CN105567259A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, polymer and compound - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, polymer and compound Download PDF

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Publication number
CN105567259A
CN105567259A CN201510725478.5A CN201510725478A CN105567259A CN 105567259 A CN105567259 A CN 105567259A CN 201510725478 A CN201510725478 A CN 201510725478A CN 105567259 A CN105567259 A CN 105567259A
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liquid crystal
compound
polymkeric substance
formula
base
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CN105567259B (en
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伊藤贤一
秋池利之
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JSR Corp
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JSR Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display device, a polymer and a compound. The invention enables the polymer (P) having a partial structure represented by the following formula (1) to be contained in the liquid crystal aligning agent, in the formula (1), A1 is a single bond or divalent organic group, and R1 is a monovalent organic group with a carbon number of 8 or more. X1 is a protecting group. "*" indicates a bond bonded to a main chain of the polymer. The liquid crystal aligning agent of the invention can balance the solubility of polymer components for a solvent and burned mark reduction of the liquid crystal display device. (img file as shown in the description)

Description

Liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, polymkeric substance and compound
Technical field
The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, polymkeric substance and compound.
Background technology
In the past, as liquid crystal display device, have developed the liquid crystal display device of electrode structure or the different various type of drive of the physical property, manufacturing process etc. of liquid crystal molecule that use, such as known twisted nematic (TwistedNematic, TN) type or STN Super TN (SuperTwistedNematic, STN) type, vertical orientated (VerticalAlignment, VA) type, coplanar switching (In-PlaneSwitching, IPS) the various liquid crystal display device of type, fringing field switching (fringefieldswitching, FFS) type etc.These liquid crystal display device have the liquid crystal orientation film making liquid crystal molecular orientation.
In recent years, in order to realize the further raising of the display performance of liquid crystal display device, various liquid crystal aligning agent is proposed.Such as, to reduce for the purpose of image retention (the burning print of image), propose and use the liquid crystal aligning agent comprising polyimide or its precursor to form liquid crystal orientation film, described polyimide or its precursor have nitrogen-atoms (for example, referring to patent documentation 1 or patent documentation 2) beyond imide.
In patent documentation 1, following situation is proposed: make to comprise 1,2,3, the tetracarboxylic dianhydride of 4-tetramethylene tetracarboxylic dianhydride with comprise the diamine reactant of the diamines with amido linkage and the polyamic acid that obtains and tetracarboxylic dianhydride and diamine reactant and the imide amination polymer of polyamic acid that obtains contains in liquid crystal aligning agent, and the ratio of the quantity of the imide ring had by the imide amination polymer in liquid crystal aligning agent is set to specified range.In patent documentation 1, the improvement of voltage retention and image retention characteristic can be realized by using this liquid crystal aligning agent.
In addition; in patent documentation 2; propose following situation: use the amino protected through third stage butoxy carbonyl (t-BOC yl) be fed to amino relative to one-level and be the aromatic diamine at ortho position, make to utilize this diamines and the polyamic acid that obtains or polyimide contain in liquid crystal aligning agent.And record: according to this technology; heating when being formed by film; remove the protection of t-BOC base and produce amino; pass through the intramolecular reaction of produced amino or intermolecular reaction (crosslinking reaction) and form heterocycle; realize the minimizing of the savings of remnant dc electricity (DirectCurrent, DC) voltage thus.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2009-294274 publication
No. 2013/115228th, [patent documentation 2] International Publication
Summary of the invention
[invention institute for solution problem]
In the liquid crystal display device of vertical orientating type or TN type, STN type etc., be used in side chain and there is the polymkeric substance of the liquid crystal aligning base of linear chain structure or mesomorphic skeleton etc. to form liquid crystal orientation film.In this situation, in order to improve the burning print (burning especially caused because of voltage of alternating current prints) of liquid crystal display device, and consider the side chain of polymkeric substance to be set to upright and outspoken structure, but then, if the side chain of polymkeric substance is set to upright and outspoken structure, then polymkeric substance reduces for the solvability of solvent.That is, the burning print of liquid crystal display device reduces and improves have compromise (tradeoff) relation with structure adaptability, and is difficult to the characteristic having both concurrently.
In addition, when making large-scale liquid crystal panel, there is following situation: after liquid crystal aligning agent printing to substrate, until carry out temporary transient keeping before carrying out next prebake conditions operation, therefore can produce storage period at printing process and prebake conditions inter process.Now, when polymkeric substance is bad for the solvability of solvent, easily produces the uneven or pin hole of printing because of placement, exist as a result and cause the worry that display quality reduces or goods yield reduces.
One object of the present invention is to provide a kind of liquid crystal aligning agent taken into account component of polymer and reduce for the solvability of solvent and the burning print of liquid crystal display device.
[means of dealing with problems]
The present inventor etc. have carried out making great efforts research to solve the problem of prior art as described above, finding by making the polymkeric substance at side chain with the structure that "-NH-" protects through protecting group contain in liquid crystal aligning agent, can solve described problem.Specifically, the present invention can provide following liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, polymkeric substance and compound.
The present invention provides a kind of liquid crystal aligning agent on the one hand, and it contains the polymkeric substance (P) of the part-structure had represented by following formula (1).
[changing 1]
(in formula (1), A 1for the concatenating group of singly-bound or divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number.X 1for protecting group." * " represents the associative key being binding on the main chain of polymkeric substance)
In addition, the present invention provides a kind of liquid crystal orientation film on the other hand, and it uses described liquid crystal aligning agent and is formed.In addition, a kind of liquid crystal display device possessing described liquid crystal orientation film is provided.
The present invention provides one to have the polymkeric substance of the part-structure represented by described formula (1) in another.In addition, the compound represented by a kind of following formula (3) and the compound represented by following formula (4) are provided.
[changing 2]
(in formula (3), A 1for the concatenating group of singly-bound or divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number.X 1for protecting group)
[changing 3]
(in formula (4), A 4for the organic radical of divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number.X 1for protecting group)
[effect of invention]
The solvability of polymkeric substance for solvent, can be set to well containing in liquid crystal aligning agent through protecting group protection by the-NH-of polymer lateral chain thus, under the state of liquid crystal aligning agent.In addition; when liquid crystal aligning agent being coated substrate and is filmed;-NH-is converted to because heating during such as masking or acid or alkali etc. cause protecting group to depart from; the high structure of orientation is regenerated thus after masking; the burning print that result can realize liquid crystal display device reduces (especially the minimizing of alternating-current (AlternatingCurrent, AC) image retention).
Accompanying drawing explanation
Fig. 1 is that expression is manufactured by embodiment and comparative example and has the explanatory view of the pattern of the nesa coating in the liquid crystal cells of patterned nesa coating.
[explanation of symbol]
A, B: glass substrate
Embodiment
Below, each composition comprised liquid crystal aligning agent of the present invention and other compositions optionally and arbitrarily allocated are described.
< polymkeric substance (P) >
Liquid crystal aligning agent of the present invention contains the polymkeric substance (P) of the part-structure had represented by following formula (1).
[changing 4]
(in formula (1), A 1for the concatenating group of singly-bound or divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number.X 1for protecting group." * " represents the associative key being binding on the main chain of polymkeric substance)
In described formula (1), A 1the concatenating group of divalence such as can enumerate: the alkyl of the divalence of carbon number 1 ~ 20; The methylene radical of alkyl is through-O-,-S-,-CO-,-COO-,-COS-,-NR a-or-CO-NR a-(wherein, R aalkyl or protecting group for the monovalence of hydrogen atom, carbon number 1 ~ 12) etc. the base of divalence that replaces; The base of the divalence that at least one hydrogen atom being binding on carbon atom of alkyl replaces through halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), hydroxyl, cyano group etc.;-CO-,-COO-,-NR a-CO-etc.
Here, in this specification sheets, " alkyl " is the implication comprising chain alkyl, ester ring type alkyl and aromatic hydrocarbyl." chain alkyl " in these refers to not containing ring texture in main chain, the straight-chain alkyl be only made up of chain-like structure and branch-like alkyl.Wherein, can be saturated also can be unsaturated." ester ring type alkyl " refer to as ring structure only comprise ester ring type hydrocarbon structure and not containing the alkyl of aromatic ring structure.Wherein, without the need to only by the Structure composing of ester ring type hydrocarbon, also comprise in its part and there is chain-like structure person." aromatic hydrocarbyl " refers to and comprises the alkyl of aromatic ring structure as ring structure.Wherein, without the need to being only made up of aromatic ring structure, the structure of chain-like structure or ester ring type hydrocarbon also can be comprised in its part.So-called " organic radical ", refers to the base comprising alkyl, also can comprise heteroatoms in the structure.
About A 1in the concrete example of alkyl of divalence of carbon number 1 ~ 20, as chain alkyl, such as, can enumerate: methylene radical, ethylidene, propane two base, butane two base, pentane two base, hexane two base, heptane two base, octane two base, nonane two base, decane two base, vinylidene, propylene two base, butylene two base etc.; As ester ring type alkyl, such as, cyclohexylidene etc. can be enumerated; As aromatic hydrocarbyl, such as, can enumerate: phenylene, biphenylene etc.
X 1as long as be the functional group in order in advance amino (-NH-) to be converted to inertia functional group, be then not particularly limited, such as, can enumerate the organic radical etc. of the monovalence departed from by heat, acid or alkali.As X 1, the organic radical of the monovalence departed from preferably by heat, as concrete example, such as, can enumerate: carbamate system protecting group, acid amides system protecting group, imide series protecting group, sulphonamide system protecting group etc.In these; be preferably carbamate system protecting group; as its concrete example; such as can enumerate: tert-butoxycarbonyl, benzyloxycarbonyl, 1; 1-dimethyl-2-halo ethoxy carbonyl, 1,1-dimethyl-2-cyanoethoxy carbonyl, 9-fluorenylmethylcarbonyl, allyloxy carbonyl, 2-(TMS) ethoxy carbonyl etc.With regard to easily carry out the deprotection caused because of heat aspect, maybe can will be derived from the X departed from by heating during masking 1compound be expelled to aspect outside film with the form of gas, be wherein preferably tert-butoxycarbonyl.
R 1it is the organic radical of the monovalence of more than 8 for carbon number.R 1as long as carbon number be more than 8, but with regard to the viewpoint of the orientation that improves liquid crystal molecule, be preferably set to more than 10, be more preferably and be set to more than 12, and then be more preferably and be set to more than 15, be especially preferably set to more than 17.There is no particular restriction for the upper limit of carbon number, such as, can be set to less than 100.R 1structure there is no particular restriction, but the base can enumerated represented by following formula (2) is as preferred concrete example.
[changing 5]
*-A 3-R 3(2)
(in formula (2), A 3for the concatenating group of singly-bound or divalence, R 3for liquid crystal aligning base or light orientation base." * " represents the associative key being binding on nitrogen-atoms)
The R of described formula (2) 3in liquid crystal aligning base and light orientation base be the base can giving tilt angle to liquid crystal molecule.Light orientation base in these is the base showing the characteristic of liquid crystal molecule being carried out to tropism control by rayed, and liquid crystal aligning base is the base that just can not be shown the characteristic of liquid crystal molecule being carried out to tropism control by rayed.As R 3liquid crystal aligning base, specifically, such as can enumerate: directly or carry out the base etc. of bond via concatenating group, these can have substituting group for the alkoxyl group of the alkyl of carbon number 8 ~ 20, the fluoroalkyl of carbon number 8 ~ 20, carbon number 8 ~ 20, the base with steroid (steroid) skeleton of carbon number 17 ~ 51 and multiple ring.
Here, as the alkyl of carbon number 8 ~ 20, such as, can enumerate: octyl group, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl etc.; As the fluoroalkyl of carbon number 8 ~ 20, such as, can enumerate: perfluoro capryl, perfluorooctylethyl group, perfluoro decyl, perfluoro decyl ethyl etc.; As the alkoxyl group of carbon number 8 ~ 20, such as, can enumerate: octyloxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, dodecyloxy, tridecane oxygen base, tetradecyloxyaniline, pentadecane oxygen base, n-Hexadecane oxygen base, heptadecane oxygen base, octadecane oxygen base, nonadecane oxygen base, eicosane oxygen base etc.;
As the base with steroid skeleton of carbon number 17 ~ 51, such as, can enumerate: cholestane base, cholesteryl, lanostane base etc.;
As multiple ring directly or carry out the base of bond via concatenating group, such as can enumerate: following formula (L-1) ~ formula (L-10)
[changing 6]
(in formula (L-1) ~ formula (L-10), X 3for singly-bound ,-C 2h 4-, * 1-COO-, * 1-OCO-, * 1-COS-, * 1-SCO-, * 1-NR bcO-, * 1-CONR b-, * 1-CH 2o-, * 1-OCH 2-, * 1-CH 2s-or * 1-SCH 2-(wherein, R bfor the alkyl of hydrogen atom, carbon number 1 ~ 6 or the organic radical of monovalence that departed from by heat." * 1 " represents the associative key with the ring structure with " * ").N is the integer of 0 ~ 20, and m is the integer of 1 ~ 20." * " represents and the A in described formula (2) 3associative key)
Base etc. respectively.The alkyl of carbon number 8 ~ 20, fluoroalkyl and alkoxyl group can be straight-chain, also can be branch-like, but are preferably straight-chain.
In described formula (L-1) ~ formula (L-5), base " C nh 2n+1-" be preferably straight-chain.In described formula (L-6) ~ formula (L-10), base " C mf 2m+1-" and base "-C nh 2n-" be preferably straight-chain respectively.N is preferably 2 ~ 20, is more preferably 3 ~ 15.M is preferably 1 ~ 15, is more preferably 1 ~ 10.
As the substituting group that liquid crystal aligning base can have, such as, can enumerate: the optical polymerism bases etc. such as (methyl) acryloxy, styryl, maleimide base, vinyl, vinyl ether group, allyl group, vinylidene.In these, with regard to the aspect that photoreactivity is high, preferably can use (methyl) acryloxy, styryl or maleimide base.In addition, " (methyl) acryloxy " is for comprising the implication of " acryloxy " and " methacryloxy ".
As A 3the concatenating group of divalence, such as can enumerate: alkane two base of carbonyl, carbon number 1 ~ 10, " * 2-CO-R c-COO-" (wherein, R cfor alkane two base or the cyclohexylidene of carbon number 1 ~ 10." * 2 " represent the associative key with nitrogen-atoms) etc.
R 3light orientation base be by photoisomerization or photodimerization, photolysis etc. and show the base of orientation restraint, as its concrete example, such as can enumerate: containing the base containing azo of azo-compound or derivatives thereof as basic framework, containing the base containing styracin of styracin or derivatives thereof as basic framework, containing the base containing phenyl styryl ketone of phenyl styryl ketone or derivatives thereof as basic framework, containing the base containing benzophenone of benzophenone or derivatives thereof as basic framework, containing the base containing tonka bean camphor of tonka bean camphor or derivatives thereof as basic framework, containing the base etc. containing tetramethylene of tetramethylene or derivatives thereof as basic framework.In these, the aspect good with regard to light orientation and be directed into polymkeric substance easness viewpoint with regard to, be preferably containing the base of azo or containing the base of styracin.
As the base containing azo, as long as have azo-group (-N=N-), then there is no particular restriction, such as, can enumerate the base etc. represented by following formula (y-1).
[changing 7]
R 4-A 5-N＝N-A 4-*(y-1)
(in formula (y-1), A 4and A 5be separately the organic radical of divalence, R 4for liquid crystal aligning base)
In formula (y-1), as A 4and A 5the organic radical of divalence, such as can enumerate: the alkyl of the divalence of carbon number 1 ~ 20; The methylene radical of alkyl is through-O-,-S-,-CO-,-COO-,-COS-,-NR a-or-CO-NR a-(wherein, R aalkyl or protecting group for the monovalence of hydrogen atom, carbon number 1 ~ 12) etc. the base of divalence that replaces; The base etc. being binding on the divalence that at least one hydrogen atom on carbon atom replaces through halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), hydroxyl, cyano group etc. of alkyl.About R 5liquid crystal aligning base, the R of described formula (2) can be applied 3the explanation of liquid crystal aligning base.
As the concrete example of the base represented by described formula (y-1), such as, can enumerate the base etc. represented by following formula (y-1-1) ~ formula (y-1-10) difference.
[changing 8]
(in formula (y-1-1) ~ formula (y-1-10), X 4for singly-bound ,-C 2h 4-, * 3-COO-, * 3-OCO-, * 3-COS-, * 3-SCO-, * 3-NR dcO-, * 3-CONR d-, * 3-CH 2o-, * 3-OCH 2-, * 3-CH 2s-or * 3-SCH 2-(wherein, R dfor alkyl or the protecting group of hydrogen atom, carbon number 1 ~ 6." * 3 " represent the associative key with azobenzene structure).N is the integer of 0 ~ 20, and m is the integer of 1 ~ 20.X 3implication and described formula (L-1) ~ formula (L-10) in X 3identical)
About the base containing styracin, as its concrete example, such as, can enumerate: the base represented by following formula (x-1) and the base etc. represented by following formula (x-2).
[changing 9]
(in formula (x-1) and formula (x-2), R 11and R 14be separately hydrogen atom, fluorine atom, the alkyl of carbon number 1 ~ 20 or the fluoroalkyl of carbon number 1 ~ 20.X 11and X 13be separately singly-bound, Sauerstoffatom, sulphur atom, *-COO-or *-OCO-(wherein, with " * " associative key respectively with R 11or R 14bond).X 12for alkane two base of singly-bound, Sauerstoffatom, sulphur atom, carbon number 1 ~ 3, *-COO-or *-OCO-are (wherein, with associative key and the R of " * " 12bond).R 12and R 15be separately Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene.X 14for alkane two base of singly-bound, carbon number 1 ~ 3, Sauerstoffatom, sulphur atom or-NH-.X 15for Sauerstoffatom, *-COO-or *-OCO-are (wherein, with associative key and the R of " * " 16bond).R 16for the thick cyclic group of the aromatic series base of divalence, the ester ring type base of divalence, the hetero ring type base of divalence or divalence.R 17for singly-bound, *-OCO-(CH 2) h-or *-O-(CH 2) i-(wherein, with associative key and the R of " * " 16bond, h and i is respectively the integer of 1 ~ 10).R 16for *-COO-or *-OCO-is (wherein, with associative key and the R of " * " 17bond).R 13and R 18be separately fluorine atom, cyano group or methyl.R 19and R 20be separately alkane two base or the Isosorbide-5-Nitrae-cyclohexylidene of carbon number 1 ~ 10.A, e and d are separately the integer of 0 ~ 3, b and f be separately 0 or 1, c and g be separately 0 ~ 4 integer)
As the concrete example of the base represented by described formula (x-1), such as, can enumerate: the base etc. represented by following formula (x-1-1) ~ formula (x-1-13) difference; As the concrete example of the base represented by described formula (x-2), such as, can enumerate: the compound etc. represented by following formula (x-2-1) ~ formula (x-2-2) difference.In addition, in addition, the base recorded in Japanese Patent Laid-Open 2011-133825 publication can be enumerated.
[changing 10]
(in formula, R 11and the R in the implication of b and described formula (x-1) 11and b is identical)
[changing 11]
(in formula, R 14and the R in the implication of f and described formula (x-2) 14and f is identical)
With regard to the aspect that the burning print minimizing effect of liquid crystal display device is high, the part-structure represented by described formula (1) is preferably following formula (1-1) or the base represented by formula (1-2).
[changing 12]
(in formula (1-1) and formula (1-2), A 2for the organic radical of singly-bound or divalence, R 2for the organic radical of monovalence.X 1, A 1and R 1implication identical with described formula (1)." * " represents the associative key be binding on the main chain of polymkeric substance)
About A 2the organic radical of divalence, the A of described formula (y-1) can be applied 4and A 5the illustration of explanation, about R 2the organic radical of monovalence, the R of described formula (1) can be applied 1the illustration of explanation.
" * " in described formula (1) represents the associative key being binding on the main chain of polymkeric substance.Here, in the bright book of this institute, " main chain " of so-called polymkeric substance, refers to the part of " backbone " of the connection chain comprising the longest atom in polymkeric substance, and so-called " side chain ", refers to the part of " backbone " branch of autohemagglutination compound.
There is no particular restriction for the main framing of polymkeric substance (P), such as, can enumerate the skeleton comprising polyamic acid, polyimide, poly amic acid ester, organopolysiloxane, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc.In these, with regard to thermotolerance or mechanical strength, with the viewpoint such as the affinity of liquid crystal with regard to, be preferably selected from least one polymkeric substance in the cohort be made up of polyamic acid, poly amic acid ester, polyimide and organopolysiloxane.In addition, (methyl) acrylate refers to and comprises acrylate and methacrylic ester.
(polyamic acid)
When polymkeric substance (P) is for polyamic acid, this polyamic acid is by making tetracarboxylic dianhydride and diamine reactant and obtaining.There is the polyamic acid of the part-structure (hereinafter also referred to " specific part structure ") represented by described formula (1) by (" * " wherein, in formula (1) represents associative key containing having specific part structure in monomer composition.About identical below monomer) tetracarboxylic dianhydride and have specific part structure diamines at least any one when polymerization and obtain.With regard to the aspect that the degree of freedom of the selection of compound is high, be preferably the diamines (hereinafter also referred to " specific diamines ") using and there is specific part structure.
(tetracarboxylic dianhydride)
As the tetracarboxylic dianhydride for the synthesis of polyamic acid, such as, can enumerate: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.About these concrete example, as aliphatics tetracarboxylic dianhydride, such as, can enumerate butane tetracarboxylic acid dianhydride etc.;
As ester ring type tetracarboxylic dianhydride, such as can enumerate: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2:3, 5:6-dianhydride, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic acid 2:4, 6:8-dianhydride, dicyclo [2.2.1] heptane-2, 3, 5, 6-tetracarboxylic acid 2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, 1,2,4, pungent-7-the alkene-2,3,5 of 5-cyclopentanetetracarboxylic dianhydride, dicyclo [2.2.2], 6-tetracarboxylic dianhydride, ethylenediamine tetraacetic acid (EDTA) dianhydride, pentamethylene tetracarboxylic dianhydride, ethylene glycol bis (dehydration trimellitate), 1,3-PD two (dehydration trimellitate) etc.,
As aromatic tetracarboxylic acid's dianhydride, such as, pyromellitic acid anhydride etc. can be enumerated; In addition, the tetracarboxylic dianhydride recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.In addition, tetracarboxylic dianhydride can be used alone the one in these tetracarboxylic dianhydrides or combinationally use two or more.
As the tetracarboxylic dianhydride for the synthesis of polyamic acid, with regard to the aspect that the various characteristics of liquid crystal display device can be made better, preferably comprise and be selected from by 1 in described tetracarboxylic dianhydride, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 5-(2, 5-dioxotetrahydro furans-3-base)-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 5-(2, 5-dioxotetrahydro furans-3-base)-8-methyl-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] at least one compound in the cohort that forms of undecane-3,5,8,10-tetraketone, dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, cyclopentanetetracarboxylic's dianhydride and pyromellitic acid anhydride.Relative to the total amount of the tetracarboxylic dianhydride for the synthesis of polyamic acid, the usage quantity (being its total amount when using two or more) of these preferred compounds is preferably set to more than 5 % by mole, be more preferably and be set to more than 10 % by mole, and then be more preferably and be set to more than 20 % by mole.
(diamines)
As long as specific diamines have described specific part structure then all the other structures there is no particular restriction, such as can enumerate the compound etc. represented by following formula (3).
[changing 13]
(in formula (3), A 1, R 1and X 1implication identical with described formula (1))
About the A of described formula (3) 1, R 1and X 1, the explanation of described formula (1) can be applied.As the concrete example of specific diamines, the compound etc. represented by following formula (3-1) ~ formula (3-19) difference can be enumerated.
[changing 14]
[changing 15]
[changing 16]
[changing 17]
(in formula, n is the integer of 0 ~ 20)
In addition, when synthesizing polyamides acid, specific diamines can be used alone one or combinationally use two or more.
Diamines for the synthesis of the polyamic acid as polymkeric substance (P) can be only specific diamines, also can also with other diamines except specific diamines.
As other diamines, such as, can enumerate: aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.About these concrete example, as aliphatie diamine, such as, can enumerate: m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, 1,3-two (amino methyl) hexanaphthenes etc.; As ester ring type diamines, such as, can enumerate: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (hexahydroaniline) etc.;
As aromatic diamine, such as, can enumerate: dodecyloxy diaminobenzene, tetradecyloxyaniline diaminobenzene, pentadecane oxygen base diaminobenzene, n-Hexadecane oxygen base diaminobenzene, octadecane oxygen base diaminobenzene, cholestane base oxygen base diaminobenzene (cholestanyloxydiaminobenzene), cholesteryl oxygen base diaminobenzene, diaminobenzoic acid cholestane base ester, diaminobenzoic acid cholesteryl ester, diaminobenzoic acid lanostane base ester, two (the 4-amino benzoyl oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene of 1,1-, N-(2,4-diamino-phenyl)-4-(4-heptyl cyclohexyl) benzamide, following formula (E-1) or following formula (E-2)
[changing 18]
(in formula (E-1) and formula (E-2), X iand X iIbe separately singly-bound ,-O-,-COO-or-OCO-, R ifor alkane two base of carbon number 1 ~ 3, R iIfor alkane two base of singly-bound or carbon number 1 ~ 3, X iIIfor hydrogen atom or optical polymerism base.R be 0 or 1, s be the integer of 0 ~ 2, t is the integer of 1 ~ 20, and u is 0 or 1.Wherein, be 0 when r and s is different.Two R in formula (E-2) iIcan identical also can be different)
Represented compounds etc. are containing the diamines of orientation base;
Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 4-aminophenyl-4 '-Aminobenzoate, 4,4 '-chrysoidine, two (4-amino-benzene oxygen) pentane of 1,5-, two (4-amino-benzene oxygen) heptane of 1,7-, two [2-(4-aminophenyl) ethyl] hexanodioic acid, two (4-aminophenyl) methylamine of N, N-, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylene diisopropylidene) dianiline, 4,4 '-(metaphenylene diisopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid etc.,
As diamino organo-siloxane, such as, can enumerate: two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc.; In addition, the diamines recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.
As the "-X in described formula (E-1) i-(R i-X iI) u-" represented by the base of divalence, be preferably alkane two base of carbon number 1 ~ 3, *-O-, *-COO-or *-O-C 2h 4-O-(wherein, with associative key and the diamino-phenyl bond of " * ").Base "-C th 2t+1" and base "-C th 2t-" be preferably straight-chain.
As X iIIoptical polymerism base, be preferably (methyl) acryloxy, styryl or maleimide base.Two amino in diamino-phenyl in described formula (E-1) and formula (E-2) are preferably positioned at 2 relative to other bases, 4-position or 3,5-position.
As the concrete example of the compound represented by described formula (E-1) and formula (E-2), such as, can enumerate: following formula (E-1-1) ~ formula (E-1-4) and the respective represented compound etc. of formula (E-2-1).
[changing 19]
As other diamines, print for the purpose of this improvement effect to improve the burning reducing the liquid crystal display device caused by volts DS, also and then the diamines with particular functional base can be used.As this diamines, such as, can enumerate: the diamines containing N structure with at least one in the cohort being selected from and being made up of nitrogen heterocyclic ring, secondary amino and tertiary amine base, or there is the diamines etc. of carboxyl.
As the diamines had containing N structure, such as can enumerate: 2,6-diamino-pyridine, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3, compound etc. represented by 6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, following formula (E-3-1) ~ formula (E-3-6) difference.
[changing 20]
As the diamines with carboxyl, such as, can enumerate: the monocarboxylic acids such as 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acids, 2,5-diaminobenzoic acids;
4,4 '-benzidine-3,3 '-dicarboxylic acid, 4,4 '-benzidine-2,2 '-dicarboxylic acid, 3,3 '-benzidine-4,4 '-dicarboxylic acid, 3,3 '-benzidine-2,4 '-dicarboxylic acid, 4,4 '-diaminodiphenyl-methane-3,3 '-dicarboxylic acid, 4,4 '-diamino-diphenyl ethane-3,3 '-dicarboxylic acid, 4, the polycarboxylic acids etc. such as 4 '-diamino-diphenyl ether-3,3 '-dicarboxylic acid.
With regard to fully obtain polymkeric substance for the deliquescent liquid crystal display device improving effect or caused by voltage of alternating current of solvent burning print reduce effect viewpoint with regard to, relative to total scale of construction of diamines, the allotment ratio of specific diamines is preferably set to more than 1 % by mole by the diamines used during synthesizing polyamides acid, be more preferably and be set to more than 3 moles %, and then be more preferably and be set to more than 5 % by mole, be especially preferably set to more than 10 % by mole.In the viewpoint that can show suitable tilt angle, the upper limit of the usage ratio of specific diamines is preferably set to less than 70 % by mole, is more preferably and is set to less than 60 % by mole, and then is more preferably less than 50 % by mole.
With regard to fully obtaining the viewpoint of the effect of the burning print minimizing of the liquid crystal display device caused by volts DS, relative to for the synthesis of in total scale of construction of diamines, the usage ratio had containing the diamines of N structure is preferably set to more than 0.1 % by mole, be more preferably 1 % by mole ~ 50 % by mole, and then be more preferably 2 % by mole ~ 30 % by mole.Relative to for the synthesis of in total scale of construction of diamines, the usage ratio with the diamines of carboxyl is preferably set to more than 1 % by mole, is more preferably 2 % by mole ~ 90 % by mole, and then is more preferably 5 % by mole ~ 80 % by mole.In addition, other diamines can be used alone one or combinationally use two or more.
(synthesis of specific diamines)
Specific diamines synthesizes by the known method of proper combination.As one example, such as, following methods can be enumerated: synthesis has the dinitrobenzene intermediate of nitro to replace the one-level in described formula (3) amino, then, uses suitable restoring system to make the method etc. of the nitro amination of the dinitrobenzene intermediate of gained.In addition, the method for synthesizing dinitrobenzene intermediate can be suitable for according to the compound as object selecting.Dinitro compound and two carbonic acid two-tertiary butyl ester such as by making to have "-NH-" react under the existence of the highly basic such as dimethyl aminopyridine, and synthesize the dinitrobenzene intermediate that "-NH-" protect through tert-butoxycarbonyl.Wherein, described in the synthetic method of specific diamines is not limited to.
(synthesis of polyamic acid)
Polyamic acid reacts by making tetracarboxylic dianhydride as described above and diamines and molecular weight adjusting agent optionally and obtains.The usage ratio of the tetracarboxylic dianhydride and diamines that are supplied to the building-up reactions of polyamic acid is preferably amino 1 equivalent relative to diamines, and the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.2 equivalent ~ 2 equivalent, is more preferably the ratio becoming 0.3 equivalent ~ 1.2 equivalent.
As molecular weight adjusting agent, such as, can enumerate: sour single acid anhydrides such as MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, the monoamine compounds such as aniline, hexahydroaniline, n-Butyl Amine 99, the monoisocyanate compound such as phenylcarbimide, naphthyl isocyanate etc.Relative to total 100 weight part of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight adjusting agent is preferably set to below 20 weight parts, is more preferably and is set to below 10 weight parts.
The building-up reactions of polyamic acid is preferably carried out in organic solvent.Temperature of reaction is now preferably-20 DEG C ~ 150 DEG C, is more preferably 0 DEG C ~ 100 DEG C.In addition, the reaction times is preferably 0.1 hour ~ 24 hours, is more preferably 0.5 hour ~ 12 hours.
As the organic solvent for reacting, such as, can enumerate: aprotic polar solvent, phenol system solvent, alcohol, ketone, ester, ether, halon, hydrocarbon etc.In these organic solvents, be preferably more than one that use and be selected from the cohort (organic solvent of the first cohort) be made up of aprotic polar solvent and phenol system solvent, or be selected from more than one and more than one the mixture be selected from the cohort (organic solvent of the second cohort) that is made up of alcohol, ketone, ester, ether, halon and hydrocarbon in the organic solvent of the first cohort.When for the latter, relative to the total amount of the organic solvent of the first cohort and the organic solvent of the second cohort, the usage ratio of the organic solvent of the second cohort is preferably less than 50 % by weight, is more preferably less than 40 % by weight, and then is more preferably less than 30 % by weight.
About especially preferred organic solvent, being preferably use is selected from by METHYLPYRROLIDONE, N, N-N,N-DIMETHYLACETAMIDE, N, more than one in the cohort that dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA, meta-cresol, xylenol and halogenation phenol form as solvent, or use these the mixture of more than one and other organic solvent in the scope of described ratio.The usage quantity (a) of organic solvent is preferably set to the total amount (a+b) relative to reaction soln, and the total amount (b) of tetracarboxylic dianhydride and diamines becomes the amount of 0.1 % by weight ~ 50 % by weight.
Obtain the reaction soln dissolved by polyamic acid in this way.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after polyamic acid contained in reaction soln can being separated, reoffer to the preparation of liquid crystal aligning agent after maybe can also carrying out purifying to be separated polyamic acid.The separation of polyamic acid and purifying can carry out according to known method.
(polyimide)
As the polyimide of polymkeric substance (P), such as, by making the polyamic acid synthesized as described above carry out dehydration closed-loop, imidization and obtaining in addition.When making polyimide when carrying out dehydration closed-loop to polyamic acid, the reaction soln of polyamic acid directly can be supplied to dehydration closed-loop reaction, also reoffer to dehydration closed-loop reaction after polyamic acid contained in reaction soln can being separated, reoffer after maybe can also carrying out purifying to be separated polyamic acid and react to dehydration closed-loop.
Polyimide can be the complete imide compound that the whole amido acid structures had the polyamic acid as its precursor carry out dehydration closed-loop, also can be and only carries out dehydration closed-loop to a part for amido acid structure and make amido acid structure and imide ring structure and the part imide compound of depositing.Imide rate for the polyimide reacted is preferably more than 10%, is more preferably 20% ~ 99%, and then is more preferably 30% ~ 99%.This imide rate is the ratio shared by quantity representing the imide ring structure of the total relative to the quantity of the amido acid structure of polyimide and the quantity of imide ring structure with percentage.Here, a part for imide ring can be different imide ring.
The dehydration closed-loop of polyamic acid carries out preferably by following methods: the method heated polyamic acid; Or polyamic acid is dissolved in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, optionally carry out the method heated.Wherein, a kind of rear method of utilization is preferably.
Add in the method for dewatering agent and dehydration closed-loop catalyzer in the solution of polyamic acid, as dewatering agent, such as, can use the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.Relative to 1 mole of the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably set to 0.01 mole ~ 20 moles.As dehydration closed-loop catalyzer, such as, can use the tertiary amines such as pyridine, collidine (collidine), two picolins (lutidine), triethylamine.Relative to used dewatering agent 1 mole, the usage quantity of dehydration closed-loop catalyzer is preferably set to 0.01 mole ~ 10 moles.As the organic solvent reacted for dehydration closed-loop, the illustrative organic solvent as the organic solvent for the synthesis of polyamic acid can be enumerated.The temperature of reaction of dehydration closed-loop reaction is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 150 DEG C.Reaction times is preferably 1.0 hours ~ 120 hours, is more preferably 2.0 hours ~ 30 hours.
The reaction soln obtained containing polyimide in this way.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer after can removing dewatering agent and dehydration closed-loop catalyzer from reaction soln to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after polyimide can being separated, maybe can also reoffer after be separated polyimide purifying to the preparation of liquid crystal aligning agent.These purification process can be carried out according to known method.
(poly amic acid ester)
Poly amic acid ester as polymkeric substance (P) such as obtains by following methods: [I] makes to have the method that the polyamic acid of described specific part structure and esterifying agent react; [II] makes the method for tetracarboxylic acid diester and diamine reactant; [III] makes the method etc. of tetracarboxylic acid diester dihalide and diamine reactant.
Here, as the esterifying agent used in method [I], such as, can enumerate: the compound of hydroxyl, acetal based compound, compound etc. containing epoxy group(ing).About these concrete example, as the compound of hydroxyl, such as, can enumerate: the alcohols such as methyl alcohol, ethanol, propyl alcohol, the phenols such as phenol, cresols etc.; As acetal based compound, such as, can enumerate: DMF diethyl acetal, N, N-diethylformamide diethyl acetal etc.; As the compound containing epoxy group(ing), such as, propylene oxide etc. can be enumerated.
The tetracarboxylic acid diester used in method [II] such as obtains by using the alcohols such as methyl alcohol or ethanol to make tetracarboxylic dianhydride's open loop illustrated in the synthesis of described polyamic acid.In addition, as the diamines used in method [II], diamines illustrated in the synthesis of polyamic acid can be enumerated, preferably comprise specific diamines.The reaction of method [II] to be preferably in organic solvent and to carry out under the existence of suitable dehydration catalyst.As organic solvent, the illustrative organic solvent as the organic solvent for the synthesis of polyamic acid can be enumerated.As dehydration catalyst, such as, can enumerate: 4-(4,6-dimethoxy-1,3,5-triazines-2-base)-4-methylmorpholine halogenide, carbonylic imidazole, phosphorus system condensing agent etc.
The tetracarboxylic acid diester dihalide used in method [III] such as obtains by making the suitable chlorination reaction such as the tetracarboxylic acid diester of gained as described above and thionyl chloride.In addition, as the diamines used in method [III], diamines illustrated in the synthesis of polyamic acid can be enumerated, preferably comprise specific diamines.The reaction of method [III] to be preferably in organic solvent and to carry out under the existence of suitable alkali.As organic solvent, the illustrative organic solvent as the organic solvent for the synthesis of polyamic acid can be enumerated.As alkali, such as, can preferably use the tertiary amine such as pyridine, triethylamine.
So obtain the reaction soln dissolved by poly amic acid ester.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after poly amic acid ester contained in reaction soln can being separated, or also can reoffer after be separated poly amic acid ester purifying to the preparation of liquid crystal aligning agent.The separation of poly amic acid ester and purifying can carry out according to known method.In addition, the poly amic acid ester contained by liquid crystal aligning agent can only have amic acid esters structure, also can be amido acid structure and amic acid esters structure and the partial esterification thing deposited.
Soltion viscosity as the polyamic acid of polymkeric substance (P), poly amic acid ester and polyimide is preferably when being made into concentration and being the solution of 10 % by weight, there is the soltion viscosity of 10mPas ~ 800mPas, be more preferably the soltion viscosity with 15mPas ~ 500mPas.In addition, the value that measures for using the polymers soln that E type rotational viscosimeter is 10 % by weight to the concentration used prepared by the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of polymkeric substance at 25 DEG C of the soltion viscosity (mPas) of polymkeric substance.
In addition, the weight average molecular weight (Mw) of the polystyrene conversion measured by gel permeation chromatography (gelpermeationchromatography, GPC) is preferably 1,000 ~ 500,000, is more preferably 2,000 ~ 300,000.In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw and the number average molecular weight (Mn) of the polystyrene conversion measured by GPC is preferably less than 15, is more preferably less than 10.
(organopolysiloxane)
As the synthetic method of the organopolysiloxane (hereinafter also referred to as " organopolysiloxane containing specific base ") of polymkeric substance (P), such as, can enumerate:
[1] make following polymkeric substance (following, also referred to as " organopolysiloxane containing epoxy group(ing) ") carry out the method for reacting with the carboxylic acid (hereinafter also referred to " specific carboxylic acid ") with described specific part structure, described polymkeric substance makes to have the water-disintegrable silane compound (ms-1) of epoxy group(ing) or this silane compound (ms-1) and the mixture of other silane compounds to be hydrolyzed condensation and obtaining;
[2] mixture of the water-disintegrable silane compound or this silane compound and other silane compounds with described specific part structure is made to be hydrolyzed the method etc. of condensation.
In these, with regard to importing with regard to the aspect of specific part structure with high-level efficiency, be preferably the method for described [1].
As the concrete example of the silane compound (ms-1) for the synthesis of the organopolysiloxane containing epoxy group(ing), such as, can enumerate: 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl diethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl-methyl dimethoxysilane, 2-glycidoxypropyl ethyl dimethyl methoxy silane, 2-glycidoxypropyl ethyl dimethylethoxysilane, 4-glycidoxypropyl butyl trimethoxy silane, 4-glycidoxypropyl butyl methyl dimethoxysilane, 4-glycidoxypropyl butyl methyl diethoxy silane, 4-glycidoxypropyl Butyldimethyl methoxy silane, 4-glycidoxypropyl Butyldimethyl Ethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-epoxycyclohexyl) ethyl triethoxysilane, 3-(3,4-epoxycyclohexyl) propyl trimethoxy silicane etc.As silane compound (ms-1), the one or used in combination two or more that can be used alone in these.
As long as other silane compounds are then not particularly limited for indicating water-disintegrable silane compound, can suitablely according to the drive pattern of liquid crystal display device etc. select.As the concrete example of other silane compounds, such as, can enumerate: the alkoxysilane compound containing trialkylsilyl group in molecular structure such as tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane;
The alkoxysilane compound containing trialkylsilyl group in molecular structure of the nitrogenous sulphur such as 3-mercaptopropyi Trimethoxy silane, 3-Mercaptopropyltriethoxysilane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, 3-ureido-propyl Trimethoxy silane, 3-TSL 8330, APTES, N-(3-Cyclohexylamino) propyl trimethoxy silicane;
3-(methyl) acryloxypropyl Trimethoxy silane, 3-(methyl) acryloxypropyl triethoxyl silane, 3-(methyl) acryloxypropyl dimethoxysilane, 3-(methyl) acryloxypropyl diethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, to the alkoxysilane compound containing trialkylsilyl group in molecular structure containing unsaturated link(age) such as styryl Trimethoxy silane;
Trimethoxysilylpropyl succinyl oxide, there is the alkoxysilane compound containing trialkylsilyl group in molecular structure etc. of silicon-silicon bond.Other silane compounds can be used alone the one in these or combinationally use two or more.
Described specific part structure can be directed into fully the side chain of polymkeric substance, and suppress in the viewpoint of the side reaction caused because epoxy group(ing) is excessive, epoxy equivalent (weight) containing the organopolysiloxane of epoxy group(ing) is preferably 80g/ mole ~ 10,000g/ mole, be more preferably 100g/ mole ~ 1,000g/ mole.Therefore, when synthesizing the organopolysiloxane containing epoxy group(ing), the mode be preferably silane compound (ms-1) and the usage ratio of other silane compounds become described scope with the epoxy equivalent (weight) of the organopolysiloxane of gained adjusts.
The hydrolysis-condensation reaction of silane compound is undertaken by making one or more and water of silane compound as described above be preferably to react under the existence of suitable catalyzer and organic solvent.During hydrolysis-condensation reaction, relative to silane compound (total amount) 1 mole, the usage ratio of water is preferably 0.5 mole ~ 100 moles, is more preferably 1 mole ~ 30 moles.
As the catalyzer used during hydrolysis-condensation reaction, such as, can enumerate: acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc.Organic bases is preferably three grades of organic amines as triethylamine, three-Tri N-Propyl Amine, three-n-Butyl Amine 99, pyridine, 4-dimethylaminopyridine, diazabicycloundecene; Level Four organic amine as tetramethyl ammonium hydroxide.
As described catalyzer, can suppress the side reactions such as the open loop of epoxy group(ing) in maybe can improve hydrolytic condensation speed in, excellent storage stability in etc. in, in these be preferably alkali metal compound or organic bases, be more preferably organic bases.
The usage quantity of organic bases is different according to the reaction conditions such as kind, temperature of organic bases etc., should set aptly, relative to all silane compounds, is preferably 0.01 times mole ~ 3 times moles, be more preferably 0.05 times mole ~ 1 times mole.
As the organic solvent used during hydrolysis-condensation reaction, such as, can enumerate: hydrocarbon, ketone, ester, ether, alcohol etc.About these concrete example, as hydrocarbon, such as, can enumerate: toluene, dimethylbenzene etc.; As ketone, such as, can enumerate: methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl n-pentyl ester ketone, metacetone, pimelinketone, cyclopentanone etc.; As ester, such as, can enumerate: ethyl acetate, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol methyl ether acetate, 3-methoxybutyl acetic ester, ethyl lactate etc.; As ether, such as, can enumerate: glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran (THF), diox etc.; As alcohol, such as, can enumerate: 1-hexanol, 4-methyl-2-amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether etc.Preferably use the non-water-soluble organic solvent in these.In addition, these organic solvents can be used alone one or combinationally use two or more.
Relative to all silane compounds 100 weight part for reacting, the usage ratio of the organic solvent in hydrolysis-condensation reaction is preferably 10 weight part ~ 10, and 000 weight part is more preferably 50 weight part ~ 1,000 weight part.
About hydrolysis-condensation reaction, preferably silane compound is as described above dissolved in organic solvent, this solution is mixed with organic bases and water, and undertaken heating and implementing by such as oil bath etc.During hydrolysis-condensation reaction, preferably Heating temperature is set to less than 130 DEG C, is more preferably and is set to 40 DEG C ~ 100 DEG C.Preferably be set to 0.5 hour ~ 12 hours heat-up time, be more preferably and be set to 1 hour ~ 8 hours.Add and hanker, can liquid be uniformly mixed, also can place under reflux.After reaction terminates, preferably utilize water to clean point organic solvent layer got from reaction solution.During this cleaning, by using the water (such as, the aqueous ammonium nitrate solution etc. of about 0.2 % by weight) comprising a small amount of salt to clean, thus cleaning operation transfiguration is easy, from this respect preferably.Cleaning is till the water layer after proceeding to cleaning becomes neutrality, then optionally utilize the siccative such as anhydrous calciumsulphate, molecular sieve (molecularsieve) by after the drying of organic solvent layer, solvent is removed, the organopolysiloxane as target can be obtained thus.
In the method for described [1], then, the organopolysiloxane containing epoxy group(ing) making to be obtained by described reaction and specific carboxylic acid reaction.Thus, the epoxy group(ing) that the organopolysiloxane containing epoxy group(ing) has and carboxylic acid reaction, and the organopolysiloxane at side chain with described specific part structure can be obtained.
As for the synthesis of specific carboxylic acid, as long as have described specific part structure then all the other structures there is no particular restriction, such as can enumerate the compound etc. represented by following formula (4).
[changing 21]
(in formula (4), A 4for the organic radical of divalence; R 1and X 1implication identical with described formula (1))
The A of described formula (4) 4the A of described formula (1) can be applied 1the explanation of organic radical of divalence, be preferably the alkyl of divalence.About R 1and X 1, the explanation of described formula (1) can be applied.As the concrete example of specific carboxylic acid, the compound etc. represented by following formula (4-1) ~ formula (4-19) difference can be enumerated.
[changing 22]
[changing 23]
[changing 24]
[changing 25]
(in formula, n is the integer of 0 ~ 20)
In addition, specific carboxylic acid can be used alone one or combinationally use two or more.
The synthetic method of specific carboxylic acid is not particularly limited, and existing known method capable of being combined is synthesized.As an example of synthetic method, such as, following methods can be enumerated: by making that there is "-NHR 1" halogenide and two carbonic acid two-tertiary butyl ester react under the existence of the highly basic such as dimethyl aminopyridine; and synthesize the compound that "-NH-" protect through tert-butoxycarbonyl; then, make the compound of gained, carry out the method etc. of reacting with the carboxylic acid with the functional group that can react with halogen atom.Wherein, described in the synthetic method of specific carboxylic acid is not limited to.
Carboxylic acid for the reaction with the organopolysiloxane containing epoxy group(ing) can be only specific carboxylic acid, also can also with other carboxylic acids except specific carboxylic acid.
As long as other carboxylic acids are the carboxylic acid without described specific part structure, as its concrete example, such as, can enumerate: the lipid acid of the carbon numbers 6 ~ 20 such as caproic acid, lauric acid, pentadecanoic acid, Palmiticacid, stearic acid, oleic acid, isooleic acid (vaccenicacid), linolic acid (linoleicacid), linolenic acid (linolenicacid), eicosanoic acid, the compound etc. represented by following formula (5-1) ~ formula (5-9) difference.
[changing 26]
(in formula, i is the integer of 0 ~ 12, and h is the integer of 1 ~ 20)
In addition, as other carboxylic acids, the one that is selected from these of can be used alone or combinationally use two or more.
Relative to the total 1 mole of the epoxy group(ing) that organopolysiloxane has, the usage ratio of the carboxylic acid reacted with the organopolysiloxane containing epoxy group(ing) is preferably set to 0.001 mole ~ 1.5 moles, is more preferably and is set to 0.01 mole ~ 1.0 moles.
In addition, relative to the total 1 mole of the epoxy group(ing) that organopolysiloxane has, the usage ratio of specific carboxylic acid is preferably set to 0.01 mole ~ 0.8 mole.If this usage ratio be set to and be less than 0.01 mole, then the import volume of specific part structure is few, thus is difficult to obtain liquid crystal aligning or burn the improvement effect printing minimizing, solvability etc.On the other hand, if more than 0.8 mole, then there is the tendency of structure adaptability deterioration.Be preferably 0.03 mole ~ 0.6 mole, be more preferably 0.05 mole ~ 0.4 mole.
Reaction containing the organopolysiloxane of epoxy group(ing) and carboxylic acid preferably can be carried out under the existence of catalyzer and organic solvent.
As containing the catalyzer used in the organopolysiloxane of epoxy group(ing) and the reaction of carboxylic acid, such as, can enumerate: acid, alkali metal compound, organic bases, titanium compound, zirconium compounds etc.Organic bases is preferably in these.Relative to organopolysiloxane 100 weight part with carboxylic acid reaction, the usage ratio of catalyzer is preferably below 100 weight parts, is more preferably 0.01 weight part ~ 100 weight part, and then is more preferably 0.1 weight part ~ 20 weight part.
As the organic solvent used in described reaction, such as, can enumerate: hydrocarbon, ether, ester, ketone, acid amides, alcohol etc.With regard to the viewpoint of the easness of raw material and the solvability of product and the purifying of product, be preferably ether, ester, ketone in these, as the concrete example of especially preferred solvent, can enumerate: 2-butanone, methyl-n-butyl ketone, methyl iso-butyl ketone (MIBK) and butylacetate etc.This organic solvent be preferably with solid component concentration (the total weight of the composition except solvent in reaction soln relative to solution gross weight shared by ratio) ratio that becomes more than 0.1 % by weight uses, the ratio being more preferably to become 5 % by weight ~ 50 % by weight uses.
Temperature of reaction in described reaction is preferably 0 DEG C ~ 200 DEG C, is more preferably 50 DEG C ~ 150 DEG C.Reaction times is preferably 0.1 hour ~ 50 hours, is more preferably 0.5 hour ~ 20 hours.In addition, after reaction terminates, preferably utilize water to clean point organic solvent layer got from reaction solution.After water cleaning, optionally utilize suitable siccative by after the drying of organic solvent layer, solvent is removed, the organopolysiloxane at side chain with described specific part structure can be obtained thus.
The organopolysiloxane containing specific base obtained in this way is preferably when being made into concentration and being the solution of 10 % by weight, has the soltion viscosity of 1mPas ~ 500mPas, is more preferably the soltion viscosity with 3mPas ~ 200mPas.In addition, the value that measures for using the polymers soln that E type rotational viscosimeter is 10 % by weight to the concentration used prepared by the good solvent (such as METHYLPYRROLIDONE etc.) of this polymkeric substance at 25 DEG C of the soltion viscosity (mPas) of described polymkeric substance.
About the organopolysiloxane containing specific base, just make the liquid crystal aligning of formed liquid crystal orientation film good and guarantee with regard to the viewpoints such as the ageing stability of its liquid crystal aligning, the weight average molecular weight (Mw) of the polystyrene conversion measured by gel permeation chromatography is preferably 1,000 ~ 50,000, be more preferably 3,000 ~ 30,000.
Other compositions of < >
Liquid crystal aligning agent of the present invention optionally also can containing other compositions except polymkeric substance (P).As other compositions, such as, can enumerate: other polymkeric substance except polymkeric substance (P), there is in molecule the compound (hereinafter referred to as " compound containing epoxy group(ing) "), functional silanes compound etc. of at least one epoxy group(ing).
[other polymkeric substance]
Other polymkeric substance described can use to improve the various characteristic such as solution properties or electrical characteristic.Other polymkeric substance described are the polymkeric substance without described specific part structure, such as, can enumerate: polyamic acid, polyimide, poly amic acid ester, organopolysiloxane, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative or be the polymkeric substance etc. of main framing with poly-(methyl) acrylate.As other polymkeric substance, in these, preferably can use at least one polymkeric substance in the cohort being selected from and being made up of polyamic acid, polyimide, poly amic acid ester and organopolysiloxane.
When other polymkeric substance are formulated in liquid crystal aligning agent, relative to total (totals of polymkeric substance (P) and other polymkeric substance) 100 weight parts of the polymkeric substance comprised in liquid crystal aligning agent, the allotment ratio of other polymkeric substance is preferably set to below 50 weight parts, be more preferably and be set to 0.1 weight part ~ 40 weight part, and then be more preferably and be set to 0.2 weight part ~ 30 weight part.
[compound containing epoxy group(ing)]
Compound containing epoxy group(ing) can in order to improve using with the cementability of substrate surface or electrical characteristic in liquid crystal orientation film.As this compound containing epoxy group(ing), such as can enumerate following compound as preferred compound: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-hexahydroaniline etc.In addition, as the example of the compound containing epoxy group(ing), the organopolysiloxane containing epoxy group(ing) that No. 2009/096598th, International Publication can be used to record.
When the compound containing epoxy group(ing) is formulated in liquid crystal aligning agent, relative to total 100 weight part of the polymkeric substance comprised in liquid crystal aligning agent, allotment ratio containing the compound of epoxy group(ing) is preferably set to below 40 weight parts, is more preferably and is set to 0.1 weight part ~ 30 weight part.
[functional silanes compound]
Functional silanes compound can use to improve the printing of liquid crystal aligning agent.As this functional silanes compound, such as, can enumerate: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl three second triamine, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.
When other functional silanes compounds are formulated in liquid crystal aligning agent, relative to total 100 weight part of the polymkeric substance comprised in liquid crystal aligning agent, the allotment ratio of other functional silanes compounds is preferably set to below 2 weight parts, is more preferably and is set to 0.02 weight part ~ 0.2 weight part.
In addition, as other compositions, except described, can enumerate: compound or antioxidant, metal chelate compound, hardening accelerator, tensio-active agent, weighting agent, dispersion agent, the light sensitizer etc. in molecule with at least one oxetanylmethoxy.
Liquid crystal aligning agent of the present invention can only contain a kind of polymkeric substance as component of polymer, also can containing two or more polymkeric substance as component of polymer.As the preferred form of component of polymer, such as, can enumerate following [1] ~ [5] etc.
[1] only containing polymkeric substance (P) as component of polymer, and polymkeric substance (P) is for being selected from the form of at least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide.
[2] polymkeric substance (P) is only contained as component of polymer, and the form that polymkeric substance (P) is organopolysiloxane.
[3] only containing polymkeric substance (P) as component of polymer, and at least one comprised in the cohort being selected from and being made up of polyamic acid, poly amic acid ester and polyimide and organopolysiloxane are as the form of polymkeric substance (P).
[4] containing polymkeric substance (P) and other polymkeric substance as component of polymer, and polymkeric substance (P) and other polymkeric substance are for being selected from the form of at least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide.
[5] containing polymkeric substance (P) and other polymkeric substance as component of polymer, and polymkeric substance (P) is for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide, other polymkeric substance are the form of organopolysiloxane.
In [4] and [5] in these; can infer because of the importing effect of protecting group and the hydrophobicity of polymkeric substance (P) increases and the polarity difference do not had between the polymkeric substance of protecting group becomes large; thus polymkeric substance (P) deflection can be made in liquid crystal orientation film to be present in upper strata, other polymkeric substance are partial to and are present in lower floor.In [4] and [5], as other polymkeric substance, with regard to can improving the effect aspect of the burning print reducing the liquid crystal display device caused by volts DS, preferably can use the polymkeric substance containing N structure of at least one in the cohort having and be selected from and be made up of nitrogenous heterocycle, secondary amino and tertiary amine base, there is the polymkeric substance of carboxyl, and described in having, contain one or more in the polymkeric substance of N structure and carboxyl.
About the allotment ratio of polymkeric substance (P) relative to the solids component (composition except solvent of liquid crystal aligning agent) of liquid crystal aligning agent, relative to total weight 100 weight part of solids component, preferably be set to more than 40 weight parts, be more preferably and be set to more than 50 weight parts, and then be more preferably more than 60 weight parts.
< solvent >
Liquid crystal aligning agent of the present invention prepares with the form of liquid composition, and described liquid composition is by polymkeric substance (P) and optionally and other compositions used preferably are dispersed or dissolved in suitable solvent and form.
As used organic solvent, such as can enumerate: METHYLPYRROLIDONE, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, n-Butyl lactate, butylacetate, methyl methoxypropionate, ethyl ethoxy-c acid esters, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, isoamyl ether, ethylene carbonate, Texacar PC etc.These can be used alone or used in combination two or more.
Solid component concentration (ratio of total weight shared by the gross weight of liquid crystal aligning agent of the composition except solvent of liquid crystal aligning agent) in liquid crystal aligning agent considers viscosity, volatility etc. and is suitable for selecting, and is preferably the scope of 1 % by weight ~ 10 % by weight.That is, liquid crystal aligning agent is coated with on the surface of the substrate as aftermentioned, preferably heats, formed thus as liquid crystal orientation film film or become the film of liquid crystal orientation film.Now, when solid component concentration is less than 1 % by weight, the thickness of film becomes too small and is difficult to obtain good liquid crystal orientation film.On the other hand, when solid component concentration is more than 10 % by weight, the thickness of film becomes excessive and is difficult to obtain good liquid crystal orientation film, and in addition, the viscosity that there is liquid crystal aligning agent increases and the tendency of coating reduction.
The scope of especially preferred solid component concentration is different according to method used during coating of liquid crystalline alignment agent on substrate.Such as when utilizing turner method to coat on substrate, be especially preferably the scope that solid component concentration (ratio of total weight shared by the gross weight of liquid crystal aligning agent of all the components except solvent in liquid crystal aligning agent) is 1.5 % by weight ~ 4.5 % by weight.When utilizing print process, especially preferably solid component concentration being set to the scope of 3 % by weight ~ 9 % by weight, thus soltion viscosity being set to the scope of 12mPas ~ 50mPas.When utilizing ink jet method, especially preferably solid component concentration being set to the scope of 1 % by weight ~ 5 % by weight, thus soltion viscosity being set to the scope of 3mPas ~ 15mPas.Temperature when preparing liquid crystal aligning agent is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.
< liquid crystal display device >
Liquid crystal display device of the present invention possess use described in illustrated liquid crystal aligning agent and the liquid crystal orientation film that formed.The operating mode of liquid crystal display device is not particularly limited, such as can be applicable to TN type, STN type, VA type (comprise vertical orientated-multidomain vertical orientation (VerticalAlignment-Multi-domainVerticalAlignment, VA-MVA) type, vertical orientated-patterned vertical orientated (VerticalAlignment-PatternedVerticalAlignment, VA-PVA) type etc.), IPS type, FFS type, the various operating mode such as optical compensation curved (OpticallyCompensatedBend, OCB) type.
The operation of liquid crystal display device such as by comprising following operation (1) ~ operation (3) manufactures.In operation (1), use different substrates according to required operating mode.Each operating mode in operation (2) and operation (3) is identical.
[operation (1): the formation of film]
First, on substrate, coating of liquid crystalline alignment agent, heats coated face then, forms film thus on substrate.
(1-A) such as when manufacturing the liquid crystal display device of TN type, STN type or VA type, first two plate bases of patterned nesa coating will be provided with as a pair substrate, on the face being formed with transparent conductive film of each substrate, preferably utilize flexographic printing process, spin-coating method, roller coating machine method or ink jet printing method to difference coating of liquid crystalline alignment agent.As substrate, such as, can use: the glass such as float glass (floatglass), soda glass; Comprise the transparency carrier of the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).As the nesa coating be arranged on a face of substrate, can use: comprise stannic oxide (SnO 2) nesa (NESA) film (PPG register of company of U.S. trade mark), comprise indium oxide-tin oxide (In 2o 3-SnO 2) tin indium oxide (IndiumTinOxide, ITO) film etc.In order to obtain patterned nesa coating, such as, following methods etc. can be utilized: formed and after patternless nesa coating, utilize photoetch (photoetching) to form the method for pattern; The method with the mask (mask) of required pattern is used when forming nesa coating.When coating of liquid crystalline alignment agent, in order to make the cementability of substrate surface and nesa coating and film better, also the pre-treatment being coated with functional silanes compound, functionality titanium compound etc. in advance can be implemented to the face forming film in substrate surface.
After coating of liquid crystalline alignment agent, in order to prevent the dropping liquid etc. of be coated with liquid crystal aligning agent, being preferably enforcement and preheating (prebake conditions).Prebake conditions temperature is preferably 30 DEG C ~ 200 DEG C, is more preferably 40 DEG C ~ 150 DEG C, is especially preferably 40 DEG C ~ 100 DEG C.The prebake conditions time is preferably 0.25 minute ~ 10 minutes, is more preferably 0.5 minute ~ 5 minutes.Then, in order to be removed completely by solvent, and optionally by the amido acid structure that is present in polymkeric substance in addition hot-imide, and implement calcining (toasting afterwards) operation.Calcining temperature (rear storing temperature) is now preferably 80 DEG C ~ 300 DEG C, is more preferably 120 DEG C ~ 250 DEG C.Post-bake times is preferably 5 minutes ~ 200 minutes, is more preferably 10 minutes ~ 100 minutes.Like this and the thickness of film formed is preferably 0.001 μm ~ 1 μm, 0.005 μm ~ 0.5 μm is more preferably.
(1-B) when manufacturing the liquid crystal display device of IPS type or FFS type, be provided with electrode substrate the face being formed with electrode, with do not arrange electrode relative substrate a face on respectively coating of liquid crystalline alignment agent, then each coated face is heated, form film thus, described electrode package contains with the patterned nesa coating of comb teeth shape or metallic membrane.About the patterning method of heating condition, nesa coating or metallic membrane after the material of now used substrate and nesa coating, coating process, coating, the pre-treatment of substrate and the preferred thickness of film that formed, identical with described (1-A).As metallic membrane, such as, the film comprising the metals such as chromium can be used.
In arbitrary situation of described (1-A) and (1-B), all on substrate after coating of liquid crystalline alignment agent, organic solvent is removed, form liquid crystal orientation film thus or become the film of liquid crystal orientation film.Now, when the polymkeric substance contained by liquid crystal aligning agent be polyamic acid or poly amic acid ester or comprise the imide amination polymer with imide ring structure and amido acid structure, also can heat further after formation film, carry out dehydration closed-loop reaction thus, thus make further through the film of imidization.
[operation (2): orientation process]
When manufacturing the liquid crystal display device of TN type, STN type, IPS type or FFS type, the process (orientation process) of giving liquid crystal aligning ability is implemented to the film formed in described operation (1).Thus, give the alignment capability of liquid crystal molecule to film and become liquid crystal orientation film.As orientation process, can enumerate: utilize the roller that wrapped around the cloth comprising the such as fiber such as nylon (nylon), artificial silk (rayon), cotton (cotton) to rub towards certain orientation to film, thus film is given to the friction treatment of liquid crystal aligning ability; Rayed is carried out to the film formed on substrate, thus gives the light orientation process etc. of liquid crystal aligning ability to film.On the other hand, when manufacturing vertical alignment-type liquid crystal display device, the film formed directly can be used as liquid crystal orientation film in described operation (1), also can to this film implementation orientation process.
Rayed in light orientation process is undertaken by following methods etc.: the method that (1a) irradiates the film after rear baking, (2a) to after prebake conditions and after the film method of irradiating before baking, (3a) at least one process of prebake conditions and rear baking, the method that the film hankered irradiates is added to film.
The light irradiated film can be set to the radioactive rays of polarisation or non-polarized.As radioactive rays, such as, can use the ultraviolet comprising the light that wavelength is 150nm ~ 800nm and visible rays.When radioactive rays are polarisation, can be linear polarization and also can be part polarisation.In addition, when used radioactive rays are for linear polarization or part polarisation, can irradiate from the direction perpendicular to real estate, also can irradiate from vergence direction, or also these directional combinations can be irradiated.When irradiating the radioactive rays of non-polarized, the direction of irradiation is set to vergence direction.
As used light source, such as, can use: Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.The ultraviolet of preferred wavelength region may is by obtaining light source and method also such as such as spectral filter, diffraction grating etc. etc.The irradiation dose of light is preferably 100J/m 2~ 50,000J/m 2, be more preferably 300J/m 2~ 20,000J/m 2.In addition, about the rayed to film, in order to improve reactivity, also one rayed can be carried out in the face of film one side of carrying out heating.Temperature when heating is generally 30 DEG C ~ 250 DEG C, is preferably 40 DEG C ~ 200 DEG C, is more preferably 50 DEG C ~ 150 DEG C.
In addition, also following process can be carried out further to the liquid crystal orientation film after friction treatment, and make liquid crystal orientation film have different liquid crystal aligning abilities in each region, describedly to be treated to: radioactive rays are irradiated to a part for liquid crystal orientation film, makes the process that the tilt angle in a part of region of liquid crystal orientation film changes thus; Or form resist film in the part on liquid crystal orientation film surface after, after carrying out friction treatment towards the direction different from friction treatment before, by the process that resist film removes.In this situation, the field-of-view characteristics of the liquid crystal display device of gained can be improved.
At manufacture polymer stabilizing orientation (polymersustainedalignment, when the liquid crystal display device of PSA) type, also directly can use the film formed in described operation (1) and implement following operation (3), in order to control the collapsing of liquid crystal molecule, utilize easy method to carry out orientation segmentation, also the orientation process such as weak friction treatment can be carried out.The liquid crystal orientation film being suitable for the liquid crystal display device of VA type also can be suitably used for the liquid crystal display device of PSA type.
[operation (3): constructing of liquid crystal cells]
(3-A) prepare the two panels substrate being formed with liquid crystal orientation film as described above, between two plate bases through being relative to the configuration, configuring liquid crystal, manufacturing liquid crystal cells thus.When manufacturing liquid crystal cells, such as, can enumerate following two methods.First method is all the time known method.First, two plate bases are relative to the configuration across gap (cell gap (cellgap)) in the mode that each liquid crystal orientation film is relative, sealing agent is used to be fitted by the periphery of two plate bases, inject filling liquid crystal in the cell gap divided by substrate surface and sealing agent after, filling orifice is sealed, manufactures liquid crystal cells thus.In addition, the second method is for being called as the method for liquid crystal drip-injection (OneDropFill, ODF) mode.On specified location on a plate base in two plate bases being formed with liquid crystal orientation film, the such as sealing agent of coated UV photo-hardening, and then after set several positions on liquid crystal aligning face drip liquid crystal, to fit another substrate in the mode that liquid crystal orientation film is relative, and liquid crystal is spread out on whole of substrate, then whole irradiating ultraviolet light of substrate is cured the sealant, manufacture liquid crystal cells thus.When utilizing either method, all it is desirable to be heated to further after used liquid crystal obtains the temperature of isotropic phase, slowly cool to room temperature, remove flow orientation when liquid crystal is filled thus to the liquid crystal cells manufactured in this way.
As sealing agent, such as, can use the epoxy resin etc. containing stiffening agent and the alumina balls as distance piece (spacer).In addition, as liquid crystal, can enumerate: nematic liquid crystal and stratose liquid crystal, wherein be preferably nematic liquid crystal, such as, can use: Schiff's base (Schiffbase) is liquid crystal, azoxy (azoxy) is liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal, ester system liquid crystal, terphenyl system liquid crystal, cyclohexyl biphenyl hexane system liquid crystal, liquid crystal, diox system of pyrimidine system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can in these liquid crystal, add following material and use: the cholesterol liquid crystals such as such as cholesteryl chloride (cholesterylchloride), n-nonanoic acid cholesteryl ester (cholesterylnonanoate), carbonic acid cholesteryl ester; As trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) and the chiral agent of selling; To oxygen base α-tolylene-to ferroelectric liquid crystals etc. such as amino-2-methyl butyl laurates (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) in the last of the ten Heavenly stems.
(3-B) when manufacturing PSA type liquid crystal display device, except injecting in the lump with liquid crystal or dripping except the aspect of photopolymerizable compound, carrying out operating in the same manner as described (3-A) and constructing liquid crystal cells.Then, execute alive state between the conducting film had a pair substrate under, rayed is carried out to liquid crystal cells.Here, the voltage of applying such as can be set to direct current or the interchange of 5V ~ 50V.In addition, as irradiated light, such as, can use the ultraviolet comprising the light that wavelength is 150nm ~ 800nm and visible rays, preferably comprise the ultraviolet that wavelength is the light of 300nm ~ 400nm.As the light source irradiating light, such as, can use Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, excimer laser etc.In addition, the ultraviolet of described preferred wavelength region may is by obtaining light source and method also such as such as spectral filter, diffraction grating etc. etc.As the irradiation dose of light, be preferably 1,000J/m 2above and be less than 200,000J/m 2, be more preferably 1,000J/m 2~ 100,000J/m 2.
(3-C) when the side chain lead-in light polymerizability base of polymkeric substance (P) or when comprising the compound containing optical polymerism base different from polymkeric substance (P) in liquid crystal aligning agent, all can adopt the method being manufactured liquid crystal display device by following operation: carry out operating in the same manner as described (3-A) and construct liquid crystal cells, then, execute alive state between the conducting film had a pair substrate under, light-struck operation is carried out to liquid crystal cells.According to the method, the advantage of PSA pattern can be realized with a small amount of rayed amount.The voltage applied or the condition of light of irradiating can apply the explanation of described (3-B).
Then, Polarizer that the outer surface of liquid crystal cells is fitted, can obtain liquid crystal display device thus.As the Polarizer be fitted on the outside surface of liquid crystal cells, can enumerate: utilize rhodia protective membrane one side to be made polyvinyl alcohol extend orientation one side and make it to absorb being called as the Polarizer of the light polarizing film clamping of " H film " or comprising the Polarizer of H film itself of iodine.
Liquid crystal display device of the present invention can be effectively applied to various device, such as can be used for the various display unit such as clock and watch, portable game machine, word processor, notebook computer, auto-navigation system (carnavigationsystem), pick up camera (camcorder), personal digital assistant (PersonalDigitalAssistant, PDA), digital camera (digitalcamera), mobile telephone, smart mobile phone, various monitor (monitor), LCD TV, information display (informationdisplay).
[embodiment]
Below, by embodiment, the present invention is more specifically illustrated, but the present invention is not restricted to these embodiments.
In following example, soltion viscosity and the epoxy equivalent (weight) of the weight average molecular weight Mw of polymkeric substance, imide rate, polymers soln measure by the following method.In addition, sometimes the compound represented by formula X is only denoted as " compounds X " below.
[the weight average molecular weight Mw of polymkeric substance]
The polystyrene conversion value of Mw for being measured by the GPC under following condition.
Tubing string: eastern Cao (Tosoh) (stock) manufactures, TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
[the imide rate of polymkeric substance]
Solution containing polyimide is put in pure water, after the throw out of gained at room temperature abundant drying under reduced pressure, is dissolved in deuterodimethylsulfoxide, tetramethylsilane is at room temperature measured as reference material 1h-NMR.According to gained 1h-NMR spectrum uses following numerical expression (1) to obtain imide rate.
Imide rate (%)=(1-A 1/ A 2× α) × 100 ... (1)
(in numerical expression (1), A 1for the peak area deriving from the proton of NH base occurred near chemical shift 10ppm, A 2for deriving from the peak area of other protons, α is the number ratios of other protons in the precursor (polyamic acid) of polymkeric substance relative to a proton of NH base)
[epoxy equivalent (weight)]
Epoxy equivalent (weight) utilizes the hydrochloric acid-methyl ethyl ketone method recorded in Japanese Industrial Standards (JapaneseIndustrialStandards, JIS) C2105 to measure.
The synthesis > of < compound
[synthesis example 1-1: the synthesis of compound (a-1)]
Synthetic compound (a-1) is carried out according to following flow process 1.
[changing 27]
The synthesis of compound (a-1-1)
Get 4-(4-pentylcyclohexyl) phenylformic acid 27.4g, 3,5-dinitraniline 18.3g to the there-necked flask of 2000mL being placed with agitator, add methylene dichloride 1200g and also stir.Then, be cooled to 0 DEG C, add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride 23.0g and N, N-dimethyl aminopyridine 2.44g wherein, at room temperature stir 20 hours.Then, after utilizing water 800mL to carry out 3 separatory cleanings to reaction solution, magnesium sulfate is utilized to carry out drying to organic layer.Then, utilize rotary evaporator slowly to concentrate till inner capacities becomes 200g, by filtering the white solid being recovered in midway and separating out.By carrying out vacuum-drying to this white solid, and obtain compound (a-1-1) 37.4g.
The synthesis of compound (a-1-2)
Get compound (a-1-1) 26.4g to the there-necked flask of 500mL being placed with agitator, add acetonitrile 300g and also stir.Then, be cooled to 0 DEG C, add two carbonic acid two-tertiary butyl ester 14.4g and N wherein, N-dimethyl aminopyridine 0.73g, at room temperature stir 6 hours.Then, utilize rotary evaporator to carry out concentrating after till reaction solution becomes 100g, being injected in water 500g, reclaiming separated out white solid by filtering.By carrying out vacuum-drying to this white solid, and obtain compound (a-1-2) 25.9g.
The synthesis of compound (a-1)
Add compound (a-1-2) 21.6g, zinc 52.3g and ammonium chloride 8.56g to the there-necked flask of 300mL being placed with agitator, carry out 3 nitrogen replacements.Then, reaction vessel is cooled to 0 DEG C, adds the tetrahydrofuran (THF) 150g and ethanol 20g stirring that bubble through nitrogen, and then add water 10g by dripping, at room temperature stir.After 3 hours, diatomite filtration is carried out to reaction solution, add ethyl acetate 300g to filtrate, utilize water 200mL to carry out 3 separatory cleanings.Then, rotary evaporator is utilized to carry out organic layer concentrated and solid.By the residue recrystallize utilizing ethanol to make gained, and obtain compound (a-1) 13.4g.
[synthesis example 1-2: the synthesis of compound (a-2)]
Synthetic compound (a-2) is carried out according to following flow process 2.
[changing 28]
The synthesis of compound (a-2-1)
Use 4-bromo-benzoic acid and 4-(4-pentylcyclohexyl) aniline as parent material, utilize the synthesizing formula same with compound (a-1-1) and obtain compound (a-2-1).
The synthesis of compound (a-2-2)
Use compound (a-2-1) to replace compound (a-1-1), utilize the synthesizing formula same with compound (a-1-2) and obtain compound (a-2-2).
The synthesis of compound (a-2)
Add compound (a-2-2) 21.1g, 4-carboxyphenyl boronic acid 6.63g, acid chloride (II) 0.225g, salt of wormwood 27.6g and 1, two (diphenylphosphino) ethane 0.797g of 2-, to the there-necked flask of 500mL being placed with agitator, carries out 3 nitrogen replacements.Add the tetrahydrofuran (THF) 80g, the water 80g that bubble through nitrogen wherein, stir 3 hours at 60 DEG C.Diatomite filtration is carried out to reaction solution, adds ethyl acetate 200g to filtrate, utilize water 150mL to carry out 3 separatory cleanings.Then, utilize the concentrated of rotary evaporator slowly to concentrate till inner capacities becomes 50g, by filtering the white solid being recovered in midway and separating out.By carrying out vacuum-drying to this white solid, and obtain compound (a-2) 15.9g.
[synthesis example 1-3: the synthesis of compound (a-3)]
Synthetic compound (a-3) is carried out according to following flow process 3.
[changing 29]
Use 4-bromaniline and 4-(4-octyl group cyclohexyl) phenylformic acid as parent material, utilize the synthesizing formula same with compound (a-2) to come synthetic compound (a-3-1), compound (a-3-2) and compound (a-3).
[synthesis example 1-4: the synthesis of compound (a-4)]
Synthetic compound (a-4) is carried out according to following flow process 4.
[changing 30]
The synthesis of compound (a-4-1)
Get 2,5-dinitraniline 18.3g, succinyl oxide 10.0g to the there-necked flask of 500mL being placed with agitator, and add acetonitrile 250g, carry out backflow 10 hours.Then, utilize rotary evaporator to make reaction solution concentrated, solid, and obtain compound (a-4-1) 25.3g.
The synthesis of compound (a-4-2)
Use beta-cholestanol and compound (a-4-1) as parent material, utilize the synthesizing formula same with compound (a-1-1) and obtain compound (a-4-2).
The synthesis of compound (a-4-3)
Get compound (a-4-2) 26.2g to the there-necked flask of 300mL being placed with agitator, add tetrahydrofuran (THF) 120g wherein, be cooled to 0 DEG C.Drip methyl-chloroformate 3.97g wherein, at room temperature stir 3 hours.Add ethyl acetate 200g to reaction solution, after utilizing the hydrochloric acid 150mL of 1mol/L and water 150mL to carry out 3 separatory cleanings, utilize magnesium sulfate to carry out drying to organic layer.Then, by utilizing rotary evaporator to concentrate, utilizing vacuum-drying to carry out solid, and obtaining compound (a-4-3) 27.1g of yellow solid.
The synthesis of compound (a-4)
Use compound (a-4-3) as parent material, utilize the synthesizing formula same with compound (a-1) and obtain compound (a-4).
[synthesis example 1-5: the synthesis of compound (a-5)]
Synthetic compound (a-5) is carried out according to following flow process 5.
[changing 31]
The synthesis of compound (a-5-1)
Add 4-(4-propylcyclohexyl) cyclohexane carboxylic acid 25.2g in the eggplant type flask of 300mL being placed with agitator, and add thionyl chloride 200g and dimethyl formamide (DimethylFormamide, DMF) 0.25g, stirs 2 hours at 80 DEG C.Then, utilize aspirator (aspirator) excessive thionyl chloride to be removed, and residue is dissolved in methylene dichloride 500g.Be set to solution A.
Disubstituted-4-hydroxy styracin 16.4g, sodium hydroxide 8g to the there-necked flask of 2000mL being placed with agitator, and then add water 500g, are cooled to 0 DEG C.Spend and drip solution A wherein in 30 minutes, at room temperature stir 5 hours.Then, after utilizing water 400mL to carry out 3 separatory cleanings to reaction solution, magnesium sulfate is utilized to carry out drying to organic layer.Then, utilize the concentrated of rotary evaporator slowly to concentrate till inner capacities becomes 50g, by filtering the white solid being recovered in midway and separating out.By carrying out vacuum-drying to this white solid, and obtain compound (a-5-1) 31.9g.
The synthesis of compound (a-5-2)
Use compound (a-5-1) and 3,5-dinitraniline as parent material, utilize the synthesizing formula same with compound (a-1-1) and obtain compound (a-5-2).
The synthesis of compound (a-5-3)
Use compound (a-5-2) as parent material, utilize the synthesizing formula same with compound (a-1-2) and obtain compound (a-5-3).
The synthesis of compound (a-5)
Use compound (a-5-3) as parent material, utilize the synthesizing formula same with compound (a-1) and obtain compound (a-5).
[synthesis example 1-6: the synthesis of compound (a-6)]
Synthetic compound (a-6) is carried out according to following flow process 6.
[changing 32]
Use 4-(4 '-amyl group-[1,1 '-bis-(hexanaphthene)]-4-base) phenylformic acid and 4 '-hydroxyazobenzene-4-carboxylic acid as parent material, utilize the synthesizing formula same with compound (a-5) and obtain compound (a-6).
[synthesis example 1-7: the synthesis of compound (a-7)]
Synthetic compound (a-7) is carried out according to following flow process 7.
[changing 33]
The synthesis of compound (a-7-1)
Get 4-fluoro-1,3-dinitrobenzene 18.6g and 4-(4-pentylcyclohexyl) aniline 24.5g to the eggplant type flask of 2000mL being placed with agitator, and add tetrahydrofuran (THF) 1000g and triethylamine 15.2g, carry out backflow 10 hours.Add ethyl acetate 1200g to reaction solution, utilize water 1000mL to carry out 3 separatory cleanings.Then, utilize the concentrated of rotary evaporator slowly to concentrate till inner capacities becomes 200g, by filtering the yellow solid being recovered in midway and separating out.By carrying out vacuum-drying to this yellow solid, and obtain compound (a-7-1) 38.3g.
The synthesis of compound (a-7-2)
Use compound (a-7-1) as parent material, utilize the synthesizing formula same with compound (a-1-2) and obtain compound (a-7-2).
The synthesis of compound (a-7)
Use compound (a-7-2) as parent material, utilize the synthesizing formula same with compound (a-1) and obtain compound (a-7).
[synthesis example 1-8: the synthesis of compound (a-9)]
Use compound 4-(4,4,4-triRuorobutyl) hexahydrobenzoic acid as parent material, utilize the synthesizing formula same with the compound (a-5) of flow process 5 and obtain compound (a-9).
[changing 34]
The synthesis > of < polymkeric substance
[synthesis example 2-1: the synthesis of polymkeric substance (PA-1)]
Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 100 molar part and be dissolved in METHYLPYRROLIDONE (NMP) as compound (a-1) 20 molar part of diamines and Ursol D 80 molar part, at room temperature carry out reaction in 6 hours, obtain the solution of the polyamic acid containing 20 % by weight.Here, the polyamic acid of gained is set to polymkeric substance (PA-1).
[synthesis example 2-2 ~ synthesis example 2-11, synthesis example 2-19]
As following table 1, change kind and the amount of used tetracarboxylic dianhydride and diamines, in addition, operate in the same manner as described synthesis example 2-1, synthesizing polyamides acid respectively.The polyamic acid of gained is set to respectively polymkeric substance (PA-2) ~ polymkeric substance (PA-7) and polymkeric substance (Ra-1) ~ polymkeric substance (Ra-5).
[table 1]
In table 1, the numeric representation in () of diamines and acid dianhydride is relative to the usage ratio [molar part] of total 100 molar part of the tetracarboxylic dianhydride for the synthesis of polymkeric substance.Acid anhydrides in table 1 and the abbreviation of diamines represent following compound respectively.
< acid dianhydride >
T-1:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
T-2: dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride
T-3:1,2,3,4-tetramethylene tetracarboxylic dianhydride
T-4: pyromellitic acid anhydride
< diamines >
A-8: the compound represented by following formula (a-8)
B-1: the compound represented by following formula (b-1)
B-2: the compound represented by following formula (b-2)
B-3: the compound represented by following formula (b-3)
B-5: the compound represented by following formula (b-5)
B-6: the compound represented by following formula (b-6)
B-7: the compound represented by following formula (b-7)
B-8: the compound represented by following formula (b-8)
B-9: the compound represented by following formula (b-9)
D-1: Ursol D
D-2:3,5-diaminobenzoic acid
D-3: the compound represented by following formula (d-3)
[changing 35]
[synthesis example 2-12: the synthesis of polymkeric substance (PI-1)]
As described table 1, change kind and the amount of used tetracarboxylic dianhydride and diamines, in addition, carry out operation and carry out synthesizing polyamides acid in the same manner as described synthesis example 2-1.Then, the polyamic acid solution to gained adds pyridine and diacetyl oxide, carries out chemical imidization.Concentrated by reaction soln after chemical imidization, the mode utilizing NMP to become 10 % by weight with concentration is prepared.The imide rate of the polymkeric substance (PI-1) of gained is about 30%.
[synthesis example 2-13: the synthesis containing the organopolysiloxane (EPS-1) of epoxy group(ing)]
In the reaction vessel possessing stirrer, thermometer, addition funnel and reflux cooling pipe, add 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, at room temperature mix.Then, spend 30 minutes after addition funnel drips deionized water 100g, mix under reflux at being incorporated in 80 DEG C and react 6 hours.After reaction terminates, extract organic layer, 0.2 % by weight aqueous ammonium nitrate solution is utilized to carry out cleaning until after water after cleaning becomes neutrality, under reduced pressure solvent and water distillation are removed, obtain the organopolysiloxane (EPS-1) of the transparent liquid as thickness thus.
This organopolysiloxane (EPS-1) is carried out 1h-NMR analyzes, and results verification arrives: near chemical shift (δ)=3.2ppm, obtain the peak value based on oxiranyl in the same manner as theoretical strength, and do not cause the side reaction of epoxy group(ing) in the reaction.The Mw of organopolysiloxane (EPS-1) is 2,200, and epoxy equivalent (weight) is 186g/ mole.
[synthesis example 2-14: the synthesis containing the organopolysiloxane (PS-1) of specific base]
In the there-necked flask of 100mL, add organopolysiloxane (EPS-1) 2.3g, cyclopentanone 11.1g synthesized in described synthesis example 2-13, compound (a-2) 1.1g (being equivalent to 30 % by mole of the Siliciumatom had relative to organopolysiloxane) and tetrabutylammonium 0.03g, react 36 hours at 90 DEG C.After reaction terminates, add methyl alcohol in the reactive mixture and generate precipitation, after 3 washings are carried out to the solution obtained in ethyl acetate by this precipitate dissolves, solvent distillation being removed, obtains the white powder of organopolysiloxane (PS-1) thus.The weight average molecular weight of organopolysiloxane (PS-1) is 2,700.
[synthesis example 2-15 ~ synthesis example 2-18]
The kind of used compound and amount are set to as following table 2, in addition, the synthesizing formula same with described synthesis example 2-14 is utilized to synthesize respectively containing organopolysiloxane (the PS-2) ~ organopolysiloxane (PS-4) containing specific base of specific base and the organopolysiloxane (Rs-1) containing specific base.
[table 2]
In table 2, the add-on [% by mole] of the Siliciumatom that the numeric representation of the allotment amount of carboxylic acid has relative to the organopolysiloxane containing epoxy group(ing).
The abbreviation of the compound of table 2 is as described below.
B-4: the compound represented by described formula (b-4)
[embodiment 1]
(1) preparation of liquid crystal aligning agent
In as the described synthesis example 2-1 of polymkeric substance gained polymkeric substance (PA-1) in add NMP as organic solvent and ethylene glycol butyl ether (ButylCellosolve, BC), the solution that solvent consists of NMP: BC=50: 50 (weight ratios), solid component concentration is 5.0 % by weight is made.Use the strainer in 1 μm, aperture to filter this solution, prepare liquid crystal aligning agent (D-1) thus.
(2) manufacture of liquid crystal display device
Be used in one side and there is the glass substrate of the transparency electrode (electrode on the electrode surface of the electrode on the electrode surface of glass substrate A and glass substrate B) of two systems comprising ito film as a pair substrate, utilize turner be coated with on this pair glass substrate described in prepared liquid crystal aligning agent (D-1), after the hot-plate of 80 DEG C carries out 1 minute prebake conditions, the hot-plate of 230 DEG C carries out toast after 10 minutes, thus form the film that thickness is about 0.08 μm.Then, after the outer rim with the face of liquid crystal orientation film of a plate base in office is coated with and adds the epoxy resin adhesive of the alumina balls having diameter 5.5 μm, across gap, two plate bases are relative to the configuration, are undertaken crimping and making adhesive hardens by against each other for outer edge.Then, after filling nematic liquid crystal (manufacture of Merck (Merck) company, MLC-6608) between from liquid crystal injecting port to a pair substrate, acrylic acid series photo-hardening caking agent is utilized to be sealed by liquid crystal injecting port.
(3) evaluation of print characteristic (AC image retention characteristic) is burnt
Under liquid crystal display device manufactured in described is placed in 25 DEG C, one atmospheric environment, not to the electrode application voltage on the electrode surface of glass substrate B, the voltage of alternating current 3.5V of 2 hours and the resultant voltage of volts DS 5V are applied to the electrode on the electrode surface of glass substrate A.Then immediately the voltage exchanging 4V is applied to both the electrodes on the electrode surface of the electrode on the electrode surface of glass substrate A and glass substrate B.Measure from start to apply the moment of the voltage exchanging 4V to two electrodes until estimate the time of the difference of the light transmission of the electrode on the electrode surface of electrode and the glass substrate B that cannot confirm on the electrode surface of glass substrate A.Is less than the average evaluation of 20 seconds this time for burning print characteristic " good 1 (◎) "; By more than 20 seconds and the average evaluation being less than 60 seconds for burning print characteristic " good 2 (zero) "; By more than 60 seconds and the average evaluation being less than 100 seconds for burning print characteristic " can 1 (△) "; By more than 100 seconds and the average evaluation being less than 150 seconds for burning print characteristic " can 2 (△ △) "; And by the average evaluation more than 150 seconds for burning print characteristic " bad (×) ", the burning print characteristic of this liquid crystal display device of result is " good 1 (◎) ".
(4) evaluation of the printing after storage period
Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), prepared liquid crystal aligning agent (D-1) in described is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode comprising ito film.After carrying out placement in 30 minutes, the hot-plate of 80 DEG C carries out heating (prebake conditions) in 1 minute and removes solvent.Then, the hot-plate of 200 DEG C carries out heating in 10 minutes (toasting afterwards), thus forms the film that average film thickness is 0.06 μm.This film of microscopic examination of multiplying power 20 times is utilized to investigate the presence or absence of printing inequality and pin hole.In addition, polymkeric substance is lower for the solvability of solvent, and the printing inequality in storage period and pin hole more easily produce.About evaluation, after storage period, printing " good (zero) " is set to by almost not observing printing situation that is uneven and pin hole, be set to printing " can (△) " by observing printing situation that is uneven and pin hole a little, at least any one the situation clearly observing the uneven and pin hole of printing is set to printing " bad (×) ".Its result, the result of this embodiment is printing " good (zero) ".
[embodiment 2 ~ embodiment 9, embodiment 11 and comparative example 1 ~ comparative example 6]
Except the kind of used polymkeric substance and amount being set to such aspect of record in following table 3, carrying out operation and prepare liquid crystal aligning agent respectively in the same manner as described embodiment 1.In addition, use prepared liquid crystal aligning agent, carry out operating in the same manner as described embodiment 1 and carry out various evaluation.These results are shown in following table 3.
[table 3]
In table 3, the numeric representation of the allotment ratio of polymkeric substance is relative to the allotment ratio [weight part] of each polymkeric substance of total 100 weight part of the component of polymer used in the preparation of liquid crystal aligning agent.
[embodiment 10]
(1) preparation of liquid crystal aligning agent
In as the described synthesis example 2-5 of polymkeric substance gained polymkeric substance (PA-5) in add NMP as organic solvent and ethylene glycol butyl ether (BC), make the solution that solvent consists of NMP: BC=50: 50 (weight ratios), solid component concentration is 5.0 % by weight.Use the strainer in 1 μm, aperture to filter this solution, prepare liquid crystal aligning agent (D-10) thus.
(2) manufacture of liquid crystal display device
Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), liquid crystal aligning agent (D-10) prepared in described is coated on each electrode surface of a pair glass substrate of the ITO electrode (electrode on the electrode surface of the electrode on the electrode surface of glass substrate A and glass substrate B) respectively with two systems, the hot-plate of 80 DEG C carries out heating (prebake conditions) and after removing solvent in 1 minute, the hot-plate of 200 DEG C carries out heating in 10 minutes (toasting afterwards), thus formation average film thickness is film, the ITO electrode (electrode on the electrode surface of the electrode on the electrode surface of glass substrate A and glass substrate B) of described two systems is patterned is divided into multiple region for striated as shown in FIG. 1.Then, in ultrapure water, carry out the ultrasonic cleaning of 1 minute, then, in the cleaning oven of 100 DEG C, carry out drying in 10 minutes, obtain the substrate with liquid crystal orientation film thus.Repeat this operation and obtain the substrate that a pair (two panels) has liquid crystal orientation film.
Secondly, for the plate base in described a pair substrate, after the outer rim coating in the face with liquid crystal orientation film adds the epoxy resin adhesive of the alumina balls having diameter 5.5 μm, a pair substrate is carried out coincidence crimping in the mode that liquid crystal orientation film is relative, and makes adhesive hardens.Then, after filling nematic liquid crystal (manufacture of Merck (Merck) company, MLC-6608) between from liquid crystal injecting port to a pair substrate, utilize acrylic acid series photo-hardening caking agent to be sealed by liquid crystal injecting port, manufacture liquid crystal cells thus.For the liquid crystal cells of gained, apply the interchange 10V of frequency 60Hz between to electrode and under the state making liquid crystal drive, use UV irradiation equipment metal halide lamp being used as light source, with 10,000J/m 2irradiation dose irradiation ultraviolet radiation.In addition, this irradiation dose uses to carry out for standard the quantorecorder measured with wavelength 365nm and measure and the value that obtains.
(3) evaluation of print characteristic (AC image retention characteristic) is burnt
Under liquid crystal display device manufactured in described is placed in 25 DEG C, one atmospheric environment, not to the electrode application voltage on the electrode surface of glass substrate B, the electrode on the electrode surface of glass substrate A is applied to the voltage of alternating current 10V of 300 hours.After 300 hours, immediately the voltage exchanging 3V is applied to both the electrodes on the electrode surface of the electrode on the electrode surface of glass substrate A and glass substrate B, measure the poor Δ T [%] of two interelectrode transmittances.Now, average evaluation Δ T being less than 2% is AC image retention characteristic " good 1 (◎) "; By more than 2% and the average evaluation being less than 3% is image retention characteristic " good 2 (zero) "; By more than 3% and the average evaluation being less than 4% is image retention characteristic " can (△) "; It is image retention characteristic " bad (×) " by the average evaluation of more than 4%.It is the evaluation of " good 1 (◎) " in this embodiment of result.
(4) evaluation of the printing after storage period
Use described in prepared liquid crystal aligning agent (D-10), operate in the same manner as described embodiment 1, the printing after storage period evaluated.Its result is the result of printing " good (zero) " in this embodiment.
According to the result of these embodiment 1 ~ embodiments 11, containing having in the liquid crystal aligning agent of polymkeric substance of described specific part structure, when the storage period setting 30 minutes after being coated with substrate, printing is also good.This hint polymkeric substance (P) is high for the solvability of solvent.
In addition, burning print characteristic (AC image retention characteristic) of liquid crystal display device is also good.According to this result, can infer: the protecting group being directed into polymkeric substance is departed from by heating during rear baking, the polymer lateral chain thus afterwards after baking becomes and has upright and outspoken structure person, and fully can reduce the AC image retention of liquid crystal display device.In contrast, in comparative example, any one of burning print characteristic and printing is all than the difference in embodiment.

Claims (8)

1. a liquid crystal aligning agent, is characterized in that: the polymkeric substance (P) containing the part-structure had represented by following formula (1),
In formula (1), A 1for the concatenating group of singly-bound or divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number; X 1for protecting group; " * " represents the associative key being binding on the main chain of polymkeric substance.
2. liquid crystal aligning agent according to claim 1, is characterized in that: described R 1for the base represented by following formula (2),
*-A 3-R 3(2)
In formula (2), A 3for the concatenating group of singly-bound or divalence, R 3for liquid crystal aligning base or light orientation base.
3. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described polymkeric substance (P) is for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester, polyimide and organopolysiloxane.
4. a liquid crystal orientation film, is characterized in that: it uses liquid crystal aligning agent according to any one of claim 1 to 3 and is formed.
5. a liquid crystal display device, is characterized in that: possess liquid crystal orientation film according to claim 4.
6. a polymkeric substance, is characterized in that: have the part-structure represented by following formula (1),
In formula (1), A 1for the concatenating group of singly-bound or divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number; X 1for protecting group; " * " represents the associative key being binding on the main chain of polymkeric substance.
7. a compound, is characterized in that: it is represented by following formula (3),
In formula (3), A 1for the concatenating group of singly-bound or divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number; X 1for protecting group.
8. a compound, is characterized in that: it is represented by following formula (4),
In formula (4), A 4for the organic radical of divalence, R 1it is the organic radical of the monovalence of more than 8 for carbon number; X 1for protecting group.
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