Polyamideimide, and electronic component

Abstract

To provide a novel polyamideimide, and an electronic component that includes the polyamideimide.SOLUTION: A polyamideimide is provided that has, as a repeating unit, the following formula (1) or a specific partial structure of the formula (1). (In the formula (1), R1 and R2 represent divalent organic groups).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyamide-imide and an electronic component. [Background technology]

[0002] Polyamide-imide (PAI) is a super engineering plastic that has high heat resistance, strength, and excellent moldability. In general, in the synthesis of PAI, imide bonds are formed by dehydration ring closure of carboxylic acid anhydrides and amines to form amide acids. Alternatively, amide bonds are formed by the reaction of carboxylic acid chlorides and amines, or by the reaction of carboxylic acids and amines using a condensing agent (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-97732 Summary of the Invention [Problem to be solved by the invention]

[0004] The structure of conventional PAIs, including that of Patent Document 1, is determined by the structure of the monomers used, such as carboxylic acid anhydrides, amines, and carboxylic acids, and the properties of the PAI are also controlled by the structure of the monomers. In recent years, the properties required of PAIs have become more sophisticated and diverse, and efforts are underway to develop PAIs that meet these requirements.

[0005] However, many studies have already been conducted on PAIs using common monomers, and further improvement of PAI properties requires the development and production of new monomers. However, the development and production of new monomers leads to an increase in the production costs of PAIs. Therefore, new PAIs that do not rely on novel monomers are needed.

[0006] The problem to be solved by the present invention is to provide a novel polyamideimide and an electronic component comprising the polyamideimide. [Means for solving the problem]

[0007] One aspect of the present invention is a polyamideimide having a repeating structure represented by either formula (1) or (2): [ka] {In formula (1), R1 and R2 represent divalent organic groups.} [ka] {In formula (2), R3 represents a divalent organic group.}

[0008] The polyamideimide of the above embodiment preferably has a repeating structure represented by any one of the following formulas (3) to (6): The polyamideimide represented by formula (3) or (4) is different from the polyamideimide represented by formula (5) or (6). [ka] {In formula (3), R1, R4, and R5 each independently represent a divalent organic group, and may be the same group or different groups.} [ka] {In formula (4), R6 and R7 each independently represent a divalent organic group, and may be the same group or different groups.} [ka] {In formula (5), R8 represents a divalent organic group.} [ka] {In formula (6), R9 represents a divalent organic group.}

[0009] Another aspect of the present invention is an electronic component, which includes the polyamide-imide of the above aspect. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a novel polyamideimide and an electronic component comprising the polyamideimide. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 shows the results of 1H-NMR analysis of polyamideimide (a4) of Example 5. [Figure 2] FIG. 2 shows the results of 1H-NMR analysis of the polyamideimide (b2) of Example 6. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the expression "a to b" in the description of a numerical range means a to b, unless otherwise specified.

[0013] In this specification, when multiple upper limit values ​​and multiple lower limit values ​​are separately described, all numerical ranges that can be set by freely combining these upper limit values ​​and lower limit values ​​are considered to be described in this specification.

[0014] In this specification, when a compound is described, its isomers are also described unless otherwise specified.

[0015] The term "aromatic ring" is not particularly limited, and unless otherwise specified, also includes heterocycles.

[0016] In this specification, the solid content refers to the components other than the solvent (particularly the organic solvent) among the components constituting the composition or each raw material, and is based on mass unless otherwise specified.

[0017] 1. Polyamide-imide (A) The polyamideimide of this embodiment has a repeating structure of either formula (1) or (2) below {hereinafter, this will be referred to as polyamideimide (A)}. [ka] (In formula (1), R1 and R2 represent divalent organic groups.) [ka] (In formula (2), R3 represents a divalent organic group.)

[0018] R1 and R2 in formula (1) and R3 in formula (2) are not particularly limited as long as they are divalent organic groups, and are, for example, residues of diamine compounds or divalent organic groups having a sulfonyl group.

[0019] The diamine compound is not particularly limited, and known diamine compounds can be used, for example, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-oxydianiline, 4,4'-oxydianiline, 2,7-diaminofluorene, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-ethylenedianiline, diethylenetriamine, 1,12-diaminododecane, 1,11-diaminoundecane, 1,10-diaminodecane, 1,9-diaminononane, 1,8-diaminooctane, 1,7-diaminoheptane, 1,6-diaminohexane, 1,5-diaminopentane, 1,4-diaminobutane, 1,3-diamino Examples of suitable alkyl acrylates include aminopropane, ethylenediamine, 3,5-diamino-1,2,4-triazole, benzoguanamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-methylenebis(2,6-diethylaniline), 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 4,4'-diaminodiphenyl sulfide, 4,4'-bis[(4-aminophenyl)sulfanylphenyl]sulfide, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, and 4,4'-bis[(4-aminophenyl)sulfonylphenyl]sulfone.

[0020] In formula (1), R2 is preferably a divalent organic group containing a sulfonyl group among the above. When R2 contains a sulfonyl group, the optical properties (transparency) of the polyamideimide are more excellent. From the same viewpoint, in formula (2), R3 is preferably a divalent organic group containing a sulfonyl group.

[0021] Hereinafter, the polyamideimide (A) of this embodiment will be described with reference to the case where R2 in the above formula (1) or R3 in the above formula (2) is a divalent organic group containing a sulfonyl group.

[0022] 2. Polyamide-imide (B) As described above, in the polyamideimide (A) of this embodiment, R2 in the above formula (1) is preferably a divalent organic group having a sulfonyl group. Similarly, R3 in the above formula (2) is preferably a divalent organic group containing a sulfonyl group. That is, the polyamideimide (A) of this embodiment preferably has a repeating structure represented by any one of the following formulas (3) to (6) {hereinafter, this will be referred to as polyamideimide (B)}. Note that the polyamideimide represented by formula (3) or (4) is different from the polyamideimide represented by formula (5) or formula (6). [ka] {In formula (3), R1, R4, and R5 each independently represent a divalent organic group, and may be the same group or different groups.} [ka] {In formula (4), R6 and R7 each independently represent a divalent organic group, and may be the same group or different groups.} [ka] {In formula (5), R8 represents a divalent organic group.} [ka] {In formula (6), R9 represents a divalent organic group.}

[0023] R1 in the above formula (3) is as described above. R4 and R5 in the above formula (3) and R6 and R7 in the above formula (4) are not particularly limited as long as they are divalent organic groups, and may be, for example, divalent organic groups including aromatic hydrocarbon groups (arylene groups), aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups), ether groups, ketone groups, ester groups, sulfonyl groups, etc.

[0024] Among the divalent organic groups described above, R4 and R5, and R6 and R7 preferably contain an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of divalent organic groups containing an aromatic hydrocarbon group include divalent organic groups containing a biphenyl skeleton, a diphenyl ether skeleton, a diphenyl thioether skeleton, a benzophenone skeleton, a diphenylmethane skeleton, a diphenylpropane skeleton, a diphenylhexafluoropropane skeleton, a diphenyl sulfoxide skeleton, a diphenyl sulfone skeleton, and a benzene skeleton. Examples of divalent organic groups having an aliphatic ring include divalent organic groups containing a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cycloundecane skeleton, a cyclododecane skeleton, and a dicyclopentadiene skeleton.

[0025] Among the divalent organic groups described above, R4 and R5, and R6 and R7 are preferably divalent organic groups containing an aromatic hydrocarbon group, more preferably divalent organic groups containing a benzene skeleton structure, and particularly preferably phenylene groups.

[0026] In the above formula (5), R1 is as described above. R8 in the above formula (5) and R9 in the above formula (6) are not particularly limited as long as they are divalent organic groups, and may be, for example, divalent organic groups including aromatic hydrocarbon groups (arylene groups), aliphatic hydrocarbon groups (alkylene groups, cycloalkylene groups), ether groups, ketone groups, ester groups, sulfonyl groups, etc.

[0027] Among the divalent organic groups mentioned above, R8 and R9 preferably contain an aromatic hydrocarbon group or an aliphatic hydrocarbon group. Examples of divalent organic groups containing an aromatic hydrocarbon group include divalent organic groups containing a biphenyl skeleton, a diphenyl ether skeleton, a diphenyl thioether skeleton, a benzophenone skeleton, a diphenylmethane skeleton, a diphenylpropane skeleton, a diphenylhexafluoropropane skeleton, a diphenyl sulfoxide skeleton, a diphenyl sulfone skeleton, a benzene skeleton, etc. Examples of divalent organic groups having an aliphatic ring include divalent organic groups containing a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a cyclooctane skeleton, a cyclononane skeleton, a cyclodecane skeleton, a cycloundecane skeleton, a cyclododecane skeleton, a dicyclopentadiene skeleton, etc.

[0028] Among the divalent organic groups described above, R8 and R9 are more preferably divalent organic groups containing an aromatic hydrocarbon group, and even more preferably divalent organic groups containing a diphenyl sulfoxide skeleton or a benzene skeleton structure.

[0029] Hereinafter, the case where R4 and R5 in the above formula (3) and R6 and R7 in the above formula (4) of the polyamideimide (B) are phenylene groups will be described.

[0030] 3. Polyamide-imide (b) As described above, in the polyamideimide (B) represented by the formula (3) or (4) of this embodiment, R4 and R5 in the formula (3) and R6 and R7 in the formula (4) are preferably phenylene groups. That is, the polyamideimide (B) represented by the formula (3) or (4) of this embodiment preferably has a repeating structure of either the following formula (3-1) or (4-1) {hereinafter, this will be referred to as polyamideimide (b)}. [ka] {In formula (3-1), R1 is as defined above.} [ka]

[0031] 3. Physical properties of polyamideimide (A) or (B) 3-1. Weight average molecular weight (Mw) The weight average molecular weight (Mw) of the polyamideimide (A) or (B) of this embodiment can be set to 2,000 to 200,000, preferably 5,000 to 180,000, more preferably 10,000 to 150,000, and even more preferably 15,000 to 140,000.

[0032] 3-2. Number average molecular weight (Mn) The number average molecular weight (Mn) of the polyamideimide (A) or (B) of this embodiment can be 2,000 to 100,000, preferably 4,000 to 80,000, more preferably 5,000 to 70,000, and even more preferably 8,000 to 60,000.

[0033] 3-3.Molecular weight dispersity (PDI) The polyamideimide (A) or (B) of this embodiment preferably has a molecular weight dispersity index (PDI) of 1.5 to 25.0, more preferably 1.5 to 16.0. The molecular weight dispersity index (PDI) is calculated by the following formula. PDI=Mw / Mn

[0034] 3-4.Measuring Method of Mw and Mn In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) are values ​​measured by gel permeation chromatography (GPC) and converted into standard polystyrene. Specific measurement conditions are as follows:

[0035] Column: TSKgel GMH HR -M (Tosoh Corporation) Column temperature: 50℃ Eluent composition: N,N-dimethylformamide solution containing 0.1 mol / L LiBr Eluent flow rate: 0.5mL / min Calibration standard: Polystyrene Detector: SPD-6A UV detector (Shimadzu Corporation) Detector wavelength: 280nm Detector temperature: Room temperature (approx. 25°C) Baseline range during analysis: 5 to 25 minutes Molecular weight calculation range during analysis: 10 to 20 minutes

[0036] 4. Method for producing polyamideimide (A) An example of a method for producing the polyamideimide (A) of this embodiment is a method of reacting, as raw materials, 1,2,3-benzenetricarboxylic acid (HMA) represented by the following formula (5-1) with a diamine compound represented by the following formula (5-2).

[0037] [ka]

[0038] [ka] {In formula (5-2), R is a divalent organic group.}

[0039] The diamine compound represented by the formula (5-2) can be any of the above-mentioned diamine compounds, and one type of diamine compound may be used, or two or more types of diamine compounds may be used.

[0040] By reacting the HMA represented by the above formula (5-1) with the diamine compound represented by the above formula (5-2), a polyamideimide (A) having a structure represented by either formula (1) or (2) can be obtained.

[0041] R1 and R in the above formula (1) 2、 Alternatively, R3 in the above formula (2) is derived from R in the above formula (5-2). In the above reaction step, the structure of R in the above formula (5-2) may be modified by oxidation or the like. In that case, the structure after modifying R in the above formula (5-2) is the same as R1, R 2、Or, it has the same structure as R3 in the above formula (2).

[0042] In the reaction of the HMA represented by the above formula (5-1) with the diamine compound represented by the above formula (5-2), an organic solvent may be used, if necessary.

[0043] The organic solvent is not particularly limited, and known organic solvents can be used. Examples include amide-based organic solvents such as pyridine, N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), and N,N-dimethylformamide; alcohol-based organic solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based organic solvents such as ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone; ether-based organic solvents such as ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, and tetrahydrofuran (THF); and aromatic hydrocarbon compound-based organic solvents such as benzene, toluene, xylene, and mesitylene. Among the above, amide-based organic solvents and aromatic hydrocarbon compound-based organic solvents are preferred.

[0044] The amount of organic solvent is not particularly limited as long as it allows the reaction to proceed efficiently, and is preferably about 50 to 500 parts by mass per 100 parts by mass of the total amount of the HMA represented by formula (5-1) above and the diamine compound represented by formula (5-2) above.

[0045] The above reaction mainly proceeds through two steps: (i) a reaction in which HMA reacts with a diamine compound and then imidizes to form a compound having an amino group and a carboxyl group in addition to an imide ring, or a compound having two carboxyl groups in addition to an imide ring (hereinafter simply referred to as an imidization reaction); and (ii) a reaction in which the amino group and the carboxyl group of a compound having an amino group and a carboxyl group in addition to an imide ring polycondenses, or a reaction in which the carboxyl group of a compound having two carboxyl groups in addition to an imide ring polycondenses with the amino group of a diamine compound (hereinafter simply referred to as a polycondensation reaction).

[0046] The reaction temperature and reaction time for the imidization reaction can be appropriately selected from conventionally known reaction conditions. For example, the reaction can be carried out at 100°C to 250°C for 1 to 30 hours under a nitrogen atmosphere. By adjusting the equivalent ratio of HMA to diamine compound during the imidization reaction, it is possible to obtain polyamideimide represented by formula (1) and polyamideimide represented by formula (2), respectively. For example, when approximately 1 equivalent of HMA is used relative to the diamine compound, a compound having an imide ring, an amino group, and a carboxyl group is obtained, and the polyamideimide represented by formula (2) can be obtained by polycondensation of this compound. Furthermore, when 2 or more equivalents of HMA are used relative to the diamine compound, a compound having two carboxyl groups in addition to the imide ring is obtained, and the polyamideimide represented by formula (1) can be obtained by polycondensation of this compound with the diamine compound.

[0047] The reaction temperature and reaction time of the polycondensation reaction can be appropriately selected from conventionally known reaction conditions. For example, the reaction can be carried out using a condensing agent at 25°C to 150°C for 1 to 10 hours. Examples of the condensing agent that can be used include triphenyl phosphite, diisopropylcarbodiimide (DIPC), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDAC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC), dicyclohexylcarbodiimide (DCC), 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMT-MM), carbonyldiimidazole, and (2,3-dihydro-2-thioxo-3-benzoxazolyl)diphenylphosphonate (DBOP).

[0048] In particular, in the polyamideimide of the present embodiment, the use of HMA allows the polycondensation reaction to be carried out by heating alone, without using a condensing agent. The reason for this is not clear, but is presumed to be as follows.

[0049] Because HMA has three adjacent carboxyl groups, the remaining carboxyl groups and imide rings are adjacent to each other after the imidization reaction. This leads to an interaction between the carboxyl groups and the imide rings, improving the reactivity of the carboxyl groups, which is thought to enable the polycondensation reaction by heating alone.

[0050] In this case, the reaction is easier than in conventional polyamideimide production methods using carboxylic acid chlorides or condensing agents, and it is also possible to obtain polyamideimide with fewer impurities such as condensing agents and chlorine. Conditions for carrying out the polycondensation reaction by heating include, for example, reaction at 200°C to 250°C in a nitrogen atmosphere for 1 to 48 hours.

[0051] When the polycondensation reaction is carried out by heating, the imidization reaction and the polycondensation reaction can be carried out in one step. In this case, the reaction can be carried out, for example, in a nitrogen atmosphere at 120°C to 250°C for 1 to 30 hours.

[0052] 5. Method for producing polyamideimide (B) An example of a method for producing the polyamideimide (B) of this embodiment includes reacting HMA represented by the above formula (5-1) with a diamine compound having a sulfide group as a raw material to produce an intermediate polyamideimide, and then oxidizing the sulfide group in the intermediate polyamideimide to a sulfonyl group.

[0053] Examples of diamine compounds having a sulfide group include 4,4'-bis[(4-aminophenyl)sulfanylphenyl]sulfide and 4,4'-diaminodiphenyl sulfide.

[0054] The HMA represented by the formula (5-1) is reacted with a diamine compound having a sulfide group, and then the sulfide group of the synthesized intermediate polyamideimide is oxidized to a sulfonyl group to obtain the polyamideimide (B). In addition to the above reaction, the method may further include a step of reacting a diamine compound other than the aromatic diamine compound having a sulfide group with the HMA represented by the formula (5-1).

[0055] The reaction of the HMA represented by the above formula (5-1) with a diamine compound having a sulfide group or the like can be carried out under the same conditions as those for the above-mentioned imidization reaction and polycondensation reaction.

[0056] The oxidation reaction of the sulfide group can be carried out under conditions appropriately selected from conventionally known reaction conditions. For example, the reaction can be carried out using an oxidizing agent at 0°C to 100°C for 0.5 to 10 hours. Examples of the oxidizing agent include m-chloroperbenzoic acid, hydrogen peroxide, and potassium permanganate.

[0057] As an example of a method for producing the polyamideimide (B) of this embodiment, for example, the above-mentioned imidization reaction and polycondensation reaction may be carried out using HMA represented by the above formula (5-1) and a diamine compound having a sulfonyl group as raw materials.

[0058] 6. Polyamide-imide film The polyamideimide film of this embodiment includes the above-mentioned polyamideimide film (A) or (B). The polyamideimide film can be obtained by dissolving polyamideimide in a solvent, applying the solution to a substrate, drying, and then peeling it off from the substrate.

[0059] The thickness of the polyamideimide film of the present embodiment is not particularly limited and can be appropriately set depending on the application. The thickness of the polyamide film can be, for example, 10 μm or more, or 20 μm or more, and can be 150 μm or less, or 100 μm or less.

[0060] 7. Electronic Components The electronic component of this embodiment contains the above-described polyamideimide (A) or (B). In particular, the polyamideimide (B) has excellent transparency and is therefore suitable for use in electronic components used in displays, waveguides, etc.

[0061] The electronic component is not particularly limited, and examples thereof include flexible printed wiring boards. [Example]

[0062] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to the following. The components used in the examples and comparative examples are as follows.

[0063] <Polyamide-imide> The polyamideimides of the examples and comparative examples were prepared as follows.

[0064] <Example 1: Polyamideimide (a1) (HMA-TDA)> (Mw:102,000, Mn:34,900, PDI:2.9) A 25 mL two-neck flask equipped with a Dean-Stark apparatus was charged with 1,2,3-benzenetricarboxylic acid (hemimellitic acid) (HMA) (0.42 g, 2.0 mmol), 4,4'-thiodianiline (TDA) (0.43 g, 2.0 mmol), 1,3-dimethyl-2-imidazolidinone (DMI) (2.5 mL), and mesitylene (1.5 mL) and stirred at 220 °C for 24 hours under a nitrogen atmosphere. After removing the mesitylene, the product was reprecipitated in water and collected by filtration. The product was washed with methanol and then vacuum-dried at 100 °C for 12 hours to obtain polyamideimide (a1) (HMA-TDA) (0.73 g) of Example 1. [ka]

[0065] <Example 2: Polyamideimide (a2) (HMA-BAP)> (Mw:103,900, Mn:45,200, PDI:2.3) Polyamideimide (a2) (HMA-BAP) (1.0 g) of Example 2 was obtained in the same manner as in Example 1, except that 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene (BAP) (0.69 g, 2.0 mmol) was used instead of 4,4'-thiodianiline (TDA) used in Example 1. [ka]

[0066] <Example 3: Polyamideimide (a3) ​​(HMA-BAPP)> (Mw:100,300, Mn:50,700, PDI:2.0) Polyamideimide (a3) ​​(HMA-BAPP) (1.13 g) of Example 3 was obtained in the same manner as in Example 1, except that 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (0.82 g, 2.0 mmol) was used instead of 4,4'-thiodianiline (TDA) used in Example 1. [ka]

[0067] Example 4 Polyamideimide (b1) (HMA-SDA) (Mw:130,800, Mn:45,100, PDI:2.9) Polyamideimide (a1) (0.37 g) of Example 1 was dissolved in N,N-dimethylacetamide (DMAc) (6 mmL), and m-chloroperbenzoic acid (mCPBA) (1.2 g, 5.0 mmol) containing approximately 30% water was added and stirred at room temperature for 2 hours. The product was reprecipitated in methanol, recovered by filtration, washed with methanol, and vacuum dried at 100°C for 12 hours to obtain polyamideimide (b1) (HMA-SDA) (0.62 g) of Example 4. [ka]

[0068] <Example 5: Polyamideimide (a4) (HMA-SDA-BAP)> (Mw:114,900, Mn:29,100, PDI:3.9) A 25 mL two-neck flask was charged with 1,2,3-benzenetricarboxylic acid (hemimellitic acid) (HMA) (0.21 g, 1.0 mmol), 4,4'-thiodianiline (TDA) (0.11 g, 0.5 mmol), DMI (1.5 mL), and toluene (1.0 mL) and stirred at 160 °C for 4 hours under a nitrogen atmosphere. After removing the toluene, 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene (BAP) (0.17 g, 0.5 mmol), lithium chloride (0.053 g, 1.25 mmol), pyridine (0.4 mL), and triphenyl phosphite (0.2 mL) were added and stirred at 120 °C for 2 hours under a nitrogen atmosphere. The product was reprecipitated in methanol, collected by filtration, washed with methanol, and dried in vacuo at 100 °C for 12 hours. The dried product was dissolved in N,N-dimethylacetamide (DMAc) (3.0 mL), mCPBA (0.32 g, 1.3 mmol) was added, and the mixture was stirred at room temperature for 2 hours. The product was reprecipitated in methanol, recovered by filtration, washed with methanol, and dried in vacuum at 100°C for 12 hours to obtain polyamideimide (a4) (HMA-SDA-BAP) (0.40 g) of Example 5. [ka]

[0069] <Example 6: Polyamideimide (b2) (HMA-BAP-SDA)> (Mw:42,400, Mn:16,600, PDI:2.6) 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene (BAP) (0.17 g, 0.5 mmol) was used instead of the 4,4'-thiodianiline (TDA) used in Example 5. Also, 4,4'-thiodianiline (TDA) (0.11 g, 0.5 mmol) was used instead of the BAP used in Example 5. Except for the above, polyamideimide (b2) (HMA-BAP-SDA) (0.39 g) of Example 6 was obtained in the same manner as in Example 5. [ka]

[0070] <Example 7: Polyamideimide (a5) (HMA-SDA-BAPP)> (Mw:92,400, Mn:23,300, PDI:4.0) Polyamideimide (b4) (HMA-SDA-BAPP) (0.43 g) of Example 7 was obtained in the same manner as in Example 5, except that 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (0.21 g, 0.5 mmol) was used instead of 1,3-bis[2-(4-aminophenyl)-2-propyl]benzene (BAP) used in Example 5. [ka]

[0071] <Example 8: Polyamideimide (b3) (HMA-BAPP-SDA)> (Mw:55,400, Mn:19,900, PDI:2.8) 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) (0.21 g, 0.5 mmol) was used instead of the 4,4'-thiodianiline (TDA) used in Example 5. Also, 4,4'-thiodianiline (TDA) (0.11 g, 0.5 mmol) was used instead of the BAP used in Example 5. Except for the above, the same procedure as in Example 5 was repeated to obtain polyamideimide (b3) (HMA-BAPP-SDA) (0.43 g) of Example 8. [ka]

[0072] <Example 9: Polyamideimide (b4) (HMA-3SDA)> (Mw:103,200, Mn:50,100, PDI:2.1) A 25 mL two-neck flask equipped with a Dean-Stark apparatus was charged with 1,2,3-benzenetricarboxylic acid (hemimellitic acid) (HMA) (0.21 g, 1.0 mmol), 4,4'-bis[(4-aminophenyl)sulfanylphenyl]sulfide (3TDA) (0.43 g, 1.0 mmol), DMI (2.0 mL), and mesitylene (1.5 mL) and stirred at 220 °C for 24 h under a nitrogen atmosphere. After removing the mesitylene, the product was reprecipitated in water and collected by filtration. The product was washed with methanol and then vacuum-dried at 100 °C for 12 h. The dried product was dissolved in DMAc (6.0 mL), mCPBA (1.8 g, 7.5 mmol) was added, and the mixture was stirred at room temperature for 2 h. The product was reprecipitated in methanol and collected by filtration, then washed with methanol and dried in vacuo at 100°C for 12 hours, to obtain polyamideimide (b4) (HMA-3SDA) (0.62 g) of Example 9. [ka]

[0073] The polyamideimides (a1) to (a5) and (b1) to (b4) of each example were subjected to the following measurements and evaluations.

[0074] (Optical property measurement) The optical properties (transparency) of the polyamideimides (a1) to (a5) and (b1) to (b4) of each Example were measured. More specifically, 0.1 g of each of the polyamideimides (a1) to (a5) and (b1) to (b4) of each Example was weighed out, dissolved in DMAc (1 mL), dropped onto a glass plate, and dried on a hot plate at 80°C. This was then vacuum dried at 100°C for 12 hours to prepare a sample film of approximately 25 μm. The transmittance (T 450 The transmittance (λ) and the wavelength at which the transmittance becomes 1% (cutoff wavelength) (λcutoff) were measured. The measuring device used was an ultraviolet-visible spectrophotometer (V-750, manufactured by JASCO Corporation). Evaluation was carried out according to the following evaluation criteria. The evaluation results are shown in Table 1 below. (Evaluation criteria) A: Transmittance is 60% or more B: Transmittance is 35% or more and less than 60% C: Transmittance less than 35% [Table 1] The results in Table 1 show that the polyamideimides of Examples 4, 6, 8, and 9, i.e., when R2 in the above formula (1) or R3 in the above formula (2) is a divalent organic group containing a sulfonyl group, were obtained, resulting in polyamideimides with particularly excellent transparency.

[0075] ( 1 H-NMR measurement) Regarding the polyamideimide (a4) of Example 5 and the polyamideimide (b2) of Example 6, 1 H-NMR measurements were carried out. A nuclear magnetic resonance spectrometer (JNM-ECZ Luminous, manufactured by JEOL Ltd.) was used for the measurements. Figures 1 and 2 show the results of the polyamideimide (a4) and (b2). 1 The H-NMR measurement results (NMR chart) and the hydrogen positions corresponding to the peaks in the NMR chart are shown.

[0076] As shown in Figures 1 and 2 1 From the H-NMR measurement results, it was confirmed that the polyamideimides (a4) and (b2) were compounds having the structures of the respective chemical formulas. [Industrial Applicability]

[0077] The polyamideimide of the present invention is a novel polyamideimide and can be used for electronic parts and the like.

Claims

1. A polyamideimide having a repeating structure represented by either formula (1) or (2): 【Chemistry 1】 {In formula (1), R １ and R ２ represents a divalent organic group. 【Chemistry 2】 {In formula (2), R ３ represents a divalent organic group.

2. The polyamideimide according to claim 1, having a repeating structure represented by any one of the following formulas (3) to (6): 【Transformation 3】 {In formula (3), R １ , R ４ , R ５ each independently represents a divalent organic group, and may be the same group or different groups. 【Chemistry 4】 {In formula (4), R ６ , R ７ each independently represents a divalent organic group, and may be the same group or different groups. 【Transformation 5】 {In formula (5), R ８ represents a divalent organic group. 【Transformation 6】 {In formula (6), R ９ represents a divalent organic group.

3. A polyamideimide film comprising the polyamideimide according to claim 1 or 2.

4. An electronic component comprising the polyamideimide according to claim 1 or 2.

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