WO2022057522A1 - 液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺 - Google Patents

液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺 Download PDF

Info

Publication number
WO2022057522A1
WO2022057522A1 PCT/CN2021/111782 CN2021111782W WO2022057522A1 WO 2022057522 A1 WO2022057522 A1 WO 2022057522A1 CN 2021111782 W CN2021111782 W CN 2021111782W WO 2022057522 A1 WO2022057522 A1 WO 2022057522A1
Authority
WO
WIPO (PCT)
Prior art keywords
segment
group
hydrophilic
hydrophobic
diamine
Prior art date
Application number
PCT/CN2021/111782
Other languages
English (en)
French (fr)
Inventor
马健
任文明
詹成勇
张然
Original Assignee
京东方科技集团股份有限公司
合肥鑫晟光电科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 京东方科技集团股份有限公司, 合肥鑫晟光电科技有限公司 filed Critical 京东方科技集团股份有限公司
Priority to US17/803,000 priority Critical patent/US20230103608A1/en
Publication of WO2022057522A1 publication Critical patent/WO2022057522A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present disclosure relates to the field of display technology, and in particular, to a liquid crystal alignment agent, a liquid crystal alignment film, a display substrate, a liquid crystal display device and a polyimide.
  • the liquid crystal display device is a large-scale display device at present, which has the advantages of low cost, lightness and thinness, and fast display speed, and has mature technology in both theoretical research and practical process.
  • a liquid crystal aligning agent comprising: at least one polymer selected from polyimides and a group of polyimides obtained by ring closure of the polyimides At least one of ; the polyimide includes the first segment formed by the reaction of the first dianhydride shown in the following formula (I) and the first diamine shown in the following formula (II) or the following formula (III) structure.
  • X 1 is a first soft segment, and the first soft segment is an amorphous segment;
  • L is selected from single bonds, double bonds and divalent carbon atoms with 1 to 3 carbon atoms. or any of the trivalent hydrocarbon groups.
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and substituted or unsubstituted aliphatic ring, aromatic ring, heterocyclic ring and any one of the fused rings, wherein one A 1 and one A 2 are respectively selected from C, and both are combined with Y 1 , and the remaining A 1 and A 2 are respectively independently selected from any one of CH, CR and N, and The number of N in both A 1 and A 2 is not more than two.
  • Z 1 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocyclic rings and condensed rings, and A 3 and A 4 are independently selected from each other. Any one of CH, CR and N, and the number of N in A 3 and A 4 is not more than two.
  • R 1 , R 2 and R are each independently selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic any one of ring, aromatic ring, heterocyclic ring and fused ring, or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from unsubstituted aliphatic ring, aromatic ring, heterocyclic ring and any one of the fused rings, the first soft segment is selected from any one of a hydrophilic segment and a segment containing at least one hydrophilic group.
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Y 1 is selected from Any one of a hydrophobic group and a hydrophilic group, the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, or, at least one substituent in Y 1
  • the group is selected from a hydrophilic group
  • the first soft segment is selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group; or , one of the at least one substituent group in Y 1 and the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the other is selected from a hydrophobic segment and Any of the segments comprising at least one hydropho
  • the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Z 1 is selected from Any one of a hydrophobic group and a hydrophilic group, the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, or, at least one substituent in Z 1
  • the group is selected from a hydrophilic group
  • the first soft segment is selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group; or , one of the at least one substituent group in Y 1 and the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the other is selected from a hydrophobic segment and Any of the segments comprising at least one hydrophobic group.
  • the first soft segment is selected from any one of a hydrophobic segment and a segment comprising at least one hydrophobic group;
  • the first diamine is selected from the structure shown in formula (II),
  • Y 1 is selected from any one of aromatic rings, heterocyclic rings and condensed rings with at least one carbon atom substituted, and at least one substituent group is selected from hydrophilic groups and at least one hydrophilic group with a carbon atom number of 1 Any of the hydrocarbon groups of ⁇ 3.
  • Y 1 in the first diamine is bonded to the para position of the amino group, and is selected from a benzene ring with one carbon atom substituted, and the substituent group is an alcoholic hydroxyl group with 1-3 carbon atoms.
  • the first soft segment is a substituted or unsubstituted alkylene segment with 10-20 carbon atoms.
  • the first dianhydride has an asymmetric structure, or the first soft segment contains asymmetric branches.
  • the polyimide further includes a second segment structure formed by the reaction of the second dianhydride of the following formula (IV) and the first diamine.
  • X 2 in the second dianhydride is selected from any one of aliphatic ring, aromatic ring, heterocyclic ring and condensed ring structure.
  • the X 2 is selected from the following structural formula, wherein R 3 and R 4 are each independently selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • the molar ratio of the first dianhydride and the second dianhydride is 10:90 ⁇ 90:10.
  • the polyimide further comprises a third segment structure formed by the reaction of the second diamine of the following formula (V) and the first dianhydride.
  • Y 2 in the second diamine is the second soft segment; one of A 5 and one A 6 are respectively selected from C, and both are combined with Y 2 , and the remaining A 5 and A 6 are independently selected from CH Any one of , CR and N, and the number of N in A 5 and A 6 is not more than two, and R is selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • the first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic rings
  • Any one of aromatic ring, heterocyclic ring and fused ring or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from unsubstituted aliphatic ring, aromatic ring, heterocyclic ring and fused ring any one of the first soft segment and the second soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group.
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Y 1 is selected from The hydrophilic group, the first soft segment and the second soft segment are each independently selected from a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group Any one of, or, at least one substituent group in Y 1 is selected from hydrophobic groups, and at least one of the first soft segment and the second soft segment is selected from hydrophilic segments and contains at least one hydrophilic segment.
  • any one of the segments of the group, and the rest are selected from any one of the hydrophobic segment and the segment comprising at least one hydrophobic group, or, at least one substituent in Y 1 , the first soft segment and the first Among the two soft segments, 1 to 2 are selected from any one of the hydrophilic segment and the segment containing at least one hydrophilic group, and the remaining 2 to 1 are selected from the hydrophobic segment and the segment containing at least one hydrophobic group. any of the segments.
  • the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Z 1 is selected from
  • the hydrophilic group, the first soft segment and the second soft segment are each independently selected from a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group Any one of, or, at least one substituent group in Z 1 is selected from hydrophobic groups, and at least one of the first soft segment and the second soft segment is selected from hydrophilic segments and contains at least one hydrophilic segment.
  • any one of the segments of the group, and the rest are selected from any one of the hydrophobic segment and the segment comprising at least one hydrophobic group, or, at least one substituent in Z 1 , the first soft segment and the first Among the two soft segments, 1 to 2 are selected from any one of the hydrophilic segment and the segment containing at least one hydrophilic group, and the remaining 2 to 1 are selected from the hydrophobic segment and the segment containing at least one hydrophobic group. any of the segments.
  • the second soft segment is a substituted or unsubstituted alkylene segment having 5-12 carbon atoms.
  • the molar ratio of the first diamine and the second diamine is 10:90 to 90:10.
  • a liquid crystal aligning agent comprising: at least one polymer selected from polyimide and a group of polyimides obtained by ring closure of the polyimide At least one of; the polyimide comprises the first segment formed by the first dianhydride shown in the following formula (I) and the first diamine shown in the following formula (II) or the following formula (III) structure, the second segment structure generated by the second dianhydride described in the following formula (IV) and the first diamine, the second segment structure generated by the second diamine described in the following formula (V) and the first dianhydride
  • X 1 in the first dianhydride is the first soft segment
  • Y 2 in the second diamine is the second soft segment, and in the first soft segment and the second soft segment At least one of them is an amorphous segment
  • L in the first dianhydride is selected from any one of a single bond, a double bond and a divalent or trivalent hydrocarbon group with 1 to 3 carbon atoms
  • Anhydride X 2 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocycles and condensed rings
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocyclic rings and fused rings, wherein one A 1 and one A 2 are respectively selected from C, and both are combined with Y 1 is combined, the remaining A 1 and A 2 are independently selected from any one of CH
  • any one, and the number of N in A 3 and A 4 is not more than two; in the second diamine, one A 5 and one A 6 are respectively selected from C, and both are combined with Y 2 , and the remaining A 5 and A 6 are independently selected from any one of CH, CR and N, and the number of N in both A 5 and A 6 is not more than two; R 1 , R 2 and R are independently selected from hydrogen and aliphatic any of the group of hydrocarbon groups.
  • the polyimide comprises a third segment structure formed by a first dianhydride represented by formula (I) and a second diamine represented by formula (V), and a structure represented by formula (V)
  • a structure represented by formula (V) In the case of the fourth segment structure formed by the reaction between the second dianhydride shown in (IV) and the second diamine shown in formula (V); if X in the second dianhydride is selected from unsubstituted aliphatic rings , any one of aromatic ring, heterocyclic ring and fused ring, the first soft segment and the second soft segment are independently selected from hydrophilic segment, hydrophobic segment, segment comprising at least one hydrophilic group and any one of the segments containing at least one hydrophobic group; if the second dianhydride X 2 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one of X 2 is substituted The group is selected from any one of a hydrophobic group and a hydrophilic
  • At least one substituent group in X 2 is selected from hydrophobic groups, and one of the first soft segment and the second soft segment is selected from hydrophilic segments and includes at least one hydrophilic group Any one of the segments of X , and the other is selected from any one of the hydrophobic segment and the segment comprising at least one hydrophobic group; or, at least one substituent group in X 2 , the first soft segment and the second One or two of the soft segments are selected from any one of hydrophilic segments and segments containing at least one hydrophilic group, and the remaining two or one are selected from hydrophobic segments and chains containing at least one hydrophobic group any of the paragraphs.
  • the polyimide includes a fourth segment structure formed by the reaction of the second dianhydride shown in formula (IV) and the second diamine shown in formula (V), and the fourth segment structure shown in formula (IV)
  • the second segment structure generated by the second dianhydride and the first diamine shown in formula (II) or formula (III) if the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and any one of unsubstituted aliphatic ring, aromatic ring, heterocyclic ring and fused ring, or, if the first diamine is selected from such as The structure shown in formula (III), and Z 1 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings any one of the rings, the second soft segment is selected from any one of
  • the polyimide includes a first dianhydride as shown in formula (I) and a third segment structure generated as a second diamine as shown in formula (V), and a third segment structure as shown in formula (IV)
  • first segment structure generated by the reaction of the first dianhydride and the first diamine shown in formula (II) or formula (III)
  • second dianhydride shown in formula (IV) and the first diamine
  • the fourth segment structure formed by the reaction of the amine and the second dianhydride if the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from a single bond, O, NH, S, a or multiple unsaturated double bonds and any
  • the first soft segment is a substituted or unsubstituted alkylene segment having 10 to 20 carbon atoms;
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of aromatic rings, heterocyclic rings and fused rings with at least one carbon atom substituted, and at least one substituent group is selected from hydrophilic groups and at least one hydrophilic group with carbon atoms ranging from 1 to 1.
  • Any one of the hydrocarbon groups of 3; the second soft segment is selected from any one of a hydrophobic segment and a segment comprising at least one hydrophobic group.
  • the second soft segment is a substituted or unsubstituted alkylene segment having 5-12 carbon atoms.
  • Y 1 in the first diamine is combined at the para position of the amino group, and is selected from a benzene ring with one carbon atom substituted, and the substituent group is an alcoholic hydroxyl group with 1-3 carbon atoms.
  • a liquid crystal aligning agent comprising: at least one polymer selected from polyimide and a group of polyimides obtained by ring closure of the polyimide At least one of the following; the polyimide comprises a fifth segment structure formed by the second dianhydride represented by the following formula (IV) and the second diamine represented by the following formula (V).
  • the second dianhydride X 2 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocyclic rings and fused rings.
  • Y 2 is a second soft segment, and the second soft segment is an amorphous segment.
  • one A 5 and one A 6 are respectively selected from C, and both are combined with Y 2 , the remaining A 5 and A 6 are respectively independently selected from any one of CH, CR and N, and A 5
  • the number of N in both and A 6 is not more than two, and R is selected from any one of hydrogen and aliphatic hydrocarbon groups; if the second dianhydride X 2 is selected from unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings Any one of the two, the second soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group; if the second dianhydride X is selected from a substituted aliphatic ring, an aromatic ring, Any one of heterocycle and fused ring, then at least one substituent group in X 2 is a hydrophilic group, and the second soft segment is selected from any one of a hydrophobic segment and a segment comprising at least one hydrophobic group , or, at least one
  • liquid crystal aligning film formed using the above-mentioned liquid crystal aligning agent.
  • the hardness of the liquid crystal alignment film is characterized by the depth at which the needle is inserted into the liquid crystal alignment film under a preset pressure, and the hardness of the liquid crystal alignment film satisfies: under a preset pressure of 150 ⁇ N, The value is less than or equal to 45 ⁇ m.
  • the toughness of the liquid crystal alignment film is characterized by the pressure corresponding to a sudden change in the depth of the needle in the thickness direction of the liquid crystal alignment film, and the value of the toughness of the liquid crystal alignment film is greater than 390 ⁇ N.
  • the water contact angle of the liquid crystal aligning film is less than or equal to 58°.
  • the molar percentage of the first diamine and the second diamine contained in the liquid crystal aligning agent is 35%: 15%, as the first diamine contained in the liquid crystal aligning agent As the ratio of the anhydride and the second dianhydride gradually increases, the hardness of the liquid crystal aligning film decreases and the toughness increases.
  • the molar percentage of the first dianhydride and the second dianhydride contained in the liquid crystal aligning agent is 10%: 40%, and Y 2 in the second diamine is a hydrophobic segment , as the ratio of the first diamine and the second diamine contained in the liquid crystal aligning agent gradually increases, the water contact angle of the liquid crystal aligning film gradually decreases.
  • a display substrate comprising: a base substrate; and a liquid crystal aligning film provided on the base substrate, the liquid crystal aligning film comprising the above-mentioned polyimide after the liquid crystal aligning agent is fired .
  • a liquid crystal display device comprising: a first substrate and a second substrate disposed opposite to each other, and a liquid crystal layer disposed between the first substrate and the second substrate; wherein the first substrate and/or The second substrate is the display substrate as described above.
  • FIG. 1 is a block diagram of a liquid crystal display device according to some embodiments
  • 2A is a top view of a display panel according to some embodiments.
  • FIG. 2B is a cross-sectional structural diagram of a liquid crystal display device according to some embodiments.
  • FIG. 3 is a comparative structural diagram of an FFS type liquid crystal display device according to some embodiments when no voltage is applied and when a voltage is applied;
  • 4A is a structural diagram of a TN-type liquid crystal display device when no voltage is applied, according to some embodiments.
  • 4B is a structural diagram of a TN-type liquid crystal display device according to some embodiments when a voltage is applied;
  • 5 is a comparative graph of hardness, toughness and chip count of sample a, samples b1 to b9 according to some embodiments;
  • FIG. 6 is a graph comparing water contact angles and debris removal rates for sample a, samples b1-b9, and samples c1-c9, according to some embodiments.
  • first and second are only used for descriptive purposes, and should not be construed as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, a feature defined as “first” or “second” may expressly or implicitly include one or more of that feature.
  • plural means two or more.
  • At least one of A, B, and C has the same meaning as “at least one of A, B, or C”, and both include the following combinations of A, B, and C: A only, B only, C only, A and B , A and C, B and C, and A, B, and C.
  • a and/or B includes the following three combinations: A only, B only, and a combination of A and B.
  • the term “if” is optionally construed to mean “when” or “at” or “in response to determining” or “in response to detecting,” depending on the context.
  • the phrases “if it is determined that" or “if a [statement or event] is detected” are optionally interpreted to mean “in determining" or “in response to determining" or “on detection of [recited condition or event]” or “in response to detection of [recited condition or event]”.
  • the expressions “coupled” and “connected” and their derivatives may be used.
  • the term “connected” may be used in describing some embodiments to indicate that two or more components are in direct physical or electrical contact with each other.
  • the term “coupled” may be used in describing some embodiments to indicate that two or more components are in direct physical or electrical contact.
  • the terms “coupled” or “communicatively coupled” may also mean that two or more components are not in direct contact with each other, yet still co-operate or interact with each other.
  • the embodiments disclosed herein are not necessarily limited by the content herein.
  • Exemplary embodiments are described herein with reference to cross-sectional and/or plan views that are idealized exemplary drawings.
  • the thickness of layers and regions are exaggerated for clarity. Accordingly, variations from the shapes of the drawings due to, for example, manufacturing techniques and/or tolerances, are contemplated.
  • example embodiments should not be construed as limited to the shapes of the regions shown herein, but to include deviations in shapes due, for example, to manufacturing. For example, an etched area shown as a rectangle will typically have curved features.
  • the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the actual shape of a region of a device and are not intended to limit the scope of example embodiments.
  • liquid crystal display device may be a liquid crystal display panel, or may include a liquid crystal display panel.
  • the liquid crystal display device may be a liquid crystal display panel, or may include a liquid crystal display panel.
  • mobile phones tablet computers, notebooks, personal digital assistants (personal digital assistants, PDAs), in-vehicle computers, etc.
  • PDAs personal digital assistants, PDAs
  • in-vehicle computers etc.
  • the liquid crystal display device when the liquid crystal display device includes a liquid crystal display panel 1 , the liquid crystal display device may further include a frame 2 , a cover glass 3 , a backlight module 4 , a circuit board 5 , and other accessories such as a camera.
  • the backlight module 4 is configured to provide backlight to the liquid crystal display panel 1 ;
  • the circuit board 5 is coupled to the liquid crystal display panel 1 and configured to provide electrical signals to the liquid crystal display panel 1 to control the liquid crystal display panel 1 to display images.
  • the longitudinal section of the frame 2 can be U-shaped, the liquid crystal display panel 1, the backlight module 4, the circuit board 5 and other electronic accessories are arranged in the frame 2, and the backlight module 4 is arranged in the liquid crystal display panel Below 1 , the circuit board 5 is arranged below the backlight module 4 , and the cover glass 2 is located on the side of the liquid crystal display panel 1 away from the backlight module 4 .
  • the liquid crystal display panel 1 includes a display area (Active Area, referred to as AA area for short) A and surrounds the display area.
  • the peripheral area S set in the area A the display area A includes a plurality of pixel areas (the dotted box in the figure indicates a pixel), each pixel area includes at least three sub-pixel areas P, and the at least three sub-pixel areas P can be respectively red sub-pixels.
  • the peripheral area S is an area other than the display area A in the liquid crystal display panel, and is used for wiring.
  • the gate driving circuit can also be arranged in the peripheral area S.
  • the liquid crystal display panel 1 includes a first substrate 11 and a second substrate 12 opposite to each other, and a liquid crystal layer 13 disposed between the first substrate 11 and the second substrate 12 .
  • the first substrate 11 and the second substrate 12 are respectively an array substrate and an opposite substrate (both the array substrate and the opposite substrate can be referred to as display substrates), and the array substrate and the opposite substrate are boxed together by a frame sealant. Therefore, the liquid crystal layer 13 is limited in the area surrounded by the frame sealant.
  • the display substrate includes a base substrate 100 and a liquid crystal alignment film 14 disposed on the base substrate 100 .
  • the liquid crystal alignment film 14 is configured to define the initial alignment of the liquid crystal molecules in the liquid crystal layer 13 (that is, the alignment of the liquid crystal molecules when no power is supplied to the liquid crystal display panel 1).
  • the display substrate not only includes the base substrate 100 and the liquid crystal alignment film 14 disposed on the base substrate 100 , but also includes a liquid crystal alignment film 14 disposed on each base substrate 100 .
  • a thin film transistor Thin Film Transistor, TFT
  • the display substrate may further include a common electrode 300 disposed in each sub-pixel region. As shown in FIG. 2B , the common electrode 300 and the pixel electrode 200 are separated by the first insulating layer 210.
  • the space between the TFT and the common electrode 300 may also be The second insulating layer 220 is provided.
  • the pixel electrode 200 is electrically connected to the drain electrode or the source electrode of the TFT through a channel located on the first insulating layer 210 , the common electrode 300 and the second insulating layer 220 .
  • the first insulating layer 210 and the second insulating layer 220 are all laid on the display area A. Parts of the area can be removed by patterning and other methods in a desired area to form a channel (also called a via).
  • the display substrate may include, in addition to the base substrate 100 and the liquid crystal alignment film 14 disposed on the base substrate 100 , the substrate The substrate 100 faces the color filter layer 400 on the surface of the liquid crystal layer 13 .
  • the opposite substrate 12 is called a color filter substrate.
  • the color filter layer 400 includes a red filter pattern in the red sub-pixel region R, a green filter pattern in the green sub-pixel region G, and a blue filter pattern in the blue sub-pixel region.
  • the display substrate may also include a black matrix (Black Matrix, BM), and the black matrix includes a plurality of parallel first light shielding strips and a plurality of parallel first light shielding strips.
  • BM Black Matrix
  • the above-mentioned liquid crystal display panel 1 is illustrated by taking the common electrode 300 disposed on the base substrate of the array substrate as an example.
  • the liquid crystal display panel 1 may be AD-SDS (Advanced-Super Dimensional Switching, Advanced Super Dimensional Switching). Field switch) type display panel, one of the pixel electrode 200 and the common electrode 300 has a slit, and the upper and lower positions of the two can be changed, but the pixel electrode 300 is connected to the drain or source of the thin film transistor.
  • the liquid crystal display panel 1 can also be a display panel of FFS (Fringe Field Switching, fringe field switching) type, IPS (In Plane Switch, lateral electric field effect) type and other types of display panels.
  • the common electrode 300 may also be disposed on the base substrate of the opposite substrate.
  • the liquid crystal display panel 1 may be a TN (Twist Nematic, twisted nematic) type display panel or the like.
  • the liquid crystal molecules are anisotropic when they are in the liquid crystal state, the photoelectric effect caused by the liquid crystal molecules will be different due to the different rotation directions.
  • the optoelectronic properties such as the turning characteristic under the influence of the electric field) and the refractive index (the characteristic that affects the polarization state of the light when the light passes through the liquid crystal molecules) have anisotropy, so these characteristics of the liquid crystal itself are used, and the voltage is appropriately used to control the
  • the rotation of the liquid crystal molecules affects the polarization state of the light to form different gray scales, so that the display can be realized.
  • the liquid crystal display panel 1 further includes a lower polarizer 15 (also referred to as a first polarizer) disposed on the side of the first substrate 11 away from the liquid crystal layer 13 and a lower polarizer 15 (also referred to as a first polarizer) disposed on the second substrate 12 away from the liquid crystal layer
  • the upper polarizer 16 on the side of 13 also referred to as the second polarizer.
  • the function of the polarizer is to allow polarized light in a direction parallel to the polarization axis (ie, the direction of transmission) to pass through, and the transmission directions of the lower polarizer 15 and the upper polarizer 16 are perpendicular or parallel.
  • the linearly polarized light emitted from the lower polarizer 15 changes its polarization state after passing through the liquid crystal layer 13 controlled by the electric field, and only the light component parallel to the transmission direction of the upper polarizer 16 can pass through the upper polarizer 16 . , so as to form the display of different gray scales.
  • the liquid crystal alignment film 14 plays the role of initial alignment of the liquid crystal molecules.
  • the vibration-transmitting direction of the upper polarizer 16 and the vibration-transmitting direction of the lower polarizer 15 are perpendicular, and are disposed on the two base substrates 100
  • the alignment directions of the liquid crystal alignment films 14 on the top are parallel to each other.
  • the liquid crystal molecules are aligned along the same direction, and the sub-pixel is in a black state.
  • the alignment directions of the liquid crystal alignment films 14 disposed on the two substrates are mutually Vertically, the liquid crystal molecules form a 90-degree twisted alignment structure.
  • the normal white mode in which the upper polarizer 16 and the lower polarizer 15 are vertically orthogonal is shown as a white state when no voltage is applied. After the voltage is applied, the liquid crystal molecules are vertically aligned. After the incident linearly polarized light passes through the liquid crystal layer 13 , the polarized light cannot pass through the upper polarizer 16 and displays a black state.
  • the liquid crystal display device cannot work normally.
  • the arrangement of the molecules will be irregular, resulting in the scattering of light, resulting in the phenomenon of light leakage.
  • some embodiments of the present disclosure provide a liquid crystal aligning film, the liquid crystal aligning film is formed by using a liquid crystal aligning agent, and includes a polyimide after the liquid crystal aligning agent is fired.
  • the liquid crystal aligning film can be rubbed and aligned to obtain the liquid crystal aligning film 14 as described above.
  • liquid crystal alignment film provided by the present disclosure can be aligned by optical action, it is also applicable to optical alignment.
  • the raw materials of the liquid crystal aligning film used in the project are mainly divided into polyimide and soluble polyimide. Dianhydride and diamine are mixed and dissolved in a specific solvent to form polyimide, and polyimide is dehydrated to form polyimide. imide.
  • the raw materials of the liquid crystal alignment film such as dianhydride and diamine can be mixed in a solvent, and stirred under the protection of nitrogen to cause a polymerization reaction to generate polyimide. After purification, it is diluted with a certain proportion of solvent to prepare a liquid crystal aligning agent.
  • the liquid crystal aligning agent is formed on the above-mentioned base substrate (here, the base substrate may be the base substrate on which the thin film transistor TFT, the pixel electrode and the common electrode have been formed, or the base substrate may be On the base substrate on which the color filter layer and the black matrix have been formed), then pre-curing (temperature: 125°C to 135°C, time: 110s to 150s), main curing (temperature: 210°C to 240°C, time : 1100s ⁇ 1500s) process to cure it, and finally dehydrate the polyimide by firing to form polyimide.
  • pre-curing temperature: 125°C to 135°C, time: 110s to 150s
  • main curing temperature: 210°C to 240°C, time : 1100s ⁇ 1500s
  • the liquid crystal aligning agent can be formed on the base substrate by a relief printing method or an inkjet method.
  • the letterpress printing method has the advantages of accurate pattern selection and uniform printing surface.
  • the inkjet method is suitable for the production of large-size display panels, and compared with the letterpress printing method, the liquid crystal aligning agent used in the inkjet method is less, and the efficiency is high and the cost is low.
  • Embodiment 1 of the present disclosure provides a liquid crystal aligning agent, comprising at least one polymer selected from polyimide and a group of polyimides obtained by ring closure of the polyimide at least one of.
  • the polyimide includes a first segment structure formed by the first dianhydride represented by the following formula (I) and the first diamine represented by the following formula (II) or the following formula (III).
  • X 1 is the first soft segment, and the first soft segment is an amorphous segment;
  • L is selected from single bonds, double bonds, and divalent or trivalent carbon atoms with 1 to 3 carbon atoms. any of the valent hydrocarbon groups.
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and substituted or unsubstituted aliphatic rings, aromatic rings, heterocycles and Any of the fused rings, wherein one A 1 and one A 2 are respectively selected from C, and both are combined with Y 1 , the remaining A 1 and A 2 are independently selected from any one of CH, CR and N, and A The number of N in both 1 and A 2 is not more than two.
  • Z 1 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocycles and condensed rings
  • a 3 and A 4 are independently selected from Any one of CH, CR and N, and the number of N in A 3 and A 4 is not more than two
  • R 1 , R 2 and R are independently selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • some molecular segments are composed of aromatic hydrocarbons, which are more rigid, called hard segments, and some molecular segments are composed of aliphatic hydrocarbons. The greater flexibility is called the soft segment.
  • the soft segment is relative to the hard segment.
  • the hard segment in addition to the aromatic hydrocarbons indicated in the block copolymer, may also include polycyclic rings, condensed rings, and conjugated systems containing aromatic rings, and the like.
  • the structure shown above for the first diamine in addition to the above-mentioned aliphatic hydrocarbons, the soft segment may also include segments composed of carbon-oxygen bonds, carbon-nitrogen bonds, carbon-silicon bonds, and silicon-oxygen bonds.
  • Polymers can be divided into crystalline and amorphous (non-crystalline) types according to the regularity of their molecular arrangement in space.
  • it can be divided into crystalline segment and amorphous segment.
  • the molecular arrangement in the segment is regular and orderly, it is called crystalline segment.
  • the molecules in the segment are arranged in a disorderly manner, which is called an amorphous segment.
  • amorphous segments are often obtained.
  • the amorphous segment refers to the segment that will not crystallize under any conditions, and in practice, the segment with very low crystallinity is often included in it.
  • Atactic is the random arrangement of substituents on both sides of the plane or the configuration of the chiral center, and random copolymerization is formed by the random arrangement of two (or more than two) monomer units. Both monomer unit sequence length distributions are each randomly distributed.
  • the first soft segment is an amorphous segment, therefore, there are two possible cases.
  • the first dianhydride has an asymmetric structure.
  • the first soft segment contains asymmetric branches.
  • Molecular symmetry means that molecules often have some symmetry because they contain several identical atoms or groups. If the molecule undergoes a certain symmetry operation (the symmetry operation has its own symmetry elements, the symmetry of the molecule can be divided into five symmetry elements: the rotation axis, the symmetry plane, the symmetry center, the rotation reflection axis and the identity element). If the original molecule of the operation cannot be distinguished, it is called the symmetry of the molecule. At this time, the structure of the molecule is a symmetric structure, otherwise, the structure of the molecule is an asymmetric structure.
  • the first dianhydride taking L selected from double bonds as an example, since the first dianhydride has two butyl dianhydrides, X 1 is connected between the two butyl dianhydrides, if R 1 and R 2 are located at The same side of X 1 , then the first dianhydride is cis, otherwise, the first dianhydride is trans, when the first dianhydride is cis, the first dianhydride is suitable for the symmetry element is the symmetry plane At this time, if the first dianhydride is mirror-symmetrical, the first dianhydride is a symmetric structure; otherwise, the first dianhydride is an asymmetric structure.
  • the first soft segment may contain an asymmetric branched chain, or may not contain Asymmetric branching, that is, the first case described above.
  • the first dianhydride is trans, the first dianhydride is applicable to the criterion that the symmetric element is the center of symmetry. At this time, if the first dianhydride is center-symmetric, the first dianhydride has a symmetrical structure, and vice versa , then the first dianhydride is an asymmetric structure.
  • the substituents R 1 and R 2 are different, in this case, similar to the first dianhydride being cis, the first dianhydride
  • the soft segment may or may not contain asymmetric branches, that is, the first case described above.
  • the first soft segment contains an asymmetric branched chain.
  • the first dianhydride is cis
  • the branch in the first soft segment is an asymmetric branch is the same as the criterion for judging whether the first dianhydride is a symmetric structure, and the symmetric element is used as the symmetry plane to judge.
  • the polyimide can be a structure with the first segment structure as a repeating unit.
  • the structure of the first diamine there are two possible structures.
  • the first structure is shown in the following formula (1).
  • the second structure is shown in the following formula (2).
  • the polyimide is formed by alternately arranging amorphous soft segments and hard segments. Therefore, by rationally proportioning the soft segments and hard segments in the molecular structure, it is possible to Endows polyimide with special properties, such as making polyimide with good rigidity and improving the toughness of polyimide.
  • polyimide has good hardness (hardness can reach 3H) in related technologies ⁇ 4H), but in the rubbing alignment, due to the high hardness, it is easy to produce debris, and it is easy to damage the rubbing cloth, causing the components in the rubbing cloth to fall off.
  • the sintered product (polyimide) of the polyimide has good ductility and can well buffer the external force generated by the rubbing cloth.
  • polyimide It is not easy to generate debris, and on the other hand, the polyimide is not easy to damage the rubbing cloth; therefore, it can effectively reduce the defective debris.
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted Any one of aliphatic ring, aromatic ring, heterocyclic ring and fused ring, or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from unsubstituted aliphatic ring, aromatic ring, heterocyclic ring and any one of the fused rings, the first soft segment is selected from any one of a hydrophilic segment and a segment containing at least one hydrophilic group.
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Y 1 is selected from Any one of a hydrophobic group and a hydrophilic group, the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, or, at least one substituent in Y 1
  • the group is selected from a hydrophilic group
  • the first soft segment is selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group; or , one of the at least one substituent group in Y 1 and the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the other is selected from a hydrophobic segment and Any of the segments comprising at least one hydropho
  • the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Z 1 is selected from Any one of a hydrophobic group and a hydrophilic group, the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, or, at least one substituent in Z 1
  • the group is selected from a hydrophilic group
  • the first soft segment is selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group; or , one of the at least one substituent group in Y 1 and the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the other is selected from a hydrophobic segment and Any of the segments comprising at least one hydrophobic group.
  • the same molecular chain contains a hydrophilic segment and a hydrophobic segment, and the hydrophobic segment is relative to the hydrophilic segment.
  • Vinyl ether segment polyvinyl alcohol segment, polyethylene imine segment, polyvinyl pyrrolidone segment, polyethylene phthalamide segment, etc.
  • the hydrophobic segments include polypropylene oxide segments, polysiloxane segments, saturated aliphatic hydrocarbon segments (such as polystyrene segments, polyethylene segments, polypropylene segments, polymethyl methacrylate segments, polymethyl acrylate segment, polybutyl acrylate segment) or unsaturated aliphatic hydrocarbon segment (such as polybutadiene segment).
  • a hydrophilic group also known as an oleophobic group, has an atomic group that is soluble in water, or easily affinity with water. May attract water molecules or dissolve in water, and the solid surface formed by such molecules is easily wetted by water. Including carboxyl group, sulfonic acid group, phosphoric acid group, amino group, quaternary ammonium group, ether group composed of oxygen-containing groups, hydroxyl group, carboxylate, block polyether, etc.
  • Hydrophobic groups also known as lipophilic groups, have no affinity for water, are insoluble in water or have minimal solubility.
  • hydrocarbon groups, ester groups, etc. wherein the hydrocarbon groups can be saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons containing double bonds, or hydrocarbon groups containing aryl groups, esters, ethers, amines, amides and other groups.
  • the first diamine when the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic
  • Z 1 is selected from unsubstituted aliphatic ring, aromatic ring, heterocycle and In any of the fused rings
  • the first diamine is a hydrophobic segment, therefore, by setting the first soft segment as a hydrophilic segment or introducing a hydrophilic group into the first soft segment, A reasonable proportion of the hydrophobic segment and the hydrophilic segment or the hydrophilic group can adjust the hydrophilic and hydrophobic properties of the polyimide.
  • the hydrophobicity of the substituted group and the hydrophobicity of the first soft segment are carried out.
  • the hydrophilic and hydrophobic properties of the polyimide can also be adjusted by adjusting and rationally mixing the substituent groups and the hydrophilic and hydrophobic groups in the first soft segment.
  • the contact angle of water on the surface is large, the wetting effect is poor, and it is not easy to form a water film.
  • the debris is adsorbed on the surface of the hydrophobic polyimide and is not easy to enter the water.
  • the contact angle of water on its surface is small, the wetting effect is good, a uniform water film is easily formed, and the debris is also easy to enter the water, and finally blown away by the air knife.
  • the hydrophilicity is too strong, it is easy to absorb the water vapor in the environment, causing the pollution of dust particles in the environment, thereby producing debris of environmental foreign matter.
  • the polyimide has suitable hydrophilicity and hydrophobicity.
  • the surface of the polyimide is subjected to Cleaning can effectively remove debris and impurities (such as fluff in the rubbing cloth) generated during the friction alignment process, which cannot be effectively cleaned before the box is formed in the related art, and the debris in the residual box is bad (such as larger ones). Debris directly leads to a decrease in yield, and smaller debris can lead to light leakage in the black state, reducing product contrast), which can avoid defective debris.
  • the first soft segment is any one of a hydrophobic segment and a segment comprising at least one hydrophobic group;
  • the first diamine is selected from the structure shown in formula (II), and Y 1 Any one of aromatic rings, heterocyclic rings and fused rings with at least one carbon atom substituted, and at least one substituent group is selected from hydrophilic groups and at least one hydrophilic group having 1 to 3 carbon atoms. any of the hydrocarbon groups.
  • the hydrophilic group when at least one substituent group is selected from a hydrophilic group, the hydrophilic group is directly connected to the ring of Y 1 , and since the Y 1 is selected from aromatic ring, heterocyclic ring and condensed ring Therefore, when the hydrophilic group is a hydroxyl group, the hydrophilic group is a phenolic hydroxyl group. And when at least one substituent group is selected from a hydrocarbon group with at least one hydrophilic group having 1 to 3 carbon atoms, the hydrophilic group is connected to the hydrocarbon group. Therefore, when the hydrophilic group is a hydroxyl group, The hydrophilic group is an alcoholic hydroxyl group.
  • Y 1 in the first diamine is combined at the para position of the amino group, and is selected from a benzene ring with one carbon atom substituted, and the substituent group is an alcoholic hydroxyl group with 1-3 carbon atoms.
  • the hydrophilic group is an alcoholic hydroxyl group.
  • Y 1 is bonded to the para position of the amino group, when A 1 and A 2 are independently selected from any one of CH and CR, the first diamine is terphenyl.
  • the first soft segment is a substituted or unsubstituted alkylene segment having 10-20 carbon atoms.
  • the first soft segment when the first soft segment is an unsubstituted alkylene segment with 10 to 20 carbon atoms, since the first soft segment is an amorphous segment, the first soft segment is The dianhydride has an asymmetric structure. In this case, the R 1 and R 2 are different.
  • the first soft segment is a substituted alkylene segment with 10 to 20 carbon atoms, since the first soft segment is an amorphous segment, the first dianhydride is an asymmetric structure, That is, in the case where the substituent group forms a symmetrical branch, the R 1 and R 2 are different.
  • the first soft segment contains an asymmetric branched chain, and in this case, the R 1 and R 2 can be the same, and the first soft segment can also be an amorphous segment.
  • the first dianhydride is an asymmetric structure or the first soft segment contains an asymmetric structure.
  • the second embodiment of the present disclosure provides a liquid crystal aligning agent, the liquid crystal aligning agent includes at least one polymer, and the at least one polymer is selected from polyimide and a group of polyimide obtained by ring-closing the polyimide at least one of amines.
  • the polyimide also includes the following The second segment structure formed by the second dianhydride represented by the formula (IV) and the first diamine represented by the above formula (II) or the above formula (III).
  • X 2 in the second dianhydride is selected from any one of aliphatic ring, aromatic ring, heterocyclic ring and condensed ring structure.
  • the second dianhydride since X in the second dianhydride is selected from any one of aliphatic ring, aromatic ring, heterocyclic ring and condensed ring structure, the second dianhydride has a plane The molecular structure is relatively rigid, and acts as a hard segment in the second segment structure formed by the reaction with the above-mentioned first diamine.
  • the acid anhydride and diamine are polymerized in a molar ratio of 1:1, when mixing, the ratio of the total molar amount of the first dianhydride and the second dianhydride to the molar amount of the first diamine can be close to 1 :1, such as 9:11 ⁇ 11:9.
  • both the first dianhydride and the second dianhydride are polymerized with the first diamine, and by adjusting the ratio of the first dianhydride and the second dianhydride, the The ratio of a segment structure and the second segment structure formed by the second dianhydride and the first diamine (that is, the first dianhydride and the second dianhydride in the polyimide obtained by the polymerization of the same first diamine).
  • the segment structure (the ratio shown by the following formula (3) or the following formula (4) depending on the structure of the first diamine) can be adjusted.
  • the polyimide is still composed of amorphous soft segments and hard segments alternately arranged, and the polyimide can be adjusted by adjusting the ratio of the first dianhydride and the second dianhydride.
  • the length of the soft segment and hard segment of the acid is adjusted, so that the hardness, toughness and brittleness of the polyimide can be adjusted, so that the polyimide has a certain hardness and good toughness, which can also solve the problem.
  • polyimide has good hardness (hardness can reach 3H-4H), it is easy to generate debris due to excessive hardness during friction alignment, and it is easy to damage the friction cloth, causing the components in the friction cloth to fall off, cause the problem of poor debris.
  • the polyamide in the case of adjusting the hydrophilic and hydrophobic properties of the polyimide, by adjusting the ratio of the second dianhydride to the first dianhydride, the technical effect of making the hydrophobicity of the polyimide suitable can also be achieved. Before improving the cleaning performance of polyimide, it can effectively remove the debris generated during the friction alignment process, and can also avoid the occurrence of defective debris.
  • the molar ratio of the first dianhydride and the second dianhydride may be 10:90 ⁇ 90:10.
  • X 2 in the second dianhydride can be selected from any one of the following structures.
  • X 2 in the second dianhydride is selected from the following structural formula, wherein R 3 and R 4 are each independently selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • Embodiment 3 of the present disclosure provides a liquid crystal aligning agent, comprising at least one polymer, and the at least one polymer is selected from at least one polyimide and a group of polyimides obtained by ring closure of the polyimide.
  • the polyimide also includes The third segment structure formed by the reaction of the second diamine represented by the following formula (V) and the first dianhydride.
  • Y 2 in the second diamine is the second soft segment; one of A 5 and one A 6 are respectively selected from C, and both are combined with Y 2 , and the remaining A 5 and A 6 are independently selected from CH, Any one of CR and N, and the number of N in A 5 and A 6 is not more than two, and R is selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • the second diamine acts as a soft segment in the third segment structure formed by the reaction with the above first dianhydride.
  • the first diamine can be The ratio of the first segment structure generated by the anhydride and the first diamine and the third segment structure generated by the first dianhydride and the second diamine (that is, the first dianhydride and the second dianhydride and the The segment structure obtained by the polymerization of the same first diamine (depending on the structure of the first diamine, it can be adjusted by the ratio shown by the following formula (5) or the following formula (6)).
  • the polyimide is still composed of amorphous soft segments and hard segments alternately arranged.
  • the polyimide can be The crystallinity of the polyimide can be adjusted so that the polyimide has a certain hardness and good toughness. It can also solve the problem that although the polyimide has good hardness (hardness can reach 3H ⁇ 4H) in the related art, the friction During alignment, due to the high hardness, it is easy to generate debris, and it is easy to damage the rubbing cloth, causing the components in the rubbing cloth to fall off, resulting in the problem of defective debris.
  • the first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted Any one of aliphatic ring, aromatic ring, heterocyclic ring and fused ring
  • Z 1 is selected from unsubstituted aliphatic ring, aromatic ring, heterocyclic ring and any one of the fused rings
  • at least one of the first soft segment and the second soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group.
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Y 1 is selected from The hydrophilic group, the first soft segment and the second soft segment are each independently selected from a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group Any one of, or, at least one substituent group in Y 1 is selected from hydrophobic groups, and at least one of the first soft segment and the second soft segment is selected from hydrophilic segments and contains at least one hydrophilic segment.
  • any one of the segments of the group, and the rest are selected from any one of the hydrophobic segment and the segment comprising at least one hydrophobic group, or, at least one substituent in Y 1 , the first soft segment and the first Among the two soft segments, 1 to 2 are selected from any one of the hydrophilic segment and the segment containing at least one hydrophilic group, and the remaining 2 to 1 are selected from the hydrophobic segment and the segment containing at least one hydrophobic group. any of the segments.
  • the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in Z 1 is selected from
  • the hydrophilic group, the first soft segment and the second soft segment are each independently selected from a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group Any one of, or, at least one substituent group in Z 1 is selected from hydrophobic groups, and at least one of the first soft segment and the second soft segment is selected from hydrophilic segments and contains at least one hydrophilic segment.
  • any one of the segments of the group, and the rest are selected from any one of the hydrophobic segment and the segment comprising at least one hydrophobic group, or, at least one substituent in Z 1 , the first soft segment and the first Among the two soft segments, 1 to 2 are selected from any one of the hydrophilic segment and the segment containing at least one hydrophilic group, and the remaining 2 to 1 are selected from the hydrophobic segment and the segment containing at least one hydrophobic group. any of the segments.
  • a hydrophilic group and a hydrophobic group are respectively introduced into the first dianhydride and the first diamine, or the first soft segment is set as a hydrophilic segment or a hydrophobic segment.
  • introducing a hydrophilic group or a hydrophobic group into the second diamine, or, setting the second soft segment as a hydrophilic segment or a hydrophobic segment, through the ratio of the first diamine and the second diamine Adjustment can also achieve the technical effect of making the hydrophobicity of the polyimide suitable, improve the cleaning performance of the polyimide before the box is formed, effectively remove the debris generated during the friction alignment process, and also avoid the generation of debris. bad.
  • the second soft segment is a substituted or unsubstituted alkylene segment with 5-12 carbon atoms. That is, when the second soft segment is an unsubstituted alkylene segment with 5 to 12 carbon atoms, the second soft segment is a hydrophobic segment.
  • the first soft segment can be selected from hydrophilic segment and contains at least one hydrophilic segment any one of the segments of the group, and if the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then If at least one substituent group in Y 1 is selected from a hydrophilic group, the first soft segment is selected from a hydrophobic segment, a segment containing at least one hydrophobic group, a hydrophilic segment, and a segment containing at least one hydrophilic group Any one of the segments of the group, if at least one substituent group in Y 1 is selected from a hydrophobic group, the first soft segment is selected from a hydrophilic segment and
  • Either, or at least one of the at least one substituent group in the Y 1 and at least one of the first soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, The remainder are selected from any of hydrophobic segments and segments comprising at least one hydrophobic group.
  • the second soft segment is an unsubstituted alkylene segment having 7 carbon atoms. That is, the second soft segment is a hydrophobic segment.
  • the molar ratio of the first diamine and the second diamine may be 10:90 ⁇ 90:10.
  • Embodiment 4 of the present disclosure provides a liquid crystal aligning agent, the liquid crystal aligning agent includes at least one polymer, and the at least one polymer is selected from polyimide and a group of polyimide obtained by ring-closing of polyimide at least one of amines.
  • the polyimide comprises the first dianhydride shown in the following formula (I) and the third segment structure formed by the second diamine shown in the following formula (V), and the second diamine shown in the following formula (V)
  • the fourth segment structure formed by the reaction of amine and the second dianhydride shown in the following formula (IV), and the first diamine shown in the following formula (II) or the following formula (III) and the following formula (IV) At least two segment structures in the second segment structure generated by the second dianhydride shown.
  • X 1 in the first dianhydride is the first soft segment
  • Y 2 in the second diamine is the second soft segment
  • at least one of the first soft segment and the second soft segment One is an amorphous segment.
  • L is selected from any one of single bonds, double bonds and divalent or trivalent hydrocarbon groups with 1 to 3 carbon atoms;
  • the second dianhydride X 2 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocyclic rings and fused rings.
  • the first diamine is shown in formula (II), Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and substituted or unsubstituted aliphatic, aromatic, heterocyclic and condensed any one of the rings, wherein one A 1 and one A 2 are respectively selected from C, and both are combined with Y 1 , the remaining A 1 and A 2 are independently selected from any one of CH, CR and N, and A 1 And the number of N in A 2 is not more than two.
  • the first diamine is shown in formula (III), Z 1 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings, and A 3 and A 4 are independently selected from CH , CR and N, and the number of N in A 3 and A 4 is not more than two.
  • one A 5 and one A 6 are respectively selected from C, and both are combined with X2, the remaining A 5 and A 6 are respectively independently selected from any one of CH, CR and N, and A 5 and The number of Ns in A6 is not more than two.
  • R 1 , R 2 and R are each independently selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • Embodiment 4 and Embodiment 5 can refer to the descriptions of Embodiment 1, Embodiment 2 and Embodiment 3 above, which will not be repeated here.
  • Embodiment 4 and Embodiment 5 and Embodiment 1, Embodiment 2 and Embodiment 3 above are respectively described.
  • the polyimide may comprise a segment structure composed of a third segment structure and a fourth segment structure (that is, the first dianhydride and the second dianhydride in the polyimide are the same as the same one
  • the segment structure obtained by the polymerization of the second diamine (which may be shown in the following formula (7)))
  • the polyimide may comprise a segment structure composed of the second segment structure and the fourth segment structure (ie The segment structure obtained by the polymerization of the first diamine and the second diamine in the polyimide with the same second dianhydride (depending on the structure of the first diamine, the following formula (8) or the following formula (9) can be used) shown)
  • the polyimide can comprise a segment structure consisting of a second segment structure, a third segment structure and a fourth segment structure (according to the structure of the first diamine, the following formula can be used) (10) or the following formula (11))).
  • the polyimide is still formed by alternating soft segments and hard segments, and because at least one of the first soft segment and the second soft segment is an amorphous chain Therefore, through a reasonable ratio of the soft segment and the hard segment in the molecular structure, the polyimide can be given special properties, such as making the polyimide have good rigidity, and can also improve the polyimide
  • the toughness of subacid is similar to that of polyimide in the related art, although polyimide has good hardness (hardness can reach 3H ⁇ 4H), but it is easy to produce debris due to excessive hardness during friction alignment, and it is easy to damage the friction cloth, causing friction Compared with the components in the cloth falling off, because the polyimide has good toughness, the rubbing cloth is used for rubbing during the rubbing alignment, and the product (polyimide) fired from the polyimide has a good The ductility of the rubbing cloth can well buffer the external force generated by the rubbing cloth. On the one hand, the polyimide itself
  • the polyimide includes a third segment structure formed by the first dianhydride shown in formula (I) and the second diamine shown in formula (V). , and in the case of the fourth segment structure generated by the reaction of the second dianhydride shown in formula (IV) and the second diamine shown in formula (V);
  • the first soft segment and the second soft segment are independently selected from hydrophilic segment , any one of a hydrophobic segment, a segment comprising at least one hydrophilic group, and a segment comprising at least one hydrophobic group;
  • the second dianhydride X 2 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituted group in X 2 is selected from any of hydrophobic groups and hydrophilic groups
  • the first soft segment and the second soft segment are independently selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, or, at least one substituent in X 2 is selected from From the hydrophobic group, one of the first soft segment and the second soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the other is selected from a hydrophobic segment and any one of the segments comprising at least one hydrophobic group; alternatively, one or both of the at least one substituent group in X 2 , the first soft segment and the second soft segment are selected from hydrophilic segments and any one of the segments comprising at least one hydrophilic group, and the remaining two or one is selected from any one of the hydrophobic segments and the
  • the polyimide includes a fourth segment structure formed by the reaction of the second dianhydride shown in formula (IV) and the second diamine shown in formula (V), and the fourth segment structure shown in formula (IV) In the case of the second segment structure generated by the second dianhydride and the first diamine represented by formula (II) or formula (III);
  • first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic, aromatic, heterocyclic and Any one of the fused rings, or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings, and the second soft segment is selected from any one of hydrophilic segments and segments comprising at least one hydrophilic group;
  • first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic, aromatic, heterocyclic and Any one of the fused rings, or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • X 2 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • X 2 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • One substituent group is selected from a hydrophilic group
  • the second soft segment is selected from any of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group.
  • One, or at least one substituent group in X 2 is selected from a hydrophobic group
  • the second soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, or, X 2
  • At least one of the at least one substituent group in and the second soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the rest are selected from a hydrophobic segment and a segment comprising at least one hydrophilic group. any of the segments of a hydrophobic group;
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, or, if the first diamine is selected from formula (III) ) shown in the structure, and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings one, then at least one substituent group in Y 1 or Z 1 is a hydrophilic group, and the second soft segment is selected from a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment and a segment comprising at least one Any one of the segments of the hydrophilic group, or, at least one substituent group in Y 1 or Z 1 is a hydrophobic group, and the second soft segment is selected from the hydrophilic segment and contains at least one hydrophilic group Any one of the
  • the first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, or, if the first diamine is selected from formula (III) ) shown in the structure, and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any of substituted aliphatic rings, aromatic rings, heterocycles and fused rings , then at least one substituent group in Y 1 or Z 1 is a hydrophilic group, at least one substituent group in X 2 is selected from any one of hydrophilic groups and hydrophobic groups, and the second soft segment is selected from Any one of the hydrophobic segment, the segment containing at least one hydrophobic group, the hydrophilic segment, and the segment containing at least one hydrophilic group, or, at least one substituted group in Y 1 or Z 1 is Hydrophobic group, at least one substituted group in X 2 is selected from
  • any one of the segments of the water group, or, at least one substituent group in Y 1 or Z 1 and at least one substituent group in X 2 are all selected from hydrophobic groups, and the second soft segment is selected from hydrophilic groups.
  • Any one of the water segment and the segment containing at least one hydrophilic group, or, at least one substituent group in Y 1 or Z 1 , at least one substituent group in X 2 and in the second soft segment At least one of them is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the rest is selected from any one of a hydrophobic segment and a segment comprising at least one hydrophobic group;
  • the polyimide includes a first dianhydride as shown in formula (I) and a third segment structure generated as a second diamine as shown in formula (V), and a third segment structure as shown in formula (IV) In the case of the second segment structure generated by the second dianhydride and the first diamine represented by formula (II) or formula (III);
  • first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic, aromatic, heterocyclic and Any one of the fused rings, or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one of the first soft segment and the second soft segment is selected from a hydrophilic segment and contains at least one any one of the segments of hydrophilic groups, and the rest are selected from any one of hydrophobic segments and segments comprising at least one hydrophobic group;
  • first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic, aromatic, heterocyclic and Any one of the fused rings, or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • X 2 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in X 2 is a hydrophilic group, and the first soft segment and the second soft segment are independent is selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group, or, at least one substituent group in X is hydrophobic group, at least one of the first soft segment and the second soft
  • first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, or, if the first diamine is selected from formula (III) ) shown in the structure, and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • at least one substituent in Y 1 or Z 1 is a hydrophilic group
  • the first soft segment and the second soft segment are independently selected from hydrophobic segments, segments comprising at least one hydrophobic group , a hydrophilic segment, and a segment comprising at least one hydrophilic group, or, at least one substituent in Y 1 or Z 1 is a hydrophobic group, and at least one of the first soft segment and the second soft segment One of them is selected from any one of a hydrophilic segment and
  • first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, or, if the first diamine is selected from formula (III) ) shown in the structure, and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any of substituted aliphatic rings, aromatic rings, heterocycles and fused rings , then at least one substituted group in Y 1 or Z 1 is a hydrophilic group, and at least one substituted group in X 2 is selected from any one of a hydrophilic group and a hydrophobic group, the first soft segment and The second soft segment is independently selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group, or, Y 1 or Z At least one substituent group in 1 is a hydropho
  • the first soft segment is a substituted or unsubstituted alkylene segment with 10 to 20 carbon atoms; the first diamine is selected from the structure shown in formula (II), And Y 1 is selected from any one of aromatic rings, heterocyclic rings and condensed rings with at least one carbon atom substituted, and at least one substituent group is selected from hydrophilic groups and at least one hydrophilic group with a carbon atom number of 1 Any one of the hydrocarbon groups of ⁇ 3; the second soft segment is any one of a hydrophobic segment and a segment comprising at least one hydrophobic group.
  • the first soft segment when the first soft segment is an unsubstituted alkylene segment with 10 to 20 carbon atoms, the first soft segment is a hydrophobic segment. to control the proportions of the first dianhydride, the second dianhydride, the first diamine and the second diamine, so as to adjust the hydrophilic and hydrophobic properties of the final polyimide produced.
  • the first soft segment is an amorphous segment
  • the first dianhydride has an asymmetric structure
  • the first soft segment contains non- Symmetrical branches.
  • the first dianhydride is an asymmetric structure.
  • the description of the asymmetric structure can refer to the above description of the asymmetric structure of the first dianhydride, which will not be repeated here.
  • the first soft segment can be an unsubstituted alkylene segment with 10 to 20 carbon atoms, and in this case, the first soft segment is an amorphous segment.
  • the first soft segment contains asymmetric branches.
  • the first soft segment may be a substituted alkylene segment having 10 to 20 carbon atoms.
  • the first soft segment is also an amorphous segment.
  • the second soft segment is a substituted or unsubstituted alkylene segment with 5-12 carbon atoms.
  • the second soft segment is an amorphous segment
  • the first diamine has an asymmetric structure.
  • the second soft segment contains asymmetric branches.
  • the first diamine is an asymmetric structure, that is, Y 1 can be attached to different positions of the amino groups on the two benzene rings (such as not all in the ortho, meta or para positions), or, The number, position or R structure of CR on the two benzene rings are different.
  • the second soft segment may be an unsubstituted alkylene segment having 5 to 12 carbon atoms, and in this case, the second soft segment is an amorphous segment.
  • the second soft segment contains an asymmetric branched chain, that is, the second soft segment is a substituted alkylene segment with 5 to 12 carbon atoms, and the substituted group forms an asymmetric branch Branched.
  • the second soft segment is also an amorphous segment, wherein the position of Y 1 , the number and position of CR on the two benzene rings, and the structure of R are not specifically limited.
  • Y 1 in the first diamine is combined at the para position of the amino group, and is selected from a benzene ring with one carbon atom substituted, and the substituent group is selected from an alcoholic hydroxyl group with 1-3 carbon atoms.
  • Y 1 is bonded to the para position of the amino group, therefore, when A 1 and A 2 are independently selected from any one of CH and CR, respectively, the first diamine is terphenyl, and at the same time,
  • the hydrophilic group is an alcoholic hydroxyl group.
  • the fifth embodiment of the present disclosure provides a liquid crystal aligning agent, the liquid crystal aligning agent includes at least one polymer, and the at least one polymer is selected from polyimide and a group of polyimide obtained by ring-closing of polyimide at least one of amines.
  • the polyimide comprises the first segment structure formed by the first dianhydride shown in the following formula (I) and the first diamine shown in the following formula (II) or the following formula (III), and the following formula (IV)
  • X 1 in the first dianhydride is the first soft segment
  • Y 2 in the second diamine is the second soft segment
  • One is an amorphous segment
  • L in the first dianhydride is selected from any one of a single bond, a double bond and a divalent or trivalent hydrocarbon group with 1 to 3 carbon atoms.
  • the second dianhydride X 2 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocyclic rings and condensed rings.
  • the first diamine is shown in formula (II), Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and substituted or unsubstituted aliphatic, aromatic, heterocyclic and condensed Any one of the rings, wherein one A 1 and one A 2 are respectively selected from C, and both are combined with Y1, the remaining A 1 and A 2 are independently selected from any one of CH, CR and N, and A 1 and The number of N in A 2 is not more than two.
  • the first diamine is shown in formula (III), Z 1 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings, and A 3 and A 4 are independently selected from CH , CR and N, and the number of N in A 3 and A 4 is not more than two.
  • one A 5 and one A 6 are respectively selected from C, and both are combined with Y 2 , the remaining A 5 and A 6 are respectively independently selected from any one of CH, CR and N, and A 5 And the number of N in A 6 is not more than two.
  • R 1 , R 2 and R are each independently selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • the structure of the polyimide may include a segment structure (according to the first diamine) composed of a first segment structure, a second segment structure, a third segment structure and a fourth segment structure
  • the structure is different, which can be shown in the following formula (12) or the following formula (13)), or it can include a segment structure composed of a first segment structure and a second segment structure, and a third segment structure and a fourth segment structure.
  • the structure of the diamine is different, and can be represented by the following formula (14) or the following formula (15)).
  • the polyimide is formed by alternating soft segments and hard segments, and since at least one of the first soft segment and the second soft segment is an amorphous segment , Therefore, through a reasonable ratio of the soft segment and the hard segment in the molecular structure, the polyimide can be given special properties, such as making the polyimide have good rigidity, it can also improve the polyimide
  • the toughness of acid although polyimide has good hardness (hardness can reach 3H ⁇ 4H) in the related art, but it is easy to produce debris due to excessive hardness during friction alignment, and it is easy to damage the friction cloth, causing friction cloth. Compared with the component shedding in the polyimide, the polyimide has good toughness.
  • the product (polyimide) fired from the polyimide has a good toughness.
  • the ductility can well buffer the external force generated by the rubbing cloth.
  • the polyimide itself is not easy to generate debris, and on the other hand, the polyimide is not easy to damage the rubbing cloth; therefore, it can effectively reduce the defect of debris.
  • the first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted Any one of aliphatic ring, aromatic ring, heterocyclic ring and fused ring
  • Z 1 is selected from unsubstituted aliphatic ring, aromatic ring, heterocyclic ring and any one of fused rings
  • X 2 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • at least one of the first soft segment and the second soft segment is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group, and the rest is selected from any one of a hydrophobic segment and a segment comprising at least one hydrophobic group;
  • first diamine is selected from the structure shown in formula (II)
  • Y 1 is selected from single bond, O, NH, S, one or more unsaturated double bonds and unsubstituted aliphatic, aromatic, heterocyclic and Any one of the fused rings, or, if the first diamine is selected from the structure shown in formula (III), and Z 1 is selected from any one of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • X 2 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituent group in X 2 is a hydrophilic group, and the first soft segment and the second soft segment are independent is selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group, or, at least one substituent group in X is hydrophobic group, at least one of the first soft segment and the second soft
  • first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, or, if the first diamine is selected from formula (III) ) shown in the structure, and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any of unsubstituted aliphatic rings, aromatic rings, heterocycles and fused rings
  • at least one substituent in Y 1 or Z 1 is a hydrophilic group
  • the first soft segment and the second soft segment are independently selected from hydrophobic segments, segments comprising at least one hydrophobic group , a hydrophilic segment, and a segment comprising at least one hydrophilic group, or, at least one substituent in Y 1 or Z 1 is a hydrophobic group, and at least one of the first soft segment and the second soft segment One of them is selected from any one of a hydrophilic segment and
  • first diamine is selected from the structure shown in formula (II), and Y 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, or if the first diamine is selected from formula (III) ) shown in the structure, and Z 1 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, and X 2 is selected from any of substituted aliphatic rings, aromatic rings, heterocycles and fused rings , then at least one substituted group in Y 1 or Z 1 is a hydrophilic group, and at least one substituted group in X 2 is selected from any one of a hydrophilic group and a hydrophobic group, the first soft segment and The second soft segment is independently selected from any one of a hydrophobic segment, a segment comprising at least one hydrophobic group, a hydrophilic segment, and a segment comprising at least one hydrophilic group, or, Y 1 or Z At least one substituent group in 1 is a hydrophobic
  • the hydrophilicity and hydrophobicity of the finally formed polyimide can be improved. Adjusting the water performance can also make the hydrophilicity and hydrophobicity of the polyimide suitable, improve the cleaning performance of the polyimide before the box is formed, effectively remove the debris generated during the friction alignment process, and avoid the technical effect of poor debris. .
  • the first soft segment is a substituted or unsubstituted alkylene segment with 10 to 20 carbon atoms;
  • the first diamine is selected from the structure shown in formula (II),
  • Y 1 is selected from any one of aromatic rings, heterocyclic rings and condensed rings with at least one carbon atom substituted, and at least one substituent group is selected from hydrophilic groups and at least one hydrophilic group with a carbon atom number of 1 Any one of the hydrocarbon groups of ⁇ 3;
  • the second soft segment is selected from any one of a hydrophobic segment and a segment comprising at least one hydrophobic group;
  • X in the second dianhydride is selected from the following structural formula, wherein, R 3 and R 4 are each independently selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • the first soft segment when the first soft segment is an unsubstituted alkylene segment with 10 to 20 carbon atoms, the first soft segment is a hydrophobic segment. to control the proportions of the first dianhydride, the second dianhydride, the first diamine and the second diamine, so as to adjust the hydrophilic and hydrophobic properties of the final polyimide produced.
  • the first soft segment is an amorphous segment
  • the first dianhydride has an asymmetric structure
  • the first soft segment contains non- Symmetrical branches.
  • the first dianhydride is an asymmetric structure.
  • the description of the asymmetric structure can refer to the above description of the asymmetric structure of the first dianhydride, which will not be repeated here.
  • the first soft segment can be an unsubstituted alkylene segment with 10 to 20 carbon atoms, and in this case, the first soft segment is an amorphous segment.
  • the first soft segment contains asymmetric branches.
  • the first soft segment may be a substituted alkylene segment having 10 to 20 carbon atoms.
  • the first soft segment is also an amorphous segment.
  • the second soft segment is a substituted or unsubstituted alkylene segment with 5-12 carbon atoms.
  • the second soft segment is an amorphous segment
  • the first diamine has an asymmetric structure.
  • the second soft segment contains asymmetric branches.
  • the first diamine is an asymmetric structure, that is, Y 1 can be attached to different positions of the amino groups on the two benzene rings (such as not all in the ortho, meta or para positions), or, The number, position or R structure of CR on the two benzene rings are different.
  • the second soft segment may be an unsubstituted alkylene segment having 5 to 12 carbon atoms, and in this case, the second soft segment is an amorphous segment.
  • the second soft segment contains an asymmetric branched chain, that is, the second soft segment is a substituted alkylene segment with 5 to 12 carbon atoms, and the substituted group forms an asymmetric branch Branched.
  • the second soft segment is an amorphous segment, wherein the position of Y 1 , the number and position of CR on the two benzene rings, and the structure of R are not specifically limited.
  • Y 1 in the first diamine is combined at the para position of the amino group, and is selected from a benzene ring with one carbon atom substituted, and the substituent group is selected from an alcoholic hydroxyl group with 1-3 carbon atoms.
  • Y 1 is bonded to the para position of the amino group, therefore, when A 1 and A 2 are independently selected from any one of CH and CR, respectively, the first diamine is terphenyl, and at the same time,
  • the hydrophilic group is an alcoholic hydroxyl group.
  • Embodiment 6 of the present disclosure provides a liquid crystal aligning agent, the liquid crystal aligning agent includes at least one polymer, and the at least one polymer is selected from polyimide and a group of polyimide obtained by ring-closing the polyimide at least one of amines.
  • the polyimide includes a fifth segment structure formed by including the second dianhydride represented by the following formula (IV) and the second diamine represented by the following formula (V).
  • the second dianhydride X 2 is selected from any one of substituted or unsubstituted aliphatic rings, aromatic rings, heterocyclic rings and fused rings.
  • Y 2 is a second soft segment, and the second soft segment is an amorphous segment.
  • one A 5 and one A 6 are respectively selected from C, and both are combined with Y 2 , the remaining A 5 and A 6 are respectively independently selected from any one of CH, CR and N, and A 5
  • the number of N in both and A 6 is no more than two, and R is selected from any one of hydrogen and aliphatic hydrocarbon groups.
  • the second soft segment is selected from hydrophilic segments and chains including at least one hydrophilic group any of the paragraphs;
  • the second dianhydride X 2 is selected from any one of substituted aliphatic rings, aromatic rings, heterocycles and fused rings, then at least one substituted group in X 2 is a hydrophilic group, and the second soft segment is selected from Any one of the hydrophobic segment and the segment containing at least one hydrophobic group, or, at least one substituent group in X 2 is a hydrophobic group, and the second soft segment is selected from the hydrophilic segment and the segment containing at least one hydrophilic group. Any one of the segments of the water group; or, one of the at least one substituent group in X 2 and the second soft segment is selected from the hydrophobic segment and the segment comprising at least one hydrophobic group. Either one, the other is selected from any one of a hydrophilic segment and a segment comprising at least one hydrophilic group.
  • the hydrophilic and hydrophobic properties of the polyimide can be adjusted, and the polyimide can also be
  • the hydrophilicity and hydrophobicity of the product is suitable, and the cleaning performance of the polyimide is improved before the box is formed, and the debris generated during the friction alignment process is effectively removed, so as to avoid the technical effect of poor debris.
  • the hardness of the above-mentioned liquid crystal alignment film is characterized by the depth at which the needle is inserted into the liquid crystal alignment film under a preset pressure, and the hardness of the liquid crystal alignment film satisfies: under the preset pressure of 150 ⁇ N, the value of less than or equal to 45 ⁇ m.
  • HYSITRON Tribo-Indenter (in situ nanomechanical measurement) equipment can be used, so that the probe of the equipment drives the needle into the liquid crystal alignment film. Under the same pressure, according to the smaller the depth of the needle into the alignment film, the hardness of the film is. bigger.
  • the value of the hardness of the liquid crystal alignment film is less than or equal to 45 ⁇ m, therefore, compared with the related art under the preset pressure of 150 ⁇ N, the value of the hardness of the liquid crystal alignment film is greater than 50 ⁇ m. Improve the hardness of the liquid crystal aligning film.
  • the toughness of the above-mentioned liquid crystal alignment film is characterized by the pressure corresponding to the sudden change of the depth of the needle in the thickness direction of the liquid crystal alignment film, and the value of the toughness of the liquid crystal alignment film is greater than 390 ⁇ N.
  • the HYSITRON Tribo-Indenter (in situ nanomechanical measurement) device described above can also be used, so that the probe of the device drives the needle into the liquid crystal alignment film.
  • the probe pressure corresponding to the sudden change of the depth of the needle in the thickness direction of the liquid crystal alignment film is less than 300 ⁇ N, which can increase the toughness of the liquid crystal alignment film.
  • the water contact angle of the above-mentioned liquid crystal aligning film is less than or equal to 58°.
  • the water contact angle of the liquid crystal alignment film can be adjusted, thereby improving debris washing. Effect.
  • the molar percentage of the first diamine and the second diamine contained in the liquid crystal aligning agent is 35%: 15%, as the first diamine contained in the liquid crystal aligning agent As the ratio of the anhydride and the second dianhydride gradually increases, the hardness of the liquid crystal aligning film described above decreases and the toughness increases.
  • the hardness and toughness of a liquid crystal aligning film can be adjusted by adjusting the ratio of the 1st dianhydride which has a soft segment, and the 2nd dianhydride which has a rigid structure.
  • the molar percentage of the first dianhydride and the second dianhydride contained in the liquid crystal aligning agent is 10%: 40%, and Y2 in the second diamine is a hydrophobic segment
  • the ratio of the hydrophilic group and the hydrophobic group of the liquid crystal aligning film can be adjusted, so that the water contact angle of the liquid crystal aligning film can be adjusted.
  • liquid crystal aligning films provided by the present disclosure will be described in detail and illustratively through the following experimental examples.
  • the preparation method is as follows:
  • the purified polyimide A with a certain solvent by GBL ( ⁇ -butyrrolactone, ⁇ -butyrolactone), NMP (N-methyl-2-pyrrolidone, N-methylpyrrolidone), BC (Butyl carbitol (Butyl Di-glycol), diethylene glycol monobutyl ether) and DAA (Diacetone alcohol, diacetone alcohol) are mixed in a ratio of 50:30:10:10) to be diluted, and the mass percentage of polyimide is 3.0% to 4.5% to prepare a coating of polyimide A.
  • GBL ⁇ -butyrrolactone, ⁇ -butyrolactone
  • NMP N-methyl-2-pyrrolidone, N-methylpyrrolidone
  • BC Butyl carbitol (Butyl Di-glycol), diethylene glycol monobutyl ether) and DAA (Diacetone alcohol, diacetone alcohol) are mixed in a ratio of 50:30:10:10) to be diluted,
  • the polyacid A is formed on the base substrate on which the thin film transistor TFT, the pixel electrode and the common electrode have been formed, or on the base substrate on which the color filter layer and the black matrix have been formed, and through
  • the polyimide A is produced by dehydration (amidation) of polyimide by pre-curing and main curing, and finally by firing.
  • the measurement method of hardness and toughness is to use the HYSITRON Tribo-Indenter (in situ nanomechanical measurement) equipment described above before forming a liquid crystal alignment film of a certain thickness on the substrate and before rubbing for alignment, so that the probe of the equipment drives the needle
  • the hardness of the liquid crystal aligning film was characterized by the depth of the needle piercing into the liquid crystal aligning film under the pressure of 150 ⁇ N of probe pressure.
  • the probe of the device drives the needle to be inserted into the liquid crystal alignment film, and drives the needle to move in the horizontal direction until the liquid crystal alignment film is peeled off and ruptured.
  • the probe pressure corresponding to the sudden change of depth in the thickness direction of the film is used to characterize the toughness of the liquid crystal alignment film.
  • the number of debris after rubbing is obtained by randomly selecting multiple groups of a certain number of pixels at different positions of the liquid crystal alignment film under the microscope, counting the number of debris on the surface, and averaging by weighting.
  • Experimental Example 2 adopts the following various experimental schemes.
  • the following experimental scheme is basically the same as the preparation process of Experimental Example 1.
  • the difference is that the experimental raw materials used in Experimental Example 2 are the dianhydrides and diamines shown below provided by the present disclosure.
  • the experimental raw materials are the first dianhydride represented by the following formula (I) and the first diamine represented by the following formula (II), wherein R 1 and R 2 are both selected from methyl groups.
  • the experimental raw materials are the first dianhydride represented by the following formula (I) and the first diamine represented by the following formula (III), wherein R 1 and R 2 are both selected from methyl groups.
  • the third experimental scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (II) and the second dianhydride shown in the following formula (IV), wherein R Both 1 and R2 are selected from methyl, and both R3 and R4 are selected from hydrogen.
  • the fourth experimental scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (III) and the second dianhydride shown in the following formula (IV), wherein R Both 1 and R2 are selected from methyl, and both R3 and R4 are selected from hydrogen.
  • the fifth test scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (II) and the second diamine shown in the following formula (V), wherein R 1 and R2 are both selected from methyl.
  • the sixth test scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (III) and the second diamine shown in the following formula (V), wherein R 1 and R2 are both selected from methyl.
  • the seventh test scheme the experimental raw materials are the second dianhydride shown in the following formula (IV), the first diamine shown in the following formula (II) and the second diamine shown in the following formula (V), wherein R Both 3 and R4 are selected from hydrogen.
  • the eighth test scheme the experimental raw materials are the second dianhydride shown in the following formula (IV), the first diamine shown in the following formula (III) and the second diamine shown in the following formula (V), wherein R Both 3 and R4 are selected from hydrogen.
  • the ninth test scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the second dianhydride shown in the following formula (IV) and the second diamine shown in the following formula (V), wherein R Both 1 and R2 are selected from methyl, and both R3 and R4 are selected from hydrogen.
  • the hardness measured in the above experimental example 1 and the hardness and toughness measured by the first test scheme to the ninth test scheme are shown in the following table 1, and the above experimental example 1
  • the measured number of chips after friction and the number of chips after friction measured from the first test scheme to the ninth test scheme are compared with hardness and toughness as shown in Figure 4.
  • the polymer is formed in the form of alternating soft and hard segments, and by adjusting the ratio of the soft segment and the hard segment, the final obtained liquid crystal aligning film can be obtained.
  • the toughness is adjusted, so that the wear resistance of the liquid crystal aligning film can be improved and debris can be reduced.
  • Experimental Example 3 adopts the following various experimental schemes.
  • the following experimental scheme is basically the same as that of Experimental Example 2.
  • the difference is that the experimental raw materials used in Experimental Example 3 also contain hydrophobic groups and hydrophilic groups.
  • the experimental raw materials are the first dianhydride represented by the following formula (I) and the first diamine represented by the following formula (II), wherein R 1 and R 2 are both selected from methyl groups.
  • the experimental raw materials are the first dianhydride represented by the following formula (I) and the first diamine represented by the following formula (III), wherein R 1 and R 2 are both selected from methyl groups.
  • the third experimental scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (II) and the second dianhydride shown in the following formula (IV), wherein R Both 1 and R2 are selected from methyl, and both R3 and R4 are selected from hydrogen.
  • the fourth experimental scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (III) and the second dianhydride shown in the following formula (IV), wherein R Both 1 and R2 are selected from methyl, and both R3 and R4 are selected from hydrogen.
  • the fifth test scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (II) and the second diamine shown in the following formula (V), wherein R 1 and R2 are both selected from methyl.
  • the sixth test scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the first diamine shown in the following formula (III) and the second diamine shown in the following formula (V), wherein R 1 and R2 are both selected from methyl.
  • the seventh test scheme the experimental raw materials are the second dianhydride shown in the following formula (IV), the first diamine shown in the following formula (II) and the second diamine shown in the following formula (V), wherein R Both 3 and R4 are selected from hydrogen.
  • the eighth test scheme the experimental raw materials are the second dianhydride shown in the following formula (IV), the first diamine shown in the following formula (III) and the second diamine shown in the following formula (V), wherein R Both 3 and R4 are selected from hydrogen.
  • the ninth test scheme the experimental raw materials are the first dianhydride shown in the following formula (I), the second dianhydride shown in the following formula (IV) and the second diamine shown in the following formula (V), wherein R 1 and R2 are both selected from methyl, R3 is selected from hydrogen, and R4 is selected from hydroxyl.
  • the water contact angle and debris removal rate measured from the first test scheme to the ninth test scheme in the above experimental example 3 (respectively denoted as c1 to c9 in one-to-one correspondence), the first test scheme in the experimental example 2 to The water contact angle and debris removal rate measured by the ninth test scheme (respectively denoted as b1 to b9), and the water contact angle and debris removal rate measured in Experimental Example 1 are shown in Table 2 and Table 2. shown in Figure 5.
  • Experimental example 4 adopts the following experimental scheme, the following experimental scheme is the same as the preparation method of experimental example 1, the difference is that the following experimental scheme adopts the first dianhydride shown in the following formula (I) and the first dianhydride shown in the following formula (II) .
  • the experimental scheme 1 includes multiple experimental groups. In the multiple experimental groups, the molar percentage of the first diamine and the second diamine is 35%: 15%, and it is fixed. In different experimental groups, the first dianhydride and the second diamine are added. The ratio of the second dianhydride is different, and the data of the specific experimental group are shown in Table 3 below. The hardness and toughness data obtained from experimental groups 1 to 6 are shown in Table 3.
  • the experimental scheme 2 includes multiple experimental groups.
  • the molar percentage of the first dianhydride and the second dianhydride is 10%: 40%, and it is fixed.
  • the first diamine and the second dianhydride are added.
  • the molar percentage of the second diamine is different, and the data of the specific experimental group are shown in Table 4 below. Among them, the water contact angle and debris removal rate obtained from experimental groups 1 to 6 are shown in Table 4.
  • the hydrophilicity and hydrophobicity of the sample can be changed. Specifically, as the molar percentage of the first diamine and the second diamine increases, the hydrophilic By measuring the change of the water contact angle from 54° to 50°, under the same conditions, the debris removal rate before and after cleaning changed from 85% to 92% and then changed to 90%. As the ratio of the first diamine to the second diamine increases, the water contact angle gradually decreases, while the debris removal first increases and then decreases. This is because when the hydrophilicity is too strong, although the debris has been generated Easy to clean, but also easy to absorb foreign matter in the environment, which increases the number of debris.
  • Experimental example 5 adopts the following experimental scheme, the following experimental scheme is the same as the preparation method of experimental example 1, the difference is that the following experimental scheme adopts the second dianhydride shown in the following formula (IV) and the first dianhydride shown in the following formula (V).
  • Didiamine wherein R 3 is selected from hydrogen, and R 4 is selected from hydroxyl group.
  • the final sample obtained for measuring water contact angle and cleaning performance is recorded as sample f, then the water contact angle and particle size of sample a and sample f are The chip removal rate is shown in Table 5 below.
  • the polyimide provided by the present disclosure can make the polyimide by introducing hydrophilic groups and hydrophobic groups in the related art, and carrying out a reasonable ratio of the hydrophobic groups and the hydrophilic groups. It has a small water contact angle, which can improve the removal rate of debris, and finally can reduce the debris generated by cleaning and avoid defective debris.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Nonlinear Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Mathematical Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

一种液晶取向剂，包括至少一种聚合物，选自聚酰亚酸和由所述聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种；聚酰亚酸包括如式(I)所示的第一双酐和如式(II)或(III)所示的第一二胺生成的第一链段结构。X 1为无定形链段；第一二胺中如式(II)所示，Y 1选自单键、O、NH、S、一个或多个不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，一个A 1和一个A 2分别选自C，并均与Y 1结合，其余A 1和A 2分别独立地选自CH、CR和N中的任一个；第一二胺中如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，A 3和A 4分别独立地选自CH、CR和N中的任一个。

Description

液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺
本申请要求于2020年09月16日提交的、申请号为202010975445.7的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本公开涉及显示技术领域，尤其涉及一种液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺。
背景技术
液晶显示装置是目前大规模使用的显示器件，其具有成本低、轻薄化、显示速度快等优点，在理论研究和实际工艺方面都有着成熟的技术。
发明内容
一方面，提供一种液晶取向剂，包括：至少一种聚合物，所述至少一种聚合物选自聚酰亚酸和由所述聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种；所述聚酰亚酸包括如下式(I)所示的第一双酐和如下式(II)或下式(III)所示的第一二胺反应生成的第一链段结构。
Figure PCTCN2021111782-appb-000001
其中，所述第一双酐中X 1为第一软链段，所述第一软链段为无定形链段；L选自单键、双键和碳原子数为1～3的二价或三价烃基中的任一个。所述第一二胺中如式(II)所示，Y 1选自单键、O、NH、S、一个或多个不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，其中一个A 1和一个A 2分别选自C，并均与Y 1结合，其余A 1和A 2分别独立地选自CH、CR和N中的任一个，且A 1和A 2中N的个数均不超过两个。
所述第一二胺中如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，且A 3和A 4分别独立地选自CH、CR和N中的任一个，且A 3和A 4中N的个数均不超过两个。
R 1、R 2和R分别独立地选自氢和脂肪族烃基中的任一个。
在一些实施例中，若所述第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若所述第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则所述第一软链段选自亲水链段和含有至少一个亲水基团的链段中的任一个。
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1中的至少一个取代基团选自亲水基团，第一软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个；或者，Y 1中的至少一个取代基团和第一软链段中其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Z 1中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Z 1中的至少一个取代基团选自亲水基团，第一软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个；或者，Y 1中的至少一个取代基团和第一软链段中其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在一些实施例中，所述第一软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个；所述第一二胺选自如式(II)所示的结构，且Y 1选自至少一个碳原子被取代的芳环、杂环和稠环中的任一个，至少一个取代基团选自亲水基团和具有至少一个亲水基团的碳原子数为1～3的烃基中的任一个。
在一些实施例中，所述第一二胺中Y 1结合在氨基的对位，且选自一个碳原子被取代的苯环，取代基团为碳原子数为1～3的醇羟基。
在一些实施例中，所述第一软链段为取代的或未取代的碳原子数为10～20的亚烷基链段。
在一些实施例中，所述第一双酐为非对称结构，或者，所述第一软链段中含有非对称支链。
在一些实施例中，所述聚酰亚酸还包括如下式(IV)所述的第二双酐和所述第一二胺反应生成的第二链段结构。
Figure PCTCN2021111782-appb-000002
其中，所述第二双酐中X 2选自脂肪环、芳环、杂环和稠环结构中的任一个。
在一些实施例中，所述X 2选自如下结构式，其中，R 3和R 4分别独立地选自氢和脂肪族烃基中的任一个。
Figure PCTCN2021111782-appb-000003
在一些实施例中，所述第一双酐和第二双酐的摩尔比为10:90～90:10。
在一些实施例中，所述聚酰亚酸还包括如下式(V)所述的第二二胺和所述第一双酐反应生成的第三链段结构。
Figure PCTCN2021111782-appb-000004
其中，所述第二二胺中Y 2为第二软链段；其中一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个，R选自氢和脂肪族烃基中的任一个。
在一些实施例中，若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段中的至 少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个。
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，Y 1中的至少一个取代基团、第一软链段和第二软链段中其中1至2个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余2至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Z 1中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Z 1中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，Z 1中的至少一个取代基团、第一软链段和第二软链段中其中1至2个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余2至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在一些实施例中，所述第二软链段为取代的或未取代的碳原子数为5～12的亚烷基链段。
在一些实施例中，所述第一二胺和所述第二二胺的摩尔比为10:90～90:10。
又一方面，提供一种液晶取向剂，包括：至少一种聚合物，所述至少一种聚合物选自聚酰亚酸和由所述聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种；所述聚酰亚酸包括如下式(I)所示的第一双酐和如下式(II)或下式(III)所示的第一二胺生成的第一链段结构，如下式(IV)所述的第二双酐和所述第一二胺生成的第二链段结构，如下式(V)所述的第二二胺和所述第一双酐生成的第三链段结构，和如下式(V)所述的第二二胺和所述第二双酐生成的第四链段结构；或者，所述聚酰亚酸包括如下式(I)所示的第一双酐和如下式(V)所示的第二二胺生成的第三链段结构，如下式(IV)所示的第二双酐和如下式(V)所示的第二二胺反应生成的第四链段结构，和如下式 (IV)所示的第二双酐和如下式(II)或下式(III)所示的第一二胺生成的第二链段结构中的至少两个链段结构。
Figure PCTCN2021111782-appb-000005
其中，所述第一双酐中X 1为第一软链段，所述第二二胺中Y 2为第二软链段，且所述第一软链段和第二软链段中的至少其中之一为无定形链段；所述第一双酐中L选自单键、双键和碳原子数为1～3的二价或三价烃基中的任一个；所述第二双酐X 2选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个；所述第一二胺中如式(II)所示，Y 1选自单键、O、NH、S、一个或多个不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，其中一个A 1和一个A 2分别选自C，并均与Y 1结合，其余A 1和A 2分别独立地选自CH、CR和N中的任一个，且A 1和A 2中N的个数均不超过两个；所述第一二胺中如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，且A 3和A 4分别独立地选自CH、CR和N中的任一个， 且A 3和A 4中N的个数均不超过两个；所述第二二胺中，一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个；R 1、R 2和R分别独立地选自氢和脂肪族烃基中的任一个。
在一些实施例中，在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(V)所示的第二二胺生成的第三链段结构，和如式(IV)所示的第二双酐和如式(V)所示的第二二胺反应生成的第四链段结构的情况下；若第二双酐中X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段分别独立地选自亲水链段、疏水链段、包含至少一个亲水基团的链段和包含至少一个疏水基团的链段中的任一个；若第二双酐X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段和第二软链段分别独立地选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中的其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个；或者，X 2中的至少一个取代基团、第一软链段和第二软链段中的一个或两个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余两个或一个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在所述聚酰亚酸包括如式(IV)所示的第二双酐和如式(V)所示的第二二胺反应生成的第四链段结构，和如式(IV)所示的第二双酐和如式(II)或式(III)所示的第一二胺生成的第二链段结构的情况下；若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个；若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团选自亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链 段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团选自疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段、包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，X 2中的至少一个取代基团选自亲水基团和疏水基团中的任一个，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，X 2中的至少一个取代基团选自亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和X 2中的至少一个取代基团均选自疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团、X 2中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(V)所示的第二二胺生成的第三链段结构，和如式(IV)所示的第二双酐和如式(II)或式(III)所示的第一二胺生成的第二链段结构的情况下；或者，在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(II)或式(III)所示的第一二胺反应生成 的第一链段结构，如式(IV)所述的第二双酐和所述第一二胺反应生成的第二链段结构，如式(V)所述的第二二胺和所述第一双酐反应生成的第三链段结构，和如式(V)所述的第二二胺和所述第二双酐反应生成的第四链段结构的情况下；若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，X 2中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；或者，Y 1或Z 1中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；若第一二胺选自如式(II)所 示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，X 2中的至少一个取代基团选自亲水基团和疏水基团中的任一个，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，X 2中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和X 2中的至少一个取代基团均选自疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段、包含至少一个疏水基团的链段中的人一个；或者，Y 1或Z 1中的至少一个取代基团、X 2中的至少一个取代基团、第一软链段和第二软链段中的其中1至3个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余3至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在一些实施例中，该第一软链段为取代的或未取代的碳原子数为10～20的亚烷基链段；该第一二胺选自如式(II)所示的结构，且Y 1选自至少一个碳原子被取代的芳环、杂环和稠环中的任一个，至少一个取代基团选自亲水基团和具有至少一个亲水基团的碳原子数为1～3的烃基中的任一个；该第二软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在一些实施例中，该第二软链段为取代的或未取代的碳原子数为5～12的亚烷基链段。
在一些实施例中，该第一二胺中Y 1结合在氨基的对位，且选自一个碳原子被取代的苯环，取代基团为碳原子数为1～3的醇羟基。
又一方面，提供一种液晶取向剂，包括：至少一种聚合物，所述至少一种聚合物选自聚酰亚酸和由所述聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种；所述聚酰亚酸包括如下式(IV)所示的第二双酐和下式(V)所示的第二二胺生成的第五链段结构。
Figure PCTCN2021111782-appb-000006
其中，该第二双酐X 2选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个。该第二二胺中Y 2为第二软链段，且该第二软链段为无定形链段。该第二二胺中，一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个，R选自氢和脂肪族烃基中的任一个；若第二双酐X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第二软链段选自亲水链段和包括至少一个亲水基团的链段中的任一个；若第二双酐X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团为亲水基团，第二软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，X 2中的至少一个取代基团为疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个；或者，X 2中的至少一个取代基团和第二软链段中的其中之一选自疏水链段和包含至少一个疏水基团的链段中的任一个，另一个选自亲水链段和包含至少一个亲水基团的链段中的任一个。
又一方面，提供一种液晶取向膜，采用如上所述的液晶取向剂形成。
在一些实施例中，所述液晶取向膜的硬度用预设压力下扎针扎入所述液晶取向膜的深度来表征，所述液晶取向膜的硬度满足：在预设压力为150μN的压力下，取值小于等于45μm。
在一些实施例中，所述液晶取向膜的韧度用扎针在所述液晶取向膜的厚度方向的深度突变所对应的压力来表征，所述液晶取向膜的韧度的取值大于390μN。
在一些实施例中，在所述液晶取向剂所包含有亲水链段和/或亲水基团的情况下，所述液晶取向膜的水接触角小于等于58°。
在一些实施例中，在所述液晶取向剂所包含的第一二胺和第二二胺的摩尔百分比为35％：15％的情况下，随着所述液晶取向剂所包含的第一双酐和 第二双酐的比例逐渐增大，所述液晶取向膜的硬度降低，韧性增大。
在一些实施例中，在所述液晶取向剂所包含的第一双酐和第二双酐的摩尔百分比为10％：40％，且第二二胺中的Y 2为疏水链段的情况下，随着所述液晶取向剂所包含的第一二胺和第二二胺的比例逐渐增大，所述液晶取向膜的水接触角逐渐降低。
又一方面，提供一种显示基板，包括：衬底基板；和设置于所述衬底基板上的液晶取向膜，该液晶取向膜包括如上所述的液晶取向剂烧成后的聚酰亚胺。
又一方面，提供一种液晶显示装置，包括：相对设置的第一基板和第二基板，以及设置于第一基板和第二基板之间的液晶层；其中，所述第一基板和/或第二基板为如上所述的显示基板。
再一方面，提供一种聚酰亚胺，由如上所述的液晶取向剂烧成得到。
附图说明
为了更清楚地说明本公开中的技术方案，下面将对本公开一些实施例中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本公开的一些实施例的附图，对于本领域普通技术人员来讲，还可以根据这些附图获得其他的附图。此外，以下描述中的附图可以视作示意图，并非对本公开实施例所涉及的产品的实际尺寸、方法的实际流程、信号的实际时序等的限制。
图1为根据一些实施例的液晶显示装置的结构图；
图2A为根据一些实施例的显示面板的俯视图；
图2B为根据一些实施例的液晶显示装置的剖视结构图；
图3为根据一些实施例的FFS型液晶显示装置未施加电压和施加电压时的对比结构图；
图4A为根据一些实施例的TN型液晶显示装置中未施加电压时的结构图；
图4B为根据一些实施例的TN型液晶显示装置施加电压时的结构图；
图5为根据一些实施例的样品a、样品b1～样品b9的硬度、韧性和碎屑数的对比图；
图6为根据一些实施例的样品a、样品b1～b9和样品c1～c9的水接触角和碎屑去除率的对比图。
具体实施方式
下面将结合附图，对本公开一些实施例中的技术方案进行清楚、完整地 描述，显然，所描述的实施例仅仅是本公开一部分实施例，而不是全部的实施例。基于本公开所提供的实施例，本领域普通技术人员所获得的所有其他实施例，都属于本公开保护的范围。
除非上下文另有要求，否则，在整个说明书和权利要求书中，术语“包括(comprise)”及其其他形式例如第三人称单数形式“包括(comprises)”和现在分词形式“包括(comprising)”被解释为开放、包含的意思，即为“包含，但不限于”。在说明书的描述中，术语“一个实施例(one embodiment)”、“一些实施例(some embodiments)”、“示例性实施例(exemplary embodiments)”、“示例(example)”、“特定示例(specific example)”或“一些示例(some examples)”等旨在表明与该实施例或示例相关的特定特征、结构、材料或特性包括在本公开的至少一个实施例或示例中。上述术语的示意性表示不一定是指同一实施例或示例。此外，所述的特定特征、结构、材料或特点可以以任何适当方式包括在任何一个或多个实施例或示例中。
以下，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本公开实施例的描述中，除非另有说明，“多个”的含义是两个或两个以上。
“A、B和C中的至少一个”与“A、B或C中的至少一个”具有相同含义，均包括以下A、B和C的组合：仅A，仅B，仅C，A和B的组合，A和C的组合，B和C的组合，及A、B和C的组合。
“A和/或B”，包括以下三种组合：仅A，仅B，及A和B的组合。
如本文中所使用，根据上下文，术语“如果”任选地被解释为意思是“当……时”或“在……时”或“响应于确定”或“响应于检测到”。类似地，根据上下文，短语“如果确定……”或“如果检测到[所陈述的条件或事件]”任选地被解释为是指“在确定……时”或“响应于确定……”或“在检测到[所陈述的条件或事件]时”或“响应于检测到[所陈述的条件或事件]”。
在描述一些实施例时，可能使用了“耦接”和“连接”及其衍伸的表达。例如，描述一些实施例时可能使用了术语“连接”以表明两个或两个以上部件彼此间有直接物理接触或电接触。又如，描述一些实施例时可能使用了术语“耦接”以表明两个或两个以上部件有直接物理接触或电接触。然而，术语“耦接”或“通信耦合(communicatively coupled)”也可能指两个或两个以上部件彼此间并无直接接触，但仍彼此协作或相互作用。这里所公开的实施例并不必然限制于本文内容。
本文参照作为理想化示例性附图的剖视图和/或平面图描述了示例性实施方式。在附图中，为了清楚，放大了层和区域的厚度。因此，可设想到由于例如制造技术和/或公差引起的相对于附图的形状的变动。因此，示例性实施方式不应解释为局限于本文示出的区域的形状，而是包括因例如制造而引起的形状偏差。例如，示为矩形的蚀刻区域通常将具有弯曲的特征。因此，附图中所示的区域本质上是示意性的，且它们的形状并非旨在示出设备的区域的实际形状，并且并非旨在限制示例性实施方式的范围。
本公开的一些实施例提供了一种液晶显示装置，该液晶显示装置可以为液晶显示面板，也可以包括液晶显示面板。例如手机、平板电脑、笔记本、个人数字助理(personal digital assistant，PDA)、车载电脑等。
如图1所示，在液晶显示装置包括液晶显示面板1的情况下，该液晶显示装置还可以包括框架2、盖板玻璃3、背光模组4、电路板5以及摄像头等其他配件。其中，背光模组4被配置为向液晶显示面板1提供背光；电路板5与液晶显示面板1耦接，被配置为向液晶显示面板1提供电信号，以控制液晶显示面板1显示图像。
其中，如图1所示，框架2的纵截面可以呈U型，液晶显示面板1、背光模组4、电路板5以及其他电子配件设置于框架2内，背光模组4设置于液晶显示面板1的下方，电路板5设置于背光模组4下方，盖板玻璃2位于液晶显示面板1远离背光模组4的一侧。
基于以上液晶显示装置的结构，本公开的一些实施例提供一种液晶显示面板1，如图2A所示，该液晶显示面板1包括显示区(Active Area，简称为AA区)A和围绕该显示区A设置的周边区S，显示区A包括多个像素区(图中的虚线框示意一个像素)，每个像素区包括至少三个子像素区P，至少三个子像素区P可以分别为红色子像素区R、绿色子像素区G和蓝色子像素区B。周边区S为液晶显示面板中除显示区A以外的区域，用于布线，此外，也可将栅极驱动电路设置于周边区S。
在一些实施例中，如图2B所示，该液晶显示面板1包括相对的第一基板11和第二基板12，以及设置于第一基板11和第二基板12之间的液晶层13。其中，该第一基板11和第二基板12分别为阵列基板和对置基板(阵列基板和对置基板均可称为显示基板)，阵列基板和对置基板通过封框胶对盒在一起，从而将液晶层13限定在封框胶围成的区域内。
如图2B所示，显示基板包括衬底基板100，以及设置于衬底基板100上的液晶取向膜14。其中，液晶取向膜14被配置为限定液晶层13中液晶分子 的初始配向(即在不给液晶显示面板1供电时液晶分子的配向)。
在此，如图2B所示，在显示基板为阵列基板的情况下，该显示基板除包括衬底基板100，以及设置于衬底基板100上的液晶取向膜14之外，还包括设置在每个子像素区内且位于衬底基板100上的薄膜晶体管(Thin Film Transistor，TFT)和与该TFT的漏极或源极电连接的像素电极200等。在此基础上，该显示基板还可以包括设置在每个子像素区内的公共电极300。如图2B所示，公共电极300和像素电极200之间通过第一绝缘层210隔离，此外，在公共电极300位于TFT和像素电极200之间的情况下，TFT和公共电极300之间也可设置第二绝缘层220。在此情况下，像素电极200通过位于第一绝缘层210、公共电极300以及第二绝缘层220上的通道与TFT的漏极或源极电连接。第一绝缘层210和第二绝缘层220均整层铺设于显示区A，可以在需要的区域通过构图等方法去除该区域的部分，形成通道(也可以称为过孔)。
如图2B所示，在显示基板为对置基板的情况下，该显示基板除包括衬底基板100，以及设置于衬底基板100上的液晶取向膜14之外，还可以包括设置在衬底基板100朝向液晶层13的表面上的彩色滤光层400。此时，该对置基板12称为彩膜基板。其中，彩色滤光层400包括位于红色子像素区R中的红色滤光图案、位于绿色子像素区G的绿色滤光图案和位于蓝色子像素区的蓝色滤光图案。
为避免相邻子像素之间发生串扰，该显示基板(这里是对置基板)还可以包括黑矩阵(Black Matrix，BM)，黑矩阵包括多条平行的第一遮光条和多条平行的第二遮光条，多条第一遮光条和多条第二遮光条围成的多个网格，每个网格为一个子像素区。
需要说明的是，上述的液晶显示面板1以公共电极300设置于阵列基板的衬底基板上为例进行示意，此时液晶显示面板1可以是AD-SDS(Advanced-Super Dimensional Switching，高级超维场开关)型的显示面板，像素电极200和公共电极300其中一者是带有狭缝的，二者的上下位置可以变换，但是和薄膜晶体管的漏极或源极相连的为像素电极300。但本申请并不限于此，例如，液晶显示面板1还可以是FFS(Fringe Field Switching，边缘场开关)型、IPS(In Plane Switch，横向电场效应)型等类型的显示面板。此外，公共电极300还可设置于对置基板的衬底基板上，此时液晶显示面板1可以是TN(Twist Nematic，扭曲向列)型等类型的显示面板。
基于以上结构，由于液晶分子处于液晶态时具有各向异性，因此液晶分子所引起的光电效应就会因为其旋转方向不同而有所差异，也就是说，液晶 分子的介电系数(液晶分子受电场的影响发生转向的特性)及折射系数(光线穿过液晶分子时影响光线的偏振状态的特性)等光电特性都具有各向异性，因而利用液晶本身的这些特性，适当的利用电压，来控制液晶分子的转动，进而影响光线的偏振状态，来形成不同的灰阶，从而可实现显示。
但是，单纯依靠液晶分子本身并无法实现显示，而需要配合偏光片以及设置于衬底基板100上的液晶取向膜14。
如图2B所示，该液晶显示面板1还包括设置于第一基板11背离液晶层13一侧的下偏光片15(还可以称为第一偏光片)和设置于第二基板12背离液晶层13一侧的上偏光片16(还可以称为第二偏光片)。
其中，偏光片的作用是允许平行于偏光轴的方向(即透振方向)的光线偏振光通过，下偏光片15和上偏光片16的透振方向垂直或平行。示例的，从下偏光片15出射的线偏振光，经过受电场控制的液晶层13后其偏振状态发生改变，而只有与上偏光片16的透振方向平行的光线分量才能通过上偏光片16，从而形成不同灰阶的显示。而在此过程中，液晶取向膜14则起到对液晶分子初始配向的作用。
在一些实施例中，以AD-SDS型液晶显示面板为例，如图3所示，上偏光片16的透振方向和下偏光片15的透振方向垂直，设置于两个衬底基板100上的液晶取向膜14的取向方向相互平行，在一个子像素未加电压时，液晶分子沿着同一个方向排列，该子像素呈黑态。在对该子像素的像素电极200和公共电极300施加电压后，在液晶层13内形成边缘电场，在边缘电场的作用下液晶分子可以平行于衬底基板100的平面内发生转动，使得液晶分子的光轴偏离下偏光片15的偏光轴(透光轴)，发生偏光现象，这部分偏振光可以顺利透过上偏光片16，从而使得该子像素呈白态显示。
在另一些实施例中，以扭曲向列(Twist Nematic，TN)型液晶显示面板为例，如图4A和图4B所示，设置于两个衬底基板上的液晶取向膜14的取向方向相互垂直，液晶分子形成一个90度的扭曲配向结构，以上偏光片16和下偏光片15垂直正交的常白模式为例，在未加电压时显示白态，在施加电压后，液晶分子垂直排列，入射的直线偏振光透过液晶层13后，偏振光无法透过上偏光片16而显示黑态。
由以上示例可知，若不设置液晶取向膜14，则该液晶显示装置是无法正常工作的，即，若液晶取向膜14不能对液晶分子起到初始配向的作用，则在未施加电压时，液晶分子的排列便会不整齐，造成光线的散射，形成漏光的现象。
基于此，本公开的一些实施例提供一种液晶取向膜，该液晶取向膜采用液晶取向剂形成，包括液晶取向剂烧成后的聚酰亚胺。该液晶取向膜可以经过摩擦配向后获得如上所述的液晶取向膜14。
当然，本领域技术人员能够理解的是，当本公开提供的液晶取向膜可以通过光学作用进行配向时，也同样适用于光学配向。
工程中使用的液晶取向膜的原料主要分为聚酰亚酸和可溶性聚酰亚胺，双酐和二胺混合溶解于特定溶剂中，可以形成聚酰亚酸，聚酰亚酸通过脱水生成聚酰亚胺。
因此，在实际制作中，可以先将液晶取向膜的原料如双酐和二胺在溶剂中进行混合，并在氮气保护下搅拌使其发生聚合反应，生成聚酰亚酸，对聚酰亚酸提纯后，以一定比例的溶剂进行稀释，制备获得液晶取向剂。而后，将该液晶取向剂形成在以上所述的衬底基板(在此，该衬底基板可以为已经形成有薄膜晶体管TFT、像素电极和公共电极的衬底基板，或者，该衬底基板为已经形成有彩色滤光层和黑矩阵的衬底基板)上，接着，通过预固化(温度：125℃～135℃，时间：110s～150s)、主固化(温度：210℃～240℃，时间：1100s～1500s)过程使其固化，最后通过烧成使聚酰亚酸脱水生成聚酰亚胺。
其中，可以通过凸版印刷方式或喷墨方式，将液晶取向剂形成在衬底基板上。凸版印刷方式具有图案选择准确、印刷表面均匀的优点。喷墨方式则适用于大尺寸显示面板的制作，且相对于凸版印刷方式而言，喷墨方式的液晶取向剂使用量少，效率高、成本低。
本公开的实施例一提供一种液晶取向剂，包括至少一种聚合物，该至少一种聚合物选自聚酰亚酸和由该聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种。该聚酰亚酸包括如下式(I)所示的第一双酐和如下式(II)或下式(III)所示的第一二胺生成的第一链段结构。
Figure PCTCN2021111782-appb-000007
Figure PCTCN2021111782-appb-000008
其中，该第一双酐中X 1为第一软链段，该第一软链段为无定形链段；L选自单键、双键和碳原子数为1～3的二价或三价烃基中的任一个。
该第一二胺中如式(II)所示，Y 1选自单键、O、NH、S、一个或多个不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，其中一个A 1和一个A 2分别选自C，并均与Y 1结合，其余A 1和A 2分别独立地选自CH、CR和N中的任一个，且A 1和A 2中N的个数均不超过两个。
该第一二胺中如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，且A 3和A 4分别独立地选自CH、CR和N中的任一个，且A 3和A 4中N的个数均不超过两个，R 1、R 2和R分别独立地选自氢和脂肪族烃基中的任一个。
其中，碳原子数为1～3的二价烃基可以包括：-CH 2-、-CH 2-CH 2-、-CH 2-CH 2-CH 2-、-CH＝CH-、-CH 2-CH＝CH-、-CH≡CH-等，碳原子数为1～3的三价烃基可以包括：＝CH-、＝CH-CH 2-、＝CH-CH 2-CH 2-、＝CH-CH＝CH-等。
在L选自单键的情况下，以上所述的式(I)的结构式可以如下式(i)所示。
Figure PCTCN2021111782-appb-000009
在L选自双键的情况下，以上所述的式(I)的结构式可以如下式(ii)所示。
Figure PCTCN2021111782-appb-000010
在L选自碳原子数为1～3的二价烃基，且碳原子数为1～3的二价烃基为-CH 2-的情况下，以上所述的式(I)的结构式可以如下式(iii)所示。
Figure PCTCN2021111782-appb-000011
在L选自碳原子数为1～3的三价烃基，且碳原子数为1～3的三价烃基为＝CH-的情况下，以上所述的式(I)的结构式可以如下式(iv)所示。
Figure PCTCN2021111782-appb-000012
在聚合物中，某些嵌段共聚物中存在着不同的分子链段，有的分子链段由芳香烃组成，刚性较大，称为硬链段，有的分子链段由脂肪烃组成，柔性较大，称为软链段。
由此可见，软链段是相对于硬链段而言的。
在本实施例中，硬链段除了嵌段共聚物中指出的芳香烃以外，还可以包括多环、稠环、以及含有芳环的共轭体系等。如以上第一二胺所示的结构。软链段除了以上所述的脂肪烃以外，还可以包括由碳氧键、碳氮键、碳硅键和硅氧键等组成的链段。
聚合物根据其分子在空间排列的规整性可分为结晶型和无定形(非结晶)两类。相应地，在聚合物中，根据分子链在空间排列的规整性可以分为结晶型链段和无定形链段，当链段中分子排列规整有序时，称为结晶型链段，若链段中分子排列杂乱无规，则称为无定形链段。
一般来说，分子具有支化、交联、无规立构、无规共聚和带有较大侧基等结构时往往得到无定形链段。严格地说，无定形链段指在任何条件下都不会结晶的链段，在实际中也常把结晶性很低的链段算入其中。
无规立构是取代基在平面两侧或手性中心的构型呈无规排列，无规共聚是由两种(或两种以上)单体单元无规则排列连接形成。两种单体单元序列长度分布各自均无规分布。
在本实施例中，该第一软链段是无定形链段，因此，具有两种可能的情况，第一种情况，该第一双酐为非对称结构。第二种情况，该第一软链段中含有非对称支链。
分子的对称性是指分子常常因含有若干相同原子或基团而具有某种对称性。如果分子经过某种对称操作(对称操作都有其对称元素，分子的对称性可分为五种对称元素：旋转轴、对称面、对称中心、旋转反映轴和恒等元素)后，与未经操作的原有分子无法分辨，则称为分子的对称性，此时，分子的结构为对称结构，反之，则该分子的结构则为非对称结构。
对于第一双酐而言，以L选自双键为例，由于第一双酐具有两个丁基二酸酐，X 1连接在两个丁基二酸酐之间，若R 1和R 2位于X 1的同侧，则该第一双酐为顺式，反之，则第一双酐为反式，当该第一双酐为顺式时，该第一双酐适用于对称元素为对称面的判断准则，此时，若第一双酐呈镜像对称，则该第一双酐为对称结构，反之，则该第一双酐为非对称结构。因此，在此情况下，为了使第一双酐为非对称结构，示例性的，取代基R 1和R 2不同，此时，第一软链段可以含有非对称支链，也可以不含有非对称支链，即以上所述的第一种情况。当该第一双酐为反式时，该第一双酐适用于对称元素为对称中心的判断准则，此时，若第一双酐呈中心对称，则该第一双酐为对称结构，反之，则该第一双酐为非对称结构。因此，在此情况下，为了使第一双酐为非对称结构，示例性的，取代基R 1和R 2不同，此时，与该第一双酐为顺式相类似的，该第一软链段可以含有非对称支链，也可以不含有非对称支链，即以上所述的第一种情况。
第二种情况，该第一软链段含有非对称支链，在此情况下，根据该第一双酐是顺式和反式，有两种可能的情形，第一种情形，该第一双酐为顺式，则该第一软链段中的支链是否为非对称支链，与第一双酐是否为对称结构的判断准则相同，是以对称元素为对称面进行判断的。第二种情形，该第一双酐为反式，则该第一软链段中的支链是否为非对称支链，与第一双酐是否为对称结构的判断准则相同，是以对称元素为对称中心进行判断的。
由以上可知，该聚酰亚酸可以是由第一链段结构作为重复单元的结构，根据第一二胺的结构不同，有两种可能的结构，第一种结构如下式(1)所示，第二种结构如下式(2)所示。
Figure PCTCN2021111782-appb-000013
由以上结构可以得知，该聚酰亚酸是由无定形的软链段和硬链段交替排列而成，因此，通过对分子结构中的软链段和硬链段进行合理配比，能够赋予聚酰亚酸特殊的性能，如使聚酰亚酸具有良好的刚性的同时，还能够提高聚酰亚酸的韧性，与相关技术中聚酰亚胺虽然具有良好的硬度(硬度可以达到3H～4H)，但是在摩擦配向时由于硬度过高而容易产生碎屑，并容易损伤摩擦布，造成摩擦布中的成分脱落相比，由于聚酰亚酸具有良好的韧性，因此，在摩擦配向时，采用摩擦布摩擦，由该聚酰亚酸烧成后的产物(聚酰亚胺)具有的良好的延展性，能够很好地缓冲摩擦布所产生的外力，一方面，聚酰亚胺本身不易产生碎屑，另一方面，该聚酰亚胺不易损伤摩擦布；因此可以有效减少碎屑不良。
基于以上结构，在一些实施例中，若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段选自亲水链段和含有至少一个亲水基团的链段中的任一个。
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1中的至少一个取代基团选自亲水基团，第一软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个；或者，Y 1中的至少一个取代基团和第一软链段中其中 之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Z 1中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Z 1中的至少一个取代基团选自亲水基团，第一软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个；或者，Y 1中的至少一个取代基团和第一软链段中其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在两亲性聚合物中，同一分子链中含有亲水链段和疏水链段，疏水链段是相对于亲水链段而言的，亲水链段可以包括聚乙二醇链段、聚乙烯醚链段、聚乙烯醇链段、聚乙烯亚胺链段、聚乙烯吡咯烷酮链段、聚乙烯酞胺链段等。疏水链段包括聚环氧丙烷链段、聚硅氧烷链段、饱和脂肪烃链段(如聚苯乙烯链段、聚乙烯链段、聚丙烯链段、聚甲基丙烯酸甲酯链段、聚丙烯酸甲酯链段、聚丙烯酸丁酯链段)或非饱和脂肪烃链段(如聚丁二烯链段)等。
亲水基团又称疏油基团，具有可溶于水，或容易与水亲和的原子团。可能吸引水分子或溶解于水，这类分子形成的固体表面易被水润湿。包括羧基、磺酸基、磷酸基、氨基、季铵基、由含氧基团组成的醚基、羟基、羧酸酯、嵌段聚醚等。
疏水基团又称亲油基团，对水无亲和力，不溶于水或溶解度极小的基团。包括烃基、酯基等，其中，烃基可以是饱和脂肪烃，也可以是含有双键的非饱和脂肪烃，还可以是含有芳基、酯、醚、胺、酰胺等基团的烃基。
在本实施例中，当该第一二胺选自如式(II)所示的结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个时，或者，当第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个时，该第一二胺为疏水链段，因此，通过将第一软链段设置为亲水链段或在该第一软链段中引入亲水基团，通过对疏水链段和亲水链段或亲水基团进行合理配比，能够对该聚酰亚酸的亲疏水性能进行调节。或者，当该第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，当第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个时，通过对取代基团的亲疏水性和第一软链段的亲疏水性进行调节，并对 取代基团和第一软链段中的亲疏水基团进行合理配比，也能够对该聚酰亚酸的亲疏水性能进行调节。
对于疏水性的聚酰亚酸而言，水在其表面的接触角大，润湿效果差，不易形成水膜，碎屑吸附在疏水性的聚酰亚酸的表面而不易进入水中，在风刀干燥过程中，聚酰亚酸表面的水快速被吹出，导致清洗效果不佳，碎屑的去除率低下。相反，对于亲水性的聚酰亚酸而言，水在其表面的接触角小，润湿效果好，易形成均一的水膜，碎屑也容易进入水中，最后被风刀吹走。而若亲水性过强，则容易吸附环境中的水汽，造成环境中粉尘颗粒的污染，从而产生环境异物类的碎屑。
因此，在本实施例中，通过对聚酰亚酸的亲疏水性能进行调节，使该聚酰亚酸具有合适的亲疏水性，在摩擦配向完成后，在成盒前通过对聚酰亚酸表面进行清洗，能够有效去除摩擦配向过程中产生的碎屑和杂质(如摩擦布中的绒毛等)，与相关技术中在成盒前不能有效清洗，残留盒内产生碎屑不良(例如较大的碎屑直接导致良率降低，较小的碎屑则会导致黑态下的漏光，降低产品对比度)相比，能够避免产生碎屑不良。
在另一些实施例中，第一软链段为疏水链段和包含至少一个疏水基团的链段中的任一个；该第一二胺选自如式(II)所示的结构，且Y 1选自至少一个碳原子被取代的芳环、杂环和稠环中的任一个，至少一个取代基团选自亲水基团和具有至少一个亲水基团的碳原子数为1～3的烃基中的任一个。
在本实施例中，当至少一个取代基团选自亲水基团时，该亲水基团直接连接在Y 1的环上，而又由于该Y 1选自芳环、杂环和稠环中的任一个，因此，当该亲水基团为羟基时，该亲水基团即为酚羟基。而当至少一个取代基团选自具有至少一个亲水基团的碳原子数为1～3的烃基时，该亲水基团连接在烃基上，因此，当该亲水基团为羟基时，该亲水基团为醇羟基。
在另一些实施例中，该第一二胺中Y 1结合在氨基的对位，且选自一个碳原子被取代的苯环，取代基团为碳原子数为1～3的醇羟基。
即，该亲水基团为醇羟基的情形。并且，在本实施例中，由于Y 1结合在氨基的对位，因此，当A 1和A 2分别独立地选自CH和CR中的任一个时，该第一二胺为三联苯。
在又一些实施例中，该第一软链段为取代的或未取代的碳原子数为10～20的亚烷基链段。
在本实施例中，当该第一软链段为未取代的碳原子数为10～20的亚烷基链段时，由于该第一软链段为无定形链段，因此，该第一双酐为非对称结构， 此时，该R 1和R 2不同，具体判断准则可参照以上对第一双酐为非对称结构的描述。当该第一软链段为取代的碳原子数为10～20的亚烷基链段时，由于该第一软链段为无定形链段，因此，该第一双酐为非对称结构，即，在取代基团形成对称支链的情况下，该R 1和R 2不同。或者，该第一软链段含有非对称支链，此时，该R 1和R 2可以相同，同样能够实现第一软链段为无定形链段。具体判断准则可参照以上对第一双酐为非对称结构或者第一软链段中含有非对称结构的描述。
本公开的实施例二提供一种液晶取向剂，该液晶取向剂包括至少一种聚合物，至少一种聚合物选自聚酰亚酸和由聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种。该聚酰亚酸除包括如上式(I)所示的第一双酐和如上式(II)或上式(III)所示的第一二胺生成的第一链段结构以外，还包括如下式(IV)所示的第二双酐和如上式(II)或上式(III)所示的第一二胺生成的第二链段结构。
Figure PCTCN2021111782-appb-000014
其中，该第二双酐中X 2选自脂肪环、芳环、杂环和稠环结构中的任一个。
在本实施例中，通过引入第二双酐，由于该第二双酐中X 2选自脂肪环、芳环、杂环和稠环结构中的任一个，因此，该第二双酐具有平面分子结构，刚性较大，在与以上的第一二胺反应生成的第二链段结构中作为硬链段。而根据酸酐和二胺以摩尔比为1:1进行聚合为例，则在混合时，第一双酐和第二双酐的总摩尔量与第一二胺的摩尔量之比可以接近于1:1，如可以为9:11～11:9。此时，该第一双酐和第二双酐均与第一二胺聚合，而通过调节第一双酐和第二双酐的比例，可以对第一双酐与第一二胺生成的第一链段结构和第二双酐与第一二胺生成的第二链段结构的比例(即该聚酰亚酸中第一双酐和第二双酐与同一个第一二胺聚合得到的链段结构(根据第一二胺的结构不同，可以如下式(3)或下式(4)所示)的比例)进行调节。
Figure PCTCN2021111782-appb-000015
由以上结构可知，该聚酰亚酸仍然由无定形的软链段和硬链段交替排列而成，通过对第一双酐和第二双酐的比例进行调节，即可对该聚酰亚酸的软链段和硬链段的长度进行调节，从而能够对聚酰亚酸的硬度、韧性和脆性进行调节，使得该聚酰亚酸具有一定硬度的同时，具有良好的韧性，同样能够解决相关技术中聚酰亚胺虽然具有良好的硬度(硬度可以达到3H～4H)，但是在摩擦配向时由于硬度过高而容易产生碎屑，并容易损伤摩擦布，造成摩擦布中的成分脱落，造成碎屑不良的问题。
同时，在以上通过在第一双酐和第一二胺中分别引入亲水基团和疏水基团，或者，将第一软链段设置为亲水链段或疏水链段，对该聚酰亚酸的亲疏水性能进行调节的情况下，通过对该第二双酐与第一双酐的比例进行调节，也同样能够达到使该聚酰亚酸的亲疏水性合适的技术效果，在成盒前提高聚酰亚酸的清洗性，有效去除摩擦配向过程中产生的碎屑，同样能够避免产生碎屑不良。
在一些实施例中，该第一双酐和第二双酐的摩尔比可以为10:90～90:10。
基于以上结构，在另一些实施例中，该第二双酐中X 2可以选自如下结构中的任一个。
Figure PCTCN2021111782-appb-000016
在又一些实施例中，该第二双酐中X 2选自如下结构式其中，R 3和R 4分别独立地选自氢和脂肪族烃基中的任一个。
Figure PCTCN2021111782-appb-000017
在这些实施例中，该第二双酐的结构式如下式所示。
Figure PCTCN2021111782-appb-000018
本公开的实施例三提供一种液晶取向剂，包括至少一种聚合物，至少一种聚合物选自聚酰亚酸和由聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种。该聚酰亚酸除包括如上式(I)所示的第一双酐和如上式(II)或上式(III)所示的第一二胺反应生成的第一链段结构以外，还包括如下式(V)所示的第二二胺和第一双酐反应生成的第三链段结构。
Figure PCTCN2021111782-appb-000019
其中，该第二二胺中Y 2为第二软链段；其中一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个，R选自氢和脂肪族烃基中的任一个。
在本实施例中，通过在第一双酐和第一二胺存在的情况下，引入第二二胺，由于该第二二胺中Y 2为第二软链段，因此，该第二二胺在与以上的第一双酐反应生成的第三链段结构中作为软链段。而通过对第二软链段的结晶度进行控制，并根据双酐和二胺以摩尔比为1:1进行聚合，通过调节第一二胺和第二二胺的比例，可以对第一双酐与第一二胺生成的第一链段结构和第一双酐与第二二胺生成的第三链段结构的比例(即该聚酰亚酸中第一双酐和第二双酐与同一个第一二胺聚合得到的链段结构(根据第一二胺的结构不同，可以如下式(5)或下式(6)所示)的比例)进行调节。
Figure PCTCN2021111782-appb-000020
由以上结构可知，该聚酰亚酸仍然由无定形的软链段和硬链段交替排列而成，通过对第一二胺和第二二胺的比例进行调节，即可对聚酰亚酸的结晶度进行调节，使得该聚酰亚酸具有一定硬度的同时，具有良好的韧性，同样能够解决相关技术中聚酰亚胺虽然具有良好的硬度(硬度可以达到3H～4H)，但是在摩擦配向时由于硬度过高而容易产生碎屑，并容易损伤摩擦布，造成 摩擦布中的成分脱落，造成碎屑不良的问题。
基于以上结构，在一些实施例中，若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个。
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，Y 1中的至少一个取代基团、第一软链段和第二软链段中其中1至2个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余2至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Z 1中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Z 1中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，Z 1中的至少一个取代基团、第一软链段和第二软链段中其中1至2个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余2至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在本实施例中，在以上第一双酐、第一二胺中分别引入亲水基团和疏水基团，或者，将第一软链段设置为亲水链段或疏水链段的基础上，在该第二二胺中引入亲水基团或疏水基团，或者，将第二软链段设置为亲水链段或疏水链段，通过对第一二胺和第二二胺的比例进行调节，也同样能够达到使聚酰亚酸的亲疏水性合适的技术效果，在成盒前提高聚酰亚酸的清洗性，有效去除摩擦配向过程中产生的碎屑，同样能够避免产生碎屑不良。
基于以上结构，在另一些实施例中，该第二软链段为取代的或未取代的碳原子数为5～12的亚烷基链段。即，当该第二软链段为未取代的碳原子数为5～12的亚烷基链段时，该第二软链段为疏水链段，此时，若第一二胺选自如式(II)所示结构，且Y 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段可以选自亲水链段和包含至少一个亲水基团的链段中的任一个，而若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则若Y 1中的至少一个取代基团选自亲水基团，则第一软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，若Y 1中的至少一个取代基团选自疏水基团，则第一软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，该Y 1中的至少一个取代基团和该第一软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在另一些实施例中，该第二软链段为未取代的碳原子数为7的亚烷基链段。即该第二软链段为疏水链段。
基于以上结构，在又一些实施例中，该第一二胺和第二二胺的摩尔比可以为10:90～90:10。
本公开的实施例四提供一种液晶取向剂，该液晶取向剂包括至少一种聚合物，至少一种聚合物选自聚酰亚酸和由聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种。该聚酰亚酸包括如下式(I)所示的第一双酐和如下式(V)所示的第二二胺生成的第三链段结构，如下式(V)所述的第二二胺和如下式(IV)所示的所述第二双酐反应生成的第四链段结构，和如下式(II)或下式(III)所示的第一二胺和如下式(IV)所示的第二双酐生成的第二链段结构中的至少两个链段结构。
Figure PCTCN2021111782-appb-000021
Figure PCTCN2021111782-appb-000022
其中，该第一双酐中X 1为第一软链段，该第二二胺中Y 2为第二软链段，且该第一软链段和第二软链段中的至少其中之一为无定形链段。第一双酐中L选自单键、双键和碳原子数为1～3的二价或三价烃基中的任一个；
该第二双酐X 2选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个。
该第一二胺如式(II)所示，Y 1选自单键、O、NH、S、一个或多个不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，其中一个A 1和一个A 2分别选自C，并均与Y 1结合，其余A 1和A 2分别独立地选自CH、CR和N中的任一个，且A 1和A 2中N的个数均不超过两个。
该第一二胺如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，且A 3和A 4分别独立地选自CH、CR和N中的任一个，且A 3和A 4中N的个数均不超过两个。
该第二二胺中，一个A 5和一个A 6分别选自C，并均与X2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个。
其中，R 1、R 2和R分别独立地选自氢和脂肪族烃基中的任一个。
其中，需要说明的是，实施例四和以下将要描述的实施例五中关于以上分子结构的描述均可以参照以上实施例一、实施例二和实施例三的描述，在此不再赘述，在以下的描述中，仅对实施例四和实施例五分别与以上实施例一、实施例二和实施例三的不同之处进行描述。
在本实施例中，该聚酰亚酸可以包含由第三链段结构和第四链段结构组 成的链段结构(即该聚酰亚酸中第一双酐和第二双酐与同一个第二二胺聚合得到的链段结构(可以如下式(7)所示))，或者，该聚酰亚酸可以包含由第二链段结构和第四链段结构组成的链段结构(即该聚酰亚酸中第一二胺和第二二胺与同一个第二双酐聚合得到的链段结构(根据第一二胺的结构不同，可以如下式(8)或下式(9)所示))，或者，该聚酰亚酸可以包含由第二链段结构、第三链段结构和第四链段结构组成的链段结构(根据第一二胺的结构不同，可以如下式(10)或下式(11)所示))。
Figure PCTCN2021111782-appb-000023
Figure PCTCN2021111782-appb-000024
由以上结构可以得知，该聚酰亚酸仍然由软链段和硬链段交替排列而成，且由于该第一软链段和第二软链段中的至少其中之一为无定形链段，因此，通过对分子结构中的软链段和硬链段进行合理配比，能够赋予聚酰亚酸特殊的性能，如使聚酰亚酸具有良好的刚性的同时，还能够提高聚酰亚酸的韧性，与相关技术中聚酰亚胺虽然具有良好的硬度(硬度可以达到3H～4H)，但是在摩擦配向时由于硬度过高而容易产生碎屑，并容易损伤摩擦布，造成摩擦布中的成分脱落相比，由于聚酰亚酸具有良好的韧性，因此，在摩擦配向时，采用摩擦布摩擦，由该聚酰亚酸烧成后的产物(聚酰亚胺)具有的良好的延展性，能够很好地缓冲摩擦布所产生的外力，一方面，聚酰亚胺本身不易产生碎屑，另一方面，该聚酰亚胺不易损伤摩擦布；因此可以有效减少碎屑不良。
基于以上结构，在一些实施例中，在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(V)所示的第二二胺生成的第三链段结构，和如式(IV)所示的第二双酐和如式(V)所示的第二二胺反应生成的第四链段结构的情况下；
若第二双酐中X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段分别独立地选自亲水链段、疏水链段、包含至少一个亲水基团的链段和包含至少一个疏水基团的链段中的任一个；
若第二双酐X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段和第二软链段分别独立地选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中的其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个；或者，X 2中的至少一个取代基团、第一软链段和第二软链段中的一个或两个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余两个或一个选自疏水链段和包含至少一个疏水基团的链段中的任一个；
在所述聚酰亚酸包括如式(IV)所示的第二双酐和如式(V)所示的第二二胺反应生成的第四链段结构，和如式(IV)所示的第二双酐和如式(II)或 式(III)所示的第一二胺生成的第二链段结构的情况下；
若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团选自亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团选自疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段、包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，X 2中的至少一个取代基团选自亲水基团和疏水基团中的任一个，第二软链段 选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，X 2中的至少一个取代基团选自亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和X 2中的至少一个取代基团均选自疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团、X 2中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(V)所示的第二二胺生成的第三链段结构，和如式(IV)所示的第二双酐和如式(II)或式(III)所示的第一二胺生成的第二链段结构的情况下；
若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，X 2中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1 选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；或者，Y 1或Z 1中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，X 2中的至少一个取代基团选自亲水基团和疏水基团中的任一个，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，X 2中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和X 2中的至少一个取代基团均选自疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段、包含至少一个疏水基团的链段中的人一个；或者，Y 1或Z 1中的至少一个取代基团、X 2中的至少一个取代基团、第一软链段和第二软链段中的其中1至3个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余3至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在本实施例中，通过分别在第一双酐、第二双酐和第二二胺中引入亲水基团和疏水基团，在第二双酐、第一二胺和第一二胺中引入亲水基团和疏水基团，或者在第一双酐、第二双酐、第一二胺和第一二胺中引入亲水基团和疏水基团，能够对最终形成的聚酰亚酸的亲疏水性能进行调节，同样能够达到使聚酰亚酸的亲疏水性合适，在成盒前提高聚酰亚酸的清洗性，有效去除摩擦配向过程中产生的碎屑，避免产生碎屑不良的技术效果。
在另一些实施例中，该第一软链段为取代的或未取代的碳原子数为10～20的亚烷基链段；该第一二胺选自如式(II)所示的结构，且Y 1选自至少一个碳原子被取代的芳环、杂环和稠环中的任一个，至少一个取代基团选自亲水基团和具有至少一个亲水基团的碳原子数为1～3的烃基中的任一个；该第二软链段为疏水链段和包含至少一个疏水基团的链段中的任一个。
在本实施例中，当该第一软链段为未取代的碳原子数为10～20的亚烷基链段时，该第一软链段为疏水链段，此时，可以根据亲疏水性来控制第一双酐、第二双酐、第一二胺和第二二胺的比例，以对最终所生成的聚酰亚酸的亲疏水性能进行调节。
其中，根据第一软链段是否为无定形链段，有两种可能的情况，第一种情况，第一双酐为非对称结构，第二种情况，该第一软链段中含有非对称支链。
在第一种情况下，该第一双酐为非对称结构，此时，非对称结构的描述可以参照如上对第一双酐为非对称结构的描述，在此不再赘述，在此情况下，该第一软链段可以为未取代的碳原子数为10～20的亚烷基链段，此时，该第一软链段为无定形链段。
在第二种情况下，该第一软链段中含有非对称支链。此时，该第一软链段可以为取代的碳原子数为10～20的亚烷基链段。具体的非对称支链的描述可以参照如上所述的非对称支链的描述，在此不再赘述，此时，该第一软链段也为无定形链段。
在另一些实施例中，该第二软链段为取代的或未取代的碳原子数为5～12的亚烷基链段。
在本实施例中，根据第二软链段是否为无定形链段，有两种可能的情况，第一种情况，该第一二胺为非对称结构。第二种情况，该第二软链段中含有非对称支链。
在第一种情况下，该第一二胺为非对称结构，即Y 1可以连接在两个苯环上的氨基的不同位置(如不都在邻位、间位或对位)，或者，两个苯环上的CR的个数、位置或R的结构不同。此时，该第二软链段可以为未取代的碳原子数为5～12的亚烷基链段，此时，该第二软链段为无定形链段。
在第二种情况下，该第二软链段中含有非对称支链，即第二软链段为取代的碳原子数为5～12的亚烷基链段，且取代基团形成非对称支链。此时，该第二软链段也为无定形链段，其中，对Y 1的位置，以及两个苯环上的CR的个数、位置以及R的结构均不做具体限定。
在又一些实施例中，该第一二胺中Y 1结合在氨基的对位，且选自一个碳原子被取代的苯环，取代基团选自碳原子数为1～3的醇羟基。
即，在本实施例中，Y 1结合在氨基的对位，因此，当A 1和A 2分别独立地选自CH和CR中的任一个时，该第一二胺为三联苯，同时，该亲水基团为醇羟基。
本公开的实施例五提供一种液晶取向剂，该液晶取向剂包括至少一种聚合物，至少一种聚合物选自聚酰亚酸和由聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种。该聚酰亚酸包括如下式(I)所示的第一双酐和如下式(II)或下式(III)所示的第一二胺生成的第一链段结构，如下式(IV)所示的第二双酐和如下式(II)或下式(III)所示的第一二胺生成的第二链段结构，如下式(IV)所示的第一双酐和如下式(V)所述的第二二胺生成的第三链段结构，和如下式(IV)所示的第二双酐和如下式(V)所示的第二二胺生成的第四链段结构。
Figure PCTCN2021111782-appb-000025
Figure PCTCN2021111782-appb-000026
其中，该第一双酐中X 1为第一软链段，该第二二胺中Y 2为第二软链段，且该第一软链段和第二软链段中的至少其中之一为无定形链段；第一双酐中L选自单键、双键和碳原子数为1～3的二价或三价烃基中的任一个。
该第二双酐X 2选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个。
该第一二胺如式(II)所示，Y 1选自单键、O、NH、S、一个或多个不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，其中一个A 1和一个A 2分别选自C，并均与Y1结合，其余A 1和A 2分别独立地选自CH、CR和N中的任一个，且A 1和A 2中N的个数均不超过两个。
该第一二胺如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，且A 3和A 4分别独立地选自CH、CR和N中的任一个，且A 3和A 4中N的个数均不超过两个。
该第二二胺中，一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个。
其中，R 1、R 2和R分别独立地选自氢和脂肪族烃基中的任一个。
在本实施例中，该聚酰亚酸的结构可以包含由第一链段结构、第二链段结构、第三链段结构和第四链段结构组成的链段结构(根据第一二胺的结构不同，可以如下式(12)或下式(13)所示)，也可以包含由第一链段结构和第二链段结构组成的链段结构，由第三链段结构和第四链段结构组成的链段结构，以及由第一链段结构和第三链段结构组成的链段结构，和由第二链段结构和第四链段结构组成的链段结构(根据第一二胺的结构不同，可以如下式(14)或下式(15)所示)。
Figure PCTCN2021111782-appb-000027
Figure PCTCN2021111782-appb-000028
由以上结构可以得知，该聚酰亚酸由软链段和硬链段交替排列而成，且由于该第一软链段和第二软链段中的至少其中之一为无定形链段，因此，通过对分子结构中的软链段和硬链段进行合理配比，能够赋予聚酰亚酸特殊的性能，如使聚酰亚酸具有良好的刚性的同时，还能够提高聚酰亚酸的韧性，与相关技术中聚酰亚胺虽然具有良好的硬度(硬度可以达到3H～4H)，但是在摩擦配向时由于硬度过高而容易产生碎屑，并容易损伤摩擦布，造成摩擦布中的成分脱落相比，由于聚酰亚酸具有良好的韧性，因此，在摩擦配向时，采用摩擦布摩擦，由该聚酰亚酸烧成后的产物(聚酰亚胺)具有的良好的延展性，能够很好地缓冲摩擦布所产生的外力，一方面，聚酰亚胺本身不易产生碎屑，另一方面，该聚酰亚胺不易损伤摩擦布；因此可以有效减少碎屑不 良。
基于以上结构，在一些实施例中，若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，X 2中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；或者，或者，Y 1或Z 1中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、 杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，X 2中的至少一个取代基团选自亲水基团和疏水基团中的任一个，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，X 2中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和X 2中的至少一个取代基团均选自疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段、包含至少一个疏水基团的链段中的人一个；或者，Y 1或Z 1中的至少一个取代基团、X 2中的至少一个取代基团、第一软链段和第二软链段中的其中1至3个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余3至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
在本实施例中，通过分别在第一双酐、第二双酐、第一二胺和第二二胺中引入亲水基团和疏水基团，能够对最终形成的聚酰亚酸的亲疏水性能进行调节，同样能够达到使聚酰亚酸的亲疏水性合适，在成盒前提高聚酰亚酸的清洗性，有效去除摩擦配向过程中产生的碎屑，避免产生碎屑不良的技术效果。
在另一些实施例中，该第一软链段为取代的或未取代的碳原子数为10～20的亚烷基链段；该第一二胺选自如式(II)所示的结构，且Y 1选自至少一个碳原子被取代的芳环、杂环和稠环中的任一个，至少一个取代基团选自亲水基团和具有至少一个亲水基团的碳原子数为1～3的烃基中的任一个；该第二软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个；该第二双酐中X 2选自如下结构式，其中，R 3和R 4分别独立地选自氢和脂肪族烃基中的任一个。
Figure PCTCN2021111782-appb-000029
在本实施例中，当该第一软链段为未取代的碳原子数为10～20的亚烷基链段时，该第一软链段为疏水链段，此时，可以根据亲疏水性来控制第一双酐、第二双酐、第一二胺和第二二胺的比例，以对最终所生成的聚酰亚酸的亲疏水性能进行调节。
其中，根据第一软链段是否为无定形链段，有两种可能的情况，第一种情况，第一双酐为非对称结构，第二种情况，该第一软链段中含有非对称支链。
在第一种情况下，该第一双酐为非对称结构，此时，非对称结构的描述可以参照如上对第一双酐为非对称结构的描述，在此不再赘述，在此情况下，该第一软链段可以为未取代的碳原子数为10～20的亚烷基链段，此时，该第一软链段为无定形链段。
在第二种情况下，该第一软链段中含有非对称支链。此时，该第一软链段可以为取代的碳原子数为10～20的亚烷基链段。具体的非对称支链的描述可以参照如上所述的非对称支链的描述，在此不再赘述，此时，该第一软链段也为无定形链段。
在另一些实施例中，该第二软链段为取代的或未取代的碳原子数为5～12的亚烷基链段。
在本实施例中，根据第二软链段是否为无定形链段，有两种可能的情况，第一种情况，该第一二胺为非对称结构。第二种情况，该第二软链段中含有非对称支链。
在第一种情况下，该第一二胺为非对称结构，即Y 1可以连接在两个苯环上的氨基的不同位置(如不都在邻位、间位或对位)，或者，两个苯环上的CR的个数、位置或R的结构不同。此时，该第二软链段可以为未取代的碳原子数为5～12的亚烷基链段，此时，该第二软链段为无定形链段。
在第二种情况下，该第二软链段中含有非对称支链，即第二软链段为取代的碳原子数为5～12的亚烷基链段，且取代基团形成非对称支链。此时，此时，该第二软链段为无定形链段，其中，对Y 1的位置，以及两个苯环上的CR的个数、位置以及R的结构均不做具体限定。
在又一些实施例中，该第一二胺中Y 1结合在氨基的对位，且选自一个碳原子被取代的苯环，取代基团选自碳原子数为1～3的醇羟基。
即，在本实施例中，Y 1结合在氨基的对位，因此，当A 1和A 2分别独立地选自CH和CR中的任一个时，该第一二胺为三联苯，同时，该亲水基团为醇羟基。
本公开的实施例六提供一种液晶取向剂，该液晶取向剂包括至少一种聚合物，至少一种聚合物选自聚酰亚酸和由聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种。该聚酰亚酸除包括如下式(IV)所示的第二双酐和下式(V)所示的第二二胺生成的第五链段结构。
Figure PCTCN2021111782-appb-000030
其中，该第二双酐X 2选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个。该第二二胺中Y 2为第二软链段，该第二软链段为无定形链段。该第二二胺中，一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个，R选自氢和脂肪族烃基中的任一个。
若第二双酐X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第二软链段选自亲水链段和包括至少一个亲水基团的链段中的任一个；
若第二双酐X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团为亲水基团，第二软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，X 2中的至少一个取代基团为疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个；或者，X 2中的至少一个取代基团和第二软链段中的其中之一选自疏水链段和包含至少一个疏水基团的链段中的任一个，另一个选自亲水链段和包含至少一个亲水基团的链段中的任一个。
在本实施例中，通过在该第二双酐和第二二胺中引入亲水基团和疏水基团，能够对聚酰亚酸的亲疏水性能进行调节，同样能够达到使聚酰亚酸的亲疏水性合适，在成盒前提高聚酰亚酸的清洗性，有效去除摩擦配向过程中产生的碎屑，避免产生碎屑不良的技术效果。
在一些实施例中，以上所述的液晶取向膜的硬度用预设压力下扎针扎入液晶取向膜的深度来表征，液晶取向膜的硬度满足：在预设压力为150μN的 压力下，取值小于等于45μm。
示例的，可以采用HYSITRON Tribo-Indenter(原位纳米力学测量)设备，使该设备的探头带动扎针扎入液晶取向膜，在相同的压力下，根据扎针进入配向膜的深度越小，则膜硬度越大。
在本实施例中，由于液晶取向膜的硬度的取值小于等于45μm，因此，与相关技术中在预设压力为150μN的压力下，液晶取向膜的硬度的取值均大于50μm相比，能够提高液晶取向膜的硬度。
在一些实施例中，以上所述液晶取向膜的韧度用扎针在液晶取向膜的厚度方向的深度突变所对应的压力来表征，液晶取向膜的韧度的取值大于390μN。
同样可以采用以上所述的HYSITRON Tribo-Indenter(原位纳米力学测量)设备，使该设备的探头带动扎针扎入液晶取向膜，根据液晶取向膜破裂剥离时，扎针在液晶取向膜的厚度方向的深度突变所对应的探头压力越大，则膜韧度越大。
在本实施例中，与相关技术中液晶取向膜破裂剥离时，扎针在液晶取向膜的厚度方向的深度突变所对应的探头压力均小于300μN相比，能够增大液晶取向膜的韧度。
在一些实施例中，在以上所述的所述液晶取向剂所包含有亲水链段和/或亲水基团的情况下，以上所述的液晶取向膜的水接触角小于等于58°。
通过引入亲水链段和/或亲水基团，并通过对疏水基团和亲水基团的比例进行调节，能够对液晶取向膜的水接触角的大小进行调节，从而能够提高碎屑洗涤效果。
在一些实施例中，在以上所述的液晶取向剂所包含的第一二胺和第二二胺的摩尔百分比为35％：15％的情况下，随着液晶取向剂所包含的第一双酐和第二双酐的比例逐渐增大，以上所述的液晶取向膜的硬度降低，韧性增大。
通过调节具有软链段的第一双酐和具有刚性结构的第二双酐的比例，能够对液晶取向膜的硬度和韧性进行调节。
在一些实施例中，在以上所述的液晶取向剂所包含的第一双酐和第二双酐的摩尔百分比为10％：40％，且第二二胺中的Y2为疏水链段的情况下，随着液晶取向剂所包含的第一二胺和第二二胺的比例逐渐增大，以上所述的液晶取向膜的水接触角逐渐降低。
通过调节第一二胺和第二二胺的比例，能够对液晶取向膜的亲水基团和疏水基团的比例进行调节，从而能够对液晶取向膜的水接触角进行调节。
以下，为了对本公开的实施例的有益技术效果进行客观评价，将通过以下实验例对本公开提供的液晶取向膜进行详细的示例性的说明。
实验例1
实验例1采用目前已经量产的两种双酐和二胺，双酐和二胺的结构式如下式(i)和下式(ii)所示。
Figure PCTCN2021111782-appb-000031
制备方法如下：
S1、将以一定量的N-甲基吡咯烷酮或DMF加入反应器中，在反应器中通入氮气保护，加入双酐(i)和二胺(ii)混合，在搅拌下，控制反应器的温度为15～30℃进行聚合反应，反应时间为4～6h，获得聚酰亚酸A。
S2、将提纯后的聚酰亚酸A以一定溶剂(由GBL(γ-butyrrolactone，γ-丁内酯)、NMP(N-methyl-2-pyrrolidone，N-甲基吡咯烷酮)、BC(Butyl carbitol(Butyl Di-glycol)，二乙二醇单丁醚)和DAA(Diacetone alcohol，二丙酮醇)按照50:30:10:10的比例混合而成)进行稀释，聚酰亚酸的质量百分比为3.0％～4.5％，制备成聚酰亚酸A的涂料。
S3、通过涂布，将聚酰亚酸A形成在已经形成有薄膜晶体管TFT、像素电极和公共电极的衬底基板，或已经形成有彩色滤光层和黑矩阵的衬底基板上，并通过预固化、主固化使其固化，最后通过烧成使聚酰亚酸脱水(酰胺化)生成聚酰亚胺A。
S4、采用绒布滚轮对聚酰亚胺A进行接触式的定向机械摩擦，并控制滚轮的转速为1000～1200RPM，同时基台的移动速度为30～40mm/s，对聚酰亚胺A进行摩擦配向，得到摩擦配向后的液晶取向膜A，从而得到阵列基板和对置基板。同时，采用HYSITRON Tribo-Indenter(原位纳米力学测量)设备测量其硬度和韧性，记为样本a，并进行配向摩擦实验，用摩擦后的碎屑数表 征其耐磨性。
其中，硬度和韧性的测量方式是在基板上形成一定厚度的液晶取向膜且未摩擦配向之前，采用以上所述的HYSITRON Tribo-Indenter(原位纳米力学测量)设备，使该设备的探头带动扎针扎入液晶取向膜，在探头压力为150μN的压力下，扎针扎入液晶取向膜的深度对液晶取向膜的硬度进行表征。以及采用以上所述HYSITRON Tribo-Indenter(原位纳米力学测量)设备，使该设备的探头带动扎针扎入液晶取向膜，并带动扎针沿水平方向运动，直至液晶取向膜剥离破裂时扎针在液晶取向膜的厚度方向进入深度突变所对应的探头压力，对液晶取向膜的韧度进行表征。
其中，摩擦后的碎屑数是在显微镜下，在液晶取向膜的不同位置，随机选取多组一定数量的像素，统计其表面的碎屑数，并通过加权求平均获得。
S5、对摩擦配向后的液晶取向膜A进行清洗，在此过程中，测量液晶取向膜A的水接触角，将水接触角测量样本记为样本a，并用清洗前后的P/T的去除率表征其清洗性能，将清洗性能表征样本记为样本a。
实验例2
实验例2采用如下多种实验方案，以下实验方案与实验例1的制备过程基本相同，不同的是，实验例2所采用的实验原料为本公开提供的如下所示的双酐和二胺。
第一种实验方案，实验原料为如下式(I)所示的第一双酐和如下式(II)所示的第一二胺，其中R 1和R 2均选自甲基。
第二种实验方案，实验原料为如下式(I)所示的第一双酐和如下式(III)所示的第一二胺，其中R 1和R 2均选自甲基。
第三种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(II)所示的第一二胺和如下式(IV)所示的第二双酐，其中R 1和R 2均选自甲基，R 3和R 4均选自氢。
第四种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(III)所示的第一二胺和如下式(IV)所示的第二双酐，其中R 1和R 2均选自甲基，R 3和R 4均选自氢。
第五种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(II)所示的第一二胺和如下式(V)所示的第二二胺，其中R 1和R 2均选自甲基。第六种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(III)所示的第一二胺和如下式(V)所示的第二二胺，其中R 1和R 2均选自甲基。第七种试验方案，实验原料为如下式(IV)所示的第二双酐、如下式(II)所示 的第一二胺和如下式(V)所示的第二二胺，其中R 3和R 4均选自氢。
第八种试验方案，实验原料为如下式(IV)所示的第二双酐、如下式(III)所示的第一二胺和如下式(V)所示的第二二胺，其中R 3和R 4均选自氢。
第九种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(IV)所示的第二双酐和如下式(V)所示的第二二胺，其中R 1和R 2均选自甲基，R 3和R 4均选自氢。
Figure PCTCN2021111782-appb-000032
以上实验例1测得的硬度和第一种试验方案到第九种试验方案所测得的硬度与韧性(分别一一对应的记为b1～b9)如下表1所示，以及以上实验例1测得的摩擦后的碎屑数和第一种试验方案到第九种试验方案所测得的摩擦后的碎屑数与硬度和韧性建立对比图如图4所示。
表1
Figure PCTCN2021111782-appb-000033
由表1和图4可知，本公开提供的技术方案中，通过软硬链段交替的形式形成聚合物，通过调节软链段和硬链段的比例，能够对最终所获得的液晶取向膜的韧性进行调节，从而能够提高液晶取向膜的耐磨性能，减少碎屑。
实验例3
实验例3采用如下多种实验方案，以下实验方案与实验例2基本相同，不同的是，实验例3所采用的实验原料中还包含有疏水基团和亲水基团。
第一种实验方案，实验原料为如下式(I)所示的第一双酐和如下式(II)所示的第一二胺，其中R 1和R 2均选自甲基。
第二种实验方案，实验原料为如下式(I)所示的第一双酐和如下式(III)所示的第一二胺，其中R 1和R 2均选自甲基。
第三种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(II)所示的第一二胺和如下式(IV)所示的第二双酐，其中R 1和R 2均选自甲基，R 3和R 4均选自氢。
第四种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(III)所示的第一二胺和如下式(IV)所示的第二双酐，其中R 1和R 2均选自甲基，R 3和R 4均选自氢。
第五种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(II)所示的第一二胺和如下式(V)所示的第二二胺，其中R 1和R 2均选自甲基。
第六种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(III)所示的第一二胺和如下式(V)所示的第二二胺，其中R 1和R 2均选自甲基。
第七种试验方案，实验原料为如下式(IV)所示的第二双酐、如下式(II)所示的第一二胺和如下式(V)所示的第二二胺，其中R 3和R 4均选自氢。
第八种试验方案，实验原料为如下式(IV)所示的第二双酐、如下式(III)所示的第一二胺和如下式(V)所示的第二二胺，其中R 3和R 4均选自氢。
第九种试验方案，实验原料为如下式(I)所示的第一双酐、如下式(IV)所示的第二双酐和如下式(V)所示的第二二胺，其中R 1和R 2均选自甲基，R 3选自氢，R 4均选自羟基。
Figure PCTCN2021111782-appb-000034
以上实验例3中第一种试验方案到第九种试验方案测得的水接触角和碎屑去除率(分别一一对应的记为c1～c9)，实验例2中第一种试验方案到第九种试验方案所测得的水接触角和碎屑去除率(分别一一对应的记为b1～b9)，与实验例1所测得的水接触角和碎屑去除率如下表2和图5所示。
表2
Figure PCTCN2021111782-appb-000035
由表2和图5可知，本公开提供的技术方案中，通过在实验例2中的第一种试验方案到第九种试验方案中引入亲水基团和疏水基团，能够对聚酰亚酸的亲疏水性进行调节，从而能够对最终所获得的液晶取向膜的亲疏水性能进行调节，最终通过清洗可以减少产生的碎屑。
实验例4
实验例4采用如下实验方案，以下实验方案与实验例1的制备方法相同，不同的是，以下实验方案采用如下式(I)所示的第一双酐、如下式(II)所示的第一二胺，如下式(IV)所示的第二双酐和如下式(V)所示的第二二胺，其中R 1和R 2均选自甲基，R 3和R 4均选自氢。
Figure PCTCN2021111782-appb-000036
Figure PCTCN2021111782-appb-000037
实验方案1包括多组实验组，多组实验组中，第一二胺和第二二胺的摩尔百分比为35％：15％，且固定不变，不同实验组中，加入第一双酐和第二双酐的比例不同，具体实验组的数据如下表3所示。其中，实验组1～实验组6所获得的硬度和韧性数据参见表3。
表3
Figure PCTCN2021111782-appb-000038
由表3可知，在第一二胺和第二二胺的摩尔百分比固定的情况下，随着加入第一双酐和第二双酐的摩尔百分比逐渐增大，硬度降低，韧性增大，反之，则韧性降低，硬度增大。
实验方案2包括多组实验组，多组实验组中，第一双酐和第二双酐的摩尔百分比为10％：40％，且固定不变，不同实验组中，加入第一二胺和第二二胺的摩尔百分比不同，具体实验组的数据如下表4所示。其中，实验组1～实验组6所获得的水接触角和碎屑去除率如表4所示。
表4
Figure PCTCN2021111782-appb-000039
由表4可知，通过对第一二胺和第二二胺进行组配，可实现样品亲疏水性的变化，具体的，随着第一二胺与第二二胺的摩尔百分比增大，亲水性增大，通过测量其水接触角由54°变化到50°，在相同条件下，进行清洗，清洗前后的碎屑去除率由85％变化到92％而后再变化到90％。随着第一二胺与第二二胺的比例增大，水接触角逐渐减小，而碎屑去除率先增大后减小，这是因为亲水性过强时，虽然已经产生的碎屑容易清洗，但是也容易吸附环境中的异物，从而使得碎屑数增大。
实验例5
实验例5采用如下实验方案，以下实验方案与实验例1的制备方法相同，不同的是，以下实验方案采用如下式(IV)所示的第二双酐和如下式(V)所 示的第二二胺，其中R 3选自氢，R 4均选自羟基，最终所获得用于测量水接触角和清洗性表征的样品记为样品f，则样品a和样品f的水接触角和碎屑去除率如下表5所示。
Figure PCTCN2021111782-appb-000040
表5
样品编号 样品a 样品f
水接触角(°) 57 53
碎屑去除率(％) 66％ 83％
由表5可知，本公开提供的聚酰亚酸通过在相关技术中引入亲水基团和疏水基团，并对疏水基团和亲水基团进行合理配比，即可使聚酰亚酸具有较小的水接触角，从而能够提高碎屑的去除率，最终通过清洗可以减少产生的碎屑，避免产生碎屑不良。
以上所述，仅为本公开的具体实施方式，但本公开的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本公开揭露的技术范围内，想到变化或替换，都应涵盖在本公开的保护范围之内。因此，本公开的保护范围应以所述权利要求的保护范围为准。

Claims (28)

  1. 一种液晶取向剂，包括：
    至少一种聚合物，所述至少一种聚合物选自聚酰亚酸和由所述聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种；
    所述聚酰亚酸包括如下式(I)所示的第一双酐和如下式(II)或下式(III)所示的第一二胺反应生成的第一链段结构；
    Figure PCTCN2021111782-appb-100001
    其中，所述第一双酐中X 1为第一软链段，所述第一软链段为无定形链段；L选自单键、双键和碳原子数为1～3的二价或三价烃基中的任一个；
    所述第一二胺中如式(II)所示，Y 1选自单键、O、NH、S、一个或多个不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，其中一个A 1和一个A 2分别选自C，并均与Y 1结合，其余A1和A2分别独立地选自CH、CR和N中的任一个，且A1和A2中N的个数均不超过两个；
    所述第一二胺中如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，且A 3和A 4分别独立地选自CH、CR和N中的任一个，且A 3和A 4中N的个数均不超过两个；
    R 1、R 2和R分别独立地选自氢和脂肪族烃基中的任一个。
  2. 根据权利要求1所述的液晶取向剂，其中
    若所述第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若所述第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则所述第一软链段选自亲水链段和含有至少 一个亲水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1中的至少一个取代基团选自亲水基团，第一软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个；或者，Y 1中的至少一个取代基团和第一软链段中其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
    若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Z 1中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Z 1中的至少一个取代基团选自亲水基团，第一软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个；或者，Y 1中的至少一个取代基团和第一软链段中其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
  3. 根据权利要求1或2所述的液晶取向剂，其中
    所述第一软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    所述第一二胺选自如式(II)所示的结构，且Y 1选自至少一个碳原子被取代的芳环、杂环和稠环中的任一个，至少一个取代基团选自亲水基团和具有至少一个亲水基团的碳原子数为1～3的烃基中的任一个。
  4. 根据权利要求3所述的液晶取向剂，其中
    所述第一二胺中Y 1结合在氨基的对位，且选自一个碳原子被取代的苯环，取代基团为碳原子数为1～3的醇羟基。
  5. 根据权利要求1-4任一项所述的液晶取向剂，其中
    所述第一软链段为取代的或未取代的碳原子数为10～20的亚烷基链段。
  6. 根据权利要求1-5任一项所述的液晶取向剂，其中
    所述第一双酐为非对称结构，或者，所述第一软链段中含有非对称支链。
  7. 根据权利要求1-6任一项所述的液晶取向剂，其中
    所述聚酰亚酸还包括如下式(IV)所述的第二双酐和所述第一二胺反应生成的第二链段结构；
    Figure PCTCN2021111782-appb-100002
    其中，所述第二双酐中X 2选自脂肪环、芳环、杂环和稠环结构中的任一个。
  8. 根据权利要求7所述的液晶取向剂，其中
    所述X 2选自如下结构式，其中，R 3和R 4分别独立地选自氢和脂肪族烃基中的任一个；
    Figure PCTCN2021111782-appb-100003
  9. 根据权利要求7或8所述的液晶取向剂，其中
    所述第一双酐和第二双酐的摩尔比为10:90～90:10。
  10. 根据权利要求1-6任一项所述的液晶取向剂，其中
    所述聚酰亚酸还包括如下式(V)所述的第二二胺和所述第一双酐反应生成的第三链段结构；
    Figure PCTCN2021111782-appb-100004
    其中，所述第二二胺中Y 2为第二软链段；
    其中一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个，R选自氢和脂肪族烃基中的任一个。
  11. 根据权利要求10所述的液晶取向剂，其中
    若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段中的至少其中之一选自亲 水链段和包含至少一个亲水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，Y 1中的至少一个取代基团、第一软链段和第二软链段中其中1至2个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余2至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Z 1中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Z 1中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，Z 1中的至少一个取代基团、第一软链段和第二软链段中其中1至2个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余2至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
  12. 根据权利要求10或11所述的液晶取向剂，其中
    所述第二软链段为取代的或未取代的碳原子数为5～12的亚烷基链段。
  13. 根据权利要求10-12任一项所述的液晶取向剂，其中
    所述第一二胺和所述第二二胺的摩尔比为10:90～90:10。
  14. 一种液晶取向剂，包括：
    至少一种聚合物，所述至少一种聚合物选自聚酰亚酸和由所述聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种；
    所述聚酰亚酸包括如下式(I)所示的第一双酐和如下式(II)或下式(III)所示的第一二胺生成的第一链段结构，如下式(IV)所述的第二双酐和所述第一二胺生成的第二链段结构，如下式(V)所述的第二二胺和所述第一双酐生成的第三链段结构，和如下式(V)所述的第二二胺和所述第二双酐生成的第四链段结构；或者
    所述聚酰亚酸包括如下式(I)所示的第一双酐和如下式(V)所示的第二二胺生成的第三链段结构，如下式(IV)所示的第二双酐和如下式(V)所示的第二二胺反应生成的第四链段结构，和如下式(IV)所示的第二双酐和如下式(II)或下式(III)所示的第一二胺生成的第二链段结构中的至少两个链段结构；
    Figure PCTCN2021111782-appb-100005
    其中，所述第一双酐中X 1为第一软链段，所述第二二胺中Y 2为第二软链段，且所述第一软链段和第二软链段中的至少其中之一为无定形链段；所述第一双酐中L选自单键、双键和碳原子数为1～3的二价或三价烃基中的任一个；
    所述第二双酐X 2选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个；
    所述第一二胺中如式(II)所示，Y 1选自单键、O、NH、S、一个或多个 不饱和双键和取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，其中一个A 1和一个A 2分别选自C，并均与Y 1结合，其余A 1和A 2分别独立地选自CH、CR和N中的任一个，且A 1和A 2中N的个数均不超过两个；
    所述第一二胺中如式(III)所示，Z 1选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个，且A 3和A 4分别独立地选自CH、CR和N中的任一个，且A 3和A 4中N的个数均不超过两个；
    所述第二二胺中，一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个；
    R 1、R 2和R分别独立地选自氢和脂肪族烃基中的任一个。
  15. 根据权利要求14所述的液晶取向剂，其中
    在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(V)所示的第二二胺生成的第三链段结构，和如式(IV)所示的第二双酐和如式(V)所示的第二二胺反应生成的第四链段结构的情况下；
    若第二双酐中X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段分别独立地选自亲水链段、疏水链段、包含至少一个亲水基团的链段和包含至少一个疏水基团的链段中的任一个；
    若第二双酐X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团选自疏水基团和亲水基团中的任一个，第一软链段和第二软链段分别独立地选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团选自疏水基团，第一软链段和第二软链段中的其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，另一个选自疏水链段和包含至少一个疏水基团的链段中的任一个；或者，X 2中的至少一个取代基团、第一软链段和第二软链段中的一个或两个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余两个或一个选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    在所述聚酰亚酸包括如式(IV)所示的第二双酐和如式(V)所示的第二二胺反应生成的第四链段结构，和如式(IV)所示的第二双酐和如式(II)或式(III)所示的第一二胺生成的第二链段结构的情况下；
    若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任 一个，则第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团选自亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团选自疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段、包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，X 2中的至少一个取代基团选自亲水基团和疏水基团中的任一个，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，X 2中的至少一个取代基团选自亲水基团，第二软链段选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和X 2中的至少一个取代基团均选 自疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团、X 2中的至少一个取代基团和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(V)所示的第二二胺生成的第三链段结构，和如式(IV)所示的第二双酐和如式(II)或式(III)所示的第一二胺生成的第二链段结构的情况下，或者，在所述聚酰亚酸包括如式(I)所示的第一双酐和如式(II)或下式(III)所示的第一二胺反应生成的第一链段结构，如式(IV)所述的第二双酐和所述第一二胺反应生成的第二链段结构，如式(V)所述的第二二胺和所述第一双酐反应生成的第三链段结构，和如式(V)所述的第二二胺和所述第二双酐反应生成的第四链段结构的情况下；
    若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自单键、O、NH、S、一个或多个不饱和双键和未取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自未取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，X 2中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，X 2中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1 选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；或者，Y 1或Z 1中的至少一个取代基团、第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段和包含至少一个疏水基团的链段中的任一个；
    若第一二胺选自如式(II)所示结构，且Y 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，或者，若第一二胺选自如式(III)所示结构，且Z 1选自取代的脂肪环、芳环、杂环和稠环中的任一个，且X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则Y 1或Z 1中的至少一个取代基团为亲水基团，X 2中的至少一个取代基团选自亲水基团和疏水基团中的任一个，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团为疏水基团，X 2中的至少一个取代基团选自亲水基团，第一软链段和第二软链段分别独立地选自疏水链段、包含至少一个疏水基团的链段、亲水链段和包含至少一个亲水基团的链段中的任一个，或者，Y 1或Z 1中的至少一个取代基团和X 2中的至少一个取代基团均选自疏水基团，第一软链段和第二软链段中的至少其中之一选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余选自疏水链段、包含至少一个疏水基团的链段中的人一个；或者，Y 1或Z 1中的至少一个取代基团、X 2中的至少一个取代基团、第一软链段和第二软链段中的其中1至3个选自亲水链段和包含至少一个亲水基团的链段中的任一个，其余3至1个选自疏水链段和包含至少一个疏水基团的链段中的任一个。
  16. 根据权利要求14或15所述的液晶取向剂，其中
    该第一软链段为取代的或未取代的碳原子数为10～20的亚烷基链段；该第一二胺选自如式(II)所示的结构，且Y 1选自至少一个碳原子被取代的芳环、杂环和稠环中的任一个，至少一个取代基团选自亲水基团和具有至少一个亲水基团的碳原子数为1～3的烃基中的任一个；该第二软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个。
  17. 根据权利要求14-16任一项所述的液晶取向剂，其中
    该第二软链段为取代的或未取代的碳原子数为5～12的亚烷基链段。
  18. 根据权利要求14-17任一项所述的液晶取向剂，其中
    该第一二胺中Y1结合在氨基的对位，且选自一个碳原子被取代的苯环，取代基团为碳原子数为1～3的醇羟基。
  19. 一种液晶取向剂，包括：
    至少一种聚合物，所述至少一种聚合物选自聚酰亚酸和由所述聚酰亚酸闭环后获得的一组聚酰亚胺中的至少一种；
    所述聚酰亚酸包括如下式(IV)所示的第二双酐和下式(V)所示的第二二胺生成的第五链段结构；
    Figure PCTCN2021111782-appb-100006
    其中，该第二双酐X 2选自取代或未取代的脂肪环、芳环、杂环和稠环中的任一个。该第二二胺中Y 2为第二软链段，且该第二软链段为无定形链段。该第二二胺中，一个A 5和一个A 6分别选自C，并均与Y 2结合，其余A 5和A 6分别独立地选自CH、CR和N中的任一个，且A 5和A 6中N的个数均不超过两个，R选自氢和脂肪族烃基中的任一个；
    若第二双酐X 2选自未取代的脂肪环、芳环、杂环和稠环中的任一个，则第二软链段选自亲水链段和包括至少一个亲水基团的链段中的任一个；
    若第二双酐X 2选自取代的脂肪环、芳环、杂环和稠环中的任一个，则X 2中的至少一个取代基团为亲水基团，第二软链段选自疏水链段和包含至少一个疏水基团的链段中的任一个，或者，X 2中的至少一个取代基团为疏水基团，第二软链段选自亲水链段和包含至少一个亲水基团的链段中的任一个；或者，X 2中的至少一个取代基团和第二软链段中的其中之一选自疏水链段和包含至少一个疏水基团的链段中的任一个，另一个选自亲水链段和包含至少一个亲水基团的链段中的任一个。
  20. 一种液晶取向膜，采用如权利要求1-19任一项所述的液晶取向剂形成。
  21. 根据权利要求20所述的液晶取向膜，其中，所述液晶取向膜的硬度用预设压力下扎针扎入所述液晶取向膜的深度来表征，所述液晶取向膜的硬度满足：在所述预设压力为150μN的压力下，取值小于等于45μm。
  22. 根据权利要求20或21所述的液晶取向膜，其中，所述液晶取向膜的韧度用扎针在所述液晶取向膜的厚度方向的深度突变所对应的压力来表征，所述液晶取向膜的韧度的取值大于390μN。
  23. 根据权利要求20～22任一项所述的液晶取向膜，其中，在所述液晶取向剂所包含有亲水链段和/或亲水基团的情况下，所述液晶取向膜的水接触角小于等于58°。
  24. 根据权利要求20～23任一项所述的液晶取向膜，其中，在所述液晶取向剂所包含的第一二胺和第二二胺的摩尔百分比为35％：15％的情况下，随着所述液晶取向剂所包含的第一双酐和第二双酐的比例逐渐增大，所述液晶取向膜的硬度降低，韧性增大。
  25. 根据权利要求20～23任一项所述的液晶取向膜，其中，在所述液晶取向剂所包含的第一双酐和第二双酐的摩尔百分比为10％：40％，且第二二胺中的Y 2为疏水链段的情况下，随着所述液晶取向剂所包含的第一二胺和第二二胺的比例逐渐增大，所述液晶取向膜的水接触角逐渐降低。
  26. 一种显示基板，包括：
    衬底基板；和
    液晶取向膜，设置于所述衬底基板上，该液晶取向膜包括如权利要求1-19任一项所述的液晶取向剂烧成后的聚酰亚胺。
  27. 一种液晶显示装置，包括：
    相对设置的第一基板和第二基板；
    液晶层，设置于第一基板和第二基板之间；
    其中，所述第一基板和/或第二基板为如权利要求26所述的显示基板。
  28. 一种聚酰亚胺，由如权利要求1-19任一项所述的液晶取向剂烧成得到。
PCT/CN2021/111782 2020-09-16 2021-08-10 液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺 WO2022057522A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US17/803,000 US20230103608A1 (en) 2020-09-16 2021-08-10 Liquid crystal aligning agent, liquid crystal alignment film, and display substrate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010975445.7 2020-09-16
CN202010975445.7A CN114262617B (zh) 2020-09-16 2020-09-16 液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺

Publications (1)

Publication Number Publication Date
WO2022057522A1 true WO2022057522A1 (zh) 2022-03-24

Family

ID=80777499

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/111782 WO2022057522A1 (zh) 2020-09-16 2021-08-10 液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺

Country Status (3)

Country Link
US (1) US20230103608A1 (zh)
CN (1) CN114262617B (zh)
WO (1) WO2022057522A1 (zh)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313180A (ja) * 2002-02-21 2003-11-06 Chisso Corp 酸無水物、液晶配向膜および液晶表示素子
CN101024773A (zh) * 2006-02-22 2007-08-29 Jsr株式会社 液晶取向剂和液晶显示元件
TW201934727A (zh) * 2017-11-29 2019-09-01 日商日產化學股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
JP2019174800A (ja) * 2018-03-27 2019-10-10 Jnc株式会社 液晶配向膜を形成するための液晶配向剤、液晶配向膜およびこれを用いた液晶表示素子
CN110499164A (zh) * 2018-05-18 2019-11-26 奇美实业股份有限公司 液晶配向剂、液晶配向膜及液晶显示元件

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313180A (ja) * 2002-02-21 2003-11-06 Chisso Corp 酸無水物、液晶配向膜および液晶表示素子
CN101024773A (zh) * 2006-02-22 2007-08-29 Jsr株式会社 液晶取向剂和液晶显示元件
TW201934727A (zh) * 2017-11-29 2019-09-01 日商日產化學股份有限公司 液晶配向劑、液晶配向膜及液晶顯示元件
JP2019174800A (ja) * 2018-03-27 2019-10-10 Jnc株式会社 液晶配向膜を形成するための液晶配向剤、液晶配向膜およびこれを用いた液晶表示素子
CN110499164A (zh) * 2018-05-18 2019-11-26 奇美实业股份有限公司 液晶配向剂、液晶配向膜及液晶显示元件

Also Published As

Publication number Publication date
US20230103608A1 (en) 2023-04-06
CN114262617B (zh) 2024-04-02
CN114262617A (zh) 2022-04-01

Similar Documents

Publication Publication Date Title
JP4788896B2 (ja) 垂直配向型液晶配向剤および垂直配向型液晶表示素子
CN101627333B (zh) 液晶取向剂和横电场式液晶显示元件
KR102425044B1 (ko) 액정 배향제, 액정 배향막 및 액정 표시 소자
JP4013052B2 (ja) 液晶配向処理剤および液晶表示素子
TWI477538B (zh) 液晶配向劑及液晶顯示元件
TWI386435B (zh) 垂直配向型液晶配向劑及垂直配向型液晶顯示元件
TW201005005A (en) Liquid crystal alignment agent and liquid crystal display element
WO2008119449A1 (en) Method of uniform and defect free liquid crystal aligning layers
US11453826B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element
TWI761521B (zh) 顯示出溶致液晶性的組成物、聚醯亞胺聚合物、液晶配向劑、液晶配向膜及其製造方法、相位差板、偏光板及液晶元件
KR100618003B1 (ko) 액정 배향제 및 액정 표시 소자
TW200846451A (en) Liquid crystal alignment agent and liquid crystal display element
TWI501011B (zh) 液晶配向劑及液晶顯示元件
KR101453089B1 (ko) 액정 배향제 및 액정 표시 소자
KR20140123424A (ko) 액정 배향제, 액정 배향막 및 액정 표시 소자와 그의 제조 방법
KR20160010567A (ko) 액정 배향제, 액정 배향막 및 그것을 사용한 액정 표시 소자
TW201005006A (en) Liquid crystal alignment agent and liquid crystal display element
WO2022057522A1 (zh) 液晶取向剂、液晶取向膜、显示基板、液晶显示装置及聚酰亚胺
TWI770018B (zh) 液晶配向劑、液晶配向膜、及使用其之液晶顯示元件
KR102341987B1 (ko) 액정 배향제, 액정 배향막, 그리고 액정 소자 및 그의 제조 방법
TWI428370B (zh) 液晶配向劑及液晶顯示元件
KR100927704B1 (ko) 액정 배향제, 이를 포함하는 액정 배향막, 및 이를포함하는 액정 표시 장치
TWI462951B (zh) 液晶配向劑及橫向電場方式液晶顯示元件
TWI816022B (zh) 液晶配向劑、液晶配向膜及使用其之液晶顯示元件
TWI422928B (zh) 橫電場式液晶顯示元件用液晶配向劑及橫電場式液晶顯示元件

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21868350

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 28/06/2023)

122 Ep: pct application non-entry in european phase

Ref document number: 21868350

Country of ref document: EP

Kind code of ref document: A1