CN105694912A - Light alignment liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display device using same - Google Patents

Abstract

The present invention provides a light alignment liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display device using the same. The light alignment liquid crystal aligning agent comprises at least one polymer selected from a group composed of polyamide acid, polyamide acid ester and polyimide obtained by imidization of the polyamide acid and the polyamide acid ester, the polyamide acid, the polyamide acid ester and the polyimide obtained by imidization of the polyamide acid and the polyamide acid ester are obtained by reaction of at least one of tetracarboxylic dianhydride and derivatives thereof and diamine, at least one of raw material monomers of the polymer has a photoisomerization structure, and the raw material monomers of the polymer comprise at least one of compounds expressed by the formula (1). By using the liquid crystal alignment film formed by using the light alignment liquid crystal aligning agent, the liquid crystal display device is provided, display quality of which cannot be decreased when exposed to strong light for a long time.

Description

Light orientation aligning agent for liquid crystal, liquid crystal orientation film and use its liquid crystal display cells

Technical field

The present invention relates to a kind of light orientation aligning agent for liquid crystal for optical alignment method and use its optical alignment film, liquid crystal display cells。

Background technology

Nowadays commercialization and the main flow of liquid crystal display cells that generally circulates are to use the display element of nematic liquid crystal to optoelectronics (optoelectronics) related elements such as various display devices and then optical print head, optical Fourier transform element, light valve such as the monitor of personal computer (personalcomputer), LCD TV, the view finder (ViewFinder) of video camera, projection type display etc.。What the display mode of nematic liquid crystal display element was widely known by the people is twisted nematic (TwistedNematic, TN) pattern, STN Super TN (SuperTwistedNematic, STN) pattern。In recent years in order to one of problem improving these patterns is that visual angle is narrow and small, propose there is the TN type liquid crystal display cells using optical compensation films, and with vertical orientated with the multizone of the technology of projection structure vertical orientated (Multi-domainVerticalAlignment, MVA) the coplanar switching (In-PlaneSwitching of pattern or Transverse electric-field type, IPS) pattern, fringing field switch (FringeFieldSwitching, FFS) pattern etc., and practical。

The development of the technology of liquid crystal display cells realizes not only by the improvement of these type of drive or component structure, but also is realized by the improvement of member of formation that uses in element。In the member of formation used in liquid crystal display cells, particularly liquid crystal orientation film is one of important materials being related to display quality, along with the high-quality of liquid crystal display cells, makes the performance of alignment films improve and becomes important。

Liquid crystal orientation film is to be formed by aligning agent for liquid crystal。At present, the main aligning agent for liquid crystal used is that the polyimides making polyamic acid or solubility dissolves solution (varnish) in organic solvent。After being coated on substrate by this solution, carry out film forming by methods such as heating, thus forming polyimides system liquid crystal orientation film。After masking, optionally implement to be suitable to the orientation process of described display pattern。

The friction that can carry out large area high speed processing in industrialness easily is taken as orientation position logos and is widely used。Friction is the cloth using and having transplanted the fibers such as nylon, artificial silk, polyester, in the process that the surface of liquid crystal orientation film is rubbed by a direction, thus can obtain the consistent orientation of liquid crystal molecule。But, it is indicated that caused the problem points such as generation of dirt, electrostatic by friction, exploitation replaces the orientation position logos of friction just energetically in recent years。

Instead the orientation position logos of friction and what receive publicity is irradiate light and light orientation position logos that implementation orientation processes。Light orientation position logos proposes the substantial amounts of orientation mechanisms (for example, referring to non-patent literature 1, patent documentation 1 and patent documentation 2) such as photolysis method, photoisomerization method, photodimerization method, optical cross-linking method。Compared with friction, the uniformity of the orientation of optical alignment method is high, and be non-contacting orientation position logos, therefore has and does not damage film, can reduce dirt or electrostatic etc. and make liquid crystal display cells generation show the advantages such as bad reason。

So far, the optical alignment film in polyamic acid structure with the photoreactivity base causing photoisomerization or photodimerization etc. is studied (for example, referring to patent documentation 1～patent documentation 7)。Wherein, by applying the technology of photoisomerization described in patent documentation 3～patent documentation 5, the anchoring energy of this optical alignment film is big, and orientation is good, and the electrical characteristics such as voltage retention are good。But, evaluation that the minimizing of the residual voltage (remnant dc electricity (DirectCurrent, DC)) as one of characteristic required in liquid crystal orientation film is carried out, research insufficient。After residual DC refers to that applying voltage makes liquid crystal drive, voltage remaining when voltage is recovered to 0V。The following phenomenon of known generation: after making liquid crystal display cells show arbitrary image for a long time, image before when becoming other images remains as image retention, so that display quality deterioration, but it is known to suppressing the accumulation of residual DC and shortening the relaxation time, described image retention (for example, referring to patent documentation 7) can be suppressed。

In recent years, in liquid crystal display cells, consider the raising of display quality or for outdoor, it may have the purposes increased before becoming the brightness ratio of the backlight of light source, even if thus it requires a kind of being exposed under strong light display quality for a long time without the liquid crystal display cells declined。Even if utilizing described technology, also it is difficult to provide the light orientation aligning agent for liquid crystal meeting described requirement。

[prior art literature]

[patent documentation]

[patent documentation 1] Japanese Patent Laid-Open 9-297313

[patent documentation 2] Japanese Patent Laid-Open 10-251646

[patent documentation 3] Japanese Patent Laid-Open 2005-275364

[patent documentation 4] Japanese Patent Laid-Open 2007-248637

[patent documentation 5] Japanese Patent Laid-Open 2009-069493

[patent documentation 6] Japanese Patent Laid-Open 2008-233713

[patent documentation 7] International Publication 2013/157463

[non-patent literature]

[non-patent literature 1] " liquid crystal " the 3rd volume, No. 4, the 262nd page, 1999

Summary of the invention

[inventing problem to be solved]

Even if the problem of the present invention is in that providing a kind of is exposed under strong light display quality for a long time without the liquid crystal display cells declined, and then provides a kind of aligning agent for liquid crystal that can provide this kind of display element and liquid crystal orientation film。

[in order to solve the technological means of problem]

Carry out make great efforts research results verification arrive: because of for a long time use and display quality decline display element after a long time use, voltage retention decline。And find the raw material as light orientation aligning agent for liquid crystal of the diamidogen represented by formula (1) of the application of the invention, even if using voltage retention without decline for a long time, even if thus providing a kind of to be exposed under strong light display quality for a long time without the liquid crystal display cells declined, and a kind of aligning agent for liquid crystal that can provide this kind of display element and liquid crystal orientation film can be provided。

The present invention comprises following composition。

[1] a kind of light orientation aligning agent for liquid crystal, it comprises at least one polymer in the group selecting free polyamic acid, poly amic acid ester and the polyimides that they carried out imidizate and obtains to form, described polyamic acid, poly amic acid ester and the polyimides they being carried out imidizate and obtaining are to make at least one being selected from tetracarboxylic dianhydride and derivant thereof and diamine reactant obtain, wherein

At least one of the starting monomer of described polymer has photoisomerization structure, and

The starting monomer of described polymer comprises at least one of the compound represented by following formula (1)；

In formula (1), R^aIt is hydrogen or methyl；

R^bTo be hydrogen ,-OH, carbon number be 1～6 alkyl or carbon number be the alkoxyl of 1～6；And

The derivant of described tetracarboxylic dianhydride refers to tetrabasic carboxylic acid diester or tetrabasic carboxylic acid diester dichloride。

[2] according to light orientation aligning agent for liquid crystal described in [1] item, it comprises: make at least one starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form and the compound represented by diamidogen contained (1) react and at least one of polymer that obtains；Or

Comprise simultaneously:

At least one of the polymer making the starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form react and to obtain；And

Any one of tetracarboxylic dianhydride and derivant and diamidogen is made all not have a photoisomerization structure and at least one starting monomer reaction that diamidogen comprises compound represented by described formula (1) and at least one of polymer that obtains。

[3] according to light orientation aligning agent for liquid crystal described in [2] item, it comprises: make at least one starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form and the compound represented by diamidogen contained (1) react and at least one of polymer that obtains；And other polymer used with described polymer mixed；And

Other polymer described are that any one starting monomer all without photoisomerization structure making tetracarboxylic dianhydride and derivant and diamidogen reacts the polymer obtained。

[4] according to light orientation aligning agent for liquid crystal described in [2] item, it comprises: make at least one starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form and the compound represented by diamidogen contained (1) react and at least one of polymer that obtains；And other polymer used with described polymer mixed；And

Other polymer are that any one at least one starting monomer all without the compound represented by photoisomerization structure and diamidogen contained (1) making tetracarboxylic dianhydride and derivant and diamidogen reacts the polymer obtained。

[5] according to light orientation aligning agent for liquid crystal described in [1] item, it comprises simultaneously: make the starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form react and at least one of polymer that obtains；And

At least one of the polymer that any one at least one starting monomer all without the compound represented by photoisomerization structure and diamidogen contained (1) making tetracarboxylic dianhydride and derivant and diamidogen reacts and obtains。

[6] according to [1] item to the light orientation aligning agent for liquid crystal according to any one of [5] item, at least one in the group that the diamidogen represented by its Chinese style (1) forms for selecting the diamidogen represented by free style (1-1) and the diamidogen represented by formula (1-2):

In formula (1-1) and formula (1-2), R^bTo be hydrogen ,-OH, carbon number be 1～6 alkyl or carbon number be the alkoxyl of 1～6。

[7] according to [1] item to the light orientation aligning agent for liquid crystal according to any one of [5] item, at least one in the group that the diamidogen represented by its Chinese style (1) forms for selecting the diamidogen represented by free following formula (1-1-1)～formula (1-1-6), formula (1-1-17), formula (1-1-18), formula (1-2-1)～formula (1-2-6), formula (1-2-17) and formula (1-2-18):

[8] according to [1] item to the light orientation aligning agent for liquid crystal according to any one of [7] item, wherein there is the tetracarboxylic dianhydride of photoisomerization structure or at least one that diamidogen is the compound represented by formula (II)～formula (VI):

R²-C≡C-R³(II)

R²-C≡C-C≡C-R³(III)

R²-C≡C-R⁴-C≡C-R³(IV)

R²-N=N-R³(V)

R⁵-CH=CH-R⁵(VI)

In formula (II)～formula (V), R²And R³For having-NH₂Any monovalent organic radical or there is any monovalent organic radical of-CO-O-CO-, in formula (IV), R⁴For divalent organic base, in formula (VI), R⁵For having-NH₂Or the aromatic rings of-CO-O-CO-。

[9] according to the light orientation aligning agent for liquid crystal described in [8] item, tetracarboxylic dianhydride or the diamidogen wherein with photoisomerization structure are at least one in the group of the compound represented by formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1)～formula (V-3), formula (VI-1) and formula (VI-2):

Described various in, it is any that binding site is not fixed to the binding site on which ring of the basis representation on structure any one carbon atom looped；

In formula (V-2), R⁶Stand alone as-CH₃、-OCH₃、-CF₃, or-COOCH₃, a is the integer of 0～2；

In formula (V-3), ring A and ring B is each independently at least one in monocyclic hydrocarbon, condensation polycyclic formula hydrocarbon and heterocycle,

R¹¹For straight-chain alkyl-sub-that carbon number is 1～20 ,-COO-,-OCO-,-NHCO-,-CONH-,-N (CH₃) CO-or-CON (CH₃)-,

R¹²For straight-chain alkyl-sub-that carbon number is 1～20 ,-COO-,-OCO-,-NHCO-,-CONH-,-N (CH₃) CO-or-CON (CH₃)-,

R¹¹And R¹²In ,-the CH of straight-chain alkyl-sub-₂-one or two can replace through-O-,

R⁷～R¹⁰It is each independently-F ,-CH₃、-OCH₃、-CF₃, or-OH, and

B～e is each independently the integer of 0～4。

[10] according to [1] item to the light orientation aligning agent for liquid crystal according to any one of [9] item, the tetracarboxylic dianhydride wherein without photoisomerization structure is at least one in the group of the tetracarboxylic dianhydride represented by following formula (AN-I)～formula (AN-VII):

In formula (AN-I), formula (AN-IV) and formula (AN-V), X stands alone as singly-bound or-CH₂-；

In formula (AN-II), G is singly-bound, carbon number be 1～20 alkylidene ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-；

In formula (AN-II)～formula (AN-IV), Y stands alone as the one in the group of the base of following trivalent,

At least one hydrogen of described base can be replaced by methyl, ethyl or phenyl；

In formula (AN-III)～formula (AN-V), ring A¹⁰Base for the base of monocyclic hydrocarbon that carbon number is 3～10 or condensation polycyclic formula hydrocarbon that carbon number is 6～30, at least one hydrogen of described base can be replaced by methyl, ethyl or phenyl, the associative key being connected on ring links with the looped arbitrary carbon of structure, and two associative keys can link with same carbon；

In formula (AN-VI), X¹⁰Being the alkylidene of 2～6 for carbon number, Me represents methyl, and Ph represents phenyl,

In formula (AN-VII), G¹⁰Stand alone as-O-,-COO-or-OCO-；And r stands alone as 0 or 1。

[11] according to the light orientation aligning agent for liquid crystal described in [10] item, wherein not there is the tetracarboxylic dianhydride of photoisomerization structure for selected from following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3), and at least one in formula (AN-16-4):

In formula (AN-1-2) and formula (AN-4-17), m is the integer of 1～12。

[12] according to [1] item to the light orientation aligning agent for liquid crystal according to any one of [11] item, wherein not there is at least one in the group that the diamidogen of photoisomerization structure forms for the free following formula of choosing (DI-1)～formula (DI-16), formula (DIH-1)～formula (DIH-3) and formula (DI-31)～formula (DI-35):

In formula (DI-1), G²⁰For-CH₂-, at least one-CH₂-can be replaced by-NH-,-O-, m is the integer of 1～12, and at least one hydrogen of alkylidene can be replaced by-OH；

In formula (DI-3) and formula (DI-5)～formula (DI-7), G²¹Stand alone as singly-bound ,-NH-,-NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONH-、-CONCH₃-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m'-、-O-(CH₂)_m'-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m'-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m'-CO-O-、-CO-O-(CH₂)_m'-O-CO-、-(CH₂)_m'-NH-(CH₂)_m'-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m')_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-or-S-(CH₂)_m'-S-, m' stand alone as the integer of 1～12, and k is the integer of 1～5, and n is 1 or 2；

In formula (DI-4), s stands alone as the integer of 0～2；

In formula (DI-6) and formula (DI-7), G²²Stand alone as singly-bound ,-O-,-S-,-CO-,-C (CH₃)₂-、-C(CF₃)₂-,-NH-or carbon number be the alkylidene of 1～10；

In formula (DI-2)～formula (DI-7), at least one hydrogen of cyclohexane ring and phenyl ring can by alkyl ,-OCH that-F ,-Cl, carbon number are 1～3₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl replace, additionally, in formula (DI-4), at least one hydrogen of phenyl ring can by a replacement in the group of the base represented by following formula (DI-4-a)～formula (DI-4-e)；

In formula (DI-4-a) and formula (DI-4-b), R²⁰Stand alone as hydrogen or-CH₃；

It is any that binding site is not fixed to the binding site on which ring of the basis representation on the looped carbon atom of structure ,-NH₂Binding site on cyclohexane ring or phenyl ring is except G²¹Or G²²Binding site beyond arbitrary position；

In formula (DI-11), r is 0 or 1；

In formula (DI-8)～formula (DI-11), the bond-NH on ring₂Binding site be arbitrary position；

In formula (DI-12), R²¹And R²²Stand alone as the alkyl or phenyl that carbon number is 1～3, G²³Standing alone as alkylidene, phenylene or the phenylene through alkyl replacement that carbon number is 1～6, w is the integer of 1～10；

In formula (DI-13), R²³Stand alone as alkyl that carbon number is 1～5, carbon number be 1～5 alkoxyl or-Cl, p stand alone as 0～3 integer, q is the integer of 0～4；

In formula (DI-14), ring B is monocyclic heteroaromatic, R²⁴For hydrogen ,-F ,-Cl, carbon number be 1～6 alkyl, carbon number be 1～6 alkoxyl, carbon number be 2～6 thiazolinyl, carbon number be the alkynyl of 1～6, q stands alone as the integer of 0～4；

In formula (DI-15), ring C is containing heteroatomic monocycle；

In formula (DI-16), G²⁴For alkylidene or Isosorbide-5-Nitrae-phenylene that singly-bound, carbon number are 2～6, r is 0 or 1；

In formula (DI-13)～formula (DI-16), it is any that binding site is not fixed to the binding site on which ring of the basis representation on the looped carbon atom of structure；

In formula (DIH-1), G²⁵For alkylidene that singly-bound, carbon number are 1～20 ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-；

In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl；

In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl, Y is singly-bound, carbon number be 1～20 alkylidene ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-；

In formula (DIH-2) and formula (DIH-3), the bond-CONHNH on ring₂Binding site be arbitrary position；

In formula (DI-31), G²⁶For singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-or-(CH₂)_m'-, m' is the integer of 1～12, R²⁵For alkyl, phenyl that carbon number is 3～30, having the base of steroid skeleton or the base represented by following formula (DI-31-a), in described alkyl, at least one hydrogen can be replaced by-F, at least one-CH₂-can be replaced by-O-,-CH=CH-or-C ≡ C-, the hydrogen of described phenyl can by-F ,-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃, carbon number be 3～30 alkyl or alkoxyl that carbon number is 3～30 replace, the bond-NH on phenyl ring₂Binding site represent in described ring for arbitrary position,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For bond base, they stand alone as singly-bound or carbon number is the alkylidene of 1～12, the more than one-CH of described alkylidene₂-can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-, ring B²¹, ring B²², ring B²³And ring B²⁴Stand alone as Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-dioxane-2,5-bis-base, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,5-bis-base, naphthalene-2,7-bis-base or anthracene-9,10-bis-base, ring B²¹, ring B²², ring B²³And ring B²⁴In, at least one hydrogen can by-F or-CH₃Replacing, s, t and u stand alone as the integer of 0～2, they add up to 1～5, when s, t or u are 2, two bond bases in each bracket can be identical, it is also possible to different, and two rings can be identical, it is also possible to different,

R²⁶Replace alkyl for the fluorine that alkyl that hydrogen ,-F ,-OH, carbon number are 1～30, carbon number are 1～30, carbon number be 1～30 alkoxyl ,-CN ,-OCH₂F、-OCHF₂, or-OCF₃, described carbon number is at least one-CH of the alkyl of 1～30₂-can be replaced by the base with the bivalence represented by following formula (DI-31-b),

In formula (DI-31-b), R²⁷And R²⁸Standing alone as the alkyl that carbon number is 1～3, v is the integer of 1～6；

In formula (DI-32) and formula (DI-33), G³⁰Stand alone as singly-bound ,-CO-or-CH₂-, R²⁹Stand alone as hydrogen or-CH₃, R³⁰Alkyl or carbon number for hydrogen, carbon number are 1～20 are the thiazolinyl of 2～20；

One hydrogen of the phenyl ring in formula (DI-33) can be replaced by the alkyl or phenyl that carbon number is 1～20, and

In formula (DI-32) and formula (DI-33), it is any that binding site is not fixed to the binding site on which ring of the basis representation on structure any one carbon atom looped；

In formula (DI-34) and formula (DI-35), G³¹Stand alone as-O-or carbon number is the alkylidene of 1～6, G³²It is the alkylidene of 1～3 for singly-bound or carbon number,

R³¹It is the alkyl of 1～20 for hydrogen or carbon number, at least one-CH of described alkyl₂-can be replaced by-O-,-CH=CH-or-C ≡ C-, R³²It is the alkyl of 6～22 for carbon number, R³³It is the alkyl of 1～22 for hydrogen or carbon number, ring B²⁵For Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1, and-the NH that bond is on phenyl ring₂Represent that binding site on which ring is any。

[13] according to the light orientation aligning agent for liquid crystal described in [12] item, wherein not there is the diamidogen of photoisomerization structure for selecting free following formula (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DI-31-44), and at least one in the group that forms of formula (DIH-2-1):

In formula (DI-5-1), formula (DI-5-12), formula (DI-5-13) and formula (DI-7-3), m is the integer of 1～12；

In formula (DI-5-30), k is the integer of 1～5；And

In formula (DI-7-3), n is 1 or 2；

[14] according to [1] item to the light orientation aligning agent for liquid crystal according to any one of [13] item, it is possibly together with at least one selecting free alkenyl substituted Na Dike imide compound, have in the compound group that the compound of free-radical polymerised unsaturated double-bond, piperazine compound, isoxazoline compound and epoxide form。

[15] according to [1] item to the light orientation aligning agent for liquid crystal according to any one of [14] item, it is for the manufacture of lateral electric-field type liquid crystal display cells。

[16] a kind of liquid crystal orientation film, it is to be formed to the light orientation aligning agent for liquid crystal according to any one of [15] item by according to [1] item。

[17] a kind of liquid crystal display cells, it includes according to the liquid crystal orientation film described in [16] item。

[18] a kind of lateral electric-field type liquid crystal display cells, it includes according to the liquid crystal orientation film described in [16] item。

[effect of invention]

Even if the liquid crystal display cells with the light orientation liquid crystal orientation film formed by the light orientation aligning agent for liquid crystal of the present invention is used for a long time, voltage retention is without decline, even and if being exposed under strong light also can to maintain high display quality。

Detailed description of the invention

< light orientation aligning agent for liquid crystal >

The light orientation aligning agent for liquid crystal of the present invention contains at least one polymer in the group selecting free polyamic acid, poly amic acid ester and the polyimides that they carried out imidizate and obtains to form, described polyamic acid, poly amic acid ester and the polyimides they being carried out imidizate and obtaining are at least one product with diamidogen in tetracarboxylic dianhydride and derivant thereof, the at least one of the starting monomer of described polymer has photoisomerization structure, and diamidogen comprises at least one of the compound represented by following formula (1)。Described polyamic acid, poly amic acid ester and the polyimides they being carried out imidizate and obtaining refer to the composition being dissolved in solvent when making the aligning agent for liquid crystal described later containing solvent, and refer to when this aligning agent for liquid crystal is made liquid crystal orientation film described later, the composition of the liquid crystal orientation film being main constituent with polyimides can be formed。Poly amic acid ester can synthesize by the following method: the method synthesized by making the reaction such as described polyamic acid and the compound of hydroxyl, halogenide, compound containing epoxy radicals, or the method by making to synthesize from the derivative tetrabasic carboxylic acid diester of acid dianhydride or tetrabasic carboxylic acid diester dichloride and diamine reactant。The alcohol of acid dianhydride and 2 equivalents such as can be made to react from the tetrabasic carboxylic acid diester that acid dianhydride is derivative and open loop and obtain, tetrabasic carboxylic acid diester dichloride can by making the chlorinating agent (such as thionyl chloride etc.) of tetrabasic carboxylic acid diester and 2 equivalents react and obtain。Furthermore, poly amic acid ester can only have amic acid esters structure, it is possible to for amic acid structure and amic acid esters structure the partial esterification thing deposited。The light orientation aligning agent for liquid crystal of the present invention can comprise a kind of described polyamic acid, poly amic acid ester and the polyimides they being carried out imidizate and obtaining, it is possible to comprises two or more。

R in formula (1)^aAnd R^bAs defined above。

The light orientation aligning agent for liquid crystal of the present invention comprises: make at least one in the group that the free tetracarboxylic dianhydride of choosing and derivant thereof and diamidogen form have a photoisomerization structure and at least one starting monomer reaction that diamidogen comprises compound represented by described formula (1) and at least one of polymer that obtains；Or comprise: at least one of the polymer that at least one starting monomer with photoisomerization structure in the group making the free tetracarboxylic dianhydride of choosing and derivant thereof and diamidogen form reacts and obtains simultaneously；At least one of the polymer reacted with at least one starting monomer that any one does not all have a photoisomerization structure and diamidogen comprises the compound represented by described formula (1) making tetracarboxylic dianhydride and derivant and diamidogen and obtain。

< photoreactivity structure >

In the present invention, photoreactivity structure is referred to and is caused isomerized photoisomerization structure by ultraviolet radiation。Can be suitable for using and be there is the starting monomer being caused isomerized structure by ultraviolet radiation。

As the monomer with described photoisomerization structure, can enumerate: there is the tetracarboxylic dianhydride of photoisomerization structure or there is the diamidogen of photoisomerization structure, it is preferably selected from least one in the group of the compound represented by the good following formula of photonasty (II)～formula (VI), the more preferably compound represented by formula (V)。

R²-C≡C-R³(II)

R²-C≡C-C≡C-R³(III)

R²-C≡C-R⁴-C≡C-R³(IV)

R²-N=N-R³(V)

R⁵-CH=CH-R⁵(VI)

In formula (II)～formula (V), R²And R³For having-NH₂Any monovalent organic radical or there is any monovalent organic radical of-CO-O-CO-, in formula (IV), R⁴For divalent organic base, in formula (VI), R⁵For having-NH₂Or the aromatic rings of-CO-O-CO-。

Photoisomerization structure can be incorporated in any one of the main chain of the polyamic acid or derivatives thereof to the present invention or side chain, by being incorporated to main chain, may be suitably used to the liquid crystal display cells of Transverse electric-field type。

As the material with described photoisomerization structure, at least one in the group of the compound represented by following formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1)～formula (V-3), formula (VI-1) and formula (VI-2) can be used aptly。

Described various in, it is any that binding site is not fixed to the binding site on which ring of the basis representation on structure any one carbon atom looped, in formula (V-2), R⁶Stand alone as-CH₃、-OCH₃、-CF₃, or-COOCH₃, a is the integer of 0～2, and in formula (V-3), ring A and ring B is each independently at least one in monocyclic hydrocarbon, condensation polycyclic formula hydrocarbon and heterocycle, R¹¹For straight-chain alkyl-sub-that carbon number is 1～20 ,-COO-,-OCO-,-NHCO-,-CONH-,-N (CH₃) CO-or-CON (CH₃)-, R¹²For straight-chain alkyl-sub-that carbon number is 1～20 ,-COO-,-OCO-,-NHCO-,-CONH-,-N (CH₃) CO-or-CON (CH₃)-, R¹¹And R¹²In ,-the CH of straight-chain alkyl-sub-₂-one or two can replace through-O-, R⁷～R¹⁰It is each independently-F ,-CH₃、-OCH₃、-CF₃, or-OH, and, b～e is each independently the integer of 0～4。

For described photosensitive viewpoint, the compound represented by described formula (V-1), formula (V-2) and formula (VI-2) can be used particularly suitablely。For the viewpoint of described orientation, can more appropriately use the compound that binding site is para-position of amino in formula (V-2) and formula (VI-2) and the compound of a=0 in formula (V-2)。

Shown in formula (II-1)～formula (VI-2) be there is the acid dianhydride that can be caused isomerized structure by ultraviolet radiation or diamidogen specifically can represent with following formula (II-1-1)～formula (VI-2-3)。

In these, by being set to comprise the compound that can be caused isomerized structure by ultraviolet radiation by formula (VI-1-1)～formula (V-3-8), it is possible to obtain the light orientation aligning agent for liquid crystal that the sensitivity of ultraviolet radiation is higher。By being set to comprise the compound that can be caused isomerized structure by ultraviolet radiation by formula (VI-1-1), formula (V-2-1), formula (V-2-4)～formula (V-2-11) and formula (V-3-1)～formula (V-3-8), it is possible to obtain the light orientation aligning agent for liquid crystal that liquid crystal molecule can be made more as one man to carry out orientation。By being set to comprise the compound that can be caused isomerized structure by ultraviolet radiation by formula (V-2-4)～formula (V-3-8), it is possible to acquisition can make the light orientation aligning agent for liquid crystal of the painted further minimizing of the alignment films formed。

And with in not there is the tetracarboxylic dianhydride of photoreactivity structure (non-photosensitive) and there is the embodiment of tetracarboxylic dianhydride of photoreactivity structure (photonasty), in order to prevent the alignment films reduction to the sensitivity of light, relative to the total amount as the tetracarboxylic dianhydride of raw material used when manufacturing the polyamic acid or derivatives thereof of the present invention, the preferred 0mol% of photonasty tetracarboxylic dianhydride (molar percentage)～70mol%, particularly preferably 0mol%～50mol%。It addition, in order to improve the described various characteristics such as the sensitivity to light, electrical characteristics, image retention characteristic, it is possible to and with two or more photonasty tetracarboxylic dianhydrides。

And with in not there is the diamidogen of photoreactivity structure (non-photosensitive) and there is the embodiment of diamidogen of photoreactivity structure (photonasty), in order to prevent the alignment films reduction to the sensitivity of light, relative to the total amount as the diamidogen of raw material used when manufacturing the polyamic acid or derivatives thereof of the present invention, preferred 20mol%～the 100mol% of photonasty diamidogen, particularly preferably 50mol%～100mol%。It addition, in order to improve the described various characteristics such as the sensitivity to light, image retention characteristic, it is possible to and with two or more photonasty diamidogen。As it has been described above, comprise the situation of the total amount occupying tetracarboxylic dianhydride with non-photosensitive tetracarboxylic dianhydride in embodiments of the present invention, even if also requiring that the minimum 20mol% of the total amount of diamidogen is photonasty diamidogen in said case。

In order to improve the described various characteristics such as the sensitivity to light, image retention characteristic, can and with photonasty tetracarboxylic dianhydride and photonasty diamidogen, it is possible to respectively and with two or more。

Diamidogen represented by the formula (1) of the present invention is illustrated。In diamidogen represented by formula (1), R^aIt is hydrogen or methyl, R^bTo be hydrogen ,-OH, carbon number be 1～6 alkyl or carbon number be the alkoxyl of 1～6。The position of substitution in the phenyl ring of two amino is not particularly limited, in order to be set to arrange more well the aligning agent for liquid crystal of liquid crystal molecule, it is generally desirable to relative to the position of substitution of amide groups be 3,5 or 2,5。

Diamidogen represented by formula (1) is classified into R^aDiamidogen represented by the formula (1-1) of hydrogen and R^aFor the diamidogen represented by the formula (1-2) of methyl。

In formula (1-1) and formula (1-2), R^bTo be hydrogen ,-OH, carbon number be 1～6 alkyl or carbon number be the alkoxyl of 1～6。

When needing the higher aligning agent for liquid crystal of the dissolubility in solvent, it is preferred to use the diamidogen of formula (1-1)。And, when needing the higher liquid crystal orientation film of reliability, it is preferred to use formula (1-1) and R in formula (1-2)^bCompound for hydrogen or-OH。

The concrete example of the diamidogen represented by formula (1-1) is the compound represented by below formula (1-1-1)～formula (1-1-28)。

The concrete example of the diamidogen represented by formula (1-2) is the compound represented by below formula (1-2-1)～formula (1-2-28)。

Can passing through to be used as to constitute by the diamidogen represented by formula (1-1-1)～formula (1-1-4), formula (1-2-1) and formula (1-2-2) one of raw material of polymer of aligning agent for liquid crystal of the present invention, long-time using display quality without the high liquid crystal orientation film of the liquid crystal aligning declined even if obtaining。

By the diamidogen represented by formula (1-2-1)～formula (1-2-6) being used as one of raw material of polymer of aligning agent for liquid crystal constituting the present invention, even and if with other diamidogen beyond the diamidogen represented by formula (1), it is also possible to suppress gelation when Macroscopic single crystal。Think that its reason is in that: the hydrogen of amide groups is by methyl substituted, so intermolecular interaction that hydrogen bond is formed disappears。

The non-photosensitive tetracarboxylic dianhydride containing at least one light orientation aligning agent for liquid crystal in polyamic acid, poly amic acid ester and polyimides in order to manufacture the present invention is illustrated。

The non-photosensitive tetracarboxylic dianhydride used in the present invention can unrestrictedly select from known non-photosensitive tetracarboxylic dianhydride。This kind of non-photosensitive tetracarboxylic dianhydride belongs to the tetracarboxylic dianhydride in arbitrary group of the direct bond of dicarboxylic anhydride fragrant family (comprising assorted aromatic ring) on aromatic rings and the dicarboxylic anhydride direct bond fatty family (comprising heterocycle system) on aromatic rings。

Suitable example as this kind of non-photosensitive tetracarboxylic dianhydride, the easiness that raw material is obtained or easiness during polymer polymerizing, film electrical characteristics viewpoint for, the tetracarboxylic dianhydride represented by formula (AN-I)～formula (AN-VII) can be enumerated。

In formula (AN-I), formula (AN-IV) and formula (AN-V), X stands alone as singly-bound or-CH₂-。In formula (AN-II), G is singly-bound, carbon number be 1～20 alkylidene ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-。In formula (AN-II)～formula (AN-IV), Y stands alone as the one in the group of the base of following trivalent, and associative key links with arbitrary carbon, and at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl。

In formula (AN-III)～formula (AN-V), ring A¹⁰Base for the base of monocyclic hydrocarbon that carbon number is 3～10 or condensation polycyclic formula hydrocarbon that carbon number is 6～30, at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl, the associative key being connected on ring links with the looped arbitrary carbon of structure, and two associative keys can link with same carbon。In formula (AN-VI), X¹⁰Being the alkylidene of 2～6 for carbon number, Me represents methyl, and Ph represents phenyl。In formula (AN-VII), G¹⁰Standing alone as-O-,-COO-or-OCO-, r stands alone as 0 or 1。

More specifically, the tetracarboxylic dianhydride represented by the formula by below formula (AN-1)～formula (AN-16-14) can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-1)]

In formula (AN-1), G¹¹For alkylidene, 1,4-phenylene or 1,4-cyclohexylidene that singly-bound, carbon number are 1～12。X¹¹Stand alone as singly-bound or-CH₂-。G¹²Stand alone as any one of base of following trivalent。

Work as G¹²During for > CH-, the hydrogen of > CH-can by-CH₃Replace。Work as G¹²During for > N-, G¹¹It is not singly-bound and-CH₂-, X¹¹It it is not singly-bound。And, R¹¹For hydrogen or-CH₃。

As the example of the tetracarboxylic dianhydride represented by formula (AN-1), the compound represented by following formula can be enumerated。

In formula (AN-1-2) and formula (AN-1-14), m is the integer of 1～12。

[tetracarboxylic dianhydride represented by formula (AN-2)]

In formula (AN-2), R¹²Stand alone as hydrogen ,-CH₃、-CH₂CH₃, or phenyl。

As the example of the tetracarboxylic dianhydride represented by formula (AN-2), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-3)]

In formula (AN-3), ring A¹¹For cyclohexane ring or phenyl ring。

As the example of the tetracarboxylic dianhydride represented by formula (AN-3), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-4)]

In formula (AN-4), G¹³For singly-bound ,-(CH₂)_m-、-O-、-S-、-C(CH₃)₂-、-SO₂-、-CO-、-C(CF₃)₂-or the base of bivalence represented by following formula (G13-1), m is the integer of 1～12。Ring A¹¹It is each independently cyclohexane ring or phenyl ring。G¹³Ring A can be binding on¹¹Arbitrary position。

In formula (G13-1), G^13aAnd G^13bIt is each independently the base of singly-bound ,-O-or the bivalence represented by-NHCO-。The preferred 1,4-phenylene of phenylene and 1,3-phenylene。

As the example of the tetracarboxylic dianhydride represented by formula (AN-4), the compound represented by following formula can be enumerated。

In formula (AN-4-17), m is the integer of 1～12。

[tetracarboxylic dianhydride represented by formula (AN-5)]

In formula (AN-5), R¹¹For hydrogen or-CH₃。Binding site is not fixed to the R constituting on the carbon atom of phenyl ring¹¹The binding site represented in phenyl ring is any。

As the example of the tetracarboxylic dianhydride represented by formula (AN-5), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-6)]

In formula (AN-6), X¹¹Stand alone as singly-bound or-CH₂-。X¹²For-CH₂-、-CH₂CH₂-or-CH=CH-。N is 1 or 2。

As the example of the tetracarboxylic dianhydride represented by formula (AN-6), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-7)]

In formula (AN-7), X¹¹For singly-bound or-CH₂-。

As the example of the tetracarboxylic dianhydride represented by formula (AN-7), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-8)]

In formula (AN-8), X¹¹For singly-bound or-CH₂-。R¹²For hydrogen ,-CH₃、-CH₂CH₃, or phenyl, ring A¹²For cyclohexane ring or cyclohexene ring。

As the example of the tetracarboxylic dianhydride represented by formula (AN-8), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-9)]

In formula (AN-9), r is each independently 0 or 1。

As the example of the tetracarboxylic dianhydride represented by formula (AN-9), the compound represented by following formula can be enumerated。

[formula (AN-10-1) and the tetracarboxylic dianhydride represented by formula (AN-10-2)]

[tetracarboxylic dianhydride represented by formula (AN-11)]

In formula (AN-11), ring A¹¹Stand alone as cyclohexane ring or phenyl ring。

As the example of the tetracarboxylic dianhydride represented by formula (AN-11), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-12)]

In formula (AN-12), ring A¹¹It is each independently cyclohexane ring or phenyl ring。

As the example of the tetracarboxylic dianhydride represented by formula (AN-12), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-13)]

In formula (AN-13), X¹³Being the alkylidene of 2～6 for carbon number, Ph represents phenyl。

As the example of the tetracarboxylic dianhydride represented by formula (AN-13), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-14)]

In formula (AN-14), G¹⁴Standing alone as-O-,-COO-or-OCO-, r stands alone as 0 or 1。

As the example of the tetracarboxylic dianhydride represented by formula (AN-14), the compound represented by following formula can be enumerated。

[tetracarboxylic dianhydride represented by formula (AN-15)]

In formula (AN-15), w is the integer of 1～10。

As the example of the tetracarboxylic dianhydride represented by formula (AN-15), the compound represented by following formula can be enumerated。

As the tetracarboxylic dianhydride beyond described, following compound can be enumerated。

The appropriate materials improving each characteristic in described acid dianhydride is described。

It is being used for using in the acid dianhydride of polymer of the monomer with photoisomerization structure, when paying attention to the orientation promoting liquid crystal, the preferably compound represented by formula (AN-1), formula (AN-3) and formula (AN-4), the more preferably compound represented by formula (AN-1-2), formula (AN-1-13), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17) and formula (AN-4-29)。In formula (AN-1-2), it is preferable that m=4 or 8。In formula (AN-4-17), it is preferable that m=4 or 8, more preferably m=8。

When paying attention to the transmitance promoting liquid crystal display cells, in described acid dianhydride, it is preferable that by the compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and formula (AN-16-4)。In formula (AN-1-2), it is preferable that m=4 or 8。In formula (AN-4-17), it is preferable that m=4 or 8, more preferably m=8。

Paying attention to promoting the voltage retention (voltageholdingratio of liquid crystal display cells, VHR) when, in described acid dianhydride, it is preferable that by the compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4)。In formula (AN-1-2), it is preferable that m=4 or 8。In formula (AN-4-17), it is preferable that m=4 or 8, more preferably m=8。

As preventing one of method burning trace, effectively the mitigation speed of the residual charge (residual DC) in alignment films is made to improve by making the volumetric resistivity value of liquid crystal orientation film reduce。When paying attention to this purpose, in described acid dianhydride, it is preferable that by the compound represented by formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and formula (AN-11-3)。

It is being used for not using in the acid dianhydride of polymer of the monomer with photoisomerization structure, when paying attention to the orientation promoting liquid crystal, the preferably compound represented by formula (AN-1), formula (AN-3) and formula (AN-4), the more preferably compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-2), formula (AN-4-17) and formula (AN-4-29)。In formula (AN-1-2), it is preferable that m=4 or 8。In formula (AN-4-17), it is preferable that m=4 or 8。

When paying attention to the transmitance promoting liquid crystal display cells, in described acid dianhydride, it is preferable that by the compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and formula (AN-16-4)。In formula (AN-1-2), it is preferable that m=4 or 8。In formula (AN-4-17), it is preferable that m=4 or 8, more preferably m=8。

When paying attention to the VHR promoting liquid crystal display cells, in described acid dianhydride, it is preferable that by the compound represented by formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4)。In formula (AN-1-2), it is preferable that m=4 or 8。In formula (AN-4-17), it is preferable that m=4 or 8, more preferably m=8。

As preventing one of method burning trace, effectively the mitigation speed of the residual charge (residual DC) in alignment films is made to improve by making the volumetric resistivity value of liquid crystal orientation film reduce。When paying attention to this purpose, in described acid dianhydride, it is preferable that by the compound represented by formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and formula (AN-11-3)。

To in order to manufacture illustrating containing the non-photosensitive diamidogen beyond the diamidogen represented by the formula (1) of at least one light orientation aligning agent for liquid crystal in polyamic acid, poly amic acid ester and polyimides and non-photosensitive two hydrazides of the present invention。When manufacturing the light orientation aligning agent for liquid crystal of the present invention, can unrestrictedly select from known non-photosensitive diamidogen and non-photosensitive two hydrazides。

Diamidogen can be divided into two kinds according to its structure。That is, having the diamidogen of side chain radical and do not have the diamidogen of side chain radical, described side chain radical is when regarding the skeleton linking two amino as main chain, the base of branch from main chain。This side chain radical is the base with the effect increasing tilt angle。Having the side chain radical of this kind of effect must be carbon number be the base of more than 3, as concrete example, can enumerate: alkoxyl that alkyl that carbon number is more than 3, carbon number are more than 3, carbon number are the alkoxyalkyl of more than 3 and have the base of steroid skeleton。Have the ring of more than one ring and its end and have alkyl that carbon number is more than 1, carbon number is the alkoxyl of more than 1 and the base of any one alternatively base of alkoxyalkyl that carbon number is more than 2 also has the effect as side chain radical。In the following description, sometimes the diamidogen with this kind of side chain radical is called side chain type diamidogen。And, sometimes the diamidogen without this kind of side chain radical is called non-side chain type diamidogen。

By non-side chain type diamidogen and side chain type diamidogen being suitably used separately, may correspond to each required tilt angle。Side chain type diamidogen preferably comes with the degree of the characteristic of the lossless present invention and uses。It addition, about side chain type diamidogen and non-side chain type diamidogen, it is preferable that use for carrying out choice selection for the purpose of the vertical orientated property of liquid crystal, voltage retention, burning trace characteristic and orientation by lifting。

Non-side chain type diamidogen is illustrated。As the known diamidogen without side chain, the diamidogen of below formula (DI-1)～formula (DI-16) can be enumerated。

In described formula (DI-1), G²⁰For-CH₂-, at least one-CH₂-can be replaced by-NH-,-O-, m is the integer of 1～12, and at least one hydrogen of alkylidene can be replaced by-OH。In formula (DI-3) and formula (DI-5)～formula (DI-7), G²¹Stand alone as singly-bound ,-NH-,-NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-or-S-(CH₂)_m-S-, m stand alone as the integer of 1～12, and k is the integer of 1～5, and n is 1 or 2。In formula (DI-4), s stands alone as the integer of 0～2。In formula (DI-6) and formula (DI-7), G²²Stand alone as singly-bound ,-O-,-S-,-CO-,-C (CH₃)₂-、-C(CF₃)₂-,-NH-or carbon number be the alkylidene of 1～10。Cyclohexane ring in formula (DI-2)～formula (DI-7) and at least one hydrogen of phenyl ring can by alkyl ,-OCH that-F ,-Cl, carbon number are 1～3₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl replace, additionally, in formula (DI-4), at least one hydrogen of cyclohexane ring and phenyl ring can by a replacement in the group of the base represented by following formula (DI-4-a)～formula (DI-4-e)。It is any that binding site is not fixed to the binding site on this ring of the basis representation on the looped carbon atom of structure。And ,-NH₂Binding site on cyclohexane ring or phenyl ring is except G²¹Or G²²Binding site beyond arbitrary position。

In formula (DI-4-a) and formula (DI-4-b), R²⁰Stand alone as hydrogen or-CH₃。

In formula (DI-11), r is 0 or 1。In formula (DI-8)～formula (DI-11), the bond-NH on ring₂Binding site be arbitrary position。

In formula (DI-12), R²¹And R²²Stand alone as the alkyl or phenyl that carbon number is 1～3, G²³Standing alone as alkylidene, phenylene or the phenylene through alkyl replacement that carbon number is 1～6, w is the integer of 1～10。In formula (DI-13), R²³Stand alone as alkyl that carbon number is 1～5, carbon number be 1～5 alkoxyl or-Cl, p stand alone as 0～3 integer, q is the integer of 0～4。In formula (DI-14), ring B is the hetero ring type aromatic series base of monocycle, R²⁴For alkyl that hydrogen ,-F ,-Cl, carbon number are 1～6, alkoxyl, vinyl, alkynyl, q stands alone as the integer of 0～4。In formula (DI-15), ring C is hetero ring type aromatic series base or hetero ring type fatty group。In formula (DI-16), G²⁴For alkylidene or Isosorbide-5-Nitrae-phenylene that singly-bound, carbon number are 2～6, r is 0 or 1。And, it is any that binding site is not fixed to the binding site on this ring of the basis representation on the looped carbon atom of structure。In formula (DI-13)～formula (DI-16), the bond-NH on ring₂Binding site be arbitrary position。

As the diamidogen without side chain of described formula (DI-1)～formula (DI-16), the concrete example of below formula (DI-1-1)～formula (DI-16-1) can be enumerated。

The example of following presentation diamidogen represented by formula (DI-1)。

In formula (DI-1-7) and formula (DI-1-8), k is each independently the integer of 1～3。

The example of following presentation diamidogen represented by formula (DI-2)～formula (DI-3)。

The example of following presentation diamidogen represented by formula (DI-4)。

The example of following presentation diamidogen represented by formula (DI-5)。

In formula (DI-5-1), m is the integer of 1～12。

In formula (DI-5-12) and formula (DI-5-13), m is the integer of 1～12。

In formula (DI-5-16), v is the integer of 1～6。

In formula (DI-5-30), k is the integer of 1～5。

In formula (DI-5-35)～formula (DI-5-37) and formula (DI-5-39), m is the integer of 1～12, formula (DI-5-38) and in formula (DI-5-39), and k is the integer of 1～5, in formula (DI-5-40), n is the integer of 1 or 2。

The example of following presentation diamidogen represented by formula (DI-6)。

The example of following presentation diamidogen represented by formula (DI-7)。

In formula (DI-7-3) and formula (DI-7-4), m is the integer of 1～12, and n stands alone as 1 or 2。

In formula (DI-7-12), m is the integer of 1～12。

The example of following presentation diamidogen represented by formula (DI-8)。

The example of following presentation diamidogen represented by formula (DI-9)。

The example of following presentation diamidogen represented by formula (DI-10)。

The example of following presentation diamidogen represented by formula (DI-11)。

The example of following presentation diamidogen represented by formula (DI-12)。

The example of following presentation diamidogen represented by formula (DI-13)。

The example of following presentation diamidogen represented by formula (DI-14)。

The example of following presentation diamidogen represented by formula (DI-15)。

The example of following presentation diamidogen represented by formula (DI-16)。

Two hydrazides are illustrated。As known two hydrazides without side chain, below formula (DIH-1)～formula (DIH-3) can be enumerated。

In formula (DIH-1), G²⁵For alkylidene that singly-bound, carbon number are 1～20 ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-。In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl。In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen of this base can be replaced by methyl, ethyl or phenyl, Y is singly-bound, carbon number be 1～20 alkylidene ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-。In formula (DIH-2) and formula (DIH-3), the bond-CONHNH on ring₂Binding site be arbitrary position。

The example of following presentation formula (DIH-1)～formula (DIH-3)。

In formula (DIH-1-2), m is the integer of 1～12。

This kind of non-side chain type diamidogen and two hydrazides have the effect making the ion concentration reduction etc. of liquid crystal display cells improve electrical characteristics。When using non-side chain type diamidogen and/or two hydrazides as in order to manufacture the diamidogen of light orientation aligning agent for liquid crystal of the polyamic acid, poly amic acid ester or the polyimides that use in the aligning agent for liquid crystal comprising the present invention, it is set to 0mol%～90mol% preferably in its ratio shared in the total amount of diamidogen and two hydrazides, is more preferably set to 0mol%～50mol%

Side chain type diamidogen is illustrated。As the side chain radical of side chain type diamidogen, following base can be enumerated。

As side chain radical, first can enumerate: alkyl, alkoxyl, alkoxyalkyl, alkyl-carbonyl, alkyl carbonyl oxy, alkoxy carbonyl, alkyl amino-carbonyl, thiazolinyl, alkene oxygen base, alkenyl carbonyl, thiazolinyl carbonyl oxygen base, allyloxycarbonyl, alkenyl amino carbonyl, alkynyl, alkynyloxy group, alkynylcarbonyl groups, alkynyl carbonyl oxygen base, alkynyloxycar bonyl, alkynylaminocarbonyl etc.。Alkyl in these bases, thiazolinyl and alkynyl are all carbon numbers is the base of more than 3。But, in alkoxyalkyl, as long as the carbon number of whole base is more than 3。These bases can be straight-chain, it is also possible to is branched。

Secondly, with the ring of end, there is the alkyl that carbon number is more than 1, carbon number be more than 1 alkoxyl or alkoxyalkyl alternatively base that carbon number is more than 2 be condition, can enumerate: phenyl, phenylalkyl, phenyl alkoxyl, phenoxy group, phenylcarbonyl group, phenyl carbonyl oxygen base, phenyloxycarbonyl, phenyl amino carbonyl, benzyl ring hexyloxy, carbon number is the cycloalkyl of more than 3, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxy carbonyl, cyclohexyl phenyl, cyclohexyl phenyl alkyl, cyclohexyl phenoxy group, double, two (cyclohexyl) oxygen base, double, two (cyclohexyl) alkyl, double, two (cyclohexyl) phenyl, double, two (cyclohexyl) phenylalkyl, double, two (cyclohexyl) oxygen base carbonyl, double, two (cyclohexyl) phenyloxycarbonyl, and the base of the ring structure such as double, two (phenyl) oxygen base carbonyls of cyclohexyl。

And then, the ring set base that can be listed below, it is the base with more than the base of plural phenyl ring, the base with plural cyclohexane ring or two rings comprising phenyl ring and cyclohexane ring, and bond base stands alone as the alkylidene that singly-bound ,-O-,-COO-,-OCO-,-CONH-or carbon number are 1～3, the fluorine that the ring of end has alkyl that carbon number is more than 1, carbon number is more than 1 replaces alkyl, carbon number is the alkoxyl of more than 1 or alkoxyalkyl alternatively base that carbon number is more than 2。The base with steroid skeleton is also effective as side chain radical。

As the diamidogen with side chain, the compound represented by below formula (DI-31)～formula (DI-35) can be enumerated。

In formula (DI-31), G²⁶For singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-or-(CH₂)_m'-, m' is the integer of 1～12。G²⁶Preferred example be singly-bound ,-O-,-COO-,-OCO-,-CH₂O-and carbon number are the alkylidene of 1～3, and example particularly preferably is singly-bound ,-O-,-COO-,-OCO-,-CH₂O-、-CH₂-and-CH₂CH₂-。R²⁵For alkyl, phenyl that carbon number is 3～30, there is the base of steroid skeleton or the base represented by following formula (DI-31-a)。In this alkyl, at least one hydrogen can be replaced by-F, and at least one-CH₂-can be replaced by-O-,-CH=CH-or-C ≡ C-。The hydrogen of this phenyl can by-F ,-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃, carbon number be 3～30 alkyl or alkoxyl that carbon number is 3～30 replace。The bond-NH on phenyl ring₂Binding site represent in this ring for arbitrary position, this binding site preferably between position or para-position。That is, when by base " R²⁵-G²⁶-" binding site when being set to 1, two binding site preferably 3 with 5 or 2 with 5。

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For bond base, they stand alone as singly-bound or carbon number is the alkylidene of 1～12, the more than one-CH of this alkylidene₂-can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-。Ring B²¹, ring B²², ring B²³And ring B²⁴Stand alone as Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-dioxane-2,5-bis-base, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,5-bis-base, naphthalene-2,7-bis-base or anthracene-9,10-bis-base, ring B²¹, ring B²², ring B²³And ring B²⁴In, at least one hydrogen can by-F or-CH₃Replacing, s, t and u stand alone as the integer of 0～2, they add up to 1～5, when s, t or u are 2, two bond bases in each bracket can be identical, it is also possible to different, and, two rings can be identical, it is also possible to different。R²⁶Replace alkyl for the fluorine that alkyl that hydrogen ,-F ,-OH, carbon number are 1～30, carbon number are 1～30, carbon number be 1～30 alkoxyl ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, this carbon number is at least one-CH of the alkyl of 1～30₂-can be replaced by the base with the bivalence represented by following formula (DI-31-b)。

In formula (DI-31-b), R²⁷And R²⁸Standing alone as the alkyl that carbon number is 1～3, v is the integer of 1～6。R²⁶Preferred example to be carbon number be 1～30 alkyl and carbon number be the alkoxyl of 1～30。

In formula (DI-32) and formula (DI-33), G³⁰Stand alone as singly-bound ,-CO-or-CH₂-, R²⁹Stand alone as hydrogen or-CH₃, R³⁰Alkyl or carbon number for hydrogen, carbon number are 1～20 are the thiazolinyl of 2～20。At least one hydrogen of phenyl ring in formula (DI-33) can be replaced by the alkyl or phenyl that carbon number is 1～20。And, it is any that binding site is not fixed to the binding site in this ring of the basis representation on structure any one carbon atom looped。Two base "-phenylene-G in preferred formula (DI-32)³⁰-O-" a bond 3 of steroid core, another bond is at 6 of steroid core。Two base "-phenylene-G in formula (DI-33)³⁰-O-" binding site on phenyl ring is preferably with respect to the binding site of steroid core, position or para-position between respectively。In formula (DI-32) and formula (DI-33), the bond-NH on phenyl ring₂The binding site represented in this ring is any。

In formula (DI-34) and formula (DI-35), G³¹Stand alone as-O-,-NH-or carbon number is the alkylidene of 1～6, G³²It is the alkylidene of 1～3 for singly-bound or carbon number。R³¹It is the alkyl of 1～20 for hydrogen or carbon number, at least one-CH of this alkyl₂-can be replaced by-O-,-CH=CH-or-C ≡ C-。R³²It is the alkyl of 6～22 for carbon number, R³³It is the alkyl of 1～22 for hydrogen or carbon number。Ring B²⁵For Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1。And, the bond-NH on phenyl ring₂Represent that binding site on this ring be arbitrarily, but preferred independence and relative to G³¹Binding site be between position or para-position。

The concrete example of side chain type diamidogen illustrated below。As the diamidogen with side chain of described formula (DI-31)～formula (DI-35), the compound represented by following formula (DI-31-1)～formula (DI-35-3) can be enumerated。

The example of following presentation compound represented by formula (DI-31)。

In formula (DI-31-1)～formula (DI-31-11), R³⁴Alkyl or carbon number for carbon number is 1～30 are the alkoxyl of 1～30, it is preferable that carbon number be 5～25 alkyl or carbon number be the alkoxyl of 5～25。R³⁵Alkyl or carbon number for carbon number is 1～30 are the alkoxyl of 1～30, it is preferable that carbon number be 3～25 alkyl or carbon number be the alkoxyl of 3～25。

In formula (DI-31-12)～formula (DI-31-17), R³⁶It is the alkyl of 4～30 for carbon number, it is preferable that carbon number is the alkyl of 6～25。R³⁷It is the alkyl of 6～30 for carbon number, it is preferable that carbon number is the alkyl of 8～25。

In formula (DI-31-18)～formula (DI-31-43), R³⁸Alkyl or carbon number for carbon number is 1～20 are the alkoxyl of 1～20, it is preferable that carbon number be 3～20 alkyl or carbon number be the alkoxyl of 3～20。R³⁹For hydrogen ,-F, carbon number be 1～30 alkyl, carbon number be 1～30 alkoxyl ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, it is preferable that carbon number be 3～25 alkyl or carbon number be the alkoxyl of 3～25。And, G³³It is the alkylidene of 1～20 for carbon number。

The example of following presentation compound represented by formula (DI-32)。

The example of following presentation compound represented by formula (DI-33)。

The example of following presentation compound represented by formula (DI-34)。

In formula (DI-34-1)～formula (DI-34-14), R⁴⁰It is the alkyl of 1～20 for hydrogen or carbon number, it is preferable that hydrogen or carbon number are the alkyl of 1～10, and, R⁴¹It is the alkyl of 1～12 for hydrogen or carbon number。

The example of following presentation compound represented by formula (DI-35)。

In formula (DI-35-1)～formula (DI-35-3), R³⁷It is the alkyl of 6～30 for carbon number, R⁴¹It is the alkyl of 1～12 for hydrogen or carbon number。

As the diamidogen in the present invention, it is possible to use the diamidogen beyond diamidogen represented by formula (DI-1-1)～formula (DI-16-1), formula (DIH-1-1)～formula (DIH-3-6) and formula (DI-31-1)～formula (DI-35-3)。As this kind of diamidogen, for instance the compound represented by following formula (DI-36-1)～formula (DI-36-13) can be enumerated。

In formula (DI-36-1)～formula (DI-36-8), R⁴²Separately represent that carbon number is the alkyl of 3～30。

In formula (DI-36-9)～formula (DI-36-11), e is the integer of 2～10, in formula (DI-36-12), and R⁴³It is each independently hydrogen ,-NHBoc or-N (Boc)₂, R⁴³At least one be-NHBoc or-N (Boc)₂, in formula (DI-36-13), R⁴⁴For-NHBoc or-N (Boc)₂, and, m is the integer of 1～12。Herein, Boc is tert-butoxycarbonyl。

The appropriate materials improving each characteristic in described diamidogen and two hydrazides is described。

In the diamidogen and two hydrazides of the polymer for using the monomer with photoisomerization structure, when paying attention to the orientation promoting liquid crystal further, in described diamidogen and two hydrazides, it is preferred to use by the diamidogen represented by formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3) and formula (DI-11-2)。In formula (DI-5-1), it is preferable that m=2,4 or 6, more preferably m=4。In formula (DI-5-12), it is preferable that m=2～6, more preferably m=5。In formula (DI-5-13), it is preferable that m=1 or 2, more preferably m=1。In formula (DI-5-30), it is preferable that k=2。In formula (DI-7-3), it is preferable that m=2,3 or 4, n=1 or 2, more preferably m=3, n=1。

When paying attention to promoting transmitance, in described diamidogen and two hydrazides, diamidogen by formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-5-5), formula (DI-5-17) and formula (DI-7-3) represented by is preferably used, more preferably the diamidogen represented by formula (DI-2-1)。In formula (DI-5-1), it is preferable that m=2,4 or 6, more preferably m=4。In formula (DI-7-3), it is preferable that m=2 or 3, n=1 or 2, more preferably m=3, n=1。

When paying attention to the VHR promoting liquid crystal display cells, in described diamidogen and two hydrazides, diamidogen by formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30) and formula (DI-13-1) represented by is preferably used, more preferably the diamidogen represented by formula (DI-2-1), formula (DI-5-1) and formula (DI-13-1)。In formula (DI-5-1), it is preferable that m=1。In formula (DI-5-30), it is preferable that k=2。

As preventing one of method burning trace, effectively the mitigation speed of the residual charge (residual DC) in alignment films is made to improve by making the volumetric resistivity value of liquid crystal orientation film reduce。When paying attention to this purpose, in described diamidogen and two hydrazides, diamidogen by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-7-12) and formula (DI-16-1) represented by is preferably used, more preferably the diamidogen represented by formula (DI-4-1), formula (DI-5-1) and formula (DI-5-13)。In formula (DI-5-1), it is preferable that m=2,4 or 6, more preferably m=4。In formula (DI-5-12), it is preferable that m=2～6, more preferably m=5。In formula (DI-5-13), it is preferable that m=1 or 2, more preferably m=1。In formula (DI-7-12), it is preferable that m=3 or 4, more preferably m=4。

In the diamidogen and two hydrazides of the polymer for not using the monomer with photoisomerization structure, paying attention to promoting further layer separation property, when the orientation of i.e. liquid crystal, in described diamidogen and two hydrazides, it is preferred to use diamidogen represented by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-5-1), formula (DI-5-9), formula (DI-5-28) and formula (DIH-2-1) and two hydrazides。In formula (DI-5-1), it is preferable that m=1,2 or 4, more preferably m=1 or 2。

When paying attention to promoting transmitance, in described diamidogen and two hydrazides, diamidogen by formula (DI-1-2), formula (DI-2-1), formula (DI-5-1) and formula (DI-7-3) represented by is preferably used, more preferably the diamidogen represented by formula (DI-2-1)。In formula (DI-5-1), it is preferable that m=1,2 or 4, more preferably m=1 or 2。In formula (DI-7-3), it is preferable that m=2 or 3, n=1 or 2, more preferably m=3, n=1。

When paying attention to the VHR promoting liquid crystal display cells, in described diamidogen and two hydrazides, diamidogen by formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30) and formula (DI-13-1) represented by is preferably used, particularly preferably the diamidogen represented by formula (DI-2-1), formula (DI-5-1) and formula (DI-13-1)。Wherein in formula (DI-5-1), particularly preferably m=1 or 2, in formula (DI-5-30), particularly preferably k=2。

As preventing one of method burning trace, effectively the mitigation speed of the residual charge (residual DC) in alignment films is made to improve by making the volumetric resistivity value of liquid crystal orientation film reduce。When paying attention to this purpose, in described diamidogen and two hydrazides, diamidogen by formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), formula (DI-7-12) and formula (DI-16-1) represented by is preferably used, particularly preferably the diamidogen represented by formula (DI-4-1), formula (DI-5-1) and formula (DI-5-12)。Wherein in formula (DI-5-1), it is preferable that m=1 or 2, in formula (DI-5-12), it is preferable that m=2～6, particularly preferably m=5, in formula (DI-5-13), it is preferable that m=1 or 2, particularly preferably m=1, in formula (DI-5-30), particularly preferably k=2。In formula (DI-7-12), it is preferable that m=3 or 4, more preferably m=4。

In each diamidogen, it is also possible in the scope that ratio is below 40mol% of the monoamine relative to diamidogen, a part for diamidogen is replaced to monoamine。This kind of replacement can cause the termination of polyreaction when generating polyamic acid, can suppress further carrying out of polyreaction。Therefore, replaced by this kind, can easily control the molecular weight of the polymer (polyamic acid, poly amic acid ester or polyimides) obtained, for instance can the effect of the lossless present invention and improve the coating characteristics of aligning agent for liquid crystal。As long as the effect of the lossless present invention, then the diamidogen being replaced to monoamine can be a kind of, it is also possible to is two or more。As described monoamine, for instance can enumerate: aniline, 4-hydroxyanilines, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, 1-Aminooctane, positive nonyl amine, n-Decylamine, positive undecylamine, n-dodecylamine, positive tridecyl amine, positive tetradecy lamine, positive pentadecyl amine, hexadecylamine, positive heptadecyl-amine, octadecyl amine and positive 20 amine。

The polyamic acid of the present invention, poly amic acid ester and polyimides can in monomer whoses and then containing monoisocyanate compound。By containing monoisocyanate compound in monomer, the end of the polyamic acid or derivatives thereof obtained is modified, and molecular weight is adjusted。By using the polyamic acid or derivatives thereof of this end modified type, for instance can the effect of the lossless present invention and improve the coating characteristics of aligning agent for liquid crystal。For described viewpoint, relative to the total amount of the diamidogen in monomer and tetracarboxylic dianhydride, the preferred 1mol%～10mol% of content of the monoisocyanate compound in monomer。As described monoisocyanate compound, for instance can enumerate: carbanil and naphthyl isocyanate。

The polyamic acid of the present invention, poly amic acid ester and polyimides can obtain by making the mixture of described anhydride react in a solvent with diamidogen。In this synthetic reaction, except the selection of raw material, it is not necessary to special condition, can directly apply the condition in the synthesis of common polyamic acid。The solvent used is by aftermentioned。

The light orientation aligning agent for liquid crystal of the present invention and then can contain other compositions beyond the polyamic acid of the present invention, poly amic acid ester and polyimides。Other compositions can be a kind of, it is also possible to is two or more。As other compositions, for instance other polymer or compounds etc. described later can be enumerated。

As other polymer, can enumerate: make not have the starting monomer reaction of the diamidogen of photoisomerization structure and not contained (1) and obtain polyamic acid, poly amic acid ester or polyimides (hereinafter referred to as " other polyamic acid or derivatives thereofs "), polyester, polyamide, polysiloxanes, cellulose derivative, polyacetals, polystyrene derivative, poly-(styrene-phenylmaleimide) derivant, poly-(methyl) acrylate etc.。Can be a kind of, it is also possible to be two or more。In these polymer, it is preferable that other polyamic acid or derivatives thereof and polysiloxanes, more preferably other polyamic acid or derivatives thereofs。

As being used for synthesizing the tetracarboxylic dianhydride of other polyamic acid or derivatives thereofs, unrestrictedly can select from the tetracarboxylic dianhydride known as the required composition of the aligning agent for liquid crystal for synthesizing the present invention and the tetracarboxylic dianhydride of polyamic acid or derivatives thereof, person identical with the tetracarboxylic dianhydride of described illustration can be enumerated。

As preferred tetracarboxylic dianhydride, can enumerate described for not using the tetracarboxylic dianhydride of the polymer of the monomer with photoisomerization structure。

As being used for synthesizing the tetracarboxylic dianhydride of other polyamic acid or derivatives thereofs, it is preferable that contain aromatic tetracarboxylic acid's dianhydride of more than 10mol% relative to all tetracarboxylic dianhydrides, more preferably contain aromatic tetracarboxylic acid's dianhydride of more than 30mol%。

As being used for synthesizing diamidogen and two hydrazides of other polyamic acid or derivatives thereofs, can enumerate with above as the identical person of the diamidogen that can be used for synthesizing illustrated in the required composition of aligning agent for liquid crystal of the present invention and other diamidogen of polyamic acid or derivatives thereof and two hydrazides and two hydrazides。

As preferred diamidogen and two hydrazides, can enumerate described for not using diamidogen and two hydrazides of the polymer of the monomer with photoisomerization structure。

As being used for synthesizing the diamidogen of other polyamic acid or derivatives thereofs, it is preferable that contain the aromatic diamine of more than 30mol% relative to all diamidogen, more preferably contain the aromatic diamine of more than 50mol%。

Other polyamic acid or derivatives thereofs can synthesize according to the method described in the synthetic method of the required composition of the following aligning agent for liquid crystal as the present invention and polyamic acid or derivatives thereof respectively。

The light orientation aligning agent for liquid crystal of the present invention is as it has been described above, comprise: make at least one in the group that the free tetracarboxylic dianhydride of choosing and derivant thereof and diamidogen form have a photoisomerization structure and at least one starting monomer reaction that diamidogen comprises compound represented by following formula (1) and at least one of polymer that obtains；Or comprise: at least one of the polymer that at least one starting monomer with photoisomerization structure in the group making the free tetracarboxylic dianhydride of choosing and derivant thereof and diamidogen form reacts and obtains simultaneously；At least one of the polymer reacted with at least one starting monomer that any one does not all have a photoisomerization structure and diamidogen comprises the compound represented by following formula (1) making tetracarboxylic dianhydride and derivant and diamidogen and obtain。

The light orientation aligning agent for liquid crystal of the present invention can contain at least two polymer。If the polymer in two kinds of polymer with photoisomerization structure is set to [A], the polymer without photoisomerization structure is set to [B], then think by the weight average molecular weight of [A] being controlled for the weight average molecular weight less than [B], the aligning agent for liquid crystal of the mixture containing two polymer is being coated substrate and is carrying out in pre-dried process, [A] segregation with photoisomerization structure can be made on the upper strata of the polymeric film formed, make [B] segregation without photoisomerization structure in lower floor。Therefore, the existence of the polymer [A] with photoisomerization structure of alignment layer surface becomes dominant trait status, even if the content with the total amount of the polymer that forms alignment films for benchmark with the polymer [A] of photoisomerization structure is few, the alignment films that the light orientation aligning agent for liquid crystal of the present invention is formed is utilized to also show that high liquid crystal aligning。

As indicated above, it is known that following phenomenon: using the aligning agent for liquid crystal comprising two kinds of polymer to be formed in the process of thin film, polymer little for surface energy is separated into upper strata, polymer big for surface energy is separated into lower floor。Whether described alignment films carries out the confirmation of layer separation such as can confirm in the following manner: measure the surface energy of the film formed, whether the value of the surface energy containing only the film that the aligning agent for liquid crystal of polymer [A] is formed with utilization is identical, or is the value close with it。

As mentioned above, in order to demonstrate good light orientation, when the polymer comprised total amount is set to 100, the content of [A] in the light orientation aligning agent for liquid crystal of the present invention needs for more than 20wt% (percentage by weight), preferred more than 30wt%, more preferably more than 50wt%。It addition, in order to remain well by the transmitance of liquid crystal orientation film, the content of [A] needs for below 90wt%, it is preferable that below 70wt%, more preferably below 50wt%。Wherein, the preferred content of [A] described herein is a criterion, changes sometimes according to the combination of the tetracarboxylic dianhydride used in raw material or diamidogen。Particularly when using the starting compound with azobenzene structure, in order to the property of will transmit through remains well, the content of [A] is set as about 10wt%～20wt% fewer than described ratio。

About the weight average molecular weight of polymer, by [A] is adjusted to 8,000～40,000, [B] is adjusted to 50,000～200,000, it is adjusted to 10,000～30 preferably by by the molecular weight (Mw) of [A], 000, the molecular weight (Mw) of [B] is adjusted to 80,000～160,000, described layer can be caused to separate。The weight average molecular weight of polymer such as can adjust according to the time making tetracarboxylic dianhydride and diamine reactant。The reactant liquor in a small amount of polyreaction can be taked, by gel permeation chromatography (GelPermeationChromatography, GPC) mensuration of method obtains the weight average molecular weight of the polymer comprised in reactant liquor, determines the terminal of reaction according to described measured value。And, what be widely known by the people is, when reaction starts, considerable amount of tetracarboxylic dianhydride and diamidogen are replaced to monocarboxylic acid or monoamine, thus causes the termination of polyreaction, thus the method controlling weight average molecular weight。

As [A] composition ratio relative to described [A] composition and the total amount of described [B] composition, it is preferable that 10wt%～100wt%, more preferably 20wt%～100wt%。

And then Japanese Patent Laid-Open 2009-036966 can be contained, Japanese Patent Laid-Open 2010-185001, Japanese Patent Laid-Open 2011-102963, Japanese Patent Laid-Open 2011-253175, Japanese Patent Laid-Open 2012-159825, International Publication 2008/044644, International Publication 2009/148099, International Publication 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, polysiloxanes disclosed in International Publication 2012/165354 grade is as described polysiloxanes。

< alkenyl substituted Na Dike imide compound >

Such as, for the purpose of the electrical characteristics long-term stability making liquid crystal display cells, the aligning agent for liquid crystal of the present invention can contain alkenyl substituted Na Dike imide compound further。Alkenyl substituted Na Dike imide compound can be used, or two or more may be used。For described purpose, relative to polyamic acid or derivatives thereof, the preferred 1wt%～100wt% of content, the more preferably 1wt%～70wt% of alkenyl substituted Na Dike imide compound, and then more preferably 1wt%～50wt%。

Hereinafter Na Dike imide compound is specifically described。

Alkenyl substituted Na Dike imide compound preferably may be dissolved in the compound in the solvent dissolving the polyamic acid or derivatives thereof used in the present invention。The example of this kind of alkenyl substituted Na Dike imide compound can enumerate the compound represented by following formula (NA)。

In formula (NA), L¹And L²Stand alone as hydrogen, aryl or benzyl that cycloalkyl that thiazolinyl that alkyl that carbon number is 1～12, carbon number are 3～6, carbon number are 5～8, carbon number are 6～12, n is 1 or 2。

In formula (NA), as n=1, W is carbon number be 1～12 alkyl, carbon number be 2～6 thiazolinyl, carbon number be 5～8 cycloalkyl, carbon number be 6～12 aryl, benzyl, by-Z¹-(O)_r-(Z²O)_k-Z³-H (herein, Z¹、Z²And Z³Standing alone as the alkylidene that carbon number is 2～6, r is 0 or 1, and, k is the integer of 1～30) represented by base, by-(Z⁴)_r-B-Z⁵-H (herein, Z⁴And Z⁵Standing alone as alkylidene that carbon number is 1～4 or carbon number is the cycloalkylidene of 5～8, B is phenylene, and, r is 0 or 1) represented by base, by-B-T-B-H (herein, B is phenylene, and, T is-CH₂-、-C(CH₃)₂-,-O-,-CO-,-S-or-SO₂-) represented by base or hydrogen～tri-hydrogen of these bases through the-OH base replaced。

Now, it is preferred that W is carbon number be 1～8 alkyl, carbon number be 3～4 thiazolinyl, cyclohexyl, phenyl, benzyl, carbon number be 4～10 a hydrogen of poly-(inferior ethoxyl) ethyl, Phenoxyphenyl, phenyl methyl phenyl, phenyl isopropylidene phenyl and these bases or two hydrogen through the-OH base replaced。

In formula (NA), as n=2, W is carbon number be 2～20 alkylidene, carbon number be 5～8 cycloalkylidene, carbon number be the arlydene of 6～12, by-Z¹-O-(Z²O)_k-Z³-(herein, Z¹～Z³, and k's is as defined above) represented by base, by-Z⁴-B-Z⁵-(herein, Z⁴、Z⁵And B's is as defined above) represented by base, by-B-(O-B)_r-T-(B-O)_r-B-(herein, B is phenylene, T is carbon number be 1～3 alkylidene ,-O-or-SO₂-, r's is as defined above) represented by base or hydrogen～tri-hydrogen of these bases through the-OH base replaced。

Now, it is preferred that W is carbon number be 2～12 alkylidene, cyclohexylidene, phenylene, benzylidene, xyxylene, by-C₃H₆-O-(Z²-O)_n-O-C₃H₆-(herein, Z²Being the alkylidene of 2～6 for carbon number, n is 1 or 2) represented by base, by-B-T-B-(herein, B is phenylene, and, T is-CH₂-,-O-or-SO₂-) represented by base, by-B-O-B-C₃H₆Base represented by-B-O-B-(herein, B is phenylene) and a hydrogen of these bases or two hydrogen are through-OH the base replaced。

This kind of alkenyl substituted Na Dike imide compound can use such as described in No. 2729565 publications of Japan Patent as, the compound obtained by keeping carrying out synthesizing for 0.5 hour～20 hours at the temperature of 80 DEG C～220 DEG C by alkenyl substituted carbic anhydride derivant and diamidogen or commercially available compound。As the concrete example of alkenyl substituted Na Dike imide compound, compound shown below can be enumerated。

N-methyl-allyl dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-allyl methyl bicycle [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-(2-ethylhexyl)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide,

N-(2-ethylhexyl)-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pi-allyl-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pi-allyl-allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Allyl-methyl pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-isopropenyl-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-isopropenyl-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-isopropenyl-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-cyclohexyl-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-cyclohexyl-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Cyclohexyl-methyl pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Phenyl-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,

N-Phenyl-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-methyl pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-ethoxy)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-ethoxy)-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-ethoxy)-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,

N-(2, 2-dimethyl-3-hydroxypropyl)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 2-dimethyl-3-hydroxypropyl)-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 3-dihydroxypropyl)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 3-dihydroxypropyl)-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxyl-1-acrylic)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxy-cyclohexyl)-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,

N-(4-hydroxyphenyl)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxyphenyl)-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxyphenyl)-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxyphenyl)-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxyphenyl)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxyphenyl)-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(to hydroxybenzyl)-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,

N-{2-(2-hydroxyl-oxethyl) ethyl }-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) ethyoxyl } ethyl]-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) ethyoxyl } ethyl]-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) ethyoxyl } ethyl]-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxyphenyl isopropylidene) phenyl }-pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxyphenyl isopropylidene) phenyl }-pi-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxyphenyl isopropylidene) phenyl }-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, and their oligomer,

N, N'-ethylidene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-trimethylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),

1, double, two { 3'-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxyl group } ethane, 1, double, two { 3'-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxyl group } ethane, 1, double, two { 3'-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxyl group } ethane, double, two [2'-{3'-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) propoxyl group } ethyl] ether, double, two [2'-{3'-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) propoxyl group } ethyl] ether, 1, double, two { 3'-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide) propoxyl group } butane, 1, double, two { 3'-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide) propoxyl group } butane,

N, N'-is to phenylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-{ (1-methyl)-2, 4-phenylene }-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde's base-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde's base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xyxylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), N, xyxylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide),

2, double, two [4-{4-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, double, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, double, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, double, two { 4-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane,

Double, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, double, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, double, two { 4-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone,

Double, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, 1, double, two (pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 6-, 3-dicarboximide)-3-hydroxy-hexane, 1, double, two (methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 12-, 3-dicarboximide)-3, 6-dihydroxy-dodecane, 1, double, two (pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 3-, 3-dicarboximide)-5-hydroxy-cyclohexan alkane, 1, double, two { 3'-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 5-, 3-dicarboximide) propoxyl group }-3-hydroxyl-pentane, 1, double, two (pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide)-2-hydroxyl-benzene,

1, double, two (allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide)-2, 5-dihydroxy-benzene, N, N'-is to (2-hydroxyl) xyxylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to (2-hydroxyl) xyxylene-bis-(allyl methyl ring [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, (2-hydroxyl) xyxylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), N, (2-hydroxyl) xyxylene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), N, N'-is to (2, 3-dihydroxy) xyxylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),

2, double, two [4-{4-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide)-2-Hydroxy-phenoxy } phenyl] propane, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-2-hydroxy-pheny } methane, double, two { 3-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-4-hydroxy-pheny } ether, double, two { 3-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-5-hydroxy-pheny } sulfone, 1, 1, 1-tri-{ 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) } phenoxymethyl propane, N, N', N "-three (ethylidene methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) fulminuric acid ester, and their oligomer etc.。

And then, the alkenyl substituted Na Dike imide compound used in the present invention can for the compound represented by following formula containing asymmetrical alkylidene phenylene。

Preferred compound in following presentation alkenyl substituted Na Dike imide compound。

N, N'-ethylidene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-trimethylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),

N, N'-is to phenylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-{ (1-methyl)-2, 4-phenylene }-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde's base-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde's base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xyxylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), N, xyxylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), 2, double, two [4-{4-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, double, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, double, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, double, two { 4-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane。

Double, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, double, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, double, two { 4-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, double, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone。

The preferred alkenyl substituted Na Dike imide compound of following presentation。

N, N'-ethylidene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-trimethylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)。

N, N'-is to phenylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-is to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-{ (1-methyl)-2, 4-phenylene }-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde's base-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N'-terephthaldehyde's base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, xyxylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide), N, xyxylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide)。

2, double, two [4-{4-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, double, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, double, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, double, two { 4-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, double, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane。

And, as alkenyl substituted Na Dike imide compound particularly preferably, can enumerate: double; two { 4-(pi-allyl dicyclo [2.2.1]-5-in the heptan alkene-2 represented by following formula (NA-1), 3-dicarboximide) phenyl methane, N represented by formula (NA-2), xyxylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2 between N'-, 3-dicarboximide) and N represented by formula (NA-3), N'-hexa-methylene-bis-(pi-allyl dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide)。

< has the compound > of free-radical polymerised unsaturated double-bond

Such as, for the purpose of the electrical characteristics long-term stability making liquid crystal display cells, the aligning agent for liquid crystal of the present invention can contain the compound with free-radical polymerised unsaturated double-bond further。The compound with free-radical polymerised unsaturated double-bond can be a kind of compound, it is also possible to be two or more compounds。Furthermore, without alkenyl substituted Na Dike imide compound in the compound with free-radical polymerised unsaturated double-bond。For described purpose, relative to polyamic acid or derivatives thereof, there is the preferred 1wt%～100wt% of content, the more preferably 1wt%～70wt% of the compound of free-radical polymerised unsaturated double-bond, and then more preferably 1wt%～50wt%。

Furthermore, ratio with respect to the compound with free-radical polymerised unsaturated double-bond of alkenyl substituted Na Dike imide compound, in order to reduce liquid crystal display cells ion concentration, suppress ion concentration through time increase so that suppress image retention generation, there is the compound/alkenyl substituted Na Dike imide compound of free-radical polymerised unsaturated double-bond with mass ratio range preferably 0.1～10, more preferably 0.5～5。

Hereinafter the compound with free-radical polymerised unsaturated double-bond is specifically described。

As the compound with free-radical polymerised unsaturated double-bond, can enumerate: (methyl) acrylic acid derivative and double; two maleimides such as (methyl) acrylate, (methyl) acrylamide。The compound with free-radical polymerised unsaturated double-bond more preferably has (methyl) acrylic acid derivative of plural free-radical polymerised unsaturated double-bond。

Concrete example as (methyl) acrylate, for instance can enumerate: (methyl) cyclohexyl acrylate, (methyl) acrylic acid-2-methyl cyclohexyl, (methyl) acrylic acid bicyclo-pentyl ester, (methyl) acrylic acid two cyclopentyloxy ethyl ester, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate and (methyl) 2-hydroxypropyl acrylate。

Concrete example as two senses (methyl) acrylate, include, for example: ethylenebis acrylate, sieve Ah Knicks M-210 (AronixM-210) as the goods of East Asia synthetic chemical industry (share), sieve Ah Knicks M-240 and sieve Ah Knicks M-6200, card Ya De HDDA (KAYARADHDDA) as the goods of Japan's chemical medicine (share), card Ya De HX-220, card Ya De R-604 and card Ya De R-684, V260 as the goods of Osaka Organic Chemical Industry (share), V312 and V335HP, and the light acrylate BA-4EA (LightAcrylateBA-4EA) of the goods as common prosperity society oil chemical industry (share), light acrylate BP-4PA and light acrylate BP-2PA。

Concrete example as multifunctional (methyl) acrylate more than trifunctional, include, for example: 4, 4'-di-2-ethylhexylphosphine oxide (N, N-dihydroxy ethylidene acrylate aniline), sieve Ah Knicks M-400 as the goods of East Asia synthetic chemical industry (share), sieve Ah Knicks M-405, sieve Ah Knicks M-450, sieve Ah Knicks M-7100, sieve Ah Knicks M-8030, sieve Ah Knicks M-8060, card Ya De TMPTA as the goods of Japan's chemical medicine (share), card Ya De DPCA-20, card Ya De DPCA-30, card Ya De DPCA-60, card Ya De DPCA-120, and the VGPT of the goods as Osaka Organic Chemical Industry (share)。

Concrete example as (methyl) acrylamide derivative, for instance can enumerate: NIPA, N-isopropyl acrylamide, N-n-pro-pyl acrylamide, N-n-pro-pyl Methacrylamide, N-cyclopropyl acrylamide, N-Cvclopropvlmethvl acrylamide, N-ethoxyethyl group acrylamide, N-ethoxyethyl group Methacrylamide, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl Methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloylpiperidine, N-acryloyl group pyrrolidine, N, N'-methylene-bisacrylamide, N,N' ethylene bis acrylamide, N, N'-dihydroxy ethylenebisacrylamide, N-(4-hydroxyphenyl) Methacrylamide, N-phenyl methacrylamide, N-butyl methyl acrylamide, N-(isobutoxymethyl) Methacrylamide, N-[2-(N, N-dimethylamino) ethyl] Methacrylamide, N, N-dimethylmethacryl amide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-(methoxy) Methacrylamide, N-(methylol)-2-Methacrylamide, N-benzyl-2-Methacrylamide, and N, N'-methylenebismethacrylamide。

Among described (methyl) acrylic acid derivative, particularly preferably N, N'-methylene-bisacrylamide, N, N'-dihydroxy ethylidene-bisacrylamide, ethylenebis acrylate and 4,4'-di-2-ethylhexylphosphine oxide (N, N-dihydroxy ethylidene acrylate aniline)。

As double; two maleimides, for instance can enumerate: BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000 that KI chemical conversion (share) BMI-70 and BMI-80 that manufacture and big and chemical conversion industry (share) manufacture。

< piperazine compound >

Such as, for the purpose of the electrical characteristics long-term stability making liquid crystal display cells, the aligning agent for liquid crystal of the present invention can contain piperazine compound further。Piperazine compound can be a kind of compound, it is also possible to be two or more compounds。For described purpose, relative to polyamic acid or derivatives thereof, the preferred 0.1wt%～50wt% of content, the more preferably 1wt%～40wt% of piperazine compound, and then more preferably 1wt%～20wt%。

Hereinafter piperazine compound is specifically described。

Piperazine compound is preferably soluble in the solvent making polyamic acid or derivatives thereof dissolve and has the piperazine compound of ring-opening polymerisation。

It addition, the quantity of the piperazine structure in piperazine compound is not particularly limited。

The structure of piperazine is known various structure。In the present invention, the structure of piperazine is not particularly limited, and in the piperazine structure in piperazine compound, can enumerate the structure that benzimidazole dihydrochloride or naphtho-piperazine etc. have the piperazine of aromatic series base containing fused-ring aromatic base。

As piperazine compound, for instance the compound shown in following formula (OX-1)～formula (OX-6) can be enumerated。Furthermore, in following formula, show that bond is constituting ring and can on any one carbon of bond substituent group towards the key table represented by Ring current distribution。

In formula (OX-1)～formula (OX-3), L³And L⁴It is the organic group of 1～30 for carbon number, in formula (OX-1)～formula (OX-6), L⁵～L⁸It is the alkyl of 1～6 for hydrogen or carbon number, in formula (OX-3), formula (OX-4) and formula (OX-6), Q¹For singly-bound ,-O-,-S-,-S-S-,-SO₂-、-CO-、-CONH-、-NHCO-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_v-、-O-(CH₂)_v-O-、-S-(CH₂)_v-S-, herein, v is the integer of 1～6, formula (OX-5) and in formula (OX-6), Q²Stand alone as singly-bound ,-O-,-S-,-CO-,-C (CH₃)₂-、-C(CF₃)₂-or carbon number be the alkylidene of 1～3, Q²In phenyl ring, the hydrogen of institute's bond is independent and can by-F ,-CH on naphthalene nucleus₃、-OH、-COOH、-SO₃H、-PO₃H₂Replace。

It addition, the piperazine compound oligomer that includes there is on side chain piperazine structure or polymer, main chain have oligomer or the polymer of piperazine structure。

As the piperazine compound represented by formula (OX-1), for instance following piperazine compound can be enumerated。

In formula (OX-1-2), L³Preferred carbon number is the alkyl of 1～30, and more preferably carbon number is the alkyl of 1～20。

As the piperazine compound represented by formula (OX-2), for instance following piperazine compound can be enumerated。

In formula, L³Preferred carbon number is the alkyl of 1～30, and more preferably carbon number is the alkyl of 1～20。

As the piperazine compound represented by formula (OX-3), the piperazine compound represented by following formula (OX-3-I) can be enumerated。

In formula (OX-3-I), L³And L⁴It is the organic group of 1～30 for carbon number, L⁵～L⁸It is the alkyl of 1～6 for hydrogen or carbon number, Q¹For singly-bound ,-CH₂-、-C(CH₃)₂-、-CO-、-O-、-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-。As the piperazine compound represented by formula (OX-3-I), for instance following piperazine compound can be enumerated。

In formula, L³And L⁴Preferred carbon number is the alkyl of 1～30, and more preferably carbon number is the alkyl of 1～20。

As the piperazine compound represented by formula (OX-4), for instance following piperazine compound can be enumerated。

As the piperazine compound represented by formula (OX-5), for instance following piperazine compound can be enumerated。

As the piperazine compound represented by formula (OX-6), for instance following piperazine compound can be enumerated。

Among these, more preferably can enumerate the piperazine compound represented by formula (OX-2-1), formula (OX-3-1), formula (OX-3-3), formula (OX-3-5), formula (OX-3-7), formula (OX-3-9), formula (OX-4-1)～formula (OX-4-6), formula (OX-5-3), formula (OX-5-4) and formula (OX-6-2)～formula (OX-6-4)。

Piperazine compound can be manufactured by the method identical with method described in International Publication 2004/009708, Japanese Patent Laid-Open 11-12258, Japanese Patent Laid-Open 2004-352670。

Piperazine compound represented by formula (OX-1) can obtain (with reference to International Publication 2004/009708) by making phenolic compounds react with primary amine and aldehyde。

Piperazine compound represented by formula (OX-2) can obtain in the following way: after adding the method for primary amine in formaldehyde lentamente and reacting, and adds the compound with naphthols system hydroxyl and reacts (with reference to International Publication 2004/009708)。

Piperazine compound represented by formula (OX-3) can obtain in the following way: under the existence of secondary fatty race amine, three grades of aliphatic amines or alkalescence nitrogen-containing heterocycle compound, makes phenolic compounds 1 mole, is at least the aldehyde of more than 2 moles relative to a phenolic hydroxyl group of this phenolic compounds and the primary amine of 1 mole reacts (reference International Publication 2004/009708 and Japanese Patent Laid-Open 11-12258) in organic solvent。

Piperazine compound represented by formula (OX-4)～formula (OX-6) can obtain in the following way: at the temperature more than 90 DEG C, 4,4'-diaminodiphenyl-methanes etc. are made to have multiple phenyl ring and carry out dehydration condensation (with reference to Japanese Patent Laid-Open 2004-352670) in n-butyl alcohol with the aldehyde such as the diamidogen of organic group of these phenyl ring bonds, formalin and phenol。

< isoxazoline compound >

Such as, for the purpose of the electrical characteristics long-term stability making liquid crystal display cells, the aligning agent for liquid crystal of the present invention can contain isoxazoline compound further。Isoxazoline compound is the compound with azoles quinoline structure。Isoxazoline compound can be a kind of compound, it is also possible to be two or more compounds。For described purpose, relative to polyamic acid or derivatives thereof, the preferred 0.1wt%～50wt% of content, the more preferably 1wt%～40wt% of isoxazoline compound, and then more preferably 1wt%～20wt%。Or, when the azoles quinoline structure in isoxazoline compound is converted into azoles quinoline, for described purpose, relative to polyamic acid or derivatives thereof, the preferred 0.1wt%～40wt% of content of isoxazoline compound。

Hereinafter isoxazoline compound is specifically described。

Isoxazoline compound can only have a kind of azoles quinoline structure in a kind of compound, it is possible to have two or more。As long as it addition, isoxazoline compound has an azoles quinoline structure in a kind of compound, but preferably there is two or more。It addition, isoxazoline compound can be the polymer on side chain with azoles quinoline structure, it is also possible to be copolymer。The polymer on side chain with azoles quinoline structure can be the homopolymer of the monomer on side chain with azoles quinoline structure, it is also possible to be the copolymer of the monomer on side chain with azoles quinoline structure and the monomer without azoles quinoline structure。The copolymer on side chain with azoles quinoline structure can be the copolymer of the two or more monomer on side chain with azoles quinoline structure, it is also possible to be the copolymer of the two or more monomer on side chain with azoles quinoline structure and the monomer without azoles quinoline structure。

The one or both of azoles quinoline the structure preferably oxygen in azoles quinoline structure and nitrogen and the carbonyl of polyamic acid can be present in the structure in isoxazoline compound in the way of reacting。

As isoxazoline compound, include, for example: 2, 2'-double, two (2-azoles quinoline), 1, 2, 4-tri--(2-azoles quinoline base-2)-benzene, 4-furan-2-methylene-2-phenyl-4H-azoles-5-ketone, 1, 4-double, two (4, 5-dihydro-2-azoles base) benzene, 1, 3-double, two (4, 5-dihydro-2-azoles base) benzene, 2, double, two (4-isopropenyl-2-azoles quinoline-2-base) butane of 3-, 2, double, two-4-benzyl-2-azoles the quinoline of 2'-, 2, double, two (isopropyl-2-azoles quinoline-2-base) pyridine of 6-, 2, 2'-isopropylidene double, two (the 4-tert-butyl group-2-azoles quinoline), 2, 2'-isopropylidene double, two (4-phenyl-2-azoles quinoline), 2, 2'-di-2-ethylhexylphosphine oxide (the 4-tert-butyl group-2-azoles quinoline), and 2, 2'-di-2-ethylhexylphosphine oxide (4-phenyl-2-azoles quinoline)。Except these isoxazoline compounds, it is also possible to enumerate the polymer with azoles base as Ai Bo Kroes (Epocros) (trade name, Japan's catalyst (share) manufactures) or oligomer。Among these isoxazoline compounds, more preferably can enumerate 1,3-double; two (4,5-dihydro-2-azoles base) benzene。

< epoxide >

Such as, for the purpose of the electrical characteristics long-term stability making liquid crystal display cells, the aligning agent for liquid crystal of the present invention can contain epoxide further。Epoxide can be a kind of compound, it is also possible to be two or more compounds。For described purpose, relative to polyamic acid or derivatives thereof, the preferred 0.1wt%～50wt% of content, the more preferably 1wt%～40wt% of epoxide, and then more preferably 1wt%～20wt%。

Hereinafter epoxide is specifically described。

As epoxide, the various compounds of the epoxide ring with one or more can be enumerated in molecule。As the compound in molecule with an epoxide ring, include, for example: phenyl glycidyl ether, butyl glycidyl ether, 3, 3, 3-trifluoromethyl expoxy propane, styrene oxide, hexafluoropropylene oxide, oxepane (cyclohexaneoxide), 3-glycidoxypropyltrimewasxysilane, 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane, N-glycidyl phthalimide, (nine fluoro-N-butyl) epoxide, perfluoro-ethyl glycidyl ether, chloropropylene oxide, epibromohydrin, N, N-diglycidylaniline, and 3-[2-(perfluoro hexyl) ethyoxyl]-1, 2-epoxy radicals propane。

As the compound in molecule with two epoxide rings, include, for example: Ethylene glycol diglycidyl ether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester and 3-(N, N-diglycidyl) TSL 8330。

As the compound in molecule with three epoxide rings, include, for example: 2-[4-(2,3-epoxy radicals propoxyl group) phenyl]-2-[4-[1, double; two [the 4-([2 of 1-, 3-epoxy radicals propoxyl group] phenyl)] ethyl] phenyl] propane (trade name " ferrum Ke Moya VG3101L (TechmoreVG3101L) ", (Mitsui Chemicals (share) manufacture))。

As the compound in molecule with four epoxide rings, for instance can enumerate: 1,3,5,6-four glycidyl group-2,4-hexanediol, N, N, N', N'-four glycidyl group-m-xylene diamine, 1, double; two (the N of 3-, N-diglycidyl amino methyl) hexamethylene, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl-methane and 3-(N-pi-allyl-N-glycidyl) TSL 8330。

Except described, it is also possible to enumerate the oligomer with epoxide ring or the polymer example as the compound in molecule with epoxide ring。As the monomer with epoxide ring, for instance can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyethylSiOi ester and (methyl) acrylic acid methylglycidyl esters。

As other monomers carrying out copolymerization with the monomer with epoxide ring, include, for example: (methyl) acrylic acid, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, styrene, methyl styrene, 1-chloro-4-methyl-benzene, (methyl) acrylic acid (3-ethyl-3-oxetanylmethoxy) methyl ester, N-cyclohexylmaleimide and N-phenylmaleimide。

As the preferred concrete example of the polymer of the monomer with epoxide ring, poly (glycidyl methacrylate) etc. can be enumerated。Additionally, preferred concrete example as the copolymer of the monomer Yu other monomers with epoxide ring, can enumerate: N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate glycidyl ester copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl ester-glycidyl methacrylate copolymer, and styrene-t glycidyl ester copolymer。

Among these examples, particularly preferably N, N, N', N'-four glycidyl group-m-xylene diamine, 1, double; two (the N of 3-, N-diglycidyl amino methyl) hexamethylene, N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl-methane, trade name " ferrum Ke Moya VG3101L ", 3,4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane。

More systematically say, as epoxide, for instance can enumerate: glycidyl ether, ethylene oxidic ester, glycidyl amine, containing the acrylic resin of epoxy radicals, glycidyl amide, fulminuric acid (+)-2,3-Epoxy-1-propanol fat, chain fatty race type epoxide and annular aliphatic type epoxide。Furthermore, epoxide refers to the compound with epoxy radicals, and epoxy resin refers to the resin with epoxy radicals。

As epoxide, for instance can enumerate: glycidyl ether, (+)-2,3-Epoxy-1-propanol fat, glycidyl amine, containing the acrylic resin of epoxy radicals, glycidyl amide, fulminuric acid ethylene oxidic ester, chain fatty race type epoxide and annular aliphatic type epoxide。

As glycidyl ether, include, for example: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, biphenol type epoxy compound, A Hydrogenated Bisphenol A-A type epoxide, A Hydrogenated Bisphenol A-F type epoxide, A Hydrogenated Bisphenol A-S type epoxide, A Hydrogenated Bisphenol A type epoxide, brominated bisphenol-A type epoxide, brominated bisphenol-F type epoxide, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy compounds, bromination cresol novolak type epoxy compound, bisphenol A novolac type epoxide, epoxide containing naphthalene skeleton, aromatic series poly epihydric alcohol ether compound, dicyclopentadiene phenol epoxide, ester ring type 2-glycidyl ether compound, aliphatic polyglycidyl ether compound, polysulfide type 2-glycidyl ether compound, and biphenyl phenolic epoxide。

As ethylene oxidic ester, for instance can enumerate: 2-glycidyl ester compounds and glycidyl ester epoxy compound。

As glycidyl amine, for instance can enumerate: poly epihydric alcohol amines and glycidyl amine type epoxy resin。

As the acrylic compounds containing epoxy radicals, for instance can enumerate: have homopolymer and the copolymer of the monomer of Oxyranyle (oxiranyl)。

As glycidyl amide, for instance can enumerate: glycidyl acid amide type epoxide。

As chain fatty race type epoxide, for instance can enumerate: the compound containing epoxy radicals that the oxidation of the carbon-to-carbon double bond of olefin(e) compound is obtained。

As annular aliphatic type epoxide, for instance can enumerate: the compound containing epoxy radicals that the oxidation of the carbon-to-carbon double bond of cyclic olefins is obtained。

As bisphenol A type epoxy compound, include, for example: jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (is trade name, Mitsubishi Chemical's (share) manufactures), the appropriate YD-128 of Ai Putuo (EpotohtoYD-128) (Dongdu chemical conversion (share) manufactures), DER-331, DER-332, DER-324 (is Dow Chemical (TheDowChemicalCompany) to manufacture), Chinese mugwort clone 840 (Epiclon840), Chinese mugwort clone 850, Chinese mugwort clone 1050 (is trade name, Di Aisheng (DIC) (share) manufactures), Ai Bo Mick R-140 (EpomikR-140), Ai Bo Mick R-301, and Ai Bo Mick R-304 (is trade name, Mitsui Chemicals (company) manufactures)。

As bisphenol F type epoxy compound, include, for example: jER806, jER807, jER4004P (be trade name, Mitsubishi Chemical's (share) manufactures), the appropriate YDF-2001 of Ai Putuo appropriate YDF-170, Ai Putuo appropriate YDF-175S, Ai Putuo (be trade name, Dongdu chemical conversion (share) manufactures), DER-354 (trade name, Dow Chemical manufacture), Chinese mugwort clone 830 and Chinese mugwort clone 835 (be trade name, Di Aisheng (share) manufactures)。

As biphenol type epoxy compound, for instance can enumerate: the epoxide of 2,2-double; two (4-hydroxyphenyl)-1,1,1,3,3,3-HFC-236fa。

As A Hydrogenated Bisphenol A-A type epoxide, for instance can enumerate: business holds in the palm appropriate ST-3000 (SuntohtoST-3000) (trade name, Dongdu chemical conversion (share) manufacture), Li Kaleixin HBE-100 (RikaresinHBE-100) (trade name, new Japan Chemical (share) manufacture) and Dai Nakeer EX-252 (DenacolEX-252) (trade name, long rapids chemical conversion (NagasechemteX) (share) manufacture)。

As A Hydrogenated Bisphenol A type epoxide, for instance can enumerate: the epoxide of double; two (4-hydroxyphenyl)-1,1,1,3,3, the 3-HFC-236fa of hydrogenation 2,2-。

As brominated bisphenol-A type epoxide, include, for example: jER5050, jER5051 (be trade name, Mitsubishi Chemical's (share) manufactures), the appropriate YDB-400 of Ai Putuo appropriate YDB-360, Ai Putuo (be trade name, Dongdu chemical conversion (share) manufactures), DER-530, DER-538 (be trade name, Dow Chemical manufactures), Chinese mugwort clone 152 and Chinese mugwort clone 153 (be trade name, Di Aisheng (share) manufactures)。

As phenol novolak-type epoxy compound, include, for example: jER152, jER154 (be trade name, Mitsubishi Chemical's (share) manufactures), YDPN-638 (trade name, Dongdu chemical conversion company manufacture), DEN431, DEN438 (be trade name, Dow Chemical manufactures), Chinese mugwort clone N-770 (trade name, Di Aisheng (share) manufacture), EPPN-201 and EPPN-202 (be trade name, Japan's chemical medicine (share) manufactures)。

As cresol novolak type epoxy compound, include, for example: jER180S75 (trade name, Mitsubishi Chemical's (share) manufacture), YDCN-701, YDCN-702 (be trade name, Dongdu chemical conversion company manufactures), Chinese mugwort clone N-665, Chinese mugwort clone N-695 (be trade name, Di Aisheng (share) manufactures), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (be trade name, Japan's chemical medicine (share) manufactures)。

As bisphenol A novolac type epoxide, for instance can enumerate: jER157S70 (trade name, Mitsubishi Chemical's (share) manufacture) and Chinese mugwort clone N-880 (trade name, Di Aisheng (share) manufacture)。

As the epoxide containing naphthalene skeleton, include, for example: Chinese mugwort clone HP-4032, Chinese mugwort clone HP-4700, Chinese mugwort clone HP-4770 (be trade name, Di Aisheng (share) manufactures), and NC-7000 (trade name, chemical medicine company of Japan manufacture)。

As aromatic series poly epihydric alcohol ether compound, include, for example: hydroquinone diglycidyl ether (following formula EP-1), DGEC (following formula EP-2), resorcinolformaldehyde resin (following formula EP-3), 2-[4-(2, 3-epoxy radicals propoxyl group) phenyl]-2-[4-[1, double, two [the 4-([2 of 1-, 3-epoxy radicals propoxyl group] phenyl)] ethyl] phenyl] propane (following formula EP-4), three (4-glycidoxypropyl phenyl) methane (following formula EP-5), jER1031S, jER1032H60 (is trade name, Mitsubishi Chemical's (share) manufactures), Plutarch replaces Ke Si-742 (TACTIX-742) (trade name, Dow Chemical manufactures), Dai Nakeer EX-201 (trade name, long rapids chemical conversion (share) manufactures), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (is trade name, Japan's chemical medicine (share) manufactures), ferrum Ke Moya VG3101L (trade name, Mitsui Chemicals (share) manufactures), compound represented by following formula EP-6, and the compound represented by following formula EP-7。

As dicyclopentadiene phenol epoxide, for instance can enumerate: Plutarch is for Ke Si-556 (trade name, Dow Chemical manufacture) and Chinese mugwort clone HP-7200 (trade name, Di Aisheng (share) manufacture)。

As ester ring type 2-glycidyl ether compound, for instance can enumerate: cyclohexanedimethanodiglycidyl diglycidyl ether compound and Li Kaleixin DME-100 (trade name, new Japan Chemical (share) manufacture)。

As aliphatic polyglycidyl ether compound, include, for example: Ethylene glycol diglycidyl ether (following formula EP-8), diethylene glycol diglycidyl glycerin ether (following formula EP-9), polyethyleneglycol diglycidylether, propylene glycol diglycidylether (following formula EP-10), tripropyleneglycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether (following formula EP-12), 1, 4-butanediol diglycidyl ether (following formula EP-13), 1, 6-hexanediol diglycidyl ether (following formula EP-14), dibromoneopentyl glycol diglycidyl ether (following formula EP-15), Dai Nakeer EX-810, Dai Nakeer EX-851, Dai Nakeer EX-8301, Dai Nakeer EX-911, Dai Nakeer EX-920, Dai Nakeer EX-931, Dai Nakeer EX-211, Dai Nakeer EX-212, Dai Nakeer EX-313 (is trade name, long rapids chemical conversion (share) manufactures), DD-503 (trade name, Ai Dike (ADEKA) (share) manufactures), Li Kaleixin W-100 (trade name, new Japan Chemical (share) manufactures), 1, 3, 5, 6-four glycidyl group-2, 4-hexanediol (following formula EP-16), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, tetramethylolmethane polyglycidyl ether, Dai Nakeer EX-313, Dai Nakeer EX-611, Dai Nakeer EX-321, and Dai Nakeer EX-411 (is trade name, long rapids chemical conversion (share) manufactures)。

As polysulfide type 2-glycidyl ether compound, for instance can enumerate: FLDP-50 and FLDP-60 (be trade name, east beautiful skilful solid happy (TorayThiokol) (share) manufactures)。

As biphenyl phenolic epoxide, include, for example: YX-4000, YL-6121H (be trade name, Mitsubishi Chemical's (share) manufactures), NC-3000P and NC-3000S (be trade name, Japan's chemical medicine (share) manufactures)。

As 2-glycidyl ester compounds, for instance can enumerate: double; two (the 2-methyl oxirane ylmethyl) ester (following formula EP-19) of terephthalic acid diglycidyl ester (following formula EP-17), o-phthalic acid diglycidyl ester (following formula EP-18), phthalic acid, hexahydrophthalic acid 2-glycidyl ester (following formula EP-20), compound represented by following formula EP-21, the compound represented by following formula EP-22 and the compound represented by following formula EP-23。

As glycidyl ester epoxy compound, include, for example: jER871, jER872 (be trade name, Mitsubishi Chemical's (share) manufactures), Chinese mugwort clone 200, Chinese mugwort clone 400 (be trade name, Di Aisheng (share) manufactures), Dai Nakeer EX-711 and Dai Nakeer EX-721 (be trade name, long rapids chemical conversion (share) manufactures)。

As poly epihydric alcohol amines, for instance can enumerate: N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-ortho-aminotoluene (following formula EP-25), N, N-diglycidyl-meta-aminotoluene (following formula EP-26), N, N-diglycidyl-2,4,6-tribromaniline (following formula EP-27), 3-(N, N-diglycidyl) TSL 8330 (following formula EP-28), N, N, O-triglycidyl group-para-aminophenol (following formula EP-29), N, N, O-triglycidyl group-m-aminophenol (following formula EP-30), N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl-methane (following formula EP-31), N, N, N', N'-four glycidyl group-m-xylene diamine (ferrum Te Lade-X (TETRAD-X) (trade name, Rhizoma Sparganii gas chemistry (share) manufactures), following formula EP-32), double, two (N, the N-diglycidyl amino methyl) hexamethylene (ferrum Te Lade-C (trade name of 1,3-, Rhizoma Sparganii gas chemistry (share) manufactures), following formula EP-33), double, two (N, the N-diglycidyl amino methyl) hexamethylene (following formula EP-34) of 1,4-, double, two (N, the N-diglycidyl amino) hexamethylene (following formula EP-35) of 1,3-, double, two (N, the N-diglycidyl amino) hexamethylene (following formula EP-36) of 1,4-, double, two (N, the N-diglycidyl amino) benzene (following formula EP-37) of 1,3-, double, two (N, the N-diglycidyl amino) benzene (following formula EP-38) of 1,4-, double, two (N, N-diglycidyl amino methyl) dicyclo [2.2.1] heptane (following formula EP-39) of 2,6-, N, N, N', N'-four glycidyl group-4,4'-diamino-dicyclohexyl methane (following formula EP-40), 2,2'-dimethyl-(N, N, N', N'-four glycidyl group)-4,4'-benzidine (following formula EP-41), N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl ether (following formula EP-42), 1,3,5-tri-(4-(N, N-diglycidyl) amino-benzene oxygen) benzene (following formula EP-43), 2,4,4'-tri-(N, N-diglycidyl amino) diphenyl ether (following formula EP-44), three (4-(N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3', 4'-tetra-(N, N-diglycidyl amino) biphenyl (following formula EP-46), 3,4,3', 4'-tetra-(N, N-diglycidyl amino) diphenyl ether (following formula EP-47), compound represented by following formula EP-48, and the compound represented by following formula EP-49。

Homopolymer as the monomer with Oxyranyle, for instance poly (glycidyl methacrylate) can be enumerated。Copolymer as the monomer with Oxyranyle, include, for example: N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-methyl propenoic acid glycidyl resin copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate glycidyl ester copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl ester-methyl propenoic acid glycidyl resin copolymer, and styrene-t (+)-2,3-Epoxy-1-propanol resin copolymer。

As the monomer with Oxyranyle, for instance can enumerate: (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxycyclohexyethylSiOi ester and (methyl) acrylic acid methylglycidyl esters。

As have Oxyranyle monomer copolymer in other monomers having beyond the monomer of Oxyranyle, include, for example: (methyl) acrylic acid, (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, styrene, methyl styrene, 1-chloro-4-methyl-benzene, (methyl) acrylic acid (3-ethyl-3-oxetanylmethoxy) methyl ester, N-cyclohexylmaleimide, and N-phenylmaleimide。

As fulminuric acid ethylene oxidic ester, for instance can enumerate: 1,3,5-triglycidyl group-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-50), 1,3-diglycidyl-5-pi-allyl-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-51) and fulminuric acid glycidyl ester type epoxy resin。

As chain fatty race type epoxide, for instance can enumerate: epoxidized polybutadiene and Ai Bo Reed PB3600 (EpoleadPB3600) (trade name, Daicel (Daicel) (share) manufacture)。

As annular aliphatic type epoxide, include, for example: 3, 4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester (silicon Luo Ji Saden 2021 (Celloxide2021) (Daicel (share) manufacture), following formula EP-52), 2-methyl-3, 4-epoxycyclohexylmethyl-2'-methyl-3', 4'-expoxycyclohexyl carboxylate (following formula EP-53), 2, 3-epoxy radicals Pentamethylene .-2', 3'-epoxy radicals Pentamethylene. ether (following formula EP-54), 6-caprolactone upgrading 3, 4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane carboxylate, 1, 2:8, 9-bicyclic oxygen limonene (Celloxide3000 (trade name, Daicel (share) manufactures), following formula EP-55), compound represented by following formula EP-56, CY-175, CY-177, CY-179 (is trade name, Ciba-Geigy Chemical Company (TheCiba-GeigyChemicalCorp.) manufactures (can step (Huntsman Japan) (share) from Japan's Hensel to obtain)), EHPD-3150 (trade name, Daicel (share) manufactures), and annular aliphatic type epoxy resin。

The preferred poly epihydric alcohol amines of epoxide, bisphenol A novolac type epoxide, cresol novolak type epoxy compound, and more than one of annular aliphatic type epoxide, more preferably N, N, N', N'-four glycidyl group-m-xylene diamine, 1, double, two (the N of 3-, N-diglycidyl amino methyl) hexamethylene, N, N, N', N'-four glycidyl group-4, 4'-diaminodiphenyl-methane, trade name " ferrum Ke Moya VG3101L ", 3, 4-epoxycyclohexyethylSiOi enylmethyl-3', 4'-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl group-para-aminophenol, bisphenol A novolac type epoxide, and more than one of cresol novolak type epoxy compound。

It addition, the aligning agent for liquid crystal of the such as present invention can contain various additive further。As various additives, for instance the macromolecular compound beyond polyamic acid and derivant thereof and low molecular compound can be enumerated, can select according to each purpose to use。

Such as, as described macromolecular compound, the macromolecular compound dissolving in organic solvent can be enumerated。For the electrical characteristics of liquid crystal orientation film that control is formed or the viewpoint of orientation, it is preferable that this kind of macromolecular compound is added in the aligning agent for liquid crystal of the present invention。As this macromolecular compound, for instance can enumerate: polyamide, polyurethanes, polyureas, polyester, polyepoxide, PEPA, silicone upgrading polyurethanes and silicone upgrading polyester。

Additionally, as described low molecular compound, such as 1) can enumerate, when expectation promotes coating, the interfacial agent meeting this purpose, 2) antistatic additive can be enumerated when needs promote antistatic, 3) silane coupler or the coupling agent of titanium system can be enumerated when expectation promotes the adhesion with substrate, it addition, 4) imidization catalyst can be enumerated when carrying out imidizate at low temperatures。

As silane coupler, include, for example: vinyltrimethoxy silane, VTES, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-amino propyl methyl trimethoxy silane, p-aminophenyl trimethoxy silane, p-aminophenyl triethoxysilane, m-aminophenyl base trimethoxy silane, m-aminophenyl ethyl triethoxy silicane alkane, 3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl dimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyi trimethoxy silane, N-(1, 3-dimethylbutylene)-3-(triethoxysilicane alkyl)-1-propylamine, and N, double, two [3-(trimethoxy silane base) propyl group] ethylenediamine of N'-。Preferred silane coupler is APTES。

As imidization catalyst, for instance can enumerate: aliphatic amines such as trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamines；N, the aromatic amine such as accelerine, N, N-diethylaniline, methyl substituted aniline, hydroxyl-substituted amine；The ring type amines such as pyridine, methyl substituted pyridine, hydroxyl substituted pyridines, quinoline, methyl substituted quinoline, hydroxyl substd quinolines, isoquinolin, methyl substituted isoquinolin, hydroxyl substituted isoquinoline, imidazoles, methyl substituted imidazoles, hydroxyl substituted imidazole。Described imidization catalyst is preferably selected from N, accelerine, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine, adjacent pyridone, a pyridone, to one or more in pyridone and isoquinolin。

The addition of silane coupler is generally the 0wt%～20wt% of the gross weight of polyamic acid or derivatives thereof, it is preferable that 0.1wt%～10wt%。

Relative to the carbonyl of polyamic acid or derivatives thereof, the addition of imidization catalyst is generally 0.01 equivalent～5 equivalent, it is preferable that 0.05 equivalent～3 equivalent。

The addition of other additives is different according to its purposes, but is generally the 0wt%～100wt% of the gross weight of polyamic acid or derivatives thereof, it is preferable that 0.1wt%～50wt%。

The polyamic acid or derivatives thereof of the present invention can manufacture in the same manner as the known polyamic acid or derivatives thereof of the formation of the film for polyimides。The total addition level of tetracarboxylic dianhydride is preferably set to the total mole number with diamidogen and substantially waits mole (mol ratio is about 0.9～1.1)。

The molecular weight of the polyamic acid or derivatives thereof of the present invention is in the weight average molecular weight (Mw) of polystyrene conversion, it is preferable that 7,000～500,000, and more preferably 10,000～200,000。The molecular weight of described polyamic acid or derivatives thereof can be obtained by the mensuration utilizing gel permeation chromatography (GPC) method。

The polyamic acid or derivatives thereof of the present invention can confirm its existence in the following way: utilizes infrared ray (Infrared, IR), the polyamic acid or derivatives thereof making the present invention is precipitated and the solid constituent that obtains is analyzed by nuclear magnetic resonance, NMR (NuclearMagneticResonance, NMR) in substantial amounts of poor solvent。Additionally, the monomer used can be confirmed in the following way: utilize gas chromatography (GasChromatography, GC), high performance liquid chromatography (HighPerformanceLiquidChromatography, or GC-MS (GasChromatography-MassSpectrometry HPLC), GC-MS), after described polyamic acid or derivatives thereof being decomposed by the aqueous solution using the highly basic such as KOH or NaOH, the extract that organic solvent extracts from its analyte is used to be analyzed。

It addition, such as the viewpoint of the coating of aligning agent for liquid crystal or the adjustment of the concentration of described polyamic acid or derivatives thereof, the aligning agent for liquid crystal of the present invention can contain solvent further。As long as described solvent has the solvent of the ability dissolving macromolecule component, then can apply with no particular limitation。Described solvent extensively comprises the manufacturing step being generally used for the macromolecule component such as polyamic acid, soluble polyimide or the solvent of purposes aspect, can be suitable for according to application target selecting。Described solvent can be a kind of, it is also possible to is two or more mixed solvents。

As solvent, the solvophilic of described polyamic acid or derivatives thereof can be enumerated or to improve other solvents for the purpose of coating。

As being solvophilic aprotic polar organic solvent relative to polyamic acid or derivatives thereof, can enumerate: METHYLPYRROLIDONE, methylimidazole alkanone (dimethylimidazolidinone), N-methyl caprolactam, N-methyl propanamide, N, N-dimethyl acetylamide, dimethyl sulfoxide, N, the lactones such as dinethylformamide, N, N-diethylformamide, diethyl acetamide, gamma-butyrolacton。

As the example to improve other solvents for the purpose of coating etc., can enumerate: lactic acid alkyl ester, 3-methyl-3-methoxybutanol, naphthane, isophorone, the ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, the diethylene glycol monoalky lethers such as diethylene glycol monoethyl ether, glycol monoalkyl acetas or ethylene glycol list phenylacetic acid ester, triethylene glycol monoalky lether, propylene glycol monomethyl ether, the propylene-glycol monoalky lethers such as propylene glycol monobutyl ether, the dialkyl malonates such as diethyl malonate, the dipropylene glycol monoalkylether such as dipropylene glycol monomethyl ether, the ester compounds such as these acetate esters。

Among these solvents, described solvent particularly preferably METHYLPYRROLIDONE, methylimidazole alkanone, gamma-butyrolacton, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether。

Preferred 0.1wt%～the 40wt% of concentration of the polyamic acid in the alignment agent of the present invention。When this alignment agent is coated on substrate, in order to adjust thickness, it is sometimes desirable to utilize the operation that contained polyamic acid is diluted by solvent in advance。

Solid component concentration in the alignment agent of the present invention is not particularly limited, as long as selecting most suitable value in conjunction with following various rubbing methods。Generally, in order to suppress inequality when being coated with or pin hole etc., relative to varnish weight, it is preferable that 0.1wt%～30wt%, more preferably 1wt%～10wt%。

The viscosity of the aligning agent for liquid crystal of the present invention due to the method for coating, the concentration of polyamic acid or derivatives thereof, the kind of polyamic acid or derivatives thereof used, solvent kind and ratio and preferably scope is different。Such as, when utilizing printer and be coated for 5mPa s～100mPa s (being more preferably 10mPa s～80mPa s)。If less than 5mPa s, then become to be difficult to obtain sufficient thickness；If more than 100mPa s, then there is the phenomenon that printing inequality becomes big。When utilizing spin coating and be coated, it is appropriate that 5mPa s～200mPa s (is more preferably 10mPa s～100mPa s)。When using ink-jet coating apparatus and be coated, it is appropriate that 5mPa s～50mPa s (is more preferably 5mPa s～20mPa s)。The viscosity of aligning agent for liquid crystal can be measured by rotational viscometry, for instance uses rotating cylinder viscometer (the TVE-20L type that east machine industry manufactures) to measure (measuring temperature is 25 DEG C)。

The liquid crystal orientation film of the present invention is described in detail。The liquid crystal orientation film of the present invention is the film by being heated being formed to the film of the aligning agent for liquid crystal of the described present invention。The liquid crystal orientation film of the present invention can obtain by making the usual way of liquid crystal orientation film from aligning agent for liquid crystal。Such as, the liquid crystal orientation film of the present invention can by through forming the step of film of aligning agent for liquid crystal of the present invention, the step being thermally dried and being heated the step of calcining and obtain。For the liquid crystal orientation film of the present invention, optionally, can as be described hereinafter as the film obtained through heat-drying step, heating and calcining step is carried out friction treatment to give anisotropy。Or, optionally, light can be irradiated after film-coating procedures, heat-drying step, or irradiation light gives anisotropy after heating and calcining step。Alternatively, it is also possible to vertical orientated (VerticalAlignment, the VA) that be used as not carry out friction treatment uses liquid crystal orientation film。

Film in the same manner as the making of common liquid crystal orientation film, can be formed by being coated on the substrate in liquid crystal display cells by the aligning agent for liquid crystal of the present invention。Substrate can be enumerated and can be provided with tin indium oxide (IndiumTinOxide, ITO), indium zinc oxide (In₂O₃-ZnO, IZO), indium gallium zinc (In-Ga-ZnO₄, IGZO) and the substrate of glass of electrode or the colored filter etc. such as electrode。

As the method being coated on by aligning agent for liquid crystal on substrate, generally oneself knows rotator method, print process, infusion process, dripping method, ink-jet method etc.。These methods can also be equally applicable in the present invention。

Generally oneself knows have the method processed that is heated in baking oven or infra-red furnace, the method etc. being heated process on hot plate to described heat-drying step。Heat-drying step is implemented preferably at the temperature in the transpirable scope of solvent, more preferably in being implement at relatively low temperature relative to the temperature in heating and calcining step。Specifically, the scope that heat drying temperature is preferably 30 DEG C～150 DEG C, the scope of more preferably 50 DEG C～120 DEG C。

Described heating and calcining step can carry out when described polyamic acid or derivatives thereof present required for dehydration closed-loop reacts。The calcining of described film is commonly known the method processed that is heated in baking oven or infra-red furnace, the method etc. being heated process on hot plate。These methods can also be equally applicable in the present invention。Generally preferable carry out at the temperature of 100 DEG C～about 300 DEG C 1 minute～3 hours, more preferably 120 DEG C～280 DEG C, and then more preferably 150～250 DEG C。

In the forming method of the liquid crystal orientation film of the present invention, in order to make liquid crystalline phase carry out orientation in one direction for horizontal direction and/or vertical direction, the known forming method such as friction or optical alignment method can be used aptly to give anisotropic method as to alignment films。

The liquid crystal orientation film of the present invention using friction can be formed through the steps: the step being coated on substrate by the aligning agent for liquid crystal of the present invention, the step that the substrate being coated with alignment agent is thermally dried, this film is heated the step of calcining and film carries out the step of friction treatment。

Friction treatment can carry out in the same manner as the friction treatment of the orientation process of liquid crystal orientation film with common, as long as the condition of delay fully can be obtained in the liquid crystal orientation film of the present invention。Preferred condition is mao intrusion is 0.2mm～0.8mm, and platform translational speed is 5mm/sec～250mm/sec, and roller rotary speed is 500rpm～2,000rpm。

The forming method of the liquid crystal orientation film of the present invention utilizing optical alignment method is described in detail。The liquid crystal orientation film using the present invention of optical alignment method can be formed in the following way: after film is thermally dried, and by irradiating the linear polarization of lonizing radiation or without polarisation, gives anisotropy to film, then described film is heated calcining。It addition, by film is thermally dried, and after being heated calcining, the linear polarization of lonizing radiation can be irradiated or formed without polarisation。For the viewpoint of orientation, it is preferable that carry out the irradiating step of lonizing radiation before heating and calcining step。

And then, in order to improve the liquid crystal aligning ability of liquid crystal orientation film, it is possible to one irradiates the linear polarization of lonizing radiation or without polarisation in the face of film is heated one side。The irradiation of lonizing radiation can the step that film is thermally dried or film is heated calcining step carry out, it is possible to carry out between heat-drying step and heating and calcining step。The scope that the heat drying temperature of this step is preferably 30 DEG C～150 DEG C, the scope of more preferably 50 DEG C～120 DEG C。And the scope of the heating and calcining temperature of this step preferably 30 DEG C～300 DEG C, the scope of more preferably 50 DEG C～250 DEG C。

As lonizing radiation, ultraviolet or the visible ray of the light of the wavelength comprising such as 150nm～800nm can be used, it is preferable that comprise the ultraviolet of the light of 300nm～400nm。Additionally can use linear polarization or without polarisation。As long as these light are the light that described film can give liquid crystal aligning ability, then it is not particularly limited, when being intended to liquid crystal watch is revealed strong orientation restraint, it is preferable that linear polarization。

Even if the liquid crystal orientation film of the present invention also can be shown that high liquid crystal aligning ability under low-energy light irradiates。The preferred 0.05J/cm of irradiation dose of the linear polarization in described lonizing radiation irradiating step²～20J/cm², more preferably 0.5J/cm²～10J/cm²。The additionally preferred 200nm～400nm of the wavelength of linear polarization, more preferably 300nm～400nm。The irradiating angle on film surface is not particularly limited by linear polarization, when being intended to liquid crystal watch is revealed strong orientation restraint, for the viewpoint that the orientation process time shortens, it is preferable that as far as possible vertical relative to film surface。It addition, the liquid crystal orientation film of the present invention is by irradiating linear polarization, direction that can be vertical towards the polarization direction relative to linear polarization makes liquid crystal aligning。

When being intended to show tilt angle, the light that described film is irradiated is same with described, can be linear polarization, it is possible to for without polarisation。The preferred 0.05J/cm of irradiation dose when being intended to show tilt angle, to the light that described film irradiates²～20J/cm², particularly preferably 0.5J/cm²～10J/cm², the preferred 250nm～400nm of its wavelength, particularly preferably 300nm～380nm。When being intended to show tilt angle, the light that described film is irradiated is not particularly limited relative to the irradiating angle on described film surface, for the viewpoint that the orientation process time shortens, it is preferable that 30 degree～60 degree。

Irradiate lonizing radiation linear polarization or without the step of polarisation in use light source in, can unrestrictedly use extra-high-pressure mercury vapour lamp, high-pressure mercury-vapor lamp, low pressure mercury lamp, deep UV (DeepUV) lamp, Halogen light, metal halide lamp, high-power metallic halide lamp, xenon lamp, mercury xenon, Excimer lamp, KrF excimer laser, fluorescent lamp, light emitting diode (lightemittingdiode, LED) lamp, sodium vapor lamp, microwave-excitation Non-polarized lamp (microwavedischargedelectrodelesslamp) etc.。

The liquid crystal orientation film of the present invention can by so that the method that comprises other steps beyond described step and obtain aptly。Such as, although the liquid crystal orientation film of the present invention not using the step that is carried out of film after utilizing cleanout fluid that calcining or lonizing radiation are irradiated as required step, but cleaning step can be set according to the situation of other steps。

As the cleaning method utilizing cleanout fluid, can enumerate: scrub, spray, steam purge or ultrasonic waves for cleaning etc.。These methods can individually carry out, it is also possible to and use。As cleanout fluid, can use: pure water, or the various alcohols such as methanol, ethanol, isopropanol, benzene,toluene,xylene etc. is aromatic hydrocarbon based, the halogen series solvent such as dichloromethane, the ketone such as acetone, methyl ethyl ketone, but is not limited to these cleanout fluid。Certainly, these cleanout fluid can use the cleanout fluid that the impurity through fully refining is few。In described cleaning step when this kind of cleaning method can also be applied to the liquid crystal orientation film forming the present invention。

In order to improve the liquid crystal aligning ability of the liquid crystal orientation film of the present invention, can in the front and back of heating and calcining step, the annealing of front and back applications exploiting heat that the front and back of rubbing process or polarisation or the lonizing radiation without polarisation irradiate or light。In this annealing, annealing temperature is 30 DEG C～180 DEG C, it is preferable that 50 DEG C～150 DEG C, preferably 1 minute～2 hours time。It addition, in being used for the annealing light made annealing treatment, UV lamp, fluorescent lamp, LED etc. can be enumerated。The preferred 0.3J/cm of irradiation dose of light²～10J/cm²。

The thickness of the liquid crystal orientation film of the present invention is not particularly limited, but preferred 10nm～300nm, more preferably 30nm～150nm。The thickness of the liquid crystal orientation film of the present invention can be measured by known determining film thickness devices such as contourograph or ellipsometers (ellipsometer)。

The liquid crystal orientation film of the present invention is characterized by the anisotropy of king-sized orientation。This kind of anisotropic big I is evaluated by the described method using polarisation IR in Japanese Patent Laid-Open 2005-275364 etc.。It addition, as shown in below example, it is also possible to by using the method for ellipsometry (ellipsometry) to evaluate。Specifically, light splitting ellipsometer can be used to measure the length of delay of liquid crystal orientation film。The length of delay of film and the degree of orientation of main polymer chain proportionally increase。That is, the film with big length of delay has the big degree of orientation, when the alignment films of the present invention is used as liquid crystal orientation film, it is believed that have bigger anisotropic alignment films and have big orientation restraint for liquid-crystal composition。

The liquid crystal orientation film of the present invention may be suitably used in the liquid crystal display cells of Transverse electric-field type。In for the liquid crystal display cells of Transverse electric-field type, Pt angle is more little, and liquid crystal aligning ability is more high, then black display level in the dark state more uprises, and contrast more improves。Preferably less than 0.1 ° of Pt angle。

Except the orientation purposes of the liquid-crystal composition of liquid crystal display, the liquid crystal orientation film of the present invention can be used for optical compensation material or the tropism control of other all liquid crystal materials。It addition, the alignment films of the present invention is owing to having big anisotropy, optical compensation material applications therefore can be individually used for。

The liquid crystal display cells of the present invention is described in detail。

The present invention provides a kind of liquid crystal display cells, it includes oppositely disposed a pair substrate, formed the pair of substrate respective to the electrode in the one or both in face, formed at the pair of substrate respective to the liquid crystal orientation film on face and form the liquid crystal layer between the pair of substrate, and described liquid crystal orientation film is the alignment films of the present invention。

As long as described electrode is formed in the electrode in the one side of substrate, then it is not particularly limited。This kind of electrode include, for example the evaporation film etc. of ITO or metal。It addition, electrode may be formed on whole of a face of substrate, it is also possible to be formed as such as patterned desired shape。The described desired shape of electrode include, for example combed or broached-tooth design etc.。Electrode may be formed on a substrate in a pair substrate, it is also possible to is formed on two substrates。The formation form of electrode is different according to the kind of liquid crystal display cells, such as when IPS type liquid crystal display cells, electrode is arranged in the one of the pair of substrate, when other liquid crystal display cells, electrode is arranged on the pair of both substrates。Described substrate or electrode are formed described liquid crystal orientation film。

Described liquid crystal layer be with by be formed liquid crystal orientation film in the face of to the pair of substrate clamp liquid-crystal composition form formed。In the forming process of liquid crystal layer, optionally can use micropartical or resin sheet etc. between the pair of substrate and form the sept at suitable interval。

There is no particular restriction for liquid-crystal composition, the various liquid-crystal compositions that dielectric constant anisotropy can be used to be plus or minus。The preferred liquid-crystal composition that dielectric constant anisotropy is positive can be enumerated: Japan Patent 3086228, Japan Patent 2635435, Japan Patent JP-A 5-501735, Japanese Patent Laid-Open 8-157826, Japanese Patent Laid-Open 8-231960, Japanese Patent Laid-Open 9-241644 (EP885272A1), Japanese Patent Laid-Open 9-302346 (EP806466A1), Japanese Patent Laid-Open 8-199168 (EP722998A1), Japanese Patent Laid-Open 9-235552, Japanese Patent Laid-Open 9-255956, Japanese Patent Laid-Open 9-241643 (EP885271A1), Japanese Patent Laid-Open 10-204016 (EP844229A1), Japanese Patent Laid-Open 10-204436, Japanese Patent Laid-Open 10-231482, Japanese Patent Laid-Open 2000-087040, liquid-crystal composition disclosed in Japanese Patent Laid-Open 2001-48822 etc.。

Even if the optically active compound adding more than one in the liquid-crystal composition that dielectric constant anisotropy is plus or minus uses, also have no effect。

The liquid-crystal composition being negative to described dielectric constant anisotropy is illustrated。The liquid-crystal composition of negative dielectric constant anisotropy include, for example the compositions as the 1st composition of at least one liquid-crystal compounds containing the group selected from the liquid-crystal compounds represented by following formula (NL-1)。

Herein, R^1aAnd R^2aStand alone as alkyl that carbon number is 1～12, thiazolinyl or the thiazolinyl that carbon number is 2～12 that replaced by fluorine of at least one hydrogen, ring A that alkoxyl that carbon number is 1～12, carbon number are 2～12²And ring B²Stand alone as Isosorbide-5-Nitrae-cyclohexylidene, Pentamethylene oxide. (tetrahydropyran)-2,5-bis-base, 1,3-dioxane-2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-base, Isosorbide-5-Nitrae-phenylene, 2-, 2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-, 2,3-bis-fluoro-1, chloro-Isosorbide-5-Nitrae-the phenylene of the fluoro-3-of 4-phenylene, 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene, 2,6-naphthalene two bases or 7,8-difluoro chromanes (chromane)-2,6-bis-base, herein, ring A²And ring B²At least one be 2,3-bis-fluoro-Isosorbide-5-Nitrae-phenylenes, the chloro-Isosorbide-5-Nitrae-phenylene of the fluoro-3-of 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene or 7,8-difluoro chromane-2,6-bis-base, Z¹Stand alone as singly-bound ,-(CH₂)₂-、-CH₂O-,-COO-or-CF₂O-, j are 1,2 or 3, j when being 2 or 3, any two ring A²Can be identical, it is also possible to different, any two Z¹Can be identical, it is also possible to different。

In order to make dielectric constant anisotropy improve, it is preferred that ring A²And ring B²Respectively 2,3-bis-fluoro-Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, in order to make decrease in viscosity, it is preferred that ring A²And ring B²Respectively 1,4-cyclohexylidene。

In order to make dielectric constant anisotropy improve, it is preferred that Z¹For-CH₂O-, in order to make decrease in viscosity, it is preferred that Z¹For singly-bound。

In order to make lower limit temperature reduce, it is preferred that j is 1, in order to make ceiling temperature improve, it is preferred that j is 2。

The concrete example of the liquid-crystal compounds of described formula (NL-1) can enumerate the compound represented by following formula (NL-1-1)～formula (NL-1-32)。

Herein, R^1aAnd R^2aStand alone as alkyl that carbon number is 1～12, thiazolinyl or the thiazolinyl that carbon number is 2～12 that replaced by fluorine of at least one hydrogen, ring A that alkoxyl that carbon number is 1～12, carbon number are 2～12²¹, ring A²², ring A²³, ring B²¹, and ring B²²Stand alone as Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, Z¹¹And Z¹²Stand alone as singly-bound ,-(CH₂)₂-、-CH₂O-or-COO-。

In order to make the stability etc. for ultraviolet or heat improve, it is preferred that R^1aAnd R^2aBe carbon number it is the alkyl of 1～12, or in order to make the absolute value of dielectric constant anisotropy improve, it is preferred that R^1aAnd R^2aBe carbon number it is the alkoxyl of 1～12。

Preferred alkyl is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group。In order to make decrease in viscosity, and then preferred alkyl is ethyl, propyl group, butyl, amyl group or heptyl。

Preferred alkoxyl be methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy or heptan oxygen base。In order to make decrease in viscosity, and then preferred alkoxyl is methoxy or ethoxy。

Preferred thiazolinyl is vinyl, 1-acrylic, 2-acrylic, 1-butylene base, crotyl, 3-cyclobutenyl, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl。In order to make decrease in viscosity, and then preferred thiazolinyl is vinyl, 1-acrylic, 3-cyclobutenyl or 3-pentenyl。The preferred spatial configuration of-CH=CH-(stericconfiguration) in these thiazolinyls depends on the position of double bond。Personal so that the aspects such as decrease in viscosity consider, preferably trans in such as 1-acrylic, 1-butylene base, 1-pentenyl, 1-hexenyl, 3-pentenyl, the such thiazolinyl of 3-hexenyl。Such as crotyl, pentenyl, the such thiazolinyl of 2-hexenyl are preferably cis。In these thiazolinyls, Comparatively speaking it is preferably the thiazolinyl of straight chain with branch。

The preferred example of the thiazolinyl that at least one hydrogen is replaced by fluorine is 2,2-difluoroethylene base, 3,3-bis-fluoro-2-acrylic, 4,4-bis-fluoro-3-cyclobutenyl, 5,5-bis-fluoro-4-pentenyl and the fluoro-5-hexenyl of 6,6-bis-。In order to make decrease in viscosity, and then preferred example is 2,2-difluoroethylene bases and 4,4-bis-fluoro-3-cyclobutenyls。

In order to make decrease in viscosity, it is preferred that ring A²¹, ring A²², ring A²³, ring B²¹, and ring B²²Respectively 1,4-cyclohexylidene。

In order to make dielectric constant anisotropy improve, it is preferred that Z¹¹And Z¹²It is-CH₂O-, in order to make decrease in viscosity, it is preferred that Z¹¹And Z¹²It it is singly-bound。

In the described liquid-crystal composition with negative dielectric constant anisotropy, as the 1st composition, preferred compound (NL-1) is compound (NL-1-1), compound (NL-1-4), compound (NL-1-7) or compound (NL-1-32)。

The preferred example of the described liquid-crystal composition with negative dielectric constant anisotropy can be set forth in Japanese Patent Laid-Open No. Sho 57-114532, Japanese Patent Laid-Open 2-4725, Japanese Patent Laid-Open 4-224885, Japanese Patent Laid-Open 8-40953, Japanese Patent Laid-Open 8-104869, Japanese Patent Laid-Open 10-168076, Japanese Patent Laid-Open 10-168453, Japanese Patent Laid-Open 10-236989, Japanese Patent Laid-Open 10-236990, Japanese Patent Laid-Open 10-236992, Japanese Patent Laid-Open 10-236993, Japanese Patent Laid-Open 10-236994, Japanese Patent Laid-Open 10-237000, Japanese Patent Laid-Open 10-237004, Japanese Patent Laid-Open 10-237024, Japanese Patent Laid-Open 10-237035, Japanese Patent Laid-Open 10-237075, Japanese Patent Laid-Open 10-237076, Japanese Patent Laid-Open 10-237448 (EP967261A1), Japanese Patent Laid-Open 10-287874, Japanese Patent Laid-Open 10-287875, Japanese Patent Laid-Open 10-291945, Japanese Patent Laid-Open 11-029581, Japanese Patent Laid-Open 11-080049, Japanese Patent Laid-Open 2000-256307, Japanese Patent Laid-Open 2001-019965, Japanese Patent Laid-Open 2001-072626, Japanese Patent Laid-Open 2001-192657, Japanese Patent Laid-Open 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Japan Patent spy table 2010-537010, Japanese Patent Laid-Open 2012-077201, liquid-crystal composition disclosed in Japanese Patent Laid-Open 2009-084362 etc.。

And, for instance certainly make the viewpoint that orientation improves consider, for instance the liquid-crystal composition used in the element of the present invention can also add additive further。This kind of additive is photopolymerization monomer, optically active compound, antioxidant, UV absorbent, pigment, defoamer, polymerization initiator, polymerization inhibitor etc.。

Most preferred structure in order to improve the orientation of liquid crystal, photopolymerization monomer or oligomer can the structure of enumerative (PM-1-1)～formula (PM-1-6)。

In order to show the effect of the incline direction of the liquid crystal after determining polymerization, photopolymerization monomer or oligomer it is desirable to more than 0.01wt%。And, in order to the orientation effect of the polymer after making polymerization is suitable for, or in order to avoid after uv irradiation, unreacted monomer or oligomer dissolution are to liquid crystal, it is generally desirable to below 30wt%。

In order to cause the helical structure of liquid crystal and give torsion angle, hybrid optical reactive compound in the composition。The example of this kind of compound is compound (PAC-1-1) to compound (PAC-1-4)。

Optically active compound be preferably in a proportion of below 5wt%。And then preferred ratio is the scope of 0.01wt% to 2wt%。

In order to prevent ratio resistance (specificresistance) caused owing to heating in an atmosphere from reducing, or in order to after long-time use element, not only at room temperature and also big voltage retention can also be maintained at high temperature, liquid-crystal composition mixes antioxidant。

The preferred example of antioxidant is w is the compound (AO-1) etc. of the integer of 1 to 10。In compound (AO-1), it is preferred that w is 1,3,5,7 or 9。And then preferred w is 1 or 7。The volatility that w is the compound (AO-1) of 1 is big, therefore effective when the ratio resistance preventing from causing owing to heating in an atmosphere reduces。The volatility that w is the compound (AO-1) of 7 is little, therefore long-time use element after, not only at room temperature and also can also effectively maintain big voltage retention at high temperature。In order to obtain its effect, the preferred ratio of antioxidant is more than 50ppm, and in order to not make ceiling temperature reduce or not make lower limit temperature improve, the preferred ratio of antioxidant is below 600ppm。And then preferred ratio is the scope of 100ppm to 300ppm。

The preferred example of UV absorbent is benzophenone derivates, benzoate derivatives, triazole derivative etc.。And, as have steric hindrance (sterichindrance) the such light stabilizer of amine it is also preferred that。In order to obtain its effect, the preferred ratio of these absorbent or stabilizer is more than 50ppm, and in order to not make ceiling temperature reduce or not make lower limit temperature improve, the preferred ratio of these absorbent or stabilizer is below 10000ppm。And then preferred ratio is the scope of 100ppm to 10000ppm。

In order to be suitable for the element of host and guest (Guesthost, GH) pattern, mixing is such as such dichromatic pigments (dichroicdye) such as azo system pigment, anthraquinone system pigments in the composition。The scope that preferred ratio is 0.01wt% to 10wt% of pigment。

In order to prevent bubbling, mix the defoamer such as dimethicone, methyl phenyl silicone oil in the composition。In order to obtain its effect, the preferred ratio of defoamer is more than 1ppm, and in order to prevent display bad, the preferred ratio of defoamer is below 1000ppm。And then preferred ratio is the scope of 1ppm to 500ppm。

In order to be suitable for the element of polymer stabilizing orientation (Polymersustainedalignment, PSA) pattern, polymerisable compound can be mixed in the composition。The preferred example of polymerisable compound is the compound that acrylate, methacrylate, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxide (oxirane, oxetanes), vinyl ketone etc. have polymerisable base。Example particularly preferably is the derivant of acrylate or methacrylate。The example of this kind of compound is compound (PM-2-1) to compound (PM-2-9)。In order to obtain its effect, the preferred ratio of polymerisable compound is about more than 0.05wt%, and in order to prevent display bad, the preferred ratio of polymerisable compound is about below 10wt%。And then preferred ratio is the scope of about 0.1wt% to about 2wt%。

Herein, R^3a、R^4a、R^5a, and R^6aStand alone as acryloyl group or methylacryloyl, R^7aAnd R^8aStand alone as the alkyl that hydrogen, halogen or carbon number are 1 to 10, Z¹³、Z¹⁴、Z¹⁵, and Z¹⁶Stand alone as singly-bound or carbon number is the alkylidene of 1 to 12, at least one-CH₂-can also be replaced by-O-or-CH=CH-, s, t and u are each independently 0,1 or 2。

As easily producing free radical or ion, cause the material that chain polymerization reaction is required, can mixed polymerization initiator。Such as, as gorgeous good solid (Irgacure) 651 (registered trade mark) of Photoepolymerizationinitiater initiater, gorgeous good solid 184 (registered trade marks) or Da Luoka (Darocure) 1173 (registered trade mark) (Qi Ba limited company of Japan (CibaJapanK.K.)) for radical polymerization suitable。Polymerisable compound is preferably in comprising Photoepolymerizationinitiater initiater in the scope of 0.1wt% to 5wt%。Particularly preferably be in the scope of 1wt% to 3wt%, comprise Photoepolymerizationinitiater initiater。

In radical polymerization assembly system, available following purpose and mixed polymerization inhibitor: promptly reacting with free radical produced by polymerization initiator or monomer and be changed to the compound of stable free radical or neutrality, its result makes polyreaction stop。Polymerization inhibitor structurally can be categorized as several。One of them be as three-p-nitrophenyl ylmethyl, two-to himself stable free radicals such such as fluorophenyl amine, the free radical that another kind is existing with paradigmatic system easily reacts and becomes stable free radical person, and its representative is nitro, nitroso-group, amino, polyol etc.。The representative of the latter can enumerate hydroquinone, dimethoxy benzene etc.。In order to obtain its effect, the preferred ratio of polymerization inhibitor is more than 5ppm, and in order to prevent display bad, the preferred ratio of polymerization inhibitor is below 1000ppm。And then preferred ratio is the scope of 5ppm to 500ppm。

The liquid crystal display cells of the present invention uses there is the liquid-crystal composition of negative dielectric constant anisotropy, image retention excellent and the good liquid crystal display cells of orientation stability thus can be provided。

[embodiment]

Hereinafter, by embodiment, the present invention is described。It addition, the assessment method used in an embodiment and compound are as described below。

1. weight average molecular weight (Mw)

The weight average molecular weight of polyamic acid is obtained in the following way: uses 2695 separation module 2414 differential refractometer (water generation (Waters) manufacture) and utilizes GPC method to measure, then carrying out polystyrene conversion。Utilize phosphoric acid-dimethylformamide (Dimethylformamide, DMF) mixed solution (phosphoric acid/DMF=0.6/100: weight ratio), in the way of polyamic acid concentration becomes about 2wt%, the polyamic acid obtained is diluted。Tubing string uses HSPgelRTMB-M (manufacture of water generation), using described mixed solution as developing solvent, tubing string temperature be 50 DEG C, flow velocity is measured when being 0.40mL/min。Polystyrene standard uses the TSK polystyrene standard that east Cao (Tosoh) (share) manufactures。

2. voltage retention

Method described in " water et al., the 14th liquid crystal symposium's collection of thesis the 78th page (1988) " is utilized to carry out。Unit (cell) is applied the square wave of wave height (waveheight) ± 5V and is measured。It is measured at 60 DEG C。This value indicates that the voltage applied keeps the index of which kind of degree afterwards in the frame period (frameperiod), if this value 100% represents keeps all of electric charge。When being more than 99.0% in the unit be equipped with positive type liquid crystal, when being more than 97.5% in the unit being equipped with negative type liquid crystal, become the liquid crystal display cells that display quality is good。

3. the ionic weight in liquid crystal measures (ion concentration)

According to " Applied Physics ", the 65th volume, No. 10, method described in 1065 (1996), liquid crystal physical property measurement system 6254 type that Dongyang technology company manufactures is used to be measured。Using frequency is the triangular wave of 0.01Hz, is measured that (area of electrode is 1cm at the ± voltage range of 10V, the temperature of 60 DEG C²)。If ion concentration is big, then easily produce the unfavorable conditions such as the burning trace that causes due to ionic impurity。That is, ion concentration is to become prediction to burn the physics value of the index that trace produces。When this value is below 40pC, become the liquid crystal display cells that display quality is good。

< tetracarboxylic dianhydride >

< diamidogen >

< other monomers >

Aniline

Phthalic anhydride

< solvent >

NMP:N-N-methyl-2-2-pyrrolidone N

BC: butyl cellosolve (ethylene glycol monobutyl ether)

GBL: gamma-butyrolacton

Diethylene glycol diethyl ether

Diisobutyl ketone

2-butoxypropanol

< additive >

Additive (Ad1): N, N, N', N'-four glycidyl group-4,4'-diaminodiphenyl-methane

Double; two (4,5-dihydro-2-azoles base) benzene of additive (Ad2): 1,3-

Additive (Ad3): 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane

The synthesis of [embodiment 1] varnish

In the there-necked flask of 100mL being provided with agitator, nitrogen ingress pipe, compound 0.2863g represented by compound 0.3075g represented by addition formula (1-1-1), the compound 2.0361g represented by formula (DI-5-1) (m=4) and formula (DI-5-30) (k=2), and add METHYLPYRROLIDONE 35.0g。After this solution is cooled to 5 DEG C under ice bath, the compound 3.3701g represented by adding type (II-1-1), at room temperature stirring 12 hours。It is added to gamma-butyrolacton 30.0g and butyl cellosolve 30.0g, it is heated stirring at 60 DEG C till the weight average molecular weight of the polymer of solute becomes required weight average molecular weight by described solution, thus the weight average molecular weight obtaining solute is approximately 13,000 and varnish 1 that resinous principle concentration is 6wt%。

[embodiment 2～embodiment 96]

Change tetracarboxylic dianhydride and diamidogen, in addition, prepare, according to embodiment 1, varnish 2～varnish 96 that polymer solids constituent concentration is 6wt%。About weight average molecular weight, the polymer using the raw material with photoisomerization structure is adjusted to about 12,000～13,000, the polymer not using the raw material with photoisomerization structure is adjusted to 40,000～50,000。The tetracarboxylic dianhydride used and diamidogen and the weight average molecular weight of polymer obtained are shown in table 1-1～table 1-9。Table 1-1 also discloses embodiment 1 again。

Table 1-1

Table 1-2

Table 1-3

Table 1-4

Table 1-5

Table 1-6

Table 1-7

Table 1-8

Table 1-9

[embodiment 97] preparation of single-layer type alignment agent, the making of electrical characteristics determining unit and electrical characteristics determining

The varnish 110.0g of synthesis in embodiment 1 is weighed in the 50mL eggplant type flask be provided with agitator, nitrogen ingress pipe, it is added to METHYLPYRROLIDONE 5.0g and butyl cellosolve 5.0g, at room temperature stirring 1 hour, it is thus achieved that resinous principle concentration is the alignment agent 1 of 3wt%。Utilize rotator that this alignment agent is coated the glass substrate with IPS electrode and the glass substrate (2,000rpm, 15 seconds) with post spacer (columnspacer)。After coating, carry out 3 minutes heating to substrate with 80 DEG C, after making solvent evaporation, use Mu Qilaite (Multi-Light) ML-501C/B that oxtail (Ushio) motor (share) manufactures, from the linear polarization of the direction vertical relative to substrate irradiation ultraviolet radiation via Polarizer。Exposure energy now is that the ultraviolet using oxtail motor (share) to manufacture adds up quantometer UIT-150 (optical receiver: UVD-S365) and measures light quantity, to become 1.3J/cm under wavelength 365nm²±0.1J/cm²Mode adjust time of exposure。Then, carry out 20 minutes calcination processing with 230 DEG C, form thickness and be approximately the liquid crystal orientation film of 100nm。Will be formed with the two of described alignment films piece substrate by make to be formed alignment films in the face of to and arrange in order to liquid-crystal composition is injected into to alignment films between space in the way of fitted。Now, the polarization direction exposing to the linear polarization of respective alignment films is set to parallel。In described unit, inject positive type liquid crystal compositions A carry out the liquid crystal cells (liquid crystal display cells) that production unit thickness is 7 μm。

< positive type liquid crystal compositions A >

Physics value: NI100.1 DEG C；Δ ε 5.1；Δ n0.093；η 25.6mPa s.

The voltage retention of this liquid crystal cells is 99.5% under 5V-30Hz, and ion concentration is 15pC。This unit is placed in the backlight testing machine through lighting, and (Fujiphoto (share) manufactures, Fuji color LED viewer (FujiCOLORLEDViewer) ProHR-2；Brightness 2,700cd/m²) on 1,000 hours and carry out reliability test。The voltage retention of the mensuration unit after reliability test is 99.4%, and ion concentration is 15pC。

[embodiment 98～embodiment 133]

Change the varnish that uses, in addition, make liquid crystal cells according to embodiment 97, and carry out voltage retention, the mensuration of ion concentration and reliability test。Measurement result and embodiment 97 are shown in table 2 in the lump。

Table 2

In all unit of embodiment 98～embodiment 133, the value after initial value, reliability test all obtains good result。Herein, after initial value refers to production unit, it is not placed in described backlight testing machine and the result that measures。

[embodiment 134] preparation of admixing type alignment agent, the making of electrical characteristics determining unit and electrical characteristics determining

The varnish 398.0g of synthesis in the varnish 62.0g and embodiment 39 synthesized in embodiment 6 is weighed in the 50mL eggplant type flask be provided with agitator, nitrogen ingress pipe, it is added to METHYLPYRROLIDONE 5.0g and butyl cellosolve 5.0g, at room temperature stirring 1 hour, it is thus achieved that resinous principle concentration is the alignment agent 38 of 3wt%。Liquid crystal cells is made according to method described in embodiment 97。The voltage retention of this liquid crystal cells is 99.8% under 5V-30Hz, and ion concentration is 10pC。The voltage retention of the mensuration unit after reliability test is 99.7%, and ion concentration is 10pC。In table 3, varnish A represents the varnish containing the polymer using the raw material with photoisomerization structure, and varnish B represents the varnish containing the polymer not using the raw material with photoisomerization structure。

[embodiment 135～embodiment 164]

Change the varnish that uses, in addition, make liquid crystal cells according to embodiment 134, and carry out voltage retention, the mensuration of ion concentration and reliability test。The varnish used and measurement result and embodiment 134 are shown in table 3 in the lump。Furthermore, in table 3, varnish A represents the varnish containing the polymer using the raw material with photoisomerization structure, and varnish B represents the varnish containing the polymer not using the raw material with photoisomerization structure。

Table 3

In all unit of embodiment 135～embodiment 164, the value after initial value, reliability test all obtains good result。

[embodiment 165]

The positive type liquid crystal compositions A being injected into unit is replaced with negative type liquid crystal compositions B, in addition, prepares alignment agent according to method described in embodiment 97, and make liquid crystal cells, thus measuring electrical characteristics。

< negative type liquid crystal compositions B >

Physics value: NI75.7 DEG C；Δ ε-4.1；Δ n0.101；η 14.5mPa s.

[embodiment 166～embodiment 201]

Change the varnish that uses, in addition, make liquid crystal cells according to embodiment 165, and carry out voltage retention, the mensuration of ion concentration and reliability test。Measurement result and embodiment 165 are shown in table 4 in the lump。

Table 4

In all unit of embodiment 166～embodiment 201, the value after initial value, reliability test all obtains good result。

[embodiment 202]

The positive type liquid crystal compositions A being injected into unit is replaced with negative type liquid crystal compositions B, in addition, prepare alignment agent according to method described in embodiment 134, and make liquid crystal cells, thus carrying out voltage retention, the mensuration of ion concentration and reliability test。

[embodiment 203～embodiment 232]

Change the varnish that uses, in addition, make liquid crystal cells according to embodiment 202, and carry out voltage retention, the mensuration of ion concentration and reliability test。Measurement result and embodiment 202 are shown in table 5 in the lump。

Table 5

In all unit of embodiment 203～embodiment 232, the value after initial value, reliability test all obtains good result。

[embodiment 233]

In the varnish that polymer solids constituent concentration is 6wt% 8 prepared by embodiment 8, interpolation is the additive (Ad1) of 5 weight portions relative to polymer 100 weight portion。This polyamic acid solution is set to varnish 97。The weight average molecular weight of the polyamic acid comprised in varnish 97 is 12,000。Then add the mixed solvent of NMP/BC=1/1 (weight ratio), the dilution of polymer solids constituent concentration is made for 3wt% alignment agent 69。Use the aligning agent for liquid crystal that obtains, utilize the method according to embodiment 97 to make liquid crystal cells, and carry out voltage retention, the mensuration of ion concentration and reliability test。

[embodiment 234]

In the varnish that polymer solids constituent concentration is 6wt% 8 prepared by embodiment 8, interpolation is the additive (Ad2) of 5 weight portions relative to polymer 100 weight portion。This polyamic acid solution is set to varnish 98。The weight average molecular weight of the polyamic acid comprised in varnish 98 is 12,000。Then add the mixed solvent of NMP/BC=1/1 (weight ratio), the dilution of polymer solids constituent concentration is made for 3wt% alignment agent 70。Use the aligning agent for liquid crystal that obtains, utilize the method according to embodiment 97 to make liquid crystal cells, and carry out voltage retention, the mensuration of ion concentration and reliability test。

[embodiment 235]

In the varnish that polymer solids constituent concentration is 6wt% 8 prepared by embodiment 8, interpolation is the additive (Ad3) of 5 weight portions relative to polymer 100 weight portion。This polyamic acid solution is set to varnish 99。The weight average molecular weight of the polyamic acid comprised in varnish 99 is 12,000。Then add the mixed solvent of NMP/BC=1/1 (weight ratio), the dilution of polymer solids constituent concentration is made for 3wt% alignment agent 71。Use the aligning agent for liquid crystal that obtains, utilize the method according to embodiment 97 to make liquid crystal cells, and carry out voltage retention, the mensuration of ion concentration and reliability test。

[embodiment 236]

To the alignment agent that polymer solids constituent concentration is 3wt% 48 prepared by embodiment 144, interpolation is the additive (Ad1) of 5 weight portions relative to polymer 100 weight portion。Use the alignment agent 72 that obtains, utilize the method according to embodiment 97 to make liquid crystal cells, and carry out voltage retention, the mensuration of ion concentration and reliability test。

[embodiment 237]

To the alignment agent that polymer solids constituent concentration is 3wt% 48 prepared by embodiment 144, interpolation is the additive (Ad2) of 5 weight portions relative to polymer 100 weight portion。Use the alignment agent 73 that obtains, utilize the method according to embodiment 97 to make liquid crystal cells, and carry out voltage retention, the mensuration of ion concentration and reliability test。

[embodiment 238]

To the alignment agent that polymer solids constituent concentration is 3wt% 48 prepared by embodiment 144, interpolation is the additive (Ad3) of 5 weight portions relative to polymer 100 weight portion。Use the alignment agent 74 that obtains, utilize the method according to embodiment 97 to make liquid crystal cells, and carry out voltage retention, the mensuration of ion concentration and reliability test。

The measurement result of embodiment 233～embodiment 238 is shown in table 6。

Table 6

In all unit of embodiment 233～embodiment 238, even if adding additive, the value after initial value, reliability test also obtains good result。

[comparative example 1～comparative example 3]

Varnish 1 is replaced with varnish 65, varnish 75 or varnish 85, in addition, makes liquid crystal cells according to method described in embodiment 97, and carry out voltage retention, the mensuration of ion concentration and reliability test。Measurement result is shown in table 7。

Table 7

In all unit of comparative example 1～comparative example 3, the result that the value after especially obtaining reliability test declines to a great extent。

[comparative example 4～comparative example 6]

The positive type liquid crystal compositions A being injected into unit is replaced with negative type liquid crystal compositions B, in addition, makes liquid crystal cells according to method described in comparative example 1～comparative example 3, and carry out voltage retention, the mensuration of ion concentration and reliability test。Measurement result is shown in table 8。

Table 8

In all unit of comparative example 4～comparative example 6, the result that the value after especially obtaining reliability test declines to a great extent。

[comparative example 7～comparative example 17]

Change the varnish that uses, in addition, make liquid crystal cells according to embodiment 134, and carry out voltage retention, the mensuration of ion concentration and reliability test。The varnish used and measurement result are shown in table 9。

Table 9

In all unit of comparative example 7～comparative example 17, the result that the value after especially obtaining reliability test declines to a great extent。

[comparative example 18～comparative example 28]

The positive type liquid crystal compositions A being injected into unit is replaced with negative type liquid crystal compositions B, in addition, makes liquid crystal cells according to method described in comparative example 7～comparative example 17, and carry out voltage retention, the mensuration of ion concentration and reliability test。Measurement result is shown in table 10。

Table 10

In all unit of comparative example 18～comparative example 28, the result that the value after especially obtaining reliability test declines to a great extent。

The synthesis of [embodiment 239～embodiment 241] varnish

Change tetracarboxylic dianhydride and diamidogen, in addition, prepare, according to embodiment 1, varnish 97～varnish 99 that polymer solids constituent concentration is 6wt%。Weight average molecular weight is adjusted to 40,000～50,000。The tetracarboxylic dianhydride used and diamidogen and the weight average molecular weight of polymer obtained are shown in table 11。

Table 11

[embodiment 242～embodiment 244] preparation of alignment agent, the making of electrical characteristics determining unit and electrical characteristics determining

Change the varnish that uses, in addition, make liquid crystal cells according to embodiment 134, and carry out voltage retention, the mensuration of ion concentration and reliability test。The varnish used and measurement result are shown in table 12。Furthermore, in table 12, varnish A represents the varnish containing the polymer using the raw material with photoisomerization structure, and varnish B represents the varnish containing the polymer not using the raw material with photoisomerization structure。

Table 12

In all unit of embodiment 242～embodiment 244, the value after initial value, reliability test all obtains good result。

[utilizing the confirmation of the printing of ink-jet method]

The aligning agent for liquid crystal of the present invention is by being suitable for the solvent selecting to use, and becomes the aligning agent for liquid crystal of the coating being suitable to utilize ink-jet method。

Ink-jet method is coated with the preparation of aligning agent for liquid crystal

[embodiment 245]

In the there-necked flask of 100mL being provided with agitator, nitrogen ingress pipe, compound 0.3451g represented by compound 0.1390g represented by addition formula (1-1-1), the compound 1.6254g represented by formula (V-2-1) and formula (DI-5-1) (m=4), and add METHYLPYRROLIDONE 34.0g。After making the cooling of this solution ice bath that liquid temperature is set to 5 DEG C, the compound 3.8905g represented by adding type (AN-4-17) (m=8), at room temperature stirring 12 hours。It is added to gamma-butyrolacton 30.0g and butyl cellosolve 30.0g, it is heated stirring at 60 DEG C till the weight average molecular weight of the polymer of solute becomes required weight average molecular weight by described solution, thus the weight average molecular weight obtaining solute is approximately 12,000 and varnish 100 that resinous principle concentration is 6wt%。

[embodiment 246]

In the there-necked flask of 100mL being provided with agitator, nitrogen ingress pipe, compound 1.5052g represented by addition formula (DI-5-9), the compound 1.6504g represented by formula (DI-13-1), and add METHYLPYRROLIDONE 34.0g。After making the cooling of this solution ice bath that liquid temperature is set to 5 DEG C, the compound 1.3539g represented by adding type (AN-1-1) and the compound 1.4905g represented by formula (AN-3-2), at room temperature stirring 12 hours。It is added to gamma-butyrolacton 30.0g and butyl cellosolve 30.0g, it is heated stirring at 60 DEG C till the weight average molecular weight of the polymer of solute becomes required weight average molecular weight by described solution, thus the weight average molecular weight obtaining solute is approximately 49,000 and varnish 101 that resinous principle concentration is 6wt%。

[embodiment 247]

The varnish 10140.8g of synthesis in the varnish 10017.5g of synthesis, embodiment 246 in weighing embodiment 245, it is added to NMP16.7g, GBL7.5g, butyl cellosolve 7.5g and diethylene glycol diethyl ether 10.0g, thus preparing solid component concentration to be 3.5wt% and group of solvents becomes NMP:GBL: butyl cellosolve: the ink-jet method of diethylene glycol diethyl ether=36.5:25:25:10 is coated with aligning agent for liquid crystal 1。

Utilize ink-jet coating apparatus (manufacture of Fujiphoto limited company, DMP-2831) that this ink-jet method is coated with aligning agent for liquid crystal 1 and coat glass substrate。Furthermore, adjust drop interval, casket (cartridge) applies voltage so that the thickness of liquid crystal orientation film becomes 100nm。After coating, by visually confirming the rectilinearity on the inequality of printing surface entirety, printing limit, but not producing inequality, rectilinearity is also good。

[embodiment 248]

The varnish 10140.8g of synthesis in the varnish 10017.5g of synthesis, embodiment 246 in weighing embodiment 245, it is added to NMP16.7g, GBL7.5g, butyl cellosolve 5.5g, diethylene glycol diethyl ether 10.0g and diisobutyl ketone 2.0g, thus preparing solid component concentration to be 3.5wt% and group of solvents becomes NMP:GBL: butyl cellosolve: diethylene glycol diethyl ether: the ink-jet method of diisobutyl ketone=36.5:25:23:10:2 is coated with aligning agent for liquid crystal 2。Confirming, according to method described in embodiment 247, the coating that ink-jet method is printed, result does not produce the inequality that printing surface is overall, and the rectilinearity on printing limit is good。

[embodiment 249] with the synthesis of amine, the polyamic acid of anhydride

In the there-necked flask of 100mL being provided with agitator, nitrogen ingress pipe, compound 0.1336g represented by addition formula (1-1-1), the compound 1.8547g represented by formula (V-2-1) and aniline 0.0865g, and add METHYLPYRROLIDONE 34.0g。After making the cooling of this solution ice bath that liquid temperature is set to 5 DEG C, the compound 3.9253g represented by adding type (AN-4-17) (m=8), at room temperature stirring 12 hours。It is added to gamma-butyrolacton 30.0g and 2-butoxypropanol 30.0g, described solution is heated at 60 DEG C stirring, till the weight average molecular weight of the polymer of solute becomes required weight average molecular weight, thus the weight average molecular weight obtaining solute is approximately 11,000 and varnish 102 that resinous principle concentration is 6wt%。

[embodiment 250]

In the there-necked flask of 100mL being provided with agitator, nitrogen ingress pipe, the compound 0.1344g represented by addition formula (1-1-1), the compound 1.9652g represented by formula (V-2-1), and add METHYLPYRROLIDONE 34.0g。After making the cooling of this solution ice bath that liquid temperature is set to 5 DEG C, compound 3.7632g, the phthalic anhydride 0.1372g represented by adding type (AN-4-17) (m=8), at room temperature stirring 12 hours。It is added to gamma-butyrolacton 30.0g and 2-butoxypropanol 30.0g, described solution is heated at 60 DEG C stirring, till the weight average molecular weight of the polymer of solute becomes required weight average molecular weight, thus the weight average molecular weight obtaining solute is approximately 10,000 and varnish 103 that resinous principle concentration is 6wt%。

[embodiment 251, embodiment 252] preparation of alignment agent, the making of electrical characteristics determining unit and electrical characteristics determining

Change the varnish that uses, in addition, make liquid crystal cells according to embodiment 134, and carry out voltage retention, the mensuration of ion concentration and reliability test。The varnish used and measurement result are shown in table 13。Furthermore, in table 13, varnish A represents the varnish containing the polymer using the raw material with photoisomerization structure, and varnish B represents the varnish containing the polymer not using the raw material with photoisomerization structure。

Table 13

Embodiment 251, embodiment 252 all unit in, the value after initial value, reliability test all obtains good result。

[industrial applicability]

If using the light orientation aligning agent for liquid crystal of the present invention, even if the liquid crystal display cells that a kind of long-time use also can maintain high voltage retention and light resistance, display quality is high then can be provided。The light orientation aligning agent for liquid crystal of the present invention can be applied to lateral electric-field type liquid crystal display cells aptly。

Claims (18)

1. a light orientation aligning agent for liquid crystal, it comprises at least one polymer in the group selecting free polyamic acid, poly amic acid ester and the polyimides that they carried out imidizate and obtains to form, described polyamic acid, poly amic acid ester and the polyimides they being carried out imidizate and obtaining are to make at least one being selected from tetracarboxylic dianhydride and derivant thereof and diamine reactant obtain

At least one of the starting monomer of described polymer has photoisomerization structure, and

The starting monomer of described polymer comprises at least one of the compound represented by following formula (1)；

In formula (1), R^aIt is hydrogen or methyl；

R^bTo be hydrogen ,-OH, carbon number be 1～6 alkyl or carbon number be the alkoxyl of 1～6；And

The derivant of described tetracarboxylic dianhydride is tetrabasic carboxylic acid diester or tetrabasic carboxylic acid diester dichloride。

2. smooth orientation aligning agent for liquid crystal according to claim 1, it comprises: make at least one starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form and the compound represented by diamidogen contained (1) react and at least one of polymer that obtains；Or

Comprise simultaneously:

At least one of the polymer making the starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form react and to obtain；And

At least one of the polymer that any one at least one starting monomer all without the compound represented by photoisomerization structure and diamidogen contained (1) making tetracarboxylic dianhydride and derivant and diamidogen reacts and obtains。

3. smooth orientation aligning agent for liquid crystal according to claim 2, it comprises: make at least one starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form and the compound represented by diamidogen contained (1) react and at least one of polymer that obtains；And other polymer used with described polymer mixed；And

Other polymer described are that any one starting monomer all without photoisomerization structure making tetracarboxylic dianhydride and derivant and diamidogen reacts the polymer obtained。

4. smooth orientation aligning agent for liquid crystal according to claim 2, it comprises: make at least one starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form and the compound represented by diamidogen contained (1) react and at least one of polymer that obtains；And other polymer used with described polymer mixed；And

Other polymer described are that any one at least one starting monomer all without the compound represented by photoisomerization structure and diamidogen contained (1) making tetracarboxylic dianhydride and derivant and diamidogen reacts the polymer obtained。

5. smooth orientation aligning agent for liquid crystal according to claim 1, it comprises simultaneously: make the starting monomer containing at least one compound with photoisomerization structure in the group selecting free tetracarboxylic dianhydride and derivant thereof and diamidogen to form react and at least one of polymer that obtains；And

At least one of the polymer that any one at least one starting monomer all without the compound represented by photoisomerization structure and diamidogen contained (1) making tetracarboxylic dianhydride and derivant and diamidogen reacts and obtains。

6. smooth orientation aligning agent for liquid crystal according to any one of claim 1 to 5, at least one in the group that the diamidogen represented by its Chinese style (1) forms for selecting the diamidogen represented by free style (1-1) and the diamidogen represented by formula (1-2):

In formula (1-1) and formula (1-2), R^bTo be hydrogen ,-OH, carbon number be 1～6 alkyl or carbon number be the alkoxyl of 1～6。

7. smooth orientation aligning agent for liquid crystal according to any one of claim 1 to 5, at least one in the group that the diamidogen represented by its Chinese style (1) forms for selecting the diamidogen represented by free following formula (1-1-1)～formula (1-1-6), formula (1-1-17), formula (1-1-18), formula (1-2-1)～formula (1-2-6), formula (1-2-17) and formula (1-2-18):

8. smooth orientation aligning agent for liquid crystal according to any one of claim 1 to 5, wherein has the tetracarboxylic dianhydride of photoisomerization structure or at least one that diamidogen is the compound represented by formula (II)～formula (VI):

R²-C≡C-R³(II)

R²-C≡C-C≡C-R³(III)

R²-C≡C-R⁴-C≡C-R³(IV)

R²-N=N-R³(V)

R⁵-CH=CH-R⁵(VI)

In formula (II)～formula (V), R2 and R3 is for having-NH₂Any monovalent organic radical or there is any monovalent organic radical of-CO-O-CO-, in formula (IV), R⁴For divalent organic base, in formula (VI), R⁵For having-NH₂Or the aromatic rings of-CO-O-CO-。

9. smooth orientation aligning agent for liquid crystal according to claim 8, the wherein said tetracarboxylic dianhydride with photoisomerization structure or diamidogen are at least one in the group of the compound represented by formula (II-1), formula (II-2), formula (III-1), formula (III-2), formula (IV-1), formula (IV-2), formula (V-1)～formula (V-3), formula (VI-1) and formula (VI-2):

Described various in, it is any that binding site is not fixed to the binding site on which ring of the basis representation on structure any one carbon atom looped；

In formula (V-2), R⁶Stand alone as-CH₃、-OCH₃、-CF₃, or-COOCH₃, a is the integer of 0～2；

In formula (V-3), ring A and ring B is each independently at least one in monocyclic hydrocarbon, condensation polycyclic formula hydrocarbon and heterocycle,

R¹¹For straight-chain alkyl-sub-that carbon number is 1～20 ,-COO-,-OCO-,-NHCO-,-CONH-,-N (CH₃) CO-or-CON (CH₃)-,

R¹²For straight-chain alkyl-sub-that carbon number is 1～20 ,-COO-,-OCO-,-NHCO-,-CONH-,-N (CH₃) CO-or-CON (CH₃)-,

R¹¹And R¹²In ,-the CH of straight-chain alkyl-sub-₂-one or two can replace through-O-,

R⁷～R¹⁰It is each independently-F ,-CH₃、-OCH₃、-CF₃, or-OH, and

B～e is each independently the integer of 0～4。

10. smooth orientation aligning agent for liquid crystal according to any one of claim 1 to 5, the tetracarboxylic dianhydride wherein without photoisomerization structure is at least one in the group of the tetracarboxylic dianhydride represented by following formula (AN-I)～formula (AN-VII):

In formula (AN-I), formula (AN-IV) and formula (AN-V), X stands alone as singly-bound or-CH₂-；

In formula (AN-II), G is singly-bound, carbon number be 1～20 alkylidene ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-；

In formula (AN-II)～formula (AN-IV), Y stands alone as the one in the group of the base of following trivalent,

At least one hydrogen of described base can be replaced by methyl, ethyl or phenyl；

In formula (AN-III)～formula (AN-V), ring A¹⁰Base for the base of monocyclic hydrocarbon that carbon number is 3～10 or condensation polycyclic formula hydrocarbon that carbon number is 6～30, at least one hydrogen of described base can be replaced by methyl, ethyl or phenyl, the associative key being connected on ring links with the looped arbitrary carbon of structure, and two associative keys can link with same carbon；

In formula (AN-VI), X¹⁰Being the alkylidene of 2～6 for carbon number, Me represents methyl, and Ph represents phenyl,

In formula (AN-VII), G¹⁰Stand alone as-O-,-COO-or-OCO-；And r stands alone as 0 or 1。

11. smooth orientation aligning agent for liquid crystal according to claim 10, the wherein said tetracarboxylic dianhydride without photoisomerization structure is selected from following formula (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3), and at least one in formula (AN-16-4):

In formula (AN-1-2) and formula (AN-4-17), m is the integer of 1～12。

12. smooth orientation aligning agent for liquid crystal according to any one of claim 1 to 5, wherein not there is at least one in the group that the diamidogen of photoisomerization structure forms for selecting free following formula (DI-1)～formula (DI-16), formula (DIH-1)～formula (DIH-3) and formula (DI-31)～formula (DI-35):

In formula (DI-1), G²⁰For-CH₂-, at least one-CH₂-can be replaced by-NH-,-O-, m is the integer of 1～12, and at least one hydrogen of alkylidene can be replaced by-OH；

In formula (DI-3) and formula (DI-5)～formula (DI-7), G²¹Stand alone as singly-bound ,-NH-,-NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、-COO-、-CONH-、-CONCH₃-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m'-、-O-(CH₂)_m'-O-、-N(CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m'-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m'-CO-O-、-CO-O-(CH₂)_m'-O-CO-、-(CH₂)_m'-NH-(CH₂)_m'-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m')_k-NH-、-CO-C₃H₆-(NH-C₃H₆)_n-CO-or-S-(CH₂)_m'-S-, m' stand alone as the integer of 1～12, and k is the integer of 1～5, and n is 1 or 2；

In formula (DI-4), s stands alone as the integer of 0～2；

In formula (DI-6) and formula (DI-7), G²²Stand alone as singly-bound ,-O-,-S-,-CO-,-C (CH₃)₂-、-C(CF₃)₂-,-NH-or carbon number be the alkylidene of 1～10；

In formula (DI-2)～formula (DI-7), at least one hydrogen of cyclohexane ring and phenyl ring can by alkyl ,-OCH that-F ,-Cl, carbon number are 1～3₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl replace, and, in formula (DI-4), at least one hydrogen of phenyl ring can by a replacement in the group of the base represented by following formula (DI-4-a)～formula (DI-4-e)；

In formula (DI-4-a) and formula (DI-4-b), R²⁰Stand alone as hydrogen or-CH₃；

It is any that binding site is not fixed to the binding site on which ring of the basis representation on the looped carbon atom of structure ,-NH₂Binding site on cyclohexane ring or phenyl ring is except G²¹Or G²²Binding site beyond arbitrary position；

In formula (DI-11), r is 0 or 1；

In formula (DI-8)～formula (DI-11), the bond-NH on ring₂Binding site be arbitrary position；

In formula (DI-12), R²¹And R²²Stand alone as the alkyl or phenyl that carbon number is 1～3, G²³Standing alone as alkylidene, phenylene or the phenylene through alkyl replacement that carbon number is 1～6, w is the integer of 1～10；

In formula (DI-13), R²³Stand alone as alkyl that carbon number is 1～5, carbon number be 1～5 alkoxyl or-Cl, p stand alone as 0～3 integer, q is the integer of 0～4；

In formula (DI-14), ring B is monocyclic heteroaromatic, R²⁴For hydrogen ,-F ,-Cl, carbon number be 1～6 alkyl, carbon number be 1～6 alkoxyl, carbon number be 2～6 thiazolinyl, carbon number be the alkynyl of 1～6, q stands alone as the integer of 0～4；

In formula (DI-15), ring C is containing heteroatomic monocycle；

In formula (DI-16), G²⁴For alkylidene or Isosorbide-5-Nitrae-phenylene that singly-bound, carbon number are 2～6, r is 0 or 1；

In formula (DI-13)～formula (DI-16), it is any that binding site is not fixed to the binding site on which ring of the basis representation on the looped carbon atom of structure；

In formula (DIH-1), G²⁵For alkylidene that singly-bound, carbon number are 1～20 ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-；

In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl；

In formula (DIH-3), ring E is each independently cyclohexane ring or phenyl ring, and at least one hydrogen of described ring can be replaced by methyl, ethyl or phenyl, Y is singly-bound, carbon number be 1～20 alkylidene ,-CO-,-O-,-S-,-SO₂-、-C(CH₃)₂-or-C (CF₃)₂-；

In formula (DIH-2) and formula (DIH-3), the bond-CONHNH on ring₂Binding site be arbitrary position；

In formula (DI-31), G²⁶For singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-or-(CH₂)_m'-, m' is the integer of 1～12, R²⁵For alkyl, phenyl that carbon number is 3～30, having the base of steroid skeleton or the base represented by following formula (DI-31-a), in described alkyl, at least one hydrogen can be replaced by-F, at least one-CH₂-can be replaced by-O-,-CH=CH-or-C ≡ C-, the hydrogen of described phenyl can by-F ,-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃, carbon number be 3～30 alkyl or alkoxyl that carbon number is 3～30 replace, the bond-NH on phenyl ring₂Binding site represent in described ring for arbitrary position,

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For bond base, they stand alone as singly-bound or carbon number is the alkylidene of 1～12, the more than one-CH of described alkylidene₂-can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-, ring B²¹, ring B²², ring B²³And ring B²⁴Stand alone as Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-dioxane-2,5-bis-base, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,5-bis-base, naphthalene-2,7-bis-base or anthracene-9,10-bis-base, ring B²¹, ring B²², ring B²³And ring B²⁴In, at least one hydrogen can by-F or-CH₃Replacing, s, t and u stand alone as the integer of 0～2, they add up to 1～5, when s, t or u are 2, two bond bases in each bracket can be identical, it is also possible to different, and two rings can be identical, it is also possible to different,

R²⁶Replace alkyl for the fluorine that alkyl that hydrogen ,-F ,-OH, carbon number are 1～30, carbon number are 1～30, carbon number be 1～30 alkoxyl ,-CN ,-OCH₂F、-OCHF₂, or-OCF₃, described carbon number is at least one-CH of the alkyl of 1～30₂-can be replaced by the base with the bivalence represented by following formula (DI-31-b),

In formula (DI-31-b), R²⁷And R²⁸Standing alone as the alkyl that carbon number is 1～3, v is the integer of 1～6；

In formula (DI-32) and formula (DI-33), G³⁰Stand alone as singly-bound ,-CO-or-CH₂-, R²⁹Stand alone as hydrogen or-CH₃, R³⁰Alkyl or carbon number for hydrogen, carbon number are 1～20 are the thiazolinyl of 2～20；

One hydrogen of the phenyl ring in formula (DI-33) can be replaced by the alkyl or phenyl that carbon number is 1～20, and

In formula (DI-32) and formula (DI-33), it is any that binding site is not fixed to the binding site on which ring of the basis representation on structure any one carbon atom looped；

In formula (DI-34) and formula (DI-35), G³¹Stand alone as-O-or carbon number is the alkylidene of 1～6, G³²It is the alkylidene of 1～3 for singly-bound or carbon number,

R³¹It is the alkyl of 1～20 for hydrogen or carbon number, at least one-CH of described alkyl₂-can be replaced by-O-,-CH=CH-or-C ≡ C-, R³²It is the alkyl of 6～22 for carbon number, R³³It is the alkyl of 1～22 for hydrogen or carbon number, ring B²⁵For Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1, and-the NH that bond is on phenyl ring₂Represent that binding site on which ring is any。

13. smooth orientation aligning agent for liquid crystal according to claim 12, the wherein said diamidogen without photoisomerization structure is the free following formula of choosing (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-17), formula (DI-5-28), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI-16-1), formula (DI-31-44), and at least one in the group that forms of formula (DIH-2-1):

In formula (DI-5-1), formula (DI-5-12), formula (DI-5-13) and formula (DI-7-3), m is the integer of 1～12；

In formula (DI-5-30), k is the integer of 1～5；And

In formula (DI-7-3), n is 1 or 2；

14. smooth orientation aligning agent for liquid crystal according to any one of claim 1 to 5, it is possibly together with at least one selecting free alkenyl substituted Na Dike imide compound, have in the compound group that the compound of free-radical polymerised unsaturated double-bond, piperazine compound, isoxazoline compound and epoxide form。

15. smooth orientation aligning agent for liquid crystal according to any one of claim 1 to 5, it is for the manufacture of lateral electric-field type liquid crystal display cells。

16. a liquid crystal orientation film, it is to be formed by the light orientation aligning agent for liquid crystal according to any one of claim 1 to 15。

17. a liquid crystal display cells, it includes liquid crystal orientation film according to claim 16。

18. a lateral electric-field type liquid crystal display cells, it includes liquid crystal orientation film according to claim 16。