CN104927880B - Compound, polymer, aligning agent for liquid crystal, liquid crystal orientation film and display element - Google Patents

Compound, polymer, aligning agent for liquid crystal, liquid crystal orientation film and display element Download PDF

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CN104927880B
CN104927880B CN201510096641.6A CN201510096641A CN104927880B CN 104927880 B CN104927880 B CN 104927880B CN 201510096641 A CN201510096641 A CN 201510096641A CN 104927880 B CN104927880 B CN 104927880B
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liquid crystal
mda
aligning agent
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compound
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CN104927880A (en
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植阪裕介
菅野尚基
秋池利之
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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

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Abstract

The present invention provides a kind of compound, polymer, aligning agent for liquid crystal, liquid crystal orientation film and display element.The aligning agent for liquid crystal can be formed after long-term and the liquid crystal orientation film of the decline of voltage retention less, excellent in reliability.Aligning agent for liquid crystal contains the polymer with structure represented by formula (1).*‑X1‑(CR1 2)m1‑Y‑(CR1 2)m2‑X2‑*(1) in formula (1), X1And X2For singly-bound, oxygen atom, sulphur atom, carbonyl or ester bond, X1And X2Two will not be singly-bound simultaneously, Y is the group for removing 2 hydrogen atoms from the heteroaromatic compound of 5 member rings or 6 member rings and obtaining, heteroaromatic compound is selected from one or more of the group as composed by nitrogen-atoms, oxygen atom and sulphur atom hetero atom comprising 1 or 2 in ring structure, and there are multiple R1For hydrogen atom or fluorine atom, the integer that m1 and m2 are 0~20, and " * " respectively indicates associative key.

Description

Compound, polymer, aligning agent for liquid crystal, liquid crystal orientation film and display element
Technical field
The present invention relates to a kind of compound, polymer, aligning agent for liquid crystal and liquid crystal display elements.Specifically, this hair Even if it is bright be related to it is a kind of can be formed under harsh use condition after long-term, the decline of voltage retention is also few, and reliability is excellent The aligning agent for liquid crystal of different liquid crystal orientation film, and after long-term and liquid crystal display element that display quality will not deteriorate.
Background technique
Liquid crystal display element can be classified as various modes according to the physical property of electrode structure and used liquid crystal molecule. Such as it has been known that there is the liquid crystal display devices of following mode etc.：
So-called twisted nematic (Twisted Nematic, TN) type (patent document 1), such as it is being provided with electrically conducting transparent The substrate surface of film forms liquid crystal orientation film as substrate used for liquid crystal display element, and 2 pieces of substrates is oppositely disposed, at it The layer with the nematic crystal of positive dielectric anisotropy is formed in gap, and the unit of interlayer (sandwich) structure is made, The long axis of liquid crystal molecule is set continuously to reverse 90 ° from one of substrate towards another piece of substrate；
STN Super TN (Super Twisted Nematic, STN) type (patent document 2), can be realized than TN type liquid crystal The high duty ratio of display element (Duty ratio)；
Vertically oriented (Vertical Alignment, VA) type (patent document 3), injection has negative Jie in clearance between poles The layer of the nematic crystal of electrical anisotropy, is orientated liquid crystalline phase substrate generally perpendicularly；
In-plane switching (In-Plane Switching, IPS) type (patent document 4 and patent document 5), by by electrode pair It is configured to comb teeth-shaped in one piece of real estate, then the driving direction of liquid crystal when electric field applies only becomes direction in real estate；
Fringing field switches (Fringe Field Switching, FFS) type (patent document 6), by the electrode structure of IPS type It is changed, improves the aperture opening ratio of display element part, increase brightness；
Optical compensation curved (Optical Compensated Bend, OCB) type (patent document 7), visual angle interdependence is few, And the high speed responsiveness of image frame is excellent.
Material as the liquid crystal orientation film in these various liquid crystal display elements, it is known to polyamic acid, polyimides, The resin materials such as polyamide, polyester, the liquid crystal orientation film especially comprising polyamic acid or polyimides is due to heat resistance, machine It is tool intensity, excellent with the compatibility of liquid crystal etc., so for (patent document 8) in plurality of liquid crystals display element.
In aligning agent for liquid crystal as described above, in recent years, it is desirable that reliability (to the long-time stability of harsh environment) compared with It is preceding to be also improved.The situation is as described below.
It is general in recent years compared with primary way, that is, PC of existing liquid crystal display element, monitor display etc. And significant LCD TV period that requires to purchase on a barter basis is long, is originally just the long-life.Herein, it is used as home theater (home in recent years Theater in the liquid crystal display element for the liquid crystal projection apparatus purposes that needs) improve, due to using metal halide lamp etc. to irradiate The very high light source of intensity, so the tolerance to light and heat becomes big problem.In addition, the mobile devices such as mobile phone use or vehicle-mounted The visibility under the sunlight comprising strong ultraviolet light is improved with the liquid crystal display element of auto navigation, it is necessary to mention The brightness of high backlight, therefore more worry the deterioration of early stage.Moreover, use these equipment as the display of video game In the case of, it can imagine and be placed under extremely prolonged Continuous Drive under the described conditions.
As described above, high-intensitive light irradiation, long-time can be exposed to multipurpose etc. in liquid crystal display element In the harsh environment that driving etc. is not considered in the past, and require further long lifetime.
In existing known liquid crystal orientation film, have been pointed out insufficient for the tolerance of the harsh environment.
[existing technical literature]
[patent document]
[patent document 1] Japanese Patent Laid-Open 4-153622 bulletin
[patent document 2] Japanese Patent Laid-Open No. Sho 60-107020 bulletin
[patent document 3] Japanese Patent Laid-Open 11-258605 bulletin
[patent document 4] Japanese Patent Laid-Open No. Sho 56-91277 bulletin
No. 5,928,733 specifications of [patent document 5] U.S. Patent No.
[patent document 6] Japanese Patent Laid-Open 2002-082357 bulletin
[patent document 7] Japanese Patent Laid-Open 9-105957 bulletin
[patent document 8] Japanese Patent Laid-Open No. Sho 62-165628 bulletin
Summary of the invention
[the problem of invention is to be solved]
The present invention is formed in view of the situation, its purpose is to provide a kind of aligning agent for liquid crystal, can be formed after The liquid crystal orientation film of long-term and voltage retention decline less, excellent in reliability.
Another object of the present invention is to provide a kind of excellent liquid crystal display element, after long-term, display quality is not It can deteriorate.
[technical means to solve problem]
According to the present invention, first, the purpose of the invention and advantage are reached by a kind of aligning agent for liquid crystal, special Sign is：
Contain the polymer with structure represented by following formula (1).
*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-* (1)
(in formula (1), X1And X2It is separately singly-bound, oxygen atom, sulphur atom, carbonyl or ester bond, wherein X1And X2Two A will not be singly-bound simultaneously,
Y is the group for removing 2 hydrogen atoms from the heteroaromatic compound of 5 member rings or 6 member rings and obtaining, the heteroaryl Fragrant compounds of group includes 1 or 21 in the group as composed by nitrogen-atoms, oxygen atom and sulphur atom in ring structure Kind or more hetero atom, wherein 2 associative keys of Y directly come from 5 member ring or 6 member rings,
There are multiple R1It is separately hydrogen atom or fluorine atom,
M1 and m2 is separately 0~20 integer, and
" * " respectively indicates associative key)
Second, the purpose of the invention and advantage are reached by a kind of liquid crystal display element, it is characterised in that：
Including the liquid crystal orientation film formed by the aligning agent for liquid crystal.
[The effect of invention]
Through the invention, providing one kind can form after long-term and the liquid of the decline of voltage retention less, excellent in reliability The aligning agent for liquid crystal of brilliant alignment films.
Liquid crystal display element of the invention including the liquid crystal orientation film formed by the aligning agent for liquid crystal after long-term and Display quality will not deteriorate.
Therefore, technology of the invention can be suitably applied such as LCD TV, liquid crystal projection apparatus, mobile phone, portable game The purposes such as machine, information display.
Detailed description of the invention
Fig. 1 is the general of the electrode pattern in the liquid crystal cells for indicating to manufacture in embodiment 12 and comparative example 6 and comparative example 7 Sketch map
Specific embodiment
Aligning agent for liquid crystal of the invention contains the polymer with structure represented by the formula (1).
Y in the formula (1) can for example enumerate the represented group of following formula difference.
[changing 1]
(in the formula, R is the alkyl of hydrogen atom or carbon number 1~6；
X is separately the alkene of halogen atom, the alkyl of carbon number 1~20, the fluoroalkyl of carbon number 1~20, carbon number 2~20 The Fluoroalkyloxy of base, the alkoxy of carbon number 1~20 or carbon number 1~20；
N1 and n4 is separately 0~2 integer；
N2 is 0 or 1；
N3 is separately 0~3 integer；And
" * " respectively indicates associative key)
The alkyl of R in above formula is preferably the alkyl of carbon number 1~3, specifically, being for example more preferably methyl, ethyl, just Propyl or isopropyl.The halogen atom of X can for example enumerate fluorine atom, chlorine atom, bromine atom and iodine atom.The alkyl of X is for example It can enumerate：Methyl, ethyl, n-propyl, isopropyl etc.；
Fluoroalkyl can for example be enumerated：Trifluoromethyl, 2,2,2- trifluoroethyl etc.；
Alkenyl can for example be enumerated：Vinyl, allyl etc.；
Alkoxy can such as be enumerated：Methoxyl group, ethyoxyl, positive propoxy etc.；
Fluoroalkyloxy can for example be enumerated：Trifluoromethoxy, 2,2,2- trifluoro ethoxy etc..N1, n4 and n5 are separately Preferably 0 or 1, more preferably 0.
Y in the formula (1) is particularly preferably sub-pyridyl group (pyridinylene), most preferably 2,5- sub-pyridyl group, 2,6- sub-pyridyl group or 3,5- sub-pyridyl group.
R in the formula (1)1Preferably hydrogen atom；
M1 and m2 in the formula (1) are separately preferably 0~2 integer.
X in the formula (1)1And X2When for ester bond, bond direction be any, but is preferably the carbonyl carbon of the ester bond Positioned inside.X1And X2Preferably one of them is oxygen atom or ester bond, another is singly-bound, oxygen atom or ester bond.
Structure represented by the formula (1) is particularly preferably the structure that for example following formula difference is represented.
[changing 2]
(" * " in the formula respectively indicates associative key)
As long as polymer contained in aligning agent for liquid crystal of the invention has the poly- of structure represented by the formula (1) Close object, then it in addition to this, can be without any appropriate use in restriction ground.Polymer contained in aligning agent for liquid crystal of the invention is preferred To have structure represented by the formula (1) on the main chain of the polymer.
Herein, the main chain of so-called polymer refers to the part of " dry " in polymer comprising longest atomic link.It is so-called There is structure represented by the formula (1) on main chain, refer to that the structure constitutes a part of main chain.In this case, the formula (1) Represented structure can be present in main chain, but and be not prohibited by the structure and be overlappingly present in the part other than main chain, such as side Chain (part that " dry " top set of auto polymerization object goes out).
Polymer with structure represented by the formula (1) contained in aligning agent for liquid crystal of the invention can for example arrange It lifts：With the polyamic acid of structure represented by the formula (1), the imide amination polymer of polyamic acid, poly amic acid ester, gather Organosiloxane, polyester, polyamide, cellulose derivative, polyacetals, polystyrene derivative, poly- (styrene-phenyl is along fourth Alkene imidodicarbonic diamide) derivative, poly- (methyl) acrylate etc..In these polymer, it is preferable to use be selected from by polyamic acid, gather The polymerization of one or more of group composed by the imide amination polymer of amic acid, poly amic acid ester and polysiloxane Object,
More preferably using poly- selected from one or more of group as composed by polyamic acid and its imide amination polymer Close object.
The polyamic acid can for example be preferably synthesized using following methods：
Make the tetracarboxylic dianhydride comprising the tetracarboxylic dianhydride with structure represented by the formula (1), carried out instead with diamines The method answered；Or
The side for making tetracarboxylic dianhydride, being reacted with the diamines comprising the diamines with structure represented by the formula (1) Method.
The imide amination polymer of the polyamic acid can be by carrying out dehydration closed-loop for the polyamic acid, by amic acid The all or part of structure carries out imidizate and obtains.
Polymer contained in aligning agent for liquid crystal of the invention be selected from by
It reacts tetracarboxylic dianhydride with the diamines comprising the diamines with structure represented by the formula (1) and obtains Polyamic acid and
The imide amination polymer that the polyamic acid is subjected to dehydration closed-loop and is obtained
One or more of composed group polymer.
Hereinafter, being illustrated to the synthetic method of the polymer particularly preferably contained in aligning agent for liquid crystal of the invention.
Workable tetracarboxylic dianhydride can for example arrange in the synthesis of polyamic acid with structure represented by the formula (1) Lift aliphatic tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride etc..Tool as these tetracarboxylic dianhydrides Body example, aliphatic tetracarboxylic dianhydride can for example enumerate：Butane tetracarboxylic acid dianhydride etc.；
Ester ring type tetracarboxylic dianhydride can for example enumerate：1,2,3,4- cyclobutane tetracarboxylic dianhydride, 2,3,5- tricarboxylic basic ring penta Guanidine-acetic acid dianhydride, 1,3,3a, 4,5,9b- hexahydro -5- (tetrahydro -2,5- dioxo -3- furyl)-naphtho- [1,2-c] furans -1, 3- diketone, 1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydro -2,5- dioxo -3- furyl)-naphtho- [1,2-c] furan It mutters -1,3- diketone, 3- oxabicyclo [3.2.1] octane -2,4- diketone -6- loop coil -3'- (tetrahydrofuran -2', 5'- diketone), 5- (2,5- dioxotetrahydro -3- furyl) -3- methyl -3- cyclohexene -1,2- dicarboxylic anhydride, 5- (2,5- dioxotetrahydro furans - 3- yl) -3a, 4,5,9b- tetrahydro naphtho- [1,2-c] furans -1,3- diketone, tri- carboxyl -2- carboxymethyl group norbornane of 3,5,6- - 2:3,5:6- dianhydride, bicyclic [3.3.0] octane -2,4,6,8- tetrabasic carboxylic acid 2:4,6:8 dianhydrides, 4,9- dioxa tricyclic [5.3.1.02,6] hendecane -3,5,8,10- tetrone etc.；
Aromatic tetracarboxylic dianhydride can for example be enumerated：Pyromellitic acid anhydride etc., in addition to this,
The tetracarboxylic dianhydride recorded in Japan Patent Patent 2009-157556 can be used.
Tetracarboxylic dianhydride used in the synthesis of the polyamic acid preferably includes the ester ring type tetrabasic carboxylic acid two in described Acid anhydride,
More preferably comprising selected from bicyclic by 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, 2,4,6,8- tetracarboxylic [3.3.0] octane -2:4,6:8- dianhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylic dianhydride with And 1, it is at least one kind of in group composed by 2,3,4- pentamethylene tetracarboxylic dianhydrides, especially preferably relative to whole tetrabasic carboxylic acids Dianhydride and include at least one kind of in these tetracarboxylic dianhydrides of 60 moles of % or more, particularly preferably include 80 moles of % More than, it is highly preferred for using only at least one kind of in these tetracarboxylic dianhydrides.
In the synthesis of polyamic acid with structure represented by the formula (1) it is preferable to use diamines include have it is described The diamines of structure represented by formula (1).
The so-called diamines with structure represented by the formula (1), refers to 2 of the structure represented by the formula (1) On associative key, the compound of amino is bonded directly or respectively via bond base appropriate.The bond base example appropriate It can such as enumerate：Phenylene, naphthylene, biphenylene etc..Aromatic rings possessed by these groups can through halogen atom, carbon number 1~ 20 alkyl, the fluoroalkyl of carbon number 1~20, the alkenyl of carbon number 2~20, the alkoxy of carbon number 1~20 or carbon number 1~20 fluorine Replaced alkoxy.In the group, bond base is preferably the phenylene that can be substituted.That is, having represented by the formula (1) The preference of the diamines of structure can enumerate compound represented by following formula (MDA).
H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2 (MDA)
(in formula (MDA), X1、X2、Y、R1, m1 and m2 be respectively it is identical as the meaning in the formula (1),
It is separately the phenylene that can be substituted there are 2 Ph)
Ph in the formula (MDA) is particularly preferably 1,4- phenylene.
In the synthesis of polyamic acid with structure represented by the formula (1) it is preferable to use diamines can Jin Shiyong have The diamines of structure represented by the formula (1), also can be used together other diamines other than it.
Other workable diamines are classified as the diamines with pre-tilt angle expression power base and do not have pre-tilt angle table herein The diamines of existing property base.
Other diamines with pre-tilt angle expression power base are preferably the aromatic diamine with pre-tilt angle expression power base, as Its concrete example, such as can enumerate：Dodecyloxy -2,4- diaminobenzene, tetradecyloxyaniline -2,4- diaminobenzene, pentadecane oxygen Base -2,4- diaminobenzene, hexadecane epoxide -2,4- diaminobenzene, octadecane epoxide -2,4- diaminobenzene, dodecyloxy -2, 5- diaminobenzene, tetradecyloxyaniline -2,5- diaminobenzene, pentadecane epoxide -2,5- diaminobenzene, hexadecane epoxide -2,5- two Aminobenzene, octadecane epoxide -2,5- diaminobenzene, cholesteric alkoxy -3,5- diaminobenzene (cholestanyloxy-3,5- Diaminobenzene), cholesterol oxygroup -3,5- diaminobenzene (cholesteryloxy-3,5-diaminobenzene), gallbladder Gonane oxygroup -2,4- diaminobenzene, cholesterol oxygroup -2,4- diaminobenzene, 3,5- diaminobenzoic acid cholesteric Arrcostab, 3,5- Diaminobenzoic acid cholesterol base ester, 3,5- diaminobenzoic acid lanostane base ester (lanostanyl 3,5- Diaminobenzoate), bis- (the 4- amino benzoyl oxygroup) cholestane of 3,6-, bis- (4- amino-benzene oxygen) cholestane of 3,6-, Bis- (4- ((aminophenyl) methyl) the phenyl) -4- butyl cyclohexanes of 1,1-, bis- (4- ((aminophenyl) methyl) the phenyl) -4- of 1,1- Heptylcyclohexane, 1,1- bis- (4- ((amino-benzene oxygen) methyl) phenyl) -4- heptylcyclohexanes, the bis- (4- ((aminophenyl) of 1,1- Methyl) phenyl) -4- (4- heptyl cyclohexyl) hexamethylene, N- (2,4- diamino-phenyl) -4- (4- heptyl cyclohexyl) benzoyl Compound represented by amine, following formula (A-1) etc..
[changing 3]
(in formula (A-1), XIAnd XIIRespectively singly-bound,*-O-、*- COO- or*- OOC- (wherein, is labeled with the associative key of " * " Towards the left direction of formula (A-I))；
RIFor the alkylidene of singly-bound, methylene or carbon number 2 or 3；
A is 0 or 1, the integer that b is 0~2, and wherein a and b will not be 0 simultaneously；
The integer that c is 1~20)
X in the formula (A-1)I-RI-XIIRepresented divalent base be preferably methylene, carbon number 2 or 3 alkylidene,*- O-、*- COO- or*-O-CH2CH2- O- (associative key and diamino-phenyl for wherein, being labeled with " * " are bonded).Group-CcH2c+1Middle c When being 3 or more, which is preferably straight-chain.2 amino in diamino-phenyl are preferably located at relative to other groups 2,4- or 3,5-.As the concrete example of compound represented by the formula (A-1), such as preferably following formula (A-1-1- 1), formula (A-1-1-2) and formula (A-1-2)
[changing 4]
(in the formula, " n- " respectively indicates straight-chain)
Represented compound respectively.
Other diamines without pre-tilt angle expression power base can be enumerated：Aliphatic two without pre-tilt angle expression power base Amine, ester ring type diamines, aromatic diamine, diamino organosiloxane etc..
In other diamines without pre-tilt angle expression power base, aliphatic diamine can for example be enumerated：1,1- m-xylene diamine (meta-xylylenediamine), 1,3- propane diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine etc.；
Ester ring type diamines can for example be enumerated：1,4- diaminocyclohexane, 4,4' methylene bis (cyclo-hexylamine), 1,3- are bis- (amino methyl) hexamethylene etc.；
Aromatic diamine can for example be enumerated：O-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 4,4'- diamino-diphenyl first Alkane, 4,4'- diamino diphenyl sulfide, 1,5- diaminonaphthalene, 2,2'- dimethyl -4,4'- benzidine, 4,4'- diamino Bis- (trifluoromethyl) biphenyl of base -2,2'-, 2,7 diamin of luorene, 4,4'- diamino-diphenyl ether, bis- [4- (the 4- aminobenzenes of 2,2- Oxygroup) phenyl] propane, bis- (4- aminophenyl) fluorenes of 9,9-, 2,2- bis- [4- (4- amino-benzene oxygen) phenyl] hexafluoropropane, 2,2- Bis- (4- aminophenyl) hexafluoropropane, 4,4'- (to phenylenediisopropylidene) dianil, 4,4'- (the sub- isopropyl of metaphenylene two Base) dianil, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (4- amino-benzene oxygen) biphenyl of 4,4'-, 2,6- diamino-pyridine, 3, 4- diamino-pyridine, 2,4- di-amino-pyrimidine, 3,6- proflavin, 3,6- diaminocarbazole, N- methyl -3,6- diamino click Azoles, N- ethyl -3,6- diaminocarbazole, N- phenyl -3,6- diaminocarbazole, N, N'- bis- (4- aminophenyl)-benzidine, N, N'- bis- (4- aminophenyl)-N, N'- dimethylbenzidine, 1,4- are bis--(4- aminophenyl)-piperazine, 3,5- diaminobenzene first Acid, 4- (4'- trifluoromethoxy benzoyloxy) cyclohexyl -3,5- diaminobenzoic acid ester, 4- (4'- trifluoromethylbenzoyl Oxygroup) cyclohexyl -3,5- diaminobenzoic acid ester, 2,4- diamino-N, N- diallyl aniline, 4- aminobenzyl amine, 3- ammonia Base benzyl amine, 1- (2,4- diamino-phenyl) piperazine -4- carboxylic acid, 4- (morpholine -4- base) benzene -1,3- diamines, the bis- (N- (4- of 1,3- Aminophenyl) piperidyl) propane, alpha-amido-omega-amino phenylalkylene, 4- (2- amino-ethyl) aniline, following formula (N) institute The compound etc. of expression；
[changing 5]
Diamino organosiloxane can for example be enumerated：1,3- bis- (3- aminopropyl)-tetramethyl disiloxanes etc., except this with Outside,
The diamines recorded in Japanese Patent Laid-Open 2010-97188 bulletin can be used.
The diamines used to synthesize the polyamic acid with structure represented by the formula (1) is preferably relative to complete Portion's diamines, and include the diamines with structure represented by the formula (1) of 1 mole of % or more, it more preferably include 3 moles of % More than, it especially preferably include 5 moles of % or more.
It is excellent in the case where aligning agent for liquid crystal of the invention to be applied to the vertical alignment-type liquid crystal display device of VA type etc. It is selected as relative to whole diamines and other diamines with pre-tilt angle expression power base comprising 3 moles of % or more, more preferably wraps It especially preferably include 10 moles of %~80 mole % containing 5 moles of %~90 mole %.On the other hand, by liquid of the invention In the case that brilliant alignment agent is applied to the horizontally oriented type liquid crystal display element such as TN type, STN type, IPS type, FFS type, preferably phase For whole diamines, the ratio of other diamines with pre-tilt angle expression power base is set as 20 moles of % hereinafter, more preferably setting For 10 moles of % or less.
The use ratio of the tetracarboxylic dianhydride and diamines that there is provided to the synthetic reaction of polyamic acid are preferably relative to diamines The anhydride group of 1 equivalent of amino contained in compound, tetracarboxylic dianhydride becomes 0.2 equivalent~2 equivalents ratio, especially preferably As 0.3 equivalent~1.2 equivalents ratio.
The synthetic reaction of polyamic acid is preferably in organic solvent, preferably at -20 DEG C~150 DEG C, more preferably 0 DEG C Under the conditions of~100 DEG C of temperature, preferably carries out 0.5 hour~24 hours, more preferably carry out 2 hours~10 hours.Herein, As long as the solvent that organic solvent can dissolve synthesized polyamic acid, then there is no particular restriction, such as can enumerate：N- first Base -2-Pyrrolidone, N- ethyl-2-pyrrolidone, DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N, N- dimethyl Imidazolidinone, N, N, 2- trimethylpropanamide, dimethyl sulfoxide, gamma-butyrolacton, tetramethylurea, hexamethylphosphoramide (hexamethylphosphortriamide) non-proton system's polar solvent such as；
Phenol systems solvents such as metacresol, xylenol, phenol, halogenation phenol etc..The usage amount (a) of organic solvent is relative to anti- Answer the total amount (a+b) of solution, the total amount (b) of tetracarboxylic dianhydride and diamine compound preferably becomes 0.1 weight of weight %~50 Measure %, more preferably as the amount of 5 weight of weight %~30 %.
As previously discussed, reaction solution made of dissolving polyamic acid is obtained.The reaction solution can be supplied directly to liquid The preparation of brilliant alignment agent is available to the system of aligning agent for liquid crystal after can also isolating polyamic acid contained in reaction solution It is standby, or isolated polyamic acid can also be available to the preparation of aligning agent for liquid crystal after purification.
It, can be direct by the reaction solution in the case where polyamic acid being carried out dehydration closed-loop and acid imide compound is made It is supplied to dehydration closed-loop reaction, it is anti-to be available to dehydration closed-loop after polyamic acid contained in reaction solution can also being isolated It answers, or isolated polyamic acid can also be available to dehydration closed-loop reaction after purification.
The isolation purifying of polyamic acid can be carried out using well known method.
The acid imide compound of polyamic acid with structure represented by the formula (1) can be by that will synthesize in this way Polyamic acid carry out dehydration closed-loop, be subject to imidizate and obtain.It is closed at this point, the whole of amic acid structure can be carried out to dehydration Ring and fully imidizate, or a part in amic acid structure only can also be subjected to dehydration closed-loop and amic acid be made Structure and imide structure and the part acid imide compound deposited.The acid imide rate of the acid imide compound of polyamic acid is preferably set It is 10% or more, is more preferably set as 30%~95%.
The dehydration closed-loop of polyamic acid can be carried out using following methods：(i) method that polyamic acid is heated；Or Polyamic acid is dissolved in organic solvent by person (ii), dehydrating agent and dehydration closed-loop catalyst is added in the solution, optionally The method heated.In these methods, the method for (ii) is preferably utilized.
On the other hand, in the method for described (ii), acetic anhydride, propionic andydride, trifluoroacetic anhydride etc. is for example can be used in dehydrating agent Acid anhydrides.Relative to 1 mole of amic acid structural unit, the usage amount of dehydrating agent is preferably set as 0.01 mole~20 moles.Separately Outside, pyridine (Pyridine), collidine (Collidine), two picolins for example can be used in dehydration closed-loop catalyst (Lutidine), the tertiary amines such as triethylamine (Triethylamine).But it is not limited to these compounds.Relative to institute The usage amount of 1 mole of the dehydrating agent used, dehydration closed-loop catalyst is preferably set as 0.01 mole~10 moles.Dehydration closed-loop is anti- Organic solvent used in answering can enumerate organic solvent used in the synthesis as polyamic acid and the organic solvent that illustrates.It is de- The reaction temperature of water ring-closure reaction is preferably 0 DEG C~180 DEG C, and more preferably 10 DEG C~150 DEG C, the reaction time is preferably 0.5 small When~20 hours, more preferably 1 hour~8 hours.
The reaction solution of the acid imide compound containing polyamic acid is obtained as described above.The reaction solution can be mentioned directly The preparation of aligning agent for liquid crystal is supplied, it can also be to be available to liquid after removal dehydrating agent and dehydration closed-loop catalyst in autoreaction solution Acid imide compound can also be isolated the preparation for being available to aligning agent for liquid crystal after purification by the preparation of brilliant alignment agent.Dehydrating agent and The removal of dehydration closed-loop catalyst and the isolation purifying of acid imide compound can be carried out using well known method.
Aligning agent for liquid crystal of the invention contains the polymer with structure represented by the formula (1) as an essential component, It is preferably configured to these polymer to be dissolved in liquid composite made of in aftermentioned solvent, optionally can also contain in turn it His ingredient.Herein, other compositions can for example be enumerated：Other polymers, intramolecular have at least one epoxy group compound (with Down referred to as " epoxide "), functional silanes compound etc..
The other polymers are the polymer without structure represented by the formula (1), can be used for improving the present invention Aligning agent for liquid crystal solution properties (coating) and electrical characteristics.
Other polymers can be enumerated：The acyl of polyamic acid, the polyamic acid without structure represented by the formula (1) Imines fluidized polymer, poly amic acid ester, polyester, polyamide, polysiloxanes, cellulose derivative, polyacetals, polystyrene are derivative Object, poly- (styrene-phenylmaleimide) derivative, poly- (methyl) acrylate etc..
Total by polymer (means there is the polymer of structure represented by the formula (1) and the conjunction of other polymers Meter；It is same as below) 100 weight % are set as, the use ratio of other polymers is preferably 90 weight % hereinafter, more preferably 50 weights % is measured hereinafter, not containing other polymers particularly preferably.
The epoxide and functional silanes compound respectively can be in order to further increase resulting liquid crystal aligning Adhesion between film and substrate, and containing in aligning agent for liquid crystal of the invention.
The epoxide can for example be enumerated：Ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, the third two Alcohol diglycidyl ether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol 2-glycidyl Ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2- dibromo Neopentylglycol diglycidyl ether, N, N, N', bis- (N, the N- 2-glycidyls of N'- four glycidyl group-m-xylene diamine, 1,3- Base amino methyl) hexamethylene, N, N, N', N'- four glycidyl group -4,4'- diaminodiphenyl-methane, N, N- 2-glycidyl Base-benzyl amine, N, N- diglycidyl-aminomethyl cyclohexane, N, N- diglycidyl-cyclo-hexylamine etc., as It is preferred that person.
Relative to total 100 parts by weight of polymer, the allotment ratio of these epoxides be preferably 40 parts by weight with Under, more preferably 0.1 parts by weight~30 parts by weight.
The functional silanes compound can for example be enumerated：3- TSL 8330, three second of 3- aminopropyl Oxysilane, 2- TSL 8330,2- aminopropyltriethoxywerene werene, N- (2- amino-ethyl) -3- amino Propyl trimethoxy silicane, N- (2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- ureido-propyl trimethoxy Silane, 3- ureidopropyltriethoxysilane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl - 3-aminopropyltriethoxysilane, N- tri-ethoxy silylpropyl diethylenetriamine, N- trimethoxysilylpropyl Diethylenetriamine, three azepine decane of 10- trimethoxy silane base -1,4,7-, three nitrogen of 10- triethoxysilicane alkyl -1,4,7- Miscellaneous decane, 9- trimethoxy silane base -3,6- diaza nonyl acetic acid esters, 9- trimethoxy silane base -3,6- diaza nonyl Acetic acid esters, 9- triethoxysilicane alkyl -3,6- diaza nonyl acetic acid esters, 9- trimethoxy silane base -3,6- diaza n-nonanoic acid Methyl esters, 9- triethoxysilicane alkyl -3,6- diaza methyl pelargonate, N- benzyl -3- TSL 8330, N- benzyl Base -3-aminopropyltriethoxysilane, N- phenyl -3- TSL 8330, three second of N- phenyl -3- aminopropyl Oxysilane etc..
Relative to total 100 parts by weight of polymer, the allotment ratio of these functional silanes compounds is preferably 2 weight Part is hereinafter, more preferably 0.02 parts by weight~0.2 parts by weight.
Aligning agent for liquid crystal of the invention is that will have the polymer of structure represented by the formula (1) and optionally appoint The other compositions of meaning allotment preferably dissolve and contain in solvent and constitute.
Workable solvent preferably uses organic solvent in aligning agent for liquid crystal of the invention, such as can enumerate：N- methyl- 2-Pyrrolidone, gamma-butyrolacton, butyrolactam, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 4- hydroxyl -4- Methyl -2 pentanone, glycol monoethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy-c acid esters, 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, two Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, diisobutyl ketone, isoamyl propionate, Isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate etc..These organic solvents can be used alone, Huo Zheke Two or more is used in mixed way.
Solid component concentration (total weight of the ingredient other than the solvent of aligning agent for liquid crystal in aligning agent for liquid crystal of the invention Measure ratio shared of the total weight of the liquid crystal alignment agent) it allows for viscosity, volatility etc. suitably to select, preferably 1 weight Measure the range of the weight of %~10 %.That is, aligning agent for liquid crystal of the invention is in a manner of aftermentioned by being coated on substrate surface, preferably It is heated, and is formed into the film of liquid crystal orientation film, but in the case where solid component concentration is less than 1 weight %, the painting The film thickness of film becomes too small, can not obtain good liquid crystal orientation film, is more than 10 weight % in solid component concentration on the other hand In the case where, the film thickness of film becomes excessive, good liquid crystal orientation film can not be obtained, in addition, the viscosity of aligning agent for liquid crystal increases Greatly, coating characteristics deteriorate.
The range of particularly preferred solid component concentration is according to used method when coating of liquid crystalline alignment agent on substrate And it is different.Such as using rotator method, solid component concentration is particularly preferably 1.5 weight of weight %~4.5 % Range.Using print process, solid component concentration is particularly preferably set as to the model of 3 weight of weight %~9 % It encloses, thus solution viscosity is set as to the range of 12mPas~50mPas.Using ink-jet method, particularly preferably Solid component concentration is set as to the range of 1 weight of weight %~5 %, solution viscosity is thus set as 3mPas~15mPas Range.
Temperature when preparing aligning agent for liquid crystal of the invention is preferably 10 DEG C~45 DEG C, more preferably 20 DEG C~30 DEG C.
Aligning agent for liquid crystal of the invention can be used to form liquid crystal orientation film.That is, can be by being coated with the present invention on substrate Aligning agent for liquid crystal and form film, preferably via implementing friction treatment to the film or the step of photo-irradiation treatment carrys out shape At liquid crystal orientation film.
Aligning agent for liquid crystal of the invention, which can be applied to manufacture, has such as TN type, STN type, IPS type, FFS type, VA type, MVA The liquid crystal display element of the liquid crystal cells appropriate such as type.However, just playing the aspect of advantageous effects of the invention to greatest extent For, preferably it is applied to the liquid crystal display with so-called horizontally oriented type liquid crystal cells such as TN type, STN type, IPS type, FFS types Element.
It is applied to TN type or STN type liquid crystal display element in the liquid crystal orientation film that will be formed by aligning agent for liquid crystal of the invention In the case where, as the substrate, 2 pieces of substrates for being provided with patterned transparent conductive film are used as a pair, the liquid crystal The formation that alignment agent is coated on each substrate has on the face of transparent conductive film.On the other hand, liquid crystal orientation film is being applied to IPS In the case where type or FFS type liquid crystal display element, as the substrate, will have transparent conductive film or metal film on one side wherein The substrate of the patterned electrode for comb teeth-shaped and the opposite substrate of not set electrode are used as a pair, the aligning agent for liquid crystal It is coated on the forming face of comb-like electrode and the wherein one side of opposite substrate.
Under described any case, the substrate be can be used：Such as float glass (float glass), soda-lime glass Etc glass；Modeling comprising polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate etc The transparent substrate etc. of material.It includes In that the transparent conductive film, which for example can be used,2O3-SnO2Tin indium oxide (indium tin Oxide, ITO) film, include SnO2Nesa (NESA) (registered trademark) film etc..The metal film can be used such as comprising chromium The film of metal.Using following methods in the patterning of transparent conductive film and metal film：Such as forming the transparent of pattern-free After conductive film, the method for pattern is formed using photo-engraving process, sputtering method etc.；And use has when forming transparent conductive film The method etc. of the mask of required pattern.
When light orientation is coated on substrate with aligning agent for liquid crystal, in order to make substrate and transparent conductive film or metal film It is better with the cementability of film, functional silanes chemical combination can be pre-coated on substrate and transparent conductive film or metal film Object, titanate compound etc..
Light orientation preferably utilizes flexographic printing process (off-set with coating of the aligning agent for liquid crystal on substrate Printing), the coating method appropriate such as method of spin coating, roll-coater method, ink jet printing method carries out, then, to coating Face is preheated (prebake conditions) and rear heating (rear baking), and film is consequently formed.Prebake conditions preferably 40 DEG C~ It is carried out 0.1 minute~5 minutes at 120 DEG C.Baking condition is preferably at 120 DEG C~300 DEG C, more preferably 150 DEG C~250 DEG C afterwards Under, it preferably carries out 5 minutes~200 minutes, more preferably 10 minutes~100 minutes.
Then, by via friction treatment or photo-irradiation treatment is implemented to the film formed in this way the step of, and Liquid crystal aligning ability is assigned to film liquid crystal orientation film is made.Herein, the X in the formula (1)1And X2At least one of In the case where for ester bond, photo-irradiation treatment is preferably carried out, friction treatment is preferably carried out other than it.
Friction treatment can carry out in the following way：Using being wound with including, for example, nylon, artificial silk (Reon), cotton etc. The roller of the cloth of fiber will be formed in the face of the film on substrate, wipe to certain orientation.
The ultraviolet light, visible of the light comprising 150nm~800nm wavelength for example can be used in the light irradiated in photo-irradiation treatment Light etc..As the light irradiated, it is preferable to use the ultraviolet light of the light comprising 200nm~400nm wavelength.Used light source Such as Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, Hg-Xe lamp, quasi- point can be used Sub- laser etc..The ultraviolet light in the optimal wavelength region can by by the light source with such as optical filter, diffraction grating simultaneously Method etc. obtains.Irradiation light can be polarisation, be also possible to non-polarized, preferably polarisation.Direction of illumination is preferably set For the direction vertical relative to real estate.
The exposure of light is preferably 100J/m2More than, more preferably 400J/m2~20,000J/m2, especially preferably 1, 000J/m2~10,000J/m2。
Aligning agent for liquid crystal of the invention can be used, form liquid crystal orientation film on substrate in this way.It should using having The substrate of liquid crystal orientation film can manufacture liquid crystal display element in the following manner.
Prepare a pair of of the substrate for being formed with liquid crystal orientation film in this way, manufacture is clamped with liquid crystal between a pair of substrate Composition liquid crystal cells.In order to manufacture liquid crystal cells, such as 2 kinds of methods below can be enumerated.
1st method can be listed below method：In such a way that each liquid crystal orientation film is opposite, via gap (unit gap) incite somebody to action A pair of of substrate is oppositely disposed, is bonded the peripheral portion of a pair of substrate using sealant, by substrate surface and appropriate close In the unit gap that is divided of envelope agent after injection filling liquid crystal, injection hole is sealed, thus manufactures liquid crystal cells.
2nd method can be listed below method (liquid crystal drip-injection (One Drop Fill, ODF) method)：It is being formed with liquid crystal aligning The specified location on one of substrate in 2 pieces of substrates of film is coated with the sealant of such as ultraviolet light photopolymerization, and then in liquid After liquid crystal is added dropwise in set several positions on crystalline substance orientation film surface, it is bonded another piece of substrate in such a way that liquid crystal orientation film is opposite, And it spreads out liquid crystal in substrate entire surface, then the entire surface irradiating ultraviolet light of substrate is cured the sealant, thus Manufacture liquid crystal cells.
Using any method, it is preferably to for liquid crystal cells are then heated to used liquid crystal Until the temperature for obtaining isotropic phase, it is then slowly cooled down to room temperature, thus removes flow orientation when liquid crystal filling.And And polarizer is bonded with set direction by the outer surface in liquid crystal cells, it can get liquid crystal display element of the invention.
Nematic crystal (nematic liquid crystal), disc-like liquid crystal (smectic for example can be used in the liquid crystal Liquid crystal) etc..
In the case where the liquid crystal display element of manufacture level type of alignment, it is however preferred to have positive dielectric anisotropy Nematic crystal, such as can be used：Biphenyl base system liquid crystal, cyclohexylbenzene system liquid crystal, ester system liquid crystal, terphenyl system liquid crystal, connection Cyclohexylbenzene system liquid crystal, pyrimidine system liquid crystal, fluorination benzene series liquid crystal, dioxane system liquid crystal, double-octane system liquid crystal, cubane It (cubane) is liquid crystal etc..Cholesteryl liquid crystal, chiral agent, ferroelectric liquid crystals can also be added in these liquid crystal (ferroelectric liquid crystal) etc. is used.On the other hand, in the liquid crystal display for manufacturing vertically oriented type In the case where element, it is however preferred to have the nematic crystal of negative dielectric anisotropy, such as usable dicyano benzene series liquid crystal, Pyridazine system liquid crystal, schiff bases (Schiff base) are liquid crystal, azoxy system liquid crystal, biphenyl system liquid crystal, cyclohexylbenzene system liquid Crystalline substance etc..
Polarizer used in the outside of liquid crystal cells can be enumerated：It is referred to as " H film " with the clamping of cellulose acetate protective film Light polarizing film made of polarizer or comprising itself polarizer etc. of H film, " the H film " is to prolong polyvinyl alcohol on one side It stretches orientation and absorbs film made of iodine on one side.
[embodiment]
< has the synthesis > of the diamines of structure represented by the formula (1)
Synthesis example MDA-1
According to following processes 1, to synthesize compound represented by formula (MDA-1) (compound (MDA-1)).
[changing 6]
(in process 1, Boc is tert-butoxycarbonyl)
In the reaction vessel, by 3,5- dibromo pyridine 11.8g (0.050 mole), three-o-tolyl phosphine 609mg (2.0 millis Mole) and acid chloride 112mg (0.5 mM) as catalyst mixed, after carrying out nitrogen displacement, add N, N- bis- Methylformamide 152mL, triethylamine 16.7mL (0.120 mole) and tert-butyl acrylate 17.5mL (0.120 mole), It carries out reacting for 3 hours while stirring at 120 DEG C.After completion of the reaction, air is blown into reaction mixture, so that acid chloride Inactivation.After removing catalyst residue by diatomite filtering, ethyl acetate 500mL is added in filtrate, it will be resulting organic Layer carries out 4 extractions using distilled water 500mL and washs.Then, for removing what solvent obtained from organic layer by depressurizing Solid is recrystallized using ethyl alcohol 150mL, obtain yellow compound (mda-1-1) 13.6g (0.041 mole, yield For 82%).
In the reaction vessel for having cock, by compound (mda-1-1) 13.6g (0.041 mole) of the acquisition with And 5 weight % palladium carbon (the 50 aqueous product of weight %) 1.36g mixed, carry out nitrogen displacement after, add tetrahydrofuran 80mL with And ethyl alcohol 80mL, the balloon for having hydrogen is added in installation in cock, is in container under hydrogen environment, in the present context at 50 DEG C It is lower to carry out reacting for 5 hours while stirring.After completion of the reaction, it is filtered in reaction mixture by diatomite and removes palladium carbon Afterwards, by decompression, solvent is removed from resulting filtrate, obtaining hazel compound (mda-1-2) 13.1g, (0.039 rubs You, yield 95%).
In the reaction vessel, by compound (mda-1-2) 13.1g (0.039 mole), the methylene chloride 80mL of the acquisition And trifluoroacetic acid 40mL is mixed, and carries out reacting for 3 hours while stirring at 20 DEG C.After completion of the reaction, for logical The solid for removing solvent and obtaining is crossed in decompression reaction mixture, is recrystallized, is obtained filbert using ethyl alcohol 120mL Compound (mda-1-3) 7.14g (0.032 mole, yield 82%).
Then, in the reaction vessel, by compound (mda-1-3) 7.14g (0.032 mole) of the acquisition, 4- (tertiary fourth Epoxide carbonyl amino) phenol 13.4g (0.064 mole) and methylene chloride 128mL mixed.Container is cold in ice bath But, so that interior temperature is maintained 5 DEG C, and add 1- (3- dimethylaminopropyl) -3- ethylcarbodiimide hydrochloride 14.7g After (0.077 mole) and N, N- dimethyl -4-aminopyridine 1.56g (0.013 mole), enter while stirring at 20 DEG C It reacts within row 2 hours.After completion of the reaction, ethyl acetate 300mL is added into reaction mixture, and resulting organic layer is utilized into distillation Water 300mL carries out 3 extractions washing.For making by depressurizing the solid for removing solvent from the organic layer after washing and obtaining It is recrystallized with ethyl alcohol 100mL, obtaining hazel compound (mda-1-4) 15.7g, (0.026 mole, yield is 81%).
In turn, in the reaction vessel, by compound (mda-1-4) 15.7g (0.026 mole), the dichloromethane of the acquisition Alkane 52mL and trifluoroacetic acid 26mL are mixed, and carry out reacting for 3 hours while stirring at 20 DEG C.After completion of the reaction, For the solid obtained by removal solvent in decompression reaction mixture, recrystallized using ethyl alcohol 100mL, thus Obtain compound (MDA-1) 8.86g (0.022 mole, yield 84%) of purple.
Synthesis example MDA-2
According to following processes 2, to synthesize compound represented by formula (MDA-2) (compound (MDA-2)).
[changing 7]
(in process 2, Boc is tert-butoxycarbonyl)
In the reaction vessel, by 3,5-, bis- picolin (lutidine) 6.43g (0.060 mole), acetonitrile 60mL, N- neoprene Imidodicarbonic diamide (N-chlorosuccinimide) 48.1g (0.360 mole) and bis- (isobutyronitrile) 2.46g of 2,2'- azo (0.015 mole) is mixed, and carries out reacting for 8 hours while stirring at 80 DEG C.After completion of the reaction, for passing through decompression The solid for removing solvent in reaction mixture and obtaining, utilizes column chromatography (packing material：Silica gel, developing solvent：Oneself Alkane/ethyl acetate=3/1 (volume ratio)) it is purified, thus to obtain hazel compound (mda-2-1) 6.65g (0.038 Mole, yield 63%).
Then, in the reaction vessel, by compound (mda-2-1) 6.65g (0.038 mole) of the acquisition, 4- (tertiary fourth Epoxide carbonyl amino) phenol 15.9g (0.076 mole), DMAC N,N' dimethyl acetamide 190mL and potassium carbonate 12.6g (0.091 Mole) mixed, it carries out reacting for 5 hours while stirring at 90 DEG C.After completion of the reaction, it is added into reaction mixture Resulting organic layer is carried out 4 extractions using distilled water 300mL and washed by ethyl acetate 300mL.For being washed certainly by decompression The solid for removing solvent in organic layer afterwards and obtaining, is recrystallized using ethyl alcohol 100mL, obtains hazel compound (mda-2-2) 16.6g (0.032 mole, yield 84%).
In turn, by compound (mda-2-2) 16.6g (0.032 mole), methylene chloride 64mL and the trifluoro of the acquisition Acetic acid 32mL is mixed, and carries out reacting for 3 hours while stirring at 20 DEG C.After completion of the reaction, for by depressurizing certainly The solid for removing solvent in reaction mixture and obtaining, is recrystallized using ethyl alcohol 100mL, thus to obtain the chemical combination of purple Object (MDA-2) 9.26g (0.029 mole, yield 90%).
Synthesis example MDA-3
According to following processes 3, to synthesize compound represented by formula (MDA-3) (compound (MDA-3)).
[changing 8]
In the flask for being equipped with Dean-Stark (Dean-Stark) pipe, by 4-aminophenol 17.9g, (0.164 rubs You), dimethyl sulfoxide 80mL, toluene 8.0mL and potassium hydroxide 9.88g (0.176 mole) mixed, stirred at 135 DEG C It mixes 4 hours, is made a return journey after water removal by azeotropic, temperature is made to be reduced to 100 DEG C, add 2,6- dichloropyridine 11.8g (0.080 mole) Afterwards, so that temperature is risen to 135 DEG C again, carry out reacting for 4 hours while stirring.After completion of the reaction, in distilled water 500mL Reaction mixture is injected, precipitate generated is recycled.For the precipitate of recycling, recrystallized using ethyl alcohol 100mL, Thus to obtain compound (MDA-3) 15.9g (0.054 mole, yield 68%) of purple.
Synthesis example MDA-4
According to following processes 4, to synthesize compound represented by formula (MDA-4) (compound (MDA-4)).
[changing 9]
(in process 4, Boc is tert-butoxycarbonyl)
In the reaction vessel, by 4- (tertbutyloxycarbonylamino) phenol 20.3g (0.097 mole), tetrahydrofuran 300mL And triethylamine 27.0mL (0.194 mole) is mixed.Container is cooled down under ice bath, and is added dropwise 5- bromination Nicotine acyl chlorides (5-bromonicotinoyl chloride) 19.4g (0.088 mM) be dissolved in tetrahydrofuran 50mL and At solution.After being added dropwise, 20 DEG C are warming up to, carries out reacting for 4 hours at such a temperature while stirring.End of reaction Afterwards, ethyl acetate 750mL is added into reaction mixture, and resulting organic layer is subjected to 4 extractions using distilled water 750mL and is washed It washs.For being tied again using ethyl alcohol 150mL by depressurizing the solid for removing solvent from the organic layer after washing and obtaining Crystalline substance obtains hazel compound (mda-4-1) 29.4g (0.075 mole, yield 85%).
Then, in the reaction vessel, by compound (mda-4-1) 29.4g (0.075 mole), the N- [4- of the acquisition (penta ring -2- base of 4,4,5,5-N- tetramethyl -1,3,2- dioxy boron) phenyl] t-butyl carbamate 23.9g (0.075 mole), Sodium carbonate 15.9g (0.150 mole) and [bis- (diphenylphosphino) ferrocene of 1,1'-] dichloro palladium 2.74g as catalyst (3.75 mMs) are mixed, and after carrying out nitrogen displacement, and then add toluene 40mL, ethyl alcohol 40mL and distilled water 40mL, It carries out reacting for 16 hours while stirring at 60 DEG C.After completion of the reaction, air is blown into reaction mixture, so that palladium is urged Agent inactivation, then, removes catalyst residue by diatomite filtering.Ethyl acetate 500mL is added into filtrate, by gained Organic layer utilize distilled water 500mL carry out 4 extraction washing.For removing solvent from the organic layer after washing by decompression And the solid obtained, it is recrystallized using ethyl alcohol 200mL, obtains hazel compound (mda-4-2) 22.8g (0.045 Mole, yield 60%).
In the reaction vessel, by compound (mda-4-2) 22.8g (0.045 mole), the methylene chloride 90mL of the acquisition And trifluoroacetic acid 45mL is mixed, and carries out reacting for 3 hours while stirring at 20 DEG C.After completion of the reaction, for logical The solid that decompression obtains to remove solvent is crossed, is recrystallized using ethyl acetate 30mL and hexane 120mL, is thus obtained Obtain compound (MDA-4) 11.0g (0.036 mole, yield 80%) of brown.
Synthesis example MDA-5
According to following processes 5, to synthesize compound represented by formula (MDA-5) (compound (MDA-5)).
[changing 10]
(in process 5, Boc is tert-butoxycarbonyl)
In the reaction vessel, by the bromo- 2- iodine pyridine 42.6g of 5- (0.150 mole), N- [4- (4,4,5,5-N- tetramethyls- Penta ring -2- base of 1,3,2- dioxy boron) phenyl] t-butyl carbamate 47.9g (0.150 mole), (0.450 rubs sodium carbonate 47.7g You) and tetrakis triphenylphosphine palladium 8.67g (7.50 mMs) as catalyst mixed, after carrying out nitrogen displacement, add Add tetrahydrofuran 500mL and distilled water 250mL, carries out reacting for 20 hours while stirring at 60 DEG C.After completion of the reaction, It is blown into air into reaction mixture, so that palladium catalyst inactivates, then, carries out diatomite filtering to remove catalyst residue. Ethyl acetate 1,000mL is added into filtrate, and resulting organic layer is subjected to 4 extractions using distilled water 800mL and is washed.For By depressurizing the solid for removing solvent from the organic layer after washing and obtaining, is recrystallized, obtained using ethyl alcohol 300mL Hazel compound (mda-5-1) 29.3g (0.084 mole, yield 56%).
Then, in the reaction vessel, by compound (mda-5-1) 29.3g (0.084 mole) of the acquisition, three-adjacent first Phenylphosphine 1.02g (3.4 mMs) and acid chloride 189mg (0.84 mM) as catalyst are mixed, and nitrogen is carried out After gas displacement, addition n,N-Dimethylformamide 255mL, triethylamine 14.0mL (0.100 mole) and tert-butyl acrylate 14.6mL (0.100 mole), carries out reacting for 4 hours while stirring at 120 DEG C.After completion of the reaction, to reaction mixture In be blown into air so that palladium catalyst inactivate, catalyst residue is removed by diatomite filtering.Acetic acid second is added into filtrate Resulting organic layer is carried out 4 extractions using distilled water 700mL and washed by ester 700mL.For the having from after washing by decompression The solid for removing solvent in machine layer and obtaining, is recrystallized using ethyl alcohol 250mL, obtains hazel compound (mda- 5-2) 26.2g (0.066 mole, yield 79%).
In the reaction vessel for having cock, by compound (mda-5-2) 26.2g (0.066 mole) of the acquisition with And 5 weight % palladium carbon (50 weight % are aqueous) 2.62g mixed, carry out nitrogen displacement after, add tetrahydrofuran 132mL and Ethyl alcohol 132mL.The balloon for having hydrogen is added in installation in the cock of reaction vessel, makes in container under hydrogen environment, at this It carries out reacting for 5 hours while stirring at 50 DEG C under environment.After completion of the reaction, autoreaction mixing is filtered by diatomite Palladium carbon is removed in object, removes solvent from resulting filtrate under reduced pressure, obtains hazel compound (mda-5-3) 24.3g (0.061 mole, yield 93%).
In the reaction vessel, by compound (mda-5-3) 24.3g (0.061 mole), the methylene chloride of the acquisition 120mL and trifluoroacetic acid 60mL are mixed, and carry out reacting for 3 hours while stirring at 20 DEG C.After completion of the reaction, right The solid for removing solvent in reaction mixture under reduced pressure and obtaining, is recrystallized using ethyl alcohol 150mL, is obtained light Compound (mda-5-4) 18.5g (0.054 mole, yield 89%) of brown.
Then in the reaction vessel, by compound (mda-5-4) 18.5g (0.054 mole) of the acquisition, 4- (tertiary fourth Epoxide carbonyl amino) phenol 11.3g (0.054 mole) and methylene chloride 108mL mixed, 5 DEG C are cooled under ice bath, And thereto add 1- (3- dimethylaminopropyl) -3- ethylcarbodiimide hydrochloride 12.4g (0.065 mole) and N, N- dimethyl -4-aminopyridine 1.32g (0.011 mole).20 DEG C are then heated to, is entered while stirring at such a temperature It reacts within row 3 hours.After completion of the reaction, ethyl acetate 500mL is added into reaction mixture, and resulting organic layer is utilized into distillation Water 500mL carries out 3 washings.For using second by depressurizing the solid for removing solvent from the organic layer after washing and obtaining Alcohol 150mL is recrystallized, and obtains hazel compound (mda-5-5) 25.6g (0.048 mole, yield 89%).
And then in the reaction vessel, by compound (mda-5-5) 25.6g (0.048 mole), the methylene chloride of the acquisition 96mL and trifluoroacetic acid 48mL are mixed, and carry out reacting for 3 hours while stirring at 20 DEG C.After completion of the reaction, right The solid that removal solvent obtains in through decompression reaction mixture, is recrystallized using ethyl alcohol 150mL, is thus obtained Obtain compound (MDA-5) 12.7g (0.038 mole, yield 80%) of purple.
Synthesis example MDA-6
According to following processes 6, to synthesize compound (compound MDA-6) represented by formula (MDA-6).
[changing 11]
(in process 6, Boc is tert-butoxycarbonyl)
In the three-necked flask for the 500mL for having dropping funel and nitrogen ingress pipe, be added 4-aminophenol 7.1g and Tetrahydrofuran 350mL.The interior temperature of flask is maintained 6 DEG C hereinafter, and being added dropwise from dropping funel by the two carbonic acid-tert-butyl ester Then solution made of 14.6g is dissolved in the tetrahydrofuran of 60mL carries out reacting for 24 hours at room temperature.After completion of the reaction, The solid obtained by removal solvent in decompression reaction mixture is dissolved in ethyl acetate 500mL, distilled water is utilized 500mL carries out liquid separation washing.After organic layer is dried with magnesium sulfate, solvent is removed by decompression, is obtained as intermediate The white crystals 12.6g of object 1.
In the three-necked flask for the 300mL for having thermometer and nitrogen ingress pipe, the intermediary of the acquisition is added 110.14g, 2,5- pyridine dicarboxylic acid 4.05g and methylene chloride 150mL, are made suspension while stirring, and are cooled to 0 DEG C. The temperature is maintained on one side, and the hydrogen chlorate of 1- (3- dimethylaminopropyl) -3- ethylcarbodiimide is added thereto on one side 12.08g and N, N- dimethyl aminopyridine 2.37g, carry out reacting for 6 hours while stirring.Then at room temperature in turn Continue stirring 6 hours.Ethyl acetate 300mL, tetrahydrofuran 300mL are added in the reaction mixture after total stirring 12 hours And distilled water 300mL carries out liquid separation washing, recycles organic layer.After resulting organic layer is concentrated into about 200mL, second is added Alcohol 100mL carries out solvent displacement, is then concentrated again, the white solid (intermediary 2) that leaching is precipitated.The production of intermediary 2 Amount is 10.0g.
In the eggplant type flask for the 300mL for having nitrogen ingress pipe, the 8.4g of the intermediary 2 of the acquisition is made to be suspended in two In chloromethanes 150mL, trifluoroacetic acid 30mL is added thereto, carries out reacting for 24 hours while stirring.After completion of the reaction, to Saturated aqueous sodium carbonate is added in reaction mixture, until pH value become 7 or more, then, add ethyl acetate 200mL and Tetrahydrofuran 200mL carries out liquid separation, recycles organic layer.After the organic layer is carried out 3 washings using distilled water 300mL, carry out Concentration.In concentration, solution becomes black.The solid that leaching is precipitated uses the mixed solvent (second comprising ethyl alcohol and pure water Alcohol：Water=4：1 (capacity ratio)) it is washed, thus to obtain compound (MDA-6) 4.2g of yellow.
< has the synthesis > of the polymer of structure represented by the formula (1)
Synthesis example PI-1~synthesis example PI-11
It, respectively will be in the table in a manner of becoming the ratio (molar ratio) that the 1st table is recorded as tetracarboxylic dianhydride and diamines The compound of the type of record is mixed, and is added n-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP), The solution that monomer concentration is 20 weight % is made.For the solution, carry out reacting for 4 hours while stirring at 40 DEG C, by This obtains the solution of the polyamic acid containing 20 weight %.In synthesis example PI-7, other than tetracarboxylic dianhydride and diamines, into And with ratio (molar ratio) that the 1st table is recorded the monoamine recorded using the table.
Then, NMP is added in the polyamic acid solution of the acquisition, is 10 weight % by polyamic acid concentration dilution, Then, remembered respectively with the relative quantity for the amount (molal quantity) of the amic acid key possessed by the polyamic acid as the 1st table The mode of the amount of load adds pyridine and acetic anhydride, stirs 4 hours at 110 DEG C to carry out dehydration closed-loop reaction.For reaction After reaction mixture, using NMP carry out solvent displacement, thus to obtain respectively containing 15 weight % imidizate polymerization Object (PI-1)~imide amination polymer (PI-9) solution.It will utilize1H- nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) resulting imide amination polymer is measured obtained by acid imide rate be shown in the 1st table together.
The synthesis > of < other polymers
Synthesis example rpi-1~synthesis example rpi-3
As tetracarboxylic dianhydride and diamines, respectively by become the 1st table record ratio (molar ratio) in a manner of come using The compound for the type recorded in the table, and
The usage amount of pyridine and acetic anhydride is adjusted to the ratio recorded in the 1st table, in addition to this, with the synthesis example The identical mode of PI-1 is operated, and imide amination polymer (rpi-1)~imidizate containing 15 weight % respectively is obtained The solution of polymer (rpi-3).It will utilize1Imidizate obtained by H-NMR is measured resulting imide amination polymer Rate is shown in together in the 1st table.
Synthesis example rpa-1~synthesis example rpa-4
As tetracarboxylic dianhydride and diamines, respectively by become the 1st table record ratio (molar ratio) in a manner of come using The compound for the type recorded in the table is operated in a manner of identical with the synthesis example PI-1, is divided in addition to this The not polyamic acid (rpa-1) containing 20 weight %~polyamic acid (rpa-4) solution.
Without dehydration closed-loop reaction in these synthesis examples, but resulting polyamic acid solution is supplied directly to liquid The preparation of brilliant alignment agent.
Abbreviation in the monomer column of 1st table is respectively following meanings.
< tetracarboxylic dianhydride >
TCA：2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride
BODA：Bicyclic [3.3.0] octane -2 of 2,4,6,8- tetracarboxylic:4,6:8- dianhydride
CB：1,2,3,4- cyclobutane tetracarboxylic dianhydride
MTDA：1,3,3a, 4,5,9b- hexahydro -8- methyl -5- (tetrahydro -2,5- dioxo -3- furyl)-naphtho- [1,2- C] furans -1,3- diketone
PMDA：Pyromellitic acid anhydride
TA-1：Compound represented by following formula (TA-1)
[changing 12]
< diamines >
[diamines with structure represented by the formula (1)]
MDA-1：The compound (MDA-1) synthesized in the synthesis example MDA-1
MDA-2：The compound (MDA-2) synthesized in the synthesis example MDA-1
MDA-3：The compound (MDA-3) synthesized in the synthesis example MDA-1
MDA-4：The compound (MDA-4) synthesized in the synthesis example MDA-1
MDA-5：The compound (MDA-5) synthesized in the synthesis example MDA-1
[other diamines]
PDA：P-phenylenediamine
HCDA：3,5- diaminobenzoic acid cholesteric Arrcostab
35DAB：3,5- diaminobenzoic acid
HCODA：Cholesteric alkoxy -2,4- diaminobenzene
LDA：4- { 4- [2- (4'- amyl -1,1'- dicyclohexyl) ethyl] phenoxy group } benzene -1,3- diamines
D-1：1,3- diamino -4- { 4- [trans- -4- (trans- -4- pentyl cyclohexyl) cyclohexyl] phenoxy group } benzene
D-2：Bis- (3- the aminopropyl)-tetramethyl disiloxanes of 1,3-
D-3：Bis- (the 4- amino benzoyl oxygroup) cholestane of 3,6-
D-5：Bis- (the trifluoromethyl) -4,4'- benzidines of 2,2'-
D-6：4,4'- diaminodiphenyl-methane
D-7：2,2'- dimethyl -4,4'- benzidine
D-8：4,4'- diamino-diphenyl ether
DA-2：Compound represented by following formula (DA-2)
DA-3：Compound represented by following formula (DA-3)
mda-1：Compound represented by following formula (mda-1)
mda-2：Compound represented by following formula (mda-2)
[changing 13]
[monoamine]
D-4：Aniline
Synthesis example rps-1
In the reaction vessel for having blender, thermometer, dropping funel (dropping funnel) and the cooling tube that flows back In, 2- (3,4- expoxycyclohexyl) ethyl trimethoxy silane 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethyl group is added Amine 10.0g, mixes at room temperature.Then, thereto, spend 30 minutes from dropping funel and deionized water 100g is added dropwise, then one Side is stirred under reflux, carries out reacting for 6 hours on one side at 80 DEG C.After completion of the reaction, organic layer is taken out, 0.2 weight % is used Aqueous ammonium nitrate solution is washed, and until the water after washing becomes neutral, then distillation removes solvent and water under reduced pressure, The polysiloxane with epoxy group is obtained in the form of sticky transparency liquid.The polysiloxane is carried out1H-NMR Analysis obtains the peak value based on epoxy group as a result near chemical shift (δ)=3.2ppm such as theoretical strength, confirms anti- The side reaction of Ying Zhongwei generation epoxy group.The weight average molecular weight Mw of the resulting polysiloxane with epoxy group is 3, 500, epoxide equivalent is 180g/ moles.
Then, in the three-necked flask of 200mL, be added the acquisition the polysiloxane 10.0g with epoxy group, Methyl iso-butyl ketone (MIBK) 30.28g as solvent, the 4- dodecyl p-methoxybenzoic acid 3.98g as carboxylic acid and as catalysis UCAT 18X (trade name, general sieve in Sanya (San-Apro) (stock) manufacture) 0.10g of agent, enters while stirring at 100 DEG C It reacts within row 48 hours.After completion of the reaction, ethyl acetate is added into reaction mixture, and resulting organic layer is subjected to 3 washings, After being dried using magnesium sulfate, distillation removal solvent, thus to obtain polysiloxane (rps-1) 9.0g.Resulting poly- have The weight average molecular weight Mw of organic siloxane (rps-1) is 9,900.
Embodiment 1
1. the preparation of aligning agent for liquid crystal
NMP and fourth are added in the solution containing the imide amination polymer (PI-1) obtained in the synthesis example PI-1 Base cellosolve (butyl cellosolve, BC), is sufficiently stirred, and solvent group is made as NMP：BC=60：40 (weight ratios) are consolidated Body constituent concentration is the solution of 2.5 mass %.The solution is filtered using the filter that aperture is 1 μm, thus preparation solution Brilliant alignment agent.
2. the evaluation of aligning agent for liquid crystal
Printing for the aligning agent for liquid crystal of the preparation and the liquid crystal display manufactured using the aligning agent for liquid crystal The reliability of element is evaluated using following methods.
Evaluation result is shown in the 2nd table.
2~embodiment of embodiment 8, embodiment 10 and embodiment 11 and 1~comparative example of comparative example 5
1. the preparation of aligning agent for liquid crystal
As the solution containing polymer, the solution containing polymer shown in the 2nd table is used respectively, in addition to this, Aligning agent for liquid crystal is prepared in such a way that " preparations of 1. aligning agent for liquid crystal " with the embodiment 1 are identical.
In addition, respectively 2 kinds of polymer are mixed with the ratio recorded in the 2nd table in embodiment 7 and embodiment 8 It uses.
2. the evaluation of aligning agent for liquid crystal
For each aligning agent for liquid crystal of the preparation, evaluated in a manner of identical with the embodiment 1.
Evaluation result is shown in the 2nd table.
Embodiment 9
1. the preparation of aligning agent for liquid crystal
In the solution containing the imide amination polymer (PI-9) obtained in the synthesis example PI-9, the synthesis is added The polysiloxane (rps-1) obtained in example rps-1, and then NMP and butyl cellosolve (BC) are added, it is sufficiently stirred, makes Become NMP at solvent group：BC=60：40 (weight ratios), the solution that solid component concentration is 2.5 mass %.Herein, imidizate Polymer (PI-9) and polysiloxane (rps-1) are with PI-9：The weight ratio of rps-1 becomes 95：5 ratio come using.
The filter for the use of aperture being 1 μm, which is filtered, aligning agent for liquid crystal is thus prepared.
2. the evaluation of aligning agent for liquid crystal
For the aligning agent for liquid crystal of the preparation, evaluated in a manner of identical with the embodiment 1.
Evaluation result is shown in the 2nd table.
Evaluation method (1) > of < aligning agent for liquid crystal
The aligning agent for liquid crystal prepared in the 1~embodiment of embodiment 11 and 1~comparative example of comparative example 5 be utilized respectively with Lower method is evaluated.
1. the evaluation of printing
About the aligning agent for liquid crystal prepared in each embodiment or comparative example, in the case where to printing is carried out continuously on substrate Printing (continuous printing) evaluated.
Firstly, using liquid crystal orientation film printing machine, (Japanese photographic printing (stock) is manufactured, the name of an article " angstrom Gus spy's Ma (Angstromer) S40L-532 "), it is dripped (about with dripping quantity of the aligning agent for liquid crystal to anilox roll (anilox roll) for round-trip 20 Each aligning agent for liquid crystal is coated on the transparent electrode face of the glass substrate with the transparent electrode comprising ito film by condition 0.2g) On.New substrate was used every 1 minute, 20 coatings are implemented to substrate.
Then, add up to and carry out 10 following operations (idle running)：Every 1 minute aligning agent for liquid crystal was distributed to (one way) in net On line roller, at that time, contact anilox roll with galley.Around here, without the printing to glass substrate.The idle running is in order to specially The operation implementing the printing of aligning agent for liquid crystal under harsh situation and carrying out.
After 10 idle running, glass substrate is continued to use formally to be printed.In formal printing, after the idling, every 30 The interval of second puts into 5 pieces of substrates, each substrate after coating of liquid crystalline alignment agent is heated to (prebake conditions) 1 minute at 80 DEG C and removed Solvent, then heating (rear baking) 10 minutes at 200 DEG C, form the film that film thickness is about 80nm.It is 20 times using multiplying power Microscope observes the film, thus evaluates printing.
It is evaluated according to following benchmark.
Not the case where precipitation of polymer is not observed in film from the 1st formal printing after idle running：A (excellent)
The precipitation of polymer is observed in the 1st time after the idling in film when formally printing, but is implementing 5 formal prints The case where precipitation of polymer is no longer observed during brush：B (good)
After 5 formal printings are repeated, the case where also not observing the precipitation of polymer in film：C (bad)
For obtaining the aligning agent for liquid crystal of A evaluation in the evaluation, the number of idle running is changed to 25 times, is carried out again same The evaluation of sample.As a result, the precipitation of polymer is not observed in film from the 1st formal printing after 25 idle running The case where be evaluated as " AA (particularly excellent) ".
2. the evaluation of liquid crystal cells
(1) manufacture of liquid crystal cells
Using liquid crystal orientation film printing machine (Japanese photographic printing (stock) manufactures), will be prepared in the Examples and Comparative Examples Each aligning agent for liquid crystal be coated on the transparent electrode comprising ito film glass substrate transparent electrode face on, at 80 DEG C Heat (prebake conditions) 1 minute in heating plate and after removing solvent, the heating (rear baking) 30 minutes in 210 DEG C of heating plate, shape The film for being 80nm at average film thickness.
The film is moved using including the friction machine for being wound with the roller of rayon cloth with roller revolving speed 500rpm, platform It moves speed 3cm/ seconds and hair is pressed into length 0.4mm to carry out friction treatment, assign liquid crystal aligning ability.Then, in ultrapure water 1 minute ultrasonic washing of middle progress, drying in 10 minutes is then carried out in 100 DEG C of cleaning ovens, is taken thus to obtain with liquid crystal To the substrate of film.Repeat the operation, obtains a pair (2 pieces) substrate with liquid crystal orientation film.
Then, the outer rim in one of face with liquid crystal orientation film in the pair of substrate is infused except liquid crystal Position coating other than entrance is added after having the epoxy resin adhesive that diameter is 5.5 μm of alumina balls, with liquid crystal orientation film A pair of of substrate is overlapped and crimps by the opposite mode in face, hardens bonding agent.Then, it is filled out from liquid crystal injecting port between a pair of of substrate After filling nematic crystal (manufacture of Merck (Merck) company, the name of an article " MLC-6221 "), made using acrylic acid series photo-hardening bonding agent Liquid crystal injecting port sealing, thus manufactures liquid crystal cells.
(2) evaluation of reliability
The liquid crystal cells of the manufacture are carried out with the evaluation of reliability.
Firstly, for liquid crystal cells, after the voltage for applying 5V with the application time of 60 microseconds, 167 milliseconds of span, measurement Voltage retention (VHR1) from applying and releasing after 167 milliseconds.Then, 80 DEG C of bakings by liquid crystal cells under LED light irradiation After standing 200 hours in case, stand at room temperature, cooled to room temperature.For liquid crystal cells after cooling, with 60 microseconds After application time, 167 milliseconds of span apply the voltage of 5V, the voltage retention from applying and releasing after 167 milliseconds is measured (VHR2)。
The change rate (Δ VHR) that voltage retention at this time is calculated using following numerical expressions (1), according to resulting Δ VHR Value, reliability is evaluated with following benchmark.
Δ VHR [%]=(VHR1-VHR2)/(VHR1) × 100 (1)
The case where Δ VHR is less than 1%：A (excellent)
Δ VHR be 1% more than and less than 2% the case where：B (good)
The situation that Δ VHR is 2% or more：C (bad)
2nd table evaluation result (1)
Embodiment 12
1. the preparation of aligning agent for liquid crystal
NMP and fourth are added in the solution containing the imide amination polymer (PA-1) obtained in the synthesis example PA-1 Base cellosolve (BC), is sufficiently stirred, and solvent group is made as NMP：BC=60：40 (weight ratios), solid component concentration are 2.5 matter Measure the solution of %.
The solution is filtered using the filter that aperture is 1 μm, thus prepares aligning agent for liquid crystal.
2. the evaluation of aligning agent for liquid crystal
Printing for the aligning agent for liquid crystal of the preparation and the liquid crystal cells manufactured using the aligning agent for liquid crystal Reliability, evaluated using following methods.
Evaluation result is shown in the 3rd table.
Comparative example 6 and comparative example 7
1. the preparation of aligning agent for liquid crystal
As the solution containing polymer, the solution containing polymer shown in the 3rd table is used respectively, in addition to this, Aligning agent for liquid crystal is prepared in such a way that " preparations of 1. aligning agent for liquid crystal " with the embodiment 12 are identical.
2. the evaluation of aligning agent for liquid crystal
For each aligning agent for liquid crystal of the preparation, evaluated in a manner of identical with the embodiment 12.
Evaluation result is shown in the 3rd table.
Evaluation method (2) > of < aligning agent for liquid crystal
The aligning agent for liquid crystal prepared in the embodiment 12 and comparative example 6 and comparative example 7 be utilized respectively following methods into Row evaluation.
1. the evaluation of printing
For each aligning agent for liquid crystal prepared in the embodiment and comparative example, using with the embodiment 1~implement Example 11 and the identical method of 1~comparative example of comparative example 5 evaluate the continuous printing to substrate, and result is that embodiment 12 is aobvious It shows compared with comparative example 6 and the more good result of comparative example 7.
2. the evaluation of liquid crystal cells
(1) manufacture of the liquid crystal cells of liquid crystal aligning, voltage retention and contrast evaluation
Using rotator, each aligning agent for liquid crystal prepared in the Examples and Comparative Examples is coated on comprising ITO On each transparent electrode face of 2 pieces of (a pair) glass substrates of the transparent electrode of film, then 1 point of the heating (prebake conditions) at 80 DEG C Clock is respectively formed film.For these film coated surfaces, using Hg-Xe lamp, the normal direction of self-reference substrate is with exposure 10,000J/ m2After irradiating the polarisation ultraviolet light of the open-wire line comprising 254nm, heating (rear baking) 1 hour in 230 DEG C of cleaning oven, Liquid crystal orientation film is respectively formed on 2 pieces of (a pair) substrates.
Then, one of in a pair of of substrate for having carried out the photo-irradiation treatment, it is being formed with liquid crystal aligning The outer peripheral edge portion in the face of film, at the position in addition to liquid crystal injecting port, it is 5.5 μm of oxidation that screen painting coating addition, which has diameter, It is opposite with liquid crystal orientation film forming face and plane of polarisation when light irradiates is on real estate after the epoxy resin adhesive of aluminium ball The consistent mode of projecting direction, a pair of of substrate is overlapped and is crimped, and is heated 1 hour at 150 DEG C, so that bonding agent is carried out heat hard Change.
Then, from liquid crystal injecting port to nematic crystal is filled between a pair of of substrate, (Merck (Merck) company is manufactured, the name of an article " MLC-7028 ") after, liquid crystal injecting port is sealed using epoxy bonding agent.In turn, in order to remove liquid crystal injection when flowing Orientation and after being heated to 150 DEG C, is slowly cooled down to room temperature, thus manufactures liquid crystal cells.
(2) evaluation of liquid crystal aligning
For the liquid crystal cells of the manufacture, observed using petrographic microscope when on-off (apply and release) is handed over The presence or absence of abnormal area when the voltage of stream 5V.
It will not be observed in display area and be evaluated as liquid crystal aligning " A (good) " the case where abnormal area, it will be aobvious Show that the case where abnormal area is observed in region is evaluated as liquid crystal aligning " C (bad) ", even if the abnormal area only has 1 Place.
(3) evaluation of voltage retention
For the liquid crystal cells of the manufacture, apply the voltage of 5V with the application time of 60 microseconds, 167 milliseconds of span Afterwards, the voltage retention from applying and releasing after 167 milliseconds is measured.
The measurement device of voltage retention is manufactured using Dongyang Te Kenika (Toyo Technica) limited liability company Pattern name " VHR-1 ".
It is evaluated according to following benchmark.
The situation that voltage retention is 98% or more：Voltage retention " A (good) "
The case where voltage retention is less than 98%：Voltage retention " C (bad) "
(4) manufacture of the liquid crystal cells of image retention characteristic evaluation
In addition to use the substrate of following composition to as a pair of of substrate other than, with described " (1) liquid crystal aligning, electricity The identical mode of the manufacture of pressure conservation rate and the liquid crystal cells of contrast evaluation " manufactures the liquid crystal list of image retention characteristic evaluation First (FFS type liquid crystal cells) are bonded polarizer on the outside two sides of substrate, thus make liquid crystal display element in turn.
Herein, electrode base board is to be formed with 2 system electrodes with comb teeth-shaped pattern and comprising chromium using shown in FIG. 1 The glass substrate of (electrode A (101) and electrode B (102))；
Opposite substrate is the glass substrate using not formed electrode.In the electrode forming surface and opposite substrate of electrode base board The wherein upper coating of liquid crystalline alignment agent of one side.
(5) evaluation of image retention characteristic (burning print (burn-in))
The liquid crystal display element of the manufacture is placed in 25 DEG C, in the environment of 1 air pressure, voltage is not applied to electrode B, it is right Electrode A applies resultant voltage 2 hours of alternating voltage 3.5V and DC voltage 5V.After 2 hours, immediately to electrode A and Electrode B two apply the voltage of exchange 4V.Moreover, measuring since at the time of applying the voltage of exchange 4V to two electrodes, directly To the time until it can not visually confirm the difference of two interelectrode translucency again.
It is evaluated according to following benchmark.
The case where time of the measurement was less than 100 seconds：Image retention characteristic " A (good) "
100 seconds more than and less than 150 seconds the case where：Image retention characteristic " B (can) "
The case where more than 150 seconds：Image retention characteristic " C (bad) "
(6) evaluation of reliability
For the liquid crystal display element of the manufacture, with the 1~embodiment of embodiment 11 and comparative example 1~compared with Identical method evaluates its reliability in example 5, and result is that embodiment 12 shows more good compared with comparative example 6 and comparative example 7 As a result.
3rd table evaluation result (2)

Claims (7)

1. a kind of aligning agent for liquid crystal, which is characterized in that containing on main chain with following structures polymer,
The structure is
* in formula respectively indicates associative key.
2. aligning agent for liquid crystal according to claim 1, which is characterized in that the polymer is by making
Tetracarboxylic dianhydride with
Diamines comprising compound represented by following formula (MDA)
The step of being reacted the polymer that synthesizes,
H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2(MDA)
In formula (MDA),*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2 - *Represented structure is
* in formula respectively indicates associative key.
3. aligning agent for liquid crystal according to claim 2, which is characterized in that the tetracarboxylic dianhydride includes
Selected from by 2,3,5- tricarboxylic cyclopentyl acetic acid dianhydride, bicyclic [3.3.0] octane -2 of 2,4,6,8- tetracarboxylic:4,6:8- bis- Acid anhydride, 1,2,3,4- cyclobutane tetracarboxylic dianhydride, 1,2,4,5- cyclopentanetetracarboxylic dianhydride and 1,2,3,4- pentamethylene tetrabasic carboxylic acid At least one of group compound composed by dianhydride.
4. a kind of liquid crystal orientation film, which is characterized in that by aligning agent for liquid crystal according to any one of claim 1 to 3 Lai It is formed.
5. a kind of liquid crystal display element, which is characterized in that including liquid crystal orientation film according to claim 4.
6. compound represented by a kind of following formula (MDA), which is characterized in that
H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2(MDA)
In formula (MDA),*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-*Represented structure is
* in formula respectively indicates associative key.
7. a kind of polymer, which is characterized in that it is by making
Tetracarboxylic dianhydride with
Diamines comprising compound represented by following formula (MDA)
The step of being reacted the polymer that synthesizes,
H2N-Ph-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-Ph-NH2(MDA)
In formula (MDA),*-X1-(CR1 2)m1-Y-(CR1 2)m2-X2-*Represented structure is
* in formula respectively indicates associative key.
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