WO2017133044A1 - 自取向液晶介质组合物及液晶显示面板 - Google Patents

自取向液晶介质组合物及液晶显示面板 Download PDF

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WO2017133044A1
WO2017133044A1 PCT/CN2016/074625 CN2016074625W WO2017133044A1 WO 2017133044 A1 WO2017133044 A1 WO 2017133044A1 CN 2016074625 W CN2016074625 W CN 2016074625W WO 2017133044 A1 WO2017133044 A1 WO 2017133044A1
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liquid crystal
additive material
additive
atom
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PCT/CN2016/074625
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French (fr)
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兰松
李泳锐
马小龙
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深圳市华星光电技术有限公司
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Priority to US15/026,598 priority Critical patent/US20180057746A1/en
Publication of WO2017133044A1 publication Critical patent/WO2017133044A1/zh

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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
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/062—Non-steroidal liquid crystal compounds containing one non-condensed benzene ring
    • 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
    • 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
    • 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
    • C09K19/58—Dopants or charge transfer agents
    • C09K19/586—Optically active dopants; chiral dopants
    • 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
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • 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
    • 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
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
    • C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/123—Ph-Ph-Ph
    • 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
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3009—Cy-Ph

Definitions

  • the present invention relates to the field of display technologies, and in particular, to a self-aligned liquid crystal medium composition and a liquid crystal display panel comprising the self-aligned liquid crystal medium composition.
  • TFT-LCD Thin Film Transistor Liquid Crystal Display
  • Most of the TFT-LCDs on the market are backlight type liquid crystal display devices, which include a liquid crystal display panel and a backlight module.
  • the working principle of the liquid crystal display panel is to place liquid crystal molecules in two parallel glass substrates, and control the liquid crystal molecules to change direction by energizing or not the glass substrate, and refract the light of the backlight module to produce a picture.
  • the liquid crystal display panel is composed of a color filter substrate (CF), a thin film transistor (TFT) substrate, a liquid crystal (LC) sandwiched between the color filter substrate and the thin film transistor substrate, and a sealant frame (Sealant).
  • the TFT substrate and the CF substrate are respectively provided with an alignment film. After the alignment film is in contact with the LC, the LC can generate a pretilt angle in a certain direction, thereby providing a bearing angle to the liquid crystal molecules (pretilt angle to the TFT) - LCD's driving voltage, contrast, response time, viewing angle, etc. have an important impact).
  • the material of the alignment film is usually made of polyimide (PI) material, which is mainly divided into friction phase-matching PI material and optical phase matching type.
  • PI materials no matter which alignment material has its own disadvantages.
  • the friction phase-matching PI material forms an alignment film by rubbing alignment method, and it is easy to cause problems such as dust particles, static electricity, and brush marks during frictional alignment to reduce the process yield.
  • the optical phase-matching PI material forms an alignment film by photo-alignment technology. Due to limited material properties, heat resistance and aging resistance are poor, and the ability to anchor LC is also weak, thereby reducing The quality of the panel.
  • the PI material itself has high polarity and high water absorption, storage and transportation are prone to deterioration, resulting in uneven phase distribution, and the PI material is expensive, and the process of forming a film on the TFT-LCD is complicated. This leads to an increase in panel costs.
  • additive material to the liquid crystal material, and the additive material can be vertically arranged on the surface of the substrate without the PI alignment film.
  • Such additive materials generally consist of two parts, a head group and a tail group.
  • the main function of the head group is to anchor to the substrate by intermolecular forces, and the main function of the tail group is to rely on a molecular branch similar to PI.
  • the action of the chain causes the liquid crystal molecules to be aligned vertically in a steric hindrance manner.
  • one is an inorganic group-containing material, such as octadecyltrichlorosilane, oligomeric silsesquioxane (POSS), etc., such materials are in liquid crystal.
  • an inorganic group-containing material such as octadecyltrichlorosilane, oligomeric silsesquioxane (POSS), etc.
  • the object of the present invention is to provide a self-aligned liquid crystal medium composition comprising two or more kinds of additive materials, and improving the quality of the self-aligned liquid crystal material composition through the collocation between different additive materials, so that the additive material reaches The best orientation effect.
  • Another object of the present invention is to provide a liquid crystal display panel.
  • the material of the liquid crystal layer is a self-aligned liquid crystal medium composition, which comprises two or more kinds of additive materials, and improves self-orientation through the compatibility between different additive materials.
  • the quality of the liquid crystal material composition allows the additive material to achieve an optimum orientation effect.
  • the present invention provides a self-aligned liquid crystal medium composition comprising a liquid crystal material, two or more additive materials mixed in the liquid crystal material;
  • the two or more additive materials are selected from the group consisting of a first additive material and a second additive material;
  • the first additive material refers to a compound of the formula A-R, wherein
  • A refers to a group containing inorganic silicon, and the inorganic silicon-containing group is -Si(CH 3 ) 3 , -Si(OCH 3 ) 3 , -SiCl 3 , or an oligomeric semi-siloxane;
  • the second additive material refers to a compound of the formula C-R', wherein
  • C refers to an organic polar group, which is a primary, secondary, tertiary, -OH, -COOH, -SH, or -CN;
  • the structural formula of the first additive material is:
  • the structural formula of the second additive material is:
  • At least one of the two or more additive materials is selected from the group consisting of a first additive material and at least one selected from the group consisting of a second additive material.
  • the two or more additive materials are each selected from the second additive material.
  • the total content of the two or more additive materials in the self-aligned liquid crystal medium composition is from 0.1 to 5% by weight.
  • the invention comprises two additive materials, the first additive material is selected from the first additive material, and the second additive material is selected from the second additive material, the molar ratio of the first additive material to the second additive material is 1:99. And the total content of the first additive material and the second additive material in the self-aligned liquid crystal medium composition is 3% by weight.
  • the liquid crystal material is a negative liquid crystal material.
  • the present invention also provides a liquid crystal display panel comprising a TFT substrate and a CF substrate disposed opposite to each other, and a liquid crystal layer between the TFT substrate and the CF substrate;
  • the material of the liquid crystal layer is a self-aligned liquid crystal medium composition as described above;
  • a first conductive film and a second conductive film are respectively disposed on a surface of the TFT substrate and the CF substrate;
  • two or more kinds of additive materials in the self-aligned liquid crystal medium composition are vertically arranged on the surface of the opposite side of the TFT substrate and the CF substrate, thereby guiding the liquid crystal molecules to be vertically aligned, thereby It acts as a liquid crystal alignment.
  • the materials of the first conductive film and the second conductive film are both ITO.
  • the present invention also provides a self-aligned liquid crystal medium composition comprising a liquid crystal material, two or more additive materials mixed in the liquid crystal material;
  • the two or more additive materials are selected from the group consisting of a first additive material and a second additive material;
  • the first additive material refers to a compound of the formula A-R, wherein
  • A refers to a group containing inorganic silicon, and the inorganic silicon-containing group is -Si(CH 3 ) 3 , -Si(OCH 3 ) 3 , -SiCl 3 , or an oligomeric semi-siloxane;
  • the second additive material refers to a compound of the formula C-R', wherein
  • C refers to an organic polar group, which is a primary, secondary, tertiary, -OH, -COOH, -SH, or -CN;
  • the liquid crystal material is a negative liquid crystal material.
  • the present invention provides a self-aligned liquid crystal medium composition and a liquid crystal display panel; the self-aligned liquid crystal medium composition of the present invention, comprising two or more kinds of additive materials, the two or two The above additive material is selected from the first additive material and the second additive material; the molecular structures of the first additive material and the second additive material are both composed of a head base and a tail base, the first additive material and the second The main function of the head base portion of the additive material is anchored on the substrate by intermolecular forces, and the main function of the tail group portion is to align the liquid crystal molecules vertically in a manner similar to the action of the PI branch in a steric manner, wherein The head group portion of the first additive material is a group containing inorganic silicon, and the head group portion of the second additive material is an organic polar group; the inorganic silicon is improved by the compatibility between different additive materials.
  • the additive material of the group is easy to aggregate, and the role of the anchoring substrate of the additive material containing the polar group is enhanced, thereby improving self-extraction.
  • the quality of the liquid crystal material composition enables the additive material to achieve an optimal orientation effect, thereby eliminating the PI alignment film process, saving production cost, and reducing energy consumption and pollution.
  • the material of the liquid crystal layer is self-aligned liquid crystal.
  • the medium composition comprises two or more kinds of additive materials, and the quality of the self-aligned liquid crystal material composition is improved by the compatibility between different additive materials, so that the additive material achieves the best orientation effect, thereby not including PI Alignment film saves production costs.
  • FIG. 1 is a schematic structural view of a first additive material in a self-aligned liquid crystal medium composition of the present invention
  • FIG. 2 is a schematic structural view of a second additive material in the self-aligned liquid crystal medium composition of the present invention
  • FIG. 3 is a schematic structural view of a preferred embodiment of a liquid crystal display panel of the present invention.
  • the present invention firstly provides a self-aligned liquid crystal medium composition comprising a liquid crystal material 53 and two or more additive materials mixed in the liquid crystal material 53;
  • the two or more additive materials are selected from the first additive material 51 and the second additive material 52;
  • the first additive material 51 refers to a compound of the formula A-R, wherein
  • A refers to a group containing inorganic silicon, and the inorganic silicon-containing group is -Si(CH 3 ) 3 , -Si(OCH 3 ) 3 , -SiCl 3 , or an oligomeric semi-siloxane;
  • the head group A is a group containing inorganic silicon, and its main function is to make a strong interaction between the first additive material 51 and the substrate.
  • the molecular force is anchored on the substrate; and the main function of the tail group R is to align the liquid crystal molecules vertically in a manner similar to the action of the PI branch in a steric barrier manner.
  • the structural formula of the first additive material 51 is:
  • the second additive material 52 refers to a compound of the formula C-R', wherein
  • C refers to an organic polar group, which is a primary, secondary, tertiary, -OH, -COOH, -SH, or -CN;
  • the head group C is an organic polar group, and its main function is to make a strong interaction between the second additive material 52 and the substrate.
  • the molecular force is anchored on the substrate; and the main function of the tail group R' is to align the liquid crystal molecules vertically in a manner similar to the action of the PI branch in a steric hindrance manner.
  • the structural formula of the second additive material 52 is:
  • At least one of the two or more additive materials is selected from the first additive material 51 and at least one is selected from the second additive material 52.
  • the two or more additive materials are selected from the second additive material 52.
  • the total content of the two or more additive materials in the self-aligned liquid crystal medium composition is from 0.1 to 5 wt%.
  • the self-aligned liquid crystal medium composition comprises two additive materials, the first additive material is selected from the first additive material 51, and the second additive material is selected from the second additive material 52, the first additive material
  • the molar ratio to the second additive material is 1:99, and the total content of the first additive material and the second additive material in the self-aligned liquid crystal medium composition is 3% by weight.
  • the liquid crystal material 53 is a negative liquid crystal material.
  • the present invention further provides a liquid crystal display panel comprising oppositely disposed TFT substrate 10 and CF substrate 20, and a liquid crystal layer 30 between the TFT substrate 10 and the CF substrate 20;
  • the material of the liquid crystal layer 30 is a self-aligned liquid crystal medium composition as described above;
  • the first conductive film 11 and the second conductive film 21 are respectively disposed on the surface of the opposite side of the TFT substrate 10 and the CF substrate 20;
  • two or more kinds of additive materials in the self-aligned liquid crystal medium composition are vertically arranged on the surface on the opposite side of the TFT substrate 10 and the CF substrate 20 to guide the liquid crystal molecules to be vertically arranged. Therefore, it functions as a liquid crystal alignment.
  • the material of the first conductive film 11 and the second conductive film 21 is indium tin oxide (ITO).
  • the self-aligned liquid crystal medium composition comprises two additive materials, and the first additive material is selected from the first additive material 51, and the structural formula is:
  • the second additive material is selected from the second additive material 52 and has the structural formula:
  • the molar ratio of the first additive material to the second additive material is 1:99, and the total content of the first additive material and the second additive material in the self-aligned liquid crystal medium composition is 3wt%.
  • the self-aligned liquid crystal medium composition of the present invention comprises two or more additive materials selected from the group consisting of a first additive material and a second additive material;
  • the molecular structures of the first additive material and the second additive material are both composed of a head group and a tail group, and the main function of the head group portion of the first additive material and the second additive material is anchored by intermolecular forces.
  • Positioned on the substrate, and the main function of the tail group portion is to vertically align the liquid crystal molecules in a sterically hindrance manner similar to the action of the PI branch, wherein the head group portion of the first additive material is a group containing inorganic silicon.
  • the head group portion of the second additive material is an organic polar group; the compatibility of the inorganic silicon group-containing additive material can be improved by the compatibility between different additive materials, and the organic polar group is enhanced.
  • the additive material anchors the substrate to improve the quality of the self-aligned liquid crystal material composition, so that the additive material achieves the best orientation effect.
  • the PI alignment film process is omitted, the production cost is saved, and the energy consumption and pollution are saved.
  • the material of the liquid crystal layer is a self-aligned liquid crystal medium composition, which includes two or more kinds of additive materials, and different
  • the collocation between the additive materials improves the quality of the self-aligned liquid crystal material composition, so that the additive material achieves an optimal orientation effect, thereby eliminating the PI alignment film and saving production costs.

Abstract

提供了一种自取向液晶介质组合物及液晶显示面板，其中的自取向液晶介质组合物包括两种或两种以上的添加剂材料，所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；所述第一添加剂材料和第二添加剂材料的分子结构均由头基和尾基两部分所组成，所述第一添加剂材料和第二添加剂材料的头基部分的主要作用是通过分子间作用力而锚定在基板上，而尾基部分的主要作用是类似于PI支链的作用以立体障碍的方式使液晶分子垂直排列，通过不同添加剂材料之间的搭配性，可改善含无机硅基团的添加剂材料容易聚集的特性，提升含有机极性基团的添加剂材料锚定基板的作用。

Description

自取向液晶介质组合物及液晶显示面板 技术领域
本发明涉及显示技术领域，尤其涉及一种自取向液晶介质组合物及包含该自取向液晶介质组合物的液晶显示面板。
背景技术
薄膜晶体管液晶显示装置(TFT-LCD，Thin Film TransistorLiquid Crystal Display)具有机身薄、省电、无辐射等众多优点，得到了广泛的应用。现有市场上的TFT-LCD大部分为背光型液晶显示装置，其包括液晶显示面板及背光模组(backlight module)。液晶显示面板的工作原理是在两片平行的玻璃基板当中放置液晶分子，通过玻璃基板通电与否来控制液晶分子改变方向，将背光模组的光线折射出来产生画面。
通常液晶显示面板由彩膜基板(CF，Color Filter)、薄膜晶体管(TFT)基板、夹于彩膜基板与薄膜晶体管基板之间的液晶(LC，Liquid Crystal)及密封胶框(Sealant)组成。其中，TFT基板及CF基板上还分别设有一层配向膜，该配向膜与LC接触后，能够使得LC产生一定方向的预倾角，从而给液晶分子提供一个承载的角度(预倾角的大小对TFT-LCD的驱动电压、对比度、响应时间、视角等具有重要影响)，目前，配向膜的材料通常选用聚酰亚胺(Polyimide，PI)材料，主要分为摩擦配相型PI材料和光配相型PI材料，但是，无论哪种配向材料都有各自的缺点。其中，摩擦配相型PI材料通过摩擦配向法(Rubbing)形成配向膜，在摩擦配向时容易造成粉尘颗粒、静电残留、刷痕等问题降低工艺良率。而光配相型PI材料通过光配向法(photo-alignment technology)形成配向膜，由于材料特性受限，耐热性和耐老化性不佳，同时锚定LC的能力也较弱，从而降低了面板的品质。除此之外，PI材料本身就具有高极性和高吸水性，存储和运送容易造成变质而导致配相不均，并且PI材料价格昂贵，在TFT-LCD上成膜的工艺也较为复杂，导致面板成本提高。
为解决上述PI配向膜所存在的问题，目前本领域内已提出一种通过在液晶材料中加入一种添加剂材料(Additive)，利用该添加剂材料可在无PI配向膜的基板表面垂直排列而起到垂直配向作用，从而取代PI配向膜的方法。这类添加剂材料一般由头基和尾基两部分组成，头基的主要作用是利用分子间作用力锚定在基板上，而尾基的主要作用是依靠类似于PI分子支 链的作用以立体障碍的方式使得液晶分子垂直排。
目前，上述添加剂材料主要有两种类型：一种是含有无机基团的材料，例如：十八烷基三氯硅烷、低聚体半硅氧烷(POSS)等，这类材料在液晶中的溶解性较差，会沉积在基板表面，从而达到使得液晶垂直取向的效果，但自身容易团聚，会引起液晶配向不良，发生暗线的现象；另一种是有机材料，例如：对辛基苯胺、正庚酸等，这类材料的主要缺点是在基板表面锚定的作用较弱，在浓度较低的时候，会使得液晶产生漏光的现象。
发明内容
本发明的目的在于提供一种自取向液晶介质组合物，包括两种或两种以上的添加剂材料，通过不同添加剂材料之间的搭配性，提高自取向液晶材料组合物的品质，使添加剂材料达到最佳的取向效果。
本发明的目的还在于提供一种液晶显示面板，液晶层的材料为自取向液晶介质组合物，其中包括两种或两种以上的添加剂材料，通过不同添加剂材料之间的搭配性，提高自取向液晶材料组合物的品质，使添加剂材料达到最佳的取向效果。
为实现上述目的，本发明提供一种自取向液晶介质组合物，包括液晶材料、混合于所述液晶材料中的两种或两种以上的添加剂材料；
所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；
所述第一添加剂材料指的是结构通式为A-R的一类化合物，其中，
A指的是指含有无机硅的基团，所述含有无机硅的基团为-Si(CH3)3、-Si(OCH3)3、-SiCl3、或低聚体半硅氧烷；
R指的是具有3～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第一基团、该烷基中的某个H原子被F或Cl原子取代后得到的第二基团、或者该第一基团中的某个H原子被F或Cl原子取代后得到的第三基团；
所述第二添加剂材料指的是结构通式为C-R’的一类化合物，其中，
C指的是有机极性基团，所述有机极性基团为伯胺基、仲胺基、叔胺基、-OH、-COOH、-SH、或-CN；
R’指的是具有5～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第四基团、该烷基中的某个H原子被F或Cl原子取代 后得到的第五基团、或者该第四基团中的某个H原子被F或Cl原子取代后得到的第六基团。
所述第一添加剂材料的结构式为：
Figure PCTCN2016074625-appb-000001
所述第二添加剂材料的结构式为：
Figure PCTCN2016074625-appb-000002
所述两种或两种以上的添加剂材料中，至少一种选自第一添加剂材料，至少一种选自第二添加剂材料。
所述两种或两种以上的添加剂材料均选自第二添加剂材料。
所述两种或两种以上的添加剂材料在自取向液晶介质组合物中的总含量为0.1～5wt％。
包括两种添加剂材料，第一种添加剂材料选自第一添加剂材料，第二种添加剂材料选自第二添加剂材料，所述第一种添加剂材料和第二种添加剂材料的摩尔比为1：99，且所述第一种添加剂材料和第二种添加剂材料在自取向液晶介质组合物中的总含量为3wt％。
所述液晶材料为负型液晶材料。
本发明还提供一种液晶显示面板，包括相对设置的TFT基板和CF基板、及位于所述TFT基板和CF基板之间的液晶层；
所述液晶层的材料为如上所述的自取向液晶介质组合物；
所述TFT基板和CF基板相对一侧的表面上分别设有第一导电膜和第二导电膜；
在分子间作用力下，所述自取向液晶介质组合物中的两种或两种以上的添加剂材料在所述TFT基板和CF基板相对一侧的表面上垂直排列，引导液晶分子垂直排列，从而起到液晶配向的作用。
所述第一导电膜和第二导电膜的材料均为ITO。
本发明还提供一种自取向液晶介质组合物，包括液晶材料、混合于所述液晶材料中的两种或两种以上的添加剂材料；
所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；
所述第一添加剂材料指的是结构通式为A-R的一类化合物，其中，
A指的是指含有无机硅的基团，所述含有无机硅的基团为-Si(CH3)3、-Si(OCH3)3、-SiCl3、或低聚体半硅氧烷；
R指的是具有3～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第一基团、该烷基中的某个H原子被F或Cl原子取代后得到的第二基团、或者该第一基团中的某个H原子被F或Cl原子取代后得到的第三基团；
所述第二添加剂材料指的是结构通式为C-R’的一类化合物，其中，
C指的是有机极性基团，所述有机极性基团为伯胺基、仲胺基、叔胺基、-OH、-COOH、-SH、或-CN；
R’指的是具有5～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第四基团、该烷基中的某个H原子被F或Cl原子取代后得到的第五基团、或者该第四基团中的某个H原子被F或Cl原子取代后得到的第六基团；
其中，所述第一添加剂材料的结构式为：
Figure PCTCN2016074625-appb-000003
其中，所述第二添加剂材料的结构式为：
Figure PCTCN2016074625-appb-000004
Figure PCTCN2016074625-appb-000005
其中，所述液晶材料为负型液晶材料。
本发明的有益效果：本发明提供一种自取向液晶介质组合物及液晶显示面板；本发明的自取向液晶介质组合物，包括两种或两种以上的添加剂材料，所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；所述第一添加剂材料和第二添加剂材料的分子结构均由头基和尾基两部分所组成，所述第一添加剂材料和第二添加剂材料的头基部分的主要作用是通过分子间作用力而锚定在基板上，而尾基部分的主要作用是类似于PI支链的作用以立体障碍的方式使液晶分子垂直排列，其中，所述第一添加剂材料的头基部分为含有无机硅的基团，所述第二添加剂材料的头基部分为有机极性基团；通过不同添加剂材料之间的搭配性，可改善含无机硅基团的添加剂材料容易聚集的特性，提升含有机极性基团的添加剂材料锚定基板的作用，从而提高自取向液晶材料组合物的品质，使添加剂材料达到最佳的取向效果，进而省去PI配向膜制程，节约生产成本，减低能耗和污染；本发明的液晶显示面板，液晶层的材料为自取向液晶介质组合物，其中包括两种或两种以上的添加剂材料，通过不同添加剂材料之间的搭配性，提高自取向液晶材料组合物的品质，使添加剂材料达到最佳的取向效果，从而不包含PI配向膜，节约生产成本。
附图说明
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图中，
图1为本发明的自取向液晶介质组合物中第一添加剂材料的结构示意图；
图2为本发明的自取向液晶介质组合物中第二添加剂材料的结构示意图；
图3为本发明的液晶显示面板一优选实施例的结构示意图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
本发明首先提供一种自取向液晶介质组合物，包括液晶材料53、混合于所述液晶材料53中的两种或两种以上的添加剂材料；
所述两种或两种以上的添加剂材料选自第一添加剂材料51和第二添加剂材料52；
所述第一添加剂材料51指的是结构通式为A-R的一类化合物，其中，
A指的是指含有无机硅的基团，所述含有无机硅的基团为-Si(CH3)3、-Si(OCH3)3、-SiCl3、或低聚体半硅氧烷；
R指的是具有3～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第一基团、该烷基中的某个H原子被F或Cl原子取代后得到的第二基团、或者该第一基团中的某个H原子被F或Cl原子取代后得到的第三基团；
具体的，如图1所示，所述第一添加剂材料51的结构通式中，头基A为含有无机硅的基团，其主要作用是使第一添加剂材料51与基板之间产生较强的分子作用力而锚定在基板上；而尾基R的主要作用是类似于PI支链的作用以立体障碍的方式使液晶分子垂直排列。
具体的，所述第一添加剂材料51的结构式为：
Figure PCTCN2016074625-appb-000006
所述第二添加剂材料52指的是结构通式为C-R’的一类化合物，其中，
C指的是有机极性基团，所述有机极性基团为伯胺基、仲胺基、叔胺基、-OH、-COOH、-SH、或-CN；
R’指的是具有5～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第四基团、该烷基中的某个H原子被F或Cl原子取代后得到的第五基团、或者该第四基团中的某个H原子被F或Cl原子取代后得到的第六基团；
具体的，如图2所示，所述第二添加剂材料52的结构通式中，头基C为有机极性基团，其主要作用是使第二添加剂材料52与基板之间产生较强的分子作用力而锚定在基板上；而尾基R’的主要作用是类似于PI支链的作用以立体障碍的方式使液晶分子垂直排列。
具体的，所述第二添加剂材料52的结构式为：
Figure PCTCN2016074625-appb-000007
可选的，所述两种或两种以上的添加剂材料中，至少一种选自第一添加剂材料51，至少一种选自第二添加剂材料52。
可选的，所述两种或两种以上的添加剂材料均选自第二添加剂材料52。
具体的，所述两种或两种以上的添加剂材料在自取向液晶介质组合物中的总含量为0.1～5wt％。
优选的，所述自取向液晶介质组合物包括两种添加剂材料，第一种添加剂材料选自第一添加剂材料51，第二种添加剂材料选自第二添加剂材料52，所述第一种添加剂材料和第二种添加剂材料的摩尔比为1：99，且所述第一种添加剂材料和第二种添加剂材料在自取向液晶介质组合物中的总含量为3wt％。
具体的，所述液晶材料53为负型液晶材料。
请参阅图3，本发明还提供一种液晶显示面板，包括相对设置的TFT基板10和CF基板20、及位于所述TFT基板10和CF基板20之间的液晶层30；
所述液晶层30的材料为如上所述的自取向液晶介质组合物；
所述TFT基板10和CF基板20相对一侧的表面上分别设有第一导电膜11和第二导电膜21；
在分子间作用力下，所述自取向液晶介质组合物中的两种或两种以上的添加剂材料在所述TFT基板10和CF基板20相对一侧的表面上垂直排列，引导液晶分子垂直排列，从而起到液晶配向的作用。
具体的，所述第一导电膜11和第二导电膜21的材料为氧化铟锡(ITO)。
优选的，所述自取向液晶介质组合物包括两种添加剂材料，第一种添加剂材料选自第一添加剂材料51，其结构式为：
Figure PCTCN2016074625-appb-000008
第二种添加剂材料选自第二添加剂材料52，其结构式为：
Figure PCTCN2016074625-appb-000009
优选的，所述第一种添加剂材料和第二种添加剂材料的摩尔比为1：99，且所述第一种添加剂材料和第二种添加剂材料在自取向液晶介质组合物中的总含量为3wt％。
综上所述，本发明的自取向液晶介质组合物，包括两种或两种以上的添加剂材料，所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；所述第一添加剂材料和第二添加剂材料的分子结构均由头基和尾基两部分所组成，所述第一添加剂材料和第二添加剂材料的头基部分的主要作用是通过分子间作用力而锚定在基板上，而尾基部分的主要作用是类似于PI支链的作用以立体障碍的方式使液晶分子垂直排列，其中，所述第一添加剂材料的头基部分为含有无机硅的基团，所述第二添加剂材料的头基部分为有机极性基团；通过不同添加剂材料之间的搭配性，可改善含无机硅基团的添加剂材料容易聚集的特性，提升含有机极性基团的添加剂材料锚定基板的作用，从而提高自取向液晶材料组合物的品质，使添加剂材料达到最佳的取向效果，进而省去PI配向膜制程，节约生产成本，减低能耗和污染；本发明的液晶显示面板，液晶层的材料为自取向液晶介质组合物，其中包括两种或两种以上的添加剂材料，通过不同添加剂材料之间的搭配性，提高自取向液晶材料组合物的品质，使添加剂材料达到最佳的取向效果，从而不包含PI配向膜，节约生产成本。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术 方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (15)

  1. 一种自取向液晶介质组合物，包括液晶材料、混合于所述液晶材料中的两种或两种以上的添加剂材料；
    所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；
    所述第一添加剂材料指的是结构通式为A-R的一类化合物，其中，
    A指的是指含有无机硅的基团，所述含有无机硅的基团为-Si(CH3)3、-Si(OCH3)3、-SiCl3、或低聚体半硅氧烷；
    R指的是具有3～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第一基团、该烷基中的某个H原子被F或Cl原子取代后得到的第二基团、或者该第一基团中的某个H原子被F或Cl原子取代后得到的第三基团；
    所述第二添加剂材料指的是结构通式为C-R’的一类化合物，其中，
    C指的是有机极性基团，所述有机极性基团为伯胺基、仲胺基、叔胺基、-OH、-COOH、-SH、或-CN；
    R’指的是具有5～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第四基团、该烷基中的某个H原子被F或Cl原子取代后得到的第五基团、或者该第四基团中的某个H原子被F或Cl原子取代后得到的第六基团。
  2. 如权利要求1所述的自取向液晶介质组合物，其中，所述第一添加剂材料的结构式为：
    Figure PCTCN2016074625-appb-100001
    Figure PCTCN2016074625-appb-100002
  3. 如权利要求1所述的自取向液晶介质组合物，其中，所述第二添加剂材料的结构式为：
    Figure PCTCN2016074625-appb-100003
  4. 如权利要求1所述的自取向液晶介质组合物，其中，所述两种或两种以上的添加剂材料中，至少一种选自第一添加剂材料，至少一种选自第二添加剂材料。
  5. 如权利要求1所述的自取向液晶介质组合物，其中，所述两种或两种以上的添加剂材料均选自第二添加剂材料。
  6. 如权利要求1所述的自取向液晶介质组合物，其中，所述两种或两种以上的添加剂材料在自取向液晶介质组合物中的总含量为0.1～5wt％。
  7. 如权利要求6所述的自取向液晶介质组合物，其中，包括两种添加 剂材料，第一种添加剂材料选自第一添加剂材料，第二种添加剂材料选自第二添加剂材料，所述第一种添加剂材料和第二种添加剂材料的摩尔比为1：99，且所述第一种添加剂材料和第二种添加剂材料在自取向液晶介质组合物中的总含量为3wt％。
  8. 如权利要求1所述的自取向液晶介质组合物，其中，所述液晶材料为负型液晶材料。
  9. 一种液晶显示面板，包括相对设置的TFT基板和CF基板、及位于所述TFT基板和CF基板之间的液晶层；
    所述液晶层的材料为自取向液晶介质组合物；所述自取向液晶介质组合物包括液晶材料、混合于所述液晶材料中的两种或两种以上的添加剂材料；
    所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；
    所述第一添加剂材料指的是结构通式为A-R的一类化合物，其中，
    A指的是指含有无机硅的基团，所述含有无机硅的基团为-Si(CH3)3、-Si(OCH3)3、-SiCl3、或低聚体半硅氧烷；
    R指的是具有3～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第一基团、该烷基中的某个H原子被F或Cl原子取代后得到的第二基团、或者该第一基团中的某个H原子被F或Cl原子取代后得到的第三基团；
    所述第二添加剂材料指的是结构通式为C-R’的一类化合物，其中，
    C指的是有机极性基团，所述有机极性基团为伯胺基、仲胺基、叔胺基、-OH、-COOH、-SH、或-CN；
    R’指的是具有5～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第四基团、该烷基中的某个H原子被F或Cl原子取代后得到的第五基团、或者该第四基团中的某个H原子被F或Cl原子取代后得到的第六基团；
    所述TFT基板和CF基板相对一侧的表面上分别设有第一导电膜和第二导电膜；
    在分子间作用力下，所述自取向液晶介质组合物中的两种或两种以上的添加剂材料在所述TFT基板和CF基板相对一侧的表面上垂直排列，引导液晶分子垂直排列，从而起到液晶配向的作用。
  10. 如权利要求9所述的液晶显示面板，其中，所述第一导电膜和第二导电膜的材料均为ITO。
  11. 一种自取向液晶介质组合物，包括液晶材料、混合于所述液晶材料中的两种或两种以上的添加剂材料；
    所述两种或两种以上的添加剂材料选自第一添加剂材料和第二添加剂材料；
    所述第一添加剂材料指的是结构通式为A-R的一类化合物，其中，
    A指的是指含有无机硅的基团，所述含有无机硅的基团为-Si(CH3)3、-Si(OCH3)3、-SiCl3、或低聚体半硅氧烷；
    R指的是具有3～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第一基团、该烷基中的某个H原子被F或Cl原子取代后得到的第二基团、或者该第一基团中的某个H原子被F或Cl原子取代后得到的第三基团；
    所述第二添加剂材料指的是结构通式为C-R’的一类化合物，其中，
    C指的是有机极性基团，所述有机极性基团为伯胺基、仲胺基、叔胺基、-OH、-COOH、-SH、或-CN；
    R’指的是具有5～20个C原子的直链或支链化的烷基、该烷基中的某个CH2基团被苯基、环烷基、-O-、-CONH-、-COO-、-O-CO-、-CO-或-CH＝CH-基团所取代后得到的第四基团、该烷基中的某个H原子被F或Cl原子取代后得到的第五基团、或者该第四基团中的某个H原子被F或Cl原子取代后得到的第六基团；
    其中，所述第一添加剂材料的结构式为：
    Figure PCTCN2016074625-appb-100004
    Figure PCTCN2016074625-appb-100005
    其中，所述第二添加剂材料的结构式为：
    Figure PCTCN2016074625-appb-100006
    其中，所述液晶材料为负型液晶材料。
  12. 如权利要求11所述的自取向液晶介质组合物，其中，所述两种或两种以上的添加剂材料中，至少一种选自第一添加剂材料，至少一种选自第二添加剂材料。
  13. 如权利要求11所述的自取向液晶介质组合物，其中，所述两种或两种以上的添加剂材料均选自第二添加剂材料。
  14. 如权利要求11所述的自取向液晶介质组合物，其中，所述两种或两种以上的添加剂材料在自取向液晶介质组合物中的总含量为0.1～5wt％。
  15. 如权利要求14所述的自取向液晶介质组合物，其中，包括两种添 加剂材料，第一种添加剂材料选自第一添加剂材料，第二种添加剂材料选自第二添加剂材料，所述第一种添加剂材料和第二种添加剂材料的摩尔比为1：99，且所述第一种添加剂材料和第二种添加剂材料在自取向液晶介质组合物中的总含量为3wt％。
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