CN105316005A - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display member and polymer and compound - Google Patents

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

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Publication number
CN105316005A
CN105316005A CN201510387134.8A CN201510387134A CN105316005A CN 105316005 A CN105316005 A CN 105316005A CN 201510387134 A CN201510387134 A CN 201510387134A CN 105316005 A CN105316005 A CN 105316005A
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liquid crystal
compound
polymkeric substance
film
carbon number
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Inventor
安池伸夫
野辺洋平
村主拓弥
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JSR Corp
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JSR Corp
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Priority claimed from JP2014206758A external-priority patent/JP6492509B2/en
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Abstract

The invention provides a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display member and a polymer and a compound. The liquid crystal alignment agent comprises at least one of the polyamide acid, the poly(amic ester) and the polyimide which are obtained through reaction between tetracarboxylic acid derivative and the diamine. The tetracarboxylic acid derivative comprises at least one of the compound shown in the following formula (1), the diester compound and the diester dihalide compound. The liquid crystal alignment agent can obtain the liquid crystal display member having good residual shadow characteristics.

Description

Liquid crystal aligning agent, liquid crystal orientation film and manufacture method thereof, liquid crystal display device, polymkeric substance and compound
Technical field
The present invention relates to a kind of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, the manufacture method of liquid crystal display device, polymkeric substance and compound.
Background technology
In the past, liquid crystal display device has developed the different multiple type of drive of the physical property, manufacturing step etc. of electrode structure or liquid crystal molecule, 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 recent years, large picture and the LCD TV of fine becomes main body, in addition, the universal propelling of the display terminal that smart mobile phone or dull and stereotyped PC etc. are small-sized, the requirement for the high-precision refinement of liquid-crystal display improves further.In order to meet this requirement, propose plurality of liquid crystals alignment agent (such as with reference to patent documentation 1) in the past.Patent Document 1 discloses 1, two (4-aminophenyl) ethane and 1 of 2-, the dehydration condensation of 3-dimethylcyclobutane tetracarboxylic dianhydride or by the aligning film material of its esterification and Ursol D and 1, the dehydration condensation of 3-dimethylcyclobutane tetracarboxylic dianhydride or by the mixture of the aligning film material of its esterification, is used as liquid crystal aligning agent.In this patent documentation 1, by the minimizing using described liquid crystal aligning agent to realize interchange (AlternatingCurrent, the AC) image retention of liquid crystal display device.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2013-178557 publication
Summary of the invention
[invention institute for solution problem]
In recent years, the requirement of the high performance of liquid crystal panel is improved further, expect to develop in order to obtain the new liquid crystal aligning agent being difficult to the liquid crystal display device producing image retention (image retention of image).
The present invention is formed in view of described situation, and one of object is for providing a kind of liquid crystal aligning agent obtaining the good liquid crystal display device of image retention characteristic.
[technique means of dealing with problems]
The people such as the present inventor are conceived to the orientation control force improving liquid crystal orientation film by giving flexibility to polymkeric substance, construct the tetracarboxylic acid derivatives with ad hoc structure.In addition, not only use the tetracarboxylic acid derivatives obtained to carry out synthetic polymer, and described polymkeric substance is used for the component of polymer of liquid crystal aligning agent.Therefore find to utilize this liquid crystal aligning agent to solve described problem, thus complete the present invention.Specifically, the manufacture method of following liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, liquid crystal display device, polymkeric substance and compound is provided by the present invention.
An aspect of of the present present invention is for providing a kind of liquid crystal aligning agent, it contains and is selected from by making tetracarboxylic acid derivatives, carry out reacting with diamines and the polyamic acid obtained, at least one polymkeric substance (A) in the cohort that poly amic acid ester and polyimide form, described tetracarboxylic acid derivatives is selected from by tetracarboxylic dianhydride, at least one in the cohort that tetracarboxylic acid diester and tetracarboxylic acid diester dihalide form, and described tetracarboxylic acid derivatives comprises the compound (a) be selected from represented by following formula (1), and at least one compound in the cohort that forms of the diester compound of this compound (a) and diester two halogen compounds.
[changing 1]
(in formula (1), R 1for divalent organic base, X 1and X 2be separately-O-C (=O)-* ,-C (=O)-O-* ,-S-C (=O)-* ,-C (=O)-S-* ,-O-,-S-or-NR 5-(wherein, R 5for the monovalent hydrocarbon of carbon number 1 ~ 6, R 5with R 1also can bond and form nitrogen heterocyclic ring, at X 1and X 2for-NR 5-when, 2 R 5also can bond and and R 1form nitrogen heterocyclic ring together; With associative key and the R of * 1bond); R 2and R 3be separately hydrogen atom or any monovalent organic radical)
An aspect of of the present present invention is for providing a kind of manufacture method of liquid crystal orientation film, and it comprises: described liquid crystal aligning agent coated step substrate being formed film and carry out rayed to the film be formed on this substrate and described film given to the step of liquid crystal aligning ability.In addition, on the other hand described liquid crystal aligning agent is used and the liquid crystal orientation film that formed for providing a kind of.In addition, a kind of liquid crystal display device possessing this liquid crystal orientation film is provided.
[effect of invention]
According to liquid crystal aligning agent of the present invention, the liquid crystal display device that image retention characteristic is good can be obtained.
Accompanying drawing explanation
Fig. 1 is the schematic configuration diagram of FFS type liquid crystal display device.
The floor map of the upper current conducting cap that (a) of Fig. 2 and (b) of Fig. 2 uses when being and manufacturing liquid crystal display device by light orientation process.The vertical view that (a) of Fig. 2 is upper current conducting cap, the magnified partial view that (b) of Fig. 2 is upper current conducting cap.
Fig. 3 is the figure of the drive electrode representing four systems.
The 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
C1: by the part of dotted line
D1: the live width of electrode
D2: interelectrode distance
A, B, C, D, E: electrode
F: pixel edge part
Embodiment
Other compositions that liquid crystal aligning agent of the present invention contains polymkeric substance (A) and optionally and arbitrarily allocates.Below each composition of liquid crystal aligning agent of the present invention is described.
< polymkeric substance (A) >
Polymkeric substance (A) is for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide, be obtain by making tetracarboxylic acid derivatives and diamines carry out reacting, described tetracarboxylic acid derivatives is for being selected from least one in the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester dihalide.
In addition, in this specification sheets so-called " tetracarboxylic acid diester ", 2 compounds through esterification in 4 carboxyls that tetracarboxylic acid has are referred to.So-called " tetracarboxylic acid diester dihalide ", refers to that in 4 carboxyls that tetracarboxylic acid has 2 are through esterification, remaining 2 compound through halogenation.
[polyamic acid]
Polyamic acid as polymkeric substance (A) such as obtains by making tetracarboxylic dianhydride and diamines carry out reacting.
[tetracarboxylic dianhydride]
The tetracarboxylic dianhydride used in synthesis as the polyamic acid of polymkeric substance (A) comprises the compound (hereinafter also referred to " compound (a) ") represented by following formula (1).
[changing 2]
(in formula (1), R 1for divalent organic base, X 1and X 2be separately-O-C (=O)-* ,-C (=O)-O-* ,-S-C (=O)-* ,-C (=O)-S-* ,-O-,-S-or-NR 5-(wherein, R 5for the monovalent hydrocarbon of carbon number 1 ~ 6, R 5with R 1also can bond and form nitrogen heterocyclic ring, at X 1and X 2for-NR 5-when, 2 R 5also can bond and and R 1form nitrogen heterocyclic ring together; With associative key and the R of * 1bond); R 2and R 3be separately hydrogen atom or any monovalent organic radical)
In described formula (1), R 1divalent organic base include, for example: bivalent hydrocarbon radical, has-O-,-COO-,-COS-,-CO-,-CONR between the C-C of bivalent hydrocarbon radical a-,-S-,-NR a-,-SO 2-,-Si (R 8) 2-wait containing heteroatomic group (wherein, R afor the alkyl of hydrogen atom or carbon number 1 ~ 5, R 8monovalent hydrocarbon for carbon number 1 ~ 12) group, there is the divalent radical etc. of heterocycle.In addition, in these each groups, at least one the be substituted base being binding on the hydrogen atom on carbon atom replaced.This substituting group include, for example: halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), hydroxyl, nitro, amino, carboxyl, thiol group, "-Si (R 9) 3" (wherein, R 9for alkyl or the alkoxyl group of carbon number 1 ~ 10, multiple R 9can be identical, also can be different), alkoxyl group etc.
Herein, in this specification sheets so-called " alkyl ", be 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, but saturated, may also be unsaturated.So-called " ester ring type alkyl " refers to that its ring structure only comprises the structure of ester ring type hydrocarbon, 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, comprise in its part yet and there is chain-like structure.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.
As R 1preference, include, for example the group represented by following formula (r-1).
[changing 3]
(in formula (r-1), R 6and R 7be separately alkane two base of carbon number 1 ~ 15, between the C-C of alkane two base of carbon number 1 ~ 15, there is-O-,-CO-,-COO-or "-Si (R 8) 2-" (wherein, R 8for the monovalent hydrocarbon of carbon number 1 ~ 12, multiple R 8can be identical, also can be different) group; Or at least 1 of the hydrogen atom had by alkane two base of carbon number 1 ~ 15 with fluorine atom or "-Si (R 9) 3" (wherein, R 9for alkyl or alkoxyl group, multiple R 9can be identical, also can be different) group that replaces; Ar 1for cyclohexylidene, phenylene, biphenylene or naphthylidene, at least 1 that is binding on ring hydrogen atom can through fluorine atom or-Si (R 9) 3replaced; D, e and f are separately 0 or 1; Wherein, d, e and f can not become 0 simultaneously)
In described formula (r-1), R 6and R 7alkane two base of carbon number 1 ~ 15 include, for example: methylene radical, ethylidene, glyceryl, Ding Erji, penta 2 bases, dihexyl, heptan two base, Xin Erji etc., these groups can be straight-chain, also can be branch-like.Making with regard to passing through to give flexibility to polymkeric substance (A) film show for the viewpoint of sufficiently high liquid crystal aligning control, being preferably straight-chain.
With regard to giving the viewpoint of flexibility, Ar 1be preferably cyclohexylidene, with regard to improving the crystalline viewpoint of polymkeric substance (A), Ar 1be preferably phenylene, biphenylene or naphthylidene.
For the viewpoint showing excellent image retention characteristic with regard to the raising by flexibility, in described group, group represented by described formula (r-1) is preferably: alkane two base of carbon number 1 ~ 20, has-O-,-CO-,-COO-or-Si (R between the C-C of alkane two base of carbon number 1 ~ 20 8) 2-group, at least one of the hydrogen atom had by alkane two base of carbon number 1 ~ 20 is with fluorine atom or-Si (R 9) 3the group replaced, or cyclohexylidene.In these groups, be preferably linear chain structure or the cyclohexylidene of carbon number more than 2, be more preferably: alkane two base of the straight-chain of carbon number 2 ~ 20, there is the group of-O-,-CO-or-COO-between the C-C of alkane two base of the straight-chain of carbon number 3 ~ 20, by at least one group replaced with fluorine atom of the hydrogen atom that alkane two base of carbon number 2 ~ 20 has, or cyclohexylidene.
With regard to the viewpoint of the synthesis easness of compound, the X in described formula (1) and formula (2) 1and X 2be preferably-O-C (=O)-* ,-S-C (=O)-* ,-O-or-S-(wherein, with associative key and the R of * 1bond), be more preferably-O-C (=O)-* or-O-.
At X 1and X 2for-NR 5-when, R 5monovalent hydrocarbon include, for example: the alkyl such as methyl, ethyl, propyl group, cyclohexyl, phenyl etc.R 5with R 1bond and the nitrogen heterocyclic ring formed and 2 R 5bond and and R 1the nitrogen heterocyclic ring formed together include, for example: piperazine ring, piperidine ring, homopiperazine ring etc.
R 2and R 3any monovalent organic radical include, for example: the fluoroalkyl etc. of the alkyl of hydroxyl, nitro, halogen atom, carbon number 1 ~ 10, the alkoxyl group of carbon number 1 ~ 10, carbon number 1 ~ 10.R 2and R 3be preferably hydrogen atom.In addition, the multiple R in formula 2can be identical, also can be different, multiple R 3can be identical, also can be different.
As the concrete example of compound (a), include, for example the compound etc. represented by following formula (a-1) ~ formula (a-19) difference.
[changing 4]
[changing 5]
In described, with regard to the image retention of image and the high aspect of the improvement effect of contrast gradient, be preferably described formula (a-1), formula (a-2), formula (a-4) ~ formula (a-19) respectively represented by compound, be more preferably described formula (a-1), formula (a-2), formula (a-4), formula (a-5), formula (a-7) ~ formula (a-19) respectively represented by compound.In addition, compound (a) can be used alone one or be used in combination of two or more.
The tetracarboxylic dianhydride used during synthesizing polyamides acid only can use compound (a), also can together with compound (a) and with other tetracarboxylic dianhydride.
Herein, other tetracarboxylic dianhydrides used in the synthesis of polyamic acid can be aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride any one.As the concrete example of these tetracarboxylic dianhydrides, aliphatics tetracarboxylic dianhydride include, for example: 1,2,3,4-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, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2: 3, 5: 6-dianhydride, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2: 4, 6: 8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] undecane-3,5,8,10-tetraketone, cyclopentanetetracarboxylic's dianhydride etc.,
Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride, 4,4 '-(hexafluoroisopropyli,ene) two Tetra hydro Phthalic anhydride and following formula (c-4) ~ formula (c-8)
[changing 6]
Compound etc. respectively;
In addition, the tetracarboxylic dianhydride etc. recorded in Japanese Patent Laid-Open 2010-97188 publication can also be used.In addition, the one of these tetracarboxylic dianhydrides can be used alone or be used in combination of two or more by other tetracarboxylic dianhydride.
With regard to the viewpoint that the image retention characteristic and contrast-response characteristic that make liquid crystal display device are good, relative to the total amount of the tetracarboxylic dianhydride used during synthesizing polyamides acid, the usage ratio of compound (a) is preferably set to more than 5 % by mole, be more preferably and be set to more than 10 % by mole, be especially preferably set to more than 20 % by mole.
[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, hexamethylene-diamine etc.; Ester ring type diamines include, for example: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (cyclo-hexylamine), 1,3-two (amino methyl) hexanaphthenes etc.
In addition, aromatic diamine include, for example: dodecyloxy diaminobenzene, tetradecyloxyaniline diaminobenzene, pentadecane oxygen base diaminobenzene, n-Hexadecane oxygen base diaminobenzene, octadecane oxygen base diaminobenzene, cholestane base oxygen base diaminobenzene, cholesteryl (cholesteryl) oxygen base diaminobenzene, diaminobenzoic acid cholestane base ester, diaminobenzoic acid cholesteryl (cholesteryl) ester, diaminobenzoic acid lanostane base ester, two (the 4-amino benzoyl oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, two (4-((aminophenyl) methyl) the phenyl)-4-butyl cyclohexane of 1,1-, two (4-((aminophenyl) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, two (4-((aminophenyl) methyl) phenyl)-4-(the 4-heptyl cyclohexyl) hexanaphthene of 1,1-, N-(2,4-diamino-phenyl)-4-(4-heptyl cyclohexyl) benzamide, following formula (D-1)
[changing 7]
(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 compounds etc. are containing the diamines of orientation base:
Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 4-aminophenyl-4 '-Aminobenzoate, 4,4 '-chrysoidine, two (4-aminophenyl) methylamine of N, N-, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine base, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine base, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes of 9,9-, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa of 2,2-, two (4-aminophenyl) HFC-236fa of 2,2-, 4,4 '-(to phenylenediisopropylidene) dianiline, 4,4 '-(metaphenylene two isopropylidene) dianiline, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 4,4 '-bis-(4-amino-benzene oxygen) xenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, other diamines such as 3,5-diaminobenzoic acid etc.,
Diamino organo-siloxane include, for example: two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc.; In addition, the diamines recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.The one of these diamines can be used alone or be used in combination of two or more by diamines.
"-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 " * ").As group "-C ch 2c+1" concrete example, include, for example: methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.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-1-3) difference.
[changing 8]
In addition, during synthesizing polyamides acid, but the one of these diamines is used alone or is used in combination of two or more.
When by the liquid crystal display device of liquid crystal aligning agent of the present invention for the manufacture of TN type, STN type or vertical orientating type, also can import the group (tilt angle expression power base) can giving tilt angle expressive ability to film on the side chain of polymkeric substance (A).Herein, tilt angle expression power base include, for example: the having the group of steroid skeleton, have the group etc. of polynuclear plane of the alkoxyl group of the alkyl of carbon number 4 ~ 20, the fluoroalkyl of carbon number 4 ~ 20, carbon number 4 ~ 20, carbon number 17 ~ 51.The polymkeric substance (A) with tilt angle expression power base such as obtains by the polymerization containing the diamines containing orientation base in monomer composition.
When using the diamines containing orientation base, with regard to showing the viewpoint of sufficiently high tilt angle characteristic, relative to the whole diamines used in synthesis, the allotment amount of the described diamines containing orientation base is preferably set to more than 3 % by mole, is more preferably and is set to 5 % by mole ~ 70 % by mole.
Utilize optical alignment method, when giving liquid crystal aligning ability to the film formed by liquid crystal aligning agent, also polymkeric substance (A) can be set to the polymkeric substance with light orientation structure.Herein, so-called light orientation structure comprises light orientation base and this concept of two of decomposition type light orientation section.Specifically, light orientation structure can adopt by photoisomerization or photodimerization, photolysis etc. and show the group of bright dipping orientation, 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 containing polyimide of polyimide or derivatives thereof as basic framework, containing following formula (p)
[changing 9]
(in formula (p), X 3for sulphur atom, Sauerstoffatom or-NR 4-(wherein, R 4for hydrogen atom or alkyl); " * " represents associative key respectively, and in 2 " * ", at least one is binding on aromatic nucleus; Wherein, tetracarboxylic acid derivatives and diamines carry out reacting and except the amido linkage formed)
Represented part-structure is as the structure etc. containing ester group of basic framework.
With regard to photoreactive viewpoint, 2 " * " in described formula (p) are preferably at least X 3be binding on aromatic nucleus.This aromatic nucleus include, for example phenyl ring, naphthalene nucleus, anthracene nucleus etc., is preferably phenyl ring or naphthalene nucleus, is more preferably phenyl ring.
The polymkeric substance (A) with light orientation structure such as by comprise in monomer composition the tetracarboxylic dianhydride with light orientation structure and the diamines with light orientation structure at least any one polymerization and obtain.In this situation, with regard to photoreactive viewpoint, relative to the total amount of the monomer used in the synthesis of polymkeric substance, the usage ratio with the monomer of light orientation structure is preferably set to more than 20 % by mole, is more preferably and is set to 30 % by mole ~ 80 % by mole.
The synthesis > of < polyamic acid
Polyamic acid, by making tetracarboxylic dianhydride as above and diamines, optionally reacts with end-capping reagent one and obtains.The usage ratio of the tetracarboxylic dianhydride and diamines that are supplied to the building-up reactions of polyamic acid is preferably amino 1 equivalent relative to diamines, and the anhydride group of tetracarboxylic dianhydride becomes the ratio of 0.2 equivalent ~ 2 equivalent, is more preferably the ratio becoming 0.3 equivalent ~ 1.2 equivalent.
Described end-capping reagent include, for example: sour single acid anhydrides such as MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, the monoamine compounds such as 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 end-capping reagent 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-N,N-DIMETHYLACETAMIDE, N, more than one in the cohort that dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA, meta-cresol, xylenol and halogenation phenol form as solvent, or 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.
Mode as previously discussed, obtains the reaction soln dissolved by polyamic acid.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also reoffer to the preparation of liquid crystal aligning agent after polyamic acid contained in reaction soln can being separated, or also can reoffer after the polyamic acid purifying of separation to the preparation of liquid crystal aligning agent.The separation of polyamic acid and purifying can carry out according to known method.
< poly amic acid ester >
Poly amic acid ester as polymkeric substance (A) can utilize following methods to obtain: [I] carrys out synthesizing polyamides acid by the tetracarboxylic dianhydride of inclusion compound (a) and the reaction of diamines, then makes the polyamic acid of gained and esterifying agent carry out the method for reacting; [II] makes the tetracarboxylic acid diester of the diester compound of inclusion compound (a), carries out the method for reacting with diamines; And [III] makes the tetracarboxylic acid diester dihalide of the diester dihalide of inclusion compound (a), carries out the method etc. of reacting with diamines.In addition, the method for these [I] ~ [III] is utilized and the poly amic acid ester obtained all is equivalent to " making tetracarboxylic acid derivatives and diamines carry out reacting and the poly amic acid ester obtained ".
Herein, the esterifying agent used in method [I] include, for example: methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, hexanol, octanol, trifluoro methyl alcohol, 2, the alcohols such as 2,2-trifluoroethanol, 2-(methyl) acryl oxygen base ethyl alcohol, 1-(methyl) acryl oxygen base-2-propyl group alcohol, 2-(methyl) acrylamide ethyl alcohol, 1-(methyl) acrylamide-2-propyl group alcohol; The halogenide such as methyl bromide, bromic ether, methyl chloride, methyl chloride; The acetal based compounds such as DMF diethyl acetal, N, N-diethylformamide diethyl acetal; Propylene oxide, there is the epoxy compounds etc. such as compound containing epoxy group(ing) of cinnamic acid structure.The concrete example of compound containing epoxy group(ing) with cinnamic acid structure include, for example record in Japanese Patent Laid-Open 2011-133825 publication etc.
The reaction of polyamic acid and esterifying agent is preferably carried out in organic solvent.Now, preferably temperature of reaction is set to-20 DEG C ~ 200 DEG C, and 0.1 hour ~ 24 hours will be set to the reaction times.Organic solvent include, for example the solvent etc. used in the synthesis of polyamic acid.
The reaction of method [II] is preferably in organic solvent, carries out under the existence of suitable dehydration catalyst and alkali.Dehydration catalyst include, for example: 4-(4,6-dimethoxy-1,3,5-triazines-2-base)-4-methylmorpholine halogenide, carbonylic imidazole, phosphorus system condensing agent etc.As alkali, such as, can preferably use the tertiary amine such as pyridine, triethylamine.Now, preferably temperature of reaction is set to-20 DEG C ~ 150 DEG C, and 0.1 hour ~ 24 hours will be set to the reaction times.
The reaction of method [III] is preferably in the presence of base, carries out in organic solvent.As alkali, such as, preferably use the basic metal classes such as the tertiary amine such as pyridine or triethylamine, sodium hydride or potassium hydride KH.In addition, preferably temperature of reaction is set to-30 DEG C ~ 150 DEG C, and 0.1 hour ~ 24 hours will be set to the reaction times.
Method [II] and the middle diamines used of method [III] can enumerate illustrative diamines in the synthesis of polyamic acid.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.
The synthesis > of < compound
The diester compound of the compound represented by described formula (1) and the compound represented by described formula (1) and diester two halogen compounds, by according to the compound as target, are synthesized appropriately combined for vitochemical well-established law.Such as, in the compound represented by described formula (1), at X 1and X 2when for Sauerstoffatom, by synthesis HO-R 1dihydro-compound represented by-OH, then according to the method for record in such as document " " synthesis " (Synthesis) 2003 the 6th phase the 863rd page ~ the 870th page ", after making the dihydro-compound of gained and N-(p-methylphenyl) maleimide carry out reacting and obtain the tetracarboxylic acid body of the compound represented by described formula (1), stir in diacetyl oxide, can target compound be obtained whereby.In addition, at X 1and X 2when for ester group, by synthesis ClOC-R 1dicarboxylic acid chloride represented by-COCl, then according to the method recorded in such as document " " European organic chemistry magazine " (EuropeanJoumalofOrganicChemistry) 2012 the 35th phase the 6841st page ~ the 6845th page ", the dicarboxylic acid chloride of gained and oxysuccinic acid is made to carry out reacting and obtaining.
The diester compound of the compound represented by described formula (1) such as can utilize and make that the esterifying agent of the compound represented by described formula (1) and alcohols carries out reacting and the method for open loop obtains.Diester two halogen compounds of the compound represented by described formula (1) such as profit can wait and obtains with the following method: make the tetracarboxylic acid diester obtained by described ring-opening reaction, and the halogenating agent suitable with thionyl chloride etc. reacts.But, described in the synthetic method of these compounds is not limited to.
< polyimide >
As the polyamic acid of polyimide such as by synthesizing in this way of polymkeric substance (A), and then carry out dehydration closed-loop, in addition imidization and obtaining.
Described polyimide can be the complete imide compound of the amido acid structure had as the polyamic acid of its precursor all being carried out dehydration closed-loop, also can be only a part for amido acid structure carried out dehydration closed-loop and make amido acid structure and imide ring structure and the part imide compound of depositing.With regard to the viewpoint of electrical characteristic, the imide rate of polyimide of the present invention is preferably more than 30%, is more preferably 50% ~ 99%, is especially preferably 65% ~ 99%.This imide rate is the total relative to the quantity of the amido acid structure of polyimide and the quantity of imide ring structure, represents the ratio shared by quantity of imide ring structure with percentage.Herein, a part for imide ring also can be different imide ring.
The dehydration closed-loop of polyamic acid preferably utilizes following methods to carry out: the method heated polyamic acid; Or polyamic acid is dissolved in organic solvent, in this solution, adds dewatering agent and dehydration closed-loop catalyzer, optionally carry out the method heated.Wherein, the method for the latter is preferably utilized.
Add in the solution of described polyamic acid in the method for dewatering agent and dehydration closed-loop catalyzer, dewatering agent such as can use the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.Relative to 1 mole of the amido acid structure of polyamic acid, the usage quantity of dewatering agent is preferably set to 0.01 mole ~ 20 moles.Dehydration closed-loop catalyzer such as can use the tertiary amine such as pyridine, collidine, two picolins, triethylamine.Relative to used dewatering agent 1 mole, the usage quantity of dehydration closed-loop catalyzer is preferably set to 0.01 mole ~ 10 moles.The organic solvent used in dehydration closed-loop reaction can enumerate the organic solvent used in the synthesis of polyamic acid.The temperature of reaction of dehydration closed-loop reaction is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 150 DEG C.Reaction times is preferably 1.0 hours ~ 120 hours, is more preferably 2.0 hours ~ 30 hours.
Obtain the reaction soln containing polyimide 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 can removing dewatering agent and dehydration closed-loop catalyzer in autoreaction solution, also reoffer to the preparation of liquid crystal aligning agent after polyimide can being separated, or can also reoffer after the polyimide purifying of separation to the preparation of liquid crystal aligning agent.These purification process can be carried out according to known method.
The polyamic acid obtained in this way, poly amic acid ester and polyimide are preferably when being made into concentration and being the solution of 15 % by weight, there is 20mPas ~ 1, the soltion viscosity of 800mPas, be more preferably and there is 50mPas ~ 1, the soltion viscosity of 500mPas.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.
Polyamic acid, poly amic acid ester and polyimide contained in liquid crystal aligning agent 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 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.
In addition, according to comprising the reason of effect of the liquid crystal aligning agent of polymkeric substance (A) and the image retention characteristic of the liquid crystal display device that is improved and uncertain, but think one of them reason be due to: by non-bond aromatic nucleus in the 5 ring anhydride group that have at compound (a), the flexibility of polymkeric substance (A) improves.Be speculated as in this situation: in light orientation process, during rear baking, component of polymer easily heats rearrangement, in friction treatment, easily produces friction, result obtains the orientation control force raising of liquid crystal molecule, the image retention of image reduces, and shows the liquid crystal display device of high-contrast.Be speculated as in addition: by the R in formula (1) 1when being set to linear chain structure (spacer structure) or cyclohexylidene, by importing linear chain structure or cyclohexylidene on the main chain of polymkeric substance, the flexibility of polymkeric substance improves further, show image retention reduce and high-contrast in become remarkable.To X 1and X 2at least any one import nitrogen-atoms when, the described effect brought by the structure of bond aromatic nucleus non-in 5 ring anhydride group, to be combined with each other with the alleviation effects of the accumulated charge to be brought by nitrogen-atoms, show image retention reduce and high-contrast in become remarkable.
Other compositions of < >
Liquid crystal aligning agent of the present invention contains described polymkeric substance (A), also optionally can contain other compositions.Other compositions that can make an addition in this liquid crystal aligning agent include, for example: the compound (hereinafter referred to as " compound containing epoxy group(ing) "), functional silanes compound etc. in other polymkeric substance beyond described polymkeric substance (A), molecule with at least one epoxy group(ing).
[other polymkeric substance]
Other polymkeric substance described can be used for improving solution properties or electrical characteristic.Other polymkeric substance described include, for example: using the polymkeric substance etc. as main framing such as the polyamic acid that obtains by not comprising the tetracarboxylic dianhydride of compound represented by described formula (1) and the reaction of diamines and its imide amination polymer and carboxylate, organopolysiloxane, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc.Relative to total 100 weight part of the polymkeric substance of allotment in liquid crystal aligning agent, the allotment ratio of other polymkeric substance is preferably set to below 90 weight parts, is more preferably and is set to below 80 weight parts, is especially preferably set to below 70 weight parts.
[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 or electrical characteristic.This kind include, for example following compound as preferably containing the compound of epoxy group(ing): 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 etc.In addition, containing the organopolysiloxane containing epoxy group(ing) that the example of the compound of epoxy group(ing) can use No. 2009/096598th, International Publication to record.
When these epoxy compoundss 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 described epoxy compounds is preferably set to below 40 weight parts, is more preferably and is set to 0.1 weight part ~ 30 weight part.
[functional silanes compound]
Described functional silanes compound can use for the object of the printing of raising liquid crystal aligning agent.Described functional silanes compound include, for example: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane, 3-ureidopropyltriethoxysilane, N-ethoxy carbonyl-3-TSL 8330, N-tri-ethoxy silylpropyl diethylenetriamine, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.
When these functional silanes compounds 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 described functional silanes compound is preferably set to below 2 weight parts, is more preferably and is set to 0.02 weight part ~ 0.2 weight part.
In addition, except described composition, other compositions include, for example in molecule the compound, antioxidant etc. with at least one oxetanylmethoxy.
< solvent >
Liquid crystal aligning agent of the present invention be prepared into described polymkeric substance (A) and optionally and allotment other compositions preferably disperse or be dissolved in the liquid composition in suitable solvent.
The organic 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, isoamyl ether, ethylene carbonate, Texacar PC etc.These organic 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 being coated on 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, the tendency that coating declines.
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, the liquid crystal aligning agent used in formation for the liquid crystal orientation film of liquid crystal display device, when utilizing turner method to be coated 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 is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.
The preferred aspects of the component of polymer of liquid crystal aligning agent can be enumerated: [I] aspect only containing polymkeric substance (A); [II] is containing polymkeric substance (A) and other polymkeric substance, and other polymkeric substance are for being selected from the aspect etc. of at least one polymkeric substance (hereinafter also referred to " polymkeric substance (B) ") in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide.In addition, when described [II], the containing ratio of the fluorine atom in polymkeric substance (A) and polymkeric substance (B) or Siliciumatom can be made different.When polymkeric substance (A) is prepared liquid crystal aligning agent with polymkeric substance (B) fusion, be speculated as: the fluorine atom had by making polymkeric substance or the containing ratio of Siliciumatom are different in polymkeric substance (A) and polymkeric substance (B), and in film, produce the deflection of the distribution of polymkeric substance.
The concrete aspect of described [II] include, for example: [II-1] polymkeric substance (A) and polymkeric substance (B) all do not have the aspect of fluorine atom or Siliciumatom; Fluorine atom in [II-2] polymkeric substance (A) or the containing ratio of Siliciumatom are higher than the aspect etc. of polymkeric substance (B).In these aspects, with regard to the image retention characteristic of liquid crystal display device and the high aspect of the improvement effect of contrast-response characteristic, be preferably set to the aspect of described [II-2].
Relative to total amount 100 weight part of polymkeric substance (A) and polymkeric substance (B), the allotment ratio of the polymkeric substance (A) in described [II] aspect is preferably set to 1 weight part ~ 99 weight part, be more preferably and be set to 5 weight part ~ 90 weight parts, be especially preferably set to 10 weight part ~ 80 weight parts.
< liquid crystal orientation film and liquid crystal display device >
Liquid crystal orientation film of the present invention can utilize the method comprised the steps to manufacture: described illustrated liquid crystal aligning agent is coated on step substrate being formed film.In addition, liquid crystal display device of the present invention possesses and uses described liquid crystal aligning agent and the liquid crystal orientation film that 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-PattemedVerticalAlignment 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 step (1) ~ step (3) manufactures.Step (1) uses different substrates according to required operating mode.Step (2) and step (3) share in each operating mode.
[step (1): the formation of film]
First, described liquid crystal aligning agent is coated on substrate, then coated face is preferably heated, on substrate, form film whereby.
(1-1) 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, preferably utilize flexographic printing process, method of spin coating, roll-coater method or ink jet printing method to difference coating of liquid crystalline alignment agent.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) tin indium oxide (IndiumTinOxide, 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.
(1-2) 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, coating of liquid crystalline alignment agent respectively, then each coated face is preferably 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 are identical with described (1-1).Metallic membrane can use the film such as comprising the metals such as chromium.
In any one situation of described (1-1) and (1-2), 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, the polyamic acid of allotment in liquid crystal aligning agent, poly amic acid ester and polyimide can be made to carry out dehydration closed-loop reaction, thus make further through the film of imidization.
[step (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 is wound with the roller of the cloth comprising the fibers such as such as nylon, artificial silk, cotton by utilizing, and by film to certain orientation wiping, thus gives liquid crystal aligning ability to film; Described smooth orientation process is carried out rayed to the film be formed on substrate and gives liquid crystal aligning ability to film.On the other hand, when manufacturing vertical alignment-type liquid crystal display device, the film formed directly can be used as liquid crystal orientation film in described step (1), but 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.In these methods, with regard to the image retention characteristic of liquid crystal display device and the high aspect of the improvement effect of contrast-response characteristic, be preferably the method utilizing [2].
The radioactive rays of polarisation or non-polarized can be set to the light of film irradiation.As radioactive rays, such as, can use ultraviolet and the visible rays of the light comprising 150nm ~ 800nm wavelength.When radioactive rays are polarisation, can be linear polarization, also can be part polarisation.In addition, when used radioactive rays are for linear polarization or part polarisation, can irradiate from the direction vertical with real estate, also can irradiate from vergence direction, or these irradiation combinations are carried out.When irradiating the radioactive rays 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 enter and 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 radioactive rays 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 (3): constructing of liquid crystal cells]
Prepare the two pieces of substrates being 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, two pieces of substrate subtends are configured via gap (cell gap) in the mode of each liquid crystal orientation film subtend, sealing agent 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 agent after, filling orifice is sealed, manufactures liquid crystal cells whereby.In addition, the second method is for being called the method for liquid crystal drip-injection (OneDropFill, ODF) mode.In the method, specified location on wherein one piece of substrate in the two pieces of substrates being formed with liquid crystal orientation film, the such as sealing agent of coated UV photo-hardening, 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 whole irradiating ultraviolet light of substrate is cured the sealant, manufacture liquid crystal cells 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, remove flow orientation when liquid crystal is filled whereby.
As sealing agent, such as, can use and contain as the alumina balls of spacer and the epoxy resin etc. of stiffening agent.
Liquid crystal can enumerate nematic liquid crystal and stratose liquid crystal (smecticliquidcrystal), wherein be preferably nematic liquid crystal, such as, can use: schiff bases (Schfffbase) is liquid crystal, azoxy (azoxy) is liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) are 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 cholesteryl liquid crystals (cholestericliquidcrystal) such as such as cholesteryl chloride (cholesterylchloride), cholesteryl nonanoate (cholesterylnonanoate), cholesteryl carbonic ether (cholesterylcarbonate); As 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.
Liquid crystal display device of the present invention can be effectively applied to multiple device, such as can be suitable as the liquid crystal display device used in the display unit such as clock and watch, pocket game machine, word processor, notes type Personal Computer, auto-navigation system, video camera, personal digital assistant (PersonalDigitalAssistant, PDA), digital camera, mobile telephone, smart mobile phone, various watch-dog, LCD TV, information display to apply.
[embodiment]
Below, by embodiment, the present invention is specifically described further, but the present invention is not limited to these embodiments.
Utilize following methods to measure the weight average molecular weight of each polymkeric substance in synthesis example.
[weight average molecular weight of polymkeric substance]
The weight average molecular weight Mw of polymkeric substance is the polystyrene conversion value utilizing the gel permeation chromatography of following condition to measure.
Tubing string: eastern Cao (Tosoh) (stock) manufactures, TSKgelGRCXLII
Solvent: tetrahydrofuran (THF)
Temperature: 40 DEG C
Pressure: 68kgf/cm 2
Below, sometimes " compound represented by formula X " is only denoted as " compounds X ".
The synthesis > of < compound (a)
[embodiment 1-1: the synthesis of compound (a-1)]
The L MALIC ACID of 3.1g is made an addition in the Adipoyl Chloride of 2.0g, stirs 10 hours at 100 DEG C.Then, heat at 120 DEG C and reduce pressure, drying is carried out to residue, obtain the compound (compound represented by described formula (a-1)) of 3.7g oily whereby with purity 99%.
In addition, about the compound represented by the compound represented by described formula (a-2), the compound represented by described formula (a-3) and described formula (a-4), also synthesize in an identical manner.
[embodiment 2-1: the synthesis of compound (a-5)]
N-(p-methylphenyl) maleimide of 16.6g and 1, the 6-hexylene glycol of 5g are made an addition to after in the chloroform of 100ml, adds the salt of wormwood of 0.36g, at room temperature stir 2 hours.Then, this solution is concentrated.Then, add the concentrated hydrochloric acid of 50ml in residue after concentration, stir after 1 hour at 100 DEG C, this solution is concentrated.The ethyl acetate of 100ml is added in residue after concentration, at room temperature stir after 1 hour, carry out filtration under diminished pressure and filtrate is concentrated, drying is carried out to the residue of gained, obtaining the 13.2g tetracarboxylic acid body corresponding with the compound represented by described formula (a-5) whereby.
In the diacetyl oxide of 100ml, the tetracarboxylic acid body of 13.2g gained is stirred 10 hours at 100 DEG C.Then, heat at 120 DEG C and reduce pressure, drying is carried out to residue, obtain the compound (compound represented by described formula (a-5)) of 11.8g oily whereby with purity 99%.
In addition, about the compound represented by described formula (a-6), also synthesize in an identical manner.
[embodiment 3: the synthesis of compound (a-15)]
In the tetrahydrofuran (THF) of 100ml, the dimethyl fumarate of 14.4g and the piperazine of 4.3g are stirred 16 hours at 60 DEG C.After being cooled to room temperature, the solid of separating out in solvent is carried out filter, dry, obtain the intermediate (a-15-1) of 15.0g whereby with purity 99%.
The intermediate (a-15-1) of 15g gained is made an addition in the methyl alcohol of 150ml, after then adding the aqueous sodium hydroxide solution of the 2mol/L of 150ml, stirs 4 hours at 60 DEG C.Then, after being cooled to room temperature, the solid of separating out in solvent being filtered, cleans with methyl alcohol.By this dissolution of solid in the pure water of 200ml, adding hydrochloric acid becomes till 3.8 until pH value, at room temperature stirs 1 hour.Then, the solid of separating out in solvent is filtered, after cleaning with the pure water of 5 DEG C, carry out drying, obtain the intermediate (a-15-2) of 11.5g whereby with purity 99%.
The intermediate (a-15-2) of 11.5g gained is made an addition in the diacetyl oxide of 22.0g, after then adding the pyridine of 14.0g, stirs 24 hours at 40 DEG C.Then, after being cooled to room temperature, the solid of separating out in solvent is filtered, after cleaning with diacetyl oxide and hexane, carry out drying, obtain the compound (a-15) of the white solid of 7.1g whereby with purity 99%.
The synthesis > of < polymkeric substance (A)
[embodiment 4: the synthesis of polymkeric substance (A-1)]
Using 100 molar part as tetracarboxylic dianhydride described formula (a-1) represented by compound, 100 molar part be dissolved in METHYLPYRROLIDONE (N-methyl-2-pyrrolidone as the Ursol D of diamines, NMP), in, reaction in 8 hours is at room temperature carried out.Whereby, the polyamic acid solution that solid component concentration is 15 % by weight is obtained.Using the polyamic acid of gained as polymkeric substance (A-1).The weight average molecular weight Mw of polymkeric substance (A-1) is 60,000.
[embodiment 5 ~ embodiment 12: the synthesis of polymkeric substance (A-2) ~ polymkeric substance (A-9)]
Except by except the kind of used tetracarboxylic dianhydride and diamines and quantitative change more as described in Table 1, carry out the operation identical with embodiment 4, obtain the polyamic acid solution that solid component concentration is 15 % by weight.The weight average molecular weight Mw of each polymkeric substance is shown in following table 1 in the lump.
[table 1]
In table 1, the allotment ratio (molar part) of the numeric representation in the parantheses on each hurdle of compound for total 100 molar part of used tetracarboxylic dianhydride."-" refers to and does not use this compound (also identical about following table).
In table 1, the abbreviation of compound is respectively following implication (following table 2 is also identical).
(tetracarboxylic dianhydride)
A-1 ~ a-6: the compound represented by described formula (a-1) ~ formula (a-6) difference
A-15: the compound represented by described formula (a-15)
C-1: pyromellitic acid anhydride
(diamines)
B-1: Ursol D
B-2:4-aminophenyl-4 '-Aminobenzoate
B-3: the compound represented by following formula (b-3)
B-4:4,4 '-chrysoidine
[changing 10]
The synthesis > of < polymkeric substance (B)
[synthesis example 1 ~ synthesis example 6: the synthesis of polymkeric substance (B-1) ~ polymkeric substance (B-6)]
Except by except the kind of used tetracarboxylic dianhydride and diamines and quantitative change more as described in Table 2, carry out the operation identical with embodiment 4, obtaining solid component concentration is the polyamic acid solution of 15%.The weight average molecular weight Mw of each polymkeric substance is shown in following table 2 in the lump.
[table 2]
In table 2, the abbreviation of compound is respectively following implication.
(tetracarboxylic dianhydride)
C-2:1,2,3,4-butane tetracarboxylic acid dianhydride
C-3: the compound represented by following formula (c-3)
C-4: the compound represented by following formula (c-4)
(diamines)
Two (4-aminophenyl) methylamine of b-5:N, N-
[changing 11]
The preparation of < liquid crystal aligning agent and the manufacture of liquid crystal display device and evaluate >
[embodiment 13]
1. the preparation of liquid crystal aligning agent
The polymkeric substance (A-2) obtained in containing described embodiment 5 is as in the solution of component of polymer, add NMP and ethylene glycol butyl ether (butylcellosolve, BC), abundant stirring, makes the solution that solvent consists of NMP: BC=70: 30 (weight ratios), solid component concentration is 3.0 % by weight.Use aperture is the strainer of 0.45 μm, is filtered by this solution, prepares liquid crystal aligning agent whereby.
2. the manufacture of the FFS type liquid crystal display device of orientation process is carried out by photo-irradiation treatment
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.
The floor map of used upper current conducting cap 13 is shown in (a) of Fig. 2 and (b) of Fig. 2.In addition, the vertical view that (a) of Fig. 2 is upper current conducting cap 13, E represents electrode, (b) of Fig. 2 be (a) of Fig. 2 by the enlarged view of the part C1 of dotted line, F represents pixel edge part.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 (Fig. 3) of the four systems of electrode A, electrode B, electrode C and electrode D.In addition, 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.
After utilizing turner to form film, film is carried out 1 minute prebake conditions on the hot-plate of 80 DEG C.Then, to each surface of film, use Hg-Xe lamp and Glan-Taylor prism (Glan-Taylorprism) to irradiate 5,000J/m 2polarisation ultraviolet, obtain and there is a pair substrate of liquid crystal orientation film.Now, polarisation ultraviolet irradiation direction is set to substrate normal direction, after the mode becoming the direction of the four-headed arrow in (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, carry out photo-irradiation treatment.After rayed, having carried out in the baking oven of nitrogen displacement in storehouse, with 230 DEG C of heating (toasting afterwards) 1 hour, form the film that average film thickness is 0.1 μm.
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 3.5 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-7028 " 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 remove 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.In addition, by by the ultraviolet irradiation amount before rear baking at 1,000J/m 2~ 30,000J/m 2scope in change respectively and implement described sequence of operations, thus manufacture the different liquid crystal display device of more than 3 of ultraviolet irradiation amount.
3. the evaluation of liquid crystal display device
Use the liquid crystal display device manufactured in described 2. to carry out the evaluation of following (1).In addition, except the aspect of Polarizer of not fitting, by carrying out manufacturing liquid crystal display device (liquid crystal cells of Polarizer of not fitting) with described 2. identical operations, carry out the evaluation of following (2).In addition, about evaluation result, from more than 3 liquid crystal display device that ultraviolet irradiation amount is different, optimum result is selected, as the evaluation result of liquid crystal display device.
(1) evaluation of AC image retention characteristic
Use the liquid crystal display device of described manufacture to evaluate AC image retention (afterimage) characteristic (image retention (imagesticking) characteristic).First, liquid crystal display device is positioned over 25 DEG C, under the environment of 1 air pressure, voltage is not applied to electrode B and electrode D, and the voltage of alternating current 2 hours of 4V is applied to electrode A and electrode C.After 2 hours, the voltage exchanging 4V is applied to all electrodes of electrode A ~ electrode D.Measure from start to apply the moment of the voltage exchanging 4V to all electrodes, drive stress to apply region (pixel region of electrode A and electrode C) to visual no longer can confirming and drive the time the luminance difference in the non-applying region of stress (pixel region of electrode B and electrode D), it can be used as the image retention cancellation time.Image retention characteristic " good (zero) " is evaluated as when this image retention cancellation time is less than 60 seconds, more than 60 seconds, be evaluated as image retention characteristic " can (△) " when being less than 100 seconds, more than 100 seconds, be evaluated as image retention characteristic " bad (×) ".Its result is, the image retention characteristic of this liquid crystal display device is " well ".
(2) evaluation of the contrast gradient after stress is driven
After the liquid crystal display device (liquid crystal cells of Polarizer of not fitting) of described manufacture is driven 30 hours with voltage of alternating current 10V, be used in the device being configured with polarizer and analyzer between light source and light quantity detector, measure the minimum relative permeability (%) represented by following numerical expression (2).
Minimum relative permeability (%)=(β-B 0)/(B 100-B 0) × 100 (2)
(in numerical expression (2), B 0for the transit dose of the light under space state and under Nicol crossed (crossednicol); B 100for the transit dose of the light under space state and under parallel Nicol; β is under Nicol crossed, clamps liquid crystal display device and become minimum light transmission amount between polarizer and analyzer.)
The black level of dark state represents with the minimum relative permeability of liquid crystal display device, and the black level under dark state is less, and contrast gradient is more excellent.Minimum relative permeability is less than 0.5% be evaluated as " good (zero) ", is less than 1.0% be evaluated as " can (△) " by more than 0.5%, by more than 1.0% be evaluated as " bad (×) ".Its result is, the contrast gradient evaluation of this liquid crystal display device is through being judged as " well ".
[embodiment 14 ~ embodiment 17 and comparative example 1 ~ comparative example 3]
Except the kind of used polymkeric substance being changed to respectively as described in Table 3, preparing liquid crystal aligning agent in the mode identical with embodiment 13, manufacturing liquid crystal display device.In addition, the various evaluations of manufactured liquid crystal display device are carried out in the mode identical with embodiment 13.Their evaluation result is shown in following table 3.
[table 3]
[embodiment 18]
1. the preparation of liquid crystal aligning agent
The polymkeric substance (A-1) obtained in containing embodiment 4 is as in the solution of component of polymer, add NMP and ethylene glycol butyl ether (BC), abundant stirring, makes the solution that solvent consists of NMP: BC=70: 30 (weight ratios), solid component concentration is 3.0 % by weight.Use aperture is the strainer of 0.45 μm, is filtered by this solution, prepares liquid crystal aligning agent whereby.
2. the manufacture of the liquid crystal display device of orientation process is carried out by friction treatment
Prepare in the mode identical with embodiment 13 to possess the glass substrate of electrode A ~ electrode D and not there is the subtend glass substrate of electrode, in the wherein one side of the face with electrode of glass substrate and subtend glass substrate, spin coater is used to be coated with the liquid crystal aligning agent of described preparation respectively.Then, after the hot-plate of 80 DEG C carries out 1 minute prebake conditions, the hot-plate of 230 DEG C carries out toast after 10 minutes, form the film that thickness is about 0.1 μm.For formed coated surface, use the friction machine with the roller that wrapped around nylon cloth, carry out friction treatment with the translational speed 25mm/ second of the rotating speed 1,000rpm of roller, platform, hair press-in length 0.4mm, give liquid crystal aligning ability.And then this substrate is carried out 1 minute ultrasonic cleaning in ultrapure water, in 100 DEG C of cleaning ovens, drying 10 minutes, obtains a pair substrate with liquid crystal orientation film whereby.
Then, the periphery with the face of liquid crystal orientation film of the wherein one piece of substrate in a pair substrate, utilizing screen painting to be coated with to add has diameter to be after the epoxy resin adhesive of the alumina balls of 3.5 μm, make the liquid crystal orientation film of a pair substrate in the face of to, become the crimping of antiparallel mode overlap with the frictional direction of each liquid crystal orientation film, at 150 DEG C, spend 1 hour make caking agent carry out heat embrittlement.Then, after filling Merck (Merck) Inc. liquid making crystalline substance " MLC-7028 " the gap between from liquid crystal injecting port to substrate, utilize epoxy caking agent to be sealed by liquid crystal injecting port.And then, in order to remove flow orientation during Liquid crystal pour, and be slowly cooled to room temperature after it being heated at 150 DEG C.Then, on the two sides, outside of substrate, make the polarization direction of Polarizer mutually orthogonal, and described Polarizer is fitted on the frictional direction of liquid crystal orientation film, manufacture liquid crystal display device whereby.
In addition, except the aspect of Polarizer of not fitting, carry out and described identical operation, manufacture liquid crystal display device (liquid crystal cells of Polarizer of not fitting) whereby.
About the various evaluations of the liquid crystal display device manufactured in this embodiment, implement AC image retention characteristic in the mode identical with embodiment 13 and drive the evaluation of the contrast gradient after stress.Its result is, in this embodiment, AC image retention characteristic and the contrast gradient evaluation after driving stress are " good (zero) ".
[embodiment 19, embodiment 20 and comparative example 4]
Except the kind of used polymkeric substance being changed to as described in Table 4, preparing liquid crystal aligning agent in the mode identical with embodiment 18, manufacturing liquid crystal display device.In addition, the method identical with embodiment 13 is utilized to carry out the various evaluations of manufactured liquid crystal display device.Their evaluation result is shown in following table 4.
[table 4]
[embodiment 21]
1. the preparation of liquid crystal aligning agent
Containing 50 weight parts described embodiment 7 in obtain polymkeric substance (A-4) and 50 weight parts described synthesis example 5 in obtain polymkeric substance (B-5) as in the solution of component of polymer, add NMP and ethylene glycol butyl ether (BC), abundant stirring, makes the solution that solvent consists of NMP: BC=70: 30 (weight ratios), solid component concentration is 3.0 % by weight.Use aperture is the strainer of 0.45 μm, is filtered by this solution, prepares liquid crystal aligning agent whereby.
2. the manufacture of liquid crystal display device and evaluation
Except using the liquid crystal aligning agent of described preparation, in the mode identical with embodiment 13, carry out orientation process by photo-irradiation treatment and manufacture liquid crystal display device.In addition, the various evaluations of manufactured liquid crystal display device are implemented in the mode identical with embodiment 13.Its result is, in this embodiment, AC image retention characteristic and the contrast gradient evaluation after driving stress are " good (zero) ".
[comparative example 5, comparative example 6]
Except the kind of used polymkeric substance being changed to respectively as described in Table 5, preparing liquid crystal aligning agent in the mode identical with embodiment 21, manufacturing liquid crystal display device.In addition, the various evaluations of manufactured liquid crystal display device are carried out in the mode identical with embodiment 13.Their evaluation result is shown in following table 5.
[table 5]
In table 5, the allotment ratio (weight part) of each polymkeric substance of numeric representation for total 100 weight part of the polymkeric substance for the preparation of liquid crystal aligning agent on the hurdle of the allotment amount of polymkeric substance.
As shown in table 3 and table 4, in the embodiment 13 ~ embodiment 20 of homopolymerization system, be the evaluation of AC image retention characteristic and contrast-response characteristic " well " or "available".Particularly use the acid anhydrides with linear chain structure or cyclohexylidene as in the embodiment of compound (a), AC image retention characteristic and contrast-response characteristic are the result of " well ".Use in the embodiment 10 of nitrogenous acid anhydrides, AC image retention characteristic and contrast-response characteristic are also the result of " well ".In addition, the performance equal with homopolymerization system is also shown in the embodiment 21 of fusion system.On the other hand, in comparative example, AC image retention characteristic and contrast-response characteristic at least any one is the evaluation of " bad ".

Claims (9)

1. a liquid crystal aligning agent, it is characterized in that: containing at least one polymkeric substance (A) be selected from cohort that the polyamic acid, poly amic acid ester and the polyimide that obtain by making tetracarboxylic acid derivatives and diamines carry out reacting form, described tetracarboxylic acid derivatives for being selected from least one in the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester two halogen compounds, and
Described tetracarboxylic acid derivatives comprises at least one compound in the cohort that the diester compound of compound (a) and the described compound (a) be selected from represented by following formula (1) and diester two halogen compounds form,
In formula (1), R 1for divalent organic base, X 1and X 2be separately-O-C (=O)-* ,-C (=O)-O-* ,-S-C (=O)-* ,-C (=O)-S-* ,-O-,-S-or-NR 5-, wherein, R 5for the monovalent hydrocarbon of carbon number 1 ~ 6, R 5with R 1also can bond and form nitrogen heterocyclic ring, at X 1and X 2for-NR 5-when, 2 R 5also can bond and and R 1form nitrogen heterocyclic ring together; With associative key and the R of * 1bond; R 2and R 3be separately hydrogen atom or any monovalent organic radical.
2. liquid crystal aligning agent according to claim 1, is characterized in that: described R 1for the group represented by following formula (r-1),
In formula (r-1), R 6and R 7be separately alkane two base of carbon number 1 ~ 15, between the C-C of alkane two base of carbon number 1 ~ 15, there is-O-,-CO-,-COO-or "-Si (R 8) 2-" group, wherein, R 8for the monovalent hydrocarbon of carbon number 1 ~ 12, multiple R 8can be identical, also can be different, or at least one of the hydrogen atom had by alkane two base of carbon number 1 ~ 15 is with fluorine atom or "-Si (R 9) 3" group that replaces, wherein, R 9for alkyl or alkoxyl group, multiple R 9can be identical, also can be different; Ar 1for cyclohexylidene, phenylene, biphenylene or naphthylidene, at least one being binding on ring hydrogen atom can through fluorine atom or-Si (R 9) 3replaced; D, e and f are separately 0 or 1; Wherein, d, e and f can not become 0 simultaneously.
3. liquid crystal aligning agent according to claim 2, is characterized in that: described R 1for alkane two base of carbon number 1 ~ 20, between the C-C of alkane two base of carbon number 1 ~ 20, there is-O-,-CO-,-COO-or-Si (R 8) 2-group, at least one of the hydrogen atom had by alkane two base of carbon number 1 ~ 20 is with fluorine atom or-Si (R 8) 3the group replaced, or cyclohexylidene.
4. liquid crystal aligning agent according to any one of claim 1 to 3, is characterized in that: described X 1and described X 2be separately-O-C (=O)-* or-O-, wherein, with associative key and the R of * 1bond.
5. a manufacture method for liquid crystal orientation film, is characterized in that comprising: liquid crystal aligning agent according to any one of claim 1 to 4 is coated step substrate being formed film; And rayed is carried out to the film be formed on described substrate and described film is given to the step of liquid crystal aligning ability.
6. a liquid crystal orientation film, is characterized in that: use liquid crystal aligning agent according to any one of claim 1 to 4 and formed.
7. a liquid crystal display device, is characterized in that: possess liquid crystal orientation film according to claim 6.
8. a polymkeric substance, it is selected from least one polymkeric substance in cohort that the polyamic acid, poly amic acid ester and the polyimide that obtain by making tetracarboxylic acid derivatives and diamines carry out reacting form, described tetracarboxylic acid derivatives is selected from least one in the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester and tetracarboxylic acid diester two halogen compounds
The feature of described polymkeric substance is: described tetracarboxylic acid derivatives comprises at least one compound in the cohort that the diester compound of compound (a) and the described compound (a) be selected from represented by following formula (1) and diester two halogen compounds form
In formula (1), R 1for divalent organic base, X 1and X 2be separately-O-C (=O)-* ,-C (=O)-O-* ,-O-or-NR 5-, wherein, R 5for the monovalent hydrocarbon of carbon number 1 ~ 6, R 5with R 1also can bond and form nitrogen heterocyclic ring, at X 1and X 2for-NR 5-when, 2 R 5also can bond and and R 1form nitrogen heterocyclic ring together; With associative key and the R of * 1bond; R 2and R 3be separately hydrogen atom or any monovalent organic radical, wherein except hydroxyl.
9. the compound represented by following formula (1) and the diester compound of described compound and diester two halogen compounds,
In formula (1), R 1for divalent organic base, X 1and X 2be separately-O-C (=O)-* ,-C (=O)-O-* ,-O-or-NR 5-, wherein, R 5for the monovalent hydrocarbon of carbon number 1 ~ 6, R 5with R 1also can bond and form nitrogen heterocyclic ring, at X 1and X 2for-NR 5-when, 2 R 5also can bond and and R 1form nitrogen heterocyclic ring together; With associative key and the R of * 1bond; R 2and R 3be separately hydrogen atom or any monovalent organic radical, wherein except hydroxyl.
CN201510387134.8A 2014-07-28 2015-06-30 Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display member and polymer and compound Pending CN105316005A (en)

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