WO2024259792A1 - 二胺化合物、聚酰亚胺以及液晶显示面板 - Google Patents

二胺化合物、聚酰亚胺以及液晶显示面板 Download PDF

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WO2024259792A1
WO2024259792A1 PCT/CN2023/111454 CN2023111454W WO2024259792A1 WO 2024259792 A1 WO2024259792 A1 WO 2024259792A1 CN 2023111454 W CN2023111454 W CN 2023111454W WO 2024259792 A1 WO2024259792 A1 WO 2024259792A1
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rings
fused
benzene
carbon atoms
single bond
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French (fr)
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易江
兰松
陈黎暄
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TCL China Star Optoelectronics Technology Co Ltd
Huizhou China Star Optoelectronics Display Co Ltd
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TCL China Star Optoelectronics Technology Co Ltd
Huizhou China Star Optoelectronics Display Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/52—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C229/54—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C07C229/60—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in meta- or para- positions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present application relates to the display field, and in particular to a diamine compound, a polyimide and a liquid crystal display panel.
  • TFT-LCD Thin film transistor liquid crystal display
  • IPS in-plane switching
  • FFS fringe field switching
  • a pre-tilt angle value close to zero and stable is usually required to avoid light leakage in the dark state of the panel. Since the deflection and arrangement of liquid crystal are affected by the alignment layer, the structure and processing design of the alignment layer play an important role in achieving high-quality TFT-LCD in practical applications.
  • LC liquid crystal
  • many alignment methods have been developed. For example, directional rubbing (Rubbing) of polymer films, evaporation of silicon dioxide, ultraviolet (UV) exposure of photopolymers, ion beam treatment of polymer substrates, and surface modification of surfactants or microgroove patterns.
  • the rubbing method is the most widely used and can provide the best electro-optical performance of liquid crystal switching and good thermal stability.
  • the corresponding impurities, electrostatic charges and mechanical damage may cause abnormal deflection of liquid crystal under voltage.
  • the uniform alignment of liquid crystals can be achieved using anisotropic polymer films.
  • the anisotropy of the photoalignment layer is generated by polarized ultraviolet irradiation.
  • photosensitive polyimide (PI) can produce a uniform arrangement of liquid crystal molecules perpendicular to the linear polarized ultraviolet light (LPUV), but the resulting polyimide surface anisotropy is small, so the azimuthal anchoring energy of the liquid crystal layer attached to the surface is also small, and it is easy to cause the problem of unstable pretilt angle.
  • the invention provides a diamine compound, a polyimide and a liquid crystal display panel capable of improving anchoring energy and reducing a pretilt angle.
  • the diamine compound of the present application has a molecular structure represented by the following formula (1):
  • R1 and R2 are each selected from an alkylene group having 1 to 5 carbon atoms.
  • R1 is selected from an alkylene group having 1 to 5 carbon atoms
  • R2 is selected from an alkylene group having 1 to 3 carbon atoms.
  • the diamine compound is any one of the following:
  • the present application also provides a polyimide having a molecular structure represented by the following formula (2):
  • R1 and R2 are each selected from an alkylene group having 1 to 5 carbon atoms;
  • R3 is a structure derived from tetracarboxylic dianhydride
  • R4 is selected from a benzene ring, a monocyclic heterocyclic ring, an aromatic group containing two or more monocyclic rings, or a heteroaryl group containing two or more monocyclic rings.
  • R1 is selected from an alkylene group having 1 to 5 carbon atoms
  • R2 is selected from an alkylene group having 1 to 3 carbon atoms.
  • R3 is selected from a benzene ring, a single heterocycle, two or more benzene rings connected by a single bond, a carbon atom or an oxygen atom, two or more mono heterocycles connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a mono heterocycle with a total number of two or more rings connected by a single bond, a carbon atom or an oxygen atom, two or more benzene rings fused together, two or more mono heterocycles fused together, and a benzene ring and a mono heterocycle with a total number of two or more rings fused together.
  • R3 is selected from 2 to 3 benzene rings connected by a single bond, carbon atoms or oxygen atoms, 2 to 3 monocyclic heterocycles connected by a single bond, carbon atoms or oxygen atoms, a combination of a benzene ring and a monocyclic heterocycle with a total number of 2 to 3 rings connected by a single bond, carbon atoms or oxygen atoms, 2 to 3 fused benzene rings, 2 to 3 monocyclic heterocycles fused, and a benzene ring and a monocyclic heterocycle with a total number of 2 to 3 fused rings.
  • R4 is selected from two or more benzene rings connected by a single bond, a carbon atom or an oxygen atom, two or more monocyclic heterocycles connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a monocyclic heterocycle having a total number of two or more rings connected by a single bond, a carbon atom or an oxygen atom, two or more benzene rings fused together, two or more monocyclic heterocycles fused together, and a total number of two or more benzene rings and a monocyclic heterocycle fused together.
  • R3 is selected from one of the following groups:
  • the wavy line between the two carbon atoms indicates that the connection point between R3 and the dianhydride is not fixed.
  • R4 is selected from one of the following groups:
  • R 4 is selected from p-biphenyl or p-terphenyl.
  • the polyimide has one of the following structural units:
  • the present application also provides a liquid crystal display panel, which includes an alignment film, wherein the alignment film includes polyimide, and the polyimide has a molecular structure represented by the following formula (2):
  • R1 and R2 are each selected from an alkylene group having 1 to 5 carbon atoms;
  • R3 is a structure derived from tetracarboxylic dianhydride
  • R4 is selected from a benzene ring, a monocyclic heterocyclic ring, an aromatic group containing two or more monocyclic rings, or a heteroaryl group containing two or more monocyclic rings.
  • R1 is selected from an alkylene group having 1 to 5 carbon atoms
  • R2 is selected from an alkylene group having 1 to 3 carbon atoms.
  • R3 is selected from a benzene ring, a single heterocycle, two or more benzene rings connected by a single bond, a carbon atom or an oxygen atom, two or more mono heterocycles connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a mono heterocycle with a total number of two or more rings connected by a single bond, a carbon atom or an oxygen atom, two or more benzene rings fused together, two or more mono heterocycles fused together, and a benzene ring and a mono heterocycle with a total number of two or more rings fused together.
  • R3 is selected from 2 to 3 benzene rings connected by a single bond, carbon atoms or oxygen atoms, 2 to 3 monocyclic heterocycles connected by a single bond, carbon atoms or oxygen atoms, a combination of a benzene ring and a monocyclic heterocycle with a total number of 2 to 3 rings connected by a single bond, carbon atoms or oxygen atoms, 2 to 3 fused benzene rings, 2 to 3 monocyclic heterocycles fused, and a benzene ring and a monocyclic heterocycle with a total number of 2 to 3 fused rings.
  • R4 is selected from two or more benzene rings connected by a single bond, a carbon atom or an oxygen atom, two or more monocyclic heterocycles connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a monocyclic heterocycle having a total number of two or more rings connected by a single bond, a carbon atom or an oxygen atom, two or more benzene rings fused together, two or more monocyclic heterocycles fused together, and a total number of two or more benzene rings and a monocyclic heterocycle fused together.
  • R3 is selected from one of the following groups:
  • the wavy line between the two carbon atoms indicates that the connection point between R3 and the dianhydride is not fixed.
  • R4 is selected from one of the following groups:
  • the polyimide has one of the following structural units:
  • the diamine compound provided in the present application has a molecular structure represented by the following formula (1):
  • R1 and R2 are selected from alkylene groups having a carbon number of 1 to 5.
  • the diphenylacetylene contained in the diamine compound of the present application can undergo a polymerization reaction to form a dimer structure, and the dimer structure of diphenylacetylene has an anchoring effect on liquid crystals, and because the dimer structure of diphenylacetylene has coplanarity, when the polyimide synthesized using the diamine compound as a raw material is used as an alignment film, the pretilt angle of the liquid crystal can be reduced.
  • FIG1 is a nuclear magnetic resonance spectrum of diamine compound A synthesized in Example 1 of the present application.
  • FIG2 is a nuclear magnetic resonance spectrum of the diamine compound A1 synthesized in Example 4 of the present application.
  • FIG. 3 is a schematic diagram of the structure of a liquid crystal display panel according to some embodiments of the present application.
  • the present application provides a diamine compound, a polyimide and a liquid crystal display panel. To make the purpose, technical solution and effect of the present application clearer and more specific, the present application is further described in detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
  • the embodiments of the present application provide a diamine compound, a polyimide and a liquid crystal display panel.
  • the following are detailed descriptions of each. It should be noted that the description order of the following embodiments is not intended to limit the preferred order of the embodiments.
  • the present application provides a polyimide having a molecular structure represented by the following formula (1):
  • R1 and R2 are each selected from an alkylene group having 1 to 5 carbon atoms;
  • R3 is a structure derived from tetracarboxylic dianhydride
  • R4 is selected from a benzene ring, a monocyclic heterocyclic ring, an aromatic group containing two or more monocyclic rings, or a heteroaryl group containing two or more monocyclic rings.
  • aromatic groups include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, spirofluorene and derivatives thereof.
  • heteroaryl groups include furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole oxazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and
  • the polyimide comprises a plurality of constituent units (a), each of which has a skeleton in the horizontal direction derived from two diamine compounds.
  • the two diamine compounds are polymerized to form a polyphenyl ring rigid structure (b) between two adjacent rows of skeletons.
  • the two diamine compounds are connected on one side in the vertical direction by a small molecule structure R 4 , and on the other side by a structure (c) derived from tetracarboxylic dianhydride.
  • the polyphenyl ring rigid structure (b) between two adjacent rows of skeletons is located between the structure (c) and R 4 derived from tetracarboxylic dianhydride in the horizontal direction.
  • one side between adjacent constituent units (a) is connected by a small molecule structure R 4 , and the other side is connected by a structure (c) derived from tetracarboxylic dianhydride.
  • the polyphenyl ring rigid structure (b) of the present application has coplanarity, and the polymerizable groups at both ends of the diamine compound undergo polymerization reaction with tetracarboxylic dianhydride and the small molecule structure R4 derived from small molecules to form a stable polymer, which can be used in the liquid crystal alignment layer to improve the alignment stability with the liquid crystal, that is, the anchoring effect.
  • the liquid crystal cell using the alignment material can obtain a lower liquid crystal pretilt angle, and can be applied to LCD display panels with horizontal electric fields such as IPS.
  • polyimide of some embodiments of the present application has one of the following structural units:
  • the diamine compound used in the present application for synthesizing polyimide is a novel diamine compound having a molecular structure represented by the following formula (2):
  • R1 and R2 are each selected from an alkylene group having 1 to 5 carbon atoms.
  • the diphenylethynyl group of the diamine compound of formula (2) is a photoalignment group, and the amine group and the vinyl group at both ends are polymerizable groups.
  • linear polarized ultraviolet light for example, 365nm linear polarized ultraviolet light
  • the diphenylethynyl group in the diamine compound of formula (2) is cleaved to undergo dimerization reaction to generate a dimer.
  • the specific reaction process is as follows:
  • the above reaction can only occur when the transition dipole moment of the diphenylacetylene group is parallel to the electric vector direction of LPUV, that is, the reaction has optical axis selectivity.
  • Anisotropic polymers can be generated through this reaction.
  • the dimer structure of diphenylacetylene generated by the above method has an anchoring effect on liquid crystals, and because the dimer structure of diphenylacetylene has coplanarity, by using the alignment layer material, the pre-tilt angle of liquid crystals can be reduced, and it is suitable for LCD display panels with horizontal electric fields such as IPS.
  • the polymerizable groups at both ends of the diamine compound can undergo polymerization reaction with tetracarboxylic dianhydride to form a stable polymer, thereby improving the alignment stability with the liquid crystal, that is, the anchoring effect.
  • R1 is selected from an alkylene group having 1 to 5 carbon atoms
  • R2 is selected from an alkylene group having 1 to 3 carbon atoms.
  • the diamine compound is any one of the following diamine compounds:
  • tetracarboxylic dianhydride compounds commonly used in the art can be used as the tetracarboxylic dianhydride compounds of the present application. That is, the present application does not specifically limit the structure derived from the tetracarboxylic dianhydride.
  • R3 is selected from a benzene ring, a single heterocycle, two or more benzene rings connected by a single bond, carbon atoms or oxygen atoms, two or more single heterocycles connected by a single bond, carbon atoms or oxygen atoms, or a combination of a benzene ring and a single heterocycle with a total number of two or more rings connected by a single bond, carbon atoms or oxygen atoms, two or more fused benzene rings, two or more fused single heterocycles, and a benzene ring and a single heterocycle with a total number of two or more fused rings.
  • the benzene ring or the single heterocycle can provide rigidity to the molecule, thereby enhancing the anchoring force.
  • examples of R3 include furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, and derivatives thereof
  • R3 is selected from 2 to 3 benzene rings connected by single bonds, carbon atoms or oxygen atoms, 2 to 3 single heterocycles connected by single bonds, carbon atoms or oxygen atoms, a combination of 2 to 3 benzene rings and single heterocycles connected by single bonds, carbon atoms or oxygen atoms, 2 to 3 fused benzene rings, 2 to 3 fused single heterocycles, and 2 to 3 fused benzene rings and single heterocycles.
  • the number of benzene rings or single heterocycles determines the rigidity and length of the group. Therefore, the rigidity of the structure (c) derived from tetracarboxylic dianhydride and the multi-benzene ring rigid structure (b) are comparable, and the length is similar, which is conducive to improving the structural stability.
  • R 3 can be one of the following groups:
  • the wavy line between the two carbon atoms indicates that the connection point between R3 and the dianhydride is not fixed.
  • the tetracarboxylic dianhydride compound is selected from one of the following compounds:
  • R4 is derived from a small molecule with a vinyl group as described below:
  • R4 is selected from two or more benzene rings connected by a single bond, a carbon atom or an oxygen atom, two or more monocyclic heterocycles connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a monocyclic heterocycle with a total number of two or more rings connected by a single bond, a carbon atom or an oxygen atom, two or more benzene rings fused together, two or more monocyclic heterocycles fused together, and a benzene ring and a monocyclic heterocycle with a total number of two or more rings fused together.
  • the double bond on one side of the diamine compound in (A) undergoes a free radical polymerization reaction with the above-mentioned small molecule structure under 365nm ultraviolet light irradiation.
  • the specific reaction process is as follows:
  • R4 is selected from two benzene rings connected by a single bond, a carbon atom or an oxygen atom, two single heterocycles connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a single heterocycle with a total number of two rings connected by a single bond, a carbon atom or an oxygen atom, two fused benzene rings, two fused single heterocycles, and a benzene ring and a single heterocycle with a total number of two fused rings.
  • the linker R4 and the polyphenyl ring rigid structure (b) have comparable rigidity and similar lengths, which is beneficial to improving structural stability.
  • R4 is selected from one of the following groups:
  • R 4 is selected from p-biphenyl or p-terphenyl.
  • R3 is selected from 2 to 3 benzene rings connected by a single bond, a carbon atom or an oxygen atom, 2 to 3 monocyclic rings connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a monocyclic ring with a total number of 2 to 3 rings connected by a single bond, a carbon atom or an oxygen atom, 2 to 3 fused benzene rings, 2 to 3 monocyclic rings fused, a benzene ring and a monocyclic ring with a total number of 2 to 3 fused rings, and R4 is selected from two benzene rings connected by a single bond, a carbon atom or an oxygen atom, two monocyclic rings connected by a single bond, a carbon atom or an oxygen atom, a combination of a benzene ring and a monocyclic ring with a total number of two rings connected by a single bond, a carbon atom or an oxygen atom,
  • the present invention polymerizes the above-mentioned (A) diamine compound, (B) dianhydride compound and (C) small molecule structure, and through the cross-linking reaction of double bonds, the generated polyimide side chains can be arranged in order, and the polyphenyl ring structure formed by the polymerization of the core alignment group diphenyl alkynyl can be further fixed to make the film anisotropic.
  • the properties are improved and the anchoring stability with the liquid crystal is enhanced, thereby improving the imaging sticking (IS) problem of the LCD.
  • Example 1 Taking R1 as an alkylene group with a carbon number of 3 and R2 as an alkylene group with a carbon number of 2 as an example, the synthesis route of the novel diamine compound A is as follows:
  • (1) to (8) are all intermediate products, and all starting materials can be commercial products with high purity (>99%).
  • the organic phase was dried over anhydrous sodium sulfate and the solvent was evaporated to obtain a crude product (7).
  • the crude product (7) was purified by chromatography (dichloromethane) to obtain a light yellow liquid product (7). Yield: 41%.
  • dianhydride compound A Taking pyromellitic dianhydride as an example of the dianhydride compound, 6.49 g (10 mmol) of diamine compound A was weighed and added to 90 g of N-methylpyrrolidone NMP. After complete dissolution, 2.18 g (10 mmol) of pyromellitic dianhydride was added. The mixture was stirred while nitrogen was introduced into a 300 mL three-necked flask. The mixture was stirred at room temperature for 12 h to obtain a polyamic acid solution.
  • PAA polyamic acid
  • the PAA prepared above was spin-coated on a 5 ⁇ 5 cm array substrate and a color filter substrate, respectively, and pre-baked at 90°C for 5 min to evaporate the solvent. The temperature was then raised to 230°C and baked for 30 min. min, and a polyimide film was obtained.
  • the baked substrate is irradiated with ultraviolet light of 500 mJ/cm 2 and a wavelength of 365 nm to cause a photodimerization reaction and generate an anisotropic thin film.
  • Example 2 The difference between Example 2 and Example 1 is that different dianhydrides are used. Specifically, the steps after the synthesis of diamine compound A include:
  • the PAA solution was spin-coated on the array substrate and the color filter substrate of 5 ⁇ 5 cm and thermally cured, and then subjected to 365 nm light treatment at a condition of 500 mJ/cm 2 .
  • liquid crystal box After the liquid crystal box is prepared, its pretilt angle and afterimage are tested.
  • Example 3 The difference between Example 3 and Example 1 is that different dianhydride compounds are used. Specifically, the steps after the synthesis of diamine compound A include:
  • the PAA solution was spin-coated on a 5 ⁇ 5 cm TFT substrate and a CF substrate and thermally cured, followed by 365 nm irradiation at 500 mJ/cm 2 .
  • liquid crystal box After the liquid crystal box is prepared, its pretilt angle and afterimage are tested.
  • Example 4 synthesizes diamine compound A1 in the same steps as Example 1 (1) to (8):
  • the synthesized diamine compound A1 was confirmed, and the nuclear magnetic resonance spectrum of the diamine compound A1 is shown in FIG2 .
  • the steps after the synthesis of diamine compound A1 include:
  • the PAA solution was spin-coated on a 5 ⁇ 5 cm TFT substrate and a CF substrate and thermally cured, followed by 365 nm irradiation at 500 mJ/cm 2 .
  • liquid crystal box After the liquid crystal box is prepared, its pretilt angle and afterimage are tested.
  • Example 5 The difference between Example 5 and Example 1 is that different small molecules are used.
  • the small molecule compound in Example 5 is:
  • the steps after the synthesis of diamine compound A include:
  • the PAA solution was spin-coated on a 5 ⁇ 5 cm TFT substrate and a CF substrate and thermally cured.
  • the irradiation treatment was performed at 365 nm and 500 mJ/cm 2 .
  • liquid crystal box After the liquid crystal box is prepared, its pretilt angle and afterimage are tested.
  • the afterimage evaluation was conducted at 8V after 12 hours of power-on. No afterimage was observed and graded as A, and slight afterimage was graded as B.
  • the present application also provides a liquid crystal display panel, which includes an alignment film, and the alignment film includes the polyimide described in any one of the above items.
  • the liquid crystal display panel 1 includes an array substrate 100, a color film substrate 200, and a liquid crystal layer 300.
  • the array substrate 100 and the color film substrate 200 are arranged opposite to each other.
  • the liquid crystal layer 300 is arranged between the array substrate 100 and the color film substrate 200.
  • the array substrate 100 includes a first alignment film 101, and the color film substrate includes a second alignment film 201.
  • the liquid crystal display panel 1 can be an IPS or FFS type liquid crystal display panel.

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Abstract

本申请提供一种二胺化合物、聚酰亚胺以及液晶显示面板。二胺化合物具有由以下式(1)所表示的分子结构：其中，R1和R2分别选自碳数为1～5的亚烷基。

Description

二胺化合物、聚酰亚胺以及液晶显示面板 技术领域
本申请涉及显示领域，尤其涉及一种二胺化合物、聚酰亚胺以及液晶显示面板。
背景技术
具有广视角和高显示质量的薄膜晶体管液晶显示器件(Thin film transistor liquid crystal display，TFT-LCD)已成为市场上的主流显示产品。其中，平面内开关(In-Plane Switching，IPS)和边缘场开关(Fringe Field Switching，FFS)类型的TFT-LCD由于具有快速响应、宽视角、功耗低的特性，已被广泛用作便携式移动通信设备，如移动电话和平板电脑的显示面板。而对于IPS-LCD或FFS-LCD来说，通常需要接近零且稳定的预倾角值，以避免面板在暗态下出现漏光的问题。由于液晶的偏转与排列受到配向层的影响，因此，在实际应用中，配向层的结构和加工设计在实现高质量的TFT-LCD方面起着重要作用。
为了获得高质量的显示效果，对液晶进行稳定均匀的配向是最重要的因素之一。为了达到液晶(LC)均匀配向的效果，许多配向方法已经被开发出来。例如，聚合物膜的定向摩擦(Rubbing)、二氧化硅的蒸发、光聚合物的紫外线(UV)曝光、聚合物基材的离子束处理以及表面活性剂或微槽图案的表面修饰等。其中，摩擦法应用最广泛，能提供最佳的液晶开关电光性能和良好的热稳定性。但是，相应的杂质、静电电荷和机械损伤可能会导致液晶在电压下偏转异常。
为了克服这些问题，近年来发展了非接触配向方法，特别是光配向法(Patternless Optical Alignment，PA)，它与摩擦法相比具有诸多优点。在光配向法中，使用各向异性聚合物薄膜可以实现液晶的均匀配向。光配向层的各向异性是由偏振紫外线照射产生的。然而，利用光降解的化学反应，光敏聚酰亚胺(Polyimide，PI)可以产生垂直于线偏紫外光(Low Pressure Ultraviolet，LPUV)的均匀液晶分子排列，但由此带来的聚酰亚胺表面各向异性小，因此，附着在该表面上的液晶层的方位锚定能量也较小，且容易带来预倾角不稳定的问题。
技术问题
本发明提供一种能够提升锚定能量、降低预倾角的二胺化合物、聚酰亚胺以及液晶显示面板。
技术解决方案
为解决上述问题，本申请提供的技术方案如下：
本申请的二胺化合物具有由以下式(1)所表示的分子结构：
其中，R1和R2分别选自碳数为1～5的亚烷基。
可选的，R1选自碳数为1～5的亚烷基，R2选自碳数为1-3的亚烷基。
可选的，所述二胺化合物为如下任意一种：
本申请还提供一种聚酰亚胺，其具有由以下式(2)所表示的分子结构：
其中，R1和R2分别选自碳数为1～5的亚烷基；
R3为来源于四羧酸二酐的结构；
R4选自苯环、单杂环、包含两个以上单环的芳香基或者包含两个以上单环的杂芳基。
可选的，R1选自碳数为1～5的亚烷基，R2选自碳数为1-3的亚烷基。
可选的，R3选自苯环，单杂环，单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数两个以上的苯环与单杂环。
可选的，R3选自单键、碳原子或者氧原子连接的2～3个苯环，单键、碳原子或者氧原子连接的2～3个单杂环，单键、碳原子或者氧原子连接的环总数为2～3的苯环与单杂环的组合，稠合的2～3个苯环，稠合的2～3个单杂环，稠合的环总数为2～3的苯环与单杂环。
可选的，R4选自单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数为两个以上的苯环与单杂环。
可选的，R3选自如下基团中的一个：
其中，两个碳原子之间的波浪线表示R3与二酐的连接位点不固定。
可选的，R4选自如下基团中的一个：
可选的，R4选自对位联苯或者对位三联苯。
可选的，所述聚酰亚胺具有以下结构单元中的一个：
本申请还提供一种液晶显示面板，其包括配向膜，所述配向膜包括聚酰亚胺，所述聚酰亚胺具有由以下式(2)所表示的分子结构：
其中，R1和R2分别选自碳数为1～5的亚烷基；
R3为来源于四羧酸二酐的结构；
R4选自苯环、单杂环、包含两个以上单环的芳香基或者包含两个以上单环的杂芳基。
可选的，R1选自碳数为1～5的亚烷基，R2选自碳数为1-3的亚烷基。
可选的，R3选自苯环，单杂环，单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数两个以上的苯环与单杂环。
可选的，R3选自单键、碳原子或者氧原子连接的2～3个苯环，单键、碳原子或者氧原子连接的2～3个单杂环，单键、碳原子或者氧原子连接的环总数为2～3的苯环与单杂环的组合，稠合的2～3个苯环，稠合的2～3个单杂环，稠合的环总数为2～3的苯环与单杂环。
可选的，R4选自单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数为两个以上的苯环与单杂环。
可选的，R3选自如下基团中的一个：
其中，两个碳原子之间的波浪线表示R3与二酐的连接位点不固定。
可选的，R4选自如下基团中的一个：
可选的，所述聚酰亚胺具有以下结构单元中的一个：
有益效果
本申请提供的二胺化合物具有由以下式(1)所表示的分子结构：

其中，R1和R2分别选自碳数为1～5的亚烷基。本申请的二胺化合物包含的二苯基乙炔能够发生聚合反应形成二聚体结构，二苯基乙炔的二聚体结构对于液晶具有锚定作用，且由于二苯基乙炔的二聚体结构具有共平面性，在将以该二胺化合物作为原料合成的聚酰亚胺作为配向膜时，可以降低液晶的预倾角。
附图说明
图1为本申请的实施例1合成的二胺化合物A的核磁谱图。
图2为本申请的实施例4合成的二胺化合物A1的核磁谱图。
图3为本申请的一些实施例的液晶显示面板的结构示意图。
本发明的实施方式
本申请提供一种二胺化合物、聚酰亚胺以及液晶显示面板，为使本申请的目的、技术方案及效果更加清楚、明确，以下参照附图并举实施例对本申请进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本申请，并不用于限定本申请。
本申请实施例提供一种二胺化合物、聚酰亚胺以及液晶显示面板。以下分别进行详细说明。需说明的是，以下实施例的描述顺序不作为对实施例优选顺序的限定。
本申请提供一种聚酰亚胺，其具有由以下式(1)所表示的分子结构：
其中，R1和R2分别选自碳数为1～5的亚烷基；
R3为来源于四羧酸二酐的结构；
R4选自苯环、单杂环、包含两个以上单环的芳香基或者包含两个以上单环的杂芳基。
具体地，芳香基的例子有：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、螺芴及其衍生物。杂芳基的例子有：呋喃、苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、二苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻 唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、喹唑啉、喹唑啉酮、及其衍生物。
上述聚酰亚胺包含多个构成单元(a)，每一构成单元(a)具有来源于两个二胺化合物的水平方向上的骨架。两个二胺化合物发生聚合形成相邻两行骨架之间的多苯环刚性结构(b)。两个二胺化合物在垂直方向的一侧上通过小分子结构R4连接，另一侧通过来源于四羧酸二酐的结构(c)连接。由此，相邻两行骨架之间的多苯环刚性结构(b)在水平方向上位于来源于四羧酸二酐的结构(c)与R4之间。并且，相邻的构成单元(a)之间的一侧通过小分子结构R4连接，另一侧通过来源于四羧酸二酐的结构(c)连接。
本申请的多苯环刚性结构(b)具有共平面性，且二胺化合物两端的可聚合基团与四羧酸二酐和来源于小分子的小分子结构R4发生聚合反应形成稳定的聚合物，可以用于液晶配向层中，能够提高与液晶的配向稳定性，即锚定作用。使用了该配向材料的液晶盒(cell)可以获得较低的液晶预倾角，可以适用于IPS等水平电场的LCD显示面板中。
具体地，本申请的一些实施例的聚酰亚胺具有以下结构单元中的一种：
以下，针对上述聚酰亚胺的各构成部分和其来源进行详细描述。
(A)二胺化合物
本申请用于合成聚酰亚胺的二胺化合物为一种新型二胺化合物，其具有由以下式(2)所表示的分子结构：
其中，R1和R2分别选自碳数为1～5的亚烷基。
式(2)的二胺化合物的二苯基乙炔基为光配向基团，两端的胺基和乙烯基为可聚合基团。在线偏振紫外光(例如，365nm的线偏振紫外光)的照射下，式(2)的二胺化合物中的二苯基乙炔基裂解发生二聚反应生成二聚体，具体反应过程如下所示：
其中，反应式中的波浪线表示省略的结构。
二苯基乙炔基的跃迁偶极矩与LPUV的电矢量方向平行时，上述反应才能发生，即该反应具有光轴选择性。通过该反应能生成具有各向异性的聚合物。通过上述方法生成的二苯基乙炔的二聚体结构对于液晶具有锚定作用，且由于二苯基乙炔的二聚体结构具有共平面性，通过使用该配向层材料，可以降低液晶的预倾角，适用于IPS等水平电场的LCD显示面板中。另外，二胺化合物两端的可聚合基团能够与四羧酸二酐发生聚合反应形成稳定的聚合物，从而提高与液晶的配向稳定性，即锚定作用。
可选的，R1选自碳数为1～5的亚烷基，R2选自碳数为1-3的亚烷基。
可选的，所述二胺化合物为如下任意一种二胺化合物：
(B)四羧酸二酐化合物
本领域中常用的四羧酸二酐化合物均可以用作本申请的四羧酸二酐化合物。即，本申请不对来源于四羧酸二酐的结构进行具体限制。
可选的，R3选自苯环、单杂环、单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，或者单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数两个以上的苯环与单杂环。苯环或者单杂环可以为分子提供刚性，进而提升锚定力。
具体地，R3的例子有：呋喃、苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、二苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、喹唑啉、喹唑啉酮、及其衍生物。
可选的，R3选自单键、碳原子或者氧原子连接的2～3个苯环，单键、碳原子或者氧原子连接的2～3个单杂环，单键、碳原子或者氧原子连接的环总数为2～3的苯环与单杂环的组合，稠合的2～3个苯环，稠合的2～3个单杂环，稠合的环总数为2～3的苯环与单杂环。苯环或者单杂环的个数决定基团的刚性以及基团的长度。由此，来源于四羧酸二酐的结构(c)和多苯环刚性结构(b)的刚性相当，长度相近，有利于提升结构稳定性。
具体地，R3可以为如下基团中的一个：
其中，两个碳原子之间的波浪线表示R3与二酐的连接位点不固定。
对应的，四羧酸二酐化合物选自以下化合物中的一个：
(C)小分子结构
R4来源于如下所述的带有乙烯基的小分子：
其中，R4选自单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数为两个以上的苯环与单杂环。
(A)中的二胺化合物一侧的双键在365nm紫外光照射下与上述小分子结构发生自由基聚合反应，具体反应过程如下：
可选的，R4选单键、碳原子或者氧原子连接的两个苯环，单键、碳原子或者氧原子连接的两个单杂环，单键、碳原子或者氧原子连接的环总数为两个的苯环与单杂环的组合，稠合的两个苯环，稠合的两个单杂环，稠合的环总数为两个的苯环与单杂环。由此，连接基R4和多苯环刚性结构(b)的刚性相当，长度相近，有利于提升结构稳定性。
可选的，R4选自如下基团中的一个：
可选的，R4选自对位联苯或者对位三联苯。
在一些实施方式中，R3选自单键、碳原子或者氧原子连接的2～3个苯环，单键、碳原子或者氧原子连接的2～3个单杂环，单键、碳原子或者氧原子连接的环总数为2～3的苯环与单杂环的组合，稠合的2～3个苯环，稠合的2～3个单杂环，稠合的环总数为2～3的苯环与单杂环，且R4选自单键、碳原子或者氧原子连接的两个苯环，单键、碳原子或者氧原子连接的两个单杂环，单键、碳原子或者氧原子连接的环总数为两个的苯环与单杂环的组合，稠合的两个苯环，稠合的两个单杂环，稠合的环总数为两个的苯环与单杂环。由此，R3和R4刚性相同，且长度相近，并且与中间的连接基团长度相近，获得的聚酰亚胺的结构更稳固。
本申请通过使上述(A)二胺化合物、(B)二酐化合物以及(C)小分子结构发生聚合，并通过双键的交联反应，可以使生成的聚酰亚胺侧链有序排列，进一步固定核心配向基团二苯基炔基聚合形成的多苯环结构，使薄膜的各向异 性提高，与液晶的锚定稳定性增强，从而改善LCD的残像(Imaging Sticking，IS)问题。
下面将结合优选实施例对本发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
实施例1
1.1新型二胺化合物A的合成
实施例1以R1为碳数为3的亚烷基，R2为碳数为2的亚烷基为例，新型二胺化合物A的合成路径如下所示：
其中，(1)至(8)均为中间产物，所有起始材料可以为高纯度(>99％)的商业产品。
(1)的合成：将16.6g(0.1mol)4-羟基苯甲酸乙酯加入到300毫升溶有4g(0.12mol)NaOH的2-丁酮中。加入15g(0.1mol)NaI和11.4g(0.12mol)3-氯-1-丙醇后，将混合物在60℃加热10h，蒸发后得到(1)。
(2)的合成：将中间产物(1)加入300毫升0.5mol/L的KOH溶液中并 回流5h。通过用二乙醚洗涤去除残留的3-氯-1-丙醇，水相用HCI中和，得到沉淀物(2)并过滤。
(3)的合成：将沉淀物(2)从乙醇中重新结晶后，将13.9g(0.11mol)的N,N-在二甲基苯胺溶于230毫升1,4-二氧六环中，再加入19.6g(0.1mol)的沉淀物(2)。在60℃时，缓慢加入10.4g(0.11mol)丙烯酰氯。2h后，通过水洗分离出(3)，并在2-丙醇中重结晶。
(4)的合成：将10g(0.04mol)重结晶得到的(3)加入到装有80ml二氯甲烷的烧瓶中，搅拌溶解后加入8.8g(0.04mol)4-碘苯酚，继续搅拌均匀后加入0.1g(0.4mmol)二环己基碳二亚胺和0.05g(0.4mmol)4-二甲氨基吡啶，继续搅拌溶解后将烧瓶放入60℃水浴中持续搅拌10h。随后通过水洗分离出(4)，并在2-丙醇中重结晶得到(4)的纯净物15.2g，产率81％。
(5)的合成：向500mL烧瓶中加入9.92g(40.0mmol)对碘苯甲酸、17.36g(280.0mmol)乙二醇和几滴甲磺酸。在115℃下搅拌4h后，将混合物倒入1升水中并用乙酸乙酯萃取几次。合并的有机溶液用去离子水洗涤几次，用饱和NaHCO3水溶液洗涤，然后用无水硫酸钠干燥。蒸发该溶液以获得粗产物(5)。通过色谱法(二氯甲烷∶乙酸乙酯＝1∶1)纯化粗产物(5)，得到深黄色油状产物(5)。产率：88％。
(6)的合成：向100mL烧瓶中，加入8.76g(30.0mmol)化合物(5)、80mL三乙胺、114.3mg(0.6mmol)碘化铜(I)和693.3mg(0.6mmol)四(三苯基膦)钯(0)。用氮气冲洗混合物，并在磁力搅拌下加入4.4g(45.0mmol)三甲基甲硅烷基乙炔。在40℃下搅拌24h后，加入14.4ml 75％(w/w)四丁基氟化铵水溶液以脱保护硅烷部分。再搅拌30分钟后，在真空下蒸发溶剂，将残余混合物溶解在二氯甲烷中并过滤。将得到的有机相用HCl水溶液洗涤几次，并用无水硫酸镁干燥。蒸发溶剂，得到粗产物，通过色谱法(二氯甲烷∶乙酸乙酯＝2∶1)进一步纯化，得到深黄色液体的产物(6)，产率：72％。
(7)的合成：向100mL烧瓶中加入3.8g(20.0mmol)化合物(6)、3.0g(30.0mmol)三乙胺和40mL二氯甲烷。用氮气冲洗混合物，在冰浴中在磁力搅拌下缓慢加入5.5g(24.0mmol)3,5-二硝基苯甲酰氯。在室温下搅拌12h后，用40mL二氯甲烷稀释溶液，然后分别用20mL 1mol/L HCl水溶液和去离 子水洗涤。用无水硫酸钠干燥有机相，蒸发溶剂，得到粗产物(7)。粗产物(7)通过色谱法(二氯甲烷)纯化，得到淡黄色液体的产物(7)。产率：41％。
(8)的合成：在250ml烧瓶中，称取纯化的(7)3.5g(0.01mol)分散在70ml乙醇和5g(0.1mol)水合肼混合溶剂中边磁力搅拌边用氮气鼓泡除氧气0.5h，鼓泡结束后，加入80mg钯碳。迅速将反应瓶置入90℃的油浴锅中，冷凝回流反应4h。反应结束后，冷却至室温，过滤除去钯碳催化剂。加水析出，过滤得到滤渣，将滤渣用DMF重结晶提纯，水洗，真空烘箱干燥2h得到(8)，产率95％。
二胺化合物A的合成：向50ml烧瓶中加入1.8g(4.0mmol)化合物(4)、1.43g(4.4mmol)化合物(8)、25ml三乙胺、25.4mg(0.13mmol)碘化铜(I)和154.1mg(0.13mol)四(三苯基膦)钯(0)。用氮气冲洗烧瓶并置于磁力搅拌下。在45℃下搅拌24h后，在真空下蒸发溶剂，将残余混合物溶解在二氯甲烷中并过滤。用0.5mol/L的HCl水溶液洗涤得到的有机相，用无水硫酸镁干燥，蒸发溶剂，得到粗产物。粗产物通过色谱法(乙酸乙酯：二氯甲烷：石油醚＝1:10:10)纯化并用乙醇重结晶几次，得到白色结晶的最终产物A。产率：70％。
对合成的二胺化合物A进行确认，二铵化合物A的1H-NMR(Nuclear Magnetic Resonance：核磁共振)谱图如图1所示。
1H-NMR的测试条件如下：
溶剂：氘代DMSO
频率：300MHz
1.2聚酰胺酸聚合
二酐化合物以均苯四甲酸二酐为例，称取6.49g(10mmol)二胺化合物A，加入到90g N-甲基吡咯烷酮NMP中，待溶解完全后加入2.18g(10mmol)均苯四甲酸二酐，在300mL三颈瓶中边通入氮气边搅拌，在常温下搅拌12h，得到聚酰胺酸溶液。
1.3活性小分子的分散
小分子以对二烯苯为例，称取1.3g(10mmol)对二烯苯，加入到15gNMP中，对混合体系进行超声使其完全溶解，随后将分散好的溶液缓慢加入到快速搅拌的聚酰胺酸(PAA)溶液中，再搅拌6h得到可用于旋涂的聚酰胺酸(PAA)溶液。
1.4面板制备和性能测试
(1)将以上制备完成的PAA，分别旋涂于5×5cm阵列基板和彩膜基板上，在90℃下预烘烤5min，使溶剂挥发，随后将温度升高到230℃，烘烤30 min，得到聚酰亚胺膜。
(2)将烘烤完毕的基板照射能量为500mJ/cm2、波长365nm的紫外光，使光二聚反应发生，生成各向异性的薄膜。
(3)在CF基板表面点胶，与TFT基板进行成盒。
(4)在真空环境下，注入负性液晶，即可获得水平配向的液晶盒。
(5)测试液晶盒的预倾角和残像情况。
实施例2
实施例2与实施例1不同之处在于使用的二酐不同。具体地，二胺化合物A的合成之后的步骤包括：
2.2聚酰胺酸聚合
将6.49g(10mmol)二胺化合物A加入100mlNMP中，搅拌至完全溶解后加入2.94g(10mmol)3,3,4,4-联苯四羧酸二酐，在氮气氛围保护下继续搅拌。
2.3活性小分子的分散
将1.3g(10mmol)对二烯苯，加入到15gNMP中，使用超声使其完全溶解，随后将分散好的溶液缓慢加入到快速搅拌的PAA溶液中，再搅拌12h后获得具有一定黏度的PAA溶液，可用于旋涂。
2.4面板制备和性能测试
将PAA溶液旋涂于5×5cm的阵列基板和彩膜基板上并进行热固化，随后进行365nm照光处理，条件为500mJ/cm2。
制备成液晶盒后测试其预倾角和残像。
实施例3
实施例3与实施例1不同之处在于使用的二酐化合物不同。具体地，二胺化合物A的合成之后的步骤包括：
3.2聚酰胺酸聚合
将6.49g(10mmol)二胺化合物A加入100mlNMP中，搅拌至完全溶解后加入3.10g(10mmol)4,4-氧双邻苯二甲酸酐，在氮气氛围保护下继续搅拌。
3.3活性小分子的分散
将1.3g(10mmol)对二烯苯，加入到15gNMP中，使用超声使其完全溶解，随后将分散好的溶液缓慢加入到快速搅拌的PAA溶液中，再搅拌12h后获得具有一定黏度的PAA溶液，可用于旋涂。
3.4面板制备和性能测试
将PAA溶液旋涂于5×5cm的TFT基板和CF基板上并进行热固化，随后进行365nm照光处理，条件为500mJ/cm2。
制备成液晶盒后测试其预倾角和残像。
实施例4
实施例4与实施例1不同之处在于使用的二胺化合物不同。实施例4以与实施例1(1)至(8)相同的步骤合成二胺化合物A1：
对合成的二胺化合物A1进行确认，二铵化合物A1的核磁共振谱图如图2所示。
1H-NMR的测试条件如下：
溶剂：氘代DMSO
频率：300MHz
二胺化合物A1的合成之后的步骤包括：
4.2聚酰胺酸聚合
将6.91g(10mmol)二胺化合物A1加入100mlNMP中，搅拌至完全溶解后加入3.10g(10mmol)4,4氧双邻苯二甲酸酐，在氮气氛围保护下继续搅拌。
4.3活性小分子的分散
将1.3g(10mmol)对二烯苯，加入到15gNMP中，使用超声使其完全溶解，随后将分散好的溶液缓慢加入到快速搅拌的PAA溶液中，再搅拌12h后获得具有一定黏度的PAA溶液，可用于旋涂。
4.4面板制备和性能测试
将PAA溶液旋涂于5×5cm的TFT基板和CF基板上并进行热固化，随后进行365nm照光处理，条件为500mJ/cm2。
制备成液晶盒后测试其预倾角和残像。
实施例5
实施例5与实施例1不同之处在于使用的小分子不同。实施例5中小分子化合物为：
二胺化合物A的合成之后的步骤包括：
5.2聚酰胺酸聚合
将6.49g(10mmol)二胺化合物A加入100mlNMP中，搅拌至完全溶解后加入3.10g(10mmol)4,4氧双邻苯二甲酸酐，在氮气氛围保护下继续搅拌。
5.3活性小分子的分散
将1.8g(10mmol)对二烯萘，加入到15gNMP中，使用超声使其完全溶解，随后将分散好的溶液缓慢加入到快速搅拌的PAA溶液中，再搅拌12h后获得具有一定黏度的PAA溶液，可用于旋涂。
5.4面板制备和性能测试
将PAA溶液旋涂于5×5cm的TFT基板和CF基板上并进行热固化，随后 进行365nm照光处理，条件为500mJ/cm2。
制备成液晶盒后测试其预倾角和残像。
对比例
称取2.00g(10mmol)4,4’-二氨基二苯醚ODA加入25.7g NMP中，充分搅拌溶解后加入2.24g(10mmol)环丁烷四甲酸二酐CBDA，在氮气氛围保护下继续搅拌12h后得到适用于旋涂的PAA溶液，可用于旋涂。
随后进行热固化，之后进行254nmLPUV的照光处理，条件为500mJ/cm2。制备成Cell后测试其预倾角。
实施例1至5与对比例的预倾角和残像检测情况如下表1所示。
表1
其中，残像评价是在8V电压下，12h通电后进行。观察不到残像评为A级，轻微残像评为B级。
从表1可以看出，相较于对比例，本申请的实施例1至5中，通过使用具有刚性的二苯基乙炔的二聚体结构、来源于四羧酸二酐的包含R3的刚性结构以及具有刚性的连接基R4，配向膜的预倾角显著减小，且能够降低残像发生 的几率。
本申请还提供一种液晶显示面板，其包括配向膜，所述配向膜包括如上任一项所述的聚酰亚胺。请参考图3，液晶显示面板板1包括阵列基板100、彩膜基板200以及液晶层300。阵列基板100和彩膜基板200相对设置。液晶层300设置于阵列基板100和彩膜基板200之间。阵列基板100包括第一配向膜101，彩膜基板包括第二配向膜201。液晶显示面板板1可以为IPS或者FFS型液晶显示面板。
可以理解的是，对本领域普通技术人员来说，可以根据本申请的技术方案及其发明构思加以等同替换或改变，而所有这些改变或替换都应属于本申请所附的权利要求的保护范围。

Claims (20)

  1. 一种二胺化合物，其中，所述二胺化合物具有由以下式(1)所表示的分子结构：
    其中，R1和R2分别选自碳数为1～5的亚烷基。
  2. 如权利要求1所述的二胺化合物，其中，R1选自碳数为1～5的亚烷基，R2选自碳数为1-3的亚烷基。
  3. 如权利要求1所述的二胺化合物，其中，所述二胺化合物为如下任意一种：
  4. 一种聚酰亚胺，其中，所述聚酰亚胺具有由以下式(2)所表示的分子结构：
    其中，R1和R2分别选自碳数为1～5的亚烷基；
    R3为来源于四羧酸二酐的结构；
    R4选自苯环、单杂环、包含两个以上单环的芳香基或者包含两个以上单环的杂芳基。
  5. 如权利要求4所述的聚酰亚胺，其中，R1选自碳数为1～5的亚烷基，R2选自碳数为1-3的亚烷基。
  6. 如权利要求4所述的聚酰亚胺，其中，R3选自苯环，单杂环，单键、 碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数两个以上的苯环与单杂环。
  7. 如权利要求4所述的聚酰亚胺，其中，R3选自单键、碳原子或者氧原子连接的2～3个苯环，单键、碳原子或者氧原子连接的2～3个单杂环，单键、碳原子或者氧原子连接的环总数为2～3的苯环与单杂环的组合，稠合的2～3个苯环，稠合的2～3个单杂环，稠合的环总数为2～3的苯环与单杂环。
  8. 如权利要求4至7任一项所述的聚酰亚胺，其中，R4选自单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数为两个以上的苯环与单杂环。
  9. 如权利要求4所述的聚酰亚胺，其中，R3选自如下基团中的一个：
    其中，两个碳原子之间的波浪线表示R3与二酐的连接位点不固定。
  10. 如权利要求4所述的聚酰亚胺，其中，R4选自如下基团中的一个：
  11. 如权利要求10所述的聚酰亚胺，其中，R4选自对位联苯或者对位三联苯。
  12. 如权利要求4所述的聚酰亚胺，其中，所述聚酰亚胺具有以下结构单元中的一个：
  13. 一种液晶显示面板，其中，包括配向膜，所述配向膜包括聚酰亚胺，所述聚酰亚胺具有由以下式(2)所表示的分子结构：
    其中，R1和R2分别选自碳数为1～5的亚烷基；
    R3为来源于四羧酸二酐的结构；
    R4选自苯环、单杂环、包含两个以上单环的芳香基或者包含两个以上单环的杂芳基。
  14. 如权利要求13所述的液晶显示面板，其中，R1选自碳数为1～5的亚烷基，R2选自碳数为1-3的亚烷基。
  15. 如权利要求13所述的液晶显示面板，其中，R3选自苯环，单杂环，单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与 单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数两个以上的苯环与单杂环。
  16. 如权利要求13所述的液晶显示面板，其中，R3选自单键、碳原子或者氧原子连接的2～3个苯环，单键、碳原子或者氧原子连接的2～3个单杂环，单键、碳原子或者氧原子连接的环总数为2～3的苯环与单杂环的组合，稠合的2～3个苯环，稠合的2～3个单杂环，稠合的环总数为2～3的苯环与单杂环。
  17. 如权利要求13至16中任一项所述的液晶显示面板，其中，R4选自单键、碳原子或者氧原子连接的两个以上苯环，单键、碳原子或者氧原子连接的两个以上单杂环，单键、碳原子或者氧原子连接的环总数为两个以上的苯环与单杂环的组合，稠合的两个以上苯环，稠合的两个以上单杂环，稠合的环总数为两个以上的苯环与单杂环。
  18. 如权利要求13所述的液晶显示面板，其中，R3选自如下基团中的一个：
    其中，两个碳原子之间的波浪线表示R3与二酐的连接位点不固定。
  19. 如权利要求13所述的液晶显示面板，其中，R4选自如下基团中的一个：
  20. 如权利要求13所述的液晶显示面板，其中，所述聚酰亚胺具有以下结构单元中的一个：
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