WO2017031775A1 - 支化型有机硅材料及制备液晶面板的方法 - Google Patents

支化型有机硅材料及制备液晶面板的方法 Download PDF

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WO2017031775A1
WO2017031775A1 PCT/CN2015/088752 CN2015088752W WO2017031775A1 WO 2017031775 A1 WO2017031775 A1 WO 2017031775A1 CN 2015088752 W CN2015088752 W CN 2015088752W WO 2017031775 A1 WO2017031775 A1 WO 2017031775A1
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group
substrate
liquid crystal
atom
silicone material
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French (fr)
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兰松
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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 RU2018109278A priority Critical patent/RU2683825C1/ru
Priority to KR1020187007583A priority patent/KR102154414B1/ko
Priority to GB1802219.4A priority patent/GB2556587B/en
Priority to JP2018510119A priority patent/JP6661752B2/ja
Priority to US14/897,783 priority patent/US10377950B2/en
Publication of WO2017031775A1 publication Critical patent/WO2017031775A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133742—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers for homeotropic alignment
    • 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
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • 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
    • G02F1/1341—Filling or closing of cells
    • 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
    • G02F1/1341—Filling or closing of cells
    • G02F1/13415—Drop filling process
    • 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
    • G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362—Active matrix addressed cells
    • G02F1/1368—Active matrix addressed cells in which the switching element is a three-electrode device

Definitions

  • the invention relates to the field of liquid crystal display and relates to a branched type silicone material.
  • the described silicone material is capable of orienting the LC vertically.
  • the invention also relates to the use of the silicone material.
  • a film material is provided, the main function of which is to arrange the liquid crystal molecules in a certain direction, which is called an alignment film (common polyimide (PI) material).
  • PI common polyimide
  • the phase-matching membrane is mainly classified into a friction phase-type PI material and a photo-phase-type PI material.
  • the friction phase is liable to cause problems such as dust particles, static electricity, and brush marks to reduce the process yield.
  • the optical phase matching material can avoid these problems, the heat resistance and aging resistance are limited due to limited material properties, and the ability to anchor LC molecules is also weak, thereby affecting the quality of the panel.
  • the PI material itself has high polarity and high water absorption, storage and transportation are prone to deterioration, resulting in uneven phase distribution, and the PI material is expensive, and the process of film formation on the TFT-LCD is complicated, resulting in panel cost. improve.
  • the present invention is intended to provide a new material and method capable of aligning liquid crystal molecules in a TFT-LCD without the PI film, which greatly simplifies the TFT-LCD process and also reduces TFT. - The production cost of LCD.
  • the present application provides a branched type silicone material used in a TFT-LCD, which can align liquid crystal molecules in the case of eliminating the PI film, thereby greatly reducing production.
  • the cost of the panel is a branched type silicone material used in a TFT-LCD, which can align liquid crystal molecules in the case of eliminating the PI film, thereby greatly reducing production.
  • branched silicone material having a molecular formula as shown in Formula I,
  • R 1 is directly bonded to a silicon atom
  • R 2 is bonded to a silicon atom through an oxygen atom, and adjacent silicon atoms are connected through an oxygen atom
  • n is an integer of 2-15
  • R 2 is a C 1 -C 5 alkyl group
  • the hetero atom comprises a halogen atom, a nitro group, an alkoxy group or the like.
  • the silicone material has a structure mainly divided into two parts of a head group A and a tail group B of a plurality of chains.
  • A refers to the Si n O 2n+1 portion, mainly a branched structure;
  • B refers to two parts of R 1 n R 2 n+2 , that is, a structure of a plurality of branches.
  • the silicone branched small molecule material of the present invention combines the characteristics of organic materials and inorganic materials, on the one hand, has low surface tension and low surface energy; on the other hand, because - The bond energy of Si-O- (462 kJ/mol) is higher than the bond energy of -CC- (347 kJ/mol), which increases the temperature resistance and oxidation resistance of the material itself.
  • —Si-O- is also a polar anchoring group that can be anchored to other materials.
  • the branched silicone material preferably has an integer of from 2 to 10, more preferably an integer of from 2 to 6.
  • R 2 is methyl, ethyl or propyl.
  • the H atom in the phenylene group or the cycloalkylene group is optionally substituted or unsubstituted with a halogen atom.
  • R 3 is hydrogen, methyl or ethyl.
  • R 2 is a methyl group, an ethyl group or a propyl group, and R 1 is selected from the group consisting of
  • organosilicon materials when n is 2, 3 or 4, are respectively represented by formula II, III or IV:
  • the branched silicone material provided according to the present invention has low surface tension and low energy, and has high temperature resistance and oxidation resistance.
  • the silicon-oxygen bond contained in the silicone material can interact with other atoms to function as an anchor.
  • the branched silicone material according to the present invention can be obtained by subjecting a silicon compound represented by the general formula R 1 Si(OR 2 ) 3 to controlled hydrolysis.
  • the silicon compound represented by the above formula R 1 Si(OR 2 ) 3 can be obtained by a method such as condensation.
  • the branched silicone material makes the liquid crystal on the surface of the first substrate and the second substrate The surfaces are arranged vertically;
  • the amount of the branched silicone material in the mixed solution is 0.1 to 5% by weight.
  • the structure of the silicone material is mainly divided into two parts of a head group A and a tail group B of a plurality of chains.
  • A refers to the Si n O 2n+1 part, mainly a branched structure, and a plurality of siloxy groups together form a head group, which can enhance the adhesion of the polar group on the surface of the substrate and enhance the anchorage with the substrate. effect.
  • the -Si-O- is a polar anchoring group whose primary function is to anchor the head group to the surface of the substrate.
  • B refers to two parts of R 1 n R 2 n+2 , that is, a structure of a plurality of branches.
  • the main function of the tail group is to vertically align the liquid crystal molecules in a steric hindrance manner.
  • the design of multiple tail groups enhances the vertical orientation of the LC molecules.
  • the reactive monomer comprises a combination of an epoxy resin and a fatty amine epoxy curing agent, an acrylate and a derivative thereof, and methacrylic acid. At least one of an ester and a derivative thereof and styrene and a derivative thereof.
  • the reactive monomer is a radiation-polymerizable compound commonly used in the field of polymers, and will not be described in detail herein.
  • the amount of the reactive monomer is from 0.01 to 0.1% by weight.
  • the polymerization is radiation polymerization.
  • the light source used for the radiation polymerization was UV light at 313 nm.
  • the radiation dose is 0.1-1 mW/cm 2 .
  • the applied voltage is 15-25 volts.
  • the first substrate is a filter film (CF) substrate
  • the second substrate is a thin film transistor (TFT) substrate.
  • TFT thin film transistor
  • the mechanism of action is mainly as follows: 1
  • the mechanism of action with ITO is to utilize the lone on the oxygen atom in the -Si-O- An empty p-orbital or d-orbital impurity in the ITO in the ITO of the electron and the substrate surface (extra-core electron arrangement: In:[Kr]4d105s25p1) or tin atom (external electron arrangement: Sn:[Kr]4d105s25p2)
  • the combination of the two bonds with SiNx utilizes an oxygen atom in the -Si-O- to interact with the nitrogen atom in the SiNx.
  • the branched type silicone material combines the characteristics of an organic material and an inorganic material, has a low surface tension, a low surface energy, and has high temperature resistance and oxidation resistance.
  • A has a plurality of -Si-O- groups, which mainly enhance the anchoring action with the substrate.
  • the structure of B having a plurality of branches mainly improves the vertical orientation of the LC.
  • the PI oriented film in the TFT-LCD is replaced by the branched organic silicon material, the PI segment process is omitted, the preparation process of the liquid crystal panel is greatly simplified, and the panel is reduced. Cost of production.
  • a liquid crystal panel comprising: a first substrate, a second substrate, a liquid crystal, a polymer, and the above-described branched silicone material.
  • the liquid crystals can be arranged in a certain direction.
  • the polymer is a polymer obtained by polymerizing a reactive monomer.
  • the liquid crystal of the present invention is a liquid crystal molecule commonly used in the art, and will not be described herein.
  • the first substrate is a filter film substrate
  • the second substrate is a thin film transistor substrate.
  • the first substrate and the second substrate are free of an alignment film.
  • a novel branched silicone material having a plurality of siloxy groups and a plurality of branched structures.
  • the branched type silicone material when used in the field of LCD, on the one hand, it can form an anchoring action with the substrate, and the effect of a plurality of branches can improve the vertical alignment effect of the liquid crystal LC.
  • the branched silicone material provided by the present invention can be used for preparing a liquid crystal panel, and a liquid crystal panel can be produced without an alignment film.
  • Figure 1 is a schematic view showing the structure of a branched silicone material according to the present invention.
  • FIG. 2 is a schematic view showing the action of a branched silicone material according to an embodiment of the present invention
  • FIG. 3 is a process flow diagram of preparing a liquid crystal panel according to an embodiment of the present invention.
  • FIG. 4 is a schematic view of a liquid crystal panel in accordance with an embodiment of the present invention.
  • FIG. 1 is a schematic view showing the structure of a branched silicone material according to the present invention.
  • the structure of the branched type silicone material is mainly divided into two parts of a head group A and a tail group B of a plurality of chains.
  • A refers to the Si n O 2n+1 portion, mainly a branched structure;
  • B refers to two parts of R 1 n R 2 n+2 , that is, a structure of a plurality of branches.
  • the first substrate 1 is a CF substrate
  • the second substrate 6 is a TFT substrate.
  • Indium tin oxide layers (ITO) 2 and 7 are respectively disposed on the first substrate 1 and the second substrate 6, wherein the ITO only partially covers the second substrate 6.
  • ITO Indium tin oxide layers
  • the liquid crystal molecules are oriented vertically.
  • the silicone material 5 functions as a vertical alignment agent.
  • FIG. 3 is a process flow diagram of preparing a liquid crystal panel in accordance with one embodiment of the present invention. a) providing a casing including the first substrate 1 and the second substrate 6, both of which do not contain an alignment film; and the reactive monomer 4 and the branched silicone material 5 are added Into the liquid crystal 3, a mixed solution is prepared; the mixed solution is dropped between the first substrate 1 and the second substrate 6 in the casing, and at this time, the branched silicone material 5 makes liquid crystal 3 is vertically arranged on the surface of the first substrate 1 and the surface of the second substrate 6. b) Applying a voltage of 20 V causes the liquid crystal to deflect.
  • the reaction type monomer 4 is polymerized on the surface of the first substrate 1 and the surface of the second substrate 6 under irradiation of UV light at 313 nm (0.5 mW/cm 2 ) to obtain a polymer 9, and the resulting polymerization is carried out.
  • the object 9 anchors the liquid crystal.
  • the liquid crystal 3 in the panel has a pretilt angle 8.
  • the reactive monomer used is methyl acrylate.
  • the amount of the reactive monomer used was 0.05% by weight, and the amount of the branched silicone material was 3% by weight.
  • n 3
  • R 2 is a methyl group.
  • Fig. 4 shows a liquid crystal panel obtained according to the present invention, in which the liquid crystal molecules are arranged normally and the picture can be normally displayed. This shows that the branched type silicone material can vertically align liquid crystal molecules, and a liquid crystal panel can be obtained without using an alignment film.
  • silicone materials The synthesis of two silicone materials is exemplified below, and other silicone materials can also be synthesized by the following methods.
  • the molar ratio of the compound of the formula i and the compound of the formula ii is 1:1 to 1:1.4, preferably 1:1.2; the compound of the formula i and the formula ii
  • the reaction temperature of the compound is from 20 ° C to 60 ° C, preferably 50 ° C, and the reaction time is from 1 h to 5 h, preferably 4 h.
  • the reaction temperature of the compound of the formula iii with the pentylamine compound of the formula iv is from 60 ° C to 90 ° C, preferably 80 ° C; and the reaction is carried out for 1 h to 5 h, preferably 3 h.
  • R 1 is R 2 is a methyl group, that is, It is a compound represented by the formula iv.
  • H 1 -NMR data are as follows: ⁇ : 0.96 (6H), 1.33 (4H), 1.29 (8H), 1.59 (4H), 3.20 (4H), 8.0 (4H), 8.13 (4H), 7.69 (4H), 3.55 (12H), 3.2 (4H), 0.88 (4H).
  • the molar ratio of the compound of the formula i to the compound of the formula v is from 1:1 to 1:1.4, preferably 1:1.2; the reaction temperature of the compound of the formula i and the compound of the formula v is from 20 to 60 ° C, preferably 40 °C, the reaction time is 1h-5h, preferably 3h.
  • the molar ratio of the compound represented by the formula vi to n-octanol was 1:1, and 1.1 times of SOCl2 was further added thereto, and the reaction was carried out for 1 hour.
  • a silicone material having n of 2 is prepared, and the molar ratio of the two reactants is from 1:1.1 to 1.5, preferably 1:1.2.
  • the reaction temperature was 50 ° C and a small amount of H 2 SO 4 was added to promote hydrolysis.
  • H 1 -NMR data are as follows: ⁇ : 0.96 (6H), 1.33 (4H), 1.29 (16H), 1.57 (4H), 4.15 (4H), 3.55 (12H), 1.93 (12H), 8.0 (2H), 3.0 (4H), 0.84 (4H).

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Abstract

涉及一种支化型有机硅材料，一种使用所述的支化型有机硅材料在无需配向膜的情形下制备液晶面板的方法，以及一种制得的液晶面板。

Description

一种支化型有机硅材料及制备液晶面板的方法
相关申请的交叉引用
本申请要求享有2015年8月25日提交的名称为“一种支化型有机硅材料及制备液晶面板的方法”的中国专利申请CN201510526256.0的优先权，其全部内容通过引用并入本文中。
技术领域
本发明涉及液晶显示领域，具有涉及一种支化型的有机硅材料。该所述的有机硅材料能够使LC垂直取向。本发明还涉及所述有机硅材料的应用。
背景技术
在液晶显示器(LCD)的CF基板和TFT基板上，均设有一层薄膜材料，其主要作用是使液晶分子按一定方向排列，我们称之为配向膜(常用聚酰亚胺(PI)材料)。这种配相膜主要分为摩擦配相型PI材料和光配相型PI材料。但是，无论那种配向材料都会有各自的缺点。首先，摩擦配相容易造成粉尘颗粒、静电残留、刷痕等问题降低工艺良率。而光配相材料虽然可以避免这些问题，但由于材料特性受限，耐热性和耐老化性不佳，同时锚定LC分子的能力也较弱，从而影响面板的品质。其次，PI材料本身就具有高极性和高吸水性，存储和运送容易造成变质而导致配相不均，并且PI材料价格昂贵，在TFT-LCD上成膜的工艺也较为复杂，导致面板成本提高。
本发明希望提供一种新的材料和方法，能够在TFT-LCD中，省去PI膜的情况下，还能使液晶分子排列，这将会大大简化TFT-LCD的制程，而且还降低了TFT-LCD的生产成本。
发明内容
针对现有技术中的不足，本申请提供了一种支化型有机硅材料，其用于TFT-LCD中，能够在省去PI膜的情况下，还能使液晶分子排列，大大降低生产 面板的成本。
根据本发明的一个方面，提供了一种一种支化型有机硅材料，其分子式如式I所示，
SinO2n+1R1 nR2 n+2，   式I
其中，R1与硅原子直接相连，R2通过氧原子与硅原子相连，相邻的硅原子通过氧原子相连；n为2-15的整数，R2为C1-C5的烷基，R1为含10-30个碳原子的基团，R1基团任选地包含或不包含选自-CR3＝CR3-、-C≡C-、C6-C20亚芳基、C3-C15亚环烷基、-CONH-和-COO-的基团，且R1基团中的一个或多个H原子任选地被杂原子取代或不取代，R3为氢或C1-C3的烷基。其中，所述杂原子包含卤素原子、硝基、烷氧基等。
根据本发明，所述有机硅材料，其结构主要分为头基A和多条链的尾基B两个部分。A指的是SinO2n+1部分，主要是一种支化结构；B指的是R1 nR2 n+2两部分，也即多条支链的结构。由于-Si-O-的独特结构，使得本发明中的有机硅支化小分子材料兼备了有机材料与无机材料的特性，一方面，具有低表面张力、低表面能；另一方面，因为-Si-O-的键能(462kJ/mol)高于-C-C-的键能(347kJ/mol)，而增加了材料本身的耐温性和耐氧化性。–Si-O-还是一种极性锚固基团，能够与其他的材料锚固。
根据本发明的一个具体实施方式，所述的支化型有机硅材料，优选n为2-10的整数，更优选为2-6的整数。优选地，R2为甲基、乙基或丙基。优选地，R1基团中包含选自-CR3＝CR3-、-C≡C-、亚苯基、C3-C6亚环烷基、-CONH-和-COO-的基团。同时，当包含亚苯基或亚环烷基时，所述亚苯基或亚环烷基中的H原子任选地被卤素原子取代或不取代。R3为氢、甲基或乙基。
根据本发明的一个优选实施方式，所述支化型有机硅材料中，R2为甲基、乙基或丙基，R1选自以下的基团，
Figure PCTCN2015088752-appb-000001
根据本发明的一个优选实施方式，当n为2、3或4时，所述有机硅材料分别为式II、III或IV所示：
Figure PCTCN2015088752-appb-000002
其中，当n增加时，所述有机硅材料的结构式中的-OR2不断被-OSiR1(OR2)2所代替。
根据本发明提供的支化型有机硅材料，具有低表面张力和低表明能，同时具有高的耐温性和耐氧化性。所述有机硅材料所含的硅氧键，能够与其他原子相互作用，起到锚固的作用。
根据本发明所述的支化型有机硅材料，其可通过将通式R1Si(OR2)3所示的硅化合物进行受控水解制得。其中，所述的通式R1Si(OR2)3所示的硅化合物可通过如缩合等方法制得。
根据本发明的另外一个方面，还提供了一种制备液晶显示器的方法，包括以下步骤：
1)设置包含第一基板和第二基板的盒体，所述第一基板和第二基板上均不 含配向膜；
2)将反应型单体和上述支化型有机硅材料加入到液晶中，制得混合溶液；
3)将所述的混合溶液滴加到所述盒体内的第一基板和第二基板之间，此时，所述支化型有机硅材料使液晶在第一基板的表面以及第二基板的表面垂直排列；
4)施加电压使液晶发生偏转，然后使反应型单体在所述第一基板的表面和第二基板的表面聚合，锚定液晶；
5)释放电压，得到所述液晶面板。
根据本发明所述方法的一个具体实施方式，在步骤2)中，所述混合溶液中，所述支化型有机硅材料的量为0.1-5wt％。所述有机硅材料的结构主要分为头基A和多条链的尾基B两个部分。A指的是SinO2n+1部分，主要是一种支化结构，多个硅氧基团共同组成头基团，可增强极性基团在基板表面的附着力，增强与基板的锚固作用。所述–Si-O-是一种极性锚固基团，其主要的作用将头基锚固在基板表面。B指的是R1 nR2 n+2两部分，也即多条支链的结构。而尾基的主要作用是以立体障碍的方式使液晶分子垂直排列。多个尾部基团的设计，可提高对LC分子垂直取向的作用。
根据本发明所述方法的另一个具体实施方式，在步骤2)中，所述反应型单体包括环氧树脂与脂肪胺类环氧固化剂的组合、丙烯酸酯及其衍生物、甲基丙烯酸酯及其衍生物和苯乙烯及其衍生物中的至少一种。所述反应型单体为高分子领域内常用的可辐射聚合的化合物，此处不再进行详细叙述。所述混合溶液中，所述反应型单体的量为0.01-0.1wt％。
根据本发明所述方法的另一个具体实施方式，在步骤4)中，所述聚合为辐射聚合。其中。所述辐射聚合使用的光源为313nm下的UV光。辐射剂量为0.1-1mW/cm2。优选所述施加的电压为15-25v。
根据本发明所述方法的另一个具体实施方式，在所述1)中，所述第一基板为滤光膜(CF)基板，所述第二基板为薄膜三极管(TFT)基板。根据所在的基板材质的不同，所述–Si-O-与基板的作用机理产生差异，作用机理主要有以下两种：①与ITO的作用机理是利用-Si-O-中氧原子上的孤对电子与基板表面的ITO中的铟原子(核外电子排列：In:[Kr]4d105s25p1)或锡原子(核外电子排列：Sn:[Kr]4d105s25p2)中的空的p轨道或d轨道杂化，以配位键的方式相结合；②与SiNx的作用机理是利用-Si-O-中的氧原子与SiNx中的氮原子相互作用。
根据本发明，所述的支化型有机硅材料兼备了有机材料与无机材料的特性，具有低表面张力、低表面能；具有高的耐温性和耐氧化性。A具有多个-Si-O-基团，主要增强与基板的锚固作用。B的具有多条支链的结构，主要可提高LC垂直取向效果。
根据本发明提供的制备液晶面板的方法，用这种支化状的有机硅材料取代TFT-LCD中的PI取向膜，省去PI段制程，大大简化了液晶面板的制备流程、降低了面板的生产成本。
根据本发明的另一个方面，还提供了一种液晶面板，包含：第一基板，第二基板，液晶，聚合物以及上述的支化型有机硅材料。
根据本发明提供的液晶面板，液晶能够按一定方向排列。其中，所述的聚合物是由反应型单体聚合得到的聚合物。
本发明的液晶为本领域内常用的液晶分子，此处不再赘述。
根据本发明所述的液晶面板的一个具体实施例，所述第一基板为滤光膜基板，第二基板为薄膜三极管基板。在另一个具体的实例中，所述第一基板和第二基板上不含配向膜。
根据本发明提供的一种新型的支化型有机硅材料，其具有多个硅氧基团和多条支链的结构。当所述的支化型有机硅材料用于LCD领域时，一方面，能够与基板形成锚固作用，而多条支链的作用又能够提高液晶LC的垂直取向的效果。根据本发明提供的支化型有机硅材料，能够用于制备液晶面板，在无需配向膜的情况下，也能够制得液晶面板。
附图说明
图1为根据本发明的支化型有机硅材料的结构示意图；
图2为根据本发明的一个实施例的支化型有机硅材料的作用示意图；
图3为根据本发明的一个实施例的制备液晶面板的工艺流程图；
图4为根据本发明的一个实施例的液晶面板的示意图。
具体实施方式
下面结合附图和具体实施例，对本发明做进一步说明，但并不构成对本发明的任何限制。
图1为根据本发明的支化型有机硅材料的结构示意图。如图1所示，所述支化型有机硅材料的结构主要分为头基A和多条链的尾基B两个部分。A指的是SinO2n+1部分，主要是一种支化结构；B指的是R1 nR2 n+2两部分，也即多条支链的结构。
图2为根据本发明一个实施例的支化型有机硅材料的作用示意图。其中，第一基板1为CF基板，第二基板6为TFT基板。在第一基板1和第二基板6上分别设置有氧化铟锡层(ITO)2和7，其中，ITO仅部分覆盖第二基板6。将包含反应型单体4、所述支化型有机硅材料5和液晶3加入到所述第一基板1和第二基板6之间，在所述支化型有机硅材料5的作用下，使液晶分子垂直取向。所述有机硅材料5起到了垂直取向剂的作用。
图3为根据本发明的一个实施例的制备液晶面板的工艺流程图。a)设置包含第一基板1和第二基板6的盒体，所述第一基板和第二基板上均不含配向膜；将反应型单体4和所述支化型有机硅材料5加入到液晶3中，制得混合溶液；将所述的混合溶液滴加到所述盒体内的第一基板1和第二基板6之间，此时，所述支化型有机硅材料5使液晶3在第一基板1的表面以及第二基板6的表面垂直排列。b)施加20V的电压使液晶发生偏转。c)在313nm处的UV光的辐射下(0.5mW/cm2)，使反应型单体4在所述第一基板1的表面和第二基板6的表面聚合，得到聚合物9，所得聚合物9锚定液晶。d)释放电压，得到所述液晶面板。所述面板中液晶3具有预倾角8。其中，所用的反应型单体为丙烯酸甲酯。所述混合溶液中，所用的反应型单体的量为0.05wt％，所述支化型有机硅材料的量为3wt％。所用的支化型有机硅材料中，n为3，R1为-(CH2)2-CONH-HC＝CH-COO-C8H17，R2为甲基。本领域技术人员可以理解到，在本发明限定范围内的其他种类及其他量的反应型单体、其他种类及其他量的支化型有机硅材料、其他电压和辐射剂量下，也能够实现本发明，得到液晶面板。
图4显示了根据本发明得到的液晶面板，液晶分子排列正常，画面能够正常显示。这说明，该支化型有机硅材料能够液晶分子垂直排列，在不使用配向膜的条件下，也能够制得液晶面板。
下面例举性地表明两种有机硅材料的合成，其他的有机硅材料也可参照以下方法合成。
实施例1
合成线性有机硅小分子，如路线①所示。其中
Figure PCTCN2015088752-appb-000003
其中，如路线①所示的合成线性小分子，式i所示化合物和式ii所示化合物的摩尔比为1:1-1:1.4，优选1:1.2；式i所示化合物和式ii所示化合物的反应温度为20℃-60℃，优选50℃，反应时间为1h-5h，优选4h。
式iii所示化合物与戊胺合成式iv所示化合物的反应温度为60℃-90℃，优选80℃；反应1h-5h，优选3h。
化合物(iv)的H1-NMR数据如下：δ:0.96(3H),1.33(2H)，1.29(2H)，1.59(2H),3.20(2H)，8.0(1H)，8.13(2H)，7.69(2H)，3.55(9H),3.2(2H)，0.88(2H)。
然后将式iv所示的硅化合物水解，得到本发明的支化型有机硅材料，如路线③所示。
Figure PCTCN2015088752-appb-000004
其中，路线③所示的反应流程中，R1为
Figure PCTCN2015088752-appb-000005
R2为甲基，也即
Figure PCTCN2015088752-appb-000006
为式iv所示的化合物。
制备n＝2的有机硅材料，式iv所示的化合物与H2O的摩尔比为1:1.1-1:1.5)，优选1:1.3，反应温度为50℃，加入少量H2SO4以促进水解，得到n为2的有机硅材料。
H1-NMR数据如下：δ:0.96(6H),1.33(4H)，1.29(8H)，1.59(4H),3.20(4H)，8.0(4H)，8.13(4H)，7.69(4H)，3.55(12H)，3.2(4H)，0.88(4H)。
本领域人可以理解，通过控制式iv所示的化合物与H2O的摩尔比以及其他条件，可得到n为其他值的有机硅材料。
实施例2
合成线性有机硅小分子，如路线②所示。式i所示化合物和式v所示化合物的摩尔比为1:1-1:1.4，优选1:1.2；式i所示化合物和式v所示化合物的反应温度为20-60℃，优选40℃，反应时间为1h-5h，优选3h。
式vi所示的化合物与正辛醇的摩尔比为1:1，再加入1.1倍的SOCl2，反应1小时。
所得到的化合物(vii)的H1-NMR数据如下：δ:0.96(3H),1.33(2H)，1.29(8H)，1.57(2H),4.15(2H)，3.55(9H)，8.0(1H)，3.0(2H)，0.84(2H),7.49(1H)，6.95(1H)；
Figure PCTCN2015088752-appb-000007
然后将式vii所示的硅化合物水解，得到本发明的支化型有机硅材料，如路线③所示。其中，路线③所示的反应流程中，R2为甲基，R1即为
Figure PCTCN2015088752-appb-000008
制备n为2的有机硅材料，两种反应物的摩尔比为1:1.1-1:1.5，优选1：1.2。反应温度为50℃并加入少量H2SO4促进水解。
H1-NMR数据如下：δ:0.96(6H),1.33(4H)，1.29(16H)，1.57(4H),4.15(4H)，3.55(12H)，1.93(12H)，8.0(2H)，3.0(4H)，0.84(4H)。
本领域人可以理解，通过控制式iv所示的化合物与H2O的摩尔比以及其他条件，可得到n为其他值的有机硅材料。
Figure PCTCN2015088752-appb-000009
应当注意的是，以上所述的实施例仅用于解释本发明，并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述，但应当理解为其中所用的词语为描述性和解释性词汇，而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明作出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。

Claims (16)

  1. 一种支化型有机硅材料，其分子式如式I所示，
    SinO2n+1R1 nR2 n+2，   式I
    其中，R1与硅原子直接相连，R2通过氧原子与硅原子相连，相邻的硅原子通过氧原子相连；n为2-15的整数，R2为C1-C5的烷基，R1为含10-30碳原子的基团，且R1基团任选地包含或不包含选自-CR3＝CR3-、-C≡C-、C6-C20亚芳基、C3-C15亚环烷基、-CONH-和-COO-的基团，且R1基团中的一个或多个H原子任选地被杂原子取代或不取代，R3为氢或C1-C3的烷基。
  2. 根据权利要求1所述的支化型有机硅材料，其中，n为2-10的整数；和/或，R2为甲基、乙基或丙基；和/或，R1基团中包含选自-CR3＝CR3-、-C≡C-、亚苯基、C3-C6亚环烷基、-CONH-和-COO-的基团，且所述亚苯基或亚环烷基中的H原子任选地被卤素原子取代或不取代，R3为氢、甲基或乙基。
  3. 根据权利要求1所述的支化型有机硅材料，其中，n为2-6的整数；和/或，R2为甲基、乙基或丙基，R1选自以下的基团，
    Figure PCTCN2015088752-appb-100001
  4. 根据权利要求1所述的支化型有机硅材料，其中，当n为2、3或4时，所述有机硅材料分别为式II、III或IV所示：
    Figure PCTCN2015088752-appb-100002
  5. 一种制备液晶面板的方法，包括以下步骤：
    1)设置包含第一基板和第二基板的盒体，所述第一基板和第二基板上均不含配向膜；
    2)将反应型单体和支化型有机硅材料加入到液晶中，制得混合溶液；
    3)将所述的混合溶液滴加到所述盒体内的第一基板和第二基板之间，此时，所述支化型有机硅材料使液晶在第一基板的表面以及第二基板的表面垂直排列；
    4)施加电压使液晶发生偏转，然后使反应型单体在所述第一基板的表面和第二基板的表面聚合，锚定液晶；
    5)释放电压，得到所述液晶面板；
    其中，所述支化型有机硅材料的分子式如式I所示，
    SinO2n+1R1 nR2 n+2，     式I
    其中，R1与硅原子直接相连，R2通过氧原子与硅原子相连，相邻的硅原子通过氧原子相连；n为2-15的整数，R2为C1-C5的烷基，R1为含10-30碳原子的基团，且R1基团任选地包含或不包含选自-CR3＝CR3-、-C≡C-、C6-C20亚芳基、C3-C15亚环烷基、-CONH-和-COO-的基团，且R1基团中的一个或多个H原子任选地被杂原子取代或不取代，R3为氢或C1-C3的烷基。
  6. 根据权利要求5所述的方法，其中，在步骤2)中，所述混合溶液中，所述支化型有机硅材料的量为0.1-5wt％。
  7. 根据权利要求5所述的方法，其中，在步骤2)中，所述反应型单体包括环氧树脂与脂肪胺类环氧固化剂的组合、丙烯酸酯及其衍生物、甲基丙烯酸酯及其衍生物和苯乙烯及其衍生物中的至少一种；和/或，所述混合溶液中，所述反应型单体的量为0.01-0.1wt％。
  8. 根据权利要求5所述的方法，其中，在步骤4)中，所述聚合为辐射聚合，和/或所述施加的电压为15-25v。
  9. 根据权利要求5所述的方法，其中，在所述1)中，所述第一基板为滤光膜基板，所述第二基板为薄膜三极管基板。
  10. 根据权利要求5所述的方法，其中，n为2-10的整数；和/或，R2为甲基、乙基或丙基；和/或，R1基团中包含选自-CR3＝CR3-、-C≡C-、亚苯基、C3-C6亚环烷基、-CONH-和-COO-的基团，且所述亚苯基或亚环烷基中的H原子任选地被卤素原子取代或不取代，R3为氢、甲基或乙基。
  11. 根据权利要求5所述的方法，其中，n为2-6的整数；和/或，R2为甲基、乙基或丙基，R1选自以下的基团，
    Figure PCTCN2015088752-appb-100003
  12. 根据权利要求5所述的方法，其中，当n为2、3或4时，所述有机硅材料分别为式II、III或IV所示：
    Figure PCTCN2015088752-appb-100004
  13. 一种液晶面板，包含：第一基板，第二基板，液晶，聚合物以及支化型有机硅材料，所述支化型有机硅材料的分子式如式I所示，
    SinO2n+1R1 nR2 n+2，    式I
    其中，R1与硅原子直接相连，R2通过氧原子与硅原子相连，相邻的硅原子通过氧原子相连；n为2-15的整数，R2为C1-C5的烷基，R1为含10-30碳原子的基团，且R1基团任选地包含或不包含选自-CR3＝CR3-、-C≡C-、C6-C20亚芳基、C3-C15亚环烷基、-CONH-和-COO-的基团，且R1基团中的一个或多个H原子任选地被杂原子取代或不取代，R3为氢或C1-C3的烷基。
  14. 根据权利要求13所述的液晶面板，其中，n为2-10的整数；和/或，R2为甲基、乙基或丙基；和/或，R1基团中包含选自-CR3＝CR3-、-C≡C-、亚苯基、C3-C6亚环烷基、-CONH-和-COO-的基团，且所述亚苯基或亚环烷基中的H原子任选地被卤素原子取代或不取代，R3为氢、甲基或乙基。
  15. 根据权利要求13所述的液晶面板，其中，n为2-6的整数；和/或，R2为甲基、乙基或丙基，R1选自以下的基团，
    Figure PCTCN2015088752-appb-100005
  16. 根据权利要求13所述的液晶面板，其中，当n为2、3或4时，所述有机硅材料分别为式II、III或IV所示：
    Figure PCTCN2015088752-appb-100006
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