the viscosity increases without decreasing. Also, R in formula (2) ２ Because it is a divalent, chain-like aliphatic group with 9 to 14 carbon atoms, it is thought that thermal decomposition and other processes are less likely to occur. By keeping the amount of amine (Z) added during the production of the polyimide resin within a predetermined range, it is thought that the increase in molecular weight during the production of the polyimide resin is not hindered, and the excessive crosslinking reaction and the resulting increase in viscosity during the thermal melting of the obtained polyimide resin are suppressed.

[0013] (Tetracarboxylic acid component (A)) Tetracarboxylic acid component (A) includes tetracarboxylic dianhydride (A1) represented by the following formula (A-1). (X is a tetravalent group with 6 to 22 carbon atoms that contains at least one aromatic ring.)

[0014] X is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring. The aromatic ring may be a monoring or a fused ring, and examples include a benzene ring, a naphthalene ring, anthracene ring, and a tetracene ring. Among these, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. The number of carbon atoms in X is 6 to 22, preferably 6 to 18. X contains at least one aromatic ring, preferably 1 to 3.

[0015] X is preferably a tetravalent group represented by any of the following formulas (X-1) to (X-4). (R １１ ~R １８ These are each independently alkyl groups having 1 to 4 carbon atoms. １１ ~p １３ Each of these is an integer between 0 and 2, preferably 0. １４ , p １５ , p １６ and p １８ Each of these is an integer between 0 and 3, preferably 0. １７ L is an integer between 0 and 4, preferably 0. １１ ~L １３ Each of these is independently a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.) Note that X is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring, so R in formula (X-2) １２ , R １３ , p １２ and p １３ The number of carbon atoms in the tetravalent group represented by formula (X-2) is selected to fall within the range of 10 to 22. Similarly, L in formula (X-3) １１ , R １４ , R １５ , p １４ and p １５The number of carbon atoms in the tetravalent group shown in formula (X-3) is selected to fall 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 The carbon atoms in the tetravalent group represented by formula (X-4) are selected such that the number of carbon atoms falls within the range of 18 to 22.

[0016] X is more preferably a tetravalent group represented by the following formula (X-5) or (X-6), and even more preferably a tetravalent group represented by the following formula (X-5).

[0017] Specific examples of tetracarboxylic dianhydride (A1) include pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 1,4,5,8-naphthalene tetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used individually or in combination of two or more. Among these, tetracarboxylic dianhydride (A1) preferably includes pyromellitic dianhydride.

[0018] The tetracarboxylic acid component (A) may include a tetracarboxylic dianhydride (A1) and a derivative of the tetracarboxylic dianhydride (tetracarboxylic acid and / or alkyl ester of tetracarboxylic acid). Examples of the above 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 preferred. Examples of alkyl esters of tetracarboxylic acid include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid dimethyl, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dimethyl, 3,3',4,4'-benzophenonetetracarboxylic acid dimethyl, 3,3',4,4'-biphenyltetracarboxylic acid dimethyl, and 1,4,5,8-naphthalenetetracarboxylic acid dimethyl. In the alkyl esters of the above-mentioned tetracarboxylic acids, the number of carbon atoms in the alkyl group is preferably 1 to 3. One or more of these tetracarboxylic acids and their derivatives can be used.

[0019] The content of the tetracarboxylic dianhydride (A1) represented by formula (A-1) in the tetracarboxylic acid component (A) is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and 100 mol% or less of the total tetracarboxylic acid component (A). Furthermore, it is preferable that the proportion of tetracarboxylic acid in the tetracarboxylic acid component (A) be small, preferably 50 mol% or less, more preferably 30 mol% or less, and even more preferably 0 mol%.

[0020] (Diamine component (B)) Diamine component (B) includes diamine (B1) represented by the following formula (B-1) and diamine (B2) represented by the following formula (B-2). ２ N-R １ -NH ２ (B-1) H ２N-R ２ -NH ２ (B-2) (R １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. R ２ is a divalent linear aliphatic group having 9 to 14 carbon atoms.)

[0021] [Diamine (B1)] Diamine (B1) is a diamine represented by the following formula (B-1). Diamine (B1) is an aliphatic diamine and does not contain an aromatic ring. H ２ N-R １ -NH ２ (B-1) (R １ 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 cycloalkane rings such as cyclohexane rings, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane rings, and bicycloalkene rings such as norbornene. Among these, cycloalkane rings are preferred, cycloalkane rings having 4 to 7 carbon atoms are more preferred, and cyclohexane rings are even more preferred. R １ has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms. R １ contains at least one alicyclic hydrocarbon structure, preferably 1 to 3 alicyclic hydrocarbon structures.)

[0022] R １ is preferably a divalent group represented by the following formula (R1-1) or (R1-2), and more preferably a divalent group represented by the following formula (R1-3). (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.) In addition, 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 cis or trans, and the ratio of cis to trans may be any value.

[0023] The diamine (B1) is more preferably a diamine represented by the following formula (B1-1). (m １１ and m １２ are each independently an integer of 0 to 2, preferably 0 or 1.)

[0024] Specific examples of the diamine (B1) 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), carbonyldiamine, limonenediamine, isophoronediamine, norbornanediamine, bis(aminomethyl)tricyclo[5.2.1.0 ２，６ decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, etc. Among these, one or more of these can be used. Among the above, the diamine (B1) preferably contains at least one selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, and more preferably contains 1,3-bis(aminomethyl)cyclohexane.

[0025] [Diamine (B2)] The diamine (B2) is a diamine represented by the following formula (B-2). H ２ N-R ２ -NH ２ (B-2) (R ２(This refers to a divalent linear aliphatic group having 9 to 14 carbon atoms.) Here, a linear aliphatic group means a group derived from a linear aliphatic compound, and the linear aliphatic compound may be saturated or unsaturated, linear or branched, and may contain heteroatoms such as oxygen atoms. ２ The alkylene group is preferably a C9-C14 alkylene group, more preferably a C9-C12 alkylene group, and even more preferably a C10 alkylene group. The alkylene group may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group. ２ Preferably, it is at least one selected from the group consisting of a nonameethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, and a tetradecamethylene group; more preferably, it is at least one selected from the group consisting of a nonameethylene group, a decamethylene group, and a dodecamethylene group; even more preferably, it contains a decamethylene group; and even more preferably, it is a decamethylene group.

[0026] Also, R ２ Another preferred embodiment is a divalent linear aliphatic group having 9 to 14 carbon atoms (preferably 9 to 12 carbon atoms, more preferably 10 carbon atoms) containing an ether group. Among these, a divalent group represented by the following formula (R2-1) or (R2-2) is preferred. (m ２１ and m ２２ Each of these is an integer between 1 and 13, preferably between 1 and 11, and more preferably between 1 and 9. ２３ ~m ２５ Each of these is an integer from 1 to 10, preferably from 1 to 8. ２ Since is a divalent chain-like aliphatic group having 9 to 14 carbon atoms (preferably 9 to 12 carbon atoms, more preferably 10 carbon atoms), in formula (R2-1) m ２１ and m ２２ The carbon atoms of the divalent group represented by formula (R2-1) are selected to fall within the range of 9 to 14 (preferably 9 to 12 carbon atoms, more preferably 10 carbon atoms). That is, m ２１ +m ２２m in formula (R2-2) is 9 to 14 (preferably 9 to 12, more preferably 10). ２３ ~m ２５ The carbon atoms of the divalent group represented by formula (R2-2) are selected to fall within the range of 9 to 14 (preferably 9 to 12 carbon atoms, more preferably 10 carbon atoms). That is, m ２３ +m ２４ +m ２５ The carbon atoms are 9 to 14 (preferably 9 to 12 carbon atoms, more preferably 10 carbon atoms).

[0027] Preferred specific examples of diamine (B2) include 1,9-nonameethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, and 1,14-tetradecamethylenediamine, and one or more of these can be used. Among the above, diamine (B2) preferably has R in formula (B-2) ２ The diamine (B2) contains a diamine which is an alkylene group having 9 to 12 carbon atoms, more preferably containing at least one selected from the group consisting of 1,9-nonameethylenediamine, 1,10-decamethylenediamine, and 1,12-dodecamethylenediamine, and even more preferably containing 1,10-decamethylenediamine. From the viewpoint of reducing environmental impact, the diamine (B2) is preferably a bio-based diamine made from biological resources such as plant biomass.

[0028] The diamine component (B) is more preferably the diamine represented by formula (B1-1) as diamine (B1) and the diamine represented by formula (B-2) as R ２The compound comprises a diamine having an alkylene group with 9 to 12 carbon atoms, more preferably diamine (B1) comprising at least one selected from the group consisting of 1,9-nonameethylenediamine, 1,10-decamethylenediamine, and 1,12-dodecamethylenediamine, and diamine (B2) comprising at least one selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane, more preferably diamine (B1) comprising 1,3-bis(aminomethyl)cyclohexane and diamine (B2) comprising 1,10-decamethylenediamine.

[0029] From the viewpoint of easily obtaining the thermoplastic polyimide resin of the present invention and improving the crystallinity and thermoformability of the obtained thermoplastic polyimide resin, the ratio of diamine (B1) to 100 mol% of the total of diamine (B1) and diamine (B2) is preferably 15 to 70 mol%, more preferably 15 to 65 mol%, even more preferably 15 to 60 mol%, even more preferably 15 to 50 mol%, even more preferably 15 mol% or more and less than 40 mol%, even more preferably 17 to 38 mol%, even more preferably 20 to 38 mol%, even more preferably 22 to 38 mol%, even more preferably 25 to 38 mol%, even more preferably 28 to 38 mol%, and even more preferably 30 to 37 mol%.

[0030] The diamine component (B) may consist only of the aliphatic diamines diamine (B1) and diamine (B2), but may also include a diamine (B3) containing an aromatic ring. The diamine (B3) containing an aromatic ring is preferably a diamine containing at least one aromatic ring, and more preferably a diamine represented by the following formula (B-3). ２ N-R ３ -NH ２ (B-3) (R ３ (This is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) The aromatic ring may be a monoring or a fused ring, and examples include a benzene ring, a naphthalene ring, anthracene ring, and a tetracene ring. Among these, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred. ３The number of carbon atoms is 6 to 22, preferably 6 to 18. ３ It contains at least one aromatic ring, preferably 1 to 3. The aromatic ring may also have a monovalent or divalent electron-withdrawing group attached. Examples of monovalent electron-withdrawing groups include nitro groups, cyano groups, p-toluenesulfonyl groups, halogens, alkyl halides, phenyl groups, and acyl groups. Examples of divalent electron-withdrawing groups include alkylene fluorides (e.g., -C(CF) ３ ) ２ -, - (CF ２ ) ｐ In addition to halogenated alkylene groups such as -CO- and -SO- (where p is an integer from 1 to 10), there are also -CO- and -SO- ２ Examples include -, -SO-, -CONH-, -COO-, etc.

[0031] R ３ Preferably, it is a divalent group represented by the following formula (R3-1) or (R3-2). (m ３１ and m ３２ Each of these is an integer between 0 and 2, preferably 0 or 1. ３３ and m ３４ Each of these is an integer between 0 and 2, preferably 0 or 1. ２１ , R ２２ , and R ２３ These are, 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 L is an integer between 0 and 4, preferably 0. ２１ (This is a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.) Note that R ３ Since is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring, m in formula (R3-1) ３１ , m ３２ , R ２１ and p ２１ The number of carbon atoms in the divalent group represented by formula (R3-1) is selected to fall within the range of 6 to 22. Similarly, L in formula (R3-2) ２１ , m３３ , m ３４ , R ２２ , R ２３ , p ２２ and p ２３ The carbon atoms in the divalent group represented by formula (R3-2) are selected to fall within the range of 12 to 22.

[0032] Specific examples of diamines (B3) include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 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, 1,5-diaminonaphthalene, etc., and one or more of these can be used in combination.

[0033] The diamine component (B) may further contain the diamine (B4) represented by the following formula (B-4). ２ N-R ４ -NH ２ (B-4) (R ４ Ha-SO ２ - or -Si(R ｘ ) (Caution ｙ ) A divalent group containing O-, R ｘ and R ｙ Each of these independently represents a chain-like aliphatic group or a phenyl group having 1 to 3 carbon atoms.

[0034] However, from the viewpoint of easily obtaining the thermoplastic polyimide resin of the present invention, the total content of diamine (B1) and diamine (B2) in diamine component (B) is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, even more preferably 90 mol% or more, and also 100 mol% or less, based on the total number of moles of diamine in diamine component (B).

[0035] The reaction molar ratio of the tetracarboxylic acid component (A) to the diamine component (B) is preferably in the range of 0.9 to 1.1 moles of the diamine component (B) per mole of the tetracarboxylic acid component (A).

[0036] (Amine (Z)) The thermoplastic polyimide resin of the present invention is obtained by reacting the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z) represented by the following formula (Z-1). ２ N-R ２ -NH-CH ２ CH ３ (Z-1) (R ２ R is a divalent, chain-like aliphatic group having 9 to 14 carbon atoms. ) In formula (Z-1), R ２ R in formula (B-2) is ２ It is the same as R in equation (Z-1) ２ R is preferably an alkylene group having 9 to 14 carbon atoms, more preferably an alkylene group having 9 to 12 carbon atoms, and even more preferably an alkylene group having 10 carbon atoms. The alkylene group may be a linear alkylene group or a branched alkylene group, but is preferably a linear alkylene group. ２ Preferably, it is at least one selected from the group consisting of a nonameethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, and a tetradecamethylene group; more preferably, it is at least one selected from the group consisting of a nonameethylene group, a decamethylene group, and a dodecamethylene group; even more preferably, it contains a decamethylene group; and even more preferably, it is a decamethylene group.

[0037] Specific examples of amine (Z) include at least one selected from the group consisting of N-ethyl nonamethylenediamine, N-ethyl decamethylenediamine, N-ethyl undecamethylenediamine, N-ethyl dodecamethylenediamine, N-ethyl tridecamethylenediamine, and N-ethyl tetradecamethylenediamine. Preferably, it includes N-ethyl nonamethylenediamine, N-ethyl decamethylenediamine, and at least one selected from the group consisting of N-ethyl nonamethylenediamine and N-ethyl decamethylenediamine, and more preferably it includes N-ethyl decamethylenediamine.

[0038] The thermoplastic polyimide resin of the present invention is obtained by reacting the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z). Here, the amount of amine (Z) per 100 parts by mass of diamine (B2) is 0.10 to 0.70 parts by mass, preferably 0.12 to 0.65 parts by mass, more preferably 0.15 to 0.60 parts by mass, even more preferably 0.20 to 0.50 parts by mass, and even more preferably 0.30 to 0.50 parts by mass, from the viewpoint of obtaining a thermoplastic polyimide resin that does not decrease viscosity during melting and exhibits a moderate increase in viscosity.

[0039] Furthermore, in the production of diamine (B2), if it is possible to adjust the catalyst and production conditions used to carry out a reaction in parallel that produces a predetermined amount of amine (Z), the product (a mixture of diamine (B2) and amine (Z)) may be used as a raw material for the thermoplastic polyimide resin of the present invention. In this case, the content of amine (Z) per 100 parts by mass of diamine (B2) can be determined by gas chromatography (GC) analysis or the like. For example, by performing GC measurement on diamine (B2) containing amine (Z), the content of amine (Z) per 100 parts by mass of diamine (B2) can be determined from the ratio of the peak area derived from diamine (B2) to the peak area derived from amine (Z), and the relative molar sensitivity.

[0040] (End-Sealing Agent) The thermoplastic polyimide resin of the present invention is more preferably obtained by reacting the tetracarboxylic acid component (A), the diamine component (B), the amine (Z), and an end-sealing agent. The end-sealing agent preferably comprises at least one selected from the group consisting of monoamines and dicarboxylic acids, more preferably monoamines, and even more preferably a linear aliphatic monoamine. From the viewpoint of improving the heat aging resistance of thermoplastic polyimide resins, the end encapsulant more preferably comprises a monoamine having a chain-like aliphatic group having 5 to 14 carbon atoms, even more preferably comprises a monoamine having a saturated linear aliphatic group having 5 to 14 carbon atoms, even more preferably comprises at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine, even more preferably comprises at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and even more preferably comprises at least one selected from the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.

[0041] When an end-capturing agent is used, the amount of end-capturing agent to react with the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z) is preferably 0.0001 to 0.1 moles, more preferably 0.001 to 0.06 moles, and even more preferably 0.002 to 0.035 moles per mole of the tetracarboxylic acid component (A), from the viewpoint of improving the heat aging resistance of the thermoplastic polyimide resin and adjusting to a desired molecular weight.

[0042] [Method for producing thermoplastic polyimide resin] The method for producing thermoplastic polyimide resin of the present invention (hereinafter also simply referred to as "the method for producing the present invention") comprises the step of reacting the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z). More preferably, the method for producing the present invention comprises the step of reacting the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z), and further comprises the step of reacting with an end encapsulant. The tetracarboxylic acid component (A), the diamine component (B), the amine (Z), and the end encapsulant are as described above.

[0043] There are no particular restrictions on the order in which the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z) are reacted. From the viewpoint of obtaining a thermoplastic polyimide resin that does not decrease in viscosity during melting and exhibits a moderate increase in viscosity, it is preferable to react the tetracarboxylic acid component (A) and the diamine component (B) first, and then react with the amine (Z), or to react the tetracarboxylic acid component (A) with the diamine component (B) and the amine (Z) simultaneously, and it is more preferable to react the tetracarboxylic acid component (A) with the diamine component (B) and the amine (Z) simultaneously.

[0044] The method for producing the thermoplastic polyimide resin of the present invention preferably comprises the following steps (I) to (IV) in order: Step (I): A step of mixing the tetracarboxylic acid component (A) and the solvent (C) to prepare a mixture 1. Step (II): A step of mixing the mixture 1 with the diamine component (B) and the amine (Z) to prepare a solution 2 containing a polyimide resin precursor containing polyamic acid. Step (III): A step of heating the solution 2 to imidize the polyimide resin precursor, precipitating polyimide resin powder in the solution, and preparing a slurry 3 containing the polyimide resin powder. Step (IV): A step of separating the slurry 3 into solid and liquid components.

[0045] <Step (I)> In Step (I), the tetracarboxylic acid component (A) and the solvent (C) are mixed to prepare mixture 1. The tetracarboxylic acid component (A) is as described above.

[0046] (Solvent (C)) From the viewpoint of easily producing the thermoplastic polyimide resin of the present invention, solvent (C) preferably includes an alkylene glycol-based solvent represented by the following formula (C-1). (Ra １ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ra ２ (wherein is a linear alkylene group having 2 to 6 carbon atoms, and n is an integer from 1 to 3.) The alkylene glycol solvent preferably has a boiling point of 140°C or higher, more preferably 160°C or higher, and even more preferably 180°C or higher, from the viewpoint of enabling the polymerization reaction of the tetracarboxylic acid component (A) and the diamine component (B) under normal pressure in steps (II) and (III).

[0047] Ra in equation (C-1) １ Ra in formula (C-1) ２is 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 (C-1), n ​​is an integer from 1 to 3, preferably 2 or 3. Specific examples of alkylene glycol solvents represented by formula (C-1) include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether (also known as 2-(2-methoxyethoxy)ethanol), triethylene glycol monomethyl ether (also known as 2-[2-(2-methoxyethoxy)ethoxy]ethanol), 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, 1,3-propanediol, etc., and one or more of these can be used. Among the above, the solvent (C) preferably comprises at least one selected from the group consisting of 2-(2-methoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol, 2-(2-ethoxyethoxy)ethanol, and 1,3-propanediol, and more preferably comprises at least one selected from the group consisting of 2-(2-methoxyethoxy)ethanol and 2-(2-ethoxyethoxy)ethanol.

[0048] The content of the alkylene glycol-based solvent in solvent (C) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, and 100% by mass or less, from the viewpoint of easily producing the thermoplastic polyimide resin of the present invention.

[0049] When solvent (C) includes the alkylene glycol-based solvent and other solvents, specific examples of "other solvents" include toluene, xylene, acetone, hexane, heptane, chlorobenzene, methanol, ethanol, n-propanol, isopropanol, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylcaprolactam, hexamethylphosphoramide, tetramethylene sulfone, dimethyl sulfoxide, o- Examples include resol, m-cresol, p-cresol, phenol, p-chlorophenol, 2-chlor-4-hydroxytoluene, diglyme, triglyme, tetraglyme, dioxane, γ-butyrolactone, dioxolane, cyclohexanone, cyclopentanone, dichloromethane, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, dibromomethane, tribromomethane, 1,2-dibromoethane, 1,1,2-tribromoethane, 2-ethylhexanol, etc., and one or more of these can be used.

[0050] Furthermore, from the viewpoint of easily producing the thermoplastic polyimide resin of the present invention, it is preferable that the solvent (C) does not contain water. The water content of solvent (C) is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0% by mass.

[0051] The method of mixing the tetracarboxylic acid component (A) and the solvent (C) in step (I) is not particularly limited, and any conventional method can be used. The concentration of the tetracarboxylic acid component (A) in the mixture 1 obtained in step (I) is preferably 5 to 70% by mass, more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, from the viewpoint of ease of controlling the reaction temperature in step (II) and improving reaction efficiency. The mixture 1 obtained in step (I) is usually in the form of a suspension.

[0052] <Step (II)> In Step (II), the mixture 1 is mixed with the diamine component (B) and the amine (Z) to prepare a solution 2 containing a polyimide resin precursor containing polyamic acid. The diamine component (B) and amine (Z) are as described above. The mixing ratio of the mixture 1 and the diamine component (B) in Step (II) is preferably in the range of 0.9 to 1.1 moles of diamine component (B) per mole of tetracarboxylic acid component (A) in the mixture 1. Furthermore, the amount of amine (Z) used in Step (II) is 0.10 to 0.70 parts by mass, preferably 0.12 to 0.65 parts by mass, more preferably 0.15 to 0.60 parts by mass, even more preferably 0.20 to 0.50 parts by mass, and even more preferably 0.30 to 0.50 parts by mass, per 100 parts by mass of the diamine (B2), from the viewpoint of obtaining a thermoplastic polyimide resin that does not decrease viscosity during melting and has an appropriate increase in viscosity.

[0053] In step (II), the mixing order of mixture 1, diamine component (B), and amine (Z) is not particularly limited, but from the viewpoint of ease of manufacture, it is preferable to mix a mixture in which diamine component (B) and amine (Z) have been mixed in advance with mixture 1. Furthermore, from the viewpoint of making it easier to control the reaction temperature between tetracarboxylic acid component (A) and diamine component (B), it is preferable to mix mixture 1 with a solution containing diamine component (B) and amine (Z), and it is even more preferable to gradually add the solution containing diamine component (B) and amine (Z) while stirring mixture 1 to mix mixture 1 with diamine component (B) and amine (Z). The solvent used in the solution containing diamine component (B) and amine (Z) can be any organic solvent capable of dissolving diamine component (B) and amine (Z), and examples include solvents similar to solvent (C) used in step (I). Preferably, the solvent used in the solution containing diamine component (B) and amine (Z) is a solvent containing an alkylene glycol-based solvent represented by formula (C-1). The concentrations of diamine component (B) and amine (Z) in the solution containing diamine component (B) and amine (Z) are not particularly limited, but from the viewpoint of making it easier to control the reaction temperature between tetracarboxylic acid component (A) and diamine component (B), and from the viewpoint of improving reaction efficiency, they are preferably 20 to 70% by mass, more preferably 30 to 50% by mass, and even more preferably 30 to 45% by mass.

[0054] The rate at which the solution containing diamine component (B) and amine (Z) is added to mixture 1 varies depending on the manufacturing scale, but from the viewpoint of easily controlling the reaction temperature between tetracarboxylic acid component (A) and diamine component (B), and from the viewpoint of easily producing powdered polyimide resin, it is preferable that the rate at which the amount of solution containing diamine component (B) and amine (Z) is added per mole of tetracarboxylic acid component (A) in mixture 1 is 0.1 moles / min or less.

[0055] Step (II) preferably includes a step of adding an end encapsulant in order to further improve the heat aging resistance of the obtained thermoplastic polyimide resin. The end encapsulant is as described above. The amount of end encapsulant added in step (II) is preferably 0.0001 to 0.1 moles, more preferably 0.001 to 0.06 moles, and even more preferably 0.002 to 0.035 moles, per mole of tetracarboxylic acid component (A) used in step (I), from the viewpoint of further improving the heat aging resistance of the thermoplastic polyimide resin and adjusting to a desired molecular weight.

[0056] In step (II), the step of adding the end-captive is preferably carried out after mixing the mixture 1 with the diamine component (B) and the amine (Z). The method of adding the end-captive is not particularly limited, but it is more preferable to add the solution of the end-captive to the mixture of mixture 1, the diamine component (B), and the amine (Z). The solvent used for the solution of the end-captive can be any organic solvent capable of dissolving the end-captive, and examples include solvents similar to solvent (C) used in step (I). Preferably, the solvent used for the solution of the end-captive is a solvent containing an alkylene glycol solvent represented by formula (C-1). The concentration of the end-captive in the solution of the end-captive is not particularly limited, but from the viewpoint of making it easier to control the reaction temperature and improving the reaction efficiency, it is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, and even more preferably 0.5 to 5% by mass.

[0057] In step (II), the temperature at which solution 2 is prepared is not particularly limited and can be appropriately selected according to the manufacturing scale, etc. Step (II) can be carried out under either atmospheric pressure or pressurized pressure, but from the viewpoint of reducing manufacturing costs, it is preferably carried out under atmospheric pressure. Furthermore, step (II) is preferably carried out under the flow of an inert gas such as nitrogen gas.

[0058] By the above method, in step (II), solution 2 containing a polyimide resin precursor containing polyamic acid is obtained. The polyimide resin precursor contained in solution 2 may consist only of polyamic acid. The solid content concentration of solution 2 is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and even more preferably 15 to 30% by mass, from the viewpoint of improving the reaction efficiency in step (III) and from the viewpoint of easily producing powdered thermoplastic polyimide resin. Here, "solid content concentration" means the concentration of the components in solution 2 excluding water and organic solvents.

[0059] <Step (III)> In step (III), the solution 2 prepared in step (II) is heated to imidize the polyimide resin precursor, causing polyimide resin powder to precipitate in the solution, and a slurry 3 containing the polyimide resin powder is prepared. In step (III), heating of solution 2 causes imidization of the polyimide resin precursor, and polyimide resin powder precipitates in the reaction solution.

[0060] The heating temperature of solution 2 in step (III) is not particularly limited as long as it is a temperature at which the polyimide resin precursor containing polyamic acid can be imidized. However, from the viewpoint of making it easier to control the reaction temperature, improving reaction efficiency, and easily producing powdered thermoplastic polyimide resin, it is preferably 100 to 250°C, more preferably 150 to 230°C, and even more preferably 180 to 220°C. Here, heating temperature refers to the upper limit of the set temperature during heating.

[0061] The heating rate of solution 2 in step (III) varies depending on the manufacturing scale, but from the viewpoint of making it easier to control the reaction temperature, improving reaction efficiency, and easily producing powdered thermoplastic polyimide resin, it is preferably 0.5 to 8°C / min, more preferably 0.5 to 6°C / min, and even more preferably 0.5 to 4°C / min.

[0062] The heating time of solution 2 in step (III) varies depending on the manufacturing scale, but from the viewpoint of making it easier to control the reaction temperature, improving reaction efficiency, and easily producing powdered thermoplastic polyimide resin, the holding time after reaching the heating temperature is preferably in the range of 10 to 240 minutes, more preferably 15 to 120 minutes, and even more preferably 15 to 60 minutes.

[0063] In step (III), as the imidization of the polyimide resin precursor in solution 2 progresses, polyimide resin powder precipitates in the solution, and the reaction solution becomes a slurry. From the viewpoint of promoting the precipitation of polyimide resin powder, it is preferable to cool the slurry 3 obtained in step (III) to 0 to 60°C before subjecting it to step (IV).

[0064] <Step (IV)> In step (IV), the slurry 3 prepared in step (III) is subjected to solid-liquid separation. The method for separating the slurry 3 from solid is not particularly limited, and conventional methods such as filtration can be used. After the solid-liquid separation, the obtained solid can be washed and dried to obtain the thermoplastic polyimide resin of the present invention in powder form.

[0065] <Structure of Thermoplastic Polyimide Resin> The thermoplastic polyimide resin of the present invention is obtained by reacting the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z), and contains repeating structural units represented by the following formula (1) and repeating structural units represented by the following formula (2), wherein the content ratio of the repeating structural units of formula (1) to the total of the repeating structural units of formula (1) and the repeating structural units of formula (2) is 15 to 70 mol%. (R １ R is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. ２ X is a divalent, chain-like aliphatic group having 9 to 14 carbon atoms. １ and X ２ Each of these is independently a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring.

[0066] In equation (1), R １R is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure, and R in formula (B-1) １ It is the same as R １ Preferably, it is a divalent group represented by the following formula (R1-1) or (R1-2), and more preferably, it is a divalent group represented by the following formula (R1-3). (m １１ and m １２ Each of these is an integer between 0 and 2, preferably 0 or 1. １３ ~m １５ Each of these is an integer between 0 and 2, preferably 0 or 1.

[0067] In equation (1), X １ X is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, and is the same as X in formula (A-1) above. That is, X １ Preferably, is a tetravalent group represented by any of the following formulas (X-1) to (X-4), more preferably a tetravalent group represented by the following formula (X-5) or (X-6), and even more preferably a tetravalent group represented by the following formula (X-5). (R １１ ~R １８ These are each independently alkyl groups having 1 to 4 carbon atoms. １１ ~p １３ Each of these is an integer between 0 and 2, preferably 0. １４ , p １５ , p １６ and p １８ Each of these is an integer between 0 and 3, preferably 0. １７ L is an integer between 0 and 4, preferably 0. １１ ~L １３ These are, independently, a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.

[0068] In equation (2), R ２ R is a divalent chain-like aliphatic group having 9 to 14 carbon atoms, and in formula (B-2) above, R ２ It is the same as R ２Preferably, it is an alkylene group having 9 to 14 carbon atoms, more preferably at least one selected from the group consisting of a nonameethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, and a tetradecamethylene group, even more preferably at least one selected from the group consisting of a nonameethylene group, a decamethylene group, and a dodecamethylene group, even more preferably it contains a decamethylene group, and even more preferably it is a decamethylene group.

[0069] X ２ This is X in equation (1). １ It is defined similarly, and the preferred mode is also similar. That is, X in formula (A-1) and X in formula (1). １ and X in formula (2) ２ is more preferably a tetravalent group represented by formula (X-5) or (X-6), and even more preferably a tetravalent group represented by formula (X-5).

[0070] The content ratio of the repeating structural units of formula (1) to the total of the repeating structural units of formula (2) is preferably 15 to 70 mol%, more preferably 15 to 65 mol%, even more preferably 15 to 60 mol%, even more preferably 15 to 50 mol%, even more preferably 15 mol% or more and less than 40 mol%, even more preferably 17 to 38 mol%, even more preferably 20 to 38 mol%, even more preferably 22 to 38 mol%, even more preferably 25 to 38 mol%, even more preferably 28 to 38 mol%, and even more preferably 30 to 37 mol%.

[0071] The thermoplastic polyimide resin may further contain repeating structural units of the following formula (3). (R ３ X is a divalent group with 6 to 22 carbon atoms that contains at least one aromatic ring. ３ (This is a tetravalent group with 6 to 22 carbon atoms that contains at least one aromatic ring.) ３ R is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring, and R in formula (B-3) above. ３ It is the same as X３ This is X in equation (1). １ It is defined similarly, and the preferred mode is also defined similarly.

[0072] The thermoplastic polyimide resin may further contain repeating structural units of the following formula (4). (R ４ Ha-SO ２ - or -Si(R ｘ ) (Caution ｙ ) A divalent group containing O-, R ｘ and R ｙ Each of these independently represents a chain-like aliphatic group or a phenyl group having 1 to 3 carbon atoms. ４ (This is a tetravalent group with 6 to 22 carbon atoms that contains at least one aromatic ring.) ４ R in formula (B-4) is ４ It is the same as X ４ This is X in equation (1). １ It is defined similarly, and the preferred mode is also defined similarly.

[0073] However, the content ratio of the total repeating units of formula (1) and formula (2) to the total repeating units constituting the thermoplastic polyimide resin is preferably 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, even more preferably 80 mol% or more, and even more preferably 90 mol% or more, and also 100 mol% or less. The "content ratio of the total repeating units of formula (1) and formula (2) to the total repeating units constituting the thermoplastic polyimide resin" here means the content ratio (mol%) of the total repeating units of formula (1) and formula (2) to the total polyimide units in the thermoplastic polyimide resin, when one repeating unit represented by formula (1) is counted as 1 mole and one repeating unit represented by formula (2) is counted as 1 mole.

[0074] The thermoplastic polyimide resin of the present invention has a structure derived from the amine (Z). Although the exact structure is not clear, it is presumed that, for example, the thermoplastic polyimide resin of the present invention has a structure derived from the amine (Z) at the end or side chain of the polyimide resin, or that the amine (Z) exists in the polyimide resin in a partially amidated state. Examples of the "structure derived from the amine (Z)" include the structures shown in the following formulas (Z-2) and (Z-3). -R ２ -NH-CH ２ CH ３ (Z-2) -R ２ -N(-CH ２ CH ３ )-C(=O)R' (Z-3) (R ２ (This is the same as above. R' is a group other than a hydrogen atom.)

[0075] In the production of the thermoplastic polyimide resin of the present invention, when an end-sealing agent is reacted, the thermoplastic polyimide resin of the present invention has a structure derived from the end-sealing agent. From the viewpoint of improving heat aging resistance, it is preferable that the thermoplastic polyimide resin of the present invention has a chain-like aliphatic group having 5 to 14 carbon atoms at its ends. The chain-like aliphatic group may be saturated or unsaturated, but it is preferably a saturated chain-like aliphatic group. Furthermore, the chain-like aliphatic group may be linear or branched. Examples of saturated chain aliphatic groups having 5 to 14 carbon atoms include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, lauryl group, n-tridecyl group, n-tetradecyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 2-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, isooctyl group, 2-ethylhexyl group, 3-ethylhexyl group, isononyl group, 2-ethyloctyl group, isodecyl group, isododecyl group, isotridecyl group, isotetradecyl group, and so on.

[0076] Among the above, the chain-like aliphatic group having 5 to 14 carbon atoms preferably includes at least one selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group; more preferably includes at least one selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, and isononyl group; and even more preferably includes at least one selected from the group consisting of n-octyl group, isooctyl group, and 2-ethylhexyl group.

[0077] From the viewpoint of exhibiting excellent heat aging resistance, the content of the above-mentioned chain-like aliphatic groups having 5 to 14 carbon atoms in the thermoplastic polyimide resin is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 0.2 mol% or more, based on 100 mol% of the total repeating structural units constituting the thermoplastic polyimide resin. Furthermore, from the viewpoint of ensuring sufficient molecular weight and obtaining good mechanical properties, the content of the above-mentioned chain-like aliphatic groups having 5 to 14 carbon atoms in the thermoplastic polyimide resin is preferably 10 mol% or less, more preferably 6 mol% or less, and even more preferably 3.5 mol% or less, based on 100 mol% of the total repeating structural units constituting the thermoplastic polyimide resin. The phrase "100 mol% of the total repeating structural units constituting the thermoplastic polyimide resin" means, for example, that if the thermoplastic polyimide resin consists only of the repeating structural units shown in formula (1) and formula (2), excluding the terminal groups, then one unit of the repeating structural unit shown in formula (1) is counted as 1 mole, and one unit of the repeating structural unit shown in formula (2) is counted as 1 mole, and the total is considered to be 100 mol%. The content of the above-mentioned chain-like aliphatic groups having 5 to 14 carbon atoms in the thermoplastic polyimide resin can be determined by depolymerizing the thermoplastic polyimide resin.

[0078] Furthermore, from the viewpoint of improving heat aging resistance, it is preferable that thermoplastic polyimide resins have only the group represented by formula (Z-2) and a chain-like aliphatic group having 5 to 14 carbon atoms at their ends, in addition to terminal amino groups and terminal carboxyl groups. If other groups are present at the ends, their content is preferably 10 mol% or less, more preferably 5 mol% or less, relative to the chain-like aliphatic group having 5 to 14 carbon atoms.

[0079] <Properties of Thermoplastic Polyimide Resin> The thermoplastic polyimide resin of the present invention is preferably a crystalline thermoplastic polyimide resin. In this specification, a crystalline thermoplastic polyimide resin refers to a polyimide resin having a melting point and a glass transition temperature.

[0080] (Thermal Properties) More specifically, the thermoplastic polyimide resin of the present invention preferably has a melting point of 360°C or lower and a glass transition temperature of 150°C or higher. From the viewpoint of improving heat resistance, the melting point Tm of the thermoplastic polyimide resin is preferably 250°C or higher, more preferably 260°C or higher, and even more preferably 270°C or higher. From the viewpoint of ease of thermoforming, it is preferably 345°C or lower, more preferably 340°C or lower, even more preferably 335°C or lower, even more preferably 320°C or lower, and even more preferably 300°C or lower. Furthermore, from the viewpoint of improving heat resistance, the glass transition temperature Tg of the thermoplastic polyimide resin is preferably 155°C or higher, more preferably 160°C or higher. From the viewpoint of ease of thermoforming, it is preferably 250°C or lower, more preferably 230°C or lower, even more preferably 200°C or lower, even more preferably 190°C or lower, and even more preferably 180°C or lower.

[0081] The crystallization temperature Tc of the thermoplastic polyimide resin is preferably 180°C or higher, more preferably 190°C or higher, and even more preferably 200°C or higher, from the viewpoint of ease of thermoforming, and preferably 350°C or lower, more preferably 320°C or lower, even more preferably 300°C or lower, even more preferably 280°C or lower, even more preferably 260°C or lower, even more preferably 250°C or lower, and even more preferably 240°C or lower.

[0082] The heat of fusion ΔHm of thermoplastic polyimide resin is preferably 5.0 mJ / mg or more, more preferably 10 mJ / mg or more, even more preferably 17 mJ / mg or more, and even more preferably 20 mJ / mg or more, from the viewpoint of improving crystallinity, heat resistance, mechanical strength, and chemical resistance. The upper limit of the heat of fusion ΔHm is not particularly limited, but is usually 45 mJ / mg or less. The heat of fusion ΔHm of thermoplastic polyimide resin is calculated from the area of ​​the heat of fusion peak (endothermic peak) near the melting point observed when the thermoplastic polyimide resin is heated at a heating rate of 10°C / min to melt it at a temperature above the melting point, then cooled at a cooling rate of 20°C / min, and then heated again at a heating rate of 10°C / min to melt it, using differential scanning calorimeter measurement.

[0083] The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and heat of fusion ΔHm of thermoplastic polyimide resin can be measured specifically by the method described in the examples.

[0084] (Weight-average molecular weight) The weight-average molecular weight Mw of the thermoplastic polyimide resin is preferably in the range of 10,000 to 150,000, more preferably 15,000 to 100,000, even more preferably 20,000 to 80,000, even more preferably 30,000 to 80,000, and even more preferably 35,000 to 75,000. If the weight-average molecular weight Mw of the thermoplastic polyimide resin is 10,000 or more, the resulting molded article will have good mechanical strength; if it is 35,000 or more, the stability of the mechanical strength will be good; and if it is 150,000 or less, the thermoformability will be good. The above weight-average molecular weight Mw can be measured by gel filtration chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.

[0085] (Viscosity during melting) The thermoplastic polyimide resin of the present invention exhibits no decrease in viscosity during melting and is accompanied by a moderate increase in viscosity. The viscosity of the thermoplastic polyimide resin during melting refers to the viscosity measured at a temperature exceeding the melting point of the thermoplastic polyimide resin using a capillary rheometer. The temperature at which viscosity is measured is preferably the melting point of the thermoplastic polyimide resin + 5°C or higher, more preferably the melting point of the thermoplastic polyimide resin + 10°C or higher, even more preferably the melting point of the thermoplastic polyimide resin + 20°C or higher, and even more preferably the melting point of the thermoplastic polyimide resin + 30°C or higher, and also preferably the melting point of the thermoplastic polyimide resin + 50°C or lower. Furthermore, the viscosity change during melting of the thermoplastic polyimide resin (retention viscosity change) can be evaluated by the rate of change in viscosity measured after preheating for a certain period of time (15 to 30 min) relative to the viscosity measured at 6 min of preheating using the method described above, at the same extrusion rate (10 mm / min or 100 mm / min). The viscosity change rate of the thermoplastic polyimide resin of the present invention is preferably in the range of 10 to 100%, more preferably 12 to 80%, even more preferably 15 to 80%, and even more preferably 20 to 75% at extrusion speeds of 10 mm / min and 100 mm / min. The viscosity and viscosity change rate can be specifically measured by the method described in the examples. The thermoplastic polyimide resin of the present invention, having a viscosity change rate within the above range, is expected to exhibit effects such as appropriate crosslinking during melting and reduction of dimensional changes after molding.

[0086] <Thermoplastic Polyimide Resin Composition> In addition, the thermoplastic polyimide resin may be further combined with additives such as fillers, matting agents, nucleating agents, plasticizers, antistatic agents, coloring inhibitors, gelation inhibitors, colorants, sliding properties improvers, conductive agents, flame retardants, and resin modifiers as needed, to the extent that they do not impair the effects of the present invention, to form a thermoplastic polyimide resin composition.

[0087] Furthermore, the thermoplastic polyimide resin composition may contain other resins besides the thermoplastic polyimide resin of the present invention, to the extent that their properties are not impaired. Preferred other resins include thermoplastic resins with high heat resistance, such as polyamide resins, polyester resins, polyimide resins other than the thermoplastic polyimide resin of the present invention, polycarbonate resins, polyetherimide resins, polyamideimide resins, polyphenylene ether resins, modified polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, polyarylate resins, liquid crystal polymers, polyetheretherketone resins, polyetherketone resins, polyetherketone ketone resins, polyetheretherketone ketone resins, polybenzimidazole resins, and the like. Among these, at least one selected from the group consisting of polyetherimide resins, polyphenylene sulfide resins, and polyetheretherketone resins is preferred from the viewpoint of heat resistance, moldability, strength, and solvent resistance. When the thermoplastic polyimide resin of the present invention is used in combination with other resins, there are no particular restrictions on the blending ratio, as long as the properties of the thermoplastic polyimide resin composition are not impaired.

[0088] [Molded Article] The present invention provides a molded article containing the thermoplastic polyimide resin of the present invention. The shape of the molded article is not particularly limited and examples include sheets, films, strands, filaments, etc. These may be intermediate components of industrial products or final products.

[0089] [Method for Manufacturing Molded Articles] Since the thermoplastic polyimide resin of the present invention, or a composition containing the same, is thermoplastic, molded articles of the present invention can be easily manufactured by thermoforming them. Examples of thermoforming methods for thermoplastic polyimide resins and compositions containing the same include injection molding, extrusion molding, inflation molding, blow molding, hot press molding, vacuum forming, pressure forming, laser molding, welding, and welding. Molding is possible by any molding method that involves a thermal melting step.

[0090] The method for producing a molded article of the present invention preferably includes a step of melting and kneading a thermoplastic polyimide resin or a composition containing the same at a temperature exceeding the melting point of the thermoplastic polyimide resin, preferably at a temperature of 5°C or higher above the melting point of the thermoplastic polyimide resin, more preferably at a temperature of 10°C or higher above the melting point of the thermoplastic polyimide resin, even more preferably at a temperature of 20°C or higher above the melting point of the thermoplastic polyimide resin, and even more preferably at a temperature of 30°C or higher above the melting point of the thermoplastic polyimide resin. Furthermore, from the viewpoint of melting the thermoplastic polyimide resin and suppressing thermal degradation, the melting and kneading temperature is preferably in the range of 250 to 400°C, more preferably at a range of 290 to 380°C.

[0091] Specific procedures for manufacturing a molded article include, for example, the following method. First, a thermoplastic polyimide resin is dry-blended with various optional components as needed, and then introduced into an extruder where it is melt-kneaded and extruded to produce pellets. Alternatively, the thermoplastic polyimide resin may be introduced into an extruder and melted, and various optional components as needed are introduced into the melt-kneaded mixture with the thermoplastic polyimide resin in the extruder, and then extruded to produce the aforementioned pellets. After drying the pellets, they can be introduced into various molding machines and thermoformed at a temperature of preferably 250 to 400°C, more preferably 290 to 380°C, to produce a molded article having the desired shape.

[0092] The shape of the molded article of the present invention is not particularly limited and examples include sheets, films, strands, filaments, etc. These may be intermediate components of industrial products or final products. The thermoplastic polyimide resin of the present invention and compositions containing the same can be formed into films and further laminated with other sheets to produce laminates. The method of laminating the film and other sheets may be by hot pressing or by using an adhesive. Since the molded article of the present invention has excellent thermal adhesion to aramid paper, a film made of the thermoplastic polyimide resin of the present invention and compositions containing the same is suitable as a film for laminating with aramid paper by thermal adhesion to produce laminates. The thickness of the film is preferably in the range of 5 to 500 μm, more preferably 10 to 400 μm, and even more preferably 20 to 300 μm, from the viewpoint of improving strength and handling, and improving thermal adhesion.

[0093] <Dielectric Properties> The thermoplastic polyimide resin, thermoplastic polyimide resin composition, and molded articles of the present invention have low dielectric properties. For example, a relative permittivity of 3.0 or less and a dielectric loss tangent of 0.005 or less can be achieved at a measurement frequency of 10 GHz. The relative permittivity is preferably 2.90 or less, more preferably 2.85 or less, even more preferably 2.70 or less, and even more preferably 2.60 or less, and the dielectric loss tangent is preferably 0.004 or less, more preferably 0.0035 or less, even more preferably 0.0032 or less, and even more preferably 0.003 or less. The relative permittivity and dielectric loss tangent can be measured specifically by the method described in the examples.

[0094] <Water Absorption> The thermoplastic polyimide resin, thermoplastic polyimide resin composition, and molded articles of the present invention have a low water absorption rate. For example, the water absorption rate of a molded article measuring 30 mm × 20 mm × 4 mm thick, measured in accordance with JIS K7209:2000, when immersed in water at 23°C for 24 hours, can be preferably 0.30% or less, more preferably 0.25% or less, even more preferably 0.20% or less, and even more preferably 0.10% or less. The above water absorption rate is obtained by reducing the mass of the molded article before immersion in water (W ０ The mass of the molded body after immersion in 23°C water for 24 hours is (W １When ) is used, the value is calculated from the following formula: Water absorption rate (%) = [(W １ -W ０ ) / W ０ ] × 100 The above water absorption rate can be measured specifically by the method described in the examples.

[0095] <Tracking Resistance> The thermoplastic polyimide resin, thermoplastic polyimide resin composition, and molded articles of the present invention exhibit high tracking resistance. For example, the comparative tracking index [CTI] measured in accordance with JIS C 2134:2007 is preferably 300 or higher, more preferably 400 or higher, even more preferably 500 or higher, even more preferably 550 or higher, and even more preferably 600 or higher. The comparative tracking index is the highest voltage value that a test piece can withstand during the measurement period without generating tracking failure or a persistent flame, when tracking resistance is evaluated by dropping 50 drops of electrolyte onto five test pieces while applying a voltage, in accordance with JIS C 2134:2007. The above comparative tracking index can be measured specifically by the method described in the examples.

[0096] <Applications> The thermoplastic polyimide resin, thermoplastic polyimide resin composition, and molded articles of the present invention are, for example, components related to 6th generation mobile communication systems (6G) using the 5G or 70G to 300GHz frequency band (smartphones, flexible printed circuit boards, metal foil laminates such as copper-clad laminates, antennas, antenna substrates, etc.), various antennas other than those mentioned 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 radar, antenna substrates for terahertz wave radar, antenna substrates for aircraft radar, antenna substrates for caterpillar-type special vehicles, WiGig antenna substrates, etc.), wire insulation materials (low-dielectric wire insulation 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, multilayer laminates, LED mounting substrates, industrial robot substrates Boards, communication substrates for home 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.), bearing coatings, heat-insulating shafts, trays, various belts (seamless belts, etc.), heat-resistant low-dielectric tapes, heat-resistant low-dielectric tubes, various sensors (touch sensors, etc.), various radars (automotive radar, aerospace radar, etc.), radomes (radar domes), optical communication modules (TOSA / ROSA), 8 It can be applied to k-TV cable mobile terminals or digital home appliances (tablet terminals, notebook PCs, flat-screen TVs, roll-up TVs, digital cameras, smart glasses, smartwatches, etc.), base stations (macrocell base stations, small cell base stations, C-RAN base stations, etc.), drones (commercial drones, long-range mobile drones, etc.), surveillance cameras, indoor or outdoor servers, artificial satellites, communication equipment for space stations, various insulation applications (inside automotive electronic equipment, inside batteries, inside motors), IC sockets, probe cards, PCB (Printed Circuit Board) inspection jigs, insulation inspection devices, and circuit board covers, etc.

[0097] The present invention will be described in more detail next with reference to examples, but the present invention is not limited thereto. Furthermore, the physical properties of the thermoplastic polyimide resins listed in Tables 1 to 3 were evaluated as follows.

[0098] <Infrared Spectroscopic Analysis (IR Measurement)> IR measurements of polyimide resin were performed using the "JIR-WINSPEC50" manufactured by JEOL Ltd.

[0099] <Melting Point, Glass Transition Temperature, Crystallization Temperature, Heat of Fusion> The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and heat of fusion ΔHm of polyimide resin were measured using a differential scanning calorimeter (TA Instruments "DSC-25"). Under a nitrogen atmosphere (nitrogen gas flow rate 50 mL / min), the polyimide resin powder (composition) sample was subjected to the following thermal history conditions. The thermal history conditions were: first heating (heating rate 10°C / min), followed by cooling (cooling rate 20°C / min), followed by a 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. For Tm, Tg, and Tc, if multiple peaks were observed, the peak top value of each peak was read. The heat of fusion ΔHm (mJ / mg) was calculated from the area of ​​the heat of fusion peak (endothermic peak) observed near the melting point when the sample was heated to a temperature above its melting point at a heating rate of 10°C / min, cooled at a cooling rate of 20°C / min, and then melted again at a heating rate of 10°C / min.

[0100] <Weight-Average Molecular Weight> The weight-average molecular weight (Mw) of the polyimide resin was measured using a gel filtration chromatography (GPC) analyzer "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°C Mobile phase flow rate: 1.0 mL / min Sample concentration: Approximately 0.1% by mass Detector: IR detector Injection volume: 100 μL Calibration curve: Standard PMMA

[0101] Comparative Example 1-1 (Production and Evaluation of Comparative Thermoplastic Polyimide Resin 1) [Step (I)] 500 g of (C-1) 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Emulsifier Co., Ltd.) and 218.12 g (1.00 mol) of (A-1) pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced into a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and four paddle blades. After nitrogen flow, the mixture was stirred at 150 rpm to obtain a homogeneous suspension solution to obtain mixture 1.

[0102] [Step (II)] Meanwhile, in a 500 mL beaker, 49.79 g (0.35 mol) of (B-1) 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., cis / trans ratio = 7 / 3) and 112.01 g (0.65 mol) of (B-2) 1,10-decamethylenediamine (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 250 g of (C-1) 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. This mixed diamine solution was gradually added to the mixture 1 in the flask using a plunger pump. Although heat was generated by the dropwise addition of the mixed diamine solution, the internal temperature was adjusted to stay between 40 and 80°C. Nitrogen flow was maintained throughout the dropwise addition of the mixed diamine solution, and the impeller rotation speed was set to 250 rpm. After the dropwise addition was complete, 130 g of (C-1)2-(2-methoxyethoxy)ethanol and 1.939 g (0.015 mol) of n-octylamine (manufactured by Kanto Chemical Co., Ltd.), which is a terminal encapsulant, were added and the mixture was further stirred. At this stage, a pale yellow polyamic acid solution 2 was obtained, which is a solution containing a polyimide resin precursor containing polyamic acid.

[0103] [Step (III)] Next, after stirring at a speed of 200 rpm, the polyamic acid solution 2 in a 2 L separable flask was heated to a range of 185 to 190°C. The heating rate was adjusted to a range of 0.5 to 4.0°C / min. During the heating process, precipitation of polyimide resin powder and dehydration due to imidization were observed when the liquid temperature was between 120 and 140°C. After holding at 185°C for 30 minutes, the solution was allowed to cool to room temperature to obtain slurry 3.

[0104] [Step (IV)] The slurry 3 obtained in Step (III) was filtered and solid-liquid separation was performed. 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 powdered comparative thermoplastic polyimide resin 1.

[0105] The obtained polyimide resin powder was used for various measurements and evaluations according to the method described above. The results are shown in Table 1. The IR spectrum of comparative thermoplastic polyimide resin 1 was measured and found to be ν(C=O) 1771, 1703 (cm²). －１ Characteristic absorption of the imide ring was observed in the following region.

[0106] Example 1-1 (Production and Evaluation of Thermoplastic Polyimide Resin 1) Step (I) was carried out in the same manner as in Comparative Example 1-1 to prepare Mixture 1. Next, in step (II), using a 500 mL beaker, 49.79 g (0.35 mol) of (B-1) 1,3-bis(aminomethyl)cyclohexane, 111.44 g (0.65 mol) of (B-2) 1,10-decamethylenediamine, and 0.19 g (0.00095 mol) of N-ethyldecamethylenediamine represented by the following structural formula (Z1) were dissolved in 250 g of (C-1) 2-(2-methoxyethoxy)ethanol to prepare a mixed amine solution. Except for adding the mixed amine solution to Mixture 1, the same procedure as in Comparative Example 1-1 was carried out to obtain powdered thermoplastic polyimide resin 1. Various measurements and evaluations were performed using the obtained polyimide resin powder according to the method described above. The results are shown in Table 1. Furthermore, when the IR spectrum of thermoplastic polyimide resin 1 was measured, ν(C=O) 1771, 1703 (cm) was obtained. －１ Characteristic absorption of the imide ring was observed in the following region.

[0107] Examples 1-2 to 1-4 (Production and Evaluation of Thermoplastic Polyimide Resins 2-4) Except for changing the amounts of (B-1) 1,3-bis(aminomethyl)cyclohexane, (B-2) 1,10-decamethylenediamine, and (Z1) N-ethyldecamethylenediamine used in Example 1-1, the same procedure was followed to obtain powdered thermoplastic polyimide resins 2-4. Various measurements and evaluations were performed using the obtained polyimide resin powder according to the method described above. The results are shown in Table 1.

[0108] Comparative Example 1-2 (Production and Evaluation of Comparative Thermoplastic Polyimide Resin 2) The same procedure as in Example 1-1 was followed, except that the amounts of (B-1) 1,3-bis(aminomethyl)cyclohexane, (B-2) 1,10-decamethylenediamine, and (Z1) N-ethyldecamethylenediamine were changed to the amounts shown in Table 1, to obtain comparative thermoplastic polyimide resin 2 in powder form. Various measurements and evaluations were performed using the obtained polyimide resin powder according to the method described above. The results are shown in Table 1.

[0109] Comparative Example 1-3 (Production and Evaluation of Comparative Thermoplastic Polyimide Resin 3) Step (I) was carried out in the same manner as in Comparative Example 1-1 to prepare Mixture 1. Next, in step (II), using a 500 mL beaker, 49.79 g (0.35 mol) of (B-1) 1,3-bis(aminomethyl)cyclohexane and 93.77 g (0.65 mol) of 1,8-octamethylenediamine were dissolved in 250 g of (C-1) 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. The same procedure as in Comparative Example 1-1 was carried out, except that the mixed diamine solution was added to Mixture 1, to obtain powdered comparative thermoplastic polyimide resin 3. Various measurements and evaluations were performed using the obtained polyimide resin powder according to the method described above. The results are shown in Table 1. The IR spectrum of comparative thermoplastic polyimide resin 3 was measured and found to be ν(C=O) 1768, 1697 (cm²). －１ Characteristic absorption of the imide ring was observed in the following region.

[0110] Comparative Example 1-4 (Production and Evaluation of Comparative Thermoplastic Polyimide Resin 4) Step (I) was carried out in the same manner as in Comparative Example 1-1 to prepare Mixture 1. Next, in step (II), using a 500 mL beaker, 28.45 g (0.20 mol) of (B-1) 1,3-bis(aminomethyl)cyclohexane and 115.41 g (0.80 mol) of 1,8-octamethylenediamine were dissolved in 250 g of (C-1) 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. The same procedure as in Comparative Example 1-1 was carried out, except that the mixed diamine solution was added to Mixture 1, to obtain powdered comparative thermoplastic polyimide resin 4. Various measurements and evaluations were performed using the obtained polyimide resin powder according to the method described above. The results are shown in Table 1. The IR spectrum of comparative thermoplastic polyimide resin 4 was measured and found to be ν(C=O) 1768, 1697 (cm²). －１ Characteristic absorption of the imide ring was observed in the following region.

[0111]

[0112] The abbreviations in Table 1 are as follows: • PMDA; pyromellitic dianhydride • 1,3-BAC; 1,3-bis(aminomethyl)cyclohexane • DMDA; decamethylenediamine (1,10-diaminodecane) • OMDA; octamethylenediamine (1,8-diaminooctane) • DMDA-Et; N-ethyldecamethylenediamine • n-OcA; n-octylamine

[0113] Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-10 (Retention Viscosity Evaluation) The powdered thermoplastic polyimide resins listed in Table 1 were introduced into a co-rotating twin-screw compounding extruder (HK-25D-41D, manufactured by Parker Corporation), and melt-kneaded under the conditions of barrel temperature: 350°C and screw rotation speed: 200 rpm to extrude strands with a diameter of 2 to 3 mm. After air-cooling the strands extruded from the extruder, they were pelletized using a pelletizer (Fan Cutter FC-Mini-4 / N, manufactured by Hoshi Plastics Co., Ltd.). The obtained pellets were dried under the conditions described in Table 2 (Tables 2-1 and 2-2 are collectively referred to as "Table 2"; the same applies hereinafter) and Table 3, and used for the retention viscosity evaluation described below.

[0114] (Evaluation of Retention Viscosity) Using the thermoplastic polyimide resin pellets prepared by the above method, the viscosity was measured at the extrusion speed and shear speed listed in Tables 2 and 3 using a capillary rheometer (Capillograph 1D, manufactured by Toyo Seiki Seisakusho Co., Ltd.) under the following conditions: cylinder: 9.55 mmΦ, die: 1 mmΦ × 10 mmL, preheating time: 6 to 30 min, cylinder temperature (viscosity measurement temperature): 320°C (Table 2) or 360°C (Table 3), capillary diameter: 1 mm, capillary length: 10 mm. This viscosity was defined as the retention viscosity.

[0115] (Retention Viscosity Change Rate) The retention viscosity change rates at extrusion speeds of 10 mm / min and 100 mm / min, as shown in Tables 2 and 3, were calculated using the following formula: Retention viscosity change rate = {(Viscosity at preheating time of 6 min, 15 min, or 30 min) - (Viscosity at preheating time of 6 min)} / (Viscosity at preheating time of 6 min) × 100 (%)

[0116]

[0117]

[0118]

[0119] Table 2 shows that the thermoplastic polyimide resins of Examples 1-1 to 1-4 have a larger value for the rate of change in stagnation viscosity than the thermoplastic polyimide resins of Comparative Examples 1-1 and 1-2. Also, as shown in Comparative Examples 2-6 to 2-10 in Table 3, R in formula (2) ２ It can be seen that when a thermoplastic polyimide resin (Comparative Examples 1-3 and 1-4) is used in which the number of carbon atoms in the corresponding divalent chain-like aliphatic group is outside the range specified in this application, the retention viscosity decreases significantly.

[0120] Example 3-1 (Preparation and evaluation of physical properties of polyimide resin film) The powdered thermoplastic polyimide resin obtained in Example 1-2 was introduced into a co-rotating twin-screw compounding extruder (HK-25D-41D, manufactured by Parker Corporation) and melt-kneaded at a barrel temperature of 290°C and a screw rotation speed of 140 rpm to extrude strands with a diameter of 2-3 mm. After air-cooling the strands extruded from the extruder, they were pelletized using a pelletizer (Fan Cutter FC-Mini-4 / N, manufactured by Hoshi Plastics Co., Ltd.). The obtained pellets were dried at 120°C for 4 hours or more. The dried pellets were put into a Φ20 mm, L / D = 25 single-screw extruder equipped with a T-die with a width of 150 mm and a lip width of 0.4 mm, and melt-kneaded at a rotation speed of 20 rpm. Then, the film was continuously extruded from the T-die of the single-screw extruder. This was taken up using a take-up roll at a take-up speed of 2.0 m / min to obtain a polyimide resin film with a thickness of 50 μm. Here, the cylinder temperature of the Φ20 mm single-screw extruder was adjusted to 290-300°C, the T-die temperature to 300°C, and the take-up roll temperature to 140°C. The obtained film was used to measure tensile strength, tensile modulus, and tensile fracture strain using the method described below. The results are shown in Table 4.

[0121] <Measurement Method for Tensile Strength, Tensile Modulus, and Tensile Nominal Strain at Break> A 100 mm x 10 mm test film was cut from the obtained polyimide resin film and used for measurement. Using a tensile testing machine (Strograph VG1E, manufactured by Toyo Seiki Seisakusho Co., Ltd.), a tensile test was performed in accordance with JIS K 7161-1:2014 at a temperature of 23°C and a test speed of 50 mm / min to measure the tensile strength, tensile modulus, and tensile nominal strain at break.

[0122] Example 3-2 A polyimide resin film was prepared and evaluated in the same manner as in Example 3-1, except that the powdered thermoplastic polyimide resin obtained in Example 1-4 was used, and the cylinder temperature of the single-screw extruder during film extrusion was changed to 290-310°C and the T-die temperature to 310°C. The results are shown in Table 4.

[0123]

[0124] Example 4-1 (Lamination and Evaluation of Polyimide Resin Film and Aramid Paper) The polyimide resin film obtained in Example 3-1 was cut to 10 cm x 10 cm. This was laminated onto aramid paper (Nomex, manufactured by DuPont Teijin Advanced Paper Co., Ltd., thickness: 50 μm) cut to 10 cm x 10 cm. The resulting laminate was hot-pressed using a vacuum press (manufactured by Kodaira Seisakusho Co., Ltd.) at the press temperature, press pressure, and press time shown in Table 5. During pressing, the laminate was sandwiched between two release films (PTFE film with a thickness of 50 μm), and this was sandwiched between two SUS plates measuring 25 cm x 25 cm x 0.5 mm thick before being placed in the press. After hot pressing, the laminate was allowed to cool for 2 minutes while sandwiched between the SUS plates, and then removed. The adhesion and curl properties were visually evaluated according to the following criteria. [Adhesion Evaluation Criteria] A: The entire surface of the laminate is adhered. B: The interface of the laminate is adhered, but partial adhesion failure is observed. C: The interface of the laminate is not adhered, or the interface easily delaminates. [Curling Evaluation Criteria] A: No deformation (curling) of the laminate is observed after cooling. B: Deformation (curling) of the laminate is observed after cooling.

[0125] Examples 4-2 to 4-5: The polyimide resin film or aramid paper used for the preparation of the laminate, the layer configuration, and the conditions during hot pressing were changed as shown in Table 5, and the laminate was prepared and evaluated in the same manner as in Example 4-1. The results are shown in Table 5. Note that "AURUM" used in Example 4-4 is a commercially available thermoplastic polyimide film (ASKUL: Model No. 3-8010-01, Tg = 258°C).

[0126]

[0127] Example 5-1 (Preparation and Evaluation of Molded Articles) The powdered thermoplastic polyimide resin obtained in Example 1-2 was pelletized using the method described in Example 3-1. The obtained pellets were dried at 120°C for 4 hours or more. The dried pellets were injection molded using an injection molding machine (FANUC Corporation's "RoboShot α-S30iA") under the conditions of cylinder setting temperature 320°C, mold temperature 160°C, and injection speed 30.8 mm / s to produce a molded article of "Multipurpose Test Specimen Type A1" as defined in JIS K7139:2009. The above test specimens were evaluated for the following items.

[0128] <Relative Permittivity and Dielectric Loss Tangent> A sample measuring L60 mm × W1.5 mm × Thickness1.5 mm was cut from the parallel section of the multipurpose test specimen. The sample was conditioned for 24 hours or more under conditions of 23 ± 1 °C and 50 ± 5% RH before being used for measurement. As the measuring equipment, a PNA network analyzer "N5222B" manufactured by Keysight Technologies, Inc. and a cavity resonator for 10 GHz "CP531" manufactured by Kanto Electronics Applied Development Co., Ltd. were used, and the relative permittivity and dielectric loss tangent were measured by the cavity resonator perturbation method in accordance with IEC 62810 at a temperature of 23 ± 1 °C, 50 ± 5% RH, and a measurement frequency of 10 GHz. The measured values ​​were the average value of n=2.

[0129] <Mean Linear Expansion Coefficient (CTE)> A sample measuring 5 mm × 4 mm × 10 mm in height was cut from the parallel section of the multipurpose test specimen. The sample was conditioned for 24 hours or more under conditions of 23 ± 1°C and 50 ± 5% RH before being used for measurement. In accordance with JIS K7197:2012, a thermomechanical analyzer "TMA7100C" manufactured by Hitachi High-Tech Science Co., Ltd. was used to perform TMA measurements under conditions of nitrogen gas flow (150 mL / min), compression mode with a load of 49 mN and a heating rate of 5°C / min, heating from 23 to 300°C. TMA measurements were performed in the flow direction (MD) and the direction perpendicular to it (TD) of the injection-molded sample, and the CTE was determined from the measured values ​​within the temperature range shown in Table 6.

[0130] <Water Absorption Rate> The water absorption rate was measured in accordance with JIS K7209:2000. A sample measuring 30 mm × 20 mm × 4 mm thick was cut from the gripping portion of the multipurpose test piece and used for measurement. The sample was dried in a hot air circulating oven at 50 ± 1 °C for 72 ± 1 hour, then returned to room temperature in a desiccator, and its mass (W) was measured in an environment of 23 ± 1 °C and 50 ± 5% RH. ０ The mass (W) was measured. Next, the sample was immersed in water at 23±1°C for 24±1 hours to absorb water. After wiping off the surface moisture, the mass (W) after 1 minute was measured. １ The water absorption rate was measured. The water absorption rate was calculated based on the following formula, and the average value for n=3 is shown in Table 6. Water absorption rate (%) = [(W １ -W ０ ) / W ０ ] × 100

[0131] Example 5-2 Molded articles were prepared and evaluated in the same manner as in Example 5-1, except that the powdered thermoplastic polyimide resin obtained in Example 1-4 was used. The results are shown in Table 6.

[0132]

[0133] As shown in Table 6, the thermoplastic polyimide resin of the present invention has a low dielectric constant and low dielectric loss tangent, a small average coefficient of linear expansion (i.e., excellent dimensional stability), and low water absorption.

[0134] Examples 6-1 to 6-4 (Evaluation of Tracking Resistance) Using the powdered thermoplastic polyimide resin obtained in Example 1-2 or 1-4, injection molding was performed using the method described in Example 5-1 to produce a flat molded body measuring 70 mm × 70 mm × 3 mm thick. This was cut into nine equal parts to produce samples measuring 20 mm × 20 mm × 3 mm thick. These samples were conditioned for 24 hours or more under conditions of 23 ± 2°C and 50 ± 5% RH before being used for measurement. Tracking resistance was evaluated using the HAT-112-3 tracking resistance tester manufactured by Yamayo Test Instruments Co., Ltd. in accordance with JIS C 2134:2007. Specifically, during measurement, the AC voltage described in Table 7 was applied between the electrodes, and the number of drops of electrolyte (solution A) described in Table 7 were dropped onto the samples to confirm whether five samples could withstand the measurement period without generating tracking breakdown or a persistent flame. The test conditions were as follows. [Test Conditions] Test electrode: Platinum (tip cutting edge angle 30°) Electrode arrangement: 4.0 mm ± 0.2 mm (opposing angle 60°) Electrolyte: Solution A (NH ４ Cl 0.1% ± 0.002%, resistivity 3.95 Ω·m ± 0.05 Ω·m) Drop count: 50 drops confirmed n=5, 100 drops confirmed n=5 Laboratory environment: 23 ± 2℃, 50 ± 5% RH

[0135] Furthermore, the erosion depth was measured for samples that did not fail after 50 drops. The erosion depth and comparative tracking index [CTI] are shown in Table 7. A smaller erosion depth and a larger comparative tracking index indicate better results.

[0136]

[0137] According to the present invention, it is possible to provide a thermoplastic polyimide resin that does not experience a decrease in viscosity during melting and exhibits an appropriate increase in viscosity, a method for producing the same, and a molded article.

Claims

1. A thermoplastic polyimide resin 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 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 15 to 70 mol%, (R ２ , ２ , ２ , ３ , １ , ２ , ２ , ２ , ２ , ２ , ２ , １ is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure. R ２ is a divalent linear aliphatic group having 9 to 14 carbon atoms. X １ and X ２ are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) The thermoplastic polyimide resin comprises a tetracarboxylic acid component (A) containing a tetracarboxylic dianhydride (A1) represented by the following formula (A-1), (X is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.) A diamine component (B) containing a diamine (B1) represented by the following formula (B-1) and a diamine (B2) represented by the following formula (B-2), H ２ N-R １ -NH ２ (B-1) H ２ N-R ２ -NH ２ (B-2) (R １ , R ２ are the same as described above.) It is obtained by reacting with an amine (Z) represented by the following formula (Z-1), H ２ N-R ２ -NH-CH ２ CH ３ (Z-1) (R ２ is the same as described above.) A thermoplastic polyimide resin in which the amount of the amine (Z) with respect to 100 parts by mass of the diamine (B2) is 0.10 to 0.70 parts by mass.

2. The thermoplastic polyimide resin according to claim 1, wherein the content ratio of the repeating structural units of formula (1) to the total of the repeating structural units of formula (1) and the repeating structural units of formula (2) is 15 mol% or more and less than 40 mol%.

3. The thermoplastic polyimide resin according to claim 1 or 2, wherein the thermoplastic polyimide resin is a crystalline thermoplastic polyimide resin.

4. The aforementioned R １ A thermoplastic polyimide resin according to any one of claims 1 to 3, wherein is a divalent group represented by the following formula (R1-1) or (R1-2). (m １１ and m １２ Each of these is an integer between 0 and 2, independently of the others. １３ ~m １５ Each of these is an integer between 0 and 2, independently of the others.

5. The aforementioned R ２ A thermoplastic polyimide resin according to any one of claims 1 to 4, wherein is an alkylene group having 9 to 14 carbon atoms.

6. X in formula (A-1) and X in formula (1) １ and X in formula (2) ２ A thermoplastic polyimide resin according to any one of claims 1 to 5, wherein is a tetravalent group represented by the following formula (X-5) or (X-6).

7. The thermoplastic polyimide resin according to any one of claims 1 to 6, wherein the thermoplastic polyimide resin is obtained by reacting the tetracarboxylic acid component (A), the diamine component (B), the amine (Z), and a terminal encapsulant.

8. A method for producing a thermoplastic polyimide resin according to any one of claims 1 to 7, comprising the step of reacting the tetracarboxylic acid component (A), the diamine component (B), and the amine (Z).

9. A method for producing a thermoplastic polyimide resin according to claim 8, comprising the following steps (I) to (IV) in order: Step (I): A step of mixing the tetracarboxylic acid component (A) and the solvent (C) to prepare a mixture 1. Step (II): A step of mixing the mixture 1 with the diamine component (B) and the amine (Z) to prepare a solution 2 containing a polyimide resin precursor containing polyamic acid. Step (III): A step of heating the solution 2 to imidize the polyimide resin precursor, precipitating polyimide resin powder in the solution, and preparing a slurry 3 containing the polyimide resin powder. Step (IV): A step of separating the slurry 3 into solid and liquid components.

10. The method for producing a thermoplastic polyimide resin according to claim 9, wherein the solvent (C) comprises an alkylene glycol-based solvent represented by the following formula (C-1). (Ra １ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Ra ２ (where n is a straight-chain alkylene group with 2 to 6 carbon atoms, and n is an integer from 1 to 3.) 11. The method for producing a thermoplastic polyimide resin according to claim 9 or 10, wherein step (II) further includes a step of adding an end-capturing agent.

12. A molded article comprising the thermoplastic polyimide resin according to any one of claims 1 to 7.

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