KR20210114880A - Diamine compound, polyimide-based polymer, polymer film, substrate for display device and optical device using the same - Google Patents

Abstract

The present invention relates to a diamine compound of a novel structure, and a polyimide-based polymer, a polymer film, a substrate and an optical device for a display device using the same. The diamine compound is represented by chemical formula 1. According to the present invention, the diamine compound can exhibit stable optical properties and excellent heat resistance.

Description

Diamine compound, polyimide-based polymer using the same, polymer film, substrate and optical device for display device

The present invention relates to a diamine compound for polyimide synthesis capable of implementing excellent transparency, high heat resistance, and low retardation, a polyimide-based polymer using the same, a polymer film, a substrate for a display device, and an optical device

The substrate market for display devices is rapidly changing mainly for flat panel displays (FPDs), which have a large area and can be thin and lightweight. Such flat panel displays include a liquid crystal display (LCD), an organic light emitting display (OLED), or an electrophoretic device.

In particular, in recent years, in order to further expand the applications and uses of the flat panel display, attention has been focused on a so-called flexible display device in which a flexible substrate is applied to the flat panel display. The application of such a flexible display device has been mainly reviewed for mobile devices such as smart phones, and its application fields are gradually being expanded and considered.

In particular, the aromatic polyimide resin is a polymer having an amorphous structure, and exhibits excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to a rigid chain structure, and may have flexibility applicable to flexible displays, / Widely used as an electronic material.

However, the polyimide resin has a dark brown color due to the formation of a charge transfer complex (CTC) of Pi-electrons in the imide chain, which makes it difficult to secure transparency. As the phase difference increases, there are limitations such as a decrease in optical properties, and thus, flexible electronic device technology has been developed to make inexpensive, easy-to-bend electronic devices and systems having excellent optical properties.

Specifically, as a diamine monomer compound used for synthesizing a polyimide resin, a method for reducing retardation by using a diamine compound capable of securing main chain flexibility and the like has been proposed.

However, polyimide introduced with a diamine compound capable of securing the flexibility of the main chain has a high coefficient of thermal expansion, and when it is used as a plastic substrate, there is a problem in that warpage occurs in the metal thin film formed on the plastic substrate.

Accordingly, there is a demand for the development of a diamine monomer compound for polyimide synthesis that can realize stable optical properties and excellent heat resistance at the same time.

An object of the present invention is to provide a diamine compound for synthesizing polyimide that can realize stable optical properties and excellent heat resistance at the same time.

In addition, the present invention is to provide a polyimide-based polymer synthesized from the diamine compound.

Another object of the present invention is to provide a polymer film using the polyimide-based polymer, a substrate for a display device, and an optical device.

In the present specification, a diamine compound having a structure represented by the following Chemical Formula 1 is provided.

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group,

i) _{at least one of L 1} to L ₄ is a monocyclic aromatic divalent functional group in which at least one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded, and the rest are each independent Or a substituted or unsubstituted aromatic divalent functional group,

ii) _{At least one of L 1} to L ₄ is an aromatic divalent functional group containing a fused polycyclic structure, and the rest are each independently a substituted or unsubstituted aromatic divalent functional group.

In the present specification, a polyimide-based polymer comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5) is is provided

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5, _{at least one of R 11} and R ₁₂ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen, and X ₁ to X- ₃ are the same as or different from each other, and are each independently a tetravalent functional group, Y _{1 To} Y _{3 Are} the same as or different from each other, and are each independently a divalent functional group represented by the following Chemical Formula 6,

[Formula 6]

In Formula 6, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, i) _{at least one of L 1} to L ₄ is an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group Any one selected from the group consisting of is a monocyclic aromatic divalent functional group bonded to one or more, the rest are each independently a substituted or unsubstituted aromatic divalent functional group, ii) at least one of _{L 1} to L _{4 is fused} It is an aromatic divalent functional group containing a polycyclic structure, and the remainder is each independently a substituted or unsubstituted aromatic divalent functional group.

In the present specification, there is also provided a polymer film comprising a cured product of the polyimide-based polymer.

In the present specification, there is also provided a substrate for a display device comprising the polymer film.

In the present specification, an optical device comprising the polymer film is also provided.

Hereinafter, a diamine compound, an acid anhydride compound, a polyimide-based polymer using the same, a polymer film, a substrate for a display device, and an optical device according to specific embodiments of the present invention will be described in more detail.

Unless explicitly stated herein, terminology is for the purpose of referring to specific embodiments only, and is not intended to limit the present invention.

As used herein, the singular forms also include the plural forms unless the phrases clearly indicate the opposite.

As used herein, the meaning of 'comprising' specifies a particular characteristic, region, integer, step, operation, element and/or component, and other specific characteristic, region, integer, step, operation, element, component, and/or group. It does not exclude the existence or addition of

And, in the present specification, terms including ordinal numbers such as 'first' and 'second' are used for the purpose of distinguishing one component from other components, and are not limited by the ordinal number. For example, within the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may be referred to as a first component.

In the present specification, the weight average molecular weight is determined using an Agilent mixed B column using an Aters alliance 2695 instrument, the evaluation temperature is 40 ° C, and Tetrahydrofuran as a solvent The flow rate was 1.0 mL/min, and the sample was prepared at a concentration of 1 mg/10 mL, and then supplied in an amount of 100 μL, and the value of Mw was obtained using a calibration curve formed using a polystyrene standard. The molecular weight of the polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

In the present specification, the term "substitution" means that another functional group is bonded instead of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent is substituted, is not limited, and when two or more substituted , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amide group; primary amino group; carboxyl group; sulfonic acid group; sulfonamide group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; alkoxysilylalkyl group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, aromatic is a characteristic that satisfies Huckel's Rule, and a case in which all of the following three conditions are satisfied according to the Huckel's rule may be defined as aromatic.

1) There must be 4n+2 electrons that are completely conjugated by empty p-orbitals, unsaturated bonds, and unpaired electron pairs.

2) 4n+2 electrons must form a planar isomer and form a ring structure.

3) All atoms of the ring must be able to participate in conjugation.

In the present specification, a multivalent functional group is a residue in a form in which a plurality of hydrogen atoms bonded to an arbitrary compound are removed, and may include, for example, a divalent functional group, a trivalent functional group, and a tetravalent functional group. For example, the tetravalent functional group derived from cyclobutane refers to a residue in which 4 hydrogen atoms bonded to cyclobutane are removed.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group is a monovalent functional group derived from an alkane, and may be straight-chain or branched, and the number of carbon atoms in the straight-chain alkyl group is not particularly limited, but is preferably 1 to 20. In addition, the number of carbon atoms of the branched chain alkyl group is 3 to 20. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl- propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2,6-dimethylheptan-4-yl, and the like. The alkyl group may be substituted or unsubstituted.

In the present specification, the haloalkyl group refers to a functional group in which a halogen group is substituted with the above-described alkyl group, and examples of the halogen group include fluorine, chlorine, bromine or iodine. The haloalkyl group may be substituted or unsubstituted.

In the present specification, the aryl group is a monovalent functional group derived from arene, and may be a monocyclic aryl group or a polycyclic aryl group. The monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto. The aryl group may be substituted or unsubstituted.

In the present specification, the heteroaryl group refers to an aryl group including at least one of O, N, Si and S as a heteroatom. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an acridyl group , pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group, indole group , carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, isoxazolyl group, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto. The hetero arylene group may be substituted or unsubstituted.

In the present specification, the arylene group is a divalent functional group derived from arene, and the description of the aryl group described above may be applied, except that these are divalent functional groups. For example, it may be a phenylene group, a biphenylene group, a terphenylene group, a naphthalene group, a fluorenyl group, a pyrenyl group, a phenanthrenyl group, a perylene group, a tetracenyl group, an anthracenyl group, and the like. The arylene group may be substituted or unsubstituted.

In the present specification, the hetero arylene group is an arylene group including at least one of O, N, Si and S, and the description of the heteroaryl group described above may be applied, except that it is a divalent functional group. The hetero arylene group may be substituted or unsubstituted.

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

means a bond connected to another substituent.

In the present specification, a direct bond or a single bond means that no atom or group of atoms is present at the corresponding position, and thus is connected by a bonding line.

I. diamine compound

According to an embodiment of the present invention, a diamine compound having a structure represented by Formula 1 may be provided.

The present inventors have found that when using an aromatic diamine containing a divalent functional group derived from Si substituted with a substituted or unsubstituted aromatic functional group as in Formula 1, as in the diamine compound of the embodiment, stable optical properties compared to conventional diamine compounds At the same time as this is implemented, it was confirmed through experiments that the heat resistance characteristics were greatly improved, and the invention was completed.

Specifically, as represented by Formula 1, the divalent functional group derived from Si substituted with a substituted or unsubstituted aromatic functional group has a bulky structure, so polyimide synthesized from the diamine compound of the embodiment Through three-dimensional structural transformation of polymers, excellent thermal stability can be secured through high glass transition temperature and low coefficient of thermal expansion.

In addition, as shown in Formula 1, the diamine compound of one embodiment uses an aromatic diamine including four or more aromatic rings as a parent, thereby forming a bulkier structure compared to a phenylene diamine matrix that has been widely used in the prior art. Accordingly, the effect of improving thermal stability according to the three-dimensional structural transformation of the polyimide polymer synthesized from the diamine compound of the embodiment can be further increased, and the dihedral angle is increased due to the bulky structure. The refractive index in the thickness direction may increase while the directional refractive index decreases.

That is, the polyimide polymer synthesized from the diamine compound of the embodiment has a decrease in the refractive index in the plane direction and a decrease in the birefringence as the refractive index in the thickness direction increases.

Looking at the diamine compound of the embodiment in more detail, it may have a structure represented by Formula 1 above.

In Formula 1, Ar ₁ and Ar ₂ may each independently be a substituted or unsubstituted aromatic monovalent functional group.

In addition, in Formula 1, i) _{at least one of L 1} to L ₄ is a monocyclic aromatic divalent in which at least one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded. functional group, and the rest are each independently a substituted or unsubstituted aromatic divalent functional group, or ii) _{at least one of L 1} to L ₄ is an aromatic divalent functional group containing a fused polycyclic structure, and the rest are each independently substituted or It may be an unsubstituted aromatic divalent functional group.

That is, the diamine compound according to an embodiment of the present invention has a structure represented by Formula 1, in Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, and L ₁ to At least one of L ₄ is a monocyclic aromatic divalent functional group to which one or more selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded, and the rest are each independently substituted or unsubstituted It may be an aromatic divalent functional group.

Alternatively, the diamine compound according to an embodiment of the present invention has a structure represented by Formula 1, in Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, and L ₁ to At least one of L ₄ may be an aromatic divalent functional group containing a fused polycyclic structure, and the rest may each independently be a substituted or unsubstituted aromatic divalent functional group.

As described above _{, at least one of L 1} to L ₄ is a monocyclic aromatic divalent functional group in which at least one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded, and the rest are When each independently a substituted or unsubstituted aromatic divalent functional group, L ₁ to L ₄ are all unsubstituted Compared with the case of a monocyclic aromatic divalent functional group, a technical effect of improving transparency while preventing conjugation of aromatics may be realized.

The type of the monocyclic aromatic divalent functional group is not particularly limited, but may be, for example, a monocyclic aromatic divalent functional group having 5 or more carbon atoms. More specifically, the monocyclic aromatic divalent functional group may be one of a phenylene group, a pyrimidylene group, and a pyridylene group, and preferably a phenylene group.

The type of the substituted or unsubstituted aromatic divalent functional group is not particularly limited, but may be, for example, an aromatic divalent functional group having 5 or more carbon atoms. More specifically, the aromatic divalent functional group may be one of a phenylene group, a pyrimidylene group, and a pyridylene group, and preferably a phenylene group.

More specifically, in Formula 1, _{at least one of L 1} to L ₄ is a monocyclic aromatic divalent functional group to which at least one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded. , and the rest are each independently a substituted or unsubstituted aromatic divalent functional group, the structure represented by Formula 1 may include a structure represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1, Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted aromatic monovalent functional group, and T ₁ to T ₄ are each independently an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group. Any one selected from the group consisting of, m1 to m4 are each independently an integer of 0 to 4, and (m1+m2+m3+m4)≥1.

In Formula 1-1, as (m1+m2+m3+m4)≥1, at least one monocyclic aromatic divalent functional group in the diamine compound including the structure represented by Formula 1-1 is an alkyl group, It may be a monocyclic aromatic divalent functional group in which at least one selected from the group consisting of a rosen group, an alkoxy group, a haloalkyl group and a cyano group is bonded.

In Formula 1-1, as (m1+m2+m3+m4)≥1, L ₁ to L ₄ are all unsubstituted Compared with the case of a monocyclic aromatic divalent functional group, a technical effect of improving transparency while preventing conjugation of aromatics may be realized.

In one embodiment of the invention, in the structure represented by Formula 1-1, m1 to m4 may each independently be an integer of 0 or 1. That is, in the diamine compound of one embodiment including the structure represented by Formula 1-1, _{at least one of L 1} to L ₄ in Formula 1 is an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group. Any one selected from the group consisting of one may be a monocyclic aromatic divalent functional group bonded to one, and the remainder may be each independently a substituted or unsubstituted aromatic divalent functional group.

When m1 to m4 are each independently an integer of 0 or 1, the structure represented by Formula 1-1 may include any one of structures represented by Formulas 1-a to 1-c below.

[Formula 1-a]

[Formula 1-b]

[Formula 1-c]

In Formula 1-a to Formula 1-c, Ar _{5 To} Ar ₁₀ is each independently a substituted or unsubstituted aromatic monovalent functional group, T ₁ ' to T ₄ ' and T ₁ ” to T ₄ ” are each independently an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group Any one selected from the group consisting of.

That is, in the diamine compound of one embodiment including the structure represented by Formula 1-a, in Formula 1, L ₁ to L ₄ is any one selected from the group consisting of an alkoxy group, a haloalkyl group, and a cyano group. It may be a monocyclic aromatic divalent functional group bonded together.

In addition, in the diamine compound of one embodiment including the structure represented by Formula 1-b, in Formula 1, L ₁ and L ₄ are each independently a substituent selected from the group consisting of an alkoxy group, a haloalkyl group and a cyano group. is a monocyclic aromatic divalent functional group to which one is bonded, and L ₂ and L ₃ may each independently be a substituted or unsubstituted aromatic divalent functional group.

In addition, in the diamine compound of one embodiment including the structure represented by Formula 1-c, in Formula 1, L ₂ and L ₃ are each independently a substituent selected from the group consisting of an alkoxy group, a haloalkyl group and a cyano group. is a monocyclic aromatic divalent functional group bonded to one, and L ₁ and L ₄ may each independently be a substituted or unsubstituted aromatic divalent functional group.

.As described above, in Formula 1, _{at least one of L 1} to L ₄ is a monocyclic aromatic divalent functional group to which one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded. and the rest are each independently a substituted or unsubstituted aromatic divalent functional group, the structure represented by Formula 1-1 may be any one selected from the group consisting of the following compounds.

.

In an embodiment of the present invention, in the structure represented by Formula 1-1, m1 to m4 may each independently be an integer of 0 or 2. That is, in the diamine compound of one embodiment including the structure represented by Formula 1-1, _{at least one of L 1} to L ₄ in Formula 1 is an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group. Any one selected from the group consisting of two may be a monocyclic aromatic divalent functional group bonded to two, and the remainder may be each independently a substituted or unsubstituted aromatic divalent functional group.

When m1 to m4 are each independently an integer of 0 or 2, the structure represented by Formula 1-1 may include any one of structures represented by Formulas 1-d to 1-f below.

[Formula 1-d]

[Formula 1-e]

[Formula 1-f]

In Formula 1-d to Formula 1-f, Ar ₅ ' to Ar ₁₀ ′ is each independently a substituted or unsubstituted aromatic monovalent functional group, and T ₅ to T ₁₂ and T ₅ ′ to T ₁₂ ′ are each independently an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group. Any one selected from the group consisting of.

That is, in the diamine compound of one embodiment including the structure represented by Formula 1-d, in Formula 1, L ₁ to L ₄ is any one selected from the group consisting of an alkoxy group, a haloalkyl group and a cyano group 2 It may be a monocyclic aromatic divalent functional group bonded together.

In addition, in the diamine compound of one embodiment including the structure represented by Formula 1-e, in Formula 1, L ₁ and L ₄ are each independently selected from the group consisting of an alkoxy group, a haloalkyl group and a cyano group. One is a monocyclic aromatic divalent functional group in which two are bonded, and L ₂ and L ₃ may each independently be a substituted or unsubstituted aromatic divalent functional group.

In addition, in the diamine compound of one embodiment including the structure represented by Formula 1-f, in Formula 1, L ₂ and L ₃ are each independently selected from the group consisting of an alkoxy group, a haloalkyl group and a cyano group. One is a monocyclic aromatic divalent functional group in which two are bonded, and L ₁ and L ₄ may each independently be a substituted or unsubstituted aromatic divalent functional group.

Meanwhile, the structure represented by Formula 1-1 may include a structure represented by Formula 1-2 below.

[Formula 1-2]

In Formula 1-2, Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted aromatic monovalent functional group, and T ₁ to T ₄ are each independently an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group. Any one selected from the group consisting of, m1 to m4 are each independently an integer of 0 to 4, and (m1+m2+m3+m4)≥1.

That is, in the diamine compound of one embodiment including the structure represented by Formula 1-2, in Formula 1, L ₁ to L ₄ is any one selected from the group consisting of an alkoxy group, a haloalkyl group and a cyano group. It may be a phenylene group bonded to more than one.

Meanwhile, in the structure represented by Chemical Formula 1, _{at least one of L 1} to L ₄ may be a divalent functional group represented by the following Chemical Formula 2, and the rest may each independently be a substituted or unsubstituted aromatic divalent functional group.

[Formula 2]

In Formula 2, R ₁ and R ₂ are each independently any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group.

That is, as described above, _{at least one of L 1} to L ₄ in Formula 1 is a monocyclic aromatic 2 in which any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded to two is a functional group, and the remainder is a substituted or unsubstituted aromatic divalent functional group, each independently selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group. The aromatic divalent functional group may be a divalent functional group represented by Formula 2 above.

As described above, in Formula 1, _{at least one of L 1} to L ₄ is a monocyclic aromatic divalent functional group in which any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded to two and the rest are each independently a substituted or unsubstituted aromatic divalent functional group, the structure represented by Formula 1-1 may be any one selected from the group consisting of the following compounds.

.

.

According to another embodiment of the present invention, in Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, and _{at least one of L 1} to L ₄ contains a fused polycyclic structure. An aromatic divalent functional group, and the remainder may each independently be a substituted or unsubstituted aromatic divalent functional group.

The aromatic divalent functional group containing the fused polycyclic structure is a naphthylene group, an anthracenylene group, a fluorenylene group, a phenanthrylene group, a pyrenylene group, a dibenzofuranylene group, a dibenzothiophenylene group, and a carbazolnylene group. , and may be any one selected from the group consisting of a thiophenylene group, preferably a naphthylene group.

Specifically, the aromatic divalent functional group containing the fused polycyclic structure may be a naphthylene group represented by the following Chemical Formula 10 or Chemical Formula 11.

[Formula 10]

[Formula 11]

.

.

In addition, in Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, _{at least one of L 1} to L ₄ is an aromatic divalent functional group containing a fused polycyclic structure, and the rest are each independently a substituted or unsubstituted aromatic divalent functional group, in the structure represented by Formula 1, L ₁ and L ₄ are each independently an aromatic divalent functional group containing a fused polycyclic structure, L ₂ and L ₃ may each independently be a substituted or unsubstituted aromatic divalent functional group.

In Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, and _{at least one of L 1} to L ₄ is an aromatic divalent functional group containing a fused polycyclic structure, the formula The structure represented by 1 may include a diamine compound represented by the following compound.

.

.

As described below, the diamine compound of one embodiment may be reacted with a tetracarboxylic dianhydride compound to synthesize a polyamic acid or polyamic acid ester polymer, and a polyimide may be obtained through a heat treatment reaction for the polyamic acid or polyamic acid ester polymer. can be synthesized. That is, the diamine compound of the embodiment may be applied for polyimide-based polymer synthesis. In this case, the polyimide-based polymer means a polyimide, including all of polyamic acid and polyamic acid ester, which are precursor polymers thereof.

As described below, the diamine compound of one embodiment may be reacted with a tetracarboxylic dianhydride compound to synthesize a polyamic acid or polyamic acid ester polymer, and a polyimide may be obtained through a heat treatment reaction for the polyamic acid or polyamic acid ester polymer. can be synthesized. That is, the diamine compound of the embodiment may be applied for polyimide-based polymer synthesis. In this case, the polyimide-based polymer means a polyimide, including all of polyamic acid and polyamic acid ester, which are precursor polymers thereof.

II. Polyimide-based polymer

On the other hand, according to another embodiment of the invention, comprising at least one repeating unit selected from the group consisting of the repeating unit represented by the formula (3), the repeating unit represented by the formula (4), and the repeating unit represented by the formula (5), A polyimide-based polymer may be provided.

The polyimide-based polymer means a polyimide, including all of polyamic acid and polyamic acid ester, which are precursor polymers thereof. That is, the polyimide-based polymer may include at least one selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit. That is, the polyimide-based polymer may include one polyamic acid repeating unit, one polyamic acid ester repeating unit, one polyimide repeating unit, or a copolymer in which two or more repeating units thereof are mixed.

Specifically, the polyimide repeating unit includes a repeating unit represented by Formula 3, the polyamic acid ester repeating unit includes a repeating unit represented by Formula 4, and the polyamic acid repeating unit is represented by Formula 5 It may include the indicated repeating unit.

At least one repeating unit selected from the group consisting of the polyamic acid repeating unit, the polyamic acid ester repeating unit, and the polyimide repeating unit may form the main chain of the polyimide-based polymer.

The polyimide-based polymer may include a combination of the diamine compound and tetracarboxylic dianhydride compound of the embodiment. The repeating unit represented by Formula 3, the repeating unit represented by Formula 4, and the repeating unit represented by Formula 5 included in the polyimide-based polymer is a reaction between the diamine compound and tetracarboxylic acid or anhydride compound of the one embodiment It may be a repeating unit contained in the compound obtained by

More specifically, by the reaction of the terminal amino group (-NH ₂ ) of the diamine compound of one embodiment and the terminal anhydride group (-OC-O-CO-) of the tetracarboxylic acid or anhydride compound thereof, the nitrogen atom of the amino group and the carbon source of the anhydride group Interterminal bonds may be formed.

Therefore, in the polyimide-based polymer of another embodiment, the effect of the diamine compound of the embodiment can be realized as it is, and specifically, it contains the repeating units of Chemical Formulas 3 to 5 derived from the diamine compound of the embodiment. As the polyimide-based polymer includes a divalent functional group derived from the diamine compound of the embodiment as shown in Chemical Formula 5, stable optical properties can be realized and heat resistance properties can be greatly improved.

In addition, as it has a bulky structure as shown in Chemical Formula 6, excellent thermal stability can be secured through a high glass transition temperature and a low coefficient of thermal expansion through three-dimensional structural transformation of the polyimide polymer.

In Formula 4, _{at least one of R 11} and R ₁₂ may be an alkyl group having 1 to 10 carbon atoms, and the rest may be hydrogen. That is, in Formula 4, R ₁₁ may be an alkyl group having 1 to 10 carbon atoms, and R ₁₂ may be hydrogen. In addition, in Formula 4, R ₁₂ may be an alkyl group having 1 to 10 carbon atoms, and R ₁₁ may be hydrogen. In addition, in Formula 4, R ₁₁ and R ₁₂ may be an alkyl group having 1 to 10 carbon atoms.

Meanwhile, in Formulas 3 to 5, X ₁ to X ₃ may be the same as or different from each other, and may each independently be a tetravalent functional group. Wherein X ₁ to X ₃ may be a functional group derived from polyamic acid, polyamic acid ester, or tetracarboxylic acid or anhydride compound thereof used in synthesizing polyimide.

More specifically, X ₁ to X ₃ may each independently be one of a tetravalent functional group represented by the following Chemical Formula 7 or a tetravalent functional group represented by the following Chemical Formula 8.

[Formula 7]

In Formula 7, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, i) L ₁ and L ₄ are each independently a monocyclic aromatic trivalent functional group, and L ₂ and L ₃ are Each independently is a monocyclic aromatic divalent functional group, and at least one of the aromatic trivalent functional group and the aromatic divalent functional group is one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group. It is a monocyclic aromatic functional group bonded above, and the rest are each independently an unsubstituted aromatic functional group,

ii) L ₁ and L ₄ are each independently an aromatic divalent functional group containing a fused polycyclic structure, L ₂ and L ₃ are each independently a substituted or unsubstituted aromatic divalent functional group,

[Formula 8]

In Formula 8, R ₁₆ to R ₂₁ are each independently hydrogen or one of an alkyl group having 1 to 10 carbon atoms, and L ₁ is a direct bond, -O-, -CO-, -S-, -SO-, - SO ₂ -, -CR ₂₂ R ₂₃ -, -CONH-, -COO-, -(CH ₂ ) _t -, -O(CH ₂ ) _t O-, -COO-(CH ₂ ) _t -OCO-, electron The attracting group is any one selected from the group consisting of substituted or unsubstituted phenylene or a combination thereof, and R ₂₂ and R ₂₃ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. and t is an integer from 1 to 10.

Meanwhile, in Formulas 3 to 5, Y ₁ to Y ₃ may be the same as or different from each other, and may each independently be a divalent functional group represented by Formula 6 above. The Y ₁ to Y ₃ may be a functional group derived from the diamine compound of the embodiment used in synthesizing polyamic acid, polyamic acid ester, or polyimide. More specifically, Y ₁ to Y ₃ may correspond to a divalent functional group derived from Chemical Formula 1, which is the structure of the diamine compound of the embodiment, and may include all of the contents described above in the embodiment.

The weight average molecular weight (measured by GPC) of the polyimide-based polymer is not particularly limited, but may be, for example, 10000 g/mol to 200000 g/mol.

In addition, the polyimide-based polymer has a glass transition temperature of 115°C or higher, or 120°C or higher.

The polyimide-based polymer according to the present invention can exhibit excellent thermal stability and optical properties while maintaining properties such as mechanical strength due to a rigid structure, and thus can be used as a substrate for a device, a cover substrate for a display, or an optical film. , IC (integrated circuit) package, electrodeposition film, multi-layer flexible printed circuit (FRC), tape, touch panel, protective film for optical disk, etc. can do.

Examples of the method for synthesizing the polyimide-based polymer are not particularly limited, but, for example, tetracarboxylic acid or anhydride thereof, for example, pyromellitic acid, which is commonly used in the preparation of polyamic acid with the diamine compound of the embodiment pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (3,3',4,4'-Biphenyl Tetracarboxylic Acid Dianhydride, BPDA), 1,2,4, 5-cyclohexanetetracarboxylic acid dianhydride (1,2,4,5-Cyclohexanetetracarboxylic Dianhydride, HPMDA), 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic acid dianhydride (DMCBDA), or their A polymer consisting of an amic acid, an amic acid ester, or a mixture thereof may be prepared by reacting with a mixture of two or more types thereof.

Or, if necessary, one or more types of diamine compounds of various types widely known in general together with the diamine compound of the embodiment, for example, p-phenylenediamine, 4,4-oxydianiline, 4,4'-methylene A polyamic acid copolymer, a polyamic acid ester copolymer, and a polyimide copolymer can be prepared by simultaneously mixing dianiline and the like. In addition, together with the diamine compound of the above embodiment, one or more types of widely known diamine compounds, for example, p-phenylenediamine, 4,4-oxydianiline, 4,4'-methylenedianiline, etc. is separately used for polymerization and then mixed to prepare a polyamic acid polymer mixture, a polyamic acid ester polymer mixture, and a polyimide polymer mixture.

The reaction conditions may be appropriately adjusted with reference to the production conditions of polyamic acid known in the art, such as solution polymerization. Specifically, it can be prepared by dissolving diamine in an organic solvent and then adding tetracarboxylic acid or anhydride thereof for polymerization. The reaction may be carried out under an inert gas or nitrogen stream, and may be carried out under anhydrous conditions. In addition, the polymerization reaction temperature may be carried out at -20 ℃ to 60 ℃, or 0 ℃ to 30 ℃.

In addition, the organic solvent that can be used for the polymerization reaction is specifically, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy- ketones such as 4-methyl-2-pentanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 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 , glycol ethers such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether (Cellosolve); Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propylene glycol, carbitol, dimethyl Acetamide (DMAc), N,N-diethylacetamide, dimethylformamide (DMF), diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 1,3-Dimethyl-2-imidazolidinone, N,N-dimethyl methoxyacetamide, dimethyl sulfoxide, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylurea, N-methylcaprolactam, tetrahydro Furan, m-dioxane, P-dioxane, 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-( 2-methoxyethoxy)] ether and mixtures thereof may be used.

On the other hand, by imidizing the amic acid, amic acid ester, or a mixture thereof obtained above, the repeating unit represented by Formula 2, the repeating unit represented by Formula 3, and the repeating unit represented by Formula 4 are grouped together. A polyimide-based polymer comprising one or more repeating units selected from may be prepared.

Specifically, the imidization process may be a chemical imidization method or a thermal imidization method. For example, after adding a dehydrating agent and an imidization catalyst to the polymerized polyamic acid or polyamic acid ester solution, it is imidized by a chemical reaction by heating to a temperature of 50 to 100 °C, or alcohol while refluxing the solution Polyimide can be obtained by imidizing by removing

In the chemical imidization method, as the imidization catalyst, pyridine, triethylamine, picoline or quinoline may be used. In addition, N- of substituted or unsubstituted nitrogen-containing heterocyclic compounds and nitrogen-containing heterocyclic compounds an oxide compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic heterocyclic compound, in particular 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2- Lower alkylimidazoles such as methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, and 5-methylbenzimidazole; imidazoles such as N-benzyl-2-methylimidazole Dazole derivatives, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, substituted pyridines such as 4-n-propylpyridine, p-toluenesulfonic acid, etc. can also be used.

As said dehydrating agent, acid anhydrides, such as acetic anhydride, can be used.

Alternatively, the polyamic acid or polyamic acid ester solution may be applied to the substrate, and heat treatment may be performed in an oven or hot plate at 100° C. to 300° C., and multi-step heat treatment at various temperatures within the temperature range may be performed. .

Ⅲ. polymer film

Meanwhile, according to another embodiment of the present invention, a polymer film including a cured product of the polyimide-based polymer of the other embodiment may be provided. The cured product of the polyimide-based polymer refers to a material obtained through the curing process of the polyimide-based polymer. The content regarding the polyimide-based polymer may include all of the content described above in the other embodiments.

As described above, when a polyimide-based polymer including at least one selected from the group consisting of a polyamic acid repeating unit, a polyamic acid ester repeating unit, and a polyimide repeating unit is used, excellent transparency and stable heat resistance can be realized. A polymer film can be prepared.

The thickness of the polymer film is not particularly limited, but can be freely adjusted within, for example, 0.01 μm to 1000 μm. When the thickness of the polymer film increases or decreases by a specific value, physical properties measured in the polymer film may also change by a specific value.

The polymer film has a transmittance of 80% or more, 80% or more and 99% or less, 81% or more and 99% or less, or 81% or more and 87% or less in the range of 0.1 ± 0.05 μm in thickness. It may be a colorless transparent polymer film having a. By having excellent light transmittance as described above, it is possible to exhibit significantly improved transparency and optical properties.

In addition, the polymer film may have a coefficient of thermal expansion of 70.0 ppm/°C or less, and a birefringence of 0.005 or less.

Specifically, the polymer film has a coefficient of thermal expansion of 70.0 ppm/℃ or less, 1.0 ppm/℃ or more and 70.0 ppm/℃ or less, 1.0 ppm/℃ or more and 60.0 ppm/℃ or less, 1.0 ppm/℃ or more and 56.0 ppm/℃ or less, 10.0 ppm /℃ or more and 56.0 ppm/℃ or less, 30.0 ppm/℃ or more and 56.0 ppm/℃ or less, or 35.0 ppm/℃ or more and 56.0 ppm/℃ or less.

The method of measuring the coefficient of thermal expansion is not particularly limited, but, for example, using TMA, from 30 ℃ to 260 ℃, after measuring under the condition of a temperature increase rate of 10 ℃ / min, the measured value in the range of 50 ℃ to 150 ℃ thermal expansion can be done by counting.

In addition, the polymer film may have a birefringence of 0.005 or less, 0.001 or more and 0.005 or less, 0.001 or more and 0.004 or less, 0.001 or more and 0.0035 or less, or 0.0015 or more and 0.0035 or less.

The method for measuring the birefringence is not particularly limited, but may be measured using, for example, an Abbe refractometer, and may mean the birefringence at D (589 nm) at 20°C.

Since the coefficient of thermal expansion of the polymer film is 70.0 ppm/℃ or less and the birefringence is 0.005 or less, shrinkage and expansion at high temperature are suppressed while exhibiting excellent optical properties, and a polymer film having remarkably excellent heat resistance can be provided.

Specifically, when the coefficient of thermal expansion of the polymer film exceeds 70.0 ppm/℃, a technical problem may occur in that the substrate is warped according to heating, and when the birefringence exceeds 0.005, the retardation increases and the optical properties are Significantly poor technical problems may arise.

That is, as the polymer film has a coefficient of thermal expansion of 70.0 ppm/° C. or less and a birefringence of 0.005 or less, a polymer film capable of implementing a low retardation while suppressing bending characteristics can be provided.

In addition, the polymer film has a retardation (Rth) of 40 nm or less. 1 nm or more and 40 nm or less, 10 nm or more and 40 nm or less, 15 nm or more and 40 nm or less, or 15 nm or more and 35 nm or less.

In general, the retardation (Rth) of a birefringent material at a given wavelength can be defined as the product of the birefringence Δ at that wavelength and the layer thickness d. In this case, the birefringence Δη can be obtained through Equation 1 below.

[Equation 1]

Δη= η _e - η ₀

In Equation 1, the refractive index in the plane direction of the polymer film is defined _{as η e} , and the refractive index in the thickness direction of the polymer film _{is defined as η 0 .}

When the retardation (Rth) exceeds 40 nm, a technical problem in which optical properties are remarkably poor may occur due to an increase in retardation.

That is, as the retardation (Rth) of the polymer film is 40 nm or less, a polymer film capable of realizing a low retardation while suppressing substrate warpage may be provided.

In addition, the glass transition temperature of the polymer film may be 318 ℃ or more, 318 ℃ or more and 400 ℃ or less, 318 ℃ or more and 350 ℃ or less, 320 ℃ or more and 350 ℃ or less, or 320 ℃ or more and 342 ℃ or less.

The method for measuring the glass transition temperature is not particularly limited, but for example, the glass transition temperature (Tg) may be measured from a midpoint in a stepped endothermic curve indicating a glass transition phenomenon among the DSC curves.

As the glass transition temperature of the polymer film is 318° C. or higher, a polymer film having remarkably excellent heat resistance may be provided.

Examples of the method for synthesizing the polymer film are not particularly limited, for example, forming a coating film by applying the polymer resin composition containing the polyimide-based polymer of the other embodiment to a substrate (step 1); drying the coating film (step 2); A method for producing a polymer film, including the step of curing the dried coating film by heat treatment (step 3), may be used.

Step 1 is a step of forming a coating film by applying the polymer resin composition containing the above-described polyimide-based polymer to a substrate. A method of applying the polymer resin composition containing the polyimide-based polymer to the substrate is not particularly limited, and for example, a method such as screen printing, offset printing, flexographic printing, and inkjet printing may be used.

In addition, the polymer resin composition containing the polyimide-based polymer may be dissolved or dispersed in an organic solvent. When having such a form, for example, when polyimide-type polymer|macromolecule is synthesize|combined in an organic solvent, the reaction solution itself obtained may be sufficient as the solution, and also what diluted this reaction solution with another solvent may be sufficient. Moreover, when polyimide-type polymer|macromolecule is obtained as powder, what was made to melt|dissolve this in an organic solvent and was made into a solution may be sufficient.

Specific examples of the organic solvent include toluene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethyl Pyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, gamma-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3- Ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoa Milk ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Acetate etc. are mentioned. These may be used alone or may be used in combination.

In addition, the polymer resin composition may further include other components in addition to the organic solvent. As a non-limiting example, when the polymer resin composition is applied, the uniformity of the film thickness or the surface smoothness is improved, the adhesion to the substrate is improved, the dielectric constant or the conductivity is changed, or the density is increased. Additives that can be added may be additionally included. Such additives may be exemplified by a surfactant, a silane-based compound, a dielectric or a crosslinking compound, and the like.

Step 2 is a step of drying the coating film formed by applying the polymer resin composition to the substrate.

The drying step of the coating film may be performed by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 50 °C to 150 °C, or 50 °C to 100 °C.

Step 3 is a step of curing the dried coating film by heat treatment. At this time, the heat treatment may be carried out by a heating means such as a hot plate, a hot air circulation furnace, an infrared furnace, and may be performed at a temperature of 180 ℃ to 300 ℃, or 200 ℃ to 300 ℃

IV. substrate for display device

Meanwhile, according to another embodiment of the present invention, a substrate for a display device including the polymer film of the other embodiment may be provided. The content regarding the polymer film may include all of the content described above in the other embodiments.

A display device including the substrate may include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display, or a rollable display or foldable display. ) and the like, but is not limited thereto.

The display device may have various structures depending on the field of application and specific form, for example, a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (OLED device, etc.), a transparent substrate, etc. have.

The polymer film of another embodiment described above may be used for various purposes such as a substrate, an external protective film, or a cover window in these various display devices, and more specifically, it may be applied as a substrate.

For example, the substrate for the display device may have a structure in which a device protection layer, a transparent electrode layer, a silicon oxide layer, a polyimide film, a silicon oxide layer, and a hard coating layer are sequentially stacked.

The transparent polyimide substrate may include a silicon oxide layer formed between the transparent polyimide film and the cured layer in terms of improving solvent resistance, moisture permeability and optical properties, wherein the silicon oxide layer is polysilazane. It may be produced by curing the

Specifically, the silicon oxide layer may be formed by coating and drying a solution containing polysilazane before forming a coating layer on at least one surface of the transparent polyimide film, and then curing the coated polysilazane. have.

The substrate for a display device according to the present invention can provide a transparent polyimide cover substrate having excellent warpage characteristics and impact resistance, and solvent resistance, optical characteristics, moisture permeability and scratch resistance by including the device protection layer described above. have.

6. Optics

Meanwhile, according to another embodiment of the present invention, an optical device including the polyimide-based resin film of the other embodiment may be provided. The content regarding the polyimide-based resin film may include all of the content described above in the embodiment.

The optical device may include all kinds of devices using properties realized by light, for example, a display device. Specific examples of the display device include a liquid crystal display device (LCD), an organic light emitting diode (OLED), a flexible display, or a rollable display or foldable display. and the like, but is not limited thereto.

The optical device may have various structures depending on the field of application and specific form, for example, a structure including a cover plastic window, a touch panel, a polarizing plate, a barrier film, a light emitting device (OLED device, etc.), a transparent substrate, etc. have.

The polyimide-based resin film of another embodiment described above may be used for various purposes such as a substrate, an external protective film, or a cover window in these various optical devices, and more specifically, may be applied to a substrate.

According to the present invention, a diamine compound for polyimide synthesis capable of realizing stable heat resistance with excellent transparency, a polyimide-based polymer using the same, a polymer film, and a substrate for a display device can be provided.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are only provided for easier understanding of the present invention, and the content of the present invention is not limited thereto.

[Synthesis Example: Preparation of diamine compound]

Synthesis Example 1: Preparation of diamine compound DA-1

100.0 g (0.49 mol) of Compound A was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 195 ml (0.49 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 52 ml of dichlorodiphenylsilane (0.24 mol) was slowly added dropwise to the reaction while maintaining -78° C., followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 61 g of Compound B (yield 59%).

61.0 g (0.14 mol) of Compound B and 179.8 g of Bis(pinacolato)diboron (0.71 mol) and 82.9 g (0.84 mol) of potassium acetate were dissolved in 1 L of Dioxane It was then heated. Bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 4.8 g (0.008 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 4.7 g (0.016 mol) after activation in dioxane (dioxane) was added dropwise to the reaction product . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 77 g of Compound C (yield 89%).

77.2 g (0.12 mol) of compound C and 48.5 g (0.24 mol) of 4-bromonitrobenzene were dissolved in 300 mL of THF solvent, and 49.8 g (0.36 mol) of potassium carbonate (K _{2 )} CO ₃ ) was dissolved in 300 mL water and stirred with heating. 8.3 g (0.007 mol) of palladium tetratriphenylphosphine was slowly added thereto, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 63 g of compound D (yield 87%).

63.3 g (0.10 mol) of Compound D, 1.9 g (3 wt%) of a palladium catalyst, and 39 mL (0.80 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 42 g of diamine DA-1 (yield 77%).

The MS measurement results of the diamine compound (DA-1) are as follows.

MS: [M+H] ⁺ = 546.2490

Synthesis Example 2: Preparation of diamine compound DA-2

100.0 g (0.52 mol) of Compound E was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 208 ml (0.52 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 50 ml of dichlorodiphenylsilane (0.26 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 58 g of compound F (yield 60%).

57.7 g (0.14 mol) of compound F, 180.7 g of bis(pinacolato)diboron (Bis(pinacolato)diboron, 0.71 mol) and 83.8 g (0.85 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. Bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 4.9 g (0.008 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 4.8 g (0.017 mol) after activation in dioxane (dioxane) was added dropwise to the reaction. . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 74 g of Compound G (yield 89%).

74.5 g (0.13 mol) of compound G and 58.3 g (0.25 mol) of 2-bromo-1,3-dimethyl-5-nitrobenzene were mixed with 300 It was dissolved in a THF solvent of mL, and 52.5 g (0.38 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL water and stirred with heating. 9.0 g (0.008 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 63 g of Compound H (yield 76%).

63.3 g (0.10 mol) of Compound H, 1.9 g (3 wt%) of a palladium catalyst, and 39 mL (0.80 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 46 g of diamine DA-2 (yield 80%).

The MS measurement results of the diamine compound (DA-2) are as follows.

MS: [M+H] ⁺ = 574.2801

Synthesis Example 3: Preparation of diamine compound DA-3

100.0 g (0.48 mol) of Compound I was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 191 ml (0.48 mol) of n-Butyllitium solution was slowly added dropwise, followed by stirring for 1 hour. After one hour, 46 ml of dichlorodiphenylsilane (0.22 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 59 g of compound J (yield 61%).

59.2 g (0.13 mol) of compound J, 165.1 g of bis(pinacolato)diboron (Bis(pinacolato)diboron, 0.65 mol) and 107.8 g (0.78 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. Bis(dibenzylideneacetone)palladium (Bis(dibenzylideneacetone)palladium) 4.5 g (0.008 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 4.4 g (0.016 mol) were activated in dioxane and then added dropwise to the reaction product. . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 71 g of Compound K (yield 87%).

70.6 g (0.11 mol) of compound K and 45.7 g (0.22 mol) of 4-bromonitrobenzene were dissolved in 300 mL of THF solvent, and 45.6 g (0.33 mol) of potassium carbonate (K _{2 )} CO ₃ ) was dissolved in 300 mL water and stirred with heating. 7.6 g (0.006 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 51 g of compound L (yield 73%).

50.7 g (0.08 mol) of Compound L, 1.5 g (3 wt%) of a palladium catalyst, and 31 mL (0.64 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 39 g of diamine DA-3 (yield 85%).

The MS measurement results of the diamine compound (DA-3) are as follows.

MS: [M+H] ⁺ = 554.1988

Synthesis Example 4: Preparation of diamine compound DA-4

50 g (0.08 mol) of compound G and 37.4 g (0.17 mol) of 1-bromo-2-fluoro-4-nitrobenzene were mixed with 300 mL of THF solvent was dissolved in, and 35.2 g (0.25 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 38 g of compound M (yield 72%).

37.6 g (0.06 mol) of compound M, 1.1 g (3 wt%) of a palladium catalyst, and 23 mL (0.48 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 30 g of diamine DA-4 (yield 89%).

The MS measurement results of the diamine compound (DA-4) are as follows.

MS: [M+H] ⁺ = 554.1989

Synthesis Example 5: Preparation of diamine compound DA-5

100.0 g (0.48 mol) of compound N was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 191 ml (0.48 mol) of n-Butyllitium solution was slowly added dropwise, followed by stirring for 1 hour. After one hour, 46 ml of dichlorodiphenylsilane (0.22 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 65 g of compound O (yield 68%).

65.1 g (0.15 mol) of compound O, 187.3 g of bis (pinacolato) diboron (Bis(pinacolato) diboron, 0.74 mol) and 86.9 g (0.88 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. 5.2 g (0.009 mol) of Bis(dibenzylideneacetone)palladium and 5.0 g (0.018 mol) of Tricyclohexylphosphine were activated in dioxane and then added dropwise to the reaction product . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 75 g of compound P (yield 81%).

74.6 g (0.12 mol) of compound P and 52.6 g (0.24 mol) of 1-bromo-2-fluoro-4-nitrobenzene in 300 mL of THF solvent was dissolved, and 49.5 g (0.36 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water and stirred with heating. 8.3 g (0.007 mol) of palladium tetratriphenylphosphine was slowly added thereto, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 55 g of compound Q (yield 71%).

55.2 g (0.08 mol) of compound Q, 1.7 g (3 wt%) of a palladium catalyst, and 31 mL (0.64 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 41 g of diamine DA-5 (yield 82%).

The MS measurement results of the diamine compound (DA-5) are as follows.

MS: [M+H] ⁺ = 590.1799

Synthesis Example 6: Preparation of diamine compound DA-6

70.6 g (0.11 mol) of compound K and 45.7 g (0.22 mol) of 4-bromo-1-nitro-2- (trifluoromethyl)benzene (4-bromo-1-nitro-2- (trifluoromethyl)benzene) was dissolved in 300 mL of THF solvent, and 45.6 g (0.33 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water, followed by heating and stirring. 7.6 g (0.006 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 65 g of compound R (yield 77%).

65.3 g (0.09 mol) of Compound R, 1.9 g (3 wt%) of a palladium catalyst, and 35 mL (0.72 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 49 g of diamine DA-6 (yield 82%).

The MS measurement results of the diamine compound (DA-6) are as follows.

MS: [M+H] ⁺ = 690.1735

Synthesis Example 7: Preparation of diamine compound DA-7

100.0 g (0.44 mol) of Compound S was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 176 ml (0.44 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 41 ml of dichlorodiphenylsilane (0.19 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 61 g of Compound T (yield 67%).

61.0 g (0.13 mol) of Compound T, 161.6 g of bis(pinacolato)diboron (Bis(pinacolato)diboron, 0.64 mol) and 76.5 g (0.76 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. Bis(dibenzylideneacetone)palladium (Bis(dibenzylideneacetone)palladium) 4.5 g (0.008 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 4.4 g (0.016 mol) were activated in dioxane and then added dropwise to the reaction product. . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 70 g of Compound U (yield 82%).

70.4 g (0.11 mol) of compound U and 50.7 g (0.21 mol) of 5-bromo-1,3-difluoro-2-nitrobenzene It was dissolved in 300 mL of THF solvent, and 45.6 g (0.33 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water, followed by heating and stirring. 7.6 g (0.006 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 52 g of compound V (yield 68%).

52.4 g (0.07 mol) of Compound V, 1.6 g (3 wt%) of a palladium catalyst, and 27 mL (0.56 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 38 g of diamine DA-7 (yield 81%).

The MS measurement results of the diamine compound (DA-7) are as follows.

MS: [M+H] ⁺ = 662.1424

Synthesis Example 8: Preparation of diamine compound DA-8

100.0 g (0.38 mol) of compound W was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 152 ml (0.38 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 24 ml of dichlorodiphenylsilane (0.19 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 67 g of compound X (yield 64%).

66.7 g (0.12 mol) of Compound X, 94.0 g of Bis(pinacolato)diboron (0.37 mol) and 60.5 g (0.62 mol) of potassium acetate were dissolved in 1 L of Dioxane It was then heated. Bis(dibenzylideneacetone)palladium 4.25 g (0.007 mol) and tricyclohexylphosphine 4.15 g (0.015 mol) were activated in dioxane and then added dropwise to the reaction product. . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 79 g of compound Y (yield 88%).

78.6 g (0.11 mol) of compound Y and 43.8 g (0.22 mol) of 4-bromonitrobenzene were dissolved in 300 mL of THF solvent, and 45.0 g (0.33 mol) of potassium carbonate (K _{2 )} CO ₃ ) was dissolved in 300 mL water and stirred with heating. 7.5 g (0.007 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 60 g of compound Z (yield 77%).

59.7 g (0.08 mol) of Compound Z, 1.8 g (3 wt%) of a palladium catalyst, and 32 mL (0.67 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 48 g of diamine DA-8 (yield 87%).

The MS measurement results of the diamine compound (DA-8) are as follows.

MS: [M+H] ⁺ = 654.1924

Synthesis Example 9: Preparation of diamine compound DA-9

50 g (0.08 mol) of compound G and 45.9 g (0.17 mol) of 1-bromo4-nitro-2- (trifluoromethyl) benzene (1-bromo-4-nitro-2- (trifluoromethyl) benzene) was dissolved in 300 mL of THF solvent, and 35.2 g (0.25 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 49 g of compound a (yield 81%).

49.2 g (0.07 mol) of compound a, 1.5 g (3 wt%) of a palladium catalyst, and 27 mL (0.55 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 38 g of diamine DA-9 (yield 85%).

MS measurement results of the diamine compound (DA-9) are as follows.

MS: [M+H] ⁺ = 654.1923

Synthesis Example 10: Preparation of diamine compound DA-10

100.0 g (0.38 mol) of compound b was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 154 ml (0.38 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 24 ml of dichlorodiphenylsilane (0.19 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 64 g of compound c (yield 61%).

63.6 g (0.12 mol) of compound c, 90.0 g of bis (pinacolato) diboron (Bis(pinacolato) diboron, 0.35 mol) and 57.7 g (0.59 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. Bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 4.1 g (0.007 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 3.9 g (0.014 mol) after activation in dioxane (dioxane) was added dropwise to the reaction . When the reaction was completed, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 72 g of compound d (yield 84%).

71.5 g (0.10 mol) of compound d and 53.3 g (0.20 mol) of 1-bromo4-nitro-2- (trifluoromethyl)benzene (1-bromo-4-nitro-2- (trifluoromethyl)benzene) was dissolved in 300 mL of THF solvent, and 40.9 g (0.30 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water and stirred with heating. 6.8 g (0.006 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 60 g of compound e (yield 72%).

60.5 g (0.07 mol) of compound e, 1.8 g (3 wt%) of a palladium catalyst, and 28 mL (0.57 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 51 g of diamine DA-10 (yield 90%).

The MS measurement results of the diamine compound (DA-10) are as follows.

MS: [M+H] ⁺ = 790.1673

Synthesis Example 11: Preparation of diamine compound DA-11

100.0 g (0.31 mol) of compound f was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 122 ml (0.31 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 19 ml of dichlorodiphenylsilane (0.15 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 69 g of compound g (yield 69%).

69.3 g (0.10 mol) of compound g, 77.9 g of bis(pinacolato)diboron (0.31 mol) and 50.2 g (0.51 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. Bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 3.5 g (0.006 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 3.4 g (0.012 mol) after activation in dioxane (dioxane) was added dropwise to the reaction product . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 76 g of compound h (yield 86%).

75.7 g (0.09 mol) of compound h and 59.5 g (0.18 mol) of 5-bromo-2-nitro-1,3-bis(trifluoromethyl)benzene (5-bromo-2-nitro-1,3 -bis(trifluoromethyl)benzene) was dissolved in 300 mL of a THF solvent, and 36.5 g (0.26 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water, followed by heating and stirring. 6.1 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 84 g of compound i (yield 85%).

84.0 g (0.07 mol) of compound i, 2.5 g (3 wt%) of a palladium catalyst, and 29 mL (0.60 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 71 g of diamine DA-11 (yield 89%).

The MS measurement results of the diamine compound (DA-11) are as follows.

MS: [M+H] ⁺ = 1062.1167

Synthesis Example 12: Preparation of diamine compound DA-12

100.0 g (0.46 mol) of compound j was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 185 ml (0.46 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 29 ml of dichlorodiphenylsilane (0.23 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 76 g of compound k (yield 72%).

75.7 g (0.17 mol) of compound k, 126.7 g of bis (pinacolato) diboron (Bis(pinacolato) diboron, 0.50 mol) and 81.6 g (0.83 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. Bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 5.7 g (0.02 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 5.6 g (0.019 mol) after activation in dioxane (dioxane) was added dropwise to the reaction. . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 91 g of compound 1 (yield 86%).

91.3 g (0.14 mol) of compound l and 57.8 g (0.29 mol) of 4-bromonitrobenzene were dissolved in 300 mL of THF solvent, and 59.3 g (0.43 mol) of potassium carbonate (K _{2 )} CO ₃ ) was dissolved in 300 mL water and stirred with heating. 9.9 g (0.008 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 75 g of compound m (yield 83%).

74.6 g (0.12 mol) of compound m, 2.2 g (3 wt%) of a palladium catalyst, and 46 mL (0.95 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 61 g of diamine DA-12 (yield 91%).

The MS measurement results of the diamine compound (DA-12) are as follows.

MS: [M+H] ⁺ = 568.2080

Synthesis Example 13: Preparation of diamine compound DA-13

50 g (0.08 mol) of compound G and 38.6 g (0.17 mol) of 2-bromo-5-nitrobenzonitrile were dissolved in 300 mL of THF solvent, 35.2 g ( 0.25 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 45 g of compound n (yield 84%).

44.9 g (0.07 mol) of compound n, 1.3 g (3 wt%) of a palladium catalyst, and 28 mL (0.57 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 35 g of diamine DA-13 (yield 85%).

MS measurement results of the diamine compound (DA-13) are as follows.

MS: [M+H] ⁺ = 568.2082

Synthesis Example 14: Preparation of diamine compound DA-14

50 g (0.08 mol) of compound G and 42.8 g (0.17 mol) of 5-bromo-2-nitroisophthalonitrile were dissolved in 300 mL of THF solvent, 35.2 g (0.25 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 45 g of compound o (yield 78%).

45.0 g (0.06 mol) of compound o, 1.3 g (3 wt%) of a palladium catalyst, and 26 mL (0.53 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 38 g of diamine DA-14 (yield 92%).

The MS measurement results of the diamine compound (DA-14) are as follows.

MS: [M+H] ⁺ = 618.1986

Synthesis Example 15: Preparation of diamine compound DA-15

100.0 g (0.45 mol) of compound p was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 181 ml (0.45 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 29 ml of dichlorodiphenylsilane (0.23 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 74 g of compound q (yield 70%).

73.6 g (0.16 mol) of compound q, 120.4 g of bis(pinacolato)diboron (Bis(pinacolato)diboron, 0.47 mol) and 77.5 g (0.79 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. 5.5 g (0.009 mol) of bis(dibenzylideneacetone)palladium and 5.3 g (0.019 mol) of tricyclohexylphosphine were activated in dioxane and then added dropwise to the reaction product. . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 81 g of compound r (yield 79%).

81.0 g (0.12 mol) of compound r and 50.4 g (0.25 mol) of 4-bromonitrobenzene were dissolved in 300 mL of THF solvent, and 51.8 g (0.37 mol) of potassium carbonate (K _{2 )} CO ₃ ) was dissolved in 300 mL water and stirred with heating. 8.6 g (0.007 mol) of palladium tetratriphenylphosphine was slowly added thereto, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 61 g of compound s (yield 76%).

60.6 g (0.09 mol) of compound s, 1.8 g (3 wt%) of a palladium catalyst, and 37 mL (0.76 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 52 g of diamine DA-15 (yield 95%).

MS measurement results of the diamine compound (DA-15) are as follows.

MS: [M+H] ⁺ = 578.2388

Synthesis Example 16: Preparation of diamine compound DA-16

50 g (0.08 mol) of compound G and 39.4 g (0.17 mol) of 1-bromo-2-methoxy-4-nitrobenzene were mixed with 300 mL of THF solvent was dissolved in, and 35.2 g (0.25 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 44 g of compound t (yield 81%).

44.0 g (0.07 mol) of compound t, 1.3 g (3 wt%) of a palladium catalyst, and 27 mL (0.55 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 37 g of diamine DA-16 (yield 92%).

The MS measurement results of the diamine compound (DA-16) are as follows.

MS: [M+H] ⁺ = 578.2387

Synthesis Example 17: Preparation of diamine compound DA-17

100.0 g (0.45 mol) of Compound I was dissolved in 200 ml of tetrahydrofuran (THF) and cooled to -78 °C. While maintaining the temperature, 181 ml (0.45 mol) of n-Butyllitium solution was slowly added dropwise and stirred for 1 hour. After one hour, 29 ml of dichlorodiphenylsilane (0.23 mol) was slowly added dropwise to the reactant while maintaining -78°C, followed by stirring for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 71 g of compound v (yield 68%).

71.5 g (0.15 mol) of compound v, 116.9 g of bis (pinacolato) diboron (Bis(pinacolato) diboron, 0.46 mol) and 75.3 g (0.77 mol) of potassium acetate were dissolved in 1 L of dioxane It was then heated. Bis (dibenzylideneacetone) palladium (Bis (dibenzylideneacetone) palladium) 5.3 g (0.009 mol) and tricyclohexylphosphine (Tricyclohexylphosphine) 5.2 g (0.018 mol) after activation in dioxane (dioxane) was added dropwise to the reaction product . Upon completion of the reaction, 1 L of ethanol was added to the reactant, and the resulting solid was filtered to synthesize 81 g of compound w (yield 81%).

80.6 g (0.12 mol) of compound w and 57.7 g (0.25 mol) of 1-bromo-2-methoxy-4-nitrobenzene were mixed with 300 mL of THF solvent was dissolved, and 51.6 g (0.37 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water and stirred with heating. 8.6 g (0.007 mol) of palladium tetratriphenylphosphine was slowly added thereto, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 69 g of compound x (yield 79%).

68.6 g (0.10 mol) of compound x, 2.1 g (3 wt%) of a palladium catalyst, and 38 mL (0.79 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 55 g of diamine DA-17 (yield 88%).

The MS measurement results of the diamine compound (DA-17) are as follows.

MS: [M+H] ⁺ = 638.2600

Synthesis Example 18: Preparation of diamine compound DA-18

50 g (0.08 mol) of compound G and 44.5 g (0.17 mol) of 2-bromo-1,3-dimethoxy-5-nitrobenzene It was dissolved in 300 mL of THF solvent, and 35.2 g (0.25 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 44 g of compound y (yield 75%).

44.5 g (0.06 mol) of compound y, 1.3 g (3 wt%) of a palladium catalyst, and 25 mL (0.51 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 38 g of diamine DA-18 (yield 93%).

The MS measurement results of the diamine compound (DA-18) are as follows.

MS: [M+H] ⁺ = 638.2659

Synthesis Example 19: Preparation of diamine compound DA-19

50 g (0.08 mol) of compound G and 44.5 g (0.17 mol) of 5-bromo-1,3-dimethoxy-2-nitrobenzene It was dissolved in 300 mL of THF solvent, and 35.2 g (0.25 mol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL of water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 40 g of compound z (yield 68%).

40.1 g (0.06 mol) of compound z, 1.2 g (3 wt%) of a palladium catalyst, and 22 mL (0.46 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 36 g of diamine DA-19 (yield 93%).

The MS measurement results of the diamine compound (DA-19) are as follows.

MS: [M+H] ⁺ = 638.2597

Synthesis Example 20: Preparation of diamine compound DA-20

50 g (0.08 mol) of compound G and 42.8 g (0.17 mol) of 2-bromo-6-nitronaphthalene were dissolved in 300 mL of THF solvent, and 35.2 g (0.25 mol) ) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 300 mL water and stirred with heating. 5.9 g (0.005 mol) of palladium tetratriphenylphosphine was slowly added, followed by heating and stirring for 12 hours. After completion of the reaction, the mixture was cooled to room temperature and extracted using water and ethyl acetate. The organic layer was dried _{using anhydrous magnesium sulfate (MgSO 4} ) and concentrated through a vacuum distillation apparatus to prepare 46 g of Compound A-1 (yield 80%).

46.1 g (0.07 mol) of Compound A-1, 1.4 g (3 wt%) of a palladium catalyst, and 26 mL (0.54 mol) of hydrazine were dissolved in 200 mL of EtOH and stirred at room temperature for 12 hours. When the reaction was completed, 400 mL of water was added to the reaction mixture, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 37 g of diamine DA-20 (yield 89%).

The MS measurement results of the diamine compound (DA-20) are as follows.

MS: [M+H] ⁺ = 618.2489

[Example: Preparation of polyamic acid solution and polyimide film]

Example

(1) Preparation of polyamic acid solution

As shown in Table 1 below, the diamine compound obtained in the above synthesis example was completely dissolved in anhydrous N-methyl pyrrolidone (NMP). Then, pyromellitic anhydride (PMDA) was added to the solution under an ice bath and stirred at room temperature for about 16 hours to synthesize a polyamic acid polymer.

The polyamic acid polymer prepared as described above was put in a mixed solvent of NMP and n-butoxyethanol, and the solution obtained by stirring at 25° C. for 16 hours was filtered under pressure using a filter made of poly(tetrafluoroethylene) material having a pore size of 0.1 μm. to prepare a polyamic acid solution.

(2) Preparation of polyimide film

The polyamic acid solution obtained in Example 1 (1) was applied to a thickness of 0.1 μm by spin coating on a rectangular glass substrate having a size of 2.5 cm x 2.7 cm. Thereafter, the substrate coated with the polyamic acid solution was placed on a hot plate at 80° C. and dried for 2 minutes. Thereafter, a polyimide film having a thickness of 0.1 μm was prepared by firing (curing) it in an oven at 230° C. for 15 minutes.

[Comparative Example: Preparation of polyamic acid solution and polyimide film]

Comparative Example 1

A polyamic acid solution and a polyimide film were prepared in the same manner as in Example 1, except that the diamine compound A represented by the following formula A was used instead of the diamine compound obtained in the Synthesis Example during the preparation of the polyamic acid solution. .

[Formula A]

[ Experimental example ]

Experimental Example 1: Glass transition temperature

For the polyimide films obtained in Examples and Comparative Examples, a DSC curve (Differential Scanning Calorimetry Thermogram) was obtained under the following thermal history conditions for a sample of 5 mg to 10 mg under a nitrogen gas atmosphere using DSC3+ equipment from Mettler Toledo. .

- Primary heating: After heating from 30°C to 200°C at a temperature increase rate of 10°C/min, hold at 200°C for 5 minutes

- Cooling: From 200 to 50 °C, the temperature is lowered at a rate of 10 °C/min and then maintained for 5 minutes.

- Secondary heating: The temperature is raised from 50°C to 300°C at a temperature increase rate of 10°C/min.

The glass transition temperature (Tg) was measured from the midpoint of the stepped endothermic curve, which means the glass transition, among the DSC curves.

Experimental Example 2: Permeability

For the polyimide films obtained in Examples and Comparative Examples, transmittance (T) for light having a wavelength of 380 to 760 nm was measured using a UV-vis spectroscopy (Agillent, UV 8453) device.

Experimental Example 3: Coefficient of Thermal Expansion (CTE)

With respect to the polyimide films obtained in Examples and Comparative Examples, using TMA (TA Instruments, Q400), after measuring from 30 ° C to 260 ° C, at a temperature increase rate of 10 ° C / min conditions, 50 ° C. to 150 ° C. The measured value was recorded as the coefficient of thermal expansion.

Experimental Example 4: Birefringence

For the polyimide films obtained in Examples and Comparative Examples, the birefringence was measured and recorded at D (589 nm) at 20° C. using an Abbe refractometer (DR-M4) manufactured by Atago.

Experimental Example 5: Retardation (Rth) in the thickness direction with respect to a wavelength of 550 nm

For the retardation (Rth) in the thickness direction, a sample having a length of 76 mm, a width of 52 mm, and a thickness of 13 μm was prepared from the polyimide resin film produced in each Example and each Comparative Example, and as a measuring device, a brand name “Exoscan” manufactured by AXOMETRICS Co., Ltd. (AxoScan)" and input the value of the refractive index of each sample (the refractive index with respect to the 550 nm light of the film obtained by the measurement of the above-mentioned refractive index) under the conditions of temperature: 25°C and humidity: 40% , using light having a wavelength of 590 nm and measuring the retardation in the thickness direction, then using the obtained retardation measurement value in the thickness direction (measured value by automatic measurement of a measuring device), retardation per 10 μm thickness of the film It was obtained by converting to a value, and it is shown in Table 1 below.

Synthesis example diamine Tg
(℃) Transmittance (%) CTE
(ppm/℃) birefringence Rth
(nm) Example 1 Synthesis Example 1 DA-1 331 83 46.3 0.0025 20 Example 2 Synthesis Example 8 DA-8 320 87 39.9 0.0015 18 Example 3 Synthesis Example 9 DA-9 326 85 40.3 0.0026 21 Example 4 Synthesis Example 13 DA-13 337 83 48.1 0.0027 23 Example 5 Synthesis Example 20 DA-20 342 81 55.2 0.0034 31 Comparative Example 1 - Formula A 317 80 71.3 0.0052 42

As shown in Table 1, the polyimide-based polymer prepared from the diamine compound obtained in Examples showed excellent optical properties and showed a small coefficient of thermal expansion, thereby suppressing shrinkage and expansion at high temperatures, and remarkably excellent heat resistance. .

On the other hand, the polyimide-based polymer prepared from the diamine compound of Comparative Examples is inferior in optical properties and heat resistance compared to the Examples, and in particular, the thermal expansion coefficient is large, so that shrinkage and expansion occurs at high temperature. could check

Claims (22)

A diamine compound having a structure represented by the following formula (1):
[Formula 1]

In Formula 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group,
i) _{at least one of L 1} to L ₄ is a monocyclic aromatic divalent functional group in which at least one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded, and the rest are each independent Or a substituted or unsubstituted aromatic divalent functional group,
ii) _{At least one of L 1} to L ₄ is an aromatic divalent functional group containing a fused polycyclic structure, and the rest are each independently a substituted or unsubstituted aromatic divalent functional group.
According to claim 1,
The structure represented by Formula 1 is,
A diamine compound comprising a structure represented by the following Chemical Formula 1-1:
[Formula 1-1]

In Formula 1-1,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted aromatic monovalent functional group,
T ₁ to T ₄ are each independently any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group,
m1 to m4 are each independently an integer of 0 to 4,
(m1+m2+m3+m4)≥1.
3. The method of claim 2,
In the structure represented by Formula 1-1,
m1 to m4 are each independently an integer of 0 or 1, a diamine compound.
4. The method of claim 3,
The structure represented by Formula 1-1 is,
A diamine compound comprising any one of the structures represented by the following formulas 1-a to 1-c:
Formula 1-a]

[Formula 1-b]

[Formula 1-c]

In Formula 1-a to Formula 1-c,
Ar ₅ to Ar ₁₀ is each independently a substituted or unsubstituted aromatic monovalent functional group,
T ₁ 'to T ₄ ' and T ₁ ” to T ₄ ” are each independently any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group.
3. The method of claim 2,
In the structure represented by Formula 1-1,
m1 to m4 are each independently an integer of 0 or 2, a diamine compound.
6. The method of claim 5,
The structure represented by Formula 1-1 is,
A diamine compound comprising any one of the structures represented by the following formulas 1-d to 1-f:
[Formula 1-d]

[Formula 1-e]

[Formula 1-f]

In Formula 1-d to Formula 1-f,
Ar ₅ ' to Ar ₁₀ ' is each independently a substituted or unsubstituted aromatic monovalent functional group,
T ₅ to T ₁₂ and T ₅ 'to T ₁₂ ' are each independently any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group.
3. The method of claim 2,
The structure represented by Formula 1-1 is,
A diamine compound comprising a structure represented by the following Chemical Formula 1-2:
[Formula 1-2]

In Formula 1-2,
Ar ₃ and Ar ₄ are each independently a substituted or unsubstituted aromatic monovalent functional group,
T ₁ to T ₄ are each independently any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group,
m1 to m4 are each independently an integer of 0 to 4,
(m1+m2+m3+m4)≥1.
According to claim 1,
In the structure represented by Formula 1,
At least one of L ₁ to L ₄ is a divalent functional group represented by the following Chemical Formula 2, and the rest are each independently a substituted or unsubstituted aromatic divalent functional group, a diamine compound:
[Formula 2]

In the above formula (2),
R ₁ and R ₂ are each independently any one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group, and a cyano group.
According to claim 1,
In the structure represented by Formula 1,
L ₁ and L ₄ are each independently an aromatic divalent functional group containing a fused polycyclic structure,
L ₂ and L ₃ are each independently a substituted or unsubstituted aromatic divalent functional group, a diamine compound.

According to claim 1,
In Formula 1,
The aromatic divalent functional group containing the fused polycyclic structure,
Any one selected from the group consisting of a naphthylene group, an anthracenylene group, a fluorenylene group, a phenanthrylene group, a pyrenylene group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolnylene group, and a thiophenylene group Phosphorus, a diamine compound.
4. The method of claim 3,
The structure represented by Formula 1-1 is,
Any one selected from the group consisting of the following compounds, diamine compounds:

. 6. The method of claim 5,
The structure represented by Formula 1-1 is,
Any one selected from the group consisting of the following compounds, diamine compounds:

.
10. The method of claim 9,
The structure represented by Formula 1 is,
A diamine compound comprising a diamine compound represented by the following compound:

.
According to claim 1,
The diamine compound is a diamine compound used for polyimide-based polymer synthesis.
A polyimide-based polymer comprising at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (4), and a repeating unit represented by the following formula (5):
[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,
At least one of R ₁₁ and R ₁₂ is an alkyl group having 1 to 10 carbon atoms, the rest is hydrogen,
X ₁ to X- ₃ are the same as or different from each other, and are each independently a tetravalent functional group,
Y _{1 To} Y _{3 Are} the same as or different from each other, and are each independently a divalent functional group represented by the following Chemical Formula 6,
[Formula 6]

In the formula (6),
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group,
i) _{at least one of L 1} to L ₄ is a monocyclic aromatic divalent functional group in which at least one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded, and the rest are each independent Or a substituted or unsubstituted aromatic divalent functional group,
ii) _{At least one of L 1} to L ₄ is an aromatic divalent functional group containing a fused polycyclic structure, and the rest are each independently a substituted or unsubstituted aromatic divalent functional group.
16. The method of claim 15,
In Formulas 3 to 5, X ₁ to X ₃ are each independently one of a tetravalent functional group represented by the following Formula 7 or a tetravalent functional group represented by the following Formula 8, a polyimide-based polymer:
[Formula 7]

In Formula 7,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aromatic monovalent functional group, i) L ₁ and L ₄ are each independently a monocyclic aromatic trivalent functional group, and L ₂ and L ₃ are each independently monocyclic An aromatic divalent functional group, wherein at least one of the aromatic trivalent functional group and the aromatic divalent functional group is a monocyclic aromatic in which at least one selected from the group consisting of an alkyl group, a halogen group, an alkoxy group, a haloalkyl group and a cyano group is bonded functional group, and the rest are each independently an unsubstituted aromatic functional group,
ii) L ₁ and L ₄ are each independently an aromatic divalent functional group containing a fused polycyclic structure, L ₂ and L ₃ are each independently a substituted or unsubstituted aromatic divalent functional group,
[Formula 8]

In the formula (8),
R ₁₆ to R ₂₁ are each independently hydrogen or one of an alkyl group having 1 to 10 carbon atoms,
L ₁ is a direct bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CR ₂₂ R ₂₃ -, -CONH-, -COO-, -(CH ₂ ) _t -, -O(CH ₂ ) _t O-, -COO-(CH ₂ ) _t -OCO-, an electron withdrawing functional group is any one selected from the group consisting of substituted or unsubstituted phenylene, or a combination thereof,
R ₂₂ and R ₂₃ are each independently one of hydrogen, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms,
t is an integer from 1 to 10;
16. The method of claim 15,
The polyimide-based polymer is a polyimide-based polymer comprising a combination of the diamine compound of claim 1 and the tetracarboxylic dianhydride compound.
A polymer film comprising the cured product of the polyimide-based polymer of claim 15 .
19. The method of claim 18,
The coefficient of thermal expansion is 70.0 ppm/℃ or less,
A polymer film having a birefringence of 0.005 or less.
19. The method of claim 18,
A polymer film having a retardation (Rth) of 40 nm or less.
A substrate for a display device comprising the polymer film of claim 18 .
An optical device comprising the polymer film of claim 18 .