CN105273725A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device - Google Patents

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

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CN105273725A
CN105273725A CN201510368769.3A CN201510368769A CN105273725A CN 105273725 A CN105273725 A CN 105273725A CN 201510368769 A CN201510368769 A CN 201510368769A CN 105273725 A CN105273725 A CN 105273725A
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liquid crystal
aligning agent
crystal aligning
polymkeric substance
film
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CN105273725B (en
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片桐宽
樫下幸志
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JSR Corp
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Abstract

The invention provides a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display device, wherein high storage stability and high coating ability on a substrate are realized. Furthermore the liquid crystal display device which has advantages of high balance, high electrical characteristic, high liquid crystal alignment property and excellent high-temperature resistance can be obtained. The liquid crystal alignment agent comprises one or more than two polymers as a polymer component. Furthermore the polymer component comprises a partial structure (a-1) which is represented by a formula (1), and a partial structure (a-2) which is represented by a formula (2). In the formula (1) and the formula (2), R1 and R2 are hydrogen atoms, alkyls of which the numbers of carbon atoms are 1-12, R3 and R4 are hydrogen atoms or substituted or unsubstituted monovalent alkyl chain of which the number of carbon atoms is 1-10; X1 and X2 are tetravalent organic groups, and Y1 and Y2 are bivalent organic groups.

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.
Background technology
In the past, liquid crystal display device has developed electrode structure or the different multiple type of drive of the physical property, manufacturing step 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) type, fringing field switch the various liquid crystal display device such as (FringeFieldSwitching, FFS) type.These liquid crystal display device have the liquid crystal orientation film making liquid crystal molecular orientation.With regard to thermotolerance, physical strength, the aspect good with the various characteristic such as the affinity of liquid crystal, the material of liquid crystal orientation film uses polyamic acid or polyimide usually.In addition, use polyamic acid or polyimide and the method that forms liquid crystal orientation film on substrate such as uses usually: by the solution coat containing polyamic acid on substrate, it is heated, substrate carries out imidization and forms the method for polyimide film; By the solution coat containing soluble polyimide on substrate, on substrate, remove solvent and form the method etc. of polyimide film.
In addition, in recent years, large picture and the LCD TV of fine becomes main body, become stricter, and requirement can also bear the liquid crystal display device that long term reliability is high under harsh and unforgiving environments for the bad requirement of minimizing display.In order to meet described requirement, propose plurality of liquid crystals alignment agent in recent years.As one of its aspect, just attempting making multiple polymers contain in liquid crystal aligning agent (such as with reference to patent documentation 1 or patent documentation 2).
Patent Document 1 discloses and not only make poly amic acid ester and polyamic acid contain in liquid crystal aligning agent as component of polymer, and make the weight average molecular weight of poly amic acid ester be less than polyamic acid.Through recording, by the liquid crystal aligning agent recorded in this patent documentation 1, the micro concavo-convex produced on the film surface of liquid crystal orientation film reduces, and can improve liquid crystal aligning and the electrical specification of liquid crystal display device.
In addition, the liquid crystal aligning agent containing poly amic acid ester and soluble polyimide is proposed in patent documentation 2.In the liquid crystal aligning agent recorded in this patent documentation 2, through recording, even if imide rate is high, also albinism can not be produced when film is formed, the rub resistance of printing and film is good, can improve liquid crystal aligning and the electrical specification of liquid crystal display device.
[prior art document]
[patent documentation]
No. 2011/115078th, [patent documentation 1] International Publication
No. 2013/147083rd, [patent documentation 2] International Publication
Summary of the invention
[invention institute for solution problem]
In recent years, the high-precision refinement of liquid-crystal display and the requirement of high life are improved further, require further to improve about the electrical specification of liquid crystal display device or the fundamental characteristics such as liquid crystal aligning, thermotolerance.In addition, as liquid crystal aligning agent, just improve with regard to convenience when industrially using or the viewpoint such as yield, require storage stability and good to the coating (printing) of substrate.
The present invention is formed in view of described problem, and one of object for providing a kind of storage stability and good to the coating of substrate, and can obtain the liquid crystal aligning agent that balance has the liquid crystal display device of electrical specification, liquid crystal aligning and thermotolerance well concurrently.
[technique means of dealing with problems]
The people such as the present inventor, first about 4 kinds of polymkeric substance of polyamic acid, polyimide, poly amic acid ester and polyisoimide, study the storage stability of each polymkeric substance, hot-imide rate and the coating to substrate.And, in these 4 kinds of polymkeric substance, be conceived to the low but hot-imide rate of storage stability and the good polyisoimide of coating, attempt being combined by different imide ring structure that polyisoimide is had and other part-structures, improve the various characteristics of liquid crystal aligning agent and liquid crystal display device.And the result that this kind is attempted is, the combination by least any portion structure of different imide ring structure and amido acid structure and amic acid esters structure solves described problem, thus completes the present invention.Specifically, by the invention provides following liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.
An aspect of of the present present invention is for providing a kind of liquid crystal aligning agent, its polymkeric substance containing one or more is as component of polymer, and the part-structure (a-1) comprised in described component of polymer represented by following formula (1) and the part-structure (a-2) represented by following formula (2).
[changing 1]
In formula (1) and formula (2), R 1and R 2be separately hydrogen atom, the alkyl of carbon number 1 ~ 12 ,-Si (R 7) 3(wherein, R 7for alkyl or alkoxyl group, multiple R 7can be identical, also can be different), have fluorine atom monad radical, there is the monad radical of (methyl) acryl or there is the monad radical of cinnamic acid structure, R 3and R 4be separately hydrogen atom or the monovalence chain alkyl of carbon number 1 ~ 10 that is substituted or is unsubstituted; X 1and X 2be separately quadrivalent organic radical, Y 1and Y 2it is separately divalent organic base.
Another aspect of the invention is provides a kind of and uses described liquid crystal aligning agent and the liquid crystal orientation film formed and the liquid crystal display device possessing this liquid crystal orientation film.
[effect of invention]
According to the present invention, storage stability and the liquid crystal aligning agent good to the coating of substrate can be obtained.In addition, by using described liquid crystal aligning agent, the liquid crystal display device that balance has electrical specification, liquid crystal aligning and thermotolerance well concurrently can be obtained.
Accompanying drawing explanation
Fig. 1 is the schematic configuration diagram of FFS type liquid crystal display device.
(a) and (b) of Fig. 2 is the floor map of upper current conducting cap.(a) of Fig. 2 is the vertical view of upper current conducting cap, and (b) of Fig. 2 is the magnified partial view of upper current conducting cap.
Fig. 3 is the schematic diagram of the drive electrode representing four systems.
[explanation of symbol]
10: liquid crystal display device
11a, 11b: glass substrate
12: liquid crystal orientation film
13: upper current conducting cap
14: insulation layer
15: bottom electrode
16: liquid crystal layer
A, B: electrode
C1: part
D1: the live width of electrode
D2: interelectrode distance
Embodiment
< component of polymer >
Liquid crystal aligning agent of the present invention comprises one or more polymkeric substance as component of polymer, and containing the part-structure (a-1) represented by described formula (1) and the part-structure (a-2) represented by described formula (2) in this component of polymer.
About part-structure (a-1), the R of described formula (1) 1and R 2for alkyl, the-Si (R of hydrogen atom, carbon number 1 ~ 12 7) 3(wherein, R 7for alkyl or alkoxyl group, multiple R 7can be identical, also can be different), have fluorine atom monad radical, there is the monad radical of (methyl) acryl or there is the monad radical of cinnamic acid structure.
Herein, the alkyl of carbon number 1 ~ 12 include, for example: methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl etc., these alkyl can be straight-chain, also can be branch-like.For rear baking during with regard to being formed by film and the viewpoint that is vaporized, alkyl is preferably carbon number 1 ~ 5, is more preferably carbon number 1 ~ 3, is especially preferably methyl or ethyl.
Group "-Si (R 7) 3" in, R 7alkyl and alkoxyl group be preferably carbon number 1 ~ 5, be more preferably carbon number 1 ~ 3.In addition, multiple R 7can be identical, also can be different.
The described monad radical with fluorine atom include, for example fluorinated alkyl, fluoridizes alkoxyl group, fluorinated alkyl ester group etc., is preferably fluorinated alkyl.Fluorinated alkyl is preferably carbon number 1 ~ 5, is more preferably carbon number 1 ~ 3.
The described monad radical with (methyl) acryl include, for example "-R 8-A 3" (wherein, R 8for divalent organic base, A 3for (methyl) acryl) represented by group etc.R 8divalent organic base include, for example-CH 2-CH 2-O-* ,-CH 2-CH 2-NH-* ,-CH (CH 3)-CH 2-O-* and-CH (CH 3)-CH 2-NH-* is (wherein, with associative key and the A of " * " 3bond) as preferred concrete example.In addition, " (methyl) acryl " is the implication comprising acryl and methacryloyl.
As long as the monad radical described with cinnamic acid structure comprises the monad radical of styracin or derivatives thereof as basic framework, and remaining structure is not particularly limited.As preferred concrete example, include, for example: the group represented by following formula (x-1) and the group etc. represented by following formula (x-2).
[changing 2]
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 11, X 12and X 13be separately singly-bound, Sauerstoffatom, sulphur atom, *-COO-or *-OCO-(wherein, with " * " associative key respectively with R 11, R 12or R 14bond); 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 O divalent aromatic base, divalence ester ring type base, bivalent heterocyclic formula base or divalence condensation cyclic group; 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); X 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; A, e and d are separately the integer of 0 ~ 3, b and f is separately the integer of 1 ~ 10, c and g is separately the integer of 0 ~ 4.
As the described Monobasic preferred concrete example with cinnamic acid structure, the group represented by described formula (x-1) include, for example the group etc. represented by following formula (x-1-1) ~ formula (x-1-11) difference; Group represented by described formula (x-2) include, for example the compound etc. represented by following formula (x-2-1) ~ formula (x-2-3) difference; The group recorded in Japanese Patent Laid-Open 2011-133825 publication can be enumerated in addition.
[changing 3]
In formula, R 11and the R in b and described formula (x-1) 11and b is identical meanings.
[changing 4]
In formula, R 14and the R in f and described formula (x-2) 14and f is identical meanings.
Just suppress because being derived from R 1and R 2impurity remain in the viewpoint that the quality that causes in film declines, the R of described formula (1) 1and R 2be preferably described in hydrogen atom or the alkyl of carbon number 1 ~ 5, and then with regard to the viewpoint of storage stability, be more preferably the alkyl of carbon number 1 ~ 5.
In addition, below, in the part-structure represented by described formula (1), by R 1and R 2the structure being hydrogen atom is called " amido acid structure ", by R 1and R 2at least any one is that structure beyond hydrogen atom is also referred to as " amic acid esters structure ".In addition, by the part-structure represented by described formula (2) also referred to as " different imide ring structure ".
R 3and R 4in the monovalence chain alkyl of carbon number 1 ~ 10 can be saturated shape, also can be unsaturated shape, specifically, the alkyl of carbon number 1 ~ 10, the thiazolinyl of carbon number 2 ~ 10, the alkynyl etc. of carbon number 2 ~ 10 can be enumerated.These groups can be straight-chain, also can be branch-like.R 3and R 4also can have substituting group, this substituting group include, for example halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), hydroxyl, cyano group, alkoxyl group etc.
Herein, in this specification sheets, so-called " alkyl " is the implication comprising chain alkyl, ester ring type alkyl and aromatic hydrocarbyl.So-called " chain alkyl ", refers to not containing ring texture on main chain, but the alkyl be only made up of chain-like structure.Wherein, chain-like structure can be straight-chain, also can be branch-like.So-called " ester ring type alkyl ", refers to that the structure only comprising ester ring type hydrocarbon is as ring structure, and does not comprise the alkyl of aromatic ring structure.But, do not need only to be made up of the structure of ester ring type hydrocarbon, be also contained in its part and there is chain-like structure.In addition, so-called " aromatic hydrocarbyl ", refers to and comprises the alkyl of aromatic ring structure as ring structure.But, do not need only be made up of aromatic ring structure, can comprise the structure of chain-like structure or ester ring type hydrocarbon yet in its part.
X in part-structure (a-1) and part-structure (a-2) 1and Y 1organic radical include, for example: the alkyl such as chain alkyl, ester ring type alkyl and aromatic hydrocarbyl;-O-,-COO-,-CO-,-NHCO-,-S-,-NH-,-SO is imported between the C-C of this alkyl 2-wait the group of functional group; The group that hydrogen atom in alkyl replaces through halogen atom, hydroxyl, nitro etc.; There is the group etc. of heterocycle.
Part-structure (a-1) and part-structure (a-2) can be present in same a part, also can be present in different molecules respectively.The preferred aspects of liquid crystal aligning agent of the present invention can enumerate following [1] and [2].
[1] aspect as component of polymer of the polymkeric substance (hereinafter also referred to " polymkeric substance (P) ") with part-structure (a-1) and part-structure (a-2) is included in a part.
[2] aspect of the polymkeric substance (hereinafter also referred to " polymkeric substance (Q) ") with part-structure (a-1) and the polymkeric substance (polyisoimide) with part-structure (a-2) is comprised.
In these aspects, with regard to the viewpoint of the concave-convex surface of film or the storage stability of liquid crystal aligning agent, preferably comprise the aspect of polymkeric substance (P).
[1] about the aspect comprising polymkeric substance (P)
Polymkeric substance (P) can synthesize according to vitochemical well-established law.As one example, include, for example following method etc.: make tetracarboxylic dianhydride and diamines carry out reaction and carry out synthesizing polyamides acid, then, use dehydrating condensation agent, the amido acid structure had by the polyamic acid of gained is carried out different imidization and after obtaining polyisoimide, the polyisoimide of gained and esterifying agent is reacted.
(1) polyamic acid and synthesis thereof
(tetracarboxylic dianhydride)
The tetracarboxylic dianhydride used in the synthesis of polyamic acid include, for example: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As the concrete example of these tetracarboxylic dianhydrides, aliphatics tetracarboxylic dianhydride include, for example: butane tetracarboxylic acid dianhydride etc.;
Ester ring type tetracarboxylic dianhydride include, for example: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 5-(2, 5-dioxotetrahydro furans-3-base)-8-methyl-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 5-(2, 5-dioxotetrahydro furans-3-base)-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-volution-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, 1,2,4,5-cyclopentanetetracarboxylic's dianhydride, dicyclo [2.2.2] pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride etc.,
Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride etc.; In addition, the tetracarboxylic dianhydride recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.In addition, the one of these tetracarboxylic dianhydrides can be used alone or be used in combination of two or more by the tetracarboxylic dianhydride used in the synthesis of polyamic acid.
With regard to liquid crystal aligning and to regard to the deliquescent viewpoint of solvent, the tetracarboxylic dianhydride used in the synthesis of polyamic acid preferably comprises and is selected from by dicyclo [2.2.1] heptane-2, 3, 5, 6-tetracarboxylic acid 2:3, 5:6-dianhydride, 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 5-(2, 5-dioxotetrahydro furans-3-base)-8-methyl-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 5-(2, 5-dioxotetrahydro furans-3-base)-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic acid 2:4, 6:8-dianhydride, 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride, and at least one compound (hereinafter also referred to " specific tetracarboxylic dianhydride ") in the cohort that forms of pyromellitic acid anhydride.
Relative to the total amount of the tetracarboxylic dianhydride used in the synthesis of polyamic acid, the usage quantity of this specific tetracarboxylic dianhydride is preferably set to more than 5 % by mole, is more preferably and is set to more than 10 % by mole, is especially preferably set to more than 20 % by mole.The one of described compound can be used alone or be used in combination of two or more by the tetracarboxylic dianhydride used in the synthesis of polyamic acid.In addition, the X of described formula (1) 1and the X of described formula (2) 2there is the structure being derived from the tetracarboxylic dianhydride used in the synthesis of polyamic acid.
(diamines)
The diamines used in the synthesis of polyamic acid include, for example: aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.
As the concrete example of these diamines, aliphatie diamine include, for example: m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, 1,3-two (amino methyl) hexanaphthenes etc.; Ester ring type diamines include, for example: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (cyclo-hexylamine) etc.;
Aromatic diamine include, for example: Ursol D, 4,4 '-ethylene aniline, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-bis-(trifluoromethyl) biphenyl, 4,4 '-diamino-diphenyl ether, 2-(4-aminophenyl) ethylamine, two (4-aminophenyl) amine, two (4-aminophenyl) methylamine of N, N-, 4,4 '-diaminobenzophenone, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylenediisopropylidene) dianiline, 4,4 '-(metaphenylene two isopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-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-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, { 4-[2-(3,5-diamino phenoxy)-oxyethyl group]-phenyl }-ethyl ketone, 3,4-diaminobenzophenone, { 4-[2-(3,5-diamino phenoxy)-oxyethyl group]-phenyl }-phenvl-methanone, { 4-[2-(2,4-diamino phenoxy)-oxyethyl group]-phenyl }-to toluyl-ketone, 2,7 diamin of luorene ketone, 2,7 diamin of luorene, and two (4-aminophenyl) fluorenes of 9,9-, following formula (D-1)
[changing 5]
In formula (D-1), 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, a be 0 or 1, b be the integer of 0 ~ 2, c is the integer of 1 ~ 20, and d is 0 or 1; Wherein, a and b can not become 0 simultaneously.
Represented compound etc., in addition,
Can enumerate: 3, 5-diaminobenzoic acid, 2, 4-diaminobenzoic acid, 2, 5-diaminobenzoic acid, 4, 4 '-benzidine base-3, 3 '-dicarboxylic acid, 4, 4 '-benzidine base-2, 2 '-dicarboxylic acid, 3, 3 '-benzidine base-2, 4 '-dicarboxylic acid, 4, 4 '-diaminodiphenyl-methane-3, 3 '-dicarboxylic acid, 4, 4 '-benzidine base-3-carboxylic acid, 4, 4 '-diaminodiphenyl-methane-3-carboxylic acid, 4, 4 '-diamino-diphenyl ethane-3, 3 '-dicarboxylic acid, 4, 4 '-diamino-diphenyl ethane-3-carboxylic acid, and 4, 4 '-diamino-diphenyl ether-3, the carboxylic diamines such as 3 '-dicarboxylic acid:
DAP, 3,4-diamino-pyridines, 2,4-di-amino-pyrimidine, 3,6-proflavins, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, following formula (d-1) ~ formula (d-3)
[changing 6]
The nitrogen heterocyclic ring diamines such as the compound respectively: following formula (d-4) ~ formula (d-7)
[changing 7]
Compound etc. respectively;
Diamino organo-siloxane include, for example: two (3-the aminopropyl)-tetramethyl disiloxane, 3 of 1,3-, 3 '-[Isosorbide-5-Nitrae-phenylene two (dimethylsilane two base)] two (1-propane amine) etc.; In addition, the diamines recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.
"-X in described formula (D-1) i-(R i-X iI) d-" represented by divalent radical 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 " * ").Group "-C ch 2c+1" be preferably straight-chain.2 amino in diamino-phenyl are preferably positioned at 2 relative to other groups, 4-position or 3,5-position.
As the concrete example of the compound represented by described formula (D-1), include, for example the compound etc. represented by following formula (D-1-1) ~ formula (D-1-5) difference.
[changing 8]
In addition, the Y of described formula (1) 1and the Y of described formula (2) 2for being derived from the structural unit of the diamines used in the synthesis of polyamic acid.The one of these compounds can be used alone or be used in combination of two or more by diamines.
The synthesis of polyamic acid
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.
During synthesizing polyamides acid, also can be described above, use suitable molecular weight regulator with tetracarboxylic dianhydride and diamines simultaneously, synthesize the polymkeric substance of end modified type.By making the polymkeric substance of described end modified type, the coating (printing) of liquid crystal aligning agent can be improved further when not undermining effect of the present invention.
Molecular weight regulator include, for example: the monoamine compounds such as sour single acid anhydride such as MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, aniline, cyclo-hexylamine, n-butylamine, the monoisocyanate compound etc. such as phenyl isocyanate, isocyanic acid naphthyl ester.Relative to total 100 weight part of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator 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.
The organic solvent used in reaction include, for example: 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.In the latter case, 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, is especially preferably less than 30 % by weight.
Being particularly preferably use is selected from by METHYLPYRROLIDONE, N, N-methylacetamide, 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 preferably use the mixture of more than one and other organic solvent of these solvents 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 reaction with dehydrating condensation agent, also reoffer to the reaction with dehydrating condensation agent after polyamic acid contained in reaction soln can being separated, or also can reoffer after the polyamic acid purifying of separation to the reaction with dehydrating condensation agent.The separation of polyamic acid and purifying can carry out according to known method.
(2) the different imidization of polyamic acid
Then, the polyamic acid synthesized in this way carried out different imidization and make polyisoimide.The polyisoimide herein obtained can be the complete different imide compound of the amido acid structure had as the polyamic acid of its precursor all being carried out dehydrating condensation, also can be the different imide compound of part of only a part for amido acid structure being carried out dehydrating condensation.Be preferably the former.
The different imidization of polyamic acid can profit carry out with the following method: be preferably dispersed or dissolved at polyamic acid in the solution in organic solvent, add dehydrating condensation agent and catalyzer optionally.
The dehydrating condensation agent used in different imidization can be enumerated: trifluoroacetic anhydride, N, N '-dicyclohexylcarbodiimide, thionyl chloride etc.Although the usage ratio of dehydrating condensation agent also depends on the ratio of required different imidization, be preferably 1 mole of the amido acid structure had relative to polyamic acid and be set to 0.01 mole ~ 20 moles.
Described catalyzer such as can use the tertiary amines such as triethylamine, pyridine, picoline.Relative to used dehydrating condensation agent 1 mole, the usage ratio of catalyzer is preferably set to 0.01 mole ~ 10 moles.
The organic solvent used in different imidization reaction can enumerate the organic solvent and illustrative compound that use in the synthesis as polyamic acid.The temperature of reaction of different imidization is preferably-20 DEG C ~ 150 DEG C, is more preferably 0 DEG C ~ 100 DEG C.Reaction times is preferably 1 hour ~ 120 hours, is more preferably 2 hours ~ 50 hours.
Obtain the reaction soln containing polyisoimide in this way.This reaction soln directly can be supplied to the reaction with esterifying agent, reoffers to the reaction with esterifying agent, or can also reoffer after the polyisoimide purifying of separation to the reaction with esterifying agent after also polyisoimide contained in reaction soln can being separated.The separation of polyisoimide and purifying can carry out according to known method.
(3) esterification of polyisoimide
Then, the polyisoimide that obtained by described building-up reactions and esterifying agent is made to react.Esterifying agent used herein include, for example alcohols, epoxy compounds etc.As the concrete example of these esterifying agents, alcohols include, for example: methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, trifluoro methyl alcohol, 2,2,2-trifluoroethanol, 2-(methyl) acryl ethoxy-ethanol, 1-(methyl) acryl oxygen base-2-propyl alcohol, 2-(methyl) acrylamide ethanol, 1-(methyl) acrylamide-2-propyl alcohol etc.; Epoxy compounds include, for example: have the compound of group represented by described formula (x-1) and epoxy group(ing), have the compound etc. of group represented by described formula (x-2) and epoxy group(ing).As esterifying agent, wherein preferably alcohols can be used.
The reaction of polyisoimide and esterifying agent is preferably carried out in organic solvent.As long as temperature of reaction now suitably sets according to the kind of esterifying agent, such as, when alcohols, be preferably-20 DEG C ~ 200 DEG C, be more preferably 0 DEG C ~ 120 DEG C.In addition, the reaction times is preferably 0.1 hour ~ 24 hours, is more preferably 0.5 hour ~ 12 hours.
The organic solvent used in reaction can enumerate the organic solvent and illustrative compound that use in the synthesis as polyamic acid, specifically, can preferably use DMF, METHYLPYRROLIDONE, gamma-butyrolactone etc.The usage quantity of organic solvent is preferably set to the total amount relative to reaction soln, and polyisoimide becomes the amount of 0.1 % by weight ~ 50 % by weight.
The usage ratio of esterifying agent proportionally suitably can to adjust according to containing of the amic acid esters structure in polymkeric substance (P) contained in liquid crystal aligning agent and different imide ring structure.For the viewpoint of the concave-convex surface of film formed with regard to improving use liquid crystal aligning agent and the improvement effect of the voltage retention of liquid crystal display device and thermotolerance, the part-structure (a-1) that polymkeric substance (P) has preferably is set to 1/99 ~ 99/1 with the molar ratio computing of part-structure (a-1)/part-structure (a-2) with part-structure (a-2) containing proportional.Be more preferably 3/97 ~ 97/3, be especially preferably 5/95 ~ 95/5.Therefore, if with the part-structure (a-1) in polymkeric substance (P) and part-structure (a-2) containing the proportional mode becoming described scope to select the usage quantity of esterifying agent.Specifically, be preferably the total 1 mole relative to the tetracarboxylic dianhydride used in the synthesis of polyisoimide, the usage ratio of carrying out the esterifying agent reacted with polyisoimide is set to 0.02 mole ~ 1.99 moles, be more preferably and be set to 0.06 mole ~ 1.94 moles, be especially preferably set to 0.1 mole ~ 1.9 moles.
Obtain the reaction soln containing polymkeric substance (P) 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 polymkeric substance (P) contained in reaction soln can being separated, or can also reoffer after polymkeric substance (P) purifying be separated to the preparation of liquid crystal aligning agent.The separation of polymkeric substance (P) and purifying can carry out according to known method.
< polyamic acid >
Liquid crystal aligning agent of the present invention only can comprise described polymkeric substance (P) as component of polymer, but with regard to the viewpoints such as cost, can be set to and comprise polymkeric substance (P) and polyamic acid simultaneously.Polyamic acid contained in liquid crystal aligning agent of the present invention such as obtains by making tetracarboxylic dianhydride and diamines carry out reacting.In addition, the tetracarboxylic dianhydride used in the synthesis of polyamic acid and the concrete example of diamines and reaction conditions can apply the explanation of described polymkeric substance (P).
With regard to the aspect that the improvement effect of the electrical specification of liquid crystal display device is high, with described polymkeric substance (P) and polyamic acid preferably have be selected from the structure represented by following formula (3-1), the structure represented by following formula (3-2) (anhydride group wherein, had with tetracarboxylic dianhydride, the reaction of amino that has with diamines and contained in the amido linkage that formed except) and the cohort that forms of nitrogen heterocyclic ring at least one structure (hereinafter also referred to ad hoc structure (x)).
[changing 9]
In formula (3-1), R 5for the alkyl of hydrogen atom, halogen atom, carbon number 1 ~ 10 or the alkoxyl group of carbon number 1 ~ 10, r is the integer of 1 or 2; In R 5when existing multiple, multiple R 5can be identical, also can be different; " * " represents associative key; In formula (3-2), R 6for the alkyl of hydrogen atom or carbon number 1 ~ 6; " * " represents associative key.
In described formula (3-1), R 5the alkyl of carbon number 1 ~ 10 include, for example: methyl, ethyl, propyl group, butyl etc., these alkyl can be straight-chain, also can be branch-like.In addition, the alkoxyl group of carbon number 1 ~ 10 can enumerate the alkyl of carbon number 1 ~ 10 and the group of Sauerstoffatom bond, specifically, include, for example methoxyl group, oxyethyl group, propoxy-etc.Halogen atom include, for example fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.R is preferably 1.
With regard to the aspect that the improvement effect of the electrical specification of liquid crystal display device is high, the R of described formula (3-2) 6be preferably the alkyl of hydrogen atom or carbon number 1 ~ 3, be more preferably hydrogen atom or methyl.
Described nitrogen heterocyclic ring include, for example: piperidine ring, pyrrolidine ring, pyridine ring, pyrazine ring, piperazine ring, pyrimidine ring, homopiperazine ring etc.In these nitrogen heterocyclic rings, with regard to the aspect that the effect with regard to making accumulated residual charge relax is high, being preferably piperidine ring or piperazine ring, being more preferably piperidine ring.
The polyamic acid with ad hoc structure (x), by when synthesizing polyamides is sour, uses the diamines with ad hoc structure (x) to obtain.Specifically, by the diamines used in the synthesis of polyamic acid is set to described carboxylic diamines at least partially, the polyamic acid of the structure had represented by described formula (3-1) can be obtained.In addition, by using two (4-aminophenyl) amine, N, two (4-aminophenyl) methylamine of N-and the compound etc. represented by described formula (d-4), can obtain the polyamic acid of the structure had represented by described formula (3-2).In addition, by using described nitrogen heterocyclic ring diamines, can obtain and there is nitrogenous heterocyclic polyamic acid.
During synthesizing polyamides acid, relative to the total amount of the monomer used in synthesis, the usage ratio with the monomer of ad hoc structure (x) is preferably set to 1 % by mole ~ 30 % by mole, is more preferably and is set to 2 % by mole ~ 20 % by mole.
In addition, using the liquid crystal aligning agent containing polymkeric substance (P) and polyamic acid, be speculated as substrate is formed film: due to the difference of the polarity of each polymkeric substance, polymkeric substance (P) is the upper strata of film partially, and polyamic acid is lower floor partially.In the fusion system of described multiple polymers, because the being separated property each other of polymkeric substance is not good, so the concave-convex surface of worry film declines, but by the liquid crystal aligning agent containing polymkeric substance (P) and polyamic acid, obtain the liquid crystal orientation film that concave-convex surface is good.
When liquid crystal aligning agent of the present invention is used for light orientation, part or all of the polyamic acid of the polymkeric substance allocated in liquid crystal aligning agent (P) and arbitrarily allotment can be set to the polymkeric substance with light orientation structure.Herein, so-called light orientation structure comprises light orientation base and the concept both decomposition type light orientation section.Specifically, light orientation structure can adopt by by photoisomerization or photodimerization, photolysis etc. and show liquid crystal aligning multiple compounds and come structure, include, for example: containing the group containing nitrogen benzide of nitrogen benzide or derivatives thereof as basic framework, containing the group with cinnamic acid structure of styracin or derivatives thereof as basic framework, containing the group containing phenyl styryl ketone of phenyl styryl ketone or derivatives thereof as basic framework, containing the group containing benzophenone of benzophenone or derivatives thereof as basic framework, containing the group containing tonka bean camphor of tonka bean camphor or derivatives thereof as basic framework, containing the structure etc. containing polyimide of polyimide or derivatives thereof as basic framework.
The polymkeric substance with light orientation structure contained in liquid crystal aligning agent of the present invention can preferably use have containing the group of cinnamic acid structure polymkeric substance and comprise the polymkeric substance of decomposition type light orientation section.The polymkeric substance had containing the group of cinnamic acid structure include, for example: the R of formula (1) described in polymkeric substance (P) 1and R 2at least any one is have the Monobasic polymkeric substance of cinnamic acid structure, on side chain, have the polyamic acid etc. of cinnamic acid structure.In addition, the polymkeric substance comprising decomposition type light orientation section preferably can use the polymkeric substance with tetramethylene skeleton or dicyclo [2.2.2] octene skeleton wherein.The polymkeric substance with these skeletons obtains by part or all of the tetracarboxylic dianhydride used in synthesis is set to such as tetramethylene tetracarboxylic dianhydride or dicyclo [2.2.2] pungent-7-alkene-2,3,5,6-tetracarboxylic dianhydride.
Utilizing optical alignment method, when giving liquid crystal aligning ability to film, relative to the total amount of component of polymer contained in liquid crystal aligning agent, the usage ratio with the polymkeric substance of light orientation structure is preferably set to more than 50 % by weight, be more preferably and be set to more than 60 % by weight, be especially preferably set to more than 70 % by weight.
Polymkeric substance (P) in the present invention and polyamic acid be preferably when being made into concentration and being the solution of 15 % by weight, have the soltion viscosity of 15mPas ~ 1500mPas, is more preferably the soltion viscosity with 20mPas ~ 1200mPas.In addition, the soltion viscosity (mPas) of described polymkeric substance is that the concentration of preparation is the polymers soln of 15 % by weight to the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance of use, use E type rotational viscosimeter, measure at 25 DEG C and the value that obtains.
Polymkeric substance (P) in the present invention and polyamic acid utilize gel permeation chromatography (GelPermeationChromatography, the weight average molecular weight (Mw) of the polystyrene conversion GPC) measured is preferably 1,000 ~ 500,000, be more preferably 2,000 ~ 300,000.In addition, by weight average molecular weight Mw, be preferably less than 15 with the molecular weight distribution (Mw/Mn) represented by the ratio of the number average molecular weight (Mn) of polystyrene conversion utilizing GPC to measure, be more preferably less than 10.By in described molecular weight ranges, good orientation and the stability of liquid crystal display device can be guaranteed.
Containing in the liquid crystal aligning agent of polymkeric substance (P) and polyamic acid, polymkeric substance (P) is preferably with the mass ratio range of polymkeric substance (P)/polyamic acid as 1/99 ~ 99/1 containing proportional with polyamic acid.Be more preferably 5/95 ~ 97/3, be especially preferably 10/90 ~ 95/5.
In addition, in the liquid crystal aligning agent of the aspect of [1], can also containing at least one polymkeric substance be selected from the cohort that is made up of poly amic acid ester and polyisoimide.When containing these polymkeric substance, with regard to the viewpoints such as cost, relative to total amount 100 weight part of polymkeric substance (P) and polyamic acid, the allotment ratio of described polymkeric substance (when containing being its total amount two or more) is preferably set to below 30 weight parts, is more preferably and is set to below 20 weight parts.
[2] about the aspect comprising polymkeric substance (Q) and polyisoimide
As polymkeric substance (Q), comprise polyamic acid and poly amic acid ester.Herein, the polyamic acid in this specification sheets refers to the R comprised in described formula (1) 1and R 2be the polymkeric substance of the part-structure (amido acid structure) of hydrogen atom.In addition, poly amic acid ester has the R in described formula (1) 1and R 2at least any one is the polymkeric substance of the part-structure (amic acid esters structure) beyond hydrogen atom.In addition, poly amic acid ester can only have amic acid esters structure, also can be amido acid structure and amic acid esters structure and the partial esterification thing deposited.
Polymkeric substance (Q) and polyisoimide can synthesize according to vitochemical well-established law.Such as, polyamic acid and polyisoimide can utilize described illustrated method and obtain.In addition, about poly amic acid ester, such as, can utilize following methods to obtain: [I] makes polyamic acid and esterifying agent carry out the method for reacting; [II] makes polyisoimide and esterifying agent carry out the method for reacting; [III] makes tetracarboxylic acid diester and diamines carry out the method for reacting; [IV] makes tetracarboxylic acid diester dihalide and diamines carry out the method for reacting; And [V] makes tetracarboxylic dianhydride, diamines and esterifying agent carry out the method etc. of reacting in organic solvent.
Herein, method [I] and the middle esterifying agent used of method [II] can enumerate compound etc. illustrated in the synthesis of described polymkeric substance (P).In these methods, the reaction of method [I] is preferably carried out in the presence of a catalyst.On the other hand, even if there is not catalyzer in method [II], the aspect that reaction is also fully carried out is preferred.The tetracarboxylic acid diester used in method [III] can utilize and make tetracarboxylic dianhydride and alcohols carry out reacting and the method for open loop, the method etc. of tetracarboxylic acid being carried out esterification obtain.In addition, the tetracarboxylic acid diester dihalide used in method [IV] obtains by making the suitable halogenating agent such as the tetracarboxylic acid diester that obtains in this way and thionyl chloride carry out reacting.Method [III] and the middle diamines used of method [IV] can enumerate the diamines and illustrative compound etc. that use in the synthesis as polyamic acid.Method [V] can be preferred for the situation obtaining silane base system poly amic acid ester.In this situation, esterifying agent such as can use: the silicon alkylamides system silane-based agents such as two (TMS) ethanamide, two (TMS) trifluoroacetamide, two (TMS) urea.
Polymkeric substance (Q) in the present invention and polyisoimide be preferably when being made into concentration and being the solution of 15 % by weight, have the soltion viscosity of 15mPas ~ 1500mPas, is more preferably the soltion viscosity with 20mPas ~ 1200mPas.In addition, the soltion viscosity (mPas) of described polymkeric substance be to the concentration using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of these polymkeric substance to prepare be 15 % by weight polymers soln, use E type rotational viscosimeter, measure at 25 DEG C and the value that obtains.
The weight average molecular weight (Mw) of the polystyrene conversion utilizing gel permeation chromatography (GPC) to measure of the polymkeric substance (Q) in the present invention and polyisoimide is preferably 1,000 ~ 500,000, be more preferably 2,000 ~ 300,000.In addition, by weight average molecular weight Mw, be preferably less than 15 with the molecular weight distribution (Mw/Mn) represented by the ratio of the number average molecular weight (Mn) of polystyrene conversion utilizing GPC to measure, be more preferably less than 10.
In the liquid crystal aligning agent comprising polymkeric substance (Q) and polyisoimide, with regard to fully obtaining the viewpoint of effect of the present invention, polymkeric substance (Q) is preferably with the mass ratio range of polyisoimide/polymkeric substance (Q) containing proportional with polyisoimide, is set to 1/99 ~ 99/1.Be more preferably 10/90 ~ 90/10, be especially preferably 15/85 ~ 85/15.
Other compositions of < >
Liquid crystal aligning agent of the present invention also can optionally and also containing other compositions beyond described polymkeric substance.These other compositions include, for example: other polymkeric substance beyond polymkeric substance (P), polymkeric substance (Q) and polyisoimide, have the compound (hereinafter referred to as " compound containing epoxy group(ing) "), functional silanes compound etc. of at least one epoxy group(ing) in molecule.
[other polymkeric substance]
Other polymkeric substance described can be used for improving solution properties or electrical specification.Other polymkeric substance described include, for example: polyimide, polyester, polymeric amide, organopolysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc.
When other polymkeric substance described are made an addition in liquid crystal aligning agent, relative to whole polymkeric substance 100 weight part in said composition, the allotment ratio of other polymkeric substance described is preferably set to below 30 weight parts, be more preferably and be set to 0.1 weight part ~ 20 weight part, be especially preferably set to 0.1 weight part ~ 10 weight part.
[compound containing epoxy group(ing)]
Compound containing epoxy group(ing) can be used for improving liquid crystal orientation film with the cementability of substrate surface.Herein, compound containing epoxy group(ing) include, for example following compound as preferably: 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-cyclo-hexylamine, the organopolysiloxane etc. containing epoxy group(ing) that No. 2009/096598th, International Publication is recorded.
When these compounds containing epoxy group(ing) are made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, the allotment ratio of the described compound containing epoxy group(ing) is preferably below 40 weight parts, is more preferably 0.1 weight part ~ 30 weight part.
[functional silanes compound]
Described functional silanes compound can be used for the printing improving liquid crystal aligning agent.This functional silanes compound include, for example: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, 3-ureido-propyl Trimethoxy silane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl diethylenetriamine, 10-Trimethoxy silane base-1, 4, 7-tri-azepine decane, 9-Trimethoxy silane base-3, 6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3, 6-diaza nonyl acetic ester, 9-triethoxysilicane alkyl-3, 6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, glycidoxypropyl Union carbide A-162 etc.
When being made an addition in liquid crystal aligning agent by functionality silane compound, relative to total 100 weight part of polymkeric substance, the allotment ratio of described functional silanes compound is preferably below 2 weight parts, is more preferably 0.02 weight part ~ 0.2 weight part.
In addition, also can following compound be made an addition in liquid crystal aligning agent: the meal chelate compounds such as diisopropoxy ethyl acetoacetic acid aluminium, aluminium tris(acetylacetonate); The hardening accelerators such as phenols, silane alcohols; The tensio-active agents such as nonionogenic tenside, anion surfactant, cats product, amphoterics, silicone surfactant, fluorochemical surfactant; The antioxidants such as phenol system antioxidant, amine system antioxidant; Glycol diacrylate, 1,6 hexanediol diacrylate etc. multifunctional (methyl) acrylate etc.
< solvent >
Liquid crystal aligning agent of the present invention is prepared into the liquid composition described polymkeric substance and other compositions of optionally using preferably are dispersed or dissolved in suitable solvent.
The solvent used include, for example: 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, ethylene 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, diisoamyl ether, ethylene carbonate, Texacar PC etc.These solvents can be used alone one or be use mixing two or more.
Solid component concentration (ratio of total weight shared by the gross weight of liquid crystal aligning agent of the composition beyond the solvent of liquid crystal aligning agent) in liquid crystal aligning agent of the present invention can consider that viscosity, volatility etc. are suitably selected, and is preferably the scope of 1 % by weight ~ 10 % by weight.That is, liquid crystal aligning agent of the present invention is by coating substrate surface in aftermentioned mode, preferably heats, thus formed 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 decline.
The scope of particularly preferred solid component concentration is different from the purposes of liquid crystal aligning agent or the method that uses during coating of liquid crystalline alignment agent on substrate.Such as, for the liquid crystal aligning agent of liquid crystal cells, when utilizing turner method to coat on substrate, solid component concentration (ratios of total weight shared by the gross weight of liquid crystal aligning agent of the whole compositions beyond the solvent in liquid crystal aligning agent) is particularly preferably the scope of 1.5 % by weight ~ 4.5 % by weight.When utilizing print process, being particularly preferably scope solid component concentration being set to 3 % by weight ~ 9 % by weight, whereby soltion viscosity being set to the scope of 12mPas ~ 50mPas.When utilizing ink jet method, being particularly preferably scope solid component concentration being set to 1 % by weight ~ 5 % by weight, whereby soltion viscosity being set to the scope of 3mPas ~ 15mPas.Temperature when preparing liquid crystal aligning agent of the present invention is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.In addition, about the liquid crystal aligning agent of phase retardation film, with regard to the coating that makes liquid crystal aligning agent and the viewpoint of the thickness appropriateness of film that formed, the solid component concentration of liquid crystal aligning agent is preferably the scope of 0.2 % by weight ~ 10 % by weight, is more preferably the scope of 3 % by weight ~ 10 % by weight.
< liquid crystal display device and phase retardation film >
By using the liquid crystal aligning agent of the present invention of described explanation to manufacture liquid crystal orientation film.In addition, the liquid crystal orientation film using liquid crystal aligning agent of the present invention to be formed can be preferably applied to the liquid crystal orientation film of (liquid crystal cells is used) used for liquid crystal display element and the liquid crystal orientation film of phase retardation film.Below, liquid crystal display device of the present invention and phase retardation film are described.
[liquid crystal display device]
The liquid crystal orientation film that liquid crystal display device of the present invention possesses the described liquid crystal aligning agent of use and formed.The operating mode of liquid crystal display device of the present invention is not particularly limited, such as can be applicable to TN type, STN type, VA type (comprise vertical orientated-multidomain vertical orientation (VerticalAlignment-MultidomainVerticalAlignment, VA-MVA) type, the vertical orientated (VerticalAlignment-PatternedVerticalAlignment of vertical orientated-pattern, VA-PVA) type etc.), IPS type, FFS type, the multiple operation mode such as optical compensation curved (OpticallyCompensatoryBend, OCB) type.The step of liquid crystal display device of the present invention such as by comprising following (1-1) ~ (1-3) manufactures.Step (1-1) uses different substrates according to required operating mode.Step (1-2) and step (1-3) share in each operating mode.
[step (1-1): the formation of film]
First, substrate is coated with liquid crystal aligning agent of the present invention, then coated face is heated, on substrate, form film whereby.
(1-1A) when the liquid crystal display device of Production Example as TN type, STN type or VA type, first, to two pieces of substrates of patterned nesa coating be provided with as a pair, in its each transparent conductive film forming surface, flexographic printing process, method of spin coating, roll-coater method or ink jet printing method is preferably utilized to be coated with liquid crystal aligning agent of the present invention respectively.Substrate such as can use: the glass such as float glass, soda glass; Comprise the transparency carrier of the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The wherein nesa coating of one side being arranged at substrate can use and 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) ito film etc.In order to obtain patterned nesa coating, such as, can utilize following methods: after forming patternless nesa coating, being formed the method for pattern by photoetch; The method etc. with the mask of required pattern is used when forming nesa coating.During coating of liquid crystalline alignment agent, in order to make the cementability of substrate surface and nesa coating and film better, also to the face forming film in substrate surface, the pre-treatment being coated with functional silanes compound, functionality titanium compound etc. in advance can be implemented.
After coating of liquid crystalline alignment agent, for the object such as sagging preventing be coated with liquid crystal aligning agent, be preferably enforcement and preheat (prebake conditions).Prebake conditions temperature is preferably 30 DEG C ~ 200 DEG C, is more preferably 40 DEG C ~ 150 DEG C, is particularly 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, remove completely for by solvent, optionally the amido acid structure be present in polymkeric substance is carried out the object of hot-imide, and implement calcining (toasting afterwards) step.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.The thickness of the film formed in this way is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.
(1-1B) when manufacturing the liquid crystal display device of IPS type or FFS type, be provided with electrode substrate electrode forming surface, with do not arrange in the one side of subtend substrate of electrode, be coated with liquid crystal aligning agent of the present invention respectively, then each coated face is heated, form film whereby, described electrode package containing patterned be nesa coating or the metallic membrane of interdigitated electrode structure.The patterning method of heating condition, nesa coating or metallic membrane after now used substrate and the material of nesa coating, coating process, coating, the pre-treatment of substrate and the preferred thickness of film formed identical with described (1-1A).Metallic membrane can use the film such as comprising the metals such as chromium.
In any one situation of described (1-1A) and (1-1B), all by after coating of liquid crystalline alignment agent on substrate, organic solvent is removed and forms liquid crystal orientation film or become the film of liquid crystal orientation film.Now, also by heating further after film is formed, and make the poly amic acid ester of allotment in liquid crystal aligning agent of the present invention and polyimide and the polyamic acid optionally allocated carry out dehydration closed-loop reaction, thus make further through the film of imidization.
[step (1-2): orientation process]
When manufacturing the liquid crystal display device of TN type, STN type, IPS type or FFS type, implement the process (orientation process) of the film formed in described step (1) being given to liquid crystal aligning ability.Whereby, the alignment capability of liquid crystal molecule is imparted to film and becomes liquid crystal orientation film.Orientation process can enumerate friction treatment, light orientation process etc., and described friction treatment utilizes the roller being wound with the cloth comprising the fibers such as such as nylon, artificial silk, cotton, by film to certain orientation wiping; Described smooth orientation process irradiates light to film.On the other hand, when manufacturing the liquid crystal display device of vertical orientating type, the film formed directly can be used as liquid crystal orientation film in described step (1), also can to this film implementation orientation process.
Rayed in light orientation process can utilize following methods to carry out: the method that [1] is irradiated the film after rear baking procedure; [2] to after pre-bake step and after film before the baking procedure method of irradiating; [3] at pre-bake step and rear baking procedure at least in any one, add the method etc. of hankering irradiating film at film.
Polarisation or non-polarized can be set to the light that film irradiates.As light, such as, can use ultraviolet and the visible rays of the light comprising 150nm ~ 800nm wavelength.When being set to polarisation, can be linear polarization, also can be part polarisation.In addition, when used light is for linear polarization or part polarisation, can irradiates from the direction vertical with real estate, also can irradiate from vergence direction, or also these can be irradiated combination and carry out.When irradiating the light of non-polarized, the direction of irradiation is set to vergence direction.
The light source used 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 can utilize light source and method also such as such as spectral filter, diffraction grating etc. etc. and obtain.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, in order to improve reactivity, can heat to film while carry out rayed to film.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 can carrying out following process 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: making by irradiating light to a part for liquid crystal orientation film the process that the tilt angle in a part of region of liquid crystal orientation film changes; Or after a part on liquid crystal orientation film surface forms resist film, after friction treatment is carried out in the direction different from friction treatment just now, by the process that resist film is removed.In this situation, the visual field characteristic of the liquid crystal display device of gained can be improved.The liquid crystal orientation film being suitable for VA type liquid crystal display device also can be suitable for the liquid crystal display device of polymer stabilizing orientation (Polymersustainedalignment, PSA) type.
[step (1-3): constructing of liquid crystal cells]
Prepare the substrate that two pieces are formed with liquid crystal orientation film in this way, between two pieces of substrates of subtend configuration, configure liquid crystal, manufacture liquid crystal cells whereby.In order to manufacture liquid crystal cells, include, for example following two kinds of methods.First method is in the past known method.First, in the mode of each liquid crystal orientation film subtend, via gap (cell gap), two pieces of substrate subtends are configured, sealing material is used to be fitted by the periphery of two pieces of substrates, inject filling liquid crystal in the cell gap divided by substrate surface and sealing material after, filling orifice is sealed, can liquid crystal cells be manufactured whereby.In addition, the second method is for being called the method for liquid crystal drip-injection (OneDropFill, ODF) mode.Specified location on wherein one piece of substrate in the two pieces of substrates being formed with liquid crystal orientation film, be coated with the sealing agent of such as ultraviolet light photopolymerization, and then after the set several positions on liquid crystal aligning face drip liquid crystal, to fit another block substrate in the mode of liquid crystal orientation film subtend, and liquid crystal is spread out on whole of substrate, then to whole irradiating ultraviolet light of substrate, sealing material is hardened, can liquid crystal cells be manufactured whereby.When utilizing any one method, all it is desirable to the liquid crystal cells to manufacturing in this way, and then be heated to till used liquid crystal obtains the temperature of isotropic phase, then slowly be cooled to room temperature, eliminate flow orientation when liquid crystal is filled whereby.
As sealing material, can use and be typically used as liquid crystal caking agent, such as, can use the epoxy resin etc. containing stiffening agent.In addition, sealing material can to use also containing the alumina balls as spacer.
Liquid crystal can enumerate nematic liquid crystal and disc-like liquid crystal, wherein be preferably nematic liquid crystal, such as, can use: schiff bases (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, xenyl hexamethylene methane series liquid crystal, pyrimidine system liquid crystal, diox system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can add following material to use in these liquid crystal: the cholesteric liquid crystals (cholestericliquidcrystal) such as such as cholesteryl chloride (cholesterylchloride), cholesteryl nonanoate (cholesterylnonanoate), cholesteryl carbonate (cholesterylcarbonate); With the chiral agent that trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) are sold; 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.
Then, liquid crystal display device of the present invention is obtained by the outer surface laminating Polarizer at liquid crystal cells.The Polarizer fitting in the outside surface of liquid crystal cells can be enumerated: be called as the Polarizer of the light polarizing film of " H film " with the clamping of rhodia protective membrane or comprise itself Polarizer of H film, and described " H film " is polyvinyl alcohol is extended film that orientation absorbs iodine.
[phase retardation film]
Then, the method using liquid crystal aligning agent of the present invention to manufacture phase retardation film is described.When manufacturing phase retardation film of the present invention, dust or electrostatic just not only can be suppressed in step to occur, and the aspect of uniform liquid crystal orientation film can be formed, and can by use suitable photomask when the irradiation of light and formed arbitrarily on substrate different multiple regions, liquid crystal aligning direction in, preferably utilize optical alignment method.Specifically, by manufacturing through following step (2-1) ~ step (2-3).
Step (2-1): liquid crystal aligning agent is coated step substrate being formed film.
Step (2-2): light-struck step is carried out to described film.
Step (2-3): the film after rayed is coated with polymerizable liquid crystal and the step making it harden.
[step (2-1): the formation utilizing the film of liquid crystal aligning agent]
First, liquid crystal aligning agent of the present invention is coated on substrate form film.Substrate used herein can be applicable to illustrating: the transparency carrier comprising the synthetic resins such as triacetyl cellulose (triacetylcellulose, TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polymeric amide, polyimide, polymethylmethacrylate, polycarbonate.In these substrates, TAC is typically used as the protective layer of the light polarizing film in liquid crystal display device.In addition, with regard to the aspect good with regard to the low aspect of the water absorbability of solvent, optical characteristics and the aspect of low cost, polymethylmethacrylate can be preferably used as the substrate of phase retardation film.In addition, for the substrate used in the coating of liquid crystal aligning agent, in order to make the adaptation of substrate surface and film better, also known pre-treatment can be implemented to the face forming film in substrate surface.
Under many circumstances, phase retardation film and light polarizing film combinationally use.Now, in order to required optical characteristics can be played, must by phase retardation film relative to the polarizing axis of light polarizing film precise angle control as specific direction is to phase retardation film of fitting.Therefore, herein, by being formed on the substrates such as TAC film or polymethylmethacrylate by the liquid crystal orientation film on the direction of first retainer with liquid crystal aligning ability, the angle of control phase difference film can be omitted while phase retardation film to be fitted in the step in light polarizing film.In addition, the productivity improving liquid crystal display device can be contributed to whereby.In order to be formed in first retainer direction on there is the liquid crystal orientation film of liquid crystal aligning ability, preferably utilize optical alignment method to carry out.
The coating of liquid crystal aligning agent on substrate can utilize suitable coating process, such as, can adopt: roll-coater method, turner method, print process, ink jet method, rod coater, extrude modulus method, direct gravure coater (directgravurecoater) method, chamber knife coater (chamberdoctorcoater) method, hectograph gravure coater (offsetgravurecoater) method, single roller kiss coater (singlerollkisscoater) method, use anti-kiss coater (reversekisscoater) method of path gravure roll, three reverse roll coater (threereverserollcoater) methods, four reverse roll coater methods, slit die (slotdie) method, Kohler coater (airdoctorcoater) method, positive rotation roll-coater (positiverotationrollcoater) method, scraper plate coating machine (bladecoater) method, scraper type coating machine (knifecoater) method, impregnation coater, MB coater, the reverse coater of MB etc.
After coating, (baking) is heated to coated face and forms film.Heating temperature now is preferably set to 40 DEG C ~ 150 DEG C, is more preferably and is set to 80 DEG C ~ 140 DEG C.Preferably be set to 0.1 minute ~ 15 minutes heat-up time, be more preferably and be set to 1 minute ~ 10 minutes.The thickness being formed at the film on substrate is preferably 1nm ~ 1, and 000nm is more preferably 5nm ~ 500nm.
[step (2-2): light irradiation step]
Then, by irradiating light to the film be formed in this way on substrate, giving liquid crystal aligning ability to film and making liquid crystal orientation film.About the kind of irradiated light, direction of illumination and light source, the explanation of described step (1-2) can be applied.The irradiation dose of light is preferably set to 0.1mJ/cm 2~ 1,000mJ/cm 2, be more preferably and be set to 1mJ/cm 2~ 500mJ/cm 2, be especially preferably set to 2mJ/cm 2~ 200mJ/cm 2.
[step (2-3): the formation of liquid crystal layer]
Then, the film after carrying out rayed is in this way coated with polymerizable liquid crystal and makes it harden.Whereby, the film (liquid crystal layer) comprising polymerizable liquid crystal is formed.Polymerizable liquid crystal used herein carries out the liquid crystalline cpd that is polymerized or liquid-crystal composition by least one process in heating and rayed.This kind of polymerizable liquid crystal can use known liquid crystal, specifically, include, for example non-patent literature 1 (" can the liquid crystal that hardens of ultraviolet (UV) and application thereof ", " liquid crystal " the 3rd volume the 1st phase (1999), the 34th page ~ the 42nd page) the middle nematic liquid crystal recorded.In addition, also can be: cholesteryl liquid crystal; Discotic mesogenic (discoticliquidcrystal); Be added with the twisted nematic alignment-type liquid crystal etc. of chiral agent.Polymerizable liquid crystal also can be the mixture of plurality of liquid crystals compound.Polymerizable liquid crystal also can be the composition also containing known polymerization starter, suitable solvent etc.
When formed liquid crystal orientation film is coated with polymerizable liquid crystal as above, such as, can adopt the coating process that excellent coater, roll-coater method, turner method, print process, ink jet method etc. are suitable.
Then, by the film to the polymerizable liquid crystal formed in this way, implement to be selected from more than one the process in heating and rayed, make this film harden and form liquid crystal layer.These processing overlapping are carried out, good orientation can be obtained, so preferably.
The Heating temperature of film suitably can be selected according to the kind of used polymerizable liquid crystal.Such as when the RMS03-013C using Merck (Merck) company to manufacture, preferably heat at the temperature of the scope of 40 DEG C ~ 80 DEG C.Be preferably 0.5 minute ~ 5 minutes heat-up time.
Irradiate the ultraviolet that light preferably can use the non-polarized of the wavelength of the scope with 200nm ~ 500nm.The irradiation dose of light is preferably set to 50mJ/cm 2~ 10,000mJ/cm 2, be more preferably and be set to 100mJ/cm 2~ 5,000mJ/cm 2.
The thickness of the liquid crystal layer formed suitably can set according to required optical characteristics.Such as when manufacture wavelength is 1/2 wavelength plate in the visible ray of 540nm, select the phase differential of the phase retardation film formed to become the thickness of 240nm ~ 300nm, if 1/4 wavelength plate, then selected phase difference becomes the thickness of 120nm ~ 150nm.The thickness obtaining the liquid crystal layer of target phase difference is different according to the optical characteristics of used polymerizable liquid crystal.Such as when the RMS03-013C using Merck (Merck) to manufacture, in order to manufacture the scope that the thickness of 1/4 wavelength plate is 0.6 μm ~ 1.5 μm.
The phase retardation film obtained in this way can preferably be applied as the phase retardation film of liquid crystal display device.The liquid crystal display device applying phase retardation film of the present invention is also unrestricted to its operating mode, such as, can be applicable to the known various patterns such as TN type, STN type, IPS type, FFS type, VA type.Described phase retardation film uses the face of the substrate-side that the outer side of the Polarizer depending on recognizing side being configured at liquid crystal display device attaches in phase retardation film.Therefore, be preferably set to following aspect: the substrate of phase retardation film is set to TAC system or acrylic acid series base material, make the substrate of this phase retardation film also as the protective membrane of light polarizing film to play function.
Liquid crystal display device of the present invention can be effectively applied to multiple device, such as can be used for: clock and watch, pocket game machine, word processor (wordprocessor), notes type Personal Computer (notetypepersonalcomputer), auto-navigation system (carnavigationsystem), video camera (camcorder), personal digital assistant (PersonalDigitalAssistant, PDA), digital camera (digitalcamera), mobile phone, smart mobile phone, various watch-dog, LCD TV, the various display unit such as information display.
[embodiment]
Below, by embodiment, the present invention is specifically described further, but the present invention is not limited to these embodiments.
The imide rate of the polyimide in following synthesis example and the soltion viscosity of each polymers soln utilize following methods to measure.
[the imide rate of polyimide]
Solution containing polyimide is fed in pure water, the precipitation of gained, at room temperature fully after drying under reduced pressure, is dissolved in deuterodimethylsulfoxide, using tetramethylsilane as primary standard, at room temperature measures 1h-nucleus magnetic resonance (NuclearMagneticResonance, 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 1the peak area being derived from the proton of NH base occurred near chemical shift 10ppm, A 2be the peak area being derived from other protons, α is the number ratios of other protons relative to 1 proton of the NH base in the precursor (polyamic acid) of polymkeric substance)
[soltion viscosity of polymers soln]
The soltion viscosity [mPas] of polymers soln is the solution being prepared into polymer concentration 15 % by weight to using set solvent, uses E type rotational viscosimeter to measure at 25 DEG C.
The synthesis > of < polyamic acid
[synthesis example 1; The synthesis of polymkeric substance (PAA-1)]
Using 2 of 90 molar part as tetracarboxylic dianhydride; 3; the pyromellitic acid anhydride of 5-tricarboxylic cyclopentyl acetic acid dianhydride and 10 molar part, as the Ursol D of 98 molar part of diamines and 3 of 2 molar part; two (the 4-amino benzoyl oxygen base) cholestane of 6-; be dissolved in METHYLPYRROLIDONE (N-mcthyl-2-pyrrolidone; NMP) in, at 60 DEG C, carry out reaction in 6 hours, obtain the polyamic acid solution that solid component concentration is 15 % by weight.The polyamic acid solution of gained is divided and takes a morsel, measure and the soltion viscosity that obtains is 420mPas.
[synthesis example 2, synthesis example 3; The synthesis of polymkeric substance (PAA-2) and polymkeric substance (PAA-3)]
Except by the kind of used tetracarboxylic dianhydride and diamines and quantitative change more as except aspect described in following table 1, obtain the solution containing polyamic acid in the mode identical with synthesis example 1.
The synthesis > of < polymkeric substance (P)
[synthesis example 4; The synthesis of polymkeric substance (PHF-1)]
By the operation identical with synthesis example 1, obtain the polyamic acid solution that solid component concentration is 15 % by weight.In this polyamic acid solution, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the triethylamine (triethylamine, TEA) of 200 molar part, then at room temperature stir 24 hours.Then, while stir at 0 DEG C, one ray flower 1 hour, in reaction soln, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the trifluoroacetic anhydride (trifluoroaceticanhydride of 200 molar part, TFAA), then, at room temperature stir 24 hours.After reaction terminates, the solution of gained is injected in excessive acetone, reaction product is precipitated.By reclaimed throw out with after acetone cleaning, under reduced pressure at 40 DEG C dry 15 hours, obtain polymkeric substance whereby.
Then, the polymkeric substance of gained is dissolved in NMP again, wherein, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the methyl alcohol of 100 molar part, stir 24 hours.Whereby, the solution containing the polymkeric substance (PHF-1) with amic acid esters structure and different imide ring structure is obtained.
[synthesis example 5 ~ synthesis example 8; The synthesis of polymkeric substance (PHF-2) ~ polymkeric substance (PHF-5)]
Except the usage quantity of the kind of used tetracarboxylic dianhydride and diamines and amount and methyl alcohol being changed to as except aspect described in following table 1, obtain the solution respectively containing polymkeric substance (PHF-2) ~ polymkeric substance (PHF-5) in the mode identical with synthesis example 4.
[synthesis example 9; The synthesis of polymkeric substance (PHF-6)]
By the operation identical with synthesis example 1, obtain the polyamic acid solution that solid component concentration is 15 % by weight.In this polyamic acid solution, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the triethylamine (TEA) of 100 molar part, then at room temperature stir 24 hours.Then, stir at 0 DEG C, a ray flower 1 hour, in reaction soln, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the trifluoroacetic anhydride (TFAA) of 100 molar part, then, at room temperature stir 24 hours.After reaction terminates, the solution of gained is injected in excessive acetone, reaction product is precipitated.By reclaimed throw out with after acetone cleaning, under reduced pressure at 40 DEG C dry 15 hours, obtain the polymkeric substance (PHF-6) with amido acid structure and different imide ring structure whereby.
The synthesis > of < polyimide
[synthesis example 10; The synthesis of polymkeric substance (PI-1)]
By the operation identical with synthesis example 1, obtain the polyamic acid solution that solid component concentration is 15 % by weight.In this polyamic acid solution, add NMP and solid component concentration is set to 10 % by weight, respectively relative to tetracarboxylic dianhydride total 100 molar part and add pyridine and the diacetyl oxide of 300 molar part, at 110 DEG C, carry out dehydration closed-loop reaction in 4 hours.After dehydration closed-loop reaction, utilize new NMP that intrasystem solvent is carried out solvent exchange (by this operation, the pyridine used in imidization reaction and diacetyl oxide are removed to system outer), obtain the solution being about the polyimide of 85% containing imide rate.Utilize NMP, in the mode becoming 15 % by weight, the polymkeric substance (PI-1) of gained is prepared into solution, measure the viscosity of this solution, result is 520mPas.
The synthesis > of < polyisoimide
[synthesis example 11; The synthesis of polymkeric substance (Piso-1)]
By the operation identical with synthesis example 1, obtain the polyamic acid solution that solid component concentration is 15 % by weight.In this polyamic acid solution, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the triethylamine (TEA) of 200 molar part, then at room temperature stir 24 hours.Then, stir at 0 DEG C, while spend 1 hour in reaction soln, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the trifluoroacetic anhydride (TFAA) of 200 molar part, then, at room temperature stirring 24 hours.After reaction terminates, the solution of gained is injected in excessive acetone, reaction product is precipitated.By reclaimed throw out with after acetone cleaning, under reduced pressure at 40 DEG C dry 15 hours, obtain polyisoimide whereby.Utilize NMP, in the mode becoming 15 % by weight, the polymkeric substance (Piso-1) of gained is prepared into solution, measure the viscosity of this solution, result is 540mPas.
The synthesis > of < poly amic acid ester
[synthesis example 12; The synthesis of polymkeric substance (PAE-1)]
By the operation identical with synthesis example 11, obtain the polyisoimide solution that solid component concentration is 15 % by weight.In this polyisoimide solution, relative to the tetracarboxylic dianhydride used in synthesis total amount 100 molar part and add the methyl alcohol of 300 molar part, stir 24 hours.After reaction terminates, the solution of gained is injected in excessive acetone, reaction product is precipitated.By reclaimed throw out with after acetone cleaning, under reduced pressure at 40 DEG C dry 15 hours, obtain poly amic acid ester whereby.Utilize NMP, in the mode becoming 15 % by weight, the polymkeric substance (PAE-1) of gained is prepared into solution, measure the viscosity of this solution, result is 400mPas.
The composition of the compound used in the synthesis of polymkeric substance is shown in following table 1.
The usage ratio (molar part) of each compound of the numeric representation in table 1 for total amount 100 molar part of the tetracarboxylic dianhydride used in the synthesis of polymkeric substance.The different imide of PAE/ than " numerical value be the calculated value of the ratio (mol ratio) of amic acid esters structure for the whole repeating units in polymkeric substance and different imide ring structure.The numerical value of " PAA/ different imide than " is the calculated value of the ratio (mol ratio) of amido acid structure for the whole repeating units in polymkeric substance and different imide ring structure.
In table 1, the abbreviation of compound is respectively following implication.
(tetracarboxylic dianhydride)
AN-1:1,2,3,4-tetramethylene tetracarboxylic dianhydride
AN-2:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
AN-3: pyromellitic acid anhydride
(diamines)
DA-1: Ursol D
DA-2: the compound represented by described formula (d-1)
Two (the 4-amino benzoyl oxygen base) cholestane of DA-3:3,6-
DA-4:3-(3,5-diaminobenzene formyl radical oxygen base) cholestane
DA-5:2,2 '-dimethyl-4,4 '-benzidine base
DA-6:3,5-diaminobenzoic acid
[embodiment 1:TN type liquid crystal display device]
(1) preparation of liquid crystal aligning agent
In the solution of the polymkeric substance (PHF-1) obtained in containing synthesis example 4, add γ-butyl lactone (BLANT), NMP and diethylene glycol diethyl ether (DEDG) and dissolve, make BLANT: NMP: DEDG=55: 30: 15 (weight ratios), solid component concentration be 6.0 % by weight solution.Utilize aperture to be that this solution filters by the strainer of 0.2 μm, prepare liquid crystal aligning agent whereby.
(2) evaluation of the concave-convex surface of film
Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), the liquid crystal aligning agent of described preparation is coated after on Silicon Wafer, utilize the hot-plate prebake conditions 1 minute of 80 DEG C.Then, utilize the hot-plate of 230 DEG C to heat (toasting afterwards) 15 minutes, forming average film thickness is whereby the film of 100nm.Utilize atomic force microscope (nanometer microscope (NanoScope) IIia, digital instrument (DigitalInstrument) company manufactures) this film is observed, measure the surface roughness Ra (arithmetic average height) of film.Evaluating as follows: average evaluation Ra being less than 2.0nm is concave-convex surface " well ", by more than 2.0nm and the average evaluation being less than 5.0nm is "available", is " bad " by the average evaluation of more than 5.0nm.In the present embodiment, Ra is 0.3nm, and concave-convex surface is " well ".
(3) evaluation of printing
Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), the liquid crystal aligning agent of described preparation is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode comprising ito film, the hot-plate of 80 DEG C heats (prebake conditions) 1 minute and removes solvent, then, the hot-plate of 200 DEG C heats (toasting afterwards) 10 minutes, forming average film thickness is film.Multiplying power is utilized to be that the microscope of 20 times is observed this film, the presence or absence that investigation thickness is uneven, orange peel defect is uneven and wire is uneven.Evaluate as follows: will for be evaluated as printing " well " uniformly in, coated face uneven without thickness, being printing "available" by the average evaluation observing orange peel defect inequality, is printing " bad " by observing the average evaluation that orange peel defect is uneven and wire is uneven.In the present embodiment, not observing thickness inequality, in addition, is that evenly printing is " well " in coated face.
(4) evaluation of the storage stability of liquid crystal aligning agent
According to the evaluation of the property separated out
The liquid crystal aligning agent of described preparation is taken care of 1 month at 5 DEG C, with the visual liquid crystal aligning agent observed after keeping.To the average evaluation of the precipitation of insolubles do not observed for " well ", will the average evaluation of the precipitation of insolubles be observed for " bad ".Its result is, is the evaluation of " well " in the present embodiment.
According to the evaluation of viscosity B coefficent
For the liquid crystal aligning agent of described preparation, take care of the soltion viscosity after 1 month after measuring just preparation respectively and at 5 DEG C, utilize following formula (2) to obtain viscosity B coefficent rate Δ η.In addition, the soltion viscosity [mPas] of liquid crystal aligning agent uses E type rotational viscosimeter, measures at 25 DEG C.
Δη＝((η AF-η BF)÷η BF)×100(2)
(in numerical expression (2), η bFthe soltion viscosity measured after just preparation, η aFthe soltion viscosity that keeping measured after 1 month at 5 DEG C)
Carry out the evaluation of storage stability as follows: if viscosity B coefficent rate Δ η is less than 5%, is then evaluated as storage stability " well ", if be greater than 5% and be less than 10%, is then evaluated as "available", if more than 10%, be then evaluated as " bad ".Its result is, is the evaluation of " well " in the present embodiment.
(5) manufacture of TN type liquid crystal cells
Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), the liquid crystal aligning agent of preparation in described (1) is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode comprising ito film, the hot-plate of 80 DEG C heats (prebake conditions) 1 minute and after removing solvent, the hot-plate of 200 DEG C heats (toasting afterwards) 10 minutes, forming average film thickness is film.To this film, utilize the friction machine with the roller being wound with artificial silk cloth, carry out friction treatment with roller rotating speed 500rpm, platform movement speed 3cm/sec, hair press-in length 0.4mm, give liquid crystal aligning ability.Then, in ultrapure water, carry out 1 minute ultrasonic cleaning, in 100 DEG C of cleaning ovens dry 10 minutes then, obtain the substrate with liquid crystal orientation film whereby.In addition, repeat described operation, obtain a pair (two pieces) substrate with liquid crystal orientation film.
Then, for the wherein one piece of substrate in described a pair substrate, after the outer rim coating in the face with liquid crystal orientation film adds and has diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, in the relative mode of liquid crystal aligning face, a pair substrate is overlapping and crimp, make adhesive hardens.Then, after filling nematic liquid crystal (Merck (Merck) company manufactures, MLC-6221) between from liquid crystal injecting port to a pair substrate, utilize acrylic acid series ray hardening type adhesive to be sealed by liquid crystal injecting port, manufacture TN type liquid crystal cells whereby.
(6) evaluation of liquid crystal aligning
For the liquid crystal cells manufactured in described (5), under Nicol crossed, utilize microscope, the presence or absence of the abnormal area in light and shade change when doubly observing on-off (applying to remove) 5V voltage with multiplying power 50.Evaluating as follows: be liquid crystal aligning " well " by the average evaluation not observing abnormal area, is liquid crystal aligning " bad " by the average evaluation observing abnormal area.In this liquid crystal cells, liquid crystal aligning " well ".
(7) evaluation of voltage retention
For the liquid crystal cells manufactured in described (5), apply 5V voltage with the application time of 60 microseconds, the span of 167 milliseconds at 23 DEG C after, measure the voltage retention (VoltageHoldingRatio, VHR) after 167 milliseconds from applying to remove.In addition, determinator uses the VHR-1 that Dongyang Te Kenika (ToyoTechnica) (stock) manufactures.The voltage retention of this liquid crystal cells is 97.8%.
(8) evaluation of thermotolerance
For the liquid crystal cells manufactured in described (5), measure voltage retention in the mode identical with described (7), using its value as initial VHR (VHR bF).Then, the liquid crystal display device after measuring initial VHR, leaves standstill 300 hours in the baking oven of 100 DEG C.Then, by this liquid crystal display device at room temperature leave standstill and place be cooled to room temperature after, to measure voltage retention (VHR with described identical mode aF).In addition, according to following numerical expression (3), obtain the velocity of variation (Δ VHR (%)) that thermal stresses gives the voltage retention of front and back.
ΔVHR＝((VHR BF-VHR AF)÷VHR BF)×100(3)
Carrying out the evaluation of thermotolerance as follows: average evaluation velocity of variation Δ VHR being less than 4% is thermotolerance " well ", by more than 4% and the average evaluation being less than 5% is "available", is thermotolerance " bad " by the average evaluation of more than 5%.Its result is, in the present embodiment, Δ VHR=3.1%, thermotolerance is " well ".
[embodiment 2 ~ embodiment 4, embodiment 7 ~ embodiment 11 and comparative example 1 ~ comparative example 7]
Except in described embodiment 1, beyond the polymkeric substance using the kind shown in following table 2 and amount respectively, prepare liquid crystal aligning agent in the same manner as example 1, and manufacture TN type liquid crystal cells to carry out various evaluation.Evaluation result is shown in following table 3.
The allotment ratio of each polymkeric substance of the numeric representation in table 2 for total amount 100 weight part of the polymkeric substance for the preparation of liquid crystal aligning agent.
[table 3]
As shown in table 3, containing having in the embodiment 1 ~ embodiment 4 of polymkeric substance (P) of amic acid esters structure or amido acid structure and different imide ring structure, embodiment 7, embodiment 8, embodiment 11, the concave-convex surface of film and the printing of liquid crystal aligning agent and storage stability all obtain good result.And then in embodiment 1 ~ embodiment 4, embodiment 7, embodiment 8, embodiment 11, the liquid crystal aligning of liquid crystal display device, voltage retention and thermotolerance are the result of " well " or "available", and known balance has various characteristic well.In addition, in the embodiment 10 of the embodiment 9 as the combination of polyisoimide and poly amic acid ester and the combination as polyisoimide and polyamic acid, the liquid crystal aligning of the concave-convex surface of film, the printing of liquid crystal aligning agent and storage stability and liquid crystal display device, voltage retention and thermotolerance are the result of " well " or "available".
On the other hand, in comparative example, in the storage stability of the concave-convex surface of film, printing, liquid crystal aligning agent, voltage retention and thermotolerance, any one characteristic is the evaluation of " bad ".
[embodiment 5: light FFS type liquid crystal display device]
(1) preparation of liquid crystal aligning agent
Use the solution containing the polymkeric substance (PAA-2) obtained in synthesis example 2 and the solution containing the polymkeric substance (PHF-2) obtained in synthesis example 5, with polymkeric substance (PAA-2): after the mode of polymkeric substance (PHF-2)=80: 20 (weight ratio) mixes, add γ-butyl lactone (BLANT), NMP and diethylene glycol diethyl ether (DEDG), make the solution that solvent consists of BLANT: NMP: DEDG=55: 30: 15 (weight ratios), solid component concentration is 6.0 % by weight.Utilize aperture to be that this solution filters by the strainer of 0.2 μm, prepare liquid crystal aligning agent whereby.
(2) evaluation of the storage stability of the concave-convex surface of film, printing and liquid crystal aligning agent
Use liquid crystal aligning agent of preparation in described (1), carry out the evaluation of the storage stability of the concave-convex surface of film, printing and liquid crystal aligning agent in the mode that (2), (3) and (4) with embodiment 1 are identical.Its result is, arbitrary characteristic is all judged as " well ".
(3) manufacture of light FFS type liquid crystal display device
FFS type liquid crystal display device 10 shown in construction drawing 1.First, using wherein one side have electrode pair glass substrate 11a, with the subtend glass substrate 11b of electrode is not set as a pair, described electrode pair is formed with the not figuratum bottom electrode of tool 15, successively as the silicon nitride film of insulation layer 14 and the patterned upper current conducting cap 13 for comb teeth-shaped, in the wherein one side of the face with transparency electrode of glass substrate 11a and subtend glass substrate 11b, use turner to be coated with the liquid crystal aligning agent of preparation in described (1) respectively, form film.Then, after this film is carried out 1 minute prebake conditions on the hot-plate of 80 DEG C, having carried out in the baking oven of nitrogen displacement in storehouse, with 230 DEG C of heating (toasting afterwards) 15 minutes, forming average film thickness is film.The floor map of upper current conducting cap 13 used herein is shown in (a) and (b) of Fig. 2.In addition, (a) of Fig. 2 is the vertical view of upper current conducting cap 13, (b) of Fig. 2 be Fig. 2 (a) by the enlarged view of the part C1 of dotted line.In the present embodiment, the live width d1 of electrode is set to 4 μm, interelectrode distance d2 is set to 6 μm.In addition, as upper current conducting cap 13, use the drive electrode of the four systems of electrode A, electrode B, electrode C and electrode D.The formation of the drive electrode used shown in Fig. 3.In this situation, bottom electrode 15 plays a role as the common electrode all acted on the drive electrode of four systems, and the region of the drive electrode of four systems becomes pixel region respectively.
Then, to each surface of these films, use Hg-Xe lamp and Glan-Taylor prism (Glan-Taylorprism) to irradiate 300J/m 2the polarisation ultraviolet comprising the open-wire line of 313nm, obtain and there is a pair substrate of liquid crystal orientation film.Now, polarisation ultraviolet irradiation direction is set to from substrate normal direction, after the mode becoming the direction of the four-headed arrow in (a) and (b) of Fig. 2 with the direction of the line segment be projected on substrate by ultraviolet for polarisation plane of polarization sets plane of polarization direction, reoffer to photo-irradiation treatment.
Then, the periphery with the face of liquid crystal orientation film of the wherein one piece of substrate in described substrate, utilizing screen painting to be coated with to add has diameter to be after the epoxy resin adhesive of the alumina balls of 5.5 μm, make the liquid crystal orientation film of a pair substrate in the face of to, ultraviolet for the polarisation plane of polarization direction be projected on substrate to be become parallel mode overlap crimping, at 150 DEG C, spend 1 hour make caking agent carry out heat embrittlement.Then, fill to substrate gap after the liquid crystal " MLC-6221 " of Merck (Merck) company manufacture from liquid crystal injecting port, utilize epoxy resin adhesive to be sealed by liquid crystal injecting port.Then, in order to eliminate flow orientation during Liquid crystal pour, and slowly room temperature is cooled to after being heated to 150 DEG C.
Then, by the two sides, outside of substrate laminating Polarizer, FFS type liquid crystal display device is manufactured.Now, in Polarizer wherein one piece be become the mode parallel with the projection direction on real estate of the ultraviolet plane of polarization of the polarisation of liquid crystal orientation film with its polarization direction to attach, another block attaches in the mode that its polarization direction is orthogonal with the polarization direction of Polarizer just now.
(4) evaluation of liquid crystal aligning, voltage retention and thermotolerance
To the light FFS type liquid crystal display device manufactured in described (3), carry out the evaluation of liquid crystal aligning in the mode that (5) with embodiment 1 are identical, the liquid crystal aligning of this liquid crystal display device is " well ".In addition, voltage retention (VHR is measured in the mode that (6) with embodiment 1 are identical bF), and the evaluation of thermotolerance (thermal stresses gives the velocity of variation of the voltage retention of front and back) is carried out in the mode identical with (7) of described embodiment 1.Its result is, VHR bFbe 99.5%.In addition, Δ VHR is 2.8%, is judged as thermotolerance " well ".
[embodiment 6:VA type liquid crystal display device]
(1) preparation of liquid crystal aligning agent
Using the polymkeric substance (PHF-3) obtained in the polymkeric substance (PAA-2) of acquisition in the synthesis example 2 of 80 weight parts as polymkeric substance and the synthesis example 6 of 20 weight parts, be dissolved in the mixed solvent (BLANT: NMP: DEDG=55: 30: 15 (weight ratio)) comprising γ-butyl lactone (BLANT), NMP and diethylene glycol diethyl ether (DEDG), make the solution that solid component concentration is 6.0 % by weight.Utilize aperture to be that this solution filters by the strainer of 0.2 μm, prepare liquid crystal aligning agent whereby.
(2) evaluation of the storage stability of the concave-convex surface of film, printing and liquid crystal aligning agent
Except using liquid crystal aligning agent of preparation in described (1), carry out the evaluation of the storage stability of the concave-convex surface of film, printing and liquid crystal aligning agent in the mode that (2), (3) and (4) with embodiment 1 are identical.Its result is, arbitrary characteristic is all judged as " well ".
(3) manufacture of VA type liquid crystal cells
Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), the liquid crystal aligning agent of preparation in described (1) is coated on the transparent electrical pole-face with the glass substrate (thickness is 1mm) of the transparency electrode comprising ito film, the hot-plate of 80 DEG C heats (prebake conditions) 1 minute, and then on the hot-plate of 200 DEG C, heat (toasting afterwards) 60 minutes, forming average film thickness is film (liquid crystal orientation film).Repeat this operation, obtain a pair (two pieces) glass substrate on nesa coating with liquid crystal orientation film.Then, for the wherein one piece of substrate in described a pair substrate, after the outer rim coating in the face with liquid crystal orientation film adds and has diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, in the relative mode of liquid crystal aligning face by the crimping of a pair substrate overlap, make adhesive hardens.Then, after filling nematic liquid crystal (Merck (Merck) company manufactures, 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 VA type liquid crystal cells whereby.
(4) evaluation of liquid crystal aligning, voltage retention and thermotolerance
For the liquid crystal cells manufactured in described (3), carry out the evaluation of liquid crystal aligning in the mode that (5) with embodiment 1 are identical, result, the liquid crystal aligning of this liquid crystal display device is " well ".In addition, voltage retention (VHR is measured in the mode that (6) with embodiment 1 are identical bF), and the evaluation of thermotolerance (thermal stresses gives the velocity of variation of the voltage retention of front and back) is carried out in the mode identical with (7) of described embodiment 1.Its result is, VHR bFbe 98.9%.In addition, Δ VHR is 1.9%, be judged as thermotolerance " well ".

Claims (11)

1. a liquid crystal aligning agent, its polymkeric substance containing one or more is as component of polymer, and the part-structure (a-1) comprised in described component of polymer represented by following formula (1) and the part-structure (a-2) represented by following formula (2)
In formula (1) and formula (2), R 1and R 2be separately hydrogen atom, the alkyl of carbon number 1 ~ 12 ,-Si (R 7) 3, have fluorine atom monad radical, there is the monad radical of (methyl) acryl or there is the monad radical of cinnamic acid structure, wherein, R 7for alkyl or alkoxyl group, multiple R 7can be identical, also can be different, R 3and R 4be separately hydrogen atom or the monovalence chain alkyl of carbon number 1 ~ 10 that is substituted or is unsubstituted; X 1and X 2be separately quadrivalent organic radical, Y 1and Y 2it is separately divalent organic base.
2. liquid crystal aligning agent according to claim 1, it contains the polymkeric substance (P) in a part with described part-structure (a-1) and described part-structure (a-2).
3. liquid crystal aligning agent according to claim 2, the described part-structure (a-1) that wherein said polymkeric substance (P) has and described part-structure (a-2) containing proportional with the molar ratio computing of part-structure (a-1)/part-structure (a-2) for 1/99 ~ 99/1.
4. liquid crystal aligning agent according to claim 2, it is also containing polyamic acid.
5. liquid crystal aligning agent according to claim 4, wherein said polymkeric substance (P) and described polyamic acid containing proportional with the mass ratio range of polymkeric substance (P)/polyamic acid for 1/99 ~ 99/1.
6. liquid crystal aligning agent according to claim 4, wherein said polyamic acid has at least one structure be selected from cohort that the structure represented by following formula (3-1), the structure represented by following formula (3-2) and nitrogen heterocyclic ring form, wherein, in structure represented by formula (3-2), the anhydride group had with tetracarboxylic dianhydride, the reaction of amino that has with diamines and contained in the amido linkage that formed except
In formula (3-1), R 5for the alkyl of hydrogen atom, halogen atom, carbon number 1 ~ 10 or the alkoxyl group of carbon number 1 ~ 10, r is 1 or 2; At R 5when existing multiple, multiple R 5can be identical, also can be different; * associative key is represented; In formula (3-2), R 6for the alkyl of hydrogen atom or carbon number 1 ~ 6; * associative key is represented.
7. liquid crystal aligning agent according to claim 1, wherein containing having the polymkeric substance of described part-structure (a-1) and having the polymkeric substance of described part-structure (a-2).
8. liquid crystal aligning agent according to any one of claim 1 to 7, wherein said R 1and described R 2it is separately the alkyl of carbon number 1 ~ 5.
9. liquid crystal aligning agent according to any one of claim 1 to 7, wherein said X 1and described X 2for being derived from the tetravalence base of following compound, described compound is for being selected from by dicyclo [2.2.1] heptane-2, 3, 5, 6-tetracarboxylic acid 2:3, 5:6-dianhydride, 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 5-(2, 5-dioxotetrahydro furans-3-base)-8-methyl-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, 5-(2, 5-dioxotetrahydro furans-3-base)-3a, 4, 5, 9b-tetrahydrochysene naphtho-[1, 2-c] furans-1, 3-diketone, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic acid 2:4, 6:8-dianhydride, 1, 2, 4, 5-cyclopentanetetracarboxylic dianhydride, and at least one compound in the cohort that forms of pyromellitic acid anhydride.
10. a liquid crystal orientation film, it uses liquid crystal aligning agent according to any one of claim 1 to 9 and is formed.
11. 1 kinds of liquid crystal display device, it possesses liquid crystal orientation film according to claim 10.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880545A (en) * 2016-09-30 2018-04-06 东京应化工业株式会社 Resin combination, the manufacture method of solidfied material and solidfied material
CN110573593A (en) * 2017-10-20 2019-12-13 株式会社Lg化学 Liquid crystal aligning agent composition, method for manufacturing liquid crystal alignment film using same, and liquid crystal alignment film using same
CN110651221A (en) * 2017-05-22 2020-01-03 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN112739800A (en) * 2018-11-30 2021-04-30 Dic株式会社 Alignment aid, liquid crystal composition and liquid crystal display element

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101856725B1 (en) 2016-05-13 2018-05-10 주식회사 엘지화학 Composition for photoinduced liquid crystal alignment, prapapation method of liquid crystal alignment film, liquid crystal alignment film using the same and liquid crystal display device
JP7375545B2 (en) * 2017-11-21 2023-11-08 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05247208A (en) * 1992-03-06 1993-09-24 Chisso Corp Coating fluid for oriented liquid-crystal film and production thereof
EP0735403A1 (en) * 1995-03-27 1996-10-02 Japan Synthetic Rubber Co., Ltd. Liquid crystal orienting agent
CN1720478A (en) * 2002-12-11 2006-01-11 日产化学工业株式会社 Liquid crystl orientating agent and liquid crystal display element using it
CN101490607A (en) * 2006-07-21 2009-07-22 东丽株式会社 Resin composition for retardation thin film, color filter substrate for liquid crystal display device, liquid crystal display device, and method for production of color filter substrate for liquid cry
CN101595164A (en) * 2006-12-12 2009-12-02 E.I.内穆尔杜邦公司 Crystalline encapsulants
CN102224452A (en) * 2008-10-29 2011-10-19 日产化学工业株式会社 Diamine, polyimide, liquid crystal aligning agent, and liquid crystal alignment film

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05247209A (en) * 1992-03-05 1993-09-24 Chisso Corp Coating fluid for oriented liquid-crystal film and production thereof
JPH07110486A (en) * 1993-10-13 1995-04-25 Japan Synthetic Rubber Co Ltd Liquid crystal orientating agent
JP3201172B2 (en) * 1994-09-08 2001-08-20 ジェイエスアール株式会社 Liquid crystal alignment agent
EP2144951A1 (en) * 2007-05-02 2010-01-20 Rolic AG Thermally stable alignment materials
CN102893208B (en) 2010-03-15 2015-07-08 日产化学工业株式会社 Liquid crystal alignment agent containing polyamic acid ester and polyamic acid, and liquid crystal alignment film
CN104204925A (en) 2012-03-30 2014-12-10 日产化学工业株式会社 Polyimide-based liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05247208A (en) * 1992-03-06 1993-09-24 Chisso Corp Coating fluid for oriented liquid-crystal film and production thereof
EP0735403A1 (en) * 1995-03-27 1996-10-02 Japan Synthetic Rubber Co., Ltd. Liquid crystal orienting agent
CN1720478A (en) * 2002-12-11 2006-01-11 日产化学工业株式会社 Liquid crystl orientating agent and liquid crystal display element using it
CN101490607A (en) * 2006-07-21 2009-07-22 东丽株式会社 Resin composition for retardation thin film, color filter substrate for liquid crystal display device, liquid crystal display device, and method for production of color filter substrate for liquid cry
CN101595164A (en) * 2006-12-12 2009-12-02 E.I.内穆尔杜邦公司 Crystalline encapsulants
CN102224452A (en) * 2008-10-29 2011-10-19 日产化学工业株式会社 Diamine, polyimide, liquid crystal aligning agent, and liquid crystal alignment film

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880545A (en) * 2016-09-30 2018-04-06 东京应化工业株式会社 Resin combination, the manufacture method of solidfied material and solidfied material
CN107880545B (en) * 2016-09-30 2022-03-18 东京应化工业株式会社 Resin composition, method for producing cured product, and cured product
CN110651221A (en) * 2017-05-22 2020-01-03 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN110651221B (en) * 2017-05-22 2021-10-22 日产化学株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
CN110573593A (en) * 2017-10-20 2019-12-13 株式会社Lg化学 Liquid crystal aligning agent composition, method for manufacturing liquid crystal alignment film using same, and liquid crystal alignment film using same
CN112739800A (en) * 2018-11-30 2021-04-30 Dic株式会社 Alignment aid, liquid crystal composition and liquid crystal display element

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