WO2013181798A1 - 一种液晶活性单体及液晶面板 - Google Patents

一种液晶活性单体及液晶面板 Download PDF

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WO2013181798A1
WO2013181798A1 PCT/CN2012/076496 CN2012076496W WO2013181798A1 WO 2013181798 A1 WO2013181798 A1 WO 2013181798A1 CN 2012076496 W CN2012076496 W CN 2012076496W WO 2013181798 A1 WO2013181798 A1 WO 2013181798A1
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liquid crystal
group
reactive monomer
formula
crystal composition
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French (fr)
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谢忠憬
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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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Priority to US13/574,524 priority Critical patent/US8968596B2/en
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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
    • C09K19/04—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
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • 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
    • C09K2019/0444—Liquid 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
    • C09K2019/0448—Liquid 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
    • 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-)
    • C09K2019/122—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
    • C09K19/10—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

Definitions

  • the present invention relates to a liquid crystal active monomer and a liquid crystal panel, and more particularly to a liquid crystal active monomer for a polyimide surface of an alignment film and a liquid crystal panel having the liquid crystal active monomer.
  • liquid crystal displays are inseparable from daily life.
  • the needs of liquid crystal displays mainly include: wide viewing angle, high contrast, fast picture switching, low power consumption and picture stability.
  • image sticking image sticking ( Image Sticking).
  • Add liquid crystal reactive monomer (Reactive Monomer, RM) can increase the placement of liquid crystal molecules, thereby improving image sticking problems, and thus as a liquid crystal display (LCD Display) Device) application.
  • the current liquid crystal reactive monomer and the liquid crystal precursor have lower solubility, lower curing speed, and have a limited effect of improving image sticking.
  • liquid crystal active monomer having a hard core having a formula of the formula III is added to the liquid crystal composition:
  • A is the hard core and contains at least one benzene ring; R1 and R2 are polymer groups, and R1 and R2 are the same group or different groups; X is selected from H, F, Cl, CF3, and straight One of a chain or a branched alkyl group.
  • Table 1 shows the different performances of liquid crystal reactive monomers with different hard core volumes. Experiments show that the placement force of liquid crystal molecules is related to the volume of hard core of liquid crystal active monomer. Large, the higher the placement of liquid crystal molecules, the better the image retention. However, simply increasing the volume of the hard core results in a decrease in the solubility of the liquid crystal reactive monomer to the liquid crystal precursor.
  • the object of the present invention is to provide a liquid crystal reactive monomer (Reactive Monomer, RM) and liquid crystal panel can simultaneously improve the placement and polymerization ability of liquid crystal molecules to solve the problem of improving image residue and shorten the curing time, and at the same time, it has good solubility with the liquid crystal matrix.
  • Reactive Monomer Reactive Monomer
  • a first object of the present invention is to provide a liquid crystal reactive monomer (Reactive Monomer (RM) can simultaneously improve the placement and polymerization ability of liquid crystal molecules to solve the problem of improving image sticking and shortening the curing time, and at the same time, it has good solubility with the liquid crystal matrix.
  • Reactive Monomer Reactive Monomer
  • the present invention discloses the following technical solution: a liquid crystal reactive monomer for a polyimide surface of an alignment film having a hard core contained in a liquid crystal composition, characterized in that Wherein: the liquid crystal reactive monomer is represented by the formula I:
  • A is a hard core, a group containing two or more benzene rings, preferably a group containing three benzene rings;
  • B1 is a linking group, and the straight chain of B1 contains at least one carbon atom;
  • R1 and R2 are a polymer group, and R1 and R2 are the same group or different groups;
  • X is selected from one of H, F, Cl, CF3, a linear or branched alkyl group
  • the liquid crystal reactive monomer has a molecular weight greater than or equal to 300.
  • the hard core A and the polymer group R2 on the linear chain of the liquid crystal reactive monomer further comprise a linking group B2, which is represented by Formula II:
  • B2 is the same as B1 is a linking group, and the linear chain of B2 contains at least one carbon atom, and the B1 and B2 are the same group or different groups.
  • the general formula of the B1 group is CjH2j and the formula of the B2 group is CkH2k, and the j or k is selected from 0, 1 or 2, and satisfies j+k ⁇ 1.
  • the polymer group is selected from the group consisting of an acrylate group or a methyl acrylate group.
  • the liquid crystal composition is a liquid crystal composition of a drop-injection technique.
  • the polyimide surface of the alignment film is formed on a transparent substrate.
  • liquid crystal reactive monomer of the polyimide surface for the alignment film is represented by Formulas III, IV, and V:
  • X is selected from H or F
  • P or q is the number of X groups, and p or q are respectively selected from integers greater than or equal to 0 (such as 0, 1, 2, 7), and satisfy p + q ⁇ 1;
  • w or z are respectively selected from integers greater than or equal to 0 (e.g., 0, 1, 2, ...), and satisfy w + z ⁇ 1.
  • X is selected from H or F
  • p, q or r is the number of X groups, and p, q or r are respectively selected from integers greater than or equal to 0 (such as 0, 1, 2, 7), and satisfy r + p + q ⁇ 1;
  • w or z are respectively selected from integers greater than or equal to 0 (e.g., 0, 1, 2, ...), and satisfy w + z ⁇ 1.
  • w or z are respectively selected from integers greater than or equal to 0 (eg, 0, 1, 2, . . . ), and satisfy w+z ⁇ 1.
  • a second object of the present invention is to provide a liquid crystal panel comprising:
  • liquid crystal reactive monomer is represented by the formula I:
  • A is the hard core and is a group containing two or more benzene rings
  • B1 is a linking group, and the straight chain of B1 contains at least one carbon atom;
  • R1 and R2 are a polymer group, and R1 and R2 are the same group or different groups;
  • X is selected from one of H, F, Cl, CF3, a linear or branched alkyl group
  • n is the number of X groups, n ⁇ 1;
  • the liquid crystal reactive monomer has a molecular weight greater than or equal to 300.
  • the hard core A and the polymer group R2 on the linear chain of the liquid crystal reactive monomer further comprise a linking group B2, which is represented by Formula II:
  • B2 is the same as B1 is a linking group, and the linear chain of B2 contains at least one carbon atom, and the B1 and B2 are the same group or different groups.
  • the general formula of the B1 group is CjH2j and the formula of the B2 group is CkH2k, and the j or k is selected from 0, 1 or 2, and satisfies j+k ⁇ 1.
  • the polymer group is selected from the group consisting of an acrylate group or a methyl acrylate group.
  • the liquid crystal composition is a liquid crystal composition of a drop-injection technique.
  • the transparent substrate is a glass substrate.
  • the transparent substrate is a flexible polymer substrate or a non-flexible polymer substrate.
  • liquid crystal panel comprises:
  • liquid crystal composition filled between the first transparent and second transparent substrates, wherein the liquid crystal composition contacts the first and second alignment films, wherein the liquid crystal composition comprises at least one liquid crystal active monomer , the liquid crystal reactive monomer is of the formula III, Formula IV or Formula V means:
  • X is selected from H or F
  • p, q or r is the number of X groups, and p, q or r are respectively selected from integers greater than or equal to 0, and satisfy p+q ⁇ 1 or r+p+q ⁇ 1;
  • w or z are respectively selected from integers greater than or equal to 0, and satisfy w + z ⁇ 1.
  • the solubility of the liquid crystal reactive monomer to the liquid crystal precursor is improved, especially when the hard core volume is too large, the solubility of the liquid crystal reactive monomer main chain can be significantly improved, and the present invention can be overcome.
  • the liquid crystal reactive monomer of the invention improves the locating power of the liquid crystal molecules to solve the image residual problem; the polymerization ability of the liquid crystal molecules is improved, and the surface polymerization curing reaction of the liquid crystal reactive monomer and the polyimide is improved.
  • the curing speed shortens the curing time and can achieve the purpose of energy saving and carbon reduction.
  • FIG. 1 shows a liquid crystal panel of the present invention, the liquid crystal panel comprising:
  • liquid crystal composition a first transparent substrate 101 having a first alignment film 201, a second transparent substrate 102 having a second alignment film 202, and a liquid crystal composition filled in the first transparent substrate 101 and the second transparent substrate 102 And the liquid crystal composition is in contact with the first and second alignment films, wherein the liquid crystal composition comprises liquid crystal molecules 301 and at least one liquid crystal reactive monomer 302, and the liquid crystal reactive monomer 302 has the formula Indicated as III, IV or V.
  • X is selected from H or F
  • P or q is the number of X groups, and p or q are respectively selected from integers greater than or equal to 0 (such as 0, 1, 2, 7), and satisfy p + q ⁇ 1;
  • w or z are respectively selected from integers greater than or equal to 0 (e.g., 0, 1, 2, ...), and satisfy w + z ⁇ 1.
  • X is selected from H or F
  • p, q or r is the number of X groups, and p, q or r are respectively selected from integers greater than or equal to 0 (such as 0, 1, 2, 7), and satisfy r + p + q ⁇ 1;
  • w or z are respectively selected from integers greater than or equal to 0 (e.g., 0, 1, 2, ...), and satisfy w + z ⁇ 1.
  • w or z are respectively selected from integers greater than or equal to 0 (e.g., 0, 1, 2, ...), and satisfy w + z ⁇ 1.
  • the liquid crystal composition is a liquid crystal composition of a dropping type injection technique.
  • the transparent substrate is a glass substrate.
  • the transparent substrate can be a flexible polymer substrate or a non-flexible polymer substrate.
  • the embodiment provides a liquid crystal active monomer, and the structural formula thereof is , the preparation path is:
  • the embodiment provides a liquid crystal active monomer, and the structural formula thereof is , the preparation path is:
  • the present embodiment provides a liquid crystal reactive monomer having a hard core contained in a liquid crystal composition, and the liquid crystal reactive monomer is represented by Formula I:
  • A is the hard core, a group containing two or more benzene rings
  • B1 is a linking group, and the straight chain of B1 contains at least one carbon atom;
  • R1 and R2 are a polymer group, and R1 and R2 are the same group or different groups;
  • X is selected from one of H, F, Cl, CF3, a linear or branched alkyl group
  • n is the number of X groups, n ⁇ 1;
  • the liquid crystal reactive monomer has a molecular weight greater than or equal to 300.
  • the hard core A and the polymer group R2 on the linear chain of the liquid crystal reactive monomer further comprise a linking group B2, represented by formula II:
  • B2 is the same as B1 is a linking group, and B1 and B2 have at least one carbon atom in a straight chain, and B1 and B2 are the same group or different groups.
  • the polymeric group is selected from the group consisting of an acrylate group or a methyl acrylate group.
  • the liquid crystal composition preferably refers to a liquid crystal composition of a drop-injection (ODF) technique.
  • ODF drop-injection
  • the polyimide surface of the alignment film is formed on a transparent substrate.
  • the transparent substrate is a glass substrate.
  • the transparent substrate may also be a flexible polymer substrate or a non-flexible polymer substrate.
  • the hard core containing 1 to 3 benzene rings a linking group having a different carbon chain length is introduced, and different liquid crystal active monomers (RM B-1 ⁇ 3 and RM) are examined.
  • C-1 ⁇ 3 liquid crystal active monomers
  • the active monomer RM In B-1 ⁇ 3 the hard core contains two benzene rings; in the active monomer RM C-1 ⁇ 3, the hard core contains three benzene rings.
  • the liquid crystal reactive monomer RM B-1 conforms to the general formula I, and the linking group B1 is a linear alkyl group containing one C.
  • the liquid crystal reactive monomer RM B-2 conforms to the general formula I, and the linking group B1 is a linear alkyl group containing 2 C.
  • Liquid crystal active monomer RM B-3 is in accordance with Formula II, the linking group B1 is a linear alkyl group containing 2 C, and the linking group B2 is a linear alkyl group containing 2 C.
  • the liquid crystal reactive monomer RM C-1 conforms to the general formula I, and the linking group B1 is a linear alkyl group containing 2 C.
  • the liquid crystal reactive monomer RM C-2 conforms to the general formula I, and the linking group B1 is a linear alkyl group containing 4 C.
  • Liquid crystal active monomer RM C-3 is in accordance with Formula II, the linking group B1 is a linear alkyl group containing 2 C, and the linking group B2 is a linear alkyl group containing 2 C.
  • Liquid crystal active monomers RM A, RM B and RM C is a comparative example, which does not contain a linking group, and the hard core contains 1 to 3 benzene rings, respectively.
  • Table 2 shows the results of examination of the curing rate, the solubility to the liquid crystal precursor, and the image sticking phenomenon under the conditions of the polyimide (PI) of the same alignment film for each of the above liquid crystal reactive monomers.
  • the liquid crystal reactive monomer of the present invention increases the main chain length of the liquid crystal reactive monomer by increasing the linking group, thereby improving the solubility of the liquid crystal reactive monomer to the liquid crystal precursor, and overcoming the improvement of image sticking phenomenon in the prior art. Contradiction with solubility.
  • Liquid crystal active monomer of the present invention overcome the defects of the existing liquid crystal reactive monomer, the solubility of the liquid crystal active monomer to the liquid crystal precursor is remarkably improved, and the image residual problem is also solved, and the liquid crystal reactive monomer and the polyacyl group are improved.
  • the curing speed of the imide surface polymerization curing reaction shortens the curing time and achieves the purpose of energy saving and carbon reduction.

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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
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Description

一种液晶活性单体及液晶面板 技术领域
本发明涉及一种液晶活性单体及液晶面板，特别是涉及一种用于配向膜的聚酰亚胺表面的液晶活性单体及具有此液晶活性单体的液晶面板。
 背景技术
近年来，液晶显示器与日常生活密不可分，对于液晶显示器的需要主要有：广视角、高对比、快速画面切换、低耗电和画面稳定；而画面稳定中有待改善的问题之一就是影像残留（Image Sticking）。
添加液晶活性单体（Reactive Monomer，RM）可以增加液晶分子的归置力，从而改善影像残留问题，进而作为液晶显示器（LCD Display Device）的应用。但是，现行的液晶活性单体与液晶母体的溶解度较低，固化速度也较低，改善影像残留的效果有限。
更详细来说，为了增加液晶分子的归置力，在液晶组成物中添加通式如式Ⅲ所示的含有一硬核的液晶活性单体：
Figure PCTCN2012076496-appb-I000001
其中：A为所述硬核，含有至少一个苯环；R1和R2为聚合物基团，所述R1和R2是相同基团或不同基团；X选自H、F、Cl、CF3、直链或支链烷基中的一种。请参见表1，表1所示的是不同硬核体积的液晶活性单体所表现的不同性能，实验表明，液晶分子的归置力与液晶活性单体硬核的体积有关，硬核体积越大，液晶分子的归置力就越高，影像残留情况也就越好。但一味地增加所述硬核的体积会使得液晶活性单体对液晶母体溶解度降低。
Figure PCTCN2012076496-appb-I000002
因此，有必要提供一种新型的液晶活性单体，以解决现有技术所存在的问题，同时提高液晶分子的归置力和聚合能力。
 技术问题
本发明的目的是提供一种液晶活性单体（Reactive Monomer，RM）及液晶面板，能同时提高液晶分子的归置力和聚合能力，以解决改善影像残留问题，并缩短固化时间，同时其与液晶母体溶解度好。
 技术解决方案
本发明的第一个目的是提供一种液晶活性单体（Reactive Monomer，RM），能同时提高液晶分子的归置力和聚合能力，以解决改善影像残留问题，并缩短固化时间，同时其与液晶母体溶解度好。
为实现上述目的，本发明公开以下技术方案：一种用于配向膜的聚酰亚胺表面的液晶活性单体，所述液晶活性单体具有一硬核，包含于液晶组成物中，其特征在于：所述液晶活性单体通式以式Ⅰ表示：
Figure PCTCN2012076496-appb-I000003
其中：
A为所述硬核，含有两个或两个以上苯环的基团，优选为含三个苯环的基团；
B1为联结基团，所述B1的直链上含有至少一个碳原子；
R1和R2为聚合物基团，所述R1和R2是相同基团或不同基团；
X选自H、F、Cl、CF3、直链或支链烷基中的一种；
所述n为X基团的数量，n≥1，优选n=3；
所述液晶活性单体的分子量大于或等于300。
在本发明的一实施例中，所述液晶活性单体直链上的硬核A和聚合物基团R2之间还包含一联结基团B2，以式Ⅱ表示：
Figure PCTCN2012076496-appb-I000004
其中B2相同于B1是为联结基团，所述B2的直链上含有至少一个碳原子，所述B1和B2是相同基团或不同基团。
在本发明一实施例中，所述B1基团的通式为CjH2j和B2基团的通式为CkH2k，所述j或k选自0、1或2，并且满足j+k≥1。
在本发明的一实施例中，所述聚合物基团选自丙烯酸酯基或丙烯酸甲酯基。
在本发明的一实施例中，所述液晶组成物为滴下式注入技术的液晶组成物。
在本发明的一实施例中，所述配向膜的聚酰亚胺表面是形成在一透明基板上。
在本发明一较优实施例中，所述用于配向膜的聚酰亚胺表面的液晶活性单体以式Ⅲ、Ⅳ、Ⅴ表示：
Figure PCTCN2012076496-appb-I000005
其中， X选自H或F；
p或q为X基团的数量，p或q分别选自大于等于0的整数（如0、1、2……），且满足p+q≥1；
w或z分别选自大于等于0的整数（如0、1、2……），且满足w+z≥1。
Figure PCTCN2012076496-appb-I000006
其中， X选自H或F；
p、q或r为X基团的数量，p、q或r分别选自大于等于0的整数（如0、1、2……），且满足r+p+q≥1；
w或z分别选自大于等于0的整数（如0、1、2……），且满足w+z≥1。
Figure PCTCN2012076496-appb-I000007
其中， w或z分别选自大于等于0的整数（如0、1、2……），且满足w+z≥1。
本发明的第二个目的是提供一种液晶面板，所述液晶面板包含：
一第一透明基板，具有一第一配向膜；
一第二透明基板，具有一第二配向膜；以及
液晶组成物，填充于所述第一透明及第二透明基板之间，且所述液晶组成物接触所述第一及第二配向膜，其中所述液晶组成物包含至少一种液晶活性单体，所述液晶活性单体通式以式Ⅰ表示：
Figure PCTCN2012076496-appb-I000008
其中：
A为所述硬核，为含有两个或两个以上苯环的基团；
B1为联结基团，所述B1的直链上含有至少一个碳原子；
R1和R2为聚合物基团，所述R1和R2是相同基团或不同基团；
X选自H、F、Cl、CF3、直链或支链烷基中的一种；
所述n为X基团的数量，n≥1；
所述液晶活性单体的分子量大于或等于300。
在本发明的一实施例中，所述液晶活性单体直链上的硬核A和聚合物基团R2之间还包含一联结基团B2，以式Ⅱ表示：
Figure PCTCN2012076496-appb-I000009
其中B2相同于B1是为联结基团，所述B2的直链上含有至少一个碳原子，所述B1和B2是相同基团或不同基团。
在本发明一实施例中，所述B1基团的通式为CjH2j和B2基团的通式为CkH2k，所述j或k选自0、1或2，并且满足j+k≥1。
在本发明的一实施例中，所述聚合物基团选自丙烯酸酯基或丙烯酸甲酯基。
在本发明的一实施例中，所述液晶组成物为滴下式注入技术的液晶组成物。
在本发明的一实施例中，所述透明基板为一玻璃基板。
在本发明的一实施例中，所述透明基板为一可挠式聚合物基板或一非可挠式聚合物基板。
在本发明一较佳实施例中，提供一种液晶面板，其中，所述液晶面板包含：
一第一透明基板，具有一第一配向膜；
一第二透明基板，具有一第二配向膜；以及
液晶组成物，填充于所述第一透明及第二透明基板之间，且所述液晶组成物接触所述第一及第二配向膜，其中所述液晶组成物包含至少一种液晶活性单体，所述液晶活性单体通式以式 Ⅲ、式 Ⅳ 或式Ⅴ表示：
Figure PCTCN2012076496-appb-I000010
其中， X选自H或F；
p、q或r为X基团的数量，p、q或r分别选自大于等于0的整数，且满足p+q≥1或r+p+q≥1；
w或z分别选自大于等于0的整数，且满足w+z≥1。
 有益效果
通过增加液晶活性单体的主链长度，改善液晶活性单体对于液晶母体的溶解度，尤其是当硬核体积过大时，通过增加液晶活性单体主链的长度可以明显改善其溶解度，克服现有技术中硬核体积与溶解度的矛盾。同时，本发明的液晶活性单体提高了液晶分子的归置力，以解决影像残留问题；提高了液晶分子的聚合能力，以提高了所述液晶活性单体与聚酰亚胺表面聚合固化反应的固化速度，缩短了固化时间，可达到节能减碳的目的。
 附图说明
图1是本发明的液晶面板，其中
101第一透明基板；102第二透明基板
201第一配向膜； 202第二配向膜
301液晶分子； 302液晶活性单体。
 本发明的最佳实施方式
以下结合实施例对本发明做详细的说明，实施例旨在解释而非限定本发明的技术方案。
实施例1
请参见附图1，附图1所示的是本发明的液晶面板，所述液晶面板包含：
一第一透明基板101，具有一第一配向膜201；一第二透明基板102，具有一第二配向膜202；以及液晶组成物，填充于所述第一透明101及第二透明基板102之间，且所述液晶组成物接触所述第一及第二配向膜，其中所述液晶组成物包含液晶分子301和至少一种液晶活性单体302，所述液晶活性单体302的通式以Ⅲ、Ⅳ或Ⅴ表示。
Figure PCTCN2012076496-appb-I000011
其中，
X选自H或F；
p或q为X基团的数量，p或q分别选自大于等于0的整数（如0、1、2……），且满足p+q≥1；
w或z分别选自大于等于0的整数（如0、1、2……），且满足w+z≥1。
Figure PCTCN2012076496-appb-I000012
其中， X选自H或F；
p、q或r为X基团的数量，p、q或r分别选自大于等于0的整数（如0、1、2……），且满足r+p+q≥1；
w或z分别选自大于等于0的整数（如0、1、2……），且满足w+z≥1。
Figure PCTCN2012076496-appb-I000013
其中，
w或z分别选自大于等于0的整数（如0、1、2……），且满足w+z≥1。
所述液晶组成物为滴下式注入技术的液晶组成物。所述透明基板为一玻璃基板。所述透明基板可以是一可挠式聚合物基板或一非可挠式聚合物基板。
实施例2
本实施例提供一种液晶活性单体，其结构式为
Figure PCTCN2012076496-appb-I000014
，制备路径为：
Figure PCTCN2012076496-appb-I000015
具体制备步骤为：
（A）制备中间体（1）
Figure PCTCN2012076496-appb-I000016
将10 mmol 2,6-二羟蒽醌（2, 6-Dihydroxyanthraquinone ）溶解于150 mL浓度为2.0 N 的Na2CO3溶液中，缓慢将127 mmol NaBH4 加入反应中。在室温下搅拌反应3小时，直至气体不再产生后，将反应加热回流10分钟。待冷却过后，缓慢滴入浓HCl，将反应酸化。过滤收集沉淀物并用丙酮（acetone）溶解，溶液用MgSO4除水并抽气过滤，然后浓缩抽真空，得一红棕色固体，最后借由硅胶管柱层析以EA/Hexane = 1/1进行纯化，用乙醇（ethanol）再结晶，得到淡红棕色结晶；
（B）制备目标产物
Figure PCTCN2012076496-appb-I000017
将4.14 mmol 中间体（1）置入250 mL双颈瓶中以真空除氧除水装置抽气、灌氮气三次后，在滴加管上接上氮气，使反应系统呈无氧无水状态。在室温下加入8.28 mmol三乙胺（Et3N）及50 mL除水后的四氢呋喃（THF）搅拌至溶解，最后在冰浴下注入9.11 mmol甲基丙烯酰氯（methacryloyl chloride），在室温下反应至隔天。用THF抽气过滤，收集滤减压浓缩，以乙胺（EA）和水萃取，用MgSO4除水并抽气过滤，然后浓缩抽真空，得一黄色固体，最后借由硅胶管柱层析以EA/Hexane = 1/6进行纯化，得到淡黄色固体（可用THF/methanol做再结晶）。
实施例3
本实施例提供一种液晶活性单体，其结构式为
Figure PCTCN2012076496-appb-I000018
，制备路径为：
Figure PCTCN2012076496-appb-I000019
制备具体步骤为：
（A）制备中间体（3）
Figure PCTCN2012076496-appb-I000020
将10 mmol 中间体（1）溶解于150 mL浓度为 2.0 N的KOH/THF 溶液中，缓慢将5 mmol 2-溴乙醇（2-bromoethanol）加入反应中。将反应加热回流24小时。待冷却过后，缓慢滴入浓HCl，将反应酸化。以EA和水萃取，用MgSO4除水并抽气过滤，然后浓缩抽真空，得一黄色液体，最后借由硅胶管柱层析以EA/Hexane = 1/1进行纯化，用乙醇再结晶，得到淡黄色液体。
（B）制备目标产物
Figure PCTCN2012076496-appb-I000021
将10 mmol中间体（3）置入250 mL双颈瓶中以真空除氧除水装置抽气、灌氮气三次后，在滴加管上接上氮气，使反应系统呈无氧无水状态。在室温下加入8.28 mmol Et3N 及50 mL除水后的 THF搅拌至溶解，最后在冰浴下注入9.11 mmol甲基丙烯酰氯（methacryloyl chloride），在室温下反应至隔天。用THF抽气过滤，收集滤减压浓缩，以EA和水萃取，用MgSO4除水并抽气过滤，然后浓缩抽真空，得一黄色固体，最后借由硅胶管柱层析以EA/Hexane = 1/6进行纯化，得到淡黄色固体（可用THF/methanol做再结晶）。
实施例4
本实施例提供一种液晶活性单体，所述液晶活性单体具有一硬核，包含于液晶组成物中，所述液晶活性单体通式以式Ⅰ表示：
Figure PCTCN2012076496-appb-I000022
其中：
A为所述硬核，含有两个或两个以上苯环的基团；
B1为联结基团，所述B1的直链上含有至少一个碳原子；
R1和R2为聚合物基团，所述R1和R2是相同基团或不同基团；
X选自H、F、Cl、CF3、直链或支链烷基中的一种；
所述n为X基团的数量，n≥1；
所述液晶活性单体的分子量大于或等于300。
优选地，所述液晶活性单体直链上的硬核A和聚合物基团R2之间还包含一联结基团B2，以式Ⅱ表示：
Figure PCTCN2012076496-appb-I000023
其中B2相同于B1是为联结基团，B1和B2的直链上含有至少一个碳原子，所述B1和B2是相同基团或不同基团。
优选地，所述聚合物基团选自丙烯酸酯基或丙烯酸甲酯基。
在本实施例中，所述液晶组成物优选是指滴下式注入(ODF)技术的液晶组成物。所述配向膜的聚酰亚胺表面是形成在一透明基板上。所述透明基板为一玻璃基板。所述透明基板也可以是一可挠式聚合物基板或一非可挠式聚合物基板。
在本实施例中，对于含有1~3个苯环的所述硬核，分别导入不同碳链长度的联结基团，考察不同液晶活性单体（RM B-1~3和RM C-1~3）在相同配向膜的聚酰亚胺（Polyimide, PI）的条件下，固化速度、对液晶母体的溶解度以及影像残留现象。具体来说，活性单体RM B-1~3中，所述硬核均含有两个苯环；活性单体RM C-1~3中，所述硬核均含有三个苯环。
液晶活性单体RM B-1符合通式式Ⅰ，联结基团B1是含有1个C的直链烷基。
液晶活性单体RM B-2符合通式式Ⅰ，联结基团B1是含有2个C的直链烷基。
液晶活性单体RM B-3符合通式式Ⅱ，联结基团B1是含有2个C的直链烷基，联结基团B2是含有2个C的直链烷基。
液晶活性单体RM C-1符合通式式Ⅰ，联结基团B1是含有2个C的直链烷基。
液晶活性单体RM C-2符合通式式Ⅰ，联结基团B1是含有4个C的直链烷基。
液晶活性单体RM C-3符合通式式Ⅱ，联结基团B1是含有2个C的直链烷基，联结基团B2是含有2个C的直链烷基。
液晶活性单体RM A、RM B和RM C是对照实施例，均不含有联结基团，硬核分别含有1~3个苯环。
请参见表2，表2是上述各液晶活性单体在相同配向膜的聚酰亚胺（PI）的条件下，对于固化速度、对液晶母体的溶解度以及影像残留现象的考察结果。
Figure PCTCN2012076496-appb-I000024
由表2中可以很明显地得出以下结论：
（1）液晶活性单体的硬核所含苯环数量越大，改善影像残留现象的效果越好，固化速度也越快 请对比RM A、RM B和RM C；RM B-2和RM C-1；RM B-3和RM C-3，上述3组对比中，只有硬核所含苯环数量（硬核体积）是唯一变量，由上述3组对比可以很明显地看出，液晶活性单体的硬核所含苯环数量越大，改善影像残留现象的效果越好，固化速度也越快。
（2）液晶活性单体的主链越长，其对液晶母体的溶解度也就越好
请对比RM B和RM B1~3、RM C和RM C1~3，当硬核所含苯环数量相同时（即硬核体积相同），液晶活性单体的主链越长，其对液晶母体的溶解度也就越好。尤其是当尤其是当硬核体积过大时（RM C及RM C1~3），这种改善十分明显。
因此，我们可以说，本发明的液晶活性单体通过增加联结基团来增加液晶活性单体的主链长度，从而改善液晶活性单体对于液晶母体的溶解度，克服现有技术中改善影像残留现象与溶解度的矛盾。
本发明的液晶活性单体（液晶活性单体RM B-1~3和RM C-1~3）克服了现有液晶活性单体的缺陷，所述液晶活性单体对液晶母体的溶解度显著提高，同时还解决了影像残留问题，提高了所述液晶活性单体与聚酰亚胺表面聚合固化反应的固化速度，缩短了固化时间，实现了节能减碳的目的。
本发明已由上述相关实施例加以描述，然而上述实施例仅为实施本发明的范例。必需指出的是，已公开的实施例并未限制本发明的范围。相反地，包含于权利要求书的精神及范围的修改及均等设置均包括于本发明的范围内。
 本发明的实施方式
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Claims (13)

  1. 一种用于配向膜的聚酰亚胺表面的液晶活性单体，所述液晶活性单体具有一硬核，包含于液晶组成物中，其中，所述液晶活性单体通式以式Ⅰ表示：
    Figure PCTCN2012076496-appb-I000025
    其中：
    A为所述硬核，含有两个或两个以上苯环的基团；
    B1为联结基团，所述B1的直链上含有至少一个碳原子；
    R1和R2为聚合物基团，所述R1和R2是相同基团或不同基团；
    X选自H、F、Cl、CF3、直链或支链烷基中的一种；
    所述n为X基团的数量，n≥1；
    所述液晶活性单体的分子量大于或等于300。
  2. 根据权利要求1所述的液晶活性单体，其中，所述液晶活性单体直链上的硬核A和聚合物基团R2之间还包含一联结基团B2，以式Ⅱ表示：
    Figure PCTCN2012076496-appb-I000026
    其中B2相同于B1为联结基团，所述B2的直链上含有至少一个碳原子，所述B1和B2是相同基团或不同基团。
  3. 一种用于配向膜的聚酰亚胺表面的液晶活性单体，所述液晶活性单体具有一硬核，包含于液晶组成物中，其中，所述液晶活性单体通式以式 Ⅲ、式 Ⅳ 或式Ⅴ表示：
    Figure PCTCN2012076496-appb-I000027
    其中， X选自H或F；
    p、q或r为X基团的数量，p、q或r分别选自大于等于0的整数，且满足p+q≥1或r+p+q≥1；
    w或z分别选自大于等于0的整数，且满足w+z≥1。
  4. 根据权利要求1或2所述的液晶活性单体，其中，所述B1基团的通式为CjH2j ，B2基团的通式为CkH2k，所述j或k选自0、1或2，并且满足j+k≥1。
  5. 根据权利要求1所述的液晶活性单体，其中，所述聚合物基团选自丙烯酸酯基或丙烯酸甲酯基。
  6. 根据权利要求1或2或3所述的液晶活性单体，其中，所述液晶组成物为滴下式注入技术的液晶组成物。
  7. 根据权利要求1或2或3所述的液晶活性单体，其中，所述配向膜的聚酰亚胺表面是形成在一透明基板上。
  8. 一种液晶面板，其中，所述液晶面板包含：
    一第一透明基板，具有一第一配向膜；
    一第二透明基板，具有一第二配向膜；以及
    液晶组成物，填充于所述第一透明及第二透明基板之间，且所述液晶组成物接触所述第一及第二配向膜，其中所述液晶组成物包含至少一种液晶活性单体，所述液晶活性单体通式以式Ⅰ表示：
    Figure PCTCN2012076496-appb-I000028
    其中：
    A为所述硬核，为含有两个或两个以上苯环的基团；
    B1为联结基团，所述B1的直链上含有至少一个碳原子；
    R1和R2为聚合物基团，所述R1和R2是相同基团或不同基团；
    X选自H、F、Cl、CF3、直链或支链烷基中的一种；
    所述n为X基团的数量，n≥1；
    所述液晶活性单体的分子量大于或等于300。
  9. 根据权利要求8所述的液晶面板，其中，所述液晶活性单体直链上的硬核A和聚合物基团R2之间还包含一联结基团B2，以式Ⅱ表示：
    Figure PCTCN2012076496-appb-I000029
    其中B2相同于B1是为联结基团， 所述B2的直链上含有至少一个碳原子，所述B1和B2是相同基团或不同基团。
  10. 一种液晶面板，其中，所述液晶面板包含：
    一第一透明基板，具有一第一配向膜；
    一第二透明基板，具有一第二配向膜；以及
    液晶组成物，填充于所述第一透明及第二透明基板之间，且所述液晶组成物接触所述第一及第二配向膜，其中所述液晶组成物包含至少一种液晶活性单体，所述液晶活性单体通式以式 Ⅲ、式 Ⅳ 或式Ⅴ表示：
    Figure PCTCN2012076496-appb-I000030
    其中， X选自H或F；
    p、q或r为X基团的数量，p、q或r分别选自大于等于0的整数，且满足p+q≥1或r+p+q≥1；
    w或z分别选自大于等于0的整数，且满足w+z≥1。
  11. 根据权利要求8或9所述的液晶面板，其中，所述B1基团的通式为CjH2j ，B2基团的通式为CkH2k，所述j或k选自0、1或2，并且满足j+k≥1。
  12. 根据权利要求8所述的液晶面板，其中，所述聚合物基团选自丙烯酸酯基或丙烯酸甲酯基。
  13. 根据权利要求8或9或10所述的液晶面板，其中，所述液晶组成物为滴下式注入技术的液晶组成物。
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