WO2017185430A1 - Liquid crystal aligning agent, diamine compound and polyamide acid - Google Patents

Liquid crystal aligning agent, diamine compound and polyamide acid Download PDF

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WO2017185430A1
WO2017185430A1 PCT/CN2016/082438 CN2016082438W WO2017185430A1 WO 2017185430 A1 WO2017185430 A1 WO 2017185430A1 CN 2016082438 W CN2016082438 W CN 2016082438W WO 2017185430 A1 WO2017185430 A1 WO 2017185430A1
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dianhydride
formula
compound represented
liquid crystal
tetracarboxylic dianhydride
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PCT/CN2016/082438
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French (fr)
Chinese (zh)
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王胜林
黎厚明
包能进
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深圳市道尔顿电子材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
    • 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
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542—Macromolecular compounds

Definitions

  • the alignment agent of the present invention is irradiated with ultraviolet light to form a photo-alignment liquid crystal which can be tilted toward the liquid crystal, and is used for a liquid crystal display device.
  • Liquid crystal aligning agent comprises an aligning agent and a liquid crystal.
  • the tilt angle control must consider the tilt angle. The size of the (pretilt angle), the uniformity of the tilt distribution, the tilt stability of the display for a long time, and the influence on the electrical and afterimage of the display assembly during the generation of the tilt angle.
  • the conventional and well-known orientation agent orientation process is Rubbing.
  • the use of a felt to rub the alignment agent causes the orientation agent to produce a directional force to the liquid crystal, the rubbing strength or depth of the orientation agent, the different roller speeds and The platform moves at a rate to control the amount of tilt of the orientation agent to the orientation of the liquid crystal.
  • static electricity generation, cleaning and drying, rubbing and scraping of the orientation agent and the unevenness of the length of the felt, resulting in uneven orientation and defects.
  • Process contamination causes electrical defects and afterimages to occur...etc.
  • With the evolution of large-scale panels there are also greater challenges in the fight against the law.
  • the present invention is a process for preparing a polyamic acid and a polyimide alignment agent by photo-crosslinking type diamine monomer.
  • the technical problem to be solved by the invention is to overcome the defects of the existing rubbing method and propose a light extraction
  • the purpose of photo-alignment can be achieved and good electrical properties can be achieved, including high voltage holding characteristics (VHR), low ion density and low accumulated charge.
  • VHR voltage holding characteristics
  • low ion density low ion density
  • low accumulated charge low ion density
  • it can improve the problems caused by the friction caused by the rubbing method, improve the reliability, and improve the overall orientation uniformity.
  • a liquid crystal aligning agent comprising a polyimide polymer cured by a polyamic acid and a high temperature thereof, the polyamic acid being composed of tetracarboxylic dianhydride and two Obtained by an amine reaction, the diamine comprising a compound represented by the formula (1) or a compound represented by the formula (2),
  • R1 and R2 are a hydrogen atom or a carbon alkyl structure, and have a carbon number of 1 - 4.
  • the present invention has the following beneficial effects:
  • the liquid crystal aligning agent of the present invention is suitable for a photo-aligned liquid crystal aligning agent for LCD applications of IPS-TFT, TN-TFT and VA-type TFTs, and has high reliability, excellent orientation effect, high orientation stability, and good afterimage performance.
  • the present invention provides a liquid crystal aligning agent comprising a polyimide polymer obtained by curing a polyamic acid and a high temperature thereof, the polyamic acid being obtained by reacting a tetracarboxylic dianhydride and a diamine, the diamine comprising the lower a compound represented by the formula (1) (No. AM-1) or a compound represented by the formula (2);
  • R1 and R2 are a hydrogen atom or a carbon alkyl structure (carbon number 1 - 4).
  • the above tetracarboxylic dianhydride may have an alicyclic structure and a benzene ring structure, and the above tetracarboxylic dianhydride comprises an alicyclic dianhydride. And/or benzene dianhydride, the above tetracarboxylic dianhydride may be one or a mixture of two or more of the following: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 3 ⁇ Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5 ⁇ (2,5-dioxotetrahydrofuranyl)-3-fluorenylcyclohexyl-l,2-dicarboxylic anhydride 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxy
  • the above diamine may be an alicyclic structure and a benzene ring structure, and the above diamine may be used in one, a mixture of two or more of the following: 1,4-p-phenylenediamine, 1,3-m-phenylenediamine , 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-diphenyl sulfide, 4,4'-diaminobenzyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4 , structurally similar or related compounds such as 4'-diaminodiphenylamine, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethan
  • a liquid crystal aligning agent comprising a polyamic acid and a polyimide polymer after curing at a high temperature, the polyamic acid being obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride using 1, 2, 3 , 4 - cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3,4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; the above diamine structure
  • a compound represented by the formula (1) (No. AM-1) is contained.
  • the alignment agent was diluted and prepared, and 274.3 g of N-methyl-2-pyrrolidone (NMP) and 125.1 g of ethylene glycol monobutyl ether (BC) were added, and the mixture was stirred and mixed for 1 hour, and diluted to a liquid crystal of 6% solid content.
  • NMP N-methyl-2-pyrrolidone
  • BC ethylene glycol monobutyl ether
  • the above liquid crystal aligning agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulating oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 .
  • Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 ⁇ m, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
  • An aligning agent comprising a polyimide polymer cured by a polyamic acid and a high temperature thereof, wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride is used 1, 2, 3,4-cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3.4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; the diamine structure
  • the compound represented by the formula (1) (No. AM-1) and the compound represented by the following formula (3) (No. AM-2) are used, and the diamine is represented by the compound represented by the formula (1) and the formula (3).
  • the compound is polymerized.
  • the above liquid crystal aligning agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulating oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 .
  • Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 ⁇ m, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
  • An aligning agent comprising a polyimide polymer cured by a polyamic acid and a high temperature thereof, wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride is used 1, 2, 3,4-cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride; the above diamine
  • the compound represented by the formula (1) (No. AM-1) and the compound represented by the following formula (4) (No. AM-3) are used, and the diamine is represented by the compound represented by the formula (1) and the formula (4).
  • the compound is polymerized.
  • orientation agent was diluted and diluted, and 143.0 g of N-methyl-2-pyrrolidone (NMP) and 446.8 g of ethylene glycol monobutyl ether (BC) were added, and the mixture was stirred and mixed for 1 hour, and diluted to a solid content of 6%.
  • Solution solution, NMP: BC 50:50.
  • the above-mentioned alignment agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulation oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 .
  • Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 ⁇ m, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
  • An aligning agent comprising a polyamic acid and a polyimide polymer after curing at a high temperature, the polyamic acid being obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride using 1, 2, 3 , 4 - cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3,4-cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride;
  • the above diamine contains a compound represented by the formula (1) (No. AM-1) and a compound represented by the following formula (5) (No. AM-4), wherein the diamine is a compound represented by the formula (1) and the formula (5) is used.
  • the compound is polymerized.
  • the alignment agent was diluted and mixed, and 93.9 g of N-methyl-2-pyrrolidone (NMP) and 339.7 g of ethylene glycol monobutyl ether (BC) were added, and the mixture was stirred and mixed for 1 hour, and diluted to a solid content of 6%.
  • Solution solution, NMP: BC 50:50.
  • the above-mentioned alignment agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulation oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 .
  • Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 ⁇ m, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
  • the polyamic acid aligning agent is a liquid crystal aligning agent obtained by polymerizing tetracarboxylic dianhydride and a diamine in a polar solvent, and the optimal polymerization ratio is: if the diamine is 1 mol equivalent, the tetracarboxylic dianhydride can be used as 0.5. 1-5 mol equivalent, most preferably 0.75 - 1.25 mol equivalent, more preferably 0.9 - 1.1 mol equivalent.
  • the polymerization temperature can be from -10 to 100 ° C, preferably from 10 to 80 ° C, and more preferably from 25 to 60 ° C.
  • the solvent may be N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethylene glycol monobutyl ether, N,N-dimethylacetamide, N-methylcaprolactone, dimethyl sulfoxide. Etc., they may be used singly or in combination.
  • the present invention uses N-methyl-2-pyrrolidone (NMP) and ethylene glycol monobutyl ether (BC) for polyamic acid polymerization and alignment agent preparation. After the synthesis of the polyamic acid, the alignment agent is formulated, and the solid content of the prepared alignment agent is preferably in the range of 1% to 10%, more preferably in the range of 4% to 7%.
  • the coating agent can be applied by spin coating, transfer printing or spray coating.
  • ITO glass is selected for use in the present invention, but is not limited to ITO glass, and any transparent conductive substrate is suitable.
  • the pre-bake temperature after coating can be in the range of 50-150 ° C, the optimum range is 60-120 ° C, the better range is 70-100 ° C, the pre-bake time can be selected in the range of 30-600 seconds, the best range is 60-300 seconds, and the better range is 120-180 seconds.
  • the curing temperature can be 150-300 ° C, preferably 180-250 ° C, more preferably 200-230 ° C, the curing time can be selected from 1 - 90 minutes, the best range is 5 - 60 minutes, better The range is 10-30 minutes.
  • the film thickness ranges from 30 to 150 nm, and the optimum range is from 50 to 120 nm, and more preferably from 60 to 100 nm.
  • the alignment agent is coated on the ITO glass for curing, the polarized light is irradiated, and the light having a wavelength of 150-800 nm is selected, and the optimum illumination wavelength range is 200-380 nm, and the preferred illumination wavelength range is 240-380 nm.
  • the glass which has been subjected to the above treatment is made into a liquid crystal cell, and it is generally preferable to use the spacer of 2 - 6 ⁇ m to form the cell of the cell thickness, but the cell thickness is not limited to 2 - 6 ⁇ m.
  • the tilt angle of the cell was tested using the liquid crystal rotation method using Shintech OPTIPRO-STD.
  • the liquid crystal cell was given a voltage of 4 V at a temperature of 25 ° C for a measurement time of 16.67 ms, and the voltage holding ratio was calculated.
  • test results are organized in the following table:
  • the photo-aligned liquid crystal aligning agent of Example 1 is suitable for a photo-aligned liquid crystal aligning agent for LCD use of IPS-TFT, and has high reliability, excellent orientation effect and high orientation stability, and good afterimage performance;
  • the photo-aligned liquid crystal aligning agent of Example 2 is applicable to a photo-aligned liquid crystal aligning agent for LCD use of TN-TFT, and has high reliability, excellent orientation effect and high orientation stability, and good afterimage performance;
  • the photo-aligned liquid crystal aligning agent of Example 3 and Example 4 can be suitably used for the photo-alignment liquid crystal aligning agent of the VA type TFT for the use of the LCD, and has high reliability, excellent orientation effect, high orientation stability, and good residual image performance. .

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Abstract

A liquid crystal aligning agent, comprising a polyamide acid and a polyimide polymer obtained after high-temperature curing of the polyamide acid. The polyamide acid is obtained by reacting a tetracarboxylic dianhydride and a diamine. The diamine comprises a compound represented by formula (1) or a compound represented by formula (2), [Formula 1], [Formula 2]. The liquid crystal aligning agent is suitable for use as an optical alignment liquid crystal aligning agent for LCD applications of IPS-TFTs, TN-TFTs and VA type TFTs, and has high reliability, excellent aligning effects and high aligning stability, and good persistence of visibility. AA%%%Formula (1) BB%%%Formula (2)

Description

液晶取向剂、二胺化合物以及聚酰胺酸Liquid crystal aligning agent, diamine compound, and polyamic acid 技术领域Technical field
本发明之取向剂经过紫外光偏振光照射，形成可对液晶定向产生倾角之光取向液晶剂，用于液晶显示组件。The alignment agent of the present invention is irradiated with ultraviolet light to form a photo-alignment liquid crystal which can be tilted toward the liquid crystal, and is used for a liquid crystal display device.
背景技术Background technique
液晶取向剂组件(Liquid Cystal Display，LCD)包含取向剂及液晶，为使光线经电场控制而有图案化的显示，取向剂对液晶的倾角控制就极为重要，此种倾角的控制须考虑倾角角度(pretilt angle)的大小、倾角分布的均匀性、长时间显示器驱动的倾角稳定性及倾角产生过程中对显示器组件电性及残像的影响。Liquid crystal aligning agent (LCD) comprises an aligning agent and a liquid crystal. In order to make the light pattern controlled by an electric field, the tilting control of the liquid crystal by the aligning agent is extremely important. The tilt angle control must consider the tilt angle. The size of the (pretilt angle), the uniformity of the tilt distribution, the tilt stability of the display for a long time, and the influence on the electrical and afterimage of the display assembly during the generation of the tilt angle.
传统且公知的取向剂定向工艺为打摩法(Rubbing)，使用毛布对取向剂进行摩擦使取向剂产生对液晶的定向力，藉由毛布对取向剂的打摩强度或深度、不同滚轮转速及平台移动速度来控制取向剂对液晶定向的倾角大小。但打摩过程中会产生几项缺点，例如:静电产生、须再进行清洗干燥、打摩刮落的毛布及刮起的取向剂碎屑残留，毛布长度高低落差导致定向不均匀及不良以及因流程污染导致电性不良及残像发生…等等。近代加上面板大型化的演进，打摩法也存在更大的挑战。The conventional and well-known orientation agent orientation process is Rubbing. The use of a felt to rub the alignment agent causes the orientation agent to produce a directional force to the liquid crystal, the rubbing strength or depth of the orientation agent, the different roller speeds and The platform moves at a rate to control the amount of tilt of the orientation agent to the orientation of the liquid crystal. However, there are several shortcomings in the process of rubbing, such as: static electricity generation, cleaning and drying, rubbing and scraping of the orientation agent, and the unevenness of the length of the felt, resulting in uneven orientation and defects. Process contamination causes electrical defects and afterimages to occur...etc. In modern times, with the evolution of large-scale panels, there are also greater challenges in the fight against the law.
为改善摩擦法的缺点，采用取向剂进行偏振紫外光照射达到化学反应进而对液晶形成取向的方法被提出，即是所谓的光取向法。然而光取向法所发生的化学反应包含光聚合型及光裂解型，但这些化学反应需考虑对显示器组件之电性及残像的影响。因此，本发明即是采用照光进行光交联型的二胺单体进行聚酰胺酸及聚酰亚胺取向剂的制备。In order to improve the shortcomings of the rubbing method, a method of irradiating polarized ultraviolet light with an aligning agent to achieve a chemical reaction and then orienting the liquid crystal is proposed, which is a so-called photo-alignment method. However, the chemical reactions that occur in photo-alignment methods include photopolymerization and photo-cleavage, but these chemical reactions need to consider the effects on the electrical and afterimage of the display components. Therefore, the present invention is a process for preparing a polyamic acid and a polyimide alignment agent by photo-crosslinking type diamine monomer.
发明内容Summary of the invention
本发明要解决的技术问题是：克服现有的打摩方法的缺陷，提出一种光取 向法，利用本发明所设计的结构，可以达到光取向的目的并保有良好的电性，包含了高电压保持特性(VHR)、低离子含量(ion density)及低积蓄电荷。此外，可改善打摩法所引起的摩擦后产生种种不良的问题、提高可靠性及提高整体取向均匀性。The technical problem to be solved by the invention is to overcome the defects of the existing rubbing method and propose a light extraction According to the structure designed by the present invention, the purpose of photo-alignment can be achieved and good electrical properties can be achieved, including high voltage holding characteristics (VHR), low ion density and low accumulated charge. In addition, it can improve the problems caused by the friction caused by the rubbing method, improve the reliability, and improve the overall orientation uniformity.
为了解决上述技术问题，本发明提出下列技术方案：一种液晶取向剂，其包含由聚酰胺酸及其高温固化后的聚酰亚胺聚合物，该聚酰胺酸由四羧酸二酐及二胺反应得到，所述二胺包含式(1)所示的化合物或式(2)所示的化合物，In order to solve the above technical problems, the present invention proposes the following technical solution: a liquid crystal aligning agent comprising a polyimide polymer cured by a polyamic acid and a high temperature thereof, the polyamic acid being composed of tetracarboxylic dianhydride and two Obtained by an amine reaction, the diamine comprising a compound represented by the formula (1) or a compound represented by the formula (2),
Figure PCTCN2016082438-appb-000001
Figure PCTCN2016082438-appb-000001
式(2)中R1及R2为氢原子或碳烷基结构，碳数1‐4。In the formula (2), R1 and R2 are a hydrogen atom or a carbon alkyl structure, and have a carbon number of 1 - 4.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明液晶取向剂适用于IPS‐TFT、TN‐TFT和VA型TFT的LCD用途的光取向液晶取向剂，具有高可靠性，优异的取向效果和高取向稳定性，以及良好的残影表现。The liquid crystal aligning agent of the present invention is suitable for a photo-aligned liquid crystal aligning agent for LCD applications of IPS-TFT, TN-TFT and VA-type TFTs, and has high reliability, excellent orientation effect, high orientation stability, and good afterimage performance.
具体实施方式detailed description
本发明提出一种液晶取向剂，其包含由聚酰胺酸及其高温固化后的聚酰亚胺聚合物，该聚酰胺酸由四羧酸二酐及二胺反应得到，所述二胺包含下式(1)(编号AM‐1)所示的化合物或式(2)所示的化合物；The present invention provides a liquid crystal aligning agent comprising a polyimide polymer obtained by curing a polyamic acid and a high temperature thereof, the polyamic acid being obtained by reacting a tetracarboxylic dianhydride and a diamine, the diamine comprising the lower a compound represented by the formula (1) (No. AM-1) or a compound represented by the formula (2);
Figure PCTCN2016082438-appb-000002
Figure PCTCN2016082438-appb-000002
式(2)中R1及R2为氢原子或碳烷基结构(碳数1‐4)。In the formula (2), R1 and R2 are a hydrogen atom or a carbon alkyl structure (carbon number 1 - 4).
上述四羧酸二酐可为脂环结构及苯环结构，上述四羧酸二酐包含脂环二酐 和/或苯环二酐，上述四羧酸二酐可使用下列物质中的一种、两种或多种的混合物：1,2,3,4‐环丁烷四羧酸二酐、1,3‐二甲基‐1,2,3,4‐环丁烷四甲酸二酐、5‐(2,5‐二氧代四氢呋喃基)‐3‐曱基环己基‐l,2‐二羧酸酐、1,2,3,4‐环戊烷四酸二酐、2,3,5‐三羧基环戊基乙酸二酐、1,2,4,5‐环己烷四酸二酐、双环〔2.2.2〕辛烷‐2,3,5,6‐四甲酸二酐、双环〔2.2.2〕辛‐7‐烯‐2,3,5,6‐四甲酸二酐、均苯四甲酸二酐、氧代联苯四甲酸二酐、联苯四甲酸二酐、六氟亚异丙基二邻苯二甲酸二酐、氧代联苯四甲酸二酐等结构类似或相关的化合物。The above tetracarboxylic dianhydride may have an alicyclic structure and a benzene ring structure, and the above tetracarboxylic dianhydride comprises an alicyclic dianhydride. And/or benzene dianhydride, the above tetracarboxylic dianhydride may be one or a mixture of two or more of the following: 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1, 3‐Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 5‐(2,5-dioxotetrahydrofuranyl)-3-fluorenylcyclohexyl-l,2-dicarboxylic anhydride 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo[ 2.2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic acid II A structurally similar or related compound such as an anhydride, oxybiphenyltetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, hexafluoroisopropylidene diphthalic acid dianhydride or oxydiphenyltetracarboxylic dianhydride.
上述二胺可为脂环结构及苯环结构，上述二胺可使用下列物质中的一种、两种或多种的混合物:1,4‐对苯二胺、1,3‐间苯二胺、4,4’‐二氨基二苯基醚、4,4’‐二氨基二苯基甲烷、4,4′‐二氨基二苯砜、2,2’‐二甲基‐4,4’‐二氨基联苯、4,4’‐二苯硫醚、4,4′‐二氨基苯偶酰、4,4’‐二氨基‐2,2’‐二(三氟甲基)联苯、4,4’‐二氨基二苯基胺、1,4‐二氨基环己烷、4,4′‐二氨基二环己基甲烷等结构类似或相关的化合物。The above diamine may be an alicyclic structure and a benzene ring structure, and the above diamine may be used in one, a mixture of two or more of the following: 1,4-p-phenylenediamine, 1,3-m-phenylenediamine , 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'- Diaminobiphenyl, 4,4'-diphenyl sulfide, 4,4'-diaminobenzyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4 , structurally similar or related compounds such as 4'-diaminodiphenylamine, 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane.
另外，为提高倾角，上述二胺可使用具有提供倾角功能的二胺，上述二胺包含具有长链烷基结构(CH2(CH2)nCH3，n＝6‐20)、液晶型结构(苯环、脂环及长链烷基链接结构)及胆甾醇结构的二胺。Further, in order to increase the tilt angle, the diamine may be a diamine having a function of providing a tilting function, the diamine comprising a long-chain alkyl structure (CH2(CH2)nCH3, n=6-20), a liquid crystal structure (benzene ring, An alicyclic and long-chain alkyl linking structure) and a diamine of a cholesteric structure.
实施例1Example 1
一种液晶取向剂，包含聚酰胺酸及其高温固化后的聚酰亚胺聚合物，该聚酰胺酸由四羧酸二酐及二胺反应得到；四羧酸二酐使用1,2,3,4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3,4‐环丁烷四羧酸二酐和均苯四甲酸二酐；上述二胺结构包含式(1)(编号AM‐1)所示的化合物。A liquid crystal aligning agent comprising a polyamic acid and a polyimide polymer after curing at a high temperature, the polyamic acid being obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride using 1, 2, 3 , 4 - cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3,4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; the above diamine structure A compound represented by the formula (1) (No. AM-1) is contained.
Figure PCTCN2016082438-appb-000003
Figure PCTCN2016082438-appb-000003
(合成例1)上述液晶取向剂的合成方法是：选用一个1000ml的四口圆底玻璃反应瓶，在氮气氛围状态下，加入1,4二氨基二苯甲烷15.84g(0.08mol)及AM‐1单体4.06g(0.02mol)，再加入N-甲基-2-吡咯烷酮226.3g，于25℃搅拌溶解，之后再加入均苯四甲酸二酐4.36g(0.01mol)及1,2,3,4‐环丁烷四羧酸二酐15.68g(0.09mol)，于50℃温度下搅拌聚合，进行聚酰胺酸聚合反应，聚合固含量15％，反应4小时。聚合反应结束后，稀释调配取向剂，加入N-甲基-2-吡咯烷酮(NMP)274.3g及乙二醇单丁醚(BC)125.1g，搅拌混合1小时，稀释成6％固含量的液晶取向剂溶液，NMP:BC＝80:20。(Synthesis Example 1) The above liquid crystal aligning agent was synthesized by using a 1000 ml four-neck round bottom glass reaction bottle and adding 1,4 diaminodiphenylmethane 15.84 g (0.08 mol) and AM- under a nitrogen atmosphere. 1 monomer 4.06g (0.02mol), then add 226.3g of N-methyl-2-pyrrolidone, stir and dissolve at 25 ° C, then add pyromellitic dianhydride 4.36g (0.01mol) and 1,2,3 Further, 15.68 g (0.09 mol) of 4-cyclobutanetetracarboxylic dianhydride was stirred and polymerized at a temperature of 50 ° C to carry out polymerization of polyamic acid, and the polymerization solid content was 15%, and the reaction was carried out for 4 hours. After the completion of the polymerization reaction, the alignment agent was diluted and prepared, and 274.3 g of N-methyl-2-pyrrolidone (NMP) and 125.1 g of ethylene glycol monobutyl ether (BC) were added, and the mixture was stirred and mixed for 1 hour, and diluted to a liquid crystal of 6% solid content. Orienting agent solution, NMP: BC = 80:20.
将上述的液晶取向剂溶液使用转印法涂布在ITO玻璃基板上，使用热板80℃预烘150秒，再放入高温热风循环烘箱中以220℃固化20分钟。之后再对该取向剂固化得到的取向膜以200-400nm的紫外光偏振光照射，照射能量为10j/cm2。取两块具取向剂经光取向后的ITO玻璃，使用间隙子尺寸4微米，再经边框胶涂布贴合成液晶盒，以热压机150℃热压90分钟，灌注液晶后即完成液晶盒的组立。The above liquid crystal aligning agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulating oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 . Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 μm, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
实施例2Example 2
一种取向剂，其包含由聚酰胺酸及其高温固化后的聚酰亚胺聚合物，该聚酰胺酸由四羧酸二酐及二胺反应得到；四羧酸二酐使用1,2,3,4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3.4‐环丁烷四羧酸二酐和均苯四甲酸二酐；所述二胺结构包含式(1)(编号AM‐1)所示的化合物和下式(3)(编号AM‐2)所示的化合物，二胺使用式(1)所示的化合物和式(3)所示的化合物进行聚合物聚合。An aligning agent comprising a polyimide polymer cured by a polyamic acid and a high temperature thereof, wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride is used 1, 2, 3,4-cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3.4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; the diamine structure The compound represented by the formula (1) (No. AM-1) and the compound represented by the following formula (3) (No. AM-2) are used, and the diamine is represented by the compound represented by the formula (1) and the formula (3). The compound is polymerized.
Figure PCTCN2016082438-appb-000004
Figure PCTCN2016082438-appb-000004
(合成例2)上述液晶取向剂的合成方法是：选用一个1000ml的四口圆底玻璃反应瓶，在氮气氛围状态下，加入1,4二氨基二苯醚14g(0.07mol)、AM‐1单体4.06g(0.02mol)及AM‐2单体4.04g(0.01mol)，再加入N-甲基-2-吡咯烷酮238.8g，于25℃搅拌溶解，之后再加入均苯四甲酸二酐4.36g(0.01mol)及1,2,3.4‐环丁烷四羧酸二酐15.68g(0.09mol)，于50℃温度下搅拌聚合，进行聚酰胺酸聚合反应，聚合固含量15％，反应6小时。聚合反应结束后，稀释调配取向剂，加入N-甲基-2-吡咯烷酮(NMP)223.3g及乙二醇单丁醚(BC)198.0g，搅拌混合1小时，稀释成6％固含量的液晶取向剂溶液，NMP:BC＝70:30。(Synthesis Example 2) The above liquid crystal aligning agent was synthesized by using a 1000 ml four-neck round bottom glass reaction bottle and adding 1,4 diaminodiphenyl ether 14 g (0.07 mol) and AM‐1 under a nitrogen atmosphere. 4.06 g (0.02 mol) of monomer and 4.04 g (0.01 mol) of AM-2- monomer, and then added 238.8 g of N-methyl-2-pyrrolidone, stirred and dissolved at 25 ° C, and then added to the pyromellitic dianhydride 4.36. g (0.01 mol) and 1,2,3.4-cyclobutane tetracarboxylic dianhydride 15.68 g (0.09 mol), stirred and polymerized at a temperature of 50 ° C to carry out polymerization of polyamic acid, polymerization solid content of 15%, reaction 6 hour. After the completion of the polymerization reaction, the orientation agent was diluted and mixed, and 223.3 g of N-methyl-2-pyrrolidone (NMP) and 198.0 g of ethylene glycol monobutyl ether (BC) were added, and the mixture was stirred and mixed for 1 hour, and diluted to a liquid crystal of 6% solid content. Orienting agent solution, NMP: BC = 70:30.
将上述的液晶取向剂溶液使用转印法涂布在ITO玻璃基板上，使用热板80℃预烘150秒，再放入高温热风循环烘箱中以220℃固化20分钟。之后再对该取向剂固化得到的取向膜以200-400nm的紫外光偏极光照射，照射能量为10j/cm2。取两块具取向剂经光取向后的ITO玻璃，使用间隙子尺寸4微米，再经边框胶涂布贴合成液晶盒，以热压机150℃热压90分钟，灌注液晶后即完成液晶盒的组立。The above liquid crystal aligning agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulating oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 . Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 μm, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
实施例3Example 3
一种取向剂，其包含由聚酰胺酸及其高温固化后的聚酰亚胺聚合物，该聚酰胺酸由四羧酸二酐及二胺反应得到；四羧酸二酐使用1,2,3,4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3,4‐环丁烷四羧酸二酐和均苯四甲酸二酐；上述二胺包含式(1)(编号AM‐1)所示的化合物和下式(4)(编号AM‐3)所示的化合物，二胺使用式(1)所示的化合物和式(4)所示的化合物进行聚合物聚合。An aligning agent comprising a polyimide polymer cured by a polyamic acid and a high temperature thereof, wherein the polyamic acid is obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride is used 1, 2, 3,4-cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and pyromellitic dianhydride; the above diamine The compound represented by the formula (1) (No. AM-1) and the compound represented by the following formula (4) (No. AM-3) are used, and the diamine is represented by the compound represented by the formula (1) and the formula (4). The compound is polymerized.
Figure PCTCN2016082438-appb-000005
Figure PCTCN2016082438-appb-000005
Figure PCTCN2016082438-appb-000006
Figure PCTCN2016082438-appb-000006
(合成例3)上述液晶取向剂的合成方法是：选用一个1000ml的四口圆底玻璃反应瓶，在氮气氛围状态下，加入二氨基二苯甲烷13.86g(0.07mol)、AM‐1单体4.06g(0.02mol)及AM‐3单体15.66g(0.01mol)，再加入N-甲基-2-吡咯烷酮303.8g，于25℃搅拌溶解，之后再加入均苯四甲酸二酐4.36g(0.01mol)及1,2,3,4‐环丁烷四羧酸二酐15.68g(0.09mol)，于50℃温度下搅拌聚合，进行聚酰胺酸聚合反应，聚合固含量15％，反应8小时。聚合反应结束后，稀释调配取向剂，加入N-甲基-2-吡咯烷酮(NMP)143.0g及乙二醇单丁醚(BC)446.8g，搅拌混合1小时，稀释成6％固含量的取向剂溶液，NMP:BC＝50:50。(Synthesis Example 3) The above liquid crystal aligning agent was synthesized by using a 1000 ml four-neck round bottom glass reaction bottle and adding 13.86 g (0.07 mol) of diaminodiphenylmethane and AM-1 monomer under a nitrogen atmosphere. 4.06g (0.02mol) and AM-3 monomer 15.66g (0.01mol), and then added 303.8g of N-methyl-2-pyrrolidone, stirred and dissolved at 25 ° C, and then added 4.36g of pyromellitic dianhydride ( 0.01 mol) and 1,2,3,4-cyclobutane tetracarboxylic dianhydride 15.68 g (0.09 mol), stirred and polymerized at a temperature of 50 ° C to carry out polymerization of polyamic acid, polymerization solid content of 15%, reaction 8 hour. After the completion of the polymerization reaction, the orientation agent was diluted and diluted, and 143.0 g of N-methyl-2-pyrrolidone (NMP) and 446.8 g of ethylene glycol monobutyl ether (BC) were added, and the mixture was stirred and mixed for 1 hour, and diluted to a solid content of 6%. Solution solution, NMP: BC = 50:50.
将上述的取向剂溶液使用转印法涂布在ITO玻璃基板上，使用热板80℃预烘150秒，再放入高温热风循环烘箱中以220℃固化20分钟。之后再对该取向剂固化得到的取向膜以200-400nm的紫外光偏极光照射，照射能量为10j/cm2。取两块具取向剂经光取向后的ITO玻璃，使用间隙子尺寸4微米，再经边框胶涂布贴合成液晶盒，以热压机150℃热压90分钟，灌注液晶后即完成液晶盒的组立。The above-mentioned alignment agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulation oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 . Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 μm, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
实施例4Example 4
一种取向剂，其包含聚酰胺酸及其高温固化后的聚酰亚胺聚合物，该聚酰胺酸由四羧酸二酐及二胺反应得到；四羧酸二酐使用1,2,3,4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3,4‐环丁烷四羧酸二酐或均苯四甲酸二酐；上述二胺包含式(1)(编号AM‐1)所示的化合物和下式(5)(编号AM‐4)所示的化合物，二胺使用式(1)所示的化合物和式(5)所示的化合物进行聚合物聚合。An aligning agent comprising a polyamic acid and a polyimide polymer after curing at a high temperature, the polyamic acid being obtained by reacting a tetracarboxylic dianhydride with a diamine; and the tetracarboxylic dianhydride using 1, 2, 3 , 4 - cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3,4-cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride; the above diamine contains a compound represented by the formula (1) (No. AM-1) and a compound represented by the following formula (5) (No. AM-4), wherein the diamine is a compound represented by the formula (1) and the formula (5) is used. The compound is polymerized.
Figure PCTCN2016082438-appb-000007
Figure PCTCN2016082438-appb-000007
Figure PCTCN2016082438-appb-000008
Figure PCTCN2016082438-appb-000008
(合成例4)上述液晶取向剂的合成方法是：选用一个1000ml的四口圆底玻璃反应瓶，在氮气氛围状态下，加入1,4‐对苯二胺5.4g(0.07mol)、AM‐5单体4.06g(0.02mol)及AM‐4单体13.86g(0.01mol)，再加入N-甲基-2-吡咯烷酮245.7g，于25℃搅拌溶解，之后再加入均苯四甲酸二酐4.36g(0.01mol)及1,2,3,4‐环丁烷四羧酸二酐15.68g(0.09mol)，于50℃温度下搅拌聚合，进行聚酰胺酸聚合反应，聚合固含量15％，反应8小时。聚合反应结束后，稀释调配取向剂，加入N-甲基-2-吡咯烷酮(NMP)93.9g及乙二醇单丁醚(BC)339.7g，搅拌混合1小时，稀释成6％固含量的取向剂溶液，NMP:BC＝50:50。(Synthesis Example 4) The above liquid crystal aligning agent was synthesized by using a 1000 ml four-neck round bottom glass reaction bottle and adding 5.4 g (0.07 mol) of 1,4-p-phenylenediamine under a nitrogen atmosphere, AM- 5 monomer 4.06g (0.02mol) and AM‐4 monomer 13.86g (0.01mol), then add 245.7g of N-methyl-2-pyrrolidone, stir and dissolve at 25 ° C, then add pyromellitic dianhydride 4.36 g (0.01 mol) and 1,2,3,4-cyclobutane tetracarboxylic dianhydride 15.68 g (0.09 mol), stirred and polymerized at a temperature of 50 ° C to carry out polymerization of polyamic acid, polymer solid content of 15% , the reaction was 8 hours. After the completion of the polymerization reaction, the alignment agent was diluted and mixed, and 93.9 g of N-methyl-2-pyrrolidone (NMP) and 339.7 g of ethylene glycol monobutyl ether (BC) were added, and the mixture was stirred and mixed for 1 hour, and diluted to a solid content of 6%. Solution solution, NMP: BC = 50:50.
将上述的取向剂溶液使用转印法涂布在ITO玻璃基板上，使用热板80℃预烘150秒，再放入高温热风循环烘箱中以220℃固化20分钟。之后再对该取向剂固化得到的取向膜以200-400nm的紫外光偏极光照射，照射能量为10j/cm2。取两块具取向剂经光取向后的ITO玻璃，使用间隙子尺寸4微米，再经边框胶涂布贴合成液晶盒，以热压机150℃热压90分钟，灌注液晶后即完成液晶盒的组立。The above-mentioned alignment agent solution was applied onto an ITO glass substrate by a transfer method, prebaked at 80 ° C for 150 seconds using a hot plate, and then placed in a high-temperature hot air circulation oven and cured at 220 ° C for 20 minutes. Thereafter, the alignment film obtained by curing the alignment agent was irradiated with ultraviolet light of 200 to 400 nm, and the irradiation energy was 10 j/cm 2 . Two ITO glasses with orienting agent after photo-alignment were used, and the liquid crystal cell was assembled by using a spacer with a gap size of 4 μm, and then heat-pressed at 150 ° C for 90 minutes. After filling the liquid crystal, the liquid crystal cell was completed. The formation of the group.
聚酰胺酸取向剂是由四羧酸二酐及二胺于极性溶剂中聚合而得的液晶取向剂，最佳聚合比例为：若二胺为1mol当量，四羧酸二酐可使用为0.5‐1.5mol当量，最佳为0.75‐1.25mol当量，更佳为0.9‐1.1mol当量。聚合温度可在‐10‐100℃，最佳为10‐80℃，更加为25‐60℃。使用溶剂为可为N-甲基-2-吡咯烷酮、γ-丁内酯、乙二醇单丁醚、N，N-二甲基乙酰胺、、N-甲基己内酯、二甲亚砜等等，可单独使用也可混合使用，本发明使用N-甲基-2-吡咯烷酮(NMP)及乙二醇单丁醚(BC)进行聚酰胺酸聚合及取向剂成品调配。聚酰胺酸合成后进行取向剂调配，调配的取向剂成品固含量最佳范围在1％‐10％，更佳的范围在4％‐7％。取向剂涂布可用旋涂法、转印法及喷涂法。涂布选用的基板因为是用于液晶显示组件，所以选用ITO玻璃用于本发明，但不限于ITO玻璃，凡属透明之导电基板皆适用， 包含AZO导电玻璃，软性塑料基板。涂布后预烘温度范围可在50‐150℃，最佳范围在60‐120℃，更佳范围在70‐100℃，预烘时间可选用的范围在30‐600秒，最佳的范围在60‐300秒，更佳的范围在120‐180秒。固化温度可使用150‐300℃，最佳在180‐250℃，更佳在200‐230℃，固化时间可选用的范围在1‐90分钟，最佳的范围在5‐60分钟，更佳的范围在10‐30分钟。固化后膜厚范围为30‐150nm，最佳范围为50‐120nm，更佳范围为60‐100nm。将取向剂涂布在ITO玻璃上进行固化后，使用偏振光照射，选用波长为150‐800nm波长的光照，最佳光照波长范围为200‐380nm，更佳光照波长范围为240‐380nm。再将上述处理完成的玻璃制成液晶盒，一般最佳是使用2‐6微米的间隙子制成此盒厚的液晶盒，但盒厚并不限于2‐6微米。The polyamic acid aligning agent is a liquid crystal aligning agent obtained by polymerizing tetracarboxylic dianhydride and a diamine in a polar solvent, and the optimal polymerization ratio is: if the diamine is 1 mol equivalent, the tetracarboxylic dianhydride can be used as 0.5. 1-5 mol equivalent, most preferably 0.75 - 1.25 mol equivalent, more preferably 0.9 - 1.1 mol equivalent. The polymerization temperature can be from -10 to 100 ° C, preferably from 10 to 80 ° C, and more preferably from 25 to 60 ° C. The solvent may be N-methyl-2-pyrrolidone, γ-butyrolactone, ethylene glycol monobutyl ether, N,N-dimethylacetamide, N-methylcaprolactone, dimethyl sulfoxide. Etc., they may be used singly or in combination. The present invention uses N-methyl-2-pyrrolidone (NMP) and ethylene glycol monobutyl ether (BC) for polyamic acid polymerization and alignment agent preparation. After the synthesis of the polyamic acid, the alignment agent is formulated, and the solid content of the prepared alignment agent is preferably in the range of 1% to 10%, more preferably in the range of 4% to 7%. The coating agent can be applied by spin coating, transfer printing or spray coating. Since the substrate selected for coating is used for a liquid crystal display device, ITO glass is selected for use in the present invention, but is not limited to ITO glass, and any transparent conductive substrate is suitable. Contains AZO conductive glass, soft plastic substrate. The pre-bake temperature after coating can be in the range of 50-150 ° C, the optimum range is 60-120 ° C, the better range is 70-100 ° C, the pre-bake time can be selected in the range of 30-600 seconds, the best range is 60-300 seconds, and the better range is 120-180 seconds. The curing temperature can be 150-300 ° C, preferably 180-250 ° C, more preferably 200-230 ° C, the curing time can be selected from 1 - 90 minutes, the best range is 5 - 60 minutes, better The range is 10-30 minutes. After curing, the film thickness ranges from 30 to 150 nm, and the optimum range is from 50 to 120 nm, and more preferably from 60 to 100 nm. After the alignment agent is coated on the ITO glass for curing, the polarized light is irradiated, and the light having a wavelength of 150-800 nm is selected, and the optimum illumination wavelength range is 200-380 nm, and the preferred illumination wavelength range is 240-380 nm. Further, the glass which has been subjected to the above treatment is made into a liquid crystal cell, and it is generally preferable to use the spacer of 2 - 6 μm to form the cell of the cell thickness, but the cell thickness is not limited to 2 - 6 μm.
预倾角测试：Pretilt test:
使用Shintech OPTIPRO‐STD，利用液晶旋转法测试液晶盒倾角。The tilt angle of the cell was tested using the liquid crystal rotation method using Shintech OPTIPRO-STD.
电性测试：Electrical test:
使用TOYO Model 6254电性量测设备，液晶盒在25℃的温度，给予4V的电压，测定时间为16.67ms，再计算其电压保持率。Using a TOYO Model 6254 electrical measuring device, the liquid crystal cell was given a voltage of 4 V at a temperature of 25 ° C for a measurement time of 16.67 ms, and the voltage holding ratio was calculated.
测试结果整理于下表:The test results are organized in the following table:
Figure PCTCN2016082438-appb-000009
Figure PCTCN2016082438-appb-000009
本发明具有以下有益效果：The invention has the following beneficial effects:
实施例1的光取向液晶取向剂适用于IPS‐TFT的LCD用途的光取向液晶取向剂，具有高可靠性，优异的取向效果和高取向稳定性，以及良好的残影表现；The photo-aligned liquid crystal aligning agent of Example 1 is suitable for a photo-aligned liquid crystal aligning agent for LCD use of IPS-TFT, and has high reliability, excellent orientation effect and high orientation stability, and good afterimage performance;
实施例2的光取向液晶取向剂可适用于TN‐TFT的LCD用途的光取向液晶取向剂，具有高可靠性，优异的取向效果和高取向稳定性，以及良好的残影表现；The photo-aligned liquid crystal aligning agent of Example 2 is applicable to a photo-aligned liquid crystal aligning agent for LCD use of TN-TFT, and has high reliability, excellent orientation effect and high orientation stability, and good afterimage performance;
实施例3和实施例4的光取向液晶取向剂可适用于VA型TFT的LCD用途的光取向液晶取向剂，具有高可靠性，优异的取向效果和高取向稳定性，以及良好的残影表现。 The photo-aligned liquid crystal aligning agent of Example 3 and Example 4 can be suitably used for the photo-alignment liquid crystal aligning agent of the VA type TFT for the use of the LCD, and has high reliability, excellent orientation effect, high orientation stability, and good residual image performance. .

Claims (10)

  1. 一种液晶取向剂，其特征在于，其包含由聚酰胺酸及其高温固化后的聚酰亚胺聚合物，该聚酰胺酸由四羧酸二酐及二胺反应得到，所述二胺包含式(1)所示的化合物或式(2)所示的化合物，A liquid crystal aligning agent comprising a polyamic acid and a polyimide polymer cured at a high temperature, the polyamic acid being obtained by reacting a tetracarboxylic dianhydride and a diamine, the diamine comprising a compound represented by the formula (1) or a compound represented by the formula (2),
    Figure PCTCN2016082438-appb-100001
    Figure PCTCN2016082438-appb-100001
    式(2)中R1及R2为氢原子或碳烷基结构，碳数1‐4。In the formula (2), R1 and R2 are a hydrogen atom or a carbon alkyl structure, and have a carbon number of 1 - 4.
  2. 根据权利要求1所述的液晶取向剂，其特征在于，上述四羧酸二酐是下列物质中的一种、两种或多种的混合物：1,2,3，4‐环丁烷四羧酸二酐、1,3‐二甲基‐1,2,3,4‐环丁烷四甲酸二酐、5‐(2,5‐二氧代四氢呋喃基)‐3‐甲基环己基‐l,2‐二羧酸酐、1,2,3,4‐环戊烷四酸二酐、2,3,5‐三羧基环戊基乙酸二酐、1,2,4,5‐环己烷四酸二酐、双环〔2.2.2〕辛烷‐2,3,5,6‐四甲酸二酐、双环〔2.2.2〕辛‐7‐烯‐2,3,5,6‐四甲酸二酐、均苯四甲酸二酐、氧代联苯四甲酸二酐、联苯四甲酸二酐、六氟亚异丙基二邻苯二甲酸二酐、氧代联苯四甲酸二酐。The liquid crystal aligning agent according to claim 1, wherein the tetracarboxylic dianhydride is one, a mixture of two or more of the following: 1,2,3,4-cyclobutane tetracarboxylic acid. Acid dianhydride, 1,3 dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 5‐(2,5-dioxotetrahydrofuranyl)‐3‐methylcyclohexyl-l , 2 -dicarboxylic anhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexane Acid dianhydride, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride And pyromellitic dianhydride, oxybiphenyltetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, hexafluoroisopropylidene diphthalic dianhydride, oxydiphenyltetracarboxylic dianhydride.
  3. 根据权利要求1或2所述的液晶取向剂，其特征在于，四羧酸二酐使用1,2,3.4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3.4‐环丁烷四羧酸二酐和均苯四甲酸二酐；上述二胺包含式(1)所示的化合物，The liquid crystal aligning agent according to claim 1 or 2, wherein the tetracarboxylic dianhydride is 1,2,3.4-cyclobutanetetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1, 2, 3.4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; the above diamine comprises a compound represented by formula (1),
    Figure PCTCN2016082438-appb-100002
    Figure PCTCN2016082438-appb-100002
  4. 根据权利要求1或2所述的液晶取向剂，其特征在于，四羧酸二酐使用 1,2,3.4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3.4‐环丁烷四羧酸二酐和均苯四甲酸二酐；所述二胺包含式(1)所示的化合物和式(3)所示的化合物，二胺使用式(1)所示的化合物和式(3)所示的化合物进行聚合物聚合，The liquid crystal aligning agent according to claim 1 or 2, wherein tetracarboxylic dianhydride is used 1,2,3.4-cyclobutane tetracarboxylic dianhydride or pyromellitic dianhydride, or a combination of 1,2,3.4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; The amine includes a compound represented by the formula (1) and a compound represented by the formula (3), and the diamine is polymer-polymerized using the compound represented by the formula (1) and the compound represented by the formula (3).
    Figure PCTCN2016082438-appb-100003
    Figure PCTCN2016082438-appb-100003
  5. 根据权利要求1或2所述的液晶取向剂，其特征在于，四羧酸二酐使用1,2,3,4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3,4‐环丁烷四羧酸二酐和均苯四甲酸二酐；上述二胺包含式(1)所示的化合物和式(4)所示的化合物，二胺使用式(1)所示的化合物和式(4)所示的化合物进行聚合物聚合，The liquid crystal aligning agent according to claim 1 or 2, wherein the tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride or pyromellitic dianhydride, or used in combination. 1,2,3,4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; the above diamine comprises a compound represented by the formula (1) and a compound represented by the formula (4), and a diamine usage formula (1) the compound shown and the compound represented by the formula (4) are polymerized,
    Figure PCTCN2016082438-appb-100004
    Figure PCTCN2016082438-appb-100004
    Figure PCTCN2016082438-appb-100005
    Figure PCTCN2016082438-appb-100005
  6. 根据权利要求1或2所述的液晶取向剂，其特征在于，四羧酸二酐使用1,2,3,4‐环丁烷四羧酸二酐或均苯四甲酸二酐，或者合并使用1,2,3.4‐环丁烷四羧酸二酐和均苯四甲酸二酐；上述二胺包含式(1)所示的化合物和式(5)所示的化合物，二胺使用式(1)所示的化合物和式(5)所示的化合物进行聚合物聚合，The liquid crystal aligning agent according to claim 1 or 2, wherein the tetracarboxylic dianhydride is 1,2,3,4-cyclobutanetetracarboxylic dianhydride or pyromellitic dianhydride, or used in combination. 1,2,3.4-cyclobutane tetracarboxylic dianhydride and pyromellitic dianhydride; the above diamine comprises a compound represented by the formula (1) and a compound represented by the formula (5), and the diamine is a formula (1) The compound shown and the compound represented by the formula (5) are polymerized,
    Figure PCTCN2016082438-appb-100006
    Figure PCTCN2016082438-appb-100006
  7. 权利要求1所记载的式(1)所示的化合物。The compound represented by the formula (1) according to claim 1.
  8. 权利要求1所记载的式(2)所示的化合物。The compound represented by the formula (2) according to claim 1.
  9. 一种聚酰胺酸，该聚酰胺酸由四羧酸二酐和权利要求1中所记载的式(1)所示的化合物的二胺反应得到。A polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine of the compound represented by the formula (1) described in Claim 1.
  10. 一种聚酰胺酸，该聚酰胺酸由四羧酸二酐和权利要求1中所记载的式(2)所示的化合物的二胺反应得到。 A polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine of the compound represented by the formula (2) described in claim 1.
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CN106842714A (en) * 2017-01-03 2017-06-13 京东方科技集团股份有限公司 Display base plate, display panel and display device
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246283A (en) * 2007-02-15 2008-08-20 Jsr株式会社 Liquid crystal aligning agnet and liquid crystal display element
CN101256314A (en) * 2007-02-26 2008-09-03 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display element
CN101256316A (en) * 2007-02-27 2008-09-03 Jsr株式会社 Lquid crystal aligning agent and luid crystal display element
JP2008287082A (en) * 2007-05-18 2008-11-27 Jsr Corp Liquid crystal orientation agent and liquid crystal display element
CN101611031A (en) * 2007-04-11 2009-12-23 第一毛织株式会社 3,4-dicarboxyl-1,2,3, the 4-tetrahydrochysene-6-tertiary butyl-1-naphthalene succinic dianhydride and comprise liquid crystal aligning agent by the polyimide of this dianhydride preparation
CN101921598A (en) * 2009-06-11 2010-12-22 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display device
CN102010719A (en) * 2009-09-04 2011-04-13 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polyamic acid and polyimide
KR101208437B1 (en) * 2011-08-29 2012-12-05 한국화학연구원 Novel aromatic diamine and photo cured polyimides with the maleimide side chain and method for preparing them
CN104193992A (en) * 2014-08-12 2014-12-10 深圳市道尔顿电子材料有限公司 Method for preparing polyimide liquid crystal aligning agent

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5013105B2 (en) * 2007-03-06 2012-08-29 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP5088563B2 (en) * 2007-03-07 2012-12-05 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP2008224832A (en) * 2007-03-09 2008-09-25 Jsr Corp Vertical alignment liquid crystal aligning agent and vertical alignment liquid crystal display element
JP2008225010A (en) * 2007-03-12 2008-09-25 Jsr Corp Liquid crystal aligning agent and liquid crystal display element
JP5013106B2 (en) * 2007-03-16 2012-08-29 Ｊｓｒ株式会社 Liquid crystal aligning agent and liquid crystal display element
JP2009031319A (en) * 2007-07-24 2009-02-12 Jsr Corp Manufacturing method for liquid crystal alignment agent, liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
JP5105092B2 (en) * 2008-01-17 2012-12-19 Ｊｓｒ株式会社 Liquid crystal alignment film, method for forming the same, and liquid crystal display element
KR101201437B1 (en) * 2010-06-04 2012-11-14 (주)현대공업 Gas vent for form plastic mold

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101246283A (en) * 2007-02-15 2008-08-20 Jsr株式会社 Liquid crystal aligning agnet and liquid crystal display element
CN101256314A (en) * 2007-02-26 2008-09-03 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display element
CN101256316A (en) * 2007-02-27 2008-09-03 Jsr株式会社 Lquid crystal aligning agent and luid crystal display element
CN101611031A (en) * 2007-04-11 2009-12-23 第一毛织株式会社 3,4-dicarboxyl-1,2,3, the 4-tetrahydrochysene-6-tertiary butyl-1-naphthalene succinic dianhydride and comprise liquid crystal aligning agent by the polyimide of this dianhydride preparation
JP2008287082A (en) * 2007-05-18 2008-11-27 Jsr Corp Liquid crystal orientation agent and liquid crystal display element
CN101921598A (en) * 2009-06-11 2010-12-22 Jsr株式会社 Liquid crystal aligning agent and liquid crystal display device
CN102010719A (en) * 2009-09-04 2011-04-13 Jsr株式会社 Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, polyamic acid and polyimide
KR101208437B1 (en) * 2011-08-29 2012-12-05 한국화학연구원 Novel aromatic diamine and photo cured polyimides with the maleimide side chain and method for preparing them
CN104193992A (en) * 2014-08-12 2014-12-10 深圳市道尔顿电子材料有限公司 Method for preparing polyimide liquid crystal aligning agent

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