WO2018120333A1 - 一种反式pdlc液晶材料组合物、基板及显示器 - Google Patents

一种反式pdlc液晶材料组合物、基板及显示器 Download PDF

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WO2018120333A1
WO2018120333A1 PCT/CN2017/071348 CN2017071348W WO2018120333A1 WO 2018120333 A1 WO2018120333 A1 WO 2018120333A1 CN 2017071348 W CN2017071348 W CN 2017071348W WO 2018120333 A1 WO2018120333 A1 WO 2018120333A1
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liquid crystal
group
crystal material
material composition
vertical alignment
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French (fr)
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兰松
陈孝贤
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TCL China Star Optoelectronics Technology Co Ltd
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Shenzhen China Star Optoelectronics Technology Co Ltd
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    • C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
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    • G02—OPTICS
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    • 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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
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    • G02—OPTICS
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    • 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
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    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
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    • 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-)
    • C09K2019/122—Ph-Ph
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    • 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
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    • 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
    • C09K2019/128—Compounds containing phenylene-1,2-diyl
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    • 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
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    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
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    • 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
    • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment

Definitions

  • the invention relates to a trans-PDLC liquid crystal material composition, and to a trans-PDLC substrate material, and a trans-PDLC display prepared thereby, belonging to the field of liquid crystal displays.
  • Polymer Dispersed Liquid Crystal is a method in which a low molecular liquid crystal is mixed with a prepolymer and polymerized under certain conditions to form micron-sized liquid crystal droplets uniformly dispersed in a polymer network and reused.
  • the dielectric anisotropy of liquid crystal molecules results in a material having electro-optical response characteristics, which mainly works between a scattering state and a transparent state and has a certain gray scale.
  • the polymer dispersed liquid crystal film (PDLC film) is a film material excellent in combination of a liquid crystal and a polymer.
  • the liquid crystal molecules impart significant electro-optical properties to the polymer-dispersed liquid crystal film, which has attracted extensive attention and has broad application prospects.
  • the polymer dispersed liquid crystal display has many advantages, such as no need for a polarizing plate and an alignment layer, a simple preparation process, and easy to manufacture a large-area flexible display, etc., which is currently in an optical modulator, thermal and Pressure sensitive devices, electronically controlled glass, light valves, projection displays, e-books, etc. are widely used.
  • the optical axis orientation of the liquid crystal particles is randomly disordered, and the effective refractive index no does not match the refractive index np of the polymer, and the light cannot pass; when an applied voltage is applied When the liquid crystals are vertically aligned, the effective refractive index matches the refractive index np of the polymer, and the light can pass (as shown in FIG. 1).
  • the factors influencing the PDLC display effect are the thickness of the film, the mixing ratio of the liquid crystal to the polymer, the time of phase separation, the temperature and the frequency of the driving voltage, and the like.
  • Such a PDLC display generally has a problem of high driving voltage, low transmittance, insufficient haze in an off state, and poor contrast.
  • the present application provides a trans-PDLC liquid crystal material composition and a substrate material and a display prepared thereby, by adding a vertical alignment agent to the trans-PDLC liquid crystal material composition.
  • the surface energy of the liquid crystal molecules in the polymer matrix is lowered, and the contact angle is increased, so that the liquid crystal molecules are vertically aligned.
  • This liquid crystal material composition was applied onto a substrate to prepare a trans PDLC substrate material.
  • the trans-PDLC display prepared by using the substrate material has vertical alignment of the liquid crystal molecules in the absence of an applied electric field, and the effective refractive index no matches the refractive index np of the polymer, and the light can pass; when the voltage is applied, the optical axis of the liquid crystal particles The orientation randomly appears disordered, and its effective refractive index no does not match the refractive index np of the polymer, and the light does not pass.
  • a trans-PDLC liquid crystal material composition comprising: a vertical alignment agent, a liquid crystal material, and an acrylic monomer; wherein the vertical alignment agent molecule contains a polar group and a non-polar group group.
  • the polar group of the vertical alignment agent and the polar group in the acrylic monomer are attracted to each other by forming an intermolecular force (for example, a hydrogen bond), and the non-polar group therein is extended into the liquid crystal to cause steric hindrance
  • the method achieves the purpose of aligning liquid crystal molecules vertically.
  • the vertical alignment agent in the liquid crystal material composition has a mass percentage of 0.01% to 5%, preferably 0.5 to 3%; and the liquid crystal material has a mass percentage of 78% to 90%. %, preferably 80-85%; the mass percentage of the acrylic monomer is 8%-20%, preferably 10%-18%.
  • the vertical alignment agent has the structural formula: QAR (I), wherein Q is a polar group selected from the group consisting of an amine group, -OH, -COOH, -SH , -CN, -Si(CH 3 ) 3 , -Si(OCH 3 ) 3 or -SiCl 3 , wherein the amine group comprises one or more of a primary amino group, a secondary amino group or a tertiary amino group;
  • A is a linking group, including a flexible linking group and/or a rigid linking group
  • the flexible linking group has the formula: -(CH 2 ) m -(II), and in the formula (II), 1 ⁇ m ⁇ 8, in some specific embodiments,
  • One or more -CH 2 - groups may be optionally -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -OCH 2 - or -CH 2 O-group substitution.
  • the structural formula of the rigid linking group is
  • A is one or more of a five-membered ring, a six-membered ring, a benzene ring or an aromatic fused ring, and 1 ⁇ n ⁇ 6, wherein one or more hydrogen atoms on the ring A are optionally It is substituted by a halogen atom, a hydrocarbon group, an alkoxy group or an ester group.
  • a particular vertical alignment agent suitable for use in the present invention may be one or more of the compounds of formula (IV)-formula (VIII):
  • the liquid crystal material is a negative liquid crystal material; and the negative liquid crystal material is not particularly limited, and a negative liquid crystal material known in the art may be selected.
  • the negative liquid crystal material suitable for use in the present invention may be a compound of formula IX, formula X or formula XI:
  • the acrylic monomer suitable for use in the present invention may be a compound as shown in formula (i), formula (ii) or formula (iii):
  • a trans PDLC substrate material comprising a substrate material obtained by coating the above liquid crystal material on a substrate and having been processed.
  • the treatment is not particularly limited and is a conventional treatment method in the art.
  • a trans PDLC display which is prepared by the following method:
  • the substrate material is butted to another substrate of the coated or uncoated liquid crystal material composition, and after sealing treatment, a liquid crystal cell is obtained;
  • the liquid crystal cell is subjected to ultraviolet irradiation treatment to obtain.
  • the trans PDLC display can be prepared as follows:
  • the substrate material may be bonded to another substrate material in the step (3), wherein the substrate material is coated with the liquid crystal material composition opposite to one side;
  • the substrate material is bonded to another substrate, and a side of the substrate material coated with the liquid crystal material composition is opposite to the substrate.
  • the curing method in the step (3) is not particularly limited, and for example, a method of curing by heat curing or ultraviolet irradiation may be employed.
  • the temperature can be 100 to 140 ° C, the time is 30 min to 90 min; the ultraviolet irradiation wavelength can be 365 nm, the illuminance can be 60 to 110 mW/cm 2 , and the time can be 20 to 50 s.
  • the ultraviolet irradiation treatment in the step (4) is not particularly limited.
  • the wavelength of the ultraviolet light can be selected from 320 to 400 nm, the illuminance is 60 to 100 mW/cm 2 , and the irradiation time is 5 to 30 min; preferably, the wavelength of the ultraviolet light is 365 nm, the illuminance is, and the irradiation time is 15 min.
  • the vertical alignment agent since the vertical alignment agent is added, it can lower the surface energy of the liquid crystal molecules in the polymer matrix, increase the contact angle, and cause the liquid crystal molecules to be vertically aligned.
  • the trans-PDLC display thus prepared has liquid crystal molecules aligned vertically when no external electric field is applied, and the effective refractive index no matches the refractive index np of the polymer, and the light can pass; when the voltage is applied, the optical axis of the liquid crystal particles is randomly oriented. Presenting a disordered state, the effective refractive index no does not match the refractive index np of the polymer, and light does not pass.
  • the trans PDLC display of the invention has low driving voltage and high contrast.
  • Figure 1 is a schematic diagram of light passage of a PDLC display without an applied voltage
  • FIG. 2 is a schematic diagram of light passage of a PDLC display when an applied voltage is applied
  • 1 is a schematic diagram of light passage of a trans PDLC display without an applied voltage
  • FIG. 2 is a schematic diagram of light passage of a trans-PDLC display with an applied voltage.
  • the vertical alignment agent is OH-CH 2 CH 2 O-OCH 2 CH 2 O-OCH 2 CH 2 OC 12 H 15
  • the negative liquid crystal material is a compound represented by formula IX
  • the acrylic monomer is represented by formula i
  • the liquid crystal cell was subjected to ultraviolet irradiation treatment, and the wavelength of the ultraviolet light was 365 nm, the illuminance was 85 mW/cm 2 , and the irradiation time was 15 min, that is, a trans PDLC display was obtained.
  • the vertical alignment agent is a compound represented by Formula V
  • the negative liquid crystal material is a compound represented by Formula X
  • the acrylic monomer is a compound represented by Formula ii;
  • the CF substrate and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell;
  • the liquid crystal cell was subjected to ultraviolet irradiation treatment, and the wavelength of the ultraviolet light was 330 nm, the illuminance was 70 mW/cm 2 , and the irradiation time was 20 min, that is, a trans PDLC display was obtained.
  • the vertical alignment agent is a compound represented by Formula VI
  • the negative liquid crystal material is a compound represented by Formula XI
  • the acrylic monomer is a compound represented by Formula iii;
  • the CF substrate material and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell;
  • the liquid crystal cell was subjected to ultraviolet irradiation treatment, and the wavelength of the ultraviolet light was 320 nm, the illuminance was 80 mW/cm 2 , and the irradiation time was 30 min, that is, a trans PDLC display was obtained.
  • the vertical alignment agent is a compound represented by formula VII
  • the negative liquid crystal material is a compound represented by formula XI
  • the acrylic monomer is a compound represented by formula iii;
  • the CF substrate material and the TFT substrate material are bonded together, sealed with a sealant, and the sealant is cured by ultraviolet irradiation to obtain a liquid crystal cell;
  • the liquid crystal cell was subjected to ultraviolet irradiation treatment, and the wavelength of the ultraviolet light was selected to be 380 nm, the illuminance was 100 mW/cm 2 , and the irradiation time was 25 min, thereby obtaining a trans PDLC display.
  • the vertical alignment agent is a compound represented by formula VIII
  • the negative liquid crystal material is a mixture of compounds represented by formula X and formula XI
  • the acrylic monomer is a compound represented by formula ii;
  • the liquid crystal cell was subjected to ultraviolet irradiation treatment, and the wavelength of the ultraviolet light was selected to be 400 nm, the illuminance was 90 mW/cm 2 , and the irradiation time was 5 min, thereby obtaining a trans PDLC display.
  • the trans-PDLC display prepared in the embodiment of the present invention has a contrast ratio of 13-14 and a transmittance of 89%-92%.
  • the contrast of the conventional PDLC display is 5-6, and the transmittance is 75%. It can be seen that the trans PDLC of the present invention can significantly improve contrast and transmittance.
  • Any numerical value mentioned in the present invention includes all values of one unit at a time from the lowest value to the highest value if there is only two unit intervals between any lowest value and any highest value. For example, if the amount of a component is declared, or the value of a process variable such as temperature, pressure, time, etc. is 50-90, it means in this specification that 51-89, 52-88, ..., and 69 are specifically listed. -71 and 70-71 values. For values other than integers, it is appropriate to consider 0.1, 0.01, 0.001 or 0.0001 as a unit. This is just a few specific examples. In the present application, all possible combinations of numerical values between the lowest and highest values recited are considered to have been disclosed.

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Abstract

公开了一种反式PDLC液晶材料组合物，包括垂直取向剂，液晶材料和丙烯酸单体；其中所述垂直取向剂分子中含有极性基团和非极性基团。所述垂直取向剂可降低液晶分子在聚合物基体中的表面能，增加接触角，使得液晶分子垂直排列。

Description

一种反式PDLC液晶材料组合物、基板及显示器
本申请要求享有2016年12月30日提交的名称为“一种反式PDLC液晶材料组合物、基板及显示器”的中国专利申请CN201611252491.4的优先权，其全部内容通过引用并入本文中。
技术领域
本发明涉及一种反式PDLC液晶材料组合物，还涉及一种反式PDLC基板材料，以及由此制备的反式PDLC显示器，属于液晶显示器领域。
背景技术
聚合物分散液晶(Polymer Dispersed Liquid Crystal,PDLC)，是将低分子液晶与预聚物混合，在一定条件下经聚合反应，形成微米级的液晶微滴均匀地分散在高分子网络中，再利用液晶分子的介电各向异性获得具有电光响应特性的材料，它主要工作在散射态和透明态之间并具有一定的灰度。聚合物分散液晶膜(PDLC膜)是将液晶和聚合物结合得到的一种综合性能优异的膜材料。液晶分子赋予了聚合物分散液晶膜显著的电光特性，使其受到了广泛的关注，并有着广阔的应用前景。
相对于传统显示器件来说，聚合物分散型液晶显示器具有很多优点，例如不需偏振片和取向层，制备工艺简单，易于制成大面积柔性显示器等,目前已在光学调制器、热敏及压敏器件、电控玻璃、光阀、投影显示、电子书等方面获得广泛应用。
在无外加电压情形下，PDLC膜间不能形成有规律电场，液晶微粒的光轴取向随机呈现无序状态，其有效折射率no不与聚合物折射率np匹配，光不可通过；当施加外加电压时，液晶垂直排列，其有效折射率与聚合物折射率np相匹配，光可通过(如图1所示)。这种PDLC显示效果的影响因素有膜的薄厚、液晶与聚合物的混合比、相分离的时间、温度与驱动电压的频率等。
但是这种PDLC显示器，通常存在驱动电压高、透过率低、关态时雾度不够的、对比度差的问题。
发明内容
为了解决现有PDLC显示器存在的技术问题，本申请提供一种反式PDLC液晶材料组合物及由此制备的基板材料和显示器，所述反式PDLC液晶材料组合物中通过加入了垂直取向剂来降低液晶分子在聚合物基体中的表面能，增加接触角，使得液晶分子垂直排列。将此液晶材料组合物涂布到基板上，制得反式PDLC基板材料。以此基板材料制备的反式PDLC显示器在在无外加电场时，液晶分子垂直排列，其有效折射率no与聚合物折射率np相匹配，光可通过；当施加电压时，液晶微粒的光轴取向随机呈现无序状态，其有效折射率no不与聚合物折射率np匹配，光不可通过。
根据本本发明的一个方面，提供了一种反式PDLC液晶材料组合物，包括：垂直取向剂、液晶材料和丙烯酸单体；其中所述垂直取向剂分子中含有极性基团和非极性基团。
垂直取向剂的极性基团与丙烯酸单体中的极性基团通过形成分子间作用力而相互吸引(例如氢键)，而其中的非极性基团伸展到液晶中，以立体障碍的方式达到使液晶分子垂直排列的目的。
根据本发明的一个优选实施例，所述液晶材料组合物中垂直取向剂的质量百分含量为0.01％-5％，优选为0.5-3％；液晶材料的质量百分含量为78％-90％，优选为80-85％；丙烯酸单体的质量百分含量为8％-20％，优选为10％-18％。
根据本发明的一个优选实施方式，所述垂直取向剂的结构通式为：Q-A-R(Ⅰ)，式(Ⅰ)中Q为极性基团，选自胺基、-OH、-COOH、-SH、-CN、-Si(CH3)3、-Si(OCH3)3或-SiCl3，其中所述胺基包括伯胺基、仲胺基或叔胺基中的一种或多种；
A为连接基团，包括柔性连接基团和/或刚性连接基团；
R为非极性基团，选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可以任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
根据本发明的一个优选实施例，所述柔性连接基团的通式为：-(CH2)m-(Ⅱ)，式(Ⅱ)中1≤m≤8，在一些具体的实施例中，其中一个或多个-CH2-基团可以任选地被-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-OCH2-或-CH2O-基团取代。
根据本发明的一个优选实施例，所述刚性连接基团的结构通式为
Figure PCTCN2017071348-appb-000001
式(Ⅲ)中A为五元环、六元环、苯环或芳香稠环中的一种或多种，1≤n≤6，其中环A上的一个或多个氢原子可任选地被卤素原子、烃基、烷氧基或酯基取代。
在一些具体的实施例中，适用于本发明的具体的垂直取向剂可以为式(Ⅳ)-式(Ⅷ)所示化合物中的一种或多种：
HO-CH2CH2O-OCH2CH2O-OCH2CH2O-C12H15              (Ⅳ)
Figure PCTCN2017071348-appb-000002
根据本发明的一个优选实施方式，所述液晶材料为负性液晶材料；对于所述负性液晶材料没有特别的限定，选择本领域公知的负性液晶材料即可。
在一些具体的实施例中，适用于本发明的负性液晶材料可以为如式Ⅸ、式Ⅹ或式Ⅺ所示的化合物：
Figure PCTCN2017071348-appb-000003
根据本发明的一个优选实施例，适用于本发明的丙烯酸单体可以为如式(ⅰ)、式(ⅱ)或式(ⅲ)所示的化合物：
Figure PCTCN2017071348-appb-000004
Figure PCTCN2017071348-appb-000005
根据本发明的另外一个方面，提供了一种反式PDLC基板材料，包括将上述液晶材料涂布在基板上，经处理后，制得的基板材料。对于所述处理没有特别的限定，为本领域内常规的处理方法。
根据本发明的另外一个方面，提供了一种反式PDLC显示器，其通过如下方法制备而成：
将上述液晶材料组合物涂布到基板上，得到至少一个基板材料；
将所述基板材料与涂布或未涂布液晶材料组合物的另一个基板对接，经密封处理后得到液晶盒；
对所述液晶盒进行紫外照射处理，即得。
在一些具体的实施例中，所述反式PDLC显示器可按照如下方法制备而成：
(1)将上述负性液晶材料、丙烯酸单体和垂直取向剂混合均匀，得到反式PDLC液晶材料组合物；
(2)将上述反式PDLC液晶材料组合物涂布到基板上，得到至少一个基板材料；
(3)在真空环境下，将所述基板材料与涂布或未涂布液晶材料组合物的另一个基板贴合在一起，以密封胶密封，并对密封胶进行固化，得到液晶盒；
(4)对上述液晶盒进行紫外照射处理，即得到所述反式PDLC显示器。
根据本发明的一个优选实施方式，步骤(3)中可将所述基板材料与另一个基板材料贴合在一起，其中所述基板材料涂布有液晶材料组合物的一侧相对；也可以将所述基板材料与另一个基板贴合在一起，所述基板材料的涂布有液晶材料组合物的一侧与所述基板相对。
根据本发明反式PDLC显示器的制备方法，对于步骤(3)中的固化方式没有特别的限定，例如可采用热固化或紫外照射固化的方式。温度可以采用100～140℃，时间 30min～90min；紫外照射波长可以为365nm，照度可以为60～110mW/cm2，时间可以为20～50s。
根据本发明反式PDLC显示器的制备方法，对于步骤(4)中的紫外照射处理没有特别的限定，例如可选择紫外光的波长为320～400nm，照度为60～100mW/cm2，照射时间为5～30min；优选选择紫外光的波长为365nm，照度为，照射时间为15min。
本发明的反式PDLC液晶材料中由于添加了垂直取向剂，其可以降低液晶分子在聚合物基体中的表面能，增加接触角，使得液晶分子垂直排列。由此制备的反式PDLC显示器在在无外加电场时，液晶分子垂直排列，其有效折射率no与聚合物折射率np相匹配，光可通过；当施加电压时，液晶微粒的光轴取向随机呈现无序状态，其有效折射率no不与聚合物折射率np匹配，光不可通过。本发明反式PDLC显示器驱动电压低，对比度高。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例共同用于解释本发明，并不构成对本发明的限制。在附图中：
图1为PDLC显示器在无外加电压时的光通过情况示意图；
图2为PDLC显示器在有外加电压时的光通过情况示意图；
图1为反式PDLC显示器在无外加电压时的光通过情况示意图；
图2为反式PDLC显示器在有外加电压时的光通过情况示意图。
具体实施方式
以下结合具体的实施例对本发明的技术方案作一步的说明。
实施例1
(1)按照如下质量百分比备料制备反式PDLC液晶材料组合物：
垂直取向剂3％，负性液晶材料85％，丙烯酸单体12％；
其中，垂直取向剂为OH-CH2CH2O-OCH2CH2O-OCH2CH2O-C12H15，负性液晶材料为式Ⅸ所示的化合物，丙烯酸单体为式ⅰ所示的化合物；
(2)将反式PDLC液晶材料组合物涂布到CF基板上，得到CF基板材料；
(3)在真空环境下，将CF基板材料和TFT基板贴合在一起，以密封胶密封，通过加热对密封胶进行固化，得到液晶盒；
(4)对液晶盒进行紫外照射处理，选择紫外光的波长为365nm，照度为85mW/cm2，照射时间为15min，即得到反式PDLC显示器。
实施例2
(1)按照如下质量百分比备料制备反式PDLC液晶材料组合物：
垂直取向剂1％，负性液晶材料84％，丙烯酸单体15％；
其中，垂直取向剂为式Ⅴ所示的化合物，负性液晶材料为式Ⅹ所示的化合物，丙烯酸单体为式ⅱ所示的化合物；
(2)将反式PDLC液晶材料组合物涂布到TFT基板上，得到TFT基板材料；
(3)在真空环境下，将CF基板和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；
(4)对液晶盒进行紫外照射处理，选择紫外光的波长为330nm，照度为70mW/cm2，照射时间为20min，即得到反式PDLC显示器。
实施例3
(1)按照如下质量百分比备料制备反式PDLC液晶材料组合物：
垂直取向剂0.01％，负性液晶材料90％，丙烯酸单体9.99％；
其中，垂直取向剂为式Ⅵ所示的化合物，负性液晶材料为式Ⅺ所示的化合物，丙烯酸单体为式ⅲ所示的化合物；
(2)将反式PDLC液晶材料组合物涂布到CF基板和TFT基板上，得到CF基板材料和TFT基板材料；
(3)在真空环境下，将CF基板材料和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；
(4)对液晶盒进行紫外照射处理，选择紫外光的波长为320nm，照度为80mW/cm2，照射时间为30min，即得到反式PDLC显示器。
实施例4
(1)按照如下质量百分比备料制备反式PDLC液晶材料组合物：
垂直取向剂2％，负性液晶材料78％，丙烯酸单体20％；
其中，垂直取向剂为式Ⅶ所示的化合物，负性液晶材料为式Ⅺ所示的化合物，丙烯酸单体为式ⅲ所示的化合物；
(2)将反式PDLC液晶材料组合物涂布到CF基板和TFT基板上，得到CF基板材料和TFT基板材料；
(3)在真空环境下，将CF基板材料和TFT基板材料贴合在一起，以密封胶密封，通过紫外照射的方式对密封胶进行固化，得到液晶盒；
(4)对液晶盒进行紫外照射处理，选择紫外光的波长为380nm，照度为100mW/cm2，照射时间为25min，即得到反式PDLC显示器。
实施例5
(1)按照如下质量百分比备料制备反式PDLC液晶材料组合物：
垂直取向剂5％，负性液晶材料87％，丙烯酸单体8％；
其中，垂直取向剂为式Ⅷ所示的化合物，负性液晶材料为式Ⅹ和式Ⅺ所示的化合物的混合物，丙烯酸单体为式ⅱ所示的化合物；
(2)将反式PDLC液晶材料组合物涂布到CF基板上，得到CF基板材料；
(3)在真空环境下，将CF基板材料和TFT基板贴合在一起，以密封胶密封，通过加热的方式对密封胶进行固化，得到液晶盒；
(4)对液晶盒进行紫外照射处理，选择紫外光的波长为400nm，照度为90mW/cm2，照射时间为5min，即得到反式PDLC显示器。
经检测，本发明实施例中制备的反式PDLC显示器的对比度为13-14，穿透率为89％-92％；而传统PDLC显示器的对比度为5-6，穿透率为75％，由此可以看出，本发明反式PDLC可显著提升对比度和穿透率。
在本发明中的提到的任何数值，如果在任何最低值和任何最高值之间只是有两个单位的间隔，则包括从最低值到最高值的每次增加一个单位的所有值。例如，如果声明一种组分的量，或诸如温度、压力、时间等工艺变量的值为50-90，在本说明书中它的意思是具体列举了51-89、52-88……以及69-71以及70-71等数值。对于非整数的值，可以适当考虑以0.1、0.01、0.001或0.0001为一单位。这仅是一些特殊指明的例子。在本申请中，以相似方式，所列举的最低值和最高值之间的数值的所有可能组合都被认为已经公开。
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性 和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。
附图标记说明
1          基板
2          聚合物
3          正性液晶材料
4          透射光
5          负性液晶材料

Claims (18)

  1. 一种反式PDLC液晶材料组合物，包括：垂直取向剂、液晶材料和丙烯酸单体；其中所述垂直取向剂分子中含有极性基团和非极性基团。
  2. 根据权利要求1所述的液晶材料组合物，其中，所述液晶材料组合物中垂直取向剂的质量百分含量为0.01％-5％；液晶材料的质量百分含量为78％-90％；丙烯酸单体的质量百分含量为8％-20％。
  3. 根据权利要求1所述的液晶材料组合物，其中，所述垂直取向剂的结构通式为：Q-A-R(Ⅰ)；式中，Q为极性基团，选自胺基、-OH、-COOH、-SH、-CN、-Si(CH3)3、-Si(OCH3)3或-SiCl3；A为连接基团，包括柔性连接基团和/或刚性连接基团；R为非极性基团，选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
  4. 根据权利要求3所述的液晶材料组合物，其中，所述柔性连接基团的通式为-(CH2)m-(Ⅱ)；式中1≤m≤8，其中的一个或多个-CH2-基团可任选地被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-OCH2-或-CH2O-基团取代。
  5. 根据权利要求3所述的液晶材料组合物，其中，所述刚性连接基团的结构通式为：
    Figure PCTCN2017071348-appb-100001
    式中A为五元环、六元环、苯环或芳香稠环中的一种或多种，1≤n≤6，环A上的一个或多个氢原子可任选地被卤素原子、烃基、烷氧基或酯基取代。
  6. 根据权利要求3所述的液晶材料组合物，其中，所述垂直取向剂包括式(Ⅳ)-式(Ⅷ)所示化合物中的一种或多种：
    OH-CH2CH2O-OCH2CH2O-OCH2CH2O-C12H15         (Ⅳ)
    Figure PCTCN2017071348-appb-100002
  7. 根据权利要求1所述的液晶材料组合物，其中，所述丙烯酸单体选自如式(ⅰ)、式(ⅱ)或式(ⅲ)所示的化合物：
    Figure PCTCN2017071348-appb-100003
  8. 根据权利要求1所述液晶材料组合物，其中，所述液晶材料为负性液晶材料。
  9. 一种反式PDLC基板材料，包括将液晶材料组合物涂布在基板上，经处理后，制得的基板材料；其中，所述液晶材料组合物包括：垂直取向剂、液晶材料和丙烯酸单体；其中所述垂直取向剂分子中含有极性基团和非极性基团。
  10. 根据权利要求9所述的基板材料，其中，所述液晶材料组合物中垂直取向剂的质量百分含量为0.01％-5％；液晶材料的质量百分含量为78％-90％；丙烯酸单体的质量百分含量为8％-20％。
  11. 根据权利要求9所述的基板材料，其中，所述垂直取向剂的结构通式为：Q-A-R(Ⅰ)；式中，Q为极性基团，选自胺基、-OH、-COOH、-SH、-CN、-Si(CH3)3、-Si(OCH3)3或-SiCl3；A为连接基团，包括柔性连接基团和/或刚性连接基团；R为非极性基团，选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-基团取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
  12. 根据权利要求11所述的基板材料，其中，所述柔性连接基团的通式为-(CH2)m-(Ⅱ)；式中1≤m≤8，其中的一个或多个-CH2-基团可任选地被-O-、-S-、-CO-、-COO-、 -OCO-、-OCOO-、-OCH2-或-CH2O-基团取代。
  13. 根据权利要求11所述的基板材料，其中，所述刚性连接基团的结构通式为：
    Figure PCTCN2017071348-appb-100004
    式中A为五元环、六元环、苯环或芳香稠环中的一种或多种，1≤n≤6，环A上的一个或多个氢原子可任选地被卤素原子、烃基、烷氧基或酯基取代。
  14. 一种反式PDLC显示器，其通过如下方法制备而成：
    将液晶材料组合物涂布到基板上，得到至少一个基板材料；
    将所述基板材料与涂布或未涂布液晶材料组合物的另一个基板对接，经密封处理后得到液晶盒；
    对所述液晶盒进行紫外照射处理，即得；
    其中，所述液晶材料组合物包括：垂直取向剂、液晶材料和丙烯酸单体；其中所述垂直取向剂分子中含有极性基团和非极性基团。
  15. 根据权利要求14所述的显示器，其中，所述液晶材料组合物中垂直取向剂的质量百分含量为0.01％-5％；液晶材料的质量百分含量为78％-90％；丙烯酸单体的质量百分含量为8％-20％。
  16. 根据权利要求14所述的显示器，其中，所述垂直取向剂的结构通式为：Q-A-R(Ⅰ)；式中，Q为极性基团，选自胺基、-OH、-COOH、-SH、-CN、-Si(CH3)3、-Si(OCH3)3或-SiCl3；A为连接基团，包括柔性连接基团和/或刚性连接基团；R为非极性基团，选自取代或未取代的C3-20的直链或支链烷基，其中一个或多个-CH2-基团可任选地被-O-、-CONH-、-COO-、-OCO-、-CO-、或-CH＝CH-取代，其中一个或多个氢原子可任选地被氟原子或氯原子取代。
  17. 根据权利要求16所述的显示器，其中，所述柔性连接基团的通式为-(CH2)m-(Ⅱ)；式中1≤m≤8，其中的一个或多个-CH2-基团可任选地被-O-、-S-、-CO-、-COO-、-OCO-、-OCOO-、-OCH2-或-CH2O-基团取代。
  18. 根据权利要求16所述的显示器，其中，所述刚性连接基团的结构通式为：
    Figure PCTCN2017071348-appb-100005
    式中A为五元环、六元环、苯环或芳香稠环中的一种或多种，1≤n≤6，环A上的一个或多个氢原子可任选地被卤素原子、烃基、烷氧基或酯基取代。
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