CN104419429A - Liquid crystal aligning agent and film thereof, display component, film and manufacturing method thereof, polymer and compound - Google Patents

Abstract

The invention provides a liquid crystal aligning agent for forming a liquid crystal aligning film which can show various characteristics required by a liquid crystal display component. The aligning agent contains at least one polymer (P) selected from a group composed of polyamide acid, polyamide acid ester and polyimide. The polymer (P) is obtained by making a tetracarboxylic acid derivative react with diamine of a compound represented by a formula (1) as follows (RA is a bivalent group containing an oxygen atom or a sulfur atom between a C-C bond of a hydrocarbyl and at at least any one position adjacent to the hydrocarbyl, and each of X1 and X2 is a single bond, an oxygen atom, a sulfur atom or a bivalent organic group).

Description

Orientation agent and film, display element, film and method for making thereof, polymkeric substance and compound

Technical field

The present invention relates to a kind of crystal aligning agent, liquid crystal orienting film, liquid crystal display device, phase retardation film and manufacture method thereof, polymkeric substance and compound.

Background technology

Before, liquid crystal display device has developed electrode structure or the different multiple type of drive of the physical property, manufacturing step etc. of liquid crystal molecule that use, such as there will be a known twisted nematic (twisted nematic, TN) type or STN Super TN (super-twisted nematic, STN) type, vertical orientation (vertical alignment, VA) type, coplanar switching (in-plane switching, IPS) type, fringing field switch the various liquid crystal display device such as (fringe fieldswitching, FFS) type.These liquid crystal display device have to make liquid crystal molecule carry out the liquid crystal orienting film of 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 orienting film uses polyamic acid or polyimide usually.

In addition, in recent years, liquid crystal display device not only as before for the display terminal of PC etc., but also for the multiple use such as such as LCD TV or auto-navigation system (car navigation system), mobile phone, smart mobile phone (smartphone), information display.With regard to this background, improve further the requirement of the high performance of liquid crystal display device, as liquid crystal orienting film, requirement makes the various characteristics required by liquid crystal display device better.In addition, polymkeric substance in this crystal aligning agent is proposed there is multiple crystal aligning agent in order to obtain this liquid crystal orienting film or allocates, in order to obtain the monomer (such as with reference to patent documentation 1, patent documentation 2) of this polymkeric substance.

Patent Document 1 discloses use 1, the polyimide that two (4-(4-aminobenzyl) phenyl) ethane of 2-, 1,6-two (4-(4-aminobenzyl) phenyl) hexanes etc. obtain by not having the diamines of polar group and the reaction of tetracarboxylic dianhydride is used as the component of polymer of crystal aligning agent.In addition, Patent Document 2 discloses use in an embodiment by 1,2,3, the reaction of two [4-(4-amino-benzene oxygen) phenoxy group] pentane of 4-tetramethylene tetracarboxylic dianhydride and 1,5-and the polyamic acid that obtains are used as the component of polymer of crystal aligning agent.

In addition, use multiple optical material in liquid crystal display device, wherein phase retardation film be for eliminate display painted object or eliminate display look and contrast gradient (contrast) use than the object of the visual angle interdependence changed along with visual direction.Described phase retardation film there will be a known the film with liquid crystal orienting film and liquid crystal layer, described liquid crystal orienting film is formed at triacetyl cellulose (triacetyl cellulose, TAC) surface of the substrate such as film, described liquid crystal layer is formed by making polymerizable liquid crystal harden on the surface of described liquid crystal orienting film.In addition, in recent years, following light orientation method is utilized when making the liquid crystal orienting film of phase retardation film, namely, give LCD alignment ability by the radioactive rays radioactivity-sensitive organic film being formed at substrate surface being irradiated to polarisation or non-polarized, and propose multiple in order to utilize described method to make the phase retardation film crystal aligning agent (such as with reference to patent documentation 3) of liquid crystal orienting film.

The method of producing phase retardation film with technical scale proposes volume to volume (roll-to-roll) mode (such as with reference to patent documentation 4).The method is to carry out following process with continuous print step, and the method that the film after these steps is made coiling body to reclaim, describedly to be treated to: on the coiling body of the base material film of strip, roll out film, the film that this rolls out is formed the process of liquid crystal orienting film; Liquid crystal orienting film is coated with polymerizable liquid crystal and carries out the process of hardening; And the process of optionally lamination protective membrane.

[prior art document]

[patent documentation]

[patent documentation 1] Japanese Patent No. 3658798 publication

No. 2004/053583rd, [patent documentation 2] International Publication

[patent documentation 3] Japanese Patent Laid-Open 2012-37868 publication

[patent documentation 4] Japanese Patent Laid-Open 2000-86786 publication

Summary of the invention

[invention institute for solution problem]

But when the component of polymer using the polyimide of record in described patent documentation 1 as crystal aligning agent, there is the tendency to the coating difference of substrate in this crystal aligning agent.In addition, when using this crystal aligning agent to make the liquid crystal orienting film of FFS type liquid crystal display device, tilt angle (pretilt angle) becomes too high, and viewing angle characteristic is poor.Use in the liquid crystal display device of the crystal aligning agent comprising the polyamic acid recorded in described patent documentation 2, voltage preserving property and poor heat resistance.

In addition, about phase retardation film, although can produce easily with technical scale by adopting described volume to volume mode, but then, when the adhesion of liquid crystal orienting film and base material film is insufficient, when film being made coiling body after step terminates, have the situation that liquid crystal orienting film is peeled off in substrate film.In said case, the problem that goods yield declines can be produced.

The present invention is formed in view of described problem, and one of object is for providing a kind of crystal aligning agent in order to form the liquid crystal orienting film that can suitably show the various characteristics required by liquid crystal display device.In addition, another object of the present invention is for providing a kind of good in order to form LCD alignment, and the crystal aligning agent of the phase retardation film liquid crystal orienting film good with the adhesion of substrate.

[means of dealing with problems]

The people such as the present inventor have carried out active research to reach the problem of prior art as above, found that, by at least any one polymkeric substance containing the polyamic acid, poly amic acid ester and the polyimide that are obtained by the condensation polymerization of the diamines and tetracarboxylic acid derivatives with ad hoc structure, described problem can be solved, thus complete the present invention.Specifically, following crystal aligning agent, liquid crystal orienting film, liquid crystal display device, phase retardation film and manufacture method thereof, polymkeric substance and compound is provided by the present invention.

An aspect of of the present present invention is for providing a kind of crystal aligning agent, it contains at least one polymkeric substance (P) in the cohort being selected from and being made up of polyamic acid, poly amic acid ester and polyimide, described polymkeric substance (P) is at least one tetracarboxylic acid derivatives by making to be selected from the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide, carries out reacting and obtain with the diamines of the compound comprised represented by following formula (1).

[changing 1]

(in formula (1), R ^abe the divalent group that at least any position of position between the C-C of the alkyl of carbon number 1 ~ 30 and adjacent with this alkyl has Sauerstoffatom or sulphur atom, at least 1 of the hydrogen atom that this alkyl has can replace through halogen atom; X ¹and X ²be separately singly-bound, Sauerstoffatom, sulphur atom or divalent organic radical; Wherein, at X ¹and X ²for Sauerstoffatom, and R ^afor-O-R ¹-O-(R ¹alkane two base for carbon number 1 ~ 18) when, described tetracarboxylic acid derivatives is except the situation of 1,2,3,4-tetramethylene tetracarboxylic dianhydride.)

Another aspect of the invention is and provide a kind of liquid crystal orienting film, it uses described crystal aligning agent and is formed.In addition, the invention provides the liquid crystal display device comprising described liquid crystal orienting film and phase retardation film.And then another aspect of the invention is the manufacture method providing a kind of phase retardation film, it comprises the following steps: described crystal aligning agent is coated on substrate and forms film; Rayed is carried out to this film; And on described film after rayed, be coated with polymerizable liquid crystal and make it harden.In addition, the present invention and then provide the diamines making the compound represented by described formula (1) and comprise this compound, carries out reacting and the polymkeric substance obtained with at least one tetracarboxylic acid derivatives be selected from the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide.

[effect of invention]

The crystal aligning agent of the polymkeric substance obtained by using the reaction of diamines and the tetracarboxylic acid derivatives comprised represented by described formula (1), can form the liquid crystal orienting film that can suitably show the various characteristics required by liquid crystal display device.In addition, according to crystal aligning agent of the present invention, the liquid crystal display device of high-quality can be manufactured.In addition, and then, use crystal aligning agent of the present invention and the liquid crystal orienting film obtained good to the adhesion of substrate.Therefore, when described liquid crystal orienting film is made coiling body come keeping etc., liquid crystal orienting film and substrate are also difficult to peel off, therefore, such as manufacture phase retardation film time, the decline of goods yield can be suppressed.

Accompanying drawing explanation

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

Fig. 2 (a), Fig. 2 (b) are the floor map of upper current conducting cap.Fig. 2 (a) is the vertical view of upper current conducting cap, and Fig. 2 (b) is the magnified partial view of upper current conducting cap.

[explanation of symbol]

10: liquid crystal display device

11a, 11b: glass substrate

12: liquid crystal orienting film

13: upper current conducting cap

14: insulation layer

15: bottom electrode

16: liquid crystal layer

D1: the live width of electrode

D2: interelectrode distance

Embodiment

Crystal aligning agent of the present invention comprises at least one polymkeric substance (P) in the cohort being selected from and being made up of polyamic acid, poly amic acid ester and polyimide, and optionally comprises other compositions.Below, each composition contained in crystal aligning agent of the present invention and other compositions of optionally and arbitrarily allocating are described.

< polymkeric substance (P): polyamic acid >

Polyamic acid (hereinafter also referred to as polyamic acid (P)) as polymkeric substance of the present invention (P) obtains by making tetracarboxylic dianhydride and diamines carry out reacting.

[tetracarboxylic dianhydride]

Tetracarboxylic dianhydride for the synthesis of 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: 1,2,3,4-butane tetracarboxylic acid dianhydride etc.;

Ester ring type tetracarboxylic dianhydride include, for example: 1, 2, 3, 4-tetramethylene tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] octane-2, 4-diketone-6-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, 2, 4, 6, 8-tetracarboxylic dicyclo [3.3.0] octane-2:4, 6:8-dianhydride, 4, 9-dioxa three ring [5.3.1.0 ^2,6] undecane-3,5,8,10-tetraketone, cyclopentanetetracarboxylic's dianhydride etc.,

Aromatic tetracarboxylic acid's dianhydride include, for example: pyromellitic acid anhydride etc.; In addition, the tetracarboxylic dianhydride recorded in Japanese Patent Laid-Open 2010-97188 publication can also be used.In addition, described tetracarboxylic dianhydride can be used alone a kind or two or more combinationally used.

The tetracarboxylic dianhydride used in synthesis preferably comprises at least one in the cohort being selected from and being made up of following compound: 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-2,4,6,8-tetracarboxylic dianhydride, ethylene diaminetetraacetic acid dianhydride and pyromellitic acid anhydride.In addition, with regard to the transparency and deliquescent viewpoint in a solvent, preferably comprise ester ring type tetracarboxylic dianhydride, with regard to the viewpoint of electrical characteristic, preferably comprise aromatic tetracarboxylic acid's dianhydride.

[diamines]

The diamines used to synthesize described polyamic acid (P) comprises the compound represented by described formula (1).

R in described formula (1) ^ait is the divalent group that at least any position of position between the C-C of the alkyl of carbon number 1 ~ 30 and adjacent with this alkyl has Sauerstoffatom or sulphur atom.Herein, " alkyl " in this specification sheets refers to the connotation comprising chain alkyl, ester ring type alkyl and aromatic hydrocarbyl.So-called " chain alkyl ", refers to and do not comprise ring texture on main chain, but the straight-chain be only made up of chain-like structure or branch-like alkyl, can be saturated, also can be unsaturated.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 be made up of the structure of ester ring type hydrocarbon, be also contained in the alkyl in its part with chain-like structure.So-called " aromatic hydrocarbyl ", refers to and comprises the alkyl of aromatic ring structure as ring structure.Wherein, do not need only be made up of aromatic ring structure, can comprise the structure of chain-like structure or ester ring type hydrocarbon yet in its part.

As the concrete example of the alkyl of carbon number 1 ~ 30, chain alkyl include, for example: methylene radical, ethylidene, propane two base, butane two base, pentane two base, hexane two base, heptane two base, octane two base, nonane two base, decane two base, dodecane two base, the tetradecane two base, pentadecane two base, n-Hexadecane two base, octadecane two base etc., these alkyl can be straight-chain, also can be branch-like.In addition, ester ring type alkyl include, for example: the group etc. obtained from middle removal 2 hydrogen atoms such as pentamethylene, hexanaphthene, methylcyclohexane, ethylcyclohexane, propyl cyclohexane, pentylcyclohexane, dimethyl cyclohexane; Aromatic hydrocarbyl include, for example: the group etc. obtained from middle removal 2 hydrogen atoms such as benzene,toluene,xylene, ethylbenzene, propylbenzene, amylbenzene.Wherein, R ^ain alkyl preferably there is divalent chain alkyl, be more preferably divalent chain alkyl, be particularly preferably alkane two base.

In addition, R ^ain alkyl at least 1 of hydrogen atom of having can replace through halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine.

R ^athe quantity (total number) of the Sauerstoffatom had, sulphur atom is not particularly limited, with regard to the viewpoint that low pre-dumping or structure adaptability improve, and can according to R ^acarbon number suitably select.Be preferably 1 ~ 5, be more preferably 1 ~ 3.In addition, at R ^awhen there is these heteroatomss multiple (Sauerstoffatom, sulphur atom), only can have any one in Sauerstoffatom and sulphur atom, also can have 2 kinds of those atoms.

The position that Sauerstoffatom or sulphur atom import can be between the C-C of alkyl, also can be the position adjacent with alkyl, or also can be these two.In addition, so-called " between the C-C of alkyl ", refers to heteroatoms X ^aposition become "-R ¹⁰-X ^a-R ¹¹-" (wherein, R ¹⁰and R ¹¹for alkyl) situation, so-called " position adjacent with alkyl ", refers to heteroatoms X ^aposition become " *-X ^a-R ¹²-" (wherein, R ¹²for alkyl, " * " is and is binding on R ^aon the associative key of phenyl ring) situation.

X ¹and X ²be separately singly-bound, Sauerstoffatom, sulphur atom or divalent organic radical.Herein, as X ¹and X ²in " divalent organic radical ", include, for example alkane two base (alkanediyl) being substituted or being unsubstituted, alkene two base (alkenediyl), carbonyl, ester group (-COO-), amide group (-CO-NH-) etc. that are substituted or are unsubstituted be used as preferred concrete example.X ¹and X ²alkane two base be preferably carbon number 1 ~ 10, be more preferably 1 ~ 5, be especially preferably 1 ~ 3.In addition, alkene two base is preferably carbon number 2 ~ 10, is more preferably 2 ~ 5, is especially preferably 2 ~ 3.In addition, the substituting group be directed on alkane two base and alkene two base include, for example: Sauerstoffatom (-O-), sulphur atom (-S-), halogen atom (fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), hydroxyl etc.

Wherein, X ¹and X ²be preferably Sauerstoffatom, ester group, amide group, alkane two base of carbon number 1 ~ 10 or alkene two base of carbon number 2 ~ 10, be more preferably Sauerstoffatom, alkane two base of carbon number 1 ~ 5 or alkene two base of carbon number 2 ~ 5, be particularly preferably Sauerstoffatom, methylene radical, ethylidene or vinylidene.

In described compound, the compound represented by described formula (1) is preferably the compound represented by following formula (1-1).

[changing 2]

(in formula (1-1), R ²for the divalent alkyl of carbon number 1 ~ 30, X ³for Sauerstoffatom or sulphur atom, X ⁴for singly-bound, Sauerstoffatom or sulphur atom; X ¹and X ²be synonymous with described formula (1).)

R in described formula (1-1) ²concrete example can apply the R of described formula (1) ^athe explanation of alkyl of carbon number 1 ~ 30.R ²be preferably divalent chain alkyl, be more preferably alkane two base.The carbon number of this alkane two base is preferably 1 ~ 20, is more preferably 1 ~ 11, is especially preferably 1 ~ 8.

X ³for Sauerstoffatom or sulphur atom, be preferably Sauerstoffatom.In addition, X ⁴for singly-bound, Sauerstoffatom or sulphur atom, be preferably singly-bound or Sauerstoffatom.

The preferred concrete example of the compound represented by described formula (1) can enumerate the compound etc. such as represented by following formula (DA-1) ~ formula (DA-15) difference.

[changing 3]

[changing 4]

With regard to fully obtaining the viewpoint of effect of the present invention, relative to total scale of construction of the diamines used in the synthesis of polyamic acid, the usage ratio of the compound represented by described formula (1) is preferably set to the scope of 1 % by mole ~ 100 % by mole.Lower value is more preferably more than 5 % by mole, is especially preferably more than 15 % by mole, is particularly preferably more than 20 % by mole.Compound represented by described formula (1) can be used alone a kind or two or more combinationally used.

In addition, the compound represented by described formula (1) is due to the group " R between 2 phenyl ring ^a" for having the alkyl of Sauerstoffatom or sulphur atom, so be speculated as: use described compound and the polymkeric substance obtained improves structure adaptability by the raising of polarity, crystal aligning agent improves the coating of substrate.Be speculated as in addition: improved by the rotatory of molecule, friction extensibility improves, and can show the low pre-dumping (visual angle raising) of liquid crystal orienting film thus.Compound represented by described formula (1) obtain by carrying out condensation polymerization with tetracarboxylic anhydride etc. the good liquid crystal orienting film such as the various characteristic that can form LCD alignment, voltage preserving property, thermotolerance polymkeric substance in, all there is identical effect.Therefore, the compound do not recorded in following examples also can use in the present invention.

[synthesis of the compound represented by described formula (1)]

Compound represented by described formula (1) is by synthesizing appropriately combined for vitochemical well-established law.One example can be listed below method: synthesis replaces the one-level in described formula (1) amino and has the dinitro intermediate of nitro, then, uses suitable restoring system, the nitro of gained gained dinitro intermediate is carried out amination.

The method of synthesizing described dinitro intermediate suitably can be selected according to the compound as target.As one example, such as, at X ¹and X ²when for Sauerstoffatom, by synthesis HO-Ph-R ^adihydro-compound represented by-Ph-OH (Ph is phenylene), makes this dihydro-compound and halonitrobenzene carry out reacting and obtaining.In addition, at X ¹and X ²when for methylene radical, by making Bz-R ^acompound represented by-Bz (Bz is phenyl) and nitrobenzoyl chloride react, and carbonyl reduction gained reaction product had is that methylene radical obtains.At X ¹and X ²when for ester group, obtain by making described dihydro-compound and nitrobenzoyl chloride carry out reacting.

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 used herein include, for example ethyl acetate, toluene, tetrahydrofuran (THF), alcohol system etc.Wherein, the synthesis program of the compound represented by described formula (1) is not limited to described method.

[other diamines]

Compound represented by described formula (1) can be used alone by the diamines used in the synthesis of described polyamic acid (P), also the compound represented by other diamines beyond this compound and described formula (1) can be used.

Herein, other diamines described include, for example: aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.As the concrete example of these diamine compounds, aliphatie diamine include, for example: m-xylene diamine, 1,3-propylene diamine, tetramethylene-diamine, five methylene diamine, hexamethylene-diamine, 1,3-two (amino methyl) hexanaphthenes etc.; Ester ring type diamines include, for example: Isosorbide-5-Nitrae-diamino-cyclohexane, 4,4 '-methylene-bis (cyclo-hexylamine) etc.;

Aromatic diamine include, for example: Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 2,2 '-bis-(trifluoromethyl)-4,4 '-benzidine, 2,7 diamin of luorene (2,7-diaminofluorene), 4,4 '-diamino-diphenyl ether, two [4-(4-amino-benzene oxygen) phenyl] propane of 2,2-, two (4-aminophenyl) fluorenes (9,9-bis (4-aminophenyl) fluorene) 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, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-bis-(4-aminophenyl)-p-diaminodiphenyl, N, N '-bis-(4-aminophenyl)-N, N '-tolidine, Isosorbide-5-Nitrae-bis--(4-aminophenyl)-piperazine, 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, 3,5-diaminobenzoic acid, cholestane base oxygen base-3,5-diaminobenzene (cholestanyl oxy-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-aminobenzoic acyl-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, 1,3-diamino-4-octadecyl oxygen base benzene, 3-(3,5-diaminobenzene methanoyl) cholestane, two (the 4-aminobenzoic acyl-oxygen base) cholestane of 3,6-, and following formula (D-1)

[changing 5]

(in formula (D-1), X ⁱand X ^iIbe separately singly-bound ,-O-,-COO-or-OCO-, R ⁱfor alkane two base of carbon number 1 ~ 3, R ^iIfor alkane two base of singly-bound or carbon number 1 ~ 3, a be 0 or 1, b be the integer of 0 ~ 2, c is the integer of 1 ~ 20, and n 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.; The diamines recorded in Japanese Patent Laid-Open 2010-97188 publication can be used in addition.

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

Group "-C _ch _2c+1" concrete example can enumerate such as: 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) can enumerate the compound etc. such as represented by following formula (D-1-1) ~ formula (D-1-5) difference.

[changing 6]

In addition, described compound can be used alone a kind or two or more combinationally used by the diamines used in the synthesis of polyamic acid (P).

When by crystal aligning agent of the present invention for the manufacture of TN type, STN type or vertical orientation type liquid crystal display device, other diamines described preferably comprise the diamines having and can give the group (hereinafter also referred to " tilt angle imparting base ") of tilt angle expressive ability to film.Tilt angle is given base and be include, for example: the having the group of steroid skeleton, have the group etc. of polynuclear plane of the alkoxyl group of the alkyl of carbon number 4 ~ 20, the fluoroalkyl of carbon number 4 ~ 20, carbon number 4 ~ 20, carbon number 17 ~ 51.

The concrete example with the diamines of tilt angle imparting base can be enumerated such as: dodecyloxy-2,4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, octadecane oxygen base-2,4-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2,5-diaminobenzene, cholestane base oxygen base-3,5-diaminobenzene, cholesteryl oxygen base-3,5-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-aminobenzoic acyl-oxygen base) 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-heptylcyclohexane of 1,1-, two (4-((amino-benzene oxygen) methyl) the phenyl)-4-heptylcyclohexane of 1,1-, diamines etc. represented by described formula (D-1).In addition, this diamines can be used alone a kind or two or more combinationally used.

When using the diamines with tilt angle imparting base, with regard to showing the viewpoint of fully high tilt angle characteristic, relative to whole diamines, the usage ratio of described diamines is preferably set to more than 5 % by mole, is more preferably and is set to more than 10 % by mole.In addition, the upper limit of this usage ratio is not particularly limited, but with regard to the viewpoint of effect brought of the use with regard to not undermining the compound represented by described formula (1), relative to whole diamines, preferably be set to less than 99 % by mole, be more preferably and be set to less than 95 % by mole.

[molecular weight regulator]

Time synthesizing polyamides acid (P), suitable molecular weight regulator can be used, come together to synthesize the polymkeric substance of end modified type with tetracarboxylic dianhydride as above and diamines.By making the polymkeric substance of described end modified type, the coating (printing) of 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 (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, dodecyl amine, Octadecane base amine 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.

[synthesis of polyamic acid]

The usage ratio of the tetracarboxylic dianhydride and diamines that are supplied to the building-up reactions of described polyamic acid (P) is 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.In addition, the building-up reactions of polyamic acid (P) 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-N,N-DIMETHYLACETAMIDE, DMF, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea (tetramethylurea), HMPA (hexamethylphosphortriamide) 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, ethylene glycol monomethyl ether etc.; Ketone include, for example: acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) etc.; Described ester include, for example: ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, diethyl malonate, isoamyl propionate, isoamyl isobutyrate etc.; Ether include, for example: diethyl ether, diisoamyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol-positive propyl ether, ethylene glycol-n-butyl ether, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, tetrahydrofuran (THF) etc.; Halon include, for example: methylene dichloride, 1,2-ethylene dichloride, Isosorbide-5-Nitrae-dichlorobutane, trichloroethane, chlorobenzene 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.In the case of the latter, relative to the total amount of the organic solvent of the first cohort and the organic solvent of the second cohort, the usage ratio of the organic solvent of the second cohort is preferably less than 50 % by weight, is more preferably less than 40 % by weight, is especially preferably less than 30 % by weight.In addition, the usage quantity (α) of organic solvent is preferably set to the total amount (alpha+beta) relative to reaction soln, and the total amount (β) of tetracarboxylic dianhydride and diamines becomes the amount of 0.1 % by weight ~ 50 % by weight.

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

< polymkeric substance (P): poly amic acid ester >

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

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 (stearyl bromide), methyl chloride, chlorooctadecane, 1, the fluoro-2-iodoethane of 1,1-tri-etc., the compound containing epoxy group(ing) include, for example propylene oxide etc.Tetracarboxylic dianhydride illustrated in the synthesis of described polyamic acid (P), such as by using described alcohols, being carried out open loop and obtaining by the tetracarboxylic acid diester compound used in method [II].In addition, the tetracarboxylic acid diester dihalide used in method [III] obtains by making the suitable chlorizating agent such as the tetracarboxylic acid diester compound that such as obtains in the above described manner and thionyl chloride carry out reacting.Method [II] and the middle diamines used of method [III] comprise the compound represented by described formula (1).In addition, also optionally other amine described can be used.In addition, poly amic acid ester can only have amic acid esters structure, also can be amido acid structure and amic acid esters structure and the partial esterification thing deposited.

< polymkeric substance (P): polyimide >

Polyimide (hereinafter also referred to " polyimide (P) ") as polymkeric substance (P) contained in crystal aligning agent of the present invention carries out dehydration closed-loop by the polyamic acid (P) that will synthesize in this way, in addition imidization and obtaining.

Described polyimide (P) can be the complete imide compound of the amido acid structure had as the polyamic acid of its precursor all being carried out dehydration closed-loop, also can be only the part in amido acid structure and amic acid esters structure is carried out dehydration closed-loop, and make at least any one and the imide ring structure in amido acid structure and amic acid esters structure and the part imide compound of depositing.With regard to can improving the aspect of voltage retention, the imide rate (imidization ratio) of polyimide (P) is preferably more than 30%, is more preferably 40% ~ 99%, is especially preferably 50% ~ 99%.This imide rate is quantity, the quantity of amic acid esters structure, the total with the quantity of imide ring structure of the amido acid structure relative to polyimide, the ratio shared by the quantity of imide ring structure is represented with percentage.Herein, a part for imide ring 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, add dewatering agent and dehydration closed-loop catalyzer, optionally carry out the method heated.Wherein, a kind of rear method of utilization is preferably.

In the solution of polyamic acid, add dewatering agent and dehydration closed-loop catalyzer in the method for carrying out imidization, dewatering agent such as can use the acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.The usage quantity of dewatering agent is preferably relative to 1 mole of amido acid structure of polyamic acid and is set to 0.01 mole ~ 20 moles.Dehydration closed-loop catalyzer such as can use: the tertiary amines such as pyridine, collidine (collidine), two picolins (lutidine), triethylamine.The usage quantity of dehydration closed-loop catalyzer is preferably set to 0.01 mole ~ 10 moles relative to used dewatering agent 1 mole.The organic solvent used in dehydration closed-loop reaction can enumerate the illustrative organic solvent as the organic solvent for the synthesis of polyamic acid.The temperature of reaction of dehydration closed-loop reaction is preferably 0 DEG C ~ 180 DEG C, is more preferably 10 DEG C ~ 150 DEG C.Reaction times is preferably 1.0 hours ~ 120 hours, is more preferably 2.0 hours ~ 30 hours.

Obtain the reaction soln containing polyimide (P) in the above described manner.This reaction soln directly can be supplied to the preparation of crystal aligning agent, also reoffer to the preparation of crystal aligning agent after can removing dewatering agent and dehydration closed-loop catalyzer in autoreaction solution, also reoffer to the preparation of crystal aligning agent after polyimide can being emanated, or can also reoffer after the polyimide purifying of segregation to the preparation of crystal aligning agent.These purification process can be carried out according to known method.

The soltion viscosity of < polymkeric substance and weight average molecular weight >

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 10 % by weight, there is the compound of the soltion viscosity of 10mPas ~ 800mPas, be more preferably the compound of the soltion viscosity with 15mPas ~ 500mPas.In addition, the soltion viscosity (mPas) of described polymkeric substance be for the concentration using the good solvent (such as gamma-butyrolactone, METHYLPYRROLIDONE etc.) of this polymkeric substance to prepare be 10 % by weight polymers soln, use E type rotational viscosimeter, measure at 25 DEG C and the value that obtains.In addition, for polyamic acid, poly amic acid ester and polyimide contained in crystal aligning agent of the present invention, utilize gel permeation chromatography (Gel Permeation Chromatography, the weight average molecular weight (Mw) of the polystyrene conversion GPC) measured is preferably 500 ~ 100,000, be more preferably 1,000 ~ 50,000.

Relative to entirety 100 weight part of the component of polymer in crystal aligning agent, the usage ratio of polymkeric substance (P) is preferably set to 50 weight part ~ 100 weight parts.If be less than 50 weight parts, then there are the misgivings that fully cannot obtain effect of the present invention.Be more preferably more than 60 weight parts, be especially preferably more than 70 weight parts.Polymkeric substance (P) can be used alone a kind or two or more combinationally used.

Other compositions of < >

Crystal aligning agent of the present invention 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, meal chelate compounds, hardening accelerator, tensio-active agent etc. in other polymkeric substance beyond described polymkeric substance (P), molecule.

[other polymkeric substance]

Other polymkeric substance described can in order to improve solution properties or electrical characteristic and use.Other polymkeric substance described include, for example: by the polyamic acid do not obtained containing the diamines of compound represented by described formula (1) and the reaction of tetracarboxylic dianhydride, the polyimide obtained by the dehydration closed-loop of this polyamic acid, as the poly amic acid ester of the carboxylate of this polyamic acid, organopolysiloxane, polyester, polymeric amide, derivatived cellulose (cellulose derivative), polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc.

In addition, when crystal aligning agent of the present invention is used for phase retardation film, other polymkeric substance described can preferably use the polymkeric substance with light regiospecific structure.Herein, so-called light regiospecific structure comprises light regiospecific base and this concept of two of decomposition type light orientation portion.Specifically, can the structure being shown bright dipping regiospecific by photoisomerization or photodimerization, photolysis etc. be enumerated, include, for example: the derivative containing nitrogen benzide, styracin (cinnamic acid), phenyl styryl ketone (chalcone), benzophenone, tonka bean camphor and polyimide and these compounds is as the group etc. of basic framework.In these polymkeric substance, preferably comprise the polymkeric substance with light regiospecific base, be more preferably the polymkeric substance comprising and be imported with the group with cinnamic acid structure (styracin or its derivative).Wherein, with regard to the easy aspect to lead-in light regiospecific base in polymkeric substance, the organopolysiloxane with cinnamic acid structure can preferably be used.

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

When other polymkeric substance are made an addition in crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in 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.

[compound containing epoxy group(ing)]

Compound containing epoxy group(ing) can in order to using with the cementability of substrate surface or electrical characteristic of improving liquid crystal orienting film.This compound containing epoxy group(ing) include, for example: 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., be used as preferred compound.In addition, containing the organopolysiloxane containing epoxy group(ing) that the example of the compound of epoxy group(ing) can use No. 2009/096598th, International Publication to record.

When these epoxy compoundss are made an addition in crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in crystal aligning agent, the allotment ratio of described epoxy compounds is preferably set to below 40 weight parts, is more preferably and is set to 0.1 weight part ~ 30 weight part.

[functional silanes compound]

Described functional silanes compound can use for the object of the printing of raising crystal aligning agent.This functional silanes compound include, for example: 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-ureido-propyl Trimethoxy silane (3-ureidopropyltrimethoxysilane), 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 crystal aligning agent, relative to total 100 weight part of polymkeric substance contained in 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.

[meal chelate compounds]

Described meal chelate compounds is when the component of polymer of crystal aligning agent has epoxy construction, for ensure the film formed by subzero treatment physical strength object and containing in crystal aligning agent (particularly phase retardation film crystal aligning agent).This meal chelate compounds 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 meal chelate compounds, relative to total 100 weight part of constituent comprising epoxy construction, the usage ratio of described meal chelate compounds 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 is the component of polymer in crystal aligning agent when having epoxy construction, in order to the ageing stability of the physical strength and LCD alignment that ensure formed liquid crystal orienting film containing in crystal aligning agent (particularly phase retardation film crystal aligning agent).This hardening accelerator such as can use the compound with phenylol, silanol group, thiol group, phosphate, sulfonic group, carboxyl, acid anhydride etc., is wherein preferably the compound with phenylol or silanol group.As its concrete example, the compound with phenylol 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 part 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 contain in crystal aligning agent (particularly phase retardation film crystal aligning agent) the coating of substrate for raising crystal aligning agent.This tensio-active agent such as can be enumerated: nonionogenic tenside, anion surfactant, cats product, amphoterics, silicone surfactant, polyalkylene oxides tensio-active agent, fluorochemical surfactant etc.Relative to total amount 100 weight part of 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, other compositions, except described composition, can enumerate in molecule the compound or antioxidant etc. with at least one oxetanyl.

< solvent >

Crystal aligning agent of the present invention is prepared to described polymkeric substance (P) and other compositions of optionally using preferably disperse or be dissolved in suitable solvent to form liquid composition.

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, methoxy methyl propionate, ethoxyl ethyl propionate, 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 (butyl cellosolve)), glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, Texacar PC etc.These solvents can be used alone or two or more is used in combination.

Solid component concentration (ratio of total weight shared by the gross weight of crystal aligning agent of the composition beyond the solvent of crystal aligning agent) in crystal aligning agent of the present invention considers that viscosity, volatility etc. are suitably selected, and is preferably the scope of 1 % by weight ~ 10 % by weight.That is, crystal aligning agent of the present invention is by coating substrate surface in aftermentioned mode, preferably heats, and formed as liquid crystal orienting film film or become the film of liquid crystal orienting 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 orienting 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 orienting film, and in addition, the viscosity that there is crystal aligning agent increases and the tendency of coating decline.

The scope of particularly preferred solid component concentration is different from the purposes of crystal aligning agent or the method that uses during coating of liquid crystalline orientation agent on substrate.Such as about the crystal aligning agent of liquid crystal orienting film, when utilizing turner method to coat on substrate, solid component concentration (total weight proportions in the gross weight of crystal aligning agent of the whole compositions beyond the solvent in 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 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 crystal aligning agent of phase retardation film, with regard to the coating that makes crystal aligning agent and the viewpoint of the thickness appropriateness of film that formed, the solid component concentration of crystal aligning agent is preferably the scope of 0.2 % by weight ~ 10 % by weight, is more preferably the scope of 3 % by weight ~ 10 % by weight.

< liquid crystal display device and phase retardation film >

By using the crystal aligning agent of the present invention of described explanation to manufacture liquid crystal orienting film.In addition, the liquid crystal orienting film using crystal aligning agent of the present invention to be formed can be preferably applied to liquid crystal orienting film used for liquid crystal display element and the liquid crystal orienting 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 orienting film using described 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 orientation-multi-zone vertical alignment nematic (Vertical Alignment-MultidomainVertical Alignment, VA-MVA) type, vertical orientation-pattern vertical orientation (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type etc.), IPS type, FFS type, the multiple type of drive such as optical compensation curved (optically compensation bend, OCB) type.Liquid crystal display device of the present invention such as manufactures by the step of 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, by being coated with crystal aligning agent of the present invention on substrate, then coated face being heated and form film on substrate.

(I-1A) when Production Example is as TN type, STN type or VA type liquid crystal display device, first, to two pieces of substrates of patterned nesa coating be provided with as a pair, in its each transparent conductive film forming surface, flexographic printing process (offset printing), method of spin coating, roll coater method or ink jet printing method is preferably utilized to be coated with crystal aligning agent of the present invention respectively.Substrate such as can use: the glass such as float glass, soda glass; Comprise the transparency carrier of the plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-(ester ring type alkene).The 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) tin indium oxide (indium tinoxide, ITO) film etc.In order to obtain patterned nesa coating, such as, can utilize following methods: after forming patternless nesa coating, being formed the method for pattern by photoetch; The method etc. with the mask of required pattern is used when forming nesa coating.During coating of liquid crystalline orientation 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 orientation agent, for the object such as sagging preventing be coated with 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 amido acid structure existing in polymkeric substance is carried out the object of hot-imide, and implement calcining (toasting afterwards) step.Calcining temperature (rear storing temperature) is now preferably 80 DEG C ~ 300 DEG C, is more preferably 120 DEG C ~ 250 DEG C.Post-bake times is preferably 5 minutes ~ 200 minutes, is more preferably 10 minutes ~ 100 minutes.The thickness of the film formed is preferably 0.001 μm ~ 1 μm, is more preferably 0.005 μm ~ 0.5 μm.

(I-1B) when manufacturing IPS type or FFS type liquid crystal display device, by 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 crystal aligning agent of the present invention respectively, then heating carried out to form film to each coated face.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).Metal films is as used the film comprising the metals such as chromium.

In any one situation of described (I-1A) and (I-1B), all by after coating of liquid crystalline orientation agent on substrate, organic solvent is removed and forms alignment film or become the film of alignment film.Now, polymkeric substance contained in 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, also can carry out dehydration closed-loop reaction by carrying out further heating after film is formed, making the film of more imidization.

[step (I-2): orientation ability gives process]

When manufacturing TN type, STN type, IPS type or FFS type liquid crystal display device, as the process of the film formed in described step (I-1) being given to LCD alignment ability, the friction treatment be implemented as follows: utilize the roller being wound with the cloth comprising the fibers such as such as nylon, artificial silk, cotton, by this film to certain orientation friction.Thus, the orientation ability of liquid crystal molecule is imparted on film and forms liquid crystal orienting film.On the other hand, when manufacturing VA type liquid crystal display device, the film formed directly can be used as liquid crystal orienting film, but also can implement friction treatment to this film in described step (I-1).In addition, following process can be carried out further to the liquid crystal orienting film after friction treatment: make by a part of irradiation ultraviolet radiation to liquid crystal orienting film the process that the tilt angle in a part of region of liquid crystal orienting film changes; Or the part on liquid crystal orienting film surface is carried out friction treatment to the direction different from friction treatment just now, is then removed the process of resist film after forming resist film; Thus make liquid crystal orienting film have different LCD alignment abilities in each region.In this situation, the visual field characteristic of gained liquid crystal display device can be improved.In addition, the liquid crystal orienting film being suitable for VA type liquid crystal display device also can be applicable to polymer-stabilized alignment (Polymer sustained alignment, PSA) type liquid crystal display device.Also can replace friction treatment to the process of film imparting LCD alignment ability and adopt the process utilizing light orientation method.

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

By preparing the 2 pieces of substrates being formed with liquid crystal orienting film in this way, between 2 pieces of substrates of subtend configuration, configure liquid crystal to manufacture liquid crystal cells.When manufacturing liquid crystal cells, include, for example 2 kinds of following methods.First method is previously known method.First, in the mode of respective liquid crystal orienting film subtend, via gap (cell gap) by 2 pieces of substrate subtend configurations, sealing material is used to be fitted by the periphery of 2 pieces of substrates, inject filling liquid crystal in the cell gap divided by substrate surface and sealing material after, filling orifice is sealed, manufactures liquid crystal cells thus.In addition, the second method is the method being called liquid crystal drip-injection (One DropFill, ODF) mode.Specified location on wherein one piece of substrate in the 2 pieces of substrates being formed with liquid crystal orienting film, be coated with the sealing material of such as ultraviolet light photopolymerization, and then after the set several positions on LCD alignment face drip liquid crystal, to fit another block substrate in the mode of liquid crystal orienting film subtend, and liquid crystal is spread out on whole of substrate, then to whole irradiating ultraviolet light of substrate, make sealing material curing, manufacture liquid crystal cells thus.When utilizing any one method, it is desirable to by the liquid crystal cells manufactured in this way, and then be heated to after used liquid crystal becomes the temperature of isotropic phase, slowly be cooled to room temperature, thus remove flowing orientation when liquid crystal is filled.

Sealing material 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 disc-like liquid crystal (smectic liquid crystal), wherein be preferably nematic liquid crystal, such as, can use: schiff bases (Schiffbase) is liquid crystal, azoxy (azoxy) is liquid crystal, biphenyl system liquid crystal, Santosol 360 system liquid crystal, ester system liquid crystal, terphenyl (terphenyl) are liquid crystal, cyclohexyl biphenyl hexane system liquid crystal, pyrimidine system liquid crystal, dioxan 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 cholesterol liquid crystals (cholesteric liquid crystal) such as such as cholesteryl chloride (cholestery chloride), cholesteryl nonanoate (cholesteryl nonanoate), cholesteryl carbonate (cholesteryl carbonate); As the chiral agent that trade(brand)name " C-15 ", " CB-15 " (manufacture of Merck (Merck) company) are sold; To oxygen base α-tolylene-to the ferroelectric liquid crystals such as amino-2-methyl butyl laurate (p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate) (ferroelectric liquid crystal) 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: the Polarizer being called as the light polarizing film of " H film " with the clamping of rhodia protective membrane, should " H film " be make polyvinyl alcohol extend orientation to make it absorb the film of iodine; Or comprise itself Polarizer of H film.

[phase retardation film]

When using crystal aligning agent of the present invention to manufacture phase retardation film, dust or electrostatic just not only can be suppressed in step to produce, and the aspect of uniform liquid crystal orienting film can be formed, and can by use suitable photomask when the irradiation of radioactive rays and formed arbitrarily on substrate different multiple regions, LCD alignment direction in, preferably utilize light orientation method.Specifically, the manufacture method comprising following step (II-1) ~ step (II-3) can be enumerated.

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

First, crystal aligning agent of the present invention is coated on substrate form film.Substrate used herein can be suitable for 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, to the substrate for coating of liquid crystalline orientation agent, in order to make the adhesion of substrate surface and film better, also existing known pre-treatment can be implemented to the face forming film in substrate surface.

As a rule, phase retardation film combinationally uses with light polarizing film.Now, in order to play required optical characteristics, must the precise angle of the polarizing axis relative to light polarizing film be controlled as specific direction, phase retardation film of fitting.Therefore, herein, by the liquid crystal orienting film on the direction of first retainer with LCD alignment ability is formed on the substrates such as TAC film or polymethylmethacrylate, can omits and control its angle and phase retardation film is fitted in 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 orienting film of LCD alignment ability, preferably use crystal aligning agent of the present invention, utilize light orientation method to carry out.

The coating of 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 method, extrusion die (extrusion die) method, direct gravure coater (direct gravure coater) method, chamber knife coater (chamber doctorcoater) method, hectograph gravure coater (offset gravure coater) method, single roller kiss-coating machine (singleroll kiss coater) method, use trans kiss-coating machine (the reverse kiss coater) method of the gravure roll of path, 3 trans roll-coater methods, 4 trans roll-coater methods, slit die (slot die) method, Kohler coater method, positive rotation roll-coater method, blade coater, scraper type coating machine (knife coater) method, impregnation coater, MB coater, the trans coater of MB etc.

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

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

Then, by irradiating light to the film be formed in this way on substrate, come to give LCD alignment ability to film.Herein, the light irradiated include, for example the ultraviolet, visible rays etc. of the light comprising 150nm ~ 800nm wavelength.In these light, preferably comprise the ultraviolet of the light of 300nm ~ 400nm wavelength.Irradiating light can be polarisation, also can be non-polarized.Polarisation is preferably the light using and comprise linear polarization.

When used light is for polarisation, the irradiation of light can be carried out to substrate from vertical direction, also can carry out the irradiation of light from vergence direction, or these can also be irradiated combination and carry out.When irradiating non-polarized, must irradiate real estate from vergence direction.

The light source used include, for example: Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, mercury-xenon lamp (Hg-Xe lamp) etc.Polarisation can by obtaining these light sources and method etc. also such as such as spectral filter, diffraction grating etc.

The irradiation dose of light is preferably set to 0.1mJ/cm ²above and be less than 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, on the film in this way after rayed, coating polymerizable liquid crystal also makes it harden.Thus, the film (liquid crystal layer) comprising polymerizable liquid crystal is formed.Polymerizable liquid crystal as used herein carries out the liquid crystalline cpd that is polymerized or liquid-crystal composition by least one process in heating and rayed.This polymerizable liquid crystal can use existing known liquid crystal, specifically, include, for example non-patent literature 1 (" can the liquid crystal of UV sclerosis and application (UV-Curable Liquid Crystals and TheirApplication) thereof ", " liquid crystal ", 3rd volume the 1st phase (1999), the 34th page to the 42nd page) the middle nematic liquid crystal recorded.In addition, also can be: cholesterol liquid crystal; Collar plate shape liquid crystal; Be added with the twisted nematic alignment-type liquid crystal etc. of chiral agent.Polymerizable liquid crystal also can be the mixture of plurality of liquid crystals compound.Polymerizable liquid crystal can also be the composition more comprising known polymerization initiators or suitable solvent etc.

When the film formed using crystal aligning agent is coated with polymerizable liquid crystal as above, such as, can adopt the coating process that rod coater method, roll coater method, turner method, print process, ink jet method etc. are suitable.

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

The Heating temperature of film suitably should be selected according to the kind of used polymerizable liquid crystal.Such as when the RMS03-013C using Merck & Co., Inc. 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 that can obtain 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 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 that the phase retardation film using crystal aligning agent of the present invention to manufacture is applied 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 the outer side to the Polarizer depending on recognizing side being configured at liquid crystal display device, and the face attaching the substrate-side in phase retardation film uses.Therefore, be preferably set to following aspect: the substrate of phase retardation film is set to TAC system or vinylformic acid base material, make the substrate of this phase retardation film also as the protective membrane of light polarizing film to play function.

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

[embodiment]

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

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

[the weight average molecular weight Mw of polymkeric substance]

Mw is the polystyrene conversion value utilizing the gel permeation chromatography of following condition to measure.

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

Solvent: tetrahydrofuran (THF)

Temperature: 40 DEG C

Pressure: 68kgf/cm ²

[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 ( ¹h-Nuclear magnetic resonance, ¹h-NMR).According to gained ¹h-NMR spectrum, uses following mathematical expression (1) to obtain imide rate.

Imide rate (%)=(1-A ¹/ A ²× α) × 100... (1)

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

[epoxy equivalent (weight)]

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

[soltion viscosity of polymers soln]

Use E type rotational viscosimeter, at 25 DEG C, measure the soltion viscosity (mPas) of polymers soln.

The synthesis > of < diamines

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

According to following flow process 1, synthesize the compound (hereinafter referred to as compound (DA-1)) represented by described formula (DA-1).

[changing 7]

In the 3L there-necked flask possessing thermometer, three-way tap, add 4-(benzyloxy) phenol 105.1g (0.53 mole), 1, pentamethylene bromide 57.5g (0.25 mole), salt of wormwood 138.2g (1.0 moles) and dimethyl formamide (dimethylformamide, DMF) 1250ml, mixes.Then, be warming up to 60 DEG C, after carrying out reaction in 6 hours, mix with ethyl acetate 2000ml, then, utilize distilled water to carry out separatory cleaning.Then, organic layer is concentrated, solid is separated out.The solid of gained is carried out recrystallize in ethyl acetate, hexane, filtered and recycled is also dry, obtains compound (being expressed as compound (the DA-1-1)) 99.6g (0.21 mole) represented by described formula (DA-1-1) thus.

Then, in the 2L there-necked flask possessing thermometer, three-way tap and addition funnel, measure compound (DA-1-1) 99.6g (0.21 mole) of described acquisition and the 5%Pd/C of 10g, carry out vacuum outgas in system, replace with nitrogen.Then, add tetrahydrofuran (THF) (THF) 1000ml, cooled in the mode being no more than 10 DEG C, drip hydrazine monohydrate 100ml lentamente on one side.Then, reaction in 6 hours is at room temperature carried out.In addition, the solvent used in reaction carries out nitrogen replacement in advance.After reaction, removing inorganic salt by filtering, in filtrate, mixing ethyl acetate 1000ml, then utilize distilled water to carry out separatory cleaning.Then, organic layer is concentrated, solid is separated out.The solid of gained is reclaimed, dry, obtain compound (being expressed as compound (the DA-1-2)) 56.4g (0.20 mole) represented by described formula (DA-1-2) thus.

Then, in the 1L there-necked flask possessing thermometer, three-way tap, add compound (DA-1-2) 56.4g (0.20 mole) of described acquisition, 4-fluoronitrobenzene 56.5g (0.40 mole), salt of wormwood 108.1g (0.78 mole) and dimethyl formamide (DMF) 500ml, mix.Then, be warming up to 60 DEG C, after carrying out reaction in 6 hours, mix with ethyl acetate 1000ml, then utilize distilled water to carry out separatory cleaning.Then, organic layer is concentrated, solid is separated out.The solid of gained is carried out recrystallize in ethyl acetate, hexane, filtered and recycled is also dry, obtains compound (being expressed as dinitro intermediate (the DA-1-3)) 74.7g (0.14 mole) represented by described formula (DA-1-3) thus.

Then, under nitrogen flowing, add described dinitro intermediate (DA-1-3) 74.7g (0.14 mole), 5%Pd/C, the ethanol 200mL of 7.5g and tetrahydrofuran (THF) 800mL in 2L autoclave after, re-start displacement with hydrogen, react with room temperature in presence of hydrogen.Utilize liquid phase chromatography to carry out reactive tracing, filter after confirming the carrying out of reaction.Filtrate is mixed with ethyl acetate 3000mL, then utilizes distilled water to carry out separatory purifying.In the organic layer of gained, remove solvent by underpressure distillation, make solid separate out thus.By making separated out solid carry out recrystallize in ethanol, and obtain compound (DA-1) 58.3g (0.12 mole).

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

According to following flow process 2, synthesize the compound (hereinafter referred to as compound (DA-2)) represented by described formula (DA-2).

[changing 8]

In the 3L there-necked flask possessing thermometer, three-way tap, add 3-phenyl propyl bromine 99.5g (0.5 mole), phenol 51.8g (0.55 mole), salt of wormwood 207.3g (1.5 moles) and dimethyl formamide (DMF) 2000ml, mix.Then, be warming up to 60 DEG C, after carrying out reaction in 6 hours, mix with ethyl acetate 2000ml, then utilize distilled water to carry out separatory cleaning.Then, organic layer is concentrated, solid is separated out.The solid of gained is carried out recrystallize in ethanol, and filtered and recycled is also dry, obtains compound (being expressed as compound (the DA-2-1)) 77.5g (0.37 mole) represented by described formula (DA-2-1) thus.

Then, in the 2L there-necked flask possessing thermometer and three-way tap, aluminum chloride 243.3g (1.83 moles) is mixed with methylene dichloride 1000mL, drops into 4-nitrobenzoyl chloride 162.6g (0.88 mole) under ice cooling, 4, make it dissolve.Then, the dichloromethane solution 400mL of inclusion compound (DA-2-1) 77.5g (0.37 mole) is dripped lentamente.After dropping terminates, return to room temperature and carry out reaction in 6 hours.After utilizing liquid phase chromatography to confirm the end of reaction, reaction solution is injected in the mixture of 10 equivalent hydrochloric acid and ice, then extracts with chloroform.Then, clean with sodium bicarbonate aqueous solution, salt solution and distilled water, organic layer is carried out drying with magnesium sulfate.Then, remove solvent by underpressure distillation, filter after crystallization is separated out fully.Screening is cleaned successively with water, ethanol, toluene, and drying under reduced pressure, obtain compound (being expressed as compound (the DA-2-2)) 95.0g (0.19 mole) represented by described formula (DA-2-2) thus.

Then, in the 1L there-necked flask possessing thermometer, addition funnel and three-way tap, add compound (DA-2-2) 95.0g and methylene dichloride 500mL, drip trifluoromethanesulfonic acid 120g lentamente under ice cooling, 4.Then, triethyl silicane 120g is dripped lentamente.After dropping terminates, return to room temperature and carry out reaction in 10 hours.After utilizing liquid phase chromatography to confirm the end of reaction, reaction solution is neutralized with aqueous sodium carbonate, and washes.Organic layer is concentrated, in toluene solvant, carry out recrystallize after solid is separated out, obtain compound (being expressed as dinitro intermediate (the DA-2-3)) 71.9g (0.15 mole) represented by described formula (DA-2-3) thus.

Then, under nitrogen flowing, add described dinitro intermediate (DA-2-3) 71.9g (0.15 mole), 5%Pd/C, the ethanol 200mL of 7.2g and tetrahydrofuran (THF) 800mL in 2L autoclave after, re-start displacement with hydrogen, react with room temperature in presence of hydrogen.Utilize high performance liquid chromatography (high performance liquid chromatography, HPLC) to carry out reactive tracing, filter after confirming the carrying out of reaction.Filtrate is mixed with ethyl acetate 3000mL, then carries out separatory purifying with distilled water.In the organic layer of gained, remove solvent by underpressure distillation, make solid separate out thus.By making separated out solid carry out recrystallize in ethanol, and obtain compound (DA-2) 53.3g (0.13 mole).

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

According to following flow process 3, synthesize the compound (hereinafter referred to as compound (DA-3)) represented by described formula (DA-3).

[changing 9]

In the 3L there-necked flask possessing thermometer and three-way tap, add 4-hydroxyl-4 '-nitrobiphenyl 180.8g (0.84 mole), 1,3-dibromopropane 80.8g (0.4 mole), salt of wormwood 221.1g (1.6 moles) and dimethyl formamide (DMF) 2000ml, mix.Then, be warming up to 60 DEG C, after carrying out reaction in 6 hours, mix with ethyl acetate 4000ml, then utilize distilled water to carry out separatory cleaning.Then, organic layer is concentrated, solid is separated out.The solid of gained is carried out recrystallize in ethanol, filtered and recycled is also dry, obtains compound (being expressed as dinitro intermediate (the DA-3-1)) 103.5g (0.22 mole) represented by described formula (DA-3-1) thus.

Then, under nitrogen flowing, add described dinitro intermediate (DA-3-1) 103.5g (0.22 mole), 5%Pd/C, the ethanol 100mL of 10.3g and tetrahydrofuran (THF) 500mL in 2L autoclave after, re-start displacement with hydrogen, react with room temperature in presence of hydrogen.Utilize HPLC to carry out reactive tracing, filter after confirming the carrying out of reaction.Filtrate is mixed with ethyl acetate 1000mL, then carries out separatory purifying with distilled water.In the organic layer of gained, remove solvent by underpressure distillation, make solid separate out thus.By separated out solid is carried out recrystallize in ethanol, and obtain compound (DA-3) 151.7g (0.37 mole).

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

According to following flow process 4, synthesize the compound (hereinafter referred to as compound (DA-4)) represented by described formula (DA-4).

[changing 10]

In the 1L there-necked flask possessing thermometer, three-way tap and addition funnel, by compound (DA-1-2) 43.4g (0.15 mole), the triethylamine (triethylamine that obtain with the method identical with described embodiment 1-1, TEA) 60.7g (0.6 mole) and the THF of 300ml mixes, and drips the solution of the THF of the 400ml of 4-nitrobenzoyl chloride 69.6g (0.38 mole) under ice cooling, 4 lentamente.After dropping, at room temperature carry out reaction in 12 hours, then mix with ethyl acetate 1000ml, then utilize distilled water to carry out separatory cleaning.Then, organic layer is concentrated, solid is separated out.The solid of gained is carried out recrystallize in ethyl acetate and hexane, filtered and recycled is also dry, obtains compound (being expressed as dinitro intermediate (the DA-4-1)) 39.6g (0.07 mole) represented by described formula (DA-4-1) thus.

Then, under nitrogen flowing, add described dinitro intermediate (DA-4-1) 39.6g (0.07 mole), 5%Pd/C, the ethanol 100mL of 4g and tetrahydrofuran (THF) 250mL in 2L autoclave after, re-start displacement with hydrogen, react with room temperature in presence of hydrogen.Utilize HPLC to carry out reactive tracing, filter after confirming the carrying out of reaction.In organic layer, remove solvent by underpressure distillation, make solid separate out thus.By separated out solid is carried out recrystallize in ethanol, and obtain compound (DA-4) 27.4g (0.05 mole).

The synthesis > of < polymkeric substance

[embodiment 2-1: the synthesis of polymkeric substance (PA-1)]

Using as tetracarboxylic dianhydride pyromellitic acid anhydride 10.7g (relative to synthesis in use diamines total scale of construction 100 molar part and be 93 molar part), and as diamines compound (DA-1) 12.41g (relative to synthesis in use diamines total scale of construction 100 molar part and be 50 molar part), 4-aminophenyl-4 '-Aminobenzoate 4.82g (relative to the diamines used in synthesis total scale of construction 100 molar part and be 40 molar part) and 4, 4 '-[4, 4 '-propane-1, two (the piperidines-1 of 3-bis-base, 4-bis-base)] pentanoic 2.07g (relative to synthesis in use diamines total scale of construction 100 molar part and be 10 molar part), be dissolved in METHYLPYRROLIDONE (N-methyl-2-pyrrolidone, NMP) 85g and gamma-butyrolactone (γ-butyllactone, in the mixed solvent of GBL) 85g, reaction in 6 hours is carried out at 30 DEG C.Then, reaction mixture is injected in excessive methyl alcohol, reaction product is precipitated.After reclaimed throw out is cleaned with methyl alcohol, under reduced pressure carry out drying in 15 hours with 40 DEG C, obtain polyamic acid (hereinafter referred to as polymkeric substance (PA-1)) 28.2g thus.By the polymkeric substance (PA-1) of gained with NMP: GBL=50: 50 solvent composition and be prepared into 15 % by weight, measure the viscosity of this solution, result is 550mPas.In addition, this polymers soln is left standstill 3 days at 20 DEG C, and result does not produce gelation, and storage stability is good.

[embodiment 2-2 ~ embodiment 2-5, embodiment 2-7, synthesis example 1, synthesis example 2]

In described embodiment 2-1, except will in reaction the kind of the tetracarboxylic dianhydride that use and diamines and quantitative change more as described in following table 1 except, obtain polymkeric substance in the mode identical with embodiment 2-1.In addition, about tetracarboxylic dianhydride, numeric representation in table 1 is relative to the usage ratio (% by mole) of total scale of construction of the tetracarboxylic dianhydride used in reaction, about diamines, the numeric representation in table 1 is relative to the usage ratio (% by mole) of total scale of construction of the diamines used in reaction.For the polymers soln of gained in embodiment, leave standstill after 3 days at 20 DEG C respectively, all do not produce gelation, storage stability is good.

[table 1]

Tetracarboxylic dianhydride in table 1 and the abbreviation of diamines are as described below.

(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: ethylene diaminetetraacetic acid dianhydride

AN-5:1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1,3-diketone

(diamines)

Da-1: the compound represented by following formula (da-1)

Da-2:4-aminophenyl-4 '-Aminobenzoate

Da-3:4,4 '-diaminodiphenyl-methane

Da-4:4,4 '-[4,4 '-propane-1,3-bis-base two (piperidines-Isosorbide-5-Nitrae-two base)] pentanoic

Da-5:2,4-diamino-N, N-diallyl aniline

Da-6:4,4 '-diamino-diphenyl amine

Da-7:3,5-diaminobenzoic acid

Da-8:3,5-diaminobenzoic acid cholestane base ester

Da-9:4-(tetradecyloxyaniline) benzene-1,3-diamines

Da-10: the compound represented by described formula (DA-15)

Da-11:1,4-pair-(5-amino-pyridine-2-base)-piperazine

[changing 11]

[embodiment 2-6: the synthesis of polymkeric substance (PI-1)]

Using as tetracarboxylic dianhydride's 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride 16.58g (relative to the diamines used in synthesis total scale of construction 100 molar part and be 98 molar part) and as compound (DA-2) 25.52g (be 80 molar part relative to total scale of construction 100 molar part of diamines used in synthesis) and 3 of diamines, 5-diaminobenzoic acid cholestane base 7.89g (relative to synthesis in use diamines total scale of construction 100 molar part and be 20 molar part), be dissolved in the NMP of 200g, at room temperature carry out reaction in 6 hours.Then, add the NMP of 250g, add pyridine 11.7g and diacetyl oxide 15.11g, at 80 DEG C, carry out dehydration closed-loop reaction in 5 hours.Then, reaction mixture is injected in excessive methyl alcohol, reaction product is precipitated.After reclaimed throw out is cleaned with methyl alcohol, under reduced pressure carry out drying in 15 hours with 40 DEG C, obtain the polyimide (hereinafter referred to as polymkeric substance (PI-1)) of imide rate about 65% thus.Utilize NMP that the polymkeric substance (PI-1) of gained is prepared into 15 % by weight.Measure the viscosity of this solution, result is 890mPas.

[synthesis example 3: the synthesis of organopolysiloxane]

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

Then, in the there-necked flask of 100mL, drop into organopolysiloxane 9.3g, the methyl iso-butyl ketone (MIBK) 26g with oxirane base 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, reaction mixture is fed in methyl alcohol, reclaim the throw out generated, this precipitate dissolves is made solution in ethyl acetate, after this solution is washed 3 times, solvent distillation is removed, obtains organopolysiloxane (S-1) 6.3g with oxirane base and cinnamic acid structure thus with the form of white powder.For this organopolysiloxane (S-1), the weight average molecular weight Mw of the polystyrene conversion utilizing gel permeation chromatography to measure is 3,500.

The preparation of < crystal aligning agent and evaluation >

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

(1) preparation of crystal aligning agent

Polymkeric substance (PA-1) 100 weight part as gained in the embodiment 2-1 of polymkeric substance is dissolved in the mixed solvent (GBL: NMP: BC=40: 40: 20 (weight ratio)) comprising gamma-butyrolactone (GBL), NMP and ethylene glycol butyl ether (BC), makes the solution that solid component concentration is 3.5 % by weight.Utilize aperture to be that this solution filters by the strainer of 0.2 μm, prepare crystal aligning agent thus.

(2) evaluation of coating

Use turner, the 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 heating in 1 hour (toasting afterwards) in the 200 DEG C of baking ovens having carried out nitrogen replacement in storehouse, forming average film thickness is thus film.Utilize multiplying power be the microscope of 100 times to observe this film, find out the presence or absence of the uneven and pin hole of thickness.Evaluation carries out as follows: by thickness, uneven and these two average evaluations be not all observed of pin hole are coating " well ", is coating " bad " by least any one the average evaluation observing thickness inequality and pin hole.In the present embodiment, thickness inequality and pin hole these two are not all observed, and coating is " well ".

(3) 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 on gained substrate by friction eliminate caused foreign matter (fragment of film), computation and measurement goes out the foreign matter number in the region of 500 μm × 500 μm.Evaluation carries out as follows: be the average evaluation of less than 3 by foreign matter number be rub resistance " well ", and 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, the rub resistance of this film is " well ".

(4) manufacture of FFS type liquid crystal display device

FFS type liquid crystal display device shown in construction drawing 1.First, using wherein one side have the electrode pair of 2 systems glass substrate 11a, with the subtend glass substrate 11b of electrode is not set as a pair, the electrode pair of described 2 systems is formed with the not figuratum bottom electrode of tool 15, successively as the silicon nitride film of insulation layer 14 and the patterned upper current conducting cap 13 for comb teeth-shaped, and in the one side of the face with transparency electrode of glass substrate 11a and subtend glass substrate 11b, use turner to be coated with the crystal aligning agent of preparation in described (1) respectively, form film.Then, after this film is carried out 1 minute prebake conditions on the hot-plate of 80 DEG C, 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.By shown in Figure 2 for the floor map of upper current conducting cap 13.In addition, Fig. 2 (a) is the vertical view of upper current conducting cap 13, Fig. 2 (b) be Fig. 2 (a) by the enlarged view of the part C1 of dotted line.In the present embodiment, the live width d1 of electrode is set to 4 μm, interelectrode distance d2 is set to 6 μm.

Then, utilize cotton, friction treatment is implemented to each surface of the film be formed on glass substrate, makes liquid crystal orienting film 12.In Fig. 2 (b), the direction of the film be formed on glass substrate 11a being implemented to friction is represented with arrow.These substrates are become antiparallel mode with the frictional direction each other of substrate 11a, substrate 11b, and the spacer being 3.5 μm across diameter is fitted, and injects liquid crystal MLC-6221 (Merck & Co., Inc.'s manufacture), forms 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 mutually orthogonal, make liquid crystal display device 10 thus.

(5) evaluation of LCD alignment

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

(6) evaluation of voltage retention

For the FFS type liquid crystal display device of described manufacture, apply the voltage of 5V 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 is 99.2%.In addition, the VHR-1 using Dongyang Te Kenika (Toyo Technica) (stock) to manufacture is as determinator.

(7) evaluation of thermotolerance

For the FFS type liquid crystal display device of described manufacture, measure voltage retention in the mode identical with described (6), using its value as initial VHR (VHR _bF).Then, the liquid crystal display device after being measured by initial VHR leaves standstill 300 hours in the baking oven of 100 DEG C.Then, by this liquid crystal display device at room temperature leave standstill and place be cooled to room temperature after, to measure voltage retention (VHR with described identical mode _aF).In addition, utilize following mathematical expression (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...(2)

The evaluation of thermotolerance carries out as follows: average evaluation velocity of variation Δ VHR being less than 4% is thermotolerance " well ", by more than 4% and the average evaluation being less than 5% is "available", is thermotolerance " bad " by the average evaluation of more than 5%.Its result is, the Δ VHR of the liquid crystal display device of the present embodiment is 1.9%, and thermotolerance is " well ".

(8) tilt angle characteristic

For the liquid crystal display device of described manufacture, by the angle tilted from real estate using the crystallization rotational method of He-Ne laser light to measure liquid crystal molecule, using this value as pretilt theta.Crystallization rotational method is according to non-patent literature 1 (people " applied physics magazine (the Joumalof Applied Physics such as T.J. Schaefer (T.J.Scheffer), J.Appl.Phys.) " the 48th volume the 1783rd page (1977)) and non-patent literature 2 (in F. the people such as wild (F.Nakano) " Japanese applied physics magazine (Japanese Journalof Applied Physics, JPN.J.Appl.Phys.) " the 19th volume the 2013rd page (1980)) in the method recorded carry out.

Evaluation carries out as follows: average evaluation pretilt theta being less than 1.0 ° is tilt angle evaluation " well ", be tilt angle evaluation " bad " by the average evaluation of more than 1.0 °, result, the tilt angle velocity of variation of this liquid crystal display device is 0.3 °, is judged as tilt angle stability " well ".

(9) the contrast gradient evaluation after stress (exchanging the evaluation of (alternating current, AC) image retention characteristic) is driven

Except in Polarizer of not fitting on the two sides, outside of substrate, carry out the operation identical with described (4), make FFS type liquid crystal cells.For this FFS type liquid crystal cells, after driving 30 hours with voltage of alternating current 10V, be used in the device being configured with polarizer and analyzer between light source and light quantity detector, measure the minimum relative permeability (%) represented by following mathematical expression (3).

Minimum relative permeability (%)=(β-B ⁰)/(B ¹⁰⁰-B ⁰) × 100... (3)

(in mathematical expression (3), B ⁰for the transit dose of the light under space state and under Nicol crossed; B ¹⁰⁰for the transit dose of the light under space state and under parallel Nicol; β is under Nicol crossed, clamps liquid crystal display device and become minimum light transmission capacity between polarizer and analyzer.)

The black level of dark state represents with the minimum relative permeability of liquid crystal display device, and in FFS type liquid crystal display device, the black level under dark state is less, then contrast gradient is more excellent.Minimum relative permeability 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 permeability of this liquid crystal cells is 0.2%, is judged as " well ".

[embodiment 3-2 ~ embodiment 3-5 and comparative example 1, comparative example 2]

In described embodiment 3-1, except using the composition of kind shown in following table 2 to be used as except polymkeric substance respectively, prepare crystal aligning agent in the mode identical with embodiment 3-1, and manufacture FFS type liquid crystal display device to carry out various evaluation.Evaluation result is shown in following table 2.

As shown in table 2, in embodiment 3-1 ~ embodiment 3-5, all obtain good result about the coating of crystal aligning agent and the rub resistance of film.In addition, be also good result about the regiospecific of the liquid crystal molecule in liquid crystal display device, voltage retention, thermotolerance, tilt angle characteristic and AC image retention characteristic.On the other hand, in comparative example 1, the coating of crystal aligning agent is " bad ", about the rub resistance of film, is the result than embodiment difference.In addition, in the liquid crystal display device of comparative example 1, voltage retention, tilt angle characteristic and AC image retention characteristic are the results than embodiment difference.In comparative example 2, though make the polymkeric substance that 1,2,3,4-tetramethylene tetracarboxylic dianhydride and compound (DA-1) carry out reacting and obtain, voltage retention is low, and the thermotolerance of liquid crystal cells is " bad ".

[embodiment 3-6:TN type liquid crystal display device]

(1) preparation of crystal aligning agent

Polymkeric substance (PA-7) 100 weight part of gained in embodiment 2-5 as polymkeric substance 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 crystal aligning agent thus.

(2) evaluation of printing

Use liquid crystal orienting film printing press (Japan's description printing (stock) manufactures), the 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.Utilize multiplying power to be that the microscope of 20 times is observed this film, find out the presence or absence of the uneven and pin hole of printing.Evaluation carries out as follows: be printing " well " by uneven for printing and these two average evaluations be not all observed of pin hole, being printing "available" by least any one the average evaluation observing the uneven and pin hole of a small amount of printing, is printing " bad " by least any one the average evaluation seeing the uneven and pin hole of a large amount of printings.In the present embodiment, printing inequality and pin hole these two are not all observed, and printing is " well ".

(3) manufacture of TN type liquid crystal cells

Use liquid crystal orienting film printing press (Japan's description printing (stock) manufactures), the 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.For 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 LCD alignment ability.Then, in ultrapure water, carry out 1 minute ultrasonic washer, in 100 DEG C of cleaning ovens dry 10 minutes then, obtain the substrate with liquid crystal orienting film thus.In addition, repeat described operation, obtain a pair (2 pieces) substrate with liquid crystal orienting 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 orienting film adds and has diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, in the relative mode of LCD alignment face, a pair substrate is overlapping and crimp, make adhesive hardens.Then, from liquid crystal injecting port to after filling nematic liquid crystal (Merck & Co., Inc. manufactures, MLC-6221) between a pair substrate, utilize acrylic acid series ray hardening type adhesive to be sealed by liquid crystal injecting port, manufacture TN type liquid crystal cells thus.

(4) evaluation of LCD alignment

For the TN type liquid crystal cells manufactured in described (3), under Nicol crossed, utilize microscope, observe the presence or absence of the abnormal area when on-off 5V voltage with multiplying power 50 times.Evaluation is carried out in the mode identical with described embodiment 3-1 (5).Its result is, LCD alignment " well " in this liquid crystal cells.

(5) evaluation of tilt angle stability

For the TN type liquid crystal cells manufactured in described (3), by using the crystallization rotational method of He-Ne laser light, measure the angle tilted from real estate of liquid crystal molecule, using this value as initial pretilt theta _iN.Crystallization rotational method is according to non-patent literature 1 (people " applied physics magazine (the Journal of Applied Physics such as T.J. Schaefer (T.J.Scheffer), J.Appl.Phys.) " the 48th volume the 1783rd page (1977)) and non-patent literature 2 (in F. the people such as wild (F.Nakano) " Japanese applied physics magazine (JapaneseJournal of Applied Physics, JPN.J.Appl.Phys.) " the 19th volume the 2013rd page (1980)) in the method recorded carry out.

Then, to determining initial pretilt theta _iNafter liquid crystal cells apply the voltage of alternating current 100 hours of 5V.Then, again to 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 (4), obtain the variable quantity (Δ θ (°)) that voltage applies the tilt angle of front and back.

Δθ＝|θ _AF-) _IN|...(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 cells of result is 2.8%, is judged as tilt angle stability " well ".

(6) evaluation of voltage retention and thermotolerance

Voltage retention (VHR is measured in the mode that (6) with described embodiment 3-1 are identical _bF), and in the identical mode in (7) with described embodiment 3-1, 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 98.9%.In addition, Δ VHR is 2.9%, is judged as thermotolerance " well ".

[embodiment 3-7:VA type liquid crystal display device]

(1) preparation of crystal aligning agent

Polymkeric substance (PI-1) 100 weight part of gained in embodiment 2-6 as polymkeric substance 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, utilize aperture to be that the strainer of 0.2 μm filters, prepare crystal aligning agent thus.

(2) evaluation of printing

Use the crystal aligning agent of preparation in described (1), find out printing, result in the mode that (2) with described embodiment 3-5 are identical, printing inequality and pin hole these two are not all observed, and printing is " well ".

(3) manufacture of VA type liquid crystal cells

Use liquid crystal orienting film printing press (Japan's description printing (stock) manufactures), the 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, 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 orienting film).Repeat this operation, obtain a pair (2 pieces) glass substrate on nesa coating with liquid crystal orienting film.Then, to the wherein one piece of substrate in described a pair substrate, after the outer rim coating in the face with liquid crystal orienting film adds and has diameter to be the epoxy resin adhesive of the alumina balls of 5.5 μm, in the relative mode of LCD alignment face, a pair substrate is overlapping and crimp, make adhesive hardens.Then, from liquid crystal injecting port to after filling nematic liquid crystal (Merck & Co., Inc. 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.

(4) evaluation of LCD alignment, voltage retention and thermotolerance

For the VA type liquid crystal cells manufactured in described (3), carry out the evaluation of LCD alignment in the mode that (5) with embodiment 3-1 are identical, result, the LCD alignment of this liquid crystal cells is " well ".In addition, voltage retention (VHR is measured in the mode that (6) with embodiment 3-1 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 (7) with described embodiment 3-1 are identical.Its result is, VHR _bFbe 99.2%.In addition, Δ VHR is 2.4%, is judged as thermotolerance " well ".

[embodiment 3-8: phase retardation film]

(1) preparation of crystal aligning agent

By organopolysiloxane (S-1) 5 weight part of gained in polymkeric substance (PA-2) 100 weight part of gained in embodiment 2-2 and synthesis example 3, be dissolved in the mixed solvent (NMP: BC=50: 50 (weight ratio)) comprising NMP and BC, make the solution that solid component concentration is 3.5 % by weight.Utilize aperture to be that this solution filters by the strainer of 0.2 μm, prepare crystal aligning agent thus.

(2) manufacture of phase retardation film

In the one side of the TAC film as substrate, use rod coater to be coated with the 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, aperture is utilized to be, after polymerizable liquid crystal (RMS03-013C, Merck & Co., Inc. manufacture) filters by the strainer of 0.2 μm, utilize rod coater, 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 LCD alignment

For the phase retardation film manufactured in described (2), by utilizing the visual and polarizing microscope under Nicol crossed (multiplying power is 2.5 times), observing the presence or absence of abnormal area, evaluating liquid crystal regiospecific.Evaluation carries out as follows: will be good at visual lower regiospecific, and the average evaluation not observing abnormal area under polarizing microscope is LCD alignment " well "; To not observe abnormal area under visual, but the average evaluation observing abnormal area under polarizing microscope is LCD alignment "available"; Be LCD alignment " bad " by the average evaluation all observing abnormal area under visual and polarizing microscope.Its result is, this phase retardation film is be evaluated as LCD alignment " well ".

(4) adhesion

Use the phase retardation film manufactured in described (2), the adhesion of the film formed by crystal aligning agent and substrate is evaluated.First, use the equally spaced spacer with guiding element, 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 till liquid crystal layer surface arrives the mid point of substrate thickness.Then, after cellophane tape being touched in the mode of whole that covers described tartan design, this cellophane tape is peeled off.By the visual notch observing the tartan design after stripping under Nicol crossed, evaluate adhesion.Evaluation carries out as follows: will be adhesion " well " along the part of incision line and the cross section of the tartan design average evaluation to peeling off unconfirmed; By the number relative to tartan design entirety, the average evaluation being less than 15% in the grid object number of described partially observable stripping is adhesion "available"; By the number relative to tartan design entirety, the average evaluation being more than 15% in the grid object number of described partially observable stripping is adhesion " bad ".Its result is, this phase retardation film is adhesion " well ".

Claims (12)

1. a crystal aligning agent, it is characterized in that: containing at least one polymkeric substance (P) be selected from the cohort that is made up of polyamic acid, poly amic acid ester and polyimide, described polymkeric substance (P) makes to be selected from least one tetracarboxylic acid derivatives in the cohort that is made up of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide, carry out reacting with the diamines of the compound comprised represented by following formula (1) and obtain

[changing 1]

In formula (1), R ^abe the divalent group that at least any position of position between the C-C of the alkyl of carbon number 1 ~ 30 and adjacent with described alkyl has Sauerstoffatom or sulphur atom, at least 1 of the hydrogen atom that described alkyl has can replace through halogen atom; X ¹and X ²be separately singly-bound, Sauerstoffatom, sulphur atom or divalent organic radical; Wherein, at X ¹and X ²for Sauerstoffatom, and R ^afor-O-R ¹-O-(R ¹alkane two base for carbon number 1 ~ 18) when, described tetracarboxylic acid derivatives is except the situation of 1,2,3,4-tetramethylene tetracarboxylic dianhydride.

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

[changing 2]

In formula (1-1), R ²for the divalent alkyl of carbon number 1 ~ 30, X ¹and X ²be separately singly-bound, Sauerstoffatom, sulphur atom or divalent organic radical, X ³for Sauerstoffatom or sulphur atom, X ⁴for singly-bound, Sauerstoffatom or sulphur atom; Wherein, at X ¹, X ², X ³and X ⁴for Sauerstoffatom, and R ²when alkane two base for carbon number 1 ~ 18, described tetracarboxylic acid derivatives is except the situation of 1,2,3,4-tetramethylene tetracarboxylic dianhydride.

3. crystal aligning agent according to claim 2, is characterized in that: described R ²for alkane two base of carbon number 1 ~ 11.

4. crystal aligning agent according to any one of claim 1 to 3, is characterized in that: described X ¹and X ²be separately Sauerstoffatom, alkane two base of carbon number 1 ~ 10, alkene two base of carbon number 2 ~ 10, ester group or amide group.

5. crystal aligning agent according to any one of claim 1 to 3, it is characterized in that: described tetracarboxylic acid derivatives comprises at least one in the cohort being selected from and being made up of following compound, namely, 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-2,4,6,8-tetracarboxylic dianhydride, ethylene diaminetetraacetic acid dianhydride and pyromellitic acid anhydride.

6. crystal aligning agent according to any one of claim 1 to 3, is characterized in that: described polymkeric substance (P) comprises the side-chain structure with tilt angle expressive ability.

7. a liquid crystal orienting film, is characterized in that: use crystal aligning agent according to any one of claim 1 to 6 and formed.

8. a liquid crystal display device, is characterized in that: comprise liquid crystal orienting film according to claim 7.

9. a phase retardation film, is characterized in that: comprise liquid crystal orienting film according to claim 7.

10. a manufacture method for phase retardation film, is characterized in that comprising the following steps:

Crystal aligning agent according to any one of claim 1 to 6 is coated on substrate and forms film;

Rayed is carried out to described film; And

On described film after rayed, be coated with polymerizable liquid crystal and make it harden.

11. 1 kinds of polymkeric substance, it is characterized in that: make to be selected from least one tetracarboxylic acid derivatives in the cohort be made up of tetracarboxylic dianhydride, tetracarboxylic acid diester compound and tetracarboxylic acid diester dihalide, carry out reacting with the diamines of the compound comprised represented by following formula (1) and obtain

[changing 3]

In formula (1), R ^abe the divalent group that at least any position of position between the C-C of the alkyl of carbon number 1 ~ 30 and adjacent with described alkyl has Sauerstoffatom or sulphur atom, at least 1 of the hydrogen atom that described alkyl has can replace through halogen atom; X ¹and X ²be separately singly-bound, Sauerstoffatom, sulphur atom or divalent organic radical; Wherein, at X ¹and X ²for Sauerstoffatom, and R ^afor-O-R ¹-O-(R ¹alkane two base for carbon number 1 ~ 18) when, described tetracarboxylic acid derivatives is except the situation of 1,2,3,4-tetramethylene tetracarboxylic dianhydride.

Compound represented by 12. 1 kinds of following formula (1), is characterized in that:

[changing 4]

In formula (1), R ^abe the divalent group that at least any position of position between the C-C of the alkyl of carbon number 1 ~ 30 and adjacent with described alkyl has Sauerstoffatom or sulphur atom, at least 1 of the hydrogen atom that described alkyl has can replace through halogen atom; X ¹and X ²be separately singly-bound, Sauerstoffatom, sulphur atom or divalent organic radical; Wherein, at X ¹and X ²for Sauerstoffatom, and R ^afor-O-R ¹-O-(R ¹alkane two base for carbon number 1 ~ 18) situation except.