KR20210018074A - Diamine compound, acid anhydride 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 and an anhydride compound having a novel structure where a carbazole-based functional group is substituted, and a polyimide-based polymer, a polymer film, a substrate for a display device, and an optical device using the same. According to the present invention, the diamine compound and the anhydride compound for polyimide synthesis capable of implementing excellent transparency, high heat resistance, and low retardation, and the polyimide-based polymer, the polymer film, and the optical device using the same can be provided.

Description

Diamine compounds, acid anhydride compounds, polyimide-based polymers, polymer films, substrates and optical devices for display devices using the same }

The present invention relates to a diamine compound and an acid anhydride compound for synthesizing polyimide, which can realize excellent transparency, high heat resistance, and low retardation, and to a polyimide-based polymer, a polymer film, a substrate for a display device, and an optical device using the same.

The market for substrates for display devices is rapidly changing, focusing on flat panel displays (FPDs) that are easy to use in large areas and are capable of being thinner and lighter. 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 application and use of such a 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 is being examined mainly for mobile devices such as smart phones, and its application field is gradually expanded and considered.

In particular, aromatic polyimide resins are mostly polymers having an amorphous structure, and exhibit excellent heat resistance, chemical resistance, electrical properties, and dimensional stability due to a rigid chain structure, and can have flexibility applicable to flexible displays. /It is widely used as an electronic material.

However, polyimide resin has a limitation in securing transparency due to the dark brown color due to the formation of CTC (charge transfer complex) of Pi-electrons present in the imide chain, and flexible electronic device technology is inexpensive, easy to bend, and transparent. It has been evolving to make electronic devices and systems with

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

However, polyimide incorporating a 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 that warpage occurs in the metal thin film formed on the plastic substrate.

Accordingly, there is a need to develop a monomer compound for synthesizing polyimide that can realize stable optical properties and excellent heat resistance at the same time.

The present invention is to provide a diamine compound for synthesizing a polyimide polymer having excellent transparency, high heat resistance, and low retardation.

In addition, the present invention is to provide an acid anhydride compound for synthesizing a polyimide-based polymer having excellent transparency, high heat resistance, and low retardation.

In addition, the present invention is to provide a polyimide polymer synthesized from the diamine compound or the acid anhydride compound.

In addition, the present invention is to provide a polymer film, a substrate for a display device, and an optical device using the polyimide polymer.

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

[Formula 1]

In Formula 1, Ar is an aromatic divalent functional group having 13 or more carbon atoms to which at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded.

In the present specification, an acid anhydride compound having a structure represented by the following formula (4) is also provided.

[Formula 4]

In Formula 4, Ar' is an aromatic tetravalent functional group having 13 or more carbon atoms to which at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded.

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 7, a repeating unit represented by the following Formula 8, and a repeating unit represented by the following Formula 9 Is provided.

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 7 to 9, at least one of R ₁ and R ₂ is an alkyl group having 1 to 10 carbon atoms, the rest are hydrogen, X ₁ to X ₃ are the same as or different from each other, and each independently a tetravalent functional group, Y ₁ to Y ₃ are the same as or different from each other, each independently a divalent functional group, and of the X ₁ to X ₃ Tetravalent functional groups and Of Y ₁ to Y ₃ Divalent functional group At least one of An aromatic n having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded is a functional group, and n is 2 or 4.

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

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

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

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

Unless expressly stated in the specification, terminology is only intended to refer to specific embodiments and is not intended to limit the invention.

The singular forms used in the present specification also include plural forms unless the phrases clearly indicate the opposite.

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

Further, 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 element may be referred to as a second element, and similarly, a second element may be referred to as a first element.

In the present specification, the weight average molecular weight is an Agilent mixed B column using an Aters alliance 2695 instrument, the evaluation temperature is 40°C, and Tetrahydrofuran is used 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 calculated 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 other functional groups are 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 can be substituted, and when two or more are substituted , Two or more substituents may be the same or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkoxysilylalkyl group; Arylphosphine group; Or it means a substituted or unsubstituted substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O and S atoms, or linked with two or more substituents among the above-exemplified substituents. . For example, "a substituent to 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 to 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 form 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 which a plurality of hydrogen atoms bonded to an arbitrary compound has been removed, and examples thereof include a divalent functional group, a trivalent functional group, and a tetravalent functional group. For example, a tetravalent functional group derived from cyclobutane refers to a residue in the form of removal of any 4 hydrogen atoms bonded to cyclobutane.

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 alkane and may be linear or branched, and the number of carbon atoms of the linear alkyl group is not particularly limited, but is preferably 1 to 20. Further, the branched chain alkyl group has 3 to 20 carbon atoms. 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, but are not limited thereto. 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, is not particularly limited, but preferably has 6 to 20 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group 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 includes at least one atom or heteroatom other than carbon, and specifically, the heteroaryl atom may include at least one atom selected from the group consisting of O, N, and S. The number of carbon atoms is not particularly limited, but is preferably 4 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, p Nanthrolinyl group (phenanthroline), thiazolyl group, isoxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, aziridyl group, azaindolyl group, isoindolyl group, inda Sleepy, purine, pteridine, beta-carbolyl, naphthyridine, ter-pyridyl, phenazinyl, imidazopyridyl, pyropyridyl, azepine , A pyrazolyl group and a dibenzofuranyl group, but are not limited thereto. The heteroaryl 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, in the present specification, the heteroarylene group has 2 to 20, or 2 to 10, or 6 to 20 carbon atoms. An arylene group containing O, N or S as a heteroatom, except that it is a divalent functional group, can be applied to the description of the heteroaryl group described above. The heteroarylene 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 exists at the corresponding position and is connected by a bonding line.

1. Diamine compound

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

The inventors of the present invention can form a more bulky structure compared to the conventionally widely used phenylene diamine matrix by using a diamine having an aromatic divalent functional group having 13 or more carbon atoms as a parent, like the diamine compound of one embodiment. , Accordingly, the effect of improving the thermal stability according to the three-dimensional structural modification 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, resulting in a surface direction refractive index. It was confirmed that the refractive index in the thickness direction could be increased while decreasing this, and the invention was completed.

In addition, as shown in Formula 1, at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded, and the substituent group including the nitrogen-containing heteroaromatic compound has a bulky structure. It was confirmed that excellent thermal stability can be secured through a high glass transition temperature and a low coefficient of thermal expansion through the three-dimensional structural modification of the polyimide polymer synthesized from the diamine compound of the embodiment.

Accordingly, the polyimide-based polymer, which is a conjugate obtained by reacting the diamine compound of the embodiment, maintains the structure derived from the diamine compound as it is, so that the heat resistance, transparency, and low phase difference characteristics of the diamine compound may be realized as it is.

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

In Formula 1, Ar is 13 or more carbon atoms, 13 or more and 50 or less carbon atoms, 13 or more and 42 or less carbon atoms, 13 or more and 36 or less carbon atoms, 13 or more and 30 or less carbon atoms, wherein at least one substituent group including nitrogen-containing heteroaromatic compounds is bonded. It may be an aromatic divalent functional group of 18 or more and 30 or less.

The diamine compound of one embodiment of the present invention has a bulky structure as a parent of a diamine compound containing an aromatic divalent functional group having 13 or more carbon atoms, and a polyimide polymer synthesized from the diamine compound of the embodiment The effect of improving the thermal stability according to the three-dimensional structural deformation of can be increased, and the refractive index in the surface direction can be decreased and the refractive index in the thickness direction can be increased as the dihedral angle increases.

The aromatic divalent functional group having 13 or more carbon atoms may include 2 or more, or 3 or more, or 3 or more and 5 or less benzene rings. Examples of the aromatic divalent functional group having 13 or more carbon atoms are not particularly limited, but, for example, among terphenylene group, quarterphenylene group, pentaphenylene group, anthracenylene group, fluorenylene group, phenanthrenylene group, or pyrenylene group It can be one.

More preferably, the aromatic divalent functional group having 13 or more carbon atoms may be a terphenylene group, a quarterphenylene group, or a pentaphenylene group, and the terphenylene group, the quarterphenylene group and the pentaphenylene group are divalent represented by the following formula It may be a functional group.

On the other hand, according to an embodiment of the present invention, at least 1 or more, 1 or more 4 or less, or 2 or more 4 or less substituents including nitrogen-containing heteroaromatic compounds in the aromatic divalent functional group having 13 or more carbon atoms I can.

As described above, at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded, and as the substituent group including the nitrogen-containing heteroaromatic compound has a bulky structure, from the diamine compound of the embodiment Excellent thermal stability can be secured through a high glass transition temperature and a low coefficient of thermal expansion through the three-dimensional structural modification of the synthesized polyimide polymer.

Substituents including the nitrogen-containing heteroaromatic compound are not greatly limited, but pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group , 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, phenanthroline group (phenanthroline), isoxazolyl group, thiadiazolyl group, or phenothiazinyl group It may be a substituent including.

The substituent including the nitrogen-containing heteroaromatic compound may mean a nitrogen-containing heteroaromatic substituent or a substituent in which a nitrogen-containing heteroaromatic compound is bonded through a linker. For example, a substituent including a carbazole group may include all substituents selected from the group represented by the following formula.

In one embodiment of the invention, the substituent including the nitrogen-containing heteroaromatic compound may include one of the substituents represented by the following Formula 2-1 or Formula 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, A ₁ to A ₁₅ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen group, It is one of a cyano group and a C1-C10 haloalkyl group.

That is, in the substituent including the nitrogen-containing heteroaromatic compound, the heteroaromatic compound containing nitrogen may be a substituted or unsubstituted carbazole, and preferably, the substituent including the heteroaromatic compound containing nitrogen is substituted or unsubstituted. It may be a ringed carbazole group.

More specifically, in Formulas 2-1 and 2-2, A ₁ to A ₁₅ may each independently be one of hydrogen or a haloalkyl group having 1 to 10 carbon atoms. That is, the substituent represented by Formula 2-1 or Formula 2-2 may be an unsubstituted carbazole group or a carbazole group substituted with a haloalkyl group having 1 to 10 carbon atoms.

Meanwhile, the diamine compound may have axial symmetry or point symmetry. The axial symmetry means overlapping when symmetrical about one straight line, and the point symmetry means overlapping when rotated 180° about a point.

For example, the diamine compound having the structure represented by Formula 1 may satisfy point symmetry.

Specifically, the structure represented by Formula 1 may include a structure represented by Formula 3 below.

[Chemical Formula 3]

In Formula 3, T is a substituent including a heteroaromatic compound containing nitrogen, m3 to m5 are each independently an integer of 0 to 4, (m3 + m4 + m5) ≥ 1, and R is an electron attracting functional group , n1 to n3 are each independently an integer of 0 to 4, and m'is an integer of 1 to 5. In Formula 3, the substituent including the heteroaromatic compound containing nitrogen may be applied as it is to all the contents described above for Formula 1.

In Formula 3, m3 to m5 are each independently an integer of 0 to 4, (m3 + m4 + m5) ≥ 1, 1 ≤ (m3 + m4 + m5) ≤ 14, 2 ≤ (m3 + m4 + m5) ≦14, or 2≦(m3+m4+m5)≦4. That is, the diamine compound including the structure represented by Formula 3 is a diamine substituted with at least one, 1 or more 14 or less, 2 or more 14 or less, or 2 or more and 4 or less substituents including nitrogen-containing heteroaromatic compounds. It can be a compound.

The electron attracting functional group may include at least one selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group and a sulfonyl group, and preferably a trifluoromethyl group (-CF ₃ ) It may be a haloalkyl group such as.

More specifically, the structure represented by Formula 1 may include a structure represented by Formula 3-1 below.

[Chemical Formula 3-1]

In Formula 3-1, T is a substituent including a heteroaromatic compound containing nitrogen, m3 to m5 are each independently an integer of 0 to 4, (m3 + m4 + m5) ≥ 1, and R is an electron attractor Is a functional group, and n1 to n2 are each independently an integer of 0 to 4. In Formula 3-1, the substituent including the heteroaromatic compound containing nitrogen may be applied as it is to all the contents described above for Formula 1.

In Formula 3-1, m3 to m5 are each independently an integer of 0 to 4, (m3 + m4 + m5) ≥ 1, 1 ≤ (m3 + m4 + m5) ≤ 14, 2 ≤ (m3 + m4 + m5) ≤ 14, or 2 ≤ (m3 + m4 + m5) ≤ 4. That is, in the diamine compound including the structure represented by Formula 3-1, at least one substituent including a nitrogen-containing heteroaromatic compound is substituted with at least one, one or more and 14 or less, 2 or more and 14 or less, or 2 or more and 4 or less. It may be a diamine compound.

The electron attracting functional group may include at least one selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group and a sulfonyl group, and preferably a trifluoromethyl group (-CF ₃ ) It may be a haloalkyl group such as.

Further, in the diamine compound having the structure represented by Formula 3, if necessary, a substituent including a nitrogen-containing heteroaromatic compound and various substituted functional groups other than the electron attracting functional group may be further bonded. Examples of such a substituted functional group are not largely limited, and examples thereof include deuterium; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkoxysilylalkyl group; Alternatively, one or more substituents selected from the group consisting of an arylphosphine group may be substituted, or two or more substituents may be substituted among the aforementioned substituents.

More specifically, in the embodiment, the structure represented by Formula 1 may be a diamine compound including a structure represented by Formula 3-a below.

[Formula 3-a]

In Formula 3-a, T ₁ to T ₂ are each independently a substituent including a nitrogen-containing heteroaromatic compound, and R ₁₅ to R ₁₆ are each independently hydrogen or an electron attracting functional group. In Formula 3-a, the substituent and the electron-attracting functional group including the heteroaromatic compound containing nitrogen may be applied as it is.

As T ₁ to T ₂ in Formula 3-a are bonded to a specific position of the benzene ring, the diamine compound of the embodiment may have axial symmetry or point symmetry. For example, the diamine compound including the structure represented by Formula 3-a may have symmetry of point symmetry.

Specific examples of the structure represented by Formula 1 may include any one of a structure represented by Formula 1-1 to Formula 1-2 below.

[Formula 1-1]

[Chemical Formula 1-2]

.

.

The diamine compound of the embodiment may be reacted with a tetracarboxylic acid dianhydride compound to synthesize a polyamic acid or polyamic acid ester polymer, as described below, and a polyimide is prepared through a heat treatment reaction for a polyamic acid or polyamic acid ester polymer. It can be synthesized. That is, the diamine compound of the embodiment may be applied for synthesis of a polyimide-based polymer. In this case, the polyimide-based polymer refers to a polyimide and a precursor polymer thereof including polyamic acid and polyamic acid ester.

2. Acid anhydride compounds

According to an embodiment of the present invention, an acid anhydride compound having a structure represented by Chemical Formula 4 may be provided.

The present inventors, like the acid anhydride compound of the above embodiment, have an aromatic tetravalent functional group having 13 or more carbon atoms as a skeleton, thereby forming a more bulky structure than the pyromellitic dianhydride matrix that has been widely used. , Accordingly, the effect of improving the thermal stability according to the three-dimensional structural deformation of the polyimide polymer synthesized from the acid anhydride compound of the embodiment can be further increased, and the dihedral angle is increased due to the bulky structure. It was confirmed that the refractive index can be decreased and the refractive index in the thickness direction can be increased, and the invention was completed.

In addition, as shown in Formula 4, at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded, and the substituent group including the nitrogen-containing heteroaromatic compound has a bulky structure. It was confirmed that excellent thermal stability can be secured through a high glass transition temperature and a low coefficient of thermal expansion through the three-dimensional structural modification of the polyimide polymer synthesized from the acid anhydride compound of the embodiment.

Therefore, the polyimide-based polymer, which is a conjugate obtained by reacting the acid anhydride compound of the embodiment, maintains the structure derived from the acid anhydride compound, so that the heat resistance, transparency, and low phase difference properties of the acid anhydride compound can be realized as it is. .

Looking at the acid anhydride compound of the embodiment in more detail, it may have a structure represented by Chemical Formula 4.

In Formula 4, Ar' represents at least one substituent group including a nitrogen-containing heteroaromatic compound bonded to 13 or more carbon atoms, 13 or more and 50 or less carbon atoms, 13 or more and 42 or less carbon atoms, 13 or more and 36 or less carbon atoms, 13 or more and 30 or less carbon atoms, It may be an aromatic tetravalent functional group having 18 or more and 30 or less carbon atoms.

The acid anhydride compound of one embodiment of the present invention has a bulky structure as a parent of the aromatic tetravalent functional group having 13 or more carbon atoms, and is a three-dimensional polyimide polymer synthesized from the acid anhydride compound of the embodiment. It is possible to further increase the effect of improving the thermal stability according to the structural deformation, and increase the refractive index in the thickness direction while decreasing the refractive index in the plane direction by increasing the dihedral angle.

The aromatic tetravalent functional group having 13 or more carbon atoms may include 2 or more, or 3 or more, or 3 or more and 5 or less benzene rings. Examples of the aromatic tetravalent functional group having 13 or more carbon atoms are not particularly limited, but may be, for example, a tetravalent functional group derived from one of terphenyl, quarterphenyl, pentaphenyl, anthracene, fluorene, phenanthrene, or pyrene. .

More preferably, the aromatic tetravalent functional group having 13 or more carbon atoms may be a tetravalent functional group derived from terphenyl, quarterphenyl, or pentaphenyl, and the tetravalent functional group derived from terphenyl, quarterphenyl, or pentaphenyl It may be a tetravalent functional group represented by the following formula.

Meanwhile, according to an embodiment of the present invention, at least 1 or more, 2 or more, or 2 or more and 4 or less substituents including nitrogen-containing heteroaromatic compounds in the aromatic tetravalent functional group having 13 or more carbon atoms may be bonded.

As described above, as the substituent including the nitrogen-containing heteroaromatic compound is bonded to at least one or more, and the substituent including the nitrogen-containing heteroaromatic compound has a bulky structure, the acid anhydride compound of the embodiment Excellent thermal stability can be secured through a high glass transition temperature and a low coefficient of thermal expansion through three-dimensional structural modification of the polyimide polymer synthesized from

Substituents including the nitrogen-containing heteroaromatic compound are not greatly limited, but pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group , 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, phenanthroline group (phenanthroline), isoxazolyl group, thiadiazolyl group, or phenothiazinyl group It may be a substituent including.

The substituent including the nitrogen-containing heteroaromatic compound may mean a nitrogen-containing heteroaromatic substituent or a substituent in which a nitrogen-containing heteroaromatic compound is bonded through a linker. For example, a substituent including a carbazole group may include all substituents selected from the group represented by the following formula.

In one embodiment of the present invention, the substituent including the nitrogen-containing heteroaromatic compound may include one of the substituents represented by the following Formula 2-1 or Formula 2-2.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, A ₁ to A ₁₅ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen group, It is one of a cyano group and a C1-C10 haloalkyl group.

That is, in the substituent including the nitrogen-containing heteroaromatic compound, the heteroaromatic compound containing nitrogen may be a substituted or unsubstituted carbazole, and preferably, the substituent including the heteroaromatic compound containing nitrogen is substituted or unsubstituted. It may be a ringed carbazole group.

More specifically, in Formulas 2-1 and 2-2, A ₁ to A ₁₅ may each independently be one of hydrogen or a haloalkyl group having 1 to 10 carbon atoms. That is, the substituent represented by Formula 2-1 or Formula 2-2 may be an unsubstituted carbazole group or a carbazole group substituted with a haloalkyl group having 1 to 10 carbon atoms.

Meanwhile, the acid anhydride compound may have axial symmetry or point symmetry. The axial symmetry means overlapping when symmetrical about one straight line, and the point symmetry means overlapping when rotated 180° about a point.

For example, the acid anhydride compound having a structure represented by Formula 4 may satisfy point symmetry.

Specifically, the structure represented by Formula 4 may include a structure represented by Formula 5 below.

[Chemical Formula 5]

In Formula 5, T is a substituent including a heteroaromatic compound containing nitrogen, m15 to m17 are each independently an integer of 0 to 4, (m15 + m16 + m17) ≥ 1, and R is an electron attracting functional group , n9 to n11 are each independently an integer of 0 to 4, and m" is an integer of 1 to 5.

In Formula 5, the substituent including the heteroaromatic compound containing nitrogen may be applied to all the contents described above for Formula 4 as it is.

In Formula 5, m15 to m17 are each independently an integer of 0 to 4, (m15 + m16 + m17) ≥ 1, 1 ≤ (m15 + m16 + m17) ≤ 14, 2 ≤ (m15 + m16 + m17) ≦14, or 2≦(m15 + m16 + m17) ≦4. That is, in the acid anhydride compound comprising the structure represented by Formula 5, at least one substituent including a heteroaromatic compound containing nitrogen is substituted with at least 1, 1 or more and 14 or less, 2 or more and 14 or less, or 2 or more and 4 or less. It may be an acid anhydride compound.

The electron attracting functional group may include at least one selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group and a sulfonyl group, and preferably a trifluoromethyl group (-CF ₃ ) It may be a haloalkyl group such as.

More specifically, the structure represented by Formula 4 may include a structure represented by Formula 5-1 below.

[Chemical Formula 5-1]

In Formula 5-1, T is a substituent including a heteroaromatic compound containing nitrogen, m15 to m17 are each independently an integer of 0 to 4, (m15 + m16 + m17) ≥ 1, and R is an electron attractor Is a functional group, and n9 to n10 are each independently an integer of 0 to 4.

In Formula 5-1, the substituent including the heteroaromatic compound containing nitrogen may be applied as it is to all the contents described above for Formula 4.

In Formula 5-1, m15 to m17 are each independently an integer of 0 to 4, (m15 + m16 + m17) ≥ 1, 1 ≤ (m15 + m16 + m17) ≤ 14, 2 ≤ (m15 + m16 + m17) ≤ 14, or 2 ≤ (m15 + m16 + m17) ≤ 4. That is, in the acid anhydride compound including the structure represented by Formula 5-1, the substituent group including the heteroaromatic compound containing nitrogen is at least 1 or more, 1 or more and 14 or less, 2 or more and 14 or less, or 2 or more and 4 or less It may be a substituted acid anhydride compound.

The electron attracting functional group may include at least one selected from the group consisting of a haloalkyl group, a halogen group, a cyano group, a nitro group, a sulfonic acid group, a carbonyl group and a sulfonyl group, and preferably a trifluoromethyl group (-CF ₃ ) It may be a haloalkyl group such as.

Further, in the acid anhydride compound having the structure represented by Formula 5-1, a substituent including a nitrogen-containing heteroaromatic compound and various substituent functional groups other than the electron attracting functional group may be further bonded, if necessary. Examples of such a substituted functional group are not largely limited, and examples thereof include deuterium; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amide group; Primary amino group; Carboxyl group; Sulfonic acid group; Sulfonamide group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkoxysilylalkyl group; Or it may be substituted with one or more substituents selected from the group consisting of an arylphosphine group, or two or more of the substituents exemplified above may be substituted.

More specifically, in the above embodiment, the structure represented by Chemical Formula 4 may be an acid anhydride compound including the structure represented by Chemical Formula 5-a.

[Formula 5-a]

In Formula 5-a, T ₇ to T ₈ are each independently a substituent including a nitrogen-containing heteroaromatic compound, and R ₂₃ to R ₂₄ are each independently hydrogen or an electron attracting functional group.

In the above formula 5-a, the substituent and the electron attracting functional group including the heteroaromatic compound containing nitrogen may be applied as it is.

As T ₇ to T ₈ in Formula 5-a are bonded to a specific position of the benzene ring, the acid anhydride compound of the embodiment may have symmetry of axial symmetry or point symmetry. For example, the acid anhydride compound including the structure represented by Formula 5-1 may have symmetry of point symmetry.

Specific examples of the structure represented by Formula 4 may include any one of a structure represented by Formula 4-1 to Formula 4-2 below.

[Formula 4-1]

[Formula 4-2]

As described below, the acid anhydride compound of the embodiment may be reacted with a diamine compound to synthesize a polyamic acid or polyamic acid ester polymer, and a polyimide may be synthesized through a heat treatment reaction for a polyamic acid or polyamic acid ester polymer. have. That is, the acid anhydride compound of the embodiment may be applied for synthesis of a polyimide-based polymer. In this case, the polyimide-based polymer refers to a polyimide and a precursor polymer thereof including polyamic acid and polyamic acid ester.

3. Polyimide polymer

Meanwhile, according to another embodiment of the present invention, including at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 7, a repeating unit represented by Formula 8, and a repeating unit represented by Formula 9, Polyimide-based polymers may be provided.

The polyimide-based polymer refers to a polyimide and a precursor polymer thereof including polyamic acid and polyamic acid ester. 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 the repeating unit represented by Formula 7, the polyamic acid ester repeating unit includes the repeating unit represented by Formula 8, and the polyamic acid repeating unit is represented by Formula 9 It may include a displayed 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 a main chain of the polyimide-based polymer.

In Chemical Formula 7, at least one of R ₁ and R ₂ may be an alkyl group having 1 to 10 carbon atoms, and the rest may be hydrogen. That is, in Formula 7, R ₁ may be an alkyl group having 1 to 10 carbon atoms, and R ₂ may be hydrogen. In addition, in Formula 7, R ₂ may be an alkyl group having 1 to 10 carbon atoms, and R ₁ may be hydrogen. In addition, in Formula 7, R ₁ and R ₂ may be an alkyl group having 1 to 10 carbon atoms.

Meanwhile, in Formulas 7 to 9, X ₁ to X ₃ may be the same as or different from each other, and may each independently be a tetravalent functional group. The X ₁ to X ₃ may be a functional group derived from a polyamic acid, a polyamic acid ester, or a tetracarboxylic acid or an anhydride compound thereof used in synthesizing a polyimide.

Meanwhile, in Formulas 7 to 9, Y ₁ to Y ₃ may be the same as or different from each other, and each independently may be a divalent functional group. The Y ₁ to Y ₃ may be a polyamic acid, a polyamic acid ester, or a functional group derived from the diamine compound of the embodiment used when synthesizing a polyimide.

In one embodiment of the invention, of the formulas 7 to 9 of X ₁ to X ₃ Tetravalent functional groups and Of Y ₁ to Y ₃ Divalent functional group At least one of Aromatic with at least 1 or more substituents including nitrogen-containing heteroaromatic compounds bonded to at least 1 carbon atom, 13 or more carbon atoms and 50 or less carbon atoms, 13 or more and 42 or less carbon atoms, 13 or more and 36 or less carbon atoms, 13 or more and 30 or less carbon atoms, 18 or more 30 or less carbon atoms n is a functional group, and n may be 2 or 4.

That is, of the X ₁ to X ₃ Tetravalent functional groups and Of Y ₁ to Y ₃ Divalent functional group At least one substituent group including a nitrogen-containing heteroaromatic compound may be bonded to at least one of them.

Specifically, i) when using the diamine compound of the embodiment, Y ₁ to Y ₃ The divalent functional group is an aromatic divalent functional group having 13 or more carbon atoms in which at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded, and ii) when the acid anhydride compound of the above embodiment is used, X ₁ to X ₃ When the tetravalent functional group is an aromatic tetravalent functional group having 13 or more carbon atoms bonded to at least one substituent group including a heteroaromatic compound containing nitrogen, and iii) the diamine compound of the embodiment and the acid anhydride compound of the embodiment are used at the same time, Of Y ₁ to Y ₃ The divalent functional group is an aromatic divalent functional group having 13 or more carbon atoms in which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded, and of X ₁ to X ₃ The tetravalent functional group may be an aromatic tetravalent functional group having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded.

In one embodiment of the present invention, Y ₁ to Y ₃ in Formulas 7 to 9 are each independently an aromatic divalent functional group having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded, and the formula 7 to X ₁ to X ₃ of 9 may each independently be one of the tetravalent functional groups described in Formula 10 below. The aromatic divalent functional group having 13 or more carbon atoms to which at least one substituent group including the nitrogen-containing heteroaromatic compound is bonded may include all the contents described above in the embodiment.

[Formula 10]

In Formula 10, R ₃ to R ₈ are each independently hydrogen or one of an alkyl group having 1 to 10 carbon atoms, and L ₄ is a direct bond, -O-, -CO-, -S-, -SO-,- SO ₂ -, -CR ₉ R ₁₀ -, -CONH-, -COO-, -(CH ₂ ) _t -, -O(CH ₂ ) _t O-, -COO-(CH ₂ ) _t -OCO-, phenyl Is any one selected from the group consisting of ene or a combination thereof, and in L ₄ , R ₉ and R ₁₀ are each independently 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.

That is, the polyimide-based polymer may include a combination of the diamine compound and the tetracarboxylic dianhydride compound of the embodiment. The repeating unit represented by Formula 7, the repeating unit represented by Formula 8, and the repeating unit represented by Formula 9 included in the polyimide-based polymer are the reaction of the diamine compound and tetracarboxylic acid or an anhydride compound thereof of the embodiment. It may be a repeating unit contained in the binder obtained by.

More specifically, the reaction between the terminal amino group (-NH ₂ ) of the diamine compound of the above embodiment and the terminal anhydride group (-OC-O-CO-) of the tetracarboxylic acid or its anhydride compound is a reaction between the nitrogen atom of the amino group and the carbon source of the anhydride group. Interpersonal bonds can be formed.

Accordingly, the polyimide-based polymer of the other embodiment may have the effect of the diamine compound of the one embodiment as it is, and specifically, containing the repeating units of Formulas 7 to 9 derived from the diamine compound of the one embodiment. As the polyimide-based polymer contains an aromatic divalent functional group having 13 or more carbon atoms in which at least one substituent including the nitrogen-containing heteroaromatic compound is bonded at the Y ₁ to Y ₃ positions, excellent transparency, high heat resistance, and low retardation Can be implemented.

Or, in one embodiment of the invention, in the polyimide-based polymer, Y ₁ to Y ₃ of Formulas 7 to 9 are each independently a divalent functional group represented by the following Formula 11, X ₁ to of Formulas 7 to 9 Each of X ₃ may independently be one of an aromatic tetravalent functional group having 13 or more carbon atoms to which at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded. The aromatic tetravalent functional group having 13 or more carbon atoms to which at least one substituent group including the nitrogen-containing heteroaromatic compound is bonded may include all the contents described above in the embodiment.

[Formula 11]

In Formula 11, R ₃₀ and R ₃₁ are each independently hydrogen, halogen, cyano, nitrile, alkyl having 1 to 10 carbon atoms, alkenyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, and 1 to 10 carbon atoms. Of haloalkyl, or haloalkoxy having 1 to 10 carbon atoms, p and q are each independently an integer of 0 to 4, A is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH-, -COO-, -(CH ₂ ) _y -, -O(CH ₂ ) _y O-, -O(CH ₂ ) _y -, -NH-, -NH(CH ₂ ) _y -NH-, -NH(CH ₂ ) _y O-, -OCH ₂ -C(CH ₃ ) ₂ -CH ₂ O-, -COO-(CH ₂ ) _y -OCO-, or -OCO-(CH ₂ ) _y -COO-, y is an integer of 1 to 10, k and m are each independently an integer of 0 to 3, r is an integer of 0 to 3 to be.

That is, the polyimide-based polymer may include a combination of a diamine compound and an acid anhydride compound of the embodiment. The repeating unit represented by Formula 7, the repeating unit represented by Formula 8, and the repeating unit represented by Formula 9 included in the polyimide polymer are bonds obtained by reaction of a diamine compound and the acid anhydride compound of the embodiment. It may be a repeating unit contained in water.

More specifically, the reaction between the terminal amino group (-NH ₂ ) of the diamine compound and the terminal anhydride group (-OC-O-CO-) of the acid anhydride compound of the above embodiment results in the bonding between the nitrogen atom of the amino group and the carbon atom of the anhydride group. Can be formed.

Accordingly, the polyimide-based polymer of another embodiment may have the effect of the acid anhydride compound of the one embodiment as it is, and specifically, the repeating units of Formulas 7 to 9 derived from the acid anhydride compound of the one embodiment The contained polyimide-based polymer contains an aromatic tetravalent functional group having 13 or more carbon atoms in which at least one substituent including the nitrogen-containing heteroaromatic compound is bonded at the X ₁ to X ₃ positions, and thus has excellent transparency, high heat resistance, and A low phase difference can be implemented.

Or, in one embodiment of the present invention, in the polyimide polymer, Y ₁ to Y ₃ of Formulas 7 to 9 are each independently an aromatic 2 having at least 1 carbon atoms bonded to at least one substituent including a heteroaromatic compound containing nitrogen Is a functional group, and X ₁ to X ₃ in Formulas 7 to 9 may each independently be one of an aromatic tetravalent functional group having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded.

That is, the polyimide-based polymer may include a combination of the diamine compound of the embodiment and the acid anhydride compound of the embodiment. The repeating unit represented by Formula 7, the repeating unit represented by Formula 8, and the repeating unit represented by Formula 9 included in the polyimide-based polymer are the diamine compound of the embodiment and the acid anhydride compound of the embodiment. It may be a repeating unit contained in the bond obtained by the reaction.

More specifically, by reaction of the terminal amino group (-NH ₂ ) of the diamine compound of the embodiment and the terminal anhydride group (-OC-O-CO-) of the acid anhydride compound of the embodiment, the nitrogen atom of the amino group and the anhydride group are Bonds between carbon atoms can be formed.

Therefore, the polyimide-based polymer of another embodiment may have the effect of the diamine compound of the one embodiment and the acid anhydride compound of the one embodiment as it is, and specifically, the diamine compound of the one embodiment and the acid of the one embodiment. In the polyimide-based polymer containing the repeating units of Formulas 7 to 9 derived from an anhydride compound, an aromatic divalent functional group having 13 or more carbon atoms bonded to at least one substituent including the nitrogen-containing heteroaromatic compound is Y ₁ to Y _Since it is contained in the ₃ position and contains an aromatic tetravalent functional group having 13 or more carbon atoms in which at least one substituent including the nitrogen-containing heteroaromatic compound is bonded to the X ₁ to X ₃ position, excellent transparency, high heat resistance, and low retardation Can be implemented.

Accordingly, the polyimide-based polymer according to an embodiment of the present invention may include a reaction product obtained from at least one monomer of the diamine compound of the embodiment and the acid anhydride compound of the embodiment. Accordingly, i) includes a combination of the diamine compound of one embodiment and a general acid anhydride compound, ii) includes a combination of a general diamine compound and the acid anhydride compound of one embodiment, or iii) the diamine of the embodiment It may include a combination of the compound and the acid anhydride compound of the embodiment.

Although the weight average molecular weight (GPC measurement) of the polyimide-based polymer is not largely limited, it may be, for example, 10000 g/mol to 200000 g/mol.

The polyimide-based polymer according to the present invention can exhibit excellent colorless and transparent properties while maintaining properties such as heat resistance and mechanical strength due to a rigid structure, such as a device substrate, a cover substrate for a display, and an optical film. , IC (integrated circuit) package, adhesive film, multi-layer FRC (flexible printed circuit), tape, touch panel, protective film for optical discs, etc., can be used in various fields, especially suitable for cover substrates for displays. have.

The example of the method for synthesizing the polyimide polymer is not largely limited, for example, the diamine compound of the embodiment is a tetracarboxylic acid or an anhydride thereof commonly used in the production of polyamic acid, for example, pyromellitic acid. Pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (3,3',4,4'-Biphenyl Tetracarboxylic Acid Dianhydride, BPDA), 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (1,2,4,5-Cyclohexanetetracarboxylic Dianhydride, HPMDA), 1,3-dimethyl-cyclobutane-1,2,3,4-tetracarboxylic dianhydride (DMCBDA) or their By reacting with a mixture of two or more types, an amic acid, an amic acid ester, or a polymer composed of a mixture thereof may be prepared.

Or, if necessary, together with the diamine compound of the embodiment, one or more of various types of diamine compounds generally known, for example, p-phenylenediamine, 4,4-oxydianiline, 4,4'-methylene Dianiline or the like can be simultaneously mixed to prepare a polyamic acid copolymer, a polyamic acid ester copolymer, and a polyimide copolymer. In addition, in addition to the diamine compound of the embodiment, one or more of various types of diamine compounds generally known, for example, p-phenylenediamine, 4,4-oxydianiline, 4,4'-methylenedianiline, etc. After polymerization by using separately, a polyamic acid polymer mixture, a polyamic acid ester polymer mixture, and a polyimide polymer mixture may be prepared.

Or, for example, the acid anhydride compound of the embodiment is a diamine compound commonly used in the preparation of polyamic acid, for example, p-phenylenediamine, 4,4-oxydianiline, 4,4'-methylene Dianiline or a mixture of two or more thereof may be reacted to prepare a polymer composed of amic acid, amic acid ester, or a mixture thereof.

Or, if necessary, together with the acid anhydride compound of the embodiment, one or more of various types of acid anhydride compounds generally known, for example, pyromellitic dianhydride (PMDA), 3, 3',4,4'-biphenyl tetracarboxylic 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 dianhydride (DMCBDA), etc. are simultaneously mixed to form a polyamic acid copolymer, a polyamic acid ester copolymer. It is possible to prepare a coalescence, polyimide copolymer. In addition, in addition to the acid anhydride compound of the embodiment, one or more of various types of acid anhydride compounds generally known, for example, 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), etc. were separately used for polymerization and then mixed, polyamic acid polymer mixture, polya Mix acid ester polymer mixtures and polyimide polymer mixtures can be prepared.

Alternatively, a polymer composed of amic acid, an amic acid ester, or a mixture thereof may be prepared by reacting the diamine compound of the embodiment with the acid anhydride compound of the embodiment.

The reaction conditions may be appropriately adjusted by referring to the production conditions of polyamic acid known in the art, such as solution polymerization. Specifically, it can be produced by dissolving diamine in an organic solvent and then adding a tetracarboxylic acid or an anhydride thereof for polymerization. The reaction can be carried out under an inert gas or nitrogen stream, and can 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, as an organic solvent that can be used in the polymerization reaction, specifically, gamma-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 (cellosolve) such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethanol, propanol, ethylene glycol, propylene glycol, carbitol, dimethyl Acetamide (DMAc), N,N-diethylacetamide, dimethylformamide (DMF), diethylformamide (DEF), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), 1,3-dimethyl-2-imidazolidinone, N,N-dimethylmethoxyacetamide, dimethyl sulfoxide, pyridine, dimethylsulfone, 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, the group consisting of the repeating unit represented by Formula 7 above, the repeating unit represented by Formula 8, and the repeating unit represented by Formula 9 by imidizing the amic acid, amic acid ester, or mixture thereof obtained above Including one or more repeating units selected from, it is possible to prepare a polyimide-based polymer.

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

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

As the dehydrating agent, an acid anhydride such as acetic anhydride can be used.

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

4. Polymer film

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

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

Although the thickness of the polymer film is not largely limited, for example, it can be freely adjusted within the range of 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 certain value.

An example of a method of synthesizing the polymer film is not limited, for example, forming a coating film by applying a polymer resin composition containing the polyimide polymer of the other embodiment to a substrate (step 1); Drying the coating film (step 2); A method of manufacturing 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 polyimide polymer to a substrate. The method of applying the polymer resin composition containing the polyimide polymer to the substrate is not particularly limited, and for example, a method such as screen printing, offset printing, flexo printing, inkjet, etc. may be used.

In addition, the polymer resin composition containing the polyimide polymer may be dissolved or dispersed in an organic solvent. In the case of having such a form, for example, when a polyimide-based polymer is synthesized in an organic solvent, the solution may be the reaction solution itself obtained, or the reaction solution may be diluted with another solvent. Further, when a polyimide polymer is obtained as a powder, it may be dissolved in an organic solvent to obtain a solution.

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 Mil 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, other components may be further included in addition to the polymer resin composition organic solvent. As a non-limiting example, when the polymer resin composition is applied, the uniformity of the film thickness or surface smoothness is improved, the adhesion to the substrate is improved, the dielectric constant or conductivity is changed, or the density is increased. Additives that can be added may be included. Examples of such additives include surfactants, silane compounds, dielectrics or crosslinkable compounds.

Step 2 is a step of drying a coating film formed by applying the polymer resin composition to a 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, or 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 hardening the dried coating film by heat treatment. In this case, the heat treatment may be performed by a heating means such as a hot plate, a hot air circulation furnace, or an infrared furnace, and may be performed at a temperature of 180°C to 300°C or 200°C to 300°C.

5. Display device substrate

Meanwhile, according to another embodiment of the present invention, a substrate for a display device including the polyimide resin film of the other embodiment may be provided. The contents of the polyimide-based resin film may include all the contents described above in the embodiment.

The display device including the substrate is 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 are not limited thereto.

The display device may have a variety of structures depending on the application field and specific shape, and may include, for example, 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 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 such various display devices, and more specifically, may be applied as a substrate.

For example, the substrate for a display device may have a structure in which a device protection layer, a transparent electrode layer, a silicon oxide layer, a polyimide resin 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 resin film and the cured layer in terms of further improving solvent resistance, moisture permeability, and optical properties, and the silicon oxide layer It may be produced by curing silazane.

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

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

6. Optical device

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

The optical device may include all types 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 are not limited thereto.

The optical device may have various structures depending on the application field and specific shape, and may be a structure including, for example, 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 resin film of another embodiment described above may be used in various applications such as a substrate, an external protective film, or a cover window in such various optical devices, and more specifically, may be applied to a substrate.

According to the present invention, a diamine compound and an acid anhydride compound for synthesizing polyimide, which can realize excellent transparency, high heat resistance, and low retardation, and a polyimide-based polymer, a polymer film, and an optical device using the same can be provided.

Hereinafter, a preferred embodiment is presented to aid the understanding of the present invention. However, the following examples are provided for easier understanding of the present invention, and the content of the present invention is not limited thereby.

[Synthesis Examples 1 to 4: Preparation of diamine and anhydride compound]

Synthesis Example 1: Preparation of diamine compound DA-1

25.0 g (91.9 mmol) of 1,4-dibromo-2,5-difluorobenzene (1,4-dibromo-2,5-difluorobenzene, compound A) and 32.3 g (19.3 mmol) of carbazole ( After dissolving carbazole, compound B) in 200 mL of dimethyl sulfoxide (DMSO), 31.7 g (22.9 mmol) of potassium carbonate (K ₂ CO ₃ ) was added and stirred at 200° C. for 12 hours. When the reaction was completed, 800 mL of water was added to the reaction product, and the resulting solid was filtered. The filtered solid was recrystallized using an ethanol solvent to synthesize 41.6 g of compound C (yield 80%).

MS and NMR measurement results of Compound C are as follows.

MS: [M+H] ⁺ = 563.9800

¹ H NMR (300 MHz, DMSO): δ 8.55 (d, J = 7.5 Hz, 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.58 (d , J = 7.5 Hz, 2H), 7.58 (s, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.35 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 7.5 Hz, 2H ), 7.16 (t, J = 7.5 Hz, 2H), 4.30 (s, 2H)

¹³ C NMR (101 MHz, CDCl ₃ ): δ 142.7, 139.7, 126.6, 122.7, 121.4, 119.8, 112.0, 109.5

41.6 g (73.4 mmol) of compound C and 37.6 g (183 mmol) of compound D were dissolved in 300 mL of THF solvent, and 30.4 g (220 mmol) of potassium carbonate (K ₂ CO ₃ ) were dissolved in 150 mL of water, and heated and stirred together. I did. 0.37 g (0.73 mmol) of bis(tri-tert-butylpostine) palladium was slowly added thereto, followed by heating and stirring for 12 hours. After the reaction was completed, it was cooled to room temperature and extracted with water and ethyl acetate. The organic layer was dried using anhydrous magnesium sulfate (MgSO ₄ ) and concentrated through a vacuum distillation apparatus to prepare 42.1 g of a diamine compound (DA-1) (yield 79%).

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

MS: [M+H] ⁺ = 726.2231

¹ H NMR (300 MHz, DMSO): δ 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz , 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.55 (d, J = 7.5 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.37 (s, 1H), 7.35 (t , J = 7.5 Hz, 2H), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H), 6.58 (d, J = 7.5 Hz, 2H), 5.28 (s, 4H )

¹³ C NMR (101 MHz, DMSO): δ 147.6, 140.5, 139.7, 130.7, 128.3, 126.6, 123.9, 122.7, 121.4, 120.7, 120.2, 119.8, 119.7, 118.4, 112.6, 109.5

Synthesis Example 2: Preparation of diamine compound DA-2

38.0 g (67.1 mmol) of compound C and 23.0 g (167 mmol) of compound E were dissolved in 280 mL of THF solvent, and 27.8 g (201 mmol) of potassium carbonate (K ₂ CO ₃ ) were dissolved in 140 mL of water and heated and stirred. I did. 0.34 g (0.67 mmol) of bis(tri-tert-butylpostine) palladium was slowly added thereto, followed by heating and stirring for 12 hours. After the reaction was completed, it was cooled to room temperature and extracted with water and ethyl acetate. The organic layer was dried using anhydrous magnesium sulfate (MgSO ₄ ) and concentrated through a vacuum distillation apparatus to prepare 31.0 g of a diamine compound (DA-2) (yield 78%).

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

MS: [M+H] ⁺ = 590.7301

¹ H NMR (300 MHz, DMSO): δ 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz , 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.44 (d, J = 7.5 Hz, 4H), 7.35 (t, J = 7.5 Hz, 2H ), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H), 6.58 (d, J = 7.5 Hz, 4H), 5.24 (s, 4H)

¹³ C NMR (101 MHz, DMSO): δ 144.5, 140.5, 139.7, 130.9, 128.7, 128.3, 126.6, 122.7, 121.4, 120.2, 119.8, 109.5

Synthesis Example 3: Preparation of anhydride compound AN-1

60.0 g (106 mmol) of compound C and 84.8 g (265 mmol) of compound F were dissolved in 440 mL of THF solvent, and 43.9 g (318 mmol) of potassium carbonate (K ₂ CO ₃ ) was dissolved in 220 mL of water, followed by heating and stirring. . 0.54g (1.06mmol) of bis(tri-tert-butylpostine) palladium was slowly added thereto, followed by heating and stirring for 12 hours. After the reaction was completed, it was cooled to room temperature and extracted with water and ethyl acetate. The organic layer was dried using anhydrous magnesium sulfate (MgSO ₄ ) and concentrated through a vacuum distillation apparatus to prepare 69.0 g of compound G (yield 82%).

The MS and NMR measurement results of Compound G are as follows.

MS: [M+H] ⁺ = 792.2470

¹ H NMR (300 MHz, DMSO): δ 8.73 (s, 2H), 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.31 (d, J = 7.5 Hz, 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.96 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.50 (t , J = 7.5 Hz, 2H), 7.35 (d, J = 7.5 Hz, 4H), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H), 3.90 (s, 12H )

¹³ C NMR (101 MHz, DMSO): δ 168.0, 140.7, 140.5, 139.7, 132.9, 132.1, 131.3, 130.6, 130.3, 128.3, 126.6, 122.7, 121.4, 120.2, 119.8, 109.5, 51.5

69.0 g (87.0 mmol) of compound G was dissolved in 450 mL of THF solvent, 39.0 g (696 mmol) of KOH was dissolved in 450 mL of water and added thereto, followed by heating and stirring for 6 hours. After the reaction was completed, it was cooled to room temperature and an aqueous layer was extracted. Hydrochloric acid was slowly added to the water layer so that the pH was 2 to 3, and the resulting solid was filtered. After drying in an oven at 120° C., 57.0 g of compound H was prepared (yield 88%).

MS and NMR measurement results of Compound H are as follows.

MS: [M+H] ⁺ = 736.1843

¹ H NMR (300 MHz, DMSO): δ 13.29 (s, 4H), 8.99 (s, 2H), 8.57 (d, J = 7.5 Hz, 2H), 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.50 (t, J = 7.5 Hz , 2H), 7.35 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H)

¹³ C NMR (101 MHz, DMSO): δ 167.6, 141.6, 140.5, 139.7, 133.4, 133.0, 131.8, 131.0, 130.7, 128.3, 126.6, 122.7, 121.4, 120.2, 119.8, 109.5

57.0 g (77.4 mmol) of the compound H was heated and stirred in 480 mL acetic anhydride and 480 mL acetic acid for 8 hours. After completion of the reaction, the mixture was cooled to room temperature and the resulting solid was filtered to prepare 50.0 g of an anhydride compound (AN-1) (yield 92%).

MS and NMR measurement results of the anhydride compound (AN-1) are as follows.

MS: [M+H] ⁺ = 700.1635

¹ H NMR (300 MHz, DMSO): δ 8.99 (s, 2H), 8.57 (d, J = 7.5 Hz, 2H), 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.35 (t , J = 7.5 Hz, 2H), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H)

¹³ C NMR (101 MHz, DMSO): δ 162.3, 141.6, 140.5, 139.7, 133.0, 131.0, 130.7, 130.1, 130.0, 128.3, 126.6, 122.7, 121.4, 120.2, 119.8, 109.5

Synthesis Example 4: Preparation of anhydride compound AN-2

56.0 g (98.9 mmol) of compound C and 95.9 g (247 mmol) of compound I were dissolved in 400 mL of THF solvent, and 41.0 g (297 mmol) of potassium carbonate (K ₂ CO ₃ ) were dissolved in 200 mL of water and heated and stirred together. I did. 0.50g (0.99mmol) of bis(tri-tert-butylpostine) palladium was slowly added thereto, followed by heating and stirring for 12 hours. After the reaction was completed, it was cooled to room temperature and extracted with water and ethyl acetate. The organic layer was dried using anhydrous magnesium sulfate (MgSO ₄ ) and concentrated through a vacuum distillation apparatus to prepare 71.6 g of compound J (yield 78%).

MS and NMR measurement results of Compound J are as follows.

MS: [M+H] ⁺ = 928.2224

¹ H NMR (300 MHz, DMSO): δ 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.31 (d, J = 7.5 Hz, 2H), 8.19 (d, J = 7.5 Hz , 2H), 8.02 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H ), 7.35 (d, J = 7.5 Hz, 4H), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H), 3.90 (s, 12H)

¹³ C NMR (101 MHz, DMSO): δ 168.2, 168.0, 140.5, 139.7, 133.9, 133.6, 132.4, 131.6, 131.0, 128.3, 128.1, 126.6, 122.7, 121.4, 120.2, 119.8, 118.7, 09.5, 51.5

71.6 g (77.1 mmol) of the compound J was dissolved in 550 mL of THF solvent, 34.6 g (617 mmol) of KOH was dissolved in 550 mL of water, and then heated and stirred for 6 hours. After the reaction was completed, it was cooled to room temperature and an aqueous layer was extracted. Hydrochloric acid was slowly added to the water layer so that the pH was 2 to 3, and the resulting solid was filtered. After drying in an oven at 120° C., 53.8 g of compound K was prepared (yield 80%).

MS and NMR measurement results of Compound K are as follows.

MS: [M+H] ⁺ = 872.1594

¹ H NMR (300 MHz, DMSO): δ 13.29 (s, 2H), 12.75 (s, 2H), 8.57 (d, J = 7.5 Hz, 2H), 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.25 (d, J = 7.5 Hz, 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.58 (d, J = 7.5 Hz , 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.35 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H )

¹³ C NMR (101 MHz, DMSO): δ 167.6, 156.1, 140.5, 139.7, 134.8, 134.0, 133.3, 132.1, 131.4, 128.6, 128.3, 126.6, 122.7, 121.4, 120.2, 119.8, 118.7, 109.5

53.8 g (61.6 mmol) of compound K obtained in the second step was heated and stirred in 450 mL acetic anhydride and 450 mL acetic acid for 8 hours. After the reaction was completed, the mixture was cooled to room temperature and the resulting solid was filtered to prepare 46.4 g of an anhydride compound (AN-2) (yield 90%).

MS and NMR measurement results of the anhydride compound (AN-2) are as follows.

MS: [M+H] ⁺ = 836.1384

¹ H NMR (300 MHz, DMSO): δ 8.57 (d, J = 7.5 Hz, 2H), 8.55 (d, J = 7.5 Hz, 2H), 8.54 (s, 2H), 8.25 (d, J = 7.5 Hz , 2H), 8.19 (d, J = 7.5 Hz, 2H), 7.94 (d, J = 7.5 Hz, 2H), 7.58 (d, J = 7.5 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H ), 7.35 (t, J = 7.5 Hz, 2H), 7.20 (t, J = 7.5 Hz, 2H), 7.16 (t, J = 7.5 Hz, 2H)

¹³ C NMR (101 MHz, DMSO): δ 166.5, 162.3, 140.5, 139.7, 134.8, 134.0, 133.3, 131.4, 129.9, 128.8, 126.6, 122.7, 121.4, 120.2, 119.8, 118.7, 109.5

[Examples 1 to 5: Preparation of polyamic acid solution and polyimide film]

Example 1

(1) Preparation of polyamic acid solution

The diamine compound DA-1 obtained in Synthesis Example 1 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 resulting solution was stirred at 25° C. for 16 hours and filtered under pressure with a filter made of poly(tetrafluoroethylene) having a pore size of 0.1 μm. Thus, a polyamic acid solution was prepared.

(2) Preparation of polyimide film

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

Example 2

In preparing the polyamic acid solution, a polyamic acid solution and a polyamic acid solution in the same manner as in Example 1, except that the diamine compound DA-2 obtained in Synthesis Example 2 was used instead of the diamine compound DA-1 obtained in Synthesis Example 1 A polyimide film was prepared.

Example 3

(1) Preparation of polyamic acid solution

Phenylene diamine was completely dissolved in anhydrous N-methyl pyrrolidone (NMP). Then, the anhydride compound AN-1 obtained in Synthesis Example 3 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 resulting solution was stirred at 25° C. for 16 hours and filtered under pressure with a filter made of poly(tetrafluoroethylene) having a pore size of 0.1 μm. Thus, a polyamic acid solution was prepared.

(2) Preparation of polyimide film

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

Example 4

In the preparation of the polyamic acid solution, a polyamic acid solution and a polyamic acid solution in the same manner as in Example 3, except that the anhydride compound AN-2 obtained in Synthesis Example 4 was used instead of the anhydride compound AN-1 obtained in Synthesis Example 3 A polyimide film was prepared.

Example 5

In the preparation of the polyamic acid solution, a polyamic acid solution and a polyimide film in the same manner as in Example 1, except that the anhydride compound AN-1 obtained in Synthesis Example 3 was used instead of the pyromellitic anhydride (PMDA). Was prepared.

[Comparative Examples 1 and 2: Preparation of polyamic acid solution and polyimide film]

Comparative Example 1

When preparing the polyamic acid solution, a polyamic acid solution and a polyimide film were prepared in the same manner as in Example 1, except that the following diamine compound DA-3 was used instead of the diamine compound DA-1 obtained in Synthesis Example 1. I did.

Comparative Example 2

When preparing the polyamic acid solution, a polyamic acid solution and a polyimide film were prepared in the same manner as in Example 3, except that the following anhydride compound AN-3 was used instead of the anhydride compound AN-1 obtained in Synthesis Example 3 I did.

[ Experimental Example ]

Experimental Example 1: Glass transition temperature

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

-1st heating: heating from 30℃ to 200℃ at a rate of 10℃/min and then holding at 200℃ for 5 minutes

-Cooling: from 200 to 50℃ at a rate of 10℃/min, then maintained for 5 minutes

-Secondary heating: From 50℃ to 300℃ at a rate of 10℃/min.

The glass transition temperature (Tg) was measured from the middle point in the stepped endothermic curve indicating the glass transition phenomenon in the DSC curve.

Experimental Example 2: transmittance

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)

The polyimide film obtained in Examples and Comparative Examples was measured from 30° C. to 260° C. under conditions of a heating rate of 10° C./min using TMA (TA Instruments, Q400), and then in the range of 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 for a wavelength of 550 nm

As 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 prepared in each Example and each comparative example, and as a measuring device, the brand name "Exoscan" manufactured by AXOMETRICS (AxoScan)" was used, and after inputting the value of the refractive index of each sample (the refractive index of the film with respect to light of 550 nm obtained by measuring the refractive index described above), under the conditions of temperature: 25°C and humidity: 40% , Using light having a wavelength of 590 nm, measuring the retardation in the thickness direction, and using the obtained thickness direction retardation measurement value (measured value by automatic measurement by a measuring device), retardation per 10 μm of the thickness of the film It was calculated by converting it to a value, and it is shown in Table 1 below.

The results for the experimental example are shown in Table 1 below.

Diamine anhydride Tg(℃) Transmittance(%) CTE Birefringence Rth(nm) Example 1 Synthesis Example 1
(DA-1) PMDA 410 86 45.5 0.0019 17 Example 2 Synthesis Example 2
(DA-2) PMDA 427 83 38.9 0.0035 28 Example 3 PDA Synthesis Example 3
(AN-1) 430 84 40.4 0.0041 31 Example 4 PDA Synthesis Example 4
(AN-2) 419 88 49.2 0.0023 20 Example 5 Synthesis Example 1
(DA-1) Synthesis Example 3
(AN-1) 408 85 56.1 0.0013 12 Comparative Example 1 DA-3 PMDA 385 79 63.4 0.0044 40 Comparative Example 2 PDA AN-3 388 80 66.9 0.0049 45

As shown in Table 1, it can be seen that the polyimide films obtained in Examples 1 to 5 exhibit a high glass transition temperature and a low coefficient of thermal expansion, as well as excellent transmittance, a low birefringence, and a small retardation value.

On the other hand, it can be seen that the obtained polyimide films of Comparative Examples 1 to 2 exhibit remarkably lower glass transition temperatures and higher coefficients of thermal expansion than those of the Examples, while exhibiting remarkably inferior transmittance, birefringence and retardation values.

Claims (24)

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

In Formula 1,
Ar is an aromatic divalent functional group having 13 or more carbon atoms to which at least one substituent group including a nitrogen-containing heteroaromatic compound is bonded.
The method of claim 1,
The aromatic divalent functional group having 13 or more carbon atoms,
A diamine compound which is one of a terphenylene group, a quarter phenylene group, a pentaphenylene group, an anthracenylene group, a fluorenylene group, a phenanthrenylene group, or a pyrenylene group.
The method of claim 1,
The substituent including the nitrogen-containing heteroaromatic compound,
Diamine compounds containing one of the substituents represented by the following formula 2-1 or formula 2-2:
[Formula 2-1]

[Formula 2-2]

In Formula 2-1 and Formula 2-2,
A ₁ to A ₁₅ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen group, a cyano group, and a haloalkyl group having 1 to 10 carbon atoms. .
The method of claim 1,
The diamine compound is a diamine compound having line symmetry or point symmetry.
The method of claim 1,
The structure represented by Chemical Formula 1,
Diamine compound containing a structure represented by the following formula (3):
[Chemical Formula 3]

In Chemical Formula 3,
T is a substituent including a heteroaromatic compound containing nitrogen,
m3 to m5 are each independently an integer of 0 to 4,
(m3 + m4 + m5) ≥ 1,
R is an electron attractor functional group,
n1 to n3 are each independently an integer of 0 to 4,
m'is an integer of 1 to 5.
The method of claim 1,
The structure represented by Chemical Formula 1,
Diamine compound comprising a structure represented by the following formula 3-a:
[Formula 3-a]

In Formula 3-a,
T ₁ and T ₂ are each independently a substituent including a nitrogen-containing heteroaromatic compound,
R ₁₅ and R ₁₆ are each independently hydrogen or an electron attracting functional group.
The method of claim 1,
The structure represented by Formula 1 is a diamine compound comprising any one of the structures represented by the following Formula 1-1 to the following Formula 1-2:
[Formula 1-1]

[Chemical Formula 1-2]

.
The method of claim 1,
The diamine compound is used for synthesis of a polyimide-based polymer, a diamine compound.
An acid anhydride compound having a structure represented by the following formula (4):
[Formula 4]

In Chemical Formula 4,
Ar' is an aromatic tetravalent functional group having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded.
The method of claim 9,
The aromatic tetravalent functional group having 13 or more carbon atoms,
An acid anhydride compound which is a tetravalent functional group derived from one of terphenyl, quarterphenyl, pentaphenyl, anthracene, fluorene, phenanthrene group, or pyrene.
The method of claim 9,
The substituent including the nitrogen-containing heteroaromatic compound,
An acid anhydride compound containing one of the substituents represented by the following formula 2-1 or formula 2-2:
[Formula 2-1]

[Formula 2-2]

In Formula 2-1 and Formula 2-2,
A ₁ to A ₁₅ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a halogen group, a cyano group, and a haloalkyl group having 1 to 10 carbon atoms. .
The method of claim 9,
The acid anhydride compound has a line symmetry or point symmetry symmetry.
The method of claim 9,
The structure represented by Chemical Formula 4,
An acid anhydride compound comprising a structure represented by the following formula (5):
[Chemical Formula 5]

In Chemical Formula 5,
T is a substituent including a heteroaromatic compound containing nitrogen,
m15 to m17 are each independently an integer of 0 to 4,
(m15 + m16 + m17) ≥ 1,
R is an electron attractor functional group,
n9 to n11 are each independently an integer of 0 to 4,
m" is an integer from 1 to 5.
The method of claim 9,
The structure represented by Chemical Formula 4,
An acid anhydride compound comprising a structure represented by the following formula 5-a:
[Formula 5-a]

In Formula 5-a,
T ₇ and T ₈ are each independently a substituent including a nitrogen-containing heteroaromatic compound,
R ₂₃ and R ₂₄ are each independently hydrogen or an electron attracting functional group.
The method of claim 9,
The structure represented by Chemical Formula 4,
An acid anhydride compound comprising one of the structures represented by the following formula 4-1 to the following formula 4-2:
[Formula 4-1]

[Formula 4-2]

.
The method of claim 9,
The acid anhydride compound is used for synthesizing a polyimide-based polymer.
A polyimide-based polymer comprising at least one repeating unit selected from the group consisting of a repeating unit represented by Formula 7 below, a repeating unit represented by Formula 8 below, and a repeating unit represented by Formula 9 below:
[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 7 to 9,
At least one of R ₁ and R ₂ is an alkyl group having 1 to 10 carbon atoms, and the others are hydrogen,
X ₁ to X ₃ are the same as or different from each other, and each independently a tetravalent functional group,
Y ₁ to Y ₃ are the same as or different from each other, and each independently a divalent functional group,
Of the X ₁ to X ₃ Tetravalent functional groups and Of Y ₁ to Y ₃ Divalent functional group At least one of An aromatic n having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded is a functional group, and n is 2 or 4.
The method of claim 17,
Y ₁ to Y ₃ in Formulas 7 to 9 are each independently an aromatic divalent functional group having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded,
X ₁ to X ₃ of Formulas 7 to 9 are each independently one of the tetravalent functional groups described in Formula 10 below, a polyimide polymer:
[Formula 10]

In Chemical Formula 10,
R ₃ to R ₈ are each independently hydrogen or one of an alkyl group having 1 to 10 carbon atoms,
L ₄ is a direct bond, -O-, -CO-, -S-, -SO-, -SO ₂ -, -CR ₉ R ₁₀ -, -CONH-, -COO-, -(CH ₂ ) _t -, -O(CH ₂ ) _t O-, -COO-(CH ₂ ) _t -OCO-, phenylene, or any one selected from the group consisting of a combination thereof,
In the L ₄ , R ₉ and R ₁₀ 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.
The method of claim 17,
Y ₁ to Y ₃ in Formulas 7 to 9 are each independently a divalent functional group represented by the following Formula 11,
X ₁ to X ₃ of Formulas 7 to 9 are each independently one of an aromatic tetravalent functional group having 13 or more carbon atoms bonded to at least one substituent including a nitrogen-containing heteroaromatic compound, a polyimide polymer:
[Formula 11]

In Formula 11,
R ₃₀ and R ₃₁ are each independently hydrogen, halogen, cyano, nitrile, alkyl having 1 to 10 carbon atoms, alkenyl having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, haloalkyl having 1 to 10 carbon atoms, or It is a haloalkoxy having 1 to 10 carbon atoms,
p and q are each independently an integer of 0 to 4,
A is a single bond, -O-, -CO-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -CONH-, -COO-, -( CH ₂ ) _y -, -O(CH ₂ ) _y O-, -O(CH ₂ ) _y -, -NH-, -NH(CH ₂ ) _y -NH-, -NH(CH ₂ ) _y O-, -OCH ₂ -C(CH ₃ ) ₂ -CH ₂ O-, -COO-(CH ₂ ) _y -OCO-, or -OCO-(CH ₂ ) _y -COO-,
y is an integer from 1 to 10,
k and m are each independently an integer of 0 to 3,
r is an integer from 0 to 3.
The method of claim 17,
Y ₁ to Y ₃ in Formulas 7 to 9 are each independently an aromatic divalent functional group having 13 or more carbon atoms to which at least one substituent including a nitrogen-containing heteroaromatic compound is bonded,
X ₁ to X ₃ of Formulas 7 to 9 are each independently an aromatic tetravalent functional group having 13 or more carbon atoms bonded to at least one substituent including a nitrogen-containing heteroaromatic compound.
The method of claim 17,
The polyimide-based polymer comprises a reaction product obtained from at least one monomer of the diamine compound of claim 1 and the acid anhydride compound of claim 9.
A polymer film comprising a cured product of the polyimide-based polymer of claim 17.
A substrate for a display device comprising the polymer film of claim 22.
An optical device comprising the polymer film of claim 22.