TWI710551B - Diamine compound, and polyimide precursor, polyimide film and flexible device prepared by using the same - Google Patents

Abstract

The present invention provides a novel diamine compound comprising a structure that an imide ring is directly bonded to a (hetero)aryl ring in the molecule thereof, and the diamine compound is used to prepare a polyimide film having improved thermal properties and storage stability. The present invention also provides a polyimide precursor and a flexible device prepared by the diamine compound.

Description

Diamine compound and polyimide precursor prepared by using it Materials, polyimide film and flexible equipment

The present invention relates to a new type of diamine compound and a polyimide precursor, polyimide film and flexible equipment prepared by using the diamine compound.

This application claims the benefit of priority based on the Korean patent application 10-2019-0009547 filed on January 25, 2019 and the Korean patent application 10-2020-0005487 filed on January 15, 2020, and All the contents disclosed in the patent documents are included as part of this specification.

Recently, in the display field, the weight and miniaturization of products are emphasized. Since the glass substrates currently in use are heavy, easy to break, and difficult to carry out continuous processing restrictions, they replace the glass substrates to have lightness, flexibility, and flexibility. Research on the application of plastic substrates with the advantages of continuous manufacturing processes to mobile phones, notebook computers, personal digital assistants (PDAs), etc. is actively being carried out.

In particular, polyimide is easy to synthesize and can be made into thin-film membranes, and It does not require a cross-linking agent for curing, so recently, due to the light weight and precision of electronic products, it has been widely used as an integrated material for liquid crystal display (LCD) and plasma display panels. , PDP) and other semiconductor materials, and a large number of researches on using polyimide for flexible display substrates (flexible plastic display boards) with light and soft properties are underway.

The polyimide film is prepared by filming the polyimide film. Generally, the polyimide film is prepared by the following method: an aromatic dianhydride (dianhydride) is combined with an aromatic diamine or an aromatic diisocyanate. Solution polymerization, after preparing the polyamic acid derivative solution, coating it on silicon wafer or glass, etc., and curing it by heat treatment.

Flexible devices accompanied by high-temperature processes require heat resistance at high temperatures, especially in the case of organic light emitting diode (OLED) devices using low temperature polysilicon (LTPS) processes. The process temperature Sometimes close to 500°C. However, at such a temperature, even polyimide having excellent heat resistance is prone to thermal decomposition due to hydrolysis. Therefore, in order to prepare a flexible device, it is necessary to develop a polyimide film that can exhibit excellent thermal characteristics and storage stability without thermal decomposition caused by hydrolysis even under a high-temperature process.

The problem to be solved by the present invention is to provide a novel diamine compound for preparing polyimide exhibiting improved heat resistance, storage stability, and the like.

Another problem to be solved by the present invention is to provide a polyimide precursor prepared by using the novel diamine compound.

Another problem to be solved by the present invention is to provide a polyimide film prepared by using the polyimide precursor and a flexible device containing the polyimide film.

In order to solve the problem of the present invention, the present invention provides a diamine compound of the following chemical formula 1:

,

,

及

的連結基，Ar₁及Ar₂分別獨立地為選自

,

,

,

,

及

的二價有機基，R₁至R₁₁分別獨立地為氘、鹵素原子、氰基、羥基、經取代或未經取代的碳數為1至30的烷基、經取代或未經取代的碳數為1至30的鹵烷基、經取代或未經取代的碳數為1至30的烷基矽基、經取代或未經取代的碳數為6至30的芳基矽基、經取代或未經取代的碳數為1至30的烷基胺基、經取代或未經取代的碳數為6至30的芳基胺基、經取代或未經取代的碳數為1至30的烷氧基、經取代或未經取代的碳數為1至30的烷硫基、經取代或未經取代的碳數為6至30的芳硫基、經取代或未經取代的碳數為6至30的芳基、經取代或未經取代的碳數為6至30的芳烷基、經取代或未經取代的碳數為6至30的芳氧基、羧基(-COOH)基、經取代或未經取代的碳數為3至30的環烷基、醯胺基、經取代或未經取代的碳數為3至30的環烷基氧基、經取代或未經取代的碳數為1至30的環烷硫基、酯基、-CD₃、疊氮基、硝基、或包含選自B、N、O、S、P(=O)、Si及P的一種以上的雜原子的經取代或未經取代的(3至30元)雜芳基，Y選自

,

,

,

,

,

及

l、m、n、o、p、q、r、s、t、u及v分別為0至4的整數，在l、m、n、o、p、q、r、s、t、u及v為2至4的整數的情況， 各個R₁至R₁₁可相同或不同。 In the chemical formula 1, L is selected from

,

,

and

, Ar ₁ and Ar ₂ are each independently selected from

,

,

,

,

and

The divalent organic group, R ₁ to R ₁₁ are each independently deuterium, halogen atom, cyano group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbons, substituted or unsubstituted carbon Haloalkyl having 1 to 30, substituted or unsubstituted alkylsilyl having 1 to 30 carbons, substituted or unsubstituted arylsilyl having 6 to 30 carbons, substituted Or unsubstituted alkylamino groups with 1 to 30 carbons, substituted or unsubstituted arylamino groups with 6 to 30 carbons, substituted or unsubstituted carbons with 1 to 30 carbons Alkoxy group, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 aryl groups, substituted or unsubstituted aralkyl groups with 6 to 30 carbons, substituted or unsubstituted aryloxy groups with 6 to 30 carbons, carboxy (-COOH) groups, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbons, an amido group, a substituted or unsubstituted cycloalkyloxy group having 3 to 30 carbons, a substituted or unsubstituted carbon Cycloalkylthio group, ester group, -CD ₃ , azide group, nitro group with a number of 1 to 30, or one or more selected from B, N, O, S, P(=O), Si and P Heteroatom substituted or unsubstituted (3- to 30-membered) heteroaryl group, Y is selected from

,

,

,

,

,

and

l, m, n, o, p, q, r, s, t, u, and v are integers from 0 to 4, respectively, where l, m, n, o, p, q, r, s, t, u and When v is an integer of 2 to 4, each of R ₁ to R ₁₁ may be the same or different.

The present invention provides a polyimide precursor, which is prepared by polymerizing a polymerization component containing the diamine compound of the above chemical formula 1 and one or more acid dianhydrides.

The present invention provides a polyimide film, which is prepared from the above-mentioned polyimide precursor.

The present invention provides a flexible device comprising the above-mentioned polyimide film as a substrate.

The diamine compound of the present invention is a novel compound containing a partial structure that directly bonds the imine ring to the (hetero) aromatic ring in the molecule, and the polyimide precursor containing it as a polymerization component can provide a kind of Polyimide film with improved thermal and mechanical properties.

The present invention can be subjected to various changes and can have various embodiments, which will be described in the following detailed description of specific embodiments of the present invention. However, it should be understood that it is not intended to limit the scope of the present invention to specific embodiments, including All changes, equivalents and substitutes of the ideas and technical scope of the invention. In the process of describing the present invention, when it is judged that the specific description of the related conventional technology will make the gist of the present invention ambiguous, the detailed description of the related conventional technology is omitted.

Aromatic polyimine is widely used in cutting-edge industries such as microelectronics, aerospace, insulating materials, and chemical resistant materials due to its excellent comprehensive properties such as thermal oxidation stability and high mechanical strength. However, aromatic polyimides with strong absorbance in the ultraviolet to visible light range are colored from light yellow to dark brown, which limits their wide use in the optoelectronics area where transparency and colorless properties are basic requirements. application. The reason for the coloration in aromatic polyimine is due to the formation of alternating electron donor (dianhydride) and electron acceptor (diamine) in the main chain of the polymer. Intermolecular charge transfer complexes (CT-complexes).

In order to solve this problem, try to introduce specific functional groups, bulky side groups, fluorinated functional groups, etc. into the polymer backbone or introduce -S-, -O-, -CH ₂ -and other methods to develop High glass transition temperature (Tg) and optically transparent polyimide film.

Based on the prior art, the inventor of the present invention has conducted in-depth research in order to solve the problems of the prior art, and found that a new diamine compound with a specific structure provides excellent thermal and mechanical properties, thus completing the present invention.

Thus, the present invention provides a diamine compound of the following chemical formula 1: [Chemical formula 1]

,

,

及

的連結基，Ar₁及Ar₂分別獨立地為選自

,

,

,

,

及

的二價有機基，R₁至R₁₁分別獨立地為氘、鹵素原子、氰基、羥基、經取代或未經取代的碳數為1至30的烷基、經取代或未經取代的碳數為1至30的鹵烷基、經取代或未經取代的碳數為1至30的烷基矽基、經取代或未經取代的碳數為6至30的芳基矽基、經取代或未經取代的碳數為1至30的烷基胺基、經取代或未經取代的碳數為6至30的芳基胺基、經取代或未經取代的碳數為1至30的烷氧基、經取代或未經取代的碳數為1至30的烷硫基、經取代或未經取代的碳數為6至30的芳硫基、經取代或未經取代的碳數為6至30的芳基、經取代或未經取代的碳數為6至30的芳烷基、經取代 或未經取代的碳數為6至30的芳氧基、-COOH基、經取代或未經取代的碳數為3至30的環烷基、醯胺基、經取代或未經取代的碳數為3至30的環烷基氧基、經取代或未經取代的碳數為1至30的環烷硫基、酯基、-CD₃、疊氮基、硝基、或包含選自B、N、O、S、P(=O)、Si及P的一種以上的雜原子的經取代或未經取代的(3至30元)雜芳基，Y選自

,

,

,

,

,

及

l、m、n、o、p、q、r、s、t、u及v分別為0至4的整數，在l、m、n、o、p、q、r、s、t、u及v為2至4的整數的情況，各個R₁至R₁₁可相同或不同。 In the chemical formula 1, L is selected from

,

,

and

, Ar ₁ and Ar ₂ are each independently selected from

,

,

,

,

and

The divalent organic group, R ₁ to R ₁₁ are each independently deuterium, halogen atom, cyano group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbons, substituted or unsubstituted carbon Haloalkyl having 1 to 30, substituted or unsubstituted alkylsilyl having 1 to 30 carbons, substituted or unsubstituted arylsilyl having 6 to 30 carbons, substituted Or unsubstituted alkylamino groups with 1 to 30 carbons, substituted or unsubstituted arylamino groups with 6 to 30 carbons, substituted or unsubstituted carbons with 1 to 30 carbons Alkoxy group, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 aryl groups, substituted or unsubstituted aralkyl groups having 6 to 30 carbons, substituted or unsubstituted aryloxy groups having 6 to 30 carbons, -COOH groups, substituted or Unsubstituted cycloalkyl with 3 to 30 carbons, amide group, substituted or unsubstituted cycloalkyloxy with 3 to 30 carbons, substituted or unsubstituted carbon number of 1 Cycloalkylthio group, ester group, -CD ₃ , azido group, nitro group to 30, or containing one or more heteroatoms selected from B, N, O, S, P (=O), Si and P A substituted or unsubstituted (3 to 30 membered) heteroaryl group, Y is selected from

,

,

,

,

,

and

l, m, n, o, p, q, r, s, t, u, and v are integers from 0 to 4, respectively, where l, m, n, o, p, q, r, s, t, u and When v is an integer of 2 to 4, each of R ₁ to R ₁₁ may be the same or different.

In the description of "substituted or unsubstituted" described in this application, "substituted" means that in some functional groups, hydrogen atoms are replaced by other atoms or other functional groups, that is, other substituents.

In the chemical formula 1, a substituted alkyl group, a substituted haloalkyl group, a substituted alkylsilyl group, a substituted arylsilyl group, a substituted alkylamino group, and a substituted arylamino group , Substituted alkoxy, substituted alkylthio, substituted arylthio, substituted aryl, substituted aralkyl, substituted aryloxy, substituted cycloalkyl, substituted The substituents of the substituted cycloalkyloxy group, the substituted cycloalkylthio group, and the substituted heteroaryl group may each independently be one or more selected from the group consisting of deuterium, halogen atom, Cyano, amine, carboxy, nitro, hydroxyl, alkyl with 1 to 30 carbons, alkenyl with 2 to 30 carbons, alkynyl with 2 to 30 carbons, and 1 to 30 carbons Alkoxy groups, alkylthio groups having 1 to 30 carbons, arylthio groups having 6 to 30 carbons, aryl groups having 6 to 30 carbons, cycloalkyl groups having 3 to 30 carbons, carbon numbers being 3 to 30 cycloalkenyl, carbon 6 to 30 aryloxy, carbon 1 to 30 alkylsilyl, carbon 6 to 30 arylsilyl, carbon 1 to 30 Alkylamino, arylamino having 6 to 30 carbons, alkylcarbonyl having 1 to 30 carbons, alkoxycarbonyl having 1 to 30 carbons, arylcarbonyl having 6 to 30 carbons , Alkyl boronyl with 1 to 30 carbons (boronyl), aryl boronyl with 6 to 30 carbons.

In the present application, "alkyl with 1 to 30 carbons" refers to a straight or branched chain alkyl with 1 to 30 carbons, preferably 1 to 20 carbons, more preferably 1 to 10. As specific examples of the alkyl group, there are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and the like.

In the present application, "alkenyl having 2 to 30 carbons" refers to straight or branched alkenyl having 2 to 30 carbons, preferably 2 to 20 carbons, more preferably 2 to 10. As specific examples of the alkenyl group, there are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-ene Base etc.

In this application, "alkynyl having 2 to 30 carbons" refers to straight or branched alkynyl having 2 to 30 carbons, preferably 2 to 20 carbons, more preferably 2 to 10. As examples of the alkynyl group, there are ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2- Alkynyl etc.

In this application, "an alkoxy group with 1 to 30 carbons" refers to 1 Up to 30 linear or branched alkoxy groups preferably have 1 to 20 carbon atoms, more preferably 1 to 10. As examples of the alkoxy group, there are methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy and the like.

In this application, "cycloalkyl with 3 to 30 carbons" refers to monocycle or polycycle hydrocarbons with 3 to 30 carbons, preferably 3 to 20 carbons , More preferably 3 to 7. As examples of the cycloalkyl group, there are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

基、稠四苯基(naphthacenyl)、熒蒽基(fluoranthenyl)等。 In this application, "(extended) aryl group with 6 to 30 carbons" refers to a monocyclic or bonded cyclic radical derived from an aromatic hydrocarbon with 6 to 30 carbons, preferably a ring skeleton The carbon number is 6 to 20, more preferably 6 to 15. As examples of the aryl group, there are phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracenyl, indenyl, trimenyl, acesulfame, and tetracenyl. , Perylene,

Group, naphthacenyl, fluoranthenyl, etc.

In this application, "(3 to 30 membered) hetero (extended) aryl group" means that the number of ring skeleton atoms is 3 to 30 and includes selected from B, N, O, S, P(=O), Si and P One or more heteroatom aryl groups in the group. Here, the number of ring skeleton atoms is preferably 3 to 20, more preferably 3 to 15. The number of heteroatoms is preferably 1 to 4, and may be a monocyclic type or a junction ring type condensed with one or more benzene rings, and may also be partially saturated. In addition, the heteroaryl group in the present application also includes more than one heteroaryl group or a form in which the aryl group is connected to the heteroaryl group through a single bond. As examples of the heteroaryl group, there are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazole Group, triazinyl, tetrazinyl, triazolyl, Tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and other monocyclic heteroaryl groups, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl , Dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzene Conjugation of thiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodiaxazolyl, etc. Cyclic heteroaryl.

In this application, "halogen" includes F, Cl, Br and I atoms.

,

,

及

的連結基，Ar₁及Ar₂分別獨立地為

，R₁至R₈分別獨立地為鹵素原子、未經取代或經鹵素原子取代的碳數為1至6的烷基、或者碳數為1至6的烷氧基，R₉為鹵素原子、或者未經取代或經鹵素原子取代的(C1-C6)烷基，Y選自

,

及

，l、m、n、o、p、q、r、s及t分別可為0至2的整數。 According to an embodiment, in the compound of formula 1, L is selected from

,

,

and

, Ar ₁ and Ar ₂ are independently

, R ₁ to R ₈ are each independently a halogen atom, an unsubstituted or substituted halogen atom-substituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R ₉ is a halogen atom, Or unsubstituted or substituted by halogen atoms (C1-C6) alkyl, Y is selected from

,

and

, L, m, n, o, p, q, r, s, and t may be integers from 0 to 2 respectively.

According to one embodiment, in the compound of Chemical Formula 1, L is: substituted with one or more substituents selected from the group consisting of trifluoromethyl, methyl, chlorine (Cl) and methoxy; Unsubstituted phenyl; biphenyl substituted or unsubstituted with one or more substituents selected from the group consisting of methyl, trifluoromethyl and chlorine; substituted with trifluoromethyl Or unsubstituted terphenyl; bis(trifluoromethylphenyl)sulfonate, bis(methylphenyl)sulfonate, {(trifluoromethylphenyl)sulfonyl}phenyl, diphenyl Sulfide, bis(methylphenyl) sulfide, bis(trifluoromethylphenyl) sulfide or diphenyl ether, Ar ₁ and Ar ₂ are independently selected from methyl, trifluoromethyl and chlorine A substituted or unsubstituted phenyl group consisting of one or more substituents, l is an integer from 0 to 2, and m, n, o, p, q, r, s, and t can be 0 or 1 respectively The integer.

According to an embodiment, the diamine compound of Chemical Formula 1 may be selected from compounds of the following structural formulas, but is not limited thereto:

According to an embodiment, the diamine compound of Chemical Formula 1 can be selected from the following compounds of Structural Formula 1 to Structural Formula 21, but is not limited thereto:

As described above, the diamine compound of the present invention has a phenylene linking group (L) that connects the amide ring in the molecule, and the amide ring is directly bonded to the aromatic ring (Ar ₁ and Ar ₂ ). The structure can provide improved thermal and mechanical properties after curing when used as a polymerization component of a polyimide precursor.

The preparation method of the diamine compound of Chemical Formula 1 according to the present invention is not particularly limited, and can be prepared by a synthetic method known in the art, for example, according to the following reaction formula 1.

In the reaction formula 1, Ar ₁ , Ar ₂ and L are the same as defined in the chemical formula 1.

The step (1) of the reaction formula 1 can be performed by reacting the reaction compound in a solvent such as acetic acid, propionic acid, etc. under reflux for 10 hours to 14 hours, for example, 12 hours.

In step (2) of the reaction formula 1, hydrogen can be injected in the presence of a palladium/carbon (Pd/C) catalyst to perform the reduction reaction. At this time, tetrahydrofuran (THF) and N-methylpyrrole can be used. As a solvent, pyridone and the like.

After the step (2), recrystallization can be performed by adding alcohols such as ethanol and isopropanol to obtain solid substances.

In addition, the present invention is a polyimide precursor (polyamide acid) prepared by polymerizing polymerization components containing more than one diamine compound and more than one acid dianhydride, and provides a The diamine compound includes a polyimide precursor of the diamine compound of Chemical Formula 1. The imidization reaction of the polyimide precursor can be performed to obtain the desired polyimide.

As the acid anhydride used in the polymerization reaction, for example, tetracarboxylic dianhydride can be used. The tetracarboxylic dianhydride may, for example, contain an aromatic, alicyclic, or aliphatic tetravalent organic group in the molecule, or as a combination group thereof to make an aliphatic, alicyclic or aromatic tetravalent organic group The tetravalent organic groups are connected to each other by a cross-linked structure. The tetracarboxylic dianhydride may preferably have a monocyclic or polycyclic aromatic, monocyclic or polycyclic alicyclic, or a structure in which two or more of them are connected by a single bond or a functional group, Or include a rigid structure as follows: the rigid structure is a ring structure such as aromatic and alicyclic A single ring structure, or a ring structure of a plurality of fused rings, or a structure in which two or more of them are connected by a single bond.

For example, tetracarboxylic dianhydride may include a tetravalent organic group selected from the following chemical formulas 2a to 2e:

[Chemical formula 2e]

In the chemical formulas 2a to 2e, R ₁₁ to R ₁₇ may be independently selected from the following: halogen atoms selected from F, Cl, Br, and I, hydroxyl, thiol (-SH), nitro, Cyano groups, alkyl groups having 1 to 10 carbons, haloalkoxy groups having 1 to 10 carbons, haloalkyl groups having 1 to 10 carbons, and aryl groups having 6 to 20 carbons, with a1 being 0 to 2 Integer, a2 is an integer from 0 to 4, a3 is an integer from 0 to 8, a4, a5, a6, a7, a8 and a9 can each independently be an integer from 0 to 3, and Ar ₁₁ and Ar ₁₂ are each independently ground Selected from a single bond, -O-, -CR'R"- (in this case, R'and R" are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, Propyl, isopropyl, n-butyl, tertiary butyl, pentyl, etc.) and the group consisting of haloalkyl groups having 1 to 10 carbons (for example, trifluoromethyl, etc.)), -C( =O)-, -C(=O)O-, -C(=O)NH-, -S-, -SO-, -SO ₂ -, -O[CH ₂ CH ₂ O] _y -(y is An integer from 1 to 44), -NH(C=O)NH-, -NH(C=O)O-, a monocyclic or polycyclic cyclic alkylene group having a carbon number of 6 to 18 (for example, a Cyclohexylene, etc.), monocyclic or polycyclic arylene groups with carbon numbers of 6 to 18 (for example, phenylene, naphthalene, fluorenene, etc.) and combinations thereof Group.

The tetracarboxylic dianhydride may also include a tetravalent organic group selected from the following chemical formulas 3a to 3n:

In the tetravalent organic groups of the chemical formulas 3a to 3n, more than one hydrogen atom may be substituted by a substituent selected from the group consisting of halogen atoms selected from F, Cl, Br and I, hydroxyl groups, thiol groups, nitro groups Group, cyano group, alkyl group having 1 to 10 carbons, haloalkoxy group having 1 to 10 carbons, haloalkyl group having 1 to 10 carbons, and aryl group having 6 to 20 carbons. For example, the halogen atom may be fluorine, and the halogenated alkyl group is a fluoroalkyl group having a carbon number of 1 to 10 containing a fluorine atom, which may be selected from fluoromethyl, perfluoroethyl, trifluoromethyl, and the like. It can be selected from methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, and the aryl group can be selected from phenyl and naphthyl, more preferably fluorine atom and fluoroalkyl group, etc. Substituents containing fluorine atoms.

According to an embodiment, when the polyimide precursor is polymerized, in addition to the diamine compound of the chemical formula 1, more than one additional diamine compound can also be used, For example, a diamine compound containing the following structure can be used: a monocyclic or polycyclic aromatic divalent organic group with a carbon number of 6 to 24, and a monocyclic or polycyclic alicyclic group with a carbon number of 6 to 18 A divalent organic group or a structure in which two or more of them are connected by a single bond or a functional group. Alternatively, it is possible to use a ring structure including a single ring structure such as aromatic, alicyclic, or the like, or a ring structure of multiple fused rings, or a structure in which two or more of them are connected by a single bond. rigid) structure of diamine compound.

For example, the additional diamine compound may include a divalent organic group selected from the following chemical formula 4a to chemical formula 4e:

[Chemical formula 4d]

In the chemical formulas 4a to 4e, R ₂₁ to R ₂₇ can be independently selected from the group consisting of halogen atoms selected from F, Cl, Br and I, hydroxyl groups, thiol groups, nitro groups, Cyano groups, alkyl groups having 1 to 10 carbons, haloalkoxy groups having 1 to 10 carbons, haloalkyl groups having 1 to 10 carbons, aryl groups having 6 to 20 carbons, A ₂₁ and A ₂₂ can be They are independently selected from the group consisting of: single bond, -O-, -CR'R"- (In this case, R'and R" are independently selected from hydrogen atoms, and alkane having 1 to 10 carbon atoms. Group (for example, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, etc.) and haloalkyl groups having 1 to 10 carbons (for example, trifluoromethyl, etc.) Group), -C(=O)-, -C(=O)O-, -C(=O)NH-, -S-, -SO-, -SO ₂ -, -O[CH ₂ CH ₂ O] _y -(y is an integer from 1 to 44), -NH(C=O)NH-, -NH(C=O)O-, monocyclic or polycyclic carbon number 6 to 18 Cycloalkylene groups of the formula (for example, cyclohexylene, etc.), monocyclic or polycyclic arylene groups having 6 to 18 carbon atoms (for example, phenylene, naphthyl, fluorenylene, etc.) and Combinations, b1 is an integer from 0 to 4, b2 is an integer from 0 to 6, b3 is an integer from 0 to 3, b4 and b5 are each independently an integer from 0 to 4, b7 and b8 are each independently from 0 to 4 An integer, and b6 and b9 are each independently an integer from 0 to 3.

For example, the additional diamine compound may include a divalent organic group selected from the following chemical formulas 5a to 5p:

Alternatively, the additional diamine compound may include a divalent organic group having an aromatic ring or an aliphatic structure to form a rigid chain structure, for example, may include a structure in which each ring is bonded with a single bond. Or a divalent organic group structure of a ring structure of a plurality of rings in which respective rings are directly fused.

According to an embodiment of the present invention, the total content of the tetracarboxylic dianhydride and the content of the diamine compound can be reacted at a molar ratio of 1:1.1 to 1.1:1. Preferably, in order to improve reactivity and processability, four It is preferable that the total content of the carboxylic dianhydride reacts in excess of the diamine compound or the content of the diamine compound reacts in excess of the total content of tetracarboxylic dianhydride.

According to an embodiment of the present invention, the tetracarboxylic dianhydride and the diamine compound may preferably be reacted at a molar ratio of 1:0.98 to 0.98:1, preferably 1:0.99 to 0.99:1.

The polymerization reaction can be carried out according to a general polymerization method of polyimide or its precursor, such as solution polymerization.

As the organic solvent used in the polymerization reaction, there are the following: γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4 -Hydroxy-4-methyl-2-pentanone and other ketones; toluene, xylene, tetramethylbenzene and other aromatic hydrocarbons; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether and other glycol ethers ( Cellosolve); ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate , Ethanol, propanol, ethylene glycol, propylene glycol, dimethylpropionamide (DMPA), diethylpropionamide (diethylpropionamide, DEPA), dimethyl acetamide (DMAc), N,N- Diethyl acetamide, dimethylformamide (dimethylformamide, DMF), diethylformamide (diethylformamide, DEF), N-methyl pyrrolidone (N-methyl pyrrolidone, NMP), N-ethyl N-ethyl pyrrolidone (N-ethyl pyrrolidone, NEP), N,N-dimethyl methoxy acetamide, dimethyl sulfide, pyridine, dimethyl sulfide, hexamethyl phosphamide, tetramethyl Urea, N-methylcaprolactam, tetrahydrofuran, m-dioxane, p-dioxane, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2- Bis(2-methoxyethoxy)ethane, bis[2-(2-methoxyethoxy)]ether, Equamide M100 (3-Methoxy-N,N-dimethylpropanamide, Idemitsu Kosan Co., Ltd.), Equamide B100 (3-butoxy -N,N-Dimethylpropanamide, Idemitsu Kosan Co., Ltd.), and one of these can be used alone or a mixture of two or more can be used.

According to an embodiment, the distribution coefficient Log P of the organic solvent at 25° C. is positive and the boiling point is below 300° C., more specifically, the distribution coefficient Log P may be 0.01 to 3, or 0.01 to 2, or 0.01 to 1. The distribution coefficient can be calculated using, for example, the ACD/LogP module of the ACD/Percepta platform of Advanced Chemical Development Co., Ltd. (ACD/Labs), and the ACD/LogP module uses the two-dimensional (2 dimensional, 2D) structure and use an algorithm based on the Quantitative Structure-Property Relationship (QSPR) methodology.

The solvent with a positive partition coefficient Log P refers to a hydrophobic solvent. According to the research of the inventors, it can be known that if a specific solvent with a positive partition coefficient Log P is used to prepare the polyimide precursor composition, it can improve Curling (edge back) phenomenon. In addition, the present invention uses a solvent with a positive distribution coefficient Log P as described above, so that even without using additives that adjust the surface tension of the material and the smoothness of the coating film, such as a leveling agent, the solution can be controlled. The curling phenomenon does not use additional additives, so it has the following effects: not only can avoid the quality and process problems of low molecular substances in the final product, but also can more effectively form a polyimide film with uniform characteristics .

For example, in the manufacture of coating the polyimide precursor composition on the glass substrate In the process, when the coating solution is placed during curing or under humidity conditions, the coating solution curls due to the shrinkage of the coating layer. The curling phenomenon of this coating solution can lead to deviations in the thickness of the film, resulting in film breakage or corner breakage during cutting due to insufficient film resistance to tortuosity, resulting in poor process workability and reduced yield The problem.

In addition, when minute foreign substances having polarity flow into the polyimide precursor composition coated on the substrate, in the polyimide precursor composition containing a polar solvent with a negative distribution coefficient Log P, Due to the polar foreign matter, local cracks or thickness changes of the coating may occur based on the position of the foreign matter. However, when a hydrophobic solvent with a positive distribution coefficient Log P is used, the minute foreign matter with polarity flows in In this case, it is also possible to reduce or suppress thickness changes caused by coating cracks.

Specifically, the polyimide precursor composition containing a solvent whose Log P is a positive number has a curl rate (edge back ratio) defined by Formula 1 below, which may be from 0% to 0.1% or less.

[Formula 1] Curl rate (%)=[(A-B)/A]×100

In the formula 1, A is the area where the polyimide precursor composition is completely coated on the substrate (100mm×100mm), and B is the self-coated polyimide precursor composition or polyimide The area where the edge of the substrate of the imide film is curled.

This kind of curling phenomenon of the polyimide precursor composition and polyimide film will occur within 30 minutes after coating the polyimide precursor composition solution, especially the curling from the edge, which will cause The thickness of the edge becomes thicker.

After the polyimide precursor composition is applied to the substrate, for example, at a temperature of 20°C to 30°C and a humidity condition of more than 40%, more specifically a humidity condition in the range of 40% to 80% , That is, 40%, 50%, 60%, 70%, and 80% humidity conditions for more than 10 minutes, for example, after more than 40 minutes, it can also show a very small curl rate of less than 0.1%, and preferably It is 0.05%, and it is more preferable to exhibit a curl rate almost close to 0%.

The crimp rate as described above is maintained even after curing by heat treatment. Specifically, it is 0.05%, and it is more preferable to exhibit a crimp rate close to 0%.

According to the polyimide precursor composition of the present invention, by solving this curling phenomenon, a polyimide film with more uniform characteristics can be obtained, and the yield of the preparation process can be improved.

In addition, the solvent used for the polymerization reaction may have a density of 1 g/cm ³ or less, as measured by the American Society for Testing Materials (ASTM) D 1475 standard measurement method, and a density of 1 g/cm ³ or more. In the case of, the relative viscosity will become higher, which will reduce the efficiency of the process.

The polymerization reaction can be carried out under an inert gas or nitrogen flow, and can be carried out under anhydrous conditions.

The polymerization reaction can be carried out at -20°C to 80°C, preferably 0 to 80°C. If the polymerization temperature is too high, the reactivity will be high and the molecular weight will increase, and the precursor will The viscosity of the composition increases, which is disadvantageous in terms of manufacturing process.

The polyimide precursor composition containing polyimide acid may be in the form of a solution dissolved in an organic solvent. In such a form, for example, in the case of synthesizing the polyimide precursor in an organic solvent, the solution It may be the obtained reaction solution itself, or it may be diluted with another solvent. In addition, when the polyimide precursor is obtained as a solid powder, it may be dissolved in an organic solvent as a solution.

According to an embodiment, an organic solvent may be added to adjust the content of the composition, so that the content of the overall polyimide precursor is 8% to 25% by weight, preferably 10% to 25% by weight, more preferably It can be adjusted to 10% by weight to 20% by weight or less. Alternatively, it is preferable to adjust the polyimide precursor composition to have a viscosity of 3,000 cP or more and 10,000 cP or less, preferably 4,000 cP or more and 9,000 cP or less, more preferably 4,000 cP. Above and below 8,000cP viscosity method to adjust. When the viscosity of the polyimide precursor composition exceeds 10,000 cP, when the polyimide film is processed, the efficiency of defoaming decreases, not only the efficiency of the process is not good, but also the prepared film generates bubbles The surface illuminance is poor, which can reduce the electrical, optical and mechanical properties.

The present invention also provides a transparent polyimide film prepared by using a chemical or thermal imidization method to imidize the polyimide precursor composition finally obtained by the polymerization reaction.

As an example, the polyimide film may be prepared by a method including the following steps: Coating the polyimide precursor composition on the carrier substrate; and heating and curing the polyimide precursor composition.

At this time, as the carrier substrate, glass, metal substrate, plastic substrate, etc. can be used without particular limitation. Among them, it is also preferable to use a glass substrate: for the imidization and curing of the polyimide precursor During the manufacturing process, the thermal stability and chemical stability are excellent, and no separate release agent is required for treatment, and the polyimide film formed after curing can be easily separated without damage.

In addition, the coating process can be carried out according to the usual coating method, specifically, spin coating, bar coating, roll coating, air knife, gravure, reverse roll, kiss roll, Scraper method, spray method, dipping method or brushing method, etc. Among them, it can be more preferably implemented by a casting method that can perform a continuous process and can increase the imidization rate of polyimide.

In addition, the polyimide precursor composition may be applied to the substrate in an amount suitable for the thickness of the display substrate, for example, a thickness of 10 μm to 30 μm in the final prepared polyimide film on.

After coating the polyimide precursor composition, before the curing process, a drying process for removing the solvent present in the polyimine precursor composition can be more selectively implemented.

The drying process can be carried out according to a usual method, and can be carried out at a temperature below 140°C, for example, 80°C to 140°C. If the implementation temperature of the drying process is less than 80° C., the drying process becomes longer, and when it exceeds 140° C., the imidization locally proceeds, making it difficult to form a polyimide film of uniform thickness.

The polyimide precursor composition coated on the substrate is heat-treated in an infrared (IR) oven or hot-air oven, or on a hot plate. At this time, the heat treatment can be performed at 300°C to 500°C It is preferably performed at 320°C to 480°C, and heating treatment can also be performed in multiple steps within the temperature range. The heat treatment process can be performed for 20 minutes to 70 minutes, and preferably can be performed for 20 minutes to 60 minutes.

After curing of the polyimide film prepared as described above, the residual stress can be 40 MPa or less, and the residual stress change value after placing the polyimide film for 3 hours at 25° C. and 50% humidity can be Below 5MPa.

The yellowness of the polyimide film may be 15 or less, preferably 13 or less. In addition, the haze of the polyimide film may be 2% or less, preferably 1% or less.

In addition, the transmittance of the polyimide film at 450 nm may be 75% or higher, the transmittance at 550 nm may be 85% or higher, and the transmittance at 630 nm may be 90% or higher.

The heat resistance of the polyimide film may be high. For example, the thermal decomposition temperature (Td_1%) resulting from a 1% mass reduction may be 500° C. or more.

The modulus (modulus of elasticity) of the polyimide film prepared as described above is 0.1 GPa to 4 GPa. If the modulus is less than 0.1 GPa, the rigidity of the film is low, and it is easy to break in the face of external impact. If the modulus exceeds 4 GPa, the rigidity of the coverlay film is excellent, but sufficient flexibility may not be ensured. The problem.

In addition, the elongation of the polyimide film may be 20% or more, and preferably 50% or more, and the tensile strength may be 130 MPa or more, preferably 140 MPa or more.

In addition, the polyimide film according to the present invention has excellent thermal stability with temperature changes. For example, in the temperature range of 100°C to 350°C, the thermal expansion coefficient after n+1 heating and cooling processes can be -10ppm /°C to 100 ppm/°C, preferably -7 ppm/°C to 90 ppm/°C, more preferably 80 ppm/°C or less (in this case, n is an integer greater than 0).

In addition, the thickness direction retardation (R _th ) of the polyimide film according to the present invention has a value of -150nm to +150nm, preferably a value of -130nm to +130nm, so that it can exhibit optical isotropy , And can improve visual perception.

According to an embodiment, the adhesive force between the polyimide film and the carrier substrate can be 5 gf/in or more, and preferably can be 10 gf/in or more.

Additionally, the present invention provides a flexible device including the polyimide film as a substrate.

As an example, the flexible device can be prepared by a method including the following steps: a polyimide prepared by heating the polyimide precursor composition after coating the carrier substrate Forming an element on the film; and peeling the polyimide film on which the element is formed from the carrier substrate.

The flexible device may be, for example, a thin film transistor, a liquid crystal display (LCD), an electronic paper, an organic electroluminescence (electroluminescence, EL) display, a plasma display panel (PDP), an integrated circuit (IC) card Wait.

Hereinafter, the embodiments of the present invention will be described in detail so that the It can be easily implemented by those with general knowledge in the technical field. However, the present invention can be implemented in many different forms, and is not limited to the embodiments described here.

<Synthesis Example 1> Preparation of Compound 1

Preparation of compound 1-3

Under a nitrogen atmosphere, compound 1-1 (108.0g, 0.65mol) and compound 1-2 (73.0g, 0.32mol) were dissolved in tetrahydrofuran (THF) (500mL), and potassium carbonate (135.2g, 0.97mol) was dissolved After adding water (250 mL), it was heated to 100°C. With the reaction mixture refluxing, palladium tetra triphenylphosphine (11.29 g) was added and stirred for 12 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to normal temperature, and ethyl acetate (250 mL) was added to separate the organic layer. The separated organic layer was dried using anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus (BUCHI Rotavapor R-300) to obtain compound 1-3 (60.3 g, yield 69%).

Preparation of compound 1-5

The compound 1-3 (20.0g, 74.3mmol) and compound 1-4 (4.0g, 37.1 After putting in propionic acid (500 mL), it refluxed and stirred for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 1-5 (21.5 g, yield 95%).

Preparation of compound 1

Compound 1-5 (21.5 g, 35.3 mmol) was dissolved in THF (200 mL) and heated to 60°C after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (200 mL) to obtain compound 1 (19.0 g, yield 98%).

C ₃₄ H ₂₂ N ₄ O ₄ (M+) high resolution (HR) liquid chromatography mass spectrometry (LC/MS/MS) mass-to-charge ratio (m/z) calculated value: 550.1641; found ): 550.1639

<Synthesis Example 2> Preparation of Compound 2

Preparation of compound 2-2

After compound 1-3 (20.0 g, 74.3 mmol) and compound 2-1 (9.07 g, 37.1 mmol) were put into propionic acid (500 mL), reflux and stirring were performed for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 2-2 (24.9 g, yield 90%).

Preparation of compound 2

Compound 2-2 (24.9 g, 33.3 mmol) was dissolved in THF (200 mL) and heated to 60°C after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (200 mL) to obtain compound 2 (21.7 g, yield 95%).

HR LC/MS/MS m/z calculated value of C ₃₆ H ₂₀ F ₆ N ₄ O ₄ (M+): 687.1422; Found: 687.1420

<Synthesis Example 3> Preparation of Compound 3

Preparation of compound 3-2

After putting compound 1-3 (20.0 g, 74.3 mmol) and compound 3-1 (5.05 g, 37.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 3-2 (21.8 g, yield 92%).

Preparation of compound 3

Compound 3-2 (21.8 g, 34.2 mmol) was dissolved in THF (200 mL) and heated to 60°C after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (200 mL) to obtain compound 3 (19.5 g, yield 99%).

Calculated HR LC/MS/MS m/z for C ₃₆ H ₂₆ N ₄ O ₄ (M+): 578.1954; found: 578.1949

<Synthesis Example 4> Preparation of Compound 4

Preparation of compound 4-2

After putting compound 1-3 (20.0 g, 74.3 mmol) and compound 4-1 (6.57 g, 37.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 4-2 (22.1 g, yield 88%).

Preparation of compound 4

Compound 4-2 (22.1 g, 32.6 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (200 mL) to obtain compound 4 (16.1 g, yield 80%).

Calculated HR LC/MS/MS m/z for C ₃₄ H ₂₀ Cl ₂ N ₄ O ₄ (M+): 618.0862; found: 618.0859

<Synthesis Example 5> Preparation of Compound 5

Preparation of compound 5-2

After putting compound 1-3 (20.0 g, 74.3 mmol) and compound 5-1 (6.57 g, 37.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 5-2 (22.9 g, yield 91%).

Preparation of compound 5

Compound 5-2 (22.9 g, 32.6 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (200 mL) to obtain compound 5 (20.0 g, yield 96%).

Calculated HR LC/MS/MS m/z for C ₃₄ H ₂₀ Cl ₂ N ₄ O ₄ (M+): 618.0862; found: 618.0860

<Synthesis Example 6> Preparation of Compound 6

Preparation of compound 6-2

After putting compound 1-3 (20.0 g, 74.3 mmol) and compound 6-1 (6.24 g, 37.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 6-2 (23.6 g, yield 95%).

Preparation of compound 6

Compound 6-2 (23.6 g, 35.3 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (200 mL) to obtain compound 6 (20.8 g, yield 97%).

Calculated HR LC/MS/MS m/z for C ₃₆ H ₂₆ N ₄ O ₆ (M+): 610.1852; found: 610.1851

<Synthesis Example 7> Preparation of Compound 7

Preparation of compound 7-2

After compound 1-3 (20.0 g, 74.3 mmol) and compound 7-1 (7.88 g, 37.1 mmol) were put into propionic acid (500 mL), reflux and stirring were performed for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 7-2 (23.6 g, yield 89%).

Preparation of compound 7

Compound 7-2 (23.6 g, 33.0 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. Use ethanol (200mL) to recrystallize the obtained solid. To compound 7 (19.9 g, yield 92%).

Calculated HR LC/MS/MS m/z for C ₄₂ H ₃₀ N ₄ O ₄ (M+): 654.2267; found: 654.2264

<Synthesis Example 8> Preparation of Compound 8

Preparation of compound 8-2

After putting compound 1-3 (20.0 g, 74.3 mmol) and compound 8-1 (11.8 g, 37.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 8-2 (29.3 g, yield 96%).

Preparation of compound 8

Compound 8-2 (29.3 g, 35.6 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen is continuously injected and the reaction mixture Stir for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (250 mL) to obtain compound 8 (24.2 g, yield 89%).

Calculated HR LC/MS/MS m/z of C ₄₂ H ₂₄ F ₆ N ₄ O ₄ (M+): 762.1702; found: 762.1700

<Synthesis Example 9> Preparation of Compound 9

Preparation of compound 9-2

After putting compound 1-3 (20.0 g, 74.3 mmol) and compound 9-1 (11.8 g, 37.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the reaction was completed, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (250 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 9-2 (29.3 g, yield 96%).

Preparation of compound 9

Compound 9-2 (29.3g, 35.6mmol) was dissolved in THF (200mL) and After adding Pd/C catalyst, heat to 60°C. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (250 mL) to obtain compound 9 (22.0 g, yield 89%).

Calculated HR LC/MS/MS m/z for C ₄₀ H ₂₄ Cl ₂ N ₄ O ₄ (M+): 694.1175; found: 694.1172

<Synthesis Example 10> Preparation of Compound 10

Preparation of compound 10-2

After putting compound 1-3 (20.0 g, 74.3 mmol) and compound 10-1 (14.7 g, 37.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After the reaction mixture was filtered, the solid obtained was washed with water and ethanol (1:1, volume ratio) to obtain compound 10-2 (32.7 g, yield 98%).

Preparation of compound 10

Compound 10-2 (32.7 g, 36.4 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (300 mL) to obtain compound 10 (27.4 g, yield 90%).

HR LC/MS/MS m/z calculated value of C ₄₈ H ₂₈ F ₆ N ₄ O ₄ (M+): 838.2015; found: 838.2011

<Synthesis Example 11> Preparation of Compound 11

Preparation of compound 11-3

Compound 11-1 (20.0g, 85.4mmol) and compound 1-2 (9.7g, 42.7mmol) were dissolved in THF (500mL) under nitrogen atmosphere, and potassium carbonate (11.8g, 85.4mmol) was dissolved in water ( 250mL) After the addition, it was heated to 100°C. With the reaction mixture refluxing, tetrakistriphenylphosphine palladium (1.48 g) was added and stirred for 12 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to normal temperature, and ethyl acetate (250 mL) was added to separate the organic layer. Use anhydrous magnesium sulfate to dry the separated organic layer, The solvent was removed by a vacuum distillation apparatus to obtain compound 11-3 (11.5 g, yield 80%).

Preparation of compound 11-5

After putting compound 11-3 (11.5 g, 34.1 mmol) and compound 11-4 (4.1 g, 17.1 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 11-5 (14.4 g, yield 96%).

Preparation of compound 11

Compound 11-5 (14.4 g, 16.3 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (150 mL) to obtain compound 11 (12.7 g, yield 95%).

HR LC/MS/MS m/z calculated value of C ₃₈ H ₁₈ F ₁₂ N ₄ O ₄ (M+): 822.1136; found: 822.1131

<Synthesis Example 12> Preparation of Compound 12

Preparation of compound 12-3

Under nitrogen atmosphere, compound 12-1 (30g, 166.6mmol) and compound 1-2 (25.2g, 111.1mmol) were dissolved in THF (500mL), and potassium carbonate (23.0g, 166.6mmol) was dissolved in water (250mL) ) After adding, heat to 100°C. With the reaction mixture refluxing, tetrakistriphenylphosphine palladium (3.84 g) was added and stirred for 12 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to normal temperature, and ethyl acetate (250 mL) was added to separate the organic layer. The separated organic layer was dried using anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus to obtain compound 12-3 (24.1 g, yield 77%).

Preparation of compound 12-5

After putting compound 12-3 (24.1 g, 58.4 mmol) and compound 12-4 (13.6 g, 42.7 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 12-5 (32.6 g, yield 90%).

Preparation of compound 12

Compound 12-5 (32.6 g, 38.4 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (250 mL) to obtain compound 12 (24.3 g, yield 80%).

C ₄₄ H ₂₈ F ₆ N ₄ O ₄ (M+) HR LC/MS/MS m/z calculated value: 790.2015; found: 790.2012

<Synthesis Example 13> Preparation of Compound 13

Preparation of compound 13-3

Under nitrogen atmosphere, compound 13-1 (30g, 128.2mmol) and compound 1-2 (19.4g, 85.4mmol) were dissolved in THF (500mL), and potassium carbonate (17.7g, 128.2mmol) was dissolved in water (250mL) ) After adding, heat to 100°C. With the reaction mixture refluxing, tetrakistriphenylphosphine palladium (2.96 g) was added and stirred for 12 hours. After the reaction was completed, the temperature of the reaction mixture was lowered to normal temperature, and ethyl acetate (250 mL) was added to separate the organic layer. The separated organic layer was dried using anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus to obtain compound 13-3 (22.1 g, yield 77%).

Preparation of compound 13-5

After putting compound 13-3 (22.1 g, 65.8 mmol) and compound 13-4 (10.5 g, 32.9 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, use water and ethyl The obtained solid was washed with alcohol (1:1, volume ratio) to obtain compound 13-5 (28.9 g, yield 92%).

Preparation of compound 13

Compound 13-5 (28.9 g, 30.2 mmol) was dissolved in THF (200 mL) and heated to 60°C after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (250 mL) to obtain compound 13 (25.8 g, yield 95%).

HR LC/MS/MS m/z calculated value of C ₄₄ H ₂₂ F ₁₂ N ₄ O ₄ (M+): 898.1449; found: 898.1444

<Synthesis Example 14> Preparation of Compound 14

Preparation of compound 14-3

Dissolve compound 14-1 (30g, 149.2mmol) and compound 1-2 (22.5g, 99.5mmol) in THF (500mL) under nitrogen atmosphere, and dissolve potassium carbonate (20.6g, 149.2mmol) in water (250mL) ) After adding, heat to 100°C. In the state of the reaction mixture refluxing, add tetrakistriphenylphosphine palladium (3.43g) and stir for 12 hours Time. After the reaction was completed, the temperature of the reaction mixture was lowered to normal temperature, and ethyl acetate (250 mL) was added to separate the organic layer. The separated organic layer was dried using anhydrous magnesium sulfate, and the solvent was removed by a vacuum distillation apparatus to obtain compound 14-3 (26.4 g, yield 88%).

Preparation of compound 14-5

After putting compound 14-3 (26.4 g, 87.2 mmol) and compound 14-4 (11.0 g, 43.6 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the solid obtained was washed with water and ethanol (1:1, volume ratio) to obtain compound 14-5 (33.4 g, yield 93%).

Preparation of compound 14

Compound 14-5 (33.4 g, 40.5 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (300 mL) to obtain compound 14 (26.9 g, yield 87%).

Calculated HR LC/MS/MS m/z for C ₄₀ H ₂₂ Cl ₄ N ₄ O ₄ (M+): 764.0366; found: 764.0363

<Synthesis Example 15> Preparation of Compound 15

Preparation of compound 15-3

Compound 15-2 (50.0 g, 0.22 mol) was dissolved in N-methylpyrrolidone (NMP) (500 mL), and compound 15-1 (26.6 g, 0.11 mol) was added in several portions and heated to 140 Stir at °C for 6 hours. After the reaction, water (1000 mL) was added to the reaction mixture and filtered, and the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 15-3 (19.6 g, yield 43%).

Preparation of compound 15-4

After compound 15-3 (19.6 g, 47.7 mmol) was dispersed in glacial acetic acid (300 mL), potassium permanganate (18.8 g, 119 mmol) was added at 0° C. and stirred for 1 hour, then the temperature was raised to normal temperature and stirred for 6 hours. After the completion of the reaction, water (600 mL) was poured into the reaction mixture and filtered, and the obtained solid was recrystallized with ethanol (300 mL) to obtain compound 15-4 (19.4 g, yield 92%).

Preparation of compound 15-5

Compound 15-4 (19.4 g, 43.7 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Continuously inject hydrogen and mix the reaction The material was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (150 mL) to obtain compound 15-5 (14.9 g, yield 89%).

Preparation of compound 15-6

After adding compound 15-5 (14.9 g, 38.9 mmol) and compound 1-3 (20.9 g, 77.9 mmol) to propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After the reaction mixture was filtered, the solid obtained was washed with water and ethanol (1:1, volume ratio) to obtain compound 15-6 (33.3 g, yield 97%).

Preparation of compound 15

Compound 15-6 (33.3 g, 37.6 mmol) was dissolved in THF (400 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (300 mL) to obtain compound 15 (28.2 g, yield 91%).

HRLC/MS/MS m/z calculated value of C ₄₂ H ₂₄ F ₆ SN ₄ O ₆ (M+): 826.1321; found: 826.1319

<Synthesis Example 16> Preparation of Compound 16

Preparation of compound 16-3

Compound 16-2 (42.7 g, 0.25 mol) was dissolved in NMP (500 mL), and compound 16-1 (30.0 g, 0.12 mol) was added in multiple portions, and then heated to 140° C. and stirred for 6 hours. After the reaction, water (1000 mL) was added to the reaction mixture and filtered, and the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 16-3 (20.5 g, yield 54%).

Preparation of compound 16-4

After compound 16-3 (20.5 g, 67.5 mmol) was dispersed in glacial acetic acid (300 mL), potassium permanganate (26.6 g, 168.7 mmol) was added at 0°C and stirred for 1 hour, then heated to room temperature and stirred for 6 hours. After completion of the reaction, water (600 mL) was poured into the reaction mixture and filtered, and the obtained solid was recrystallized with ethanol (200 mL) to obtain compound 16-4 (19.7 g, yield 87%).

Preparation of compound 16-5

Compound 16-4 (19.7 g, 58.6 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Continuously inject hydrogen and mix the reaction The material was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (150 mL) to obtain compound 16-5 (14.7 g, yield 91%).

Preparation of compound 16-6

After putting compound 16-5 (14.7 g, 53.3 mmol) and compound 1-3 (28.7 g, 106.7 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 16-6 (39.4 g, yield 95%).

Preparation of compound 16

Compound 16-6 (39.4 g, 50.7 mmol) was dissolved in THF (500 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (350 mL) to obtain compound 16 (33.8 g, yield 93%).

C ₄₂ H ₃₀ SN ₄ O ₆ (M+) HR LC/MS/MS m/z calculated value: 718.1886; found: 718.1883

<Synthesis Example 17> Preparation of Compound 17

Preparation of compound 17-3

Compound 17-1 (30.0 g, 0.13 mol) and compound 17-2 (31.0 g, 0.2 mol) were dissolved in dimethylformamide (DMF) (600 mL), potassium carbonate was added, and then heated to 150°C. After completion of the reaction, water (1000 mL) was added to the reaction mixture and filtered, and the obtained solid was recrystallized with ethanol (350 mL) to obtain compound 17-3 (34.8 g, yield 76%).

Preparation of compound 17-4

After compound 17-3 (34.8 g, 101.3 mmol) was dispersed in glacial acetic acid (400 mL), potassium permanganate (40.0 g, 253.3 mmol) was added at 0°C and stirred for 1 hour, then heated to room temperature and stirred for 6 hours. After completion of the reaction, water (800 mL) was poured into the reaction mixture and filtered, and the obtained solid was recrystallized with ethanol (300 mL) to obtain compound 17-4 (32.3 g, yield 85%).

Preparation of compound 17-5

Compound 17-4 (32.3 g, 85.9 mmol) was dissolved in THF (300 mL) and heated to 60° C. after adding Pd/C catalyst. Continuously inject hydrogen and mix the reaction The material was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol to obtain compound 17-5 (25.8 g, yield 95%).

Preparation of compound 17-6

After putting compound 17-5 (25.8 g, 81.6 mmol) and compound 1-3 (43.9 g, 163.3 mmol) into propionic acid (500 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (500 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 17-6 (58.7 g, yield 88%).

Preparation of compound 17

Compound 17-6 (58.7 g, 71.8 mmol) was dissolved in THF (600 mL) and heated to 60°C after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (500 mL) to obtain compound 17 (50.1 g, yield 92%).

Calculated HR LC/MS/MS m/z of C ₄₁ H ₂₅ F ₃ SN ₄ O ₆ (M+): 758.1447; found: 758.1443

<Synthesis Example 18> Preparation of Compound 18

Preparation of compound 18-2

Compound 18-1 (15.0 g, 54.3 mmol) was dissolved in THF (200 mL) and heated to 60°C after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (100 mL) to obtain compound 18-2 (11.0 g, yield 94%).

Preparation of compound 18-3

After putting compound 18-2 (11.0 g, 51.0 mmol) and compound 1-3 (27.4 g, 102.1 mmol) into propionic acid (400 mL), reflux and stirring for 12 hours. After the reaction was completed, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (400 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 18-3 (31.5 g, yield 86%).

Preparation of compound 18

Compound 18-3 (31.5 g, 43.9 mmol) was dissolved in THF (300 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the reaction is over, the temperature of the reaction mixture is lowered to room temperature before entering Filter to obtain a solid. The obtained solid was recrystallized with ethanol (250 mL) to obtain compound 18 (26.5 g, yield 93%).

Calculated HR LC/MS/MS m/z of C ₄₀ H ₂₆ SN ₄ O ₄ (M+): 658.1675; found: 658.1670

<Synthesis Example 19> Preparation of Compound 19

Preparation of compound 19-2

Compound 19-1 (15.0 g, 49.3 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (110 mL) to obtain compound 19-2 (11.7 g, yield 98%).

Preparation of compound 19-3

After putting compound 19-2 (11.7 g, 48.3 mmol) and compound 1-3 (26.0 g, 96.7 mmol) into propionic acid (400 mL), reflux and stirring for 12 hours. After the reaction is over, after the temperature of the reaction mixture is lowered to room temperature, ethanol (400 mL) to disperse the resulting solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 19-3 (34.9 g, yield 97%).

Preparation of compound 19

Compound 19-3 (34.9 g, 46.9 mmol) was dissolved in THF (400 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (300 mL) to obtain compound 19 (27.3 g, yield 85%).

C ₄₂ H ₃₀ SN ₄ O ₄ (M+) HR LC/MS/MS m/z calculated value: 686.1988; found: 686.1986

<Synthesis Example 20> Preparation of Compound 20

Preparation of compound 20-2

Compound 20-1 (15.0 g, 36.4 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the reaction is over, the temperature of the reaction mixture is lowered to room temperature before entering Filter to obtain a solid. The obtained solid was recrystallized with ethanol (150 mL) to obtain compound 20-2 (12.1 g, yield 95%).

Preparation of compound 20-3

After putting compound 20-2 (12.1 g, 34.5 mmol) and compound 1-3 (18.6 g, 69.1 mmol) into propionic acid (300 mL), reflux and stirring for 12 hours. After the completion of the reaction, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (300 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 20-3 (26.5 g, yield 90%).

Preparation of compound 20

Compound 20-3 (26.5 g, 31.1 mmol) was dissolved in THF (300 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (250 mL) to obtain compound 20 (22.4 g, yield 91%).

Calculated HRLC/MS/MS m/z of C ₄₂ H ₂₄ SN ₄ O ₄ (M+): 794.1422; found: 794.1419

<Synthesis Example 21> Preparation of Compound 21

Preparation of compound 21-2

Compound 21-1 (15.0 g, 57.6 mmol) was dissolved in THF (200 mL) and heated to 60° C. after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the completion of the reaction, the temperature of the reaction mixture was lowered to normal temperature and then filtered to obtain a solid. The obtained solid was recrystallized with ethanol (100 mL) to obtain compound 21-2 (10.6 g, yield 92%).

Preparation of compound 21-3

After putting compound 21-2 (10.6 g, 53.0 mmol) and compound 1-3 (28.5 g, 106.1 mmol) into propionic acid (400 mL), reflux and stirring for 12 hours. After the reaction was completed, after the temperature of the reaction mixture was lowered to normal temperature, ethanol (400 mL) was added to disperse the generated solid. After filtering the reaction mixture, the obtained solid was washed with water and ethanol (1:1, volume ratio) to obtain compound 21-3 (36.1 g, yield 97%).

Preparation of compound 21

Compound 21-3 (36.1 g, 51.4 mmol) was dissolved in THF (300 mL) and heated to 60°C after adding Pd/C catalyst. Hydrogen was continuously injected and the reaction mixture was stirred for 4 hours. After the reaction is over, the temperature of the reaction mixture is lowered to room temperature before entering Filter to obtain a solid. The obtained solid was recrystallized with ethanol (300 mL) to obtain compound 21 (29.4 g, yield 89%).

Calculated HR LC/MS/MS m/z for C ₄₀ H ₂₆ N ₄ O ₅ (M+): 642.1903; found: 642.1901

<Example 1>

After filling the organic solvent N,N-diethylacetamide (DEAc) (100mL) in a stirrer with a nitrogen flow, the temperature of the reactor was maintained at 25°C. 24.2 g (0.031 mol) of the diamine compound 8 prepared in Synthesis Example 8 was added and dissolved at the same temperature. Add 9.12g (0.031mol) of biphenyl-tetracarboxylic acid dianhydride (BPDA) as the acid anhydride to the solution added with the compound 8 at the same temperature, and stir for 24 hours to obtain the polyimide precursor Composition.

<Example 2>

After filling the organic solvent DEAc (150 mL) in a stirrer with a nitrogen flow, while keeping the temperature of the reactor at 25°C, 33.8 g (0.041 mol) was added at the same temperature in the synthesis example 15. The prepared diamine compound 15 was dissolved. At the same temperature, 12.1 g (0.041 mol) of BPDA was added as an acid anhydride to the solution to which the compound 15 was added, and stirred for 24 hours to obtain a polyimide precursor composition.

<Example 3>

After filling the organic solvent DEAc (150 mL) in a stirrer with a nitrogen flow, while keeping the temperature of the reactor at 25°C, add 30.5 g (0.040 mol) at the same temperature as the one used in Example 1. The same diamine compound 8 was dissolved. Add 17.7g (0.040mol) 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (4,4'-(hexafluoroisopropylidene)diphthalic anhydride) to the solution added with the compound 8 at the same temperature anhydride, 6-FDA) was used as the acid anhydride and stirred for 24 hours to obtain the polyimide precursor composition.

<Example 4>

After filling the organic solvent DEAc (200 mL) in a stirrer with a nitrogen flow, while keeping the temperature of the reactor at 25°C, 37.2 g (0.045 mol) was added at the same temperature as used in Example 2. The same diamine compound 15 was dissolved. At the same temperature, 20.0 g (0.045 mol) of 6-FDA was added as an acid anhydride to the solution to which the compound 15 was added, and stirred for 24 hours to obtain a polyimide precursor composition.

<Comparative Example 1>

After filling the organic solvent DEAc (150 mL) in a stirrer with a nitrogen flow, while keeping the temperature of the reactor at 25°C, 27.8 g (0.087 mol) 2,2'-bis( Trifluoromethyl)benzidine (2,2'-bis(trifluoromethyl)benzidine, TFMB) is used as a diamine compound and dissolved. At the same temperature, 25.6 g (0.087 mol) of BPDA was added as an acid anhydride to the solution to which TFMB was added, and stirred for 24 hours to obtain a polyimide precursor composition.

<Comparative Example 2>

After filling the organic solvent DEAc (100 mL) in a stirrer with a nitrogen flow, while keeping the temperature of the reactor at 25°C, 22.4 g (0.070 mol) of TFMB was added as a diamine compound at the same temperature and It dissolves. At the same temperature, 31.1 g (0.070 mol) of 6-FDA was added as an acid anhydride to the solution added with TFMB, and stirred for 24 hours to obtain a polyimide precursor composition.

<Comparative Example 3>

The same process as in Example 1 was performed, but the following reference compound C with no aromatic rings bonded to the amide rings on both sides was used instead of the diamine compound 8 to obtain the polyimide precursor composition.

<Comparative Example 4>

The same process as in Example 3 was performed, but the following reference compound C, which was not bonded to aromatic rings on both sides of the amide ring, was used instead of the diamine compound 8 to obtain a polyimide precursor composition.

The solid content and viscosity of each polyimide precursor composition obtained in the aforementioned Examples 1 to 4 and Comparative Examples 1 to 4 are described in Table 1 below.

<Experimental example 1>

Each polyimide precursor composition (solution) manufactured in Example 1 to Example 4 and Comparative Example 1 to Comparative Example 2 was spin-coated on a glass substrate. The glass substrate coated with each polyimide precursor solution was placed in an oven and heated at a rate of 5°C/min, maintained at 80°C for 30 minutes, and at 430°C for 30 minutes, to perform a curing process to prepare each Polyimide film.

<Performance Evaluation of Polyimide Film>

1. Thermal expansion coefficient (CTE)

After preparing each polyimide film obtained in the experimental example 1 into a test plate with a size of 5 mm×20 mm, it was loaded with an accessory of a thermomechanical analyzer (TMA) (Q400 of TA Company). The length of the actually measured film test plate was unified to 16 mm. Set the force of the tensile film test panel to 0.02N, and use TMA (TA Company’s Q400) to perform the first heating process at a temperature range of 100°C to 350°C at a heating rate of 5°C/min. At 350°C to Changes in thermal expansion during a cooling process in a temperature range of 100°C at a cooling rate of 4°C/min.

2. Thermal decomposition temperature

The temperature (Td1%) at which the weight reduction rate of the polyimide film test plate is 1% is measured by using a thermal gravimetric analyzer (TGA) (TGA8000 ^TM , PerkinElmer) in a nitrogen environment ).

The measured CTE and Td1% values of the polyimide film are shown in Table 1 below.

According to the table 1, it can be seen that the polyimide film (Example 1 to Example 4) prepared by using the polyimine precursor composition containing the novel diamine compound according to the present invention under the condition of using the same acid anhydride Compared with the polyimide film of Comparative Example 1 to Comparative Example 4 prepared by using a diamine compound having a structure different from the diamine compound of the present invention, it exhibits a lower CTE value. This means that the shrinking behavior or change of the polyimide film according to the present invention due to heating is very small, and it can be seen that the polyimide film according to the present invention The imide film has excellent heat resistance.

Above, the specific part of the content of the present invention has been described in detail through various embodiments. It is obvious to those with ordinary knowledge in the corresponding technical field that this specific description is only a preferred embodiment and not This limits the scope of the present invention. Therefore, the essential scope of the present invention is defined by the appended claims and their equivalents.

Claims (8)

A diamine compound, which is a diamine compound of the following chemical formula 1:

In the chemical formula 1, L is selected from

,

,

and

, Ar ₁ and Ar ₂ are each independently selected from

,

,

,

,

and

The divalent organic group, R ₁ to R ₁₁ are each independently deuterium, halogen atom, cyano group, hydroxyl group, substituted or unsubstituted alkyl group having 1 to 30 carbons, substituted or unsubstituted carbon Haloalkyl having 1 to 30, substituted or unsubstituted alkylsilyl having 1 to 30 carbons, substituted or unsubstituted arylsilyl having 6 to 30 carbons, substituted Or unsubstituted alkylamino groups with 1 to 30 carbons, substituted or unsubstituted arylamino groups with 6 to 30 carbons, substituted or unsubstituted carbons with 1 to 30 carbons Alkoxy group, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 aryl groups, substituted or unsubstituted aralkyl groups with 6 to 30 carbons, substituted or unsubstituted aryloxy groups with 6 to 30 carbons, carboxy (-COOH) groups, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbons, an amido group, a substituted or unsubstituted cycloalkyloxy group having 3 to 30 carbons, a substituted or unsubstituted carbon Cycloalkylthio group, ester group, -CD ₃ , azide group, nitro group with a number of 1 to 30, or one or more selected from B, N, O, S, P(=O), Si and P Heteroatom substituted or unsubstituted (3- to 30-membered) heteroaryl group, Y is selected from

,

,

,

,

,

and

l, m, n, o, p, q, r, s, t, u, and v are integers from 0 to 4, respectively, where l, m, n, o, p, q, r, s, t, u and When v is an integer of 2 to 4, each of R ₁ to R ₁₁ can be the same or different. The diamine compound according to claim 1, wherein L of the chemical formula 1 is selected from

,

,

and

, Ar ₁ and Ar ₂ are independently

, R ₁ to R ₈ are each independently a halogen atom, an unsubstituted or substituted halogen atom-substituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R ₉ is a halogen atom, Or unsubstituted or halogen-substituted alkyl having 1 to 6 carbons, Y is selected from

,

and

, L, m, n, o, p, q, r, s, and t are integers from 0 to 2 respectively. The diamine compound according to claim 1, wherein L of the chemical formula 1 is substituted by one or more selected from the group consisting of trifluoromethyl, methyl, chlorine (Cl), and methoxy A substituted or unsubstituted phenyl group; biphenyl substituted or unsubstituted by one or more substituents selected from the group consisting of methyl, trifluoromethyl and chlorine (Cl); Terphenyl substituted or unsubstituted by trifluoromethyl; bis(trifluoromethylphenyl)sulfonate, bis(methylphenyl)sulfonate, {(trifluoromethylphenyl)sulfonyl } Phenyl, diphenyl sulfide, bis(methylphenyl) sulfide, bis(trifluoromethylphenyl) sulfide or diphenyl ether, Ar ₁ and Ar ₂ are each independently selected from methyl, A substituted or unsubstituted phenyl group consisting of one or more substituents of trifluoromethyl and chlorine (Cl), l is an integer from 0 to 2, m, n, o, p, q, r, s and t are integers of 0 or 1, respectively. The diamine compound according to claim 1, wherein the diamine compound of the chemical formula 1 is selected from compounds of the following structural formulas 1 to 21:

A polyimide precursor comprising the diamine compound of Chemical Formula 1 and one or more acid dianhydrides as described in any one of Claims 1 to 4 Prepared by polymerization. The polyimide precursor according to claim 5, wherein the acid dianhydride comprises biphenyl-tetracarboxylic acid dianhydride (BPDA), 4,4'-(hexafluoroisopropylidene ) Diphthalic anhydride (4,4'-(hexafluoroisopropylidene) diphthalic anhydride, 6-FDA) or a mixture thereof. A polyimide film, which is prepared from the polyimide precursor as described in claim 5. A flexible device comprising the polyimide film according to claim 7 as a substrate.