WO2019019226A1 - 液晶显示面板及其制作方法、柱状隔垫物 - Google Patents

液晶显示面板及其制作方法、柱状隔垫物 Download PDF

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WO2019019226A1
WO2019019226A1 PCT/CN2017/097191 CN2017097191W WO2019019226A1 WO 2019019226 A1 WO2019019226 A1 WO 2019019226A1 CN 2017097191 W CN2017097191 W CN 2017097191W WO 2019019226 A1 WO2019019226 A1 WO 2019019226A1
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group
liquid crystal
formula
alignment layer
columnar spacer
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French (fr)
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杨勇
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Wuhan China Star Optoelectronics Technology Co Ltd
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Wuhan China Star Optoelectronics Technology Co Ltd
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Priority to US15/577,716 priority Critical patent/US10634957B2/en
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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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13394—Gaskets; Spacers; Sealing of cells spacers regularly patterned on the cell subtrate, e.g. walls, pillars
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0273—Polyamines containing heterocyclic moieties in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • 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
    • 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
    • C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
    • 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
    • G02F1/133354—Arrangements for aligning or assembling substrates
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • G02F1/13398—Spacer materials; Spacer properties

Definitions

  • the present invention relates to the field of liquid crystal display panels, and in particular to a column spacer in a liquid crystal display panel, a liquid crystal display panel having the column spacer, and a method of fabricating the liquid crystal display panel.
  • the liquid crystal display panel has a structure as shown in FIG. 1 , which includes a TFT substrate 1 and a CF substrate 2 disposed opposite to each other, and a liquid crystal layer 3 interposed between the TFT substrate 1 and the CF substrate 2, wherein the TFT substrate 1 is A lower alignment layer 11 is disposed on a side adjacent to the liquid crystal layer 3, an upper alignment layer 21 is disposed on a side of the CF substrate 2 adjacent to the liquid crystal layer 3, and a columnar spacer 4 is disposed between the upper alignment layer 21 and the lower alignment layer 11.
  • Post Spacer referred to as the PS column).
  • the material of the PS pillar 4 is generally sprayed in the liquid crystal layer 3 by a spraying process to support the liquid crystal layer 3 and control the thickness of the liquid crystal cell.
  • the material of the PS column 4 is mostly made of a conventional resin type material.
  • liquid crystal molecules close to the TFT substrate 1 and the CF substrate 2 side are subjected to liquid crystal alignment by rubbing alignment or photoalignment, and the PS pillar 4 is used. Since the surrounding liquid crystal molecules are affected by the material of the PS column 4, the alignment direction thereof may be deviated, resulting in a change in the deflection of the liquid crystal, as shown in FIG. 2, thereby causing a relatively serious light leakage phenomenon around the PS column 4.
  • FIG. 1 the alignment direction thereof may be deviated, resulting in a change in the deflection of the liquid crystal, as shown in FIG. 2, thereby causing a relatively serious light leakage phenomenon around the PS column 4.
  • the liquid crystal molecules of the normal alignment and the alignment abnormality are denoted by 31 and 32, respectively; in addition, for the flexible LCD display device, the adhesion between the PS pillar 4 and the upper alignment layer 21 and the lower alignment layer 11 is higher. Small, may cause the PS column 4 to fall off, resulting in a change in the thickness of the liquid crystal cell, affecting the display effect.
  • the present invention provides a column spacer, a liquid crystal display panel having the column spacer, and a method of fabricating the liquid crystal display panel, wherein the column spacer is made of a material Modified, so that when it is applied to a liquid crystal display panel, it controls the alignment of the liquid crystals around it, reduces light leakage, and increases the alignment
  • the adhesion between the layers ensures that the cell is thick and stable and the display is normal.
  • a column spacer for use in a liquid crystal display panel the material of the column spacer has a structure as shown in Formula 1:
  • the X group includes at least one of the formula 2-1, the formula 2-2, the formula 2-3, the formula 2-4, and the formula 2-5:
  • the Y group includes at least one structure of Formula 3-1 and Formula 3-2:
  • the molecular chain end of the X group and/or the molecular chain end of the Y group have a first group capable of chemically crosslinking with a material of the alignment layer in the liquid crystal display panel; and the X group and The / or Y group has a molecular side chain having a second group capable of generating a hydrogen bond or an intermolecular force with a material of the liquid crystal molecule in the liquid crystal display panel.
  • the first group is at least one selected from the group consisting of an azo group, an imide group, and an amine group;
  • the second group is selected from an alkyl chain of 8C to 20C, and a cyano group. At least one of a fluorine group, a hydroxyl group, and an ester group.
  • the material of the liquid crystal molecule has at least one of an alkyl chain, a cyano group, a fluorine group, a hydroxyl group, and an ester group of 8C to 20C.
  • the material of the alignment layer has at least one of an epoxy group, a hydroxyl group, and a carboxyl group.
  • the material of the column spacer has a structure as shown in Formula 4-1 or Formula 4-2:
  • the material of the columnar spacer has a network structure or a linear structure having a relative molecular mass of 50,000 to 100,000.
  • Another object of the present invention is to provide a liquid crystal display panel including a TFT substrate and a CF substrate disposed opposite to each other, and a liquid crystal layer interposed between the TFT substrate and the CF substrate, the TFT substrate being adjacent to the liquid crystal a side of the layer is provided with a lower alignment layer, an upper alignment layer is disposed on a side of the CF substrate adjacent to the liquid crystal layer, and a column spacer is disposed between the upper alignment layer and the lower alignment layer;
  • the columnar spacer is a columnar spacer as described above a pad; wherein a molecular chain end in the material of the column spacer has a chemical cross-linking relationship with a material of the upper alignment layer and the lower alignment layer, and a side chain in the material of the column spacer And having a hydrogen bond or an intermolecular force between the liquid crystal molecules of the liquid crystal layer, so that the liquid crystal molecules have an alignment with the upper alignment layer and the lower alignment layer.
  • Another object of the present invention is to provide a method for fabricating a liquid crystal display panel, comprising the steps of:
  • the TFT substrate and the CF substrate are paired, and the lower alignment layer and the upper alignment layer are Forming a column spacer to form a liquid crystal cell; wherein the column spacer is the column spacer according to any one of claims 1-7;
  • the method for fabricating the column spacer is selected from any one of spraying, photolithography, stamping, and self-assembly.
  • the present invention modifies the material of the column spacer so that when it is applied to a liquid crystal display panel, on the one hand, the material of the column spacer can generate, for example, a hydrogen bond or a liquid crystal molecule in the liquid crystal layer. Intermolecular forces, thereby changing the disordered arrangement of liquid crystal molecules around the column spacers in the prior art, so that these liquid crystal molecules form an alignment effect similar to or similar to the alignment layer, reducing internal stress between liquid crystal molecules, thereby reducing columnarity Light leakage around the spacer; on the other hand, the column spacer can chemically crosslink with the material of the alignment layer under ultraviolet light, thereby fixing the column spacer well Between the lower alignment layers, thereby, when the liquid crystal display panel is flexible or curved, the sliding of the column spacers does not easily occur, and at the same time, the column spacer material having a higher relative molecular mass is preferably provided. Higher strength and toughness ensure the stability of the upper and lower substrates and the thickness of the liquid crystal cell, ensuring the normal display
  • FIG. 1 is a schematic structural view of a liquid crystal display panel in the prior art
  • FIG. 2 is a schematic view showing an abnormal alignment of a liquid crystal around a columnar spacer in the prior art
  • Figure 3 is a schematic illustration of normal alignment of liquid crystals around a column spacer in accordance with the present invention.
  • the present invention provides a liquid crystal display panel comprising a TFT substrate and a CF substrate disposed opposite to each other, and a liquid crystal layer interposed between the TFT substrate and the CF substrate; wherein a side of the TFT substrate adjacent to the liquid crystal layer is provided with a lower alignment layer An upper alignment layer is disposed on a side of the CF substrate adjacent to the liquid crystal layer, a column spacer is disposed between the upper alignment layer and the lower alignment layer, and an active device is further included in the TFT substrate, and the CF substrate further includes a photoresist and an upper alignment.
  • a lower polarizer and an upper polarizer are respectively attached to the outer side of the TFT substrate and the CF substrate; the structure of the liquid crystal display panel is not special, and those skilled in the art can refer to the prior art. Let me repeat.
  • the material of the column spacer in the liquid crystal display panel of the present invention has chemical cross-linking between the material of the upper alignment layer and the lower alignment layer, and the column spacer
  • the material of the material has hydrogen bonding or intermolecular force between the liquid crystal molecules of the liquid crystal layer, so that the liquid crystal molecules around the column spacer can be the same as the liquid crystal molecules near the TFT substrate and the CF substrate side, and the alignment is generated.
  • the alignment of the layer and the lower alignment layer are consistent.
  • the chemical cross-linking function can also fix the columnar spacer well between the upper and lower alignment layers.
  • the sliding of the column spacers does not easily occur, thereby ensuring The stability of the TFT substrate and the CF substrate and the fixing of the thickness of the liquid crystal cell ensure the normal display screen.
  • the material of the column spacer has a structure as shown in Formula 1:
  • the X group includes at least one of the following formula 2-1, formula 2-2, formula 2-3, formula 2-4, and formula 2-5:
  • the Y group includes at least one of the following formula 3-1 and formula 3-2:
  • the molecular chain end of the X group and/or the molecular chain end of the Y group have a first group capable of chemically crosslinking the material of the upper and lower alignment layers, and the first group is preferably an azo group.
  • the molecular side chain has a second group capable of generating a hydrogen bond or an intermolecular force with a material of the liquid crystal molecule, and the second group is preferably an alkyl chain having a carbon chain length of 8 to 20, and a cyano group (-CN)
  • the alignment layer is an organic film layer containing a chemical group such as an epoxy group (-CH(O)CH-), a hydroxyl group (-OH), or a carboxyl group (-COOH), these are located at the end of the molecular chain.
  • the first group can be chemically cross-linked with the materials of the upper and lower alignment layers; at the same time, since the material of the liquid crystal molecules generally has an alkyl chain of 8C to 20C, a cyano group, a fluorine group, a hydroxyl group, an ester group, etc.
  • the group, these second groups in the side chain are also similar to the polar liquid crystal molecules, so that hydrogen bonding or intermolecular force can be generated between the liquid crystal molecules to change the liquid crystal molecules around the column spacers.
  • the arrangement of the liquid crystal molecules forms an alignment effect similar to or similar to that of the alignment layer, reduces internal stress between liquid crystal molecules, and thereby reduces light leakage around the column spacers.
  • the material of the column spacer provided by the present invention is according to any one of the formula 2-1 to the formula 2-5 and the structure of any one of the formula 3-1 to the formula 3-2.
  • the form is connected to form a basic skeleton of the molecule; and on the basis of the skeleton, the ends of the molecular chain on both sides thereof have the first group capable of chemically crosslinking with the materials of the upper and lower alignment layers, and the molecular side
  • the chain has the above-mentioned second group capable of generating hydrogen bonds or intermolecular forces with the material of the liquid crystal molecules; it is worth noting that these first groups and the second groups may be groups of the skeleton itself, It may be another substituent attached to the backbone.
  • the material of the columnar spacer has a network structure or a linear structure having a relative molecular mass of 50,000 to 100,000; thus, the material of the column spacer having a large relative molecular mass also has higher strength. And toughness, thereby further ensuring the stability of the TFT substrate and the CF substrate and fixing the thickness of the liquid crystal cell.
  • the material of the above-mentioned columnar spacer will be described by way of a specific embodiment.
  • the material of the columnar spacer in the liquid crystal display panel according to the present invention is not limited to the following embodiments, and the embodiments are Provide only examples of some of the specific materials.
  • the material of the column spacer provided in this embodiment has the structure shown in Formula 4-1:
  • the preparation process of the material of the column spacer of the present embodiment is as follows:
  • the method includes a three-step reaction step: the reaction 1 is a methylolation reaction of melamine and formaldehyde under weak alkaline conditions, specifically, reacting at 50 ° C to 80 ° C for 2 h to 10 h to form hexamethylol melamine; reaction 2 is The hexamethylol melamine is partially etherified in an acidic medium of an alcohol solution, and the reaction time is controlled to be 1 h to 3 h to form a monomethylol derivative; the reaction 3 is a monomethylol derivative which is esterified under alkaline conditions. The reaction produces a monomethylol monoester derivative; thus, a polymer having a linear structure as shown in Formula 4-1 is formed.
  • the reaction 1 is a methylolation reaction of melamine and formaldehyde under weak alkaline conditions, specifically, reacting at 50 ° C to 80 ° C for 2 h to 10 h to form hexamethylol melamine
  • reaction 2 is The
  • the material of the column spacer provided in this embodiment has a structure as shown in Formula 4-2:
  • the preparation process of the material of the column spacer of the present embodiment is as follows:
  • the method includes a two-step reaction step: the reaction 1 is a complete hydroxylation reaction of melamine and excess formaldehyde under weak alkaline conditions, specifically, reacting at 50 ° C to 80 ° C for 2 h to 10 h to form hexamethylol melamine; reaction 2 is The hydroxyammonia condensation reaction between hexamethylol melamine and melamine under alkaline conditions results in a polymer having a bulk network structure as shown in Formula 4-2 due to a large number of reaction sites of the reactants.
  • the manufacturing method of the above liquid crystal display panel includes the following steps:
  • step S1 a TFT substrate and a CF substrate which are oppositely disposed are provided.
  • a lower alignment layer is provided on a side of the TFT substrate facing the CF substrate
  • an upper alignment layer is provided on a side of the CF substrate facing the TFT substrate.
  • Step S2 After coating the liquid crystal on the lower alignment layer and/or the upper alignment layer, the TFT substrate and the CF substrate are paired, and a column spacer is formed between the lower alignment layer and the upper alignment layer to form a liquid crystal cell.
  • the column spacer is made here, that is, the material of the column spacer as described above, and can be fabricated by any process of spraying, photolithography, imprinting, self-assembly, and the specific manufacturing process here. No longer.
  • Step S3 irradiating the liquid crystal cell with ultraviolet light, so that the molecular chain end in the material of the column spacer material is chemically cross-linked with the material of the lower alignment layer and the upper alignment layer to obtain a liquid crystal display panel.
  • the liquid crystal cell obtained by irradiating ultraviolet light with a wavelength of 245 nm for 30 min to 60 min because the cover plate in the packaged liquid crystal cell is transparent, the material of the column spacer can be combined with the upper and lower alignment layers.
  • the chemical cross-linking reaction occurs between the materials under the action of ultraviolet light, and the degree of cross-linking can be determined by means of characterization such as infrared spectroscopy.

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Abstract

一种柱状隔垫物(4)，具有柱状隔垫物(4)的液晶显示面板及制作方法。柱状隔垫物(4)的材料具有如式1所示的结构；其中，X基团包括式2-1～式2-5中的至少一种结构，式2-1，式2-2，式2-3，式2-4，式2-5，Y基团包括式3-1、式3-2中的至少一种结构，X基团的分子链末端和/或Y基团的分子链末端具有能够与配向层的材料发生化学交联作用的基团；X基团的分子侧链和/或Y基团的分子侧链具有能够与液晶分子(31)的材料之间产生氢键或分子间作用力的基团。柱状隔垫物(4)一方面通过与液晶分子(31)之间产生的氢键或分子间作用力而改变了其周围液晶分子(31)杂乱无章的排列情况，减少漏光情况；另一方面在紫外光的照射下与配向层的材料之间发生化学交联，更好地固定在上下配向层之间。

Description

液晶显示面板及其制作方法、柱状隔垫物 技术领域
本发明属于液晶显示面板技术领域，具体地讲，涉及一种液晶显示面板中的柱状隔垫物、具有该柱状隔垫物的液晶显示面板、以及该液晶显示面板的制作方法。
背景技术
一般地，液晶显示面板具有如图1所示的结构，其包括相对设置的TFT基板1和CF基板2、夹设于TFT基板1和CF基板2之间的液晶层3，其中，TFT基板1靠近液晶层3的一侧设有下配向层11，CF基板2靠近液晶层3的一侧设有上配向层21，上配向层21和下配向层11之间设有柱状隔垫物4(Post Spacer，简称PS柱)。
在传统的液晶显示面板中，一般采用喷涂工艺将PS柱4的材料喷洒在液晶层3中，以起到支撑液晶层3、控制液晶盒厚度的目的。然而，PS柱4的材料多采用一些传统的树脂型材料，在液晶层3中，靠近TFT基板1和CF基板2侧的液晶分子通过摩擦配向或者光配向的方式进行液晶配向，而PS柱4周围的液晶分子由于受到PS柱4的材料的影响，其配向的方向会出现偏差，导致液晶的偏转发生变化，如图2所示，由此在PS柱4的周围产生较为严重的漏光现象，在图2中，分别以31和32表示配向正常和配向异常的液晶分子；另外，对于可挠式LCD显示装置，由于PS柱4与上配向层21、下配向层11之间粘附力较小，可能会造成PS柱4的脱落，从而导致液晶盒厚发生变化，影响显示效果。
发明内容
为解决上述现有技术存在的问题，本发明提供了一种柱状隔垫物、以及具有该柱状隔垫物的液晶显示面板及该液晶显示面板的制作方法，该柱状隔垫物通过对材料进行改性，从而当其应用于液晶显示面板中时，既控制了其周围的液晶的配向，减少漏光，又增加了与配向 层之间的粘附力，保证液晶盒厚稳定和显示画面正常。
为了达到上述发明目的，本发明采用了如下的技术方案：
一种柱状隔垫物，应用于液晶显示面板中；所述柱状隔垫物的材料具有如式1所示的结构：
Figure PCTCN2017097191-appb-000001
所述X基团包括式2-1、式2-2、式2-3、式2-4、式2-5中的至少一种结构：
Figure PCTCN2017097191-appb-000002
所述Y基团包括式3-1、式3-2中的至少一种结构：
Figure PCTCN2017097191-appb-000003
Figure PCTCN2017097191-appb-000004
其中，X基团的分子链末端和/或Y基团的分子链末端具有能够与所述液晶显示面板中配向层的材料发生化学交联作用的第一基团；并且所述X基团和/或Y基团具有分子侧链，所述分子侧链具有能够与所述液晶显示面板中液晶分子的材料之间产生氢键或分子间作用力的第二基团。
进一步地，所述第一基团选自偶氮基团、酰亚胺基团、胺基基团中的至少一种；所述第二基团选自8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种。
进一步地，所述液晶分子的材料具有8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种基团。
进一步地，所述配向层的材料具有环氧基团、羟基、羧基中的至少一种基团。
进一步地，所述柱状隔垫物的材料具有如式4-1或式4-2所示的结构：
Figure PCTCN2017097191-appb-000005
Figure PCTCN2017097191-appb-000006
进一步地，所述柱状隔垫物的材料具有网状结构、或具有相对分子质量为50000～100000的线性结构。
本发明的另一目的在于提供一种液晶显示面板，包括相对设置的TFT基板和CF基板，夹设于所述TFT基板和所述CF基板之间的液晶层，所述TFT基板靠近所述液晶层的一侧设有下配向层，所述CF基板靠近所述液晶层的一侧设有上配向层，所述上配向层和所述下配向层之间设有柱状隔垫物；所述柱状隔垫物为如上任一所述的柱状隔 垫物；其中，所述柱状隔垫物的材料中的分子链末端与所述上配向层、下配向层的材料之间具有化学交联作用，所述柱状隔垫物的材料中的侧链与所述液晶层的液晶分子之间具有氢键或分子间作用力，以使所述液晶分子具有与所述上配向层、下配向层相一致的配向。
本发明的另一目的还在于提供一种液晶显示面板的制作方法，包括步骤：
S1、提供相对设置的TFT基板和CF基板；其中，所述TFT基板的朝向所述CF基板的一侧设有下配向层，所述CF基板的朝向所述TFT基板的一侧设有上配向层；
S2、在所述下配向层和/或所述上配向层上涂布液晶后，将所述TFT基板和所述CF基板进行对盒，并在所述下配向层和所述上配向层之间制作柱状隔垫物，形成液晶盒；其中，所述柱状隔垫物为如权利要求1-7任一所述的柱状隔垫物；
S3、采用紫外光照射所述液晶盒，使得所述柱状隔垫物的材料中的分子链末端与所述下配向层、上配向层的材料发生化学交联反应，获得液晶显示面板。
进一步地，所述柱状隔垫物的制作方法选自喷涂、光刻、压印、自组装中的任意一种。
本发明通过对柱状隔垫物的材料进行改性，使得当其应用于液晶显示面板中时，一方面，该柱状隔垫物的材料能与液晶层中的液晶分子之间产生例如氢键或分子间作用力，从而改变现有技术中柱状隔垫物周围液晶分子杂乱无章的排列情况，使得这些液晶分子形成与配向层相一致或类似的配向效果，降低液晶分子间的内应力，从而减少柱状隔垫物周围的漏光情况；另一方面，该柱状隔垫物能够在紫外光的照射下，与配向层的材料之间发生化学交联反应，从而将柱状隔垫物很好地固定在上、下配向层之间，由此，当液晶显示面板可挠或弯曲时，不会轻易发生柱状隔垫物的滑动，同时，优选具有较高相对分子质量的柱状隔垫物材料，也可具有更高的强度和韧性，从而保证了上下基板的稳定和液晶盒厚的固定，保证了显示画面的正常。
附图说明
通过结合附图进行的以下描述，本发明的实施例的上述和其它方面、特点和优点将变得更加清楚，附图中：
图1是现有技术中液晶显示面板的结构示意图；
图2是现有技术中柱状隔垫物周围液晶配向异常的示意图；
图3是根据本发明的柱状隔垫物周围液晶配向正常的示意图。
具体实施方式
以下，将参照附图来详细描述本发明的实施例。然而，可以以许多不同的形式来实施本发明，并且本发明不应该被解释为限制于这里阐述的具体实施例。相反，提供这些实施例是为了解释本发明的原理及其实际应用，从而使本领域的其他技术人员能够理解本发明的各种实施例和适合于特定预期应用的各种修改。在附图中，为了清楚起见，可以夸大元件的形状和尺寸，并且相同的标号将始终被用于表示相同或相似的元件。
本发明提供了一种液晶显示面板，其包括相对设置的TFT基板和CF基板、夹设于TFT基板和CF基板之间的液晶层；其中，TFT基板靠近液晶层的一侧设有下配向层，CF基板靠近液晶层的一侧设有上配向层，上配向层和下配向层之间设有柱状隔垫物，TFT基板中还包括有源器件，CF基板中还包括光阻、上配向层；TFT基板和CF基板背离彼此的外侧还分别贴设有下偏光片和上偏光片；该液晶显示面板的结构并无特殊之处，本领域技术人员参照现有技术即可，此处不再赘述。
要尤为强调的是本发明的液晶显示面板中的柱状隔垫物的材料，该柱状隔垫物的材料与上配向层、下配向层的材料之间具有化学交联作用，并且该柱状隔垫物的材料与液晶层的液晶分子之间具有氢键作用或分子间作用力，以使该柱状隔垫物周围的液晶分子能够与靠近TFT基板及CF基板侧的液晶分子相同，产生与上配向层、下配向层相一致的配向。
如此，当本发明的液晶显示面板中使用上述柱状隔垫物时，一方面，该柱状隔垫物的材料与液晶层中的液晶分子之间产生的氢键作用或分子间作用力可以改变现有技术中柱状隔垫物周围液晶分子杂乱无章的排列情况，使得这些液晶分子形成与配向层相一致或类似的配向效果，如图3所示，降低了液晶分子间的内应力，柱状隔垫物4周围的液晶分子的配向也与靠近TFT基板和CF基板侧的液晶分子31配向一致，从而减少柱状隔垫物周围的漏光情况；另一方面，其与上、下配向层的材料之间存在的化学交联作用也能够将该柱状隔垫物很好地固定在上、下配向层之间，当该液晶显示面板可挠或弯曲时，不会轻易发生柱状隔垫物的滑动，从而保证了TFT基板及CF基板的稳定和液晶盒厚的固定，保证了显示画面的正常。
具体地，该柱状隔垫物的材料具有如式1所示的结构：
Figure PCTCN2017097191-appb-000007
X基团包括下述式2-1、式2-2、式2-3、式2-4、式2-5中的至少一种结构：
Figure PCTCN2017097191-appb-000008
而Y基团则包括下述式3-1、式3-2中的至少一种结构：
Figure PCTCN2017097191-appb-000009
其中，X基团的分子链末端和/或Y基团的分子链末端具有能够与上、下配向层的材料发生化学交联作用的第一基团，第一基团优选为偶氮基团(-N＝N-)、酰亚胺基团(-CO-NH-)、胺基基团(-NH-)中的至少一种；并且X基团和/或Y基团具有分子侧链，分子侧链具有能够与液晶分子的材料之间产生氢键或分子间作用力的第二基团，第二基团优选为碳链长度为8～20的烷基链、氰基(-CN)、氟基(-F)、羟基(-OH)、酯基(-COOR)中的至少一种。由于配向层是一类含有环氧基团(-CH(O)CH-)、羟基(-OH)、羧基(-COOH)等化学基团的有机膜层，由此，这些位于分子链末端的第一基团即可与上、下配向层的材料之间发生化学交联作用；同时，由于液晶分子的材料一般具有8C～20C的烷基链、氰基、氟基、羟基、酯基等基团，这些位于侧链中的第二基团也与极性的液晶分子相类似，从而可与液晶分子之间产生氢键作用或分子间作用力，以改变柱状隔垫物周围液晶分子杂乱无章的排列情况，使得这些液晶分子形成与配向层相一致或类似的配向效果，降低液晶分子间的内应力，从而减少柱状隔垫物周围的漏光情况。
换句话说，本发明提供的柱状隔垫物的材料以式2-1～式2-5中的任意一种结构与式3-1～式3-2中的任意一种结构按照式1中的形式相连，形成了分子基本骨架；而在该骨架的基础上，其两侧的分子链末端具有上述能够与上、下配向层的材料发生化学交联作用的第一基团，并且分子侧链具有上述能够与液晶分子的材料之间产生氢键或分子间作用力的第二基团；值得说明的是，这些第一基团及第二基团可以是该骨架自身的基团，也可以是连接在该骨架上的其他取代基。
进一步地，所述柱状隔垫物的材料具有网状结构、或具有相对分子质量为50000～100000的线性结构；如此，具有较大相对分子质量的柱状隔垫物的材料也具有更高的强度和韧性，从而进一步地保证TFT基板及CF基板的稳定和液晶盒厚的固定。
以下，将通过具体的实施例来说明上述柱状隔垫物的材料，当然，根据本发明的液晶显示面板中的柱状隔垫物的材料并不限于下述实施例所述，而这些实施例的提供仅是其中某些具体材料的示例。
实施例1
本实施例提供的柱状隔垫物的材料具有如式4-1所示的结构：
Figure PCTCN2017097191-appb-000010
具体来讲，本实施例的柱状隔垫物的材料的制备过程参见如下反应式：
Figure PCTCN2017097191-appb-000011
其中包括三步反应步骤：反应1为三聚氰胺与甲醛在弱碱性条件下的羟甲基化反应，具体为在50℃～80℃下反应2h～10h，生成六羟甲基三聚氰胺；反应2为六羟甲基三聚氰胺在醇溶液的酸性介质中进行部分醚化反应，反应时间控制为1h～3h，生成单羟甲基衍生物；反应3为单羟甲基衍生物在碱性条件下发生酯化反应，生成单羟甲基单酯基衍生物；由此，即形成了如式4-1所示的具有线性结构的聚合物。
实施例2
本实施例提供的柱状隔垫物的材料具有如式4-2所示的结构：
Figure PCTCN2017097191-appb-000012
具体来讲，本实施例的柱状隔垫物的材料的制备过程参见如下反应式：
Figure PCTCN2017097191-appb-000013
其中包括2步反应步骤：反应1为三聚氰胺与过量甲醛在弱碱性条件下的完全羟化反应，具体为在50℃～80℃下反应2h～10h，生成六羟甲基三聚氰胺；反应2为六羟甲基三聚氰胺与三聚氰胺在碱性条件下发生羟氨缩合反应，由于反应物反应位点较多，即生成了如式4-2所示的具有体形网状结构的聚合物。
值得说明的是，在本发明的液晶显示面板的制作过程中，除参照一般液晶显示面板的制作方法以外，还在液晶盒制作完成后，对柱状隔垫物的材料进行处理，才可形成液晶显示面板。具体来讲，上述液晶显示面板的制作方法包括下述步骤：
步骤S1、提供相对设置的TFT基板和CF基板。
具体来讲，TFT基板的朝向CF基板的一侧设有下配向层，CF基板的朝向TFT基板的一侧设有上配向层。
步骤S2、在下配向层和/或上配向层上涂布液晶后，将TFT基板和CF基板进行对盒，并在下配向层和上配向层之间制作柱状隔垫物，形成液晶盒。
具体来讲，此处制作柱状隔垫物即采用如上所述的柱状隔垫物的材料，并且可通过喷涂、光刻、压印、自组装中的任意工艺来制作，此处对具体制作工艺不再赘述。
步骤S3、采用紫外光照射液晶盒，使得柱状隔垫物的材料中的分子链末端与下配向层、上配向层的材料发生化学交联反应，获得液晶显示面板。
优选地，以波长为245nm的紫外光照射获得的液晶盒30min～60min，由于已封装完成的液晶盒中的盖板是透明的，因此，柱状隔垫物的材料即可与上、下配向层的材料之间在紫外光的作用下发生化学交联反应，具体可通过红外光谱测试等表征手段对交联程度进行测定。
如此，仅需以本申请所提供的柱状隔垫物替代现有技术中的柱状隔垫物，并且在封装获得液晶盒后，增加一步紫外光照射处理，即可同时解决现有技术中的液晶显示面板所存在的柱状隔垫物周围的液晶分子的偏转发生变化而导致其周围较为严重的漏光现象、以及当液晶显示面板可挠或弯曲时易造成柱状隔垫物脱落而导致液晶盒厚发生变化，影响显示效果的问题。
虽然已经参照特定实施例示出并描述了本发明，但是本领域的技术人员将理解：在不脱离由权利要求及其等同物限定的本发明的精神和范围的情况下，可在此进行形式和细节上的各种变化。

Claims (20)

  1. 一种柱状隔垫物，应用于液晶显示面板中；其中，所述柱状隔垫物的材料具有如式1所示的结构：
    Figure PCTCN2017097191-appb-100001
    所述X基团包括式2-1、式2-2、式2-3、式2-4、式2-5中的至少一种结构：
    Figure PCTCN2017097191-appb-100002
    所述Y基团包括式3-1、式3-2中的至少一种结构：
    Figure PCTCN2017097191-appb-100003
    其中，X基团的分子链末端和/或Y基团的分子链末端具有能够与所述液晶显示面板中配向层的材料发生化学交联作用的第一基团；并且所述X基团和/或Y基团具有分子侧链，所述分子侧链具有能够与所述液晶显示面板中液晶分子的材料之间产生氢键或分子间作用力的第二基团。
  2. 根据权利要求1所述的柱状隔垫物，其中，所述第一基团选自偶氮基团、酰亚胺基团、胺基基团中的至少一种；所述第二基团选自8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种。
  3. 根据权利要求2所述的柱状隔垫物，其中，所述液晶分子的材料具有8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种基团。
  4. 根据权利要求2所述的柱状隔垫物，其中，所述配向层的材料具有环氧基团、羟基、羧基中的至少一种基团。
  5. 根据权利要求2所述的柱状隔垫物，其中，所述柱状隔垫物的材料具有如式4-1或式4-2所示的结构：
    Figure PCTCN2017097191-appb-100004
  6. 根据权利要求5所述的柱状隔垫物，其中，所述柱状隔垫物的材料具有网状结构、或具有相对分子质量为50000～100000的线性结构。
  7. 一种液晶显示面板，包括相对设置的TFT基板和CF基板，夹设于所述TFT基板和所述CF基板之间的液晶层，所述TFT基板靠近所述液晶层的一侧设有下配向层，所述CF基板靠近所述液晶层 的一侧设有上配向层，所述上配向层和所述下配向层之间设有柱状隔垫物；其中，所述柱状隔垫物的材料具有如式1所示的结构：
    Figure PCTCN2017097191-appb-100005
    所述X基团包括式2-1、式2-2、式2-3、式2-4、式2-5中的至少一种结构：
    Figure PCTCN2017097191-appb-100006
    所述Y基团包括式3-1、式3-2中的至少一种结构：
    Figure PCTCN2017097191-appb-100007
    X基团的分子链末端和/或Y基团的分子链末端具有能够与所述上配向层、下配向层的材料发生化学交联作用的第一基团；并且所述X基团和/或Y基团具有分子侧链，所述分子侧链具有能够与所述液晶层中液晶分子的材料之间产生氢键或分子间作用力的第二基团；
    其中，所述柱状隔垫物的材料中的分子链末端与所述上配向层、下配向层的材料之间具有化学交联作用，所述柱状隔垫物的材料中的侧链与所述液晶分子之间具有氢键或分子间作用力，以使所述液晶分 子具有与所述上配向层、下配向层相一致的配向。
  8. 根据权利要求7所述的液晶显示面板，其中，所述第一基团选自偶氮基团、酰亚胺基团、胺基基团中的至少一种；所述第二基团选自8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种。
  9. 根据权利要求8所述的液晶显示面板，其中，所述液晶分子的材料具有8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种基团；所述上配向层、下配向层的材料均具有环氧基团、羟基、羧基中的至少一种基团。
  10. 根据权利要求8所述的液晶显示面板，其中，所述柱状隔垫物的材料具有如式4-1或式4-2所示的结构：
    Figure PCTCN2017097191-appb-100008
  11. 根据权利要求8所述的液晶显示面板，其中，所述柱状隔垫物的材料具有网状结构、或具有相对分子质量为50000～100000的线性结构。
  12. 根据权利要求10所述的液晶显示面板，其中，所述柱状隔垫物的材料具有网状结构、或具有相对分子质量为50000～100000的线性结构。
  13. 一种液晶显示面板的制作方法，其中，包括步骤：
    S1、提供相对设置的TFT基板和CF基板；其中，所述TFT基板的朝向所述CF基板的一侧设有下配向层，所述CF基板的朝向所述TFT基板的一侧设有上配向层；
    S2、在所述下配向层和/或所述上配向层上涂布液晶后，将所述TFT基板和所述CF基板进行对盒，并在所述下配向层和所述上配向层之间制作柱状隔垫物，形成液晶盒；其中，所述柱状隔垫物的材料具有如式1所示的结构：
    Figure PCTCN2017097191-appb-100009
    所述X基团包括式2-1、式2-2、式2-3、式2-4、式2-5中的至少一种结构：
    Figure PCTCN2017097191-appb-100010
    所述Y基团包括式3-1、式3-2中的至少一种结构：
    Figure PCTCN2017097191-appb-100011
    其中，X基团的分子链末端和/或Y基团的分子链末端具有能够 与所述上配向层、下配向层的材料发生化学交联作用的第一基团；并且所述X基团和/或Y基团具有分子侧链，所述分子侧链具有能够与所述液晶的材料之间产生氢键或分子间作用力的第二基团；
    S3、采用紫外光照射所述液晶盒，使得所述柱状隔垫物的材料中的分子链末端与所述下配向层、上配向层的材料发生化学交联反应，获得液晶显示面板。
  14. 根据权利要求13所述的制作方法，其中，所述第一基团选自偶氮基团、酰亚胺基团、胺基基团中的至少一种；所述第二基团选自8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种。
  15. 根据权利要求14所述的制作方法，其中，所述液晶的材料具有8C～20C的烷基链、氰基、氟基、羟基、酯基中的至少一种基团；所述上配向层、下配向层的材料均具有环氧基团、羟基、羧基中的至少一种基团。
  16. 根据权利要求14所述的制作方法，其中，所述柱状隔垫物的材料具有如式4-1或式4-2所示的结构：
    Figure PCTCN2017097191-appb-100012
  17. 根据权利要求14所述的制作方法，其中，所述柱状隔垫物 的材料具有网状结构、或具有相对分子质量为50000～100000的线性结构。
  18. 根据权利要求16所述的制作方法，其中，所述柱状隔垫物的材料具有网状结构、或具有相对分子质量为50000～100000的线性结构。
  19. 根据权利要求13所述的制作方法，其中，所述柱状隔垫物的制作方法选自喷涂、光刻、压印、自组装中的任意一种。
  20. 根据权利要求18所述的制作方法，其中，所述柱状隔垫物的制作方法选自喷涂、光刻、压印、自组装中的任意一种。
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