CN109468137A

CN109468137A - Light orientation aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display element, polymer and diamines

Info

Publication number: CN109468137A
Application number: CN201810970717.7A
Authority: CN
Inventors: 小関洋平; 塚田裕以智; 大木洋郎; 大木洋一郎
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: Changsha Dao'anjie New Materials Co ltd
Priority date: 2017-09-08
Filing date: 2018-08-24
Publication date: 2019-03-15
Anticipated expiration: 2038-08-24
Also published as: TW201912679A; KR20190028287A; CN109468137B; JP2019049700A; JP7180196B2

Abstract

The present invention is to be related to a kind of light orientation aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display element, polymer and diamines, and the light orientation aligning agent for liquid crystal contains the polymer with the Component units for represented by following formula (1) including photonasty base.Aligning agent for liquid crystal through the invention and show high liquid crystal aligning, and the liquid crystal orientation film with high transmitance can be formed.The present invention provides a kind of novel photonasty diamines of raw material as polymer used in the light orientation aligning agent for liquid crystal in turn.In formula (1), R¹And R²It independently is the alkyl of hydrogen or carbon number 1~10；The binding site that binding site is not secured to constitute the bond key on any one carbon of ring and indicates on the ring be it is any, the hydrogen of phenyl ring can be replaced by substituent group.

Description

Light orientation aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal display element, polymer and Diamines

Technical field

The present invention is to be related to a kind of aligning agent for liquid crystal, liquid crystal orientation film and the liquid crystal display element using it.Specifically, It is to be related to a kind of liquid crystal aligning of liquid crystal orientation film (hereinafter, being abbreviated as optical alignment film sometimes) to form aligned setting of light Agent, the liquid crystal orientation film of the aligned setting of light formed using the aligning agent for liquid crystal and the liquid with the liquid crystal orientation film Crystal display element.Still further, it is being related to the condensates such as polyamic acid or polyimides used in a kind of aligning agent for liquid crystal And the diamine compound as its raw material.

Background technique

As liquid crystal display element, it is known to twisted nematic (Twisted Nematic, TN) mode, STN Super TN (Super Twisted Nematic, STN) mode, coplanar switching (In-Plane Switching, IPS) mode, fringing field are cut Change (Fringe Field Switching, FFS) mode, the vertical orientation of vertical orientating type (Vertical Alignment, VA) (multidomain vertical orientation (Multi-domain Vertical Alignment)) mode etc., and it is used for TV, mobile phone Etc. various purposes.In order to operate these liquid crystal display elements, it is necessary to there is certain rule for the substrate of element It is orientated liquid crystal to property.Being formed on substrate with the purpose is liquid crystal orientation film.Liquid crystal orientation film is taken by liquid crystal To dosage form at.Currently, main aligning agent for liquid crystal to be used is to keep polyamic acid, soluble polyimides or poly amic acid ester molten Solution in organic solvent made of solution (varnish).By the solution coating after on substrate, carried out by the methods of heating Film, to form polyimides system liquid crystal orientation film.After film, optionally implement the orientation position for being suitable for the display pattern Reason.As method for orientation treatment, rubbing manipulation is practical with optical alignment method.Optical alignment method is non-contacting orientation position logos, because This has many advantages, such as not damage film, can lower dirt or electrostatic etc. that liquid crystal display element is made to generate the bad reason of display.

The development of the technology of liquid crystal display element not only realized by the improvement of driving method, component structure, but also It is realized by member of formation used in element.In member of formation used in liquid crystal display element, especially liquid crystal Alignment films are to be related to one of important materials of display quality, with the high-quality of liquid crystal display element, improve liquid crystal aligning The performance of film becomes important.

Using any orientation position logos of rubbing manipulation and optical alignment method, to spy required by liquid crystal orientation film Also there is liquid crystal aligning in property.By using the high liquid crystal orientation film of liquid crystal aligning, it is possible to provide contrast or image retention characteristic are high Liquid crystal display element (for example, patent document 4 and patent document 5).Compared with rubbing manipulation, the uniformity of the orientation of optical alignment method It is high.Wherein, pass through the technology of documented photoisomerization in application 1~patent document of patent document 5, it is possible to provide anchoring energy it is big and The good optical alignment film of liquid crystal aligning.However, the further high-quality of display quality is required liquid crystal display element, to liquid Brilliant alignment films also require higher liquid crystal aligning.

As to characteristic required by liquid crystal orientation film, in addition to liquid crystal aligning, there are also the high degree of transmitance.Liquid In crystal display element, if the liquid crystal orientation film low using transmitance, the brightness that can lead to the problem of liquid crystal display element is reduced. Disclosed in patent document 6 have it is a kind of using the optical alignment film with azo group and the excellent diamine compound of photonasty.The light In alignment films, conjugated system is shortened by interval base, thus improves transmitance.However, the even described technology, also requires high The further raising of transmitance, therefore still have room for improvement.

[existing technical literature]

[patent document]

[patent document 1] Japanese Patent Laid-Open 2005-275364

[patent document 2] Japanese Patent Laid-Open 2007-248637

[patent document 3] Japanese Patent Laid-Open 2009-069493

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

[patent document 5] International Publication 2013/157463

[patent document 6] Japanese Patent Laid-Open 2014-205659

Summary of the invention

[problem to be solved by the invention]

Problem of the invention is that providing a kind of liquid crystal aligning for showing high liquid crystal aligning and there is high transmitance Film.In turn, be to provide it is a kind of can form the aligning agent for liquid crystal of the film, and provide a kind of using the liquid crystal orientation film Liquid crystal display element.In addition, being to provide a kind of novel photonasty diamines that can be used in the aligning agent for liquid crystal.

[technical means to solve problem]

The inventors of the present invention people's discovery by by acylhydrazone (acylhydrazone) structure represented in formula (1) with photonasty The form of base has the liquid crystal orientation film of high orientation and high transmitance for obtaining in the raw material of aligning agent for liquid crystal, from And complete the present invention.The present invention includes the following contents.

[1] a kind of light orientation aligning agent for liquid crystal contains with the structure for represented by following formula (1) including photonasty base At the polymer of unit；

In formula (1),

R¹And R²It independently is the alkyl of hydrogen or carbon number 1~10；

The bond key that binding site is not secured to constitute on any one carbon of ring indicates that the binding site on the ring is to appoint Meaning, the hydrogen of phenyl ring can be replaced by substituent group.

[2] the light orientation aligning agent for liquid crystal according to item [1] contains as next self-contained tetracarboxylic dianhydride and two The polymer of the reaction product of the raw material of amine；

The diamines contains at least one of diamines represented by following formula (2)；

Herein, the polymer is selected from by polyamic acid, polyimides, part polyimides, poly amic acid ester, polyamides At least one of group composed by amino acid-polyamide copolymer and polyamidoimide；

In formula (2), R¹And R²It independently is the alkyl of hydrogen or carbon number 1~10；

R⁴And R⁶It independently is straight-chain alkyl-sub ,-COO- ,-OCO- ,-NHCO- ,-CONH-, the-N (CH of carbon number 1~20₃) CO-、-CON(CH₃)-or singly-bound；

R⁴And R⁶In ,-the CH of straight-chain alkyl-sub₂Two of one or not adjacent can be replaced by-O-；

R⁵And R⁷It independently is monocyclic hydrocarbon, condensation polycyclic formula hydrocarbon, heterocycle or singly-bound；Moreover,

[3] the light orientation aligning agent for liquid crystal according to item [2], wherein the diamines contains represented by following formula (3) Diamines at least one.

In formula (3), R⁴And R⁶Independently be the straight-chain alkyl-sub of carbon number 1~20 ,-COO- ,-OCO- ,-NHCO- ,- CONH-、-N(CH₃)CO-、-CON(CH₃)-or singly-bound；

R⁴And R⁶In ,-the CH of straight-chain alkyl-sub₂One or two can be replaced by-O-；

The bond key that binding site is not secured to constitute on any one carbon of ring indicates that the binding site on the ring is to appoint Meaning.

[4] the light orientation aligning agent for liquid crystal according to item [2] or item [3], wherein the diamines contains following formula (4) At least one of diamines represented by~formula (7)；

In formula (4)~formula (7), R⁴And R⁶It independently is the straight-chain alkyl-sub or singly-bound of carbon number 1~2；Moreover,

[5] the light orientation aligning agent for liquid crystal according to any one of item [2] to item [4], wherein the diamines contains Represented by following formula (4-1), formula (4-2), formula (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2) At least one of diamines；

[6] the light orientation aligning agent for liquid crystal according to any one of item [2] to item [5], wherein the raw material is in turn Comprising selected from least one of group as composed by following formula (II)~formulas (VI)；

R⁴-C≡C-R⁵ (II)

R⁴-C≡C-C≡C-R⁵ (III)

R⁴-C≡C-R⁶-C≡C-R⁵ (IV)

R⁴- N=N-R⁵ (V)

R⁵- CH=CH-R⁷ (VI)

In formula (II)~formula (VI), R⁴And R⁵For with-NH₂Any monovalent organic radical or monovalence with-CO-O-CO- it is organic Base；

In formula (IV), R⁶For divalent organic base；

In formula (VI), R⁷For with-NH₂Or the aromatic rings of-CO-O-CO-.

[7] the light orientation aligning agent for liquid crystal according to any one of item [1] to item [6], is used for lateral electric-field type The manufacture of liquid crystal display element.

[8] a kind of liquid crystal orientation film is to be taken as the light orientation according to any one of item [1] to item [7] with liquid crystal It is formed to agent.

[9] a kind of liquid crystal display element has the liquid crystal orientation film according to item [8].

[10] a kind of lateral electric-field type liquid crystal display element has the liquid crystal orientation film according to item [8].

[11] a kind of diamines, by formula (4-2), formula (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2) is indicated.

[12] a kind of polymer, wherein the polymer be selected from by polyamic acid, polyimides, part polyimides, At least one of group composed by poly amic acid ester, polyamic acid-polyamide copolymer and polyamidoimide, wherein institute State the reaction product that polymer is tetracarboxylic dianhydride at least one diamines containing diamines represented by following formula (2)；

[13] polymer according to item [12], wherein the diamines contains diamines represented by following formula (3) extremely Few one kind；

[14] polymer according to item [12] or item [13], wherein the diamines contains following formula (4)~formula (7) institute At least one of the diamines of expression；

[15] polymer according to any one of item [12] to item [14], wherein the diamines contains following formula (4- 1), diamines represented by formula (4-2), formula (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2) is at least It is a kind of；

[The effect of invention]

The light that use of the invention contains the polymer with the Component units for represented by formula (1) including photonasty base takes Into the liquid crystal orientation film formed with aligning agent for liquid crystal, compared with azo group, the visible light region as caused by acylhydrazone structure Light absorption it is few, therefore, as a result can get with high transmitance liquid crystal orientation film.Technology of the invention is in light orientation side Especially excellent effect is played in the field of the liquid crystal orientation film of formula.

Detailed description of the invention

Fig. 1 is the UV-Vis spectrum of liquid crystal orientation film 1 obtained in embodiment 1.

Fig. 2 is the UV-Vis spectrum of liquid crystal orientation film obtained in comparative example 1.

Specific embodiment

Hereinafter, the present invention is described in detail.The explanation for the constitutive requirements recorded below is sometimes based upon representative Embodiment or concrete example form, but the present invention is not limited to such embodiments.Furthermore in this specification, sometimes will " aligning agent for liquid crystal of aligned setting of light " is known as " light orientation aligning agent for liquid crystal ".In addition, sometimes will described in " aligned setting of light Aligning agent for liquid crystal " or " light orientation aligning agent for liquid crystal " are abbreviated as " aligning agent for liquid crystal ".

Light orientation < of the invention aligning agent for liquid crystal >

Light orientation aligning agent for liquid crystal of the invention contains the polymer with Component units represented by formula (1).

In formula (1), R¹And R²It independently is the alkyl of hydrogen or carbon number 1~10；Binding site is not secured to constitute any of ring Bond key on a carbon indicate the binding site on the ring be it is any, the hydrogen of phenyl ring can be replaced by substituent group.

In formula (1), R¹And R²In alkyl can be straight-chain, branch-like, cricoid any.The preferred carbon number of alkyl is 1 ~6, more preferably 1~4, and then more preferably 1~3.It as the concrete example of alkyl, can illustrate: methyl, ethyl, propyl, isopropyl Base, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, isopentyl, neopentyl, tertiary pentyl, 1- methyl butyl, 1- ethyl propyl, Hexyl, isohesyl, 1- methyl amyl, 1- ethyl-butyl etc..

The hydrogen of phenyl ring in formula (1) can be replaced by substituent group.It as the preference of substituent group, can enumerate: alkyl, alcoxyl Base, halogenated alkyl, halogen, carboxyalkyl.Alkyl can be straight-chain, branch-like, cricoid any.The preferred carbon number of alkyl is 1~4, more preferably 1~2.As the concrete example of alkyl, can illustrate: methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, Sec-butyl, tert-butyl etc..The preferred carbon number of alkoxy is 1~4, more preferably 1~2.It, can example as the concrete example of alkoxy Show: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy etc..As halogenation The concrete example of alkyl can illustrate trifluoromethyl etc..It as the concrete example of halogen, can list: fluorine, chlorine, bromine, iodine etc..As carboxyl The concrete example of alkyl can illustrate carboxymethyl group, carboxy ethyl etc..

Component units represented by formula (1) have acylhydrazone structure.Acylhydrazone structure by irradiation light generate trans- body with it is suitable The isomerization reaction of formula body.

There is no particular restriction for the wavelength of the light of generation isomerization reaction, preferably 150nm~800nm, more preferably 200nm ~400nm, and then more preferably 300nm~400nm.In addition, light needed for generating structure change in photoreactivity structure irradiates Intensity is preferably 0.05J/cm²~20J/cm²。

If aligning agent for liquid crystal of the invention is coated on substrate, after being made it dry by preheating, via polarizer And irradiate linear polarization, then the acylhydrazone structure of the main polymer chain substantially parallel with polarization direction can cause isomerization reaction.It is logical The main chain of the polymer substantially parallel with polarization direction is crossed by selectively isomerization, is formed in the main chain of the polymer of film, court It is that the ingredient in approximate right angle direction occupies ascendancy to the polarization direction relative to the ultraviolet light irradiated.Thereafter, pass through The film through light orientation is heated and is calcined and forms liquid crystal orientation film.It is selected from by polyamides in the polymer Amino acid, polyimides, part polyimides, poly amic acid ester, polyamic acid-polyamide copolymer and polyamidoimide institute group At at least one of group in the case where, the step of irradiation light can the heating stepses to carry out polyimides it Before, it can also be after being heated and being subject to polyimides.

< polymer >

Polymer used in aligning agent for liquid crystal of the invention: with photonasty base represented in formula (1) in main chain. Polymer used in aligning agent for liquid crystal of the invention can be a kind of polymer, can also be two or more.The type of polymer Be not particularly limited, such as can enumerate: polyamic acid, polyamic acid derivative, polyester, polyamide, polysiloxanes, cellulose spread out Biology, polyacetals, polystyrene derivative, poly- (styrene-phenylmaleimide) derivative, poly- (methyl) acrylic acid Ester etc..

Herein, polyamic acid is polymerizeing by diamines represented by formula (DI) and tetracarboxylic dianhydride represented by formula (AN) The polymer of reaction and synthesis, and there are Component units represented by formula (PAA).By making polyamic acid carry out dehydration closed-loop, The polyimide liquid crystal direct action membrane with Component units represented by formula (PI) can be formed.By using with the institute in formula (1) The binding site of the structure of expression is linked with the compound of the structure of amino as diamines, and can be easy will be represented in formula (1) Structure is directed into main chain.Amino in diamines can directly be bonded in formula (1) binding site of represented structure, can also be via Bivalence linking base connection.

In formula (AN), formula (PAA) and formula (PI), X¹Indicate quadrivalent organic radical.In formula (DI), formula (PAA) and formula (PI), X² Indicate divalent organic base.About X¹In quadrivalent organic radical preferred scope and concrete example, can refer to following tetracarboxylic dianhydrides one Structure corresponding to the tetracarboxylic dianhydride recorded in column.About X²In divalent organic base preferred scope and concrete example, can join According to note relevant to structure corresponding to the diamines or two hydrazides recorded in formula (1) or following known diamines, two hydrazides, one column It carries.

The derivative of so-called polyamic acid, which refers to, is dissolved in solvent when the aftermentioned aligning agent for liquid crystal containing solvent is made In ingredient, and refer to when liquid crystal orientation film is made in the aligning agent for liquid crystal, can be formed using polyimides as principal component The ingredient of liquid crystal orientation film.As the derivative of such polyamic acid, such as soluble polyimide, polyamic acid can be enumerated More specifically ester and polyamic acid amide etc. can be enumerated: 1) all amino of polyamic acid and carboxyl carry out dehydration closed-loop Polyimides made of reaction, 2) partly carry out dehydration closed-loop reaction made of part polyimides, 3) by polyamic acid Carboxyl is transformed into poly amic acid ester made of ester, 4) by a part substitution of acid dianhydride contained in tetracarboxylic dianhydride's compound At organic dicarboxylic acid and is reacted and polyamic acid-polyimide copolymer for obtaining and 5) make the polyamic acid-poly- Part or all of imide copolymer carries out polyamidoimide made of dehydration closed-loop reaction.In these derivatives, example It is such as used as polyimides, can enumerate with Component units person represented by the formula (PI), as poly amic acid ester, tool can be enumerated There is Component units person represented by following formula (PEA).

In formula (PAE), X¹Indicate quadrivalent organic radical, X²Indicate that divalent organic base, Y independently indicate alkyl.About X¹、X² Preferred scope and concrete example, can refer to formula (PAA) in X¹、X²Relevant record.Explanation and preferred scope, tool about Y Body example can refer to explanation relevant to the alkyl of substituent group of phenyl ring as the formula (1) and preferred scope, concrete example.

In these polymer, be preferably selected from the group as composed by polyamic acid and its derivative at least one Kind.Hereinafter, polymer is set as the case where polyamic acid and its derivative, details is illustrated.

< polyamic acid and its derivative >

With photonasty represented in formula (1) in the polyamic acid and its derivative main chain of embodiments of the present invention Base, such as can be obtained by at least one that at least one of starting monomer includes compound represented by formula (2).In addition, As long as the polyamic acid and its derivative are the polymer of the structure of the reaction product with tetracarboxylic dianhydride and diamines, Following reaction product can also be contained: using other raw materials, pass through other reactions other than the reacting of tetracarboxylic dianhydride and diamines ?.

Polyamic acid of embodiments of the present invention or derivatives thereof can be used in the formation with the film of polyimides Well known polyamic acid or derivatives thereof similarly manufactures.Total input amount of tetracarboxylic dianhydride is preferably to be set as always rubbing with diamines That number substantially equimolar (molar ratio 0.9~1.1 or so).

In addition, the polyamic acid of embodiments of the present invention to be set as to the polyimides as polyamic acid derivative In the case of, can make the acid anhydrides such as polyamic acid solution obtained and acetic anhydride, propionic andydride, trifluoroacetic anhydride as dehydrating agent and The tertiary amines such as triethylamine, pyridine, collidine as dehydration closed-loop catalyst carry out acyl at 20 DEG C~150 DEG C of temperature together Imidization obtains.Or, it is possible to use a large amount of bad solvent (alcohol such as methanol, ethyl alcohol, isopropanol system's solvent or glycol It is solvent) and polyamic acid is precipitated from polyamic acid solution obtained, and make polyamic acid be precipitated in toluene, diformazan It is sub- to carry out acyl in the solvents such as benzene at 20 DEG C~150 DEG C of temperature together with the identical dehydrating agent and dehydration closed-loop catalyst Aminating reaction.

In the imidization reaction, total usage amount of dehydrating agent and dehydration closed-loop catalyst is preferably relative to described The mole of tetracarboxylic dianhydride used in the synthesis of polyamic acid adds up to and is 1.5 times moles~10 times moles.Dehydration The ratio of agent and dehydration closed-loop catalyst is preferably 0.1~10 (molar ratio).By adjusting chemically acid imide described in the two Dehydrating agent, catalytic amount, reaction temperature and the reaction time of change can control the degree of imidizate, to obtain part polyamides Imines.Polyimides obtained can also be separated with solvent and be re-dissolved in the solvent and be used as aligning agent for liquid crystal, or It can not also be separated with solvent and be used as aligning agent for liquid crystal.

The poly amic acid ester can synthesize by the following method: the chemical combination by making the polyamic acid and hydroxyl The reactions such as object, halide, compound containing epoxy group and synthetic method, or by making the tetracarboxylic acid from derived from tetracarboxylic dianhydride Acid diesters or tetracarboxylic acid acid diesters dichloride and diamine reactant and synthetic method.The tetracarboxylic acid acid diesters from derived from tetracarboxylic dianhydride Such as can make tetracid dianhydride reacted with the alcohol of 2 equivalents and open loop and obtain, tetracarboxylic acid acid diesters dichloride can be by making tetrabasic carboxylic acid Diester is reacted with the chlorinating agent (such as thionyl chloride etc.) of 2 equivalents and is obtained.Furthermore poly amic acid ester can only have amic acid esters Structure can also be amic acid structure and amic acid esters structure and the partial esterification object deposited.Light orientation liquid crystal aligning of the invention Agent may include a kind of polyamic acid, poly amic acid ester and they is subject to imidizate and the polyimides that obtains, can also Comprising two or more.

The weight average that the molecular weight of the polyamic acid of embodiments of the present invention or derivatives thereof is converted with polystyrene Molecular weight (Mw) meter, preferably 7,000~500,000, more preferably 10,000~200,000.The polyamic acid or its spread out The molecular weight of biology can be according to the measurement using gel permeation chromatography (Gel Permeation Chromatography, GPC) method To find out.

Polyamic acid of embodiments of the present invention or derivatives thereof can confirm its presence in the following way: utilize Infrared ray (Infrared, IR), nuclear magnetic resonance (Nuclear Magnetic Resonance, NMR) are to making implementation of the invention The solid component that polyamic acid of mode or derivatives thereof is precipitated in a large amount of poor solvent and obtained is analyzed.In addition, It can confirm in the following way used monomer: utilize gas chromatography (Gas Chromatography, GC), efficient liquid Phase chromatography (High Performance Liquid Chromatography, HPLC) or gas chromatography mass spectrometry (Gas Chromatography-Mass Spectrometry, GC-MS) to using the aqueous solution of the highly basic such as KOH or NaOH described poly- After amic acid or derivatives thereof decomposes, analyzed using the extract that organic solvent is extracted from its decomposition product.

Diamines > < of the invention

Diamines represented by formula (2) to embodiments of the present invention is illustrated.

In formula (2), R¹And R²It independently is the alkyl of hydrogen or carbon number 1~10.R in formula (2)¹And R²Example can refer to R in formula (1)¹And R²Example.

R⁴And R⁶It independently is straight-chain alkyl-sub ,-COO- ,-OCO- ,-NHCO- ,-CONH-, the-N (CH of carbon number 1~20₃) CO-、-CON(CH₃)-or singly-bound.R⁴And R⁶In ,-the CH of straight-chain alkyl-sub₂Two of one or not adjacent can be taken by-O- Generation.R⁵And R⁷For monocyclic hydrocarbon, condensation polycyclic formula hydrocarbon, heterocycle or singly-bound.

R⁵And R⁷In monocyclic hydrocarbon can be alicyclic ring, can also be aromatic rings.The carbon number of monocyclic hydrocarbon is preferably 6~12, more excellent It is selected as 6~10, and then more preferably 6~8.It as the concrete example of monocyclic hydrocarbon, can enumerate: phenyl ring, cyclohexane ring, cyclohexene Ring.

R⁵And R⁷In the carbon number of condensation polycyclic formula hydrocarbon be preferably 10~20, more preferably 10~18, and then more preferably 10 ~14.It as the concrete example of condensation polycyclic formula hydrocarbon, can enumerate: naphthalene nucleus, anthracene nucleus, phenanthrene ring.

R⁵And R⁷In heterocycle can be alicyclic ring, can also be aromatic rings.The carbon number of heterocycle is preferably 1~26, more preferably 3~ 14, and then more preferably 3~8.As the hetero atom that heterocycle is included in the form of ring element, can enumerate: nitrogen, oxygen, sulphur.As miscellaneous The concrete example of ring can be enumerated: pyridine ring, pyridine ring, pyrimidine ring, pyridazine ring, indole ring, oxazole ring.

The bond key that binding site is not secured to constitute on any one carbon of ring indicates that the binding site on the ring is to appoint Meaning, the hydrogen of phenyl ring can be replaced by substituent group.About the preferred scope and concrete example of substituent group, can refer in the general formula (1) It may replace the preferred scope and concrete example in the substituent group on phenyl ring.

In formula (2), for the aspect of the height of orientation, preferably diamine compound represented by following formula (3).

In formula (3), R⁴And R⁶Independently be the straight-chain alkyl-sub of carbon number 1~20 ,-COO- ,-OCO- ,-NHCO- ,- CONH-、-N(CH₃)CO-、-CON(CH₃)-or singly-bound.R⁴And R⁶In ,-the CH of straight-chain alkyl-sub₂One or not adjacent two It is a to be replaced by-O-.R⁵And R⁷For monocyclic hydrocarbon, condensation polycyclic formula hydrocarbon, heterocycle or singly-bound.R⁵And R⁷In monocyclic hydrocarbon, condensation The example of polycycle hydrocarbon or heterocycle can refer to the R in formula (2)⁵And R⁷Example.Binding site is not secured to constitute either one or two of ring Bond key on carbon indicates that the binding site on the ring is any.

In formula (3), for the aspect for the easiness that raw material obtains, preferably two represented by following formula (4)~formula (7) Amine compounds.

In formula (4)~formula (7), R⁴And R⁶It independently is the straight-chain alkyl-sub or singly-bound of carbon number 1~2.Moreover, binding site Being not secured to constitute the bond key on any one carbon of ring indicates that the binding site on the ring is any.

In formula (4)~formula (7), for the aspect of the height of orientation, preferably following formula (4-1), formula (4-2), formula Diamine compound represented by (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2).

The synthesis > of diamines < of the invention

Formula (4-1), formula (4-2), formula (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2) institute table The diamines shown can synthesize in the manner as described below.

Diamines represented by the formula (4-1) and formula (4-2) of embodiments of the present invention can be by by commercially available nitrobenzoyl After sour methyl esters is subject to hydrazides, supplies commercially available nitrobenzaldehyde and obtain dinitro compound.Thereafter, by restoring nitro And it obtains.

Diamines represented by the formula (5-1) and formula (5-2) of embodiments of the present invention can be by commercially available 4- bromobenzoic acid After methyl esters and nitrophenyl boronic acid are subject to cross-coupling (cross coupling), obtained by the method.

Diamines represented by the formula (6-1) and formula (6-2) of embodiments of the present invention can by commercially available bromo nitryl benzene with After 4- formyl phenylboronic acid is subject to cross-coupling, obtained by the method.

Diamines represented by the formula (7-1) and formula (7-2) of embodiments of the present invention can pass through the combination of the method It obtains.

These compounds can also be purified by recrystallization or column chromatography to use.

In order to provide the aligning agent for liquid crystal that can form the higher liquid crystal orientation film of orientation, in these compounds, preferably By at least one of diamine compound represented by formula (4-1), formula (5-1), formula (6-1) and formula (7-1) in raw material.

< tetracarboxylic dianhydride >

Tetracarboxylic dianhydride to the polyamic acid and its derivative that manufacture embodiments of the present invention is illustrated.This Tetracarboxylic dianhydride used in invention can unlimitedly select from well known tetracarboxylic dianhydride.Such tetracarboxylic dianhydride can be Belong to aromatic system (comprising miscellaneous aromatic ring) that dicarboxylic anhydride is directly bonded on aromatic rings and dicarboxylic anhydride is not bonded directly Tetracarboxylic dianhydride in the group of any one of the fatty family (including heterocycle system) on aromatic rings.

As the suitable example of such tetracarboxylic dianhydride, what easiness or condensate with regard to raw material acquisition manufactured is easy For property, the aspect of the electrical characteristics of film, tetracarboxylic dianhydride represented by formula (AN-I)~formula (AN-V) can be enumerated.

In formula (AN-I), formula (AN-IV) and formula (AN-V), X independently is singly-bound or-CH₂-.In formula (AN-II), G is single Key, the alkylidene of carbon number 1~20 ,-CO- ,-O- ,-S- ,-SO₂-、-C(CH₃)₂Or-C (CF₃)₂-.Formula (AN-II)~formula (AN- IV in), Y independently is one of the group selected from following triads, and bond key and arbitrary carbon link, and the base is at least One hydrogen can be replaced by methyl, ethyl or phenyl.

In formula (AN-III)~formula (AN-V), ring A¹⁰For the condensation of the base or carbon number 6~30 of the monocyclic hydrocarbon of carbon number 3~10 At least one hydrogen of the base of polycycle hydrocarbon, the base can be replaced by methyl, ethyl or phenyl, bond key and the structure being connected on ring The arbitrary carbon connection of cyclization, two bond keys can link with the same carbon.

More specifically, tetracarboxylic dianhydride represented by following formula (AN-1)~formula (AN-16-15) can be enumerated.

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

In formula (AN-1), G¹¹For singly-bound, the alkylidene of carbon number 1~12,1,4- phenylene or 1,4- cyclohexylidene.X¹¹Solely It is on the spot singly-bound or-CH₂-。G¹²It independently is any of following triads.

Work as G¹²When for > CH-, the hydrogen of > CH- can be by-CH₃Replace.Work as G¹²When for > N-, G¹¹It is not singly-bound and-CH₂, X¹¹It is not singly-bound.Moreover, R¹¹For hydrogen or-CH₃。

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

In formula (AN-1-2) and formula (AN-1-14), m be 1~12 integer.

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

In formula (AN-2), R⁶¹It independently is the alkyl or phenyl of hydrogen, carbon number 1~5.

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

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

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

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

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

In formula (AN-4), G¹³For singly-bound ,-(CH₂)_m-、-O-、-S-、-C(CH₃)₂-、-SO₂-、-CO-、-C(CF₃)₂Under or State bilvalent radical represented by formula (G13-1), the integer that m is 1~12.Ring A¹¹It independently is cyclohexane ring or phenyl ring.G¹³It can be bonded In ring A¹¹Arbitrary position.

In formula (G13-1), G^13aAnd G^13bIt independently is bilvalent radical represented by singly-bound ,-O- or-NHCO-.Phenylene is preferred For 1,4- phenylene and 1,3- phenylene.

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

In formula (AN-4-17), m be 1~12 integer.

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

In formula (AN-5), R¹¹It independently is hydrogen or-CH₃.Binding site is not secured to constitute the R on the carbon of phenyl ring¹¹It indicates Binding site on phenyl ring is any.

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

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

In formula (AN-6), X¹¹It independently is singly-bound or-CH₂-。X¹²For-CH₂-、-CH₂CH₂Or-CH=CH-.N is 1 or 2.

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

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

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

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

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

In formula (AN-8), X¹¹For singly-bound or-CH₂-。R¹²For hydrogen ,-CH₃、-CH₂CH₃Or phenyl, ring A¹²For cyclohexane ring or Cyclohexene ring.

As the example of tetracarboxylic dianhydride represented by formula (AN-8), 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 tetracarboxylic dianhydride represented by formula (AN-9), compound represented by following formula can be enumerated.

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

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

In formula (AN-11), ring A¹¹It independently is cyclohexane ring or phenyl ring.

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

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

In formula (AN-12), ring A¹¹It is separately cyclohexane ring or phenyl ring.

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

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

In formula (AN-15), w be 1~10 integer.

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

As the tetracarboxylic dianhydride other than described, following compounds can be enumerated.

The appropriate materials for each characteristic that aftermentioned liquid crystal orientation film is improved in the tetracarboxylic dianhydride are described.In weight In the case where orientation depending on improving liquid crystal, preferably compound represented by formula (AN-1), formula (AN-3) and formula (AN-4), more Preferably chemical combination represented by formula (AN-1-2), formula (AN-1-13), formula (AN-3-2), formula (AN-4-17) and formula (AN-4-29) Object, in formula (AN-1-2), preferably m=4 or 8, in formula (AN-4-17), preferably m=4 or 8, more preferably m=8.

In the case where paying attention to improving the transmitance of liquid crystal display element, preferably formula (AN-1-1), formula (AN-1-2), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10-1), formula (AN-16- 3), compound represented by formula (AN-16-4) and formula (AN-2-1), wherein in formula (AN-1-2), preferably m=4 or 8, formula (AN-4-17) in, preferably m=4 or 8, more preferably m=8.

In voltage retention (hereinafter referred to as VHR (the Voltage Holding for paying attention to improving liquid crystal display element Ratio in the case where)), preferably formula (AN-1-1), formula (AN-1-2), formula (AN-3-1), formula (AN-4-17), formula (AN-4- 30), compound represented by formula (AN-7-2), formula (AN-10-1), formula (AN-16-3), formula (AN-16-4) and formula (AN-2-1), In formula (AN-1-2), preferably m=4 or 8, in formula (AN-4-17), preferably m=4 or 8, more preferably m=8.

As one of the method for preventing burn mark, effectively make liquid and reducing the volumetric resistivity value of liquid crystal orientation film The mitigation speed of residual charge (remnant dc electricity (Direct Current, DC)) in brilliant alignment films improves.Described in attention In the case where purpose, preferably formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and formula (AN-11- 3) compound represented by.

Diamines and two hydrazides > other than diamines represented by < formula (2)

The diamines and two hydrazides of polyamic acid and its derivative to manufacture embodiments of the present invention are illustrated. It, can also be without limitation in addition to the diamines represented by formula (2) when manufacturing the polyamic acid or derivatives thereof of embodiments of the present invention Ground is selected from well known diamines and two hydrazides.

Diamines can be divided into two kinds according to its structure.That is, the diamines with side chain radical and the diamines without side chain radical, institute Stating side chain radical is the base of branch from main chain when regarding the skeleton for linking two amino as main chain.Below in explanation, sometimes will Diamines with such side chain radical is known as side chain type diamine.Moreover, the diamines for not having such side chain radical is known as non-side sometimes Chain diamines.The side chain radical is the base increase with pre-tilt angle.

By the way that non-side chain type diamine to be suitably used separately with side chain type diamine, respectively required pre-dumping can correspond to Angle.

Side chain type diamine is preferably used together with the degree of lossless characteristic of the invention.In addition, about side chain type diamine and Non-side chain type diamine, preferably to improve for the vertical orientation of liquid crystal, voltage retention, burn mark characteristic and orientation as mesh Carry out accept or reject selection to use.

Known diamines, two hydrazides described below.

In the formula (DI-1), G²⁰For-CH₂Or formula (DI-1-a), in G²⁰For-CH₂In the case where, at least one- CH₂It can be replaced by-NH- ,-O-, the integer that m is 1~12, m-CH₂At least one hydrogen can be replaced by-OH or methyl, G²⁰In the case where formula (DI-1-a), m 0.

In formula (DI-1-a), v be 1~6 integer.

In formula (DI-3), formula (DI-6) and formula (DI-7), G²¹It independently is singly-bound ,-NH- ,-NCH₃-、-O-、-S-、-S- S-、-SO₂-、-CO-、-COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N (CH₃)-(CH₂)_k-N(CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO- O-(CH₂)_m-O-CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO- C₃H₆-(NH-C₃H₆)_n- CO- or-S- (CH₂)_m- S-, m independently are 1~12 integer, the integer that k is 1~5, and n is 1 or 2.Formula (DI-4) in, s independently is 0~2 integer.

In formula (DI-5), G³³It independently is singly-bound ,-NH- ,-NCH₃-、-O-、-S-、-S-S-、-SO₂-、-CO-、- COO-、-CONCH₃-、-CONH-、-C(CH₃)₂-、-C(CF₃)₂-、-(CH₂)_m-、-O-(CH₂)_m-O-、-N(CH₃)-(CH₂)_k-N (CH₃)-、-(O-C₂H₄)_m-O-、-O-CH₂-C(CF₃)₂-CH₂-O-、-O-CO-(CH₂)_m-CO-O-、-CO-O-(CH₂)_m-O- CO-、-(CH₂)_m-NH-(CH₂)_m-、-CO-(CH₂)_k-NH-(CH₂)_k-、-(NH-(CH₂)_m)_k-NH-、-CO-C₃H₆-(NH-C₃H₆ )_n- CO- or-S- (CH₂)_m-S-、-N(Boc)-(CH₂)_e-N(Boc)-、-NH-(CH₂)_e-N(Boc)-、-N(Boc)-(CH₂)_e-、- (CH₂)_m-N(Boc)-CONH-(CH₂)_m-、-(CH₂)_m-N(Boc)-(CH₂)_m, following formula (DI-5-a) or following formula (DI-5-b) Represented base, m independently are 1~12 integer, and the integer that k is 1~5, the integer that e is 2~10, n is 1 or 2.Boc is uncle Butoxy carbonyl.

In formula (DI-6) and formula (DI-7), G²²It independently is singly-bound ,-O- ,-S- ,-CO- ,-C (CH₃)₂-、-C(CF₃)₂Or The alkylidene of carbon number 1~10.

At least one hydrogen of cyclohexane ring and phenyl ring in formula (DI-2)~formula (DI-7) can be by-F ,-Cl, carbon number 1~3 Alkyl ,-OCH₃、-OH、-CF₃、-CO₂H、-CONH₂、-NHC₆H₅, phenyl or benzyl replace, in addition, in formula (DI-4), hexamethylene At least one of ring and phenyl ring hydrogen can by the base represented by following formula (DI-4-a)~formula (DI-4-i) group in one A substitution in formula (DI-5), works as G³³When for singly-bound, at least one hydrogen of cyclohexane ring and phenyl ring can be by NHBoc or N (Boc)₂It takes Generation.

About at least one of cyclohexane ring and phenyl ring hydrogen, binding site is not secured to constitute the bond key table on the carbon of ring Show that the binding site on the ring is any.Moreover,-NH₂Binding site on cyclohexane ring or phenyl ring is except G²¹、G²²Or G³³Binding site other than arbitrary position.

In formula (DI-4-a) and formula (DI-4-b), R²⁰It independently is hydrogen or-CH₃.In formula (DI-4-f) and formula (DI-4-g), The integer that m is 0~12, Boc is tert-butoxycarbonyl.

In formula (DI-5-a), q independently is 0~6 integer.R⁴⁴For hydrogen ,-OH, the alkyl of carbon number 1~6 or carbon number 1~6 Alkoxy.

In formula (DI-11), r is 0 or 1.In formula (DI-8)~formula (DI-11) ,-NH that is bonded on ring₂Binding site For arbitrary position.

In formula (DI-12), R²¹And R²²It independently is the alkyl or phenyl of carbon number 1~3, G²³It independently is carbon number 1~6 Alkylidene, phenylene or by alkyl-substituted phenylene, the integer that w is 1~10.

In formula (DI-13), R²³It independently is the alkyl of carbon number 1~5, the alkoxy or-Cl of carbon number 1~5, p independently is 0 ~3 integer, the integer that q is 0~4.

In formula (DI-14), ring B is the hetero ring type aromatic series base of monocycle, R²⁴For hydrogen ,-F ,-Cl, the alkyl of carbon number 1~6, alkane Oxygroup, alkenyl, alkynyl, q independently are 0~4 integer.In formula (DI-15), ring C is hetero ring type aromatic series base or hetero ring type rouge Fat race base.In formula (DI-16), G²⁴For singly-bound, the alkylidene or Isosorbide-5-Nitrae-phenylene of carbon number 2~6, r is 0 or 1.Moreover, bond position The bond key set on the carbon for being not secured to constitute ring indicates that the binding site on the ring is any.Formula (DI-13)~formula (DI- 16) in ,-the NH that is bonded on ring₂Binding site be arbitrary position.

As diamines of the formula (the DI-1)~formula (DI-16) without side chain, can enumerate following formula (DI-1-1)~ The concrete example of formula (DI-16-1).

The example of diamines represented by formula (DI-1) described below.

In formula (DI-1-7) and formula (DI-1-8), k is separately 1~3 integer.In formula (DI-1-9), v is 1~6 Integer.

The example of diamines represented by formula (DI-2) described below~formula (DI-3).

The example of diamines represented by formula (DI-4) described below.

In formula (DI-4-20) and formula (DI-4-21), m independently is 1~12 integer.

The example of diamines represented by formula (DI-5) described below.

In formula (DI-5-1), m be 1~12 integer.

In formula (DI-5-12) and formula (DI-5-13), m be 1~12 integer.

In formula (DI-5-16), v be 1~6 integer.

In formula (DI-5-30), k be 1~5 integer.

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

In formula (DI-5-42)~formula (DI-5-44), the integer that e is 2~10, in formula (DI-5-45), R⁴³For hydrogen, NHBoc Or N (Boc)₂.In formula (DI-5-42)~formula (DI-5-44), Boc is tert-butoxycarbonyl.

The example of diamines represented by formula (DI-6) described below.

The example of diamines represented by formula (DI-7) described below.

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

The example of diamines represented by formula (DI-8) described below.

The example of diamines represented by formula (DI-9) described below.

The example of diamines represented by formula (DI-10) described below.

The example of diamines represented by formula (DI-11) described below.

The example of diamines represented by formula (DI-12) described below.

The example of diamines represented by formula (DI-13) described below.

The example of diamines represented by formula (DI-14) described below.

The example of diamines represented by formula (DI-15) described below.

The example of diamines represented by formula (DI-16) described below.

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

In formula (DIH-1), G²⁵For singly-bound, the alkylidene of carbon number 1~20 ,-CO- ,-O- ,-S- ,-SO₂-、-C(CH₃)₂Or- C(CF₃)₂-。

In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, at least one hydrogen of the base can be by methyl, ethyl Or phenyl replaces.In formula (DIH-3), ring E is separately cyclohexane ring or phenyl ring, at least one hydrogen of the base can be by first Base, ethyl or phenyl replace, and Y is singly-bound, the alkylidene of carbon number 1~20 ,-CO- ,-O- ,-S- ,-SO₂-、-C(CH₃)₂Or-C (CF₃)₂-.In formula (DIH-2) and formula (DIH-3) ,-CONHNH that is bonded on ring₂Binding site be arbitrary position.

Formula (DIH-1) described below~formula (DIH-3) example.

In formula (DIH-1-2), m be 1~12 integer.

Diamines and two hydrazides as described above have the improvement electrical characteristics such as reduces the ion concentration of liquid crystal display element Effect.

The diamines for the purpose for being suitable for increasing pre-tilt angle is illustrated.As the purpose and tool for being suitable for increase pre-tilt angle There is the diamines of side chain radical, formula (DI-31)~formula (DI-35), formula (DI-36-1)~formula (DI-36-8) can be enumerated.

In formula (DI-31), G²⁶For singly-bound ,-O- ,-COO- ,-OCO- ,-CO- ,-CONH- ,-CH₂O-、-OCH₂-、- CF₂O-、-OCF₂Or-(CH₂)_m', m' be 1~12 integer.G²⁶Preference be singly-bound ,-O- ,-COO- ,-OCO- ,-CH₂O- And the alkylidene of carbon number 1~3, example particularly preferably are singly-bound ,-O- ,-COO- ,-OCO- ,-CH₂O-、-CH₂And-CH₂CH₂-。 R²⁵For base represented by the alkyl of carbon number 3~30, phenyl, the base with steroid skeleton or following formula (DI-31-a).The alkane In base, at least one hydrogen can be replaced by-F, and at least one-CH₂It can be replaced by-O- ,-CH=CH- or-C ≡ C-.It is described The hydrogen of phenyl can be by-F ,-CH₃、-OCH₃、-OCH₂F、-OCHF₂、-OCF₃, the alkyl of carbon number 3~30 or the alcoxyl of carbon number 3~30 Base replaces.- the NH being bonded on phenyl ring₂Binding site expression be arbitrary position in the ring, but the binding site Preferably meta or para position.That is, working as base " R²⁵-G²⁶" binding site when being set as 1, two binding sites are preferably 3 With 5 or 2 and 5.

In formula (DI-31-a), G²⁷、G²⁸And G²⁹For bond base, they independently are the alkylidene of singly-bound or carbon number 1~12, More than one-the CH of the alkylidene₂It can be replaced by-O- ,-COO- ,-OCO- ,-CONH- ,-CH=CH-.Ring B²¹, ring B²²、 Ring B²³And ring B²⁴Independently be 1,4- phenylene, 1,4- cyclohexylidene, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl, Pyridine -2,5- diyl, naphthalene -1,5- diyl, naphthalene -2,7- diyl or anthracene -9,10- diyl, ring B²¹, ring B²², ring B²³And ring B²⁴In, At least one hydrogen can be by-F or-CH₃Replace, s, t and u independently are 0~2 integer, they add up to 1~5, as s, t or u When being 2, two bond bases in each bracket can be identical, can also be different, moreover, two rings can be identical, it can also be different.R²⁶For Hydrogen ,-F ,-OH, the alkyl of carbon number 1~30, carbon number 1~30 fluorine replace alkyl, the alkoxy of carbon number 1~30 ,-CN ,- OCH₂F、-OCHF₂Or-OCF₃, at least one-CH of the alkyl of the carbon number 1~30₂It can be by following formula (DI-31-b) institute table The bilvalent radical shown replaces.

[changing 112]

In formula (DI-31-b), R²⁷And R²⁸It independently is the alkyl of carbon number 1~3, the integer that v is 1~6.R²⁶Preference For the alkyl of carbon number 1~30 and the alkoxy of carbon number 1~30.

In formula (DI-32) and formula (DI-33), G³⁰It independently is singly-bound ,-CO- or-CH₂, R²⁹It independently is hydrogen or-CH₃, R³⁰For the alkenyl of hydrogen, the alkyl of carbon number 1~20 or carbon number 2~20.At least one hydrogen of phenyl ring in formula (DI-33) can be by carbon number 1~20 alkyl or phenyl replaces.Moreover, binding site is not secured to constitute described in the bond key expression on any one carbon of ring Binding site on ring is any.Two bases "-phenylene-G preferably in formula (DI-32)³⁰It is solid that one of-O- " is bonded to class 3 of alcohol core, another is bonded to 6 of steroids core.Two bases "-phenylene-G in formula (DI-33)³⁰- O- " is in phenyl ring On binding site be preferably binding site relative to steroids core, respectively meta or para position.Formula (DI-32) and formula (DI- 33) in ,-the NH that is bonded on phenyl ring₂Indicate that the binding site on the ring is any.

In formula (DI-34) and formula (DI-35), G³¹It independently is the alkylidene of-O- or carbon number 1~6, G³²For singly-bound or carbon The alkylidene of number 1~3.R³¹For hydrogen or the alkyl of carbon number 1~20, at least one-CH of the alkyl₂It can be by-O- ,-CH= CH- or-C ≡ C- replaces.R³²For the alkyl of carbon number 6~22, R³³For hydrogen or the alkyl of carbon number 1~22.Ring B²⁵For 1,4- phenylene Or 1 or 4 cyclohexylidene, r are 0 or 1.Moreover, being bonded to the-NH on phenyl ring₂Indicate that the binding site on the ring is any, but Preferably independently and relative to G³¹Binding site be meta or para position.

The example of compound represented by formula (DI-31) described below.

In formula (DI-31-1)~formula (DI-31-11), R³⁴It is excellent for the alkyl of carbon number 1~30 or the alkoxy of carbon number 1~30 It is selected as the alkyl of carbon number 5~25 or the alkoxy of carbon number 5~25.R³⁵For the alkyl of carbon number 1~30 or the alcoxyl of carbon number 1~30 Base, the preferably alkoxy of the alkyl of carbon number 3~25 or carbon number 3~25.

In formula (DI-31-12)~formula (DI-31-17), R³⁶For the alkyl of carbon number 4~30, the preferably alkane of carbon number 6~25 Base.R³⁷For the alkyl of carbon number 6~30, the preferably alkyl of carbon number 8~25.

In formula (DI-31-18)~formula (DI-31-43), R³⁸For the alkyl of carbon number 1~20 or the alkoxy of carbon number 1~20, The preferably alkoxy of the alkyl of carbon number 3~20 or carbon number 3~20.R³⁹For hydrogen ,-F, the alkyl of carbon number 1~30, carbon number 1~30 Alkoxy ,-CN ,-OCH₂F、-OCHF₂Or-OCF₃, the preferably alkoxy of the alkyl of carbon number 3~25 or carbon number 3~25.And And G³³For the alkylidene of carbon number 1~20.

The example of compound represented by formula (DI-32) described below.

The example of compound represented by formula (DI-33) described below.

The example of compound represented by formula (DI-34) described below.

In formula (DI-34-1)~formula (DI-34-12), R⁴⁰For hydrogen or the alkyl of carbon number 1~20, preferably hydrogen or carbon number 1~ 10 alkyl, moreover, R⁴¹For hydrogen or the alkyl of carbon number 1~12.

The example of compound represented by formula (DI-35) described below.

In formula (DI-35-1)~formula (DI-35-3), R³⁷For the alkyl of carbon number 6~30, R⁴¹For hydrogen or the alkane of carbon number 1~12 Base.

Compound represented by formula (DI-36-1) described below~formula (DI-36-8).

In formula (DI-36-1)~formula (DI-36-8), R⁴²Separately indicate the alkyl of carbon number 3~30.

The appropriate materials for each characteristic for improving aftermentioned liquid crystal orientation film in the diamines and two hydrazides are described.? In the case that attention further increases the orientation of liquid crystal, it is preferable to 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 formula (DI-11-2) compound represented by.In formula (DI-5-1), preferably m=2,4 or 6, more preferably m=4.Formula (DI-5-12) In, preferably m=2~6, more preferably m=5.In formula (DI-5-13), preferably m=1 or 2, more preferably m=1.

Pay attention to improve transmitance in the case where, it is preferable to use formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), Diamines represented by formula (DI-5-5), formula (DI-5-24) and formula (DI-7-3), more preferably chemical combination represented by formula (DI-2-1) Object.In formula (DI-5-1), preferably m=2,4 or 6, more preferably m=4.In formula (DI-7-3), preferably m=2 or 3 and n=1 Or 2, more preferably m=3 and n=1.

Pay attention to improve liquid crystal display element VHR in the case where, it is preferable to use formula (DI-2-1), formula (DI-4-1), Formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-4-22), formula (DI-5-28), formula (DI-5-30) and formula (DI-13-1) two represented by the compound represented by, more preferably formula (DI-2-1), formula (DI-5-1) and formula (DI-13-1) Amine.In formula (DI-5-1), preferably m=1.In formula (DI-5-30), preferably k=2.

As one of the method for preventing burn mark, effectively make liquid and reducing the volumetric resistivity value of liquid crystal orientation film The mitigation speed of residual charge (residual DC) in brilliant alignment films improves.In the case where paying attention to the purpose, it is preferable to 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), chemical combination represented by formula (DI-5-28), formula (DI-4-20), formula (DI-4-21), formula (DI-7-12) and formula (DI-16-1) Compound represented by object, more preferably formula (DI-4-1), formula (DI-5-1) and formula (DI-5-13).In formula (DI-5-1), preferably For m=2,4 or 6, more preferably m=4.In formula (DI-5-12), preferably m=2~6, more preferably m=5.Formula (DI-5-13) In, preferably m=1 or 2, more preferably m=1.In formula (DI-7-12), preferably m=3 or 4, more preferably m=4.

It, can also be in the range that monoamine is 40 moles of % or less relative to the ratio of diamines, by the one of diamines in each diamines Part is replaced to monoamine.Such substitution can cause the termination of polymerization reaction when generating polyamic acid, can inhibit polymerization reaction It is further to carry out.Therefore, by such substitution, condensate obtained (polyamic acid or derivatives thereof) can easily be controlled Molecular weight, such as can lossless effect of the invention and improve the coating characteristics of aligning agent for liquid crystal.As long as lossless effect of the invention Fruit, then it can also be two or more that the diamines for being substituted into monoamine, which can be one kind,.As the monoamine, such as can enumerate: aniline, 4- hydroxyanilines, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, 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 of embodiments of the present invention or derivatives thereof can include monoisocyanates in monomer in turn Close object.By including monoisocyanate compound in monomer, the end of polyamic acid obtained or derivatives thereof is repaired Decorations, molecular weight are adjusted.By using the polyamic acid or derivatives thereof of the end modified type, such as can the lossless present invention Effect and improve the coating characteristics of aligning agent for liquid crystal.For the viewpoint, monoisocyanate compound in monomer contains Amount is preferably the total amount relative to diamines and tetracarboxylic dianhydride in monomer and is 1 mole of %~10 mole %.As the list Isocyanate compound, such as phenyl isocyanate and naphthyl isocyanate can be enumerated.

< has the monomer > of photoreactivity structure

When manufacturing the polyamic acid or derivatives thereof of embodiments of the present invention, in addition to the diamines represented by formula (2), It can be used together with the monomer with other photoreactivity structures.Other so-called photoreactivity structures, such as can enumerate: pass through purple Outside line is irradiated and the formula (P- that causes photoisomerization structure represented by formula (P-1)~formula (P-3) of isomerization, cause dimerization 5) photodimerization structure represented by~formula (P-7) etc..

As the compound with photoisomerization structure represented by formula (P-1)~formula (P-3), it is preferably selected from photonasty At least one of group of compound represented by good following formula (II)~formulas (VI), more preferably represented by formula (V) Compound.

R²-C≡C-R³ (II)

R²-C≡C-C≡C-R³ (III)

R²Mono- R of-C ≡ C⁴-C≡C-R³ (IV)

R²- N=N-R³ (V)

R⁵- CH=CH-R⁵ (VI)

In formula (II)~formula (V), R²And R³For with-NH₂Any monovalent organic radical or monovalence with-CO-O-CO- it is organic Base, in formula (IV), R⁴For divalent organic base, in formula (VI), R⁵Independently being has-NH₂Or the aromatic rings of-CO-O-CO-.

Photoisomerization structure can be incorporated to the main chain of polyamic acid into the present invention or derivatives thereof or any of side chain In person, by being incorporated into main chain, the liquid crystal display element of Transverse electric-field type may be suitably used to.

As the material with the photoisomerization structure, can properly use selected from following formula (II-1), formula (II-2), Formula (III-1), formula (III-2), formula (IV-1)~formula (IV-3), formula (V-1)~formula (V-3), formula (VI-1) and formula (VI-2) institute At least one of group of compound of expression.

It is described it is various in, the bond key that binding site is not secured to constitute on any one carbon of ring indicates key on the ring Knot position be it is any, in formula (IV-3), r is integer of 1 to 10, in formula (V-2), R⁶It independently is-CH₃、-OCH₃、-CF₃Or- COOCH₃, a independently is 0~2 integer, and in formula (V-3), ring A and ring B are separately more selected from monocyclic hydrocarbon, condensation At least one of ring type hydrocarbon and heterocycle, R¹¹For the straight-chain alkyl-sub of carbon number 1~20 ,-COO- ,-OCO- ,-NHCO- ,- CONH-、-N(CH₃) CO- or-CON (CH₃)-, R¹²For the straight-chain alkyl-sub of carbon number 1~20 ,-COO- ,-OCO- ,-NHCO- ,- CONH-、-N(CH₃) CO- or-CON (CH₃)-, R¹¹And R¹²In ,-the CH of straight-chain alkyl-sub₂One or two can be taken by-O- Generation, R⁷~R¹⁰It is separately-F ,-CH₃、-OCH₃、-CF₃Or-OH, moreover, b~e is separately 0~4 integer.

It, can be particularly suitablely using the formula (V-1), formula (V-2) and formula (VI-2) for the photosensitive aspect Represented compound.For the aspect of the orientation, amino in formula (V-2) and formula (VI-2) can be more appropriately used Binding site is the compound of a=0 in the compound and formula (V-2) of contraposition.Compound represented by formula (IV-3) can also be with Show the purpose other than photonasty come using.

There is the tetrabasic carboxylic acid for the structure for causing isomerization using ultraviolet light irradiation shown in formula (II-1)~formula (VI-2) Dianhydride or diamines can specifically be indicated by following formula (II-1-1)~formula (VI-2-3).

In formula (IV-3-1), r is integer of 1 to 10.

In these, cause isomery comprising irradiating using ultraviolet light by being set as formula (VI-1-1)~formula (V-3-8) The compound of the structure of change can get the higher light orientation aligning agent for liquid crystal of sensitivity irradiated to ultraviolet light.By by formula (V- 1-1), formula (V-2-1), formula (V-2-4)~formula (V-2-11) and formula (V-3-1)~formula (V-3-8) are set as comprising using ultraviolet Line irradiates and causes the compound of the structure of isomerization, and the light orientation that can get can be such that liquid crystal molecule is orientated more consistently is used Aligning agent for liquid crystal.Wherein, for showing bigger anisotropic aspect when forming liquid crystal orientation film, can more appropriately make The compound represented by formula (V-2-1).

As the compound with photoreactivity structure represented by formula (P-5)~formula (P-7), following formula can be enumerated (PDI-9) diamine compound represented by~formula (PDI-13).

In formula (PDI-12), R⁵⁴For the alkyl or alkoxy of carbon number 1~10, at least one hydrogen of alkyl or alkoxy can quilt Fluorine replaces.

The formula (PDI-9) and formula (PDI-11) can be properly used.

And with do not have photoreactivity structure (non-photosensitive) tetracarboxylic dianhydride and have photoreactivity structure it is (photosensitive Property) tetracarboxylic dianhydride embodiment in, reduction of the liquid crystal orientation film to the sensitivity of light in order to prevent, photonasty tetrabasic carboxylic acid two Four used in raw material when acid anhydride is preferably relative to as the polyamic acid or derivatives thereof for manufacturing embodiments of the present invention The total amount of carboxylic acid dianhydride and be 0 mole of %~70 mole %, more preferably 0 mole of %~50 mole %.In addition, in order to improve pair Various characteristics described in sensitivity, electrical characteristics, image retention characteristic of light etc., can also and with two or more photonasty tetracarboxylic dianhydrides.

And with not having the diamines of photoreactivity structure (non-photosensitive) and with photoreactivity structure (photonasty) In the embodiment of diamines, reduction of the liquid crystal orientation film to the sensitivity of light in order to prevent, photonasty diamines is preferably relative to work The total amount of diamines used in raw material when polyamic acid or derivatives thereof to manufacture embodiments of the present invention and be 20 to rub You are %~100 mole %, more preferably 50 moles of %~100 mole %.In addition, in order to improve the sensitivity to light, image retention characteristic Etc. the various characteristics, can also and with two or more photonasty diamines.As described above, including in embodiments of the present invention The case where occupying the total amount of tetracarboxylic dianhydride with non-photosensitive tetracarboxylic dianhydride, even if also requiring the total of diamines in said case Minimum 20 moles of % of amount are photonasty diamines.

< aligning agent for liquid crystal >

Aligning agent for liquid crystal of the invention may include a kind of polymer of embodiments of the present invention, can also mix two or more Embodiments of the present invention polymer.But if considering, storage stability, the aligning agent for liquid crystal of aligning agent for liquid crystal are being shown Printing on device substrate and the characteristic for being formed by liquid crystal orientation film, then preferably by polyamic acid or derivatives thereof that This mixing or polyamic acid or derivatives thereof and diamines represented by unused formula (2) as the polyamic acid of raw material or its spread out The mixing of biology and the aligning agent for liquid crystal that obtains.Furthermore in present specification, sometimes by the liquid comprising a kind of polymer Brilliant alignment agent is known as single-layer type aligning agent for liquid crystal.Sometimes the aligning agent for liquid crystal for mixing the two or more polymer is known as mixing Miscellaneous type aligning agent for liquid crystal.

It is not used in manufacture of the diamines as the polyamic acid and its derivative of raw material represented by formula (2), it can be suitably Use the tetracarboxylic dianhydride, diamines and two hydrazides.

In the polymeric situation using such two kinds of ingredients, such as have following embodiment: one of them selection exists There are the condensate of excellent performance, electrical characteristics of the another one selection for improvement liquid crystal display element in terms of liquid crystal aligning ability For with excellent performance condensate.It in said case, can be by controlling each polymeric structure or molecular weight Aligning agent for liquid crystal made of these condensates being made to be dissolved in solvent as be described hereinafter is coated on substrate and carries out predrying During forming film, the condensate in terms of liquid crystal aligning ability with excellent performance is made to be segregated in the upper layer of film, The condensate for the electrical characteristics for improving liquid crystal display element with excellent performance is set to be segregated in the lower layer of film.Its In, in the condensate being mixed, upper layer, the big polymerization of surface energy can be located away from using by the small condensate of surface energy Body is located away from the phenomenon that lower layer.Such layer of separation is approved in the following manner really to confirm: being formed by liquid crystal orientation film Surface energy is the surface energy phase with the film formed by containing only the intentional polymeric aligning agent for liquid crystal for being segregated in upper layer With or with its similar in be worth.

As the method for presentation layer separation, the polymeric molecular weight for reducing upper layer to be segregated in can also be enumerated.

Comprising that can also be set by being intended to be segregated in the condensate on upper layer in the mutual mixed aligning agent for liquid crystal of polyamic acid Carry out presentation layer separation for polyimides.

Diamines represented by the formula (2) of embodiments of the present invention can be used as the condensate for being segregated in the upper layer of the film Starting monomer, it is also possible to be segregated in the polymeric starting monomer of the lower layer of film.In addition, also acting as two kinds of condensates Starting monomer.

It, can nothing as to synthesize the tetracarboxylic dianhydride for being segregated in the polyamic acid on upper layer or derivatives thereof of the film It is selected in well known tetracarboxylic dianhydride illustrated by limitation ground is certainly described.

To synthesize, to be segregated in the tetracarboxylic dianhydride of the polyamic acid on upper layer or derivatives thereof of film be preferably formula (AN- 1-1), compound, more preferably formula (AN-4-17) represented by formula (AN-4-17) and formula (AN-2-1).In formula (AN-4-17), Preferably m=4 or 8, more preferably m=8.

It, can be unlimited as to synthesize the diamines and two hydrazides that are segregated in the polyamic acid on upper layer or derivatives thereof of film It is selected in well known diamines illustrated by system ground is certainly described and two hydrazides.

As to synthesize the diamines and two hydrazides that are segregated in the polyamic acid on upper layer or derivatives thereof of film, preferably Use compound represented by formula (DI-4-1), formula (DI-5-1) and formula (DI-7-3).Wherein, in formula (DI-5-1), preferably m =1,2 or 4, more preferably m=4.In formula (DI-7-3), preferably m=3 and n=1.

To synthesize the non-photosensitive diamines for being segregated in the polyamic acid on upper layer or derivatives thereof of film preferably two Include the aromatic diamine of 30 moles of % or more in the total amount of amine, more preferably includes 50 moles of % or more.

Acid dianhydride and diamines with the photoisomerization structure can be suitably to synthesize the upper layer for being segregated in film Polyamic acid or derivatives thereof.

It, can be without limitation as to synthesize the tetracarboxylic dianhydride for being segregated in the polyamic acid of lower layer or derivatives thereof of film It is selected in well known tetracarboxylic dianhydride illustrated by ground is certainly described.

As to synthesize the tetracarboxylic dianhydride for being segregated in the polyamic acid of lower layer or derivatives thereof of film, preferably formula (AN-1-1), compound, more preferably formula (AN-1-1) represented by formula (AN-1-13), formula (AN-3-2) and formula (AN-4-21) And formula (AN-3-2).

To synthesize the tetracarboxylic dianhydride for being segregated in the polyamic acid of lower layer or derivatives thereof of film preferably in tetracarboxylic acid Include the aromatic tetracarboxylic dianhydride of 10 moles of % or more in the total amount of acid dianhydride, more preferably includes 30 moles of % or more.

It, can be unlimited as to synthesize the diamines and two hydrazides that are segregated in the polyamic acid of lower layer or derivatives thereof of film It is selected in well known diamines illustrated by system ground is certainly described and two hydrazides.

As to synthesize the diamines and two hydrazides that are segregated in the polyamic acid of lower layer or derivatives thereof of film, preferably Formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-5-9), formula (DI-5-28), formula (DI-5-30) and formula (DIH- Compound represented by 2-1).Wherein, in formula (DI-5-30), the preferably diamines of k=2.

To synthesize the diamines for being segregated in the polyamic acid of lower layer or derivatives thereof of film preferably relative to all two Amine and include 30 moles of % or more aromatic diamine, more preferably include 50 moles of % or more.

Be segregated in polyamic acid on upper layer of film or derivatives thereof and be segregated in the lower layer of film polyamic acid or its Derivative can respectively according to essential component, that is, polyamic acid as aligning agent for liquid crystal of the invention or derivatives thereof synthesis Method and be recorded in method hereafter to synthesize.

Polyamides as polyamic acid on upper layer for being segregated in film or derivatives thereof relative to the upper layer for being segregated in film The ratio of the total amount of amino acid or derivatives thereof and the polyamic acid of lower layer for being segregated in film or derivatives thereof, preferably 5 weights Measure the weight % of %~50, more preferably 10 weight of weight %~40 %.

< solvent >

In addition, for example, the adjustment of the concentration of coating or the polyamic acid or derivatives thereof with regard to aligning agent for liquid crystal Viewpoint for, aligning agent for liquid crystal of the invention can also contain solvent in turn.As long as the solvent be with dissolution macromolecule at The solvent for the ability divided, then can apply with no particular limitation.The solvent includes commonly used in polyamic acid, soluble poly extensively The manufacturing step or the solvent in terms of purposes of the macromolecule components such as acid imide can be suitable for selection according to purpose is used.It is described molten Agent can be one kind, can also be two or more mixed solvents.

As solvent, the solvophilic of described polyamic acid or derivatives thereof can be enumerated or for the purpose of improving coating Other solvents.

As the aprotic polar organic solvent for relative to polyamic acid or derivatives thereof being solvophilic, can enumerate: N-methyl-2-pyrrolidone, N- ethyl-2-pyrrolidone, methylimidazole alkanone (dimethylimidazolidinone), N- methyl caprolactam, N- methyl propanamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide, N,N-dimethylformamide, N, N- Diethylformamide, diethyl acetamide, N, the lactones such as N- dimethyl isobutyl amide, gamma-butyrolacton.

It as the example of other solvents for the purpose of improving coating etc., can enumerate: diisobutyl ketone, lactic acid alkyl The ethylene glycol monoalkyl ethers such as ester, diacetone alcohol, 3- methyl -3- methoxybutanol, naphthane, isophorone, ethylene glycol monobutyl ether, The diethylene glycols such as diethylene glycol monoethyl ether monoalky lether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethylene glycol fourth The diethylene glycol dialkyl ethers such as ylmethyl ether, glycol monoalkyl acetic acid esters or ethylene glycol list phenylacetic acid ester, triethylene glycol list The malonic acid dialkyl group such as the propylene-glycol monoalky lethers such as alkyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethyl malonate The ester compounds such as the dipropylene glycol monoalkylethers such as ester, dipropylene glycol monomethyl ether, these acetate esters.

In these solvents, the solvent be preferably n-methyl-2-pyrrolidone, methylimidazole alkanone, gamma-butyrolacton, Diisobutyl ketone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, diethyl Glycol butyl methyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether.

The concentration of polyamic acid in aligning agent for liquid crystal of the invention is preferably 0.1 weight of weight %~40 %.When by institute When stating aligning agent for liquid crystal and being coated on substrate, in order to adjust film thickness, it is sometimes desirable in advance using solvent to contained polyamide The operation that acid is diluted.

Solid component concentration in aligning agent for liquid crystal of the invention is not particularly limited, as long as in conjunction with following various rubbing methods And select most suitable value.In general, in order to inhibit unevenness or the pin hole etc. when coating, relative to varnish weight, preferably 0.1 weight of weight %~30 %, the more preferable 1 weight weight of %~10 %.

The viscosity of aligning agent for liquid crystal of the invention according to the concentration of coating method, polyamic acid or derivatives thereof, used Polyamic acid or derivatives thereof type, the type of solvent and ratio and preferred range is different.For example, utilizing printing machine It is in the case where being coated 5mPas~100mPas (more preferably 10mPas~80mPas).If being less than 5mPa S then becomes difficult to obtain sufficient film thickness；If more than 100mPas, the case where becoming larger there are print unevenness.Utilizing rotation In the case that painting is coated, it is appropriate that 5mPas~200mPas (more preferably 10mPas~100mPas).? In the case where being coated using ink-jet coating apparatus, it is appropriate that 5mPas~50mPas (more preferably 5mPas ~20mPas).The viscosity of aligning agent for liquid crystal can be measured by rotational viscometry, such as use rotational viscometer (east The TVE-20L type of machine industry manufacture) measure (measuring temperature: 25 DEG C).

< alkenyl replaces nadikimide compound >

For example, for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term, aligning agent for liquid crystal of the invention Nadikimide compound can be replaced containing alkenyl in turn.Alkenyl replaces nadikimide compound that one kind can be used, Can and with two or more.For the purpose, alkenyl replaces the content of nadikimide compound preferably relative to poly- Amic acid or derivatives thereof and be the 1 weight % of weight %~100, the more preferably 1 weight % of weight %~70, so more preferably 1 weight of weight %~50 %.

Alkenyl replaces nadikimide compound to be preferably to be dissolvable in water polyamic acid used in the dissolution present invention Or derivatives thereof solvent in compound.Preferred alkenyl replaces nadikimide compound that can enumerate Japanese Patent Laid-Open Alkenyl disclosed in 2013-242526 etc. replaces nadikimide compound.Alkenyl more preferably replaces nadik Imide compound can be enumerated: bis- { 4- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide) phenyl } first Alkane, N, xyxylene-bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximides), N between N'-, six methylene of N'- Base-is bis- (pi-allyl bicyclic [2.2.1] hept- 5- alkene -2,3- dicarboximide).

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

For example, for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term, aligning agent for liquid crystal of the invention It can be in turn containing the compound with free-radical polymerised unsaturated double-bond.Chemical combination with free-radical polymerised unsaturated double-bond Object can be a kind of compound, can also be two or more compounds.Furthermore in the change with free-radical polymerised unsaturated double-bond It closes in object and replaces nadikimide compound without alkenyl.For the purpose, have free-radical polymerised unsaturated double The content of the compound of key is preferably the 1 weight % of weight %~100 relative to polyamic acid or derivatives thereof, more preferably The 1 weight % of weight %~70, and then more preferably 1 weight of weight %~50 %.

Furthermore replace nadikimide relative to alkenyl about the compound with free-radical polymerised unsaturated double-bond The ratio of compound, in order to lower the ion concentration of liquid crystal display element, the time dependent increase for inhibiting ion concentration and then inhibition The generation of image retention, the compound with free-radical polymerised unsaturated double-bond/alkenyl replace nadikimide compound with weight Amount is than meter preferably 0.1~10, more preferably 0.5~5.

Preferably the compound with free-radical polymerised unsaturated double-bond can enumerate Japanese Patent Laid-Open 2013-242526 The compound with free-radical polymerised unsaturated double-bond Deng disclosed in.

< oxazines compound >

For example, for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term, aligning agent for liquid crystal of the invention Oxazines compound can be contained in turn.Oxazines compound can be a kind of compound, can also be two or more compounds.With regard to the mesh For, the content of oxazines compound is preferably the 0.1 weight % of weight %~50 relative to polyamic acid or derivatives thereof, The more preferably 1 weight % of weight %~40, and then more preferably 1 weight of weight %~20 %.

Oxazines compound is preferably in the solvent for dissolving in and dissolving polyamic acid or derivatives thereof and to have ring-opening polymerisation The oxazines compound of property.About preferred oxazines compound, oxazines represented by formula (OX-3-1), formula (OX-3-2) can be enumerated Close oxazines compound disclosed in object and Japanese Patent Laid-Open 2013-242526 etc..

< oxazoline compound >

For example, for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term, aligning agent for liquid crystal of the invention Oxazoline compound can be contained in turn.Oxazoline compound is the compound with oxazoline structure.Oxazoline compound can be A kind of compound can also be two or more compound.For the purpose, the content of oxazoline compound is preferably opposite In polyamic acid or derivatives thereof be the 0.1 weight % of weight %~50, more preferably 1 weight of weight %~40 %, Jin Ergeng Preferably 1 weight of weight %~20 %.Alternatively, when the oxazoline structure in oxazoline compound is converted into oxazoline, just For the purpose, the content of oxazoline compound be preferably relative to polyamic acid or derivatives thereof 0.1 weight %~ 40 weight %.

Preferred oxazoline compound can enumerate oxazoline chemical combination disclosed in Japanese Patent Laid-Open 2013-242526 etc. Object.Bis- (4,5- dihydro -2- oxazolyl) benzene of 1,3- can more preferably be enumerated.

< epoxide >

For example, for the purpose for keeping the electrical characteristics of liquid crystal display element steady in a long-term, aligning agent for liquid crystal of the invention Epoxide can be contained in turn.Epoxide can be a kind of compound, can also be two or more compounds.With regard to the mesh For, the content of epoxide is preferably the 0.1 weight % of weight %~50 relative to polyamic acid or derivatives thereof, The more preferably 1 weight % of weight %~40, and then more preferably 1 weight of weight %~20 %.

As epoxide, epoxide disclosed in Japanese Patent Laid-Open 2013-242526 etc. can be enumerated.Make For preferred epoxide, can enumerate: N, N, N', N'- four glycidyl group -4,4'- diaminodiphenyl-methane, 3- shrink Glycerol oxygroup propyl trimethoxy silicane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 2- (3,4- epoxy hexamethylene Base) ethyl triethoxysilane, (3,3', 4,4'- bicyclic oxygen) dicyclohexyl (trade name: Sai Luo West Germany (Celloxide) 8000)。

< additive >

In addition, for example, aligning agent for liquid crystal of the invention can also contain various additives in turn.As various additives, example The high-molecular compound and low molecular compound other than polyamic acid and its derivative can be such as enumerated, can be selected according to each purpose Select use.

As the high-molecular compound, such as the macromolecule chemical combination with solubility can be enumerated for organic solvent Object.For control is formed by the electrical characteristics of liquid crystal orientation film or the viewpoint of orientation, preferably by such macromolecule chemical combination Object makes an addition in aligning agent for liquid crystal of the invention.It as the high-molecular compound, such as can enumerate: polyamide, poly- amino first Acid esters, polyureas, polyester, polyepoxide, polyester polyol, silicone modification polyurethanes and silicone modify polyester.

In addition, as the low molecular compound, such as following material can be enumerated.It 1), can when expectation improves coating Enumerate the surfactant for meeting the purpose.2) when needing to improve antistatic, antistatic agent can be enumerated.3) when expectation improves When with the adhesion of substrate, the coupling agent of silane coupling agent or titanium system can be enumerated.It 4), can when carrying out imidizate at low temperature Enumerate imidization catalyst.As silane coupling agent, silicon disclosed in Japanese Patent Laid-Open 2013-242526 etc. can be enumerated Alkane coupling agent.Preferred silane coupling agent is 3-aminopropyltriethoxysilane.As imidization catalyst, can enumerate day Imidization catalyst disclosed in this patent special open 2013-242526 etc..

Liquid crystal orientation film (optical alignment film) > of < aligned setting of light

Optical alignment film of the invention is described in detail.Optical alignment film of the invention can be by being taken by light orientation with liquid crystal It is obtained to the usual way of agent production optical alignment film.For example, optical alignment film of the invention can be by by forming the present invention Light orientation aligning agent for liquid crystal film the step of, the step of of being thermally dried, irradiation light and assign anisotropic step It is rapid and obtain the step of carry out heating and calcining.It, optionally can be dry in film-coating procedures, heating for optical alignment film of the invention After dry step irradiation light assigns anisotropy, or irradiation light can also assign anisotropy after heating and calcining step.

Film can be in the same manner as the production of common liquid crystal orientation film, by the way that aligning agent for liquid crystal of the invention is coated on liquid It is formed on substrate in crystal display element.Substrate can enumerate settable tin indium oxide (Indium Tin Oxide, ITO), oxygen Change indium zinc (In₂O₃- ZnO, IZO), indium gallium zinc (In-Ga-ZnO₄, IGZO) electrodes such as electrode or colored filter etc. glass The substrate of glass system, silicon nitride system, acrylic acid system, polycarbonate system, polyimides etc..

Be coated on the method on substrate as by aligning agent for liquid crystal, usually oneself know have rotator method, print process, infusion process, Dripping method, ink-jet method etc..These methods can also be equally applicable in the present invention.

Usually oneself knows there is the method heated in baking oven or infra-red furnace, in heating plate to the heat-drying step On the method etc. that is heated.Heat-drying step is preferably implemented in the range where the solvent can be evaporated, more Preferably implement at a temperature of being relatively low relative to the temperature in heating and calcining step.Specifically, heat drying temperature Preferably 30 DEG C~150 DEG C of range, more preferably 50 DEG C~120 DEG C of range.

Item needed for dehydration closed-loop reaction can be presented in described polyamic acid or derivatives thereof in the heating and calcining step It is carried out under part.The calcining of the film is commonly known to have the method heated in baking oven or infra-red furnace, in heating plate On the method etc. that is heated.These methods can also be equally applicable in the present invention.Preferably generally 100 DEG C~ Carry out 1 minute~3 hours at a temperature of 300 DEG C or so, more preferably 120 DEG C~280 DEG C, and then more preferably 150 DEG C~250 ℃.In addition, heating for multiple times calcining can be carried out at different temperature.The multiple heating dress for being set as different temperature can be used It sets, it is possible to use a heating device, successively variation is different temperature to carry out.When carry out at different temperature twice plus When forged is burnt, preferably carried out at 90 DEG C~180 DEG C for the first time, second 185 DEG C or more at a temperature of carry out.In addition, Temperature can be made to be calcined from low temperature variation for high temperature.In the case where making temperature change and calcined, initial temperature Preferably 90 DEG C~180 DEG C.Final temperature is preferably 185 DEG C~300 DEG C, more preferably 190 DEG C~230 DEG C.

In the forming method of optical alignment film of the invention, in order to make liquid crystal relative to horizontal direction and/or vertical direction exists It is orientated on one direction, well known optical alignment method can be properly used and be used as to the anisotropic method of film imparting.

The forming method of liquid crystal orientation film of the invention using optical alignment method is described in detail.Use optical alignment method Liquid crystal orientation film of the invention can be formed in the following way: by after being thermally dried to film film irradiate The linear polarization of radioactive ray or without polarisation, and anisotropy is assigned to film, and heating and calcining is carried out to the film.Alternatively, can By being thermally dried to film, and carry out heating and calcining after, to film irradiation radioactive ray linear polarization or without polarisation and It is formed.For the aspect of orientation, the irradiating step of radioactive ray is preferably carried out before heating and calcining step.

In turn, in order to improve the liquid crystal aligning ability of liquid crystal orientation film, one heating one side can also be carried out in face of film irradiate The linear polarization of radioactive ray or without polarisation.The irradiation of radioactive ray can the step of being thermally dried to film or carry out heating forge It carries out, can also be carried out between heat-drying step and heating and calcining step in the step of burning.Heat drying in the step Temperature is preferably 30 DEG C~150 DEG C of range, more preferably 50 DEG C~120 DEG C of range.In addition, the heating in the step is forged Burn the range that temperature is preferably 30 DEG C~300 DEG C, more preferably 50 DEG C~250 DEG C of range.

As radioactive ray, such as the ultraviolet light or visible light of the light of the wavelength comprising 150nm~800nm can be used, preferably For the ultraviolet light of the light comprising 300nm~400nm.In addition, linear polarization can be used or without polarisation.As long as these light is can be to institutes The light that film assigns liquid crystal aligning ability is stated, then is not particularly limited, is being intended to the case where strong orientation restraint is shown to liquid crystal Under, preferably linear polarization.

Even if liquid crystal orientation film of the invention can also show high liquid crystal aligning ability under the light irradiation of low energy.It is described The exposure of linear polarization in radioactive ray irradiating step is preferably 0.05J/cm²~20J/cm², more preferably 0.5J/cm²~ 10J/cm².In addition, the wavelength of linear polarization is preferably 200nm~400nm, more preferably 300nm~400nm.Linear polarization pair The irradiating angle of film surface is not particularly limited, in the case where being intended to show strong orientation restraint to liquid crystal, with regard to orientation process It is preferably vertical as far as possible relative to film surface for the viewpoint that time shortens.In addition, liquid crystal orientation film of the invention passes through irradiation Linear polarization can make liquid crystal aligning on the rectangular direction of the polarization direction relative to linear polarization.

It, can be unlimitedly using super in light source used in the step of irradiating the linear polarization of radioactive ray or without polarisation High-pressure mercury-vapor lamp, high-pressure mercury-vapor lamp, Cooper-Hewitt lamp, deep UV (Deep UV) lamp, halogen lamp, metal halide lamp, big function Rate metal halide lamp, xenon lamp, mercury xenon, Excimer lamp, KrF excimer laser, fluorescent lamp, light emitting diode (light Emitting diode, LED) lamp, sodium vapor lamp, microwave-excitation Non-polarized lamp (microwave discharged electrodeless Lamp) etc..

Liquid crystal orientation film of the invention can by include the step other than other steps method and suitably It obtains.For example, although liquid crystal orientation film of the invention will not carry out clearly the film after calcining or radioactive ray irradiation using cleaning solution The step of washing is set as required, but cleaning step can be arranged according to the case where other steps.

As the cleaning method using cleaning solution, can enumerate: scrub (brushing), spraying (jet spray), steam are clear It washes or ultrasonic cleaning etc..These methods can be carried out individually, can also be used in combination.As cleaning solution, can be used: pure water or methanol, second The various alcohols such as alcohol, isopropanol, benzene,toluene,xylene etc. is aromatic hydrocarbon, the halogen-based solvents such as methylene chloride, acetone, methyl The ketones such as ethyl ketone, but it is not limited to these.Certainly, the cleaning that these cleaning solutions can be used the impurity through sufficiently purifying few Liquid.Such cleaning method can also be applied to be formed in the cleaning step in liquid crystal orientation film of the invention.

It, can be before and after heating and calcining step or inclined in order to improve the liquid crystal aligning ability of liquid crystal orientation film of the invention The front and back of light or the radioactive ray irradiation without polarisation uses the annealing using heat or light.In the annealing, annealing temperature It is 30 DEG C~180 DEG C, preferably 50 DEG C~150 DEG C, the time is preferably 1 minute~2 hours.In addition, used in annealing Annealing light can enumerate UV lamp, fluorescent lamp, LED light etc..The exposure of light is preferably 0.3J/cm²~10J/cm²。

The film thickness of liquid crystal orientation film of the invention is not particularly limited, but preferably 10nm~300nm, more preferably 30nm ~150nm.The film thickness of liquid crystal orientation film of the invention can pass through film well known to contourgraph or ellipsometer (ellipsometer) etc. Thick measurement device measures.

Liquid crystal orientation film of the invention: the anisotropy with king-sized orientation.Such anisotropic size can lead to Cross evaluating using the method for polarisation IR of recording in Japanese Patent Laid-Open 2005-275364 etc..In addition, can also be by using ellipse The method of inclined surveying (ellipsometry) is evaluated.Specifically, liquid crystal orientation film can be measured by light splitting ellipsometer Length of delay.The length of delay of film and the degree of orientation of polymeric backbone proportionally increase.That is, the polymer with big length of delay Film have the big degree of orientation, be used as liquid crystal orientation film in the case where, it is believed that have bigger anisotropic liquid crystal take There is big orientation restraint for liquid-crystal composition to film.

Liquid crystal orientation film of the invention may be suitably used in the liquid crystal display element of Transverse electric-field type.For laterally In the case where in the liquid crystal display element of Electric Field Mode, the angle Pt is smaller, and liquid crystal aligning ability is higher, then in the dark state black Display level becomes higher, and contrast more improves.The angle Pt is preferably 0.1 ° or less.

Liquid crystal orientation film of the invention can be used for the liquid crystal displays such as smart phone, input board, on-board screen, TV use Liquid-crystal composition tropism control.In addition to the orientation purposes of the liquid-crystal composition of liquid crystal display, it may also be used for optics The tropism control of compensating material or other all liquid crystal materials.In addition, liquid crystal orientation film of the invention has big anisotropy, Therefore optical compensation material applications can be individually used for.

< liquid crystal display element >

Liquid crystal display element of the invention is described in detail.The present invention provides a kind of liquid crystal display element comprising Oppositely disposed a pair of of substrate, one of be formed in the respective opposite surface of the pair of substrate or both on electrode, be formed in Liquid crystal orientation film in the pair of respective opposite surface of substrate, the liquid crystal layer being formed between the pair of substrate, to clamp A pair of of light polarizing film, backlight and driving device that the mode of opposite substrate is arranged are stated, and in the liquid crystal display element, the liquid crystal Alignment films are liquid crystal orientation film of the invention.

As long as the electrode is the electrode being formed in the one side of substrate, it is not particularly limited.Such electrode for example may be used Enumerate the evaporation film etc. of ITO or metal.In addition, electrode can be formed in the entire surface in a face of substrate, can also in for example through Patterned desired shape is formed.The desired shape of electrode can for example enumerate combed or broached-tooth design etc..Electricity Pole can be formed on a substrate in a pair of of substrate, can also be formed on two substrates.The formation form of electrode is according to liquid crystal The type of display element and it is different, such as in the case where IPS type liquid crystal display element, by electrode configuration in the pair of substrate One of on, in the case where other liquid crystal display elements, by electrode configuration in the pair of substrate the two.In the substrate Or the liquid crystal orientation film is formed on electrode.

In the case where parallel-oriented liquid crystal display element (for example, IPS, FFS etc.), as composition, from backlight side At least there is backlight, the first light polarizing film, first substrate, the first liquid crystal orientation film, liquid crystal layer, the second substrate, the second light polarizing film, institute The polarizing axis for stating light polarizing film is handed over the polarizing axis of the first light polarizing film (direction that polarisation absorbs) and the polarizing axis of the second light polarizing film The mode of poor (preferably orthogonal) is arranged.At this point it is possible to which the polarizing axis of the first light polarizing film is parallel or orthogonal with liquid crystal aligning direction Mode be arranged.The liquid crystal display element being arranged in the polarizing axis of the first light polarizing film mode parallel with liquid crystal aligning direction is claimed For O- mode, the liquid crystal display element being arranged in an orthogonal manner is known as E- mode.Liquid crystal orientation film of the invention can also answer For O- mode, E- mode any one in, can be selected according to purpose.

Can be used in a large amount of photoisomerization type material has dichromatic compound.Therefore, when making in order to liquid crystal Alignment agent add anisotropy and the polarizing axis of polarisation that irradiates be originated from the polarisation for being configured at the polarisation of light polarizing film of backlight side When axis parallel and consistent (using aligning agent for liquid crystal of the invention, being set as the configuration of O- mode), liquid crystal orientation film Light absorption wavelength region transmitance rise.Therefore, the transmitance of liquid crystal display element can further be improved.

The liquid crystal layer be with using be formed with liquid crystal orientation film in face of to the pair of substrate clamp liquid crystal group The form for closing object is formed.It, can be optionally and using particulate or resin sheet etc. between described one in the forming process of liquid crystal layer To between substrate and forming the spacer at interval appropriate.

Forming method as liquid crystal layer, it is known to vacuum impregnation or liquid crystal drip-injection (One Drop Fill, ODF) method.

In vacuum impregnation, gap (cell gap) is arranged relatively in a manner of by liquid crystal alignment film surface, and leave liquid crystal Inlet and printing and sealing agent and adhesive base plate.Using vacuum differential pressure between the unit divided by substrate surface and sealant In gap after injection filling liquid crystal, inlet is closed, to manufacture liquid crystal display element.

In ODF method, the periphery printing and sealing agent of a liquid crystal alignment film surface in a pair of of substrate and into sealant After liquid crystal is added dropwise in the region of side, another substrate is bonded in a manner of by liquid crystal alignment film surface relatively.Then, liquid crystal is pressed and is extended In in the front surface of substrate, then, the entire surface irradiating ultraviolet light of substrate is cured the sealant, to manufacture liquid crystal display Element.

Sealant used in bonding about substrate, in addition to UV constrictive type, it is also known that have thermmohardening type.Sealant Printing can for example be carried out by screen printing.

There is no particular restriction for liquid-crystal composition, and it is positive or negative various liquid-crystal compositions that dielectric anisotropy, which can be used,.It is situated between The preferred liquid-crystal composition that electrical anisotropy is positive can be enumerated: Japan Patent 3086228, Japan Patent 2635435, Japan are specially Sharp special table level 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 Flat 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, Japanese Patent Laid-Open 2001-48822 Liquid-crystal composition Deng disclosed in.

As the preference of the liquid-crystal composition with negative dielectric anisotropy, can enumerate: Japanese Patent Laid-Open Clear 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, Japan The flat 10-236993 of open patent, Japanese Patent Laid-Open 10-236994, Japanese Patent Laid-Open 10-237000, Japan Patent Japanese Laid-Open Patent Publication 10-237004, Japanese Patent Laid-Open 10-237024, Japanese Patent Laid-Open 10-237035, Japanese Patent Laid-Open Flat 10-237075, Japanese Patent Laid-Open 10-237076, Japanese Patent Laid-Open 10-237448 (EP967261A1), Japan The flat 10-287874 of open patent, Japanese Patent Laid-Open 10-287875, Japanese Patent Laid-Open 10-291945, Japan Patent Japanese Laid-Open Patent Publication 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 special table 2010-537010, Japan are special Liquid-crystal composition disclosed in sharp special open 2012-077201, Japanese Patent Laid-Open 2009-084362 etc..

Even if being to add more than one optically active compound in positive or negative liquid-crystal composition to dielectric anisotropy It uses, also has no effect.

In addition, for example, for the viewpoint for improving orientation, such as liquid used in liquid crystal display element of the invention Brilliant composition can also add additive in turn.Such additive be photopolymerization monomer, optically active compound, antioxidant, Ultraviolet absorbing agent, pigment, defoaming agent, polymerization initiator, polymerization inhibitor etc..Preferred photopolymerization monomer, optical activity Compound, antioxidant, ultraviolet absorbing agent, pigment, defoaming agent, polymerization initiator, polymerization inhibitor can enumerate International Publication Compound disclosed in 2015/146330.

In order to be suitable for the liquid crystal of polymer stabilizing orientation (polymer sustained alignment, PSA) mode Show element, polymerizable compound can be mixed into liquid-crystal composition.The preference of polymerizable compound is acrylate, first Base acrylate, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxide (oxirane, oxa- ring Butane), the compound with polymerizable base such as vinyl ketone.Preferred compound can be enumerated in International Publication 2015/146330 Revealed compound.

[embodiment]

Hereinafter, by embodiment come the present invention will be described.Furthermore evaluation assessment used in embodiment and compound As described below.

1. weight average molecular weight (Mw)

The weight average molecular weight of polyamic acid is to find out in the following way: being shown using 2695 separation modules 2414 Poor refractometer (water generation (Waters) manufacture) is simultaneously measured using GPC method, and carries out polystyrene conversion.Utilize phosphoric acid-two Methylformamide (Dimethylformamide, DMF) mixed solution (phosphoric acid/DMF=0.6/100: weight ratio), with polyamide Acid concentration is diluted polyamic acid obtained as the mode of about 2 weight %.Tubing string is (fertile using HSPgel RT MB-M Special generation (Waters) manufacture), using the mixed solution as solvent, in tubing string temperature 50 C, the item of flow velocity 0.40mL/min It is measured under part.The TSK standard polystyren that standard polystyren uses Tosoh (Tosoh) (share) to manufacture.

2. transmitance

The transmitance of the transparent glass substrate of not formed liquid crystal orientation film is set as 100%, measurement is aftermentioned to be formed with liquid The transmitance of the substrate of brilliant alignment films, and calculate the average value of the transmitance of 390nm~410nm.Ultraviolet-uisible spectrophotometer It uses ultraviolet-uisible spectrophotometer V-660 (light splitting limited liability company, Japan manufactures).Using single-layer type aligning agent for liquid crystal In the case where, it will transmit through rate as 75% or more and be judged as good, be judged as optimal for 80% or more.In addition, using doping type liquid In the case where brilliant alignment agent, it will transmit through rate as 90% or more and be judged as good, be judged as optimal for 92% or more.

3. alternating current (Alternating Current, AC) image retention measures (evaluation of liquid crystal aligning)

Measure the brightness-voltage characteristic (B-V characteristic) of aftermentioned liquid crystal cells.It is set to apply the brightness-before stress Voltage characteristic: B (preceding (before)).Then, after the alternating current for applying 20 minutes 4.5V, 60Hz to liquid crystal cell, short circuit 1 second, Then brightness-voltage characteristic (B-V characteristic) is measured again.Brightness-voltage characteristic after being set to application stress: B (after (after)).Based on these values, rate of change of brightness Δ B (%) is estimated using following formula.

Δ B (%)=[B (rear (after))-B (preceding (before))]/B (preceding (before)) (formula AC1)

These, which are measured, is carried out with reference to International Publication 2000/043833.It may be said that the value of the Δ B (%) under voltage 1.3V It is smaller, more can inhibit the generation of AC image retention, by 6.0% or more situation be judged as it is bad, 3.0% or more and less than 6.0% Situation be judged as it is good, it is less than 3.0% the case where be judged as optimal.Have in International Publication 2000/043833 and implies following situation Record: with the raising of orientation restraint of alignment films, the generation of AC image retention is inhibited, and it is uneven as a result to mitigate display.Separately Outside, it grasps in the Japanese Patent Laid-Open 2016-095537 of invention relevant to the improvement of light orientation processing and records liquid crystal aligning The raising of the orientation order of film is especially effective for the attenuating of AC image retention.According to these situations, it is believed that: measurement can be passed through The Δ B (%) of the liquid crystal display element and to the liquid crystal aligning of liquid crystal orientation film used in the liquid crystal display element It is evaluated.

Diamines > < of the invention

< tetracarboxylic dianhydride >

< diamines >

< solvent >

N-methyl-2-pyrrolidone

Butyl cellosolve (ethylene glycol monobutyl ether)

Gamma-butyrolacton

Diisobutyl ketone

< additive >

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

Additive (Ad2): bis- (4,5- dihydro -2- oxazolyl) benzene of 1,3-

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

Additive (Ad4): Sai Luo West Germany (Celloxide) 8000 (trade name, Daicel (share) manufacture)

The synthesis of [synthesis example 1] compound (4-1)

The < first stage: the synthesis > of hydrazides

4- nitrobenzoic acid first is added into the 1000mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe Ester (25.0g, 138.0mmol), hydrazine monohydrate (35.0mL) and ethyl alcohol (600mL).Thereafter, solution is returned in a nitrogen environment Stream stirring 5 hours.Into reaction solution after additional water (150mL), it is filtered and obtains 4- nitrobenzoyl hydrazides (yield 18.8g, yield 75%).

< second stage: dehydration >

4- nitrobenzoyl hydrazides is added into the 500mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe (18.8g, 103.8mmol), 4- nitrobenzaldehyde (15.7g, 103.9mmol), trifluoroacetic acid (1.02g, 10.4mmol) and second Alcohol (200mL).In a nitrogen environment by solution return stirring 1 hour, filtered after cooling, to obtain following compounds (yield 32.7g, yield 100%).

The < phase III: reduction reaction >

It is added obtained in second stage into the 500mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe Compound (32.7g, 103.8mmol), vulcanized sodium nonahydrate (149.9g, 624.1mmol), ethyl alcohol (2000mL) and water (700mL).Thereafter, in a nitrogen environment by solution return stirring 6 hours.After solvent decompression is evaporated, add water (1000mL) Operation is extracted with ethyl acetate (1000mL).After keeping organic layer dry using magnesium sulfate, solvent decompression is evaporated and is obtained Obtain runic.Runic is purified using silica gel chromatography and obtains compound (4-1) (yield 16.4g, yield 62%).

The synthesis of [synthesis example 2] compound (5-1)

The < first stage: suzuki reaction >

4- bromobenzoic acid first is added into the 1000mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe Ester (25.0g, 116.3mmol), 4- nitrophenyl boronic acid (21.3g, 127.9mmol), potassium carbonate (32.1g, 232.6mmol), PdCl₂(dppf)CH₂Cl₂(1.90g, 2.33mmol), water (200mL) and 1,4- dioxanes (200mL).Thereafter, in nitrogen environment It is lower by solution return stirring 3 hours.Reaction solution is poured into saturated sodium bicarbonate water (200mL), ethyl acetate is added (300mL) operates to extract.After keeping organic layer dry using magnesium sulfate, solvent decompression is evaporated and obtains runic.It utilizes Silica gel chromatography purifies runic and obtains following compounds (yield 29.6g, yield 99%).

< second stage: the synthesis > of hydrazides

It adds into the 2000mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe and is obtained in the first stage Compound (29.6g, 115.1mmol), hydrazine monohydrate (30.0mL) and the ethyl alcohol (750mL) obtained.Thereafter, in a nitrogen environment By solution return stirring 5 hours.Into reaction solution after additional water (150mL), it is filtered and obtains following compound (yield 20.7g, yield 70%).

The < phase III: dehydration >

It adds into the 1000mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe and is obtained in second stage Compound (20.7g, 80.57mmol), 4- nitrobenzaldehyde (12.2g, 80.57mmol), trifluoroacetic acid (0.79g, 8.06mmol) and ethyl alcohol (500mL).In a nitrogen environment by solution return stirring 1 hour, filtered after cooling, to obtain Obtain following compounds (yield 27.7g, yield 88%).

< fourth stage: reduction reaction >

It adds into the 3000mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe and is obtained in the phase III Compound (27.7g, 70.90mmol), vulcanized sodium nonahydrate (51.1g, 212.7mmol), ethyl alcohol (1500mL) and the water obtained (500mL).Thereafter, in a nitrogen environment by solution return stirring 6 hours.After solvent decompression is evaporated, add water (1000mL) Operation is extracted with ethyl acetate (500mL).After keeping organic layer dry using magnesium sulfate, solvent decompression is evaporated and is obtained Runic.Runic is purified using silica gel chromatography and obtains compound (5-1) (yield 13.6g, yield 58%).

The synthesis of [synthesis example 3] compound (6-1)

The < first stage: suzuki reaction >

The bromo- 4- nitrobenzene of 1- is added into the 1000mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe (25.0g, 123.8mmol), 4- formyl phenylboronic acid (20.4g, 136.2mmol), potassium carbonate (34.2g, 247.6mmol), PdCl₂(dppf)CH₂Cl₂(2.02g, 2.48mmol), water (200mL) and 1,4- dioxanes (200mL).Thereafter, in nitrogen environment It is lower by solution return stirring 3 hours.Reaction solution is poured into saturated sodium bicarbonate water (200mL), ethyl acetate is added (300mL) operates to extract.After keeping organic layer dry using magnesium sulfate, solvent decompression is evaporated and obtains runic.It utilizes Silica gel chromatography purifies runic and obtains following compounds (yield 27.6g, yield 98%).

< second stage: dehydration >

It adds into the 1000mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe and is obtained in the first stage Compound (27.6g, 121.3mmol), 4- nitrobenzoyl hydrazides (22.0g, 121.3mmol), trifluoroacetic acid (1.19g, 12.1mmol) and ethyl alcohol (500mL).In a nitrogen environment by solution return stirring 1 hour, filtered after cooling, to obtain Obtain following compounds (yield 43.6g, yield 92%).

The < phase III: reduction reaction >

It is added obtained in second stage into the 500mL three-necked flask for being equipped with return pipe, thermometer, nitrogen ingress pipe Compound (43.6g, 111.6mmol), vulcanized sodium nonahydrate (80.4g, 334.8mmol), ethyl alcohol (2400mL) and water (800mL).Thereafter, in a nitrogen environment by solution return stirring 6 hours.By solvent decompression evaporate after, addition water (200mL) with Ethyl acetate (1000mL) operates to extract.After keeping organic layer dry using magnesium sulfate, solvent decompression is evaporated and is obtained Runic.Runic is purified using silica gel chromatography and obtains compound (6-1) (yield 18.8g, yield 51%).

The synthesis of [synthesis example 4] varnish

The formula (4-1) that 2.3092g is added into the 100mL three-necked flask for being equipped with stirring wing, nitrogen ingress pipe is represented Compound, 74.0g n-methyl-2-pyrrolidone.The solution is heated and after liquid temperature is set as 60 DEG C, addition Compound represented by the formula (AN-4-17, m=8) of 3.6908g, is stirred at room temperature 12 hours.Add 10.0g's thereto The butyl cellosolve of gamma-butyrolacton and 10.0g carries out heating stirring to the solution at 80 DEG C, until as the poly- of solute Until the weight average molecular weight of conjunction object becomes desired weight average molecular weight, to obtain the weight averaged molecular of solute Amount is about 11,000 and resin component concentration is the varnish 1 of 6 weight %.

[5~synthesis example of synthesis example 31]

In addition to change tetracarboxylic dianhydride and diamines, it is 6 weights that polymer solids constituent concentration is prepared according to synthesis example 4 Measure 2~varnish of varnish 28 of %.About weight average molecular weight, a kind of polymer of the compound (2) as raw material will be used Be adjusted to about 5,000 to 20,000, by unused compound (2) as a kind of polymer of raw material be adjusted to 45,000 to 50,000.By the weight average molecular weight of used tetracarboxylic dianhydride and diamines and polymer obtained it is shown in table 1~table 2 In.Numerical value in square brackets indicates allotment than (molar ratio).Also synthesis example 4 is disclosed in table 1 again.Table 1

Table 2

[compare synthesis example 1~compare synthesis example 2]

In addition to change tetracarboxylic dianhydride and diamines, it is 6 weights that polymer solids constituent concentration is prepared according to synthesis example 4 Measure 29~varnish of varnish 30 of %.By used tetracarboxylic dianhydride and the weight averaged molecular of diamines and polymer obtained Amount is shown in Table 3.

Table 3

[embodiment 1] preparation of single-layer type aligning agent for liquid crystal, the formation of liquid crystal orientation film, transmitance measurement

It is synthesized in the synthesis example 4 for weighing 10.0g into the 50mL eggplant type flask for being equipped with stirring wing, nitrogen ingress pipe clear Paint 1 adds n-methyl-2-pyrrolidone, the butyl cellosolve of 0.5g and the diisobutyl ketone of 0.5g of 1.0g, in room thereto Temperature lower stirring 1 hour, to obtain the aligning agent for liquid crystal 1 of 5 weight % of resin component concentration.Using rotator method by the liquid crystal Alignment agent 1 is coated on transparent glass substrate (2,000rpm, 15 seconds).After coating, substrate add within 1 minute at 60 DEG C Heat, after evaporating solvent, Mu Qilaite (Multi-Light) ML-501C/B manufactured using oxtail motor (share), from relatively The linear polarization of ultraviolet light is irradiated via polarizer in substrate and the direction of vertical.Exposure energy at this time is using oxtail electricity The ultraviolet light of machine (share) manufacture adds up quantometer UIT-150 (optical receiver: UVD-S365) to measure light quantity, in wavelength Become 2.0 ± 0.1J/cm under 365nm²Mode adjust the time for exposure.30 minutes calcination processings are carried out at 230 DEG C, thus shape At the film of film thickness about 100nm.The UV-Vis of liquid crystal orientation film 1 obtained is measured using the V-660 of Japan's light splitting manufacture Spectrum is simultaneously shown in Figure 1.Transmitance of the average value of the transmitance of 390nm~410nm as liquid crystal orientation film 1 is calculated, as a result It is 85%.

[2~embodiment of embodiment 20]

In addition to changing used varnish, formation, the transmitance measurement of liquid crystal orientation film are carried out according to embodiment 1. Used varnish and measurement result are shown in Table 4 together with embodiment 1.

Table 4

Be used alone diamines of the invention as with photoreactivity structure raw material 1~embodiment of embodiment 3, implement In 10~embodiment of example 14 and 17~embodiment of embodiment 20, transmitance is 80% or more and is optimal.In addition, and with the present invention Diamines and structure in reality of the diamines represented by the formula (V-2-1) with azobenzene as the raw material with photoreactivity structure It applies in 4~embodiment of example 9, embodiment 15 and embodiment 16, transmitance is 75%~81% and also good.

[1~comparative example of comparative example 2]

In addition to changing used varnish, the measurement of UV-Vis spectrum is carried out according to embodiment 1.It will be used clear Paint and measurement result are shown in Table 5.The UV-Vis spectrum of comparative example 1 is shown in Figure 2.

Table 5

In comparative example 1 and comparative example 2, transmitance is 67% and 71%, poor compared with 1~embodiment of embodiment 20.Its Reason is: formula (V-2-1) with azobenzene structure and formula (V-3-1) is used only as having light anti-in varnish 29 and varnish 30 The raw material of answering property structure.Azobenzene has in visible light region to be absorbed, it is thus regarded that by the aligning agent for liquid crystal that azobenzene is used only The liquid crystal orientation film of formation can not obtain good result in terms of the value of transmitance.

[embodiment 21] the AC image retention measurement production and evaluation of liquid crystal cells

Separately using rotator method by aligning agent for liquid crystal 1 be coated on glass substrate with FFS electrode and with intercolumniation every On the glass substrate of object (column spacer) (2,000rpm, 15 seconds).After coating, substrate add within 1 minute at 60 DEG C Heat, after evaporating solvent, Mu Qilaite (Multi-Light) ML-501C/B manufactured using oxtail motor (share), from relatively The linear polarization of ultraviolet light is irradiated via polarizer in substrate and the direction of vertical.Exposure energy at this time is using oxtail electricity The ultraviolet light of machine (share) manufacture adds up quantometer UIT-150 (optical receiver: UVD-S365) to measure light quantity, in wavelength Become 2.0 ± 0.1J/cm under 365nm²Mode adjust the time for exposure.30 minutes calcination processings are carried out at 230 DEG C, thus shape At the film of film thickness about 100nm.Then, these are formed with two plate bases of liquid crystal orientation film so as to be formed with liquid crystal orientation film In face of to and it is opposite to liquid crystal orientation film between be arranged and pasted to inject the mode in the gap of liquid-crystal composition It closes.At this point, keeping the polarization direction of the linear polarization irradiated to each liquid crystal orientation film parallel.Into these units, vacuum injection is negative Type liquid-crystal composition A, and inlet is closed using photo-hardening agent, thus 4 μm of production unit thickness of liquid crystal cells (liquid crystal Show element).The AC image retention of liquid crystal display element obtained is measured, as a result Δ B is 3.1%.

< negative type liquid crystal composition A >

Physics value: 75.7 DEG C of NI；Δε-4.1；Δn 0.101；η14.5mPa·s.

[embodiment 22]

In addition to used aligning agent for liquid crystal is changed to aligning agent for liquid crystal 4, liquid crystal list is made according to embodiment 21 First (liquid crystal display element).The AC image retention of liquid crystal display element obtained is measured, as a result Δ B is 2.0%.

According to embodiment 21, embodiment 22 as a result, confirming: using aligning agent for liquid crystal of the invention liquid crystal display Element has good orientation.

[embodiment 23] preparation of doping type aligning agent for liquid crystal, the formation of liquid crystal orientation film, transmitance measurement

It is synthesized in the synthesis example 4 for weighing 3.0g into the 50mL eggplant type flask for being equipped with stirring wing, nitrogen ingress pipe clear The varnish 21 synthesized in the synthesis example 24 of 1 and 7.0g is painted, adds n-methyl-2-pyrrolidone, the fourth of 1.0g of 3.0g thereto The diisobutyl ketone of base cellosolve and 1.0g is stirred at room temperature 1 hour, to obtain the liquid of 4 weight % of resin component concentration Brilliant alignment agent 23.Using aligning agent for liquid crystal 23 obtained, and according to the method recorded in embodiment 1 and in transparent glass substrate Upper formation liquid crystal orientation film 23.UV-Vis spectrum is measured, as a result the average value of the transmitance of 390nm~410nm is 93%.

[24~embodiment of embodiment 66]

In addition to changing used varnish, the measurement of UV-Vis spectrum is carried out according to embodiment 23.It will be used Varnish and measurement result are shown in Table 6 together with embodiment 23.Furthermore in table 6, varnish A is indicated containing using with light reaction Property structure raw material polymer varnish, varnish B indicate containing be not used with photoreactivity structure raw material polymer Varnish.

In 23~embodiment of embodiment 66, transmitance is 90% or more and is good.By using doping type liquid crystal aligning Agent can get high transmitance compared with using single-layer type aligning agent for liquid crystal.

[3~comparative example of comparative example 4]

In addition to changing used varnish, the measurement of UV-Vis spectrum is carried out according to embodiment 23.It will be used Varnish and measurement result are shown in Table 7.Furthermore in table 7, varnish A is indicated containing using the raw material with photoreactivity structure The varnish of polymer, varnish B indicate the varnish containing the polymer that the raw material with photoreactivity structure is not used.

Table 7

In comparative example 3 and comparative example 4, compared with 23~embodiment of embodiment 66, transmitance is poor.Its reason is: varnish 29 and varnish 30 formula (V-2-1) with azobenzene and formula (V-3-1) is used only as the raw material with photoreactivity structure.? In the case where using doping type aligning agent for liquid crystal, azobenzene has in visible light region to be absorbed, it is thus regarded that by azo is used only The liquid crystal orientation film that the aligning agent for liquid crystal of benzene is formed can not also obtain good result in terms of the value of transmitance.

[embodiment 67]

It is synthesized in the synthesis example 4 for weighing 3.0g into the 50mL eggplant type flask for being equipped with stirring wing, nitrogen ingress pipe clear The varnish 21 synthesized in the synthesis example 24 of 1 and 7.0g is painted, adds n-methyl-2-pyrrolidone, the fourth of 1.0g of 4.0g thereto The additive (Ad1) of base cellosolve and 30mg, is stirred at room temperature 1 hour, thus obtain resin component concentration be 4 weight %, Additive concentration is the aligning agent for liquid crystal 69 of 5 parts by weight relative to 100 parts by weight of resin component.It is taken using liquid crystal obtained To agent 69, and liquid crystal orientation film 69 is formed according to the method recorded in embodiment 1 and on transparent glass substrate.To UV-Vis light Spectrum is measured, and as a result the average value of the transmitance of 380nm~780nm is 93%.

[68~embodiment of embodiment 110]

In addition to changing used varnish, the measurement of UV-Vis spectrum is carried out according to embodiment 67.It will be used Varnish and measurement result are shown in Table 8 together with embodiment 67.Furthermore in table 8, varnish A is indicated containing using with light reaction Property structure raw material polymer varnish, varnish B indicate containing be not used with photoreactivity structure raw material polymer Varnish.

In 67~embodiment of embodiment 110, transmitance is 90% or more and is good.Known to: the liquid crystal containing additive In alignment agent, high transmitance is also shown.

[5~comparative example of comparative example 6]

In addition to changing used varnish and additive, the measurement of UV-Vis spectrum is carried out according to embodiment 67.It will Used varnish and measurement result are shown in Table 9.Furthermore in table 9, varnish A is indicated containing using with photoreactivity structure Raw material polymer varnish, varnish B indicate containing be not used with photoreactivity structure raw material polymer varnish.

Table 9

In comparative example 5 and comparative example 6, compared with 67~embodiment of embodiment 110, transmitance is poor.Its reason is: varnish 29 and varnish 30 formula (V-2-1) with azobenzene and formula (V-3-1) is used only as the raw material with photoreactivity structure.Contain Have in the aligning agent for liquid crystal of additive, azobenzene has in visible light region to be absorbed, it is thus regarded that by the liquid that azobenzene is used only The liquid crystal orientation film that brilliant alignment agent is formed can not also obtain good result in terms of the value of transmitance.

[32~synthesis example of synthesis example 42]

In addition to change tetracarboxylic dianhydride and diamines, it is 6 weights that polymer solids constituent concentration is prepared according to synthesis example 4 Measure 31~varnish of varnish 41 of %.About weight average molecular weight, a kind of polymer of the compound (2) as raw material will be used Be adjusted to about 5,000 to 20,000, by unused compound (2) as a kind of polymer of raw material be adjusted to 45,000 to 50,000.The weight average molecular weight of used tetracarboxylic dianhydride and diamines and polymer obtained are shown in Table 10.

Table 10

[111~embodiment of embodiment 116]

In addition to changing used varnish, formation, the transmitance measurement of liquid crystal orientation film are carried out according to embodiment 1. Used varnish and measurement result are shown in Table 11.

Table 11

111~the embodiment of embodiment 116 of diamines of the invention as the raw material with photoreactivity structure is used alone In, transmitance is 80% or more and is optimal.

[117~embodiment of embodiment 139]

In addition to changing used varnish, the measurement of UV-Vis spectrum is carried out according to embodiment 23.It will be used Varnish and measurement result are shown in Table 12.Furthermore in table 12, varnish A is indicated containing using the raw material with photoreactivity structure Polymer varnish, varnish B indicate containing be not used with photoreactivity structure raw material polymer varnish.

Table 12

In 117~embodiment of embodiment 139, transmitance is 90% or more and is good.It is taken by using doping type liquid crystal To agent, compared with using single-layer type aligning agent for liquid crystal, high transmitance can get.

[140~embodiment of embodiment 162]

In addition to changing used varnish, the measurement of UV-Vis spectrum is carried out according to embodiment 67.It will be used Varnish and measurement result are shown in Table 13.Furthermore in table 13, varnish A is indicated containing using the raw material with photoreactivity structure Polymer varnish, varnish B indicate containing be not used with photoreactivity structure raw material polymer varnish.

Table 13

In 140~embodiment of embodiment 162, transmitance is 90% or more and is good.Known to: the liquid crystal containing additive In alignment agent, high transmitance is also shown.

[industrial availability]

It is used by utilizing using the diamines of embodiments of the present invention as the liquid crystal of the polyamic acid of raw material or derivatives thereof Alignment agent can get transmitance and the high liquid crystal orientation film of orientation.The aligning agent for liquid crystal can suitably be applied to laterally electricity Field pattern liquid crystal display element.

Claims

1. a kind of light orientation aligning agent for liquid crystal contains with the composition list for represented by following formula (1) including photonasty base The polymer of member；

In formula (1),

R¹And R²It independently is the alkyl of hydrogen or carbon number 1~10；

The bond key that binding site is not secured to constitute on any one carbon of ring indicates that the binding site on the ring is any, benzene The hydrogen of ring can be replaced by substituent group.

2. light orientation aligning agent for liquid crystal according to claim 1 contains as next self-contained tetracarboxylic dianhydride and two The polymer of the reaction product of the raw material of amine；

Herein, the polymer is selected from by polyamic acid, polyimides, part polyimides, poly amic acid ester, polyamide At least one of group composed by acid-polyamide copolymer and polyamidoimide；

R⁴And R⁶It independently is straight-chain alkyl-sub ,-COO- ,-OCO- ,-NHCO- ,-CONH-, the-N (CH of carbon number 1~20₃)CO-、- CON(CH₃)-or singly-bound；

3. light orientation aligning agent for liquid crystal according to claim 2, wherein the diamines contains represented by following formula (3) At least one of diamines；

In formula (3), R⁴And R⁶It independently is straight-chain alkyl-sub ,-COO- ,-OCO- ,-the NHCO- ,-CONH- ,-N of carbon number 1~20 (CH₃)CO-、-CON(CH₃)-or singly-bound；

The bond key that binding site is not secured to constitute on any one carbon of ring indicates that the binding site on the ring is any.

4. light orientation aligning agent for liquid crystal according to claim 2 or 3, wherein the diamines contains following formula (4)~formula (7) at least one of the diamines represented by；

5. light orientation aligning agent for liquid crystal according to any one of claim 2 to 4, wherein the diamines contains following formula Diamines represented by (4-1), formula (4-2), formula (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2) It is at least one；

6. the light orientation aligning agent for liquid crystal according to any one of claim 2 to 5, wherein the raw material includes choosing in turn Freely at least one of group composed by following formula (II)~formulas (VI)；

R⁴-C≡C-R⁵ (II)

R⁴-C≡C-C≡C-R⁵ (III)

R⁴-C≡C-R⁶-C≡C-R⁵ (IV)

R⁴- N=N-R⁵ (V)

R⁵- CH=CH-R⁷ (VI)

In formula (II)~formula (VI), R⁴And R⁵For with-NH₂Any monovalent organic radical or any monovalent organic radical with-CO-O-CO-；

In formula (IV), R⁶For divalent organic base；

In formula (VI), R⁷For with-NH₂Or the aromatic rings of-CO-O-CO-.

7. light orientation aligning agent for liquid crystal according to any one of claim 1 to 6, is used for lateral electric-field type liquid crystal Show the manufacture of element.

8. a kind of liquid crystal orientation film, the shape by light orientation aligning agent for liquid crystal according to any one of claim 1 to 7 At.

9. a kind of liquid crystal display element, with liquid crystal orientation film according to claim 8.

10. a kind of lateral electric-field type liquid crystal display element, with liquid crystal orientation film according to claim 8.

11. a kind of diamines, by formula (4-2), formula (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2) It indicates；

12. a kind of polymer, wherein the polymer is selected from by polyamic acid, polyimides, part polyimides, polyamide At least one of group composed by acid esters, polyamic acid-polyamide copolymer and polyamidoimide, wherein the polymerization Object is the reaction product of tetracarboxylic dianhydride at least one diamines containing diamines represented by following formula (2):

13. polymer according to claim 12, wherein the diamines contains diamines represented by following formula (3) at least It is a kind of；

14. polymer according to claim 12 or 13, wherein the diamines contains represented by following formula (4)~formula (7) Diamines at least one；

15. polymer described in any one of 2 to 14 according to claim 1, wherein the diamines contains following formula (4-1), formula At least one of diamines represented by (4-2), formula (5-1), formula (5-2), formula (6-1), formula (6-2), formula (7-1) or formula (7-2)；