CN107022358A - Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines - Google Patents

Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines Download PDF

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CN107022358A
CN107022358A CN201611221886.8A CN201611221886A CN107022358A CN 107022358 A CN107022358 A CN 107022358A CN 201611221886 A CN201611221886 A CN 201611221886A CN 107022358 A CN107022358 A CN 107022358A
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liquid crystal
formula
bond
base
compound
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CN107022358B (en
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秋池利之
中岛彰男
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JSR Corp
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    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/10—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/06—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C275/14—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton being further substituted by nitrogen atoms not being part of nitro or nitroso groups
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C275/42—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton being further substituted by carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
    • C07D211/18—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D211/26—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

The present invention provides a kind of aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines, can obtain AC image retentions characteristic and the good liquid crystal cell of voltage retention.Contain in aligning agent for liquid crystal：Polymer selected from the part-structure represented by least one of group that polyamic acid, poly amic acid ester and polyimides are constituted and with following formula (0).(R1For with cyclic group and " NR3" at least one of base and alkane diyl bilvalent radical or " X20‑R20‑*1”(X20For singly-bound, ehter bond etc., R20For alkane diyl), R2For divalent organic base, R6For cyclic group.In R1For " X20‑R20‑*1" in the case of, R2For the divalent organic base with urea bond, divalence chain alkyl or divalence alicyclic type hydrocarbon).

Description

Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines
Technical field
The present invention relates to a kind of aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal cell, polymer and diamines.
Background technology
Liquid crystal cell is included to the liquid crystal orientation film for the orientation for controlling the liquid crystal molecule in liquid crystal cells.With regard to heat resistance, For the good aspect of various characteristics such as mechanical strength and the compatibility of liquid crystal, the material of liquid crystal orientation film is usually using polyamides Amino acid or polyimides.
In recent years, for the further raising of the display performance of seeking liquid crystal panel, and various aligning agent for liquid crystal (examples are proposed Such as, with reference to patent document 1, patent document 2).Propose to use 4,4 '-two by making to contain in aligning agent for liquid crystal in patent document 1 Amino-diphenyl-amine and the polyamic acid or polyimides obtained, and realize the improvement of voltage retention performance or burn attached reduce.Separately Outside, Patent Document 2 discloses by making to contain the polyimides obtained using the diamines with urea bond in aligning agent for liquid crystal Precursor or polyimides, can be obtained with good liquid crystal aligning and rub resistance, ion concentration is small and fringing field switches The few liquid crystal orientation film of accumulated charge in (Fringe Field Switching, FFS) mode liquid crystal display element.
[prior art literature]
[patent document]
No. 4052307 publications of [patent document 1] Japanese Patent No.
[patent document 2] International Publication No. 2013/008906
The content of the invention
[invention problem to be solved]
As the rubbing manipulation that one of anisotropic method is found in liquid crystal orientation film, because of taking for easy and liquid crystal molecule Tropism is good and is typically used.However, the good existing aligning agent for liquid crystal of rub resistance in most cases can be because with friendship Flow the charge accumulation of the application of voltage and easily produce image retention or voltage retention decline, i.e., AC image retentions characteristic and voltage are kept Rate is in compromise.
The present invention be in view of the problem and complete, one of purpose be provide one kind can obtain AC image retentions characteristic and The aligning agent for liquid crystal of the good liquid crystal cell of voltage retention.
[technological means for solving problem]
The present inventor etc. have carried out positive research to reach the problem, as a result find, by making aligning agent for liquid crystal In contain with specific structure polymer, the problem is can solve the problem that, so as to complete the present invention.Specifically there is provided following Means.
<1>A kind of aligning agent for liquid crystal, it contains selected from the group being made up of polyamic acid, poly amic acid ester and polyimides At least one of group and the polymer [P] with the part-structure represented by following formula (0)；
[changing 1]
(in formula (0), R1For with cyclic group and "-NR3- " (wherein, R3For hydrogen atom or any monovalent organic radical) at least A kind of base and the bilvalent radical or "-X of alkane diyl20-R20-*1" (wherein, X20For singly-bound, ehter bond, thioether bond, ester bond or-CONRb- (RbFor hydrogen atom or any monovalent organic radical), R20For alkane diyl；“*1" represent to be bonded to the associative key of nitrogen-atoms in urea bond), R2For Divalent organic base, R6For cyclic group；Wherein, in R1For "-X20-R20*1" in the case of, R2For the divalent organic base with urea bond, Divalence chain alkyl or divalence alicyclic type hydrocarbon；" * " represents associative key).
<2>A kind of liquid crystal orientation film, it is using described<1>Aligning agent for liquid crystal and formed.
<3>A kind of liquid crystal cell, it includes described<2>Liquid crystal orientation film.
<4>A kind of polymer, it is in the group being made up of polyamic acid, poly amic acid ester and polyimides It is at least one and with the construction unit for the compound being derived from represented by following formula (1)；
[changing 2]
(in formula (1), R1For with cyclic group and "-NR3- " (wherein, R3For hydrogen atom or any monovalent organic radical) at least A kind of base and the bilvalent radical or "-X of alkane diyl20-R20-*1" (wherein, X20For singly-bound, ehter bond, thioether bond or ester bond, R20For alkane Diyl；“*1" represent to be bonded to the associative key of nitrogen-atoms in urea bond), R2For divalent organic base；Wherein, in R1For "-X20- R20-*1" in the case of, R2For the divalent organic base with urea bond, divalence chain alkyl or divalence alicyclic type hydrocarbon).
<5>A kind of diamines, it is represented by the formula (1).
[The effect of invention]
According to the disclosure, voltage retention and the good liquid crystal cell of image retention characteristic can be obtained.Even if the effect with It can also be obtained in the case of the heating carried out when lower temperature implements to be formed liquid crystal orientation film, low temperature calcination can be carried out, just For in this respect preferably.
Embodiment
Hereinafter, contained by aligning agent for liquid crystal of this disclosure each composition and the other compositions optionally and arbitrarily allocated Illustrate.
<Aligning agent for liquid crystal>
The aligning agent for liquid crystal of the disclosure contains selected from the group being made up of polyamic acid, poly amic acid ester and polyimides At least one of and with the polymer [P] of the part-structure represented by the formula (0).
In the formula (0), R1In alkane diyl be preferably carbon number 1~6, can for example enumerate：Methylene, ethylidene, the third two Base, fourth diyl, penta diyl, dihexyl etc..These alkane diyls can be alternatively branch-like, preferably straight-chain for straight-chain.
Cyclic group is that base obtained by 2 hydrogen atoms is removed from the ring for being substituted or being unsubstituted.As the ring, for example Aromatic ring, aliphatic ring, heterocycle etc. can be enumerated, specifically, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, cyclohexane ring, pyridine ring, Piperidine ring, piperazine ring, pyrimidine ring etc..In addition, the substituent that can have as these rings, such as can enumerate：The alkane of carbon number 1~5 Base, the alkoxy of carbon number 1~5, halogen atom etc..The electrical characteristics of liquid crystal cell that are just obtained and the rub resistance of film change For the high aspect of kind effect, R1Cyclic group be preferably the phenylene or piperidyl for being substituted or being unsubstituted.
“-NR3- " (wherein, R3For hydrogen atom or any monovalent organic radical) in R3Any monovalent organic radical be preferably carbon number 1~5 Monovalent hydrocarbon or protection group.As protection group, it is protection group, the protection of acid amides system that can for example enumerate mephenesin Carbamate (carbamate) Base, imide series protection group, sulphonyl amine system protection group etc., wherein preferably tert-butoxycarbonyl.Furthermore, "-NR3- " also can structure Into a part for amido link, urea bond or amino-formate bond.
R in the formula (0)1Base represented by base, following formula (3) or following formula preferably represented by following formula (2) (4) base represented by.
[changing 3]
(in formula (2), A1For the divalent organic base with cyclic group, singly-bound, methylene, ethylidene, ehter bond, thioether bond or Ester bond, a is 1~6 integer.Wherein, in A1In the case of singly-bound, methylene, ethylidene, ehter bond, thioether bond or ester bond, institute State R2For divalence chain alkyl or alicyclic type hydrocarbon.In formula (3), B1For singly-bound or bivalence linking base, A2For singly-bound or cyclic group, R3For hydrogen atom or any monovalent organic radical, b is 1~6 integer.In formula (4), A3For the divalent organic base with cyclic group, c is 1~ 6 integer." * " represents the associative key with the nitrogen-atoms in urea bond).
In the formula (2), A is used as1Preference, can for example enumerate the base represented by following formula (2-1).Furthermore, on A in following formula (2-1)11Cyclic group, the R can be applied1The explanation for the cyclic group being had.
[changing 4]
(in formula (2-1), A11For cyclic group, X1For singly-bound, methylene, ethylidene, ehter bond, thioether bond, ester bond or- CONRb-(RbIt is same as below for hydrogen atom, the monovalent hydrocarbon of carbon number 1~6 or protection group), Y1 is singly-bound, ehter bond, ester bond, thioether Key ,-CONRb- or-NRb-.P is 0 or 1, and " * " represents the associative key with alkane diyl).
In the formula (3), B1Bivalence linking base be preferably carbon number 1~6 alkane diyl, more preferably carbon number 1~3 alkane Diyl.A on the formula (3)2Cyclic group and the formula (4) A3The cyclic group being had, can apply the R1Had Cyclic group explanation.Furthermore, with A3The divalent organic base of cyclic group can only have cyclic group, can also have two More than.
It is used as R2Organic group, can for example enumerate：The alkyl of carbon number 1~40, include between the carbon-carbon bond of the alkyl Base containing heteroatomic base, the alkyl are with containing base that heteroatomic base is bonded etc..In addition, at least one hydrogen of these bases Atom such as can through halogen atom, nitro, cyano group, hydroxyl substituent replace.Wherein, in R1For "-X20-R20- * " situation Under, R2For the divalent organic base with urea bond, divalence chain alkyl or divalence alicyclic type hydrocarbon.
It is used as R6Cyclic group, the R can be enumerated1Cyclic group explanation in the base that illustrates.Preferably R6For phenylene or Pyridine radicals, more preferably phenylene.
Herein, in this specification, so-called " chain alkyl " refers to without cyclic structure, the straight chain being only made up of chain structure The alkyl of shape or branch-like.So-called " alicyclic type hydrocarbon " refers to only comprising alkyl of the ester ring type hydrocarbon structure as ring structure.Wherein, Only it need not be made up of ester ring type hydrocarbon structure, one part can also have chain structure.So-called " aromatic hydrocarbyl " refers to comprising virtue Fragrant ring structure as ring structure alkyl.Wherein, without being only made up of aromatic ring structure, one part can also include chain structure Or ester ring type hydrocarbon structure.So-called " organic group " refers to the base for including alkyl, and hetero atom can be also included in the structure.It is so-called " to contain miscellaneous The base of atom " refers to base more than heteroatomic divalence, for example, to enumerate：-O-、-CO-、-COO-、-CONRb-、- NRb-、-NRbCONRb-、-OCONRb-、-S-、-COS-、-OCOO-、-SO2- etc..
Polymer [P] is as long as with the part-structure represented by the formula (0), particularly preferably with from described The construction unit of diamines (hereinafter referred to as " specific diamines ") represented by formula (1).R in the formula (1)1For the formula (2) in the case of the base represented by, as the preferred concrete example of specific diamines, the compound represented by following formula (11) can be enumerated And the compound represented by following formula (12) etc..
[changing 5]
(in formula (12), R4For the divalence chain alkyl or alicyclic type hydrocarbon of carbon number 1~10, p is 0 or 1.Formula (11) and formula (12) in, a is 1~6 integer.A11、X1And Y1It is respectively identical meanings with the formula (2-1).Multiple A in formula (11)11, it is many Individual X1, multiple Y1And multiple a may be the same or different respectively).
On the formula (11), A11Cyclic group be preferably Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-Asia pyridine radicals, Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-piperidyl or Isosorbide-5-Nitrae-piperazinyl, these cyclic groups can replace through methyl or fluorine atom.Particularly preferably Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-piperidyl.A is preferably 2~4.
As the preferred concrete example of the compound represented by the formula (11), for example, it can enumerate following formula (1-1)~formula (1- 5) represented compound of difference etc..
[changing 6]
(in formula (1-1)~formula (1-5), R8For hydrogen atom, the alkyl or tert-butoxycarbonyl of carbon number 1~3.R9For hydrogen atom Or methyl.A is 1~6 integer.Multiple a, multiple R in formula8, multiple R9It may be the same or different respectively).
On the formula (12), X1Preferably ethylidene, ester bond or-CONRb-。Y1Preferably singly-bound or ehter bond.A11Ring Shape base is preferably Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-Asia pyridine radicals, Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-piperidyl or Isosorbide-5-Nitrae-piperazinyl, these rings Shape base can replace through methyl or fluorine atom.R4Base preferably represented by the alkane diyl of carbon number 2~6 or following formula (6).
[changing 7]
(in formula (6), d is 1~3 integer." * " represents to be bonded to the associative key of one-level amino).
As the preferred concrete example of the compound represented by the formula (12), for example, it can enumerate following formula (2-1)~formula (2- 7) represented compound of difference etc..In these compounds, compound and following formula preferably represented by following formula (2-1) Compound represented by (2-3).
[changing 8]
(in formula (2-1)~formula (2-7), R10For hydrogen atom, the alkyl or tert-butoxycarbonyl of carbon number 1~3.A is 1~6 Integer, e is 1~10 integer).
R in the formula (1)1In the case of for the base represented by the formula (3), the preferred specific of specific diamines is used as Example, can enumerate compound represented by the compound and following formula (14) represented by following formula (13) etc..
[changing 9]
(in formula (13) and formula (14), R5For divalent organic base, the integer of g and k separately for carbon number 1~6.R3, b with The formula (3) is identical meanings.Multiple R in formula3, multiple b may be the same or different respectively).
In the formula (13), R3Preferably hydrogen atom, methyl or tert-butoxycarbonyl.B is preferably 1~4.
It is used as R5Divalent organic base, can for example enumerate：The alkyl of carbon number 1~40, between the carbon-carbon bond of the alkyl Comprising the base containing heteroatomic base, the alkyl with containing base that heteroatomic base is bonded etc..In addition, at least the one of these bases Individual hydrogen atom such as can through halogen atom, nitro, cyano group, hydroxyl substituent replace.It is used as R5Preference, can enumerate following Base represented by formula (7) etc..
[changing 10]
(in formula (7), A13For cyclic group, X3For singly-bound, methylene, ethylidene, ehter bond, thioether bond, ester bond or-CONRb-, Y3For singly-bound, ehter bond, ester bond, thioether bond ,-CONRb- or-NRb-." * " represents to be bonded to the associative key of one-level amino.H, r, q and S is separately 0~6 integer).
As the preferred concrete example of the compound represented by the formula (13), for example, it can enumerate following formula (3-1) and formula (3- 2) represented compound of difference etc..H in following formula (3-1) and formula (3-2) is preferably 1 or 2.
[changing 11]
(in formula (3-1) and formula (3-2), b is 1~6 integer, and h is 0~6 integer).
In the formula (14), R3Preferably hydrogen atom, methyl or tert-butoxycarbonyl.B, g and k are respectively preferably 1~3. As the preferred concrete example of the compound represented by the formula (14), for example, it can enumerate following formula (4-1) and formula (4-2) institute respectively Compound of expression etc..
[changing 12]
(in formula (4-1) and formula (4-2), b, g and k are separately the integer of carbon number 1~6).
R in the formula (1)1In the case of for the base represented by the formula (5), the preferred specific of specific diamines is used as Example, can enumerate compound represented by following formula (15) etc..
[changing 13]
(in formula (15), R11For divalent organic base, c is 1~6 integer.Multiple c in formula can it is mutually the same not yet Together).
R in the formula (15)11Preferably the divalence chain alkyl of carbon number 1~10, the carbon-carbon bond in the chain alkyl Between include containing heteroatomic base base or the alkyl with containing heteroatomic base be bonded base.C is preferably 1~3. As the preferred concrete example of the compound represented by the formula (15), for example, it can enumerate following formula (5-1) and formula (5-2) institute respectively Compound of expression etc..
[changing 14]
(in formula (5-1) and formula (5-2), c is 1~6 integer, and x and y are separately 2~6 integer.It is many in formula Individual c may be the same or different).
Specific diamines can be synthesized by method known to proper combination.As one example, for example, it can enumerate：Synthesis has The nitro intermediate of nitro replaces the one-level amino in the formula (1), then using appropriate reducing agent by the nitre obtained The method of the nitro amino of base intermediate；The one-level amino in the formula (1) is synthesized through in the protections such as tert-butoxycarbonyl Mesosome, the method for being then deprotected the intermediate obtained etc..
The method of synthesizing nitryl intermediate can suitably be selected according to target compound.For example, can enumerate：In double (4- nitros Phenyl) make with R in the presence of carbonic ester1Nitrobenzene derivative reaction method；Make to have and be derived from R1And R2Part-structure The halide reaction such as compound containing urea groups and nitrobenzoyl chloride method；Make with R1Or R2Isocyanate compound With with R2Or R1Amines reaction method etc..Wherein, the synthetic method of specific diamines is not limited to methods described.
(polyamic acid)
In the case where polymer [P] is polyamic acid, the polyamic acid (hereinafter also referred to as " polyamic acid [P] ") For example can be by making tetracarboxylic dianhydride be obtained with the diamine reactant comprising the specific diamines.
As the tetracarboxylic dianhydride used in the synthesis of polyamic acid, for example, it can enumerate：Aliphatic tetracarboxylic dianhydride, alicyclic ring Formula tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc..It is used as the concrete example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydride example 1,2,3,4- butane tetracarboxylic acid dianhydrides etc. can such as be enumerated.
Ester ring type tetracarboxylic dianhydride can for example enumerate：1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,3- dimethyl -1,2,3, 4- cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydrochysenes -2,5- Dioxo -3- furyls)-naphtho- [1,2-c] furans -1,3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydrochysene - 2,5- dioxo -3- furyls)-naphtho- [1,2-c] furans -1,3- diketone, 3- oxabicyclos [3.2.1] octane -2,4. diketone - 6- loop coils -3 '-(tetrahydrofuran -2 ', 5 '-diketone), 5- (2,5- dioxotetrahydro -3- furyls) -3- methyl -3- cyclohexene - 1,2- dicarboxylic anhydride, 3,5,6- tri- carboxyl -2- carboxymethyl groups norbornanes -2: 3,5: 6- dianhydride, 2,4,6,8- tetracarboxylics are bicyclic [3.3.0] octane -2: 4,6: 8- dianhydride, the ring [5.3.1.0 of 4,9- dioxas three2,6] hendecane -3,5,8,10- tetrones, pentamethylene Tetracarboxylic dianhydride, cyclopentanetetracarboxylic's dianhydride etc..
Aromatic tetracarboxylic acid's dianhydride is such as can enumerate pyromellitic acid anhydride, in addition, it is also possible to use Japan Patent Tetracarboxylic dianhydride described in JP 2010-97188 publications.Furthermore, a kind of tetracarboxylic dianhydride's or combination that can be used alone makes With two or more.
As the tetracarboxylic dianhydride used in synthesis, just with making the electrical characteristics of liquid crystal cell better in the combination of specific diamines For good aspect, preferably comprising ester ring type tetracarboxylic dianhydride person.Relative to the tetrabasic carboxylic acid used in the synthesis of polyamic acid The total amount of dianhydride, the use ratio of ester ring type tetracarboxylic dianhydride is preferably 5 moles of more than %, more preferably 10 moles more than %, And then preferably 30 moles %~100 mole %.
At synthesizing polyamides sour [P], can be used alone specific diamines, it is possible to use diamines beyond specific diamines (with Under, referred to as " other diamines ").
As other diamines, for example, it can enumerate aliphatic diamine, ester ring type diamines, aromatic diamine, diaminourea organosilicon Oxygen alkane etc..As the concrete example of these other diamines, aliphatic diamine can for example enumerate m-xylene diamine, 1,3- propane diamine, five Methylene diamine, hexamethylene diamine etc.；Ester ring type diamines can for example enumerate Isosorbide-5-Nitrae-diaminocyclohexane, 4,4 '-di-2-ethylhexylphosphine oxide (cyclo-hexylamine) etc..
Aromatic diamine can for example enumerate dodecyloxy diaminobenzene, tetradecyloxyaniline diaminobenzene, octadecane epoxide Diaminobenzene, cholesteric alkoxy diaminobenzene, cholesterine epoxide diaminobenzene, diaminobenzoic acid cholesteric Arrcostab, diaminourea Double (the 4- aminobenzoics acyloxy) cholestane of cholesterol benzoate, diaminobenzoic acid lanostane base ester, 3,6-, 3,6- are double (4- amino-benzene oxygens) cholestane, 1,1- double (4- ((aminophenyl) methyl) phenyl) -4- butyl cyclohexanes, following formula (E-1) The diamines of the bases containing orientation such as represented compound.
[changing 15]
(in formula (E-1), X1And X11It is separately singly-bound ,-O- ,-COO- or-OCO-, R1For the alkane two of carbon number 1~3 Base, R11For the alkane diyl of singly-bound or carbon number 1~3, the integer that a is 0 or 1, b are 0~2, c is 1~20 integer, and d is 0 or 1.Its In, a and b will not be simultaneously for 0).
P-phenylenediamine, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 4- aminophenyls -4 '-ammonia Yl benzoic acid ester, 4,4 '-chrysoidine, 1,5- double (4- amino-benzene oxygens) pentane, double [2- (4- aminophenyls) ethyls] Adipic acid, N, N- double (4- aminophenyls) methyl amine, 2,2 '-dimethyl -4,4 '-benzidine, 2,2 '-bis- (fluoroforms Base) -4,4 '-benzidine, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminobenzene formailide, 4,4 '-(to phenylene Two isopropylidenes) dianil, 4,4 '-(isopropylidene of metaphenylene two) dianils, Isosorbide-5-Nitrae-bis- (4- amino-benzene oxygens) benzene, 4, 4 '-bis- (4- amino-benzene oxygens) biphenyl, N, N '-bis- (4- aminophenyls)-benzidine, Isosorbide-5-Nitrae-bis--(4- aminophenyls)-piperazine, 4- (4- amino-benzene oxygens carbonyl) -1- (4- aminophenyls) piperidines, 4,4 '-[4,4 '-propane -1,3- diyl it is double (piperidines-Isosorbide-5-Nitrae - Diyl)] non-side chain type diamine such as diphenylamines, 3,5- diaminobenzoic acids etc..
Diaminourea organosiloxane can for example be enumerated：1,3- double (3- aminopropyls)-tetramethyl disiloxanes etc., except this with Outside, it is also possible to use the diamines described in Japanese Patent Laid-Open 2010-97188 publications.
As the concrete example of the compound represented by the formula (E-1), for example, it can enumerate represented by following formula (E-1-1) Compound represented by compound, following formula (E-1-2) etc..
[changing 16]
At synthesizing polyamides sour [P], the rub resistance of film and the electrical characteristics of liquid crystal cell are just fully obtained and residual For the viewpoint of the improvement of picture characteristic, the total amount of the diamines used in the synthesis relative to polyamic acid [P], specific two The use ratio of amine is preferably to be set to 5 moles of more than %.More preferably 10 moles %~70 mole %, and then preferably 10 rub You are %~50 mole %.Furthermore, specific diamines and other diamines can be used alone one kind respectively, or suitably selection uses two kinds More than.
(synthesis of polyamic acid)
Polyamic acid [P] can be by making described tetracarboxylic dianhydride optionally together be reacted with molecular weight regulator with diamines And obtain.It is preferably the ammonia relative to diamines for the tetracarboxylic dianhydride of the synthetic reaction of polyamic acid and the use ratio of diamines The equivalent of base 1, the anhydride group of tetracarboxylic dianhydride turns into the ratio of the equivalent of 0.2 equivalent~2.As molecular weight regulator, for example, it can arrange The monoamine compounds such as the single acid anhydride of the acid such as act maleic anhydride, phthalic anhydride, itaconic anhydride, aniline, cyclo-hexylamine, n-butylamine, Monoisocyanate compounds such as phenyl isocyanate, naphthyl isocyanate etc..Relative to used tetracarboxylic dianhydride and diamines Total 100 mass parts, the use ratio of molecular weight regulator is preferably below 20 mass parts.
The synthetic reaction of polyamic acid is preferably to be carried out in organic solvent.Reaction temperature now is preferably -20 DEG C~ 150℃.Reaction time is preferably 0.1 hour~24 hours.As the organic solvent used in reaction, for example, it can enumerate non-proton Property polarity solvent, phenol system solvent, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon etc..On particularly preferred organic solvent, it is preferable to use Selected from by METHYLPYRROLIDONE, DMA, DMF, dimethyl sulfoxide (DMSO), γ-Ding Nei In the group that ester, tetramethylurea, HPT, metacresol, xylenols and halogenation phenol are constituted it is a kind of with On as solvent, or using these solvents more than one with other organic solvents (for example, butyl cellosolve, diethylene glycol Diethyl ether etc.) mixture.The usage amount (a) of organic solvent be preferably tetracarboxylic dianhydride and diamines total amount (b) relative to The total amount (a+b) of reaction solution and as the mass % of 0.1 mass %~50 amount.
The reaction solution of dissolving polyamic acid can be obtained in this way.The reaction solution can be directly for liquid crystal The preparation of alignment agent, preparation that also can be after by polyamic acid separation contained in reaction solution for aligning agent for liquid crystal.
(poly amic acid ester)
For example can be by making the side of tetracarboxylic acid acid diesters dihalide and diamine reactant as the poly amic acid ester of polymer [P] Method and obtain.
Used tetracarboxylic acid acid diesters dihalide can be by making the appropriate chlorinating agents such as tetracarboxylic acid acid diesters and thionyl chloride React and obtain.The tetracarboxylic dianhydride illustrated in the synthesis that tetracarboxylic acid acid diesters for example can be by making polyamic acid and methanol or ethanol React and obtain Deng alcohols.As diamines, can be used alone specific diamines, and can also use other diamines.It is used as used two The specific diamines and other diamines illustrated in the concrete example of amine, the explanation for the synthesis that polyamic acid can be enumerated.
It is preferably relative for the tetracarboxylic acid acid diesters dihalide of the synthetic reaction of polymer [P] and the use ratio of diamines In the equivalent of amino 1 of diamines, the base "-COX- (X is halogen atom) " of tetracarboxylic acid acid diesters dihalide is worked as 0.2 equivalent~2 The ratio of amount.The reaction of tetracarboxylic acid acid diesters dihalide and diamines is preferably to be carried out in the presence of base in organic solvent.This When reaction temperature be preferably -30 DEG C~150 DEG C, the reaction time is preferably 0.1 hour~48 hours.It is used as what is used in reaction Organic solvent, can apply the explanation of workable organic solvent in the synthetic reaction of polyamic acid.As being used in the reaction Alkali, such as preferably using the tertiary amine such as pyridine, triethylamine, N- ethyls-N, N- diisopropylamine；Sodium hydride, hydrogenation The alkali metal class such as potassium, sodium hydroxide, potassium hydroxide, sodium, potassium.The usage amount of alkali is preferably to be set to 2 relative to 1 mole of diamines and rub You~4 moles.
The reaction solution of dissolving poly amic acid ester can be obtained in the above described manner.The reaction solution can be directly for liquid The preparation of brilliant alignment agent, preparation that also can be after by poly amic acid ester separation contained in reaction solution for aligning agent for liquid crystal. Poly amic acid ester can only have an amic acid esters structure, or amic acid structure and amic acid esters structure and the partial esterification deposited Thing.Furthermore, be not limited to the synthetic method as the poly amic acid ester of polymer [P], such as also can by the following method And obtain, methods described is, for example, to make polyamic acid [P], the method for alcohols or halogenated alkyl reaction, make tetracarboxylic acid acid diesters and two Method of amine reaction etc..
(polyimides)
As polymer [P] polyimides for example can by by the polyamic acid synthesized as described above [P] dehydration closed-loop, And be subject to imidizate and obtain., can be by polyamic acid by polyamic acid dehydration closed-loop and in the case of polyimides is made Reaction solution directly for dehydration closed-loop reaction, also can be after by polyamic acid separation contained in reaction solution for dehydration Ring-closure reaction.
Polyimides can be the amic acid structure fully dehydrating closed loop with the polyamic acid as its precursor and Complete acid imide compound or only a part of dehydration closed-loop of amic acid structure is made amic acid structure and acyl sub- Amine ring structure and the part acid imide compound deposited.The acid imide rate of the polyimides used in reaction is preferably more than 20%, More preferably 30%~99%.The acid imide rate is the quantity that imide ring structure is represented with percentage relative to polyamides The quantity of the amic acid structure of imines and the quantity of imide ring structure it is total for shared ratio.Herein, imide ring It is a part of can be different imide ring.
The dehydration closed-loop of polyamic acid is preferably that profit is carried out with the following method, and methods described heats polyamic acid Method or polyamic acid is dissolved in organic solvent, dehydrating agent and dehydration closed-loop catalyst are added in the solution, depending on Need the method heated.Wherein, the method for the latter is preferably utilized.Dehydrating agent is added in the solution of polyamic acid and de- In the method for water ring-closing catalyst, as dehydrating agent, the acid anhydrides such as usable acetic anhydride, propionic andydride, TFAA.Relatively In 1 mole of the amic acid structure of polyamic acid, the usage amount of dehydrating agent is preferably to be set to 0.01 mole~20 moles.It is used as dehydration Ring-closing catalyst, for example, can be used：Pyridine, collidine (collidine), two picolins (lutidine), triethylamine etc. three Level amine.Relative to used 1 mole of dehydrating agent, the usage amount of dehydration closed-loop catalyst is preferably to be set to 0.01 mole~10 to rub You.As the organic solvent used in dehydration closed-loop reaction, it can enumerate as the organic solvent of the synthesis for polyamic acid The organic solvent of illustration.The reaction temperature of dehydration closed-loop reaction is preferably 0 DEG C~180 DEG C.Reaction time is preferably 1.0 hours~ 120 hours.
The reaction solution containing polyimides can be obtained in this way.The reaction solution can be directly for liquid crystal aligning The preparation of agent, can also remove the preparation after dehydrating agent and dehydration closed-loop catalyst for aligning agent for liquid crystal in autoreaction solution, Preparation that can also be after polyimides is separated for aligning agent for liquid crystal.
The solution viscosity of polymer [P] is preferably when being made into the solution that concentration is 10 mass %, with 10mPa S~800mPas solution viscosity person, the solution viscosity person more preferably with 15mPas~500mPas.Furthermore, gather The solution viscosity (mPas) of compound [P] be use E type rotation viscometers, to using polymer [P] good solvent (such as γ- Butyrolactone, METHYLPYRROLIDONE etc.) and the concentration of preparation is 10 mass % polymer solution, is surveyed at 25 DEG C It is worth obtained by fixed.
The utilization gel permeation chromatography (gel permeation chromatography, GPC) of polymer [P] is determined Obtained by polystyrene conversion weight average molecular weight (Mw) be preferably 1,000~500,000, more preferably 2,000~ 300,000.In addition, Mw is with utilizing represented by the ratio of the number average molecular weight (Mn) of polystyrene conversion obtained by GPC measure Molecular weight distribution (Mw/Mn) be preferably less than 15, more preferably less than 10.
(other compositions)
The aligning agent for liquid crystal of the disclosure can also contain the other compositions beyond polymer [P].It is used as such a other compositions, example It can such as enumerate：The polymer (hereinafter referred to as " other polymers ") different from the polymer [P], intramolecular have at least one Compound (hereinafter also referred to " compound containing epoxy radicals ") of individual epoxy radicals etc..
The other polymers can be in order to improve the various characteristics such as the electrical characteristics such as image retention, the transparency or for low cost Change etc. purpose and use.As such a other polymers, for example, it can enumerate：Selected from by polyamic acid, poly amic acid ester and polyamides The construction unit that not having at least one of group that imines is constituted is derived from the compound represented by the formula (1) Polymer, polysiloxane, polyester, polyamide, cellulose derivative, polyacetals, polystyrene derivative, it is poly- (styrene- Phenyl maleimide) derivative etc..Relative to the total amount of component of polymer contained in aligning agent for liquid crystal, other polymers Allotment ratio be preferably to be set to below 95 mass %, be more preferably set to the mass % of 10 mass %~90.
Compound containing epoxy radicals is to make to improve liquid crystal orientation film with the cementability or electrical characteristics of substrate surface With.As such a compound containing epoxy radicals, for example, it can enumerate ethylene glycol diglycidylether, polyethylene glycol diglycidyl Ether, propylene glycol diglycidylether, 1,6- hexanediol diglycidyl ethers, trihydroxymethylpropanyltri diglycidyl ether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3- double (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N '-four glycidyl group [4,4 '-methylene dianiline], N, N- diglycidyls-benzyl amine, N, N- diglycidyls- Aminomethyl cyclohexane, N, N- glycidyls-cyclo-hexylamine etc. are used as preferred person.In addition, it is possible to use International Publication The polysiloxane containing epoxy radicals of No. 2009/096598 record.Taken the compound containing epoxy radicals is allocated in liquid crystal In the case of into agent, its allotment ratio is preferably relative to total 100 mass parts of polymer contained in aligning agent for liquid crystal It is set to below 40 mass parts, is more preferably set to the mass parts of 0.1 mass parts~30.
Furthermore, other compositions can enumerate functional silanes compound, intramolecular in addition to described, also at least has one It is the compound of oxetanylmethoxy, antioxidant, metal chelate compound, hardening accelerator, surfactant, filler, scattered Agent, light sensitizer etc..As long as the allotment ratio of these other compositions can be according to each in the range of the effect of the disclosure is not undermined Compound is suitably selected.
On the aligning agent for liquid crystal of the disclosure, just realize the electrical characteristics of liquid crystal cell and goodization of image retention characteristic aspect and Speech, relative to the total amount of component of polymer contained in aligning agent for liquid crystal, the allotment ratio of polymer [p] is preferably to be set to 5 More than quality %, is more preferably set to more than 10 mass %.In addition, in aligning agent for liquid crystal the situation containing other polymers Under, relative to the mass parts of total amount 100 of polymer [p] and other polymers contained in aligning agent for liquid crystal, preferably will The allotment ratio of polymer [p] is set to the mass parts of 5 mass parts~99, is more preferably set to the mass parts of 10 mass parts~95, and then Preferably it is set to the mass parts of 10 mass parts~80.
It, with the construction unit from specific diamines, is preferably specifically to have to be selected under that polymer [p], which is preferably, State at least one in the group that the part-structure represented by formula (p-1) and the part-structure represented by following formula (p-2) are constituted Plant part-structure.
[changing 17]
(in formula (p-1), formula (p-2), R51For quadrivalent organic radical, R52For hydrogen atom or any monovalent organic radical, R53For described in The remaining base of 2 one-level amino is removed in specific diamines.Multiple R52It may be the same or different).
It is used as the R in the formula (p-1)52Any monovalent organic radical, can for example enumerate the monovalent hydrocarbon of carbon number 1~10, have Base of cinnamic acid structure etc..R51Quadrivalent organic radical for from tetracarboxylic dianhydride remove 2 anhydride groups remaining base.Make For the concrete example of the tetracarboxylic dianhydride, tetracarboxylic dianhydride of the illustration etc. can be enumerated.
(solvent)
The aligning agent for liquid crystal of the disclosure be with polymer [P] and the other compositions optionally used be preferably it is scattered or It is prepared by the form of the composition for the liquid being dissolved in appropriate solvent.
As used organic solvent, for example, it can enumerate：METHYLPYRROLIDONE, N- ethyl-2-pyrrolidones, 1,2- dimethyl -2- imidazolidinones, gamma-butyrolacton, butyrolactam, DMF, N, N- dimethylacetamides Amine, 4- hydroxy-4-methyl-2-pentanones, glycol monoethyl ether, butyl lactate, butyl acetate, methoxy methyl propionate, ethyoxyl Ethyl propionate, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl Cellosolve), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, DIBK, third Isoamyl valerate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate etc..These organic solvents can individually make With a kind of or be use mixing two or more.
(total quality of the composition beyond the solvent of aligning agent for liquid crystal is in liquid crystal for solid component concentration in aligning agent for liquid crystal Shared ratio in the gross mass of alignment agent) it is to consider viscosity, volatility etc. and suitably select, the matter of preferably 1 mass %~10 Measure % scope.I.e., as described below, aligning agent for liquid crystal is coated on substrate surface, preferably heated, formed therefrom Film as liquid crystal orientation film or the film as liquid crystal orientation film.Now, it is less than 1 mass %'s in solid component concentration In the case of, the thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, it is super in solid component concentration In the case of crossing 10 mass %, the thickness of film becomes too much and is difficult to obtain good liquid crystal orientation film, in addition, there is liquid crystal to take Increase and the tendency of coating decline to the viscosity of agent.
<Liquid crystal cell>
The liquid crystal cell of the disclosure is including the use of liquid crystal orientation film formed by illustrated aligning agent for liquid crystal in described.Liquid The operating mode of liquid crystal in crystal cell is not particularly limited, for example, can be applied to twisted nematic (Twisted Nematic, TN) Type, STN Super TN (Super Twisted Nematic, STN) type, vertical orientated (Vertical Alignment, VA) type (include vertical orientated-multidomain vertical orientation (Vertical Alignment-Multi-domain Vertical Alignment, VA-MVA) type, vertical orientated (the Vertical Alignment-Patterned of vertical orientated-pattern Vertical Alignment, VA-PVA) type etc.), coplanar switching (In-Plane Switching, IPS) type, FFS types, optics The multiple operation modes such as compensated bend (Optically Compensated Bend, OCB) type.Applied to TN types, STN types, Liquid crystal cell of IPS types, FFS types or OCB types etc. must take to carrying out imparting liquid crystal using film formed by aligning agent for liquid crystal To the processing of ability pattern in the case of, just can also be obtained even with rubbing manipulation and show good voltage retention and residual For the aspect of the liquid crystal cell of picture characteristic preferably.The liquid crystal cell of the disclosure for example can be by comprising the following steps 1~step Rapid 3 method is manufactured.Step 1 uses different substrates according to required operating mode.Step 2 and step 3 are in each running It is common in pattern.
[step 1：The formation of film]
The coating of liquid crystalline alignment agent first on substrate, then forms on substrate and applies by being heated to coated face Film.As substrate, for example, it can be used：The glass such as float glass (float glass), soda-lime glass (soda glass)；Comprising poly- The plastics such as PETP, polybutylene terephthalate, polyether sulfone, makrolon, poly- (ester ring type alkene) it is saturating Bright substrate.As the nesa coating for the one side for being arranged at substrate, it can be used and include tin oxide (SnO2) nesa (NESA) film (PPG register of company of U.S. trade mark), include indium oxide-tin oxide (In2Os-SnO2) indium tin oxide (Indium Tin Oxide, ITO) film etc..In the case of manufacture TN types, STN types or VA type liquid crystal cells, it is provided with using two pieces through pattern The substrate of the nesa coating of change.In the case of manufacture IPS types or FFS type liquid crystal cells, included using being provided with through figure Case turns to the substrate of the nesa coating of interdigitated electrode structure or the electrode of metal film and is not provided with the opposite substrate of electrode.As Metal film, the film of metal such as can be used comprising chromium.It is preferably to utilize graph to being coated on electrode forming surface for substrate Brush method, spin-coating method, rolling method or ink jet printing method are carried out.
After coating of liquid crystalline alignment agent, for purposes such as the saggings for preventing be coated with aligning agent for liquid crystal, preferably implement pre- Heat (prebake conditions).Prebake conditions temperature is preferably 30 DEG C~200 DEG C.The prebake conditions time is preferably 0.25 minute~10 minutes.So Afterwards, solvent is removed completely, optionally implemented for by the purpose of amic acid structure hot-imide present in polymer Calcining (rear baking) step.Calcining heat (rear baking temperature) now is preferably 80 DEG C~300 DEG C, and post-bake times are preferably 5 minutes~200 minutes.The thickness of thus formed film is preferably 0.001 μm~1 μm.By on substrate coating of liquid crystalline take To after agent, remove organic solvent to form liquid crystal orientation film or film as liquid crystal orientation film.
[step 2：Orientation process]
In the case of manufacture TN types, STN types, IPS types, FFS types or OCB type liquid crystal cells, to shape in the step 1 Into film implement assign liquid crystal aligning ability processing (orientation process).Thus, the alignment capability of liquid crystal molecule is imparted to On film and as liquid crystal orientation film.As orientation process, it can enumerate：Included using being wound with such as nylon, artificial silk, cotton The roller of the cloth of fiber, is wiped towards fixed-direction and film is assigned the friction treatment of liquid crystal aligning ability to film；To base The film formed on plate carries out light irradiation and light orientation processing of liquid crystal aligning ability etc. is assigned to film.On the other hand, exist In the case of manufacturing vertical alignment-type liquid crystal element, the film formed in the step 1 can be directly used as liquid crystal orientation film, but Orientation process can also be implemented to the film.
[step 3：Liquid crystal cells are constructed]
By preparing two pieces of substrates for being formed with liquid crystal orientation film in this way, match somebody with somebody between two pieces of oppositely disposed substrates Liquid crystal is put to manufacture liquid crystal cells.As the method for manufacture liquid crystal cells, for example, it can enumerate：(1) with each liquid crystal orientation film to Mode, it is across gap (cell gap) that two pieces of substrates are oppositely disposed, the periphery of two pieces of substrates is fitted using sealant, In substrate surface and the cell gap divided by sealant after injection filling liquid crystal, by the sealed method of hand-hole；(2) exist The predetermined portion on one of substrate in two pieces of substrates, is coated with the sealant of such as ultraviolet light photopolymerization, and then in liquid crystal The defined several positions being orientated on film surface are added dropwise after liquid crystal, by liquid crystal orientation film to another piece of substrate of being fitted in the way of, and And spread out liquid crystal in the entire surface of substrate, method for then hardening sealant etc..
As sealant, such as can be used the epoxy resin containing curing agent and as the alumina balls of sept. As liquid crystal, nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid can be enumerated Crystal), wherein preferably nematic liquid crystal, such as can be used：Schiff bases (Schiff base) are liquid crystal, azoxy (azoxy) it is that liquid crystal, biphenyl system liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) are liquid crystal, connection Cyclohexylbenzene system liquid crystal, pyrimidine system liquid crystal, dioxanes system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal Deng.Alternatively, it is also possible to add such as cholesteric crystal (cholesteric liquid crystal), hand in these liquid crystal Property agent, ferroelectric liquid crystal (ferroelectric liquid crystal) etc. are used.
Then, by the outer surface laminating Polarizer if necessary in liquid crystal cells, liquid crystal cell can be obtained.It is used as polarisation Plate, can be enumerated：With cellulose acetate diaphragm clamp be referred to as " H films " light polarizing film Polarizer or comprising H films its The Polarizer of itself, " the H films " is to make polyvinyl alcohol extension orientation while making its film for absorbing iodine.
Herein, in the liquid crystal cell of the horizontal electric field types such as FFS, when found because of friction treatment in liquid crystal orientation film it is each to When different in nature, in order to further make display quality good by realizing the improvement of contrast or the reduction of image retention, and start to apply Strong friction.Therefore, the problem of liquid crystal orientation film easily produces orientation defect by skiving, and presence in friction treatment.The opposing party Face, the good existing aligning agent for liquid crystal of rub resistance in most cases can be because of the charge accumulation of the application with alternating voltage Easily produce image retention or voltage retention declines, AC image retentions characteristic and voltage retention are in and traded off.In this connection, root According to the aligning agent for liquid crystal containing polymer [P], the rub resistance that can obtain film is good, defect is orientated as caused by friction treatment Less and AC image retentions characteristic and the good liquid crystal cell of voltage retention.
Additionally, it is believed that for example in color liquid crystal display device, colored filter is produced because forming heat during liquid crystal orientation film A problem that contained fuel changes colour in mating plate.If in addition, being also considered as that high temperature must be carried out in the formation of liquid crystal orientation film Heat treatment, the then application of the insufficient substrate of the heat resistance in the manufacture of liquid crystal cell such as plastic base is restricted. In this connection, containing polymer [P] even if the disclosure aligning agent for liquid crystal compared with low temperature carry out after toast when plus In the case of heat, so that it may obtain for the aspect for showing high voltage retention and low image retention it is also preferred that.
Furthermore, according to the aligning agent for liquid crystal for including polymer [P], the reasons why can obtaining the effect is simultaneously indefinite, for example Can be as considered below.The monomer size of monomer with the part-structure represented by the formula (0) is larger, is entered with identical molecular weight In the case that row compares, the carboxylic acid concentration in polymer [P] is relatively low.Thus, one can be speculated：By the low acyl with low temperature calcination The influence that voltage retention caused by imidization declines is suppressed, and AC image retentions are reduced because of the urea bond in the formula (0), by This can obtain the liquid crystal cell for showing good voltage retention and AC image retention characteristics.In addition, by polymer [P] and other In the case of polymer-doped, it is also considered as by the relatively low caused polymer [P] of carboxylic acid concentration easily in upper strata distribution, thus shows Go out good voltage retention and AC image retention characteristics.But this is to speculate, does not limit content of this disclosure.
The liquid crystal cell of the disclosure can be effectively applied to a variety of devices, for example, can be used in：Clock and watch, portable game machine (portable game), word processor (word processor), notes type personal computer (note type Personal computer), it is auto-navigation system (car navigation system), video camera (camcorder), personal Digital assistants (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, intelligence The various display devices or light modulation film etc. such as mobile phone, various monitors, LCD TV.In addition, also the liquid of the disclosure can will be used The liquid crystal cell that brilliant alignment agent is formed is applied to phase retardation film.
[embodiment]
Hereinafter, further it is specifically described by embodiment, but the present invention is not restricted by the embodiments.
In following example, the acid imide rate of polymer, the solution viscosity of polymer solution, the weight average of polymer Molecular weight Mw and epoxide equivalent are determined using following methods.Hereinafter, the compound represented by formula (X) is abbreviated as sometimes " compound (X) ".
[the acid imide rate of polymer] put into the solution containing polyimides in pure water, at room temperature to being obtained After precipitation is fully dried under reduced pressure, deuterated dimethyl sulfoxide is dissolved in, using tetramethylsilane as primary standard substance in room temperature It is lower to determine1H-NMR.According to what is obtained1H-NMR spectrum, acid imide rate is obtained using following numerical expressions (1).
Acid imide rate (%)=(1-A1/A2×α)×100…(1)
(in numerical expression (1), A1For the peak area of the proton from the NH bases occurred near chemical deviation 10ppm, A2For source From the peak area of other protons, α is the number of other protons relative to the NH bases in the precursor (polyamic acid) of polymer The ratio of one proton.)
[solution viscosity (mPas) of polymer solution] is measured using E types rotation viscometer at 25 DEG C.
[the weight average molecular weight Mw of polymer]：Using following device, according to the gel utilized in following condition Permeation chromatography and the result determined, are obtained using monodisperse polystyrene as standard substance and with polystyrene scaled value.
Determine device：Eastern Cao's (Tosoh) (stock) manufacture, model " 8120-GPC "
Tubing string：Eastern Cao's (Tosoh) (stock) manufacture, " tsk gel (TSKgel) GRCXLII "
Solvent：Tetrahydrofuran
Sample solution concentration：5 weight %
Sample injection rate：100μL
Tubing string temperature：40℃
Tubing string pressure：68kgf/cm2
[epoxy list amount]：Determined according to JIS C2105 " hydrochloric acid-methyl ethyl ketone method ".
<The synthesis of compound>
[synthesis example 1：The synthesis of compound (1-1-1)]
Such as following flows 1 synthesis compound (1-1-1).
[changing 18]
The synthesis of compound (1-1-1A)
Load hydroxy benzaldehyde into the three-necked flask for the 200mL for possessing nitrogen ingress pipe, thermometer and return duct 12.2g, nitrophenyl-acetic acid 18.1g and piperidinyl-1 7.0g, react 4 hours at 140 DEG C.After the completion of reaction, add 100mL's Ethanol, precipitation is filtered, and is cleaned using ethanol, is then recrystallized simultaneously with the mixed solvent of tetrahydrofuran and ethanol It is subject to drying, the crystallization of 19.3g compound (1-1-1A) is obtained therefrom.
The synthesis of compound (1-1-1C)
Compound (1-1-1A) is added into the three-necked flask for the 1000mL for possessing nitrogen ingress pipe, thermometer and return duct 19.3g, compound (1-1-1B) 24.4g, potassium carbonate 13.2g and DMF 400mL, are stirred at room temperature 12 small When.After the completion of reaction, the precipitation that reaction solution is injected into 2L water and produced is filtered and is subject to drying.Secondly, The precipitation 39.8g, tetrahydrofuran are added into the three-necked flask for the 1000mL for possessing nitrogen ingress pipe, thermometer and return duct 200mL, ethanol 200mL and hydrazine monohydrate 9.61g, flow back within 5 hours.After the completion of reaction, add tetrahydrofuran 1L and Toluene 500mL, is carried out after point liquid cleaning using water, is dried, is concentrated under reduced pressure and to the precipitation of generation using magnesium sulfate Thing is filtered, dried, and 19.2g compound (1-1-1C) is obtained therefrom.
The synthesis of compound (1-1-1D)
Compound (1-1-1C) 19.2g, double (4- are added into the three-necked flask for the 2L for possessing nitrogen ingress pipe and thermometer Nitrobenzophenone) carbonic ester 9.58g, tetrahydrofuran 1200mL, triethylamine 40.6g and N, N- dimethyl aminopyridine 1.63g, Stir 12 hours at room temperature.After the completion of reaction, precipitation is filtered, cleaned using water with methanol, and then utilize four The mixed solvent of hydrogen furans and ethanol is recrystallized, and is filtered, dried, and 12.0g compound (1-1- is obtained therefrom 1D)。
The synthesis of compound (1-1-1)
Compound (1-1-1D) is added into the three-necked flask for the 500mL for possessing return duct, nitrogen ingress pipe and thermometer 12.0g, 5% palladium carbon 6.03g, tetrahydrofuran 240mL, ethanol 120mL and hydrazine monohydrate 6.03g, flow back within 4 hours. After reaction terminates, untill the filtered fluid for filtering and obtaining through diatomite is concentrated under reduced pressure into 120mL, it is in 1.2L water and right to be injected into The precipitation of generation is filtered, and is cleaned using methanol, and is dried in vacuo, and 9.74g compound (1- is obtained therefrom 1-1)。
[synthesis example 2：The synthesis of compound (1-2-1)]
As following flows are 2-in-1 into compound (1-2-1).As following flows 2 carry out generation using 4- nitrobiphenyl phenol as raw material Alternative compound (1-1-1A), in addition, is synthesized in the same manner as compound (1-1-1).
[changing 19]
[synthesis example 3：The synthesis of compound (1-3-1)]
Such as following flows 3 synthesis compound (1-3-1).
[changing 20]
The synthesis of compound (1-3-1B)
Compound (1-3-1A) 23.6g, tetrahydrochysene are added into the three-necked flask for the 1L for possessing thermometer and nitrogen ingress pipe Furans 400mL, double (4- nitrobenzophenones) carbonic ester 15.2g, triethylamine 20.2g and N, N- dimethyl aminopyridine 1.22g, React 4 hours at room temperature.After the completion of reaction, filtered to being injected into the precipitation obtained in 4L water, carry out vacuum and do It is dry and move to the material obtained in 500mL eggplant type flask, dichloromethane 200mL and trifluoroacetic acid 100mL is added, in room The lower reaction of temperature 2 hours.After the completion of reaction, after solid using aspirator progress, tetrahydrofuran 200mL and ethyl acetate are added 200mL is simultaneously carried out once using saturated aqueous sodium carbonate, three points of liquid cleanings is carried out using water, then using magnesium sulfate to having Machine layer is dried, and is concentrated and is filtered the crystallization of precipitation, dried, 11.4g compound (1-3- is obtained therefrom 1B)。
The synthesis of compound (1-3-1C)
Compound (1-3-1B) is added into the three-necked flask for the 500mL for possessing thermometer, return duct and nitrogen ingress pipe 11.4g, tetrahydrofuran 300mL, 4- fluoronitrobenzene 14.0g and triethylamine 10.0g, diel is reacted at 40 DEG C.In reaction After end, ethyl acetate 300mL is added, and three points of liquid are carried out using water and is cleaned, then organic layer is carried out using magnesium sulfate Dry, be concentrated under reduced pressure and filtered the crystallization of precipitation, dried, 19.9g compound (1-3-1C) is obtained therefrom.
The synthesis of compound (1-3-1)
Compound (1-3-1C) is added into the three-necked flask for the 500mL for possessing return duct, thermometer and nitrogen ingress pipe 19.9g, 5% palladium carbon 1.0g, tetrahydrofuran 200mL, ethanol 100mL and hydrazine monohydrate 12g, flow back within 2 hours.In reaction After end, untill the filtered fluid for filtering and obtaining through diatomite is concentrated under reduced pressure into 200mL, it is injected into 1L water and to acquisition Precipitation is filtered, and is cleaned using ethanol, and is dried in vacuo, and 15.7g compound (1-3-1) is obtained therefrom.
[synthesis example 4：The synthesis of compound (1-4-1)]
Such as following flows 4 synthesis compound (1-4-1).
[changing 21]
The synthesis of compound (1-4-1A)
Compound (R-1) is added into the three-necked flask for the 500mL for possessing return duct, thermometer and nitrogen ingress pipe After 14.9g and pyridine 300mL, 4- nitrobenzoyl chloride 20.4g are added, flow back within 6 hours.After the completion of reaction, it is injected into Filter, be dried in vacuo in 3L water and to the precipitation of precipitation, then tied again using DMA Crystalline substance, and filtered, be dried in vacuo, compound (1-4-1A) is obtained therefrom.
The synthesis of compound (1-4-1B)
Compound (1-4-1A) 26.8g, N, N- are added into the three-necked flask for the 1L for possessing thermometer and nitrogen ingress pipe Dimethyl aminopyridine 2.20g, dimethyl sulfoxide (DMSO) 300mL and two carbonic acid-tert-butyl ester 29.4g, diel is reacted at 40 DEG C. After reaction terminates, it is injected into 3L water and the precipitation of precipitation is filtered, carries out methanol cleaning, vacuum drying, therefrom Obtain 34.1g compound (1-4-1B).
The synthesis of compound (1-4-1)
Compound (1-4-1B) 34.1g, 5% palladium carbon 1.70g, tetrahydrofuran 300mL and second are added in 1L autoclave Alcohol 200mL, is blown into hydrogen untill 0.4MPa, reacts 4 hours at room temperature.After the completion of reaction, will be through diatomite filtering Untill the filtered fluid of acquisition is concentrated under reduced pressure into 200mL, adds ethyl acetate 1000mL and carry out three points of liquid using water and clean, it is right Organic layer is concentrated under reduced pressure and the solid of precipitation is filtered, and is dried in vacuo, and 29.5g compound is obtained therefrom (1-4-1)。
[platform is into example 5：The synthesis of compound (2-1-1-1)]
Such as following flows 5 synthesis compound (2-1-1-1).
[change 221
The synthesis of compound (2-1-1-1A)
4- nitrophenethyl isocyanides are added into the three-necked flask for the 1L for possessing dropping funel, thermometer and nitrogen ingress pipe Acid esters 19.0g and tetrahydrofuran 200mL.Load N- (tert-butoxycarbonyl)-EDA 16.0g in dropping funel And tetrahydrofuran 200mL, spend after dropwise addition in 1 hour, be stirred at room temperature 1 hour.After the completion of reaction, reaction solution is depressurized Concentration, is filtered to precipitate, carries out ethanol cleaning, vacuum drying, 33.5g compound (2-1-1- is obtained therefrom 1A)。
The synthesis of compound (2-1-1-1)
Into the three-necked flask for the 500mL for possessing return duct and nitrogen ingress pipe add compound (2-1-1-1A) 33.5g, 5% palladium carbon 1.68g, tetrahydrofuran 300mL and ethanol 150mL, are then slowly added to hydrazine monohydrate 28.5g, return within 2 hours Stream.After the completion of reaction, untill the solution decompression for filtering and obtaining through diatomite being concentrated into 300mL, ethyl acetate is added 300mL, carries out three points of liquid using water and cleans, then organic layer is concentrated under reduced pressure and the precipitate of generation was carried out Filter, vacuum drying, obtain 16.9g compound (2-1-1-1) therefrom.
[synthesis example 6：The synthesis of compound (2-1-2)]
Such as following flows 6 synthesis compound (2-1-2).
[changing 23]
Compound (2-1-2A)
Into 1L autoclave add compound (2-1-1-1A) 17.6g, 5% palladium carbon 0.88g, tetrahydrofuran 200mL and Ethanol 100mL, is blown into hydrogen untill 0.4MPa, reacts 4 hours at room temperature.After the completion of reaction, it will be filtered through diatomite And untill the filtered fluid obtained is concentrated under reduced pressure into 150mL, adds ethyl acetate 300mL and carry out three points of liquid using water and clean, Organic layer is concentrated under reduced pressure, it is solid, vacuum drying, therefrom obtain 14.5g compound (2-1-2A).
Compound (2-1-2B)
Compound (2-1-2A) 14.5g, 4- (uncle is added into the three-necked flask for the 1L for possessing nitrogen ingress pipe and thermometer Butoxycarbonylamino group) benzoic acid 10.7g and dichloromethane 400mL, ice bath is cooled to less than 5 DEG C.Next, addition 1- ethyls- 3- (3- dimethylaminopropyls) carbodiimide hydrochloride 9.49g and N, N- dimethyl aminopyridine 1.10g, react 2 at 5 DEG C Hour, diel is reacted at room temperature.After the completion of reaction, ethyl acetate 1L is added, and three points of liquid are carried out using water and is cleaned, After organic layer is dried using magnesium sulfate, concentrated, it is solid, be then again dissolved in tetrahydrofuran, utilize alumina tube Post (developing solvent；Chloroform: ethanol=9: 1) carry out point taking, concentrated, solid, therefrom acquisition 14.6g compound (2- 1-2B)。
Compound (2-1-2)
Compound (2-1-2B) 14.6g, dichloromethane are added into the eggplant type flask for the 500mL for possessing nitrogen ingress pipe 200mL and trifluoroacetic acid 100mL, and react 2 hours at room temperature.After the completion of reaction, be concentrated under reduced pressure, it is solid, add Ethyl acetate 300mL and tetrahydrofuran 300mL, and using saturated aqueous sodium carbonate carry out once, utilize water carry out three times points Liquid clean, then organic layer is concentrated, it is solid, vacuum drying, therefrom acquisition 9.24g compound (2-1-2).
[synthesis example 7：The synthesis of compound (3-1-1)]
Such as following flows 7 synthesis compound (3-1-1).
[changing 24]
Compound (3-1-1A)
Load N- (tert-butoxy carbonyls into the three-necked flask for the 500mL for possessing return duct, thermometer and nitrogen ingress pipe Base)-EDA 16.0g, acetonitrile 300mL, triethylamine 12.1g and 4- fluoronitrobenzene 14.1g, at 50 DEG C react Diel.After the completion of reaction, untill being concentrated under reduced pressure into 50mL, aluminum oxide tubing string (developing solvent is utilized；Chloroform: ethanol=8: 2) object is carried out after point taking, be concentrated under reduced pressure, solid.Secondly, dichloromethane 300mL and trifluoroacetic acid 150mL is added, React 2 hours at room temperature.After the completion of reaction, be concentrated under reduced pressure, it is solid, add ethyl acetate 200mL and tetrahydrofuran 200mL, and three points of liquid cleanings once, using water are carried out using saturated aqueous sodium carbonate progress, then entered using magnesium sulfate Row drying, be concentrated under reduced pressure, it is solid, vacuum drying, therefrom obtain 14.5g compound (3-1-1A).
Compound (3-1-1B)
4- nitrophenethyl isocyanides are added into the three-necked flask for the 1L for possessing dropping funel, thermometer and nitrogen ingress pipe Acid esters 15.4g and tetrahydrofuran 200mL.Load compound (3-1-1A) 14.5g and tetrahydrofuran 200mL in dropping funel, Spend after dropwise addition in 1 hour, be stirred at room temperature 1 hour.After the completion of reaction, it is concentrated under reduced pressure, precipitate is filtered, is entered The cleaning of row ethanol, vacuum drying, obtain 28.4g compound (3-1-1B) therefrom.
Compound (3-1-1)
Into the three-necked flask for the 500mL for possessing return duct and nitrogen ingress pipe load compound (3-1-1B) 28.4g, 5% palladium carbon 1.42g, tetrahydrofuran 300mL and ethanol 150mL, are then slowly added to hydrazine monohydrate 20.4g, return within 2 hours Stream.After the completion of reaction, untill the filtered fluid for filtering and obtaining through diatomite being concentrated under reduced pressure into 300mL, ethyl acetate is added 300mL, carries out three points of liquid using water and cleans, then organic layer is concentrated under reduced pressure and the precipitate of generation was carried out Filter, vacuum drying, obtain 20.4g compound (3-1-1) therefrom.
[synthesis example 8：The synthesis of compound (4-1-1)]
Such as following flows 8 synthesis compound (4-1-1).
[changing 25]
Compound (4-1-1A)
Compound (R-1) 14.9g, tetrahydrofuran 300mL are added into the eggplant type flask for the 500mL for possessing nitrogen ingress pipe And two carbonic acid-tert-butyl ester 24.0g, diel is stirred at room temperature.After the completion of reaction, reaction solution is concentrated under reduced pressure into 200mL Untill, it is injected into 2L methanol and the precipitation of generation is filtered, carries out methanol cleaning, vacuum drying, obtain therefrom 22.4g compound (4-1-1A).
Compound (4-1-1B)
Compound (4-1-1A) is added into the three-necked flask for the 1L for possessing dropping funel, thermometer and nitrogen ingress pipe 22.4g, is repeated vacuum/nitrogen displacement and will be dehydrated in system, then add the double (front threes of tetrahydrofuran 200mL and 1.3M Base silane base) acid amides lithium tetrahydrofuran solution 70mL, ice bath is cooled to less than 5 DEG C.Secondly, it is slowly added dropwise 4- nitrobenzene second Bromide 41.4g is dissolved in after the solution of 400mL tetrahydrofuran, is slowly added to methanol 70mL and is stopped reaction.Secondly, add Water 400mL and ethyl acetate 600mL, is removed after water layer, and then carries out three points of liquid cleanings using water.Secondly, magnesium sulfate is utilized After organic layer is dried, it is concentrated under reduced pressure and the precipitation of precipitation is filtered, dried, obtains 28.7g's therefrom Compound (4-1-1B).
Compound (4-1-1)
Compound (4-1-1B) 28.7g, 5% palladium carbon 1.44g, tetrahydrofuran 300mL and second are added into 1L autoclave Alcohol 150mL, is blown into hydrogen untill 0.4MPa, reacts 4 hours at room temperature.After the completion of reaction, will be through diatomite filtering Untill the filtered fluid of acquisition is concentrated under reduced pressure into 200mL, it is injected into 2L methanol and the precipitation of generation is filtered, carries out first Alcohol cleaning, vacuum drying, obtain 23.9g compound (4-1-1) therefrom.
[synthesis example 9：The synthesis of compound (1-5-1)]
Such as following flows 9 synthesis compound (1-5-1).
[changing 26]
Compound (1-5-1A)
Compound (4-1-1A) is added into the three-necked flask for the 1L for possessing dropping funel, thermometer and nitrogen ingress pipe 24.9g, is repeated vacuum/nitrogen displacement and will be dehydrated in system, then add the double (front threes of tetrahydrofuran 250mL and 1.3M Base silane base) acid amides lithium tetrahydrofuran solution 77mL, ice bath is cooled to less than 5 DEG C.Secondly, it is slowly added dropwise 4- nitrobenzoyls Acyl chlorides 37.1g is dissolved in after the solution of 400mL tetrahydrofuran, is slowly added to methanol 80mL and is stopped reaction.Secondly, add Water 500mL and ethyl acetate 600mL, is removed after water layer, and then carries out three points of liquid cleanings using water.Secondly, magnesium sulfate is utilized After organic layer is dried, it is concentrated under reduced pressure and the precipitation of precipitation is filtered, dried, obtains 31.9g's therefrom Compound (1-5-1A).
Compound (1-5-1)
Compound (1-5-1A) 39.1g, 5% palladium carbon 1.60g, tetrahydrofuran 300mL and second are added into 1L autoclave Alcohol 150mL, is blown into hydrogen untill 0.4MPa, reacts 4 hours at room temperature.After the completion of reaction, will be through diatomite filtering Untill the filtered fluid of acquisition is concentrated under reduced pressure into 200mL, it is injected into 2L methanol and the precipitation of generation is filtered, carries out first Alcohol cleaning, vacuum drying, obtain 26.5g compound (1-5-1) therefrom.
<The synthesis of polymer>
[polymerization example 1]
The 1R, 2S, 4S, 5R-1,2 of tetracarboxylic dianhydride, the molar part of 4,5- cyclopentanetetracarboxylic's dianhydride 100, conduct will be used as The molar part of compound 70 represented by the molar part of compound (1-1-1) 30 and following formula (D-1) of diamines is dissolved in N- methyl -2- In pyrrolidones (N-methy1-2-pyrrolidone, NMP), carry out reacting for 6 hours at room temperature, and obtain and contain 20 matter Measure the solution of % polyamic acids.Divide the polyamic acid solution for taking and being obtained on a small quantity, NMP is added, with the matter of polyamic acid concentration 10 Solution viscosity obtained by measuring % solution measure is 95mPas.Herein, the polyamic acid obtained is set to polymer (PAA- 1)。
[changing 27]
[polymerize example 2~polymerization example 11, compare polymerization example 1, compare polymerization example 2]
The species and amount of tetracarboxylic dianhydride and diamines, in addition, polymerize example with described as used in being changed table 1 below 1 is similarly respectively synthesized polyamic acid.In addition, on polymerization example 9, pyridine 100 is added in the polyamic acid solution obtained Molar part and the molar part of acetic anhydride 100,8 hours are spent at 90 DEG C and carries out chemical imidization.Will be anti-after chemical imidization Answer solution to concentrate, prepared in the way of concentration turns into 10 mass % using NMP.
[table 1]
In table 1, the numerical value of monomer composition represents each compound phase for the total amount 100 of the tetracarboxylic dianhydride used in polymerization The use ratio [molar part] of molar part.Being referred to as compound is as described below.
A-1：1R, 2S, 4S, 5R-1,2,4,5- cyclopentanetetracarboxylic's dianhydrides
D-2：Compound represented by following formula (D-2)
D-3：Compound represented by following formula (D-3)
D-4：2,2 '-dimethyl -4,4 '-benzidine
[changing 28]
[embodiment 1]
<The preparation of aligning agent for liquid crystal>
To the mass parts of polymer (PAA-1) 20 and the polymerization example obtained in the polymerization example 1 as polymer Obtained in 10 the mass parts of polymer (BPA) 80 and the N as epoxy additive, N, N ', N '-four glycidyl group [4, 4 '-methylene dianiline] (compound represented by following formula (e-1)) 5 mass parts (are total 100 matter relative to polymer Measure the amount of part) the middle NMP and butyl cellosolve (butyl cellosolve, BC) added as organic solvent, solvent group is made As NMP: BC=50: 50 (mass ratioes), the solution that solid component concentration is 4.0 mass %.Use the filter that aperture is 1 μm The solution is filtered, aligning agent for liquid crystal (G-1) is prepared therefrom.
[changing 29]
<The evaluation of the foreign matter amount produced by friction treatment>
The aligning agent for liquid crystal (G-1) of the preparation is coated on the glass with the transparency electrode comprising ito film using spin coating The transparency electrode face of glass substrate, after (prebake conditions) 1 minute are heated on 80 DEG C of hot plate and solvent is removed, in 230 DEG C of cleaning In heated under nitrogen (rear baking) 15 minutes in baking oven, forms film of the average film thickness for 100nm.Using with being tied with cotton The rubbing machine of roller, by 1000rpm of roller rotating speed, platform translational speed be 2cm/ seconds, fine hair press-in length be that 0.4mm is applied to described Film implements 5 friction treatments, and obtains foreign matter amount evaluation substrate.The foreign matter amount evaluation obtained using observation by light microscope With the foreign matter on substrate, the foreign matter number in the region of 500 μm of 500 μ m is calculated, and judge rub resistance using following benchmark.
Foreign matter amount ×：Foreign matter number in the region of 500 500 μm of μ ms is more than 10
Foreign matter amount △：Foreign matter number in the region of 500 500 μm of μ ms is 5~10
Foreign matter amount zero：Foreign matter number in the region of 500 500 μm of μ ms is less than 4
As a result, unconfirmed in embodiment 1 arrive foreign matter, the rub resistance of the film is good.
<The manufacture of friction orientation liquid crystal cells>
As substrate one side have comprising the patterned chromium for comb teeth-shaped two system metal electrode (electrode A and Electrode B) glass substrate on, the aligning agent for liquid crystal (G-1) of the preparation is coated with using circulator, is carried out on 80 DEG C of hot plate After the prebake conditions of one minute, toasted after being carried out 10 minutes on 230 DEG C of hot plate, and form thickness about 80nm film.Use The rubbing machine of roller with the cloth for being tied with nylon, by 1000rpm of roller rotating speed, platform translational speed be 25mm/ seconds, fine hair pressure Enter length and friction treatment is implemented to the coated surface formed by 0.4mm, and assign liquid crystal aligning ability.And then, in ultra-pure water Ultrasonic wave cleaning in one minute is carried out to the substrate, dries 10 minutes, is thus manufactured with comb in 100 DEG C of cleaning oven There is the substrate of liquid crystal orientation film on the face of the chromium electrode of dentation.The substrate with liquid crystal orientation film is set to " substrate A ".
In addition, the thickness 1mm without electrode glass substrate one side, taken with the liquid crystal that is identically formed To the film and progress friction treatment of agent, and cleaned and dried, and manufacture the substrate on one side with liquid crystal orientation film. The substrate with liquid crystal orientation film is set to " substrate B ".
Then, the outer rim coating addition in the face of the liquid crystal orientation film with rubbed processing of substrate has a diameter of 5.5 μ After the epoxy resin adhesive of m alumina balls, antiparallel mode is turned into the frictional direction in each liquid crystal orientation film, by two Block substrate A, substrate B are oppositely disposed across gap, abut outer edge each other and are crimped and harden bonding agent.Then, certainly Liquid crystal injecting port between a pair of substrates to filling after nematic liquid crystal (Merck ＆ Co., Inc. manufactures, MLC-2042), with acrylic acid series photo-hardening Bonding agent seals liquid crystal injecting port, and the liquid crystal cells of lateral electric field type are manufactured therefrom.
<The evaluation of image retention characteristic (burning attached characteristic)>
The liquid crystal cells of the manufacture are positioned over 25 DEG C, in the environment of 1 air pressure, voltage are not applied to electrode B, and to electricity Pole A applies the alternating voltage 3.5V and DC voltage 5V of 2 hours resultant voltage.Thereafter both electrode A and electrode B are applied at once Plus exchange 4V voltage.Determining from the time point for starting the voltage that two electrodes are applied with exchange 4V extremely can not visually confirm electricity Time untill the difference of pole A and the photopermeability of electrode B.The time is evaluated as AC image retentions spy for the situation within 50 seconds Property " very good (◎) ", " good (zero) " will be evaluated as more than 50 seconds and less than the situation of 100 seconds, by more than 100 seconds and not The situation of full 150 seconds is evaluated as " can (△) ", and the situation more than 150 seconds is evaluated as " bad (×) ".As a result, institute State in embodiment and be evaluated as " very good (◎) ".
<The evaluation of voltage retention>
After the liquid crystal cells of the manufacture are applied with the 5V of 60 microseconds voltage and is applied with 167 milliseconds of span, Determine the voltage retention after 167 milliseconds from applying and releasing.Voltage retention is set to " very good for more than 99.5% (◎) ", " good (zero) " is set to by more than 99.0% and less than 99.5%, by more than 98.0% and be set to less than 99.0% " can (△) ", will be set to " bad (×) " less than 98.0%, as a result in the embodiment voltage retention be judged as it is " very good (◎)”.Furthermore, as the measure device of voltage retention, use Dongyang Te Kenika (Toyo Technica) (stock) company system The model name " VHR-1 " made.
<Utilize the evaluation of low temperature calcination>
Rear baking temperature is changed to 150 DEG C from 230 DEG C, in addition, carried out in the same manner as described because of friction treatment The evaluation of the foreign matter amount of generation, and manufacture friction orientation is with liquid crystal cells and carries out the evaluation of image retention characteristic and voltage retention. As a result, evaluation during with rear baking temperature being set into 230 DEG C on an equal basis can be obtained in embodiment, it is resistance to even if carrying out low temperature calcination Frictional property, voltage retention and AC image retention characteristics are also good.
[2~embodiment of embodiment 9, comparative example 1, comparative example 2]
Respectively as table 2 below record change used in polymer species and composition, in addition, using with the reality Apply the same method of example 1 and prepare aligning agent for liquid crystal respectively.In addition, on each aligning agent for liquid crystal, entering in the same manner as the embodiment 1 The evaluation for the foreign matter amount that row is produced by friction treatment, and the liquid crystal cells of manufacture horizontal electric field type, carry out image retention characteristic and voltage The evaluation of conservation rate.On 2~embodiment of embodiment 9 and comparative example 1, comparative example 2, similarly to Example 1 on after two kinds (230 DEG C, 150 DEG C) of baking temperature carries out various evaluate.These results are shown in table 2 below.
[table 2]
As shown in table 2, the AC image retentions characteristic of the aligning agent for liquid crystal (1~embodiment of embodiment 18) comprising polymer [P] and Being evaluated as of voltage retention " very good (◎) " or " good (zero) ", and the evaluation of rub resistance is "○", various spies Property obtain balance.On the other hand, for 1~comparative example of comparative example 4 without polymer [P] is compared to 1~embodiment of embodiment 9 Rub resistance, AC image retentions characteristic and voltage retention at least any one is poor.In addition, in embodiment, even if being toasted by after In the case that temperature drop is 150 DEG C, good result is also showed that in various evaluations, on the other hand, in a comparative example, because Decline rear baking temperature, as a result hydraulic performance decline.In this way, according to the aligning agent for liquid crystal of the disclosure comprising polymer [P], it is known that Can obtain film rub resistance is good and AC image retentions characteristic and the good liquid crystal cell of voltage retention.
<The synthesis of polymer>
[polymerize example 12~polymerization example 15 and compare polymerization example 3]
The species and amount of tetracarboxylic dianhydride and diamines, in addition, polymerize example with described as used in being changed Table 3 below 1 is similarly respectively synthesized polyamic acid.In addition, on the polyamic acid solution obtained, chemistry is carried out in the same manner as polymerization example 9 Imidizate, is respectively synthesized polyimides.
[table 3]
In table 3, the numerical value of monomer composition represents each compound phase for the total amount 100 of the tetracarboxylic dianhydride used in polymerization The use ratio [molar part] of molar part.Being referred to as compound is as described below.
A-2：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydrides
D-5：Cholesteric alkyl oxy -2,4- diaminobenzene
[polymerization example 16]
The molar part of p-phenylenediamine 100 as diamines, the molar part of pyridine 220 as alkali are added, and is dissolved in NMP.Its It is secondary, the diamine solution is simultaneously stirred, following formula (ta-1) institute table as tetracarboxylic acid derivatives of 100 molar parts is simultaneously added The compound shown, reacts 24 hours at 15 DEG C.After stirring 24 hours, the acryloyl chloride of 30 molar parts is added, at 15 DEG C Reaction 4 hours.The solution of the poly amic acid ester obtained is put into 2- propyl alcohol when stirring, to the white precipitate of precipitation Filtered.Then, 5 cleanings are carried out using 2- propyl alcohol, and is subject to drying, the poly amic acid ester resin of white is obtained therefrom Powder (is set to polymer (PAE1)).The solution viscosity of polymer (PAE1) is 96mPas.
[changing 30]
[polymerization example 17]
In the reaction vessel for possessing mixer, thermometer, dropping funel and the cooling tube that flows back, load 2- (3,4- epoxies Butylcyclohexyl) ethyl trimethoxy silane 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, mix at room temperature. Then, 30 minutes are spent from dropping funel to be added dropwise after deionized water 100g, is mixed under reflux, and reaction 6 is small at 80 DEG C When.After the completion of reaction, organic layer is taken out, it is carried out to clean using 0.2 mass % aqueous ammonium nitrate solutions until after cleaning Untill water is changed into neutrality, under reduced pressure by solvent and water distillation remove, thus using in the form of sticky transparency liquid obtain as The polymer (EPS1) of polysiloxane containing epoxy radicals.The polymer (EPS1) is carried out1H-NMR is analyzed, as a result really Recognize the peak value based on oxiranyl for being obtained near chemical deviation (δ)=3.2ppm and meeting theoretical strength, in the reaction The side reaction of epoxy radicals is not caused.The weight average molecular weight of the polymer (EPS1) is 2,200, and epoxide equivalent is 186g/ Mole.
Then, polymer (EPS1) 9.3g, the methyl iso-butyl ketone (MIBK) of the acquisition are loaded in 100mL three-necked flask Compound 5.6g represented by 26g, following formula (CA-1) (rubs the 20 of the silicon atom having equivalent to polymer (EPS1) You are %) and trade name " UCAT 18X " (the level Four amine salt of Sanya general sieve (San-Apro) company manufacture) 0.10g, at 80 DEG C, 12 are stirred small to be reacted at present.After the completion of reaction, reactant mixture is put into methanol and returns the sediment of generation Receive, be dissolved in ethyl acetate and solution is made, distillation removes solvent after the solution is washed three times, thus with white powder The form at end obtains the 14.7g polymer (ESSQ1) as polysiloxane.The weight of the polymer (ESSQ1) is put down Average molecular weight Mw is 8000.
[changing 31]
[embodiment 19]
<The preparation of aligning agent for liquid crystal>
Adding to be used as in the mass parts of polymer (PI-2) 100 obtained in the polymerization example 12 as polymer has The NMP and butyl cellosolve (BC) of machine solvent, are made solvent group as NMP: BC=50: 50 (mass ratioes), solid component concentration For 4.0 mass % solution.The solution is filtered for 1 μm of filter using aperture, liquid crystal aligning is prepared therefrom Agent (G-19).
<Adhesion evaluation to substrate>
The aligning agent for liquid crystal (G-19) of the preparation is coated on the glass with the transparency electrode comprising ito film using spin coating The transparency electrode face of glass substrate, after (prebake conditions) 1 minute are heated on 80 DEG C of hot plate and solvent is removed, in 230 DEG C of cleaning In heated under nitrogen (rear baking) 15 minutes in baking oven, forms film of the average film thickness for 100nm.Using with being tied with cotton The rubbing machine of roller, by 1000rpm of roller rotating speed, platform translational speed be 2cm/ seconds, fine hair press-in length be that 0.4mm is applied to described Film implements 5 friction treatments and applies load to film, and obtains adhesion evaluation substrate.Obtained using observation by light microscope The foreign matter on adhesion evaluation substrate obtained, calculates the foreign matter number in the region of 500 μm of 500 μ m, and utilize following base Standard judges adhesion.Furthermore, film is better to the adhesion of substrate, even if then applying load to film, foreign matter number is also few, so that good It is good.
Foreign matter amount ×：Foreign matter number in the region of 500 500 μm of μ ms is more than 10
Foreign matter amount △：Foreign matter number in the region of 500 500 μm of μ ms is 5~10
Foreign matter amount zero：Foreign matter number in the region of 500 500 μm of μ ms is less than 4
As a result, unconfirmed in embodiment 19 arrive foreign matter, the adhesion of the film is good.
<The manufacture of VA type liquid crystal cells>
Prepare two pieces of glass substrates for carrying the transparency electrode comprising ito film, using spin coater by the liquid crystal of the preparation Alignment agent (G-19) is coated on each transparency electrode face.Then, 1 minute prebake conditions is carried out on 80 DEG C of hot plate, then right (rear baking) 30 minutes is heated in the baking oven that nitrogen displacement is carried out in storehouse at 230 DEG C, thickness about 80nm film is formed.After And, the outer rim coating addition in the face with liquid crystal orientation film of one of substrate in a pair of substrates has a diameter of 5.5 μm Alumina balls epoxy resin adhesive after, so that the relative mode of liquid crystal aligning film surface to a pair of substrates overlap crimping Harden bonding agent.Then, from liquid crystal injecting port to filling nematic liquid crystal between a pair of substrates (Merck ＆ Co., Inc. manufactures, MLC-6608) Afterwards, liquid crystal injecting port is sealed with acrylic acid series photo-hardening bonding agent, and manufactures liquid crystal cells.
<The evaluation of voltage retention>
To the VA type liquid crystal cells of the manufacture, the evaluation of voltage retention is carried out similarly to Example 1, it is as a result described Voltage retention is evaluated as " very good (◎) " in embodiment.
[20~embodiment of embodiment 26 and comparative example 5, comparative example 6]
Respectively as table 4 below record change used in polymer species and composition, in addition, using with the reality Apply the same method of example 19 and prepare aligning agent for liquid crystal respectively.In addition, for each aligning agent for liquid crystal, in the same manner as the embodiment 19 The evaluation to the adhesion of substrate is carried out, and manufactures VA types liquid crystal cells and determines voltage retention.These results are shown in down State in table 4.
[embodiment 27]
<The preparation of aligning agent for liquid crystal>
The mass parts of polymer (PAA-1) 60 and polymerization example obtained in the polymerization example 1 as polymer The NMP and butyl cellosolve (BC) as organic solvent are added in the mass parts of polymer (PAE1) 40 obtained in 16, is made Solvent group turns into the solution that NMP: BC=50: 50 (mass ratioes), solid component concentration are 4.0 mass %.The use of aperture it is 1 μm Filter is filtered to the solution, and aligning agent for liquid crystal (G-27) is prepared therefrom.
<Adhesion evaluation to substrate>
Using aligning agent for liquid crystal (G-27), in addition, the adhesion to substrate is carried out in the same manner as the embodiment 19 Evaluate.As a result, unconfirmed in the embodiment arrive foreign matter, the adhesion of film is good.
<The manufacture of the liquid crystal cells handled using light orientation>
By the glass substrate with the metal electrode comprising the patterned chromium for comb teeth-shaped, be not provided with electrode to Glass substrate is set to a pair, and the polymer composition (G-27) of the preparation is coated on into glass substrate respectively using spin coater Face with electrode and to the one side to glass substrate.Then, 1 minute prebake conditions is carried out on 80 DEG C of hot plate, in storehouse Carry out heating (rear baking) 1 hour in the baking oven of nitrogen displacement at 230 DEG C.Then, using Hg-Xe lamps and Glan-Taylor's rib Mirror (Glan-Taylor Prism) is with 2,000J/m2Exposure from the vertical direction of real estate to being coated with aligning agent for liquid crystal (G-27) the polarisation ultraviolet of open-wire line of the substrate surface irradiation comprising 254nm of side.Furthermore, the exposure is used with ripple The quantometer determined on the basis of long 254nm be measured obtained by value.Then, carry out heating for 10 minutes on 230 DEG C of hot plate. A pair of substrates of the liquid crystal orientation film with about 0.1 μm of thickness are obtained therefrom.
Then, the epoxy resin adhesive for adding the alumina balls for there are a diameter of 3.5 μm is coated with using silk-screen printing Behind the periphery in the face with liquid crystal orientation film of one piece of substrate in a pair of substrates, face the liquid crystal orientation film of a pair of substrates To the mode in opposite direction of each substrate during with irradiation polarisation ultraviolet is overlapped and crimped, and 1 hour is spent at 150 DEG C will Bonding agent thermmohardening.Then, from liquid crystal injecting port to the liquid crystal " MLC-7028 " of the gap filling Merck ＆ Co., Inc. manufacture between substrate Afterwards, liquid crystal injecting port is sealed using epoxy bonding agent.And then, in order to remove liquid crystal injection when flow orientation, and by its Untill being slowly cooled down to room temperature after being heated at 150 DEG C, so as to obtain liquid crystal cells.
<The evaluation of voltage retention>
To the liquid crystal cells manufactured using optical alignment method, the evaluation of voltage retention is carried out similarly to Example 1, as a result Voltage retention is evaluated as " very good (◎) " in the embodiment.
[28~embodiment of embodiment 30 and comparative example 7]
Respectively as table 4 below record change used in polymer species and composition, in addition, using with the reality Apply the same method of example 27 and prepare aligning agent for liquid crystal respectively.In addition, for each aligning agent for liquid crystal, in the same manner as the embodiment 19 Carry out the evaluation to the adhesion of substrate, and the liquid crystal in the same manner as the embodiment 27 using optical alignment method manufacture horizontal electric field type Unit simultaneously determines voltage retention.These results are shown in table 4 below.
[table 4]
As shown in table 4, it is known that according to the aligning agent for liquid crystal for including polymer [P], it can obtain good to the adhesion of substrate Liquid crystal orientation film, and the VA type liquid crystal display cells for showing high voltage retention can be obtained.In addition, on being taken using light The liquid crystal display cells manufactured to method, can obtain the result for showing high voltage retention.

Claims (7)

1. a kind of aligning agent for liquid crystal, it is characterised in that：Containing selected from being made up of polyamic acid, poly amic acid ester and polyimides At least one of group and with the polymer [P] of the part-structure represented by following formula (0)；
In formula (0),
R1For with cyclic group and-NR3- at least one of base and alkane diyl bilvalent radical or-X20-R20-*1, wherein R3For hydrogen Atom or any monovalent organic radical, X20For singly-bound, ehter bond, thioether bond or ester bond, R20For alkane diyl, *1Represent the nitrogen being bonded in urea bond The associative key of atom；R2For divalent organic base；R6For cyclic group；Wherein, in R1For-X20-R20-*1In the case of, R2For with urea Divalent organic base, divalence chain alkyl or the divalence alicyclic type hydrocarbon of key；* associative key is represented.
2. aligning agent for liquid crystal according to claim 1, it is characterised in that：The polymer [P], which has, is derived from following formula (1) The construction unit of represented diamines；
In formula (1), R1And R2It is respectively identical meanings with the formula (0).
3. aligning agent for liquid crystal according to claim 1 or 2, it is characterised in that：The R1For the base represented by following formula (2), The base represented by base or following formula (4) represented by following formula (3)；
In formula (2), A1For the divalent organic base with cyclic group, singly-bound, methylene, ethylidene, ehter bond, thioether bond or ester bond, a For 1~6 integer；Wherein, in A1In the case of for singly-bound, methylene, ethylidene, ehter bond, thioether bond or ester bond, the R2For Divalence chain alkyl or alicyclic type hydrocarbon；In formula (3), B1For singly-bound or bivalence linking base, A2For singly-bound or cyclic group, R3For hydrogen Atom or any monovalent organic radical, b are 1~6 integer；In formula (4), A3For the divalent organic base with cyclic group, c for 1~6 it is whole Number；* the associative key with the nitrogen-atoms in urea bond is represented.
4. a kind of liquid crystal orientation film, it is characterised in that：It is taken using liquid crystal according to any one of claim 1 to 3 To liquid crystal orientation film formed by agent.
5. a kind of liquid crystal cell, it is characterised in that：Including liquid crystal orientation film according to claim 4.
6. a kind of polymer, it is characterised in that：It is selected from the group being made up of polyamic acid, poly amic acid ester and polyimides Group at least one of and be derived from following formula (1) represented by compound construction unit；
In formula (1), R1For with cyclic group and-NR3- at least one of base and alkane diyl bilvalent radical or-X20-R20-*1, its Middle R3For hydrogen atom or any monovalent organic radical, X20For singly-bound, ehter bond, thioether bond or ester bond, R20For alkane diyl, *1Expression is bonded to urea The associative key of nitrogen-atoms in key；R2For divalent organic base；Wherein, in R1For-X20-R20-*1In the case of, R2For with urea bond Divalent organic base, divalence chain alkyl or divalence alicyclic type hydrocarbon.
7. a kind of diamines, it is characterised in that：It is represented by following formula (1)；
In formula (1), R1For with cyclic group and-NR3- at least one of base and alkane diyl bilvalent radical or-X20-R20-*1, its Middle R3For hydrogen atom or any monovalent organic radical, X20For singly-bound, ehter bond, thioether bond or ester bond, R20For alkane diyl, *1Expression is bonded to urea The associative key of nitrogen-atoms in key；R2For divalent organic base；Wherein, in R1For-X20-R20-*1In the case of, R2For with urea bond Divalent organic base, divalence chain alkyl or divalence alicyclic type hydrocarbon.
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