CN105524626A - Liquid crystal orientation agent containing polyamide acid and ramification thereof, liquid crystal orientation film and liquid crystal display element - Google Patents

Abstract

The invention relates to liquid crystal orientation agent containing polyamide acid and ramification thereof, a liquid crystal orientation film and a liquid crystal display element. The liquid crystal orientation agent contains at least one polymer (A) selected from polyamide acid and ramification thereof obtained by allowing tetracarboxylic acid dianhydride to react with diamine. The tetracarboxylic acid dianhydride contains at least one kind of tetracarboxylic acid dianhydride and at least one kind of tetracarboxylic acid dianhydride with alicyclic structures or aliphatic series structures represented by the following formula (1). The diamine contains at least one kind of diamine with photoreactive structures. By use of the liquid crystal orientation agent, a liquid crystal orientation film which is not liable to peel off or damage can be easily formed. In addition, a liquid crystal display element with the liquid crystal orientation film is characterized in that even if the liquid crystal display element is exposed in intense light for a long time, the display quality will not decrease and so-called spots or incidental images will not be generated.

Description

Comprise the liquid crystal aligning agent of polyamic acid or derivatives thereof, liquid crystal orientation film and liquid crystal display device

Technical field

The present invention relates to a kind of containing using the liquid crystal aligning agent of specific tetracarboxylic dianhydride and the polyamic acid or derivatives thereof that obtains, use this liquid crystal aligning agent and the liquid crystal orientation film that formed and the liquid crystal display device with this liquid crystal orientation film.Moreover the term " liquid crystal aligning agent " in the present invention refers to the composition containing polymkeric substance forming liquid crystal orientation film.

Background technology

The various display unit such as view finder, projection display equipment of the watch-dog (monitor) of Personal Computer (personalcomputer), liquid crystal TV set, pick up camera, and then the nowadays commercialization and the main flow of the liquid crystal display device generally circulated is the display element using nematic liquid crystal such as the photoelectron related elements such as optical print head, optical Fourier transform element, light valve.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 order to one of problem improving these patterns, namely visual angle is narrow and small in recent years, propose there is the TN type liquid crystal display device using optical compensation films, and with vertical orientated (Multi-domainVerticalAlignment vertical orientated with the multizone of the technology of pop-up structure thing, MVA) the coplanar switching (In-PlaneSwitching of pattern or Transverse electric-field type, IPS) pattern, fringing field switch (FringeFieldSwitching, FFS) pattern, and practical.

The development of the technology of liquid crystal display device is not only realized 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 device, particularly liquid crystal orientation film is one of important materials being related to display quality, along with the high-quality of liquid crystal display device, makes the performance boost of alignment films become important.

Liquid crystal orientation film uses liquid crystal aligning agent and formed.At present, the main liquid crystal aligning agent used is the polyimide dissolving solution (varnish) in organic solvent making polyamic acid or solubility.After this solution coat is on substrate, carries out film forming by methods such as heating and form polyimide system liquid crystal orientation film.

About in order to arrange the orientation process method of liquid crystal molecule at liquid crystal orientation film rule of surface, industrially widely use the rubbing manipulation can carrying out big area high speed processing easily.Rubbing manipulation uses to plant the cloth that hair has the fibers such as nylon, artificial silk, polyester, in the process that the surface of a direction to liquid crystal orientation film rubs, can obtain the consistent orientation of liquid crystal molecule thus.But, the problem dust that liquid crystal orientation film produces because of wearing and tearing being indicated for friction treatment or display quality is declined to the scuffing caused by liquid crystal orientation film and produce the problems such as electrostatic, thus replace the exploitation of the orientation process method of rubbing manipulation to come to life.

Instead rubbing manipulation orientation process method and what attracted attention is irradiate light to carry out the light orientation process method of implementation orientation process.Light orientation process method is there has been proposed the multiple epitaxy mechanisms such as photolysis method, photoisomerization method, photodimerization method, optical cross-linking method (such as with reference to non-patent literature 1, patent documentation 1 and patent documentation 2).Compared with rubbing manipulation, optical alignment method has as inferior advantage: the homogeneity of orientation is high, and is non-contacting orientation process method because of it, therefore film can not be impaired, can reduce airborne dust or electrostatic etc. and can produce the bad reason of the display of liquid crystal display device.But for rubbing manipulation, anchoring energy (anchoringenergy) is little and orientation is low, its response speed becoming liquid crystal molecule reduces or produces the reason of burning trace, therefore seeks improvement.

In order to overcome the shortcoming of this kind of light orientation process method, following material is proposed: use has the polyimide of liquid crystal liquid crystal property and heat-treats this material when masking, the material (such as with reference to patent documentation 3, patent documentation 4) making the anisotropy of film strengthen thus.But the optical alignment film applying this kind of technology exists following problem: easily produce film when making panel and peel off or wear and tear, the foreign matter produced can make the display quality of panel decline.

[prior art document]

[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 2010-049230

[patent documentation 4] Japanese Patent Laid-Open 2010-197999

[non-patent literature]

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

Summary of the invention

[inventing problem to be solved]

Problem of the present invention is to provide a kind of liquid crystal aligning agent, even if it can provide to be exposed to the liquid crystal aligning agent that display quality under strong light also can not decline, the liquid crystal orientation film that can not produce the liquid crystal display device of so-called spot or image retention has for a long time, the problems such as film peels off, wearing and tearing can be solved and described liquid crystal orientation film can be formed.

[solving the technique means of problem]

The people such as the present inventor find: by using the liquid crystal aligning agent containing polyamic acid or derivatives thereof, can obtain film hardness is improved, do not produce described as the liquid crystal orientation film of foreign matter, thus completing the present invention, described polyamic acid or derivatives thereof is simultaneously using the tetracarboxylic dianhydride represented by formula (1), be synthesized into as raw material with the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure.

The present invention is made up of following item.

[1] liquid crystal aligning agent, it contains to be selected from makes tetracarboxylic dianhydride and diamines carry out reacting and at least one polymkeric substance (a) in the polyamic acid obtained and derivative thereof, and

Described tetracarboxylic dianhydride contains at least one of the tetracarboxylic dianhydride represented by following formula (1) and at least one in being selected from the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure,

Described diamines contains the diamines that at least one has photoreactivity structure,

In formula (1), m is the integer of 1 ~ 10.

[2] liquid crystal aligning agent Gen Ju [1], the tetracarboxylic dianhydride of tetracarboxylic dianhydride represented by following formula (1-8) of its Chinese style (1):

[3] according to [1] or the liquid crystal aligning agent described in [2], wherein there is the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure for being selected from least one in the compound represented by following formula (3) ~ formula (9):

At least one of hydrogen in above-mentioned formula can by-CH ₃,-CH ₂cH ₃or phenyl replaces.

[4] according to [1] or the liquid crystal aligning agent described in [2], wherein there is the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure for being selected from least one in the compound represented by following formula (3-1):

In formula (3-1), R is hydrogen ,-CH independently ₃,-CH ₂cH ₃or phenyl.

[5] according to [1] or the liquid crystal aligning agent described in [2], the tetracarboxylic dianhydride wherein with alicyclic structure is 1,2,3,4-tetramethylene tetracarboxylic dianhydride.

[6] according to the liquid crystal aligning agent according to any one of [1] to [5], the diamines wherein with photoreactivity structure is 4,4 '-chrysoidine.

[7] according to the liquid crystal aligning agent according to any one of [1] to [6], at least one wherein in the group of diamines also containing the compound be selected from represented by following formula (D-1) ~ formula (D-5):

In formula (D-2) and formula (D-4), X and Y is the alkylidene group of singly-bound ,-O-,-NH-,-S-or carbon number 1 ~ 6;

At least one hydrogen of phenyl ring can by-CH ₃replace;

In formula (D-4), a is the integer of 1 ~ 8; And,

In formula (D-5), Ra is the alkyl of carbon number 1 ~ 3.

[8] according to liquid crystal aligning agent according to any one of [1] to [5], it is also containing at least one polymkeric substance (b) be selected from polyamic acid and derivative thereof that the tetracarboxylic dianhydride making not have photoreactivity structure and the diamines without photoreactivity structure carry out reacting and obtain.

[9] liquid crystal aligning agent Gen Ju [8], the tetracarboxylic dianhydride used in the synthesis of wherein polymkeric substance (b) contains at least one be selected from following formula (3) ~ formula (13):

At least one of hydrogen in above-mentioned formula can by-CH ₃,-CH ₂cH ₃or phenyl replaces.

[10] according to [8] or the liquid crystal aligning agent described in [9], the diamines used in the synthesis of wherein polymkeric substance (b) contains at least one be selected from following formula (D-1) ~ formula (D-5):

In formula (D-2) and formula (D-4), X and Y is the alkylidene group of singly-bound ,-O-,-NH-,-S-or carbon number 1 ~ 6;

At least one hydrogen of phenyl ring can by-CH ₃replace;

In formula (D-4), a is the integer of 1 ~ 8; And,

In formula (D-5), Ra is the alkyl of carbon number 1 ~ 3.

[11] according to the liquid crystal aligning agent according to any one of [1] to [10], it is also containing at least one be selected from the group of the compound be made up of oxazine compounds, oxazoline compound, epoxy compounds and silane coupling agent.

[12] liquid crystal aligning agent Gen Ju [11], wherein silane coupling agent is for being selected from by 2-(3,4-expoxycyclohexyl) at least one in the group of compound that forms of ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane, p-aminophenyl Trimethoxy silane, p-aminophenyl triethoxyl silane, 3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane and 3-glycidoxypropyl triethoxyl silane.

[13] according to the liquid crystal aligning agent according to any one of [1] to [12], it contains at least one solvent be selected from alcohol, ether and ketone.

[14] according to the liquid crystal aligning agent according to any one of [1] to [13], it contains at least one solvent be selected from aklylene glycol alkyl ether derivative, two alkylene glycol dialkylether derivatives and propanediol derivative.

[15] liquid crystal orientation film, it is formed by the liquid crystal aligning agent according to any one of [1] to [14].

[16] liquid crystal display device, it comprises the liquid crystal orientation film Gen Ju [15].

[effect of invention]

Be coated with liquid crystal aligning agent of the present invention, carry out calcining the film hardness of formed liquid crystal orientation film excellence, liquid crystal aligning is also good, and described liquid crystal aligning agent contains tetracarboxylic dianhydride represented by contained (1), have the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure and have the raw material of compound of photoreactivity structure and the polymkeric substance that obtains.In addition, the liquid crystal display device comprising liquid crystal orientation film of the present invention has good display characteristic, and electrical characteristic are also good.And, the liquid crystal aligning agent that described polymkeric substance is prepared with other polymer blend is also demonstrated same effect.

Embodiment

Polymkeric substance (a) is that the raw material of the compound making the tetracarboxylic dianhydride represented by contained (1), have the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure and have photoreactivity structure carries out reacting and the polymkeric substance obtained.The starting compound used in the synthesis of polymkeric substance is specifically described.

The concrete example of the tetracarboxylic dianhydride represented by formula (1) is represented by following formula (1-1) ~ formula (1-10).

In order to promote the orientation of liquid crystal, the importantly rectilinearity at alkylidene group position, preferred compound is the following formula (1-4) of even number, formula (1-6), formula (1-8) or formula (1-10) by the carbon number of the alkylidene group linked between the two.

Wherein, just demonstrate with regard to maximum orientation, the compound more preferably represented by following formula (1-8).

There is the concrete example of the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure represented by formula (3) ~ formula (9).

At least one of hydrogen in above-mentioned formula can by-CH ₃,-CH ₂cH ₃or phenyl replaces.

Wherein, the tetracarboxylic dianhydride represented by formula (3) of the particular significant effect of electrical characteristic is preferably promoted.

Tetracarboxylic dianhydride represented by formula (3) more specifically can be represented by following formula (3-1).

In formula (3-1), R is hydrogen ,-CH independently ₃,-CH ₂cH ₃or phenyl.

The concrete example of the tetracarboxylic dianhydride represented by formula (3-1) can enumerate the compound represented by following formula (3-1-1) ~ formula (3-1-7).

In order to make polymkeric substance (a) have photoreactivity structure, preferably the diamines with photoreactivity structure or the tetracarboxylic dianhydride with photoreactivity structure are used for raw material.Also can be used together the diamines with photoreactivity structure and the tetracarboxylic dianhydride with photoreactivity structure.These have the compound of preferred example represented by following formula (I-1) ~ formula (I-4) of the monomer of photoreactivity structure.

Wherein, manifest with regard to larger anisotropy during with regard to forming alignment films, the compound more preferably represented by formula (I-3).

The tetracarboxylic dianhydride with alicyclic structure or aliphatic structure is 10 % by weight ~ 90 % by weight relative to the copolymerization ratio of the tetracarboxylic dianhydride represented by formula (1), with regard to the viewpoint of the orientation of liquid crystal molecule, and preferably 10 % by weight ~ 60 % by weight.And then with regard to the viewpoint improving electrical characteristic or film hardness, copolymerization ratio more preferably 20 % by weight ~ 50 % by weight.

In polymkeric substance (a), except the diamines shown in described formula (I-1) ~ formula (I-3), also can make following formula (D-1), formula (D-2-1) ~ formula (D-2-9), formula (D-3), formula (D-4-1) ~ formula (D-4-72) and the diamines represented by formula (D-5-1) ~ formula (D-5-3).

Secondly, to polymkeric substance (a) fusion and the polymkeric substance (b) that uses is described in detail.Polymkeric substance (b) uses the polymkeric substance synthesized by tetracarboxylic dianhydride or diamines without photoreactivity structure.For the tetracarboxylic dianhydride used in the synthesis of polymkeric substance (b), there is no particular restriction, the compound of concrete example represented by formula (3) ~ formula (13) of the tetracarboxylic dianhydride that can preferably use.

At least one of hydrogen in above-mentioned formula can by-CH ₃,-CH ₂cH ₃or phenyl replaces.

The diamines used in the synthesis of polymkeric substance (b) is also not particularly limited, the concrete example of the diamines that can preferably use is formula (D-1), formula (D-2-1) ~ formula (D-2-9), formula (D-3), formula (D-4-1) ~ formula (D-4-72) and the compound represented by formula (D-5-1) ~ formula (D-5-3).

The scope that ratio of components (weight ratio) when using at the middle blending of polymers (b) of polymkeric substance (a) is polymkeric substance (a)/polymkeric substance (b)=1/9 ~ 9/1, with regard to the aspect of liquid crystal aligning, the scope of content preferred polymers (a)/polymkeric substance (b)=2/8 ~ 7/3, and then with regard to the aspect of electrical characteristic, the scope of more preferably polymkeric substance (a)/polymkeric substance (b)=2/8 ~ 5/5.

In addition, tetracarboxylic dianhydride other than the above or diamines can be used in scope electrical characteristic or orientation not impacted.

Tetracarboxylic dianhydride other than the above for the manufacture of polyamic acid of the present invention and derivative thereof is described.Tetracarboxylic dianhydride used in the present invention can select in known tetracarboxylic dianhydride.This kind of tetracarboxylic dianhydride can be the tetracarboxylic dianhydride in the arbitrary group belonging to the fragrant family of the direct bond of dicarboxylic anhydride on aromatic nucleus (comprising assorted aromatic ring) and the not direct fatty family of bond on aromatic nucleus (comprising heterocycle system) of dicarboxylic anhydride.

Specifically following formula (AN-1), tetracarboxylic dianhydride represented by formula (AN-3) ~ formula (AN-16-14) can be enumerated.

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

In formula (AN-1), G ¹¹for the alkylidene group of singly-bound, carbon number 1 ~ 12, Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene.X ¹¹be singly-bound or-CH independently ₂-.G ¹²for following base.

And, R ¹¹for hydrogen or-CH ₃.

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-3)]

In formula (AN-3), ring A ¹¹for 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), G ¹³for singly-bound ,-(CH ₂) _m-,-O-,-S-,-C (CH ₃) ₂-,-SO ₂-,-CO-,-C (CF ₃) ₂-or the base of the following divalence represented by formula (G13-1), m is the integer of 1 ~ 12.Ring A ¹¹be separately cyclohexane ring or phenyl ring.G ¹³ring A can be binding on ¹¹arbitrary position.

In formula (G13-1), G ^13aand G ^13bthe base of the divalence separately represented by singly-bound ,-O-or-NHCO-.Preferred Isosorbide-5-Nitrae-the 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), R ¹¹for hydrogen or-CH ₃.Binding site is not fixed on the R on the carbon atom forming phenyl ring ¹¹represent that the binding site 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), X ¹¹be singly-bound or-CH independently ₂-.X ¹²for-CH ₂-,-CH ₂cH ₂-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), X ¹¹for singly-bound.

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), X ¹¹for singly-bound or-CH ₂-.R ¹²for hydrogen ,-CH ₃,-CH ₂cH ₃or phenyl, ring A ¹²for 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 separately 0 or 1.

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

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

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

In formula (AN-11), ring A ¹¹be cyclohexane ring or phenyl ring independently.

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 A ¹¹be separately 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), X ¹³for the alkylidene group of carbon number 2 ~ 6, 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), G ¹⁴be-O-,-COO-or-OCO-independently, r is 0 or 1 independently.

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 tetracarboxylic dianhydride other than the above, following compound can be enumerated.

Carry out describing to the appropriate materials improving each characteristic in above-mentioned acid dianhydride.When paying attention to the orientation promoting liquid crystal, preferred formula (AN-1), formula (AN-3) and the compound represented by formula (AN-4), particularly preferably formula (AN-1-2), formula (AN-3-2), formula (AN-4-17) and the compound represented by formula (AN-4-29), wherein in formula (AN-1-2), be preferred during m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.

When paying attention to the transmitance promoting liquid crystal display device, in above-mentioned acid dianhydride, preferred formula (AN-1-2), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-16-3) and the compound represented by formula (AN-16-4), wherein in formula (AN-1-2), be preferred during m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.

Paying attention to the voltage retention (voltageholdingratio promoting liquid crystal display device, VHR) when, in above-mentioned acid dianhydride, preferred formula (AN-1-2), formula (AN-4-17), formula (AN-4-30), formula (AN-16-3) and the compound represented by formula (AN-16-4), wherein in formula (AN-1-2), be preferred during m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.

As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (remnant dc electricity (DirectCurrent, DC)) in alignment films is improved.When paying attention to this object, in above-mentioned acid dianhydride, preferred formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and the compound represented by formula (AN-11-3).

Diamines for the manufacture of polyamic acid of the present invention and derivative thereof is described.Diamines can enumerate the compound represented by group be made up of following formula (DI-1) ~ formula (DI-16), formula (DIH-1) ~ formula (DIH-3) and formula (DI-31) ~ formula (DI-35).Moreover, about described diamines, formula (D-1) is contained in formula (DI-4), formula (D-2) and formula (D-5) are contained in formula (DI-5), formula (D-3) is contained in formula (DI-13), and formula (D-4) is contained in formula (DI-7).

In formula (DI-1), G ²⁰for-CH ₂-, at least one-CH ₂-can be replaced by-NH-,-O-, m is the integer of 1 ~ 12, and at least one hydrogen of alkylidene group can be replaced by-OH.In formula (DI-3) and formula (DI-5) ~ formula (DI-7), G ²¹be singly-bound ,-NH-,-NCH independently ₃-,-O-,-S-,-S-S-,-SO ₂-,-CO-,-COO-,-CONH-,-CONCH ₃-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-(CH ₂) _{m '}-,-O-(CH ₂) _{m '}-O-,-N (Ra)-(CH ₂) _k-N (Ra)-,-(O-C ₂h ₄) _{m '}-O-,-O-CH ₂-C (CF ₃) ₂-CH ₂-O-,-O-CO-(CH ₂) _{m '}-CO-O-,-CO-O-(CH ₂) _{m '}-O-CO-,-(CH ₂) _{m '}-NH-(CH ₂) _{m '}-,-CO-(CH ₂) _k-NH-(CH ₂) _k-,-(NH-(CH ₂) _{m '}) _k-NH-,-CO-C ₃h ₆-(NH-C ₃h ₆) _n-CO-or-S-(CH ₂) _{m '}the integer of-S-, m ' be independently 1 ~ 12, Ra is the alkyl of carbon number 1 ~ 3, and k is the integer of 1 ~ 5, and n is 1 or 2.In formula (DI-4), s is the integer of 0 ~ 2 independently.In formula (DI-6) and formula (DI-7), G ²²be singly-bound ,-O-,-S-,-CO-,-C (CH independently ₃) ₂-,-C (CF ₃) ₂-or the alkylidene group of carbon number 1 ~ 10.In formula (DI-2) ~ formula (DI-7), at least one hydrogen of cyclohexane ring and phenyl ring can by the alkylidene group ,-OCH of-F ,-Cl, carbon number 1 ~ 3 ₃,-OH ,-CF ₃,-CO ₂h ,-CONH ₂,-NHC ₆h ₅, phenyl or benzyl replace, in addition, in formula (DI-4), at least one hydrogen of phenyl ring can by a replacement in the group of the base be selected from represented by following formula (DI-4-a) ~ formula (DI-4-e).The binding site of basis representation on this ring that binding site is not fixed on the carbon atom forming ring is any ,-NH ₂binding site on cyclohexane ring or phenyl ring is for removing G ²¹or G ²²binding site beyond arbitrary position.

In formula (DI-4-a) and formula (DI-4-b), R ²⁰be hydrogen or-CH independently ₃.

In formula (DI-11), r is 0 or 1.In formula (DI-8) ~ formula (DI-11) ,-NH of bond on ring ₂binding site be arbitrary position.

In formula (DI-12), R ²¹and R ²²be the alkyl or phenyl of carbon number 1 ~ 3 independently, G ²³be the alkylidene group of carbon number 1 ~ 6, phenylene or the phenylene through alkyl replacement independently, w is the integer of 1 ~ 10.In formula (DI-13), R ²³be the alkyl of carbon number 1 ~ 5 independently, the alkoxyl group of carbon number 1 ~ 5 or-Cl, p be independently 0 ~ 3 integer, q is the integer of 0 ~ 4.In formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴for alkyl, the alkoxyl group of carbon number 1 ~ 6, the thiazolinyl of carbon number 2 ~ 6, the alkynyl of carbon number 1 ~ 6 of hydrogen ,-F ,-Cl, carbon number 1 ~ 6, q is the integer of 0 ~ 4 independently.In formula (DI-15), ring C is for comprising heteroatomic monocycle.In formula (DI-16), G ²⁴for alkylidene group or the Isosorbide-5-Nitrae-phenylene of singly-bound, carbon number 2 ~ 6, r is 0 or 1.In formula (DI-13) ~ formula (DI-16), the binding site of basis representation on this ring that binding site is not fixed on the carbon atom forming ring is any.

In formula (DIH-1), G ²⁵for alkylidene group ,-CO-,-O-,-the S-,-SO of singly-bound, carbon number 1 ~ 20 ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-.In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of this ring can be replaced by methyl, ethyl or phenyl.In formula (DIH-3), ring E is separately cyclohexane ring or phenyl ring, and at least one hydrogen of this ring can be replaced by methyl, ethyl or phenyl, and Y is alkylidene group ,-CO-,-O-,-the S-,-SO of singly-bound, carbon number 1 ~ 20 ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-.In formula (DIH-2) and formula (DIH-3) ,-CONHNH of bond on ring ₂binding site be arbitrary position.

As the diamines without side chain of above-mentioned formula (DI-1) ~ formula (DI-16), the concrete example of following formula (DI-1-1) ~ formula (DI-16-1) can be enumerated.

The example of the diamines represented by following expression (DI-1).

In formula (DI-1-7) and formula (DI-1-8), k is separately the integer of 1 ~ 3.

The example of the diamines represented by following expression (DI-2) ~ formula (DI-3).

The example of the diamines represented by following expression (DI-4).

The example of the diamines represented by following expression (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, in formula (DI-5-38) and formula (DI-5-39), k is the integer of 1 ~ 5, in formula (DI-5-40), n is the integer of 1 or 2.

The example of the diamines represented by following expression (DI-6).

The example of the diamines represented by following expression (DI-7).

In formula (DI-7-3) and formula (DI-7-4), m is the integer of 1 ~ 12, and n is 1 or 2 independently.

The example of the diamines represented by following expression (DI-8).

The example of the diamines represented by following expression (DI-9).

The example of the diamines represented by following expression (DI-10).

The example of the diamines represented by following expression (DI-11).

The example of the diamines represented by following expression (DI-12).

The example of the diamines represented by following expression (DI-13).

The example of the diamines represented by following expression (DI-14).

The example of the diamines represented by following expression (DI-15).

The example of the diamines represented by following expression (DI-16).

Two hydrazides are described.As known two hydrazides without side chain, following formula (DIH-1) ~ formula (DIH-3) can be enumerated.

In formula (DIH-1), G ²⁵for alkylidene group ,-CO-,-O-,-the S-,-SO of singly-bound, carbon number 1 ~ 20 ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-.In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of this ring can be replaced by methyl, ethyl or phenyl.In formula (DIH-3), ring E is separately cyclohexane ring or phenyl ring, and at least one hydrogen of this ring can be replaced by methyl, ethyl or phenyl, and Y is alkylidene group ,-CO-,-O-,-the S-,-SO of singly-bound, carbon number 1 ~ 20 ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-.In formula (DIH-2) and formula (DIH-3) ,-CONHNH of bond on ring ₂binding site be arbitrary position.

The example of following expression (DIH-1) ~ formula (DIH-3).

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

This kind of non-side chain type diamines and two hydrazides have the effect making the ion density reduction etc. of liquid crystal display device improve electrical characteristic.When using non-side chain type diamines and/or two hydrazides as diamines in order to be manufactured on the polyamic acid or derivatives thereof used in liquid crystal aligning agent of the present invention, preferably its ratio shared in the total amount of diamines and two hydrazides is set to 0mol% (molar percentage) ~ 90mol%, is more preferably set to 0mol% ~ 50mol%

Side chain type diamines is described.As the side chain radical of side chain type diamines, following base can be enumerated.

As side chain radical, first can enumerate: alkyl, alkoxyl group, 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 bases of carbon number 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, also can be branched.

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

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

As the diamines with side chain, the compound represented by following formula (DI-31) ~ formula (DI-35) can be enumerated.

In formula (DI-31), G ²⁶for singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH ₂o-,-OCH ₂-,-CF ₂o-,-OCF ₂-or-(CH ₂) _{m '}-, m ' is the integer of 1 ~ 12.R ²⁵for the base represented by the alkyl of carbon number 3 ~ 30, phenyl, the base with steroid skeleton or following formula (DI-31-a).In this alkyl, at least one hydrogen can be replaced by-F, at least one-CH ₂-can be replaced by-O-,-CH=CH-or-C ≡ C-.The hydrogen of this phenyl can by-F ,-CH ₃,-OCH ₃,-OCH ₂f ,-OCHF ₂,-OCF ₃, the alkyl of carbon number 3 ~ 30 or carbon number 3 ~ 30 alkoxyl group replace.-the NH of bond on phenyl ring ₂binding site represent for arbitrary position in this ring, this binding site preferably between position or contraposition.

In formula (DI-31-a), G ²⁷, G ²⁸and G ²⁹for bond base, they are the more than one-CH of the alkylidene group of singly-bound or carbon number 1 ~ 12, this alkylidene group independently ₂-can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-.Ring B ²¹, ring B ²², ring B ²³and ring B ²⁴be Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-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 independently, ring B ²¹, ring B ²², ring B ²³and ring B ²⁴in, at least one hydrogen can by-F or-CH ₃replace, s, t and u are the integer of 0 ~ 2 independently, and they add up to 1 ~ 5, when s, t or u are 2,2 bond bases in each bracket can be identical, also can be different, and 2 rings can be identical, also can be different.R ²⁶for alkyl, the fluorine substituted alkyl of carbon number 1 ~ 30, alkoxyl group ,-the CN ,-OCH of carbon number 1 ~ 30 of hydrogen ,-F ,-OH, carbon number 1 ~ 30 ₂f ,-OCHF ₂, or-OCF ₃, at least one-CH of the alkyl of this carbon number 1 ~ 30 ₂-can the base of divalence represented by following formula (DI-31-b) replace.R ²⁶preferred example be the alkyl of carbon number 1 ~ 30 and the alkoxyl group of carbon number 1 ~ 30.

In formula (DI-31-b), R ²⁷and R ²⁸be the alkyl of carbon number 1 ~ 3 independently, v is the integer of 1 ~ 6.

In formula (DI-32) and formula (DI-33), G ³⁰be singly-bound ,-CO-or-CH independently ₂-, R ²⁹be hydrogen or-CH independently ₃, R ³⁰for the alkyl of hydrogen, carbon number 1 ~ 20 or the thiazolinyl of carbon number 2 ~ 20.At least one hydrogen of phenyl ring in formula (DI-33) can be replaced by the alkyl or phenyl of carbon number 1 ~ 20.And in formula (DI-32) and formula (DI-33), the binding site of basis representation in this ring that binding site is not fixed on any one carbon atom forming ring is any.

In formula (DI-34) and formula (DI-35), G ³¹be the alkylidene group of-O-or carbon number 1 ~ 6 independently, G ³²for the alkylidene group of singly-bound or carbon number 1 ~ 3.R ³¹for the alkyl of hydrogen or carbon number 1 ~ 20, at least one-CH of this alkyl ₂-can be replaced by-O-,-CH=CH-or-C ≡ C-.R ³²for the alkyl of carbon number 6 ~ 22, R ³³for the alkyl of hydrogen or carbon number 1 ~ 22.Ring B ²⁵for Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1.And ,-the NH of bond on phenyl ring ₂represent that binding site on this ring be arbitrarily, but preferably independence and relative to G ³¹binding site be between position or contraposition.

The concrete example of following Exemplary sidechain type diamines.As the diamines with side chain of above-mentioned 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 the compound represented by following expression (DI-31).

In formula (DI-31-1) ~ formula (DI-31-11), R ³⁴for the alkyl of carbon number 1 ~ 30 or the alkoxyl group of carbon number 1 ~ 30, the alkyl of preferred carbon number 5 ~ 25 or the alkoxyl group of carbon number 5 ~ 25.R ³⁵for the alkyl of carbon number 1 ~ 30 or the alkoxyl group of carbon number 1 ~ 30, the alkyl of preferred carbon number 3 ~ 25 or the alkoxyl group of carbon number 3 ~ 25.

In formula (DI-31-12) ~ formula (DI-31-17), R ³⁶for the alkyl of carbon number 4 ~ 30, the alkyl of preferred carbon number 6 ~ 25.R ³⁷for the alkyl of carbon number 6 ~ 30, the alkyl of preferred carbon number 8 ~ 25.

In formula (DI-31-18) ~ formula (DI-31-43), R ³⁸for the alkyl of carbon number 1 ~ 20 or the alkoxyl group of carbon number 1 ~ 20, the alkyl of preferred carbon number 3 ~ 20 or the alkoxyl group of carbon number 3 ~ 20.R ³⁹for the alkyl of hydrogen ,-F, carbon number 1 ~ 30, alkoxyl group ,-the CN ,-OCH of carbon number 1 ~ 30 ₂f ,-OCHF ₂or-OCF ₃, the alkyl of preferred carbon number 3 ~ 25 or the alkoxyl group of carbon number 3 ~ 25.And, G ³³for the alkylidene group of carbon number 1 ~ 20.

The example of the compound represented by following expression (DI-32).

The example of the compound represented by following expression (DI-33).

The example of the compound represented by following expression (DI-34).

In formula (DI-34-1) ~ formula (DI-34-12), R ⁴⁰for the alkyl of hydrogen or carbon number 1 ~ 20, the alkyl of preferred hydrogen or carbon number 1 ~ 10, and, R ⁴¹for the alkyl of hydrogen or carbon number 1 ~ 12.

The example of the compound represented by following expression (DI-35).

In formula (DI-35-1) ~ formula (DI-35-3), R ³⁷for the alkyl of carbon number 6 ~ 30, R ⁴¹for the alkyl of hydrogen or carbon number 1 ~ 12.

As the diamines in the present invention, the diamines beyond formula (DI-1-1) ~ formula (DI-16-1), formula (DIH-1-1) ~ formula (DIH-3-6) and the diamines represented by formula (DI-31-1) ~ formula (DI-35-3) also can be used.As this kind of diamines, include, for example the compound represented by following formula (DI-36-1) ~ formula (DI-36-13).

In formula (DI-36-1) ~ formula (DI-36-8), R ⁴²separately represent the alkyl of carbon number 3 ~ 30.

In formula (DI-36-9) ~ formula (DI-36-11), e is the integer of 2 ~ 10, in formula (DI-36-12), and R ⁴³be separately hydrogen ,-NHBoc or-N (Boc) ₂, R ⁴³at least one be-NHBoc or-N (Boc) ₂, in formula (DI-36-13), R ⁴⁴for-NHBoc or-N (Boc) ₂, and m is the integer of 1 ~ 12.Herein, Boc is tert-butoxycarbonyl.

When paying attention to the orientation promoting liquid crystal further, in above-mentioned diamines and two hydrazides, preferred use 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 the diamines represented by formula (DI-11-2), wherein in formula (DI-5-1), preferred m=2, 4 or 6, particularly preferably m=4, in formula (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in formula (DI-5-13), preferred m=1, or 2, particularly preferably m=1.

When paying attention to promoting transmitance, in above-mentioned diamines and two hydrazides, preferred use formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-5-5), formula (DI-5-24) and the diamines represented by formula (DI-7-3), the diamines particularly preferably represented by formula (DI-2-1).In formula (DI-5-1), m=2,4 or 6 time be preferably, particularly preferably m=4, in formula (DI-7-3), preferred m=2 or 3, n=1 or 2, particularly preferably m=1.

When paying attention to the VHR promoting liquid crystal display device, in above-mentioned diamines and two hydrazides, preferred use 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 the diamines represented by formula (DI-13-1), particularly preferably formula (DI-2-1), formula (DI-5-1) and the diamines represented by formula (DI-13-1).Wherein in formula (DI-5-1), particularly preferably m=1, in formula (DI-5-30), particularly preferably k=2.

As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, in above-mentioned diamines and two hydrazides, preferred use 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) and the diamines represented by formula (DI-16-1), particularly preferably formula (DI-4-1), formula (DI-5-1) and the diamines represented by formula (DI-5-13).Wherein in formula (DI-5-1), preferred m=2,4 or 6, particularly preferably m=4, in formula (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in formula (DI-5-13), preferred m=1 or 2, particularly preferably m=1.

In each diamines, can be also in the scope of below 40mol% relative to the ratio of diamines at monoamine, a part for diamines 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, easily can control the molecular weight of obtained polymkeric substance (polyamic acid or derivatives thereof), such as, can can't harm effect of the present invention and improve the coating characteristics of liquid crystal aligning agent.As long as harmless effect of the present invention, then the diamines being replaced to monoamine can be a kind of, also can be two or more.As described monoamine, include, for example: aniline, 4-hydroxyanilines, hexahydroaniline, n-Butyl Amine 99, n-amylamine, just amine, positive heptyl amice, n-octyl amine, 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.

Polyamic acid or derivatives thereof of the present invention and then can comprise monoisocyanate compound in monomer whose.By comprising 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, such as, can can't harm effect of the present invention and improve the coating characteristics of liquid crystal aligning agent.With regard to described viewpoint, relative to the total amount of the diamines in monomer and tetracarboxylic dianhydride, the preferred 1mol% ~ 10mol% of content of the monoisocyanate compound in monomer.As described monoisocyanate compound, include, for example: phenylcarbimide and naphthyl isocyanate.

Polyamic acid of the present invention and derivative thereof obtain by making the mixture of above-mentioned acid anhydrides and diamines carry out in a solvent reacting.In this building-up reactions, except the selection of raw material, without the need to special condition, the condition in the synthesis of common polyamic acid directly can be applied.The solvent used is by aftermentioned.

Other compositions that liquid crystal aligning agent of the present invention can and then contain beyond polyamic acid or derivatives thereof.Other compositions can be a kind of, also can be two or more.As other compositions, include, for example other polymkeric substance or compounds etc. described later.

Other polymkeric substance that liquid crystal aligning agent of the present invention can and then contain beyond polyamic acid or derivatives thereof of the present invention.As other polymkeric substance, can enumerate: carry out reacting with the tetracarboxylic dianhydride of tetracarboxylic dianhydride not containing formula (1) [the present invention] and the polyamic acid or derivatives thereof (hereinafter referred to as " other polyamic acid or derivatives thereofs "), polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenylmaleimide) derivative, poly-(methyl) acrylate etc. that obtain.Can be a kind of, also can be two or more.In these polymkeric substance, preferably other polyamic acid or derivatives thereof and polysiloxane, more preferably other polyamic acid or derivatives thereofs.

By in the alignment agent of polyamic acid or derivatives thereof of the present invention and other polyamic acid or derivatives thereof fusion (blend), control structure or the molecular weight of each polymkeric substance, then as aftermentioned, be coated on substrate, and carry out predrying, polyamic acid or derivatives thereof composition (A) of the present invention can be separated into upper strata thus, other polyamic acid or derivatives thereof compositions (B) are separated into lower floor.It is by utilizing following phenomenon to control: in the polymkeric substance that mixing exists, the polymkeric substance that surface energy is little is separated into upper strata, and the polymkeric substance that surface energy is large is separated into lower floor.Layer is separated approves that the surface energy passing through formed alignment films is that the value identical or close with the surface energy of the film formed by the liquid crystal aligning agent only containing (A) composition confirms really.

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, the polysiloxane disclosed in International Publication 2012/165354 grade is as described polysiloxane.

< oxazine compounds >

Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention can so that Han You oxazine compounds.Oxazine compounds can be a kind of compound, also can be two or more compounds.With regard to above-mentioned purpose, relative to the content preferably 0.1 % by weight ~ 50 % by weight of polyamic acid or derivatives thereof ， oxazine compounds, more preferably 1 % by weight ~ 40 % by weight, and then more preferably 1 % by weight ~ 20 % by weight.

Yi Xia paroxazine compound is specifically described.

Oxazine compounds preferably to dissolve in the solvent that polyamic acid or derivatives thereof is dissolved and has ring-opening polymerization oxazine compounds.

The quantity of Ling Wai ， oxazine compounds Zhong oxazine structure is not particularly limited.

The structure of oxazine there will be a known various structure.The structure of Zhong ， oxazine of the present invention is not particularly limited in ， oxazine compounds Zhong oxazine structure, can enumerate the structure that benzoxazine or Nai Bing oxazine etc. have the aromatic series Ji oxazine comprising fused-ring aromatic base.

Zuo is oxazine compounds, include, for example the compound shown in following formula (OX-1) ~ formula (OX-6).Moreover, in following formula, show that bond is at formation ring and can on bond any one carbon substituent towards the key table represented by Ring current distribution.

In formula (OX-1) ~ formula (OX-3), L ³and L ⁴for the organic radical of carbon number 1 ~ 30, in formula (OX-1) ~ formula (OX-6), L ⁵~ L ⁸for the alkyl of hydrogen or carbon number 1 ~ 6, in formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹for singly-bound ,-O-,-S-,-S-S-,-SO ₂-,-CO-,-CONH-,-NHCO-,-C (CH ₃) ₂-,-C (CF ₃) ₂-,-(CH ₂) _v-,-O-(CH ₂) _v-O-,-S-(CH ₂) _v-S-, herein, v is the integer of 1 ~ 6, in formula (OX-5) and formula (OX-6), Q ²be singly-bound ,-O-,-S-,-CO-,-C (CH independently ₃) ₂-,-C (CF ₃) ₂-or the alkylidene group of carbon number 1 ~ 3, Q ²in phenyl ring, the hydrogen of institute's bond is independent and can be substituted by-F ,-CH on naphthalene nucleus ₃,-OH ,-COOH ,-SO ₃h ,-PO ₃h ₂.

Ling Wai ， oxazine compounds comprises oligomer or the polymkeric substance of Ju You oxazine structure in the oligomer of Ju You oxazine structure on side chain or polymkeric substance, main chain.

As oxazine compounds represented by formula (OX-1), include, for example oxazine compounds Xia Yi.

In formula (OX-1-2), L ³the alkyl of preferred carbon number 1 ~ 30, the more preferably alkyl of carbon number 1 ~ 20.

As oxazine compounds represented by formula (OX-2), include, for example oxazine compounds Xia Yi.

In formula, L ³the alkyl of preferred carbon number 1 ~ 30, the more preferably alkyl of carbon number 1 ~ 20.

As oxazine compounds represented by formula (OX-3), oxazine compounds represented by following formula (OX-3-I) can be enumerated.

In formula (OX-3-I), L ³and L ⁴for the organic radical of carbon number 1 ~ 30, L ⁵~ L ⁸for the alkyl of hydrogen or carbon number 1 ~ 6, Q ¹for singly-bound ,-CH ₂-,-C (CH ₃) ₂-,-CO-,-O-,-SO ₂-,-C (CH ₃) ₂-or-C (CF ₃) ₂-.As oxazine compounds represented by formula (OX-3-I), include, for example oxazine compounds Xia Yi.

In formula, L ³and L ⁴the alkyl of preferred carbon number 1 ~ 30, the more preferably alkyl of carbon number 1 ~ 20.

As oxazine compounds represented by formula (OX-4), include, for example oxazine compounds Xia Yi.

As oxazine compounds represented by formula (OX-5), include, for example oxazine compounds Xia Yi.

As oxazine compounds represented by formula (OX-6), include, for example oxazine compounds Xia Yi.

Among these, more preferably can oxazine compounds represented by enumerative (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).

Oxazine compounds can utilize the method identical with method described in International Publication 2004/009708, Japanese Patent Laid-Open 11-12258, Japanese Patent Laid-Open 2004-352670 to manufacture.

Oxazine compounds represented by formula (OX-1) obtains by making phenolic compound and primary amine and aldehyde carry out reacting (with reference to International Publication 2004/009708).

Oxazine compounds represented by formula (OX-2) is by such as under type acquisition: after utilizing the method for adding primary amine in formaldehyde lentamente to react, and adds the compound with naphthols system hydroxyl and carries out reacting (with reference to International Publication 2004/009708).

Oxazine compounds represented by formula (OX-3) obtains by such as under type: under the existence of secondary fatty race amine, three grades of fatty amines or alkaline nitrogen-containing heterocycle compound, make phenolic compound 1 mole, be at least the aldehyde of more than 2 moles relative to 1 phenolic hydroxyl group of this phenolic compound and the primary amine of 1 mole carries out reacting (reference International Publication 2004/009708 and Japanese Patent Laid-Open 11-12258) in organic solvent.

Oxazine compounds represented by formula (OX-4) ~ formula (OX-6) is by such as under type acquisition: at the temperature more than 90 DEG C, make 4,4 '-diaminodiphenyl-methane etc. have multiple phenyl ring and in propyl carbinol, carry out dehydration condensation (with reference to Japanese Patent Laid-Open 2004-352670) with the aldehyde such as diamines, formaldehyde of the organic radical of these phenyl ring bonds and phenol.

< oxazoline compound >

Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention can so that Han You oxazoline compound.Oxazoline compound is the compound of Ju You oxazoline structure.Oxazoline compound can be a kind of compound, also can be two or more compounds.With regard to above-mentioned purpose, relative to the content preferably 0.1 % by weight ~ 50 % by weight of polyamic acid or derivatives thereof ， oxazoline compound, more preferably 1 % by weight ~ 40 % by weight, and then more preferably 1 % by weight ~ 20 % by weight.Or, when Jiang oxazoline compound Zhong oxazoline structure Huan Suan oxazoline, with regard to above-mentioned purpose, relative to the content preferably 0.1 % by weight ~ 40 % by weight of polyamic acid or derivatives thereof ， oxazoline compound.

Yi Xia Dui oxazoline compound is specifically described.

Oxazoline compound only can have Yi Zhong oxazoline structure in 1 compound, also can have two or more.As long as Ling Wai ， oxazoline compound has 1 Ge oxazoline structure in 1 compound, but preferably has more than 2.Ling Wai ， oxazoline compound can be the polymkeric substance of Ju You oxazoline structure on side chain, also can be multipolymer.On side chain, the polymkeric substance of Ju You oxazoline structure can be the homopolymer of the monomer of Ju You oxazoline structure on side chain, also can be the multipolymer of the monomer of Ju You oxazoline structure on side chain and the monomer of Bu Ju You oxazoline structure.On side chain, the multipolymer of Ju You oxazoline structure can be the multipolymer of the two or more monomer of Ju You oxazoline structure on side chain, also can be the multipolymer of the two or more monomer of Ju You oxazoline structure on side chain and the monomer of Bu Ju You oxazoline structure.

Oxazoline structure optimization is the structure that the carbonyl of one or two and polyamic acid of oxygen in Yi oxazoline structure and nitrogen can carry out in the mode Cun Yu oxazoline compound reacted.

Zuo is oxazoline compound, include, for example: 2, 2 '-bis-(2-oxazoline), 1, 2, 4-tri--(2-oxazolinyl-2)-benzene, 4-furans-2-methylene-2-phenyl-4H-oxazole-5-ketone, 1, 4-two (4, 5-dihydro-2-oxazolyl) benzene, 1, 3-two (4, 5-dihydro-2-oxazolyl) benzene, 2, two (4-pseudoallyl-2-oxazoline-2-base) butane of 3-, 2, 2 '-bis--4-benzyl-2-oxazoline, 2, two (sec.-propyl-2-oxazoline-2-base) pyridine of 6-, 2, 2 '-isopropylidene two (4-tributyl-2-oxazoline), 2, 2 '-isopropylidene two (4-phenyl-2-oxazoline), 2, 2 '-methylene-bis (4-tributyl-2-oxazoline), and 2, 2 '-methylene-bis (4-phenyl-2-oxazoline).Except this little oxazoline compound, the tool also can enumerated as Ai Bo Kroes (Epocros) (trade(brand)name, Japanese catalyst (share) manufactures) has polymkeric substance or the oligomer of oxazolyl.Among Zhe Xie oxazoline compound, more preferably can enumerate two (4, the 5-dihydro-2-oxazolyl) benzene of 1,3-.

< epoxy compounds >

Such as, with regard to making the object of the electrical characteristic long-term stability of liquid crystal display device, liquid crystal aligning agent of the present invention and then can contain epoxy compounds.Epoxy compounds can be a kind of compound, also can be two or more compounds.With regard to above-mentioned purpose, relative to polyamic acid or derivatives thereof, the content of epoxy compounds preferably 0.1 % by weight ~ 50 % by weight, more preferably 1 % by weight ~ 40 % by weight, and then more preferably 1 % by weight ~ 20 % by weight.

Below epoxy compounds is specifically described.

As epoxy compounds, the various compounds of the oxirane ring with more than 1 or 2 can be enumerated in molecule.As the compound in molecule with 1 oxirane ring, include, for example: phenyl glycidyl ether, butylglycidyl ether, 3, 3, 3-trifluoromethyl propylene oxide, Styrene oxide 98min., Propylene oxide hexafluoride, epoxy cyclohexane (cyclohexaneoxide), 3-glycidoxypropyltrimewasxysilane, 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3, 4-expoxycyclohexyl) ethyl triethoxysilane, N-glycidyl phthalic imidine, (nine fluoro-N-butyl) epoxide, perfluoro-ethyl glycidyl ether, Epicholorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3-[2-(perfluoro hexyl) oxyethyl group]-1, 2-epoxy group(ing) propane.

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

As the compound in molecule with 3 oxirane rings, include, for example: 2-[4-(2,3-epoxy group(ing) propoxy-) phenyl]-2-[4-[1, two [the 4-([2 of 1-, 3-epoxy group(ing) propoxy-] phenyl)] ethyl] phenyl] propane (trade(brand)name " iron Ke Moya VG3101L (TechmoreVG3101L) ", (Mitsui Chemicals (share) manufacture)).

As the compound in molecule with 4 oxirane rings, include, for example: 1,3,5,6-four glycidyl group-2,4-hexylene glycol, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane and 3-(N-allyl group-N-glycidyl) TSL 8330.

Than that described above, the oligomer with oxirane ring or polymkeric substance can also be enumerated as the example of compound in molecule with oxirane ring.As the monomer with oxirane ring, include, for example: (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxycyclohexyethylSiOi ester and (methyl) vinylformic acid methylglycidyl esters.

Other monomers of copolymerization are carried out as with the monomer with oxirane ring, include, for example: (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, vinylbenzene, vinyl toluene, 1-chloro-4-methyl-benzene, (methyl) vinylformic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, N-cyclohexylmaleimide and N-phenylmaleimide.

As the preferred concrete example of polymkeric substance of monomer with oxirane ring, poly (glycidyl methacrylate) etc. can be enumerated.In addition, as the preferred concrete example of the multipolymer of the monomer and other monomers with oxirane 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 esters-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, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, trade(brand)name " TechmoreVG3101L ", 3, 4-epoxycyclohexyethylSiOi enylmethyl-3 ', 4 '-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2-(3, 4-expoxycyclohexyl) ethyl trimethoxy silane or 2-(3, 4-expoxycyclohexyl) ethyl triethoxysilane.

More systematically say, as epoxy compounds, include, for example: glycidyl ether, glycidyl ester, glycidyl amine, acrylic resin, glycidyl acid amides, isocyanuric acid Racemic glycidol fat, chain fatty race type epoxy compounds and annular aliphatic type epoxy compounds containing epoxy group(ing).Moreover epoxy compounds refers to the compound with epoxy group(ing), epoxy resin refers to the resin with epoxy group(ing).

As epoxy compounds, include, for example: glycidyl ether, Racemic glycidol fat, glycidyl amine, acrylic resin, glycidyl acid amides, isocyanuric acid glycidyl ester, chain fatty race type epoxy compounds and annular aliphatic type epoxy compounds containing epoxy group(ing).

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 epoxy compounds, A Hydrogenated Bisphenol A-F type epoxy compounds, A Hydrogenated Bisphenol A-S type epoxy compounds, A Hydrogenated Bisphenol A type epoxy compounds, brominated bisphenol-A type epoxy compounds, brominated bisphenol-F type epoxy compounds, 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 epoxy compounds, epoxy compounds containing naphthalene skeleton, aromatic series poly epihydric alcohol ether compound, dicyclopentadiene phenol epoxy compounds, ester ring type 2-glycidyl ether compound, aliphatic polyglycidyl ether compound, polysulfide type 2-glycidyl ether compound, and biphenyl phenolic epoxy compounds.

As glycidyl ester, include, for example: 2-glycidyl ester cpds and glycidyl ester epoxy compound.

As glycidyl amine, include, for example: poly epihydric alcohol amine compound and glycidyl amine type epoxy resin.

As the acrylic compounds containing epoxy group(ing), include, for example: homopolymer and the multipolymer with the monomer of Oxyranyle (oxiranyl).

As glycidyl acid amides, include, for example: glycidyl acid amide type epoxy compounds.

As chain fatty race type epoxy compounds, include, for example: the compound containing epoxy group(ing) that the oxidation of the carbon-to-carbon double bond of olefin(e) compound is obtained.

As annular aliphatic type epoxy compounds, include, for example: the compound containing epoxy group(ing) 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(brand)name, Mitsubishi Chemical's (share) manufactures), Ai Putuo appropriate (Epotohto) YD-128 (Dongdu changes into (share) manufactures), DER-331, DER-332, DER-324 (being Dow Chemical (TheDowChemicalCompany) to manufacture), Chinese mugwort clone (Epiclon) 840, Epiclon850, Epiclon1050 (is trade(brand)name, Di Aisheng (DIC) (share) manufactures), Ai Bo Mick (Epomik) R-140, EpomikR-301, and EpomikR-304 (is trade(brand)name, Mitsui Chemicals (company) manufactures).

As bisphenol F type epoxy compound, include, for example: jER806, jER807, jER4004P (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), EpotohtoYDF-170, EpotohtoYDF-175S, EpotohtoYDF-2001 (be trade(brand)name, Dongdu change into (share) manufacture), DER-354 (trade(brand)name, Dow Chemical manufacture), Epiclon830 and Epiclon835 (be trade(brand)name, Di Aisheng (share) manufactures).

As biphenol type epoxy compound, include, for example: the epoxide of 2,2-two (4-hydroxyphenyl)-1,1,1,3,3,3-HFC-236fa.

As A Hydrogenated Bisphenol A-A type epoxy compounds, include, for example: business holds in the palm appropriate (Suntohto) ST-3000 (trade(brand)name, Dongdu change into (share) and manufacture), Li Kaleixin (Rikaresin) HBE-100 (trade(brand)name, new Japan Chemical (share) manufacture) and Dai Nakeer (Denacol) EX-252 (trade(brand)name, Chang Lai change into (NagasechemteX) (share) manufacture).

As A Hydrogenated Bisphenol A type epoxy compounds, include, for example: the epoxide of hydrogenation 2,2-two (4-hydroxyphenyl)-1,1,1,3,3,3-HFC-236fa.

As brominated bisphenol-A type epoxy compounds, include, for example: jER5050, jER5051 (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), EpotohtoYDB-360, EpotohtoYDB-400 (be trade(brand)name, Dongdu change into (share) manufacture), DER-530, DER-538 (be trade(brand)name, Dow Chemical manufactures), Epiclon152 and Epiclon153 (be trade(brand)name, Di Aisheng (share) manufactures).

As phenol novolak-type epoxy compound, include, for example: jER152, jER154 (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), YDPN-638 (trade(brand)name, Dongdu change into company and manufacture), DEN431, DEN438 (be trade(brand)name, Dow Chemical manufactures), EpiclonN-770 (trade(brand)name, Di Aisheng (share) manufacture), EPPN-201 and EPPN-202 (be trade(brand)name, Japanese chemical drug (share) manufactures).

As cresol novolak type epoxy compound, include, for example: jER180S75 (trade(brand)name, Mitsubishi Chemical's (share) manufacture), YDCN-701, YDCN-702 (be trade(brand)name, Dongdu change into company manufacture), EpiclonN-665, EpiclonN-695 (be trade(brand)name, Di Aisheng (share) manufactures), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (be trade(brand)name, Japanese chemical drug (share) manufactures).

As bisphenol A novolac type epoxy compounds, include, for example: jER157S70 (trade(brand)name, Mitsubishi Chemical's (share) manufacture) and EpiclonN-880 (trade(brand)name, Di Aisheng (share) manufacture).

As the epoxy compounds containing naphthalene skeleton, include, for example: EpiclonHP-4032, EpiclonHP-4700, EpiclonHP-4770 (be trade(brand)name, Di Aisheng (share) manufactures), and NC-7000 (trade(brand)name, Japanese chemical drug Inc. make).

As aromatic series poly epihydric alcohol ether compound, include, for example: Resorcinol diglycidylether (following formula EP-1), DGEC (following formula EP-2), resorcinol diglycidyl ether (following formula EP-3), 2-[4-(2, 3-epoxy group(ing) propoxy-) phenyl]-2-[4-[1, two [the 4-([2 of 1-, 3-epoxy group(ing) propoxy-] phenyl)] ethyl] phenyl] propane (following formula EP-4), three (4-glycidoxypropyl phenyl) methane (following formula EP-5), jER1031S, jER1032H60 (is trade(brand)name, Mitsubishi Chemical's (share) manufactures), Plutarch is for Ke Si-742 (TACTIX-742) (trade(brand)name, Dow Chemical manufactures), DenacolEX-201 (trade(brand)name, long rapids change into (share) manufactures), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (is trade(brand)name, Japan's chemical drug (share) manufactures), TechmoreVG3101L (trade(brand)name, Mitsui Chemicals (share) manufactures), compound represented by following formula EP-6, and the compound represented by following formula EP-7.

As dicyclopentadiene phenol epoxy compounds, include, for example: TACTIX-556 (trade(brand)name, Dow Chemical manufacture) and EpiclonHP-7200 (trade(brand)name, Di Aisheng (share) manufacture).

As ester ring type 2-glycidyl ether compound, include, for example: cyclohexanedimethanodiglycidyl diglycidyl ether compound and RikaresinDME-100 (trade(brand)name, new Japan Chemical (share) manufacture).

As aliphatic polyglycidyl ether compound, include, for example: ethylene glycol diglycidylether (following formula EP-8), diethylene glycol diglycidyl glyceryl 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 diglycidylether (following formula EP-15), DenacolEX-810, DenacolEX-851, DenacolEX-8301, DenacolEX-911, DenacolEX-920, DenacolEX-931, DenacolEX-211, DenacolEX-212, DenacolEX-313 (is trade(brand)name, long rapids change into (share) manufactures), DD-503 (trade(brand)name, Ai Dike (ADEKA) (share) manufactures), RikaresinW-100 (trade(brand)name, new Japan Chemical (share) manufactures), 1, 3, 5, 6-four glycidyl group-2, 4-hexylene glycol (following formula EP-16), glycerine polyglycidyl ether, sorbyl alcohol polyglycidyl ether, TriMethylolPropane(TMP) polyglycidyl ether, tetramethylolmethane polyglycidyl ether, DenacolEX-313, DenacolEX-611, DenacolEX-321, and DenacolEX-411 (is trade(brand)name, long rapids change into (share) manufactures).

As polysulfide type 2-glycidyl ether compound, include, for example: FLDP-50 and FLDP-60 (be trade(brand)name, beautiful skilful solid happy (TorayThiokol) (share) in east manufactures).

As biphenyl phenolic epoxy compounds, include, for example: YX-4000, YL-6121H (be trade(brand)name, Mitsubishi Chemical's (share) manufactures), NC-3000P and NC-3000S (be trade(brand)name, Japanese chemical drug (share) manufactures).

As 2-glycidyl ester cpds, include, for example: terephthalic acid diglycidyl ester (following formula EP-17), o-phthalic acid diglycidyl ester (following formula EP-18), phthalic acid two (2-methyl oxirane ylmethyl) ester (following formula EP-19), hexahydrophthalic acid 2-glycidyl ester (following formula EP-20), the 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(brand)name, Mitsubishi Chemical's (share) manufactures), Epiclon200, Epiclon400 (be trade(brand)name, Di Aisheng (share) manufacture), DenacolEX-711 and DenacolEX-721 (be trade(brand)name, Chang Lai change into (share) and manufacture).

As poly epihydric alcohol amine compound, include, for example: N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-Ortho Toluidine (following formula EP-25), N, N-diglycidyl-meta-aminotoluene (following formula EP-26), N, N-diglycidyl-2, 4, 6-bromamide (following formula EP-27), 3-(N, N-diglycidyl) TSL 8330 (following formula EP-28), N, N, O-triglycidyl group-p-aminophenol (following formula EP-29), N, N, O-triglycidyl group-Metha Amino Phenon (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 (iron Te Lade-X (TETRAD-X) (trade(brand)name, Mitsubishi's gas chemistry (share) manufactures), following formula EP-32), 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene (TETRAD-C (trade(brand)name, Mitsubishi's gas chemistry (share) manufactures), following formula EP-33), 1, two (the N of 4-, N-diglycidyl amino methyl) hexanaphthene (following formula EP-34), 1, two (the N of 3-, N-diglycidyl is amino) hexanaphthene (following formula EP-35), 1, two (the N of 4-, N-diglycidyl is amino) hexanaphthene (following formula EP-36), 1, two (the N of 3-, N-diglycidyl is amino) benzene (following formula EP-37), 1, two (the N of 4-, N-diglycidyl is amino) benzene (following formula EP-38), 2, two (the N of 6-, N-diglycidyl amino methyl) dicyclo [2.2.1] heptane (following formula EP-39), 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 oxide (following formula EP-42), 1, 3, 5-tri-(4-(N, N-diglycidyl) amino-benzene oxygen) benzene (following formula EP-43), 2, 4, 4 '-three (N, N-diglycidyl is amino) phenyl ether (following formula EP-44), three (4-(N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3, 4, 3 ', 4 '-four (N, N-diglycidyl is amino) biphenyl (following formula EP-46), 3, 4, 3 ', 4 '-four (N, N-diglycidyl is amino) phenyl ether (following formula EP-47), compound represented by following formula EP-48, and the compound represented by following formula EP-49.

As the monomer with Oxyranyle, include, for example: (methyl) glycidyl acrylate, (methyl) vinylformic acid 3,4-epoxycyclohexyethylSiOi ester and (methyl) vinylformic acid methylglycidyl esters.

As have Oxyranyle monomer multipolymer in the monomer with Oxyranyle beyond other monomers, include, for example: (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, vinylbenzene, vinyl toluene, 1-chloro-4-methyl-benzene, (methyl) vinylformic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, N-cyclohexylmaleimide, and N-phenylmaleimide.

As isocyanuric acid glycidyl ester, include, for example: 1,3,5-triglycidyl group-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-50), 1,3-diglycidyl-5-allyl group-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-51) and isocyanuric acid glycidyl ester type epoxy resin.

As chain fatty race type epoxy compounds, include, for example: epoxidized polybutadiene and Ai Bo Reed (Epolead) PB3600 (trade(brand)name, Daicel (Daicel) (share) manufacture).

As annular aliphatic type epoxy compounds, include, for example: 3, 4-epoxycyclohexyethylSiOi enylmethyl-3 ', (match Luo Saide (Celloxide) 2021 (Daicel (share) manufacture) of 4 '-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, following formula EP-52), 2-methyl-3, 4-epoxycyclohexylmethyl-2 '-methyl-3 ', 4 '-expoxycyclohexyl carboxylicesters (following formula EP-53), 2, 3-epoxy group(ing) pentamethylene-2 ', 3 '-epoxy group(ing) pentamethylene ether (following formula EP-54), 6-caprolactone modification 3, 4-epoxycyclohexylmethyl-3 ', 4 '-epoxycyclohexane carboxylate, 1, 2: 8, 9-bicyclic oxygen limonene (Celloxide3000 (trade(brand)name, Daicel (share) manufactures), following formula EP-55), compound represented by following formula EP-56, CY-175, CY-177, CY-179 (is trade(brand)name, Ciba-Geigy Chemical Company (TheCiba-GeigyChemicalCorp.) manufactures (can step (HuntsmanJapan) (share) from Japanese Hensel to obtain)), EHPD-3150 (trade(brand)name, Daicel (share) manufactures), and annular aliphatic type epoxy resin.

The preferred poly epihydric alcohol amine compound of epoxy compounds, bisphenol A novolac type epoxy compounds, cresol novolak type epoxy compound, and more than one of annular aliphatic type epoxy compounds, more preferably N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, trade(brand)name " TechmoreVG3101L ", 3, 4-epoxycyclohexyethylSiOi enylmethyl-3 ', 4 '-epoxycyclohexyethylSiOi olefinic carboxylic acid ester, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl group-p-aminophenol, bisphenol A novolac type epoxy compounds, and more than one of cresol novolak type epoxy compound.

In addition, such as liquid crystal aligning agent of the present invention and then can contain various additive.As various additive, include, for example the macromolecular compound beyond polyamic acid and derivative thereof and low molecular compound, can according to each object choice for use.

Such as, as described macromolecular compound, the macromolecular compound dissolving in organic solvent can be enumerated., preferably this kind of macromolecular compound is added in liquid crystal aligning agent of the present invention with regard to the electrical characteristic of liquid crystal orientation film that formed or the viewpoint of orientation with regard to controlling.As this macromolecular compound, include, for example: polymeric amide, polyurethane(s), polyureas, polyester, polyepoxide, polyester polyol, silicone modified polyurethane(s) and silicone modified polyester.

In addition, as described low molecular compound, such as, 1) when expecting can enumerate the tensio-active agent meeting this object when promoting coating, 2) static inhibitor can be enumerated when needs promote antistatic, 3) when expecting the coupler can enumerating silane coupling agent or titanium system when promoting the adhesion with substrate, in addition, 4) imidization catalyst can be enumerated when carrying out imidization at low temperatures.

As silane coupling agent, include, for example: vinyltrimethoxy silane, vinyltriethoxysilane, 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 triethoxyl silane, m-aminophenyl base Trimethoxy silane, m-aminophenyl ethyl triethoxy silicane alkane, 3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane, 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, N '-bis-[3-(Trimethoxy silane base) propyl group] quadrol.Preferred silane coupling agent is 3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane, 2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane.

As imidization catalyst, include, for example: the aliphatics amines such as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine; The aromatic amines such as DMA, N, N-Diethyl Aniline, 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, isoquinoline 99.9, methyl substituted isoquinoline 99.9, hydroxyl substituted isoquinoline, imidazoles, methyl substituted imidazoles, hydroxyl substituted imidazole.Described imidization catalyst be preferably selected from DMA, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine, adjacent pyridone, a pyridone, to one or more in pyridone and isoquinoline 99.9.

The addition of silane coupling agent is generally 0 % by weight ~ 30 % by weight of the gross weight of polyamic acid or derivatives thereof, and preferably 0.1 % by weight ~ 15 % by weight.

Relative to the carbonyl of polyamic acid or derivatives thereof, the addition of imidization catalyst is generally 0.01 equivalent ~ 5 equivalent, preferably 0.05 equivalent ~ 3 equivalent.

The addition of other additives is different according to its purposes, but is generally 0 % by weight ~ 100 % by weight of the gross weight of polyamic acid or derivatives thereof, and preferably 0.1 % by weight ~ 50 % by weight.

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 polyimide.The total addition level of tetracarboxylic dianhydride is preferably set to and roughly waits mole (mol ratio is about 0.9 ~ 1.1) with the total mole number of diamines.

The molecular weight of polyamic acid or derivatives thereof of the present invention in the weight average molecular weight of polystyrene conversion (Mw), preferably 7,000 ~ 500,000, more preferably 10,000 ~ 200,000.The molecular weight of described polyamic acid or derivatives thereof can by utilizing the mensuration of gel permeation chromatography (GelPermeationChromatography, GPC) method to obtain.

Polyamic acid or derivatives thereof of the present invention confirms its existence by such as under type: utilize infrared rays (Infrared, IR) solids component that, nucleus magnetic resonance (NuclearMagneticResonance, NMR) obtains making polyamic acid or derivatives thereof of the present invention precipitate in a large amount of poor solvents is analyzed.In addition, by confirm as under type the monomer that uses: utilize vapor-phase chromatography (GasChromatography, GC), high performance liquid chromatography (HighPerformanceLiquidChromatography, or GC-MS (GasChromatography-MassSpectrometry HPLC), GC-MS) to using the aqueous solution of the highly basic such as KOH or NaOH by after described polyamic acid or derivatives thereof decomposition, the extract with an organic solvent extracted from its resolvent is analyzed.

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

As solvent, can enumerate described polyamic acid or derivatives thereof solvophilic 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 alkane ketone (dimethylimidazolidinone), N-methyl caprolactam, N-methyl propanamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N, the lactones such as dinethylformamide, N, N-diethylformamide, diethyl acetamide, gamma-butyrolactone.

Preferred use, to improve other solvents for the purpose of coating etc., is particularly selected from least one solvent in the group be made up of alcohol, ether, ketone.

As above-mentioned alcohol, can enumerate: ethylene glycol butyl ether (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, 1-butoxy-2-propyl alcohol, 2-(2-methoxy propoxy) propyl alcohol, ethyl lactate, methyl lactate, propyl lactate, n-Butyl lactate etc.

As above-mentioned ether, can enumerate: the alkane such as glycol dimethyl ether, ethylene glycol diethyl ether glycol dialkyl ether; The dioxane glycol dialkyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; The dioxane glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, DPE; The alkane glycol alkyl ether acetic ester such as ethylene glycol mono-n-butyl ether acetic ester, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic ester, diethylene glycol monoethyl ether acetic ester, ethylene glycol monomethyl ether acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, propylene glycol monopropyl ether acetic ester, propylene glycol monobutyl ether acetic ester; The propylene-glycol monoalky lether propionic esters such as propylene glycol monomethyl ether propionate, dihydroxypropane single-ether propionic ester, propylene glycol monopropyl ether propionic ester, propylene glycol monobutyl ether propionic ester; The cyclic ethers etc. such as tetrahydrofuran (THF).

As above-mentioned ketone, can enumerate: methyl ethyl ketone, methyl iso-butyl ketone (MIBK), pimelinketone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, methyl-3-methoxy propyl acid esters etc.

Among these, described solvent is METHYLPYRROLIDONE, methylimidazole alkane ketone, gamma-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether and 1-butoxy-2-propyl alcohol particularly preferably.

The concentration of the polyamic acid in alignment agent of the present invention preferably 0.1 % by weight ~ 40 % by weight.When being coated on substrate by this alignment agent, in order to adjust thickness, sometimes need the operation utilizing solvent to dilute contained polyamic acid in advance.

Solid component concentration in alignment agent of the present invention is not particularly limited, as long as select most suitable value in conjunction with following various coating method.Usually, in order to suppress inequality when being coated with or pin hole etc., relative to varnish weight, preferably 0.1 % by weight ~ 30 % by weight, more preferably 1 % by weight ~ 10 % by weight.

The viscosity of liquid crystal aligning agent of the present invention is because of the method for coating, the concentration of polyamic acid or derivatives thereof, the kind of polyamic acid or derivatives thereof used, the kind of solvent and ratio and preferably scope is different.Such as, when utilizing printing press to be coated be 5mPas ~ 100mPas (being more preferably 10mPas ~ 80mPas).If be less than 5mPas, then become and be difficult to obtain sufficient thickness; If more than 100mPas, then there is the phenomenon that the uneven change of printing is large.When utilizing spin coating to be coated with, what be applicable to is 5mPas ~ 200mPas (being more preferably 10mPas ~ 100mPas).When using ink-jet coating apparatus to be coated with, what be applicable to is 5mPas ~ 50mPas (being more preferably 5mPas ~ 20mPas).The viscosity of liquid crystal aligning agent utilizes rotational viscometry and measures, such as, use rotational viscosimeter (the TVE-20L type that eastern machine industry manufactures) and measure (measuring temperature is 25 DEG C).

Liquid crystal orientation film of the present invention is described in detail.Liquid crystal orientation film of the present invention is by heating formed film to the film of described liquid crystal aligning agent of the present invention.Liquid crystal orientation film of the present invention can utilize and makes the usual method of liquid crystal orientation film from liquid crystal aligning agent and obtain.Such as, liquid crystal orientation film of the present invention can by through formation liquid crystal aligning agent of the present invention film step, carry out heat drying step and carry out the step of heating and calcining and obtain.For liquid crystal orientation film of the present invention, optionally, can as aftermentioned to through heat-drying step, heating and calcining step the film that obtains carry out friction treatment to give anisotropy.Or, optionally, light can be irradiated after film-coating procedures, heat-drying step, or after heating and calcining step, irradiate light to give anisotropy.In addition, vertical orientated (VerticalAlignment, the VA) that also can 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 by liquid crystal aligning agent of the present invention on substrate in liquid crystal display device.Substrate can be enumerated and can be provided with tin indium oxide (IndiumTinOxide, ITO), indium zinc oxide (In ₂o ₃-ZnO, IZO), Indium sesquioxide gallium zinc (In-Ga-ZnO ₄, IGZO) and the substrate of glass of electrode or the colored filter etc. such as electrode.

As the method be coated on by liquid crystal aligning agent on substrate, usually there will be a known turner method, print process, pickling process, dripping method, ink jet method etc.These methods also can similarly be applied in the present invention.

Described heat-drying step there will be a known the method for carrying out heat treated in baking oven or infra-red furnace, the method etc. of carrying out heat treated on hot plate usually.Implement at the temperature of heat-drying step preferably in the transpirable scope of solvent, more preferably implement under being lower 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.

Carry out under the condition that described heating and calcining step can present required for dehydration closed-loop reaction at described polyamic acid or derivatives thereof.The calcining of described film there will be a known the method for carrying out heat treated in baking oven or infra-red furnace, the method etc. of carrying out heat treated on hot plate usually.These methods also can similarly be applied in the present invention.Usually preferably at the temperature of 100 DEG C ~ about 300 DEG C, 1 minute ~ 3 hours are carried out, more preferably 120 DEG C ~ 280 DEG C, and then more preferably 150 DEG C ~ 250 DEG C.

The formation method of the liquid crystal orientation film of the present invention utilizing optical alignment method is described in detail.Use the liquid crystal orientation film of the present invention of optical alignment method to be formed by such as under type: after carrying out heat drying to film, irradiate radioactive rays linear polarization or without polarisation, give anisotropy to film thus, then heating and calcining carried out to this film.Or, by carrying out heat drying to film, and after carrying out heating and calcining, irradiating the linear polarization of radioactive rays or being formed without polarisation.With regard to the viewpoint of orientation, the irradiating step of radioactive rays is preferably carried out before heating and calcining step.

And then, in order to improve the liquid crystal aligning ability of liquid crystal orientation film, also can one in the face of film carry out heat one side irradiate radioactive rays linear polarization or without polarisation.The irradiation of radioactive rays can be carried out in the step of film being carried out to heat drying or the step of carrying out heating and calcining, also can carry out between heat-drying step and heating and calcining step.The scope that heat drying temperature in this step is preferably 30 DEG C ~ 150 DEG C, the scope of more preferably 50 DEG C ~ 120 DEG C.In addition, the scope that the heating and calcining temperature in this step is preferably 30 DEG C ~ 300 DEG C, the scope of more preferably 50 DEG C ~ 250 DEG C.

As radioactive rays, such as, can use ultraviolet or the visible ray of the light of the wavelength comprising 150nm ~ 800nm, preferably comprise the ultraviolet of the light of 300nm ~ 400nm.In addition, linear polarization can be used or without polarisation.As long as these light can give the light of liquid crystal aligning ability to described film, be then not particularly limited, but when for revealing strong orientation restraint to liquid crystal, preferred linear polarization.

Even if low-energy rayed, liquid crystal orientation film of the present invention also can demonstrate high liquid crystal aligning ability.The preferred 0.05J/cm of irradiation dose of the linear polarization in described radiation exposure step ²~ 20J/cm ², more preferably 0.5J/cm ²~ 10J/cm ².In addition, the preferred 200nm ~ 400nm of wavelength of linear polarization, more preferably 300nm ~ 400nm.Linear polarization is not particularly limited for the irradiating angle on film surface, but when for revealing strong orientation restraint to liquid crystal, with regard to shortening the viewpoint of orientation process time, preferably vertical as far as possible relative to film surface.In addition, by irradiating linear polarization, liquid crystal orientation film of the present invention can make liquid crystal carry out orientation on the direction vertical relative to the polarization direction of linear polarization.

When making tilt angle manifest, can be and described identical linear polarization also can be without polarisation to the light that described film irradiates.When making tilt angle manifest, to the preferred 0.05J/cm of the irradiation dose of the light that described film irradiates ²~ 20J/cm ², particularly preferably 0.5J/cm ²~ 10J/cm ², the preferred 250nm ~ 400nm of its wavelength, particularly preferably 300nm ~ 380nm.When making tilt angle manifest, the light irradiated described film is not particularly limited for the irradiating angle on described film surface, but with regard to the viewpoint shortening the orientation process time, preferably 30 degree ~ 60 degree.

Irradiate radioactive rays linear polarization or without the step of polarisation in the light source that uses unrestrictedly can use extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamp, deep UV (DeepUltraviolet, DeepUV) lamp, halogen lamp, metal halide lamp, high-power metal halide lamp, xenon lamp, mercury xenon, Excimer lamp, KrF excimer laser, luminescent lamp, photodiode (LightEmittingDiode, LED) lamp, sodium vapor lamp, microwave-excited electrodeless lamp etc.

Liquid crystal orientation film of the present invention also can utilize rubbing manipulation to give anisotropy.The liquid crystal orientation film of the present invention of rubbing manipulation is used to can be passed through following step and formed: liquid crystal aligning agent of the present invention to be coated on the step on substrate, the substrate being coated with alignment agent to be carried out to the step of heat drying, this film to be carried out to the step of heating and calcining and film carried out to the step of friction treatment.

Friction treatment can be carried out in the same manner as the friction treatment of the common orientation process for liquid crystal orientation film, as long as can obtain the condition postponed fully in liquid crystal orientation film of the present invention.Preferred condition is mao intrusion is 0.2mm ~ 0.8mm, and platform movement speed is 5mm/sec ~ 250mm/sec, and roller speed of rotation is 500rpm ~ 2,000rpm.

Liquid crystal orientation film of the present invention by so that comprise the method for other steps beyond described step and obtain aptly.Such as, although liquid crystal orientation film of the present invention is not using utilizing scavenging solution to the film step of cleaning after calcining or radiation exposure as required step, cleaning step can be set according to the situation of other steps.

As the purging method utilizing scavenging solution, can enumerate: scrub, spray, steam purge or ultrasonic cleaning etc.These methods can be carried out separately, also can be used together.As scavenging solution, can use: pure water, or the various alcohols such as methyl alcohol, ethanol, Virahol, the halogen series solvents such as benzene,toluene,xylene etc. are aromatic hydrocarbon based, methylene dichloride, the ketone such as acetone, methyl ethyl ketone, but be not limited to these scavenging solutions.Certainly, these scavenging solutions can use through the few scavenging solution of fully refining impurity.This kind of purging method also can be applied in the described cleaning step forming liquid crystal orientation film of the present invention.

In order to promote the liquid crystal aligning ability of liquid crystal orientation film of the present invention, can at the front and back of the front and back of heating and calcining step, rubbing process or polarisation or without the front and back applications exploiting heat of the radiation exposure of polarisation or the anneal of light.In this anneal, annealing temperature is 30 DEG C ~ 180 DEG C, preferably 50 DEG C ~ 150 DEG C, preferably 1 minute ~ 2 hours time.In addition, in the annealing light of anneal, UV lamp, luminescent lamp, LED etc. can be enumerated.The preferred 0.3J/cm of irradiation dose of light ²~ 10J/cm ².

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

Liquid crystal orientation film of the present invention has the anisotropy of king-sized orientation.This kind of anisotropic size is evaluated by the method for use polarisation IR described in Japanese Patent Laid-Open 2005-275364 etc.In addition, as shown in following embodiment, also by using the method for ellipsometry (ellipsometry) to evaluate.Specifically, the length of delay of liquid crystal orientation film is measured by light splitting ellipsometer.The length of delay of film and the orientation degree of main polymer chain increase pro rata.That is, the film with large length of delay has large orientation degree, when alignment films of the present invention is used as liquid crystal orientation film, can think that having larger anisotropic alignment films has large orientation restraint for liquid-crystal composition.

Liquid crystal orientation film of the present invention can be suitably used in the liquid crystal display device of Transverse electric-field type.In for the liquid crystal display device of Transverse electric-field type, Pt angle is less, and liquid crystal aligning ability is higher, then black reveal competence in the dark state more uprises, and contrast gradient more improves.Preferably less than 0.1 °, Pt angle.

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

Liquid crystal display device of the present invention is described in detail.

The invention provides a kind of liquid crystal display device, it comprises a pair substrate of subtend configuration, the electrode be formed on the one or both sides in described a pair substrate subtend face separately, the liquid crystal layer that is formed in the liquid crystal orientation film on described a pair substrate subtend face separately and is formed between described a pair substrate, and described liquid crystal orientation film is alignment films of the present invention.

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

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

There is no particular restriction for liquid-crystal composition, can use the various liquid-crystal compositions that dielectric constant anisotropy is plus or minus.Dielectric constant anisotropy is that positive preferred liquid-crystal composition can be enumerated: Japanese Patent 3086228, Japanese Patent 2635435, Japanese 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, the liquid-crystal composition disclosed in Japanese Patent Laid-Open 2001-48822 etc.

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

Be that negative liquid-crystal composition is illustrated to described dielectric constant anisotropy.The liquid-crystal composition of negative dielectric constant anisotropy include, for example the composition of at least one liquid crystalline cpd in the group containing the liquid crystalline cpd be selected from represented by following formula (NL-1) as the 1st composition.

Herein, R ^1aand R ^2abe the thiazolinyl of the carbon number 2 ~ 12 that the alkyl of carbon number 1 ~ 12, the alkoxyl group of carbon number 1 ~ 12, the thiazolinyl of carbon number 2 ~ 12 or at least one hydrogen are replaced by fluorine independently, ring A ²and ring B ²be Isosorbide-5-Nitrae-cyclohexylidene, tetrahydropyrans-2,5-bis-base (tetrahydropyran-2 independently, 5-diyl), 1,3-diox-2,5-bis-base, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-bis-fluoro-Isosorbide-5-Nitrae-phenylenes, 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 base or 7,8-difluoro chroman-2,6-bis-base (7,8-difluorochroman-2,6-diyl), herein, ring A ²and ring B ²at least one be the fluoro-Isosorbide-5-Nitrae-phenylene of 2,3-bis-, 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 chroman-2,6-bis-base, Z ¹be singly-bound ,-(CH independently ₂) ₂-,-CH ₂o-,-COO-or-CF ₂o-, j are 1,2 or 3, j when being 2 or 3, any two ring A ²can be identical, also can be different, any two Z ¹can be identical, also can be different.

In order to improve dielectric constant anisotropy, preferred ring A ²and ring B ²be respectively the fluoro-Isosorbide-5-Nitrae-phenylene of 2,3-bis-or tetrahydropyrans-2,5-bis-base, in order to reduce viscosity, preferred ring A ²and ring B ²be respectively Isosorbide-5-Nitrae-cyclohexylidene.

In order to improve dielectric constant anisotropy, preferred Z ¹for-CH ₂o-, in order to reduce viscosity, preferred Z ¹for singly-bound.

In order to reduce lower limit temperature, preferred j is 1, and in order to improve ceiling temperature, preferred j is 2.

As the concrete example of the liquid crystalline cpd of above-mentioned formula (NL-1), the compound represented by following formula (NL-1-1) ~ formula (NL-1-32) can be enumerated.

Herein, R ^1aand R ^2abe the thiazolinyl of the carbon number 2 ~ 12 that the alkyl of carbon number 1 ~ 12, the alkoxyl group of carbon number 1 ~ 12, the thiazolinyl of carbon number 2 ~ 12 or at least one hydrogen are replaced by fluorine independently, ring A ²¹, ring A ²², ring A ²³, ring B ²¹, and ring B ²²be Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene independently, Z ¹¹and Z ¹²be singly-bound ,-(CH independently ₂) ₂-,-CH ₂o-or-COO-.

In order to improve the stability etc. for ultraviolet or heat, preferred R ^1aand R ^2athe alkyl of carbon number 1 ~ 12, or in order to improve the absolute value of dielectric constant anisotropy, preferred R ^1aand R ^2ait is the alkoxyl group of carbon number 1 ~ 12.

Preferred alkyl is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group.In order to reduce viscosity, and then preferred alkyl is ethyl, propyl group, butyl, amyl group or heptyl.

Preferred alkoxyl group be methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy or heptan oxygen base.In order to reduce viscosity, and then preferred alkoxyl group is methoxy or ethoxy.

Preferred thiazolinyl is vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 3-butenyl, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl.In order to reduce viscosity, and then preferred thiazolinyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl.The preferred steric configuration of-CH=CH-in these thiazolinyls (stericconfiguration) depends on the position of double bond.Consider from order to reduce the aspects such as viscosity, preferably trans in the thiazolinyl as 1-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl.Cis is preferably in the thiazolinyl as crotyl, pentenyl, 2-hexenyl.In these thiazolinyls, with the thiazolinyl of branch's Comparatively speaking preferred straight chain.

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-propenyl, 4,4-bis-fluoro-3-butenyls, 5,5-bis-fluoro-4-pentenyls and the fluoro-5-hexenyl of 6,6-bis-.In order to reduce viscosity, and then preferred example is the fluoro-3-butenyl of 2,2-difluoroethylene base and 4,4-bis-.

In order to reduce viscosity, preferred ring A ²¹, ring A ²², ring A ²³, ring B ²¹, and ring B ²²be respectively Isosorbide-5-Nitrae-cyclohexylidene.

In order to improve dielectric constant anisotropy, preferred Z ¹¹and Z ¹²-CH ₂o-, in order to reduce viscosity, preferred Z ¹¹and Z ¹²it is singly-bound.

Described have in the liquid-crystal composition of negative dielectric constant anisotropy, and 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 described preferred example with the liquid-crystal composition of 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, Japanese Patent spy table 2010-537010, Japanese Patent Laid-Open 2012-077201, the liquid-crystal composition disclosed in Japanese Patent Laid-Open 2009-084362 etc.

Such as, and such as consider from the viewpoint making orientation promote, the liquid-crystal composition used in element of the present invention can also add additive further.This kind of additive is photopolymerization monomer, optically active compound, antioxidant, UV light absorber, pigment, defoamer, polymerization starter, polymerization retarder etc.

For improving the object of orientation of liquid crystal and the most preferred structure of the photopolymerization monomer added or oligomer can the structure of enumerative (PM-1-1) ~ formula (PM-1-6).

In order to show the effect of the vergence direction of the liquid crystal after determining polymerization, photopolymerization monomer or oligomer it is desirable to more than 0.01 % by weight.And in order to make the orientation effect of the polymkeric substance after polymerization be suitable for, or in order to avoid after uv irradiation, unreacted monomer or oligomer stripping, in liquid crystal, it is desirable to less than 30 % by weight.

The object of torsion(al)angle is given, hybrid optical active compound in the composition for causing the spirane structure of liquid crystal.The example of this kind of compound is that compound (PAC-1-1) is to compound (PAC-1-4).The preferred proportion of optically active compound is less than 5 % by weight.And then preferred ratio is the scope of 0.01 % by weight to 2 % by weight.

Reduce to prevent the ratio resistance (specificresistance) caused owing to heating in an atmosphere, or in order to after long-time use element, not only at room temperature and at high temperature also maintain large voltage retention, in liquid-crystal composition, mix antioxidant.

The compound (AO-1) etc. of the preferred example of antioxidant to be w the be integer of 1 to 10.In compound (AO-1), preferred w is 1,3,5,7 or 9.And then preferred w is 1 or 7.W is that the volatility of the compound (AO-1) of 1 is large, therefore effective when the ratio resistance preventing from causing owing to heating in an atmosphere reduces.W is that the volatility of the compound (AO-1) of 7 is little, therefore after long-time use element, not only at room temperature and at high temperature also effectively maintains large voltage retention.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 light absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc.And, as also preferred in the photostabilizer there is the amine of steric hindrance (sterichindrance).In order to obtain its effect, the preferred ratio of these absorption agents or stablizer 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 absorption agents or stablizer is below 10000ppm.And then preferred ratio is the scope of 100ppm to 10000ppm.

In order to the element of applicable host and guest (Guesthost, GH) pattern, the dichroism pigment (dichroicdye) of mixing as azo system pigment, anthraquinone system pigment etc. so in the composition.The preferred ratio of pigment is the scope of 0.01 % by weight to 10 % by weight.

In order to prevent bubbling, mix the defoamer such as dimethyl silicone oil, 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 the element of applicable polymer stabilizing orientation (Polymersustainedalignment, PSA) pattern, polymerisable compound can be mixed in the composition.The compound that the preferred example of polymerisable compound is acrylate, methacrylic ester, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxy compounds (oxirane, trimethylene oxide), vinyl ketone etc. have polymerisable base.More preferred example is the derivative of acrylate or methacrylic ester.The example of this kind of compound is that compound (PM-2-1) is to compound (PM-2-9).In order to obtain its effect, the preferred ratio of polymerisable compound is more than about 0.05 % by weight, and in order to prevent display bad, the preferred ratio of polymerisable compound is less than about 10 % by weight.And then preferred ratio is the scope of about 0.1 % by weight to about 2 % by weight.

Herein, R ^3a, R ^4a, R ^5a, and R ^6abe acryl or methacryloyl independently, R ^7aand R ^8abe the alkyl of hydrogen, halogen or carbon number 1 to 10 independently, Z ¹³, Z ¹⁴, Z ¹⁵, and Z ¹⁶be the alkylidene group of singly-bound or carbon number 1 to 12 independently, at least one-CH ₂-also can be replaced by-O-or-CH=CH-, s, t and u are separately 0,1 or 2.

The material caused required for chain polymerization reaction as easy generation free radical or ion, can mixed polymerization initiator.Such as, as gorgeous good solid (Irgacure) 651 (registered trademark), the Irgacure184 (registered trademark) of Photoepolymerizationinitiater initiater or Da Luoka (Darocure) 1173 (registered trademark) (Japanese Qi Ba limited-liability company (CibaJapanK.K.)) suitable for radical polymerization.Polymerisable compound preferably comprises Photoepolymerizationinitiater initiater in the scope of 0.1 % by weight to 5 % by weight.Particularly preferably be and comprise Photoepolymerizationinitiater initiater in the scope of 1 % by weight to 3 % by weight.

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

Use in liquid crystal display device of the present invention and there is the liquid-crystal composition of negative dielectric constant anisotropy, image retention excellent can be provided thus and the good liquid crystal display device of orientation stability.

[embodiment]

Below, by embodiment, the present invention is described.Moreover, evaluation assessment used in an embodiment and compound as described below.

< evaluation assessment >

1. weight average molecular weight (Mw)

The weight average molecular weight of polyamic acid is obtained in the following way: use 2695 separation module 2414 differential refractometer (water generation (Waters) manufacture) and utilize GPC method to measure, then carrying out polystyrene conversion.Utilize phosphoric acid-dimethyl formamide (Dimethylformamide, DMF) mixing solutions (phosphoric acid/DMF=0.6/100: weight ratio), the mode becoming about 2 % by weight with polyamic acid concentration is diluted obtained polyamic acid.Tubing string uses HSPgelRTMB-M (manufacture of water generation), using described mixing solutions as developping agent, tubing string temperature be 50 DEG C, flow velocity measures under being the condition of 0.40mL/min.The TSK polystyrene standard that polystyrene standard uses eastern Cao (Tosoh) (share) to manufacture.

2. pencil hardness

With reference to the method for Japanese Industrial Standards (JapaneseIndustrialStandards, JIS) specification " JIS-K-5400,8.4, pencil test ".With the scale of hardness of the core clamping pen, result is shown.If pencil hardness is low, then easily produces and peel off or wear and tear, if this value is greater than 2H, then can obtain the alignment films not easily producing wearing and tearing.

3. foreign matter test

The foreign matter test of liquid crystal display device described later is that force use value is measured (FORCEMEASUREMENT), DS2-50N (reaching (IMADA) limited-liability company according to dream to manufacture) and carries out.With 60 beats/min, the power of 9.8N is stressed on made liquid crystal display device 1 minute.Utilize microscopic examination liquid crystal display device, confirm there is foreign after the pressurizing.

4. contrast gradient

The contrast gradient of liquid crystal cell described later uses luminance meter (Yokogawa (YOKOGAWA) 3298F) and evaluates.Under the polarizing microscope of cross Nicols state, configure liquid crystal display device, measure and become minimum brightness as black luminance.Secondly, arbitrary square-wave voltage is applied to element, measure become maximum brightness as white luminance.The value of this white luminance/black luminance is spent as a comparison.Contrast gradient less than 2500 time be judged to be not good enough, be judged to be good when contrast gradient is more than 2500, when contrast gradient is more than 3000, be judged to be the best.

5. alternating-current (AlternatingCurrent, AC) image retention measures

Measure the brightness-voltage characteristic (B-V characteristic) of liquid crystal display device described later.It can be used as the brightness-voltage characteristic before stress application: B (front).Then, the alternating-current of 4.5V, 60Hz is applied after 20 minutes to element, short circuit 1 second, and then measure brightness-voltage characteristic (B-V characteristic).It can be used as the brightness-voltage characteristic after stress application: B (afterwards).Based on these values, following formula is used to carry out estimated brightness velocity of variation Δ B (%).

Δ B (%)=[B (afterwards)-B (front)]/B (front) (formula AC1)

These measure is carry out with reference to International Publication No. 2000/43833 specification sheets.Can say that the value of the Δ B (%) in voltage 0.75V is less, more can suppress the generation of AC image retention, preferably less than 3.0%.

< tetracarboxylic dianhydride >

(1-8): two (3,4-dicarboxylic acid phenyl) the octane dianhydride of 1,8-

(3-1-1): 1,2,3,4-tetramethylene tetracarboxylic dianhydride

(4): 1,2,3,4-butane tetracarboxylic acid dianhydride

(5): 1,2,4,5-cyclopentanetetracarboxylic dianhydride

(6): ethylenediamine tetraacetic acid (EDTA) dianhydride

(7): 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride

(9): octahydro pentalene-1,3,4,6-tetracarboxylic acid-1,3,4,6-dianhydride

(10): pyromellitic acid anhydride

(11): biphenyl-3,3 ', 4,4 '-tetracarboxylic dianhydride

(12): 4,4 '-oxygen base diphthalic anhydrides

(13): 4-(2,5-dioxotetrahydro furans-3-base)-1,2,3,4-naphthane-1,2-dicarboxylic acid anhydrides

(1-6): two (3,4-dicarboxylic acid phenyl) the hexane dianhydride of 1,6-

(1-4): Isosorbide-5-Nitrae-bis-(3,4-dicarboxylic acid phenyl) butane dianhydride

(3-1-5): 1,3-dimethyl-1,2,3,4-tetramethylene tetracarboxylic dianhydride

< diamines >

(I-3): 4,4 '-chrysoidine

(D-1): Isosorbide-5-Nitrae-phenylenediamine

(D-2-1): 4,4 '-diaminodiphenyl-methane

(D-2-2): 4,4 '-diamino-diphenyl ethane

(D-2-4): 4,4 '-diamino-diphenyl butane

(D-2-7): 4，4′-diaminodipohenyl ether

(D-3): 4,4 '-N, N '-bis-(4-aminophenyl) piperazine

(D-4-3): two (4-((4-aminophenyl) methyl) phenyl) propane of 1,3-

(D-5-1): N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-ethylenediamine

< solvent >

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

DMI:1,3-dimethyl-2-imidazolidone

GBL: gamma-butyrolactone

BC: ethylene glycol butyl ether (ethylene glycol monobutyl ether)

EDE: diethylene glycol diethyl ether

BP:1-butoxy-2-propyl alcohol

< additive >

Two (4, the 5-dihydro-2-oxazolyl) benzene of Add.1:1,3-

Add.2:2-(3,4-expoxycyclohexyl) ethyl trimethoxy silane

Add.3:2-(3,4-expoxycyclohexyl) ethyl triethoxysilane

Add.4:3-glycidoxypropyltrimewasxysilane

Positive type liquid crystal composition:

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

Negative type liquid crystal composition:

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

The synthesis > of < polyamic acid

[synthesis example A-1]

To possessing thermometer, stirrer, raw material drop into the diamines 3.3066g and dehydration NMP100.0g that add formula (1-3) in the brown four-hole boiling flask of the 200mL adding mouth and nitrogen inlet, under drying nitrogen air-flow, carry out stirring and dissolving.Secondly, add the tetracarboxylic dianhydride 3.1658g of formula (1-8) and the tetracarboxylic dianhydride 1.5276g of formula (3-1-1) and then add dehydration NMP52.0g, and at room temperature Keep agitation 24 hours.In this reaction soln, add BC40.0g, obtain the polyamic acid solution that polymer solids constituent concentration is 4 % by weight.This polyamic acid solution is set to PA-1.The weight average molecular weight of polyamic acid contained in PA-1 is 18,300.

[synthesis example A-2 ~ synthesis example A-31 and synthesis example B-1 ~ synthesis example B-13]

Except change tetracarboxylic dianhydride, diamines and solvent composition, prepare according to synthesis example 1 polyamic acid solution (PA-2) ~ polyamic acid solution (PA-31) and polyamic acid solution (the PB-1) ~ polyamic acid solution (PB-13) that polymer solids constituent concentration is 4 % by weight.Be shown in table 1 and table 2.Also again synthesis example A-1 is disclosed.

Table 1

Table 1 (Continued)

Table 2

< polymer blend >

[synthesis example PC-1]

Be the polyamic acid solution (PA-1) of 4 % by weight by the polymer solids constituent concentration prepared in [A] synthesis example A-1, being 4 % by weight with the polymer solids constituent concentration prepared in [B] synthesis example B-1, polyamic acid solution (PB-1) is mixed with the ratio of mixture of weight ratio [A]/[B]=3/7.Obtained polyamic acid solution is set to PC-1.

[synthesis example PC-2 ~ synthesis example PC-38]

By a kind of polyamic acid solution be selected from [A] polyamic acid solution (PA-1) ~ polyamic acid solution (PA-31), mixed with the ratio of mixture of weight ratio [A]/[B]=3/7 with a kind of polyamic acid solution be selected from [B] polyamic acid solution (PB-1) ~ polyamic acid solution (PB-13), prepared polyamic acid solution (PC-1) ~ polyamic acid solution (PC-38).Be shown in Table 3.Also again synthesis example PC-1 is disclosed.

Table 3

[synthesis example PD-1]

Be in the polyamic acid solution (PA-1) of 4 % by weight at polymer solids constituent concentration, to be ratio interpolation additive (Add.1) of 10 % by weight relative to polymer weight.Obtained polyamic acid solution is set to PD-1.

[synthesis example PD-2 ~ synthesis example PD-28]

Except change polyamic acid solution and additive kind and except measuring, foundation PD-1 and prepare polyamic acid solution (PD-2) ~ polyamic acid solution (PD-28) that polymer solids constituent concentration is 4 % by weight.Be shown in Table 4.Also again PD-1 is disclosed.

Table 4

[embodiment 1]

The making method of < mensuration substrate and determination of pencil hardness >

Be that the polyamic acid solution (PA-1) of 4 % by weight is as liquid crystal aligning agent using polymer solids constituent concentration prepared in synthesis example 1, coating on the glass substrate to utilize turner (meter Ka Sa (Mikasa) limited-liability company manufactures, spin coater (1H-DX2)).Moreover also comprise later embodiment, comparative example, the viscosity corresponding to liquid crystal aligning agent adjusts the speed of rotation of turner, makes the thickness that alignment films becomes following.After film, hot plate (sub-speed prosperous (ASONE) limited-liability company manufactures, EC hot plate (EC-1200N)) carries out 80 seconds heat dryings with 70 DEG C.Secondly, the multiple smooth ML-501C/B (MultiLightML-501C/B) that oxtail (Ushio) motor (share) manufactures is used, from vertical via the linear polarization of Polarizer to substrate irradiation ultraviolet radiation.Exposure energy now uses oxtail motor (share) ultraviolet that manufactures to add up quantorecorder UIT-150 (optical receiver UVD-S365) to measure light quantity, and to become 1.0 ± 0.1J/cm under wavelength 365nm ²mode adjust the time shutter.Then, in cleaning oven (Ace peck (Espec) limited-liability company, PVHC-231), carry out 15 minutes heat treated with 230 DEG C, and form the alignment films that thickness is 100 ± 10nm.Measure the pencil hardness of obtained substrate, result is 3H.

The confirmation that the making method of <FFS unit, the confirmation of flow orientation, foreign matter produce and AC image retention measure >

Make 2 be formed on substrate the substrate of alignment films be formed alignment films in the face of to, parallel mode is become with frictional direction in respective alignment films, and then fit behind the space being formed in order to inject positive type liquid crystal composition between the alignment films towards subtend, thus be assembled into the empty FFS unit that element thickness is 4 μm.In made empty FFS unit, vacuum injects above-mentioned positive type liquid crystal composition, and makes FFS liquid crystal display device.Confirm the orientation of liquid crystal in obtained liquid crystal display device, result does not see flow orientation.Then, the liquid crystal display device after utilizing microscopic examination foreign matter to test, result does not see the generation of foreign matter.In addition, measure the value of contrast gradient, result is 2730, measures AC image retention, and result Δ B is 2.6%.

[embodiment 2 ~ embodiment 41, comparative example 1 ~ comparative example 9]

Change the polyamic acid solution being used as liquid crystal aligning agent, utilize according to the method for embodiment 1 and make mensuration substrate, pencil hardness is measured.In addition, utilize according to the method for embodiment 1 and make FFS unit, carrying out the confirmation of flow orientation, foreign matter test, contrast gradient measures and AC image retention measures.The polyamic acid solution and each measurement result that are used as liquid crystal aligning agent are shown in table 5-1.Also again embodiment 1 is disclosed.

Table 5-1

Table 5-1 (Continued)

As shown in Table 5-1, the pencil hardness of the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention is more than 2H, demonstrates high film hardness.Confirm in addition, in liquid crystal display device of the present invention, do not cause the generation of foreign matter, contrast gradient is also high, and AC image retention is also inhibited.

[embodiment 42 ~ embodiment 68, comparative example 10 ~ comparative example 13]

Be used as, except liquid crystal aligning agent, utilize according to the method for embodiment 1 and make mensuration substrate, measuring pencil hardness except by the polyamic acid solution shown in table 5-2.The result of the pencil hardness of gained is recorded in table 5-2.

In embodiment 1, the polyamic acid solution shown in table 5-2 is used as liquid crystal aligning agent, and replaces above-mentioned positive type liquid crystal composition and vacuum injects above-mentioned negative type liquid crystal composition, in addition, utilize according to the method for embodiment 1 and make FFS liquid crystal display device.By being used as the polyamic acid solution of liquid crystal aligning agent, the confirmation of flow orientation, foreign matter test, contrast gradient measures and AC image retention measures result be shown in table 5-2.

Table 5-2

As showing shown in 5-2, even if use negative type liquid crystal composition, the pencil hardness of the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention is also more than 2H, still demonstrates high film hardness.Confirm in addition, in liquid crystal display device of the present invention, do not cause the generation of foreign matter, contrast gradient is also high, and AC image retention is also inhibited.

[embodiment 69]

Polymer solids constituent concentration fusion preparation obtained is that the polyamic acid solution (PC-1) of 4 % by weight is as liquid crystal aligning agent, utilize ink-jet coating apparatus (Fujiphoto (Fujifilm) limited-liability company manufactures, DMP-2831) by the coating of this liquid crystal aligning agent on the glass substrate.Moreover, voltage adjustment is applied to drop interval, box (cartridge), makes the thickness that liquid crystal orientation film becomes following.After film, hot plate (Ya Suwang limited-liability company manufactures, EC hot plate (EC-1200N)) carries out 80 seconds heat dryings with 70 DEG C.Secondly, the MultiLightML-501C/B that oxtail motor (share) manufactures is used, from vertical via the linear polarization of Polarizer to substrate irradiation ultraviolet radiation.Exposure energy now uses oxtail motor (share) ultraviolet that manufactures to add up quantorecorder UIT-150 (optical receiver UVD-S365) to measure light quantity, and to become 1.0 ± 0.1J/cm under wavelength 365nm ²mode adjust the time shutter.Then, in cleaning oven (Ace peck limited-liability company, PVHC-231), carry out 15 minutes heat treated with 230 DEG C, and form the liquid crystal orientation film that thickness is 100 ± 10nm.Measure the pencil hardness of obtained substrate, result is 3H.

Make 2 be formed on substrate the substrate of liquid crystal orientation film be formed alignment films in the face of to, parallel mode is become with the ultraviolet polarization direction irradiated respective liquid crystal orientation film, and then fit behind the space of formation in order to injection liquid crystal composite between the alignment films towards subtend, thus be assembled into the empty FFS unit that element thickness is 4 μm.In made empty FFS unit, vacuum injects above-mentioned positive type liquid crystal composition, and makes FFS liquid crystal display device.Confirm the orientation of liquid crystal in obtained liquid crystal display device, result does not see flow orientation.Then, the liquid crystal display device after utilizing microscopic examination foreign matter to test, result does not see the generation of foreign matter.In addition, measure the value of contrast gradient and the result that obtains is 3010, measure AC image retention, result Δ B is 2.0%.

[embodiment 70 ~ embodiment 75, comparative example 14 ~ comparative example 18]

Be used as, except liquid crystal aligning agent, utilize according to the method for embodiment 69 and make mensuration substrate, measuring pencil hardness except by the polyamic acid solution shown in table 5-3.In addition, utilize according to the method for embodiment 69 and make FFS unit, carrying out the confirmation of flow orientation, foreign matter test, contrast gradient measures and AC image retention measures.Measurement result is shown in table 5-3.

Table 5-3

As showing shown in 5-3, even if utilize ink-jetting style to print liquid crystal aligning agent, the pencil hardness of the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention is also more than 2H, still demonstrates high film hardness.Confirm in addition, in liquid crystal display device of the present invention, do not cause the generation of foreign matter, contrast gradient is also high, and AC image retention is also inhibited.

[utilizability in industry]

Confirm liquid crystal aligning agent of the present invention and can form the liquid crystal orientation film that film hardness is high, demonstrate excellent liquid crystal aligning.Confirm the liquid crystal display device comprising the liquid crystal orientation film formed by liquid crystal aligning agent of the present invention and there is following excellent specific property: not easily cause foreign matter during touch screen operation to produce, demonstrate high contrast gradient, not easily cause AC image retention etc.Liquid crystal aligning agent of the present invention especially can use aptly in transverse electric field type liquid crystal display element.

Claims (16)

1. a liquid crystal aligning agent, it contains to be selected from makes tetracarboxylic dianhydride and diamines carry out reacting and at least one polymkeric substance (a) in the polyamic acid obtained and derivative thereof, and the feature of described liquid crystal aligning agent is:

Described tetracarboxylic dianhydride contains at least one of the tetracarboxylic dianhydride represented by following formula (1) and at least one in being selected from the tetracarboxylic dianhydride with alicyclic structure or aliphatic structure,

Described diamines contains the diamines that at least one has photoreactivity structure,

In formula (1), m is the integer of 1 ~ 10.

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

3. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described in there is the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure for being selected from least one in the compound represented by following formula (3) ~ formula (9):

At least one of hydrogen in described formula can by-CH ₃,-CH ₂cH ₃or phenyl replaces.

4. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described in there is the tetracarboxylic dianhydride of alicyclic structure or aliphatic structure for being selected from least one in the compound represented by following formula (3-1):

In formula (3-1), R is hydrogen ,-CH independently ₃,-CH ₂cH ₃or phenyl.

5. liquid crystal aligning agent according to claim 1 and 2, is characterized in that: described in there is alicyclic structure tetracarboxylic dianhydride be 1,2,3,4-tetramethylene tetracarboxylic dianhydride.

6. liquid crystal aligning agent according to claim 1, is characterized in that: described in there is photoreactivity structure diamines be 4,4 '-chrysoidine.

7. liquid crystal aligning agent according to claim 1, is characterized in that: described diamines is also containing being selected from following formula (D-1) ~ formula (D _-5) at least one in the group of the compound represented by:

In formula (D-2) and formula (D-4), X and Y is the sub-a heatable brick bed base of singly-bound ,-O-,-NH-,-S-or carbon number 1 ~ 6;

At least one hydrogen of phenyl ring can by-CH ₃replace;

In formula (D-4), a is the integer of 1 ~ 8; And,

In formula (D-5), Ra is the alkyl of carbon number 1 ~ 3.

8. liquid crystal aligning agent according to claim 1, is characterized in that: also containing at least one polymkeric substance (b) be selected from polyamic acid and derivative thereof that the tetracarboxylic dianhydride making not have photoreactivity structure and the diamines without photoreactivity structure carry out reacting and obtain.

9. liquid crystal aligning agent according to claim 8, is characterized in that: the tetracarboxylic dianhydride used in the synthesis of described polymkeric substance (b) contains at least one be selected from following formula (3) ~ formula (13):

At least one of hydrogen in described formula can by-CH ₃,-CH ₂cH ₃or phenyl replaces.

10. liquid crystal aligning agent according to claim 8 or claim 9, is characterized in that: the diamines used in the synthesis of described polymkeric substance (b) contains at least one be selected from following formula (D-1) ~ formula (D-5):

In formula (D-2) and formula (D-4), X and Y is the alkylidene group of singly-bound ,-O-,-NH-,-S-or carbon number 1 ~ 6;

At least one hydrogen of phenyl ring can by-CH ₃replace;

In formula (D-4), a is the integer of 1 ~ 8; And,

In formula (D-5), Ra is the alkyl of carbon number 1 ~ 3.

11. liquid crystal aligning agent according to claim 1, is characterized in that: also containing at least one be selected from the group of the compound be made up of oxazine compounds, oxazoline compound, epoxy compounds and silane coupling agent.

12. liquid crystal aligning agent according to claim 11, it is characterized in that: described silane coupling agent is for being selected from by 2-(3,4-expoxycyclohexyl) at least one in the group of compound that forms of ethyl trimethoxy silane, 2-(3,4-expoxycyclohexyl) ethyl triethoxysilane, p-aminophenyl Trimethoxy silane, p-aminophenyl triethoxyl silane, 3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane and 3-glycidoxypropyl triethoxyl silane.

13. liquid crystal aligning agent according to claim 1, is characterized in that: containing at least one solvent be selected from alcohol, ether and ketone.

14. liquid crystal aligning agent according to claim 1, is characterized in that: containing at least one solvent be selected from aklylene glycol alkyl ether derivative, two alkylene glycol dialkylether derivatives and propanediol derivative.

15. a liquid crystal orientation film, it is characterized in that: formed by the liquid crystal aligning agent according to any one of claim 1 to 14.

16. 1 kinds of liquid crystal display device, is characterized in that: comprise liquid crystal orientation film according to claim 15.