Use of semiconductor resin material

Abstract

The present invention relates to a semiconductor resin material comprising: a polyimide resin (A) containing repeating constituent units derived from aromatic tetracarboxylic acid components and aliphatic diamine components.

Description

Technical Field

[0001] This invention relates to semiconductor resin materials, their molded forms, their uses, and flexible printing materials. Prior Technology

[0002] In recent years, efforts have been made to develop organic semiconductor (OSC) materials in order to manufacture more versatile electronic devices at a lower cost. These materials have been found in various devices and apparatuses, including, among others, organic field-effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic photodiodes (OPDs), organic photoelectric conversion (OPV) cells, sensors, memory elements, and logic circuits.

[0003] Furthermore, organic semiconductor materials have the following advantages: (1) they can reduce the cost of device fabrication; (2) they are easy to scale up; (3) they are easier to make flexible compared to inorganic materials such as silicon; and (4) they can easily change their properties by changing their molecular structure.

[0004] The performance of such organic semiconductor materials has been improving recently. In particular, the options for organic materials exhibiting p-type functionality have expanded, and many compounds are under investigation. On the other hand, while the number of organic compounds exhibiting n-type functionality is limited, fullerene (C60) is one example that has been shown to have carrier mobility comparable to silicon. Furthermore, recently, some people have also been developing novel fullerene derivatives that can replace fullerene (C60) (Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2019-142775 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] However, fullerenes and fullerene derivatives are relatively expensive among organic materials, and their physical properties, such as solubility, light stability and thermal stability, have problems that limit their use in commercial applications.

[0008] Therefore, the purpose of this invention is to provide a semiconductor resin material with high free radical generation efficiency, stable free radicals, and excellent heat resistance and productivity, as a novel organic semiconductor material to replace high-cost organic materials such as fullerenes and to be used as n-type and p-type semiconductors; and to provide molded articles of semiconductor resin materials, uses of semiconductor resin materials, and flexible printing materials. [Methods for solving problems]

[0009] The inventors conducted a thorough study and discovered that by using a specific polyimide resin, a semiconductor resin material with high free radical generation efficiency, stable free radicals, and excellent heat resistance and productivity can be obtained, thus completing this invention.

[0010] That is, the main components of the present invention are as follows. [1] A semiconductor resin material comprising: a polyimide resin (A) containing repeating constituent units derived from an aromatic tetracarboxylic acid component and an aliphatic diamine component. [2] As described in [1] above, the semiconductor resin material generates free radical species that can be observed using single electron transfer. [3] The semiconductor resin material as described in [2] above, wherein the aforementioned free radical species are generated by ultraviolet light irradiation and can be detected by electron spin resonance (ESR) measurement. [4] As described in [3] above, the half-life of the free radical species generated by ultraviolet light irradiation is more than 1 second when measured by ESR. [5] In the semiconductor resin material described in [3] or [4] above, the free radical species generated by ultraviolet light irradiation is one or more of the group consisting of free oxygen free radical species and nitrogen free radical species. [6] The semiconductor resin material as described in any of [1] to [5] above, wherein the glass transition temperature of the aforementioned polyimide resin (A) is 150°C or higher. [7] The semiconductor resin material as described in any of [1] to [6] above, wherein the aforementioned polyimide resin (A) is a semi-aromatic polyimide resin mainly comprising repeating constituent units derived from aromatic tetracarboxylic acid components and aliphatic diamine components. [8] The semiconductor resin material as described in any of [1] to [7] above, wherein the aforementioned polyimide resin (A) is a polyimide resin (A1), the aforementioned polyimide resin (A1) comprises repeating constituent units represented by formula (1) and repeating constituent units represented by formula (2), and the content ratio of the repeating constituent units of formula (1) to the total of the repeating constituent units of formula (1) and the repeating constituent units of formula (2) is 20 to 70 mol%. [Chemistry 1] R1 is a divalent aliphatic group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure, R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, and X1 and X2 are each independently a tetravalent aromatic group with 6 to 22 carbon atoms. [9] The semiconductor resin material of any one of [1] to [8] above further contains resin (B), wherein the aforementioned resin (B) is selected from one or more of the group consisting of polyamine resin, polyamine imide resin, epoxy resin, carbamate resin, urea resin, phenolic resin, cyanate resin, polythiophene resin, polyurethane resin, polyacetylene resin, poly(p-phenylenevinylene) resin, polyvinylcarbazole resin, polyetherimide resin, and polyimide resin other than the aforementioned polyimide resin (A).

[10] A molded body is made of a semiconductor resin material as described in any one of [1] to [9] above.

[11] The use of a semiconductor resin material is in organic electronic devices using any of the semiconductor resin materials described in [1] to [9] above.

[12] As described in

[11] above, the use of semiconductor resin materials, wherein the aforementioned organic electronic devices are selected from the group consisting of organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic light-emitting diodes (OLED), organic photoelectric conversion (OPV) cells, organic optical detectors and organic light receivers.

[13] A flexible printing material is composed of a semiconductor resin material as described in any one of [1] to [9] above. [Effects of the Invention]

[0011] According to the present invention, semiconductor resin materials with high free radical generation efficiency, stable free radicals, and excellent heat resistance and manufacturability, molded articles thereof, their uses, and flexible printing materials are provided. Implementation

[0012] Embodiments of the semiconductor resin material, its molded body, its uses, and the flexible printing material according to the present invention will be described in detail below. In addition, in this specification, the term "A to B" for numerical values means "A or more and B or less" (when A < B) or "A or less and B or more" (when A > B). Also, in the present invention, combinations of preferred embodiments are even more preferred embodiments.

[0013] [Semiconductor Resin Material] The semiconductor resin material of the present invention contains: a polyimide resin (A) including repeating structural units derived from an aromatic tetracarboxylic acid component and an aliphatic diamine component.

[0014] Due to the above structure, the semiconductor resin material of the present invention (hereinafter sometimes simply referred to as "resin material") has a high radical generation efficiency, the generated radicals are stable, and it has excellent heat resistance and productivity.

[0015] Although the reason why the resin material of the present invention achieves the above effects is not yet clear, it is speculated as follows. Generally, when a compound absorbs energy by energy irradiation such as light irradiation, electrons migrate from a filled electron HOMO (highest occupied molecular orbital), etc. to a LUMO (lowest unoccupied molecular orbital), etc., but usually the two electron spin states remain opposite and the spin states maintain a paired state. However, when an electron is extracted from the excited state of a molecule, radical cations and radical anions may sometimes be generated. Even if radicals are generated in ordinary organic compounds, they cannot be observed at room temperature (for example, 15 to 30°C) and in an atmospheric environment because of their high reactivity. In contrast, since the resin material of the present invention contains a polyimide resin (A) having a predetermined structure, it is considered that after absorbing energy, it easily causes energy transfer in the excited state and easily generates radical species. In addition, it is considered that the polyimide resin (A) can suppress the re-bonding of the generated radical species due to its predetermined structure and can exist stably for a long time. Furthermore, the polyimide resin (A) has excellent heat resistance due to its predetermined structure.

[0016] Furthermore, in this specification, "semiconductor resin material" refers to resin materials exhibiting semiconductor properties and resin materials capable of exhibiting semiconductor properties. Here, "semiconductor properties" refers to the properties of a p-type semiconductor, which readily donates electrons, or the properties of an n-type semiconductor, which readily accepts electrons. Also, "resin material capable of exhibiting semiconductor properties" refers to a resin material that does not exhibit semiconductor properties in its original state, but can exhibit semiconductor properties by generating free radical species through energy irradiation, such as light irradiation.

[0017] The resin material of this invention ideally generates free radical species that can be observed using single-electron transfer. Therefore, it can exhibit excellent semiconductor properties. Here, "can be observed using single-electron transfer" means that the electron spin resonance (ESR) measurement and other methods can be used to observe the state of (1) the electron being removed from the bonding orbital of the molecule and oxidized as a single electron, and (2) the electron entering the antibonding orbital of the molecule and reduced as a single electron. Furthermore, regarding free radical species that can be observed using single-electron transfer, examples include free radical cations, free radical anions, or neutral free radicals. There are no particular limitations on the methods used to induce single-electron transfer. Examples include irradiation with light energy such as ultraviolet light, irradiation with heat energy such as heating, and chemical reactions using oxidizing or reducing agents. Regarding light energy irradiation, examples include irradiation from sunlight and irradiation from light sources that emit light in the desired wavelength range. Preferred irradiation is light in the wavelength range of 200 nm to 750 nm.

[0018] Furthermore, the aforementioned free radical species are preferably generated by ultraviolet light irradiation and can be detected by electron spin resonance (ESR) measurement. The resin material of the present invention, by generating such free radical species, can exhibit excellent semiconductor properties.

[0019] Furthermore, the aforementioned free radical species are preferably not generated before ultraviolet light irradiation, or even if they are generated, they are below the detection limit in ESR measurements, and only become detectable in ESR measurements after ultraviolet light irradiation. The resin material of this invention, by having no free radical species detectable in ESR measurements before ultraviolet light irradiation, and generating detectable free radical species only after ultraviolet light irradiation, can easily control the manifestation of semiconductor properties, thus its application range as a semiconductor material is expected to expand. There are no particular restrictions on the type of ultraviolet light being irradiated, but it is preferable to use light with a wavelength range of less than 380 nm, and even more preferably light with a wavelength range of more than 200 nm and less than 380 nm. Furthermore, the resin material of this invention generates free radical species immediately upon ultraviolet light irradiation, making it detectable in ESR measurements. Therefore, the irradiation time is not particularly limited, but considering the viewpoint of ensuring sufficient generation of free radical species, it is preferable to irradiate for more than 1 hour, and more preferably for more than 2 hours.

[0020] Furthermore, the half-life of the free radical species generated by ultraviolet light irradiation, as measured by ESR, is preferably 1 second or more, more preferably 10 seconds or more, more preferably 100 seconds or more, and even more preferably 1000 seconds or more. The longer the half-life, the more stable the free radical species, and the better the semiconductor properties. Moreover, reactive species such as free radicals, which are reactive intermediates of conventional organic compounds, are considered "long-lived" reactive species if their lifetime is greater than microseconds (0.000001 seconds). Therefore, the half-life of the free radical species generated by ultraviolet light irradiation in the semiconductor resin material of this invention is very long.

[0021] Furthermore, the free radical species generated by ultraviolet light irradiation are preferably one or more species from a group consisting of oxygen free radical species and nitrogen free radical species. The classification of free radical species can be inferred by analyzing the spectrum obtained by ESR measurement, especially by the g-value, linewidth, and splitting pattern specific to free radicals.

[0022] ESR determination can be performed using known methods, specifically using the methods described in the examples.

[0023] In the diffuse reflectance spectral analysis of the resin material of this invention after light irradiation, an ideal absorption band is observed in the visible light region (above 380 nm and below 800 nm), and an even more ideal absorption band is observed in the longer wavelength portion of the visible light region (e.g., around 716 nm). Quantum chemical calculations show that such absorption bands originate from free radical cations / anions. That is, the presence of an absorption band in the visible light region in the diffuse reflectance spectral analysis after light irradiation indicates the formation of free radical species.

[0024] Furthermore, quantum chemical calculations performed on the resin material of this invention show that the generated free radical cations have the potential to be used in n-type semiconductors, while the generated free radical anions have the potential to be used in p-type semiconductors. Materials possessing semiconductor properties of both p-type and n-type are called bipolar transistors, and have the potential to be used in both p-type and n-type semiconductors. The resin material of this invention has a lower energy level in the empty orbital domain (where electrons can flow) due to the electron-withdrawing effect of the carboxyl groups in the resin skeleton, thus the free radical system is stable and it is more likely to be used to make n-type semiconductors.

[0025] <Polyimide Resin (A)> The polyimide resin (A) used in this invention is a polyimide resin comprising repeating units derived from aromatic tetracarboxylic acid components and aliphatic diamine components, preferably a semi-aromatic polyimide resin primarily comprising repeating units derived from aromatic tetracarboxylic acid components and aliphatic diamine components. The term "mainly comprises" here refers to the total number of repeating units derived from tetracarboxylic acid and diamine components constituting the main chain of polyimide resin. The content of repeating units derived from aromatic tetracarboxylic acid and aliphatic diamine components is preferably 50-100 mol%, more preferably 60-100 mol%, even more preferably 75-100 mol%, even more preferably 80-100 mol%, and even more preferably 85-100 mol%.

[0026] The polyimide resin (A) used in this invention is a thermoplastic resin, and its form is not particularly limited. The thermoplastic polyimide resin is different from, for example, polyimide resins that do not have a glass transition temperature (Tg) formed by molding polyimide precursors such as polyacrylic acid and then closing the amide ring, or polyimide resins that have been decomposed at a temperature lower than the glass transition temperature.

[0027] Furthermore, regarding the glass transition temperature of polyimide resin (A), considering heat resistance, it is preferably above 150°C, more preferably above 160°C, and even more preferably above 170°C. Considering high processability, it is ideally below 250°C, more preferably below 230°C, and even more preferably below 200°C. Specifically, considering both heat resistance and high processability, the glass transition temperature of polyimide resin (A) is preferably 150~250°C, more preferably 160~230°C, and even more preferably 170~200°C. The glass transition temperature of the polyimide resin (A) can be determined using a differential scanning pyrometry instrument, specifically, using the method described in the examples.

[0028] [, , ] Regarding polyimide resin (A), from the viewpoint of heat resistance and molding processability, it is preferable to be a semi-aromatic polyimide resin that mainly comprises repeating constituent units derived from aromatic tetracarboxylic acid components and aliphatic diamine components. Specifically, it is more preferable to select one or more from the group consisting of polyimide resin (A1), polyimide resin (A2) and polyimide resin (A3) described below, and even more preferably to select one or more from the group consisting of polyimide resin (A1) and polyimide resin (A2), and even more preferably polyimide resin (A1).

[0029] [, , ] The polyimide resin (A1) comprises repeating constituent units represented by formula (1) and repeating constituent units represented by formula (2), wherein the content ratio of the repeating constituent units of formula (1) to the total of the repeating constituent units of formula (1) and formula (2) is 20 to 70 mol% of the polyimide resin. [Chemistry 2] R1 is a divalent aliphatic group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure, R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, and X1 and X2 are each independently a tetravalent aromatic group with 6 to 22 carbon atoms.

[0030] [, , ] Polyimide resin (A2) is a polyimide resin composed of repeating constituent units represented by the following formula (1). [Chemistry 3] R1 is a divalent aliphatic group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure, and X1 is a tetravalent aromatic group with 6 to 22 carbon atoms.

[0031] [, , ] Polyimide resin (A3) is a polyimide resin composed of repeating constituent units represented by formula (2) and repeating constituent units represented by formula (3). [Chemistry 4] R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, R3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring, X2 is a tetravalent aromatic group with 6 to 22 carbon atoms, and X3 is a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring.

[0032] The following section will use polyimide resin (A1) as an example to illustrate the ideal state of polyimide resin (A).

[0033] The repeating constituent units of equation (1) will be described in detail below. R1 is a divalent group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure. Here, alicyclic hydrocarbon structure refers to a ring derived from an alicyclic hydrocarbon compound, which can be saturated or unsaturated, and can be monocyclic or polycyclic. Examples of alicyclic hydrocarbon structures include cycloalkanes such as cyclohexane, cycloalkenes such as cyclohexene, bicycloalkanes such as norcamphene, and bicycloalkenes such as norcamphene, but these are not limited to these. Among these, cycloalkanes are preferred, more preferably cycloalkanes with 4 to 7 carbon atoms, and even more preferably cyclohexane. The number of carbons in R1 is 6 to 22, preferably 8 to 17. R1 contains at least one alicyclic hydrocarbon structure, preferably one to three.

[0034] R1 is preferably a divalent base represented by the following formula (R1-1) or (R1-2). [Chemistry 5] m11 and m12 are each independent integers from 0 to 2, preferably 0 or 1. m13 to m15 are each independent integers from 0 to 2, preferably 0 or 1.

[0035] R1 is preferably a divalent base expressed by the following formula (R1-3) or the following formula (R1-4), and is particularly preferably a divalent base expressed by the following formula (R1-3). [Chemistry 6] Furthermore, in the divalent groups represented by the above formulas (R1-3) and (R1-4), the positional relationship of the two methylene groups relative to the cyclohexane ring can be either cis or trans, and the ratio of cis to trans can be any value.

[0036] X 1 is a tetravalent group containing at least one aromatic ring with 6 to 22 carbon atoms. The aforementioned aromatic ring can be a monocyclic or condensed ring, and examples include benzene rings, naphthalene rings, anthracene rings, tetracene rings, and perylene rings, but are not limited to these. Among these, benzene rings, naphthalene rings, and perylene rings are preferred, and benzene rings are even more preferred. The number of carbons in X 1 is 6 to 22, preferably 6 to 20. X 1 contains at least one aromatic ring, preferably one to three.

[0037] X1 is preferably a 4-valent base represented by any of the following formulas (X-1) to (X-6). [Chemistry 7] R11 to R24 are each independently an alkyl group having 1 to 4 carbon atoms. p11 to p13 and p19 to p24 are each independently an integer from 0 to 2, preferably 0. p14, p15, p16 and p18 are each independently an integer from 0 to 3, preferably 0. p17 is an integer from 0 to 4, preferably 0. L11 to L13 are each independently a single bond, a carbonyl group or an alkyl group having 1 to 4 carbon atoms. Furthermore, X1 is a tetravalent group with 6 to 22 carbons containing at least one aromatic ring. Therefore, R12, R13, p12 and p13 in formula (X-2) are selected in such a way that the number of carbons of the tetravalent group represented by formula (X-2) falls within the range of 10 to 22. Similarly, L11, R14, R15, p14, and p15 in equation (X-3) are selected such that the number of carbons in the tetravalent groups represented by equation (X-3) falls within the range of 12 to 22; L12, L13, R16, R17, R18, p16, p17, and p18 in equation (X-4) are selected such that the number of carbons in the tetravalent groups represented by equation (X-4) falls within the range of 18 to 22; R19, R20, p19, and p20 in equation (X-5) are selected such that the number of carbons in the tetravalent groups represented by equation (X-5) falls within the range of 10 to 22; and R21, R22, R23, R24, p21, p22, p23, and p15 in equation (X-6) are selected such that the number of carbons in the tetravalent groups falls within the range of 10 to 22. 24 is selected in a way that the number of carbons in the tetravalent group, expressed by formula (X-6), falls within the range of 20 to 22.

[0038] X1 is a tetravalent base represented by any one of the following formulas (X-7) to (X-10). [Chemistry 8]

[0039] Next, the repeating constituent units of equation (2) will be described in detail below. R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, preferably with 6 to 14 carbon atoms, more preferably with 7 to 12 carbon atoms, and even more preferably with 8 to 10 carbon atoms. Here, chain aliphatic group means a group derived from a chain aliphatic compound, which can be saturated or unsaturated, and can be linear or branched. R2 is preferably an alkyl group having 5 to 16 carbon atoms, more preferably an alkyl group having 6 to 14 carbon atoms, even more preferably an alkyl group having 7 to 12 carbon atoms, and even more preferably an alkyl group having 8 to 10 carbon atoms. The aforementioned alkyl group can be a straight-chain alkyl group or a branched alkyl group, but is preferably a straight-chain alkyl group. R2 is preferably selected from one or more of the group consisting of octamethylene and decamethylene, and is particularly preferably octamethylene.

[0040] The X2 system has the same definition as X1 in equation (1), and the ideal state is also the same.

[0041] The content ratio of the repeating constituent unit of formula (1) to the total of the repeating constituent units of formula (1) and formula (2) is 20 to 70 mol%. When the content ratio of the repeating constituent unit of formula (1) is within the above range, the polyimide resin can be fully crystallized. If the content ratio is less than 20 mol%, the molding processability will decrease, and if it exceeds 70 mol%, the crystallinity will decrease, and therefore the heat resistance will decrease. The ratio of the repeating constituent unit in Equation (1) to the total of the repeating constituent units in Equation (1) and Equation (2) is preferably 65 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and even more preferably less than 40 mol% from the perspective of exhibiting high crystallinity. If the content ratio of the repeating constituent unit of formula (1) to the total of the repeating constituent units of formula (1) and formula (2) is 20 mol% or more but less than 40 mol%, the crystallinity of the polyimide resin (Al) increases, resulting in a resin material with superior heat resistance. From the viewpoint of processability, the above content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 32 mol% or more. From the viewpoint of exhibiting high crystallinity, it is even more ideal to be 35 mol% or less. Specifically, from the viewpoints of processability and exhibiting high crystallinity, the above content ratio is preferably 25-35 mol%, more preferably 30-35 mol%, and even more preferably 32-35 mol%.

[0042] The total of the repeating constituent units of formula (1) and formula (2) relative to the total content of all repeating constituent units constituting polyimide resin (A1) is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, even more preferably 80 to 100 mol%, and still more preferably 85 to 100 mol%.

[0043] The polyimide resin (A1) may also contain repeating units of formula (3). In this case, the content of repeating units of formula (3) relative to the total content of repeating units of formula (1) and repeating units of formula (2) is preferably 25 mol% or less. On the other hand, there is no particular limitation on the lower limit, and it is acceptable to exceed 0 mol%. In the case of repeating constituent units containing formula (3), the ratio of the repeating constituent units of formula (3) to the total of the repeating constituent units of formula (1) and formula (2), from the viewpoint of improving heat resistance, is preferably 5 mol% or more, more preferably 10 mol% or more. On the other hand, from the viewpoint of maintaining crystallinity, it is ideally 20 mol% or less, more preferably 15 mol% or less. Specifically, from the viewpoints of improving heat resistance and maintaining crystallinity, the above-mentioned content ratio is preferably 5 to 20 mol%, more preferably 10 to 15 mol. [Chemistry 9] R3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring, and X3 is a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring.

[0044] R3 is a divalent group containing at least one aromatic ring with 6 to 22 carbon atoms. The aforementioned aromatic ring can be a monocyclic or condensed ring, and examples include benzene rings, naphthalene rings, anthracene rings, and fused tetraphenyl rings, but are not limited to these. Among these, benzene rings and naphthalene rings are preferred, and benzene rings are even more preferred. The number of carbons in R3 is 6 to 22, preferably 6 to 18. R 3 contains at least one aromatic ring, preferably one to three.

[0045] R3 is preferably a divalent base represented by the following formula (R3-1) or (R3-2). [Chemistry 10] m31 and m32 are each independently an integer from 0 to 2, preferably 0 or 1. m33 and m34 are each independently an integer from 0 to 2, preferably 0 or 1. R21, R22, and R23 are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. p21, p22, and p23 are integers from 0 to 4, preferably 0. L21 is a single bond, an ether bond (-O-), a carbonyl group, or an alkyl group having 1 to 4 carbon atoms. Furthermore, R3 is a divalent group with 6 to 22 carbons containing at least one aromatic ring. Therefore, m31, m32, R21 and p21 in formula (R3-1) are selected in such a way that the number of carbons of the divalent group represented by formula (R3-1) falls within the range of 6 to 22. Similarly, L 21, m 33, m 34, R 22, R 23, p 22 and p 23 in formula (R3-2) are selected in such a way that the number of carbons in the divalent group, as expressed in formula (R3-2), falls within the range of 12 to 22.

[0046] The X3 series has the same definition as X1 in equation (1), and the ideal state is also the same.

[0047] There are no particular restrictions on the end structure of polyimide resin (A1), but considering the viewpoint of obtaining a semiconductor resin material with high free radical generation efficiency and stable free radicals, it is more ideal to have amine groups at the end. Considering the viewpoint of improving heat aging resistance, it is more suitable to have chain aliphatic groups with 5 to 14 carbons at the end. The chain-like aliphatic group can be saturated or unsaturated, and can be linear or branched. When the polyimide resin (A1) has the above-mentioned specific groups at the end, a resin composition with excellent heat aging resistance can be obtained. Examples of saturated chain aliphatic groups with 5 to 14 carbon atoms include n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, lauryl, n-tridecyl, n-tetradecyl, isopentyl, neopentyl, 2-methylpentyl, 2-methylhexyl, 2-ethylpentyl, 3-ethylpentyl, isooctyl, 2-ethylhexyl, 3-ethylhexyl, isononyl, 2-ethyloctyl, isodecyl, isododecyl, isotridecyl, isotetradecyl, etc. For unsaturated chain aliphatic groups with 5 to 14 carbon atoms, examples include 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl, 2-octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, etc. Of these, saturated chain aliphatic groups are preferred, and saturated linear aliphatic groups are even more preferred. Furthermore, considering heat aging resistance, the aforementioned chain aliphatic groups preferably have 6 or more carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, ideally 12 or fewer carbon atoms, even more ideally 10 or fewer carbon atoms, and even more ideally 9 or fewer carbon atoms. The aforementioned chain aliphatic groups may be of only one type or may be of two or more types. The aforementioned chain-like aliphatic group is preferably selected from one or more of the group consisting of n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, isonyl, n-decyl, and isodexyl, more preferably selected from one or more of the group consisting of n-octyl, isooctyl, 2-ethylhexyl, n-nonyl, and isonyl, and most preferably selected from one of the group consisting of n-octyl, isooctyl, and 2-ethylhexyl. Furthermore, considering heat aging resistance, polyimide resin (A1) preferably has only chain-like aliphatic groups with 5 to 14 carbon atoms at its ends, in addition to terminal amine and terminal carboxyl groups. When the ends have groups other than those mentioned above, their content is preferably 10 mol% or less relative to the chain-like aliphatic groups with 5 to 14 carbon atoms, more preferably 5 mol% or less.

[0048] The content of the aforementioned chain-like aliphatic groups with carbon numbers of 5 to 14 in the polyimide resin (A1), considering the viewpoint of exhibiting excellent heat aging resistance, is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 0.2 mol% or more, relative to the total of all repeating constituent units constituting the polyimide resin (A1) in 100 mol%. Furthermore, to ensure sufficient molecular weight and obtain good mechanical properties, the content of the aforementioned chain-like aliphatic groups with carbon numbers of 5 to 14 in the polyimide resin (A1) is preferably 10 mol% or less, more preferably 6 mol% or less, even more preferably 3.5 mol% or less, even more preferably 2.0 mol% or less, and even more preferably 1.2 mol% or less, relative to the total of all repeating constituent units constituting the polyimide resin (A1) in 100 mol%. The content of the chain aliphatic groups with carbon numbers of 5 to 14 in the polyimide resin (A1) can be determined by depolymerizing the polyimide resin (A1).

[0049] Polyimide resin (A1) has an ideal melting point below 360°C and a glass transition temperature above 150°C. For polyimide resin (A1), considering heat resistance, the melting point is preferably above 280°C, and even more preferably above 290°C. Considering high processability, the ideal melting point is below 345°C, even more preferably below 340°C, and even more preferably below 335°C. Specifically, considering both heat resistance and high processability, the melting point of polyimide resin (A1) is preferably 280~345°C, even more preferably 280~340°C, and still even more preferably 290~335°C. Furthermore, considering heat resistance, the glass transition temperature of polyimide resin (A1) is preferably above 160°C, and even more preferably above 170°C. Considering high processability, it is ideally below 250°C, even more preferably below 230°C, and even more preferably below 200°C. Specifically, considering both heat resistance and high processability, the glass transition temperature of polyimide resin (A1) is preferably 160~250°C, more preferably 160~230°C, and even more preferably 170~200°C. Furthermore, considering improvements in crystallinity, heat resistance, mechanical strength, and chemical resistance, the heat at the crystallization exothermic peak observed when the polyimide resin (A1) is melted and cooled at a rate of 20°C / min using a differential scanning pyrometry apparatus (hereinafter also referred to as "crystallization exothermic heat") is preferably 5.0 mJ / mg or higher, more preferably 10.0 mJ / mg or higher, and even more preferably 17.0 mJ / mg or higher. There is no particular upper limit to the crystallization exothermic heat, but it is typically below 45.0 mJ / mg. The melting point, glass transition temperature, and heat of crystallization of polyimide resin (A1) can all be determined using a differential scanning calorimeter, specifically using the method described in the examples.

[0050] The weight-average molecular weight (Mw) of the polyimide resin (A1) is preferably in the range of 40,000 to 150,000, more preferably 40,000 to 100,000, even more preferably 42,000 to 80,000, even more preferably 45,000 to 70,000, and even more preferably 45,000 to 65,000. If the weight-average molecular weight (Mw) of the polyimide resin (A1) is above 40,000, the heat distortion temperature (HDT) under low load conditions will be improved, and the mechanical strength will also be good. Furthermore, if Mw is below 150,000, the processability is good. The weight average molecular weight Mw of polyimide resin (A1) can be determined by gel filtration chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample. Specifically, it can be determined using the method described in the examples.

[0051] The logarithmic viscosity of a 0.5% by mass concentrated sulfuric acid solution of polyimide resin (A1) at 30°C is preferably in the range of 0.8~2.0 dL / g, more preferably 0.9~1.8 dL / g. If the logarithmic viscosity is 0.8 dL / g or higher, it becomes easier to form a microphase separation structure in the resulting resin material, and sufficient mechanical strength can be obtained. If the logarithmic viscosity is 2.0 dL / g or lower, the molding processability and handling become good. The logarithmic viscosity μ is obtained by measuring the flow time of concentrated sulfuric acid and the above-mentioned polyimide resin solution at 30°C using a Cannon-Fenske viscometer, and is calculated using the following formula. Specifically, it can be measured using the method described in the examples. μ=ln[(ts / t 0) / C] t0: Flow time of concentrated sulfuric acid ts: Flow time of polyimide resin solution C: 0.5 (g / dL)

[0052] (Manufacturing method of polyimide resin (A1)) Polyimide resin (A1) can be manufactured by reacting a tetracarboxylic acid component with a diamine component. The tetracarboxylic acid component includes a tetracarboxylic acid containing at least one aromatic ring and / or its derivatives, and the diamine component includes a diamine containing at least one alicyclic hydrocarbon structure and a chain aliphatic diamine.

[0053] Ideally, a tetracarboxylic acid containing at least one aromatic ring should be a compound in which four carboxyl groups are directly bonded to the aromatic ring, and its structure may also contain an alkyl group. Furthermore, it is preferable that the aforementioned tetracarboxylic acid has 6 to 26 carbon atoms. Among the aforementioned tetracarboxylic acids, 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 are preferred. Of these, pyromellitic acid is even more preferred.

[0054] Regarding tetracarboxylic acid derivatives containing at least one aromatic ring, examples include anhydrides or alkyl esters of tetracarboxylic acids containing at least one aromatic ring. Ideally, the aforementioned tetracarboxylic acid derivatives should have 6 to 38 carbon atoms. Examples of tetracarboxylic acid anhydrides include pyromellitic tetracarboxylic acid monoanhydride, pyromellitic tetracarboxylic acid dianhydride, 2,3,5,6-toluenetetracarboxylic acid dianhydride, 3,3',4,4'-diphenyltinyl tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, and 1,4,5,8-naphthalenetetracarboxylic acid dianhydride. Examples of alkyl esters of tetracarboxylic acids include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylate, dimethyl 3,3',4,4'-diphenyltrimethyltetracarboxylate, dimethyl 3,3',4,4'-benzophenonetetracarboxylate, dimethyl 3,3',4,4'-biphenyltetracarboxylate, and dimethyl 1,4,5,8-naphthalenetetracarboxylate. Among these alkyl esters of tetracarboxylic acids, an alkyl group with 1 to 3 carbon atoms is ideal.

[0055] With regard to tetracarboxylic acids and / or their derivatives containing at least one aromatic ring, at least one of the compounds selected above may be used alone or in combination of two or more compounds.

[0056] Ideally, the diamine containing at least one alicyclic hydrocarbon structure should have 6 to 22 carbon atoms, and preferably include, for example, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine), carvone diamine, limonene diamine, isophorone diamine, norcamphene diamine, bis(aminomethyl)tricyclo[5.2.1.0 2,6]decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, etc. These compounds can be used alone or in combination of two or more selected compounds. Among these, 1,3-bis(aminomethyl)cyclohexane is ideally used. Furthermore, diamines containing alicyclic hydrocarbon structures generally have structural isomers, but the ratio of their cis to trans isomers is not limited.

[0057] The chain-like aliphatic diamine can be linear or branched, with 5-16 carbon atoms being preferred, 6-14 being more preferred, and 7-12 being even more preferred. Furthermore, if the chain portion has 5-16 carbon atoms, it may also contain ether bonds. For example, chain-like aliphatic diamines, preferred ones include 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tetridemethylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, and 2,2'-(epyleneethyldioxy)bis(epyleneethylamine). One type or a mixture of multiple chain aliphatic diamines may be used. Among these, chain aliphatic diamines with 8 to 10 carbon atoms are ideally used, and one or more types selected from the group consisting of 1,8-octamethylenediamine and 1,10-decamethylenediamine are particularly ideal.

[0058] When manufacturing polyimide resin (A1), the amount of diamine containing at least one alicyclic hydrocarbon structure added is preferably 20 to 70 mol% relative to the total molar ratio of diamine containing at least one alicyclic hydrocarbon structure and chain aliphatic diamine. This molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, and even more preferably 32 mol% or more. Considering the viewpoint of exhibiting high crystallinity, it is ideally 60 mol% or less, more preferably 50 mol% or less, even more preferably less than 40 mol%, and even more preferably 35 mol% or less.

[0059] Furthermore, the aforementioned diamine components may also include diamines containing at least one aromatic ring. Ideally, diamines containing at least one aromatic ring should have 6 to 22 carbon atoms. Examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,2-diethynylphenylenediamine, 1,3-diethynylphenylenediamine, 1,4-diethynylphenylenediamine, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, α,α'-bis(4-aminophenyl)1,4-diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,4-diisopropylbenzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,6-diaminonaphthalene, and 1,5-diaminonaphthalene.

[0060] In the above, the amount of diamine containing at least one aromatic ring added relative to the molar ratio of the total amount of diamine containing at least one alicyclic hydrocarbon structure and chain aliphatic diamine is preferably 25 mol% or less, more preferably 20 mol% or less, and even more preferably 15 mol% or less. There is no particular limitation on the lower limit of the aforementioned molar ratio, but considering the viewpoint of improving heat resistance, it is preferable to be 5 molar% or more, and even more preferably 10 molar% or more. On the other hand, considering the viewpoint of reducing the coloring of polyimide resin, the aforementioned molar ratio is more ideally 12 molar% or less, more ideally 10 molar% or less, more ideally 5 molar% or less, and even more ideally 0 molar.

[0061] When manufacturing polyimide resin (A1), the preferred ratio of the aforementioned tetracarboxylic acid component to the aforementioned diamine component is 0.9 to 1.1 mol of diamine component relative to 1 mol of tetracarboxylic acid component.

[0062] Furthermore, in the manufacture of polyimide resin (A1), in addition to the aforementioned tetracarboxylic acid component and diamine component, a capping agent may also be mixed in. Regarding the capping agent, it is preferable to select one or more from the group consisting of monoamines and dicarboxylic acids. The amount of capping agent used should be sufficient to introduce the desired amount of terminal groups into the polyimide resin (A1). It is preferable to use 0.0001 to 0.1 mol relative to 1 mol of the aforementioned tetracarboxylic acid and / or its derivatives, more preferably 0.001 to 0.06 mol, even more preferably 0.002 to 0.035 mol, even more preferably 0.002 to 0.020 mol, and even more preferably 0.002 to 0.012 mol. Among them, the end-capping agent is preferably a monoamine end-capping agent. Considering the view that the heat aging resistance can be improved by introducing the aforementioned chain aliphatic group with 5 to 14 carbons into the end of the polyimide resin (A1), it is more preferably a monoamine with chain aliphatic group with 5 to 14 carbons, and even more preferably a monoamine with saturated straight-chain aliphatic group with 5 to 14 carbons. The capping agent is preferably selected from one or more of the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isonylamine, n-decylamine, and isodecanamine; more preferably, it is selected from one or more of the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isonylamine; and most preferably, it is selected from one or more of the group consisting of n-octylamine, isooctylamine, and 2-ethylhexylamine.

[0063] Regarding the polymerization method used to manufacture polyimide resin (A1), known polymerization methods can be applied, and the method described in International Publication No. 2016 / 147996 can be used.

[0064] [, , ] Next, we will explain the polyimide resin (A2). Polyimide resin (A2) is a polyimide resin composed of repeating constituent units represented by the following formula (1). [Chemistry 11] R1 is a divalent aliphatic group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure, and X1 is a tetravalent aromatic group with 6 to 22 carbon atoms.

[0065] The repeating constituent unit of formula (1) is as described in the example of polyamide resin (A1) above. In particular, the divalent base represented by the following formulas (R1-3) and (R1-4) is more ideal. When R1 is a divalent base represented by the following formulas (R1-3) and (R1-4), the proportion of the divalent base represented by formula (R1-3) relative to all R1 is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol. [Chemistry 12] Furthermore, the manufacturing method of polyimide resin (A2) can be set to the same state as that of polyimide resin (A1).

[0066] [, , ] Next, we will explain the polyimide resin (A3). Polyimide resin (A3) is a polyimide resin composed of repeating units of formula (2) and repeating units of formula (3). [Chemistry 13] R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, R3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring, X2 is a tetravalent aromatic group with 6 to 22 carbon atoms, and X3 is a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring.

[0067] The repeating constituent units of formula (2) and formula (3) are respectively as described in the example of polyamine resin (A1) above. In particular, R2 is preferably selected from one or more of the group consisting of octamethylene and decamethylene, and more preferably octamethylene. Also, R3 is preferably a divalent group represented by the formula (R3-1) or (R3-2), and more preferably a divalent group represented by (R3-2). [Chemistry 14] m31 and m32 are each independently an integer from 0 to 2, preferably 0 or 1. m33 and m34 are each independently an integer from 0 to 2, preferably 0 or 1. R21, R22, and R23 are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms. p21, p22, and p23 are integers from 0 to 4, preferably 0. L21 is a single bond, an ether bond (-O-), a carbonyl group, or an alkyl group having 1 to 4 carbon atoms. In the polyimide resin (A3), the ratio of the repeating unit of formula (2) to the total of the repeating units of formula (2) and formula (3) is preferably 50 to 95 mol%, more preferably 60 to 85 mol. Furthermore, the manufacturing method of polyimide resin (A3) can be set to the same state as that of polyimide resin (A1).

[0068] Furthermore, the resin material of the present invention may consist solely of polyimide resin (A), or may contain resins other than polyimide resin (A) as needed. Moreover, considering the effect of the present invention, the content of polyimide resin (A) in the resin material is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. The upper limit is 100% by mass.

[0069] <Resin (B)> The resin material of the present invention preferably comprises one or more resins selected from the group consisting of polyamine resin, polyamine-imide resin, epoxy resin, carbamate resin, urea resin, phenolic resin, cyanate resin, polythiophene resin, polyvinylene resin, poly(p-phenylenevinylene) resin, polyvinylcarbazole resin, polyether-imide resin, and polyimide resin other than the aforementioned polyimide resin (A). By mixing the aforementioned resin (B) with a polyimide resin (A) having a predetermined structure, the semiconductor properties of the resulting resin material can be improved. Furthermore, with the addition of resin (B), molded articles can be obtained not only by compression molding but also by injection molding, thus improving the freedom of shape design for the molded articles.

[0070] Resin (B) is preferably selected from one or more of the group consisting of polyamine resin, polyamine-imide resin, epoxy resin, carbamate resin, urea resin, phenolic resin, cyanate resin, polythiophene resin, polyvinylene resin, poly(p-phenylenevinylene) resin, polyvinylcarbazole resin, polyether-imide resin, and polyimide resin other than the aforementioned polyimide resin (A). It is more preferably selected from one or more of the group consisting of polyamine resin, polyamine-imide resin, epoxy resin, carbamate resin, urea resin, phenolic resin, cyanate resin, and polythiophene resin. It is even more preferably polyamine resin.

[0071] Examples of polyamide resins include polyamide 6 (PA6), polyamide 66, polyamide 66 / 6, polyamide 46, polyamide 11, polyamide 12, MXD6, and polyamide 9T. Regarding polyamide-imide resins, examples include Torlon (manufactured by Solvay). In the case of epoxy resins, examples include bisphenol A type epoxy resin, etc. Examples of carbamate resins include thermoplastic carbamate resins. Regarding urea resins, examples include pure polyurea, hybrid polyurea, and urea carbamate. Regarding phenolic resins, examples include phenolic varnish-type phenolic resins and methyl phenolic resins. In terms of cyanate ester resins, examples include CYTESTER (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Examples of polythiophene resins include poly(3-hexylthiophene) (P3HT), diketopyrrolopyrrolo-thiophene (DPP-T), and poly(2,5-thiophene ethylene) resin. Resin (B) can be used alone or in combination with two or more of the above-mentioned resins.

[0072] When the resin material contains resin (B), the mass ratio (A / B) of polyimide resin (A) to resin (B) in the resin material is preferably in the range of 1 / 99 to 99 / 1, more preferably 5 / 95 to 95 / 5, even more preferably 10 / 90 to 90 / 10, and still more preferably 15 / 85 to 85 / 15. Within the above range, the dispersibility between the resins becomes good, and the reduction in the mechanical strength of the resin material can be suppressed.

[0073] Furthermore, considering the effect of the present invention, the total content of polyimide resin (A) and resin (B) in the resin material is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. The upper limit is 100% by mass.

[0074] <Compound (C)> Furthermore, the resin material of the present invention may also contain existing OFET materials as needed. Specifically, considering the ease of performance demonstration as an OFET material, the resin material of the present invention may further contain one or more compounds selected from the group consisting of red fluorene, condensed tetraphenylene, condensed pentaphenylene, 6,13-bis(triisopropylsilylethynyl)condensed pentaphenylene, perylene diimide (PTCDI), tetracyanoquinone dimethane (TCNQ), fullerenes, carbon nanotubes, graphenes, phthalocyanines, and perylene compounds (C).

[0075] When the resin material contains compound (C), there is no particular limitation on the content of compound (C) in the resin material. However, considering the viewpoint of maintaining the physical properties derived from polyimide resin (A) and the ease of exhibiting performance as an OFET material, it is preferable to be 0.01% by mass or more and 50% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less.

[0076] <Metal Compounds (D)> Furthermore, the resin material of the present invention may also contain dopants for p-type semiconductors or n-type semiconductors as needed. Specifically, considering the viewpoint of maximizing semiconductor performance, the resin material of the present invention may further contain one or more metal compounds (D) selected from the group consisting of molybdenum compounds, cesium compounds, aluminum compounds, zinc compounds, ruthenium compounds, and chromium compounds. Among these, selecting one or more from the group consisting of cesium compounds, rhodium compounds, ruthenium compounds, and chromium compounds is preferred.

[0077] Regarding metal compounds (D), examples include oxides, carbonates, and organometallic complexes of various metals. For instance, molybdenum oxide is an example of a molybdenum compound, cesium oxide is an example of a cesium compound, rhodium thiocenene and 1,2,3,4,5-pentamethylrhodium thiocenene are examples of rhodium thiocenene compounds, and pentamethylcyclopentadienyltrimethylbenzene ruthenium and trichloro(4,4',5,5'-tetramethyl-2,2'-bipyridine)chromium are examples of ruthenium compounds. Furthermore, molybdenum oxide is suitable as a dopant for p-type semiconductors, and cesium oxide is suitable as a dopant for n-type semiconductors.

[0078] When the resin material contains a metal compound (D), there is no particular limitation on the content of the metal compound (D) in the resin material. However, considering the viewpoint of maintaining the physical properties derived from the polyimide resin (A) and exhibiting the effect of the metal compound (D) as a dopant, it is preferable to be 1% or more and 30% or less by mass, and more preferably 3% or more and 10% or less by mass.

[0079] <Other Additives> The resin material of this invention may also contain fillers, matting agents, nucleating agents, plasticizers, antistatic agents, anti-coloring agents, anti-gelling agents, flame retardants, colorants, lubrication modifiers, conductive materials, antioxidants, resin modifiers and other additives as needed. When the resin material contains additives, there is no particular limitation on the content of the additives in the resin material. However, considering the viewpoint of maintaining the physical properties derived from polyimide resin (A) and exhibiting the effect of the additives, it is usually less than 50% by mass, preferably 0.0001 to 30% by mass, more preferably 0.0001 to 15% by mass, even more preferably 0.001 to 10% by mass, and even more preferably 0.01 to 8% by mass.

[0080] The shape of the resin material in this invention is not particularly limited, but powders and pellets are examples. Furthermore, considering the efficiency of free radical generation and the longevity of the generated free radicals, the more robust the molecular structure, the better. Even with resin materials of the same composition, pellets will improve the efficiency of free radical generation and the half-life of the generated free radicals more than powders.

[0081] [molded body] The molded body made of the semiconductor resin material of the present invention has excellent heat resistance and exhibits excellent semiconductor properties.

[0082] The semiconductor resin material of this invention, when molded into a shaped body, further improves semiconductor properties. Although the reason is not yet clear, it is believed that because the molecular structure of the shaped body is more robust than that of the powder, the energy movement of the excited state becomes easier, the generation efficiency of free radicals is improved, and the rebonding of the generated free radicals is suppressed, thereby extending the lifetime of free radicals.

[0083] [Manufacturing Method of Molded Objects] Because the polyimide resin (A) contained in the molded body of the present invention is thermoplastic, the molded body can be easily manufactured by thermoforming the resin composition containing the polyimide resin (A). Regarding thermoforming methods, examples include compression molding, injection molding, extrusion molding, blow molding, laser molding, ultrasonic heating molding, welding, and fusion. Any molding method involving a heat-melting step can be used. Thermoforming is more ideal because it allows forming without setting the molding temperature to, for example, above 400°C. Compression molding and injection molding are particularly ideal because they do not require setting the molding temperature or the mold temperature to high levels. The following will use compression molding and injection molding as examples for detailed explanation.

[0084] <1> Compression molding Regarding the method of using compression molding to produce shaped objects, known methods can be used. Regarding the specific steps involved in producing, for example, a molded body made solely of polyimide resin (A), the following methods can be listed.

[0085] (Preforming) First, the powder of polyimide resin (A) is placed into a mold and compressed to perform preforming.

[0086] The ideal powder of polyimide resin (A) is obtained after proper cleaning and drying following resin synthesis. The drying process can be carried out using a hot air dryer, a dehumidifying dryer, or other known methods. The preferred drying temperature is 80–160°C, more preferably 120–150°C. The preferred drying time is 6–24 hours, more preferably 8–16 hours. By performing drying treatment as a pretreatment of polyimide resin (A) powder, molded articles with excellent flexural strength and heat resistance can be obtained.

[0087] The volume average particle size (D50) of the polyimide resin (A) powder is preferably 10~100 μm. Within this range, the workability, processability, and formability of the polyimide resin (A) powder are good. Therefore, the polyimide resin (A) may also be pulverized or granulated before molding to achieve the aforementioned volume average particle size, as required. The volume average particle size (D50) of the polyimide resin (A) powder can be determined using the method described in the examples.

[0088] The mold can be selected appropriately according to the shape of the molded object and the molding conditions; known molds can be used. Furthermore, it is ideal to pre-apply a release agent to the mold.

[0089] As for the apparatus for performing preforming, examples include cooling and pressing apparatus. In terms of preforming conditions, molding under conditions such as gauge pressure of 20~25MPa, room temperature (15~25℃), and inert gas environment is more ideal.

[0090] (Thermoforming) After preforming, the material is compressed and shaped simultaneously to obtain the shaped body. As for the apparatus for performing thermoforming, examples include vacuum pressing apparatus, autoclave apparatus, and double-belt pressing apparatus.

[0091] The preferred temperature for thermoforming is 335~385℃, more preferably 350~370℃. By setting the temperature within the above range, good molded products can be obtained. The environment during thermoforming can include, for example, an atmospheric environment, an inert gas environment, and a vacuum environment. Among these, considering the prevention of coloration of the molded body caused by heating, thermoforming in a vacuum environment (below -0.1 bar) is more ideal. The preferred pressure during thermoforming is 5~30MPa, and the preferred processing time is 10~20 minutes.

[0092] (cool down) The heat-treated molded part is removed from the mold and compressed and cooled. As for devices that implement compression cooling, examples include cooling compression devices. In terms of compression and cooling conditions, it is ideal to perform the process at room temperature (15~25℃) in an atmospheric environment with the same pressure and processing time as during thermoforming.

[0093] <2> Injection molding In terms of methods for manufacturing molded objects using injection molding, known methods can be used. Regarding the specific steps in making a molded article, for example, containing polyimide resin (A) and the aforementioned resin (B), the following methods can be listed.

[0094] First, polyimide resin (A), resin (B), and any other desired components are added, dried, and mixed. The mixture is then introduced into an extruder, preferably melted at 290-350°C, and melt-mixed and extruded within the extruder. The resulting filaments are cooled and then pelletized using a granulator. Alternatively, polyimide resin (A) can be introduced into an extruder, preferably melted at 290-350°C, and then mixed with resin (B) and any other desired components. The mixture is then melt-mixed and extruded with the polyimide resin (A) within the extruder. The resulting filaments are cooled and then pelletized using a granulator.

[0095] After the pellets are dried, they are fed into various molding machines and preferably thermoformed at 290~350°C to produce resin molded bodies with the desired shapes. The thermoforming temperature is preferably 310~350°C.

[0096] [use] The semiconductor resin material of this invention has excellent heat resistance and semiconductor properties, and therefore can be ideally used in various organic electronic devices. In terms of organic electronic devices, the group selected from organic integrated circuits (OIC), organic field-effect transistors (OFET), organic thin-film transistors (OTFT), organic light-emitting diodes (OLED), organic photoelectric conversion (OPV) cells, organic optical detectors, and organic light receivers is more ideal.

[0097] Flexible printing materials The semiconductor resin material of this invention is particularly well-suited for use as a flexible printing material. The flexible printing material of this invention is composed of the semiconductor resin material of this invention, thus exhibiting excellent flexibility, heat resistance, manufacturability, and electrical properties. Such flexible printed materials are ideal for use in organic integrated circuits (OICs).

[0098] The embodiments of the present invention have been described above, but the above embodiments are merely one example of the present invention. The present invention includes all the forms contained in the concept of the present invention and the claims of the invention, and various modifications can be made within the scope of the present invention. [Example]

[0099] The present invention is described in more detail below with reference to examples, but the present invention is not limited thereto. Furthermore, the various measurements and evaluations in the examples and comparative examples are performed as follows.

[0100] Infrared Spectrophotometry (IR Measurement) The IR measurement of polyimide resin was performed using a "JIR-WINSPEC50" manufactured by Nippon Electronics Co., Ltd.

[0101] <Logarithmic viscosity μ> After drying the polyimide resin at 190-200°C for 2 hours, a polyimide resin solution prepared by dissolving 0.100 g of the polyimide resin in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Chemical Co., Ltd.) was used as the test sample. The solution was measured using a Canon Finsker viscometer at 30°C. The logarithmic viscosity μ was obtained by the following formula. μ=ln(ts / t 0) / C t0: Flow time of concentrated sulfuric acid ts: Flow time of polyimide resin solution C: 0.5g / dL

[0102] Melting point, glass transition temperature, crystallization temperature, heat of crystallization The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and exothermic crystallization ΔHc of polyimide resin were measured using a differential scanning calorimeter (DSC-6220 manufactured by SII NanoTechnology Co., Ltd.). The following thermal process was applied to polyimide resin under a nitrogen atmosphere. The thermal process conditions were: a first heating (up to 380°C, heating rate 10°C / min), followed by cooling (up to 40°C, cooling rate 20°C / min), and then a second heating (up to 380°C, heating rate 10°C / min). The melting point Tm is determined by the peak value of the endothermic peak observed during the second heating. The glass transition temperature Tg is determined by the value observed during the second heating. The crystallization temperature Tc is determined by the peak value of the exothermic peak observed during cooling. Furthermore, for Tm, Tg, and Tc, if multiple peaks are observed, the peak values ​​of each peak are taken. Furthermore, the exothermic heat of crystallization ΔHc (mJ / mg) is calculated from the area of ​​the exothermic peak observed during cooling.

[0103] <Semi-crystallization time> The semi-crystallization time of polyimide resin was determined using a differential scanning pyrolysis apparatus (DSC-6220 manufactured by SII NanoTechnology Co., Ltd.). The semi-crystallization time was determined under nitrogen atmosphere and at 420°C for 10 minutes to completely melt the polyimide resin. A rapid cooling operation at a rate of 70°C / min was then performed. The time taken from the appearance of the observed crystallization peak to its peak was calculated. Furthermore, in Table 1, a semi-crystallization time of 20 seconds or less is indicated as "<20".

[0104] <Weight Average Molecular Weight> The weight average molecular weight (Mw) of the polyimide resin was determined using a gel filtration chromatography (GPC) apparatus, "Shodex GPC-101", manufactured by Showa Denko Corporation, under the following conditions. String: Shodex HFIP-806M Mobile phase solvent: HFIP containing 2 mM sodium trifluoroacetate Column temperature: 40℃ Mobile phase flow rate: 1.0 mL / min Sample concentration: approximately 0.1% by mass Detector: IR detector Injection volume: 100μm Measurement line: Standard PMMA

[0105] <Volume average particle size (D50)> The D50 of polyimide resin particles is determined by laser diffraction particle size distribution measurement. For the measuring apparatus, a laser diffraction light scattering particle size analyzer (Malvern LMS-2000e) was used. Water was used as the dispersion medium for the D50 determination of resin particles, taking advantage of the sufficient dispersion of resin particles under ultrasonic conditions. The measurement range was set to 0.02~2000 μm.

[0106] <Light exposure> For the resin material powders, pellets, and molded articles of the embodiments and comparative examples, ultraviolet light was irradiated under the following conditions. [UV irradiation conditions] • Apparatus: UV light source (Hamamatsu Photonics "LIGHTNINGCURE LC8 L9566-01A") UV wavelength: mainly 365nm • Intensity (365nm): Approximately 30mW / cm² • Light exposure time: 4 hours

[0107] <ESR measurement> The ESR measurement is carried out using the following conditions. 〔Measurement device〕 Regarding the measurement device, an electron spin resonance analyzer (「E500」manufactured by Bruker Corporation) is used and set to the following settings. ･Measurement mode: cw mode ･Microwave frequency: approximately 9.4 GHz ･Microwave intensity: shown in Table 2. ･Scanning magnetic field range: shown in Table 2. ･Modulation magnetic field amplitude: shown in Table 2. ･Measurement temperature: 296 - 298 K ･Standard sample: For the confirmation of the g value, DPPH (1,1 - diphenyl - 2 - picrylhydrazyl) is used.

[0108] Each sample is introduced into a quartz ESR sample tube in the amounts shown in Table 2 and defined as an analysis sample. For this analysis sample, light irradiation is performed from the outside of the test tube under the above conditions, and ESR measurement is carried out. The measured ESR spectrum is analyzed using the software attached to the device, and the g value, radical amount, and half - life of the observed radical species are calculated. Furthermore, the radical concentration shown in Table 3 is a value calculated from the above radical amount by the calculation of the following formula (I). Molar concentration (mol / g) = radical amount (spins) / (measured weight × Avogadro's constant) ··· (I) Also, the half - life of the radical is calculated from the time when the intensity of the ESR spectrum becomes 1 / 2, but for those with slower decay, it is calculated from the time when the intensity becomes 1 / 2 of 0.5. In Table 3, for the decay time calculated from the time when the intensity becomes 1 / 2 of 0.5, a "*" is marked on the value in Table 3. [[ID=三十四]]

[0109] [[ID=三十五]] [[ID=三十六]]<Diffuse reflection measurement> [[ID=三十七]] [[ID=三十八]] [[ID=三十九]] [[ID=四十]] [[ID=四十一]] [[ID=四十二]]･Start wavelength: 810 nm [[ID=四十三]] ​​• End wavelength: 240nm • Data interval: 1nm • Scanning speed: Medium Types of photometric values: reflectance • Slit width: 20nm Slit Program: Standard • Detector unit: External • S / R switching: Standard • Grating switching wavelength: 720nm Reference object: BaSO4 whiteboard

[0110] The presence of a maximum peak in the visible light region (380~800nm) of the measured diffuse reflectance spectrum was confirmed.

[0111] (Example 1) In a 2L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and four impellers, 500g of 2-(2-methoxyethoxy)ethanol (manufactured by Nippon Emulsifier Co., Ltd.) and 218.12g (1.00mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced and purged with nitrogen. The mixture was then stirred at 150 rpm to form a homogeneous suspension. Meanwhile, in a 500mL beaker, 49.79g (0.35mol) of 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., cis / trans ratio = 7 / 3) and 93.77g (0.65mol) of 1,8-octamethylenediamine (manufactured by Kanto Chemical Co., Ltd.) were dissolved in 250g of 2-(2-methoxyethoxy)ethanol to prepare a mixed diamine solution. This mixed diamine solution was slowly added using a plunger pump. Because the dropwise addition causes exothermic reactions, the internal temperature was adjusted to be controlled between 40 and 80°C. The addition of the mixed diamine solution was carried out under nitrogen purging throughout, with the stirring speed set to 250 rpm. After the dropwise addition was complete, 130 g of 2-(2-methoxyethoxy)ethanol and 1.284 g (0.0100 mol) of n-octylamine (manufactured by Kanto Chemical Co., Ltd.) as a capping agent were added, and the mixture was stirred further. At this stage, a pale yellow polyamide solution was obtained. Next, the stirring speed was set to 200 rpm, and the polyamide solution in the 2L separable flask was heated to 190°C. During the heating process, precipitation of polyimide resin powder and dehydration accompanied by amide formation were observed between 120 and 140°C. After maintaining the temperature at 190°C for 30 minutes, the solution was cooled to room temperature (23°C) and filtered. The obtained polyimide resin powder was obtained by washing and filtering with 300g of 2-(2-methoxyethoxy)ethanol and 300g of methanol, and then drying it at 150°C for 12 hours to obtain 317g of polyimide resin 1 powder.

[0112] The IR spectrum of polyimide resin 1 was measured, and the characteristic absorption of the imidin ring was confirmed at ν(C=O) 1768 and 1697 (cm⁻¹). The logarithmic viscosity μ was 1.30 dL / g, the melting point Tm was 323℃, the glass transition temperature Tg was 184℃, the crystallization temperature Tc was 266℃, the exothermic heat of crystallization ΔHc was 21.0 mJ / mg, the semi-crystallization time was less than 20 seconds, the weight average molecular weight (Mw) was 55,000, and the volume average particle size (D50) was 17 μm.

[0113] Next, the obtained polyimide resin 1 powder was extruded using a LABO PLASTOMILL (manufactured by Toyo Seiki Co., Ltd.) at a barrel temperature of 350°C and a screw speed of 70 rpm. The extruded strands were then air-cooled and pelletized using a granulator (HOSHIPLA Co., Ltd. "FAN-CUTTER FC-Mini-4 / N") to produce pellets.

[0114] Next, 100g of the obtained polyimide resin 1 powder was introduced into a positive mold (φ100mm) pre-coated with a release agent. Cooling pressing was used to compress the powder within the mold for pre-forming. Then, a manual hydraulic vacuum press (IMC-1AEA type, manufactured by Iigen Manufacturing Co., Ltd.) was used to press the upper plate in a vacuum environment (-0.1 bar) at 350°C for 7 minutes (preheating process), and the pressure was slowly increased and maintained at 10MPa for 10 minutes (pressurization process). The press was then removed from the mold and cooled, held at room temperature (23°C) in an atmospheric environment at 10MPa for 10 minutes (cooling process), resulting in a molded body (100mm in diameter, 10mm in thickness) made of polyimide resin 1.

[0115] ESR measurements were performed on the obtained polyimide resin 1 powder, pellets, and molded articles before and after light irradiation (UV irradiation). Furthermore, diffuse reflectance measurements were also performed on the molded articles of polyimide resin 1 after light irradiation (UV irradiation). Moreover, for the molded articles, samples approximately 10 mm × 1 mm × 1 mm were machined as samples for ESR measurement.

[0116] (Example 2) Without using a capping agent, the polyimide resin 2 powder was obtained using the same method as in Example 1. The IR spectrum of polyimide resin 2 was measured, and the characteristic absorption of the imidin ring was confirmed at ν(C=O) 1767 and 1696 (cm⁻¹). The melting point Tm is 323℃, the glass transition temperature Tg is 185℃, the crystallization temperature Tc is 263℃, the exothermic heat of crystallization ΔHc is 26.3 mJ / mg, the semi-crystallization time is less than 20 seconds, the weight average molecular weight (Mw) is 71,500, and the volume average particle size (D50) is 27 μm.

[0117] The obtained polyimide resin 2 powder was further used to make pellets using the same method as in Example 1. Furthermore, the ESR of the obtained polyimide resin 2 powder was measured before and after light irradiation (UV irradiation).

[0118] (Example 3) Instead of 1,8-octamethylenediamine, 112.01 g (0.65 mol) of 1,10-decamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. Otherwise, the polyimide resin 3 powder was obtained using the same method as in Example 2. The IR spectrum of polyimide resin 3 was measured, and the characteristic absorption of the imidin ring was confirmed at ν(C=O) 1769 and 1697 (cm⁻¹). The melting point Tm is 280℃, the glass transition temperature Tg is 167℃, the crystallization temperature Tc is 227℃, the exothermic heat of crystallization ΔHc is 21.0 mJ / mg, the semi-crystallization time is less than 20 seconds, the weight average molecular weight (Mw) is 54700, and the volume average particle size (D50) is 24 μm.

[0119] The obtained polyimide resin 3 powder was further used to make pellets using the same method as in Example 1. Furthermore, the ESR of the obtained polyimide resin 3 powder was measured before and after light irradiation (UV irradiation).

[0120] (Example 4) Instead of 1,8-octamethylenediamine, 92.46 g (0.65 mol) of 1,4-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd., cis / trans ratio = 15 / 85) was used, and otherwise, polyimide resin 4 powder was obtained using the same method as in Example 2. The IR spectrum of polyimide resin 4 was measured, and the characteristic absorptions of the amide ring were confirmed at ν(C=O) 1769 and 1697 (cm⁻¹). The weight-average molecular weight (Mw) was 29,000. Furthermore, no endothermic melting peak was observed in the DSC measurements of polyimide resin 4.

[0121] The ESR of the obtained polyimide resin 4 powder was measured before and after light irradiation (UV irradiation).

[0122] (Example 5) Instead of 1,3-bis(aminomethyl)cyclohexane, 70.08 g (0.35 mol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, and the polyimide resin 5 powder was obtained using the same method as in Example 2. The IR spectrum of polyimide resin 5 was measured, and the characteristic absorption of the amide ring was confirmed at ν(C=O) 1769 (cm⁻¹). The volume average particle size (D50) was 15 μm. Furthermore, polyimide resin 5 did not melt even when heated to 400 °C during DSC analysis. Also, because polyimide resin 5 is insoluble in HFIP, the mobile phase solvent used in GPC, the weight average molecular weight was not determined.

[0123] The ESR of the obtained polyimide resin 5 powder was measured before and after light irradiation (UV irradiation).

[0124] (Example 6) Polyimide resin 1 obtained in Example 1 and polyimide resin PA6 (Ube Industries, Inc. "UBE NYLON 1030B", melting point 215~225°C, glass transition temperature 50°C) were prepared in a mass ratio of 30:70. Next, PA6 was introduced into the hopper on the root side of a co-rotating twin-screw extruder (PARKER CORPORATION, Inc. "HK-25D"), and polyimide resin 1 powder was introduced into the extruder through a side feeder. The mixture was kneaded under conditions of a cylinder temperature of 260°C, a feed rate of 6 kg / h, and a screw speed of 200 rpm, and extruded into strands. After the extruded strands are cooled with water, pellets are made using a granulator (HOSHIPLA FAN-CUTTER FC-Mini-4 / N).

[0125] The ESR of the pellets containing polyimide resin 1 and polyimide resin were measured before and after light irradiation (UV irradiation), and the diffuse reflectance was measured after light irradiation (UV irradiation).

[0126] (Comparative Example 1) ESR measurements were performed on granular polyamide resin PA6 (as above) before and after light irradiation (UV irradiation).

[0127] (Comparative Example 2) ESR measurements were performed on granular polycarbonate resin (Iupilon manufactured by Mitsubishi Engineering-Plastics Co., Ltd., glass transition temperature 150°C) before and after light irradiation (UV irradiation).

[0128] The composition of the polyimide resins in Examples 1-5 is shown in Table 1. Furthermore, the molar percentages of the tetracarboxylic acid and diamine components in Table 1 are calculated from the amounts of each component added during the manufacturing of the polyimide resin.

[0129] [Table 1] Tetracarboxylic acid components (mole of all tetracarboxylic acid components) Diamine component (mole of all diamine components) End capping agent PMDA 1,3-BAC 1,4-BAC 4,4'-ODA OMDA DMDA OcA Example 1 Polyimide resin 1 100 35 - - 65 - 0.01 2 Polyimide resin 2 100 35 - - 65 - - 3 Polyimide resin 3 100 35 - - - 65 - 4 Polyimide resin 4 100 35 65 - - - - 5 Polyimide resin 5 100 - - 35 65 - -

[0130] The abbreviations in Table 1 are as follows. PMDA: Pyromellitic dianhydride ･1,3-BAC:1,3-bis(aminomethyl)cyclohexane ･1,4-BAC:1,4-bis(aminomethyl)cyclohexane ･4,4'-ODA: 4,4'-Diaminodiphenyl ether OMDA: 1,8-Octamethylenediamine DMDA: 1,10-Decamethyldiamine OcA: n-Octylamine

[0131] The different ESR determination conditions for each sample are shown in Table 2.

[0132] [Table 2] Sample weight microwave intensity Scanning magnetic field range Modulated magnetic field amplitude mg μW mT mT Example 1 powder 15.92 32 10 0.0375 pellets 15.28 8 10 0.0250 Formed body 14.03 0.5 20 0.0375 Example 2 powder 18.27 8 10 0.2000 Example 3 powder 18.26 8 10 0.2000 Example 4 powder 18.27 8 10 0.2000 Example 5 powder 18.63 32 10 0.2000 Example 6 pellets 15.06 8 10 0.0250 Comparative Example 1 pellets 15.91 502 20 0.8000 Comparative Example 2 pellets 15.04 126 10 0.2000

[0133] Table 3 shows the various measurement results before and after light irradiation for the examples and comparative examples.

[0134] [Table 3] Example Comparative example 1 2 3 4 5 6 1 2 Resin material composition (mass %) (A) Polyimide resin 1 100 - - - - 30 - - Polyimide resin 2 - 100 - - - - - - Polyimide resin 3 - - 100 - - - - - Polyimide resin 4 - - - 100 - - - - Polyimide resin 5 - - - - 100 - - - (B) Polyamine resin - - - - - 70 100 - (b) polycarbonate resin - - - - - - - 100 Feature Evaluation shape evaluate project unit light exposure Example Comparative example 1 2 3 4 5 6 1 2 powder g value - back 2.0043 2.0041 2.0042 2.0042 2.0045 - - - Free radical concentration ×10⁻⁸ / mol / g forward 0 0 0 0 7 - - - back 7 10 5 4 19 - - - half life Second back 190 290 130 220 12000 * - - - pellets g value - back 2.0043 - - - - 2.0044 2.0048 2.0044 Free radical concentration ×10⁻⁸ / mol / g forward 0 - - - - 0 0 0 back 46 - - - - 100 3 2 half life Second back 11400 * - - - - 29000 * 432000 * 6000 * Formed body g value - back 2.0045 - - - - - - - Free radical concentration ×10⁻⁸ / mol / g forward 0 - - - - - - - back 112 - - - - - - - half life Second back 15000 * - - - - - - - *The decay time calculated from the time it takes for the intensity to become 1 / 2 0.5

[0135] As shown in Table 3, resin materials (Examples 1-6) containing polyimide resin (A) comprising repeating units derived from aromatic tetracarboxylic acid and aliphatic diamine components exhibit higher free radical concentrations upon light irradiation compared to polyimide resins and polycarbonate resins (Comparative Examples 1 and 2), confirming high free radical generation efficiency. Furthermore, the half-life of the free radicals generated by light irradiation in any of the resin materials is greater than 1 second, confirming the stability of the generated free radicals. In particular, resin materials containing polyimide resin 1-3 (Examples 1-3 and 6) and polyimide resin 4 (Example 4) containing polyimide resin (A2) were confirmed to have free radicals not observed before light irradiation, but only after light irradiation. In contrast, the resin material containing polyimide resin 5 (Example 5) containing polyimide resin (A3) was found to have a certain amount of free radical species observed before light irradiation.

[0136] Furthermore, analysis of the ESR spectrum revealed that the free radical species detected after light irradiation were inferred to be oxygen free radicals (CO2) based on their g-value, linewidth, and splitting pattern.

[0137] Furthermore, it was confirmed that resin materials containing polyimide resin (A) can be pelletized or molded to further improve the efficiency of free radical generation and the stability (half-life) of the generated free radicals (Example 1).

[0138] Furthermore, the results of spectral analysis of diffuse reflectance measurements after light irradiation of the molded body made of the resin material of Example 1 and the pellets made of the resin material of Example 6 confirmed the existence of a special absorption band in the long wavelength portion (716 nm) of the visible light region.

[0139] Based on the above, it is confirmed that the resin materials containing polyimide resin (A) (Examples 1-6) are semiconductor materials with high free radical generation efficiency and stable free radicals generated. [Industrial applicability]

[0140] According to the present invention, semiconductor resin materials with high free radical generation efficiency, stable free radicals, and excellent heat resistance and manufacturability, molded articles thereof, their uses, and flexible printing materials are provided.

Claims

1. Use of a semiconductor resin material for use in p-type semiconductors and n-type semiconductors, the semiconductor resin material comprising: a polyimide resin (A) comprising repeating units derived from an aromatic tetracarboxylic acid component and an aliphatic diamine component, the polyimide resin (A) comprising one or more selected from the group consisting of polyimide resin (A1), polyimide resin (A2) and polyimide resin (A3); the polyimide resin (A1) comprises repeating units represented by formula (1) and repeating units represented by formula (2), and the content ratio of the repeating unit of formula (1) to the total content of the repeating units of formula (1) and the repeating units of formula (2) is 20-70 mol%. R1 is a divalent aliphatic group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure, R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, and X1 and X2 are each independently a tetravalent aromatic group with 6 to 22 carbon atoms; the polyimide resin (A2) is composed of repeating units represented by the following formula (1); R1 is a divalent aliphatic group with 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure, and X1 is a tetravalent aromatic group with 6 to 22 carbon atoms; the polyimide resin (A3) is composed of repeating units represented by the following formula (2) and repeating units represented by the following formula (3); R2 is a divalent chain aliphatic group with 5 to 16 carbon atoms, R3 is a divalent group with 6 to 22 carbon atoms containing at least one aromatic ring, X2 is a tetravalent aromatic group with 6 to 22 carbon atoms, and X3 is a tetravalent group with 6 to 22 carbon atoms containing at least one aromatic ring.

2. The use of the semiconductor resin material as described in claim 1, which generates free radical species that can be observed using single-electron transfer.

3. The use of the semiconductor resin material as described in claim 2, wherein, This free radical species is generated by ultraviolet light irradiation and can be detected by electron spin resonance (ESR) measurement.

4. The use of the semiconductor resin material as described in claim 3, wherein, The half-life of the free radical species generated by ultraviolet light irradiation, as measured by ESR, is more than 1 second.

5. The use of the semiconductor resin material as described in claim 3 or 4, wherein, The free radical species generated by ultraviolet light irradiation is selected from one or more species in the group consisting of oxygen free radical species and nitrogen free radical species.

6. The use of the semiconductor resin material as described in any of claims 1 to 4, wherein, The glass transition temperature of the polyimide resin (A) is above 150°C.

7. The use of the semiconductor resin material as described in any of claims 1 to 4, wherein, The polyimide resin (A) is the polyimide resin (A1).

8. The use of the semiconductor resin material as described in any of claims 1 to 4, wherein, The semiconductor resin material further contains resin (B), which is selected from one or more of the group consisting of polyamine resin, polyamine-imide resin, epoxy resin, carbamate resin, urea resin, phenolic resin, cyanate resin, polythiophene resin, polyurethane resin, polyacetylene resin, poly(p-phenylenevinylene) resin, polyvinylcarbazole resin, polyether-imide resin, and polyimide resin other than the polyimide resin (A).