WO2014043956A1 - 液晶介质混合物及使用其的液晶显示器 - Google Patents

液晶介质混合物及使用其的液晶显示器 Download PDF

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WO2014043956A1
WO2014043956A1 PCT/CN2012/082997 CN2012082997W WO2014043956A1 WO 2014043956 A1 WO2014043956 A1 WO 2014043956A1 CN 2012082997 W CN2012082997 W CN 2012082997W WO 2014043956 A1 WO2014043956 A1 WO 2014043956A1
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liquid crystal
medium mixture
polymerizable
carbon atoms
crystal medium
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PCT/CN2012/082997
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French (fr)
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冯惺
钟新辉
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深圳市华星光电技术有限公司
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Priority to US13/703,466 priority Critical patent/US20140085594A1/en
Publication of WO2014043956A1 publication Critical patent/WO2014043956A1/zh

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/062Non-steroidal liquid crystal compounds containing one non-condensed benzene ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098Unsaturated non-aromatic rings, e.g. cyclohexene rings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0444Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
    • C09K2019/0448Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the end chain group being a polymerizable end group, e.g. -Sp-P or acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/08Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/10Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
    • C09K19/12Non-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
    • C09K2019/121Compounds containing phenylene-1,4-diyl (-Ph-)
    • C09K2019/122Ph-Ph
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06Non-steroidal liquid crystal compounds
    • C09K19/34Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54Additives having no specific mesophase characterised by their chemical composition
    • C09K19/542Macromolecular compounds
    • C09K2019/548Macromolecular compounds stabilizing the alignment; Polymer stabilized alignment
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/13Devices 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
    • G02F1/137Devices 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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering
    • G02F1/13775Polymer-stabilized liquid crystal layers

Definitions

  • the present invention relates to liquid crystal display technology, and more particularly to a liquid crystal medium mixture and a liquid crystal display using the same. Background technique
  • the liquid crystal used for the TN (Twisted nematic) or STN (Super Twisted Nematic) liquid crystal display is a positive liquid crystal, and the long axis of the liquid crystal molecules is parallel to the surface of the substrate when the power is not applied.
  • the alignment direction of the liquid crystal molecules on the surface of the substrate is determined by the rubbing direction of the alignment layer (Polyimide).
  • the alignment direction of the two substrates is perpendicular, so the molecules of the liquid crystal layer from one substrate surface to the other substrate surface. It is in a continuous twisting state. When a voltage is applied, the long axes of the liquid crystal molecules will tend to align in the direction of the electric field.
  • the disadvantage of the TN/STN type liquid crystal display is that the viewing angle is small, the luminance difference and the chromatic aberration are large at a large viewing angle, and it is required to be improved by the compensation film, thereby improving the manufacturing cost of the display.
  • MVA Multi-domain vertical alignment
  • TFT-LCD 4 solves the problem of viewing angle limitation of TN/STN display. It uses negative liquid crystal and vertical alignment film materials. When no voltage is applied, the long axis of the liquid crystal molecules is perpendicular to the surface of the substrate, and application of a voltage causes the liquid crystal molecules to pour, and the long axes of the liquid crystal molecules tend to be aligned in the direction of the vertical electric field.
  • one sub-pixel is divided into a plurality of regions, so that the liquid crystal molecules are tilted in different directions, so that the effects seen by the display from different directions tend to be uniform. There are various methods for directing liquid crystal molecules of different regions into different directions within one sub-pixel.
  • the first is to make a Bump (bulge) on the upper and lower substrates of the LCD by exposure and development, so that the liquid crystal molecules around the Bump generate a certain pretilt angle, and the liquid crystal molecules are directed to tilt in a fixed direction; the second is on the upper and lower substrates.
  • a Bump bulge
  • this technique is called PVA (Patterned Vertical Alignment) technology; the third is forming ITO slit (crack) on the TFT side of the LCD substrate, the other side For Full ITO, a polymerizable monomer is added to the liquid crystal medium, and the liquid crystal molecules are first poured by an electric field, and the panel is irradiated with ultraviolet light to polymerize the monomer to form a polymer particle having a liquid crystal molecule to be poured, and deposited on the surface of the substrate. As a function of alignment, this technique becomes a PSVA (Polymer stabilized vertical alignment) technology.
  • PSVA Polymer stabilized vertical alignment
  • the reaction rate of the polymerizable monomer, the size and distribution of the polymer, the uniformity of the surface of the substrate, and the strength of the alignment force have important influences on the optical taste and mass production stability of the panel. These factors are affected by the process conditions. In addition, the main reason for determining these factors is the molecular structure of the polymerizable monomer, because the molecular structure of the polymerizable monomer directly determines the speed of its photoreaction, the characteristics of the polymer formed, the alignment force to the liquid crystal, and the like. Since the existing liquid crystal medium generally contains an alkenyl compound, which is advantageous for obtaining a low rotational viscosity, the response of the liquid crystal medium can be improved.
  • the existing liquid crystal medium generally contains an alkenyl compound, it is advantageous to obtain a low rotational viscosity.
  • Increasing the response of the liquid crystal medium, and the alkenyl compound contained in the liquid crystal medium easily affects the reaction polymerization of the polymerizable monomer, thereby affecting the alignment of the liquid crystal medium, so usually, usually, a single polymerizable monomer It is difficult to achieve these factors, and the situation is often due to the loss of uniformity of the polymer, but the formation of the polymer is not enough, or the alignment force is too strong, but the reaction speed is too slow and so on. Summary of the invention
  • the technical problem to be solved by the present invention is to provide a liquid crystal medium mixture which is reasonably matched by using two or more polymerizable monomers having different functionalities, a reaction speed of the polymerization reaction, uniformity of forming a polymer, and The strength of the alignment force can reach equilibrium at the same time, and both get higher levels.
  • liquid crystal display wherein the liquid crystal medium mixture is properly matched by two or more polymerizable monomers having different functionalities, the reaction speed of the polymerization of the monomer, the uniformity of forming the polymer, and the strength of the alignment force. It can achieve balance at the same time, and both get higher levels, which improves the optical taste and overall performance of the panel and achieves stable mass production.
  • embodiments of the present invention provide a liquid crystal medium mixture including components: a liquid crystal material and two polymerizable monomers which are polymerizable under ultraviolet light irradiation, and the liquid crystal material is included in the polymerizable single
  • the alkenyl compound which is stable to the polymerization during the bulk polymerization, and the polymerizable monomer accounts for 0.1% to 1% by weight of the total liquid crystal medium mixture;
  • the first polymerizable monomer is composed of a benzene ring directly bonded to at least two polymerizable groups selected from the group consisting of mercapto acrylates or acrylates, ethyl women's groups, and ethylene.
  • An oxy group or an epoxy group, and the at least two polymerizable groups are not all decyl acrylate groups at the same time; the molecular formula of the second polymerizable monomer is:
  • Pl, P2, and P3 represent a polymerizable group, and each independently represents a mercapto acrylate or acrylate, an ethyl group, a vinyloxy group, an epoxy group, and P1, P2, and P3 are not all thiol groups.
  • Acid ester
  • the hydrogen atom on any aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group such as -F, -Cl, -Br, fluorenyl or -CN.
  • first polymerizable monomer is specifically one of the following formulas:
  • the content ratio of the two polymerizable monomers in the liquid crystal medium mixture is 1:5.
  • R1 represents a straight or branched alkenyl group having 2 to 9 carbon atoms
  • R2 represents a straight or branched alkyl group having 1 to 12 carbon atoms
  • X independently represents 11, F, Cl, OCF 3 or CF 3 ;
  • n 1;
  • n and k represent 0 ⁇ 3 respectively.
  • an embodiment of the present invention provides a liquid crystal display, including: An upper substrate and a lower substrate, and a liquid crystal medium mixture disposed between the upper substrate and the lower substrate, the liquid crystal medium mixture comprising: a liquid crystal material and two polymerizable monomers which are polymerizable under ultraviolet light irradiation, The polymerizable monomer is calculated by weight of the total amount of the liquid crystal medium mixture
  • the first polymerizable monomer is composed of a benzene ring directly bonded to at least two polymerizable groups selected from the group consisting of mercapto acrylates or acrylates, ethyl women's groups, and ethylene.
  • An oxy group or an epoxy group, and the at least two polymerizable groups are not all decyl acrylate groups at the same time; the molecular formula of the second polymerizable monomer is:
  • Pl, P2, and P3 represent a polymerizable group, and each independently represents a mercapto acrylate or acrylate, an ethyl group, a vinyloxy group, an epoxy group, and P1, P2, and P3 are not all thiol groups.
  • Acid ester
  • the hydrogen atom on any aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group such as -F, -Cl, -Br, fluorenyl or -CN.
  • first polymerizable monomer is specifically one of the following formulas:
  • R1 represents a straight or branched alkenyl group having 2 to 9 carbon atoms
  • R2 represents a straight or branched alkyl group having 1 to 12 carbon atoms
  • X independently represents 11, F, Cl, OCF 3 or CF 3 ;
  • n 1;
  • n and k represent 0 ⁇ 3 respectively.
  • Embodiments of the present invention have the following beneficial effects:
  • the liquid crystal medium mixture of the present invention adopts two or more kinds of polymerizable monomers which can be polymerized under ultraviolet light irradiation and a reasonable ratio thereof, and can be polymerized to obtain polymer protrusions with small size and uniformity.
  • the phenomenon that the liquid crystal alignment is poor and the dark state of the liquid crystal panel is avoided is avoided, so that the response speed of the liquid crystal panel is increased and high contrast is obtained.
  • Applying it to a liquid crystal display improves the optical taste and overall performance of the liquid crystal display panel, and achieves stable mass production. detailed description
  • the present invention provides a liquid crystal medium mixture for a liquid crystal display, the liquid crystal medium mixture comprising the following components: a liquid crystal material and two polymerizable monomers which are polymerizable under irradiation of ultraviolet light; the polymerizable monomer 0.1% to 1% by weight of the total amount of the liquid crystal medium mixture; wherein the first polymerizable monomer is composed of a benzene ring, and the benzene ring is directly bonded to at least two polymerizable groups,
  • the polymerizable group is selected from the group consisting of methacrylate or acrylate, ethoxylate, vinyloxy or epoxy, and the at least two polymerizable groups are not all decyl acrylate groups at the same time;
  • the second polymerizable monomer is directly connected by two benzene rings, one of which is connected to the ring
  • the structural formula of the first polymerizable monomer is one of the following:
  • Pl, P2, and P3 represent a polymerizable group, and each independently represents a mercapto acrylate or acrylate, an ethyl ethoxy group, a vinyloxy group, an epoxy group, and P1, P2, and P3 are not all thioglycol at the same time. ester.
  • the hydrogen atom on any aromatic ring in the structural formula of the polymerizable monomer may be substituted with a group: -F, -Cl, -Br, fluorenyl or -CN.
  • the first polymerizable monomer is specifically one of the following formulas:
  • the molar ratio of the two polymerizable monomers in the liquid crystal medium mixture is 1:5.
  • the gynecyl compound has the following structural formula:
  • R1 represents a straight or branched alkenyl group having 2 to 9 carbon atoms
  • R2 represents a straight or branched alkyl group having 1 to 12 carbon atoms
  • X independently represents 11, F, Cl, OCF 3 or CF 3 ;
  • n 1;
  • n and k represent 0 ⁇ 3 respectively.
  • Example 1 The embodiments of the present invention will be described below by way of specific embodiments. Example 1
  • the liquid crystal medium mixture uses a negative liquid crystal material and two polymerizable monomers, as follows:
  • RM-B1 The structural formula of RM-B1 is as follows:
  • the molar ratio of RM-A1 to RM-B1 is 1:5, and the total content of both accounts for 10,000 ppm of the liquid crystal dielectric layer.
  • RM-A1 and RM-B1 are mixed, and the polymer generated by ultraviolet irradiation is small in size and uniform, and there is no dark state of light.
  • the liquid crystal medium mixture uses a negative liquid crystal material and two polymerizable monomers, as follows:
  • the two polymerizable monomers are RM-A2 and RM-B1, respectively, and the structural formula of RM-A2 is as follows:
  • RM-B1 The structural formula of RM-B1 is as follows:
  • the molar ratio of RM-A2 to RM-B1 is 1:5, and the total content of both accounts for 10,000 ppm of the liquid crystal dielectric layer.
  • RM-A2 and RM-B1 are mixed and the polymer produced by ultraviolet irradiation is small in size and uniform, and there is no dark state of light.
  • the liquid crystal medium mixture for liquid crystal display of the present invention passes through two or more kinds of polymerizable monomers which can be polymerized under ultraviolet light irradiation and suitable for the liquid crystal medium mixture.
  • the polymerization reaction can be controlled to form the size and uniformity of the polymer protrusions, and the poor alignment of the liquid crystal and the dark spot phenomenon of the liquid crystal panel are avoided, so that the liquid crystal panel obtains good optical performance, such as high contrast and high response speed. .
  • the liquid crystal medium mixture of the present invention is applicable to a display, and the liquid crystal display using the liquid crystal medium mixture of the present invention comprises: an upper substrate and a lower substrate disposed opposite to each other, and a liquid crystal medium disposed between the upper substrate and the lower substrate
  • the mixture, the liquid crystal medium mixture is the above-mentioned liquid crystal medium mixture of the present invention, which will not be described herein.
  • the liquid crystal medium mixture can simultaneously achieve a balance between the reaction rate of the polymerizable reaction, the uniformity of formation of the polymer, and the strength of the alignment force, and a higher level is obtained, that is, When the polymerization rate is fast, the uniformity of the polymer formation and the strength of the alignment force are also high, so that the optical taste and overall performance of the liquid crystal display panel can be improved, and stable mass production can be achieved.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal Substances (AREA)

Abstract

公开了一种液晶介质混合物及使用其的液晶显示器,该液晶介质混合物包括组分:至少一种各相异性液晶材料、及两种或两种以上可在紫外光照射下发生聚合反应的可聚合单体;该可聚合单体按重量份计算占液晶介质混合物总量的0.1%-1%。该液晶介质混合物及使用其的液晶显示器中,液晶介质混合物通过采用两种或两种以上可在紫外光照射下发生聚合反应的可聚合单体以及合适配比,可以聚合反应得到尺寸较小、均匀性好的聚合物突起物,避免了液晶配向不良、液晶面板暗态亮点现象的发生,从而使液晶面板响应速度变快并获得高对比度,实现稳定的量产。

Description

液晶介质混合物及使用其的液晶显示器 本申请要求于 2012 年 9 月 21 日提交中国专利局、 申请号为 201210360710.6、 发明名称为 "液晶介质混合物及使用其的液晶显示器" 的 中国专利申请的优先权, 上述专利的全部内容通过引用结合在本申请中。 技术领域
本发明涉及液晶显示技术, 尤其涉及一种液晶介质混合物及使用其的液 晶显示器。 背景技术
TN ( Twisted nematic, 扭曲向列型)或 STN ( Super twisted nematic, 超 扭曲向列型 )液晶显示器所用的液晶为正型液晶, 未加电时液晶分子长轴平 行于基板表面。 基板表面液晶分子的排列方向由配向层 ( Alignment layer, 材质通常为 Polyimide ) 的摩擦方向 (Rubbing direction ) 决定, 两基板表面 配向方向垂直, 所以从一个基板表面到另一个基板表面, 液晶层的分子呈连 续扭转排列状态。 当施加电压之后, 液晶分子的长轴将倾向于沿电场的方向 排列。 TN/STN型液晶显示器的缺点是可视角小, 在大视角下的亮度差异和 色差严重, 需要通过补偿膜对此进行改善, 从而提高了显示器的制造成本。
MVA ( Multi-domain vertical alignment, 多象限垂直配向型) TFT-LCD 4艮好的解决了 TN/STN显示器视角限制的问题, 它采用负型液晶与垂直配向 膜材料。 未施加电压时, 液晶分子长轴均垂直于基板表面, 施加电压会使液 晶分子倾倒,液晶分子长轴倾向于沿垂直电场方向排列。为了解决视角问题, 一个亚像素被分成多个区域, 使液晶分子朝不同的方向倾倒, 让显示器从不 同的方向看到的效果趋于一致。在一个亚像素内使不同区域的液晶分子导向 不同的方向有多种方法。 第一种是通过曝光显影的办法在 LCD的上下基板 制作出 Bump (***物 ), 使 Bump周围的液晶分子产生一定的预倾角, 引导 液晶分子朝固定方向倾倒; 第二种是在上下基板上形成具有一定图案的 ITO ( Indium Tin Oxide, 氧化铟锡 )像素电极, 由此产生的电场具有一定的倾斜 角度, 从而控制不同区域的液晶分子的导向, 此技术被称为 PVA ( Patterned vertical alignment, 垂直取向构型 )技术; 第三种是在 LCD基板的 TFT侧形 成 ITO slit(裂缝),另一侧为 Full ITO,在液晶介质中添加可聚合的 monomer (单体), 先通过电场使液晶分子倾倒, 同时用紫外光照射面板使 monomer 聚合形成具有引导液晶分子倾倒的聚合物颗粒,沉积在基板表面起到配向的 作用, 这种技术成为 PSVA ( Polymer stabilized vertical alignment, 聚合物稳、 定垂直对齐)技术。
可聚合单体的反应速度、 聚合物的大小及分布、 在基板表面均匀性、 配 向力的强弱等因素对面板的光学品味、 量产稳定性有重要影响, 这些因素除 了受制程条件的影响之外, 决定这些因素的主要原因是可聚合单体的分子结 构, 因为可聚合单体的分子结构直接决定了其光反应的快慢、 形成聚合物的 特性、对液晶的配向力强弱等。由于现有的液晶介质中一般含有烯基化合物, 有利于获得低的旋转粘度, 因而可提高液晶介质的响应, 由于现有的液晶介 质中一般含有烯基化合物, 有利于获得低的旋转粘度以提高液晶介质的响 应, 而在液晶介质中含有的烯基化合物容易影响可聚合单体的反应聚合, 从 而影响到液晶介质的配向, 故通常情况, 故通常情况, 单一一种可聚合单体 ί艮难达到让这几个因素都处于有利的情况, 出现的情况往往是顾此失彼, 比 如形成聚合物的均匀性好但是配向力不够,或配向力强但是反应速度太慢等 诸如此类问题。 发明内容
本发明的所要解决的技术问题在于, 提供一种液晶介质混合物, 采用两 种或两种以上功能性不同的可聚合单体进行合理搭配,其聚合反应的反应速 度、 形成聚合物的均匀性及配向力的强度能同时达到平衡, 且均得到较高的 水平。
以及提供一种液晶显示器,其液晶介质混合物采用两种或两种以上功能 性不同的可聚合单体进行合理搭配, 单体的聚合反应的反应速度、 形成聚合 物的均匀性及配向力的强度能同时达到平衡, 且均得到较高的水平, 提高了 面板的光学品味和总体表现, 实现稳定的量产性。 为解决上述技术问题, 本发明实施例提供一种液晶介质混合物, 其包括 组分: 液晶材料和两种可在紫外光照射下发生聚合反应的可聚合单体, 该液 晶材料包括在可聚合单体聚合时对聚合反应稳定的烯基化合物,所述可聚合 单体按重量份计算占所述液晶介质混合物总量的 0.1%-1%; 其中,
第一种可聚合单体由一个苯环构成,所述苯环上直接连接至少有两个可 聚合基团, 所述可聚合基团选自曱基丙烯酸酯或丙烯酸酯、 乙婦基、 乙烯氧 基或环氧基, 且所述至少两个可聚合基团不同时全为曱基丙烯酸酯基; 第二种可聚合单体的分子式为:
Figure imgf000004_0001
其中, 所述第一种可聚合单体的结构通式为下述中之一种: II
Figure imgf000004_0002
式 III
Figure imgf000004_0003
其中, Pl、 P2、 P3 代表可聚合基团, 分别独立的表示曱基丙烯酸酯或 丙烯酸酯、 乙婦基、 乙烯氧基、 环氧基, 且 Pl、 P2、 P3不同时全为曱基丙 酸酯'
其中 , 所述可聚合单体的结构通式中的任意芳香环上的氢原子可以被如 下基团取代: -F、 -Cl、 -Br、 曱基或 -CN。
其中, 所述第一种可聚合单体具体为下述分子式中的一个:
Figure imgf000005_0001
其中,所述两种可聚合单体在液晶介质混合物中的含量摩尔比例为 1:5。
Figure imgf000005_0002
R1表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
相应地, 本发明实施例提供一种液晶显示器, 其包括: 相对平行设置的 上基板与下基板、 及设于该上基板与下基板之间的液晶介质混合物, 该液晶 介质混合物包括组分: 液晶材料和两种可在紫外光照射下发生聚合反应的可 聚合单体, 所述可聚合单体按重量份计算占所述液晶介质混合物总量的
0.1%-1%; 其中,
第一种可聚合单体由一个苯环构成,所述苯环上直接连接至少有两个可 聚合基团, 所述可聚合基团选自曱基丙烯酸酯或丙烯酸酯、 乙婦基、 乙烯氧 基或环氧基, 且所述至少两个可聚合基团不同时全为曱基丙烯酸酯基; 第二种可聚合单体的分子式为:
Figure imgf000006_0001
其中, 所述第一种可聚合单体的结构通式为下述中之一种: II
Figure imgf000006_0002
式 III
Figure imgf000006_0003
其中, Pl、 P2、 P3 代表可聚合基团, 分别独立的表示曱基丙烯酸酯或 丙烯酸酯、 乙婦基、 乙烯氧基、 环氧基, 且 Pl、 P2、 P3不同时全为曱基丙 酸酯'
其中 , 所述可聚合单体的结构通式中的任意芳香环上的氢原子可以被如 下基团取代: -F、 -Cl、 -Br、 曱基或 -CN。
其中, 所述第一种可聚合单体具体为下述分子式中的一个:
Figure imgf000007_0001
其中,所述两种可聚合单体在液晶介质混合物中的含量摩尔比例为 1:
其具有如下结构通式:
Figure imgf000007_0002
其中,
Figure imgf000007_0003
R1表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
实施本发明的实施例, 具有如下有益效果: 本发明的液晶介质混合物,采用两种或两种以上可在紫外光照射下发生 聚合反应的可聚合单体及其合理配比, 可以聚合反应得到尺寸较小、 均匀性 好的聚合物突起物, 避免了液晶配向不良、 液晶面板暗态亮点现象的发生, 从而使液晶面板响应速度变快并获得高对比度。。将其应用于液晶显示器中, 提高了液晶显示器面板的光学品味和总体表现, 实现稳定的量产性。 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。
本发明提供一种用于液晶显示器的液晶介质混合物,所述液晶介质混合 物包括如下组分: 液晶材料及两种可在紫外光照射下发生聚合反应的可聚合 单体; 所述可聚合单体按重量份计算占液晶介质混合物总量的 0.1%-1%; 其中, 第一种可聚合单体由一个苯环构成, 所述苯环上直接连接至少有 两个可聚合基团, 所述可聚合基团选自曱基丙烯酸酯或丙烯酸酯、 乙婦基、 乙烯氧基或环氧基, 且所述至少两个可聚合基团不同时全为曱基丙烯酸酯 基;
第二种可聚合单体由两个苯环直接连接 , 环上均连接一个
可聚合基团, 具体地, 其分子式为:
Figure imgf000008_0001
具体地, 所述第一种可聚合单体的结构通式为下述中之一种:
Figure imgf000008_0002
式 III
Figure imgf000008_0003
其中, Pl、 P2、 P3 代表可聚合基团, 分别独立的表示曱基丙烯酸酯或 丙烯酸酯、 乙婦基、 乙烯氧基、 环氧基, 且 Pl、 P2、 P3不同时全为曱基丙 烯酸酯。所述可聚合单体的结构通式中的任意芳香环上的氢原子可以被如下 基团取代: -F、 -Cl、 -Br、 曱基或 -CN。
一些实施例中, 第一种可聚合单体具体为下述分子式中的一个:
Figure imgf000009_0001
在一个实施例中, 所述两种可聚合单体在液晶介质混合物中的含量摩尔 比例为 1:5。
所述婦基化合物, 其具有如下结构通式:
Figure imgf000009_0002
Figure imgf000009_0003
Rl表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
下面通过具体实施例, 说明本发明实施方式。 实施例 1 :
所述液晶介质混合物采用负型液晶材料及两种可聚合单体, 具体如下:
、o—
负型液晶材料的结构式为
M-A1与 RM-B1 , RM-A1的结构式如下所示:
Figure imgf000010_0001
RM-B1的结构式如下所示:
Figure imgf000010_0002
RM-A1 与 RM-B1 的摩尔比是 1:5 , 两者的总含量占液晶介质层的 10000ppm。 液晶介质混合物中, 混合使用 RM-A1和 RM-B1 , 通过紫外线照 射生成的聚合物 bump的尺寸小、 均匀, 不存在暗态亮光现象。
实施例 2:
所述液晶介质混合物采用负型液晶材料及两种可聚合单体, 具体如下:
Figure imgf000010_0003
两种可聚合单体分别为 RM-A2与 RM-B1 , RM-A2的结构式如下所示:
Figure imgf000011_0001
RM-B1的结构式如下所示:
Figure imgf000011_0002
RM-A2 与 RM-B1 的摩尔比是 1:5 , 两者的总含量占液晶介质层的 10000ppm。 液晶介质混合物中, 混合使用 RM-A2和 RM-B1 , 通过紫外线照 射生成的聚合物 bump的尺寸小、 均匀, 不存在暗态亮光现象。
综上所述, 本发明所述的用于液晶显示器的液晶介质混合物, 通过该液 晶介质混合物中含有的两种或两种以上可在紫外光照射下发生聚合反应的 可聚合单体以及合适配比, 可以控制聚合反应形成聚合物突起物的大小和均 匀性, 避免了液晶配向不良、 液晶面板暗态亮点现象的发生, 以此使得液晶 面板获得好的光学表现, 如高对比度和高响应速度。
本发明的液晶介质混合物可应用于显示器, 本发明的使用上述液晶介质 混合物的液晶显示器, 其包括: 相对平行设置的上基板与下基板、 及设于该 上基板与下基板之间的液晶介质混合物, 该液晶介质混合物即为本发明上述 的液晶介质混合物, 在此不累赘述之。 液晶介质混合物通过使用功能性不同 的可聚合单体, 使得可聚合单体在聚合反应的反应速度、 形成聚合物的均匀 性及配向力的强度能同时达到平衡, 且获得较高的水平, 即, 聚合反应速度 快的同时, 形成聚合物均匀性及配向力强度也高, 从而可提高液晶显示器面 板的光学品味和总体表现, 实现稳定的量产性。
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

权 利 要 求
1、 一种液晶介质混合物, 其特征在于, 其包括组分: 液晶材料和两种 可在紫外光照射下发生聚合反应的可聚合单体,该液晶材料包括在可聚合单 体聚合时对聚合反应稳定的烯基化合物, 所述可聚合单体按重量份计算占所 述液晶介质混合物总量的 0.1%-1%; 其中,
第一种可聚合单体由一个苯环构成,所述苯环上直接连接至少有两个可 聚合基团, 所述可聚合基团选自曱基丙烯酸酯或丙烯酸酯、 乙烯基、 乙烯氧 基或环氧基, 且所述至少两个可聚合基团不同时全为曱基丙烯酸酯基;
第二种可聚合单体的分子式为:
式 I
Figure imgf000012_0001
2、 如权利要求 1所述的一种液晶介质混合物, 其特征在于, 所述第一 种可聚合单体的结构通式为下述中之一种:
Figure imgf000012_0002
其中, Pl、 P2、 P3 代表可聚合基团, 分别独立的表示曱基丙烯酸酯或 丙烯酸酯、 乙婦基、 乙烯氧基、 环氧基, 且 Pl、 P2、 P3不同时全为曱基丙
3、 如权利要求 1所述的液晶介质混合物, 其特征在于, 所述可聚合单 体的结构通式中的任意芳香环上的氢原子可以被如下基团取代: -F、 -Cl、 -Br、 曱基或 -CN。
4、 如权利要求 2所述的液晶介质混合物, 其特征在于, 所述第一种可 聚合 的一个:
Figure imgf000013_0001
5、 如权利要求 4所述的液晶介质混合物, 其特征在于, 所述两种可聚 合单体在液晶介质混合物中的含量摩尔比例为 1 :5。
6、 如权利要求 1所述的液晶介质混合物, 其特征在于, 所述婦基化合
Figure imgf000013_0002
R1表示具有 2-9个碳原子的直链或支链烯基; R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
7、 如权利要求 2所述的液晶介质混合物, 其特征在于, 所述婦基化合
Figure imgf000014_0001
R1表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
8、 如权利要求 3所述的液晶介质混合物, 其特征在于, 所述婦基化合 物, 其具有如下结构通式:
Figure imgf000015_0001
Figure imgf000015_0002
Rl表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
9、 如权利要求 4所述的液晶介质混合物, 其特征在于, 所述婦基化合
Figure imgf000015_0003
Figure imgf000016_0001
Rl表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
10、 如权利要求 5所述的液晶介质混合物, 其特征在于, 所述婦基化合
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000017_0001
Rl表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
11、 一种液晶显示器, 其特征在于, 其包括: 相对平行设置的上基板与 下基板、 及设于该上基板与下基板之间的液晶介质混合物, 该液晶介质混合 物包括组分: 液晶材料和两种可在紫外光照射下发生聚合反应的可聚合单 体, 该液晶材料包括在可聚合单体聚合时对聚合反应稳定的烯基化合物, 所 述可聚合单体按重量份计算占所述液晶介质混合物总量的 0.1%-1%; 其中, 第一种可聚合单体由一个苯环构成,所述苯环上直接连接至少有两个可 聚合基团, 所述可聚合基团选自曱基丙烯酸酯或丙烯酸酯、 乙烯基、 乙烯氧 基或环氧基, 且所述至少两个可聚合基团不同时全为曱基丙烯酸酯基; 二种可聚合单体的分子式为:
Figure imgf000017_0002
12、 如权利要求 11 述的一种液晶显示器, 其特征在于, 所述第 聚合单体的结构通式为下述中之一种:
Figure imgf000017_0003
其中, Pl、 P2、 P3 代表可聚合基团, 分别独立的表示曱基丙烯酸酯或 丙烯酸酯、 乙婦基、 乙烯氧基、 环氧基, 且 Pl、 P2、 P3不同时全为曱基丙
13、 如权利要求 12所述的液晶显示器, 其特征在于, 所述可聚合单体 的结构通式中的任意芳香环上的氢原子可以被如下基团取代: -F、 -Cl、 -Br、 曱基或 -CN。
14、 如权利要求 12所述的液晶显示器, 其特征在于, 所述第一种可聚 合单 一个:
Figure imgf000018_0001
15、 如权利要求 14所述的液晶显示器, 其特征在于, 所述两种可聚合 单体在液晶介质混合物中的含量摩尔比例为 1:5。
16、 如权利要求 11所述的液晶显示器, 其特征在于, 所述烯基化合物, 其具有如下结构通式:
Figure imgf000018_0002
Figure imgf000018_0003
Figure imgf000019_0001
Rl表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
17、 如权利要求 12所述的液晶显示器, 其特征在于, 所述婦基化合物:
Figure imgf000019_0002
其中,
Figure imgf000019_0003
R1表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
18、 如权利要求 13所述的液晶显示器, 其特征在于, 所述婦基化合物,
Figure imgf000020_0001
R1表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
19、 如权利要求 14所述的液晶显示器, 其特征在于, 所述婦基化合物, 其
Figure imgf000020_0002
或 /及
Figure imgf000021_0001
Figure imgf000021_0002
Rl表示具有 2-9个碳原子的直链或支链烯基;
R2表示具有 1-12个碳原子的直链或支链烷基;
X分别独立的表示11、 F、 Cl、 OCF3或 CF3;
m表示 1-4;
n、 k分别表示 0~3。
20、 如权利要求 15所述的液晶显示器, 其特征在于, 所述婦基化合物:
Figure imgf000021_0003
Figure imgf000022_0001
Rl表示具有 2-9个碳原子的直链或支链烯基; R2表示具有 1-12个碳原子的直链或支链烷基; X分别独立的表示11、 F、 Cl、 OCF3或 CF3; m表示 1-4;
n、 k分别表示 0~3。
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