CN104845642A

CN104845642A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, phase difference film, manufacturing method for the phase difference film, polymer and compound

Info

Publication number: CN104845642A
Application number: CN201510053738.9A
Authority: CN
Inventors: 樫下幸志
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2014-02-13
Filing date: 2015-02-02
Publication date: 2015-08-19
Anticipated expiration: 2035-02-02
Also published as: KR102209444B1; JP2015166844A; TWI709611B; CN104845642B; KR20150095561A; JP6492564B2; TW201531530A

Abstract

The invention provides a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display device, a phase difference film, a manufacturing method for the phase difference film, a polymer and a compound. The liquid crystal alignment agent can acquire the liquid crystal display device with excellent balance performance and various characteristics. The liquid crystal aligning agent comprises a polymer (P) acquired by making at least one polymer (C') selected from a group composed of a free polymer (C) and a polymer (C1) reacted. The polymer (C) has the structure (a) and the structure (B). The polymer (C1) has the structure (a) and the structure (b1). No reaction group participating in polymerization is bonded on the aromatic cyclic foundation in the structure (a). (a) is an aromatic amine structure form by two or three aromatic cyclic foundations bonded on the same nitrogen atom to form. (b) is a chain typed structure of 2-price chain-type alkyl radicals with more than six carbon numbers. (b1) is a structure among that of 2-price chain-type alkyl radicals with 1-5 carbon numbers, a -o- structure, a -s- structure.

Description

Liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, phase retardation film and manufacture method thereof, 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, phase retardation film, the manufacture method of phase retardation film, polymkeric substance and compound.

Background technology

In the past, liquid crystal display device develops electrode structure or the different multiple type of drive of the physical property, manufacturing step etc. of liquid crystal molecule that use, such as known twisted nematic (Twisted Nematic, TN) type or STN Super TN (Super TwistedNematic, STN) type, vertical orientated (Vertical Alignment, VA) type, coplanar switching (In-Plane Switching, IPS) type, fringing field switch the various liquid crystal display device such as (Fringe Field Switching, FFS) type.These liquid crystal display device have the liquid crystal orientation film making liquid crystal molecular orientation.With regard to thermotolerance, physical strength, the aspect good with the various characteristic such as the affinity of liquid crystal, the material of liquid crystal orientation film uses polyamic acid or polyimide usually.

In addition, in recent years, along with the high-precision refinement of liquid crystal display device, the requirement reducing afterimage phenomena or suppress contrast gradient to decline being improved, having proposed plurality of liquid crystals alignment agent (such as with reference to patent documentation 1 ~ patent documentation 6) to meet described requirement.Recording in liquid crystal aligning agent in these patent documentation 1 ~ patent documentations 6, by being directed in liquid crystal aligning agent by diphenylamine unit, realizing the minimizing of the accumulated charge in liquid crystal display device or the suppression etc. of contrast gradient decline.

Specifically, Patent Document 1 discloses and comprise 4 by making, the polyamic acid that the diamines of 4 '-diamino-diphenyl amine and tetracarboxylic dianhydride carry out reacting and obtain or polyimide are contained in liquid crystal aligning agent.Patent Document 2 discloses making to comprise (4-aminophenyl) that (polyimide that the diamines of the oligomerization aniline such as 4-((4-aminophenyl) is amino) phenyl amine and tetracarboxylic dianhydride carry out reacting and obtain is contained in liquid crystal aligning agent.In addition, Patent Document 3 discloses the compound with more than 2 diphenylamine unit to separate with the polymkeric substance such as polyamic acid or polyimide and add, or the polyamic acid that the diamines and tetracarboxylic dianhydride that make to have more than 2 diphenylamine unit carry out reacting and obtain is contained in liquid crystal aligning agent.

Patent Document 4 discloses and will make to comprise 1, the polyamic acid that two-4-(N, N-(4-aminophenyl) aminophenyl) propane of 3-carries out reacting as the diamines of compound and tetracarboxylic dianhydride in molecule with 2 diphenylamine structures and obtains is contained in liquid crystal aligning agent.In addition, patent documentation 5 and Patent Document 6 discloses and comprise N by making, the polyamic acid that the diamines of N '-bis-(4-aminophenyl)-N, N '-dimethyl-ethylenediamine and tetracarboxylic dianhydride carry out reacting and obtain is contained in liquid crystal aligning agent.

In addition, in liquid crystal display device, use multiple optical material, wherein, for eliminating the painted object of display or eliminating display look and contrast gradient than the object of the visual angle interdependence changed along with visual direction, and use phase retardation film.Described phase retardation film is known to be comprised: triacetyl cellulose (triacetyl cellulose, TAC) film etc. is formed at the liquid crystal orientation film on the surface of substrate and is formed at the liquid crystal layer on the surface of described liquid crystal orientation film by making polymerizable liquid crystal harden.In addition, in recent years, when making the liquid crystal orientation film in phase retardation film, utilize following optical alignment method: by irradiating the radioactive rays of polarisation or non-polarized to the organic film of the radioactivity-sensitive being formed at substrate surface, and give liquid crystal aligning ability to described organic film; Propose useful to utilize described method to make the liquid crystal aligning agent (such as with reference to patent documentation 7) of the phase retardation film of liquid crystal orientation film.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent No. 4052307 publication

[patent documentation 2] Japanese Patent Laid-Open 2000-44683 publication

[patent documentation 3] Japanese Patent No. 4924832 publication

[patent documentation 4] Japanese Patent Laid-Open 2011-207786 publication

[patent documentation 5] Japanese Patent Laid-Open 2012-155311 publication

[patent documentation 6] Japanese Patent the 5130907th publication

[patent documentation 7] Japanese Patent Laid-Open 2012-37868 publication

Summary of the invention

[invention institute for solution problem]

But when using the liquid crystal aligning agent of patent documentation 1, in liquid crystal display device, the residual mitigation of direct current (direct current, DC) is insufficient, there is the tendency of the time length to image retention disappears.In addition, comprise and be used as in the available liquid crystal alignment agent of the polymkeric substance of monomer by the diamines with multiple diphenylamine unit, although the performance that DC remains mitigation improves, aromatic series concentration rises, and therefore there is the shortcomings such as the transmissivity of liquid crystal orientation film is low.In addition, interchange (Alternating Current, AC) the image retention performance as one of the contrast gradient characteristic bringing impact on liquid crystal display device is insufficient, and balance can not possess various characteristic well.In addition, along with the multi-usage of liquid crystal display device in recent years, liquid crystal display device is envisioned for under harsher situation, and requires the liquid crystal display device of excellent heat resistance.

Liquid-crystal display is by a pair substrate being formed with liquid crystal orientation film is carried out subtend configuration, configures liquid crystal to manufacture between a pair substrate that described subtend configures.Now, use the sealing agents such as epoxy resin by a pair baseplate-laminating.Herein, in the display panel of the touch panel formula representated by smart mobile phone or panel computer, in order to expand the movable area of touch panel further, and take into account the miniaturization of liquid crystal panel (element), and attempt realizing narrow frame.Along with the narrow frame of described liquid crystal panel, have at sealing agent periphery depending on recognizing the uneven situation of display, cannot be satisfactory fully in display quality.In order to realize high-precision refinement, the high life of liquid-crystal display, and require the liquid crystal display device of the display inequality (resistance to frame (bezel) inequality is high) be difficult to depending on recognizing described sealing agent periphery.

The present invention is formed in view of described problem, one of object is for providing a kind of liquid crystal aligning agent in order to obtain liquid crystal display device, the transmissivity of the liquid crystal orientation film of described liquid crystal display device is good, the display inequality of sealing agent periphery is few, and balance has the various characteristics such as image retention characteristic, high-contrast, thermotolerance well concurrently.

[means of dealing with problems]

The present inventor carries out active research to reach the problem of prior art as above, finding that the polymkeric substance by making to have ad hoc structure is contained in as component of polymer in liquid crystal aligning agent, can solve described problem, thus completing the present invention.Specifically, the manufacture method of following liquid crystal aligning agent, liquid crystal orientation film, liquid crystal display device, phase retardation film, phase retardation film, polymkeric substance and compound is provided by the present invention.

Of the present invention wherein on the one hand for providing a kind of liquid crystal aligning agent, it contains the polymkeric substance (P) obtained for reacting by least one compound (C ') in the cohort selecting free compound (C) and compound (C1) to form, described compound (C) has following structure (a) and following structure (b), and described compound (C1) has following structure (a) and following structure (b1) and on aromatic series cyclic group in described structure (a), non-bond has the reactive base participating in polymerization.

A () 2 or 3 aromatic ring bases are binding on the aromatic amine structure on same nitrogen-atoms.

(b) be selected from by the divalent chain alkyl of carbon number more than 6 and by least 1 methylene radical in this chain alkyl with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂chain-like structure in the cohort that the divalent base that-(R is hydrogen atom or 1 valency organic radical) replaces forms.

(b1) be selected from by the divalent chain alkyl of carbon number 1 ~ 5, by least 1 methylene radical in this chain alkyl with-O-,-S-,-CO-,-NR ³-,-NR ³cO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of-replacement ,-O-,-S-,-CO-,-NR ³cO-(R ³for hydrogen atom or 1 valency organic radical) ,-COO-,-COS-and-Si (CH ₃) ₂structure in the-cohort that forms.

Another aspect of the invention is provides a kind of and uses described liquid crystal aligning agent and the liquid crystal orientation film formed.In addition, provide a kind of comprise the liquid crystal display device of described liquid crystal orientation film and comprise the phase retardation film of described liquid crystal orientation film.And then the opposing party is for providing a kind of manufacture method of phase retardation film, and it comprises: described liquid crystal aligning agent is coated step substrate being formed film; Light-struck step is carried out to this film; And on described film after rayed, be coated with polymerizable liquid crystal and the step making it harden.

The compound, the compound represented by following formula (1-2) and the compound represented by following formula (1-3) that there is provided represented by following formula (1-1) are provided.In addition, polymkeric substance in the cohort being selected from and being made up of polyamic acid, poly amic acid ester and polyimide is provided, described polyamic acid, poly amic acid ester and polyimide are at least one compounds that will be selected from the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide, obtain for reaction with the diamines comprising at least one be selected from cohort that the compound represented by the compound represented by following formula (1-1), the compound represented by following formula (1-2) and following formula (1-3) forms.

[changing 1]

(in formula (1-1), A ¹and A ³be separately hydrogen atom or 1 valency organic radical, A ²and A ⁴be separately singly-bound or divalent organic radical; B ¹and B ²be separately singly-bound or divalent organic radical; Wherein, at B ¹when for singly-bound, A ¹and A ²at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ¹when for divalent organic radical, A ¹, A ²and B ¹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; B ²when for singly-bound, A ³and A ⁴at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ²when for divalent organic radical, A ³, A ⁴and B ²in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ¹¹for comprising at least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of the group that-(R is hydrogen atom or 1 valency organic radical) replaces; Wherein, at L ¹¹when there is alkane two base of carbon number 1 ~ 5, A ¹and A ³at least any one is hydrogen atom, or B ¹and B ²at least any one is divalent organic radical)

[changing 2]

(in formula (1-2), L ¹²for comprising the divalent base of the divalent chain alkyl of carbon number more than 6; A ¹, A ², A ³, A ⁴, B ¹and B ²be and described formula (1-1) identical meanings; Wherein, at L ¹²when alkane two base for carbon number 6 ~ 10, A ¹and A ³at least any one is 1 valency organic radical, or B ¹and B ²at least any one is divalent organic radical)

[changing 3]

(in formula (1-3), A ⁷for hydrogen atom or 1 valency organic radical, A ⁸and A ⁹be separately singly-bound or divalent organic radical; Wherein, A ⁷, A ⁸and A ⁹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ⁴for described structure (b1), L ⁵for singly-bound or divalent organic radical)

[effect of invention]

Utilize containing the liquid crystal aligning agent of described polymkeric substance (P) as component of polymer, the display inequality that can obtain sealing agent periphery is few, and balance has the liquid crystal display device of the various characteristics such as low image retention, high-contrast and thermotolerance well concurrently.In addition, the good liquid crystal orientation film of transmissivity can be obtained.In addition, and then described polymkeric substance (P) is to the favorable solubility of solvent, and the storage stability of liquid crystal aligning agent is also good.

Accompanying drawing explanation

Fig. 1 is the schematic configuration diagram of FFS type liquid crystal cells.

The floor map of the top electrodes that Fig. 2 (a) and Fig. 2 (b) uses when being and utilizing optical alignment method to manufacture liquid crystal display device.The vertical view that Fig. 2 (a) is top electrodes, the magnified partial view that Fig. 2 (b) is top electrodes.

Fig. 3 is the figure of the drive electrode representing 4 systems.

The floor map of the top electrodes that Fig. 4 (a) and Fig. 4 (b) uses when being and manufacturing liquid crystal display device by friction treatment.The vertical view that Fig. 4 (a) is top electrodes, the magnified partial view that Fig. 4 (b) is top electrodes.

The explanation of symbol

10: liquid crystal display device

11a, 11b: glass substrate

12: liquid crystal orientation film

13: top electrodes

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

Embodiment

Below, each composition contained in liquid crystal aligning agent of the present invention and other compositions of optionally and arbitrarily allocating are described.

< polymkeric substance (P) >

Liquid crystal aligning agent of the present invention comprises the polymkeric substance (P) that obtained for reacting by least one compound (C ') in the cohort selecting free compound (C) and compound (C1) to form as component of polymer, described compound (C) has described structure (a) and described structure (b), and described compound (C1) has described structure (a) and described structure (b1) and on aromatic series cyclic group in described structure (a), non-bond has the reactive base participating in polymerization.In addition, below, by described structure (a) also referred to as " aromatic amine structure (a) ", by described structure (b) also referred to as " chain-like structure (b) ".

Compound (C)

(aromatic amine structure (a))

Aromatic amine structure (a) that described compound (C) has is the structure that 2 or 3 aromatic ring bases are binding on same nitrogen-atoms.As long as aromatic series cyclic group removes the group of hydrogen atom in the loop section of aromatic ring, specifically, include, for example from aromatic hydrocarbons rings such as phenyl ring, toluene ring, naphthalene nucleus, anthracene nucleus, in the loop section in the aromatic rings such as heteroaromatic such as pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, remove the group etc. of hydrogen atom.In these groups, with regard to the viewpoint good with the affinity of liquid crystal, be preferably phenyl ring.

The quantity of intramolecular aromatic amine structure (a) of described compound (C) is more than 1 or 2, with regard to improving the viewpoint of the performance that residual DC relaxes, is preferably more than 2.In addition, with regard to the transmissivity of liquid crystal orientation film and the viewpoint of structure adaptability, be more preferably 2 ~ 4, be especially preferably 2 or 3.

(chain-like structure (b))

The divalent chain alkyl that the chain-like structure (b) that described compound (C) has is carbon number more than 6, or by least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂the group that-(R is ammonia atom or 1 valency organic radical) replaces.

Divalent chain alkyl in described chain-like structure (b), to refer on main chain not containing ring texture, but the alkyl be only made up of the chain-like structure of straight-chain or branch-like.As long as the divalent chain alkyl in described chain-like structure (b) is carbon number more than 6, its concrete example include, for example: dihexyl, heptan two base, Xin Erji, the ninth of the ten Heavenly Stems two base, the last of the ten Heavenly stems two base, dodecane two base, the tetradecane two base, the carbon number 6 ~ 30 such as eicosane two base saturated shape alkyl; At least 1 C-C of the saturated shape alkyl of carbon number 6 ~ 30 is the unsaturated alkyl etc. of the carbon number 6 ~ 30 of double bond or triple bond.These alkyl can be straight-chain, also can be branch-like, are preferably straight-chain.

When the divalent chain alkyl that described chain-like structure (b) is carbon number more than 6, the carbon number of this chain alkyl is preferably 6 ~ 30, is more preferably 6 ~ 20.

With-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH by least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 described chain-like structure (b) ₃) ₂when the group that-(R is hydrogen atom or 1 valency organic radical) replaces, the quantity of this replacement can be 1, also can be multiple, suitably can set according to carbon number.By methylene radical, the carbon number be substituted by before described functional group is preferably 6 ~ 30, is more preferably 7 ~ 20.

The 1 valency organic radical of described R include, for example: the chain alkyl of the carbon numbers such as alkyl or alkenyl 1 ~ 5, and the group between the C-C of the chain alkyl of carbon number 1 ~ 5 with-O-,-CO-etc., amino protecting group etc.The concrete example of amino protecting group include, for example: tert-butoxycarbonyl, benzyloxycarbonyl, 1; 1-dimethyl-2-halogenated ethyl oxygen base carbonyl, 1; 1-dimethyl-2-cyano ethyl oxygen base carbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2-(TMS) ethoxy carbonyl etc., be preferably tert-butoxycarbonyl.

The quantity of the intramolecular described chain-like structure (b) of described compound (C) can be 1, also can be more than 2.Be preferably 1 ~ 5, be more preferably 1 ~ 3.In addition, compound (C) is preferably at the main chain of compound (C), specifically for carbochain the longest in compound (when having functional group for comprising the most Long carbon chain of this functional group) has aromatic amine structure (a) and chain-like structure (b).

With regard to reducing the aspect of the concave-convex surface of liquid crystal orientation film, the molecular weight of described compound (C) is preferably 1, less than 200.Therefore, preferably the quantity of described aromatic amine structure (a) and the chain length of described chain-like structure (b) is set in the mode of molecular weight in described scope of compound (C).Being more preferably molecular weight is 1, less than 000, is especially preferably less than 800.

Compound (C1)

Described compound (C1) has described aromatic amine structure (a) and described structure (b1).Wherein, in compound (C1), in the aromatic series cyclic group in aromatic amine structure (a), non-bond has the reactive base participating in polymerization.Described reactive base is different according to the main framing of polymkeric substance (P), such as when the main framing of polymkeric substance (P) be polyamic acid or polyimide, described reactive base is that anhydride group or one-level are amino, in the case of polyesters, described reactive base is hydroxyl or carboxyl, when polymeric amide, described reactive base is that carboxyl or one-level are amino.

The explanation of the aromatic ring of aromatic amine structure (a) that compound (C1) has can the explanation of application compound (C).Aromatic amine structure (a) in a part of compound (C1) is preferably 1.

The structure (b1) that compound (C1) has for be selected from by the divalent chain alkyl of carbon number 1 ~ 5, by least 1 methylene radical in this chain alkyl with-O-,-S-,-CO-,-NR ³-,-NR ³cO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of-replacement ,-O-,-S-,-CO-,-NR ³cO-,-COO-,-COS-and-Si (CH ₃) ₂-(R ³for hydrogen atom or 1 valency organic radical) structure in the cohort that forms.In addition, compound (C1) only can have a kind in these structures in molecule, also can have two or more in molecule.

The concrete example of the divalent chain alkyl of the carbon number 1 ~ 5 in described structure (b1) include, for example: methylene radical, ethylidene, glyceryl, Ding Erji, penta 2 bases, vinylidene, propylene two base, butylene two base, amylene two base etc.These alkyl can be straight-chain, also can be branch-like, are preferably straight-chain.

Be with-O-,-S-,-CO-,-NR by least 1 methylene radical in the divalent chain alkyl of carbon number 1 ~ 5 in described structure (b1) ³-,-NR ³cO-,-COO-,-COS-or-Si (CH ₃) ₂-replace divalent base when, the quantity of this replacement can be 1, also can be multiple, suitably can set according to carbon number.R ³the explanation of 1 valency organic radical can the explanation of R of application compound (C).

The quantity of the intramolecular described structure (b1) of compound (C1) can be 1, also can be more than 2.Be preferably more than 2, be particularly preferably 2.The molecular weight of compound (C1) can apply the explanation of described compound (C).

The main framing of described polymkeric substance (P) include, for example the skeleton comprising polyamic acid, polyimide, poly amic acid ester, polyester, polymeric amide, polysiloxane, organopolysiloxane, derivatived cellulose, polyacetal derivative, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate derivative etc.Described polymkeric substance (P) can according to the purposes etc. of liquid crystal aligning agent, and suitably the one kind or two or more of polymkeric substance be selected from these uses.In addition, (methyl) acrylate refers to and comprises acrylate and methacrylic ester.Polymkeric substance (P) can have described aromatic amine structure (a) and described chain-like structure (b) or structure (b1) in any one of the main chain of polymkeric substance and side chain, preferably on the main chain of polymkeric substance, has described structure.

Wherein, the main framing of polymkeric substance (P) is preferably selected from least one in the cohort be made up of polyamic acid, polyimide and poly amic acid ester, is more preferably at least one in the cohort being selected from and being made up of the polyamic acid on main chain with described aromatic amine structure (a) and described chain-like structure (b) or structure (b1), polyimide and poly amic acid ester.The polymkeric substance that described compound (C ') preferably obtains for monomer by described polymkeric substance (P).

Herein, " main chain " of the so-called polymkeric substance in the present invention, refers in polymkeric substance " doing " part comprising the longest atomchain.In addition, allow that this " is done " part and comprises ring structure.Therefore, so-called " on the main chain of polymkeric substance, having described aromatic amine structure (a) and described chain-like structure (b) or structure (b1) ", refers to a part for these Structure composing main chains.Wherein, in polymkeric substance (P), do not get rid of described aromatic amine structure (a), described chain-like structure (b) and structure (b1) and be present in part beyond main chain, such as, situation on side chain (part of " doing " top set of autohemagglutination compound) yet.

[polyamic acid (P)]

When described polymkeric substance (P) is for polyamic acid (hereinafter also referred to " polyamic acid (P) "), such as, obtain by making tetracarboxylic dianhydride and diamines carry out reacting.

(tetracarboxylic dianhydride)

Tetracarboxylic dianhydride for the synthesis of described polyamic acid (P) include, for example: aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As the concrete example of these tetracarboxylic dianhydrides, aliphatics tetracarboxylic dianhydride include, for example: butane tetracarboxylic acid dianhydride etc.;

Ester ring type tetracarboxylic dianhydride include, for example: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 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-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norbornane-2:3, 5:6-dianhydride, dicyclo [3.3.0] octane-2, 4, 6, 8-tetracarboxylic acid 2:4, 6:8-dianhydride, dicyclo [2.2.1] heptane-2, 3, 5, 6-tetracarboxylic acid 2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, the pungent-7-alkene-2 of dicyclo [2.2.2], 3,5,6-tetracarboxylic dianhydride, ethylenediamine tetraacetic acid (EDTA) dianhydride, pentamethylene tetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride ester) (ethylene glycol bis (anhydrotrimellitate)), two (trimellitic anhydride ester) (1,3-propyleneglycol bis (anhydrotrimellitate)) of 1,3-PD etc.,

Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride etc.; In addition, the tetracarboxylic dianhydride recorded in Japanese Patent Laid-Open 2010-97188 publication can be used.In addition, 1 of these compounds kind can be used alone or two or more be combinationally used by the tetracarboxylic dianhydride for the synthesis of polyamic acid.

Just can make liquid crystal aligning and to regard to the aspect of the favorable solubility of solvent, tetracarboxylic dianhydride for the synthesis of described polyamic acid (P) preferably comprises and is selected from by 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-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxyl norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, dicyclo [3.3.0] octane-2,4, at least one compound (hereinafter also referred to " specific tetracarboxylic dianhydride ") in the cohort that 6,8-tetracarboxylic dianhydride, ethylenediamine tetraacetic acid (EDTA) dianhydride, pentamethylene tetracarboxylic dianhydride, 1,3-PD two (trimellitic anhydride ester) and pyromellitic acid anhydride form.Relative to the total amount of the tetracarboxylic dianhydride for the synthesis of polyamic acid, the usage quantity of this specific tetracarboxylic dianhydride is preferably set to more than 5 % by mole, is more preferably and is set to more than 10 % by mole, is particularly preferably and is set to more than 20 % by mole.

(diamines)

At least one compound (C ') in the cohort being selected from and being made up of the diamines with described aromatic amine structure (a) and described chain-like structure (b) (hereinafter also referred to " diamines (C) ") and the compound (C1) with described structure (a1) and described structure (b1) is preferably comprised for the synthesis of the diamines of described polyamic acid (P).

Diamines (C)

Diamines (C) preferably has the structure that described aromatic amine structure (a) and described chain-like structure (b) can be directed in the main chain of polymkeric substance (P), specifically, the compound represented by following formula (1) is preferably.

[changing 4]

(in formula (1), A ¹and A ³be separately hydrogen atom or 1 valency organic radical, A ²and A ⁴be separately singly-bound or divalent organic radical; B ¹and B ²be separately singly-bound or divalent organic radical; Wherein, at B ¹when for singly-bound, A ¹and A ²at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ¹when for divalent organic radical, A ¹, A ²and B ¹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; At B ²when for singly-bound, A ³and A ⁴at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ²when for divalent organic radical, A ³, A ⁴and B ²in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ¹for comprising the divalent base of described structure (b))

About described formula (1), A ¹and A ³in 1 valency organic radical include, for example: 1 valency alkyl, imports the 1 valency base of the functional group such as-O-,-COO-,-CO-,-NHCO-,-S-,-NH-between the C-C in 1 valency alkyl, and the protecting group etc. of amino.In addition, A ¹and A ³in, can replacing through halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.) or hydroxyl etc. with the hydrogen atom of carbon atom bond of described alkyl.The concrete example of amino protecting group can enumerate group illustrated in the explanation of the R of chain-like structure (b).Be preferably tert-butoxycarbonyl.

Described alkyl can enumerate chain alkyl, ester ring type alkyl and aromatic hydrocarbyl.Herein, in this specification sheets, so-called " chain alkyl " is described above.So-called " ester ring type alkyl ", refers to that the structure only comprising ester ring type hydrocarbon is as ring structure, and does not comprise the alkyl of aromatic ring structure.Wherein, do not need only to be made up of the structure of ester ring type hydrocarbon, be also contained in the alkyl in its part with chain-like structure.In addition, so-called " aromatic hydrocarbyl ", refers to and comprises the alkyl of aromatic ring structure as ring structure.Wherein, do not need only to be made up of aromatic ring structure, in its part, comprise the structure of chain-like structure or ester ring type hydrocarbon yet.

As A ¹and A ³in the concrete example of 1 valency alkyl, chain alkyl include, for example: the alkyl of the carbon numbers 1 ~ 30 such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, eicosyl; The thiazolinyl of the carbon numbers 2 ~ 30 such as vinyl, propenyl, butenyl; The alkynyl etc. of the carbon number such as ethynyl, proyl 2 ~ 30; These alkyl can be straight-chain, also can be branch-like.In addition, ester ring type alkyl include, for example: cyclopentyl, cyclohexyl, norcamphyl, adamantyl etc.; Aromatic hydrocarbyl include, for example: phenyl, tolyl, benzyl, styroyl etc.

A ², A ⁴, B ¹and B ²in divalent organic radical include, for example: divalent alkyl, the divalent base etc. of the functional groups such as-O-,-COO-,-CO-,-NHCO-,-S-,-NH-is imported, can replacing through halogen atom or hydroxyl etc. with the hydrogen atom of carbon atom bond of these each groups between the C-C in divalent alkyl.The concrete example of divalent alkyl can enumerate the group etc. removing 1 hydrogen atom in each group illustrated in described 1 valency alkyl.In addition, in the compound represented by described formula (1), the structure of the encirclement nitrogen-atoms in described formula (1) is corresponding with described aromatic amine structure (a).

B ¹and B ²being preferably at least one is singly-bound, is more preferably B ¹and B ²be singly-bound.

L ¹for comprising the divalent base of described chain-like structure (b).L ¹preferred concrete example include, for example: the group etc. represented by following formula (2).

[changing 5]

(in formula (2), L ²and L ³it is separately described structure (b); The divalent base of Q represented by following formula (3) or formula (4); N is the integer of 0 ~ 4; " * " represents associative key)

[changing 6]

(in formula (3), A ⁵for hydrogen atom or 1 valency organic radical; R ¹and R ²for substituting group, each other can be identical, also can be different; " * " represents associative key)

[changing 7]

(in formula (4), A ⁶for hydrogen atom or 1 valency organic radical; " * " represents associative key)

In described formula (3), formula (4), A ⁵and A ⁶1 valency organic radical can apply A ¹and A ³the explanation of 1 valency organic radical.N in described formula (2) is preferably 0 or 1.

The concrete example of the group represented by described formula (2) include, for example the group etc. represented by following formula (2-1) ~ formula (2-25) difference.

[changing 8]

[changing 9]

(in formula, " * " represents associative key)

The preferred concrete example of the compound represented by described formula (1) include, for example the compound represented by following formula (1-1) and the compound etc. represented by following formula (1-2).

[changing 10]

(in formula (1-1), L ¹¹for comprising at least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of the group that-(R is hydrogen atom or 1 valency organic radical) replaces; A ¹, A ², A ³, A ⁴, B ¹and B ²be and described formula (1) identical meanings; Wherein, at L ¹¹when there is alkane two base of carbon number 1 ~ 5, A ¹and A ³at least any one is hydrogen atom, or B ¹and B ²at least any one is divalent organic radical)

[changing 11]

(in formula (1-2), L ¹²for comprising the divalent base of the divalent chain alkyl of carbon number more than 6; A ¹, A ², A ³, A ⁴, B ¹and B ²be and described formula (1) identical meanings)

L in described formula (1-1) ¹¹only can have 1 by least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂-the group that replaces, also can have multiple.L ¹¹preferred concrete example can enumerate group (wherein, L represented by described formula (2) ²and L ³for by least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂-the group that replaces) etc.

At L ¹¹when comprising alkane two base of carbon number 1 ~ 5, A ¹and A ³at least one be hydrogen atom, be preferably A ¹and A ³be hydrogen atom.

L in described formula (1-2) ¹²only can have the divalent chain alkyl of 1 carbon number more than 6, also can have multiple.L ¹²preferred concrete example can enumerate group (wherein, L represented by described formula (2) ²and L ³divalent chain alkyl for carbon number more than 6) etc.

At L ¹²when alkane two base had is carbon number 6 ~ 10, the compound represented by described formula (1-2) is preferably A ¹and A ³at least any one is 1 valency organic radical, or B ¹and B ²at least any one is divalent organic radical.A in described formula (1-1) ¹and A ³when for hydrogen atom, L ¹²be preferably the L of the group represented by described formula (2) ²and L ³for the divalent chain alkyl of carbon number more than 7, be more preferably the group of the divalent chain alkyl of carbon number more than 11.

The preferred concrete example of described diamines (C) include, for example following formula (DA-1) ~ formula (DA-10) and the compound etc. represented by formula (DA-41) difference.In addition, described diamines (C) can be used alone a kind or two or more combinationally used.

[changing 12]

[changing 13]

(in formula, Ph represents phenyl)

Diamines (C1)

Diamines (C1) preferably has the structure that described aromatic amine structure (a) and described structure (b1) can be directed in the main chain of polymkeric substance (P), specifically, the compound represented by following formula (1-3) is preferably.

[changing 14]

About described formula (1-3), A ⁷1 valency organic radical can apply the A of described formula (1) ¹and A ³the explanation of 1 valency organic radical.A ⁸and A ⁹divalent organic radical can apply the A of described formula (1) ²and A ⁴explanation.L ⁵divalent organic radical include, for example: the divalent chain alkyl of carbon number 1 ~ 20, by least 1 methylene radical in this chain alkyl with-O-,-S-,-CO-,-NR ⁴-,-NR ⁴cO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of-replacement ,-O-,-S-,-CO-,-NR ⁴cO-,-COO-,-COS-and-Si (CH ₃) ₂-(R ⁴for hydrogen atom or 1 valency organic radical) etc.In these organic radicals, L ⁵be preferably structure (b1).

The preferred concrete example of described diamines (C1) include, for example the compound etc. represented by following formula (DA-22) ~ formula (DA-40) difference.In addition, described diamines (C1) can be used alone a kind or two or more combinationally used.

[changing 15]

[changing 16]

The diamines used time synthesizing polyamides acid (P) can be only described diamines (C '), also can together with diamines (C ') and with other diamines beyond described.

Other diamines spendable include, for example herein: 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.;

Aromatic diamine include, for example: O-Phenylene Diamine, mphenylenediamine, Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 4,4 '-diamino-diphenyl amine, two (4-amino-benzene oxygen) heptane of 1,7-, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 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) biphenyl, DAP, 2,4-di-amino-pyrimidine, 3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecane acyloxy-2,4-diaminobenzene, tetradecane acyloxy-2,4-diaminobenzene, pentadecane acyloxy-2,4-diaminobenzene, n-Hexadecane acyloxy-2,4-diaminobenzene, octadecane acyloxy-2,4-diaminobenzene, dodecane acyloxy-2,5-diaminobenzene, tetradecane acyloxy-2,5-diaminobenzene, pentadecane acyloxy-2,5-diaminobenzene, n-Hexadecane acyloxy-2,5-diaminobenzene, octadecane acyloxy-2,5-diaminobenzene, cholestane base oxygen base-3,5-diaminobenzene, cholesteryl oxygen base-3,5-diaminobenzene, cholestane base oxygen base-2,4-diaminobenzene, cholesteryl oxygen base-2,4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, two (the 4-amino benzoyl oxygen base) cholestane of 3,6-, two (4-amino-benzene oxygen) cholestane of 3,6-, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethylbenzoyl oxygen base) cyclohexyl-3,5-diaminobenzoic acid ester, 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-, 2,4-diamino-N, N-diallyl aniline, 4-aminobenzyl amine, 3-aminobenzyl amine, 1-(2,4-diamino-phenyl) piperazine-4-carboxylic acid, two (N-(4-aminophenyl) piperidyl) propane of 1,3-, alpha-amino group-omega-amino-phenylalkylene, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethylammonium-1H-indenes-6-amine, 4-aminophenyl-4 '-Aminobenzoate, 4,4 '-[4,4 '-propane-1,3-bis-base two (piperidines-Isosorbide-5-Nitrae-two base)] pentanoic, 4-(4-amino-benzene oxygen carbonyl)-1-(4-aminophenyl) piperidines, following formula (DA-18)

[changing 17]

Represented compound and following formula (D-1)

[changing 18]

(in formula (D-1), X ⁱand X ^iIbe separately singly-bound ,-O-, *-COO-or *-OCO-(* represents the associative key with the phenyl ring bond in formula), R ¹for 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 be 0 simultaneously)

Represented compound etc.;

Diamino organo-siloxane include, for example: two (3-aminopropyl)-tetramethyl disiloxanes of 1,3-etc., in addition, can use the diamines recorded in Japanese Patent Laid-Open 2010-97188 publication.

"-X in described formula (D-1) ⁱ-(R ⁱ-X ^iI) _d-" represented by divalent base be preferably alkane two base of carbon number 1 ~ 3, *-O-, *-COO-or *-O-C ₂h ₄-O-(wherein, with associative key and the diamino-phenyl bond of " * ").Base "-C _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.

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 19]

In addition, 1 of these compounds kind can be used alone or suitably select two or more to use by described other diamines for the synthesis of polyamic acid.

Diamines for the synthesis of polyamic acid of the present invention (P) is preferably the total amount relative to the diamines used in synthesis, and the usage ratio of described diamines (C ') is set to more than 0.5 % by mole.If be less than 0.5 % by mole, then there is the tendency that fully cannot obtain effect of the present invention.Be more preferably more than 2 % by mole, be especially preferably more than 5 % by mole, be particularly preferably more than 10 % by mole.In addition, relative to the total amount of the diamines used in synthesis, the upper limit of the usage ratio of described diamines (C ') at random can set in the scope below 100 % by mole.When realizing improvement effect (such as printing, voltage retention, the liquid crystal aligning etc.) brought because adding other diamines, preferably the usage ratio of described diamines (C ') is set to less than 95 % by mole.

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, the polymkeric substance contained (P) can be set to the polymkeric substance having and can give the group (hereinafter also referred to " tilt angle expression power base ") of tilt angle expressive ability to film at least partially in this liquid crystal aligning agent.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.

In order to obtain the polyamic acid (P) with tilt angle expression power base, with regard to the aspect of the importing easness of tilt angle expression power base, carry out preferably by the polymerization comprising the diamines with tilt angle expression power base in monomer composition.Specifically, by using the diamines with tilt angle expression power base to synthesize as other diamines.

When synthesizing polyamides acid (P), use has the diamines of tilt angle expression power base, with regard to fully showing the viewpoint of high tilt angle characteristic, relative to the whole diamines used in synthesis, the usage quantity of described diamines is preferably set to more than 5 % by mole, is more preferably and is set to more than 10 % by mole.

Utilizing optical alignment method, when giving liquid crystal aligning ability to using the film that makes of liquid crystal aligning agent of the present invention, polymkeric substance (P) contained in this liquid crystal aligning agent can be set to the polymkeric substance with light orientation structure at least partially.Herein, so-called light orientation structure is the concept of two comprising light orientation base and 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 etc. containing polyimide of polyimide or derivatives thereof as basic framework.

Such as, when there is light orientation structure as the polyamic acid of described polymkeric substance (P), polyimide and poly amic acid ester, preferably there is decomposition type light orientation section as this light orientation structure, specifically preferably there is the polymkeric substance of dicyclo [2.2.2] octene skeleton or tetramethylene skeleton.By having specific skeleton as above, the liquid crystal aligning of film can be made better.Such as, there is the polyamic acid (P) of dicyclo [2.2.2] octene skeleton or tetramethylene skeleton by comprising the pungent-7-alkene-2 of dicyclo [2.2.2], 3, in 5,6-tetracarboxylic dianhydride and tetramethylene tetracarboxylic dianhydride at least any one tetracarboxylic dianhydride, with comprise described diamines (C ') diamines reaction and obtain.

[molecular weight regulator]

Time synthesizing polyamides acid (P), also can be described above, use suitable molecular weight regulator to synthesize the polymkeric substance of end modified type with tetracarboxylic dianhydride and diamines simultaneously.By being set to the polymkeric substance of described end modified type, the coating (printing) of liquid crystal aligning agent can be improved further when not undermining effect of the present invention.

Molecular weight regulator include, for example: sour single acid anhydride, monoamine compound, monoisocyanate compound etc.As the concrete example of these compounds, sour single acid anhydride include, for example: MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl Succinic anhydried, dodecyl Succinic anhydried, n-tetradecane base Succinic anhydried, n-hexadecyl Succinic anhydried etc.; Monoamine compound include, for example: aniline, cyclo-hexylamine, n-butylamine, n-pentyl amine, n-hexyl amine, n-heptyl amine, n-octylamine etc.; Monoisocyanate compound include, for example: phenyl isocyanate, isocyanic acid naphthyl ester etc.

Relative to total 100 weight part of used tetracarboxylic dianhydride and diamines, the usage ratio of molecular weight regulator is preferably set to below 20 weight parts, is more preferably and is set to below 10 weight parts.

Described diamines (C) and diamines (C1) are by synthesizing appropriately combined for vitochemical well-established law.As an example of described method, such as about the compound represented by described formula (1), method can be listed below: the one-level in synthesis replacement formula is amino and have the dinitro intermediate of nitro, then, use suitable reduction system that the nitro of the dinitro intermediate of gained is carried out amination.

The method of synthesizing described dinitro intermediate suitably can be selected according to the compound as target.As an example of described method, if enumerate the compound represented by described formula (1), include, for example following methods: make that there is corresponding A ¹, A ²and L ¹secondary amino compounds and halonitrobenzene carry out the method for reacting; Make that there is corresponding A ¹, A ²and L ¹halogenide and the method for carrying out reacting containing the secondary amino compounds of nitrophenyl; Make to have the carboxylic acid of corresponding aminophenyl and nitro, with there is corresponding L ¹glycol carry out the method for reacting; Make that there is corresponding A ¹, A ²and L ¹diamine compound, and there is corresponding B ¹halonitrobenzene carry out the method for reacting; Make to have the compound of the hydroxyl of corresponding aminophenyl and nitro, with there is corresponding L ¹halogenide carry out the method etc. of reacting.

Reaction in order to obtain described nitro intermediate is preferably carried out in organic solvent.Herein, as long as organic solvent is not to reacting the solvent impacted, include, for example: methyl alcohol, ethanol, tetrahydrofuran (THF), toluene, dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE, METHYLPYRROLIDONE etc.In addition, this reaction also can optionally be carried out in the presence of a catalyst.

The reduction reaction of described dinitro intermediate is preferably in organic solvent, uses the catalyzer such as such as palladium carbon, platinum oxide, zinc, iron, tin, nickel to implement.Organic solvent as used herein include, for example: ethyl acetate, toluene, tetrahydrofuran (THF), alcohol system etc.Wherein, the synthesis program of diamines (C) and diamines (C1) is not limited to described method.

[synthesis of polyamic acid (P)]

The tetracarboxylic dianhydride provide the building-up reactions of polyamic acid of the present invention (P) and the usage ratio of diamines are preferably amino 1 equivalent relative to diamines, 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.

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.

Herein, organic solvent include, for example: aprotic polar solvent, phenol series solvent, alcohol, ketone, ester, ether, halon, hydrocarbon etc.As the concrete example of these organic solvents, aprotic polar solvent include, for example: METHYLPYRROLIDONE, N,N-dimethylacetamide, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.; Phenol series solvent include, for example: phenol, meta-cresol, xylenol, halogenation phenol etc.;

Alcohol include, for example: methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, BDO, triethylene glycol, ethylene glycol monomethyl ether etc.; Ketone include, for example: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.; Described ester include, for example: ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methyl methoxypropionate, ethyl ethoxy-c acid esters, diethyl oxalate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate etc.; Ether include, for example: diethyl ether, isoamyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-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, tetrahydrofuran (THF) etc.; Halon include, for example: methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.; Described hydrocarbon include, for example: hexane, heptane, octane, benzene,toluene,xylene 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 series solvent, or be selected from more than one and more than one the mixture be selected from the cohort (organic solvent of the second cohort) that is made up of alcohol, ketone, ester, ether, halon and hydrocarbon in the organic solvent of the first cohort.When rear kind, 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.The total amount (β) that the usage quantity (α) of organic solvent is preferably set to tetracarboxylic dianhydride and diamines relative to reaction soln total amount (alpha+beta) and become 0.1 % by weight ~ 50 % by weight amount.

As previously discussed, the reaction soln dissolved by polyamic acid (P) is obtained.This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, also can reoffer after polyamic acid (P) contained in reaction soln segregation to the preparation of liquid crystal aligning agent, or also can reoffer after polyamic acid (P) purifying of segregation to the preparation of liquid crystal aligning agent.When making polyimide when polyamic acid (P) is carried out dehydration closed-loop, described reaction soln directly can be supplied to dehydration closed-loop reaction, also can reoffer after polyamic acid (P) contained in reaction soln segregation to dehydration closed-loop reaction, or also can react reoffering after polyamic acid (P) purifying of segregation to dehydration closed-loop.The segregation of polyamic acid and purifying can carry out according to known method.

[poly amic acid ester (P)]

Poly amic acid ester (hereinafter also referred to poly amic acid ester (P)) as described polymkeric substance (P) such as can utilize following methods to obtain: compound, the halogenide of the polyamic acid (P) that [I] obtains by making to utilize described building-up reactions and hydroxyl, carry out reacting the method for synthesizing containing the compound etc. of epoxy group(ing); [II] makes tetracarboxylic acid diester and diamines carry out the method for reacting; And [III] makes tetracarboxylic acid diester dihalide and diamines carry out the method for reacting.

In addition, in this specification sheets so-called " tetracarboxylic acid diester ", to refer in 4 carboxyls that tetracarboxylic acid has 2 esterified, and all the other 2 is the compound of carboxyl.So-called " tetracarboxylic acid diester dihalide ", to refer in 4 carboxyls that tetracarboxylic acid has 2 esterified, and all the other 2 compounds be halogenated.

Herein, the compound of the hydroxyl used in method [I] include, for example: the alcohols such as methyl alcohol, ethanol, propyl alcohol; The phenols such as phenol, cresols etc.In addition, halogenide include, for example: methyl bromide, bromic ether, bromo-octadecane, methyl chloride, chlorooctadecane, 1,1,1-tri-fluoro-2-iodoethane etc., the compound containing epoxy group(ing) include, for example propylene oxide etc.The tetracarboxylic acid diester used in method [II] obtains by using described alcohols that tetracarboxylic dianhydride is carried out open loop.In addition, the tetracarboxylic acid diester dihalide used in method [III] obtains by making the suitable chlorizating agent such as the tetracarboxylic acid diester that obtains in this way and thionyl chloride carry out reacting.Method [II] and the middle diamines used of method [III] preferably comprise described diamines (C '), also optionally can use other diamines described.In addition, poly amic acid ester (P) can only have amic acid esters structure, also can be amido acid structure and amic acid esters structure and the partial esterification thing deposited.

[polyimide (P)]

Polyimide (hereinafter also referred to polyimide (P)) as described polymkeric substance (P) carries out dehydration closed-loop by the polyamic acid (P) that will such as synthesize in this way, and in addition imidization obtains.

Described polyimide (P) can be the complete imide compound of the amido acid structure had as the polyamic acid (P) 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.The imide rate of polyimide contained in liquid crystal aligning agent of the present invention is preferably more than 30%, is more preferably 40% ~ 99%, is especially preferably 50% ~ 99%.This imide rate is the total of amido acid number of structures relative to polyimide and imide ring number of structures, represents the ratio shared by imide ring number of structures 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 utilizing rear kind is preferably.

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.Dehydration closed-loop reaction in use organic solvent can enumerate as the synthesis of polyamic acid and illustrative organic solvent.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.

Acquisition described above contains the reaction soln of polyimide (P).This reaction soln directly can be supplied to the preparation of liquid crystal aligning agent, 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 emanated, or also can reoffer after the polyimide purifying of segregation to the preparation of liquid crystal aligning agent.These purification process can be carried out according to known method.In addition, polyimide (P) also can pass through the imidization of poly amic acid ester (P) and obtain.

The polyamic acid as polymkeric substance (P) 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 be to the concentration using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance to prepare be 15 % by weight polymers soln, use E type rotational viscosimeter to measure at 25 DEG C and the value that obtains.

Described polyamic acid, poly amic acid ester and polyimide utilize gel permeation chromatography (Gel PermeationChromatography, 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, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw and the severals molecular-weight average (Mn) of polystyrene conversion utilizing GPC to measure preferably less than 15, is more preferably less than 10.By in described molecular weight ranges, good orientation and the stability of liquid crystal display device can be guaranteed.

Other compositions of < >

Liquid crystal aligning agent of the present invention, as mentioned above containing polymkeric substance (P), also optionally can contain other compositions.Other compositions described include, for example: have the compound (hereinafter referred to as " compound containing epoxy group(ing) ") of at least one epoxy group(ing), functional silanes compound, metal chelate compound, hardening accelerator, tensio-active agent etc. in other polymkeric substance beyond described polymkeric substance (P), molecule.

[other polymkeric substance]

Other polymkeric substance described can be used for improving solution properties or electrical characteristic.Other polymkeric substance described include, for example the polymkeric substance not using described compound (C ') and acquisition, are not particularly limited its main framing.Specifically, include, for example, on main framing, there is the polymkeric substance etc. such as polyamic acid, polyimide, poly amic acid ester, organopolysiloxane, polyester, polymeric amide, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate.

When other polymkeric substance 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 other polymkeric substance described is preferably set to below 50 weight parts, be more preferably and be set to 0.1 weight part ~ 40 weight part, be especially preferably set to below 0.1 weight part ~ 30 weight part.

In addition, utilizing optical alignment method, when the film formed gives liquid crystal aligning ability, the polymkeric substance with light orientation structure can used as other polymkeric substance described to using liquid crystal aligning agent of the present invention.Such as when the liquid crystal aligning agent of phase retardation film, preferably can use and there is the polymkeric substance of light orientation base as light orientation structure, specifically can enumerate the polymkeric substance etc. being imported with the group with cinnamic acid structure (styracin or derivatives thereof).Wherein, with regard to the easy aspect to lead-in light orientation base in polymkeric substance, the organopolysiloxane with cinnamic acid structure can preferably be used.

In addition, the polymkeric substance with light orientation base can utilize existing known method to synthesize.Such as, as other polymkeric substance the organopolysiloxane with light orientation base by make to have epoxy group(ing) organopolysiloxane, with there is the carboxylic acid of light orientation base, be preferably in the organic solvents such as ether, ester, ketone, and carry out reacting synthesizing under the existence of the catalyzer such as quarternary ammonium salt.

When coming when utilizing optical alignment method to give liquid crystal aligning ability to film, relative to the total amount of the polymkeric substance for the preparation of liquid crystal aligning agent of the present invention, the usage ratio (being their total amount when polymkeric substance (P) and other polymkeric substance have light orientation structure) with the polymkeric substance of described smooth orientation structure is preferably set to more than 3 % by weight, be more preferably and be set to 5 % by weight ~ 100 % by weight, be especially preferably set to 10 % by weight ~ 100 % by weight.

[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.The described compound containing epoxy group(ing) include, for example following compound as preferably: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidylether, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-aminomethyl cyclohexane, N, N-diglycidyl-cyclo-hexylamine 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 compounds containing epoxy group(ing) are made an addition in liquid crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in liquid crystal aligning agent, the allotment ratio of the described compound containing epoxy group(ing) is preferably 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 improving 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, 10-Trimethoxy silane base-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-Trimethoxy silane base-3,6-diaza nonyl acetic ester, 9-Trimethoxy silane base-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-phenyl-3-TSL 8330, glycidoxypropyl methyltrimethoxy silane, 2-glycidoxypropyl ethyl trimethoxy silane, 3-glycidoxypropyltrimewasxysilane etc.

When 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.

[metal chelate compound]

Described metal chelate compound is for when the component of polymer of liquid crystal aligning agent has epoxy construction, guarantees the physical strength of the film formed by subzero treatment and is contained in liquid crystal aligning agent (particularly the liquid crystal aligning agent of phase retardation film).This metal chelate compound is preferably the Acetyl Acetone complex compound or etheric acid complex compound that use the metal be selected from aluminium, titanium and zirconium.Specifically, include, for example: diisopropoxy ethyl acetoacetic acid aluminium, three (Acetyl Acetone acid) aluminium, three (ethyl acetoacetic acid) aluminium, two (ethyl acetoacetic acid) titanium of diisopropoxy, diisopropoxy two (Acetyl Acetone acid) titanium, three-n-butoxyethyl etheric acid zirconium, two (ethyl acetoacetic acid) zirconiums of two-n-butoxy etc.When adding described metal chelate compound, relative to total 100 weight part of constituent comprising epoxy construction, the usage ratio of described metal chelate compound is preferably below 50 weight parts, be more preferably 0.1 weight part ~ 40 weight part, be especially preferably 1 weight part ~ 30 weight part.

[hardening accelerator]

Described hardening accelerator be in order to the component of polymer in liquid crystal aligning agent there is epoxy construction, guarantee the physical strength of formed liquid crystal orientation film and the ageing stability of liquid crystal aligning and be contained in liquid crystal aligning agent (particularly the liquid crystal aligning agent of phase retardation film).This hardening accelerator such as can use the compound with phenolic group, silanol group, thiol group, phosphate, sulfonic group, carboxyl, acid anhydride etc., wherein preferably has the compound of phenolic group or silanol group.As its concrete example, the compound with phenolic group include, for example: cyanophenol, nitrophenols, methoxyphenoxy phenol, sulfo-phenoxy phenyl, 4-benzylphenol etc.; The compound with silanol group include, for example: trimethyl silicane alkanol, triethyl silicane alcohol, 1,1,3,3-tetraphenyl-1,3-sily oxide glycol, Isosorbide-5-Nitrae-bis-(hydroxyl dimethylsilyl) benzene, tri-phenyl-silane alcohol, three (p-methylphenyl) silanol, diphenyl silanodiol etc.When adding hardening accelerator, relative to total 100 weight of constituent comprising epoxy construction, the usage ratio of described hardening accelerator is preferably below 50 weight parts, is more preferably 0.1 weight part ~ 40 weight part, is especially preferably 1 weight part ~ 30 weight part.

[tensio-active agent]

Described tensio-active agent can be contained in liquid crystal aligning agent (particularly the liquid crystal aligning agent of phase retardation film) the object of the coating of substrate for raising liquid crystal aligning agent.This tensio-active agent such as can be enumerated: nonionogenic tenside, anion surfactant, cats product, amphoterics, silicone surfactant, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.Relative to total amount 100 weight part of liquid crystal aligning agent, the usage ratio of tensio-active agent is preferably set to below 10 weight parts, is more preferably and is set to below 1 weight part.

In addition, except described composition, other compositions can be set forth in molecule the compound or antioxidant etc. with at least one oxetanylmethoxy.

< solvent >

Liquid crystal aligning agent of the present invention is prepared into and described polymkeric substance (P) and other compositions of optionally using preferably is disperseed or are 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, diisoamyl ether, ethylene carbonate, Texacar PC etc.These organic solvents can be used alone or two or more is used in combination.

Solid component concentration (ratio of total weight shared by the gross weight of liquid crystal aligning agent of the composition beyond the solvent of liquid crystal aligning agent) in liquid crystal aligning agent of the present invention can consider that viscosity, volatility etc. are suitably selected, and is preferably the scope of 1 % by weight ~ 10 % by weight.That is, liquid crystal aligning agent of the present invention is by coating substrate surface in aftermentioned mode, preferably heating, 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 according to the purposes of liquid crystal aligning agent or different when the method used during coating of liquid crystalline alignment agent on substrate.Such as about the liquid crystal aligning agent of liquid crystal orientation film, when utilizing turner method to coat on substrate, solid component concentration (ratios of total weight shared by the gross weight of liquid crystal aligning agent of the whole compositions beyond the solvent in liquid crystal aligning agent) is particularly preferably the scope of 1.5 % by weight ~ 4.5 % by weight.When utilizing print process, being particularly preferably scope solid component concentration being set to 3 % by weight ~ 9 % by weight, thus 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, thus soltion viscosity being set to the scope of 3mPas ~ 15mPas.Temperature when preparing liquid crystal aligning agent of the present invention is preferably 10 DEG C ~ 50 DEG C, is more preferably 20 DEG C ~ 30 DEG C.In addition, about the liquid crystal aligning agent of phase retardation film, become with regard to the viewpoint of appropriateness with regard to the coating that makes liquid crystal aligning agent and the thickness of film that formed, the solid component concentration of liquid crystal aligning agent is preferably the scope of 0.2 % by weight ~ 10 % by weight, is more preferably the scope of 3 % by weight ~ 10 % by weight.

In addition, the result of study of the present inventor shows, utilizes the liquid crystal aligning agent comprising described polymkeric substance (P), can form (concave-convex surface is good) film that surface is smooth.Its reason may not be clear and definite, but be presumed as follows.Remain the performance of mitigation if improve DC and import aromatic amine structure (a), then, except crystallinity rises, polymkeric substance becomes rigidity (rigid), think thus and become easy cohesion (crystallization).In this situation, imagine the polymer chain when film is formed and can tangle each other, cause the decline of the concave-convex surface of film.On the other hand, in the polymkeric substance (P) that compound (C) is obtained for reacting, import the chain-like structure (b) of sufficiently long chain length as spacer unit with aromatic amine structure (a) simultaneously, thus, heating (toasting afterwards) when being formed by film, polymer chain entanglement is each other untied, and in the film thinking after the heating, concave-convex surface becomes good.In addition, about the polymkeric substance (P) that compound (C1) is obtained for reacting, also inferring due to identical reason and obtaining described effect.

< liquid crystal display device and phase retardation film >

By using the liquid crystal aligning agent of the present invention of described explanation to manufacture liquid crystal orientation film.In addition, the liquid crystal orientation film using liquid crystal aligning agent of the present invention to be formed can be preferably applied to liquid crystal orientation film used for liquid crystal display element and the liquid crystal orientation film of phase retardation film.Below, liquid crystal display device of the present invention and phase retardation film are described.

[liquid crystal display device]

Liquid crystal display device of the present invention comprises the liquid crystal orientation film using described liquid crystal aligning agent to be 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 (Vertical Alignment-Multidomain Vertical Alignment, VA-MVA) type, vertical orientated (the Vertical Alignment-Patterned Vertical Alignment of vertical orientated-pattern, VA-PVA) type etc.), IPS type, FFS type, the multiple type of drive such as optical compensation curved (Optically Compensatory Bend, OCB) type.Liquid crystal display device of the present invention manufactures by the step of such as following (I-1) ~ (I-3).Step (I-1) uses different substrates according to required operating mode.Step (I-2) and step (I-3) share in each operating mode.

[step (I-1): the formation of film]

First, substrate is coated with liquid crystal aligning agent of the present invention, then coated face is heated, on substrate, form film thus.

(I-1A) when the liquid crystal display device of Production Example as TN type, STN type or VA type, first, to two pieces of substrates of patterned nesa coating be provided with as a pair, in described each transparent conductive film forming surface, flexographic printing process, method of spin coating, roll-coater method or ink jet printing method is preferably utilized to be coated with liquid crystal aligning agent of the present invention respectively.Substrate such as can use: the glass such as float glass (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 nesa coating being arranged at the one side of substrate can use and comprise stannic oxide (SnO ₂) nesa (NESA) film (PPG register of company of U.S. trade mark), comprise indium oxide-tin oxide (In ₂o ₃-SnO ₂) ito film etc.In order to obtain patterned nesa coating, such as, can utilize following methods: after forming patternless nesa coating, being formed the method for pattern by photoetch; The method etc. with the shade 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 to burn till (toasting afterwards) step.Firing 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.

(I-1B) when manufacturing the liquid crystal display device of IPS type or FFS type, be provided with comprise the patterned substrate for the nesa coating of interdigitated electrode structure or the electrode of metallic membrane electrode forming surface, with do not arrange in the one side of subtend substrate of electrode, be coated with liquid crystal aligning agent of the present invention respectively, then each coated face is heated, form film thus.About the patterning method of heating condition, nesa coating or metallic membrane after the material of the substrate now used and nesa coating, coating process, coating, the pre-treatment of substrate and the preferred thickness of film that formed, identical with described (I-1A).Metallic membrane can use the film such as comprising the metals such as chromium.

In any one situation of described (I-1A) and (I-1B), all by after coating of liquid crystalline alignment agent on substrate, organic solvent is removed and is formed into the film of alignment films.Now, polymkeric substance contained in liquid crystal aligning agent of the present invention is polyamic acid, or be poly amic acid ester, or for there is imide ring structure and amido acid structure imide amination polymer when, carrying out dehydration closed-loop reaction by heating further after film is formed, making further through the film of imidization.

[step (I-2): alignment capability gives process]

When manufacturing the liquid crystal display device of TN type, STN type, IPS type or FFS type, the process of giving liquid crystal aligning ability is implemented to the film formed in described step (I-1).Thus, the alignment capability of liquid crystal molecule is imparted to film and becomes liquid crystal orientation film.This process can enumerate following process etc.: friction treatment, utilizes the roller being wound with the cloth comprising the fibers such as such as nylon, artificial silk, cotton, by film to certain orientation wiping; And light orientation process, film is irradiated to the radioactive rays of polarisation or non-polarized.On the other hand, when manufacturing VA type liquid crystal display device, the film formed directly can be used as liquid crystal orientation film, also can give process to this film implementation orientation ability in described step (I-1).

In light orientation process, such as can use ultraviolet and the visible rays of the light comprising 150nm ~ 800nm wavelength to the radioactive rays of film irradiation.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 carry out 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 means also such as such as strainer, diffraction grating etc. etc. and obtain.The irradiation dose of radioactive rays 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 while carry out the rayed to film 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 carry 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: make by a part of irradiation ultraviolet radiation to 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 polymer stabilizing orientation (Polymer sustained alignment, PSA) type liquid crystal display device.

[step (I-3): constructing of liquid crystal cells]

Prepare the substrate 2 pieces being formed with liquid crystal orientation film in this way, between 2 pieces of substrates of subtend configuration, configure liquid crystal, manufacture liquid crystal cells thus.In order to manufacture liquid crystal cells, include, for example 2 kinds of following methods.First method is in the past known method.First, 2 pieces of substrate subtends are configured via gap (unit space) in the mode of each liquid crystal orientation film subtend, sealing agent is used to be fitted by the periphery of 2 pieces of substrates, inject filling liquid crystal in the unit space divided by substrate surface and sealing agent after, filling orifice is sealed, can liquid crystal cells be manufactured thus.In addition, the second method is for being called the method for liquid crystal drip-injection (One Drop Fill, ODF) mode.Specified location on wherein one piece of substrate in the 2 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, can liquid crystal cells be manufactured thus.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 thus.

As sealing agent, such as, can use the epoxy resin etc. containing stiffening agent and the alumina balls as spacer.In addition, liquid crystal can enumerate nematic liquid crystal (nematic liquid crystal) and smectic liquid crystal (smectic liquid crystal), wherein be preferably nematic liquid crystal, such as, can use: schiff bases (Schiff base) 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, cyclohexyl biphenyl hexane system liquid crystal, liquid crystal, diox system of pyrimidine system liquid crystal, double-octane system liquid crystal, cubane (cubane) are liquid crystal etc.In addition, also can add following material to use in these liquid crystal: the cholesteryl liquid crystals (cholesteric liquidcrystal) such as such as cholesteryl chloride (cholesteryl chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl carbonate); As the chiral agent (chiralagent) that trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) are sold; To oxygen base α-tolylene-to the ferroelectric liquid crystals such as amino-2-methyl butyl laurate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) (ferroelectric liquidcrystal) etc. 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, should " H film " be make polyvinyl alcohol extension orientation make it absorb the film of iodine.

[phase retardation film]

When using liquid crystal aligning agent of the present invention to manufacture phase retardation film, the generation of dust or electrostatic just can be suppressed in step, and the aspect of uniform liquid crystal orientation film can be formed, and can by irradiate radioactive rays time use suitable light shield and be formed arbitrarily on substrate different multiple regions, liquid crystal aligning direction in, preferably utilize optical alignment method.Specifically, by manufacturing through following step (II-1) ~ step (II-3).

[step (II-1): the formation utilizing the film of liquid crystal aligning agent]

First, liquid crystal aligning agent of the present invention is coated on substrate form film.Substrate as used herein can be applicable to illustrating: the transparency carrier comprising the synthetic resins such as triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polymeric amide, polyimide, polymethylmethacrylate, polycarbonate.In these substrates, TAC is typically used as the protective layer of the light polarizing film in liquid crystal display device.In addition, with regard to the aspect good with regard to the low aspect of the water absorbability of solvent, optical characteristics and the aspect of low cost, polymethylmethacrylate can be preferably used as the substrate of phase retardation film.In addition, for the substrate used in the coating of liquid crystal aligning agent, in order to make the adhesivity of substrate surface and film better, also existing known pre-treatment can be implemented to the face forming film in substrate surface.

Under many circumstances, phase retardation film and light polarizing film combinationally use.Now, in order to required optical characteristics can be played, must by phase retardation film relative to the polarizing axis of light polarizing film precise angle control as specific direction is to phase retardation film of fitting.Therefore, herein, by being formed on the substrates such as TAC film or polymethylmethacrylate by the liquid crystal orientation film on the direction of first retainer with liquid crystal aligning ability, the angle of control phase difference film can be omitted while phase retardation film to be fitted in the step in light polarizing film.In addition, the productivity improving liquid crystal display device can be contributed to thus.In order to be formed in first retainer direction on there is the liquid crystal orientation film of liquid crystal aligning ability, preferably use liquid crystal aligning agent of the present invention, utilize optical alignment method to carry out.

The coating of liquid crystal aligning agent on substrate can utilize suitable coating process, such as, can adopt: roll-coater method, turner method, print process, ink jet method, rod coater, extrude modulus method, direct gravure coater (direct gravure coater) method, chamber wing coating machine (chamber doctor coater) method, Offset gravure coating machine (offset gravure coater) method, single roller kiss coater (single roll kiss coater) method, use anti-kiss coater (reverse kisscoater) method of path gravure roll, three reverse roll coater (three reverse roll coater) methods, four reverse roll coater methods, slit die (slotdie) method, Kohler coater (air doctor coater) method, positive rotation roll-coater (positive rotation roll coater) method, scraper plate coating machine (blade coater) method, scraper type coating machine (knife coater) method, impregnation coater, MB coater, the reverse coater of MB etc.

After coating, coated face is carried out heating (baking) and forms film.Heating temperature now is preferably set to 40 DEG C ~ 150 DEG C, is more preferably and is set to 80 DEG C ~ 140 DEG C.Preferably be set to 0.1 minute ~ 15 minutes heat-up time, be more preferably and be set to 1 minute ~ 10 minutes.The thickness being formed at the film on substrate is preferably 1nm ~ 1, and 000nm is more preferably 5nm ~ 500nm.

[step (II-2): light irradiation step]

Then, by irradiating light to the film be formed in this way on substrate, come to give liquid crystal aligning ability to film.Herein, about kind, the explanation of light source that uses of the wavelength of irradiated light, light, the explanation of the light orientation process of described step (I-2) can be applied.The irradiation dose of light is preferably set to 0.1mJ/cm ²~ 1,000mJ/cm ², be more preferably and be set to 1mJ/cm ²~ 500mJ/cm ², be especially preferably set to 2mJ/cm ²~ 200mJ/cm ².

[step (II-3): the formation of liquid crystal layer]

Then, the film after carrying out rayed is in this way coated with polymerizable liquid crystal and makes it harden.Thus, the film (liquid crystal layer) comprising polymerizable liquid crystal is formed.Polymerizable liquid crystal used herein carries out the liquid crystalline cpd that is polymerized or liquid-crystal composition by least one process in heating and rayed.Described polymerizable liquid crystal can use existing known liquid crystal, specifically, include, for example non-patent literature 1 (" can the liquid crystal that hardens of ultraviolet (UV) and application thereof ", " liquid crystal " the 3rd volume the 1st phase (1999), the 34th page ~ the 42nd page) in the nematic liquid crystal recorded.In addition, also can be: cholesteryl liquid crystal; Discotic mesogenic (discotic liquid crystal); Be added with the twisted nematic alignment-type liquid crystal etc. of chiral agent.Polymerizable liquid crystal can be the mixture of plurality of liquid crystals compound.Polymerizable liquid crystal also can be the composition more containing known polymerization starter, suitable solvent etc.

In order to the film that formed being coated with polymerizable liquid crystal as above using liquid crystal aligning agent, such as, can adopt the coating process that excellent coater, roll-coater method, turner method, print process, ink jet method etc. are suitable.

Then, by the film to the polymerizable liquid crystal formed in this way, implement more than one process be selected from heating and rayed, and make the sclerosis of this film form liquid crystal layer.These processing overlapping are carried out, good orientation can be obtained so preferably.

The Heating temperature of film suitably can be selected according to the kind of used polymerizable liquid crystal.Such as when the RMS03-013C using Merck (Merck) company to manufacture, preferably heat at the temperature of the scope of 40 DEG C ~ 80 DEG C.Be preferably 0.5 minute ~ 5 minutes heat-up time.

Irradiate the ultraviolet that light preferably can use the non-polarized of the wavelength with 200nm ~ 500nm scope.The irradiation dose of light is preferably set to 50mJ/cm ²~ 10,000mJ/cm ², be more preferably and be set to 100mJ/cm ²~ 5,000mJ/cm ².

The thickness of the liquid crystal layer formed suitably sets according to required optical characteristics.Such as when manufacture wavelength is 1/2 wavelength plate of the visible ray of 540nm, select the phase differential of the phase retardation film formed to become the thickness of 240nm ~ 300nm, if 1/4 wavelength plate, then selected phase difference becomes the thickness of 120nm ~ 150nm.The thickness obtaining the liquid crystal layer of target phase difference is different according to the optical characteristics of used polymerizable liquid crystal.Such as when the RMS03-013C using Merck (Merck) to manufacture, in order to manufacture the scope that the thickness of 1/4 wavelength plate is 0.6 μm ~ 1.5 μm.

The phase retardation film obtained in this way can preferably be applied as the phase retardation film of liquid crystal display device.The liquid crystal display device of the phase retardation film that application uses liquid crystal aligning agent of the present invention to manufacture is also unrestricted to its type of drive, such as, can be applicable to the known various modes such as TN type, STN type, IPS type, FFS type, VA type.Described phase retardation film is that the face that the substrate attached in phase retardation film the outer side of the Polarizer depending on recognizing side being configured at liquid crystal display device is surveyed uses.Therefore, be preferably set to following aspect: the substrate of phase retardation film is set to TAC system or acrylic acid series base material, make the substrate of this phase retardation film also play function as the protective membrane of light polarizing film.

Herein, the method for producing phase retardation film with technical scale has volume to volume (roll-to-roll) mode.The method is with continuous print step to carry out following process, the method that the film after these steps is made coiling body to reclaim, described in be treated to: on the coiling body of the base material film of strip, roll out film, the film that this rolls out formed the process of liquid crystal orientation film; Liquid crystal orientation film is coated with polymerizable liquid crystal and carries out the process of hardening; And the process of optionally lamination protective membrane.Use liquid crystal aligning agent of the present invention and the phase retardation film that formed to the good adhesion of substrate, when being made into coiling body and carrying out keeping etc., liquid crystal orientation film and substrate are also difficult to peel off.Therefore, it is possible to suppress the decline of goods yield when utilizing volume to volume mode to manufacture phase retardation film.

Liquid crystal display device of the present invention can be effectively applied to multiple device, such as can be used for: clock and watch, pocket game machine, word processor (word processor), notes type PC (note type personal computer), auto-navigation system (car navigation system), video camera (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart mobile phone, various watch-dog, LCD TV, the various display unit such as information display.

[embodiment]

Below, by embodiment, the present invention is specifically described further, but the present invention is not limited to these embodiments.

In following embodiment and synthesis example, utilize following methods to measure the soltion viscosity of the weight average molecular weight Mw of polymkeric substance, imide rate and epoxy equivalent (weight) and polymers soln.

[the weight average molecular weight Mw of polymkeric substance]

Mw is the polystyrene conversion value utilizing the GPC under following condition to measure.

Tubing string: eastern Cao (Tosoh) (stock) manufactures, TSKgelGRCXLII

Solvent: the DMF solution containing tetrahydrofuran (THF) or lithiumbromide and phosphoric acid

Temperature: 40 DEG C

Pressure: 68kgf/cm ²

[the imide rate of polymkeric substance]

Solution containing polyimide is fed in pure water, the precipitation of gained, at room temperature fully after drying under reduced pressure, is dissolved in deuterodimethylsulfoxide, using tetramethylsilane as primary standard, at room temperature measures ¹h-nucleus magnetic resonance (NuclearMagnetic Resonance, NMR).According to gained ¹h-NMR spectrum, uses following mathematical expression (EX-1) to obtain imide rate.

Imide rate (%)=(1-E ¹/ E ²× α) × 100 (EX-1)

(in mathematical expression (EX-1), E ¹the peak area being derived from the proton of NH base occurred near chemical shift 10ppm, E ²be the peak area being derived from other protons, α is the number ratios of other protons relative to 1 proton of the NH base in the precursor (polyamic acid) of polymkeric substance)

[epoxy equivalent (weight)]

Epoxy equivalent (weight) utilizes the hydrochloric acid-methyl ethyl ketone method recorded in JIS C 2105 to measure.

[soltion viscosity of polymers soln]

The soltion viscosity (mPas) of polymers soln uses E type rotational viscosimeter, measures at 25 DEG C.

The synthesis > of < compound (C)

[synthesis example 1-1: the synthesis of compound (DA-1)]

Synthetic compound (DA-1) is carried out according to following flow process 1.In addition, in formula, Bn represents benzyl (following identical).

[changing 20]

The reaction of first stage utilizes Williamson to react (Williamson reaction) to synthesize.First, in the 2L there-necked flask possessing addition funnel, mixing N-benzyl-4-hydroxyanilines 83.7g (0.2 mole), 1, pentamethylene bromide 46g (0.42 mole), cesium fluoride 121.5g (0.8 mole) and dimethyl formamide 800mL, make it dissolve, stir at 60 DEG C and react for 4 hours.After reaction, add ethyl acetate 2000mL and extract, add distilled water 200mL and carry out separatory purifying.After described abstraction purification is carried out 5 times repeatedly, in organic layer, remove solvent by underpressure distillation, obtain dibenzyl intermediate (compound represented by described formula (DA-1-1)) 76.4g (0.16 mole) thus.

The reaction of subordinate phase is synthesized by Liv Ullmann condensation reaction (Ullmann condensation reaction).Under nitrogen flowing, described dibenzyl intermediate (DA-1-1) 76.4g (0.16 mole), 4-iodonitrobenzene 81.5g (0.33 mole), phenanthroline (phenanthroline) 59g (0.33 mole), Tripotassium phosphate 139g (0.65 mole), cupric iodide 9.4g (0.05 mole) and N,N-DIMETHYLACETAMIDE 600mL is added in 2L there-necked flask, make their mixed dissolutions, stir under reflux and react for 24 hours.After reaction terminates, after reacting liquid filtering is removed catalyzer, its filtrate is injected in distilled water 2000mL, makes crystallization.By filtering, separated out solid being reclaimed, fully washing with ethanol, making it in tetrahydrofuran (THF), carry out recrystallize, obtaining nitro intermediate (compound represented by described formula (DA-1-2)) 35g (0.05 mole) thus.

The reaction of phase III is synthesized by hydrogen reduction reaction.Under nitrogen flowing, add 5%Pd/C, the ethanol 50mL of described nitro intermediate (DA-1-2) 35g, 3g, tetrahydrofuran (THF) 50mL and hydrazine monohydrate 35mL in 500mL there-necked flask after, again replace with hydrogen, at room temperature react in the presence of hydrogen.Utilize high performance liquid chromatography (HighPerformance Liquid Chromatography, HPLC) to carry out reactive tracing, confirm that reaction is filtered after carrying out.In filtrate, add ethyl acetate 1000mL, add distilled water 100mL and carry out separatory purifying.After described abstraction purification is carried out 5 times repeatedly, in organic layer, remove solvent by underpressure distillation, make solid separate out thus.Make separated out solid carry out recrystallize in the mixed solvent of tetrahydrofuran (THF), ethanol, obtain compound (DA-1) 18.5g (0.04 mole) thus.

[synthesis example 1-2: the synthesis of compound (DA-2)]

According to following flow process 2, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-2).

[changing 21]

[synthesis example 1-3: the synthesis of compound (DA-3)]

According to following flow process 3, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-3).In addition, the reaction of subordinate phase uses the method recorded in non-patent literature 2 (organic chemistry magazine " The Journal of Organic Chemistry ", 2002,67,6479) to synthesize.

[changing 22]

[synthesis example 1-4: the synthesis of compound (DA-4)]

According to following flow process 4, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-4).In addition, the reaction of subordinate phase is synthesized by hydrolysis reaction, and the phase III is by utilizing the condensation reaction of 1-ethyl-3-(3-dimethylaminopropyl) carbon imide hydrochloride to synthesize.

[changing 23]

[synthesis example 1-5: the synthesis of compound (DA-5)]

According to following flow process 5, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-5).

[changing 24]

[synthesis example 1-6: the synthesis of compound (DA-6)]

According to following flow process 6, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-6).

[changing 25]

[synthesis example 1-7: the synthesis of compound (DA-7)]

According to following flow process 7, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-7).

[changing 26]

[synthesis of synthesis example 1-8:DA-8]

According to following flow process 8, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-8).In addition, first stage in the synthesis of single nitro list iodine intermediate (compound represented by described formula (DA-8-1)) utilizes Knut Fridell-Kerafyrm thatch reaction (Friedel-Crafts reaction) to synthesize, subordinate phase is under the existence of the trifluoromethanesulfonic acid as strong acid, uses and utilizes the reduction reaction of the silane carbonyl of triethyl silicane to synthesize.

[changing 27]

[synthesis example 1-9: the synthesis of compound (DA-9)]

According to following flow process 9, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-9).

[changing 28]

[synthesis example 1-10: the synthesis of compound (DA-10)]

According to following flow process 10, the building-up reactions formula identical with compound (DA-1) is used to obtain compound (DA-10).In addition; first stage in the synthesis of single nitro monohydroxy intermediate (compound represented by described formula (DA-10-1)) utilizes Knut Fridell-Kerafyrm thatch reaction to synthesize; subordinate phase is that the deprotection reaction of methoxyl group by utilizing lithiumbromide synthesizes; phase III is under the existence of the trifluoromethanesulfonic acid as strong acid, uses and utilizes the reduction reaction of the silane carbonyl of triethyl silicane to synthesize.

[changing 29]

The synthesis > of < compound (C1)

[synthesis example 1-11: the synthesis of compound (DA-22)]

According to following flow process 11, obtain compound (DA-22).In addition, the synthesis of first stage obtains intermediate (compound represented by following formula (DA-22-1)) by Knoevenagel reaction (Knoevenagel reaction).Subordinate phase utilizes the method identical with compound (DA-1) to reduce.

[changing 30]

[synthesis example 1-12: the synthesis of compound (DA-23)]

According to following flow process 12, in the presence of zinc, using water as catalyzer, compound (DA-22-1) is reduced, obtain compound (DA-23) thus.

[changing 31]

The synthesis > of < polymkeric substance

The synthesis of polyamic acid

[synthesis example 2-1: the synthesis of polymkeric substance (PAm-1)]

To in reaction vessel, with in following table 1 record blending ratio (molar part) and add tetracarboxylic dianhydride and diamines in the mode adding up to weight to become 30g, and then add METHYLPYRROLIDONE (N-methyl-2-pyrrolidone, NMP) 170g dissolves, and carries out reaction in 6 hours at 60 DEG C.Then, the reaction mixture of gained is injected in excessive methyl alcohol, reaction product is precipitated.By reclaimed throw out with after methanol wash, under reduced pressure at 40 DEG C dry 15 hours, obtain polymkeric substance (PAm-1) thus.In addition, about tetracarboxylic dianhydride, numeric representation in table 1 is relative to the usage ratio (% by mole) of the total amount of the tetracarboxylic dianhydride used in reaction, and about diamines, the numeric representation in table 1 is relative to the usage ratio (% by mole) of the total amount of the diamines used in reaction.Then, the polymkeric substance (PAm-1) of described acquisition is dissolved in NMP in the mode becoming 15 % by weight, measures respective soltion viscosity.Measurement result is shown in following table 1 in the lump.In addition, for the polymers soln of described acquisition, at 20 DEG C, leave standstill result after 3 days do not carry out gelation, storage stability is good.

[synthesis example 2-2 ~ synthesis example 2-18: the synthesis of polymkeric substance (PAm-2) ~ polymkeric substance (PAm-18)]

Except the blending ratio of tetracarboxylic dianhydride and diamines being changed to the numerical value of record in following table 1 and table 2, carry out the operation identical with synthesis example 2-1, obtain polymkeric substance (PAm-2) ~ polymkeric substance (PAm-18) respectively.The soltion viscosity of each polymkeric substance will be measured and the results are shown in following table 1 and table 2 of obtaining in the mode identical with synthesis example 2-1.In addition, for each polymers soln of described acquisition, leave standstill after 3 days at 20 DEG C, result does not all carry out gelation except polymkeric substance (PAm-14), and storage stability is good.Polymkeric substance (PAm-14) carries out gelation, and mobility disappears.

The synthesis of polyimide

[synthesis example 3-1: the synthesis of polymkeric substance (PIm-1)]

With in following table 2 record blending ratio (molar part) and add tetracarboxylic dianhydride and diamines in the mode adding up to weight to become 30g, and then interpolation 170g NMP, carry out synthesizing polyamides acid by the operation identical with synthesis example 2-1.Then, add the NMP of 200g, add pyridine and the diacetyl oxide of the amount (molar part of numeric representation for total 100 molar part of acid dianhydride) shown in following table 2, at 80 DEG C, carry out dehydration closed-loop reaction in 6 hours.Then, reaction mixture is injected in excessive methyl alcohol, reaction product is precipitated.By reclaimed throw out with after methanol wash, under reduced pressure at 40 DEG C dry 15 hours, obtain polymkeric substance (PIm-1) thus.

Then, the polymkeric substance (PIm-1) of described acquisition is dissolved in NMP in the mode becoming 15 % by weight, measures respective soltion viscosity.In addition, imide rate is also measured.Their measurement result is shown in following table 2.And then for the polymers soln of described acquisition, leave standstill result after 3 days and do not carry out gelation at 20 DEG C, storage stability is good.

[synthesis example 3-2: the synthesis of polymkeric substance (PIm-2)]

Except the blending ratio of tetracarboxylic dianhydride and diamines being changed to the numerical value of record in following table 2, carry out the operation identical with synthesis example 3-1, obtain polymkeric substance (PIm-2).The soltion viscosity of polymkeric substance (PIm-2) will be measured and the measurement result of the result obtained and imide rate is shown in following table 2 in the lump in the mode identical with synthesis example 3-1.In addition, for the polymers soln of described acquisition, at 20 DEG C, leave standstill result after 3 days do not carry out gelation, storage stability is good.

[table 1]

[table 2]

Compound in table 1 and table 2 referred to as following implication.In addition, in table 2, the molar part of numeric representation for total 100 molar part of the tetracarboxylic dianhydride used in reaction of pyridine and diacetyl oxide.

(tetracarboxylic dianhydride)

AN-1:1,2,3,4-tetramethylene tetracarboxylic dianhydride

AN-2: pyromellitic acid anhydride

AN-3:2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride

AN-4: ethylenediamine tetraacetic acid (EDTA) dianhydride

AN-5:5-(2,5-trioxy-tetrahydrofuran (THF)-3-base)-8-methyl-3a, 4,5,9b-tetrahydrochysene naphtho-[1,2-c] furans-1,3-diketone

AN-6: dicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride

AN-7:1, ammediol two (trimellitic anhydride ester)

AN-8:1,2,3,4-pentamethylene tetracarboxylic dianhydride

(diamines)

Two (4-amino-benzene oxygen) heptane of DA-11:1,7-

DA-12:4,4 '-diamino-diphenyl amine

DA-13: the compound represented by following formula (DA-13)

DA-14: the compound represented by following formula (DA-14)

DA-15: the compound represented by following formula (DA-15)

DA-16:4,4 '-diaminodiphenyl-methane

DA-17:4-aminophenyl-4 '-Aminobenzoate

DA-18: the compound represented by described formula (DA-18)

DA-19:4-(4-amino-benzene oxygen carbonyl)-1-(4-aminophenyl) piperidines

DA-20:4-(tetradecane acyloxy) benzene-1,3-diamines

DA-21:3,5-diaminobenzoic acid cholestane base ester

[changing 32]

Containing the synthesis of the organopolysiloxane of light orientation base

[synthesis example 4-1: the synthesis of polymkeric substance (PSi-1)]

In the reaction vessel possessing stirrer, thermometer, addition funnel and reflux cooling pipe, add 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane 100.0g, methyl iso-butyl ketone (MIBK) 500g and triethylamine 10.0g, at room temperature mix.Wherein, after addition funnel spends 30 minutes dropping deionized water 100g, mix under reflux, while carry out reaction in 6 hours at 80 DEG C.After reaction terminates, take out organic layer, utilize 0.2 % by weight aqueous ammonium nitrate solution by described organic layer washing to the water after washing becomes neutrality, then under reduced pressure solvent and water are removed in distillation, obtain the organopolysiloxane with oxiranyl thus with the form of the transparent liquid of thickness.The organopolysiloxane that this has oxiranyl is carried out ¹h-NMR analyzes, and result, near chemical shift (δ)=3.2ppm, obtains the peak value based on oxiranyl as theoretical strength, confirms the side reaction not producing oxiranyl in reaction.Measure the epoxy equivalent (weight) that this has the organopolysiloxane of oxiranyl, result is 186g/ equivalent.

Then, in the there-necked flask of 100mL, add organopolysiloxane 9.3g, the methyl iso-butyl ketone (MIBK) 26g with oxiranyl of described acquisition, 4-phenoxy group styracin 3g and UCAT 18X (trade(brand)name, Sanya general sieve (San-Apro) (stock) manufactures) 0.10g, stirs and carries out reaction in 12 hours at 80 DEG C.After reaction terminates, reclaim the throw out being fed into by reaction mixture and generating in methyl alcohol, described precipitate dissolves is made solution in ethyl acetate, after this solution is washed 3 times, solvent is removed in distillation, obtains organopolysiloxane (PSi-1) 6.3g with oxiranyl and cinnamic acid structure thus with the formation of white powder.To this organopolysiloxane (PSi-1), measure with GPC and the weight average molecular weight Mw of polystyrene conversion that obtains for 3,500.

[embodiment 1-1: light orientation FFS type liquid crystal display device]

(1) preparation of liquid crystal aligning agent

Using polymkeric substance (PAm-11) 50 weight part obtained in polymkeric substance (PAm-4) 50 weight part obtained in the synthesis example 2-4 of polymkeric substance and synthesis example 2-11, be dissolved in and comprise gamma-butyrolactone (γ-butyrolactone, GBL), METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (butyl cellosolve, BC), in mixed solvent (GBL: NMP: BC=40: 40: 20 (weight ratio)), the solution that solid component concentration is 3.5 % by weight is made.This solution is filtered with the strainer that aperture is 0.2 μm, prepares liquid crystal aligning agent thus.

(2) evaluation of the concave-convex surface of film

Use turner, the liquid crystal aligning agent of described preparation is coated on glass substrate, after the hot-plate of 80 DEG C carries out 1 minute prebake conditions, will carry out in 200 DEG C of baking ovens of nitrogen replacement in storehouse, heating (toasting afterwards) 1 hour, forming average film thickness is thus film.Utilize atomic force microscope (Atomic Force Microscope, AFM) to observe this film, measure center average roughness (Ra).Evaluating as follows: average evaluation Ra being less than 2.0nm is concave-convex surface " well ", by more than 2.0nm and the average evaluation being less than 5.0nm is "available", is " bad " by the average evaluation of more than 5.0nm.Ra=0.8nm in the present embodiment, concave-convex surface is " well ".

(3) evaluation of transmissivity

To the film of described acquisition, use spectrophotometer (the 150-20 type twin-beam that Hitachi (stock) manufactures), the light transmittance (%) under wavelength 400nm is evaluated.Evaluate as follows: by light transmittance be the average evaluation of more than 97% for " well ", by more than 95% and the average evaluation being less than 97% is "available", the average evaluation that will be less than 95% is " bad ".Its result is, the light transmittance of this film is 99.0%, transmissivity " well ".

(4) evaluation of orientation

For the film of described acquisition, use Hg-Xe lamp and Glan-Taylor prism (Glan-Taylor prism), irradiate the polarisation ultraviolet 300J/m comprising the open-wire line of 313nm from substrate normal direction ²carry out implementation orientation process.For this glass substrate with alignment films, the liquid crystal aligning film detection apparatus that uses Mo Ruisi (MORITEX) company to manufacture (Leix may (LayScan)) measures refractive anisotrop (nm).Evaluate as follows: by the average evaluation of more than 0.020nm for " well ", will be less than 0.020nm and the average evaluation of more than 0.010nm is "available", the average evaluation that will be less than 0.010 is " bad ".Its result is, the refractive anisotrop of this substrate is 0.037nm, orientation " well ".

(5) manufacture of the FFS type liquid crystal display device of optical alignment method is used

FFS type liquid crystal display device 10 shown in construction drawing 1.First, at one side, will there is electrode pair and described electrode pair be formed successively the figuratum bottom electrode 15 of not tool, as insulation layer 14 silicon nitride film and be patterned as the glass substrate 11a of top electrodes 13 of comb teeth-shaped, with the subtend glass substrate 11b of electrode is not set as a pair, in the one side of the face with transparency electrode of glass substrate 11a and subtend glass substrate 11b, use turner, be coated with the liquid crystal aligning agent of preparation in described (1) respectively and form film.Then, after this film is carried out 1 minute prebake conditions on the hot-plate of 80 DEG C, carrying out heating in 15 minutes (toasting afterwards) by the baking oven having carried out nitrogen replacement in storehouse with 230 DEG C, forming average film thickness is film.The floor map of top electrodes 13 as used herein is shown in Fig. 2 (a) and Fig. 2 (b).In addition, Fig. 2 (a) is the vertical view of top electrodes 13, and Fig. 2 (b) is Fig. 2 (a) by the enlarged view of the part C1 of dotted line.In the present embodiment, the live width d1 with electrode is used to be 4 μm and interelectrode distance d2 is the substrate of the top electrodes of 6 μm.In addition, top electrodes 13 is the drive electrodes of 4 systems using electrode A, electrode B, electrode C and electrode D.The formation of the drive electrode of this liquid crystal display device is represented in Fig. 3.In this situation, bottom electrode 15 acts on whole drive electrodes of 4 systems as common electrode, the region of the drive electrode of 4 systems becomes pixel region respectively.

Then, for each surface of these films, use Hg-Xe lamp and Glan-Taylor prism respectively, irradiate the polarisation ultraviolet 300J/m comprising the open-wire line of 313nm from substrate normal direction ², obtain a pair substrate with liquid crystal orientation film.Now, polarisation ultraviolet irradiation direction is set to from substrate normal direction, after the mode becoming the direction of the four-headed arrow in Fig. 2 (a) and Fig. 2 (b) 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.

Then, the periphery with the face of liquid crystal orientation film of the wherein 1 piece of substrate in described substrate, after being coated with and adding by screen painting and have diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, make the liquid crystal orientation film of 1 pair of substrate in the face of to, crimp ultraviolet for the polarisation plane of polarization direction be projected on substrate to be become parallel mode overlap, at 150 DEG C, spend 1 hour make caking agent carry out heat embrittlement.Then, fill the liquid crystal " MLC-6221 " of Merck (Merck) company manufacture in substrate gap from liquid crystal injecting port after, epoxy resin adhesive is utilized to be sealed by liquid crystal injecting port.Then, in order to remove flow orientation during Liquid crystal pour, after being heated to 150 DEG C, slowly room temperature is cooled to.

Then, by the two sides, outside of substrate laminating Polarizer, FFS type liquid crystal display device is manufactured.Now, in Polarizer wherein 1 piece be become parallel mode with its polarization direction and the projection direction of the ultraviolet plane of polarization of the polarisation of liquid crystal orientation film to real estate to attach, another block attaches in the mode that its polarization direction is orthogonal with the polarization direction of Polarizer just now.

Described method is carried out repeatedly, manufactures the FFS type liquid crystal display device of total 5, in the evaluation of the evaluation of following liquid crystal aligning, the evaluation of thermotolerance, resistance to frame inequality, image retention characteristic and contrast-response characteristic, respectively provide 1.Wherein, in any one situation, all do not carry out the uviolizing under voltage applying.In addition, about the liquid crystal cells used in the evaluation of contrast-response characteristic, Polarizer of not fitting.

(6) evaluation of liquid crystal aligning

For the FFS type liquid crystal display device of described manufacture, microscope is utilized to observe the presence or absence of the abnormal area in the light and shade change when on-off (ONOFF) (apply remove) 5V voltage with multiplying power 50 times.Evaluating as follows: be liquid crystal aligning " well " by the average evaluation not observing abnormal area, is liquid crystal aligning " bad " by the average evaluation observing abnormal area.Liquid crystal aligning " well " in this liquid crystal display device.

(7) evaluation of voltage retention

For the FFS type liquid crystal display device of described manufacture, apply 5V voltage with the application time of 60 microseconds, the span of 167 milliseconds at 23 DEG C after, measure the voltage retention (VHR) after 167 milliseconds from applying to remove, result, voltage retention is 99.4%.In addition, determinator is the VHR-1 using Dongyang Te Kenika (Toyo Technica) (stock) to manufacture.

(8) evaluation of thermotolerance

Voltage retention is measured, using its value as initial VHR (VHR in the mode identical with the evaluation of described (7) voltage retention _bF).Then, the liquid crystal display device after measuring for initial VHR, leaves standstill 500 hours in the baking oven of 100 DEG C.Then, by this liquid crystal display device at room temperature leave standstill and place be cooled to room temperature after, to measure voltage retention with described identical mode, using its value as VHR _aF.In addition, according to following mathematical expression (EX-2), obtain the velocity of variation (Δ VHR (%)) that thermal stresses gives the voltage retention of front and back.

ΔVHR(％)＝((VHR _BF-VHR _AF)÷VHR _BF)×100 (EX-2)

Carrying out the evaluation of thermotolerance as follows: average evaluation velocity of variation Δ VHR being less than 4% is thermotolerance " well ", by more than 4% and the average evaluation being less than 5% is thermotolerance "available", is thermotolerance " bad " by the average evaluation of more than 5%.Its result is, Δ VHR is 2.9%, and the thermotolerance of this liquid crystal display device is " well ".

(9) the uneven patience (resistance to frame inequality) of sealing agent periphery

For the FFS type liquid crystal display device of described manufacture, 25 DEG C, keeping 30 days under the condition of 50%RH, then, carry out driving to observe illuminating state with voltage of alternating current 5V.Evaluate as follows: if at sealing agent periphery depending on not recognizing luminance difference (more black (more black) or whiter (more white)), be then evaluated as " excellent "; Though if depending on recognizing, after striking within 5 minutes, luminance difference disappears, be then evaluated as " well "; If more than 5 minutes and within 20 minutes, luminance difference disappears, be then evaluated as "available"; Even if if through 20 minutes, still depending on recognizing the average evaluation of luminance difference for " bad ".Its result is, depending on not recognizing the luminance difference of this liquid crystal display device, is judged as " excellent ".

(10) evaluation (evaluation of DC image retention) of image retention characteristic

The light alignment-type liquid crystal display device of described manufacture is placed in 25 DEG C, under the environment of 1 air pressure.Using the common electrode of bottom electrode as whole drive electrodes of 4 systems, be 0V current potential (earthing potential) by the potential setting of bottom electrode.Make electrode B and electrode D and common electrode short circuit and be set to 0V and apply state, and electrode A and electrode C are applied to comprise the resultant voltage 2 hours of voltage of alternating current 3.5V and volts DS 1V.After 2 hours, at once 1.5V voltage is exchanged to whole applyings of electrode A ~ electrode D.Then, measure from the moment starting whole drive electrode to apply to exchange 1.5V voltage, until driving stress applying region (pixel region of electrode A and electrode C) not apply the time till the luminance difference of region (pixel region of electrode B and electrode D) with driving stress with visual cannot confirming again, it can be used as the image retention cancellation time.In addition, this time is shorter, is more difficult to produce image retention.Is less than the average evaluation of 30 seconds the image retention cancellation time for " well ", by more than 30 seconds and the average evaluation being less than 120 seconds is "available", be " bad " by the average evaluation of more than 120 seconds, result, the image retention cancellation time of the liquid crystal display device of the present embodiment is 1 second, is evaluated as image retention characteristic " well ".

(11) evaluation (evaluation of AC image retention) of the contrast-response characteristic after stress is driven

After the FFS type liquid crystal cells (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 transmittance (%) represented by following mathematical expression (EX-3).

Minimum relative transmittance (%)=(β-B ₀)/(B ₁₀₀-B ₀) × 100 (EX-3)

(in mathematical expression (EX-3), B ₀for the blank and transmission amount of light under cross Nicols; B ₁₀₀for the blank and transmission amount of light under parallel Nicol; β is under cross Nicols, clamps liquid crystal display device and become minimum light transmission capacity between polarizer and analyzer)

The black level (black level) of dark state represents with the minimum relative transmittance of liquid crystal display device, and the black level under dark state is less, and contrast-response characteristic is more excellent.Minimum relative transmittance is less than 0.5% be evaluated as " well ", by more than 0.5% and be less than 1.0% be evaluated as "available", by more than 1.0% be evaluated as " bad ".Its result is, the minimum relative transmittance of this liquid crystal display device is 0.2%, and contrast-response characteristic is judged as " well ".

[embodiment 1-2, embodiment 1-3 and comparative example 1-1]

Except the kind of the polymkeric substance used in the preparation of liquid crystal aligning agent and amount being set to respectively except as described in following table 3, preparing liquid crystal aligning agent respectively in the mode identical with described embodiment 1-1, manufacturing liquid crystal display device and evaluating.Evaluation result is shown in following table 3.

[embodiment 2-1: friction FFS type liquid crystal display device]

(1) preparation of liquid crystal aligning agent

The polymkeric substance (PAm-1) obtained in the synthesis example 2-1 of polymkeric substance is dissolved in the mixed solvent (GBL: NMP: BC=40: 40: 20 (weight ratio)) comprising gamma-butyrolactone (GBL), METHYLPYRROLIDONE (NMP) and ethylene glycol butyl ether (BC), makes the solution that solid component concentration is 3.5 % by weight.This solution is filtered with the strainer that aperture is 0.2 μm, prepares liquid crystal aligning agent thus.

(2) evaluation of the concave-convex surface of film

Use turner, the liquid crystal aligning agent of described preparation is coated on glass substrate, after carrying out 1 minute prebake conditions with the hot-plate of 80 DEG C, heating in the 200 DEG C of baking ovens having carried out nitrogen replacement in storehouse (toasting afterwards) 1 hour, forming average film thickness is thus film.For this film, carry out the evaluation of the concave-convex surface of coated film in the mode that (2) with described embodiment 1-1 are identical.Its result is, the Ra of this film is 0.9nm, and concave-convex surface is " well ".

(3) evaluation of transmissivity

For the film of described acquisition, evaluate transmissivity in the mode that (3) with described embodiment 1-1 are identical.Its result is, the transmissivity of this film is 98.5%, transmissivity " well ".

(4) evaluation of rub resistance

For the film of described acquisition, utilize and there is the friction machine of the roller being wound with cotton, implement 7 friction treatment with roller rotating speed 1000rpm, platform movement speed 20cm/ second, hair press-in length 0.4mm.Utilize opticmicroscope to observe the foreign matter (fragment of film) caused because of friction grinding on gained substrate, measure the foreign matter number in the region of 500 μm × 500 μm.Evaluate as follows: be the average evaluation of less than 3 by foreign matter number be rub resistance " well ", being "available" by the average evaluation of more than 4, less than 7, is rub resistance " bad " by the average evaluation of more than 8.Its result is, does not observe foreign matter, and the rub resistance of this film is " well ".

(5) evaluation of orientation

For the glass substrate with alignment films implementing friction orientation process of described acquisition, with the mode evaluation approach identical with (4) of described embodiment 1-1.Its result is, in this substrate, refractive anisotrop is 0.031nm, is " well ".

(6) manufacture of the FFS type liquid crystal display device of rubbing manipulation is used

In the mode that (5) with described embodiment 1-1 are identical, the FFS type liquid crystal display device shown in construction drawing 1.The floor map of top electrodes 13 used herein is shown in Fig. 4 (a) and Fig. 4 (b).In addition, Fig. 4 (a) is the vertical view of top electrodes 13, and Fig. 4 (b) is Fig. 4 (a) by the enlarged view of the part C1 of dotted line.In the present embodiment, use the substrate that the live width d1 with electrode is 4 μm, interelectrode distance d2 is the top electrodes of 6 μm.

Then, utilize cotton, friction treatment is implemented to each surface of the film be formed on glass substrate, makes liquid crystal orientation film 12.In Fig. 4 (b), represent to the frictional direction of the film be formed on glass substrate 11a with arrow.These substrates are become antiparallel mode with the frictional direction of substrate 11a each other, substrate 11b, the spacer being 3.5 μm via diameter is fitted, inject liquid crystal MLC-6221 (manufacture of Merck (Merck) company), form liquid crystal layer 16.And then, on the two sides, outside of substrate 11a, substrate 11b, to fit Polarizer (diagram slightly) in the mode that the polarization direction of 2 pieces of Polarizers is orthogonal, make liquid crystal display device 10 thus.

(7) evaluation of liquid crystal aligning

For the friction FFS type liquid crystal display device of described manufacture, carry out the evaluation of liquid crystal aligning in the mode that (6) with described embodiment 1-1 are identical.Its result is, liquid crystal aligning " well " in this liquid crystal display device.

(8) evaluation of voltage retention and thermotolerance

For the friction FFS type liquid crystal display device of described manufacture, voltage retention (VHRBF) is measured in the mode that (7) with described embodiment 1-1 are identical, and in the mode that (8) with described embodiment 1-1 are identical, the velocity of variation of the voltage retention before and after giving according to thermal stresses carrys out the thermotolerance of evaluating liquid crystal display element.Its result is, VHR _bFbe 99.4%.In addition, Δ VHR is 1.6%, is judged as thermotolerance " well ".

In the mode that (9) with described embodiment 1-1 are identical, evaluate resistance to frame inequality.Its result is, depending on not recognizing the luminance difference of this liquid crystal display device, is judged as resistance to frame inequality " excellent ".

The evaluation of DC image retention is carried out in the mode identical with described embodiment 1-1 (10).Its result is, the image retention cancellation time of this liquid crystal display device is 2 seconds, is evaluated as " well ".

The evaluation of AC image retention is carried out in the mode identical with described embodiment 1-1 (10).In addition, also use the liquid crystal cells of Polarizer of not fitting to evaluate in this case.Its result is, minimum relative transmittance is 0.1%, is judged as contrast-response characteristic " well ".

[embodiment 2-2 ~ embodiment 2-15 and comparative example 2-1 ~ comparative example 2-5]

Except being set to the kind of the polymkeric substance used in the preparation of liquid crystal aligning agent and amount as except record in following table 4 respectively, preparing liquid crystal aligning agent respectively in the mode identical with described embodiment 2-1, manufacturing liquid crystal display device and evaluating.Wherein, about comparative example 2-4, liquid crystal aligning is poor, does not carry out the evaluation about liquid crystal cells.Evaluation result is shown in following table 4 and table 5.

[table 4]

[table 5]

As shown in table 3 ~ table 5, comprise and use compound (C ') and in the liquid crystal aligning agent of polymkeric substance that obtains, all obtain good result about the concave-convex surface of film, transmissivity, rub resistance and orientation.In addition, in the liquid crystal display device using these liquid crystal aligning agent to make, all obtain good result about the orientation of liquid crystal molecule, voltage retention, thermotolerance, resistance to frame inequality, image retention characteristic (DC image retention) and contrast-response characteristic (AC image retention), and balance has various characteristic well concurrently.

On the other hand, use and do not have aromatic amine structure and only have in the comparative example 2-1 of the diamines of chain-like structure, image retention characteristic is " bad ", and resistance to frame inequality and thermotolerance are the result poor compared with embodiment, for reach for object of the present invention and insufficient.

In addition, use and only have in comparative example 1-1, the comparative example 2-2 of the diamines of aromatic amine structure, comparative example 2-3, the thermotolerance of liquid crystal display device, resistance to frame inequality and contrast-response characteristic are " bad ".In addition, use storage stability, the concave-convex surface of film, the transmission rate variance of the polymkeric substance of the comparative example 4 of PAm-14, the poor orientation of liquid crystal, be therefore not sufficient to be used as liquid crystal display device.And then in comparative example 2-5, thermotolerance and resistance to frame inequality are " bad ".In addition, if synthetically consider the orientation of the liquid crystal in the transmissivity of film, rub resistance and orientation and liquid crystal display device, voltage retention, thermotolerance, resistance to frame inequality, image retention characteristic and contrast-response characteristic, then arbitrary comparative example all becomes the result poor compared with embodiment.

[embodiment 3-1:TN type liquid crystal display device]

(1) preparation of liquid crystal aligning agent

Polymkeric substance (PAm-16) the 50 amount part obtained in polymkeric substance (PAm-3) 50 weight part obtained in the synthesis example 2-3 of polymkeric substance and synthesis example 2-16 is dissolved in the mixed solvent (NMP: BC=50: 50 (weight ratio)) of NMP and BC, makes the solution that solid component concentration is 6.5 % by weight.After this solution is fully stirred, utilize aperture to be that the strainer of 0.2 μm filters, prepare liquid crystal aligning agent thus.

(2) evaluation of printing

Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), the liquid crystal aligning agent of preparation in described (1) is coated the transparent electrical pole-face of the glass substrate with the transparency electrode comprising ito film, the hot-plate of 80 DEG C heats (prebake conditions) 1 minute and after removing solvent, the hot-plate of 200 DEG C heats (toasting afterwards) 10 minutes, forming average film thickness is film.Utilize multiplying power be the microscope of 20 times to observe this film, the presence or absence of the uneven and pin hole of investigation printing.Evaluate as follows: by printing, uneven and pin hole these two all unobservable average evaluations are printing " well ", being printing "available" by least any one the average evaluation observing the uneven and pin hole of printing a little, is printing " bad " by least any one the average evaluation seeing the uneven and pin hole of a large amount of printing.In the present embodiment, printing inequality and pin hole these two are not all observed, and printing is " well ".

(3) evaluation of transmissivity

For the film of described acquisition, evaluate transmissivity in the mode that (3) with described embodiment 1-1 are identical.Its result is, the transmissivity of this film is 98.4%, is " well ".

(4) manufacture of TN type liquid crystal cells

Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), the liquid crystal aligning agent of preparation in described (1) is coated on the transparent electrical pole-face with the glass substrate of the transparency electrode comprising ito film, the hot-plate of 80 DEG C heats (prebake conditions) 1 minute and after removing solvent, the hot-plate of 200 DEG C heats (toasting afterwards) 10 minutes, forming average film thickness is film.To this film, utilize and there is the friction machine of the roller being wound with artificial silk cloth, carry out friction treatment with roller rotating speed 500rpm, platform movement speed 3cm/ second, hair press-in length 0.4mm, give liquid crystal aligning ability.Then, in ultrapure water, carry out 1 minute ultrasonic washing, in 100 DEG C of cleaning ovens dry 10 minutes then, obtain the substrate with liquid crystal orientation film thus.In addition, described operation is carried out repeatedly, obtain a pair (2 pieces) substrate with liquid crystal orientation film.

Then, on wherein one piece of substrate in described a pair substrate, after the outer rim coating in the face with liquid crystal orientation film adds and has diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, in the relative mode of liquid crystal aligning face, a pair substrate is overlapping and crimp, make adhesive hardens.Then, to between a pair substrate, nematic liquid crystal (Merck (Merck) company manufacture is filled in liquid crystal injecting port, MLC-6221) after, utilize acrylic acid series ray hardening type adhesive to be sealed by liquid crystal injecting port, manufacture TN type liquid crystal cells thus.

(5) evaluation of liquid crystal aligning

For the liquid crystal cells manufactured in described (4), under cross Nicols, utilize microscope, the presence or absence of abnormal area when doubly observing on-off 5V voltage with multiplying power 50.Evaluate in the mode that (6) with described embodiment 1-1 are identical.Its result is, liquid crystal aligning " well " in this liquid crystal display device.

(6) evaluation of tilt angle stability

For the liquid crystal cells manufactured in described (4), utilize the angle using the crystallization rotational method of He-Ne laser light to measure liquid crystal molecule to tilt from real estate, using this value as initial pretilt theta _iN.Crystallization rotational method is according to the non-patent literature 3 (people such as T.J. Schaefer (T.J.Scheffer), " applied physics magazine (Journal of Applied Physics, J.Appl.Phys.) the 48th phase the 1783rd page (1977)) and non-patent literature 4 (people such as wild (F.Nakano) in F., " Japanese applied physics magazine (Japanese Journal ofApplied Physics, JPN.J.Appl.Phys.) the 19th phase the 2013rd page (1980)) in record method carry out.

Then, to the initial pretilt theta of mensuration _iNafter liquid crystal cells apply the voltage of alternating current 100 hours of 5V.Then, utilize and again measure tilt angle with described identical method, using this value as the pretilt theta after voltage applying _aF.These measured values are substituted in following mathematical expression (EX-4), obtain the variable quantity (Δ θ (°)) that voltage applies the tilt angle of front and back.

Δθ＝|θ _AF-θ _IN| (EX-4)

Average evaluation Δ θ being less than 3% is tilt angle stability " well ", by more than 3% and the average evaluation being less than 4% is tilt angle stability "available", be tilt angle stability " bad " by the average evaluation of more than 4%, the tilt angle velocity of variation of this liquid crystal display device of result is 1.6%, is judged as tilt angle stability " well ".

(7) evaluation of voltage retention and thermotolerance

Voltage retention (VHR is measured in the mode that (7) with described embodiment 1-1 are identical _bF), and in the mode identical with (8) of the firm 1-1 of described enforcement, the velocity of variation of the voltage retention before and after giving according to thermal stresses carrys out the thermotolerance of evaluating liquid crystal display element.Its result is, VHR _bFbe 98.6%.In addition, Δ VHR is 2.1%, is judged as thermotolerance " well ".

(8) the uneven patience (resistance to frame inequality) of sealing agent periphery

Resistance to frame inequality is evaluated in the mode that (9) with described embodiment 1-1 are identical.Its result is, depending on not recognizing the luminance difference of this liquid crystal display device, is judged as " excellent ".

(9) evaluation (evaluation of DC image retention) of image retention characteristic

The evaluation of DC image retention is carried out in the mode identical with described embodiment 1-1 (10).Its result is, the image retention cancellation time of this liquid crystal display device is 12 seconds, is evaluated as " well ".

[embodiment 4-1:VA type liquid crystal display device]

(1) preparation of liquid crystal aligning agent

Polymkeric substance (PAm-3) 80 weight part obtained in polymkeric substance (PIm-2) 20 weight part obtained in the synthesis example 3-2 of polymkeric substance and synthesis example 2-3 is made an addition in NMP and BC, makes the solution that solid component concentration is 6.5 % by weight, the ratio of mixture of solvent is NMP: BC=50: 50 (weight ratios).After this solution is fully stirred, filter with the strainer that aperture is 0.2 μm, prepare liquid crystal aligning agent thus.

(2) evaluation of printing

Use the liquid crystal aligning agent of preparation in described (1), investigate printing in the mode that (2) with described embodiment 3-1 are identical, printing inequality and pin hole these two are not all observed, and printing is " well ".

(3) evaluation of transmissivity

For the film of described acquisition, evaluate transmissivity in the mode that (3) with described embodiment 1-1 are identical.Its result is, this film is 99.2%, and the transmissivity of film is " well ".

(4) manufacture of VA type liquid crystal cells

Use liquid crystal orientation film printing press (Japan's description printing (stock) manufactures), the liquid crystal aligning agent of described preparation is coated on the transparent electrical pole-face with the glass substrate (thickness is 1mm) of the transparency electrode comprising ito film.Then, the hot-plate of 80 DEG C heats (prebake conditions) 1 minute, and then on the hot-plate of 200 DEG C, heat (toasting afterwards) 60 minutes, forming average film thickness is film (liquid crystal orientation film).This operation is carried out repeatedly, obtains a pair (2 pieces) glass substrate on nesa coating with liquid crystal orientation film.Then, for the wherein one piece of substrate in described a pair substrate, after the outer rim coating in the face with liquid crystal orientation film adds and has diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, in the relative mode of liquid crystal aligning face by the crimping of a pair substrate overlap, make adhesive hardens.Then, from liquid crystal injecting port to after filling nematic liquid crystal (Merck (Merck) company manufactures, MLC-6608) between a pair substrate, utilize acrylic acid series photo-hardening caking agent to be sealed by liquid crystal injecting port, manufacture VA type liquid crystal cells thus.

(5) evaluation of liquid crystal aligning, voltage retention and thermotolerance

For the liquid crystal cells manufactured in described (4), carry out the evaluation of liquid crystal aligning in the mode that (6) with embodiment 1-1 are identical, the liquid crystal aligning of this liquid crystal cells of result is " well ".In addition, voltage retention (VHR is measured in the mode that (7) with embodiment 1-1 are identical _bF), and the evaluation of thermotolerance (thermal stresses gives the velocity of variation of the voltage retention of front and back) is carried out in the mode that (8) with described embodiment 1-1 are identical.Its result is, VHR _bFbe 99.0%.In addition, Δ VHR is 2.3%, is judged as thermotolerance " well ".

(6) the uneven patience (resistance to frame inequality) of sealing agent periphery

Resistance to frame inequality is evaluated in the mode that (9) with described embodiment 1-1 are identical.Its result is, depending on not recognizing the luminance difference of this liquid crystal cells, is judged as " well ".

[embodiment 5-1: phase retardation film]

(1) preparation of liquid crystal aligning agent

Polymkeric substance (PSi-1) 10 weight part obtained in the polymkeric substance obtained in synthesis example 2-1 (PAm-1) 100 weight part and synthesis example 4-1 is dissolved in the mixed solvent (NMP: BC=50: 50 (weight ratio)) comprising NMP and BC, makes the solution that solid component concentration is 3.5 % by weight.This solution is filtered with the strainer that aperture is 0.2 μm, prepares liquid crystal aligning agent thus.

(2) manufacture of phase retardation film

In the one side of the TAC film as substrate, use excellent coating machine to be coated with the liquid crystal aligning agent of described preparation, in baking oven, form with 120 DEG C of bakings 2 minutes the film that thickness is 100nm.Then, to this film coated surface, use Hg-Xe lamp and Glan-Taylor prism, vertically irradiate the polarisation ultraviolet 10mJ/cm of the open-wire line comprising 313nm from substrate normal ².Then, after being filtered with the strainer that aperture is 0.2 μm by polymerizable liquid crystal (RMS03-013C, Merck (Merck) company manufactures), utilize excellent coating machine, this polymerizable liquid crystal is coated on the film after rayed, form the film of polymerizable liquid crystal.In temperature after toasting 1 minute in the baking oven being adjusted to 50 DEG C, use Hg-Xe lamp, from vertical direction, coated surface is irradiated to the ultraviolet 1,000mJ/cm comprising the non-polarized of the open-wire line of 365nm ², make polymerizable liquid crystal harden and form liquid crystal layer, manufacture phase retardation film thus.

(3) evaluation of liquid crystal aligning

For the phase retardation film manufactured in described (2), observed the presence or absence of abnormal area by the visual and polarizing microscope (multiplying power is 2.5 times) under cross Nicols, evaluate liquid crystal orientation (light orientation) thus.Evaluate as follows: by good and utilize polarizing microscope not observe the average evaluation of abnormal area for liquid crystal aligning " well " at visual lower orientation; Abnormal area will do not observed under visual, but utilize polarizing microscope and observe the average evaluation of abnormal area for liquid crystal aligning "available"; Be liquid crystal aligning " bad " by the average evaluation being observed abnormal area by visual and polarizing microscope.Its result is, this phase retardation film is be evaluated as liquid crystal aligning " well ".

(4) adhesivity

Use the phase retardation film manufactured in described (2), the film formed utilizing liquid crystal aligning agent and the adhesivity of substrate are evaluated.First, use the spacer at equal intervals with guiding piece, utilize cutters, from the face of the liquid crystal layer side of phase retardation film incision otch, in the scope of 1cm × 1cm, form the tartan design of 10 × 10.The degree of depth of each otch is set to till liquid crystal layer surface arrives the half of substrate thickness.Then, after the mode adherent glass paper of whole covering described tartan design, this glassine paper is peeled off.By the visual notch observing the tartan design after stripping under cross Nicols, evaluate adhesivity.Evaluate as follows: will be adhesivity " well " along the part of cut line and the cross section of the tartan design average evaluation to peeling off unconfirmed; By the number relative to tartan design entirety, be the average evaluation being less than 15% in the number of the grid of described partially observable stripping be adhesivity "available"; By the number relative to tartan design entirety, the average evaluation being more than 15% in the number of the grid of described partially observable stripping is adhesivity " bad ".Its result is, this phase retardation film is adhesivity " well ".

Claims

1. a liquid crystal aligning agent, it is characterized in that: containing the polymkeric substance (P) that at least one sharp compound (C ') in the cohort selecting free compound (C) and compound (C1) to form is obtained for reacting, described compound (C) has following structure (a) and following structure (b), and described compound (C1) has following structure (a) and following structure (b1) and on aromatic series cyclic group in described structure (a), non-bond has the reactive base participating in polymerization;

A () 2 or 3 aromatic ring bases are binding on the aromatic amine structure on same nitrogen-atoms;

(b) be selected from by the divalent chain alkyl of carbon number more than 6 and by least 1 methylene radical in described chain alkyl with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂chain-like structure in the-cohort that forms of divalent base that replaces, wherein R is hydrogen atom or 1 valency organic radical; And

(b1) be selected from by the divalent chain alkyl of carbon number 1 ~ 5, by least 1 methylene radical in described chain alkyl with-O-,-S-,-CO-,-NR ³-,-NR ³cO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of-replacement ,-O-,-S-,-CO-,-NR ³cO-,-COO-,-COS-and-Si (CH ₃) ₂structure in the-cohort that forms, wherein R ³for hydrogen atom or 1 valency organic radical.

2. liquid crystal aligning agent according to claim 1, is characterized in that: described compound (C) is the compound in molecule with 2 the above aromatic amine structures.

3. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described polymkeric substance (P) is for being selected from least one in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide.

4. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: the compound of described compound (C) represented by following formula (1),

[changing 1]

In formula (1), A ¹and A ³be separately hydrogen atom or 1 valency organic radical, A ²and A ⁴be separately singly-bound or divalent organic radical; B ¹and B ²be separately singly-bound or divalent organic radical; Wherein, at B ¹when for singly-bound, A ¹and A ²at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ¹when for divalent organic radical, A ¹, A ²and B ¹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; At B ²when for singly-bound, A ³and A ⁴at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ²when for divalent organic radical, A ³, A ⁴and B ²in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ¹for comprising the divalent base of described structure (b).

5. liquid crystal aligning agent according to claim 4, is characterized in that: described B ¹and described B ²at least any one is singly-bound.

6. liquid crystal aligning agent according to claim 4, is characterized in that: described L ¹represented by following formula (2),

[changing 2]

In formula (2), L ²and L ³it is separately described structure (b); The divalent base of Q represented by following formula (3) or formula (4); N is the integer of 0 ~ 4; " * " represents associative key;

[changing 3]

In formula (3), A ⁵for hydrogen atom or 1 valency organic radical; R ¹and R ²for substituting group, each other can be identical, also can be different; " * " represents associative key;

[changing 4]

In formula (4), A ⁶for hydrogen atom or 1 valency organic radical; " * " represents associative key.

7. liquid crystal aligning agent according to claim 4, is characterized in that: the compound of described compound (C) represented by following formula (1-1),

[changing 5]

In formula (1-1), L ¹¹for comprising at least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of the group of-replacement, wherein R is hydrogen atom or 1 valency organic radical; A ¹, A ², A ³, A ⁴, B ¹and B ²be and described formula (1) identical meanings; Wherein, at L ¹¹when there is alkane two base of carbon number 1 ~ 5, A ¹and A ³at least any one is hydrogen atom, or B ¹and B ²at least any one is divalent organic radical.

8. liquid crystal aligning agent according to claim 4, is characterized in that: the compound of described compound (C) represented by following formula (1-2),

[changing 6]

In formula (1-2), L ¹²for comprising the divalent base of the divalent chain alkyl of carbon number more than 6; A ¹, A ², A ³, A ⁴, B ¹and B ²be and described formula (1) identical meanings.

9. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: the compound of described compound (C1) represented by following formula (1-3),

[changing 7]

In formula (1-3), A ⁷for hydrogen atom or 1 valency organic radical, A ⁸and A ⁹be separately singly-bound or divalent organic radical; Wherein, A ⁷, A ⁸and A ⁹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ⁴for described structure (b1), L ⁵for singly-bound or divalent organic radical.

10. liquid crystal aligning agent according to claim 1 and 2, it is characterized in that: described polymkeric substance (P) for being selected from by making tetracarboxylic dianhydride, carry out reacting with the diamines that comprises described compound (C ') and at least one in cohort that the polyamic acid, poly amic acid ester and the polyimide that obtain form, and

Described tetracarboxylic dianhydride comprises and is selected from by 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-volution-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydro-3-furyl)-3-methyl-3-tetrahydrobenzene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxyl norbornane-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, dicyclo [3.3.0] octane-2,4, at least one in the cohort that 6,8-tetracarboxylic dianhydride, ethylenediamine tetraacetic acid (EDTA) dianhydride, pentamethylene tetracarboxylic dianhydride, 1,3-PD two (trimellitic anhydride ester) and pyromellitic acid anhydride form.

11. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: the molecular weight of described compound (C ') is 1, less than 000.

12. 1 kinds of liquid crystal orientation films, is characterized in that: it uses the liquid crystal aligning agent according to any one of claim 1 to 11 and is formed.

13. 1 kinds of liquid crystal display device, is characterized in that: comprise liquid crystal orientation film according to claim 12.

14. 1 kinds of phase retardation films, is characterized in that: comprise liquid crystal orientation film according to claim 12.

The manufacture method of 15. 1 kinds of phase retardation films, is characterized in that comprising: the liquid crystal aligning agent according to any one of claim 1 to 11 is coated substrate is formed film step, light-struck step is carried out to described film; And on described film after rayed, be coated with polymerizable liquid crystal and the step making it harden.

16. 1 kinds of polymkeric substance, is characterized in that, it is for being selected from the polymkeric substance in the cohort that is made up of polyamic acid, poly amic acid ester and polyimide, and

It is at least one compound that will be selected from the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide, obtain for reaction with the diamines comprising at least one be selected from cohort that the compound represented by the compound represented by following formula (1-1), the compound represented by following formula (1-2) and following formula (1-3) forms

[changing 8]

In formula (1-1), A ¹and A ³be separately hydrogen atom or 1 valency organic radical, A ²and A ⁴be separately singly-bound or divalent organic radical; B ¹and B ²be separately singly-bound or divalent organic radical; Wherein, at B ¹when for singly-bound, A ¹and A ²at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ¹when for divalent organic radical, A ¹, A ²and B ¹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; At B ²when for singly-bound, A ³and A ⁴at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ²when for divalent organic radical, A ³, A ⁴and B ²in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ¹¹for comprising at least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of the group of-replacement, wherein R is hydrogen atom or 1 valency organic radical; Wherein, at L ¹¹when there is alkane two base of carbon number 1 ~ 5, A ¹and A ³at least any one is hydrogen atom, or B ¹and B ²at least any one is divalent organic radical;

[changing 9]

In formula (1-2), L ¹²for comprising the divalent base of the divalent chain alkyl of carbon number more than 6; A ¹, A ², A ³, A ⁴, B ¹and B ²be and described formula (1-1) identical meanings; Wherein, at L ¹²when alkane two base for carbon number 6 ~ 10, A ¹and A ³at least any one is 1 valency organic radical, or B ¹and B ²at least any one is divalent organic radical;

[changing 10]

In formula (1-3), A ⁷for hydrogen atom or 1 valency organic radical, A ⁸and A ⁹be separately singly-bound or divalent organic radical; Wherein, A ⁷, A ⁸and A ⁹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ⁴for the divalent chain alkyl of carbon number 1 ~ 5, by least 1 methylene radical in described chain alkyl with-O-,-S-,-CO-,-NR ³-,-NR ³cO-,-COO-,-COS-or-Si (CH ₃) ₂-replace divalent base ,-O-,-S-,-CO-,-NR ³cO-,-COO-,-COS-or-Si (CH ₃) ₂-, wherein R ³for hydrogen atom or 1 valency organic radical; L ⁵for singly-bound or divalent organic radical.

17. 1 kinds of compounds, is characterized in that, it is represented by following formula (1-1),

[changing 11]

In formula (1-1), A ¹and A ³be separately hydrogen atom or 1 valency organic radical, A ²and A ⁴be separately singly-bound or divalent organic radical; B ¹and B ²be separately singly-bound or divalent organic radical; Wherein, at B ¹when for singly-bound, A ¹and A ²at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ¹when for divalent organic radical, A ¹, A ²and B ¹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; At B ²when for singly-bound, A ³and A ⁴at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ²when for divalent organic radical, A ³, A ⁴and B ²in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ¹¹for comprising at least 1 methylene radical in the divalent chain alkyl of carbon number more than 6 with-O-,-S-,-CO-,-NR-,-NRCO-,-COO-,-COS-or-Si (CH ₃) ₂the divalent base of the group of-replacement, wherein R is hydrogen atom or 1 valency organic radical; Wherein, at L ¹¹when there is alkane two base of carbon number 1 ~ 5, A ¹and A ³at least any one is hydrogen atom, or B ¹and B ²at least any one is divalent organic radical.

18. 1 kinds of compounds, is characterized in that, it is represented by following formula (1-2),

[changing 12]

In formula (1-2), A ¹and A ³be separately hydrogen atom or 1 valency organic radical, A ²and A ⁴be separately singly-bound or divalent organic radical; B ¹and B ²be separately singly-bound or divalent organic radical; Wherein, at B ¹when for singly-bound, A ¹and A ²at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ¹when for divalent organic radical, A ¹, A ²and B ¹in at least 2 be binding on nitrogen-atoms with aromatic nucleus; At B ²when for singly-bound, A ³and A ⁴at least 1 be binding on nitrogen-atoms with aromatic nucleus, at B ²when for divalent organic radical, A ³, A ⁴and B ²in at least 2 be binding on nitrogen-atoms with aromatic nucleus; L ¹²for comprising the divalent base of the divalent chain alkyl of carbon number more than 6; Wherein, at L ¹²when alkane two base for carbon number 6 ~ 10, A ¹and A ³at least any one is 1 valency organic radical, or B ¹and B ²at least any one is divalent organic radical.

19. 1 kinds of compounds, is characterized in that, it is represented by following formula (1-3),

[changing 13]