WO2017008330A1 - 用作取向膜材料的聚合物及取向膜的制备方法 - Google Patents

用作取向膜材料的聚合物及取向膜的制备方法 Download PDF

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WO2017008330A1
WO2017008330A1 PCT/CN2015/085148 CN2015085148W WO2017008330A1 WO 2017008330 A1 WO2017008330 A1 WO 2017008330A1 CN 2015085148 W CN2015085148 W CN 2015085148W WO 2017008330 A1 WO2017008330 A1 WO 2017008330A1
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siloxane compound
alignment film
molecule
precursor material
compound
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French (fr)
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兰松
马小龙
李泳锐
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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 US14/785,855 priority Critical patent/US20170160594A1/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
    • G02F1/1337—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
    • G02F1/133723—Polyimide, polyamide-imide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007—After-treatment
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/16—Polyester-imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C09D179/085—Unsaturated polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2505/00—Polyamides
    • B05D2505/50—Polyimides
    • 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
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133715—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films by first depositing a monomer
    • 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
    • G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane

Definitions

  • the present invention relates to the field of display manufacturing, and more particularly to a method for preparing a polymer used as an alignment film material and an alignment film.
  • Liquid crystal display has many advantages such as thin body, power saving, and no radiation, and has been widely used.
  • Most of the liquid crystal display devices on the market are backlight type liquid crystal display devices, which include a liquid crystal display panel and a backlight module.
  • the working principle of the liquid crystal display panel is to place liquid crystal molecules in two parallel glass substrates, and control the liquid crystal molecules to change direction by energizing or not the glass substrate, and refract the light of the backlight module to produce a picture.
  • a liquid crystal display panel consists of a color filter substrate (CF), a thin film transistor substrate (TFT, Thin Film Transistor), a liquid crystal (LC) sandwiched between a color filter substrate and a thin film transistor substrate, and a sealant frame ( Sealant), the molding process generally includes: front array (Array) process (film, yellow, etching and stripping), middle cell (Cell) process (TFT substrate and CF substrate bonding) and rear module assembly Process (drive IC and printed circuit board is pressed).
  • Array array
  • Cell middle cell
  • rear module assembly Process drive IC and printed circuit board is pressed.
  • the front Array process mainly forms a TFT substrate to control the movement of liquid crystal molecules; the middle Cell process mainly adds liquid crystal between the TFT substrate and the CF substrate; the rear module assembly process is mainly to drive the IC to press and print the circuit.
  • the integration of the plates drives the liquid crystal molecules to rotate and display images.
  • the liquid crystal display panel usually forms an alignment film on the thin film transistor substrate and the color film substrate respectively. After the alignment film is in contact with the LC, the LC can generate a pretilt angle in a certain direction, thereby providing a bearing angle to the liquid crystal molecules (pre The size of the tilt angle has an important influence on the driving voltage, contrast, response time, viewing angle, and the like of the TFT-LCD.
  • the material of the alignment film is usually a polyimide (PI) material.
  • Rubbing which is a contact-oriented mechanical friction on a surface of a polymer PI with a flannel roller, rubbing the energy provided by the surface of the polymer to make the polymer
  • the main chains are oriented by extension, thereby controlling the branches to interact with the LC, aligning the LCs in the direction of the pretilt angle.
  • Photo-alignment technology which uses photochemical reaction of ultraviolet photopolymer monomer material to generate anisotropy, and liquid crystal molecules interact with the surface of the alignment film to achieve a minimum energy stable state.
  • the liquid crystal molecules are arranged along the direction in which the light alignment defines the greatest force.
  • An object of the present invention is to provide a polymer which is used as an alignment film material, which can realize a liquid crystal molecule pretilt angle which is controllable over a wide range, and which has excellent heat resistance and mechanical properties.
  • Another object of the present invention is to provide a method for preparing an oriented film.
  • the method has simple steps, and the prepared oriented film can realize liquid crystal molecule pretilt angle controllable in a wide range, and has excellent heat resistance and mechanical properties.
  • the present invention provides a polymer used as an alignment film material, comprising a polyimide molecular chain, and a siloxane compound molecule linked to the polyimide molecular chain in a branched form.
  • the siloxane compound molecule has a linking group R and a functional group R' for linking to the polyimide molecular chain, the functional group R 'Used to control the pretilt angle of liquid crystal molecules to play an alignment role.
  • siloxane compound molecule and the polyimide molecular chain are linked by one of two ways:
  • a linking group R in the molecule of the siloxane compound is incorporated into the chain of the polyimide molecule such that a portion of the siloxane compound molecule other than the linking group R is branched a chain form suspended from a side of the polyimide molecular chain;
  • a linking group R in the molecule of the siloxane compound is linked to the chain of the polyimide molecule such that the entire siloxane compound molecule is suspended in the form of a chain at the polyimide molecule The side of the chain.
  • the structural formula of the polyimide molecular chain is or Where n and m are natural numbers greater than zero.
  • the dendritic siloxane compound has a particle diameter of from 1 to 3 nm.
  • the cage type oligomeric silsesquioxane compound has a particle diameter of from 1 to 3 nm.
  • the mass percentage of the siloxane compound molecule in the polymer is from 1 to 50% by weight.
  • the invention also provides a preparation method of an oriented film, comprising the following steps:
  • Step 1 the silicone compound, the dianhydride monomer, and the molar ratio of the siloxane compound, the dianhydride monomer, and the diamine monomer are from 1 to 50:100:50 to 99. Diamine monomer;
  • Step 2 providing an appropriate amount of solvent, the dianhydride monomer, the siloxane compound, and the diamine monomer weighed in step 1 are dissolved in the solvent to obtain an oriented film precursor material;
  • Step 3 providing a substrate, the alignment film precursor material prepared in the step 2 is applied to the surface of the substrate;
  • Step 4 pre-curing the alignment film precursor material coated on the surface of the substrate, the pre-curing temperature is 100-130 ° C, and the pre-curing duration is 1-10 min;
  • Step 5 Perform main curing on the alignment film precursor material coated on the surface of the substrate, the temperature of the main curing is 210 to 240 ° C, and the duration of the main curing is 20 to 40 min to obtain an oriented film.
  • the silicone compound is a dendritic siloxane compound or a cage oligomeric silsesquioxane compound.
  • the solvent is a combination of one or more of N-methylpyrrolidone, N-ethylpyrrolidine and butyrolactone.
  • the oriented film precursor material obtained in the step 2 comprises a siloxane compound, a dianhydride monomer, a diamine monomer, and a solvent, wherein the molar content of the siloxane compound is n1,
  • the mass percentage of the siloxane compound in the alignment film precursor material is 0.01 to 0.5% by weight.
  • the invention also provides a preparation method of an oriented film, comprising the following steps:
  • Step 1 the silicone compound, the dianhydride monomer, and the molar ratio of the siloxane compound, the dianhydride monomer, and the diamine monomer are from 1 to 50:100:50 to 99. Diamine monomer;
  • Step 2 providing an appropriate amount of solvent, the dianhydride monomer, the siloxane compound, and the diamine monomer weighed in step 1 are dissolved in the solvent to obtain an oriented film precursor material;
  • Step 3 providing a substrate, the alignment film precursor material prepared in the step 2 is applied to the surface of the substrate;
  • Step 4 pre-curing the alignment film precursor material coated on the surface of the substrate, the pre-curing temperature is 100-130 ° C, and the pre-curing duration is 1-10 min;
  • Step 5 performing main curing on the alignment film precursor material coated on the surface of the substrate, the temperature of the main curing is 210-240 ° C, and the duration of the main curing is 20-40 min, to obtain an oriented film;
  • the siloxane compound is a dendritic siloxane compound or a cage oligomeric silsesquioxane compound
  • the solvent is a combination of one or more of N-methylpyrrolidone, N-ethylpyrrolidine and butyrolactone;
  • the oriented film precursor material obtained in the step 2 comprises a siloxane compound, a dianhydride monomer, a diamine monomer, and a solvent, wherein the molar content of the siloxane compound is n1
  • the mass percentage of the siloxane compound in the alignment film precursor material is 0.01 to 0.5% by weight.
  • the present invention provides a polymer for use as an alignment film material and a method for producing an alignment film which is formed by linking a siloxane compound molecule to a molecular chain of a polyimide, by controlling The content of the siloxane compound molecule in the polymer can achieve controllability of the liquid crystal molecule pretilt angle in a wide range, and the polymer has excellent heat resistance and mechanical properties; and the preparation method of the oriented film provided by the present invention By dissolving a siloxane compound and a polyimide precursor (diamine monomer, dianhydride monomer) in a solvent to obtain an alignment film precursor material, and then coating the alignment film precursor material On the substrate, after pre-curing and main curing, an oriented film is obtained.
  • the method has a simple step, and the obtained alignment film has a large pretilt angle range, thereby realizing liquid crystal molecules in the liquid crystal panel using the alignment film.
  • the controllability of the dip in a wide range.
  • FIG. 1 is a schematic view showing a molecular structure of a polymer used as an alignment film material of the present invention
  • FIG. 2 is a schematic flow chart of a method of preparing an oriented film of the present invention.
  • the present invention firstly provides a polymer useful as an alignment film material comprising a polyimide molecular chain, and a siloxane compound linked to the polyimide molecular chain in a branched form.
  • a molecule having a siloxane compound molecule having a linking group R and a functional group R' for linking to the polyimide molecular chain the functional group R' is used to control the pretilt angle of the liquid crystal molecules to play an alignment role.
  • siloxane compound molecule and the polyimide molecular chain are linked by one of two ways:
  • a linking group R in the molecule of the siloxane compound is incorporated into the chain of the polyimide molecule such that a portion of the siloxane compound molecule other than the linking group R is branched a chain form suspended from a side of the polyimide molecular chain;
  • a linking group R in the molecule of the siloxane compound is linked to the chain of the polyimide molecule such that the entire siloxane compound molecule is suspended in the form of a chain at the polyimide molecule The side of the chain.
  • the structural formula of the polyimide molecular chain is or Where n and m are natural numbers greater than zero.
  • the silicone compound may be a dendritic siloxane compound or a cage oligomeric silsesquioxane compound.
  • the R group is a linking group for linking with a molecular chain of a polyimide
  • the R' group is a functional group for controlling the pretilt angle of the liquid crystal molecules to function as an alignment.
  • the dendritic siloxane compound has a particle diameter of from 1 to 3 nm.
  • the R group is a linking group for linking with a molecular chain of a polyimide
  • the R' group is a functional group for controlling the pretilt angle of the liquid crystal molecules to function as an alignment.
  • the cage-type oligomeric silsesquioxane compound has a particle diameter of 1-3 nm.
  • FIG. 1 is a schematic view showing a molecular structure of a polymer used as an alignment film material of the present invention, as shown in FIG. 1, the polymer comprising a polyimide molecular chain and in a branched form with the polyamid a dendritic siloxane compound molecule in which an amine molecular chain is bonded, the dendritic siloxane compound having a structure as shown in formula (A), wherein the dendritic siloxane compound molecule has an R group and a polyimide molecule The chains are linked such that the entire dendritic siloxane compound molecule is pendant in the side of the polyimide molecular chain.
  • the molecular weight of the siloxane compound molecule in the polymer is from 1 to 50% by weight.
  • the mechanism by which the siloxane compound molecule can control the liquid crystal molecules to produce a pretilt angle on the surface of the alignment film is:
  • the action mechanism of the siloxane compound molecule in the oriented film is similar to the rubbing alignment, which can produce an azimuth angle on the surface of the alignment film, so that the long axis of the liquid crystal molecule and the siloxane compound molecule
  • the branching R' direction is uniform to achieve the lowest energy stable state, and the liquid crystal molecules are arranged along a certain direction, and the degree of such energy reduction is closely related to the content of the dendritic siloxane compound molecules in the oriented film.
  • the more the content of the siloxane compound molecule the greater the degree of reduction in the surface energy of the alignment film, thereby achieving controllable liquid crystal molecule pretilt angle.
  • the siloxane compound molecules mainly rely on the R' functional group in the oriented film to cause the liquid crystal molecules to have a pretilt angle in a steric barrier manner, and this orientation effect is accompanied by the siloxane compound.
  • the difference in the content of the molecules is determined by the number of R' functional groups.
  • the present invention provides a polymer for use as an alignment film material, the polymer comprising a polyimide molecular chain, and a siloxane compound molecule linked to the polyimide molecular chain in a branched form
  • the siloxane compound molecule has a linking group R to be bonded to the polyimide molecular chain, and also has a functional group R' to control the pretilt angle of the liquid crystal molecule, specifically, by controlling polymerization
  • the content of the siloxane compound molecule in the liquid crystal molecule can be changed from 0° to 90°, so that the alignment film has a large pretilt angle range, and liquid crystal in the liquid crystal panel using the alignment film is realized. Controllability of a wide range of molecular pretilt angles; at the same time the polymer It also has good heat resistance and mechanical properties.
  • the present invention also provides a method for preparing an oriented film, which comprises the following steps:
  • Step 1 the silicone compound, the dianhydride monomer, and the molar ratio of the siloxane compound, the dianhydride monomer, and the diamine monomer are from 1 to 50:100:50 to 99. Diamine monomer.
  • the silicone compound is a dendritic siloxane compound or a cage oligomeric silsesquioxane compound.
  • the structural formula of the dianhydride monomer may be:
  • the structural formula of the diamine monomer can be:
  • Step 2 An appropriate amount of a solvent is supplied, and the dianhydride monomer, the siloxane compound, and the diamine monomer weighed in the step 1 are dissolved in the solvent to obtain an oriented film precursor material.
  • the solvent is a combination of one or more of N-methylpyrrolidone, N-ethylpyrrolidine, and butyrolactone.
  • the oriented film precursor material obtained in the step 2 comprises a siloxane compound, a dianhydride monomer, a diamine monomer, and a solvent, wherein the molar content of the siloxane compound is n1,
  • the mass percentage of the siloxane compound in the oriented film precursor material is 0.01 to 0.5% by weight.
  • Step 3 Providing a substrate, and applying the alignment film precursor material obtained in the step 2 to the surface of the substrate.
  • Step 4 Pre-curing the alignment film precursor material coated on the surface of the substrate, the pre-curing temperature is 100-130 ° C, and the pre-curing duration is 1-10 min.
  • Step 5 Perform main curing on the alignment film precursor material coated on the surface of the substrate, the temperature of the main curing is 210 to 240 ° C, and the duration of the main curing is 20 to 40 min to obtain an oriented film.
  • the method for producing an oriented film comprises dissolving a siloxane compound and a polyimide precursor (diamine monomer, dianhydride monomer) in a solvent to obtain an oriented film precursor.
  • the material is coated on the substrate, and after the pre-curing and the main curing, the oriented film is obtained.
  • the method has simple steps, and the obtained oriented film has a large pretilt angle range, thereby realizing the use of the material.
  • the controllability of the liquid crystal molecule pretilt angle in the liquid crystal panel of the alignment film in a wide range.
  • Step 2 the dendritic siloxane compound (b), the dianhydride monomer (a), and the diamine monomer (c) are fed to N-methylpyrrolidone, N-ethylpyrrolidine, and After dissolving in a mixed solvent of butyrolactone, an oriented film precursor material is obtained.
  • Step 3 providing a substrate, the alignment film precursor material prepared in the step 2 is applied to the surface of the substrate;
  • Step 4 pre-curing the alignment film precursor material coated on the surface of the substrate, the pre-curing temperature is 100-130 ° C, and the pre-curing duration is 1-10 min;
  • Step 5 Perform main curing on the alignment film precursor material coated on the surface of the substrate, the temperature of the main curing is 210 to 240 ° C, and the duration of the main curing is 20 to 40 min to obtain an oriented film.
  • the chemical reaction of the alignment film precursor material applied to the surface of the substrate during pre-curing and main curing is as follows:
  • the dendritic siloxane compound (b) molecule has a linking group thereof Binding to the molecular chain of the polyimide, such that the dendrimer of the dendritic siloxane compound The other portion is suspended in the side of the polyimide molecular chain in the form of a branch.
  • the present invention provides a polymer for use as an alignment film material and a method for preparing an alignment film which is formed by attaching a siloxane compound molecule to a molecular chain of a polyimide by controlling polymerization.
  • the content of the siloxane compound molecule in the product can achieve controllability of the liquid crystal molecule pretilt angle in a wide range, and the polymer has excellent heat resistance and mechanical properties;
  • the preparation method of the oriented film provided by the present invention The alignment film precursor material is obtained by dissolving a siloxane compound and a polyimide precursor (diamine monomer, dianhydride monomer) in a solvent, and then coating the alignment film precursor material to On the substrate, after pre-curing and main curing, an oriented film is obtained, the method is simple in steps, and the obtained alignment film has a large pretilt angle range, thereby realizing liquid crystal molecule pretilt angle in the liquid crystal panel using the alignment film. Controllability over a wide range.

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Abstract

本发明提供一种用作取向膜材料的聚合物及取向膜的制备方法，该聚合物由硅氧烷化合物分子连接在聚酰亚胺分子链上形成，通过控制聚合物中硅氧烷化合物分子的含量可以实现液晶分子预倾角在宽范围内的可控性，且该聚合物具有优异的耐热性和机械性能；本发明提供的一种取向膜的制备方法，通过将硅氧烷化合物和聚酰亚胺前体物质(二胺类单体、二酐类单体)溶解于溶剂中，制得取向膜前体材料，再将取向膜前体材料涂布到基板上，通过预固化和主固化之后，得到取向膜，该方法步骤简单，制得的取向膜有较大的预倾角范围，从而实现了使用所述取向膜的液晶面板中的液晶分子预倾角在宽范围内的可控性。

Description

用作取向膜材料的聚合物及取向膜的制备方法 技术领域
本发明涉及显示器制造领域，尤其涉及一种用作取向膜材料的聚合物及取向膜的制备方法。
背景技术
液晶显示装置(LCD，Liquid Crystal Display)具有机身薄、省电、无辐射等众多优点，得到了广泛的应用。现有市场上的液晶显示装置大部分为背光型液晶显示装置，其包括液晶显示面板及背光模组(backlight module)。液晶显示面板的工作原理是在两片平行的玻璃基板当中放置液晶分子，通过玻璃基板通电与否来控制液晶分子改变方向，将背光模组的光线折射出来产生画面。
通常液晶显示面板由彩膜基板(CF，Color Filter)、薄膜晶体管基板(TFT，Thin Film Transistor)、夹于彩膜基板与薄膜晶体管基板之间的液晶(LC，Liquid Crystal)及密封胶框(Sealant)组成，其成型工艺一般包括：前段阵列(Array)制程(薄膜、黄光、蚀刻及剥膜)、中段成盒(Cell)制程(TFT基板与CF基板贴合)及后段模组组装制程(驱动IC与印刷电路板压合)。其中，前段Array制程主要是形成TFT基板，以便于控制液晶分子的运动；中段Cell制程主要是在TFT基板与CF基板之间添加液晶；后段模组组装制程主要是驱动IC压合与印刷电路板的整合，进而驱动液晶分子转动，显示图像。
液晶显示面板通常会在薄膜晶体管基板及彩膜基板上分别形成一层取向膜，该取向膜与LC接触后，能够使得LC产生一定方向的预倾角，从而给液晶分子提供一个承载的角度(预倾角的大小对TFT-LCD的驱动电压、对比度、响应时间、视角等具有重要影响)，取向膜的材料通常选用聚酰亚胺(Polyimide,PI)材料。取向膜形成方法主要有两种：(1)摩擦配向法(Rubbing)，这种方法是在高分子PI表面用绒布滚轮进行接触式的定向机械摩擦，摩擦高分子表面所提供的能量使高分子主链因延伸而定向排列，从而控制支链与LC相互作用，使LC按照预倾角的方向排列。(2)光配向法(photo-alignment technology)，该方法是利用紫外光敏聚合物单体材料的光化学反应产生各向异性，液晶分子与配向膜表面支链相互作用，为达到能量最小的稳定状态，液晶分子沿着光配向所定义的受力最大的方向排列。 虽然这两种方法都可以帮助LC分子产生预倾角，但是只能在小范围内控制预倾角的变化，并不能大范围的对预倾角进行控制。
发明内容
本发明的目的在于提供一种用作取向膜材料的聚合物，能够实现液晶分子预倾角在较大范围内可控，且具有优异的耐热性和机械性能。
本发明的目的还在于提供一种取向膜的制备方法，方法步骤简单，所制备的取向膜能够实现液晶分子预倾角在较大范围内可控，且具有优异的耐热性和机械性能。
为实现上述目的，本发明提供一种用作取向膜材料的聚合物，包含聚酰亚胺分子链、及以支链的形式与所述聚酰亚胺分子链相连接的硅氧烷化合物分子，所述硅氧烷化合物分子具有连接性基团R及功能性基团R’，所述连接性基团R用于与所述聚酰亚胺分子链相连接，所述功能性基团R’用于控制液晶分子的预倾角，起到配向作用。
所述硅氧烷化合物分子与聚酰亚胺分子链通过以下两种方式之一进行连接：
(Ⅰ)所述硅氧烷化合物分子中的连接性基团R结合到所述聚酰亚胺分子链中，使得所述硅氧烷化合物分子中除该连接性基团R以外的部分以支链的形式悬挂在所述聚酰亚胺分子链的侧部；
(Ⅱ)所述硅氧烷化合物分子中的连接性基团R与所述聚酰亚胺分子链相连接，使得整个硅氧烷化合物分子以支链的形式悬挂在所述聚酰亚胺分子链的侧部。
所述聚酰亚胺分子链的结构式为
Figure PCTCN2015085148-appb-000001
Figure PCTCN2015085148-appb-000002
或
Figure PCTCN2015085148-appb-000003
其中，n和m为大于0的自然数。
所述硅氧烷化合物为树形硅氧烷化合物，所述树形硅氧烷化合物的分子式为R1SinOn-1R’2n+1，其中，n＝4或13，R为-(CO)OH，-(CO)NH2，-OH， 或
Figure PCTCN2015085148-appb-000004
R’为具有3-10个碳原子的直链烷基或支链烷基、其中某个CH2基团被-CH＝CH-、-C≡C-、苯基、环烷基所取代的具有3-10个碳原子的直链烷基或支链烷基、或苯基；
所述树形硅氧烷化合物的粒径为1-3nm。
所述硅氧烷化合物为笼型低聚倍半硅氧烷化合物，所述笼型低聚倍半硅氧烷化合物的分子式为R1SinO1.5nR’n-1，其中，n＝6,8,10,或12，R为-(CO)OH，-(CO)NH2，-OH，或
Figure PCTCN2015085148-appb-000005
R’为具有3-10个碳原子的直链烷基或支链烷基、其中某个CH2基团被-CH＝CH-、-C≡C-、苯基、环烷基所取代的具有3-10个碳原子的直链烷基或支链烷基、或苯基；
所述笼型低聚倍半硅氧烷化合物的粒径为1-3nm。
所述硅氧烷化合物分子在所述聚合物中的质量百分比为1～50wt％。
本发明还提供一种取向膜的制备方法，包括如下步骤：
步骤1、按照硅氧烷化合物、二酐类单体、及二胺类单体的摩尔比为1～50：100：50～99的比例称取硅氧烷化合物、二酐类单体、及二胺类单体；
步骤2、提供适量溶剂，将步骤1所称取的二酐类单体、硅氧烷化合物、及二胺类单体溶解于所述溶剂中，制得取向膜前体材料；
步骤3、提供一基板，将所述步骤2制得的取向膜前体材料涂布到基板表面；
步骤4、对涂布在所述基板表面的取向膜前体材料进行预固化，预固化的温度为100～130℃，预固化的持续时间为1～10min；
步骤5、对涂布在基板表面的取向膜前体材料进行主固化，主固化的温度为210～240℃，主固化的持续时间为20～40min，制得取向膜。
所述步骤1中，所述硅氧烷化合物为树形硅氧烷化合物或笼型低聚倍半硅氧烷化合物。
所述步骤2中，所述溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷和丁内酯中的一种或多种的组合。
所述步骤2制得的一种取向膜前体材料，包含硅氧烷化合物、二酐类单体、二胺类单体、及溶剂，其中，所述硅氧烷化合物的摩尔含量n1、所述二酐类单体的摩尔含量n2、及所述二胺类单体的摩尔含量n3之间的比例为n1：n2：n3＝1～50：100：50～99，且n2＝n1+n3；
并且所述硅氧烷化合物在所述取向膜前体材料中的质量百分比为0.01～0.5wt％。
本发明还提供一种取向膜的制备方法，包括如下步骤：
步骤1、按照硅氧烷化合物、二酐类单体、及二胺类单体的摩尔比为1～50：100：50～99的比例称取硅氧烷化合物、二酐类单体、及二胺类单体；
步骤2、提供适量溶剂，将步骤1所称取的二酐类单体、硅氧烷化合物、及二胺类单体溶解于所述溶剂中，制得取向膜前体材料；
步骤3、提供一基板，将所述步骤2制得的取向膜前体材料涂布到基板表面；
步骤4、对涂布在所述基板表面的取向膜前体材料进行预固化，预固化的温度为100～130℃，预固化的持续时间为1～10min；
步骤5、对涂布在基板表面的取向膜前体材料进行主固化，主固化的温度为210～240℃，主固化的持续时间为20～40min，制得取向膜；
其中，所述步骤1中，所述硅氧烷化合物为树形硅氧烷化合物或笼型低聚倍半硅氧烷化合物；
其中，所述步骤2中，所述溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷和丁内酯中的一种或多种的组合；
其中，所述步骤2制得的一种取向膜前体材料，包含硅氧烷化合物、二酐类单体、二胺类单体、及溶剂，其中，所述硅氧烷化合物的摩尔含量n1、所述二酐类单体的摩尔含量n2、及所述二胺类单体的摩尔含量n3之间的比例为n1：n2：n3＝1～50：100：50～99，且n2＝n1+n3；
并且所述硅氧烷化合物在所述取向膜前体材料中的质量百分比为0.01～0.5wt％。
本发明的有益效果：本发明提供一种用作取向膜材料的聚合物及一种取向膜的制备方法，该聚合物由硅氧烷化合物分子连接在聚酰亚胺分子链上形成，通过控制聚合物中硅氧烷化合物分子的含量可以实现液晶分子预倾角在宽范围内的可控性，且该聚合物具有优异的耐热性和机械性能；本发明提供的一种取向膜的制备方法，通过将硅氧烷化合物和聚酰亚胺前体物质(二胺类单体、二酐类单体)溶解于溶剂中，制得取向膜前体材料，再将取向膜前体材料涂布到基板上，通过预固化和主固化之后，得到取向膜，该方法步骤简单，制得的取向膜有较大的预倾角范围，从而实现了使用所述取向膜的液晶面板中的液晶分子预倾角在宽范围内的可控性。
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为本发明的用作取向膜材料的聚合物的一种分子结构示意图；
图2为本发明的取向膜的制备方法的示意流程图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
本发明首先提供一种可用作取向膜材料的聚合物，所述聚合物包含聚酰亚胺分子链、及以支链的形式与所述聚酰亚胺分子链相连接的硅氧烷化合物分子，所述硅氧烷化合物分子具有连接性基团R及功能性基团R’，所述连接性基团R用于与所述聚酰亚胺分子链相连接，所述功能性基团R’用于控制液晶分子的预倾角，起到配向作用。
具体的，所述硅氧烷化合物分子与聚酰亚胺分子链通过以下两种方式之一进行连接：
(Ⅰ)所述硅氧烷化合物分子中的连接性基团R结合到所述聚酰亚胺分子链中，使得所述硅氧烷化合物分子中除该连接性基团R以外的部分以支链的形式悬挂在所述聚酰亚胺分子链的侧部；
(Ⅱ)所述硅氧烷化合物分子中的连接性基团R与所述聚酰亚胺分子链相连接，使得整个硅氧烷化合物分子以支链的形式悬挂在所述聚酰亚胺分子链的侧部。
具体的，所述聚酰亚胺分子链的结构式为
Figure PCTCN2015085148-appb-000006
Figure PCTCN2015085148-appb-000007
或
Figure PCTCN2015085148-appb-000008
其中，n和m为大于0的自然数。
具体的，所述硅氧烷化合物可以为树形硅氧烷化合物或笼型低聚倍半硅氧烷化合物。
所述树形硅氧烷化合物的分子式为R1SinOn-1R’2n+1，其中，n＝4或13，R为-(CO)OH，-(CO)NH2，-OH，或
Figure PCTCN2015085148-appb-000009
等基团；R’为具有3-10个碳原子的直链烷基或支链烷基、其中某个CH2基团被-CH＝CH-、-C≡C-、苯基、环烷基所取代的具有3-10个碳原子的直链烷基或支链烷基、或苯基等基团。
具体的，所述R基为连接性基团，用于与聚酰亚胺分子链相连接，所述R’基为功能性基团，用于控制液晶分子的预倾角，起到配向作用。
当所述树形硅氧烷化合物的分子式R1SinOn-1R’2n+1中n分别为4，13时，所述树形硅氧烷化合物的结构式分别如式(A)和式(B)所示：
Figure PCTCN2015085148-appb-000010
具体的，所述树形硅氧烷化合物的粒径为1-3nm。
所述笼型低聚倍半硅氧烷化合物的分子式为R1SinO1.5nR’n-1，其中，n＝6,8,10,或12，R为-(CO)OH，-(CO)NH2，-OH，或
Figure PCTCN2015085148-appb-000011
等基团；R’为具有3-10个碳原子的直链烷基或支链烷基、其中某个CH2基团被-CH＝CH-、-C≡C-、苯基、环烷基所取代的具有3-10个碳原子的直链烷基或支链烷基、或苯基等基团。
具体的，所述R基为连接性基团，用于与聚酰亚胺分子链相连接，所述R’基为功能性基团，用于控制液晶分子的预倾角，起到配向作用。
具体的，所述笼型低聚倍半硅氧烷化合物的粒径为1-3nm。
当所述笼型低聚倍半硅氧烷化合物的分子式R1SinO1.5nR’n-1中n分别为6,8,10,12时，所述笼型低聚倍半硅氧烷化合物的结构式分别如式(E)、(F)、(G)、(H)所示：
Figure PCTCN2015085148-appb-000012
图1为本发明的用作取向膜材料的聚合物的一种分子结构示意图，如图1所示，所述聚合物包含聚酰亚胺分子链和以支链的形式与所述聚酰亚胺分子链相连接的树形硅氧烷化合物分子，所述树形硅氧烷化合物的结构如式(A)所示，所述树形硅氧烷化合物分子以R基与聚酰亚胺分子链相连接，使得整个树形硅氧烷化合物分子以支链的形式悬挂在所述聚酰亚胺分子链的侧部。
优选的，所述硅氧烷化合物分子在所述聚合物中的质量百分比为1～50wt％。
具体的，所述硅氧烷化合物分子在取向膜表面能够控制液晶分子产生预倾角的机理为：
(1)从能量的角度解释：所述硅氧烷化合物分子在取向膜中的作用机理类似于摩擦配向，可以使取向膜表面产生一个方位角，使得液晶分子的长轴和硅氧烷化合物分子的支链R’方向一致，以达到能量最低的稳定状态，实现液晶分子沿着一定的方向排列，而这种能量的降低程度跟树形硅氧烷化合物分子在取向膜中的含量密切相关，硅氧烷化合物分子的含量越多，取向膜表面能降低的程度越大，从而实现液晶分子预倾角的可控。
(2)从表面分子链取向理论解释：硅氧烷化合物分子在取向膜中主要依靠R’官能基以立体障碍的方式使得液晶分子产生预倾角，而这种取向效果会随着硅氧烷化合物分子的含量而产生差异，也就是由R’官能基数量多少决定的。
本发明提供的一种用作取向膜材料的聚合物，所述聚合物包含聚酰亚胺分子链、及以支链的形式与所述聚酰亚胺分子链相连接的硅氧烷化合物分子，所述硅氧烷化合物分子具有连接性基团R以与所述聚酰亚胺分子链相连接，同时还具有功能性基团R’以控制液晶分子的预倾角，具体的，通过控制聚合物中硅氧烷化合物分子的含量可以实现液晶分子预倾角从0°至90°的变化，使得所述取向膜具有较大的预倾角范围，实现了使用所述取向膜的液晶面板中的液晶分子预倾角宽范围的可控性；同时所述聚合物 还具有较好的耐热性和机械性能。
请参阅图2，本发明还提供一种取向膜的制备方法，其包括以下步骤：
步骤1、按照硅氧烷化合物、二酐类单体、及二胺类单体的摩尔比为1～50：100：50～99的比例称取硅氧烷化合物、二酐类单体、及二胺类单体。
具体的，所述硅氧烷化合物为树形硅氧烷化合物或笼型低聚倍半硅氧烷化合物。
所述树形硅氧烷化合物和笼型低聚倍半硅氧烷化合物的结构在前面已做详细描述，此处不再赘述。
具体的，所述二酐类单体的结构式可以为：
Figure PCTCN2015085148-appb-000013
或
Figure PCTCN2015085148-appb-000014
所述二胺类单体的结构式可以为：
Figure PCTCN2015085148-appb-000015
或
Figure PCTCN2015085148-appb-000016
步骤2、提供适量溶剂，将步骤1所称取的二酐类单体、硅氧烷化合物、及二胺类单体溶解于所述溶剂中，制得取向膜前体材料。
具体的，所述溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷和丁内酯中的一种或多种的组合。
所述步骤2制得的一种取向膜前体材料，包含硅氧烷化合物、二酐类单体、二胺类单体、及溶剂，其中，所述硅氧烷化合物的摩尔含量n1、所述二酐类单体的摩尔含量n2、及所述二胺类单体的摩尔含量n3之间的比例为n1：n2：n3＝1～50：100：50～99，且n2＝n1+n3。
优选的，所述硅氧烷化合物在所述取向膜前体材料中的质量百分比为0.01～0.5wt％。
步骤3、提供一基板，将所述步骤2制得的取向膜前体材料涂布到基板表面。
步骤4、对涂布在所述基板表面的取向膜前体材料进行预固化，预固化的温度为100～130℃，预固化的持续时间为1～10min。
步骤5、对涂布在基板表面的取向膜前体材料进行主固化，主固化的温度为210～240℃，主固化的持续时间为20～40min，制得取向膜。
本发明提供的一种取向膜的制备方法，通过将硅氧烷化合物和聚酰亚胺前体物质(二胺类单体、二酐类单体)溶解于溶剂中，制得取向膜前体材料，再将取向膜前体材料涂布到基板上，通过预固化和主固化之后，得到取向膜，该方法步骤简单，制得的取向膜有较大的预倾角范围，从而实现了使用所述取向膜的液晶面板中的液晶分子预倾角在宽范围内的可控性。
本发明的取向膜的制备方法的优选实施例1：
步骤1、按照树形硅氧烷化合物(b)、二酐类单体(a)、及二胺类单体(c)的摩尔量之比为m:n:(n-m)＝1～50：100：50～99的比例称取树形硅氧烷化合物、二酐类单体、及二胺类单体。
步骤2、将所述树形硅氧烷化合物(b)、二酐类单体(a)、及二胺类单体(c)投入到由N-甲基吡咯烷酮、N-乙基吡咯烷和丁内酯组成的混合溶剂中，溶解后，得到取向膜前体材料。
步骤3、提供一基板，将所述步骤2制得的取向膜前体材料涂布到基板表面；
步骤4、对涂布在所述基板表面的取向膜前体材料进行预固化，预固化的温度为100～130℃，预固化的持续时间为1～10min；
步骤5、对涂布在基板表面的取向膜前体材料进行主固化，主固化的温度为210～240℃，主固化的持续时间为20～40min，制得取向膜。
具体的，所述步骤4-5中，涂布到基板表面的取向膜前体材料在预固化和主固化的过程中发生的化学反应如下：
Figure PCTCN2015085148-appb-000017
所述步骤5制得的一种取向膜，该取向膜的材料为一种聚合物，所述聚合物的结构式为
Figure PCTCN2015085148-appb-000018
其中，m＝20～500，n＝20～2000，且n＞m，从该聚合物的结构式中可见，所述树形硅氧烷化合物(b)分子以其连接性基团
Figure PCTCN2015085148-appb-000019
结合到聚酰亚胺分子链中，使得所述树形硅氧烷化合物分子中除该连接性基团
Figure PCTCN2015085148-appb-000020
以外的部分以支链的形式悬挂在所述聚酰亚胺分子链的侧部。
综上所述，本发明提供一种用作取向膜材料的聚合物及一种取向膜的制备方法，该聚合物由硅氧烷化合物分子连接在聚酰亚胺分子链上形成，通过控制聚合物中硅氧烷化合物分子的含量可以实现液晶分子预倾角在宽范围内的可控性，且该聚合物具有优异的耐热性和机械性能；本发明提供的一种取向膜的制备方法，通过将硅氧烷化合物和聚酰亚胺前体物质(二胺类单体、二酐类单体)溶解于溶剂中，制得取向膜前体材料，再将取向膜前体材料涂布到基板上，通过预固化和主固化之后，得到取向膜，该方法步骤简单，制得的取向膜有较大的预倾角范围，从而实现了使用所述取向膜的液晶面板中的液晶分子预倾角在宽范围内的可控性。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明权利要求的保护范围。

Claims (11)

  1. 一种用作取向膜材料的聚合物，包含聚酰亚胺分子链、及以支链的形式与所述聚酰亚胺分子链相连接的硅氧烷化合物分子，所述硅氧烷化合物分子具有连接性基团R及功能性基团R’，所述连接性基团R用于与所述聚酰亚胺分子链相连接，所述功能性基团R’用于控制液晶分子的预倾角，起到配向作用。
  2. 如权利要求1所述的用作取向膜材料的聚合物，其中，所述硅氧烷化合物分子与聚酰亚胺分子链通过以下两种方式之一进行连接：
    (Ⅰ)所述硅氧烷化合物分子中的连接性基团R结合到所述聚酰亚胺分子链中，使得所述硅氧烷化合物分子中除该连接性基团R以外的部分以支链的形式悬挂在所述聚酰亚胺分子链的侧部；
    (Ⅱ)所述硅氧烷化合物分子中的连接性基团R与所述聚酰亚胺分子链相连接，使得整个硅氧烷化合物分子以支链的形式悬挂在所述聚酰亚胺分子链的侧部。
  3. 如权利要求1所述的用作取向膜材料的聚合物，其中，所述聚酰亚胺分子链的结构式为
    Figure PCTCN2015085148-appb-100001
    Figure PCTCN2015085148-appb-100002
    其中，n和m为大于0的自然数。
  4. 如权利要求1所述的用作取向膜材料的聚合物，其中，所述硅氧烷化合物为树形硅氧烷化合物，所述树形硅氧烷化合物的分子式为R1SinOn-1R’2n+1，其中，n＝4或13，R为-(CO)OH，-(CO)NH2，-OH，或
    Figure PCTCN2015085148-appb-100003
    R’为具有3-10个碳原子的直链烷基或支链烷基、其中某个CH2基团被-CH＝CH-、-C≡C-、苯基、环烷基所取代的具有3-10个碳原子的直链烷基或支链烷基、或苯基；
    所述树形硅氧烷化合物的粒径为1-3nm。
  5. 如权利要求1所述的用作取向膜材料的聚合物，其中，所述硅氧烷 化合物为笼型低聚倍半硅氧烷化合物，所述笼型低聚倍半硅氧烷化合物的分子式为R1SinO1.5nR’n-1，其中，n＝6,8,10,或12，R为-(CO)OH，-(CO)NH2，-OH，或
    Figure PCTCN2015085148-appb-100004
    R’为具有3-10个碳原子的直链烷基或支链烷基、其中某个CH2基团被-CH＝CH-、-C≡C-、苯基、环烷基所取代的具有3-10个碳原子的直链烷基或支链烷基、或苯基；
    所述笼型低聚倍半硅氧烷化合物的粒径为1-3nm。
  6. 如权利要求1所述的用作取向膜材料的聚合物，其中，所述硅氧烷化合物分子在所述聚合物中的质量百分比为1～50wt％。
  7. 一种取向膜的制备方法，包括如下步骤：
    步骤1、按照硅氧烷化合物、二酐类单体、及二胺类单体的摩尔比为1～50：100：50～99的比例称取硅氧烷化合物、二酐类单体、及二胺类单体；
    步骤2、提供适量溶剂，将步骤1所称取的二酐类单体、硅氧烷化合物、及二胺类单体溶解于所述溶剂中，制得取向膜前体材料；
    步骤3、提供一基板，将所述步骤2制得的取向膜前体材料涂布到基板表面；
    步骤4、对涂布在所述基板表面的取向膜前体材料进行预固化，预固化的温度为100～130℃，预固化的持续时间为1～10min；
    步骤5、对涂布在基板表面的取向膜前体材料进行主固化，主固化的温度为210～240℃，主固化的持续时间为20～40min，制得取向膜。
  8. 如权利要求7所述的取向膜的制备方法，其中，所述步骤1中，所述硅氧烷化合物为树形硅氧烷化合物或笼型低聚倍半硅氧烷化合物。
  9. 如权利要求7所述的取向膜的制备方法，其中，所述步骤2中，所述溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷和丁内酯中的一种或多种的组合。
  10. 如权利要求7所述的取向膜的制备方法，其中，所述步骤2制得的一种取向膜前体材料，包含硅氧烷化合物、二酐类单体、二胺类单体、及溶剂，其中，所述硅氧烷化合物的摩尔含量n1、所述二酐类单体的摩尔含量n2、及所述二胺类单体的摩尔含量n3之间的比例为n1：n2：n3＝1～50：100：50～99，且n2＝n1+n3；
    并且所述硅氧烷化合物在所述取向膜前体材料中的质量百分比为0.01～0.5wt％。
  11. 一种取向膜的制备方法，包括如下步骤：
    步骤1、按照硅氧烷化合物、二酐类单体、及二胺类单体的摩尔比为1～50：100：50～99的比例称取硅氧烷化合物、二酐类单体、及二胺类单体；
    步骤2、提供适量溶剂，将步骤1所称取的二酐类单体、硅氧烷化合物、及二胺类单体溶解于所述溶剂中，制得取向膜前体材料；
    步骤3、提供一基板，将所述步骤2制得的取向膜前体材料涂布到基板表面；
    步骤4、对涂布在所述基板表面的取向膜前体材料进行预固化，预固化的温度为100～130℃，预固化的持续时间为1～10min；
    步骤5、对涂布在基板表面的取向膜前体材料进行主固化，主固化的温度为210～240℃，主固化的持续时间为20～40min，制得取向膜；
    其中，所述步骤1中，所述硅氧烷化合物为树形硅氧烷化合物或笼型低聚倍半硅氧烷化合物；
    其中，所述步骤2中，所述溶剂为N-甲基吡咯烷酮、N-乙基吡咯烷和丁内酯中的一种或多种的组合；
    其中，所述步骤2制得的一种取向膜前体材料，包含硅氧烷化合物、二酐类单体、二胺类单体、及溶剂，其中，所述硅氧烷化合物的摩尔含量n1、所述二酐类单体的摩尔含量n2、及所述二胺类单体的摩尔含量n3之间的比例为n1：n2：n3＝1～50：100：50～99，且n2＝n1+n3；
    并且所述硅氧烷化合物在所述取向膜前体材料中的质量百分比为0.01～0.5wt％。
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CN104356413A (zh) * 2014-11-11 2015-02-18 西北工业大学 一类包含八聚笼型倍半硅氧烷结构的抗原子氧聚酰亚胺杂化薄膜制备方法

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