WO2017054274A1 - 配向膜、制备方法及其液晶面板 - Google Patents

配向膜、制备方法及其液晶面板 Download PDF

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WO2017054274A1
WO2017054274A1 PCT/CN2015/093099 CN2015093099W WO2017054274A1 WO 2017054274 A1 WO2017054274 A1 WO 2017054274A1 CN 2015093099 W CN2015093099 W CN 2015093099W WO 2017054274 A1 WO2017054274 A1 WO 2017054274A1
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group
branch
alignment film
carbon atoms
liquid crystal
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French (fr)
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兰松
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深圳市华星光电技术有限公司
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Priority to US14/894,930 priority Critical patent/US10093859B2/en
Publication of WO2017054274A1 publication Critical patent/WO2017054274A1/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
    • C09K19/542—Macromolecular compounds
    • 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
    • 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
    • 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
    • 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
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by 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
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by 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
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/02—Alignment layer characterised by chemical composition
    • C09K2323/027—Polyimide
    • 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
    • G02F1/133738—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homogeneous alignment
    • 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
    • G02F1/133753—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle
    • G02F1/133761—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers with different alignment orientations or pretilt angles on a same surface, e.g. for grey scale or improved viewing angle with different pretilt angles

Definitions

  • the present invention relates to the field of liquid crystal display technology, and in particular to an improved structure of the liquid crystal panel thereof.
  • VA Vertical Alignment
  • MVA Multi-domian Vertical Alignment
  • PVA Plasma Planar Alignment
  • CPA Continuous Pinwheel Alignment
  • a common PSVA liquid crystal panel includes two oppositely disposed substrates, the substrate generally including an outer glass sheet G and a circuit board ITO attached to the inner side of the glass sheet; A liquid crystal LC with a photopolymerizable monomer (RM, Reactive Mesogen) is disposed between the substrates.
  • the RM is a phototaxis monomer containing a double bond.
  • the tilt directions of the liquid crystal molecules are different for different domains.
  • specific UV light is irradiated.
  • RM is polymerized into a polymer network structure RM', and the liquid crystal molecules of the surface layer are attracted to form a fixed pretilt angle (see Fig. 1(c)).
  • the applied voltage is removed, and the liquid crystal LC molecules maintain a pretilt angle at a certain angle (see Fig. 1(d)).
  • RM irradiated with UV light
  • radical polymerization occurs. If the UV irradiance is too high, a high primary radical concentration will be generated at the initial stage of the reaction, resulting in an excessive RM reaction, forming a surface bump (RM polymerization).
  • the particle size of the formed bumps may increase, causing poor alignment of the LC and occurrence of broken spots.
  • a common method is to add a certain amount (usually between 0.1% and 1%) of a polymerization inhibitor in the LC.
  • the polymerization inhibitor mainly includes the following two types, one is a phenol, and the other is a phenol.
  • the inhibition of the above two polymerization inhibitors is to reduce the radical concentration of RM in the primary reaction, slow down the reaction speed of RM, to reduce the particle size of bump, and improve the uniformity of bump dispersion.
  • bisphenols will be converted into diterpenes, and benzoquinones will be converted into active group-containing fragments.
  • P-benzoquinone This structural change will cause changes in LC physical property parameters, such as ⁇ n, ⁇ , etc., thereby affecting LC optical properties and reducing panel quality.
  • the present invention provides an alignment film for a PSVA liquid crystal display panel, comprising bonding a first branch M and a second branch Q on a polyimide as a main chain, so that an alignment film Having the structure of formula 1;
  • the first branch M is a group for deflecting the liquid crystal in a power distribution state
  • the second branched chain Q is a group containing a nitrophenyl group or a phenylhydrazine group
  • the x, y represent the degree of polymerization of the first branched chain M and the second branched chain Q, respectively;
  • the structural unit A represents:
  • a cycloalkane group an aromatic hydrocarbon group or a fused ring aromatic hydrocarbon group having not more than 12 carbon atoms;
  • a cycloalkyl group an aromatic group or a fused ring aromatic group having not more than 12 carbon atoms, and one or more H atoms on the cycloalkyl group, the aryl group or the fused ring aromatic group are halogen atoms, alkoxy groups or esters Substituted by the base.
  • the ratio of the amount of the first branched chain M and the second branched chain Q is 1:0.1 to 1; the amount of the monomer corresponding to the main chain is not less than the first branched chain M The sum of the amounts of the substances corresponding to the monomer and the second branched Q corresponding to the monomer.
  • the second branch Q is of a structure such as Equation 2:
  • R 1 represents a hydrocarbon group having 2 to 10 carbon atoms, or a group containing -O(CO)-, having 2 to 10 carbon atoms, or containing -N(CO)-, and A group having 2 to 10 carbon atoms; and the group B represents a phenylhydrazine group or a nitrophenyl group.
  • Equation 3 the structure of the first branch M is as shown in Equation 3:
  • R 2 represents a hydrocarbon group having 2 to 10 carbon atoms, or a group containing -O(CO)-, having 2 to 10 carbon atoms, or containing -N(CO)- And a group having 2 to 10 carbon atoms;
  • the group E is represented by including 2 to 5 five-membered rings and/or six-membered rings and/or benzene rings and/or fused rings a group;
  • R 3 represents a hydrocarbon group having 1 to 12 carbon atoms, or a carbon number of 1 to 12, and the H atom is -F, -Cl, -CF 3 , -CN, -NCS, -OCF 3 Any group substituted with one or more groups.
  • the present invention also provides a liquid crystal panel comprising two oppositely disposed substrates, a liquid crystal with a photopolymerizable monomer disposed between the two substrates, and a side of the substrate adjacent to the liquid crystal is further provided with the above structure Characteristic alignment film.
  • the invention also provides a preparation method of the alignment film for a PSVA liquid crystal display panel, comprising the following steps:
  • a dianhydride monomer p and a diamine monomer n containing a first branch and a diamine monomer m containing a second branch are added to an organic solvent, and the reaction is stirred for 24 hours or more to obtain a alignment.
  • n: m 1: 0.1 ⁇ 1, and p ⁇ n + m;
  • the alignment film precursor to the substrate; baking at 180-230 ° C for 30 minutes or more, dehydrating and polymerizing the alignment film precursor into a polymer to form an alignment film; the alignment film has The polyimide is bonded to the first branch M and the second branch Q as a main chain, and has a structure of Formula 1;
  • the first branch M is a group for deflecting the liquid crystal in a power distribution state
  • the second branch Q is a group containing a nitrophenyl group or a phenylhydrazine group
  • x, y represent the degree of polymerization of the first branch M and the second branch Q, respectively;
  • the structural unit A represents:
  • a cycloalkane group an aromatic hydrocarbon group or a fused ring aromatic hydrocarbon group having not more than 12 carbon atoms;
  • a cycloalkyl group an aromatic group or a fused ring aromatic group having not more than 12 carbon atoms, and one or more H atoms on the cycloalkyl group, the aryl group or the fused ring aromatic group are halogen atoms, alkoxy groups or esters Substituted by the base.
  • the organic solvent is one or more of N-methylpyrrolidone solution, N-ethylpyrrolidine, ⁇ -caprolactone, dimethyl sulfoxide and dichloromethane.
  • the present invention means that a group having a property of inhibiting properties is linked to an alignment film (PI) in a short side chain.
  • the group having the polymerization inhibiting property can extend into the LC and contact with the RM, thereby slowing down the RM polymerization rate, improving the bump uniformity, and improving the problem of broken spots in the panel; on the other hand, due to the short
  • the branching is fixed in the alignment film, so that the polymerization inhibitor does not need to be directly added to the LC, which effectively limits the influence of the structural change of the polymerization inhibitor on the physical parameters of the LC after illumination, and improves the quality of the panel.
  • FIG. 1 is a schematic diagram showing the working flow of a conventional PSVA liquid crystal display panel
  • FIG. 2 is a schematic view showing the structure of an alignment film of the present invention.
  • the present invention provides a novel alignment film material having a polymerization inhibitory property, the alignment film having the structure of Formula 1, which includes a first branch M and a second branch Q:
  • x and y represent the degree of polymerization of the first branch M and the second branch Q, respectively, and the molecular weight of the alignment film formed is generally 5 ⁇ 10 3 to 5 ⁇ 10 5 ; x, y
  • the range can be adjusted according to the molecular weight of the branch, and the molecular weight of the alignment film can be controlled within a suitable range.
  • the structural unit A represents:
  • a cycloalkane group an aromatic hydrocarbon group or a fused ring aromatic hydrocarbon group having not more than 12 carbon atoms;
  • a cycloalkyl group an aromatic group or a fused ring aromatic group having not more than 12 carbon atoms, and one or more H atoms on the cycloalkyl group, the aryl group or the fused ring aromatic group are halogen atoms, alkoxy groups or esters Substituted by the base. .
  • the ratio of the amounts of the substances of the first branched chain M and the second branched chain Q is 1:0.1 to 1.
  • the amount of the monomer corresponding to the main chain is not less than the first branch M corresponding monomer and the second branch Q The sum of the amounts of the substances corresponding to the monomers.
  • the first branch M is a side chain having a rigid group and a long-chain alkyl group such as a benzene ring, and the function is to cause the LC to vertically orient the molecular column in an initial state
  • the first branch M Structure 3 shows:
  • R 2 represents a hydrocarbon group having 2 to 10 carbon atoms, or a group containing -O(CO)-, having 2 to 10 carbon atoms, or containing -N(CO)- And a group having 2 to 10 carbon atoms;
  • the group E is represented by including 2 to 5 five-membered rings and/or six-membered rings and/or benzene rings and/or fused rings a group;
  • R 3 represents a hydrocarbon group having 1 to 12 carbon atoms, or a carbon number of 1 to 12, and the H atom is -F, -Cl, -CF 3 , -CN, -NCS, -OCF 3 any one or more substituent groups groups.
  • the second branch Q is a side chain containing a structure having a polymerization inhibitory property, which contains a group of a nitrophenyl group or a phenylhydrazine group.
  • the structure of the second branch Q is as shown in Equation 2:
  • R 1 represents a hydrocarbon group having 2 to 10 carbon atoms, or a group containing -O(CO)-, having 2 to 10 carbon atoms, or containing -N(CO)-, and a group having 2 to 10 carbon atoms; and the group B represents a group having a polymerization inhibitory property such as a phenylhydrazine group or a nitrophenyl group.
  • benzoquinones such as p-diphenyl hydrazine, see formula 4:
  • Nitrobenzene see formula 5
  • meta-trinitrobenzene see formula 6
  • the phenylhydrazine group or the nitrophenyl group is generally attached to the end of the second branch Q to maximize contact with the RM, slow down the reaction speed of the RM, and reduce the bump.
  • the particle size increases the uniformity of bump dispersion.
  • the alignment film structure of the present invention can be schematically illustrated in Figure 2.
  • the longer first branch M maintains a stable alignment of the LC; the shorter second branch Q provides a inhibition.
  • the second branch Q can extend into the LC to contact the RM, thereby slowing down the RM polymerization rate and improving the bump uniformity; on the other hand, since the second branch is fixed in the alignment film Therefore, the polymerization inhibitor does not need to be directly added to the liquid crystal, which effectively limits the amount of the inhibitory substance remaining in the LC after the light conversion, so that the subsequent quality of the LC is ensured.
  • a dianhydride monomer p polymerizable before the main chain of the present embodiment, as shown in Reaction Scheme 7 (a)
  • a monomer molecule before polymerization corresponding to the first branch M A diamine monomer, as shown in Reaction Scheme 7 (b)
  • the amount of the substance is not less than the sum of n and m.
  • NMP N-methylpyrrolidone
  • the solvent used may also be one or more of N-ethylpyrrolidine, ⁇ -caprolactone, dimethyl sulfoxide and dichloromethane
  • PAA Polyamic acid
  • the PAA is coated on a substrate and baked at 180 to 230 ° C for 30 minutes, so that the solvent is sufficiently volatilized, and the PAA is also dehydrated into a ring to form a PI film.
  • a PSVA liquid crystal panel formed by using such an alignment film comprising two oppositely disposed substrates, wherein a liquid crystal with a photopolymerizable monomer is disposed between the two substrates, and a side of the substrate adjacent to the liquid crystal is further provided
  • An alignment film comprising a first branch M and a second branch Q bonded to each other on a polyimide as a main chain, such that the alignment film has a structure as in Formula 1 and its action.

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Abstract

一种涉及液晶技术领域的用于PSVA液晶显示器面板的配向膜，包括在聚酰亚胺作为主链上键合第一支链M、第二支链Q，使得配向膜具有结构式（Ｉ）其中，所述第一支链M为用于使所述液晶在配电状态下发生偏转的基团；所述第二支链Q为包含硝基苯基或苯醌基的基团。提供采用这种配向膜组成液晶显示面板，有效改善面板中碎亮点问题，提升面板品质。

Description

一种配向膜、制备方法及其液晶面板 技术领域
本发明涉及液晶显示器技术领域，尤其是其液晶面板的改进结构。
背景技术
现有的TFT-LCD显示器中，VA(Vertical Alignment)显示以其宽视野角、高对比度和无需摩擦配向等优势，成为大尺寸电视的常用模式。VA主要分为MVA(Multi-domian Vertical Alignment)技术、PVA(Patterned Vertial Alignment)技术和CPA(Continuous pinwheel Alignment)。这些VA技术，都需要在CF(滤光片)侧设计Protrusion(凸起)或Slit(间隙)，在增加成本的同时，还会降低显示屏的光透过率，为解决CF侧由点控或者线控实现到面控的问题，产生了新的VA显示技术，叫做聚合物稳定垂直配向(Polymer Stabilization Vertical Alignment，简称PSVA)技术。
PSVA技术最大的特点是在配向膜上生成一层可以使VA液晶形成预倾角的聚合物层。在图1(a)中所示，常见的PSVA液晶面板，包括两相对设置的基板，所述基板一般包括外层的玻璃板G以及贴于所述玻璃板内侧的电路板ITO；所述两基板之间设置带有光聚合单体(RM，Reactive Mesogen)的液晶LC。所述RM这是一种含有双键的趋光性单体。在UV光照射前，先在两基板上外加一个电压，使得液晶LC产生一个预倾角，如图1(b)所示，对应不同的畴，液晶分子的倾斜方向不同。用外加电压确定好预倾角度后，进行特定的UV光照射，这时，RM聚合成高分子网络结构RM’，吸引表层的液晶分子使之形成固定的预倾角(见图1(c))；UV照射完成后，撤去外加电压，液晶LC分子依旧保持一定角度的预倾角(见图1(d))。
然而，RM在UV光进行照射的时候，会发生自由基聚合反应，如果UV光照度过高，会在反应初期会产生较高的初级自由基浓度，导致RM反应过快，形成表面bump(RM聚合后形成的***物)的粒径会增大，从而引起LC的配向不良，出现碎亮点。
目前，为解决这个问题，常用的方法是在LC中添加一定用量(通常0.1％-1％之间)阻聚剂，这类阻聚剂主要包含以下两种类型，一种是酚类，另一种是醌类，它们的阻聚机理如下式所示：
Figure PCTCN2015093099-appb-000001
上述两种阻聚剂的阻聚本质都是降低RM在初级反应时候的自由基浓度，减缓RM的反应速度，以减小bump的粒径，提高bump分散的均匀性。而在这两类阻聚剂中，无论何种类型的阻聚剂都会使自身的结构发生变化，双酚类会转变为二醌类，对苯二醌类会转变成含活性基团片段的对苯二醌。这种结构的变化都会引起LC物理特性参数的变化，如△n，△等，从而影响LC光学特性，降低面板品质。
发明内容
为克服现有技术的不足，本发明提供一种用于PSVA液晶显示器面板的配向膜，包括在聚酰亚胺作为主链上键合第一支链M、第二支链Q，使得配向膜具有如式1结构；
Figure PCTCN2015093099-appb-000002
其中，所述第一支链M为用于使所述液晶在配电状态下发生偏转的基团； 所述第二支链Q为包含硝基苯基或苯醌基的基团；所述x、y分别代表所述第一支链M、第二支链Q的聚合度；
所述结构单元A代表为：
碳原子数不超过12个的环烷烃基、芳香烃基或稠环芳香烃基；或者是
碳原子数不超过12个的环烷基、芳香基或稠环芳香基，所述环烷基、芳香基或稠环芳香基上的一个或多个H原子被卤素原子、烷氧基或酯基所取代。
其中，所述第一支链M、第二支链Q的物质的量的比为1:0.1～1；所述主链所对应的单体的物质的量不小于所述第一支链M对应单体与第二支链Q对应单体的物质的量总和。
其中，第二支链Q是的结构如式2：
Figure PCTCN2015093099-appb-000003
所述R1表示含碳原子数为2～10的烃基、或者是含有-O(CO)-、且碳原子数为2～10个的基团、或者是含有-N(CO)-、且碳原子数为2～10个的基团；所述基团B表示苯醌基或硝基苯基。
其中，所述基团B结构式为如式4或式5或式6所示：
Figure PCTCN2015093099-appb-000004
其中，所述第一支链M的结构如式3所示：
Figure PCTCN2015093099-appb-000005
其中，所述R2表示含碳原子数为2～10的烃基、或者是含有-O(CO)-、且碳原子数为2～10个的基团、或者是含有-N(CO)-、且碳原子数为2～10个的基团；所述基团E表示包括有2～5个五元环和/或六元环和/或苯环和/或稠环顺连而成的基团；R3表示含有碳原子数为1～12的烃基、或者是含有碳原子数为1～12，且H原子被-F、-Cl、-CF3、-CN、-NCS、-OCF3任意一个或多个基团取 代的基团。
本发明还提供这种液晶面板，包括两相对设置的基板，所述两基板之间设置带有光聚合单体的液晶，所述基板与所述液晶相邻的一侧还设有具备上述结构特征的配向膜。
本发明还提供这种用于PSVA液晶显示器面板的配向膜的制备方法，包括如下步骤：
Ⅰ、将一种二酐类单体p与含有第一支链的二胺类单体n、含有第二支链的二胺类单体m加入到有机溶剂中，搅拌反应24h以上，得到配向膜前驱体；
其中，所述n:m＝1:0.1～1、且p≥n+m；
Ⅱ、将所述配向膜前驱体涂覆到基板上；在180～230℃下烘烤30分钟以上，使所述配向膜前驱体脱水聚合成聚合物，形成配向膜；所述配向膜具有在聚酰亚胺作为主链上键合所述第一支链M、第二支链Q，具有如式1的结构；
Figure PCTCN2015093099-appb-000006
其中，所述第一支链M为用于使所述液晶在配电状态下发生偏转的基团；所述第二支链Q为包含硝基苯基或苯醌基的基团；所述x、y分别代表所述第一支链M、第二支链Q的聚合度；
所述结构单元A代表为：
碳原子数不超过12个的环烷烃基、芳香烃基或稠环芳香烃基；或者是
碳原子数不超过12个的环烷基、芳香基或稠环芳香基，所述环烷基、芳香基或稠环芳香基上的一个或多个H原子被卤素原子、烷氧基或酯基所取代。
其中，所述有机溶剂为N-甲基吡咯烷酮溶液中、N-乙基吡咯烷、γ-己内酯、二甲基亚砜和二氯甲烷的一种或多种。
有益效果：
本发明是指将一类具有阻聚性质的基团以短侧链的方式连接配向膜(PI) 上，一方面具有阻聚性质的基团能伸入至LC中与RM接触，起到减缓RM聚合速率、提高bump均匀性的作用，改善面板中碎亮点的问题；另一方面，由于该短支链是固定于所述配向膜当中的，使得阻聚物质并不需要直接添加到LC中，有效限制了阻聚物质在光照后结构改变对LC物理参数的影响，提升面板品质。
附图说明
图1为现有PSVA液晶显示面板的工作流程示意图；
图2为本发明配向膜的结构示意图。
具体实施方式
下面，将结合附图对本发明的实施例作详细介绍。
本发明提供一种新型的具有阻聚性质的配向膜材料，这种配向膜具有如式1结构，其包括第一支链M、第二支链Q：
Figure PCTCN2015093099-appb-000007
其中，所述x、y分别代表所述第一支链M、第二支链Q的聚合度，一般而言所形成的配向膜分子量为5×103～5×105；x、y的范围可根据支链的分子量调整，将配向膜的分子量控制在合适范围内。
所述结构单元A代表为：
碳原子数不超过12个的环烷烃基、芳香烃基或稠环芳香烃基；或者是
碳原子数不超过12个的环烷基、芳香基或稠环芳香基，所述环烷基、芳香基或稠环芳香基上的一个或多个H原子被卤素原子、烷氧基或酯基所取代。。
所述第一支链M、第二支链Q的物质的量的比为1:0.1～1。为了保证第一支链M、第二支链Q与主链反应完全，所述主链所对应的单体的物质的量不小于所述第一支链M对应单体与第二支链Q对应单体的物质的量总和。
其中，所述第一支链M为含有苯环等具有刚性基团和长链烷基的侧链，其作用是使得LC在起始状态垂直取向排分子列，所述第一支链M的结构如式 3所示：
Figure PCTCN2015093099-appb-000008
其中，所述R2表示含碳原子数为2～10的烃基、或者是含有-O(CO)-、且碳原子数为2～10个的基团、或者是含有-N(CO)-、且碳原子数为2～10个的基团；所述基团E表示包括有2～5个五元环和/或六元环和/或苯环和/或稠环顺连而成的基团；R3表示含有碳原子数为1～12的烃基、或者是含有碳原子数为1～12，且H原子被-F、-Cl、-CF3、-CN、-NCS、-OCF3任意一个或多个基团取代的基团。
所述第二支链Q为含有阻聚性质结构的侧链，其包含硝基苯基或苯醌基的基团。第二支链Q是的结构如式2所示：
Figure PCTCN2015093099-appb-000009
所述R1表示含碳原子数为2～10的烃基、或者是含有-O(CO)-、且碳原子数为2～10个的基团、或者是含有-N(CO)-、且碳原子数为2～10个的基团；所述基团B表示苯醌基或硝基苯基等具有阻聚性质的基团。
例如，苯醌类如对二苯醌，见式4：
Figure PCTCN2015093099-appb-000010
硝基苯(见式5)或间三硝基苯(见式6)，如：
Figure PCTCN2015093099-appb-000011
为了使得阻聚作用获得最佳的效果，一般将苯醌基或硝苯基连接到第二支链Q的末端，以最大程度与RM接触、减缓RM的反应速度，以减小bump 的粒径，提高bump分散的均匀性。
本发明的配向膜结构可示意如图2所示，在实际工作中，较长的第一支链M维持稳定的对LC的配向作用；较短的第二支链Q提供阻聚作用。第二支链Q一方面能伸入至LC中与RM接触，起到减缓RM聚合速率、提高bump均匀性的作用；另一方面，由于该第二支链是固定于所述配向膜当中的，使得阻聚物质并不需要直接添加到液晶中，有效限制了阻聚物质在光照转化后残留在LC中的量，使得LC的后续质量得到保证。
下面，将介绍一下本发明的配向膜的制备方法。
将一种二酐类单体p(聚合为本实施的主链之前的单体分子，列举如反应式7(a)所示)与第一支链M所对应的聚合前的单体分子n(一种二胺类单体，列举如反应式7(b)所示)、第二支链Q所对应的聚合前的单体分子m(一种二胺类单体，列举如反应式7(c)所示)，第一支链M、第二支链Q分别所对应的单体分子物质的量之比为n:m＝1:0.1～1，本实施例中二酐类单体的物质的量不小于n、m之和。
将所述第一支链M、第二支链Q分别所对应的单体分子溶解在有机溶剂N-甲基吡咯烷酮(NMP)溶液中，其中NMP占所述配向膜溶液的质量百分比为90～95％(所用溶剂还可以是N-乙基吡咯烷、γ-己内酯、二甲基亚砜和二氯甲烷的一种或多种)，在室温下搅拌反应24小时，得到配向膜前驱体聚酰胺酸(PAA，如反应式7(d)所示)；
然后再将所述PAA涂覆于一基板上，在180～230℃的条件下烘烤30min，使得溶剂充分挥发的同时，也使得PAA脱水成环，形成PI膜。
Figure PCTCN2015093099-appb-000012
Figure PCTCN2015093099-appb-000013
采用这种配向膜形成的PSVA液晶面板，其包括两相对设置的基板，所述两基板之间设置带有光聚合单体的液晶，所述基板与所述液晶相邻的一侧还设有配向膜，所述配向膜包括在聚酰亚胺作为主链上键合第一支链M、第二支链Q，使得配向膜具有如式1结构及其作用。

Claims (10)

  1. 一种用于液晶显示器面板的配向膜，其中，包括在聚酰亚胺作为主链上键合第一支链M、第二支链Q，使得配向膜具有如式1结构；
    Figure PCTCN2015093099-appb-100001
    其中，所述第一支链M为用于使所述液晶在配电状态下发生偏转的基团；所述第二支链Q为包含硝基苯基或苯醌基的基团；所述x、y分别代表所述第一支链M、第二支链Q的聚合度；
    所述结构单元A代表为：
    碳原子数不超过12个的环烷烃基、芳香烃基或稠环芳香烃基；或者是
    碳原子数不超过12个的环烷基、芳香基或稠环芳香基，所述环烷基、芳香基或稠环芳香基上的一个或多个H原子被卤素原子、烷氧基或酯基所取代。
  2. 根据权利要求1所述的配向膜，其中，所述第一支链M、第二支链Q的物质的量的比为1:0.1～1；所述主链所对应的单体的物质的量不小于所述第一支链M对应单体与第二支链Q对应单体的物质的量总和。
  3. 根据权利要求1所述的配向膜，其中，第二支链Q的结构如式2：
    Figure PCTCN2015093099-appb-100002
    所述R1表示含碳原子数为2～10的烃基、或者是含有-O(CO)-或-N(CO)-、且碳原子数为2～10个的基团；所述基团B表示苯醌基或硝基苯基。
  4. 根据权利要求2所述的配向膜，其中，第二支链Q的结构如式2：
    Figure PCTCN2015093099-appb-100003
    所述R1表示含碳原子数为2～10的烃基、或者是含有-O(CO)-或-N(CO)-、且碳原子数为2～10个的基团；所述基团B表示苯醌基或硝基苯基。
  5. 根据权利要求4所述的配向膜，其中，所述基团B结构式为如式4或式5或式6所示：
    Figure PCTCN2015093099-appb-100004
  6. 根据权利要求1所述的配向膜，其中，所述第一支链M的结构如式3所示：
    Figure PCTCN2015093099-appb-100005
    其中，所述R2表示含碳原子数为2～10的烃基、或者是含有-O(CO)-或-N(CO)-、且碳原子数为2～10个的基团；所述基团E表示包括有2～5个五元环和/或六元环和/或苯环和/或稠环顺连而成的基团；R3表示含有碳原子数为1～12的烃基、或者是含有碳原子数为1～12，且H原子被-F、-Cl、-CF3、-CN、-NCS、-OCF3任意一个或多个基团取代的基团。
  7. 根据权利要求2所述的配向膜，其中，所述第一支链M的结构如式3所示：
    Figure PCTCN2015093099-appb-100006
    其中，所述R2表示含碳原子数为2～10的烃基、或者是含有-O(CO)-或-N(CO)-、且碳原子数为2～10个的基团；所述基团E表示包括有2～5个五元环和/或六元环和/或苯环和/或稠环顺连而成的基团；R3表示含有碳原子数为1～12的烃基、或者是含有碳原子数为1～12，且H原子被-F、-Cl、-CF3、-CN、-NCS、-OCF3任意一个或多个基团取代的基团。
  8. 一种液晶面板，包括两相对设置的基板，所述两基板之间设置带有光 聚合单体的液晶，所述基板与所述液晶相邻的一侧还设有配向膜，其中，所述配向膜包括在聚酰亚胺作为主链上键合第一支链M、第二支链Q，使得配向膜具有如式1结构；
    Figure PCTCN2015093099-appb-100007
    其中，所述第一支链M为用于使所述液晶在配电状态下发生偏转的基团；所述第二支链Q为包含硝基苯基或苯醌基的基团；所述x、y分别代表所述第一支链M、第二支链Q的聚合度；
    所述结构单元A代表为：
    碳原子数不超过12个的环烷烃基、芳香烃基或稠环芳香烃基；或者是
    碳原子数不超过12个的环烷基、芳香基或稠环芳香基，所述环烷基、芳香基或稠环芳香基上的一个或多个H原子被卤素原子、烷氧基或酯基所取代。
  9. 一种用于液晶显示器面板的配向膜的制备方法，其中，包括如下步骤：
    Ⅰ、将二酐类单体p与含有第一支链的二胺类单体n、含有第二支链的二胺类单体m加入到有机溶剂中，搅拌反应24h以上，得到配向膜前驱体；
    其中，所述n:m＝1:0.1～1、且p≥n+m；
    Ⅱ、将所述配向膜前驱体涂覆到基板上；在180～230℃下烘烤30分钟以上，使所述配向膜前驱体脱水聚合成聚合物，形成配向膜；所述配向膜具有在聚酰亚胺作为主链上键合所述第一支链M、第二支链Q，具有如式1的结构；
    Figure PCTCN2015093099-appb-100008
    其中，所述第一支链M为用于使所述液晶在配电状态下发生偏转的基团；所述第二支链Q为包含硝基苯基或苯醌基的基团；所述x、y分别代表所述第 一支链M、第二支链Q的聚合度；
    所述结构单元A代表为：
    碳原子数不超过12个的环烷烃基、芳香烃基或稠环芳香烃基；或者是
    碳原子数不超过12个的环烷基、芳香基或稠环芳香基，所述环烷基、芳香基或稠环芳香基上的一个或多个H原子被卤素原子、烷氧基或酯基所取代。
  10. 根据权利要求9所述的配向膜的制备方法，其中，所述有机溶剂为N-甲基吡咯烷酮溶液中、N-乙基吡咯烷、γ-己内酯、二甲基亚砜和二氯甲烷的一种或多种。
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CN101611031A (zh) * 2007-04-11 2009-12-23 第一毛织株式会社 3,4-二羧基-1,2,3,4-四氢-6-叔丁基-1-萘琥珀酸二酐及包括由该二酐制备的聚酰亚胺的液晶取向剂
WO2011055643A1 (ja) * 2009-11-09 2011-05-12 Jnc株式会社 液晶表示素子、液晶組成物及び配向剤並びに液晶表示素子の製造方法及びその使用
CN102893207A (zh) * 2010-03-15 2013-01-23 日产化学工业株式会社 聚酰胺酸酯液晶取向剂和使用其的液晶取向膜

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