KR20240072502A - Multi-component polyimide composition having self-healing property by carbon chain control and film comprising the same - Google Patents

Abstract

In the present specification, a polyimide resin composition that exhibits excellent transparency and mechanical properties while enabling repeated self-restoration by combining multi-component polyimides and controlling the hydrocarbon length of the diamine-based compound, and a film containing the same are provided. The film according to the present disclosure exhibits self-healing properties that can self-heal damage such as cracks or shape deformation occurring at room temperature, and has repeatability, thereby extending the life of the film and making it reusable. The present disclosure can be used as an adhesive or coating agent for electrical and electronic materials, and can be usefully used as a cover window for surface protection of mobile devices or displays, for example.

Description

Multi-component polyimide composition having self-healing property by carbon chain control and film comprising the same}

This specification discloses a multi-component polyimide composition and a film containing the same.

Self-healing material refers to a material that can easily and quickly restore the damaged area using external energy such as heat, light, or electricity when its properties and lifespan are reduced due to physical damage. It is divided into an external method used and an internal method in which the polymer itself detects and heals the wound. The internal method is a method that detects and heals damage to the material itself. It has the advantage of enabling repeated healing through rapid interchange between molecules through reversible bonding within the polymer or entanglement and diffusion of polymer chains. there is. However, the use of previously reported self-healing materials is very limited due to the high temperature range in which self-healing is possible, and the recently reported materials that can be used at room temperature or 40-60°C exhibit mechanical properties similar to hydrogels or elastomers, narrowing the range of application. There is a limit to In order to lower the healing temperature, the glass transition temperature of the polymer, where the polymer chains begin to move, must be controlled. In order to lower the glass transition temperature, the polymer structure must be designed flexibly to increase the mobility of the polymer, resulting in low mechanical properties. There was a downside.

Polyimide is a representative engineering plastic material with excellent heat resistance, chemical resistance, and excellent mechanical and electrical properties. Polyimide began to be developed in the 1960s and is still used in various industrial fields such as aerospace, insulators, and electronic devices. Recently, highly transparent polyimide (Colorless polyimide, CPI) was developed as an alternative material for glass substrates (liquid crystals). It is becoming. However, with the recent emphasis on the portability and wearable characteristics of electronic devices, there is a demand for CPI-based display exterior materials that are highly transparent, bendable, and foldable. However, existing polyimide or highly transparent polyimide films suffer from deterioration of physical properties and physical properties due to repeated use and impact. There were functional limitations such as shortened lifespan.

Fully aromatic polyimide has a charge transfer complex (CTC) between the chains within the polyimide molecule resulting from the conjugated system of pi electrons located in the main chain, causing a change in the visible light range around 550 nm. It mainly absorbs light, giving it a dark brown color, and has a high glass transition temperature (above 200°C) by inducing the rigidity of the polymer chain. Because the strong rigidity of polyimide hinders the mobility of the polymer chain, in order to develop polyimide as a self-healing material, the mobility of the polyimide polymer chain must be increased to allow self-healing to proceed at low temperatures, while at the same time reducing the mechanical properties. It must be reduced.

In order to lower the glass transition temperature of polyimide, research results have been reported using branched aliphatic diamine monomers that induce steric hindrance to design a structure with a glass transition temperature close to room temperature. However, it has low mechanical properties like elastomers. There was a limit to . Accordingly, a semi-aromatic polyimide structure was proposed through a combination of an aliphatic diamine monomer containing a disulfuric acid bond and an ether functional group, but although it has high mechanical properties of over 60 MPa while lowering the glass transition temperature to below 100°C. These mechanical properties are lower than those of Kapton PI (fully aromatic structure polyimide), which is widely used commercially, and it still has the disadvantage of having a high healing temperature range.

Republic of Korea Patent Publication No. 10-2401307

In one aspect, the present disclosure seeks to provide a polyimide-based resin composition having self-restoring properties capable of controlling self-healing temperature and a film containing the same.

From one perspective, the present disclosure seeks to provide a polyimide-based resin composition having excellent transparency and mechanical properties, a film containing the same, and a method for manufacturing the same.

In order to achieve the above-described purpose, one implementation according to the present disclosure is,

Phthalic anhydride-based monomer containing a trifluoromethyl group;

Aromatic diamine-based monomer containing a disulfide bond; and

Aliphatic diamine-based monomers with a chain structure having 9 to 16 carbon atoms;

It is copolymerized including,

Containing hydrogen bonds and disulfide bonds in the main chain or side chains,

A polyimide resin composition is provided.

Another embodiment according to the present disclosure provides a polyimide film including the polyimide resin composition.

In another embodiment according to the present disclosure, a phthalic anhydride-based monomer containing a trifluoromethyl group, an aromatic diamine-based monomer containing a disulfide bond, and an aliphatic diamine-based monomer having a chain structure of 9 to 16 carbon atoms are added to an organic solvent, Preparing a polyamic acid solution by reacting under an inert atmosphere; and

Preparing a polyimide resin composition by imidizing the polyamic acid solution;

It provides a method for producing the polyimide resin composition comprising.

Another embodiment according to the present disclosure includes preparing the polyimide resin composition; and

Coating the prepared polyimide resin composition on a substrate;

It provides a method for manufacturing a polyimide film comprising.

An embodiment of the present disclosure provides a polyimide resin composition that includes a combination of multi-component polyimides, allows repeated self-restoration by controlling the hydrocarbon length of the diamine-based compound, and exhibits excellent transparency and mechanical properties, and a film containing the same. do. The film according to the present disclosure exhibits self-healing properties that can self-heal damage such as cracks or shape deformation occurring at room temperature, and has repeatability, so it has the technical advantage of extending the life of the film and enabling reuse. have One embodiment of the present disclosure can be used as an adhesive or coating agent for electrical and electronic materials, and can be usefully used as a cover window to protect the surface of a mobile device or display, for example.

Figure 1 shows an image taken with an optical microscope to show the degree of self-healing at the glass transition temperature (Tg) after scratching the film of Comparative Example 1.
Figure 2 shows an image taken with an optical microscope to show the degree of self-healing at the glass transition temperature (Tg) after scratching the film of Example 6.
Figure 3 shows an image taken with an optical microscope to show the degree of self-healing at the glass transition temperature (Tg) after scratching the film of Example 7.
Figure 4 shows an image taken with an optical microscope to show the degree of self-healing at the glass transition temperature (Tg) after scratching the film of Example 8.

Hereinafter, embodiments of the present disclosure will be described in more detail.

The embodiments of the present disclosure disclosed in the text are illustrative only for illustrative purposes, and the embodiments of the present disclosure may be implemented in various forms and should not be construed as limited to the embodiments described in the text. . The present disclosure can be subject to various changes and may take various forms. The embodiments are not intended to limit the present disclosure to a specific disclosed form, and all changes, equivalents, or substitutes included in the spirit and technical scope of the present disclosure are included. It should be understood as including.

Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof.

One embodiment of the present disclosure is a phthalic anhydride-based monomer containing a trifluoromethyl group; Aromatic diamine-based monomer containing a disulfide bond; and an aliphatic diamine-based monomer having a chain structure of 9 to 16 carbon atoms, and which contains a hydrogen bond and a disulfide bond in the main chain or side chain.

Conventional multi-component polyimide resin compositions secure transparency by including a high content of CF ₃ through 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), but do not contain trifluoromethyl group (-CF ₃ ). There was a disadvantage in that the main backbone became rigid due to the high repulsion between polymer chains. However, one embodiment of the present disclosure is a phthalic anhydride-based monomer containing a trifluoromethyl group; Aromatic diamine-based monomer containing a disulfide bond; and copolymerization with an aliphatic diamine-based monomer, and by controlling the chain length by controlling the carbon number of the aliphatic diamine-based monomer, the hydrocarbon chain spacing within the polymer and the fluidity inside/outside the chain are affected, resulting in self-recovery temperature and self-recovery rate; Tensile strength, etc. can be adjusted.

In this specification, the term 'self-healing' is used in the same sense as self-healing, and when the physical properties and lifespan of the material are reduced due to physical damage to the material, external energy such as heat, light, or electricity can be used to easily and quickly repair the damaged area. It refers to characteristics that can be restored. In the present disclosure, the self-restoration or self-healing includes both external methods using external substances and internal methods of detecting and healing damage by the polymer itself, and specifically, reversible bonding within the polymer or entanglement of polymer chains ( Entanglement may be due to rapid exchange bonding between molecules due to diffusion. Additionally, in one embodiment of the present disclosure, the self-restoration or self-healing may include repetitive restoration or healing.

Existing polyimide materials with self-restoring properties have a high glass transition temperature (Tg) of 200°C or higher, or when they have a low glass transition temperature, there is a problem that their mechanical properties are poor, making practical application difficult. However, an embodiment of the present disclosure This is a novel multi-component system that exhibits excellent self-restoration at a low glass transition temperature and has high mechanical properties by simultaneously improving the mechanical properties and flexibility of polymer materials in a trade-off relationship by adjusting the hydrocarbon chain length. A polyimide resin composition can be provided.

As an example, the phthalic anhydride-based monomer containing the trifluoromethyl group may be 4,4'-(Hexafluoroisopropylidene)diphthalic anhydride (6FDA). .

As an example, the aromatic diamine monomer is 4,4'-dithioaniline (4AD), 2,2'-dithioaniline, 2-hydroxyl disulfide, 3,3'-dithiodipropionic acid, 2,2' -(dithiodimethylene)difuran, 4-aminophenyl disulfide, 2,2'-diaminodiethyl disulfide dihydrochloride, and 3,3'-dihydroxydiphenyl disulfide. .

As an example, the aliphatic diamine-based monomer is 1,9-diaminononane, 1,10-diaminodecane, and 1,12-diaminododecane. It may be one or more selected from the group consisting of (1,12-diaminododecane) and 4,7,10-trioxa-1,13-tridecanediamine (TTDA). As an example, the aliphatic diamine-based monomer may further include an ether bond in the hydrocarbon chain.

As an example, the polyimide resin composition may be a compound represented by Formula 1 below. Specifically, the composition may have a polydispersity index (PDI) of 1.3 to 2.5 based on the repeating units below.

[Formula 1]

In the above formula, n may be any integer from 6 to 13, and m may be any integer from 1 to 100.

In view of providing self-restoration at low temperatures by having a low glass transition temperature along with high mechanical properties and transparency, the composition according to one embodiment includes the above-described composition for the phthalic anhydride-based monomer containing the trifluoromethyl group. The aliphatic diamine-based monomer and the aromatic diamine-based monomer may be copolymerized at a molar ratio of 10:5 to 15. Specifically, the molar ratio of the sum of the aliphatic diamine-based monomer and the aromatic diamine-based monomer to the phthalic anhydride-based monomer containing the trifluoromethyl group is 10: 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10. It may be 11 or more, 12 or more, 13 or more, or 14 or more, and may be 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, or 6 or less.

The composition according to one embodiment may be a copolymerization of an aromatic diamine-based monomer containing a disulfide bond and an aliphatic diamine-based monomer having a chain structure of 9 to 16 carbon atoms at a molar ratio of 1:2 to 8. Specifically, the molar ratio of the aliphatic diamine-based monomer to the aromatic diamine-based monomer may be 1: 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, or 7 or more, 8 or less, 7 or less, 6 or less, It may be 5 or less, 4 or less, or 3 or less. If it is outside the above range, the magnetic restoration property due to disulfide bond (S-S) may decrease or the glass transition temperature may increase due to an increase in the aromatic ring group.

As an example, the polyimide resin composition may have a weight average molecular weight of 5,000 to 70,000 g/mol and a polydispersity index (PDI) of 1.3 to 2.5. If the composition exceeds the weight average molecular weight and polydispersity index of the above-mentioned ranges, mechanical properties may be deteriorated or transparency and self-restoring properties may be deteriorated.

As an example, the present disclosure may provide a polyimide film containing the polyimide resin composition. At this time, the composition of the polyimide resin composition is as described above.

As an example, the film may further include a substrate onto which the polyimide resin composition is applied. Specifically, the substrate may include one or more of ceramics, polymers, and metals, but is not limited thereto. For example, the ceramic may include glass, silicon wafer, etc. The polymer may include polyimide-based, polyurethane-based, polyester-based, polystyrene-based, polyethylene-based, polyethylene terephthalate, etc. For example, the metal may include aluminum, iron, nickel, stainless steel, metal alloy, etc.

As an example, the thickness of the polyimide film is not limited, but may be, for example, 1 to 100 ㎛. Specifically, the thickness of the polyimide film is 1 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 60 μm or more, 70 μm or more, 80 μm or more, 90 μm or more, or 100 μm or more. It may be 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less, 30 μm or less, 20 μm or less, or 10 μm or less.

As an example, the polyimide film may have a light transmittance of 90% or more in a wavelength range of 450 to 800 nm based on a film thickness of 30 ㎛. Specifically, the light transmittance may be 91% or more, 92% or more, 93% or more, 94% or more, 95% or more, and 96% or more. Specifically, the light transmittance may be 90 to 95%.

The film according to an embodiment of the present disclosure includes the multi-component polyimide resin composition as described above, thereby exhibiting excellent mechanical strength while having flexibility that does not tear even during repeated bending, and at the same time, protecting against a separate external stimulus ( Not only is self-restoration possible through entanglement of polymer chains without using heat, light, etc., but the self-restoration temperature range can be lowered to about 100°C.

From the above perspective, the polyimide film according to one embodiment may exhibit a self-recovery rate of 90% or more for 20 minutes at a temperature of 100 to 165 ° C. Specifically, the self-recovery temperature is 100 ℃ or higher, 105 ℃ or higher, 110 ℃ or higher, 115 ℃ or higher, 120 ℃ or higher, 125 ℃ or higher, 130 ℃ or higher, 135 ℃ or higher, 140 ℃ or higher, 145 ℃ or higher, 150 ℃ or higher. It may be above 155℃ or above 160℃, below 165℃, below 160℃, below 155℃, below 150℃, below 145℃, below 140℃, below 135℃, below 130℃, below 125℃, below 120℃. Below, it may be 115°C or less, 110°C or less, or 105°C or less. Specifically, the self-recovery rate may be 90% or higher, 91% or higher, 92% or higher, 93% or higher, 94% or higher, 95% or higher, 96% or higher, 97% or higher, or 98% or higher.

As an example, the time required for self-restoration may be 10 to 60 minutes. Specifically, the time required for self-restoration may be 10 minutes or more, 15 minutes or more, 20 minutes or more, 25 minutes or more, 30 minutes or more, 35 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, or 55 minutes or more. and may be 60 minutes or less, 55 minutes or less, 50 minutes or less, 45 minutes or less, 40 minutes or less, 35 minutes or less, 30 minutes or less, 25 minutes or less, 20 minutes or less, or 15 minutes or less. More specifically, the self-recovery time may be 30 minutes or less.

As an example, the polyimide film may have a tensile strength of 60 MPa or more, 65 MPa or more, or 70 MPa or more. Specifically, the tensile strength of the polyimide film may be 60 to 75 MPa.

As an example, the film may exhibit antifouling and/or antibacterial properties.

As an example, the film may be a coating film or an adhesive film. As an example, the film may be a display surface protection film. Specifically, the film may be a film for a display cover window.

As an example, the present disclosure can provide an electronic device including the polyimide film. As an example, the electronic device may be any one selected from a display, a semiconductor, a transistor, a light emitting diode, and a laser device, but is not limited thereto.

Additionally, as an example, the present disclosure may provide a method for producing the polyimide resin composition as described above. Specifically, the method involves adding a phthalic anhydride monomer containing a trifluoromethyl group, an aromatic diamine monomer containing a disulfide bond, and an aliphatic diamine monomer having a chain structure of 9 to 16 carbon atoms into an organic solvent and reacting under an inert atmosphere. Preparing a polyamic acid solution; and preparing a polyimide resin composition by subjecting the polyamic acid solution to an imidization reaction.

According to one embodiment, the phthalic anhydride-based monomer containing a trifluoromethyl group, the aromatic diamine-based monomer containing a disulfide bond, and the aliphatic diamine-based monomer having a chain structure of 9 to 16 carbon atoms are added in a molar ratio range of the aromatic diamine-based monomer. For examples of specific types, the description of the polyimide resin composition described above applies equally.

As an example, the organic solvent is N,N-dimethylacetamide, N-methylpyrrolidone, N,N-dimethylformamide, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, Tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, meta-cresol, gamma-butyrolactone, ethylcellosolve, butylcellosolve, ethylcarbitol, butylcarbitol, ethylcarbitol acetate, butylcarbitol. It may be one or more selected from the group consisting of acetate, ethylene glycol, ethyl lactate, butyl lactate, cyclohexanone, and cyclopentanone, but is not limited thereto.

As an example, the inert atmosphere may be an atmosphere in which one or more inert gases selected from the group consisting of nitrogen, argon, hydrogen, helium, neon, xenon, and krypton are supplied, but is not limited thereto. Specifically, the inert gas may be nitrogen.

As an example, the step of preparing the polyamic acid solution includes reacting at -5 to 5°C for 30 minutes to 2 hours, and then stirring at 20 to 25°C for 10 to 14 hours to prepare the polyamic acid solution. can do.

As an example, the imidization reaction step may include adding an imidization catalyst and a dehydrating agent to the polyamic acid solution to perform an imidization reaction. Specifically, the imidization catalyst may be one or more of pyridine, isoquinoline, and beta-picoline. Specifically, the dehydrating agent may include acetic anhydride.

As an example, the imidization reaction may be performed at 40 to 60°C for 5 to 15 hours.

One embodiment of the present disclosure includes preparing a polyimide resin composition according to the method described above; and

Coating the prepared polyimide resin composition on a substrate;

A method for producing a polyimide film comprising a can be provided.

As an example, the coating step is not limited to the method as long as the composition of the present disclosure can be coated on a substrate, for example, bar coating, spin-coating, or dip coating. -Coating), drop-casting, gravure roll coating, or inkjet printing.

Hereinafter, the present disclosure will be described in more detail through examples. These examples are only for illustrating the present disclosure, and it will be apparent to those skilled in the art that the scope of the present disclosure should not be construed as limited by these examples.

[Preparation Example 1] Preparation of polyimide resin composition

A polyimide resin composition was synthesized through a two-step polymerization process using three different monomers as follows. Phthalic anhydride-based monomers containing a trifluoromethyl group include 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) (99%, Changzhou Sunlight Pharmaceutical Co., Ltd.), which contains a disulfide bond. 4,4'-dithioaniline (4AD) (98%, Tokyo Chemical Industry) was used as the aromatic diamine monomer. Examples of aliphatic diamine-based monomers with a chain structure of 9 to 16 carbon atoms include 1,9-diaminononane (Example 1) (95%, Sigma-Aldrich) and 1,10-diaminodecane (Example 2) (95). %, Sigma-Aldrich), 1,12-diaminododecane (Example 3) (95%, Sigma-Aldrich) or 4,7,10-trioxa-1,13-tridecanediamine (TTDA, Example 4) (97%, Sigma-Aldrich) was used, respectively.

At this time, the molar ratio between the sum of the phthalic anhydride-based monomer (6FDA) containing the trifluoromethyl group and the two types of diamine-based monomers was 1:1. Among these, the molar ratio of the aromatic diamine monomer containing a disulfide bond and the aliphatic diamine monomer having a chain structure of 9 to 16 carbon atoms was 1:4.

The synthesis was performed in N,N-dimethylacetamide (DMAc, Daejung Chemical) polar aprotic solvent with a total solids (monomer) content of 25 wt%. Two diamine-based monomers (4AD and TTDA) (20 mmol total) were added to each sample of DMAc. Phthalic anhydride-based monomer (6FDA) containing a trifluoromethyl group (total 20 mmol) was added to the solution. The added solution was stirred at 0°C for 1 hour and then stirred overnight at room temperature in a nitrogen atmosphere. The first reaction step was polyamic acid (PAA) reaction through ring dehydration, and the second reaction step was chemical imidization using pyridine and acetic anhydride. The final reacted solution was precipitated in a methanol/deionized water mixed solution and washed with ethanol. After the washing step, each polyimide resin composition prepared was dried at 70°C for 12 hours to remove residual solvent, and finally, a solid polyimide resin composition with a fibrous structure was obtained.

[Preparation Example 2] Preparation of polyimide film

As an example of the present disclosure, each of the solid polyimide resin compositions of Examples 1 to 4 prepared above was dissolved in DMAc solvent at a concentration of 25% by weight, and then bubbles were removed from the dissolved solution under vacuum at room temperature. . Each composition from which bubbles were sufficiently removed was spin-coated on a glass substrate to prepare a film. The spin coating was maintained for 10 seconds at a speed of 500 to 1000 rpm depending on the film thickness. Films (Examples 5 to 8) having a thickness ranging from 30 to 80 μm were obtained depending on the speed of the spin coater.

[Comparative Manufacturing Example 1]

The same as Preparation Examples 1 and 2 except that it was prepared using 1,6-diaminohexane (Comparative Example 1) or 1,8-diaminoctane (Comparative Example 2) having 6 carbon atoms as an aliphatic diamine monomer. A transparent polyimide film with a thickness of 30 ㎛ was prepared using this method.

[Test Example 1]

Before confirming the physical properties of the polyimide films of Examples 5 to 8 and Comparative Examples 1 and 2, the glass transition temperature (Tg) of each film was measured by thermogravimetric analysis (TGA, Q50, TA Instruments, USA). Analyzed by differential scanning calorimetry (DSC, Q20, TA Instruments, USA). Specifically, thermogravimetric analysis was performed by heating 10 mg of each of Examples 5 to 8 and Comparative Examples 1 and 2 from 35°C to 800°C at a rate of 10°C/min in a nitrogen atmosphere. DSC measurements were performed by (1) heating from 35°C to 300°C at a rate of 10°C/min; (2) cooling to 0°C; and (3) repeating steps (1) and (2). Tg was determined from the second heating cycle and the results are shown in Table 1 below.

Next, as shown in FIGS. 1 to 4, a force of 1N was applied to each of the films through a scratch tester (Zest Co. Ltd. South Korea) using a cross-sectional view (DN-52, DORCO), and then 1N/min. A scratch with a width of 30㎛ was created at a speed of . After placing each scratched film on a glass substrate, the temperature of the hot plate (IKA, C-MAG HP 7) was adjusted based on the respective glass transition temperature, heat treated for 20 minutes, and the degree of healing was measured using an optical microscope (Olympus). , SZX16 optical microscope) was photographed and confirmed, and the self-restoration rate was measured.

The mechanical properties of the films of Examples 5 to 8 and Comparative Examples 1 and 2 were measured using a universal tensile machine (UTM, Instron model 5567A) according to the ASTM D638 test method at a load cell of 100N, gauge length of 10mm, and crosshead speed of 5mm/min. and analyzed. A dogbone dumbbell specimen was used, and the dimensions of the specimen were 30 (length) Х5 (width) Х10 (length of narrow part) Х1.5 (width of narrow part) Х0.03 (thickness) mm. A minimum of 10 samples of each film were tested and the average of each set of measurements was used.

Self-recovery temperature (℃) Self-recovery rate (%) Self-recovery time (min) Tensile strength (MPa) Comparative Example 1 175±5 90±3 20 - Comparative Example 2 165±5 - Example 5 160±5 70±1.5 Example 6 155±5 67±2.2 Example 7 145±5 65±2.5 Example 8 110±5 ≥95±4 65±3.0

As a result, the self-recovery temperature, self-recovery rate, and tensile strength were different depending on the hydrocarbon chain length of the aliphatic diamine monomer. Comparative Examples 1 and 2, which contain an aliphatic diamine-based monomer with a chain structure of 6 or 8 carbon atoms, were unable to measure tensile strength because the film itself was not formed, and showed a higher self-restoration temperature than Examples 5 to 8. On the other hand, it was confirmed that Examples 5 to 8 according to one embodiment of the present disclosure showed a relatively low self-recovery temperature and excellent mechanical properties by including an aliphatic diamine-based monomer with a chain structure of 9 or more carbon atoms.

The embodiments of the present disclosure described above should not be construed as limiting the technical idea of the present disclosure. The scope of protection of this disclosure is limited only by the matters stated in the claims, and those skilled in the art can improve and change the technical idea of this disclosure into various forms. Accordingly, such improvements and changes will fall within the scope of protection of the present disclosure as long as they are obvious to those skilled in the art.

Claims (17)

Phthalic anhydride-based monomer containing a trifluoromethyl group;
Aromatic diamine-based monomer containing a disulfide bond; and
Aliphatic diamine-based monomers with a chain structure having 9 to 16 carbon atoms;
It is copolymerized including,
Containing hydrogen bonds and disulfide bonds in the main chain or side chains,
Polyimide resin composition. The polyimide resin composition according to claim 1, wherein the phthalic anhydride-based monomer containing a trifluoromethyl group is 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). The method of claim 1, wherein the aromatic diamine-based monomer is 4,4'-dithioaniline (4AD), 2,2'-dithioaniline, 2-hydroxyl disulfide, 3,3'-dithiodipropionic acid, 2, At least one selected from the group consisting of 2'-(dithiodimethylene)difuran, 4-aminophenyl disulfide, 2,2'-diaminodiethyl disulfide dihydrochloride, and 3,3'-dihydroxydiphenyl disulfide. , polyimide resin composition. The method of claim 1, wherein the aliphatic diamine monomer is 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminode. A polyimide resin composition, which is at least one selected from the group consisting of decane (1,12-diaminododecane) and 4,7,10-trioxa-1,13-tridecanediamine (TTDA). The polyimide resin composition according to claim 1, wherein the polyimide resin composition is a compound represented by the following formula (1):
[Formula 1]

In the above formula, n is any integer from 6 to 13, and m is any integer from 1 to 100. The polyimide resin of claim 1, wherein the composition is a copolymerization of an aromatic diamine-based monomer containing a disulfide bond and an aliphatic diamine-based monomer having a chain structure of 9 to 16 carbon atoms at a molar ratio of 1:2 to 8. Composition. The method of claim 1, wherein the composition is copolymerized in a molar ratio of 10:5 to 15, wherein the sum of the aliphatic diamine monomer and the aromatic diamine monomer relative to the phthalic anhydride monomer containing the trifluoromethyl group is 10:5 to 15. Polyimide resin composition. The polyimide resin composition of claim 1, wherein the polyimide resin composition has a weight average molecular weight of 5,000 to 70,000 g/mol and a polydispersity index (PDI) of 1.3 to 2.5. A polyimide film comprising the polyimide resin composition according to any one of claims 1 to 8. According to clause 9, A polyimide film further comprising a substrate onto which the polyimide resin composition is applied. According to clause 9,
The polyimide film has a thickness of 1 to 100 ㎛. The polyimide film according to claim 9, wherein the polyimide film has a light transmittance of 90% or more in a wavelength range of 450 to 800 nm. The polyimide film of claim 9, wherein the polyimide film exhibits a self-recovery rate of 85% or more for 20 minutes at a temperature of 100 to 165°C. The polyimide film according to claim 9, wherein the polyimide film has a tensile strength of 60 to 75 MPa. The polyimide film of claim 9, wherein the film is a coating film or an adhesive film. An electronic device comprising the polyimide film of claim 9. The electronic device according to claim 16, wherein the electronic device is any one selected from a display, a semiconductor, a transistor, a light emitting diode, and a laser device.