CN113166046A - Diamine compound, and polyimide precursor and polyimide film using same - Google Patents

Abstract

Disclosed is a novel diamine compound comprising a structure in which diphenyl sulfide in a molecule is bonded to a benzene ring substituted with an amine group through an amide bond. The polyimide film prepared by polymerizing the novel diamine compound exhibits improved mechanical and thermal characteristics and an increased refractive index.

Description

Diamine compound, and polyimide precursor and polyimide film using same

Technical Field

This application claims the benefit of priority from korean patent application No. 10-2019-0023818, filed on 28.2.2019, and korean patent application No. 10-2020-0006133, filed on 16.1.2020, the entire disclosures of which are incorporated herein by reference.

The present invention relates to a novel diamine, and a polyimide precursor and a polyimide film using the same.

Background

In recent years, weight reduction and miniaturization of products have been emphasized in the field of displays. The glass substrates currently used are heavy and brittle and are difficult to apply to a continuous process. Therefore, studies are actively conducted: a plastic substrate which has advantages of light weight, flexibility and applicability to a continuous process and can replace a glass substrate is applied to a mobile phone, a notebook computer and a PDA (Personal Digital Assistant).

Polyimide has heat resistance and chemical resistance, and particularly aromatic polyimide exhibits excellent characteristics such as excellent mechanical characteristics and electrical insulation due to its rigid main chain structure. In addition, since polyimide is easily synthesized, can be formed into a thin film, and does not require a crosslinking agent for curing, it is widely used as a material for integration in semiconductors, such as automobile and aerospace materials, Liquid Crystal Displays (LCDs), and Plasma Display Panels (PDPs), and daily necessities. In addition, many studies have been made on applying polyimide to a flexible plastic display panel having light weight and flexible characteristics.

A polyimide film produced by forming a polyimide film is generally prepared by: the method includes the steps of solution-polymerizing an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative solution, coating the solution on a silicon wafer or glass, and curing it by heat treatment.

Flexible devices that involve high temperature processes require heat resistance at high temperatures. In particular, the process temperature of an Organic Light Emitting Diode (OLED) device manufactured using a Low Temperature Polysilicon (LTPS) process may be close to 500 ℃. However, at this temperature, even with polyimide having excellent heat resistance, thermal decomposition due to hydrolysis tends to occur. Therefore, in order to manufacture a flexible device, it is required to develop a polyimide film exhibiting excellent thermal characteristics and storage stability so that thermal decomposition due to hydrolysis during a high temperature process does not occur.

Disclosure of Invention

The problem to be solved by the present invention is to provide a novel diamine compound for producing a polyimide having improved thermal and mechanical properties and an improved refractive index.

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

Still 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 including the polyimide film.

In order to solve the problems of the present invention, there is provided a diamine compound of the following formula 1:

[ formula 1]

In the formula 1, the first and second groups,

z is-NH-,

R₁to R₄Each independently hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 1 to 30 carbon atomsAn alkylamino group, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, an amide group, a substituted or unsubstituted cycloalkyloxy group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkylthio group having 1 to 30 carbon atoms, an ester group, an azide group, a nitro group, or a substituted or unsubstituted amino group containing a substituent selected from B, C, O, C, N, O, S, P (═ O), a (3-to 30-membered) heteroaryl group of at least one heteroatom of Si and P, and

a. b, c and d are each an integer of 0 to 4, and when a, b, c and d are each an integer of 2 to 4, each of a, b, c and d may be the same or different.

Advantageous effects

The diamine compound of the present invention is a novel compound including a structure in which diphenyl sulfide in a molecule is bonded to an amine group-substituted benzene ring via an amide bond, and a polyimide including the novel diamine compound as a polymerization component can provide a polyimide film having improved heat resistance and mechanical characteristics after curing and exhibiting an improved refractive index.

Detailed Description

Since various modifications and changes can be made in the present invention, specific embodiments are shown in the drawings and will be described in detail herein. It should be understood, however, that the invention is not intended to be limited to the particular embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. In the following description of the present invention, a detailed description of known functions will be omitted if it is determined that the detailed description of the known functions may obscure the gist of the present invention.

Aromatic polyimides are widely used in high-tech industries such as microelectronics, aerospace, insulating materials and refractory materials due to their excellent bulk properties (e.g., thermo-oxidative stability, high mechanical strength). However, aromatic polyimides having a strong absorption in the ultraviolet-visible region show color development from light yellow to dark brown. This limits its widespread use in the field of optoelectronics where transparency and colorless properties are essential requirements. Aromatic polyimides develop color because intramolecular charge transfer complexes (CT-complexes) are formed between alternating electron donors (dianhydrides) and electron acceptors (diamines) in the polymer backbone.

To solve this problem, introduction of specific functional groups, bulky side groups, fluorinated functional groups, etc. into the polymer main chain or introduction of-S-, -O-, -CH has been studied₂And the like to develop an optically transparent polyimide film having a high glass transition temperature (Tg).

The inventors of the present invention have conducted extensive studies to solve the problems of the prior art and found that a novel diamine compound having a specific structure provides excellent thermal and mechanical properties, thereby completing the present invention.

Accordingly, the present invention provides diamines of the formula 1:

[ formula 1]

In the formula 1, the first and second groups,

z is-NH-,

R₁to R₄Each independently hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 6 to 30 carbon atom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, an amide group, a substituted or unsubstituted cycloalkyloxy group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkylthio group having 1 to 30 carbon atoms, an ester group, an azide group, a nitro group, or a substituted or unsubstituted amino group containing a substituent selected from the group consisting of B, N, O, S, P (═ O), a (3-to 30-membered) heteroaryl group of at least one heteroatom of Si and P, and

a. b, c and d are each an integer of 0 to 4, and when a, b, c and d are each an integer of 2 to 4, each of a, b, c and d may be the same or different.

The term "substituted" in the description of "substituted or unsubstituted" as used herein means that the hydrogen atom in any functional group is replaced with another atom or another functional group (i.e., another substituent).

In formula 1, the substituents of substituted alkyl, substituted haloalkyl, substituted alkylsilyl, substituted arylsilyl, substituted alkylamino, substituted arylamino, substituted alkoxy, substituted alkylthio, substituted arylthio, substituted aryl, substituted aralkyl, substituted aryloxy, substituted cycloalkyl, substituted cycloalkyloxy, substituted cycloalkylthio, and substituted heteroaryl are each independently at least one selected from the group consisting of: deuterium, a halogen atom, a cyano group, an amino group, a carboxyl group, a nitro group, a hydroxyl group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an arylthio group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, a cycloalkenyl group having 3 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, an arylcarbonyl group having 6 to 30 carbon atoms, a carboxyl group having 2 to 30 carbon atoms, a carboxyl group, an alkoxy group having 1 to 30 carbon atoms, an arylcarbonyl group having 6 to 30 carbon atoms, an aryl group, An alkylboron group having 1 to 30 carbon atoms, an arylboron group having 6 to 30 carbon atoms, and a (3-to 7-membered) heterocycloalkyl group.

As used herein, "alkyl group having 1 to 30 carbon atoms" means a straight-chain or branched alkyl group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like.

As used herein, "alkenyl group having 2 to 30 carbon atoms" means a straight-chain or branched alkenyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Specific examples of alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, and the like.

As used herein, "alkynyl group having 2 to 30 carbon atoms" means a straight-chain or branched alkynyl group having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, and the like.

As used herein, "alkoxy group having 1 to 30 carbon atoms" means a straight-chain or branched alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, 1-ethylpropoxy, and the like.

As used herein, "cycloalkyl group having 3 to 30 carbon atoms" means a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 7 carbon atoms. Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

As used herein, "aryl (ene) group having 6 to 30 carbon atoms" means a monocyclic or fused cyclic group derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, preferably having 6 to 20 ring skeleton carbon atoms, more preferably having 6 to 15 ring skeleton carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthryl, anthracyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, phenanthrenyl, indenyl, triphenylenyl, perylene, and the like,

Naphthyl, naphthylnaphthyl, fluoranthenyl, and the like.

As used herein, "(3-to 30-membered) (arylene) heteroaryl" means an aryl group having 3 to 30 ring backbone atoms and containing one or more heteroatoms selected from B, N, O, S, P (═ O), Si, and P. The aryl group preferably has 3 to 20 ring skeleton carbon atoms, more preferably 3 to 15 ring skeleton carbon atoms, and preferably contains 1 to 4 hetero atoms. The aryl group may be a monocyclic group or a fused ring group fused to one or more benzene rings and may be partially saturated. Furthermore, heteroaryl as used herein includes one or more heteroaryl groups or heteroaryl groups linked to an aryl group by a single bond. Examples of heteroaryl groups include: monocyclic heteroaryl groups such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl

Azolyl group,

Azolyl group,

Oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinylPyrimidinyl and pyridazinyl; and fused cyclic heteroaryl groups such as benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl

Azolyl, benzo

Azolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cyclinyl, quinazolinyl, quinoxalinyl, carbazolyl, thiophene

Oxazinyl, phenanthridinyl and benzodioxolyl.

As used herein, "halogen" includes F, Cl, Br, and I atoms.

As used herein, "(3-to 7-membered) heterocycloalkyl" means a cycloalkyl group having 3 to 7 ring backbone atoms and containing one or more heteroatoms selected from B, N, O, S, P (═ O), Si, and P, preferably one or more heteroatoms selected from O, S and N, for example pyrrolidine, oxathiolane, tetrahydropyran, and the like.

According to one embodiment, in the compound of formula 1, R₁To R₄Each independently hydrogen, a halogen atom, a cyano group, or an unsubstituted or halogen atom-substituted alkyl group having 1 to 6 carbon atoms, and a, b, c, and d are each an integer of 0 to 2.

According to one embodiment, in the compound of formula 1, R₁To R₄May each independently be hydrogen, methyl, trifluoromethyl, F, Cl, or cyano, and a, b, c, and d may each be an integer of 0 to 2.

According to one embodiment, the diamine compound of formula 1 may be selected from the compounds of the following structural formula, but is not limited thereto.

According to one embodiment, the diamine compound of formula 1 may be selected from the compounds of the following structural formulae 1 to 16, but is not limited thereto.

As described above, the diamine compound of the present invention has a structure containing amine-substituted benzene rings located on both sides of the molecule and diphenyl sulfide (introduced-S-) at the center of the molecule. Therefore, when the diamine compound of the present invention is used as a polymerization component of a polyimide precursor, a film after curing may have improved heat resistance and mechanical properties and an improved refractive index after curing.

The method for preparing the diamine compound of formula 1 according to the present invention is not particularly limited, and may be prepared by synthetic methods known to those skilled in the art, for example, according to the following reaction scheme 1.

[ reaction scheme 1]

In reaction scheme 1, R₁、R₂、R₃、R₄A, b, c and d are the same as defined in formula 1, and Hal is a halogen atom.

Step 1 of reaction scheme 1 may be performed by reacting the reaction compound in a solvent such as N-methylpyrrolidone or tetrahydrofuran at an elevated temperature of 180 ℃ to 220 ℃ for 6 hours to 10 hours, such as 8 hours.

Steps 2 and 4 of reaction scheme 1 may be carried out as a reduction reaction by injecting hydrogen in the presence of a Pd/C catalyst, wherein ethanol or the like may be used as a solvent.

Step 3 of reaction scheme 1 may be performed by reacting the reaction compound at an elevated temperature of 100 to 130 ℃ for about 20 hours in the presence of a base such as Triethylamine (TEA), wherein toluene may be used as a solvent.

Further, the present invention provides a polyimide precursor (polyamic acid) prepared by polymerizing polymerization components including at least one diamine compound and at least one acid dianhydride, wherein the diamine compound includes the diamine compound of formula 1. Imidization of the polyimide precursor may be performed to obtain the desired polyimide.

As the acid anhydride used for the polymerization reaction, for example, tetracarboxylic dianhydride can be used. For example, the tetracarboxylic dianhydride includes a tetracarboxylic dianhydride comprising an aliphatic, alicyclic or aromatic tetravalent organic group or a combination thereof in the molecule, wherein the aliphatic, alicyclic or aromatic tetravalent organic groups are linked to each other via a crosslinking structure. Preferably, the tetracarboxylic dianhydride comprises an acid dianhydride comprising the structure: having a monocyclic or polycyclic aromatic group, a monocyclic or polycyclic cycloaliphatic group, or two or more of them linked by a single bond or a functional group. Alternatively, the tetracarboxylic dianhydride may include a tetracarboxylic dianhydride comprising a rigid structure (e.g., a tetravalent organic group having an aliphatic ring or an aromatic ring), wherein each ring is a single ring structure, each ring is fused to form a heterocyclic structure, or two or more rings are connected to each other by a single bond.

For example, the tetracarboxylic dianhydride may comprise a tetravalent organic group selected from the following formulae 2a to 2 e:

[ formula 2a ]

[ formula 2b ]

[ formula 2c ]

[ formula 2d ]

[ formula 2e ]

In formulae 2a to 2e, R₁₁To R₁₇May each be independently selected from: a halogen atom selected from F, Cl, Br and I; a hydroxyl group; a thiol group (-SH); a nitro group; a cyano group; an alkyl group having 1 to 10 carbon atoms; haloalkoxy having 1 to 10 carbon atoms; a haloalkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 20 carbon atoms, a1 may be an integer of 0 to 2, a2 may be an integer of 0 to 4, a3 may be an integer of 0 to 8, a4, a5, a6, a7, a8, and a9 may each independently be an integer of 0 to 3, a₁₁And A₁₂May each be independently selected from a single bond, -O-, -CR 'R "- (wherein 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, t-butyl, pentyl, etc.), and a haloalkyl group having 1 to 10 carbon atoms (e.g., trifluoromethyl, etc.)), -C (═ O) -, -C (═ O) O-, -C (═ O) NH-, -S-, -SO-, -and —)₂-、-O[CH₂CH₂O]_y- (y is an integer of 1 to 44), -NH (C ═ O) NH-, -NH (C ═ O) O-, monocyclic or polycyclic cycloalkylene having 6 to 18 carbon atoms (e.g., cyclohexylene and the like), monocyclic or polycyclic arylene having 6 to 18 carbon atoms (e.g., phenylene, naphthylene, fluorenylene and the like), and combinations thereof.

Further, the tetracarboxylic dianhydride may comprise a tetravalent organic group selected from the following formulas 3a to 3 n:

at least one hydrogen atom in the tetravalent organic group of formulae 3a to 3n may be substituted with a substituent selected from: a halogen atom selected from F, Cl, Br and I; a hydroxyl group; a thiol group; a nitro group; a cyano group; an alkyl group having 1 to 10 carbon atoms; haloalkoxy having 1 to 10 carbon atoms; haloalkyl having 1 to 10 carbon atoms; and an aryl group having 6 to 20 carbon atoms. For example, the halogen atom may be F, and the haloalkyl group may be a fluoroalkyl group having 1 to 10 carbon atoms containing a fluorine atom, selected from a fluoromethyl group, a perfluoroethyl group, a trifluoromethyl group, and the like. The alkyl group may be selected from methyl, ethyl, propyl, isopropyl, t-butyl, pentyl and hexyl, and the aryl group is selected from phenyl and naphthyl. More preferably, the substituent may be a fluorine atom or a substituent containing a fluorine atom (e.g., fluoroalkyl group).

According to one embodiment, in the polymerization of the polyimide precursor, one or more additional diamine compounds may be used in addition to the diamine compound of formula 1. For example, the additional diamine compound may include a diamine compound comprising a divalent organic group selected from: a monocyclic or polycyclic aromatic divalent organic group having 6 to 24 carbon atoms, a monocyclic or polycyclic alicyclic divalent organic group having 6 to 18 carbon atoms, or a divalent organic group having two or more of them connected by a single bond or a functional group. Alternatively, the additional diamine compound may include a diamine compound comprising a divalent organic group having an aliphatic ring or an aromatic ring (wherein each ring is a single ring structure, each ring is fused to form a heterocyclic structure, or two or more rings are connected to each other by a single bond).

For example, the additional diamine compound may comprise a divalent organic group selected from the following formulas 4a to 4 e:

[ formula 4a ]

[ formula 4b ]

[ formula 4c ]

[ formula 4d ]

[ formula 4e ]

In formulae 4a to 4e, R₂₁To R₂₇May each be independently selected from: a halogen atom selected from F, Cl, Br and I; a hydroxyl group; a thiol group; a nitro group; a cyano group; an alkyl group having 1 to 10 carbon atoms; haloalkoxy having 1 to 10 carbon atoms; haloalkyl having 1 to 10 carbon atoms and aryl having 6 to 20 carbon atoms, A₂₁And A₂₂May be each independently selected from-O-, -CR 'R "- (wherein 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, t-butyl, pentyl, etc.), and a haloalkyl group having 1 to 10 carbon atoms (e.g., trifluoromethyl, etc.)), -C (═ O) -, -C (═ O) O-, -C (═ O) NH-, -S-, -SO-, -and —)₂-、-O[CH₂CH₂O]_y- (y is an integer of 1 to 44), -NH (C ═ O) NH-, -NH (C ═ O) O-, monocyclic or polycyclic cycloalkylene groups having 6 to 18 carbon atoms (e.g., cyclohexylene and the like), monocyclic or polycyclic arylene groups having 6 to 18 carbon atoms (e.g., phenylene, naphthyl, fluorenylene and the like), and combinations thereof, b1 is an integer of 0 to 4, b2 is an integer of 0 to 6, b3 is an integer of 0 to 3, b4 and b5 are each independently an integer of 0 to 4, b7 and b8 are each independently an integer of 0 to 4And b6 and b9 are each independently an integer of 0 to 3.

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

alternatively, the additional diamine compound may comprise a divalent organic group in which an aromatic ring or an aliphatic structure forms a rigid chain structure, for example, a divalent organic group having an aliphatic ring or an aromatic ring (in which each ring is a single ring structure, each ring is connected by a single bond, or each ring is fused to form a heterocyclic structure).

According to one embodiment of the present invention, the reaction molar ratio of the total tetracarboxylic dianhydride to the diamine may be 1:1.1 to 1.1: 1. In order to improve the reactivity and the processability, it is preferable that the total tetracarboxylic dianhydride is reacted in an excess amount with respect to the diamine compound, or the diamine compound is reacted in an excess amount with respect to the total tetracarboxylic dianhydride.

According to one embodiment of the present invention, the tetracarboxylic dianhydride and the diamine compound may be reacted in 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 by a conventional polymerization method of polyimide or a precursor thereof, for example, solution polymerization.

Organic solvents that may be used in the polymerization reaction may include: ketones such as gamma-butyrolactone, 1, 3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, and 4-hydroxy-4-methyl-2-pentanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers (cellosolves) such as 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 and triethylene glycol monoethyl ether; 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, diethylene glycol monoethyl ether acetateMethylpropionamide (DMPA), Diethylamide (DEPA), dimethylacetamide (DMAc), N-diethylacetamide, Dimethylformamide (DMF), Diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), N-dimethylmethoxyacetamide, dimethylsulfoxide, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, tetrahydrofuran, m-dimethyldiformylacetamide

Alkane, para-di

Alkane, 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy)]Ethers, Equamide M100 (3-methoxy-N, N-dimethylpropionamide, Idemitsu Kosan co., Ltd.), Equamide B100 (3-butoxy-N, N-dimethylpropionamide, Idemitsu Kosan co., Ltd.), etc., and these solvents may be used alone or as a mixture of two or more.

According to one embodiment, the organic solvent may have a boiling point of 300 ℃ or less and a positive partition coefficient Log P at 25 ℃, more specifically, a partition coefficient Log P of 0.01 to 3, or 0.01 to 2, or 0.01 to 1. The distribution coefficients may be calculated using an ACD/LogP module from the ACD/Percepta platform of ACD/Labs. The ACD/LogP module uses an algorithm based on QSPR (Quantitative Structure-Property Relationship) methodology that utilizes 2D molecular Structure.

A solvent having a positive partition coefficient Log P refers to a hydrophobic solvent. According to the studies of the present inventors, it was found that when a specific solvent having a positive partition coefficient Log P is used to prepare a polyimide precursor composition, an edge receding phenomenon (edge back phenomenon) is improved. Further, in the present invention, by using the solvent having the positive distribution coefficient Log P as described above, it is possible to control the edge receding phenomenon of the solution without using an additive (e.g., a leveling agent) for controlling the surface tension of the material and the smoothness of the coating film. Since no additional additives are used, quality and process problems (e.g., the presence of low molecular substances in the final product) can be eliminated and a polyimide film having uniform characteristics can be formed more efficiently.

For example, in the process of coating a polyimide precursor composition on a glass substrate, an edge receding phenomenon may occur due to shrinkage of a coating layer during curing or under a condition in which a coating solution is left to stand under a humid condition. The edge receding phenomenon of the coating solution may cause a variation in film thickness. Therefore, the film may be cracked or edge-cracked at the time of cutting due to lack of bending resistance of the film, resulting in problems of poor process processability and reduced yield.

In addition, when a fine foreign substance having polarity is introduced into the polyimide precursor composition applied on the substrate, for the polyimide precursor composition including the polar solvent having the negative partition coefficient Log P, sporadic coating cracks or thickness variation may occur depending on the position of the foreign substance due to the polarity of the foreign substance. In the case of using a hydrophobic solvent having a positive partition coefficient Log P, even when fine foreign substances having polarity are introduced, the occurrence of thickness variation due to cracking of the coating layer can be reduced or suppressed.

Specifically, in the polyimide precursor composition including a solvent having a positive Log P, the edge receding rate defined by the following equation 1 may be 0% to 0.1% or less.

[ equation 1]

Edge receding rate (%) [ (a-B)/a ] × 100

Wherein the content of the first and second substances,

a: the area of the polyimide precursor composition completely coated on the substrate (100mm x 100mm),

b: an area after an edge receding phenomenon from the edge of the substrate on which the polyimide precursor composition or the polyimide film is coated.

The edge receding phenomenon of the polyimide precursor composition and the polyimide film may occur within 30 minutes after the polyimide precursor composition solution is coated, and in particular, the film may be rolled up from the edge such that the thickness of the edge is thicker.

After the polyimide precursor composition is coated on a substrate and then allowed to stand for 10 minutes or more, for example, 40 minutes or more under a temperature of 20 ℃ to 30 ℃ and a humidity condition of 40% or more, more specifically, under a humidity condition of 40% to 80%, that is, each of 40%, 50%, 60%, 70% and 80%, the edge receding rate of the coated composition solution may be 0.1% or less, preferably 0.05%, more preferably almost 0%.

The edge receding rate as described above is maintained even after curing by heat treatment, and specifically, the edge receding rate may be 0.05% or less, more preferably almost 0%.

By solving this edge receding phenomenon, the polyimide precursor composition according to the present invention can obtain a polyimide film having more uniform characteristics, thereby further improving the yield of the manufacturing process.

Furthermore, the solvent used in the polymerization reaction may have a density, measured by the standard ASTM D1475, of 1g/cm³Or smaller. If the density is more than 1g/cm³The relative viscosity may increase and the process efficiency may decrease.

The polymerization reaction may be carried out in a flow of inert gas or nitrogen and may be carried out under anhydrous conditions.

The reaction temperature during the polymerization reaction may be-20 ℃ to 80 ℃, preferably 0 ℃ to 80 ℃. If the reaction temperature is too high, the reactivity may become high and the molecular weight may become large, and the viscosity of the precursor composition may increase, which may be disadvantageous in the process.

The polyimide precursor composition including the polyamic acid may be in the form of a solution dissolved in an organic solvent. For example, when the polyimide precursor is synthesized in an organic solvent, the solution may be the obtained reaction solution or may be obtained by diluting the reaction solution with another solvent. When the polyimide precursor is obtained as a solid powder, it may be dissolved in an organic solvent to prepare a solution.

According to one embodiment, the content of the composition may be adjusted by adding an organic solvent such that the total polyimide precursor content is 8 to 25 wt%, preferably 10 to 25 wt%, more preferably 10 to 20 wt%. The polyimide precursor composition may be adjusted to have a viscosity of 3,000cP or more and 10,000cP or less, preferably 4,000cP or more and 9,000cP or less, more preferably 4,000cP or more and 8,000cP or less. When the viscosity of the polyimide precursor composition exceeds 10,000cP, defoaming efficiency during processing of the polyimide film is reduced. This not only results in a decrease in the efficiency of the process, but also the surface roughness of the produced film is deteriorated due to the generation of bubbles. This may cause deterioration of electrical, optical, and mechanical characteristics.

Then, a polyimide precursor resulting from the polymerization reaction may be imidized by chemical imidization or thermal imidization to prepare a transparent polyimide film.

According to one embodiment, a polyimide film may be manufactured by a method including:

applying a polyimide precursor composition to a carrier substrate; and

the applied polyimide precursor composition is heated and cured.

As the carrier substrate, a glass substrate, a metal substrate, a plastic substrate, or the like can be used without any particular limitation. Among them, a glass substrate may be preferable, which is excellent in thermal stability and chemical stability during imidization and curing processes for a polyimide precursor, and can be easily separated even without any treatment with an additional release agent, while not damaging a polyimide film formed after curing.

The application process can be carried out according to conventional application methods. Specifically, a spin coating method, a bar coating method, a roll coating method, an air knife method, a gravure printing method, a reverse roll method, a kiss roll method, a doctor blade method, a spray method, a dipping method, a brush coating method, or the like can be used. Among them, it is more preferable to carry out by a casting method which allows a continuous process and can improve the imidization rate of polyimide.

Further, the polyimide precursor composition may be applied on the substrate in a thickness range such that the finally produced polyimide film has a thickness suitable for a display substrate. For example, the polyimide precursor composition may be applied in an amount such that the thickness of the film is from 10 μm to 30 μm.

After the polyimide precursor composition is applied, a drying process for removing the solvent remaining in the polyimide precursor composition may be optionally performed before the curing process.

The drying process may be carried out according to a conventional method. Specifically, the drying process may be performed at a temperature of 140 ℃ or less, or 80 ℃ to 140 ℃. If the drying temperature is lower than 80 deg.C, the drying process becomes longer. If the drying temperature exceeds 140 ℃, imidization rapidly proceeds, making it difficult to form a polyimide film having a uniform thickness.

The polyimide precursor composition is then applied to a substrate and heat treated in an IR oven, in a hot air oven, or on a hot plate. The heat treatment temperature may be in the range of 280 ℃ to 500 ℃, preferably 300 ℃ to 450 ℃. The heat treatment may be performed in a multi-step heating process in the above temperature range. The heat treatment process may be performed for 20 minutes to 70 minutes, and preferably for 20 minutes to 60 minutes.

The residual stress immediately after curing of the polyimide film prepared as described above may be 40Mpa or less, and the residual stress change value after standing the polyimide film at 25 ℃ and 50% humidity for 3 hours may be 5Mpa or less.

The polyimide film may have a yellowness of 15 or less, and preferably 13 or less. Further, the haze of the polyimide film may be 2% or less, and preferably 1% or less.

Further, the polyimide film may have a transmittance at 450nm of 75% or more, a transmittance at 550nm of 85% or more, and a transmittance at 630nm of 90% or more.

The polyimide film may have high heat resistance, for example, the thermal decomposition temperature (Td — 1%) at which 1% mass loss occurs may be 500 ℃ or more.

The modulus of the polyimide film prepared as described above may be 0.1Gpa to 4 Gpa. When the modulus (elastic modulus) is less than 0.1GPa, the film has low rigidity and is easily broken by external impact. When the modulus exceeds 4GPa, the cover film (cover film) has excellent rigidity, but sufficient flexibility cannot be secured.

Further, the polyimide film may have an elongation of 20% or more, preferably 50% or more, and a tensile strength of 130Mpa or more, preferably 140Mpa or more.

In addition, the polyimide film according to the present invention may have excellent thermal stability against temperature change. For example, the polyimide film according to the present invention may have a coefficient of thermal expansion of-10 ppm/deg.C to 100 ppm/deg.C, preferably-7 ppm/deg.C to 90 ppm/deg.C, more preferably 80 ppm/deg.C or less after n +1 times (n is an integer of at least 0) heating and cooling processes within a temperature range of 100 deg.C to 350 deg.C.

Further, the thickness direction retardation (R) of the polyimide film according to the present invention_th) May be-150 nm to +150nm, preferably-130 nm to +130nm, to exhibit optical isotropy to improve visual sensitivity.

According to one embodiment, the adhesion force of the polyimide film to the carrier substrate may be 5gf/in or more, preferably 10gf/in or more.

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

In one embodiment, the flexible device may be manufactured by a method comprising:

applying a polyimide precursor composition on a carrier substrate and heating it to form a polyimide film, and then forming a device on the polyimide film; and

the polyimide film on which the device is formed is peeled from the carrier substrate.

The flexible device may be, for example, a thin film transistor, a Liquid Crystal Display (LCD), electronic paper, an organic EL display, a Plasma Display Panel (PDP), or an IC card.

EMBODIMENTS FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

< Synthesis example 1> preparation of Compound 1

Preparation of Compound 1-1

4-Fluoronitrobenzene (60g, 425mmol) and sodium sulfide (Na)₂S) (16g, 212mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (300mL) at 200 ℃ for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (600mL) was poured in, and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (400mL) and extracted with water (400 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (450mL) to obtain 49g of compound 1-1 (yield 85%).

Preparation of Compounds 1-2

Compound 1-1(49g, 177mmol) and 3 wt% (based on the weight of compound 1-1) of a Pd/C catalyst were stirred in an ethanol solvent (300mL), and then an 80% hydrazine solution (86mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (590mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 24g of compound 1-2 (yield 65%).

Preparation of Compounds 1-3

Compound 1-2(24g, 111mmol) and 4-nitrobenzoyl chloride (43g, 233mmol) were stirred in toluene solvent (300mL) while Triethylamine (TEA) (44g, 444mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (400mL) to obtain 42g of the compounds 1 to 3 (yield 75%).

Preparation of Compound 1

The compounds 1 to 3(42g, 81mmol) and 3 wt% (based on the weight of the compounds 1 to 3) of a Pd/C catalyst were stirred in an ethanol solvent (300mL), and then an 80% hydrazine solution (39mL) was slowly dropped into the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (350mL) to obtain 25g of compound 1 (yield 70%).

For C₂₆H₂₂N₄O₂S calculated HR LC/MS/MS M/z (M +): 454.1463, respectively; actually measuring: 454.1461

< Synthesis example 2> preparation of Compound 2

Preparation of Compound 2-1

2-chloro-5-nitrotoluene (60g, 350mmol) and sodium sulfide (Na)₂S) (13g, 175mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (300mL) at 200 deg.C for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (600mL) was poured in and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (550mL) and extracted with water (550 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (480mL) to obtain 43g of compound 2-1 (yield 82%).

Preparation of Compound 2-2

Compound 2-1(43g, 141mmol) and 3 wt% (based on the weight of compound 2-1) of a Pd/C catalyst were stirred in an ethanol solvent (440mL), and then an 80% hydrazine solution (68mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (500mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (330mL) to obtain 23g of compound 2-2 (yield 68%).

Preparation of Compounds 2-3

Compound 2-2(23g, 94mmol) and 4-nitrobenzoyl chloride (36g, 197mmol) were stirred in toluene solvent (350mL) while Triethylamine (TEA) (38g, 376mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (420mL) to obtain 40g of compound 2-3 (yield 80%).

Preparation of Compound 2

Compound 2-3(40g, 73mmol) and 3 wt% (based on the weight of compound 2-3) of Pd/C catalyst were stirred in an ethanol solvent (340mL), and then 80% hydrazine solution (35mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (500mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 26g of compound 2 (yield 75%).

For C₂₈H₂₆N₄O₂S calculated HR LC/MS/MS M/z (M +): 482.1776, respectively; actually measuring: 482.1779

< Synthesis example 3> preparation of Compound 3

Preparation of Compound 3-1

2-chloro-5-nitrobenzotrifluoride (60g, 266mmol) and sodium sulfide (Na)₂S) (10g, 133mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (460mL) at 200 ℃ for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (920mL) was poured in and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (550mL) and extracted with water (550 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (460mL) to obtain 45g of compound 3-1 (yield 83%).

Preparation of Compound 3-2

Compound 3-1(45g, 109mmol) and 3 wt% (based on the weight of compound 3-1) of a Pd/C catalyst were stirred in an ethanol solvent (360mL), and then an 80% hydrazine solution (53mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (410mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (320mL) to obtain 26g of compound 3-2 (yield 69%).

Preparation of Compound 3-3

Compound 3-2(26g, 73mmol) and 4-nitrobenzoyl chloride (28g, 155mmol) were stirred in toluene solvent (370mL) while Triethylamine (TEA) (29g, 295mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (430mL) to obtain 39g of compound 3-3 (yield 83%).

Preparation of Compound 3

Compound 3-3(39g, 59mmol) and 3 wt% (based on the weight of compound 3-3) of Pd/C catalyst were stirred in an ethanol solvent (400mL), and then 80% hydrazine solution (29mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (380mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 27g of compound 3 (yield 77%).

For C₂₈H₂₀F₆N₄O₂S calculated HR LC/MS/MS M/z (M +): 590.1211, respectively; actually measuring: 590.1210

< Synthesis example 4> preparation of Compound 4

Preparation of Compound 4-1

4-Nitro-thiophenol (30g, 193mmol), 2-chloro-5-nitrotoluene (33g, 193mmol) and calcium carbonate (32g) were heated and stirred in dimethyl sulfoxide (DMSO) solvent (400mL) at 190 ℃ for 6 hours. After stirring, the reaction was allowed to cool to room temperature, water (800mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (460mL) and extracted with water (460 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (500mL) to obtain 53g of compound 4-1 (yield 95%).

Preparation of Compound 4-2

Compound 4-1(53g, 182mmol) and 3 wt% (based on the weight of compound 4-1) of the Pd/C catalyst were stirred in an ethanol solvent (420mL), and then an 80% hydrazine solution (88mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (340mL) to obtain 27g of compound 4-2 (yield 66%).

Preparation of Compound 4-3

Compound 4-2(27g, 117mmol) and 4-nitrobenzoyl chloride (45g, 246mmol) were stirred in toluene solvent (400mL) while Triethylamine (TEA) (47g, 469mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (480mL) to obtain 47g of compound 4-3 (yield 76%).

Preparation of Compound 4

Compound 4-3(47g, 88mmol) and 3 wt% (based on the weight of compound 4-3) of the Pd/C catalyst were stirred in an ethanol solvent (400mL), and then an 80% hydrazine solution (43mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 30g of compound 4 (yield 74%).

For C₂₇H₂₄N₄O₂S calculated HR LC/MS/MS M/z (M +): 468.1620, respectively; actually measuring: 468.1622

< Synthesis example 5> preparation of Compound 5

Preparation of Compound 5-1

4-Nitro-thiophenol (25g, 161mmol), 2-chloro-5-nitrotrifluorotoluene (36g, 161mmol) and calcium carbonate (26g) were heated and stirred in dimethyl sulfoxide (DMSO) solvent (350mL) at 190 ℃ for 6 hours. After stirring, the reaction was allowed to cool to room temperature, water (700mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (600mL) and extracted with water (600 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (550mL) to obtain 54g of compound 5-1 (yield 98%).

Preparation of Compound 5-2

Compound 5-1(54g, 156mmol) and 3 wt% (based on the weight of compound 5-1) of Pd/C catalyst were stirred in an ethanol solvent (490mL), and then 80% hydrazine solution (76mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (500mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 29g of compound 5-2 (yield 67%).

Preparation of Compound 5-3

Compound 5-2(29g, 102mmol) and 4-nitrobenzoyl chloride (39g, 214mmol) were stirred in toluene solvent (400mL) while Triethylamine (TEA) (41g, 408mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (450mL) to obtain 48g of compound 5-3 (yield 82%).

Preparation of Compound 5

Compound 5-3(48g, 82mmol) and 3 wt% (based on the weight of compound 5-3) of Pd/C catalyst were stirred in an ethanol solvent (500mL), and then 80% hydrazine solution (40mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (500mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (360mL) to obtain 34g of compound 5 (yield 80%).

For C₂₇H₂₁F₃N₄O₂S calculated HR LC/MS/MS M/z (M +): 522.1337, respectively; actually measuring: 522.1334

< Synthesis example 6> preparation of Compound 6

Preparation of Compound 6-1

4-Nitro-thiophenol (30g, 193mmol), 2-chloro-5-nitrobenzonitrile (35g, 193mmol) and calcium carbonate (32g) were heated and stirred in dimethyl sulfoxide (DMSO) solvent (400mL) at 190 ℃ for 6 hours. After stirring, the reaction was allowed to cool to room temperature, water (800mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (600mL) and extracted with water (600 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (500mL) to obtain 51g of compound 6-1 (yield 89%).

Preparation of Compound 6-2

Compound 6-1(51g, 169mmol) and 3 wt% (based on the weight of compound 6-1) of Pd/C catalyst were stirred in an ethanol solvent (500mL), and then 80% hydrazine solution (82mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (500mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 26g of compound 6-2 (yield 65%).

Preparation of Compound 6-3

Compound 6-2(26g, 107mmol) and 4-nitrobenzoyl chloride (41g, 226mmol) were stirred in toluene solvent (400mL) while Triethylamine (TEA) (43g, 431mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (400mL) to obtain 44g of compound 6-3 (yield 76%).

Preparation of Compound 6

Compound 6-3(44g, 81mmol) and 3 wt% (based on the weight of compound 6-3) of the Pd/C catalyst were stirred in an ethanol solvent (400mL), and then an 80% hydrazine solution (39mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (500mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 25g of compound 6 (yield 65%).

For C₂₇H₂₁N₅O₂S calculated HR LC/MS/MS M/z (M +): 479.1416, respectively; actually measuring: 479.1420

< Synthesis example 7> preparation of Compound 7

Preparation of Compound 7-1

4-Fluoronitrobenzene (60g, 425mmol) and sodium sulfide (Na)₂S) (16g, 212mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (400mL) at 200 ℃ for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (800mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was removedDrying in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (500mL) to obtain 49g of compound 7-1 (yield 85%).

Preparation of Compound 7-2

Compound 7-1(49g, 177mmol) and 3 wt% (based on the weight of compound 7-1) of a Pd/C catalyst were stirred in an ethanol solvent (450mL), and then an 80% hydrazine solution (86mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 24g of compound 7-2 (yield 65%).

Preparation of Compound 7-3

Compound 7-2(24g, 111mmol) and 2-methyl-4-nitrobenzoyl chloride (46g, 233mmol) were stirred in toluene solvent (300mL) while Triethylamine (TEA) (44g, 444mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (450mL) to obtain 46g of compound 7-3 (yield 78%).

Preparation of Compound 7

Compound 7-3(46g, 84mmol) and 3 wt% (based on the weight of compound 7-3) of a Pd/C catalyst were stirred in an ethanol solvent (500mL), and then an 80% hydrazine solution (41mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 29g of compound 7 (yield 73%).

For C₂₈H₂₆N₄O₂S calculated HR LC/MS/MS M/z (M +): 482.1776, respectively; actually measuring: 482.1777

< Synthesis example 8> preparation of Compound 8

Preparation of Compound 8-1

4-fluoronitrobenzene (40g, 283mmol) and sodium sulfide (Na)₂S) (11g, 141mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (400mL) at 200 ℃ for 8 h. After stirring, the reaction was allowed to cool to room temperature, water (800mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (400mL) to obtain 33g of compound 8-1 (yield 85%).

Preparation of Compound 8-2

Compound 8-1(33g, 119mmol) and 3 wt% (based on the weight of compound 8-1) of the Pd/C catalyst were stirred in an ethanol solvent (380mL), and then 80% hydrazine solution (58mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (250mL) to obtain 16g of compound 8-2 (yield 65%).

Preparation of Compound 8-3

Compound 8-2(16g, 74mmol) and 4-nitro-2- (trifluoromethyl) benzoyl chloride (39g, 155mmol) were stirred in toluene solvent (400mL) while Triethylamine (TEA) (29g, 296mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (400mL) to obtain 39g of compound 8-3 (yield 82%).

Preparation of Compound 8

Compound 8-3(39g, 59mmol) and 3 wt% (based on the weight of compound 8-3) of Pd/C catalyst were stirred in an ethanol solvent (400mL), and then 80% hydrazine solution (29mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (250mL) to obtain 28g of compound 8 (yield 80%).

For C₂₈H₂₀F₆N₄O₂S calculated HR LC/MS/MS M/z (M +): 590.1211, respectively; actually measuring: 590.1210

< Synthesis example 9> preparation of Compound 9

Preparation of Compound 9-1

4-Fluoronitrobenzene (50g, 354mmol) and sodium sulfide (Na)₂S) (13g, 177mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (300mL) at 200 deg.C for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (600mL) was poured in and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (400mL) to obtain 41g of compound 9-1 (yield 85%).

Preparation of Compound 9-2

Compound 9-1(41g, 148mmol) and 3 wt% (based on the weight of compound 9-1) of a Pd/C catalyst were stirred in an ethanol solvent (400mL), and then an 80% hydrazine solution (72mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (260mL) to obtain 20g of compound 9-2 (yield 65%).

Preparation of Compound 9-3

Compound 9-2(20g, 92mmol) and 3-fluoro-4-nitrobenzoyl chloride (39g, 194mmol) were stirred in toluene solvent (400mL) while Triethylamine (TEA) (37g, 370mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (400mL) to obtain 40g of compound 9-3 (yield 80%).

Preparation of Compound 9

Compound 9-3(40g, 72mmol) and 3 wt% (based on the weight of compound 9-3) of the Pd/C catalyst were stirred in an ethanol solvent (400mL), and then an 80% hydrazine solution (35mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 27g of compound 9 (yield 77%).

For C₂₆H₂₀F₂N₄O₂S calculated HR LC/MS/MS M/z (M +): 490.1275, respectively; actually measuring: 490.1271

< Synthesis example 10> preparation of Compound 10

Preparation of Compound 10-1

4-fluoronitrobenzene (40g, 283mmol) and sodium sulfide (Na)₂S) (14g, 141mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (400mL) at 200 ℃ for 8 h. After stirring, the reaction was allowed to cool to room temperature, water (800mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (350mL) to obtain 33g of compound 10-1 (yield 85%).

Preparation of Compound 10-2

Compound 10-1(33g, 119mmol) and 3 wt% (based on the weight of compound 10-1) of a Pd/C catalyst were stirred in an ethanol solvent (370mL), and then an 80% hydrazine solution (58mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (230mL) to obtain 16g of compound 10-2 (yield 65%).

Preparation of Compound 10-3

Compound 10-2(16g, 74mmol) and 2-chloro-4-nitrobenzoyl chloride (34g, 155mmol) were stirred in toluene solvent (350mL) while Triethylamine (TEA) (29g, 296mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 31g of compound 10-3 (yield 74%).

Preparation of Compound 10

Compound 10-3(31g, 53mmol) and 3 wt% (based on the weight of compound 10-3) of a Pd/C catalyst were stirred in an ethanol solvent (320mL), and then an 80% hydrazine solution (25mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (300mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (260mL) to obtain 20g of compound 10 (yield 72%).

For C₂₆H₂₀Cl₂N₆O₂S calculated HR LC/MS/MS M/z (M +): 522.0684, respectively; actually measuring: 522.0685

< Synthesis example 11> preparation of Compound 11

Preparation of Compound 11-1

4-fluoronitrobenzene (40g, 283mmol) and sodium sulfide (Na)₂S) (11g, 141mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (370mL) at 200 deg.C for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (740mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (450mL) and extracted with water (450 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 33g of compound 11-1 (yield 85%).

Preparation of Compound 11-2

Compound 11-1(33g, 119mmol) and 3 wt% (based on the weight of compound 11-1) of a Pd/C catalyst were stirred in an ethanol solvent (350mL), and then an 80% hydrazine solution (58mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (300mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (240mL) to obtain 16g of compound 11-2 (yield 65%).

Preparation of Compound 11-3

Compound 11-2(16g, 74mmol) and 3, 5-dimethyl-4-nitrobenzoyl chloride (33g, 155mmol) were stirred in toluene solvent (350mL) while Triethylamine (TEA) (29g, 296mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (360mL) to obtain 33g of compound 11-3 (yield 80%).

Preparation of Compound 11

Compound 11-3(33g, 57mmol) and 3 wt% (based on the weight of compound 11-3) of a Pd/C catalyst were stirred in an ethanol solvent (410mL), and then an 80% hydrazine solution (28mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (310mL) to obtain 22g of compound 11 (yield 77%).

For C₃₀H₃₀N₄O₂S calculated HR LC/MS/MS M/z (M +): 510.2089, respectively; actually measuring: 510.2090

< Synthesis example 12> preparation of Compound 12

Preparation of Compound 12-1

2-chloro-5-nitrotoluene (60g, 350mmol) and sodium sulfide (Na)₂S) (13g, 175mmol) in N-Methyl-2-pyrrolidone (NMP) solvent (460mL) was heated and stirred at 200 ℃ for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (920mL) was poured in and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (470mL) to obtain 43g of compound 12-1 (yield 81%).

Preparation of Compound 12-2

Compound 12-1(43g, 141mmol) and 3 wt% (based on the weight of compound 12-1) of a Pd/C catalyst were stirred in an ethanol solvent (430mL), and then an 80% hydrazine solution (68mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (260mL) to obtain 23g of compound 12-2 (yield 68%).

Preparation of Compound 12-3

Compound 12-2(23g, 94mmol) and 2-methyl-4-nitrobenzoyl chloride (39g, 197mmol) were stirred in toluene solvent (380mL) while Triethylamine (TEA) (38g, 376mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (420mL) to obtain 43g of compound 12-3 (yield 81%).

Preparation of Compound 12

Compound 12-3(43g, 75mmol) and 3 wt% (based on the weight of compound 12-3) of the Pd/C catalyst were stirred in an ethanol solvent (390mL), and then 80% hydrazine solution (36mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 29g of compound 12 (yield 77%).

For C₃₀H₃₀N₄O₂S calculated HR LC/MS/MS M/z (M +): 510.2089, respectively; actually measuring: 510.2093

< Synthesis example 13> preparation of Compound 13

Preparation of Compound 13-1

2-chloro-5-nitrotoluene (50g, 292mmol) and sodium sulfide (Na)₂S) (11g, 146mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (370mL) at 200 deg.C for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (740mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (330mL) to obtain 36g of compound 13-1 (yield 81%).

Preparation of Compound 13-2

Compound 13-1(36g, 118mmol) and 3 wt% (based on the weight of compound 13-1) of a Pd/C catalyst were stirred in an ethanol solvent (350mL), and then an 80% hydrazine solution (57mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (220mL) to obtain 19g of compound 13-2 (yield 68%).

Preparation of Compound 13-3

Compound 13-2(19g, 77mmol) and 4-nitro-2- (trifluoromethyl) benzoyl chloride (41g, 163mmol) were stirred in toluene solvent (380mL) while Triethylamine (TEA) (31g, 311mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (400mL) to obtain 43g of compound 13-3 (yield 83%).

Preparation of Compound 13

Compound 13-3(43g, 63mmol) and 3 wt% (based on the weight of compound 13-3) of the Pd/C catalyst were stirred in an ethanol solvent (400mL), and then an 80% hydrazine solution (30mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 31g of compound 13 (yield 81%).

For C₃₀H₂₄F₆N₄O₂S calculated HR LC/MS/MS M/z (M +): 618.1524, respectively; actually measuring: 618.1521

< Synthesis example 14> preparation of Compound 14

Preparation of Compound 14-1

2-chloro-5-nitrobenzotrifluoride (50g, 222mmol) and sodium sulfide (Na)₂S) (8g, 111mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (460mL) at 200 ℃ for 8 h. After stirring, the reaction was allowed to cool to room temperature, water (920mL) was poured in and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer is optionally treated withThe mixture was dried over magnesium sulfate and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (380mL) to obtain 37g of compound 14-1 (yield 83%).

Preparation of Compound 14-2

Compound 14-1(37g, 89mmol) and 3 wt% (based on the weight of compound 14-1) of a Pd/C catalyst were stirred in an ethanol solvent (400mL), and then an 80% hydrazine solution (43mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (220mL) to obtain 21g of compound 14-2 (yield 69%).

Preparation of Compound 14-3

Compound 14-2(21g, 59mmol) and 4-nitro-2- (trifluoromethyl) benzoyl chloride (31g, 125mmol) were stirred in toluene solvent (300mL) while Triethylamine (TEA) (24g, 238mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (350mL) to obtain 38g of compound 14-3 (yield 83%).

Preparation of Compound 14

Compound 14-3(38g, 48mmol) and 3 wt% (based on the weight of compound 14-3) of a Pd/C catalyst were stirred in an ethanol solvent (400mL), and then an 80% hydrazine solution (23mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (350mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (260mL) to obtain 28g of compound 14 (yield 82%).

For C₃₀H₁₈F₁₂N₄O₂S calculated HR LC/MS/MS M/z (M +): 726.0959, respectively; actually measuring: 726.0960

< Synthesis example 15> preparation of Compound 15

Preparation of Compound 15-1

3-Nitro-thiophenol (25g, 161mmol), 1-chloro-3-nitrobenzene (25g, 161mmol) and calcium carbonate (26g) were heated and stirred in dimethyl sulfoxide (DMSO) solvent (300mL) at 190 ℃ for 6 hours. After stirring, the reaction was allowed to cool to room temperature, water (600mL) was poured in and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (380mL) to obtain 40g of compound 15-1 (yield 90%).

Preparation of Compound 15-2

Compound 15-1(40g, 144mmol) and 3 wt% (based on the weight of compound 15-1) of a Pd/C catalyst were stirred in an ethanol solvent (300mL), and then an 80% hydrazine solution (70mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (200mL) to obtain 20g of compound 15-2 (yield 66%).

Preparation of Compound 15-3

Compound 15-2(20g, 95mmol) and 4-nitro-2- (trifluoromethyl) benzoyl chloride (49g, 194mmol) were stirred in toluene solvent (450mL) while Triethylamine (TEA) (37g, 370mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (460mL) to obtain 47g of compound 15-3 (yield 79%).

Preparation of Compound 15

Compound 15-3(47g, 72mmol) and 3 wt% (based on the weight of compound 15-3) of the Pd/C catalyst were stirred in an ethanol solvent (440mL), and then an 80% hydrazine solution (35mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 31g of compound 15 (yield 75%).

For C₂₈H₂₀F₆N₄O₂S calculated HR LC/MS/MS M/z (M +): 590.1211, respectively; actually measuring: 590.1212

< Synthesis example 16> preparation of Compound 16

Preparation of Compound 16-1

4-Fluoronitrobenzene (50g, 354mmol) and sodium sulfide (Na)₂S) (13g, 177mmol) was heated and stirred in N-methyl-2-pyrrolidone (NMP) solvent (400mL) at 200 deg.C for 8 hours. After stirring, the reaction was allowed to cool to room temperature, water (800mL) was poured and the resulting solid was filtered. The filtered solid was dissolved in ethyl acetate (500mL) and extracted with water (500 mL). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (380mL) to obtain 41g of compound 16-1 (yield 85%).

Preparation of Compound 16-2

Compound 16-1(41g, 148mmol) and 3 wt% (based on the weight of compound 16-1) of a Pd/C catalyst were stirred in an ethanol solvent (390mL), and then an 80% hydrazine solution (72mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (200mL) to obtain 20g of compound 16-2 (yield 65%).

Preparation of Compound 16-3

Compound 16-2(20g, 95mmol) and 3-nitrobenzoyl chloride (35g, 194mmol) were stirred in toluene solvent (360mL) while Triethylamine (TEA) (37g, 370mmol) was added dropwise to the reaction at room temperature. The mixture was heated at 120 ℃ and stirred for 20 hours. After stirring, the reaction was cooled to room temperature and extracted with water and ethyl acetate (1: 1). The organic layer was dried over anhydrous magnesium sulfate, and the solvent was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (300mL) to obtain 36g of compound 16-3 (yield 76%).

Preparation of Compound 16

Compound 16-3(36g, 70mmol) and 3 wt% (based on the weight of compound 16-3) of the Pd/C catalyst were stirred in an ethanol solvent (400mL), and then 80% hydrazine solution (34mL) was slowly added dropwise to the stirred solution at room temperature, heated at 100 ℃ and stirred for 12 hours. After stirring, tetrahydrofuran solvent (400mL) was added to the reaction and the mixture was filtered through Celite to remove the catalyst. The solvent in the filtrate was dried in a vacuum distillation apparatus. After drying, recrystallization was performed in an ethanol solvent (200mL) to obtain 22g of compound 16 (yield 72%).

For C₂₆H₂₂N₄O₂S calculated HR LC/MS/MS M/z (M +): 454.1463, respectively; actually measuring: 454.1460

< example 1>

An organic solvent DEAc (N, N-diethylacetamide) (225mL) was charged into a reactor in a nitrogen stream, and then 45g (0.055mol) of the diamine compound 1 prepared in synthesis example 1 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which compound 1 was added, 16g (0.055mmol) of BPDA (biphenyl-tetracarboxylic dianhydride) as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< example 2>

An organic solvent DEAc (130mL) was charged into a reactor in a nitrogen stream, and then 26g (0.054mol) of the diamine compound 2 prepared in Synthesis example 2 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which the compound 2 was added, 15g (0.054mol) of BPDA as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< example 3>

An organic solvent DEAc (150mL) was charged into a reactor in a nitrogen stream, and then 27g (0.046mol) of the diamine compound 3 prepared in Synthesis example 3 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which the compound 3 was added, 13g (0.046mol) of BPDA as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< example 4>

An organic solvent DEAc (140mL) was charged into a reactor in a nitrogen stream, and then 28g (0.047mol) of the diamine compound 8 prepared in Synthesis example 8 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which the compound 8 was added, 13g (0.047mol) of BPDA as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< example 5>

An organic solvent DEAc (100mL) was charged into a reactor in a nitrogen stream, and then 20g (0.038mol) of the diamine compound 10 prepared in Synthesis example 10 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which compound 10 was added, 11g (0.038mol) of BPDA as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< example 6>

An organic solvent DEAc (140mL) was charged into a reactor in a nitrogen stream, and then 28g (0.038mol) of the diamine compound 14 prepared in Synthesis example 14 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which compound 14 was added, 11g (0.038mol) of BPDA as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< example 7>

An organic solvent DEAc (130mL) was charged into a reactor in a nitrogen stream, and then 26g (0.053mol) of the diamine compound 2 prepared in Synthesis example 2 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which the compound 2 was added, 11g (0.053mol) of pyromellitic dianhydride (PMDA) as an acid anhydride was added and stirred at the same temperature for 24 hours to obtain a polyimide precursor composition.

< example 8>

An organic solvent DEAc (140mL) was charged into a reactor in a nitrogen stream, and then 28g (0.047mol) of the diamine compound 8 prepared in Synthesis example 8 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which the compound 8 was added, 10g (0.047mol) of PMDA as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< example 9>

An organic solvent DEAc (100mL) was charged into a reactor in a nitrogen stream, and then 20g (0.034mol) of the diamine compound 10 prepared in Synthesis example 10 was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which compound 10 was added, 7g (0.034mol) of PMDA as an acid anhydride was added and stirred at the same temperature for 24 hours to obtain a polyimide precursor composition.

< comparative example 1>

An organic solvent DEAc (30mL) was charged into a reactor in a nitrogen stream, and then 6g (0.063mol) of p-Phenylenediamine (PDA) as a diamine compound was added to dissolve it while keeping the reactor temperature at 25 ℃. To the PDA-added solution, 18g (0.063mol) of BPDA as an acid anhydride was added and stirred at the same temperature for 24 hours to obtain a polyimide precursor composition.

< comparative example 2>

An organic solvent DEAc (110mL) was charged into a reactor in a nitrogen stream, and then 22g (0.071mol) of 2,2' -bis (trifluoromethyl) benzidine (TFMB) as a diamine compound was added to dissolve it while maintaining the reactor temperature at 25 ℃. To the solution to which TFMB was added, 15g (0.071mol) of PMDA as an acid anhydride was added and stirred for 24 hours at the same temperature to obtain a polyimide precursor composition.

< comparative example 3>

A polyimide precursor composition was obtained according to the same procedure as in example 1, except that the following control compound C in which the-NH- (C ═ O) -substituted benzene ring was not bonded at both ends of the molecule was used instead of the diamine compound 1.

< Experimental example 1>

Each of the polyimide precursor compositions (solutions) prepared in examples 1 to 9 and comparative examples 1 to 3 was spin-coated on a glass substrate. The glass substrate coated with each polyimide precursor solution was put into an oven, heated at a rate of 5 ℃/min, cured at 80 ℃ for 30 minutes and at 300 ℃ for 30 minutes to prepare each polyimide film.

< evaluation of characteristics of polyimide film >

1. Yellowness Index (YI)

The Yellowness Index (YI) was measured with a Color Eye 7000A.

2. Transmittance of light

The transmittance at a wavelength of 550nm was measured with a transmittance meter (model name HR-100, Murakami Color Research Laboratory) based on JIS K7105.

3. Refractive index

For each polyimide film prepared in experimental example 1, the refractive index at a wavelength of 532nm was measured using a prism coupler.

4. Glass transition temperature (Tg)

Each of the polyimide films obtained in experimental example 1 was cut into 5mm × 20mm to prepare a sample, and then the sample was loaded using an accessory of TMA (thermo-mechanical analyzer) (Q400, TA Instruments). The first warming step is carried out at a heating rate of 5 ℃/min from 100 ℃ to 350 ℃ and then the cooling step is carried out at a cooling rate of 4 ℃/min from 350 ℃ to 100 ℃. An inflection point shown by the temperature rising portion during the second temperature rising step is defined as Tg.

The yellowness index, transmittance, refractive index and Tg values of the polyimide film are shown in table 1 below.

[ Table 1]

As can be seen from table 1, it was found that the polyimide films (examples 1 to 9) prepared by using the polyimide precursor compositions comprising the novel diamine compounds according to the present invention had excellent light transmittance and yellowness index as a whole and improved refractive index, as compared to the polyimide films of comparative examples 1 to 3 prepared by using the polyimide precursor compositions comprising the same acid anhydride but the structure of the diamine compound was different from that of the diamine compound of the present invention.

While this invention has been particularly shown and described with references to particular embodiments thereof, it will be obvious to those skilled in the art that the particular description is of preferred embodiments only and that the scope of the invention is not limited thereto. It is therefore intended that the scope of the invention be defined by the following claims and their equivalents.

Claims (8)

1. A diamine compound of the following formula 1:

[ formula 1]

In the case of the above-mentioned formula 1,

z is-NH-,

R₁to R₄Each independently hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted haloalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, a substituted or unsubstituted arylsilyl groupA substituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, an amido group, a substituted or unsubstituted cycloalkyloxy group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamino group, an arylamino group having 1 to 30 carbon atoms, an arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted arylamino group, an arylamino group having a substituted or unsubstituted arylamino group, an arylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group, a substituted or an arylamino group, An ester group, an azide group, a nitro group, or a substituted or unsubstituted (3-to 30-membered) heteroaryl group containing at least one heteroatom selected from B, N, O, S, P (═ O), Si, and P, and

a. b, c and d are each an integer of 0 to 4, and when a, b, c and d are each an integer of 2 to 4, each of a, b, c and d is the same or different.

2. The diamine compound of formula 1 according to claim 1, wherein R₁To R₄Each independently hydrogen, a halogen atom, a cyano group, or an unsubstituted or halogen atom-substituted alkyl group having 1 to 6 carbon atoms, and a, b, c, and d are each an integer of 0 to 2.

3. The diamine compound of formula 1 according to claim 1, wherein R₁To R₄Each independently hydrogen, methyl, trifluoromethyl, F, Cl, or cyano, and a, b, c, and d are each integers from 0 to 2.

4. The diamine compound of formula 1 according to claim 1, wherein the diamine compound of formula 1 is selected from the group consisting of compounds of the following structural formulae 1 to 16:

5. a polyimide precursor prepared by polymerizing polymerization components comprising at least one diamine compound of formula 1 according to any one of claims 1 to 4 and at least one acid dianhydride.

6. The polyimide precursor according to claim 5, wherein the acid dianhydride comprises BPDA (biphenyl-tetracarboxylic acid dianhydride), PMDA (pyromellitic acid dianhydride), or a mixture thereof.

7. A polyimide film prepared from the polyimide precursor according to claim 5.

8. A flexible device comprising the polyimide film according to claim 7 as a substrate.